Shriver, The Manipulation of Air-Sensitive Compounds BOOK

I
scNnodr[oc
l^tilsN]s-dtv
JONO|rytndrNVlN
lHl
THEMANIPULATION
OF
AIR.SENSITIVE
COMPOUNDS
SECOND EDITION
D. F.SHRIVER
Nort hu'est ertt U tt i versi I v
Evonstott. Illinois
M. A. DREZDZON
Antoco C hetn icu ls Contpurty,
Nuperville, Illittois
A Wiley-lnfersciencePublicotion
JOHNWITEY& SONS
New York / Chichester / Brisbqne / Toronlo / Singopore
C o p v r i g h t i ' 1 9 8 6b v J o h n W i l e l c t S o n s . I n c .
A l l r i g h t sr e s e r v e ' dP.u b l i s h e ds i n r u l t a n e o u silnt C a n a d a .
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b e 1 ' o n dt h a t p e r n r i t t e db 1 ' S e c t i o n1 0 7o r l 0 U o f t h e
1 9 7 6U n i t e d S t a t e sC o p l ' r i g h t A c r \ \ ' i t h o u tt h e p c r n r i s s i o n
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t u n c r i s u n l a u f u l . I l c q u c s t sf o r
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t h e P e r m i s s i o nDs e p a r t m c n l .J o h n W i l o & S o n s .I n c .
Libru4' td Congre.ssCutaloging in Publication Data:
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l n c l u d e s b i b l i o g r a p h i c a lr e f e r e n c e sa n d i n d e x .
l. Chemistrv-Manipulation. 2. Vacuumtechnology.
3. Protectiva
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I . D r e z d z o n .M . A . ( M a r k A . ) I I . T i t l e .
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PREFACE
The continued importanceof researchand developmentwith air-sensitivecompounds,coupledwith the generallack of publicationsor undergraduateinstruction on the techniquesused in this area, prompted us to revisethis monograph.
The levelof presentationis designedto make the book usefulto the chemistwho
is beginning work in the field. In addition, considerabletechnicaldata and information are given that should aid chemistsat all levelsof proficiencyin the
designof experiments.
In the belief that the beginner needsa selectiveapproachand the more seasonedworker will exercisehis ingenuity,we haverefrainedfrom presentingbrief
referencesto many similar items of equipment, but have attempted to present
rational approachesto the common operationsinvolvedin the synthesis,separation, and characterizationof air-sensitivematerials,and to illustratethesewith
typical apparatus. Wheneverpossible,theseexamplesare basedon equipment
with which we havehad experienceor on firsthand observationof the equipment
usedby others. This has resultedin a somewhatpersonalizedaccount,which we
hope will ensure reliability without being objectionableto establishedworkers
with different preferencesin equipment design.The techniquesdiscussedhere
were largely developedfor use with inorganic and organometalliccompounds;
however,they are generallyusefulfor problens involvinggasesand air-sensitive
solids or liquids, so they find application in all areas of chemistry, as well as
biology and physics.
We had two goals in mind while writing this secondedition. The first was to
bring the text up to date. Although there have been no radical new developments, there has been a steadyimprovementin technique.Our secondobjective
was to make the book more accessible
to the readerinterestedin a specifictechnique. Thus more section headingsare used and more detailed examplesare
given.
PREFACE
The continued importanceof researchand developmentwith air-sensitivecompounds,coupledwith the generallack of publicationsor undergraduateinstruction on the techniquesused in this area, prompted us to revisethis monograph.
The levelof presentationis designedto make the book usefulto the chemistwho
is beginning work in the field. In addition, considerabletechnicaldata and information are given that should aid chemistsat all levelsof proficiencyin the
designof experiments.
In the belief that the beginnerneedsa selectiveapproachand the more seasonedworker will exercisehis ingenuity,we haverefrainedfrom presentingbrief
referencesto many similar items of equipment, but have attemptedto present
rational approachesto the common operationsinvolvedin the synthesis.separation, and characterizationof air-sensitivematerials,and to illustratethesewith
typical apparatus. Wheneverpossible,theseexamplesare basedon equipment
with which we havehad experienceor on firsthand observationof the equipment
usedby others.This has resultedin a somewhatpersonalizedaccount,which we
hope will ensure reliability without being objectionableto establishedworkers
with different preferencesin equipment design.The techniquesdiscussedhere
were largely developedfor use with inorganic and organometalliccompounds;
however,they are generallyusefulfor problemsinvolvinggasesand air-sensitive
solids or liquids, so they find application in all areasof chemistry, as well as
biology and physics.
We had two goals in mind while writing this secondedition. The first was to
bring the text up to date. Although there have been no radical new developments, there has been a steadyimprovementin technique.Our secondobjective
was to make the book more accessible
to the readerinterestedin a specifictechnique. Thus more section headingsare used and more detailed examplesare
given.
PREFACE
In the preparationof the first edition of this book aid u'asreceivedfrom nrany
p e o p l e :A . L . A l l r e d , F . B a s o l o ,R . L . B u r w e l l , J r . ,E . W . S c h l a g ,P a u l T r e i c h e l ,
R. W. Fowells,and Shirley Shriver. Useful suggestionsfor the secondedition
were providedby L. Aspry, R. L. Burwell, Jr., P. Bogdan. N. J. Cooper,
D . K u r t z . J . M a l m , a n d S . H . S t r a u s sF
. or aidin proofreading
w e a p p r e c i a t et h e
h e l p o f A n n C r e s p i , C y n t h i aS c h a u e r ,D a n i e l S h r i v e ra n d R a l p h S p i n d l e r .
D. F. Ssnrvrn
M. A. DnpzpzoN
Evanston. Illinois
Nuperville. Illinois
Februum, I986
CONTENTS
INTRODUCTION
PART4 INERT-ATMOSPHERE
TECHNIOUES
'l grNcx-roprNERT-ATMospHERETEcHNToUES
l.l
1.2
1.3
1.4
I .5
1.6
l 7
T e c h n i q u e sf o r P u r g i n ga n d D r y i n g A p p a r a t u s ,7
A d a p t a t i o n so f S t a n d a r dG l a s s w a r eI, I
S y r i n g ea n d C a n n u l aT e c h n i q u e s l,3
Q u a n t i t a t i v eG a s M a n i p u l a t i o n ,2 4
-Iechniques,
30
Schlenk
P
r
e
s
s
u
r
e
R
e
actors,4l
Cappable
T
H o t T u b e a n d S e a l e d u b e T e c h n i o u e s4. 2
G e n e r a lR e f e r e n c e s . 4 4
GLovEBoxEs
2 INERT-ATMosPHERE
45
2 . 1 G e n e r a lD e s i g na n d A p p l i c a t i o n s 4, 5
2 . 2 R e p l a c e m e not f A i r b y a n I n e r t A t m o s p h e r e4. 7
2.3 Sourcesof and Reductionof Impurities in Glove Box
A t m o s p h e r e s5. 1
2.4 Glove Box Hardware and Procedures,59
2.5 Typical Glove Box Systems,62
2 . 6 E q u i p m e n ta n d O p e r a t i o n s 6
,4
General References.66
puRrFrcATroN
GASES
ANDTHErR
3 INERT
68
snd Purity,68
3.1 Sourcea
3 . 2 P u r i f i c a t i o no f G a s e s .6 9
vll
CONTENTS
viii
3 . 3 I n e r t - G a sP u r i f i c a t i o nS y s t e m s8, 0
3 . 4 D e t e c t i o no f I m p u r i t i e s ,8 3
ANDREAGENTS
oF sotvENTs
4 puRrFrcATroN
4.1
4.2
4.3
4.4
4.5
4.6
84
S o l v e n tP u r i f i c a t i o n .8 4
SolventStorage,89
D e t e c t i n gI m p u r i t i e s ,8 9
P u r i f i c a t i o no f S p e c i f i cS o l v e n t s9, 0
P u r i f i c a t i o no f S o m eC o m m o n l yU s e d G a s e s ,9 2
A n h y d r o u sM e t a l H a l i d e s ,9 5
G e n e r a lR e f e r e n c e s . 9 6
PART2 VACUUM LINEMANIPULATIONS

5 vAcuuM LINE
DESTeN
ANDoPERAIToN
99
5 . 1 G e n e r a lD e s i g n ,9 9
5 . 2 I n i t i a l E v a c u a t i o n .1 0 3
5 . 3 M a n i p u l a t i o no f V o l a t i l eL i q u i d s a n d
C o n d e n s a b lG
e a s e s .1 0 4
5 . 4 L o r v - T e n r p e r a t u rBea t h s . 1 0 9
5.5 Vapor Pressureas a CharacteristicProperty, I l3
5 . 6 M a n i p u l a t i o no f N o n c o n d e n s a b lGe a s e s ,I l 3
5 . 7 S a f e t y ,1 1 6
G e n e r a lR e f e r e n c e sl l. 7
FoRRoUGH
ANDHIGHvAcuuM
6 PUMPs
.t.t8
6 . 1 R o u g h - V a c u u nS
l y s t e m s l, l 8
6 . 2 H i g h - V a c u u mP u m p i n gS y s t e m sI,l 9
AND
7 PRESsURE
ANDFLOwMEAsUREMENT
IEAKDETECTION
7 . 1 M a n o m e t r y( l - 7 6 0 t o r r ) , 1 2 9
7 . 2 M e d i u m -a n d H i g h - V a c u u m
M e a s u r e m e n t( s1 0 r - 1 0 6 t o r r ) . 1 3 7
7 . 3 L e a k D e t e c t i o n .1 4 3
7 . 4 F l o w M e a s u r e m e n t 1. 4 6
7.5 Flow Control. 149
G e n e r a lR e f e r e n c e s1. 5 0
t29
CONTENTS
8 JorNTs,
sToPcocKs,
ANDvALVES
IX
152
8 . 1 J o i n t s ,1 5 2
8 . 2 S t o p c o c k s1
, 61
8 . 3 V a l v e s .1 6 4
9 spEcrALrzED
vAcuuMLINE
EeutpMENT
ANDopERATtoNs .r68
9.1
9.2
9.3
9.4
9.5
C h a r a c t e r i z a t i o n1. 6 8
S e p a r a t i o n s1, 9 0
Storageof Gasesand Solvents,200
SealedTube Reactions.202
M i s c e l l a n e o uTs e c h n i q u e s2, 0 6
'10 MEIALsYsTEMS
210
l0.l CompresseG
d a s e s ,2 1 0
1 0 . 2 C u t t i n g a n d B e n d i n gT u b i n g , 2 1 4
1 0 . 3 T u b i n g , J o i n t s ,a n d F i t t i n g s ,2 1 5
1 0 . 4 H e a v y - W a l l e dT u b i n g a n d P i p eJ o i n t s ,2 1 9
1 0 . 5 V a l v e s2
. 22
10.6 PressureGauges,227
1 0 . 7 T y p i c a l M e t a l S y s t e m s2, 2 7
APPENDIX
I SAFETY
I.l
I.2
I.3
L4
I.5
I.6
I.7
C o m b u s t i b l e s2, 3 7
U n s t a b l eC o m p o u n d s 2
, 38
S o m eD a n g e r o u sM i x t u r e s ,2 3 8
Disposalof ReactiveWastes,239
H i g h - P r e s s u rG
e a s C y l i n d e r s2
. 40
A s p h y x i a t i o nb y I n e r t G a s e s ,2 4 0
E x t i n g u i s h i n gF i r e s ,2 4 0
APPENDIX
II GLASS
ANDGLASSBLOWING
II.l
IL2
II.3
II.4
ll.5
IL6
II.7
I-
237
P r o p e r t i e so f G l a s s e s2, 4 2
E q u i p m e n ta n d M a t e r i a l s ,2 4 5
Sequence
of Operations2
. 47
Annealing,247
C u t t i n g G l a s sT u b i n g , 2 4 8
B e n d i n gG l a s sT u b i n g , 2 4 9
T e s t - T u b eE n d s a n d F i r e C u t o f f s .2 4 9
242
CONTENTS
II.8
IL9
II.l0
I I. I I
II.l2
II.l3
IL14
E n d - t o - E n dS e a l s 2. 5 1
T - S e a l s .2 5 3
R i n g S e a l s 2. 5 3
C l o s e dC i r c u i t s .2 5 5
Metal-to-GlasS
s e a l s .2 5 5
H e a l i n gC r a c k sa n d P i n H o l e s ,2 5 6
S e a l i n gT u b i n g u n d e r V a c u u m , 2 5 7
APPENDIXIII PLASTICSAND ELASTOMERS

III.I
IlL2
III.3
III.4
lll.5
259
P l a s t i c sG
: e n e r a lP r o p e r t i e sa n d F a b r i c a t i o n . 2 6 0
C e l l u l a rP l a s t i c s 2. 6 5
P r o p e r t i e so f S p e c i f i cP l a s t i c s 2, 6 7
Elastomers.272
P r o p e r t i e so f S p e c i f i cE l a s t o n r e r s2, 7 2
IV METATS
APPENDIX
275
I V . l P r o p e r t i e so f S p e c i f i cM e t a l s ,2 7 6
APPENDIXV
VAPOR PRESSURES
OF PURESUBSTANCES
28tl
V.l Analy'ticalRepresentationof Vapor

P r e s s u r eD a t a . 2 8 1
V.2 Least-SquaresFitting Procedurefor the
A n t o i n e E q u a t i o n ,2 8 . 1
V . 3 C o r r e l a t i o na n d E s t i m a t i o no f
Vapor Pressures,286
V . 4 T a b l e o f V a p o r P r e s s u r e s2.8 9
V . 5 S o u r c e so f V a p o r P r e s s u r eD a t a . 3 1 3
VI PRESSURE
APPENDIX
ANDFLOWCONVERSIONS
3,15
INDEX
3.19
INTRODUCTION
A. Generol Mefhods.
The most widely usedmethodsfor handling air-sensitivecompoundsare basedon the useof an inert gas atmosphereto excludeair.
This approachmay be further subdividedinto ( 1) thosetechniqueswhich involve
bench-top operationswith specialglassware(often called Schlenktechniques,
Chapter 1) and (2) glove box techniquesin which conventionalmanipulations
are perfornredin an inert-atmospherebox (Chapter 2). Both of these methods
may be used to handle large quantitiesof solidsand liquids; however,the Schlenk type equipment is generallymuch more efficientand more securefrom the
atmospherethan the dry box. The principal advantagesof the dry box lie in its
use for intricate manipulationsof solidsand for the containmentof radioactive
and/ or highly poisonoussubstances.
More rigorous exclusionof air and the quantitativemanipulation of gasesis
achievedin a previouslyevacuatedapparatus.This vacuum line method is outlined in Chapter 5, wherethe basic operationsare described,such as quantitative transfer and pressure-volume-temperature
measurementof gases,trap-totrap separations of volatile materials, and the use of vapor pressuresto
characterizesubstances.Succeedingchapters(6-8) describein detail the individual vacuum line componentssuch as stopcocks,joints, diffusion pumps, and
manometers.Many accessoryitems such as spectroscopycells, vapor-pressure
thermometers,and gas-chromatography
apparatusare describedin Chapter 9.
This set of chapters, plus supplementarymaterial in the Appendixes,form a
guide to modern glassvacuum line practice.This techniquehas been usedsuccessfullyin the synthesisand manipulationof hydrides,halides,and many other
volatile substances.However, glass vacuum systemsare not appropriate for
hydrogenfluoride and someother reactivefluorides.Theseare best handled in
the metal or fluorocarbonapparatusdescribedin Chapter 10. The strengthsof
thesevarioustechniquesfor handling air-sensitivematerialsare summarizedin
Table l
INTRODUCTION
Toble '1. Comporisonof lnert-Almosphere

ond Vocuum LineTechniques
Technique
Exclusionof Air Quantities"
OutstandingFeatures
Schlenk and
syringe
Good to very
good
Medium to
large
Glove box
Poor to very
good
Small to very
large
Vacuumline
Very good to
excellent
Very small to
medium
Rapid and easymanipulation

of solutions;simple fansfer
of solids
lntricate transferoperations;
containmentof poisonousand
radioactivesubstances
Quantitativegas handling;
transfer and storageof volatile
solvents ithoutcontaminalion
l r a m s l l a r g e , h u n d r e d so f g r a m s ;
"Very small, about I mgl small. about 100mgl medium, severag
very large.kilogranrs.
B. Plonning lhe Expeliment.

Whatevergeneraltechniqueis used,it is important to plan each new experiment in detail. Impassescan be avoided b1'
sketchingthe setupat eachstepwith due attentionpaid to the methodfor transferring materials.If measurementsare involved,a simpleestimateof the potential errors should precedethe newly planned experimentto ensurethat results
will be determinedwith meaningfulaccuracv.Frequently.such an estimatewill
suggestconditionsand apparatusdesignswhich will minimize the errorswithout
i n t r o d u c i n ga n y n e w c o m p l i c a t i o n s .
C. Appololus Design. Sometimesit is necessaryto design and construct
special apparatus. Three criteria for a good design are: (1) Is it the sinrplest
design consistentwith its intended purpose?(2) Is it robust? (3) Is it easyto
clean?To ensurethat an item is sturdy it should be designedso that stresses
are
not concentratedin small sectionsof glass.For pernranentinstallations,such as
a v a c u u ml i n e . a l l h e a v yi t e n t sa r e i n d i v i d u a l l ys u p p o r t e d r. v h i l et h e l i g h t e rs e c tions are clampedat the minimum number of points u'hichsufficeto supportthe
apparatusand avoid leverage.Generall,v.portableglass\'are
shouldbe designed
as one strong, compact unit \r'hich may be supportednear a point of balance.
F i n a l l y ,t h e m a t e r i a l so f c o n s t r u c t i o nm u s t r v i t h s t a n dt h e c h e m i c a l sa n d s o l v e n t s
w h i c h a r e t o b e h a n d l e d . T h e m o s t f r e q u e n t p r o b l e m sa r i s e w i t h s t o p c o c k
greases,\\'axes,rubbers, and plastics.Theseproblen'lsmay be minimized by selecting materialson the basisof the information on chemicaland solventresistance which is preserrtedin Chapter 8 and Appendix IIl. To aid in the proper
choiceof metals,information on their corrosionresistanceis givenin Chapter 10
a n d A p p e n d i xI V .
's{?OJ
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PARII
Inert-Atmosphere
Techniques
TEcHNtoUES
TNERI-ATMoSpHERE
eENcH-Top
e v a c u a t i o no f t h e a p p a r a t u s a
, n d i f t h e r e a r e n o l e a k si n t h e a p p a r a t u sn, r e p e t i tions of the pump-and-fill processwill reducethe fraction of atmosphericgases
A, to
(l)
The secondmethod for removingatmosphericgasesinvolvessweepingair out
of the apparatusby a flush of inert gas. The factorswhich influencethis type of
processare discussedin detail in Chapter 2. For the present.it is adequateto
note that a continuousflush of inert gas, u'hich pushesthe atmosphericgases
from one extremeof the apparatusto an outlet on another extreme,as in Fig.
1 . 1 , i s m o s t e f f i c i e n t .T h i s s o - c a l l e dp l u g f l o w i s d i f f i c u l t t o a c h i e v ew i t h s i n g l e neck flasks and similar apparatus.A flow of inert gaswhich bypassespart of the
apparatusis relativelyinefficient.
B. Purging on Open Vessel. In many operationsdescribedin this chapter, it is necessary
to open the apparatusbriefly while an inert-atmosphere
flush
is maintained out of the opening to minimize the entranceof air. Even under
conditions in which there is little turbulence in the flowing inert gas stream,
In e r l - g a s
r n l e t2
--\
To
nooo
water
\
Mineral
oil bubbler
Fig. l.l.
T h r e e - n e c k e dr e a c t i o nf l a s k w i t h d r o p p i n g f u n n e l . s t i r r e r , a n d r e f l u x c o n d e n s e r .W i t h
t h e d r o p p i n g f u n n e l s t o p c o c ki n t h e o p e n p o s i t i o n .a f l o u o f i n e r t g a s f r o m i n l e t I t h r o u g h t h e m i n e r a l o i l b u b b l e r e f f i c i e n t l yp u r g e st h e a p p a r a t u so f a t m o s p h e r i cg a s e s .D u r i n g r e a c t i o na n d s u b s e q u e n t c o o l i n go f t h e r e a c t i o n m i x t u r e . a s l o w f l o w o f i n e n g a s f r o n r i n l e t 2 t h r o u g h t h e m i n e r a l o i l
b u b b l e r p r e v e n t sa t m o s p h e r i cg a s e sf r o m b a c k i n g u p i n t o t h e s y s t e m .a n d t h i s c o n f i g u r a t i o nm i n i m i z e se x p o s u r eo f t h e r e a c t i o n m i x t u r e t o i m p u r i t i e s i n t h c -i n e r t g a s .
TECHNIOUES
FORPURGINGAND DRYINGAPPARATUS
there will be countercurrentdiffusion of atmosphericgases.An estimateof the

flow rateI necessary
to maintain the partial pressureP11
of an atmosphericcomponent at some desiredpartial pressureP inside the apparatusis given by the
equationl
L -
-(ADt.2/X)ln(P/Po)
Q)
where,4is the cross-sectional

areaof the tube through which the gasis issuing,X
is the length of this tube, and D1.2is the diffusion coefficientof the impurity gas
I in the inert gas 2. In round numbers, the diffusion coefficientof oxygenin
nitrogenis 0.2 cm2ls at I atm total pressure,and a desirablepartial pressurefor
oxygenwithin the apparatusmight be 10-rtorr. If we assumethat the neck of a
flask is 1.5 cm in diameter and 5 cm long. Eq. (2) indicatesthat a nitrogenflow
rate of only 50 cm3/min would be required to maintain this low levelof oxygen.
Experienceteachesus that far larger flow ratesare required; somethingon the
order of severalliters per minute would be typical under theseconditions.Even
though Eq. (2) doesnot appearto apply to the rather largeopeningscommon to
many preparative-scale
apparatus designs,it is probably much more accurate
for the less turbulent flow of gas from smaller-diametertubing. The general
form of the equationis sensible,suggestingthat the entranceof air is reducedby
a long-neckedflask with a small crosssectionfor this neck.
Pure inert gas.generallynitroC. Monifold fot Inert Gos ond Vocuum.
gen but sometimesargon or helium, is required for the operationsdescribedin
this chapter. As describedearlier, equipment is filled with the gas by purging
with a large volume of gas, or evacuationfollowed by filling with the gas. To
accomplishthesepurging operationsin an efficient manner it is handy to have
an inert-gasmanifold with severalheavy-walledflexible vinyl or rubber tubes
attachedto provide inert gasto separatepiecesof apparatus.A mineral oil bubbler, or occasionallya mercury bubbler, is attachedto the gas outlet on the apparatusto protect againstexcessivepressure.
When the pump-and-fill techniqueis used,a more complexmanifold for the
distribution of inert gas and vacuunl is generallyemployed,in conjunctionwith
a liquid nitrogen-cooledtrap, mechanicalvacuum pump, and pressurerelease
b u b b l e r s( F i g . 1 . 2 ) .
This manifold can be usedto purge severalpiecesof apparatusat once, and
the two-way stopcocksor valvesprovide a ready means of switching betweeninert gas and vacuum. Sourcesof purified inert gas and vacuum are attachedto
this manifold. An oil bubbler on the inert gas inlet servesas an approximateflow
indicator. The inert gas is controlledat the tank with a high-qualitydual-stage
diaphragm regulator which is designedfor good regulation around 3 psig (915
torr). A pressurereleasebubbler is often included on the inert gas line. Glass
stopcocksattachedto thesemanifolds will becomedislodgedby the small positive pressureof inert gas. Therefore,it is essentialto securethesestopcocks,and
r G . A n t o s . P h . D . T h e s i s ,N o r t h w e s t e r nU n i v e r s i t v .1 9 7 3 .
,10
TECHNIQUES
BENCH.TOP
INERT-ATMOSPHERE
To vacuum
pump
release
Pressure
bubbler
.r'
To apparatus
Low-temoerature
trao
F i g . 1 . 2 . M a n i f o l d f o r m e d i u m v a c u u ma n d i n e r t g a s .A l o w - t e m p e r a t u r e
t r a p , o n t h e r i g h t s i d eo f
t h e f i g u r e , i s u s e di n t h e v a c u u m l i n e t o p r o t e c tt h e p u m p f r o m h a r m f u l v a p o r s .W h e n t h e a p p a r a t u s
i s b e i n g f i l l e d u ' i t h g a s o r p u r g e d * ' i t h i n e r t g a s . t h e v a l v e o n t h e p r e s s u r er e l e a s eb u b b l e r ( u h i c h
c o n t a i n sa c h e c kv a l v et o p r e v e n to i l f r o m b a c k i n g u p i n t o t h e l i n e ) i s o p e n e dt o a v o i de x c e s sp r e s s u r e
u ' h i c hw o u l d b l o * t h e a p p a r a t u sa p r t . O f l e n a m i n e r a l o i l b u b b l e r ( n o l s h o w nh e r e )i s c o n n e c t e di n
l i n e u ' i t h t h e i n e r t - g a ss o u r c et o p r o v i d ev i s u a l i n d i c a t i o no f t h e i n e r t - g a sf l o w .
a l l o t h e r s u s e d o n i n e r t - a t m o s p h e r ee q u i p m e n t , w i t h h i g h - q u a l i t y p l u g
retainers.2
Details on the purification of inert gasescan be found in Chapter 3. The
sourceof vacuum is generallya rotary mechanicalvacuum pump. The pump is
protectedfrom chemicalsand solventvapor by meansof a trap cooledby Dry Ice
or, preferably,liquid nitrogen.CAUTION: A liquid nitrogentrap must neverbe
connectedto a manifold where the vacuum sourcehas been turned off. Failure to
removea liquid nitrogen trap from a manifold after shutting off the vacuum will
result in the condensationof liquid air in the trap. If warmed up, this liquid air
will evaporate and may pressurizethe apparatus, presenting an extreme explosion hazard. It is desirablefor this trap to be deepenoughto extendto the bottom of a l-L Dewar, thus permitting long-termcooling.The trap shouldbe easily removedso that accumulatedcondensablescan be readily (and frequently)
discarded.
D. PUrging Sylinges. Syringes

purgedfrom an inert-gas
are conveniently
sourcesuchasa tubewith a rapidlyflowinginert-gas
streamor a specialseptum
attachedto the inert-gasmanifold.Two or threecyclesof filling, removingthe
' E x c e l l e n tr e t a i n e r s( K - 8 0 9 0 0 0 ) .w h i c h m u s t b e u s e d u ' i t h s t o p c o c kp l u g s f r o n t
t u r e r , a r e a v a i l a b l ef r o n r K o n t e s G l a s s C o . V i n e l a n d N J .
t h e s a n r em a n u f a c
ADAPTATIONS
OF STANDARD
GLASSWARE
11
needlefrom the inert-gassource,and expellingthe gas are sufficient.If the syringe is going to be used to remove liquid fronr a flask which is being rapidly
flushed, the inert gas may be drawn from the flask and expelledoutsideof the
flask to purge the syringe. When highly moisture-sensitive
materials, such as
aluminum alkyls and activeborohydrides,are being handled, the syringeparts
should be stored in a drying oven around 130"C and removedjust prior to
purging.
E. Drying Glosswore.
The purging proceduresdescribedthus far remove
relativelylittle of the moisturewhich is adsorbedon glasssurfaces.When handling compounds which are highly moisture sensitive.such as aluminum hydrides. borane adducts, and lithiunr alkyls, it is often in'rportantto employ special drying procedures.A drying oven set at around l30oC can be usedto bake
out glasswarefor severalhours prior to use. This glasswareshould be flushed
with dry inert gas as it cools.To preventapparatusfrom stickingtogether,standard taper joints, stopcocks,and syringesshould be completelydisassenrbled
before they are placed in the oven.
Alternatively, the glasswaremay be flushed while it is being heated with a
Bunsenburner or heat gun. CAUTION: When using a Bunsenburner or heat
gun to dry glassware,all flammable materials must be removedfrom the area. If
the glasswarehas been rinsed with a volatile solvent, such as acetoneor methanol, to aid the drying process, the residual solvent vapors should be removed
from the glasswareprior to drying by purging severalminutes with inert gas. The
heatingis startednear the inert-gasinlet and carriedalongthe apparatustou'ard
t h e g a so u t l e t .
Silylatingagentshavealsobeenusedto treat glassrvare
beforehandling nrttist u r e - s e n s i t i vceo m p o u n d s .F o r e x a m p l e ,a c h l o r i n e - t e r n r i n a t epdo l - y d i n t e t h s- yi -l
-lhese
l o x a n ei s a v a i l a b l ec o n t n t e r c i a l l y . r
r e a g e n t ss u p p r e s st h e b a s i c i t l ' o f t h e
glassand provide a hydrophobicsurface.
4.2 ADAprATroNs
oFsTANDARD
GrAsswARE
Many operationsrvith air-sensitiveliquids can be perfornredin standardtaper
glasswarefitted with a bubbler and inert-gassource.NOTE: To avoid blowing
apparatus apart, stills and reaction pots should be vented to a bubbler before
they are heated. Figure I . I illustratesa typical setup for a three-neckreaction
flask equipped rvith a dropping funnel, stirrer, and reflux condenser.This arrangementprovidesseveralimportant featuresfor safeand efficientoperation.
Inert-gasinlet I and the oulet through the mineral oil bubbler are positionedfor
efficientinitial purge. Pressurebuildup, especiallyduring heating,is avoidedby
allowing pressurereleasethrough the bubbler. A constantslowflow of inert gas
r T h i s n r a t e r i a li s s o l d u n d e r t h e n a n r eG l a s s c l a db v P e t r a r c h
S l s t c m s .I n c . . B a r t r a n r R o a d . B r i s t o l .
PA 19007.
HJ
S t rIl - h e a d
thermometer
Insulated
v r g e r au x
column
to
nooo
I n e r l - g as
inlet 3
Mrneral
oil bubbler
Receiver
Heatrng
mantle
F i g . 1 . 3 . D i s t i l l a t i o n u n d e r i n e r t a t n r o s p h e r eu s i n g m o d i f i e d s t a n d a r dt a p e r \ r ' a r e .N o t e t h e s i d e a r n r a d d e d t o t h e s t a n d a r d s i n g l e - n e c k e ds t i l l p o t a n d r e c e i v e r .T h e s i d e a r mo n t h e s t i l l p o t a l l o w s
e f f i c i e n ti n i t i a l p u r g i n g o f t h e a p p a r a t u s ,w h i l e t h e s i d e a r mo n t h e r e c e i v e ra l l o u ' so n e t o m a i n t a i n a
b r i s k i n e r t - g a sf l o w o v e r t h e d i s t i l l e ds o l v e n tw h e n t h e r e c e i v e ri s r e n r o v e df r o m t h e s t i l l . T h e a p p a r a t u s i s i n i t i a l l l ' p u r g e d a s f o l l o ns : ( I ) T h e e n t i r e a p p a r a t u s ,e x c e p tf o r t h e r e c e i v e r i.s a s s e m b l e d(.2 )
I n e r t - g a si n l e t I i s o p e n e d u h i c h p u r g e s t h e s t i l l p o t . c o l u n r n , a n d c o n d e n s e r (. 3 ) T h e r e c e i v e ri s
a t t a c h e dt o i n e n - g a si n l e t 3 a n d p u r g e d s e p a r a t e l y(. 4 ) A f t e r b o t h t h e r e c e i v e ra n d t h e m a i n p a n o f
t h e a p p a r a t u sh a v e b e e n s u f f i c i e n t l yp u r g e d ( a b o u t 3 - 5 m i n ) , t h e r e c e i v e ri s a t t a c h e dt o t h e m a i n
a p p a r a t u ss ' h i l e m a i n t a i n i n g t h e i n e r t - g a sf l o w f r o n r b o t h i n l e t s I a n d 3 . W h e n t h e r e c e i v e ri s a t t a c h e d , t h e r e w i l l b e a v i g o r o u si n e r t - g a sf l o u ' t h r o u g h t h e m i n e r a l o i l b u b b l e r . ( 5 ) A s l o w f l o w o f
i n e r t g a s i s s t a r t e df r o m i n l e t 2 . T h e i n e r t - g a sf l o u ' f r o m i n l e t s I a n d 3 i s n o u t e r m i n a t e d .D i s t i l l a t i o n
m a y n o u b e g i n . T h e s l o * f l o * o f i n e r t - g a sf r o m i n l e t 2 t h r o u g h t h e m i n e r a l o i l b u b b l e r w i l l p r e v e n t
a i r f r o m b a c k i n g u p i n t o t h e a p p a r a t u su h i l e m i n i m i z i n g e x p o s u r eo f t h e s o l v e n tt o a n y i m p u r i t i e s
p r e s e n ti n t h e i n e r t g a s . I f t h e i n e r t - g a sf l o u i s m a i n t a i n e dt h r o u g h t h e s t i l l p o t d u r i n g t h e d i s t i l l a t i o n , t h e e f f i c i e n c yo f t h e s e p a r a t i o nw o u l d b e d e g r a d e d .W h e n t h e d i s t i l l a t i o ni s c o m p l e t e .t h e i n e r t g a s f l o w f r o m i n l e t J i s r e s u n r e db e f o r ed i s c o n n e c t i n gt h e r e c e i v e rf r o m t h e a p p a r a t u s .
12
SYRINGE
AND CANNULATECHNIOUES
43
:hrough inlet 2, with no flow from inlet 1, preventsair contaminationduring the

.rru15.o* the reactionwhile not exposingthe entire systemto any impuritiesthat
:rav be presentin the inert-gasstream.This slowinert-gasflow from inlet 2 also
rreventsair from being sucked in while the apparatusis cooling after the reac:ron l'lasbeen completed. Finally, this arrangementpreventsthe depletion of
: iqhly volatile solvents.
An apparatusfor distillation under inert atmosphere,illustratedin Fig. 1.3,
:ncorporatesthe samefeaturesseenin the inert-atmospherereactionapparatus
F i g . l . l ) . T h e d i s t i l l a t i o n a p p a r a t u sa l s o c o n t a i n ss o m e s l i g h t l y m o d i f i e d
round-bottomflasks for more efficient initial purging. Thesemodificationswill
re discussedin greater detail in the following section.
To minimize leakage,joints are either lightly greasedor equippedwith Teflon
.lc-eves,
and are held togetherwith springs,specialclips, or rubber bands.When
rr can be used,greaseprovidesthe tightestseal;however,Teflon sleevesare gen.:rally used for connectionsto still pots and similar harsh environnents. The
rarious types of stopcock grease,including the new solvent-resistant
Teflonhasedlubricants, are summarizedin Chapter 8. Greasedstandardtaper joints
rre readilyavailableand are adequatefor most purposes;however,O-ring joints
.rre superiorfor most inert-atmosphereapparatus.The advantagesof O-joints
arethat they are resistantto solvents,and the clampsusedwith thesejoints hold
rhe apparatustogethermuch more positivelythan do the springsand other derices used on standard taper joints. Very satisfactoryoperationis possiblewith
either standard O-joints or the Teflon-supportedO-ring joints (Solv-Seals).
Thesetypesof joints are describedfurther in Chapter8. If standardO-joints are
used, the O-ring material should match the solventsbeing handled; again,
Chapter 8 should be consultedfor details.
The principal drawbacksof the standard apparatusis that it is difficult to
flush efficiently and liquid transfer operationsare awkward. With little addirional complexity,the apparatuscan be adaptedfor efficientpurging and solution transfer by syringeor cannula.
{ ,3 syRrNeE
ANDcANNULA
TEcHNrouEs
A. TypicolAppololus.
A simplemodificationwhich improvesthe utility of
a one-neckstill pot or solventreceiveris a sidearm,which can be usedfor flushing the flask. This simple modification facilitatesthe initial flush of the apparatus shown in Fig. 1.3. Furthermore,the sidearmprovidesseveralalternatives
for the removalof solventsfrom a receiver,such as flushing the flask while solvent is removedthrough the standardtaperjoint, or removalof solventthrough
the sidearm, as illustrated in Fig. 1.4. The sidearmalso permits the flask to be
maintained under a constant flush of inert gas when it is attachedto another
p i e c eo f a p p a r a t u s( F i g . 1 . 5 ) .
TECHNIOUES
BENCH.IOP
INERT.ATMOSPHERE
(b)
F i g . 1 . 4 . T r a n s f e ro f s o l v e n tb y s y r i n g ef r o m a s t o r a g ef l a s k u ' i t h l h e e x c l u s i o no f a i r . ( a ) S o l v e n li s
r e m o v e dt h r o u g h t h e n e c k o f t h e s t o r a g ef l a s k w h i l e m a i n t a i n i n ga b r i s k f l o r v o f i n e r t g a s f r o m t h e
s i d e a r n t .( 6 ) S o l v e n ta l s o m a y b e r e m o v e dt h r o u g h t h e s i d e a r mw h i l e r r a i n t a i n i n g I a t m o f p r e s s u r e
i n t h e f l a s k b y a d m i t t i n g i n e r t g a st h r o u g h t h e i n l e t . I n b o t h ( a ) a n d ( b ) , t h e s y r i n g ei s i n i t i a l l y p u r g e d
b y s a m p l i n g i n e r t g a s f r o m t h e s t o r a g ef l a s k a n d e x p e l l i n gt h i s g a s o u t s i d et h e s t o r a g ef l a s k .
B. Septo ond Olher Closules. Rubber septamay be attachedin a variety

of ways,as illustratedin Fig. 1.6. The flat varietyis held in placeby screwcaps,
crinped caps, or beveledholders. Various manufacturersprovide apparatus
with thesetypesof septumclosures.a
Of greaterversatilityare the sleeveseptum
stoppers(Fig. 1.7), which can be attachedto straight tubes or standardtaper
joints without any specialfixtures.s
Two problemswith all septaare their sensitivityto solventsand chemicalsand
leakagethrough the punctured septum. Flat compositesepta minimize these
problenrs.Theseconsistof a central core of a compliant rubber, such as a soft
a S p e c i asl e p t u m c l o s u r e sa n d a p p a r a t u sw i t h t h e s ec l o s u r e sa r e m a n u f a c t u r e db y A c e G l a s s C o . ,
A l d r i c h C h e n r i c a lC o . . K o n t e sG l a s sC o . , a n d W h e a t o n G l a s sC o . i n t h e U n i t e d S t a t e s ,a n d S o v i r e l
in France.
s S l e e v e - t y psee p t u n r c l o s u r e sa r e u ' i d e l y a v a i l a b l ef r o m c h e m i c a l a n d h o s p i t a l s u p p l y h o u s e s .A n
e x c e l l e n ts l e e v es e p t u n rs t o p p e r ,p r o d u c e db y t h e S u b a S e a lC o . i n t h e U n i t e d K i n g d o m , i s a v a i l a b l e
t h e r e f r o m G a l l e n k a m p sa n d f r o m S t r e m C h e m i c a lC o . i n t h e U n i t e d S t a t e s .
SYRINGE
AND CANNUTATECHNIOUES
,15
F i g . 1 . 5 . J o i n i n g t w o p i e c e so f e q u i p m e n t u n d e r i n e r t - g a sf l u s h . B o t h p i e c e sa r e i n i t i a l l y p u r g e d
with inert gas separately before joining. Note the use of wire hooks and rubber bands to secure
i n d i v i d u a l p i e c e so f g l a s s w a r e I. f t h e g l a s s w a r ei s c o n s t r u c t e du s i n g O - r i n g j o i n t s , t h e O - r i n g j o i n t
c l a m p s h o l d t h e a p p a r a t u st o g e t h e r .
siliconerubber, sandwichedbetweenthin sheetsof Teflon. The siliconerubber

imparts good sealingaction, and the Teflon is highly resistantto solventsand to
permeationby atmosphericgases.Direct contact of solventswith septa should
be minimized and septa should be replacedoften. When organic solventsare
being used, one must be wary of impurities extractedfrom septa,joints, and
tubing. Theseextracted impurities may foul reactionsand causeconsiderable
confusionin the interpretationof IR and NMR spectra.The prime offendersare
hydrocarbonand siliconestopcockgreases,dibutyl phthalateand similar plasticizersfrom Tygon tubing, and variousextractsfrom rubber goods. Somespectral methodsfor identificationof thesenuisancesare collectedin Table 1.1. The
pickup of impurities from septa can be greatly minimized by prior extraction
with an appropriate hot solvent followed by pumping off the absorbed solvent
beforeuse.Septamake poor closuresfor containersusedfor the long-termstorage of highly air-sensitivematerials, since atmosphericgasesdiffuse through
R u b b e rs e P t u m-
\_
/@\
t_lTl
ltt
Itl
U/r
(b)
Gloss
To ooDorotus
(o)
F i g . 1 . 6 . M e t h o d s f o r a t t a c h i n g r u b b e r s e p t a t o g l a s s a p p a r a t u s .( a ) A m o d i f i e d S w a g e l o k - t y p e
f i t t i n g . T h e l i p o n o n e e n d o f t h e f i t t i n g i s t u r n e d d o r v n o n a l a t h e , a n d t h e s e p t u m r e p l a c e st h e
f e r r u l e s .O n t h e o t h e r e n d , a T e f l o n f r o n t f e r r u l e i s u s e dt o n r a k et h e c o n n e c t i o nu i t h a g l a s st u b e . ( )
A n a l l - g l a s ss e p t u n rh o l d e r . ( c ) C r o s ss e c t i o no f a p l a s t i ct h r e a d e dc a p s e p t u mh o l d e r o n a t h r e a d e d
g l a s ss i d e a r m( m a n u f a c t u r e db y W h e a t o n G l a s s C o . ) .
nn
W
NN
\trN
(a)
(b)
F i g , 1 . 7 . S e c u r i n ga S u b a - s e ailn t o a g l a s st u b e . ( a ) C r o s ss e c t i o no f S u b a - s e aal s i t i s i n s e r t e di n t o a
g l a s st u b e . ( b ) A f t e r i n s e r t i n g .t h e f l a p o n t h e S u b a - s e ails f o l d e d o v e r t h e t u b e . ( c ) T h e f l a p m a y b e
s e c u r e dt o t h e t u b e b y w i r c .
Ioble '1.'l SpeclrolSignoluresof lmpuriliesfrom SfopcockGreoseond

Rubberond Plosliclfems
Source
N i r t u r eo f I n r p u r i t !
Spectroscopic
Identification
Rubber septa
or tubing
D y e s .a n t i o x i d a n t s ,
etc.
Vis-UVabsorption
T_vgonand other
f l e x i b l ep o l y ( v i n y l
c h l o r i d e )t u b i n g
D i b u t y l p h t h a l a t ea n d
other plasticizers
N M R :M u l t .7 . 5 .d u b .4 . 5
M u l t .l . l - 1 . 9 ,
M u l t . 0 . 9 2p p m
Stopcocksand
joints
Siliconegrease
Apiezon L
N M R : c a .0 . 1p p m
N M R :c a .1 . 2 50, . 9p p m
ti6
SYRINGE
AND CANNULATECHNIOUES
17
\cpta and the rubber is likely to undergo chemical breakdown. One possible
.:rceptionto this statement is the use of unpunctured Teflon-coatedsepta as
>c'als;
but evenhere one is better off using sealedglassampulesfor storage.
C. Syringes. The principal variationsin availablesyringesare in the design
,rf the tips and plungers.For most preparative-scale
work, syringeswith removable needlesare employed.The removableneedlewith a femalejoint hub is atrached to a male tapered joint on the syringe. This male Luer tip may be a
straightinner joint fashionedfrom glassor metal or a metal joint with surrounding locking devicewhich holds the needlesecurelyin place. The metal locking
variety is preferable because it prevents the detachment of the needle during
critical transfer operationsand the metal tip is more robust than a glass tip.
Glass tips are desirablewhen highly corrosiveliquids are handled. The Luer
taper joints are widely adopted but not universal.Nonstandardtapers do not
sive an air tight sealif mixed with a Luer component.Microliter syringes,which
are useful for sampling small volumesof liquids, often have needleswhich are
permanentlyattachedto the barrels.
The standard small syringesare often constructed with individually matched
plungersand barrels which are given matching code numbers. Theseplungers
and barrels are not interchangeablewith those from other syringes.Larger syringes often have interchangeable parts. Leakage of air past the plunger is a
constantproblem with thesetypes of syringes.When a light coatingof mineral
,ril on the plunger can be tolerated,this providesan effectivemeansof reducing
the leakage.It also is possibleto reducethe entranceof air past the plunger by
forcing the solution into the syringewith a small positivepressurerather than
suckingthe material into the syringeby pulling on the plunger. For example,the
three-needletechniqueillustratedin Fig. 1.8 may be usedto fill a syringeunder
controlledpositivepressure.The variousmethodsof forcing the solutioninto the
svringeare done with the greatestcontrol by using a metal syringe holder which
limits plungertravel and thus avoidsthe possibilityof the plungerpoppingout of
the syringe(one such holder is illustratedin Fig. 1.9). It is especiallyhelpfulto
use a metal syringeholder when pyrophoric materials,such as neat aluminum
alkyls, are transferredby syringe.The metal holder also has the convenienceof
permitting one-handedoperationof the syringe.
Tighter sealsbetweenthe plunger and barrel are achievedwith so-calledgas
tight syringesin which a Teflon-tippedplungeror an O-ring-equippedplunger is
employed.Very good leak resistanceis also displayedby the inexpensive"disposablesyringes," which consistof a polypropyleneshell and a rubber-tipped
plunger. Unfortunately, the rubber swellsand sticks in the barrel when most
organic solventsare transferred; but these disposablesyringesare excellentfor
work with aqueoussolutions.
D. Sytinge Needles.
Syringecannulae,which will be referredto as needles
throughout this discussion,are most commonly constructedfrom stainlesssteel
tubing fitted to a metal or plastichub. Chromium-platedbrasshubs are perhaps
Ne --r
Vent
Serumbottle
cop
\wirs
F i g , l . E . T h e t h r e e - n e e d l et e c h n i q u ef o r u i t h d r a u ' i n g l i q u i d f r o m a s t o r a g et u b e . T h e s y r i n g ei s
i n i t i a l l y p u r g e d b y s a m p l i n gi n e r t g a sf r o m t h e t u b e a n d e x p e l l i n gt h e g a so u t s i d et h e t u b e . T o f i l l t h e
syringe, the vent is briefly coveredwith a finger, forcing the solution into the syringe.
B - D C o r n w o lm
l etol
holder
l/
Luer-Lokvolve
/,prPettrng
1C C s t z e
8 - D N oM S 0 9
B - D Y o l e r e g u l o rp o r n
2 0 g o u g e h y p o d e r m i cn e e d l e
( L u e r - L o k )1 j n . l o n g
A s s e m b l e d h y p o d e r m r cs y r i n g ei n m e t o l p r p e f t i n g h o l d e r
Plunger
T e n s r o ns p r r n g
-oooo
oooSN\
ooooo
Reto ne. wosher
Groduotions,cc
'\
B - D C o r n w o l Js y r r n g e( L u e r - L o k )
t cc sjze
Plungerossembly
Fig. 1.9.
,t8
Assembled hypodermic syringe in metal pipette holder.
19
AND CANNUTATECHNIQUES
SYRINGE
rhe most common variety. Leaks in the Luer taper joint betweenthe needleand
svringebody nraybe minimized by the useof a small amount of stopcockgrease
on the syringejoint. A checkfor grossleaksis performedby pulling air into the
svringe, inserting the needle into a rubber stopper, compressingthe syringe
plunger to about half of the original volume, and noting whether the plunger
returns to its original volume mark when released.Poorly fitting needlesor syringe parts should be discarded.Needletips are easilyblunted and bent over in
rhe courseof laboratorywork, so a small, fine-grainedwhetstoneshouldbe kept
handy to resharpenthe point. A needletip that is curled back or has a burr on
rhe point is especiallydamagingto septa.A sharp needlenot only makes insertion easier but also reducesleakage through the punctured septum. The socallednoncoringor deflectingtip, which has a sideopeningor a l2o beveledtip,
is preferredoverother typesof needlesbecauseit doesthe leastdamageto septa.
A flat-cut point shouldbe avoided.When working with unstableor reactivesubstances,it is important to flush a needleand syringewith pure solventimntediately after use. Stiff metal cleaning rviresare often provided with neu' needles
and are useful for removing depositsfrom the interior of the needle.
The outsidediameterof the needleis generallyspecifiedin the United States
by its wire gauge. Table 1.2 presentsthe metric equivalentof comnron wire
gaugesand the sizesof matching syringes.The latter are provided as a convenient guide and not as a set of rules. Teflon needlesare convenientfor transferring highly corrosivematerials; however.these are not generalsubstitutesfor
metal syringesbecausethey cannot penetratesepta. A range of specialsyringe
The small stopfittings is available.such as crosses,filters, T's. and stopcocks.b
c o c k so r v a l v e sf i n d u s ei n r e t a i n i n gl i q u i d si n s y r i n g e sT. h e s ea r e e s p e c i a l l uy s e f u l i n c o n j u n c t i o n w i t h l a r g e - v o l u m es y r i n g e s o r u ' h e n h a n d l i n g h i g h l y
p y r o p h o r i cm a t e r i a l s ,s u c h a s a l u m i n u m a l k y l s . A s e t u p i n c l u d i n g a s y r i n g e
s t o p c o c ka l o n gw i t h a s y r i n g eh o l d e rh a s a l r e a d yb e e ni l l u s t r a t e d( F i g . 1 . 9 ) .A n other applicationof theseitems is the adapterfor the removalof aluminum alkyls and other reactiveliquids from a small cylinder describedin the following
example.
I o b l e ' 1 . 2 . N e e d l e S i z e so n d M o l c h i n g s y r i n g e s
Gauge
25
23
20
l8
l4
'The
o.d. (nrnr)
A p p r o x i r r r a tV
e o l u n r eo f M a t c h i n gS v l i n g e
0.46
0.57
0.81
1.02
r.63
Microliters
0 . 2 - 2n L
l-5 mL
5-50 nrl
5 0 - 1 0 0n r L
c o n s t r u c t i o no f a l a r g e s y r i n g ef o r d i s p e n s i n gq a s e si s d e s c l i b e db 1 ' G . W . K r a n t e r , J . C h c m '
E d a c . . 5 0 . 2 2 1 \ 1 9 7 3 ) . S y r i n g eT ' s , s t o p c o c k s .a n d n e e d l es t o c k f o r c a n n u l a ea r e a v a i l a b l cf r o m
A l d r i c h C h e n r i c aC
l o . . P . O . B o x 3 5 5 . M i l u a u k c c .W l 5 3 2 0 1 .
20
IECHNIQUES
BENCH.TOP
INERT-ATMOSPHERE
M e t a lc y l r n d e r
Lead gaskel
@'
W r e n c hf o r
valve
{u---'
5
l6
3 2t h r e a d
t fl-ll n
In e r t g a s
Three way
Luer-lok
S y r i n g en e e d l e
Ht/
r-1\l/
@iM
l+J'
Stopcock
Lu er - l ok
E. Exomple:Wifhdrowolof Highly Reoclive liquids from Mefol

Tonks. Highly reactive liquids such as aluminum alkyls can be withdrawn
f r o m a l o w - p r e s s u r cey l i n d e ru s i n g t h e a p p a r a t u ss h o w ni n F i g . l . l 0 a . C A U TION: Highly reactive liquids should be handled in a hood which contains a
minimum of flammable material or chemicals.After attaching the syringeapparatus to the cylinder, the needle is purged with inert gas for severalminutes.
While purging, the needleis insertedthrough the septuminto the reactionflask.
' Q I N G EA N D C A N N U L AT E C H N I O U E S
24
F i g . 1 . 1 0 , T r a n s f e r o f a i r - s e n s i t i v el i q u i d s f r o m m e t a l c y l i n d e r s .( a ) A t h r e e - w a ym e t a l s t o p c o c k
. , ' n s t r u c t e df o r u s e w i t h s y r i n g e sm a y b e m o d i f i e d b y t h e a d d i t i o n o f a t h r e a d e df i t t i n g s o t h a t i t
: r a t e sw i t h a l e c t u r eb o t t l e . T h e s i d e i n l e t i s u s e dt o p u r g e t h e a p p a r a t u si n i t i a l l y a n d t o b l o u , l i q u i d
, u t o f t h e s y r i n g en e e d l ea t t h e c o m p l e t i o no f t h e t r a n s f e r .T h e c y l i n d e ri s p u t u n d e r a l o u ' p r e s s u r eo I
: n c r t g a s b e f o r e t h e t r a n s f e r i s b e g u n . ( ) S o m e t i m e sa i r - s e n s i t i v el i q u i d s a r e s o l d i n s i p h o n - t y p e
; r l i n d e r s , a n d t h e l i q u i d f r o n r s u c h a c y l i n d e rc a n b e d i s p e n s e da s s h o w nh e r e . A s w i t h t h e p r e v i o u s
r r a m p l e , i n e r t g a s i s u s e dt o f o r c e t h e l i q u i d o u t o f t h e c y l i n d e r .
The three-wayvalve is then switchedto allow liquid dispensing.When the desired quantity of liquid has been removed from the cylinder, the cylinder is
closedand the three-wayvalve switchedback to inert gas, so that the needleis
purged by inert gas before it is removed from the reaction flask.
An apparatusfor the withdrawalof reactiveliquids from metal cylindershaving a siphon tube is shown in Fig. 1.10. This setup is operatedin much the
sameway as the syringeapparatus,the main differencebeing the useof inert gas
to force the liquid out of the cylinder containingthe siphon tube.
22
TECHNIQUES
INERT.AIMOSPHERE
BENCH.TOP
F. Liquid llonsfer Connuloe.

The transfer of liquids betweentwo flasks
m a y b e a c c o m p l i s h ew
d i t h a c a n n u l aa l o n e( F i g . 1 . 1 1 ) .T h e s ec a n n u l a eu s u a l l y
are constructedfrom syringe needle stock which is commerciallyavailablein
convenientlengths.6In addition to simple liquid transfer, specialfiltration cannulae can be constructed.In a recentdesignby M. L. H. Green, a stainless-steel
cannula is cementedwith epoxy resin to a short length of heavy-walledglass
capillary tubing which has a slightly flared and fire-polishedopening (Fig.
l.l2a). This opening is coveredby hardenedfilter paper which is neatlyfolded
back on the glassfitting and wired in place,as illustratedin Fig. |.l2b . A sleevetype septum stopper is pushedonto this filter apparatus,with the stopperend
toward the filter. This assemblymay then be attachedto a receiverand flask as
i l l u s t r a t e di n F i g . 1 . 1 1 . F i l t r a t i o n w i t h m o r e c o n v e n t i o n ael q u i p m e n ti s i l l u s tratedin Fig. 1.13.
In comparisonwith syringetechniques,the use of cannulaeprovidesbetter
air exclusionand greater conveniencefor the transfer of large volumesof solution. However,syringetechniquesare much better suited for the quantitative
dispensingof Iiquids, as demonstratedin the following example.
G. Exomple: Quonlitotive Dispensing of Liquids. Moderate accuracy
in liquid-transfer operationscan be achievedusing syringe graduations. Air
should first be expelledfrom the filled syringeby pointing the needleup and
squirting out all bubbles. Higher accuracycan be achievedby weighingthe dispensedliquid. The syringeis filled and the needletip is stopperedby insertion
into a small rubber stopper.This assemblyis weighed,the liquid dispensed,and
the syringeplus rubber stopperis reweighed.If the syringeis not going to be re-
Fig. Lll.
S o l u t i o nt t a n s f e r u s i n g a s t a i n l e s ss t e e lc a n n u l a .T h e s o l u t i o ni s f o r c e dt h r o u g h t h e n e e dle by meansof the pressutedifferential createdby opening the inert gas inlet, which pressurizesthe
r i g h t - h a n d f l a s k . T h e r e c e i v i n gf l a s k i s e i t h e r m a i n t a i n e d a t I a t m b y o p e n i n g t h e s i d e a r m t o a
b u b b l e r , o r i s m a i n t a i n e d a t s l i g h t l y l e s st h a n I a t m b y o p e n i n g t h e s i d e a r m b r i e f l y t o a v a c u u m
source.
fUES
asks
tally
ein
laniteel
lass
Fig.
ded
)ve:nd
ias
uster
luive
23
SYRINGE
AND CANNULATECHNIQLJES
lrl l u r a l l
rt
Lsausecanr
lf
||
| | ,-Eporv cement
11 K
||
/-t\
llll,-Grassrttng
W^
-wrretre.down
@FrterPaPer
(4.)
(D)
F i g . 1 . 1 2 . A s s e n r b l yo f a f i l t e r c a n n u l a o r " G r e e n f i l t e r . " ( a ) A p i e c e o f g l a s s c a p i l l a r y t u b i n g ,
u h i c h h a s b e e nb l o u ' no p e n a n d f i r e - p o l i s h e dt o f o r m a l i p o n o n e e n d . i s a t t a c h e dt o t h e c a n n u l au i t h
c p o x y c e m e n t .( ) F i l t c r p a p e r i s f o l d e d o v e r t h e g l a s sc a p i l l a r l a n d s e c u r e d* i t h u ' i r e .
I n e r tg a s
To bubbler
rcy
\ir
nd
isf,n
:td
'e-
t i g . 1 . 1 3 . V a r i a t i o no n t h e c a n n u l at e c h n i q u cT. h e g l a s st u b c u i t h f r i t t e df i l t e ra n d t h e g l a s sd e l i r - : \ 1 u b e s a r e a t t a c h e d t o t h e g l a s s s t a n d a r d t a p e r j o i n t s b J ' m e a n s o f p l a s t i c a d a p t oKr so(net.egs. K

, I - ' r E 0 0 ) . T h e f l e x i b l c p l a s t i c t u b i n g c o n n e c t i n gt h e t $ o p a r t s s h o u l d b e i n r p e r i ' i o u st o s o l v e n t s .
I r i l o n t u b i n g i s b e s t a n d . t o p r c v c n t c o n t a m i n a t i o no f t h c f i l t r a t e , T 1 ' g o nt u b i n g s h o u l d b e a v o i d e d
r r r ' l 'l , r g a n i cs o l v e r r tasr c u s e d .
used imnlediately,it should be rinsed u'ith degassedsolventimmediatelyafter

use, to avoid the buildup of depositsof decompositionproducts in the syringe
and needle.However,if it is to be re-usedsoonwith the samesolution,the stopper may be left on the needletip and both rinsing and inert-gasflush may be
omitted before the syringeis filled again.
H. Specfloscopic Meosuremenls.
The samplingof air-sensitiveliquids
for NMR and IR spectroscopy
is often most convenientlyperformedby syringe.
Small rubber septaare availablewhich fit 5-mm and other sn.rallNMR tubesand
2A
BENCH-TOP
INERT-ATMOSPHERE
IECHNISUES
a l s of i t t h e L u e r i n l e t so n I R c e l l s .T h e N M R t u b e m a y b e p u r g e db y p u r n p - a n d f i l l o p e r a t i o n su, ' h e r e a sI R c e l l sa r e e a s i l yf l u s h e db y i n e r t g a s .T h e f i l l i n g o f t h e
IR cell is accornplishedby insertingthe syringeneedleinto the septumon the cell
i n l e t . a n d t h e o u t l e t s e p t u mi s p i e r c e dr v i t ha s m a l ln e e d l e A
. n e x c e so
sf liquid is
f l u s h e dt h r o u g ht h e c e l lt o e x c l u d eg a sb u b b l e s .A s o m e w h alte s sa i r - f r e eo p e r a t i o n i s a c h i e v e db y f l u s h i n gt h e c e l l a n d t h e n a t t a c h i n ea s v r i n g ec o n t a i n i n gt h e
l i q u i d b y j o i n i n g t h e L u e r f i t t i n g s o n t h e s y r i n g ea n d c e l l . A n e m p t y s y r i n g ei s
attachedto the cell exit to serveas a reservoirfor excessliquid u'hich is forced
t h r o u g h t h e c e l l . O n c e t h e c e l l i s f i l l e d . t h e i n l e t a n d o u t l e t a r e c a p p e dr v i t h
Teflon stoppers.Conventionalvisible-UV cells can also be fitted rvith syringe
caps for air-free spectroscopy.A visible-UV cell that has been used for a u'ide
varietyof air-sensitiveinorganicand biologicalcon.rpounds
is illustratedin Fig.
1 . 1 4 .M o r e s o p h i s t i c a t e sdp e c t r o s c o p ci ce l l s .s o m eo f r v h i c ha r e s u i t a b l ef o r u s e
in conjunction with syringetechniques.are describedin Chapter 9.
4 ,4 euANTrTATrvE
GASMANIPULATToN
A . D i s p e n s i n g G o s e s . T h e d i s p e n s i n go f g a s t o a s o l u t i o nc a n b e a c c o m p l i s h e di n s e v e r aul ' a y s .F o r e x a m p l e ,a s o l u t i o nm a y b e s a t u r a t e db y b u b b l i n g
Needle- volve
l-cm
,singlepiece
CUVCTTE
ReseTvorr':
Fig. Ll4.
E v a c u a b l ec e l l l o r U V - r ' i s i b l es p e c t r a . ' I ' h i sc e l l i s e v a c u a t e da n d t h e n f l u s h e dt h r o u g h a r
'l'he
i n e r t - g a si n l c t a t t a c h e d t o t h c O - r i n g j o i n t .
T e f l o n s t e n ro f t h e v a l v c i s r e m o v e du n d e r f l u s h
s o l u t i o n sa r e i n t r o d u c r - dt h r o u g h t h i s o p e n i n g . a n d t h e n t i p p e d o v e r i n t o t h e c u l e t t e a f t e r t h e v a l r r
s t e m h a s b c e n r e p l a c e d .A l t c r n a t i v e l l . c t > n d e n s a b lset > l v e ' nat sn d s o l u t c sm a 1 'b e c o n d e n s e di n t o t h
r e s e r v o i ro n a v a c u u n rI i n e .
,ES
:, ANIITAIIVE
GAS MANIPULAIION
U-
-:: through it from a syringeneedle attachedto a tube and low pressuregas

u r c e( F i g . 1 . 1 5 ) .
'f
he quantitativedeliveryof a gas is somewhatmore involved.While it is true
'- JI a vacuum systemoften permits the most satisfactorymethod of quantitative
-,,: handling, some adequateproceduresexist which are basedon simple, con: ntional inert-atmosphereapparatus.A largegastightsyringeis one of the most
rvious devicesfor the measurementof an aliquot of gas.bA sampleof gas may
^.: drawn into the syringefrom a streamof the gas connectedto an exit bubbler.
\nother method for dispensinggiven quantitiesof gas is a gas buret, similar to
re describedlater in connectionwith the measurementof evolvedgases.TStill
i:r()thersimple schemeis to flush a bulb of known volume with the desiredgas,
,nd then bubble this gas into the reaction flask by means of a slow inert-gas
. : r e a m( F i g 1 . 1 6 ) .C o n d e n s a b l ge a s e sm a y b e t r a p p e d .m e a s u r e db y v o l u m eo f
'.reliquid, and dispensedby controlledwarming of the gas.A suitableapparatus
',r this purposeis illustrated in Fig 1.17. Gaseswhich are condensableat Dry
: r e t e m p e r a t u r e ,- 7 8 o C , c a n b e h a n d l e db y t h i s t e c h n i q u e .
Finally, it is often possibleto generatequantitativelythe desiredgas from
:reasuredamountsof liquid or solid reagents.The generatedgas is then quanti:.ltivelytransferred by inert-gasflush into a reaction mixture. The automatic
:lsimeter developedby C. S. Brown and H. C. Brown is usefulwhen it is neces.rrv to know the quantity of gas consumedin the courseof a reaction.sThis
rpparatus can be applied to the generationof a variety of gases,such as H2,E
he
ell
is
'ahe
is
:d
rh
i!
le
]
T ob u b b l e r
_>
To hood
F i g . 1 . 1 5 . D i s p e n s i n gg a s d i r e c t l yf r o m a t a n k . l - h e n e e d l ev a l v ei s u s e dt o c o n t r o lt h e g a s f l o w i n t o
t h c s o l u t i o n ,a n d a m e r c u r y - f i l l e db u b b l e r p r e v e n t se x c e s s i v p
e r e s s u r eb u i l d u p .
T . N . S o r r e l la n d M . R . M a l a c h o u ' s k i I, n o r g . C h e m . , 2 2 . l 8 8 J ( 1 9 8 3 ) ,p r o v i d ea r e c e n td e s c r i p t i o n
, , f g a s u p t a k e e x p e r i m e n t sw i t h a g a s b u r e t .
'C.
A . B r o w n a n d H . C . B r o $ ' n , . / .O r p . C h e m . . 3 1 . 3 9 8 9( 1 9 6 b ) .
26
INERT.ATMOSPHERE
TECHNIOUES
BENCH.TOP
R e a g e n tg a s
r nl e I
To reactron
v e s s eI
C a l i b r a t e dv o l u m e
--.>
Inertgas
V
Tobubbler
In hood
F i g . 1 . 1 6 , G a s - s a m p l i n gt u b e . T h e t u b e i s f l u s h e dw i t h t h e r e a g e n tg a s b y o p e n i n gt o t h e r e a g e n t
g a s i n l e t a n d v e n t i n gt o a m i n e r a l o i l b u b b l e r . A f t e r s e v e r a m
l i n u t e s ,t h e f l u s h i s t e r m i n a t e db y f i r s t
c l o s i n gt h e i n l e t s t o p c o c k ,t h e n t h e o u t l e t s t o p c o c k .( T h i s e n s u r e st h a t t h e p r e s s u r ei n s i d et h e ( u b e
e q u a l s t h r - l a b o r a t o r y a t m o s p h e r i cp r e s s u r e . )T h e l a b o r a t o r Jt e n i p e r a t u r ea n d p r e s s u r ea r e t h e n
m e a s u r e df o r u s ei n c a l c u l a t i n gt h e a n o u n t o f g a s d i s p e n s e dF
. i n a i i y .t h e k n o w n q u a n t i t ] 'o f r e a g e n t
g a s i s d i s p e n s e dt o t h e r e a c t i o nv e s s ebl y o p e n i n gt h e i n l e t s t o p c o c kt o i n e r t g a s .t h e o u t l e t s t o p c o c k
t o t h e r e a c t i o nv e s s e l ,a n d f l u s h i n g t h e t u b e r v i t h i n e r t g a s f o r s e Y e r anl r i n u t e s .
C O , eh y d r o g e nh a l i d e s , r 0I '0r 2 , r 2e t h y l e n e , rar n d S O t ,r r b u t n o t g a s e sw h i c hr e a c t
with mercury. By means of a clever liquid inlet device,gas is produced in the
generatorin responseto the amount consumedin an attachedreactor.This liqu i d i n l e t v a l v e( F i g . 1 . 1 8 ) ,c o n s i s t so f a t u b e p a r t i a l l yf i l l e d u ' i t h m e r c u r y .T h e
tube has provisionfor the inlet of liquid from a needleattachedto a buret and for
the controlledflor.r'of this liquid into the reactionvesselvia severalsmall holes
abovethe mercury level.Liquid from this inlet valvedrops into the gas generator, and the evolvedgas is conductedfrom there to a reactionflask. The flou'of
liquid can be initially adjustedby the depth to which the needleprojectsinto the
mercury pool of the valve.When the systemis properly balanced.the pressure
drop causedby gas consumptionin the reactorpulls the reagentfor gas generation in through the liquid control valve. As the pressurebuilds up, this flow of
reagentstops, only to resumeagain when the reaction consumessome of the
generatedgas. When the quantitative measurementof gas consumptionis required, the exit bubbler servesonly as a safetydeviceand the systemmust be set
up so that there is no gas expelledthrough the bubbler during the courseof the
reaction.
B. Meosuremenf of Evolved Goses. The measurementof evolvedgases
providesa ready meansof conductingcertain analysesand followingthe course
' q M .W . R a t h k ea n d H . C . B r o u n . , / .A n t . C h e n t .S o c . . 8 8 . 2 6 0 6( 1 9 6 6 ) .
l " H . C . B r o * ' n a n d N . - H . R e i , " / .O r e . C h e n t . , 3 1
,1090(19b6).
I r G . W . K r a n t e r . A . B . L e v v , a n d M . M . M i d l a n d . i n H . C . B r o r v n ,O r g a n r ' c . i . r ' r r / l t c svei asB o r u n e s ,
N e l ' Y o r k l W i l e y , 1 9 7 3 ,p . 2 1 8 .
r 2 H .C . B r o w n . M . M . M i d l a n d , a n d G . W . K a b a l k a ,J . A n t . C h e n t .S o c . . 9 3 , 1 0 2 4( 1 9 7 1 ) .
27
O UANIITATIVE
GAS MANIPULAIION
I n e r t ' g a sI n l e t
,1,
To reactron
VESSCI
To gas absorber
or hood
A r . r t r D kaucp
trap
Mercury
bubbler
C a l r b r a t e dl o w t e m p e r a t u r e
t r a p t o r l t q u r t t e dg a s
F i g . 1 . 1 7 . A p p a r a t u sf o r d i s p e n s i n gk n o u n q u a n t i t i e so f c o n d e n s a b l e
g a s e sT
. he trap may be cali'orated
b y u s i n g w a t e r ( f o r l a r g e v o l u m e s )o r m e r c u r y ( f o r s m a l l v o l u m e s ) .A n r e r c u r yb u b b l e r i s
r n c l u d e dt o p r e \ e n t b l o w i n g t h e a p p a r a t u sa p a r t .
A f t e r a s s e m b l i n gt h e a p p a r a t u s ,t h e e n t i r e s y s t e mi s t h o r o u g h l yp u r g c d u i t h i n e r t g a s . S t o p c o c k
B i s t h e n t u r n e d t o r o u t e g a s t o a h o o d o r g a s a b s o r b e r ,t h e i n e r t - g a sf l o w i s t e r n r i n a t e d ,a n d a s l o u
f l o u o f t h e d e s i r e dg a s i s a d n r i t t e df r o n r a c y l i n d e re q u i p p e dw i t h a p r e s s u r er e g u l a t o ra n d n e e d l e
r a l v ef o r f l o u ' c o n t r o l . A D e u a r c o n t a i n i n g r e f r i g e r a n tc a p a b l eo f l i q u i f v i n gt h e g a s ( s e eT a b l e 5 . I ) i s
t h e n r a i s e da r o u n d t h e t r a p . A f t e r t h e d e s i r e dv o l u m e o f l i q u i d i s c o l l e c t e d ,t h e r e a g e n tg a s f l o u i s
t e r m i n a t e d ,s t o p c o c kA i s c l o s e d ,a n d s t o p c o c kB i s t u r n e d t o d i r e c t g a s t o t h e r e a c t i o nv e s s e l T
. he
D e w a r i s t h e n l o w e r e df r o m t h e t r a p . a l l o r v i n gt h e c o l l e c t e dg a s t o b o i l o f f . T h e r a t e o f v a p o r i z a t i o n
m a y b y c o n t r o l l e db y r a i s i n g a n d l o w e r i n gt h e D e u a r . W h e n t h e t r a p a p p e a r st o h a v eb e e ne m p t i e d .
a f l u s h o f i n e r t g a s n r a y b e u s e dt o f l u s h o u t r e m a i n i n gr e a g e n tv a p o r .
of a reaction.For example,the analysisof activehydridesand alkyl compounds

can often be conductedby quantitative hydrolysisto produce hydrogenor alkane. A simplegasburet system,illustratedin Fig. 1.19,is usefulfor thesetypes
of measurements.It also may be usedto dispensespecificquantitiesof gas to an
inert-gasstreamfor introduction into a reactionmixture. The procedurefor using this gas buret apparatus for the analysisof active hydrides or alkyl compounds by hydrolysisis describedin the following example.
of AcfiveHydridesor AlkylCompoundsUsing
C. Exomple:Anolysis
o G o s B u r e l . T h i s p r o c e d u r eu t i l i z e st h e g a s b u r e t i l l u s t r a t e di n F i g . l . l 9 t o
analyzeactivehydridesor alkyls. First, the water levelsin the reservoirand buret
s i d e sa r e a d j u s t e dt o e q u a lh e i g h ta n d a n i n i t i a l b u r e t r e a d i n gi s t a k e n .A s a m p l e
of known weight is introducedinto the hydrolysisflask using a syringe.After gas
Reagentinlet
trom buret
Reagentoverflowto
generator
flask
ng
Reaction
vessel
F i g . I . 1 8 . B r o * n l g a s g e n e r a t o ra n c la p p a r a t u sf o r r e a c t i o n sw i t h g a s e s .R e a g e n t sa r e m i x e d i n t h e
g a sg e n e r a t o ra n d t h e r e s u l r i n gg a s e sa r e p a s s e di n t o t h e r e a c t i o nv e s s e lT
. h e n r e r c u r vb u b b l e r o n t h e
f a r l e f t h a s a f l o a t c h e c k v a l Y er v h i c h p r e v e n t sn r c r c u r ya n d a i r f r o n r b e i n g s u c k e d b a c k i n t o t h e
r e a c t i o nv e s s e l T
. h e k e y t o t h i s a p p a r a t u si s t h e a u t o m a t i c I i q u i d i n t e t v a l v e ,s h o u ' ni n d e t a i l o n t h e
r i g h t . A d r o p i n g a s p r e s s u r er v i t h i n t h e a p p a r a t u sp u l l s l i q u i d f r o n r t h e b u r e t t h r o u g h t h e s y r i n g e
n e e d l ea n d t h e n t e r c u r v .T h e r a t e o f d e l i v e r t o f r e a g e n ti s a d j u s t e db y r a i s i n go r l o w e r i n gt h e b u r e t
a n d a t t a c h e ds - y r i n g e
needle.
28
tig. 1.19. A gas buret for the measuremeno

t r d e l i v e r yo f g a s e s .W h e n t h e e l b o u ( o n l e f t ) i s a t ''rrhedto the
t o p o f t h e b u r e t , g a s i s c o l l e c t e da n d i t s v o l u m e i s m e a s u r e da f t e r e q u a l i z i n gt h e m e r ' u r r l e v c l s . F o r e x a n r p l e , a h y d r o l y s i s f l a s k s i n r i l a r t o t h e r e a c t i o n f l a sl .kl 8
i nmFai gy .b e a t t a c h e d
' ' l h l s e l b o w .W h e n
t h e s t o p c o c ka s s e m b l yi s u s e d( a r t h e r i g h t ) , t h e b u r e t c a n b e f i l l e d u i t h s a s a n d
, n ) e a s u r e dv o l u n t co f t h i s g a s c a n b e i n j e c t e di n t o a s t r e a mo f f l o u , i n gi n e r t g a s .
29
r_
30
IECHNIQUES
INERT.AIMOSPHERE
BENCH.TOP
evolutionhas ceased.the water levelsare again matched.and both a buret and

barometricpressuremeasurementare taken. A correctionmust be made for the
vapor pressureof the solventused in the system,especiallyif the solventis very
volatile.
'1,5 scHLENK
TEcHNToUES
The original Schlenk tube consistedof a long tube
A. Bosic Apporolus.
with a sidearm near the top which permitted the removalof air by evacuation
and filling rvith inert gas. A completemethodologyfor rvork with air-sensitive
liquids has evolvedfrom the original Schlenktube. The Schlenktube described
here has a teardrop shapeto facilitate the stirring of reactionmixtures and the
vacuum evaporationof solvents,while still maintaining easeof pouring and
scrapingsolidsfrom the Schlenktube. The currently popular Schlenkware permits the transfer of liquids or solids by pouring within a closedapparatusor
under an inert-gasflush. Since it is possibleto perform fairly complex solids
transfer u'ith this type of apparatus.the needfor glovebox opetationsis minimized. Someof the basic items of equipment include a Schlenktube (which is
used as a reactionflask), a fritted funnel, a dropping funnel, and a solidscont a i n e r ( F i g . 1 . 2 0 ) .M o s t S c h l e n kw a r e p i e c e sa r e f i t t e d u ' i t h a s i d e a r mt h r o u g h
which the apparatuscan be evacuatedand filled with inert gas. Somebasicoperations using severalof thesepiecesare describedbelow.
it\,
rW\
tr
l"\
(\,
V/'
(c)
(d)
F i g . 1 . 2 0 . B a s i cp i e c e so f i n e r t - a l m o s p h e r eS c h l e n k - t y p ca p p a r a t u s .( r ) S c h l e n kt u b e . T h i s i s u s e f u l a s a r e a c t i o nv e s s eal n d f i l t r a t e r e c e i v e r .T h e p e a r s h a p eo f t h e v e s s efl a c i l i t a t e ss t i r r i n g t h e c o n t e n t s w i t h a s t i r b a r a n d m a g n e t i cs t i r r e r , a n d r e m o v i n gs o l i d s .( b ) F r i t t e o r f r i t t e d f u n n e l . T h i s i s
u s e df o r f i l t r a t i o n s . T h e T e f l o n v a l v ei s u s e f u lw h e n c o n t a m i n a t i o nb y s t o p c o c kg r e a s ei s o b j e c t i o n a b l e . D o u b l e - e n d e df r i t t e s( F i g . 1 . 5 )a r e a l s ou s e f u l .( c ) D r o p p i n g f u n n e l . A s i n t h e c a s eo f t h e f r i t t e d
f u n n e l , t h e T e f l o n v a l v ei s u s e dt o a v o i d c o n t a m i n a t i o no f t h e s o l u t i o r rb y s t o p c o c kg r e a s e .( 2 . /S) o l i d s
c o n t a i n e r .T h i s i s u s e d f o r a d d i n g , r e c e i v i n g .a n d s t o r i n g a i r - s e n s i t i v es o l i d s .( R e p r o d u c e db y p e r n r i s s i o no f t h e c o p y r i g h to * n e r , K o n t e s G l a s s C o . )
TECHNIQUES
SCHLENK
31
B . E x o m p l e : P u r g i n g S c h l e n k W o r e . I n g e n e r a l ,a h i g h v a c u u m i s n o t
r e q u i r e df o r t h e p u m p - a n d - f i l l t y p e o f p u r g eu s e di n S c h l e n kt e c h n i q u e sS
. evcral cyclesof pumping and filling rvith inert gas are sufficientto reducethe oxygen and other atmosphericgasesto very low levels.For example. supposethe
\ \ ' s t e mi s e v a c u a t e dt o 2 t o r r . A p p l y i n g E q . ( 1 ) , a f t e r t h e s e c o n dp u m p i n g a n d
r i l l i n gt h e p r e s s u r eo f r e s i d u a la i r i s 2 x 2 i 7 6 0 t o r r , a n d a f t e rt h e t h i r d i t i s 2 X
I 160)2torr, or approximately l0'i torr. Becauseof the frequencywith which
:hcsepump-and-fill cyclesare performed, it is useful to ernploya manifold for
' h c d i s t r i b u t i o n ov fa c u u m a n d i n e r t g a s , s u c h a s t h e u n i t i l l u s t r a t e d i n1 F
. 2i g. .
C . E x o m p l e : J o i n i n g T w o P i e c e s o f S c h l e n k W o r e . A n o t h e rb a s i co p J r a t i o ni s t h e j o i n i n g o f a p p a r a t u su n d e r a n i n e r t - g a sf l u s h . F o r e x a m p l e ,t h e
:ransferof a reactivesolid from a solidscontainerto a Schlenktube requiresthe
:ube to be stopperedand carried through severalpurge cycles. Then, with both
:riccesopen to a nitrogen source,the cap is removedfrom the solidscontainer,
:he stopper is removedfrom the Schlenktube, and the tu'o piecesare quickly
ioinedwhile air is excludedby the flow of inert gas out of the two piecesof appam t u s , a s p r e v i o u s l yi l l u s t r a t e di n F i g . 1 . 5 . T h e s eo p e r a t i o n sr e q u i r e t h a t t h e
l)ressurein the systenrbe only slightly aboveatnrosphericpressureso that the
closedapparatusis not blown apart. A two stageregulatorrvith good control in
rhe low pressurerange is essential,and additional protectionagainstoverpre\surization can be achievedby the pressurereleasebubbler illustrated in Fig.
1 . 2 .T o m a i n t a i n i n t e g r i t yo f t h e a p p a r a t u s s, p r i n g s ,c l i p s ,o r r u b b e r b a n d sa r e
u s e dt o s e c u r ee a c hj o i n t , a n d s t o p c o c k sa l e h e l d i n p l a c ew i t h s t u r d yr e t a i r r e r s . l
A sinrilar sequenceof operationsis used for changing the configurationof all
tipes of Schlenk apparatusduring the courseof a synthesisor purification.
The apparatus for severalother comnlon Schlenk operationsare sho*'n in
F i g u r e1 . 2 1 .T h e s eo p e r a t i o n si n c l u d ef i l t r a t i o n( F i g . 1 . 2 1 c ) ,t r a n s f e r r i n gs o l i d s
f r o m a f i l t e r t o a s o l i d sc o n t a i n e r( F i g . 1 . 2 1 ) ,a n d t r a n s f e r r i n gs o l i d sf r o m a
s o l i d sc o n t a i n e rt o a n a n r p u l ew h i c h w i l l b e s e a l e do f f ( F i B . l . 2 l c ) . A l t e r n a t i v e s
for adding solidsto an.rpulesare illustratedin Fig. 1,22.
D. Quonfilotive Addition of liquids ond Solids. The quantitativemeasuremeno
t f a i r - s e n s i t i vseo l i d sa n d l i q u i d sc a n b e a c c o m p l i s h e idn a n u m b e ro f
u ays.Chapter2 will coverglovebox operationswhich are suitedfor the measurement of solids.The quantitativedeliveryof solutionsis readily accomplishedby
the syringetechniques,which have been discussedearlier in this chapter (Sect i o n 1 . 3 . G ) .I n a d d i t i o n ,l i q u i d sc a n b e a d d e df r o n rg r a d u a t e dS c h l e n k - t y pvee s s e l su ' h i c ha r ef i t t e d w i t h a s i d e a r mf o r f l u s h i n g .M i c r o w e i g h i n gt u b e s( F i g . 1 . 2 3 )
are usefulfor the deliveryof small known u'eightsof compoundsto Schlenkapparatus. The solid is introduced into the tube in an inert-atnrosphere
glovebox
and the tube and contentsare then weighed.With a flush of inert-gasissuing
f r o m t h e S c h l e n ka p p a r a t u s ,t h e w e i g h i n gt u b e i s q u i c k l y u n c a p p e d .i n s e r t e d
into the Schlenk apparatus, and shakento deliver its contents.The tube is removedand quickly recappedand reweighedto give the tare weight. Sodium-and
32
TECHNIOUES
INERT.ATMOSPHERE
BENCH.IOP
(c)
'fvpical
Fig. l.2l,
assemblieo
s f S c h l e n ku a r e . C o n r n r e r c i aal p p a r a t u si s i l l u s t r a t e d :s i n t i l a ra p p a r a t u s s ' i l h O - r i n g j o i n t s i n p l a c e o f s t a n d a r dt a p e r j o i n t s i s p l e f e n ' e db v t h e a u t h o r s .( a ) F i l t e r a n d
S c h l e n kf l a s k r c c e i v c n( ) p o u r i n g s o l i d f r o m a f i l t e r i n t o a s o l i d ss t o r a g et u b e ; ( c ) p o u r i n g s o l i df r o m
t h c s o l i d ss t o r a g cl u b e i n t o a n a n r p u l e .s ' h i c h c a n b e s e a l c do f f . A l l a p p a r a t u si s p u r g e d b i p u n t p a n d - f i l l o p e r a t i o n s .W h e n o e r t h e a p p a r a t u si s o p e n e do r b e i n gi o i n e ' d .a p u r g eo f i n e r t g a s f r o m t h e
s i d e a r mi s u s e dt o e x c l u d ea i r . ( R e p r o d u c e db l p e r n i i s s i o no f t h e c o p y r i g h to s n e r K o r l t e sG l a s sC o .)
p o t a s s i u m - f i l l etdu b e sc a n b e c u t , m e a s u r e da. n d d r o p p e di n t o a r e a c t i o nv e s s e l
rapidly to dispensea known rveightof thesemetals.Another methodfor dispensi n g w e i g h e da m o u n t so f a l k a l i m e t a l si n t h i n b r e a k a b l eb u l b s i s d e s c r i b e di n
S e c t i o n9 . 4 A . S o l i d sa l s oc a n b e d i s p e n s e fdr o n r s e a l e da n r p u l e sw
, h i c ha r eb r o k e n o p e n u n d e r a n i n e r t a t m o s p h e r e(.F i g . 1 . 2 4 )a n d q u i c k l y p o u r e di n t o S c h l e n k a p p a r a t u su n d e r a n i n e r t - g a sf l u s h . A f u l l a m p u l ec a n b e r v e i g h e d
and the
parts tared after the solid is added, or a method describedin the next paragraph
m a y b e u s e dt o d e t e r m i n et h e w e i q h to f s a m p l e .
A kno*'n anrount of nraterial may be sealedin an ampule by u'eighingthe
a m p u l e ,a d d i n gs o l i d ,s e a l i n g w
. e i g h i n gt h e p a r t s ,a n d d e t e r m i n i n gt h e w e i g h to f
the contentsby difference.Filling an ampuleis accomplishedwith the apparatus
i l l u s t r a t e di n F i g . I . 2 1 o r 1. 2 2 , o r i n a g l o v eb o x . I n o r d e rt o a c h i e v ea g o o ds e a l ,
the systemmust be under vacuunror at most at atmosphericpressure.When the
ampule is attached to a Schlenkapparatus,the systemcan be partially evacuated and the seal then rnade. or a remote sectionof the Schlenk line can be
momentarily opened up to vent the systemwhile the seal is being nrade. Similarll'. an anrpule*'hich has been filled in an inert-atmosphereglovebox may be
\
Rubber
stopper
7*ffi
-*5'----l
S c h t e nt u
t <b e
I
Y
-_
Inertsas
or vacuum
F i g . 1 . 2 2 , S o l i d st r a n s f e ru n d e r a n i n e r t a t m o s p h e r e (. c ) S o l i d sa r e p o u r e d d o w n t h i s s o l i d sm a n i f o l d i n t o a m p u l e s ,w h i c h a r e t h e n s e a l e do f f . ( ) A n a m p u l e i s p u r g e d i n t h e e v a c u a b l ec y l i n d e r ,a n d
u n d e r a n i n e r t - g a sp u r g e t h e s t o p p e ro n t h e c y l i n d e ri s r e m o v e da n d s o l i d sa r e t r a n s f e r r e df r o n r t h e
S c h l e n kt u b e a d a p t e r i n t o t h e v i a l . T h e l a t t e r i s q u i c k l y r e m o v e df r o m t h e c y l i n d e ra n d s e a l e do f f .
33
TECHNIOUES
INERT-ATMOSPHERE
BENCH-TOP
34
-..--<-
\-,4.5f-
^.-.-Fig. 1.23. Weighing pigswith caps'
F i g ' l . 2 4 . O p e n i n g a s c a | c d r n l p u | c ' l . J ) T h e n e c k o | ' t h e a n r p u l c i s c a r e fnue| c| rks' cl noerret gdauss i n g

a m p u l e n e c k i s p l a c e do v ; r t f e
knife. (b) A metal tube ol largeriuttttt than the
the neckis
e
x
p
o
s
u
r eo f t h e a m p u l ec o n t e n t st o a i r o n c e
f l o w i n gt h r o u g h t h e m e t a tt u b l u . i l l m i n i m i z e
(
t
a
t
t
he score'
o
f
f
)
n
e
c
k
t
h
e
tube' u'hichsnaps
b r o k e n . A q u i c k j e r k i s t h e n a p p l i e dt o t h e m e i a l
to the ampule
i
s
a
d
m
i
n
i
s
t
e
r
e
d
s
c
o
r
e
T
h
e
b
o
x
.
g
l
o
v
e
i
n
a
u
s
e
T h i s o p e r a t i o ni s e a s i t ym o i f i e df o r
T h e a n r p u l ei s c l a n r p e dt o a s t a n d i n t h e g l o v e
n e c k b e f o r et r a n s f e r r i n gt h e a n r p u l et o t h e g l o v e o x .
boxandthenecksnappedusingacorkborer.Thisnrininrizesthechancesofglassfragnrentscutt
a glove.
stopperedwithaSleeveseptumcapwhichispiercedwitha'smallneedlej
beforetheanrpuleissealed'Asmallresidueofthecompoundremaininginth
neckoftheampulen1aycauSedefectsinthesealwhichallowtheentranceo
in the usual sealingoperaTo minimize this probiem. the glassis first collapsed
portion, the parts are pulled
tion, and then, as the flanre is kept on the collapsed
is generallyadequate
apart with a twisting motion. Leis than one full revolution
develop.Details on this
to closethe threadlike channelwhich would otherwise
SCHLENK
TECHNISUES
35
and other glassblowing operationsare givenin Appendix Il. When an evacuated

ampule is broken open, there is an inrush of air. To minimize exposureof the
contentsto air, the ampule may be broken open as illustratedin Fig. 1.24 and
the contentsquickly poured into Schlenkapparatuswhich is being flushedwith
i n e r tg a s .
E. SeporofiOns. The basic filtration operation has been previouslyillustrated. Low-temperaturefiltrations for the collectionof thermallysensitivecompoundsor productswhich are solubleat higher tenrperaturesmay be performed
*'ith an H-type Schlenk tube, Fig. 1.30, in a large low-temperaturebath. The
jacketed,fritted funnel illustratedin Fig. 1.25 alsopermits low-temperaturefiltration.
Crystallizationis performedin Schlenkapparatusunder an inert atnrosphere
usingfamiliar techniques:partial removalof solventby evacuation,addition of a
solventin which the solute has reducedsolubility, and cooling.Thesemethods
are often combined; for example, a second,poorer solvent,chosenso that its
vapor pressureis lessthan that of the more powerful. original solvent,may be
added. Partial evacuationwill then concentratethe solutionand changethe solient compositionto favor crystallization.The complicationwhich air-sensitive
t i g . I . 2 5 . L o w - t e m p e r a t u r ef i l f f a t i o n a p p a r a t us . T h i s i s u t i l i z e dt h e s a n r eu a y a s t h e f r i t t e p i c t u r e d
' Fig. I.20. The outerjacket is filled u ith a Dry lce/acetone
s o l u t i o ns ' h e n f i l t e r i n g h e a t - s e n s i t i v e
, , n r p o u n d s l,i q u i d a m n r o n i as o l u t i o n s ,e t c . I R e p r o d u c e db y p e r m i s s i o no f t h e c o p y r i g h to w n e r .T h e
\ n r c r i c a n C h e n r i cSaol c i e t y , f r o m J , E . E l l i s , K . L . F j a r e , a n d T . G . H a y e sA. "n/t.. C h e n . . ! o c .1 0 3 .
. : r r 0( 1 9 8 1 ) . 1
f,-
36
TECHNIQUES
INERT.ATMOSPHERE
BENCH.TOP
materialspresentis that impurities createdby partial reactionwith adventitious

air or moisture may make a product difficult to crystallize.If these impurities
are insoluble, they can be filtered off before the crystallizationoperation; but
soluble impurities presenta more seriousproblem. The layeringof a poor solvent on a solutionof a compoundis often usedto grow crystalsfor crystalstructure determinations.In this case,the crystalsgrow at the interfacebetweenthe
two liquid phases.If the two liquid phaseshavesignificantlydifferent densities,
the more denseshould be placed in the bottom of the tube. It is best for the
initial solution to be far from the saturation concentrationof the compound.
Tubes fitted with sleeve-typeserum caps can be used for moderatelysensitive
compounds,and a right-angleTeflon valvecan be usedto closethe crystalgrowing tube for more sensitivecompounds.When suitablecrystalshavegrown, the
G l a s sw o o l
0il bath
F i g . 1 . 2 6 . S u b l i m a t i o na p p a r a t u s .S o l i d sa r e i n t r o d u c e du n d e r i n e r t - g a sf l u s h , a n d a l o o s ep l u g o f
'fhe
g l a s su o o l i s i n t r o d u c e d .
o i l b a t h s h o u l d e x t e n d a b o v et h e g l a s sr v o o l . H i g h v a c u u m m a l ' b e
a p p l i e d t h r o u g h t h c s t a n d a r dt a p c r j o i n t . A l o u e r v a c u u n rm a l b e a p p l i e d t h r o u g h t h e s i d e a r n r .
TECHNIOUES
SCHLENK
J/
liquids may be carefullyremovedby syringeand crystalsshakenfrom the tube in

a glove box. Sometimesit is necessaryto break the tube to gain accessto the
crystals.
Sublimationis readily performedin Schlenkapparatusof the type illustrated
in Fig. 1.26. The sublimate,which collectson the upper walls, may be collected
by positioningthe apparatus horizontally and scraping the product into a receiverattached to the side joint while an inert-gasflush is maintained on the
equipment.
Column chromatographyunder an inert atmosphereis made possibleby the
apparatusillustratedin Fig. 1.27.Most common adsorbentscontainlargequantitiesof moistureand air, the eliminationof which is difficult. For example,it is
generallyimpractical to eliminate all of the surfacehydroxyl groups from alun r i n a .A l s o , t h e a b s o r b e n coy f i n o r g a n i cs o l i d ss u c ha s s i l i c ag e l a n d a l u m i n ai s
\)ften a strong function of adsorbedmoisture. A convenientprocedurefor degassingand partial moisture removalof the adsorbentis to warm the solid in a
Schlenktube while carryingout a seriesof pump-and-fill operations.(To avoid
particlesof adsorbatef lying throught the Schlenkmanifold, a small plug of glass
s o o l i s p l a c e di n t h e n e c k o f t h e f l a s k . a n d v a c u u mi s a p p l i e ds l o w l yw h i l e t h e
r esselis swirled.) Under a blanket of inert gas,air-freesolventcan then be added
u ith a dropping funnel and the slurry poured into the column (generally.a transfer crossis necessaryso that the slurry can be washedinto the column by means
of solventintroducedby syringe).Alternatively,the dry adsorbentin the column
plug
_/-Gloss wool
A d s o rb e n t
G l o s s- w o o l p l u g
S t o p c o c kw i t h
T e f l o np l u g
. y p i c a l s i z e :l ; l / 3 5 3 j o i n t s , 4 5 - m m - d i a m e t e r
F I G . t . 2 7 . C o l u n r n f o r a d s o r p t i o nc h r o m a t o g r a p h yT
u p p e r s e c t i o n ,2 0 - m m - d i a m e t e rc o l u m n , a n d a 5 0 0 - m m c o l u m n l e n g t h .O - j o i n t sa n d T e f l o n - i n - g l a s s
v a l v e sp r o v i d eg r e a t e r s o l v e n tr e s i s t a n c et h a n t h e g r e a s e df i t t i n g s i l l u s t r a t e dh e r e .
38
TECHNIOUES
INERT-ATMOSPHERE
BENCH-TOP
can be deaeratedby pump-and-fill operations.and solvent added later. Occluded gas is then eliminated under an inert-gasflush by stirring the column
with a long wire or rocking the slurry back and forth in the closedcolunrn. One
sidearm on the column is used to provide a nitrogen flush *'hen the systemis
open to the air, and anothermay be added for the introductionof snlall samples
by syringe.
Molecular weightsof slightly airF. Moleculor Weight Delerminofions.
sensitivecompoundscan be determinedin standardcomntercialvapor pressure
osmometersequippedrvith an inert-gaspurging line. Argon is preferredto nitrogen for purging this apparatus;the primary leakagepaths are around the top of
the apparatusand thus a heavygas is desirable.Standardboiling point elevation
apparatuscan be equippedwith an inert-gassupplyto providevery good exclusion of air and thus permit the collectionof molecularrveightdata on highly airsensitivecompounds.rl
The measurementof molecular weightsby freezingpoint depressionis con'
venientlyaccomplishedon air-sensitivecompoundsby meansof the apparatus
i l l u s t r a t e di n F i g . 1 . 2 8 .I n t h i s d e s i g n t. h e s a m p l ei s i n t r o d u c e dt o t h e c e l lf r o m a
weighingtube or syringeunder a nitrogen flush, or it may be introducedin an
inert-atmosphereglovebox. The microstirringbar in the sidearmof this apparatus is cooled with liquid nitrogen and flicked by nreansof a magnet into the
cell when the solution supercools.The temperatureis sensedrvitlr a thermistor.
and a stripchart recordingof the cooling curve may be extrapolatedby a linear
approximationif the region of supercoolingis short, or by more complexfunct i o n s d e s c r i b e di n t h e l i t e r a t u r e . l l
Cell designsto satisfya variety of needsare describedin the literature.rsra
G. Voriolions in Schlenk Wore. A large number of modificationsof the
basic Schlenkware are in use.The double-endedfilter is a commonlyusedvariant of the standard Schlenkfilter. The particular unit illustratedin Fig. 1.29 is
equippedwith O-ring joints rather than standardtaperjoints. (SeeChapter8 for
or modified Oa discussionof joints and O-ring materials.)Either con.ventional
joints,
have
ring
severaladvansuch as the Fischerand Porter Co. Solv-Seals,
joints
for Schlenkapparatus:theseO-joints are nlore
tagesover standard taper
resistantto solventsthan the conventionalstandardtaper ware, the O-joints are
more readilyclampedtogether,and, unlike standardtaperjoints, the two halves
r r F . W . W a k e r a n d E . C . A s h b y . J . C h e m .E d u c . . 4 5 , 6 5 4 ( 1 9 6 8 ) .
I ] W . J . T a y l o r a n d F . D . R o s s i n i ,J . R e s .N u t l . B u r . S t t l . , 3 2 , 1 9 7( 1 9 1 4 ) .
r : E n c l o s e dc e l l f o r c r y o s c o p ,ivn s u l f u r i ca c i d , u s i n ga P t r e s i s t a n c teh e r m o m e t e r :R . J . G i l l e s p i e ,J . B .
M i l n e . a n d R . C . T h o n r p s o nI.n o r g . C h e n t . ,5 , 4 6 8 ( 1 9 6 b ) .
r n E n c l o s ecdr y o s c o p -cve l l u i t h t h e r m i s t o rs e n s o r :T . L . B r o u ' n .C . L . G e r t e i s ,D . A . B a f u s , a n d J . A .
L a d d , , / .A n t . C h e n t .S o c . , 8 6 , 2 1 3 5( 1 9 6 4 ) .
j-Enclosed
c e l l u ' i t h a c o n v e n t i o n atl h e r n r o m c t e r :S . U . C h o i , W . C . F r i t h , a n d H . C . B r o w n , J . , 4 n r .
Chent9
. o c . . 8 8 .4 1 2 8( 1 S 6 6 ) .
39
> C H L E NTKE C H N I O U E S
N e e d l e- v o l v e
>o'|eno'o
Vent
note
L_:
Needle- volve
+To
omplifier
- Micro
stlrnng
bor
-z
Re f r t g e r o n t
- Dewor
(o)
f i g . 1 . 2 8 . C r v o s c o p lc- e l l . ( a ) T J p i c a l d i n r e n s i o n so f t h e l o $ ' c rs e c t i o na r e 2 6 0 - n r n rh e i g h t a n d 2 0 ' :r tlianreterT
. h e t h e r m i s t o ru ' e l l i s a b o u t 2 7 m n r . ( b ) C o o l i n ga p p a r a t u sf o l t h e c r ) o s c o p vc el l . T h c
. - . ( ) s c o p es l i p s i n t o t h e j a c k e t e dt u b e . T h e j a c k e t i s e v a c u a t e do r p a r t i a l l y e v a c u a t e dt o c o n t r o l t h c
.,,lrngrate.Electricalreadoutisachievedrvithadigitalmultimeterolcomnrercialelectronicsfor
' :c r r r i s t o r t h e r m o n r e t e r s .
,f theseO-ring joints are identical.When moderatequantitiesof solidsare being

randled, a fairly completesetupfor inert-atmosphere
preparationsand purifica:ronsconsistsof the double-endedfilter in conjunctionwith Schlenktubes. sol, c n t s t o r a g ef l a s k s .s o l i d ss t o r a g et u b e s .s y r i n g e sa, n d a d d i t i o nf u n n e l s .
The H-type Schlenktube, sometimescalleda double Schlenktube, is yet ano t h e r t y p e o f g e n e r a l - p u r p o s e i n e r t - a t m o s p h e r e a p p a r a t u s , (1F.i3g0. ) . T h i s a p paratusis basicallya combinationof two Schlenktubes and a filter. One advantageof the H-type Schlenktube is that it forms a very sturdy, leak-tightunit. In
addition to the usual pouring of solutionsthrough the filter, it permitsthe distillation of volatilesolventsfrom one leg to the other. This last featurecan be used
to wash and dry a precipitate.The H-type Schlenktube also is more satisfactory
than conventionalSchlenkwarefor low-temperaturefiltration. Weighedagainst
theseadvantages,the H designis unnecessarily
bulky for someoperationsand it
is somewhatmore difficult to use for large quantitiesof solids.As with the con-
F i g . 1 . 2 9 . D o u b l e - c n d e fdi l t e r . T h i s t v p c 0 f a p p a r a l u si s a g o o d a l t e r n a l i v et o t l r e r . n o r es t a n d a r d
S c h l e n kf i l t e r . T h e v e r s i o ni l l u s t r a t e di s b a s e do n g r e a s c l e sjso i n t s a n d v a l v e s .
F i g . 1 . 3 0 . H - S c h l e n kt u b e . l n a d d i t i o n t o r e p l a c i n gt h e s t a n d a r dS c h l e n kf i l t e r f o r r o u t i n e o p e r a t i o n s , t h i s a p p a r a t u sp e r m i t s l o r v - t e n t p e r a t u rfei l t r a t i o n i f a l a r g cc o o l i n gb a t h i s u s e d .S e eC h a p t e r 5
f o r t h e u s e o f t h c H - t u b e i n t h e W a y d a - D y ev a c u u n ra p p a r a t u s .
40
44
PRESSURE
REACTORS
OAPPABTE
!entional designs,a complete set of common operationsfor synthesisand,/or

purification can be designedaround the H-tube.
L6
PREssURE
REAcToRs
cAPPABLE
\ completemethodologyfor the manipulation and reactionof air-sensitive

solu:ronshas evolvedaround cappableglasspressurebottles. Soft-drink bottlesare
\()nletimesused (hencetheseproceduresare sometimesreferredto as "pop bot:le techniques");however,heavy-walledborosilicateglasspressurereactionves.r'ls are superior. In contrast to the modified standard taper ware discussed
.'bove,this pressureapparatus offers advantageswhere modest pressuresare
rccessaryand wherethe centrifugationof precipitatesis preferableto filtration.
Ihese techniquesare especiallypopular in the preparative-scale
study of cata.r'ticreactionsof small molecules,such as olefin polymerization.The pressure
r o t t l e i s f i t t e d w i t h a c a p c o n t a i n i n gt w o 1 / 8 i n . h o l e sa n d a r u b b e r l i n e r , w h i c h
: s s e c u r e db y m e a n so f a h a n d - o p e r a t e b
d o t t l e c a p p e r( F i g . l . 3 l ) . ' 8
Dependingon their sensitivity,solidsare loadedinto pressurereactionbottles
:n the air or in an inert-atmosphereglove box. The bottle is cappedand may be
carriedthrough severalpurge cyclesby meansof a hypodermicneedleattached
ryD-il:"':',
F i g , 1 . 3 1 . H e a v y - w a l l e dc e n t r i f u g e - t u b er, u b b e r c a p l i n e r , a n d c a p . ( " P o p b o t t l e " r e a c t o r . )T u b e s

q i t h v o l u m e s r a n g i n g f r o m 2 0 t o 2 5 0 m L a r e a v a i l a b l ef r o m L a b G l a s s . N o r t h W e s t B o u l e v a r d .
Vineland.NJ 08360.
I ' C a p p a b l er e a c t i o n b o t t l e s , c a p s , a n d t h e r u b b e r l i n e r s e p t a a r e a v a i l a b l ef r o m L a b G l a s s . I n c . ,
V i n e l a n d , N J a n d f r o m A l d r i c h C h e n r i c a lC o . , M i l w a u k e e . W l . E o t t l e c a p p e r sa r e a v a i l a b l ef r o n t
large hardware stores.
42
TECHNIOUES
BENCH-TOP
INERT-ATMOSPHERE
t o a d u a I i n e r t - g a sa n d v a c u u mm a n i f o l d( F i g . 1 . 2 ) .O r d i n a r i l y ,t h e r e a c t o ri s l e f t
under a small positivepressure(900-1000torr, 3-5 psig), rvhichminimizesthe
entranceof air and facilitatesthe removalof liquids by meansof a syringe.Reactions u'hichevolveIargequantitiesof gas ma1'requireoccasionalventingthrough
a hypodermic needle. Pressuresin excessof 3,300 torr (50 lblin.2) should be
avoided. The solution may be agitated by means of a shaking machine or by
means of a magnetic stirring bar which was included with the initial charge.
Since the bottles are easilythermostatedand samplesare readily removedby
syringe,the cappable reactorshave proven useful for kinetic investigationsof
air-sensitivesolutions.Thesereactorsare availablein shapeswhich fit largecentrifuges, and are therefore quite useful for separatingsolutions from solids
which do not filter well. Reactivesolids transfer operationsare readily performed in a glovebox becausethesesealedreactionvesselsare easilytransferred
t h r o u g ha v a c u u ml o c k .
4 ,7 HoTTUBE
ANDSEALED
TUBE
rEcHNrouES
A . H o t T u b e R e o c t o r s . M a n y s i m p l em e t a l h a l i d e s ,n i t r i d e s ,a n d t h e l i k e
are convenientlysynthesized,and sometimespurified, at elevatedtemperatures
in an apparatusdesignedto fit in a tube furnace.The generalstrategyis to contain one or nrore of the starting materialswithin the heatedtube. Often a reactive gas is passedthrough the tube. ln many instancesthe reactivegas is diluted
with an inert gas, and the inert gas is usedrvhenpurifying the product by sublim a t i o n . O n e e x a m p l e .g i v e n i n F i g . 1 . 3 2 , i s t h e p r e p a r a t i o no f a n o n v o l a t i l e
product, magnesiumnitride, from magnesiummetal and nitrogen gas. When
the reaction is complete. a back-flush of nitrogen is maintained from the attached Schlenktube as the inlet joint is removed.A long, stiff wire is then used
to push the boats containing the magnesiumnitride into the attachedSchlenk
tube. The secondexample in this same figure illustratesthe proceduresfor a
volatileproduct, gallium chloride.reIn this casethe reactionis performedin an
HCI stream and the product is subsequentlysublimed into a seriesof bulbs,
which can then be sealedoff. The streamof inert gashasto be adjustedcarefully
during the sublimation, so that the product is carried into the bulbs, but the
inert-gasstream should not be so rapid that the sublimateis swept out of the
apparatus.In the courseof a typical hot tube reaction,largevolumesof gas are
exposedto highly reactivematerialsin the reactor,thus exposingthe materials
therefore,to
to the cumulativeamount of impurities in the gas. It is necessary,
use pure gasesor to purify all gasesby appropriate dessicantsand/or oxygen
scavengers.
Chapter 3 may be consultedfor detailson inert-gaspurification.
f' W . C . J o h n s o na n d C . A . H a s k e w ,I n o r g . S y n t h . . l , 2 b ( 1 9 3 9 ) .p r e s e n td e t a i l so f t h e g a l l i u n rc h l o ride synthesis.
43
TECHNIQUES
TUEE
IOT TUBE
AND SEALED
To bubbler
N 2s o u r c e)
-Tube
furnoce
N2
(o)
H C Io r
N2
bubbler
tb)
F i g . 1 . 3 2 . R e a c t i o n si n h e a t e dt u b c s . ( a ) A p p a r a t u s f o r t h e p r e p a t a t i o na n d c o l l c c t i o no f n l a g n e : r u m n i t r i d e . H i g h l y p u r i f i e d n i t r o g e n i s u s e d . a n d o n l y t h e p r o d u c t f r o n r t h e s e c o n db o a l t s c o l t e c t e d .S a m p l ec o l l e c t i o ni s p e r f o r n e d a f t e r t h e t u b e c o o l sb 1 ' r e v e r s i n tgh e n i t r o g e nf l o u t h r o u g h t h e
r p p a r a t u s , i n s e r t i n ga l o n g , s t i f f w i r e f r o m t h e r i g h t e n d . a n d p u s h i n g t h e b o a t i n t o t h e S c h l e n k
v djusted
r u b e . ( b ) P r e p a r a t i o no f a v o l a t i l eh a l i d e . V e r y d r y g a s i s u s e d .a n d i t s f l o u r a t e i s c a r e f u l l , a
s o t h a t t h e h a l i d e n e i t h e r d i f f u s e sb a c k t o i v a r d t h e g a s s o u r c en o r i s s u e p t p a s t t h e f i r s t b u l b . A f t e r
r h e r e a c t i o ni s c o m p l e t e .t h e h a l i d e n r a y b e r e s u b l i m e di n a g a s s t r e a ma n d t h e n s e a l e do f f i n o n e o r
n r o r eo f t h e b u l b s .
B. SeOled TUbe PrepOrOliOnS. Sealedtube reactionsand purificationsafford good exclusionof the atmosphereand permit opel'ationsat nloderatepressures.The latter capability makes it possibleto work with highlv volatile solvents. such as liquid ammonia, at roonr temperature.Sincethe sealedtube is
often loadedon a high-vacuumline, the detailson thesetechniquesare given in
Chapter 9.
Another type of sealedtube processis employedfor chemicalvapor transport
usedto synthesizeand purify many inorgatlics,such as metal disulfides.In the
most comnton applicationsof these techniquesa tube \\'ith one end sealedis
chargedwith an impure or polycrystallinesampleof the desiredconrpoundplus
a small quantity of a transport reagent.The tube is then evacuatedand sealedat
t h e o t h e r e n d . T h e s e a l e dt u b e i s p l a c e di n a f u r n a c ec a p a b l eo f m a i n t a i n i n ga
temperaturegradient, with the hotter end correspondingto the chargedmaterials and the coolerend empty. For example,the materialto be purified might be
TaS2with a small amount of 12added as transportagent. Reactionof this trans-
44
TECHNIQUES
INERT-ATMOSPHERE
BENCH.TOP
port agent *'ith the TaS2yieldsvolatileproducts,u'hich are reconstitutedas purified singlecrystalsof TaS2at the colder end of the tube.20'2r
REFERENCES
GENERAL
A n g e l i c i . R . J . l 9 7 7 , . S r r r t f t e s ius n d T e c h n i q u ei n I n o r g u n i c C h e n t i s t r y , 2 n de d . , W . B . S a u n d e r s .
Philadelphia.
B r a u e r , G . , E d , . , H u n d h u c h d t , r P r e p u r a t i v e n A n o r g a n i s < h e n C h e n t i e , 3 r d e d .l , V1o9l 7
. 5;Vol.2,
1 9 7 8 ;V o l . 3 , 1 9 8 1 .T h i s b o o k c o n t a i n ss o n r eg e n e r a ls e c t i o n so n l a b o r a t o r yt e c h n i q u ea n d n r a n y
e x a n r p l c so f t h e u s eo f i n e r t a t n r o s p h e r et e c h n i q u e si n t h e i n d i v i d u a lp r o c e d u r e sf o r t h e s _ y n t h e s i s o f i n o r g a n i c c o m p o u n d s . S e ee s p e c i a l l y" P r e p a r a t i v eM e t h o d e n . " p . l . V o l . l , b v P . W .
S c h e n k .R . S t e u d e l ,a n d G . B r a u e r ; a n d " M e t a l l o r g a n i s c h eK o m p l e x v e r b i n d u n g e n ,b" y W . P .
F e h l h a n r n t e r ,W . A . H e r r n r a n n ,a n d K . O f e l e , V o l . 3 , p . 1 9 7 8 .T h e s e c o n de d i t i o n i s a v a i l a b l e
i n a n E n g l i s h t r a n s l a t i o nb u t i s l e s su p t o d a t e t h a n t h e a b o v en r a t e r i a l .
Brou n , H. C. , I 9 73, Orguttic .trrrr/resesviu Borunes, Wiley- l nterscience.Neu York. SeeChapter 9.
v p e r a t i o n su ' i t h A i r - S e n s i t i v eS u b s t a n c e s , b
p . l 9 l . " L a b o r a t o r _O
" y G. W. Kramer. A. B. Levy.
a n d M . M . M i d l a n d . w h i c h s t r e s s e s y r i n g et e c h n i q u e s .
E i s c h ,J . J . . a n d R . B . K i n g , E d , s . . O r g u n o n t e r u l l iSc t ' n t h e s e sA.c a d e m i cP r e s s ,N e w Y o r k , V o l . l . b y
R . B . K i n g , 1 9 6 5 :V o l . 2 . b y J . J . E i s c h . 1 9 8 2 .
G y s l i n g .H . J . . a n d A . L . T h u n b e r g , l 9 S b " T e c h n i q u c s f o r H a n d l i n g A i r S e n s i t i v ea n d T o x i c M a t e r i a l s . " i r r B . W . R o s s i t e rP
. h r s i c u tM t ' r h o t l so l C h e m i s t n - .W i l e y - l n t e r s c i e n c eN, e u Y o r k , V o l . l .
19E6p
, . 373.
H e r z o g . S . . J . D e h n e r t . a n d K . L u h d e r . 1 9 6 8 , i n H . B . J o n a s s e na n d A . W e i s s b e r g e rE
. ds. ?'ecn i t l u e o l l r t o r g u n i c C h e n t i s t n ' , , W i l e y - l n t e r s c i e n c eN, e w Y o r k . p . I 1 9 .
J o l l y . W . L . , 1 9 7 0 . T h e S v n t h e s i sa n d C h a r a c t e r i z a t i o ,0t . l l n o r g a n i c C o n t p o u n d s .P r e n t i c e - H a l l ,
E n g l e w o o dC l i f f s , N . J .
r o G r e a l e rd e t a i l a n d f u r t h t ' r c x a m p l e sn r a v b e f o u n d i n H . S c h a e f e r .C h t n t i c u l V u l x t r T r u n s p o r l
R e s c t i u t r sN
, e * Y o r k . A c a d e n r i c .1 9 6 , 1 .
r l T h e s v n t h e s i so f t u n g s t c no x 1 ' h a l i d ebs y t h i s p r o c e s si s d e s c r i b e db y J . T i l l a c k , I n o r g . S y n t h . , 1 4 .
1 0 9( 1 9 7 3 )a n d d e t a i l so f t h e 1 a S 1p u r i f i c a t i o na r e g i v e nb 1 J . F . R e v c l l i .I r n r g . S t , t t t h . ,1 9 . 3 5 ( 1 9 7 9 ) .
INERT.ATMOSPHERE
GLOVEBOXES
his chapter describesthe principlesof inert-atnrosphere

glovebox operation,
:redesignof gloveboxes, and glovebox procedures.The beginnerin a labora, r v * ' i t h a n o p e r a t i n gg l o v eb o x m a y w i s h t o s t a r t b y r e a d i n gS e c t i o n2 . 1 , a n d
' : r ec o n c l u d i n gs e c t i o n ," E q u i p m e n t a n d O p e r a t i o n s . "O t h e r s e c t i o n sc a n t h e n
-r consultedas the needarises.If the purchaseor designof a new systentis being
- , ' n s i d e r e dt ,h e w h o l eo f t h i s c h a p t e rs h o u l db e u s e f u l .T h e p u r i f i c a t i o no f i n e r t
..rses,discussedin Chapter 3, is also reconlmendedfor individualswho wish to
:.rin a thorough understandingof inert-atmosphereglove boxes.
2 I GENERAL
DEsTGN
ANDAppLrcATroNs
i he inert-atmosphereglove box providesa straightforwardmeansof handling
, , i r - s e n s i t i vseo l i d sa n d l i q u i d s .l n i t s s i m p l e s ft o r m . i t c o n s i s t so f a g a st i g h t b o x
:itted with a window, a pair of gloves,and a gas tight door or transferport. The
- ' n t i r eb o x i s f l u s h e dw i t h a n i n e r t g a s ,a f t e r w h i c h s a m p l e sm a y b e m a n i p u l a t e d
:n the inert atmosphere.
T h e g l o v eb a g i s a s i m p l ea n d i n e x p e n s i vvea r i a n to f t h e d r y b o x . I t c o n s i s t o
sf
.i largepolyethylenebag fitted *'ith a nitrogeninlet and an open end, rvhichmay
'oe
closedby rolling and clamping. The bag is purged by severalcyclesof filling
' . r i t hi n e r t g a s a n d c o l l a p s i n g o
, r b 1 ' a c o n t i n u o u sf l u s h . [ n i t s p r i n r i t i v ef o r m ,
nranipulationsare accomplishedin an ordinary bag. but comn.rercially
available
45
46
INERT.ATMOSPHERE
GLOVEBOXES
glove bags with integral polyethyleneglovesare much more convenient(Fig.

2.1).1
A s u ' i l l b e d e s c r i b e do. n e o f t h e p r i n r a r l ' s o u r c eos f c o n t a m i n a t i o no f t h e d r y
box atmosphereis diffusion of air through the gloves,In a few casesthis contami n a t i o n h a s p r o m p t e dt h e u s eo f m a n i p u l a t o r sw h i c h , f o r s i m p l et a s k s ,n e e dn o t
be intricate. However, the use of manipulators has not met with u'ide favor,
p r o b a b l yb e c a u s eo t h e r m e t h o d sa r e s i n r p l e ra n d c h e a p e r .
The appealingsimplicityof glovebox manipulationsmust be weighedagainst
the disadvantages,which are the slownessof operation and the difficulty in
maintaining a water- and oxygen-freeatntosphere.Work in a dry box can be
slow becauseof the need to passmaterialsthrough an air lock and becausethe
glovesand glove ports reducethe experimentalist'sdexterity.In addition, there
is the problem of nraintainingan air-free atmosphere,which is complicatedby
i m p u r i t i e si n t h e i n e r t - g a ss u p p l y ,l e a k si n t h e g l o v eb o x . a n d d i f f u s i o no f m o i s ture and oxygenthrough the gloves.Solventvaporsor volatilereagentscontanrinatethe atmosphere,and this sourceof cross-contamination
can becomeserious
if severalindividuals handling quite different materialsare using the same dry
box. As describedlater in this chapter, a recirculatinggas purifier or a rapid
':.Nitrogen
_/
.)
f]^ ,i,_a)
6
,ra,\
{,.-)
'-7a
t\
,,4tnlel
,-1"1^: )
dri?"j
(3\\
.-),-'-
'\z-'. /.-.,
i
i
Entronce sleeve
\
R o l l u p o n d c l o s e w i t h f h e s p r i n gc l i p s\
:::=::::-=::
F i g . 2 . 1 . P o l v e t l t r ' l c ngcl o v eb a g . S e v e r a sl i z c sa r e a v a i l a b l e .i n c l u d i n gg l o v eb a g su ' i t h t * o p a i r s o f

g l o v c s .( A d a p t e d f r o n r I n s t r u n r e n t sf o r R e s e a r c ha n d I n d L r s t l v .C h e l t e n h a n r .P A . G l o v e B a g b l o c h u r e .)
r G l t t v eb a g sa r c a v a i l a b l el r o n r l n s t r u n r e u (fso r R c s e a l c ha r r dI n d u s t r t .C h e l t e n h a n rP. A I 9 0 1 2 .a n d
A l d r i c h C h e n r i c aC
l o . . P . O . B o r 3 5 5 .M i l * a u k e e .W I - S 3 2 0 1 .
ATMOSPHERE
REPLACEMENT
OF AIR BYAN INERT
47
flush of inert gasthrough the box is often employedto ntinimizeimpuritiesin the

glovebox atmosphere.The most commonlyusedinert gas is nitrogen;but rvhen
the materialsbeing handled form nitrides, helium or argon is used.
Somevery activeresearchlaboratoriesin the United Statesusegloveboxesfor
practicallyall of their chemicaloperations,including reactionsin solvents.In
general,thesesituationsinvolveone glovebox per investigatorand specialfeatureswhich allow quick entry and exit from the glovebox. By contrast.in many
Europeanlaboratories,very little, if any, use is made of glove boxes. Instead,
variousnleansare devisedfor handling solidswith Schlenk-typeequipment. In
the authors'laboratories,gloveboxesare usedfor intricatesolidstransferoperations, but nrost reactionsand the handling of solutionsare perforned in Schl e n k - t y p ea p p a r a t u so r i n a c h e m i c a vl a c u u ml i n e . O p e r a t i o n s u c ha s w e i g h i n g
reactivesolids, making mulls for infrared spectroscopy,and loading capillary
tubes for X-ray diffraction are convenientlyperformed in a glovebox or glove
bag.
In addition to their use for handling air-sensitivecompounds,glove boxes
havebeen usedto good advantagein the transferof radioactive.poisonous,and
hazardousbiological materials. The strong feature of the glove box for these
applicationscomesfrom the easeof containment.Becauseof this characteristic,
nruch of the developmentof inert-atmosphereglovebox designhas occurredin
conjunctionwith atomic energyprograms.
gloveboxesare availablecommercially,so
General-purposeinert-atmosphere
it rarely makes senseto constructa systemof this type locally.2Nevertheless,
a
knowledgeof the constructionfeaturesis usefulfor the choiceof an appropriate
glovebox and for the maintenanceand nrodificationof an existinginert-atmosphereenclosure.In addition, there are somespecialtypesof gloveboxeswhich
n.rustbe constructedby the user becausethey are not generallyavailablecommercially.
2,2 REpLAcEMENT
oF ArRByANINERT
ATMospHERE
There are two common methods of replacing air by an inert gas in the main
chamber of an inert-atmosphereglove box: evacuationfollowed by filling with
the desiredinert gas, or a lengthypurge of the box by the inert gas. The second
alternativeis generallyemployedfor largeboxes,sinceextremelyheavyand wellbraced construction is necessaryto prevent the collapseof a large evacuated
chamber. On a small scale,the structural problemsare not so formidable, so a
pump-down dry box is attractiveif a compact unit is satisfactory.Similarly, a
r M a n u f a c t u r e r so f i n e r t - a t m o s p h e r g
e l o v eb o x e sa n d a c c e s s o r i ei sn c l u d eV a c u u m A t m o s p h e r e sC o . .
4 6 5 2W . R o s e c r a n sA v e . , H a u t h o r n e , C A 9 0 2 5 0( a l u m i n u n ro r s t a i n l e s s t e e lc o n s t r u c t i o n ) K
; ewaun e e S c i e n t i f i c E n g i n e e r i n g C o . . A d r i aMnl , 4 9 2 2 l( m e t a lc o n s t r u c t i o n L
) :a b c o n c o C o r p . , S S lP
l rosp e c t . K a n s a sC i t y , M O 6 4 1 3 2 ( f i b e r g l a s s - r e i n f o r c epdo l y e s t e rc o n s t r u c t i o n ) ;M a n o s t a t C o r p . , 5 1 8
8 t h A v e . , N e w Y o r k , N Y 1 0 0 1 8( p o l y m e t h a c r y l a t e
construction).
4B
GLOVEBOXES
INERT.ATMOSPHERE
small punlpabletransfer lock is generallyattachedto a largebox to facilitatethe

introduction of apparatusu'ith minintum contaminationof the glovebox atnlosphere.
P r o v i d i n gt h e a p p a r a t u si s l e a k - t i g h t i.t i s n o t n e c e s s a r y
A. Pump-ond-Fill.
t o a t t a i n a h i g h v a c u u n ti n a p u m p - a n d - f i l l o p e r a t i o nf o r e l i m i n a t i n ga i r f r o m a
t r a n s f e rl o c k o r m a i n c h a n r b e ro f a g l o v eb o x . A s d i s c u s s e di n C h a p t e r1 . t h e
pump-and-fill processmav be repeateduntil the desireddegreeof purity is atis attainedon eachof rl
tained. For the casein u'hich a vacuunl of.l'atmospheres
c y ce
f so f p u n r p i n ga n d f i l l i n g . t h e f r a c t i o no l a i rA , r e m a i n i n gi s g i v e nb y E q . ( l ) :
A, :j\
(l)
T h u s , a p u n r p r v h i c hi s c a p a b l eo f q u i c k l l a c h i e v i n gI t o r r ( 1 . 3 x 1 0 - r a t m )
o f 1 . 7 p a r t so f a i r p e r m i l l i o n p a r t so f g a s
u ' i l l y i e l d a r e s i d u a la i r c o n c e n t r a t i o n
after two cycles.lt must be stressed.however.that the limitation on the vacuunt
m u s t n o t b e l e a k a g e .b e c a u s ei n t h i s c a s et h e p u r i t y o f t h e g a s c a n n o tb e i m provedby repeatedpump-and-fill cycles.Therefore,the standardsof construction of the apparatusshouldbe appropriatefor high vacuut'll,eventhough a high
vacuum is neverachieved.To ensurethat the systenlis leak-tight,the chamber
a n d p l u m b i n g t o t h e p u n l p c a n b e s u b j e c t e dt o a h e l i u m l e a k t e s t e r( S e c t i o n
7 . 3 D ) . S i m i l a r l y ,t h e p u m p c a n b e c h e c k e do n a h i g h - v a c u u mt e s tb e n c ho r v a c uum line.
Sinceevacuationis usuallythe slou'eststep.sonleattentionshouldbe givento
m a t c h i n gt h e p u m p t o t h e s y s t e m .F o r a c h a m b e ro f v o l u m e V a n d a p u m p o f
pumping speedS, the time requiredto reducethe pressurefrom P1 to P2 is given
bv Eq. (2).
PzV
r:;sP'l'
Q)
Sincethe pumping speedof a mechanicalpump doesnot vary greatlyat modera t e p r e s s u r e s( e . g . , F i g . 6 . 3 ) . i t i s r e a s o n a b l et o a s s u m ea n a v e r a g ec o n s t a n t

punrping speedif very low pressuresare not involved. Integration then yields
Eq.(3).
t:
P,
2.3V
toBP,
.,
(3)
As an example,considerthe time required to pump a large air lock with a volume of 50 L from a pressureof 760 to 0.5 torr. The free-air capacityof a widely
a v a i l a b l ep u n r pi s 1 4 0L / m i n , b u t t h r e e - f o u r t hos f t h i s i s a m o r er e a s o n a b laev e r agepumping speedfor the abovepressurerange.Insertionof thesenumbersinto
E q . ( 3 ) g i v e sa p u m p - d o w nt i n t eo f 3 . 5 m i n . T h i s v a l u em a y s o m e w h aut n d e r e s t i m a t e t h e p u m p i n g t i m e . b u t t h e c a l c u l a t i o ni l l u s t r a t e sa m e t h o df o r a p p r o x i mately matching the pump to the patienceof the experimentalist.
49
REPLACEMENT
ATMOSPHERE
OF AIR BYAN INERT
B. Pulging. Figure 2.2 illustratesthree simplemodelsfor flushing air from a

chamber by a stream of inert gas: perfect displacement,perfect mixing, and
:hort circuit. The most desirablecondition for purging would be perfect displacement, since this involvesa gradually moving front of purge gas which
pushesall of the unwanted air ahead of it (Figure 2.2a).Under this condition
,)nly one chamber volunte of inert gas would be required to obtain a perfect
purge. In any practical case,perfectdisplacementcannot be attained,owing to
interdiffusion,turbulence,and lack of an idea[geometryfor the chamber.After
due regard is taken to ensurethe proper positioningof the gasinlet and outlet, it
rppearsthat interdiffusionis a nlajor limiting factor in the attainmentof perfect
.lisplacement.Thus, rapid flushing has been found to be more efficient than
'lou'flushing.3If, on the other hand, the perfectmixing situationoccurred,the
!'nteringpurge gas would inrmediatelymix with the gas in the chanrberand the
nrixturewould exit the chamber at a rate equal to that of the enteringpurge gas
, Figure 2.2b). The differentialequation for the latter casemay be integratedto
vield a simple exponentialdecayof the fraction of air remaining,/, in terms of
the number of chamber volumesof gas passedthrough the system,r, giving Eq.
|{r:
Ai:
(4)
g-'
In contrastto perfectdisplacement,Eq. (4) demonstratesthat perfectmixing

leadsto a reductionin the air contentby a factor of e-' (0.37)after one chamber
volumeof purge gas is consumed.Similarly, it may be shownthat 8.8 chamber
rolumes are required to reduce the air content to 150 ppm, and about l0 are
necessary
to attain 45 ppm. Unlessa short circuit occursbecauseof the inappropriate placementof entranceand exit ports (Fig.2.2c), the actual situationcan
be expectedto fall betweenperfect displacementand perfect mixing. Experi-
(b)
l---F*
|
\5ffi+
(c )
F i g . 2 . 2 . S c h e m a t i cr e p r e s e n t a t i o nos f i d e a l i z e dp u r g i n g c o n d i t i o n s .( o ) P e r f e c td i s p l a c e m e n t(; b )
p e r f e c tn r i x i n g ; ( c ) s h o r t c i r c u i t c a u s e db y t h e i n t r o d u c t i o no f a l i g h t g a s a t t h e b o t t o n ro f t h e c h a m ber.
' S . l . C o h e na n d J . M . P e e l e ,U S A E C R e p o r tO R N L - C F - S S - 1 0 - 1 (3129 5 5 ) .
50
INERT.ATMOSPHERE
GLOVEBOXES
mental results which illustrate this situation are presentedin Fig. 2:3, and a
recommendedarrangementfor the inert-gasinlet and outlet is illustratedin Fig.
2.4a.
C. Recommended Conditions.
Becauseof structural considerations.it
is generallymost satisfactoryto use the purging method for large chambers,
such as the main chamber of a large dry box. For smallergloveboxesand glove
box antechanbers,air is convenientlyremovedby either pump-and-fill operations or purging. If purging is the method chosenfor replacingair in the antechamber, it is desirableto include a small manifold in the chanrberso that the
interior of flasks or vials can be efficientlyflushed (Fig. 2.4b).
In summary,the previousdiscussionindicatesthat three principlesshouldbe
followed:(1) to avoid short circuits, gaseswhich are more densethan air (e.g.,
argon) should be introduced at the bottom of a chamber and conversely,less
densegases(e.g., helium) shoutdbe introducedat the top; (2) interdiffusionof
the incominggaswith that in the chamberis a significantfactor, so a fast flush is
more effectivethan a slow flush; (3) experimentalresultsindicatethat a chamber is purged at a rate slowerthan predictedby perfectdisplacementand faster
than that indicated by perfect mixing. Therefore,the perfect mixing equation
100
70
50
s30
-20
o
X
o7
rn
-C 5
o
c_
CJ
P
z
c
o
o
.,1
o.z
o5
o3
o.?
g
9
o
o
o
l
o. 1
@
o
o
o
l
o
o
J
o
f
1?345678
N o . o f b o x v o l u m ec h o n o e s
F i g . 2 . 3 . C o n r p a r i s o no f e x p e r i m e n l a lr e s u l t sw i t h i d e a l i z e dp u r g e c o n d i t i o r r s .A , B , a n d C a r e
e x p e r i m e n t a l ,w i t h v a r i o u s d e s i g n sf o r t h e g a s i n l e t a n d o u t l e t . T h e b e s t o f t h e s e ,C , w a s o b t a i n e d
w i t h t h e p u r g i n g a r r a n g e m e n ti l l u s t r a t e di n F i g u r e 2 . 4 a . P o i n t D w a s o b t a i n e dw i t h t h e h e a v yg a s
( C O z )e n t e r i n ga t t h e t o p o f t h e b o x , a n d p o i n t E w a s o b t a i n e dw i t h a l i g h t g a s ( H e ) e n t e r i n ga t t h e
b o t t o m . T h e l a t t e r c o n d i t i o n sr e s u l t i n s o m e s h o r t - c i r c u i tf l o w . ( R e p r o d u c e db y p e r m i s s i o no f t h e
c o p y r i g h t o w n e r . B u t t e r w o r t h f r o m P . A . F . W h i t e a n d S . E . S m i t h , I u e r t A t n t o s l t h e r e s ,B u t t e r w o r t h , L o n d o n , 1 9 6 2 ,p . 1 4 8 . )
IN ATMOSPHERE
SOURCES
OF AND REDUCTION
OF IMPURITIES
5,1
(b)
(o)
F i g , 2 , 4 . A r r a n g e n r e n to f p u r g e l i n e s .( a ) F o r t h e m a i n b o x t h e l o u ' e rm a r r i { o l ds h o u l d b e t h e i n l e t
* i t h a d e n s eg a s ( f o r i n s t a n c e ,A r ) a n d t h e o u t l e t w i t h a l i g h t g a s ( f o r i n s t a n c e .H e ) . ( ) A p u r g e - g a s
n r a n i f o l di n t h e t r a n s f e r p o r t e q u i p p e dw i t h o u t l e t j e t s t o f l u s h v o l u m e t r i ce q u i p m e n t
providesan ample margin of safety in estimatingthe volume of purge gas required. Theserecommendationsare basedon the assumptionthat the chan.rber
can be flushed by smooth linesof gas flow betweenthe gas inlet and outlet. The
placenlentof the gas inlet and outlet to achievesuch flow is illustratedin Fig.
2.4a.
Box
2,3 souRcEs
oFANDREDUcTToN
oFrMpuRrTrEs
rNGLovE
AIMOSPHERES
A. Confominofion by Oulgossing.
After the initial renoval of air from a
glove box chamber. the impurity levelswill gradually rise due to a variety of
s o u r c e s (: 1 ) o u t g a s s i n go f h y d r o u so r p o r o u sm a t e r i a l ss u c h a s w o o d . p a p e r ,
cloth. asbestos,and corrodedmetal; (2) leakagethrough seamsand joints; and
(3) diffusion of atmosphericgasesthrough permeablematerials,such as rubber
g l o v e s r, u b b e r g a s k e t s a
, n d p l a s t i cw i n d o w s .I t e m s2 a n d 3 w i l l b e d i s c u s s e idn
following section.Becauseof the first factor, wood or conposition board is not
glovebox; and u'ood.paper,
suitablefor the constructionof an inert-atmosphere
cloth, and asbestositems are not taken into the box when moistureis objectionable. A good substitutefor paper or cloth rvipesin cleaningup spilled solids is
the soft polyethylenesealingfilm sold by laboratorysupply houses(e.g., Parafilm). When paper or cloth wipesmust be used,a considerablequantity of moisture may be removedprior to useby storageof theseitems in a desiccatorover a
drying agent.
B. LeOks. Small leaks through seamsand gasketsare a significantproblem
*'ith poorly constructedgloveboxes.The maintenanceof a small positivepres-
52
GLOVEBOXES
INERT-ATMOSPHERE
sure in the box doeslittle to reducethe influx of air through small leaksbecause
countercurrentdiffusion of air is rapid. To reducetheseproblems,it hasbecome
fairly standard practice to adopt constructionpracticeswhich approachthose
used in high-vacuumapparatus.Thus. permanentmetal seamsare best welded
in a smooth and continuousfashion, and permanentseamsin poly(methylmethacrylate)are best bondedwith a solventcement(Appendix III). Perhapssomewhat lessdesirablebut still satisfactoryseamscan be made with rubber cements
and rubberized caulking compoundson reasonablymatched mating surfaces.
This practicesuffersfrom the potential deteriorationof the sealingcompound.
Room temperaturevulcanizingsiliconesealantsare good for most dry box sealing applications.A pitfall to be avoidedis to purchasea poorly made glovebox
or build one with sloppy constructiontechniques,with the thought that the assembledbox can be patchedby the applicationof paintsor sealants.In practice.
sealantsapplied over a leak are likely to crack or channel,so one is foreverchasing leaks.
Gross leaks may be detectedby slightly pressurizingthe box and painting
suspectedareas with soap solution. NOTE: A normal nonevacuableglove box
will tolerate only a small pressure or vacuum before the windows crack, the
glovespop off, or the box is distorted. The most satisfactorymeans of finding
small leaksis a halogenor helium leak tester(Chapter7). In this casethe box is
filled with Freon or helium and the "sniffer" of the leak testeris passedoverthe
suspectedareas.Someglovebox manufacturerswill guaranteea low leak rate as
certified by halogenor helium leak testing at the factory.
C. Glove Box Dools ond Removoble Ponels. Temporary sealscannot
be avoidedon the entrancedoorsand on panelswhich must be removedto reconfigure the glove box. These sealsare best made with high-quality firm rubber
gasketsor O-rings. It is important that the surfaceswhich are being joined are
sufficientlyheavy so that they do not buckle when clamped together,and the
panel or door should be clampedevenly.The incorporationof thesefeaturesin a
suitableentranceport is accomplishedby the use of a floating hinge that does
not constrainthe door, and the useof a latchingsystemthat exertsits force in an
even fashion. Successfuldoor latches involve an autoclave-typeclosure (Fig.
2.5a), a centrally located screw (Fig. 2.5), and evenlydistributed clamps or
bolts (Fig. 2.5c). Large panelsare generallybolted togetherat closelyand evenly
spacedintervalsaround the perimeter.
D. Diffusion of Ait inlo lhe Box. With good design and workmanship,
leakagethrough seamscan be reducedto negligiblevalues.This leavesone remaining major sourceof atmosphericimpurities: diffusion of air through gloves
and, to a lesserextent, through rubber gasketsand plasticwindows.Diffusion
also is a significant sourceof impurities in plastic gloveboxesor glovebags. A
few calculationswill illustrate the magnitudeof the problem.
When the glovebox is constructedentirelyfrom plastic,the diffusion of oxy-
SOURCES
OF AND REDUCTION
OF IMPURITIES
IN ATMOSPHERE
Undercut
/lo recetve
c l o m p i n gf i n g e r s
53
lock bor
,,-Htnged
-Flootrnqhinoe
Clomping
\
F l o o t i n gh i n g e s
H r n q e dc o t c h f o r
\lock- bo,
(b)
(o)
F l o o t r n gh i n g e
Y o k e sl o r e c e t v eb o l t s
K.oo"'.,,
w t t h w i n gn u t s
(c)
F i g . 2 . 5 . S o m ed e s i g n sf o r a n t i c h a m b e rd o o r s .( a ) A u t o c l a v et y p e . W h e n
t h e h a n d w h e e li s t u r n e d ,
t h e w e d g e - s h a p e cdl a m p i n g f i n g e r se x t e n d o r r e t r a c t . T h e d o o r i s c l a m p e ds h u t w h e n
t h e s ef i n g e r s
r r e w e d g e di n t o a n u n d e r c u to n t h e f l a n g e .( ) A c e n t r a ls c r e wl o c k d e s i g n .( c ) A
h i n g e d - b o l td e s i g n .
T h e r e a r e m a n y v a r i a n t so f t h i s . A g r o u p o f c a m - a c t i o nc l a m p s i s s o m e t i m e s
u s e di i p l a c eo f b o l t s .
gen through the walls is significant. For an average-size

glove box constructed
from l/2-inch-thick poly(methylmethacrylate),a calculationof diffusion
rates
indicatesthat the influx of oxygenthrough the walls is about equal
to oxygen
diffusion through the gloves.
Using the diffusion coefficientdata in Appendix III, and assuminga typical
glovebag sizeof 8,600 cm2and a thicknessof 5.2 x l0 r cm, 12.-,
of o"yg"n
n'ill diffuse into the bag at 25'C in one hour and, at a relativehumidity
of 504,
approximately30 cm3 (gas at STp) of moisture will diffuse into the bag
in the
same time period. For a neoprenegrovewith an area of 1,900 cm2 and with
a
t h i c k n e s so f 7 . 5 x l 0 - 2 c m , a n i n f l u x o f 0 . 5 6 c m 3o f o x y g e np e r h o u r i s
calculated' An experimentalvalue for the moisturediffusion rate oi 12.5 cm3(gas
at
STP) is availablein the literature for 25oc and 50% relativehumidity.afuhen
the glovebox is in use,the worker generatesboth sweatand heat, and the rate
of
diffusionof moistureincreasesby approximatelya factor of ten.l In other words.
'J. E. Ayers,
R . M . M a 1 4 i e l da, n d D . R . S c h m i t t , N u c t . S c i .E t t g . , g , 2 7 4 ( 1 9 6 0 ) .
trA
INERT.ATMOSPHERE
GLOVEBOXES
when a dry box with two glovesis idle, the influx of impurities will be about a
m i l l i m o l eo f a t m o s p h e r i ci m p u r i t i e sp e r h o u r . A s s u m i n ga t y p i c a lg l o v eb o x v o l ume of 212 L, this amountsto an increaseof atmosphericimpuritiesby 59 ppm/
h . W h e n t h e b o x i s i n u s e ,t h e i n f l u x m a y i n c r e a s et o a b o u t 5 0 0 p p m / h .
E. Moinfenonce of on Inert Atmosphele.
From the previousdiscussion
it is clearthat the dry box atmosphererequirescontinualpurificationto balance
t h e i n f l u x o f c o n t a m i n a n t sA
. n u n r b e ro f m e t h o d so f w i d e l yv a r y i n gc o m p l e x i t y
havebeen used.The simplestand most common schemeis to maintain a continuous purge of the box. This also may be supplemented*'ith the useof an open
dish of desiccantin the box. If the expenseof a continuouspurge of inert gas is
too great, a recirculatingsystemis necessary.The n.rostcomnlon recirculators
are basedon an oxygenscavenger,such as supportedCu or MnO, and a desiccant, such as molecularsieves.(The nature of and regenerationof oxygenscavengersand desiccantsare discussedin Chapter 3.) Systemsof this type may be
constructed.as outlined in Fig. 2.6, or purchased.Commercial systemsare
availablewhich regeneratethe columnsautomatically.Satisfactoryoperationis
possiblewith manual regenerationbecausethe unit can be arrangedso a set of
columns can be switchedfrom purification to regenerationby attending a ferv
valvesand switches.One of the sinrplestcommercialunits is nrountedon the side
of the box, and large-diametercolumnswith large-particlepackingare used.An
air blower in the box is sufficientto force the inert gasthrough the colunrn(Fig.
2 . 7 ) . M o u n t i n g t h e b l o w e ri n t h e b o x s i m p l i f i e st h e d e s i g nb e c a u s ei t a v o i d st h e
leakagewhich is a problem with many pumps, and it avoidsany sourceof oil
mist which can result from a pump. If an externalpump is used, a unit with a
metal diaphragm is often preferred. Pumps with ordinary shaft sealsmay be
n r o u n t e di n a m e t a l b o x w h i c h i s p u r g e db y i n e r t g a s . 'ni
One earlytest of glovebox impuritiesindicatedthat a circulationrate of 5 box
volumesper hour through the glovebox and MnO purificationtrain would lead
to a steadystateconcentrationof 50 ppm of atmosphericgasesin an argon-filled
b o x . F o r a n r o d e r nc o m m e r c i a p
l u r i f i c a t i o nu n i t t h e m a n u f a c t u r e rc l a i m st h a t
the moisture and oxygenlevelsare reducedbelow I ppm by purging in a large
g l o v eb o x a t a c i r c u l a t i o nr a t e o f a b o u t 5 0 b o x v o l u m e sp e r h o u r .
A schemefor removalof nitrogenfrom a heliun-filled glovebox can be based
on low-temperatureadsorptionon charcoalor molecularsievesheld at - 196oC.
There appearsto be no easily regeneratednitrogen scavengeru'hen the more
condensableinert gas argon is employed.In this casea getterof hot calciunror
hot zirconium-titaniumalloy is used.When the column of gettermaterialis consumed,it ntust be replaced.The heat introducedfrom this or other sourcesis atr
annoyancefor the glovebox user. This problem may be reducedby including a
heat exchangerin the inert-gasstream. Both water-cooledand refrigeratedheat
exchangershave been used successfully.
' 8 . C . A s h b y a n d I l . D . S c h w a r t zJ. . C h e n t .E r l r c . . S l , 6 5 ( 1 9 7 4 ) .
" P . A . F . W h i t e a n d S . E . S m i t h ( G e n e r a lR e f c r e n c e sp,. 6 7 ) .
SOURCES
OF AND REDUCTION
OF IMPURITIES
IN ATMOSPHERE
55
13X
4A
13X
F i g . 2 . 6 . S c h e m a t i cr e p r e s e n t a t i o no f a d r y - b o x p u r i f i c a t i o n s c h e m e .( A ) G l o v e b o x ; ( B ) t a n k a r g o n ; ( C ) p u r g e l i n e f o r p u n r p c o n t a i n e r :( D ) g a s t i g h tp u n r p c o n t a i n e r i( E ) . 2 . 7 f t r / m i n g r a p h i t er i n g
p u m p ; ( F ) b u b b l e r ; ( G ) p u r i f i c a t i o n t r a i n c o n s i s t i n go f L i u d e l 3 X a n d 4 , 4 M o l e c u l a r S i e v e s ,a n d
V e r n r i c u l i t e - s u p p o r t eM
d n O a t r o o n l t e n l p e r a t u r e( s e eC h a p t e r 3 ) . I n s o n r ei n s t a l l a t i o n sa n a d d i t i o n a l d r y i n g c o l u m n f o l l o w st h e M n O c o l u m n . A p p r o x i n r a t ec o l u m n d i m e n s i o n sa r e 3 - i n . d i a n t e t e r
b y 4 - f t l e n g t h .( U n p u b l i s h e dd e s i g no f T . L . B r o u n . )
Hydrocarbonsand polar solvents,which are sometimesinadvertentlyor intentionally introduced into a glove box, presenta contaminationproblem and
may have a deleteriousinfluenceon some oxygenscavengers.Volatile sulfides
and halocarbonsare particularly strong poisonsfor copper-basedoxygenscavengers.Removalof thesetypes of materialscan be effectedby l3X molecular
sieves;thesein turn can be regeneratedat slightly elevatedtemperaturesas describedin Chapter3. Alternatively,the solventvaporsand much of the moisture
can be removedby rrreansof lou'-temperaturetraps held at -78oC.5
The pressurein a dry box must be closeto I atm for easymanipulationof the
gloves.Significantdeviationsfrom 1 atm for a nonevacuable
glovebox can damage the windou's,gloves,or box walls. If the dry box atmosphereis maintained
by a continuouspurge, a large mineral oil bubbler on the exit will ensurethe
proper pressure.With a closed recirculatingpurifier, a pressurecontroller is
desirablebecauselargefluctuationsin the dry box pressurecan resultfrom run-
56
INERT-ATMOSPHERE
GLOVEBOXES
lbtlbl-
F i g . 2 . 7 . R e c i r c u l a t i o nu n i t i n s t a l l e do n a d r y b o x . ( R e p r o d u c e db y p e r m i s s i o nf r o m V a c u u m A t mospheresCorp. )
ning the glovesin and out during routine manipulations.Commercialunits are

availableand a descriptionof the necessaryparts for the constructionof such a
unit are given in the literature.s-r
F. Moniloting lmpurifies. Becauseof cost and complexity,the automatic
monitoring of the glove box atmosphereis not comnlon in academiclaboratories, but someindustrial and many atomic energyinstallationsemploy continuous monitoring. Water is easierto nleasurethan oxygenand fairly simple mois'D.
E u b a n k sa n d F . J . A b b o t t , A n u l . C h e n t . , 4 l . 1 7 0 9( 1 9 6 9 ) .
IN ATMOSPHERE
SOURCES
OF AND REDUCTION
OF IMPURITIES
57
rure metersare availablewhich operatein the parts per million range.8These

nretersare basedon a varietyof principles,the most common being the conductivity of a hygroscopicmaterial. If the dry box atmospherewill be contaminated
b-vvolatile solvents,a meter should be chosenwhich is insensitiveto those solrents. In addition, a simpledewpointmeter may be built into the box in the form
of a well which can be chargedwith a coolantsuch as Dry Ice.eThis well should
extenddown far enoughinto the box so that its polishedsurfacecan be observed
for signsof condensation.A dew point of -78"C correspondsto about 0.7 ppm
of water vapor.
Oxygen meters are commercially available, but their operation in conjunction
*'ith glove boxespresentssome complications.r0One method for the measurement of low oxygenconcentrationsis basedon the potential acrossa solid oxide
electrolytecomposedof CaO-dopedZrO2. Unfortunately,this systemworks at
elevated temperatures where reducing vapors affect the reading. Another
schemeinvolvesan electrochemicalcell having an aqueouselectrolyte.rrSince
this schemeintroducesmoisture into the gas stream, it is best placed on the
outlet from the glovebox. Owing to the lack of simpleand inexpensive
detectors,
a varietyof qualitativetestsare employed.The most popular of theseis the light
bulb test. In this test, the total oxygenand moistureis estimatedby the lengthof
time it takes a light bulb filament to burn out while it is exposed to the
glovebox atmosphere.The filament of a standard115-V,25-W light bulb with a
hole broken in the envelopewill burn for days to weekswhen the oxygenplus
moisture contamination is 5 ppm or lower. If the flow rate and nature of the
filament are controlled in a reproduciblemanner, a calibration curve can be
obtained; one such curve is presentedin Fig. 2.8.7
Often it is sufficient to determine oxygen and moisture by noting the changes
which occur upon exposureof a highly sensitivecompound. Noe:The common
cobalt-impregnated desiccants, which turn from blue to nearly colorless when
saturated with water, undergo this color change at far too high a moisture level
to be useful for sensitivematerials. A qualitative test sometimesrecommended
for moisture is the brief opening of a bottle of TiClr in the glovebox. If smoke
doesnot appear,the moisturecontentis below 10 ppm. Triethyl aluminum or a
hydrocarbon solution of diethylzinc will not fume when opened briefly in a box
with oxygenin the low parts per million range. Theseparticular testshavethe
nSourcesof moisture meters include Vacuum Atmospheres Co. (see footnote 2); Dupont Instrum e n t s , W i l m i n g t o n , D E 1 9 8 9 8 ;P a n a m e t r i c s ,I n c . , 2 2 l C r e s c e n tS t . , W a l t h a m . M A 0 2 2 5 4 : B e c k m a n I n s t r u m e n t s ,I n c . , 2 5 0 0 H a r b o r B o u l e v a r d ,F u l l e r t o n , C A 9 2 6 3 4 .
qS.
Y . T y r e e , I r . , J . C h e n t .E d u c . , 3 1 , 6 0 3 ( 1 9 5 4 ) .
r 0 S o u r c eosf o x y g e n n r e t e r si n c l u d e : V a c u u m A t n r o s p h e r e sC o . ( s e en . 2 ) ; A n a c o n D i v i s i o n o f H i g h
V o l t a g e E n g i n e e r i n gC o r p . , F . C . B o x 4 1 6 , S o u t h B e l f o r d S t . , B u r l i n g t o n , M A 0 1 8 0 3 ;M i n e S a f e t y
A p p l i a n c e C o . , 6 0 0 P e n n C e n t e r B o u l e v a r d ,P i t t s b u r g h ,P A 1 5 2 3 5( m o d e l 8 0 3 c a n b e m o d i f i e d f o r
u s ei n t h e p p m r a n g e ) .
l r W . B a h n r e t a n d P . A . H e r s c h , r cC
l . h e n t . , 4 3 . 8 0 3 ( 1 9 7 1D).:R . K e n d a l l . . 4 n a l . C h e n t . . 4 3 . 9 4 4
( l 9 7 1) .
58
INERT-AIMOSPHERE
GLOVEBOXES
c
c,
o)
X
tr
102
oo-
o246810121416
F r l a m e n tt i l e m i n
F i g . 2 . 8 . O x y g e nc o n c e n t r a t i o nv e r s u sf i l a m e n t l i f e t i m ef o r a n e x p o s e dl i g h t b u l b f i l a m e n t b u r n i n g
i n a n i n e r t a t m o s p h e r e .B y n o t i n g h o u l o r r gt h e l i g h t b u l b s t a y sl i t , a r e a s o n a b l ee s t i n r a t eo f t h e
o x y g e np l u s m o i s t u r ei m p u r i t y l e v e lc a n b e o b t a i n e d .T h e s ed a t a c o r r e s p o n dt o a n A / C N o . 6 3 b u i b
f i l a m e n t r u n * ' i t h l 0 V p o t e n t i a la n d a g a sf l o w r a t e o f l . l L / m i n .
great disadvantages
of contaminatingthe glovebox atmosphereand contributing to undesirabledepositson the glovebox walls. If ethersor hydrocarbonscan
be tolerated in the glove box atmosphere, a solution of Cp2TiCl2ZnCl1solvent
can be usedas a test for oxygen.r2A small amount of solution is introducedby
syringeinto an open aluminum pan in the dry box; if the compoundretainsits
original greencolor as the solventevaporates,the oxygencontentof the dry box
atmosphereis lessthan 5 ppm. At higher oxygenlevelsthe color changesto olive
green or yellow; and if the oxygen contamination is very large, it will turn
orange.The compound may be preparedby allowingCp2TiCl2(Alpha Inorganics) to react with a slight molar excessof zinc metal powderin dried and deoxygenatedtetrahydrofuran,benzene,or toluene.The reactionma-ybe run by stirring the mixture for approxim ately 12 hours in a 50-mL Erlenmeyerfitted with a
serum cap.
Manganousoxide supportedon silicagel has a very high affinity for oxygen,
and the reactionis accompaniedby a vivid color changefrom Iight greento dark
brown. A tube of this material in an inert-gasstream is used in the authors'
r 2 D .G . S e k u t o u ' s kai n d G . D . S t u c k v J. . C h e n r .E d u c . . 5 3 . l l 0 ( 1 9 7 6 ) .
59
AND PROCEDURES
GLOVEBOX HARDWARE
laboratoryto measurethe oxygenimpurity level.and recentlya commercialdetector of this type has come availablefor use in gas chromatographicsystems.
Sincethe kineticsof this reactionare fast and the line of demarcationis distinct.
a measurementof the length of progressof the brown region along the tube can
be convertedto the amount of oxygenabsorbed.The levelof impurities can be
measuredusing this schemeby knowing the quantity of manganeseon the silica
gel, the volume of gas passedthrough the tube. and the stoichiometryof the
reaction,Eq.(a). Although it has not yet beendone to the authors'knowledge,a
small unit equipped with a simple hand-operatedpump could be readily constructedfor the periodic check of the atmosphereinsidethe glovebox.
2MnO + l/20z:
Mn2O3
(4)
2,4 GLovEBox HARDwARE

ANDpRocEDUREs
A. Gloves ond Glove Porls. Judging from the permeabilitydata in Appendix III, butyl rubber glovesshould reducethe influx of water by one-halfto
one-tenthand that of oxygenby one-thirdof that givenfor neoprenegloves.Owing to this advantage,butyl rubber is routinely used on most inert-atmosphere
glove boxes. Natural-rubber glovesare sometimesused becausethey afford a
better senseof touch and better dexteritythan the synthetics;however,natural
rubber is much more permeable to atmospheric gasesand less resistant to
solvents.To improve dexteritywithout a large increasein the diffusion of atnrosphericgases,glovesare often constructedwith a thin crosssectionin the region
of the fingers and thicker rubber elsewherebecausethe thicker materialshave
reducedpermeability.When dexterityis not critical, someworkersusea pair of
gauntletglovesinsidethe regular gloves.This practiceundoubtedlyreducesdiffusion of moistureinto the glovebox, and it providesan extra protectivebarrier
when hazardousmaterialsare handled.
The accumulationof sweatin the glovesbecomesa great annoyance,which
can be alleviatedby a small tube carryingair taped into eachgloveand terminating at the back of the hand, or divided and terminatedat the back of eachfinger
opening. Electrician'stape may be used to hold the tube in place. Ideally, the
glove should ride in and out with the experimentalist'shands. To improve the
adherenceof the glovesto the hands, glovesmay be mounted palm side up,
which resultsin a slight twist of the glovearound the wrist when the hands are in
an ordinary working position. Also, to avoid "losing" the gloves,they shouldbe
no longerthan the worker'sreach.This is particularlyimportant when the box is
operated at slightly reduced pressures.Some manufacturersoffer gloveswith
accordionsleeveswhich are supposedto providefree in-out travel of the gloves.
In practicethe authorsfind theseto be cumbersome,and the complexconstruction is likely to invite pinhole leaks.
When a new glove box is being designedor an old one modified, the glove
ports should be positionedto provideaccessto the entire bottom of the box and
GLOVEBOXES
INERT.ATMOSPHERE
60
to any shelvesor mounting bars on the back wall. With a large box, this may
require the use of more than two glove ports. One fairly common practiceis to
provide a third glove port closeto the antechamberside of the box. A glove in
this position provideseasyhandling of the inside antechamberdoor and allows
one to reach into the antechamber.
The glove must be securelyfastened to the port so that it does not unexpectedly pop off of the box. One common procedureis to use a large O-ring which
holds the cuff of the glove to a groove in the glove port (Fig. 2.9a), and the glove
must be further securedby electrician'stape and/or a steelclamping band. If
the glovebox is of the evacuabletype, it is necessary
to pump on both the inside
and outside of the glove to preventthe glovesfrom being sucked into the box.
Figure 2.9 illustratesa designfor a vacuum-tightglove port coverwhich permits evacuationof the outer side of the glove. The box may be brought up to
atmosphericpressurebeforethe outsideof the gloveis vented,or the two opera-
I n t e r i o ro f b o x
(o)
\\.\
\,,'\.- - - f I- - \ - - ! - -
\-
ossoge
for
evocuotron
I n f e r i o or f b o x
(b)
Fig.2.9, Gloveports.(a) A conventional
gloveport.(b) Gloveportwithcoverto allouevacuation.
(AdaptedfronrUSAECReportTID-16020.
N. Garden,Ed.. 1962.)
61
GLOVEBOX HARDWARE
AND PROCEDURES
tionsmay be nearlysimultaneous.Once the systemis up to latm of pressure,the

vacuum-tight cover is removed to provide unobstructed use of the gloves.
B. Confoinmenf of Hozoldous Moleriols. To reducethe chanceof loss
of materialsfrom a containmentenclosure,the glovebox is operatedat slightly
below the ambient atmosphericpressure.For glove boxesin which major conraminationof the atmospherecannot be toleratedduring the glovechangingoperation,and for gloveboxeswhich serveas radioactiveor biologicalcontainment
.'hambers,the gloveports should be designedwith a doublerib (Fig. 2.9) so that
rhe new glovecan be installedbeforethe old one is removed.In preparationfor
rhisglovechange(Fig. 2.10),the leakygloveis stuffedinsidethe box and the rib
irn the cuff of this gloveis advancedto the outer groove.A new glove(which may
be flushedout with inert gas)is slippedoverthe old one and its rib is securedon
the inner groove.The old gloveis pulled off the gloveport and into the interior of
rhe box. If this glove is contaminated,it may be baggedout of the box as describedbelow. If radioactivematerial is involved,the whole operationmust be
nronitored.As mentionedearlier, it is common practiceto wear an additional
pair of gauntlet glovesinsidethe dry box glovesto provideadditional protection
of the experimentalistin the eventthat a leak developsin the gloveson the inertatmosoherechamber.
( l n s i d e) G l o v e
box...--
Glove
ene)
C l o m pr i n g
( s t e e )l
0 - ring
(neoprene)
R e m o v es t e e l
clomp rrng
G l o v eb o x
inside
O-ring (do not

disturb)
Glove beod
(foldos shown)
OU
(lnside)
Glove box
-Clomp ring
(steel)
Oldglove
glove
. ' (Nsel iwp
over
old cnd clomp
os shown)
C l o m pr i n g
O l d O- r i n 9
( s t ee l)
g l o v e( r e m o v e
o s o c + i v ew o s t e )
G l o v eb o x
(inside)--
N e wr i n g
(neoprene)
F i g . 2 . 1 0 . C h a n g i n gg l o v e s .T h e p r o c e d u r eo u t l i n e dh e r ep r e v e n t st h e l o s so f r a d i o a c t i v i t yf r o m t h e
b o x a n d m i n i m i z e s t h e i n t r o d u c t i o n o f a i r . ( A d a p t e d f r o m G . N . W a l t o n E d . , G l o v e B o x e sa n d
Shielded Cel/s. Butteru'orth. London. 1958.)
62
INERT-ATMOSPHERE
GLOVEBOXES
The bagging-outprocess,illustratedin Fig. 2.1l, providesa method for discarding waste materials and used gloveswhich have been contanrinated.This
processis widely used for radioactivewastes.A heavy polyethylenebag is atport similar to a gloveport. When the time comesfor
tachedto a double-grooved
removalof the wastesdepositedinto this bag, it is heat sealedand cut along the
sealso that the disposableportion of the bag attachedto the box is neveropened
to the atmosphere.A fresh bag is then attached to the inner groove and the
remnant of the old bag is taken into the box by the procedureoutlined for the
g l o v ec h a n g i n go p e r a t i o n ,i n F i g . 2 . 1 0 .
2.5 TYPTcAL
GLovEBoxsYsTEMs
ln this sectionsome glove box systemswill be discussedwith commentswhich
will put them into perspectivefor potential applications.
When a laboratory is equipped with good Schlenk-typeapparatus and/or
vacuum systenls,the glovebox will be neededfor only occasionaltransferoperations. In this situation a commercialglovebag (Fig. 2.1), may be perfectlyadequate for transferringsolids.Bulk materialsor microcrystallinesolidsare often
much more resistantto oxidation or hydrolysisthan solutions.It must be borne
in mind, however,that the volume of a glovebox or glovebag is large and that
prolongedexposureof a sampleto a contaminatedatmosphereruns the risk of
decomposition.Thus it is best to work as rapidly as possible.particularly in a
glovebag which is not providedfor efficientpurging. The mounting of air-sensitive crystalsinto small glasscapillariesfor singlecrystalX-ray diffraction may
sometimesbe convenientlyperformed in a glovebag fitted around a binocular
microscope(Fig.2.12). This operationis tediousat best, and the lack of dexterity is particularly troublesomewhen handling the fragile capillaries.To aid in
the manipulation of these capillaries.a capillary holder which is describedin
S e c t i o n2 . 6 . E i s a t r e m e n d o u sa i d .
The mounting of highly reactivecrystalsmay require the use of a glovebox.
I n s i d eb o x
Loborotory side
F i g . 2 . 1 1 . B a g g i n g r a d i o a c t i v e w a s t e s .( A d a p t e d f r o m G . N . W a l t o n E d . , G l o v e B o x e s a n d
Shielded Cel/s. Butterworth. London. 1958.)
63
TYPICAL
GLOVE BOX SYSTEMS
___.._.-{-*-*--j_)-,---.--.j-
l-\
\-l
N2 Inlet
.'---.._
F i g . 2 . l 2 . G l o v e b a g f i t t e d a r o u n d a b i n o c u l a rm i c r o s c o p e A
. h o l e l a r g ee n o u g ht o f i t t h e e y e p i c c e
, f t h e m i c r o s c o p ei s c u t i n t h e t o p o f t h e g l o v eb a g . T h e g l o v eb a g i s t h e n f a s t e n e dt o t h e m i c r o s c o p e
i r s i n ge l e c t r i c a lt a p e a n d p u r g e d o f a t m o s p h e r i cg a s e s .
Unfortunately,the working distancefor commercialstereomicroscopes

is rather
short, and the microscopealso does not accommodatereadily the usual large
glove box with a vertical or slightly inclined window. A single-chamberevacuable dry box is availablecommerciallywhich would appearto be satisfactoryfor
crystalnlounting and other operationsin which the apparatusis not large.2
For generaluse with only moderatelyair-sensitivecompounds,a plastic dry
box may be more convenientthan a glove bag. Boxes constructedfrom poly(methylmethacrylate)or from fiberglass-reinforced
polyesterare availablecommercially.2As discussedearlier, the diffusion of atmosphericgasesthrough the
former material is significant.and it is likely to be lessbut still appreciablefor
the fiberglassboxes. Theseboxes are light and relativelyeconomicaland they
are useful for all but the most air-sensitivematerials.
A c o m m e r c i aw
l e l d e da l u m i n u m d r y b o x , i l l u s t r a t e di n F i g . 2 . 1 3 , 2h a s a h e lium-leak-testedevacuabletransfer chamber and an overheadwindow to provide light. A stainless-steel
tray inside of the box protectsthe aluminum from
spills, and a sliding tray in the antechamberfacilitatesthe transferof materials
into and out of this box. The two large doorson the transfer locks are mounted
on a pivot arm through a central screw.Thesedoors are equippedwith O-ring
seals.The O-ring on these doors and similar gasket materialson other glove
boxesshould be inspectedoften. This critical sealis subjectto the collectionof
64
INERT.ATMOSPHERE
GLOVEBOXES
*,
F i g ' 2 ' 1 3 ' C o n t m e r c i a lm e t a l g l o v eb o x . A n a l u m i n u m g l o v eb o x w i t h

a r e c i r c u l a t i n gg a s - p u r i f i c a t i o n s y s t e m( R e p r o d u c e d b y p e r m i s s i o n o f t h e c o p y r i g h t o u . n e r V a c u u r n A t n r o s p h e r e i C o r p . , N o r t h
Hollp'ood. Calif.)
debris from the materiarsbeing handred, and it can be nicked if improperry

treated' The supplier for this glove box offers efficient recirculating
inert-gas
pu rif iers.
2,6 EoutpMENT
ANDopERATtoNs
A. Trqnsfer into o Glove Bog. It is cumbersometo transfer
rarge items
into a glove bag once work is underway.Thereforeall of the itenrs
to be used
should be placed into the bag, which is then fully deflatedand sealedby
rolling
and clamping the inlet flap. Inert gas may then be introducedand
the bag may
be flushedthrough an exit tube and bubbrer,or openedstightty,coilapsed,
and
inflated severaltimes to expel air.
AND OPERAIIONS
: OUIPMENI
65
B. Exomple: Tronsferof Moferiols through on Evocuoble Air

tock. To introduce a samplefrom the laboratorythe inner door of the port is
-.,)sedand then the outer door is opened.Samplesare placedin the lock and the
'rrer door is clamped shut. The lock is evacuatedand filled severaltimes with
:.rertgas. After the lock is brought to atmosphericpressurethe final time, the
:ner door may be openedand samplestransferredinto the box. Care has to be
:iken when filling the antechamberto avoid diverting too much gas from the
:rain chamber if the box is not fitted with an automatic pressurecontrol. An'rher point requiring attention is the nature of the apparatuswhich is put into
:ne evacuablelock. A closedvesselwith standard taper fittings will fly apart
.:ndervacuum unlessthe joints are securedwith heavyspringsor heavyrubber
rands. or unlessthe apparatushas beenevacuatedbeforeit is placedin the port.
O-ring ware has a big advantagebecausethe clamps usedto securethosejoints
,rill hold securelyunder vacuum. Of course,closedcontainersgoing into the
rlove box should have been previouslypurged or evacuatedto eliminateair. As
mentionedin an earlier section,wood, paper, cloth, corrodedmetal, and asbes:os are ordinarily not transferredinto the glovebox becausethey containconsid.:rablemoisture.
C. Weighing Solids. There are severalmethodsfor weighingair-sensitive
solids.(As mentionedin Chapter l, this processmay be carriedout without a dry
box if the sample is containedin a sealedampule of known weight.) The most
obvious method of weighing in an inert-atmosphereglove box is to employ a
balancewhich is insidethe box. A sinrpletriple-beambalanceis very usefulfor
some types of weighing, and a torsion balance or electronicbalance is useful
*'hen higher sensitivityis required. Staticbuild-up and flexing of the box are two
problemsencounteredin making preciseweighings.The antistaticdevicesnrentioned in the following sectionalleviatethis problem to someextent.
Another method for weighingan air-sensitivematerial is to introduceit into a
cappableweighingcontainerin the box and transferit out to perform the weighi n g . T h e w e i g h i n gt u b e w i t h c a p ( F i g . t . 2 3 ) i s u s e f u l w h e nt h e s a m p l ei s t o b e
shakeninto a reaction vesselon a vacuum line or other apparatusoutsidethe
glovebox. It is filled and capped inside the box, transferredout and weighed,
and quickly opened and shaken into the receivingcontainer under a flush of
inert gas. A tare weight is then obtainedon the empty weighingtube. Vials filled
in the box can be stopperedwith a septum cap, removedfrom the box, and
sealedoff at the glassblowingbench. Before the seal is made a fine needleis
insertedthrough the serum cap to relievethe buildup of pressureas the ampule
is being sealed.To determinethe quantity of material in the vial, it is weighed
beforegoing into the glove box, the parts are weighedafter it is sealedoff, and
the weight of the contentsdeterminedby difference.
D. Sfofic Buildup. The very dry atmosphereof a glove box or glove bag is
conduciveto the buildup of static electricity,which can scattera finely divided
INERT-ATMOSPHERE
GLOVEBOXES
material, causesmall crystallographic-size

crystalsto fly into oblivion, throw off
balancereadings,and causesimilar vexingproblems.There is no completesolution to this problem, but two typesof antistaticdevicesare availablewhich usually reducethe problem to manageableproportions.The headof an alpha-partiTo
cle static eliminator can be pointed toward the items being manipulated.13
provide a sufficientflux of alpha particles,the radioactivesourceshould be replaced frequently. The alpha particles have a rather short range in the glovebox
atmosphereand they do not passthrough the gloves;so the radioactivesource
has to be placedvery closeto the work. Another type of static eliminator is the
gunlike unit built for removingstatic from phonographrecords.This unit producesionized gas particleswhen a trigger is actuated,and thesecan be "shot"
into vesselsand the like. Upon long standinginsidethe dry box thesedeviceslose
their effectiveness,
so it is common practiceto take the staticeliminator into the
box only when it is needed.It alsois worth noting that flint glassis more resistant
to static buildup than borosilicateglass.
E. Ofhet llems ond Useful Operolions.
A variety of small items which
are generallyuseful in a glove box are catalogedhere. The static eliminators,
weighing tube, and Parafilm have already been mentioned. To preservethe
cleanlinessof the dry box a sheetof aluminum foil is often taken in with eachjob
to cover the working area. Cleanlinessis a seriousproblem, particularly in a
communal glove box. If capillariesfor X-ray diffraction are kept in the glove
box, they should be coveredso as to not collect small particleswhich fly about
becauseof a staticcharge.A very usefulholder for X-ray capillarytubesconsists
of a glasstube about 15 cm long, rvith an internal diameterof about 3 mm and a
small flare at one end. This flared portion of the tube is lined with a small piece
of Parafilm, which doesnot block the openingin the tube. When an X-ray capillary tube is pushedinto the film, it sticks in place and the tube can be grasped
firmly without danger to the capillary. Finely drawn glass rods or fine, hard
stainless-steel
wires are usefulfor transportinga singlecrystalinto a capillaryor
for tapping a collectionof fine crystalsin an X-ray capillary. Other potentially
useful items include a collectionof spatulasand tweezers.lf the box is large, a
pair of tongs may help to retrieveitems rvhich are out of reach. For infrared
spectroscopy
on air-sensitivesolids,samplesmay be mulled with mineral oil and
sandwichedbetweeninfrared transmitting plates.A tissuegrinding apparatusis
useful as a mulling tool and a supply of degassedmulling oil may be kept on
hand in the box for this purpose.
GENERAL
REFERENCES
B a r t o n , C . J . . 1 9 7 9 . " G l o v e B o . r T e c h n i q u e s . " i n E . S . P e r r y a n d A . W e i s s b e r g e rT e c h n i q u e so . l
C h e n t i s t r v ,V o l . 8 , W i l e y - I n t e r s c i e n c eN, e w Y o r k . p . 2 2 1 . A c o l l e c t i o no f r e f e r e n c e s .
r i N u c l e a r P r o d u c t sC o . . E l M o n t e . C A .
:OUIPMENIAND OPERATIONS
67
: : n o n , C . J . , l 9 6 3 , " G l o v e B o x T e c h n i q u e s , "i n H . B . J o n a s s e na n d A . W e i s s b e r g e re. d s . , f e c f t n i q u e o f I t t o r g u n i c C h e n t i s t r y ,V

, ew York, p. 259. This chapter
, o l . 3 , W i l e v - l n t e r s c i e n c eN
s t r e s s e tsh e c o n t a i n m e n to f t o x i c m a t e r i a l sa n d p r e s e n t sa l a r g e c o l l e c t i o no f r e f e r e n c e o
sn the
u s e o f g l o v eb o x e s .
. : c r f e y ,J . M . I n d . E n g . C h e n t . . 4 6 , 4 3 5( 1 9 5 4 ) T
; . R . P . G i b b , J r . , A n u l . C h e m . ,2 9 , ( 1 9 5 7 ) lR . E .
J o h n s o nJ, . C h e n t .E d u c . , 3 4 , 8 0 ( I 9 5 7 ) . D e t a i l so n t h e c o n s t r u c t i o na n d o p e r a t i o no f g l o v eb o x
systems.
, \ h i t e , P . A . F . , a n d S . E . S m i t h , 1 9 6 2 , I n e r t A n n o s p h e r c s ,B u t t e r w o r t h , L o n d o n . T h i s b o o k
p r e s e n t sa n e x c e l l e n td i s c u s s i o no f t h e p u r i f i c a t i o no f g l o v eb o x a t n r o s p h e r e sa.n d a g o o d o v e r v i e w o f g l o v eb o x n r e t h o d sa s p r a c t i c e di n t h e U n i t e d K i n g d o m a t o m i c e n e r g ye s t a b l i s h n r e n t s .
S t i l l t h e b e s t g e n e r a lr e f e r e n c ei n t h e f i e l d .
INERTGASESAND
THEIRPURIFICATION
Nitrogen, argon, and helium are the most commonly used inert gasesfor inertatmospherework. There are, however,specificsituationsin which a more reactive gas such as carbon dioxide, hydrogen,or the like is usedto excludeair. Of
the inert gases,nitrogen has the advantageof being quite cheap and readily
available. On the other hand, nitrogen is reactivewith some metals, such as
lithium, at room temperature.Nitrogenalsoreactswith many metalsat elevated
temperaturesas well as with some metal complexes.Helium and argon are
highly inert and similar in price, so the choicebetweenthem generallyhingeson
the differencesin their properties.Helium is the easiestto purify becausenitrogen and other gasescan be removedby low-temperatureadsorption.Argon n'rust
be purified by chemicalmeans,sinceit has low-temperatureadsorptionproperties similar to nitrogen and oxygen.The advantagesof argon are that it doesnot
diffuse out of systemsas rapidly as helium and it is heavier than air, which
makes it easierto maintain an inert atmospherein casesu'herea flask must be
momentarily opened.
Inert gasesare generallyavailablein high-pressurecompressedgas cylinders
and, in somecases,in medium-pressureDewars.Detailson handling high-pressure compressedgas cylindersare given in Chapter 10. The presentchapterwill
concentrateon the purification of inert gases.
3,'1 souRcEs
ANDpuRtTy
A. Sourcgs. In the United States high-pressurecompressednitrogen is
availablein severalpurity grades. For example, the Matheson Company sells
68
9URIFICATION
OF GASES
\c'\'engradesranging from "extra dry" (which is quoted to be 99.9% pure) to

'prepurified"
grade (with 99.998% purity) at relatively economical prices.
Other grades,such as "oxygen free" (Oz < 5 ppm) and one called "Matheson
Purity" (with the sum of 02, Ar, CO2,H2O, and hydrocarbonsequal to lessthan
: ppm) are considerablyhigher in price. The moisture content of the gas will
rncrease
as the tank is emptied,becauseadsorbedmoistureexertsa roughlycon\rant partial pressurein the interior of the cylinder. Thus, as the total cylinder
pressureis reduced,there will be an increasein the molar ratio of water vapor to
:as. High-purity liquid nitrogen is availablein most metropolitanareasat prices
lhat work out to be cheaperthan that for the compressedgas. For applications
',rhichrequire a large quantity of high-purity nitrogen, such as a continuous
glovebox purge, large pressurizedDewarsof high purity liquid nitrogen are ofien the most economicalsourceof inert gas. TheseDewarsare availablein gasor
Iiquid take-off designs.
High-purity gradesof nitrogen, helium, and argon are often satisfactoryfor
applicationsin which impurity levelsof approximately50 ppm are tolerable.If
relativelylarge volumes of gas are required and higher purity is needed,it is
generallymost economicalto purify high purity or lowergradegas, as described
below.lt must be rememberedthat the purity levelis rapidly degradedby diffusionof air through rubber tubing or the rubber diaphragmsof ordinary pressure
regulators.Specialregulators,with metal diaphragms,greatlydecreasecontamination by atmosphericgasesand are availablefor use on ultra-high purity gas
c1'linders.
B. Pulity Requiremenfs.
As an illustration of the purity neededin some
specificapplications,considera closedglassapparatusof 500-mL volume. If the
inert gas in this apparatus contains 50 ppm of water and oxygen, the total
amount of impurity is about 0.001 mmol. This impurity levelwill be neglegible
in a preparativesituation if much more than a millimole of compound is being
handled. If, on the other hand, the experimentrequiresa continuousstreamof
gas, such as in a hot tube reactionor a catalyticflow reactor,50 ppm of impurities is likely to be unacceptable.It can be seenthat it is necessary
to estimatethe
purity requirementson the basis of the amounts of material which are being
handled and the total volume of gas to which this material will be exposed.It is
not difficult to purify inert gasesso that the total oxygenand moistureis below5
ppm, this being a safe standard for most preparative-scale
work. When ultrapure gas is needed(parts per billion range), as in quantitativeresearchon supported catalysts,helium is the inert gas of choicebecauseit is amenableto purification by a combination of low-temperatureadsorption as well as chemical
methods.
3,2 PURrFrcATroN
oFGAsEs
A. Principles. A majority of the inert-gaspurification schemesemployedin
the laboratory are basedon passingthe gas through a bed of solid reactantor
70
PURIFICATION
INERT
GASESAND THEIR
adsorbent.In general,the purificationprocessis fasterfor finer particlesand for

highly porous particles.Often the adsorptionprocessis controlledby the rate of
diffusionthrough the gasfilm within the microporousparticle,and in this caseit
is advantageous
to employa long and narrow bed rather than a short bed of large
diameter.Theseconditionsof fine particle sizeand largelength-to-diameterratio increasethe pressuredrop acrossthe column, so it is necessaryto strike a
compromisebetweenefficiencyand tolerablepressuredrop.
Data are availablein the literaturefor gas purification installationsranging
from small laboratoryexperimentsto plant-scaleoperations.To put this information on a common basis,gas velocitiesare often quoted in terms of the space
velocity,rvhich is defined in Eq. (1).
sDacevelocttv : -
( v o l u m ef l o u o f g a s a t S T P )
( v o l u m eo f t h e p a c k i n g )
(l)
The three primary methods for the removal of water from a gas stream are:
( 1) Iou'-temperature
condensation,(2) compressionof the gas so that the partial
pressureof water increasesand condensationresults,and (3) the use of drying
agents.Thesemethodsare sometimescombined.For example,a molecularsieve
desiccantwill take up more moistureper mole of inert gas at reducedtemperatures and at high pressures.The primary methodfor the removalof oxygenfrom
an inert-gasstreamis reactionwith a solid or liquid reducingagent.In the case
of helium, low-temperatureadsorptioncan be usedto removeboth oxygenand
nitrogen. The following sectionspresentthe detailsof thesepurification methods.
B. DesiCconls. There are significantdifferencesbetweenthe water absorption isothermsfor substanceswhich form definite solid phasesupon interaction
with water and for adsorbentsand liquid desiccantswhich undergoa continuous
increasein water content without the formation of new phases.For example,
Mg(ClO,r)zforms definite hydrates.As is characteristicwith such materials,the
absorptionisotherm displaysplateauscorrespondingto the coexistenceof two
solid phases(Fig. 3.1). An analogoussituation is encounteredwith CaH2.where
the reactionwith H2O producesCa(OH)2.This leadsto a broad region in which
the equilibrium vapor pressureof water is constant.and in this caseextremely
low. By contrast,adsorbents(suchas molecularsieves)or liquid desiccants(such
as sulfuric acid) display a steadyincreasein vapor pressureas more water is
taken up (Fig. 3.1). The adsorbent-typedesiccantsalsointeractwith many polar
molecules,so competitivebinding resultswith a changein the equilibrium vapor
pressureof water and with the total capacity for water. This factor is of little
importancewhen thesedesiccantsare usedto clean up an inert-gasstream,but
they may be very important when the desiccantis incorporatedin a recirculating
purifier of a glove box.
Rough equilibrium vapor pressuresfor H2O abovea varietyof common desiccants are given in Table 3.1 along with commentson other propertiessuch as
H2O capacity.Additional factorsthat are particularlyimportant in the drying of
71
PURIFICAIION
OF GASES
o
T
E
E
L-
Io-4
10 - 5
010?4304050
W e r g hIl n c r e o s e , 7 "
F i g . 3 . 1 . E q u i l i b r i u m v a p o r p r e s s u r e sv s . c a p a c i t vf o t ' s o n r c c o m m o n d e s i c c a n t s(.A ) W i d e - p o r e
s i l i c ag e l ; ( B ) n a r r o * ' - p o r es i l i c ag e l ; ( C ) C a C l : , C a C l 2 H z O , a n d C a C l l 2 H 2 O ; ( D ) H z S O r ;( E ) M C t C l O r ) : a n d i t s h y d r a t e s ;( F ) P r O r 0a n d H r P O r ; ( G ) M o l e c u l a rs i e v e s4 4 .
a stream of gas are the flow rate and the physicalforn.rof the desiccant.For
example, PaO16is excellentfrom the standpointof equilibriunl vapor pressure
a n d , a s s h o w n i n F i g . 3 . l , t h e u l t i m a t ec a p a c i t yi s n o t b a d ; h o w e v e r ,P q O l si s
ordinarily supplied as a fine powder which virtually blocks the gas flow if this
desiccantis packed into a drying tube. Furthermore, this material is quickly
coveredwith a viscousfilm of phosphoricacid which drasticallyreducesthe rate
of further water uptake. (A supportedform of PrOro,availablefrom the J. T.
Baker Co., overconressome of these problems.) A similar complicationis encounteredwhen CaH2 is employedas a desiccant,becausethe product of the
reactionwith water, Ca(OH)2.is produced as a fine powder which may clog a
column.
Somedesiccantsintroduceimpuritiesinto the gasstreamwhich may be objectionable. This situation is obviouswith CaH2 and other activemetal hydrides,
where a mole of hydrogenis produced for every mole of water adsorbed.Less
obviousis the productionof tracesof phosphineby the tracesof phosphorus(III)
impurity presentin PaOle.
CAUTION: Magnesium perchlorate, which from many standpoints is an excellent desiccant, presents a serious explosion hazard.in the presenceof reducing
agents,such as organic materials, CaH2,etc. This hazard is exacerbatedby mineral acids, such as H3POa,or substanceswhich can hydrolyze to acids, such as
Ploro.
Of all the desiccants,molecularsieves44 or 5A are perhapsthe best for allaround use. Two obviousadvantagesare their high affinity for H2O and good
capacity.They are fairly inert and. becauseof their sizeexclusionof large molecules, are less susceptiblethan many adsorbentsto competitiveadsorptionof
other polar molecules.Molecular sievesare usuallycompactedwith a clay binder
into the form of small rods, which minimizes the restriction of gas flowing
INERT
GASESAND IHEIRPURIFICATION
72
Ioble 3.'l. Desicconls
Agent
Approximate
Water Vapor
Pressureat
2 5 o C( t o r r )
Proro
< l0 5
2 x 10 5
Mg(ClOr):
5 x 10 I
BaO
7 x 10 {
CaH:
Remarks
Evolveshvdrogenlno regeneration;bastc
Capacitylimited by formation of a
surfacefilm; acidic; tracesof PH3 evolved
Good capacity;regenerateat 250'C in
vacuo; dangerousu'ith reducing agents
Small capacity;regenerationis unhandv; basic
Linde Molecular
Sieves,4A or 5A
Alumina (active)
I x 10-r
Good capacity;regenerateat 400'C in

vacuo or in a "drY" gas streanl
I X l0 I
Fair capacity;regenerateat 500"C in

vacuo or in a "drY" gas stream,or
700oCin arr
Silica gel (narrou

pore)
2 X l0 I
Fair capacity;regenerateat 300'C

Small capacitvou'ing to coatingof solid
KOH
2 x l0-r
CaO
3 x l0 I
Limited capacity;especiallyin the

Presenceof C02; basic
HzSOr (concentrated)
H:POr (syrupy)
3 x l0 I
O x i d i z i n ga g e n t ;a c i d i c
3 X 10-r
Acidic
C a S O r( D r i e r i t e )
5 X l0-r
q ' i t h s o l u t i o n :b a s i c
CaCl2
0.2
R e g e n e r a t eadt 2 5 0 ' C
Good caPacitY;slightlYacidic
perthrough a drying tube. The regenerationof these moleculaf sievescan be

folmed in vacuunror inert atmosphereat 400'C'
c.Low-TemperolureTroppingondAdsolptionofWolel.Alowtemperaturetrap is an effectivemeansof reducingthe moisturein a gasto a very

lowlevel. Equilibrium vapor pressuresgiven in Table 3.2 demonstratethat at
l0 3
Dry Ice temperature, -78oC, the water vapor pressureis approximately
torr. There are. however,difficultiesin achievingthe equilibrium vapor pressure
when a stream of inert gas flows through a low-temperaturetrap, becausefine
crystallitesof water form in the gasphaseand are readilysweptthrough the trap
to
by the streamof gas. Packingthe trap with glasshelicesor glasswool is likely
73
PURIFICATION
OF GASES
(P)of lce ol VoriousTemperolures(t)o

Toble3.2. Vopor Pressures
toC
-90
-80
-70
-60
-50
-40
-30
-20
-10
0
P (torr)
7.0 x
4.0 X
1 . 9 4x
8 . 0 8x
2.96 x
9 . 6 6x
2 . 8 6x
7 . 7 6x
1.95
4.58
10 s
10-4
I0-3
10 3
10-2
10-2
l0-,
l0 |
" 8 . W . W a s h b u r n , I n t e r n e t i o n a l C r i t i c a l T a b l e s ,Y o l . 3 , p . 2 1 0 .
improve this situation. Also, two cold traps in seriesafford better trapping becausethe ice crystallitesvolatilizebetweenthe traps.
Adsorbentsalso have lower equilibrium water vapor pressuresat low temperatures, but this advantagemay be offset by a lower rate of moisture uptake.
Someisothermsfor silica gel and molecular sievesare presentedin Fig. 3.1. A
trap containing molecular sievesat liquid nitrogen temperature, - 196oC, is
particularly effectivein removing moisture from a helium stream, and it also
reducesoxygenand nitrogento low levels.The molecularsieveadsorbentcan be
readily regeneratedby heating in vacuum or in a flowing streamof inert gas as
describedpreviously.
D. Adsolplion from o Complessed Gos. The efficiencyof a desiccantis
increasedat high pressures.The principle involvedis that when a gas is compressed,the partial pressureof moisturein the systemis held constantor nearly
constantby the desiccant.Thus the molar ratio of moisture to inert gas is decreased.For example,if a desiccantlowersthe partial pressureof H2O to I torr,
a compressedgas storedover this desiccantat a pressureof 1,000psig will contain approximately19 ppm H2O; at 2,000psig the gaswill containabout 10 ppm
H2O. This techniqueis usedin many commercialair dryers.The processis generally basedon an automatedtwo-column system,with the moisturebeing adsorbedon one column at high pressurewhile a small amount of this dry gas is
divertedto dry out a secondcolumn at atmosphericpressure.The gas streams
are switchedautomaticallyso each column is periodicallyregenerated.Systems
of this type can achievemoisturelevelsin the parts per million rangeand the air
materialsin
produced by these dryers is useful for handling moisture-sensitive
commercialoperations.Theseair dryersalso are commonlyusedto providedry
air for instrumentssuch as infrared spectrometersand NMR samplespinners.
74
INERT
ANDTHEIR
GASES
PURIFICAIION
E. Oxygen Scovengels.
A wide varietyof reducingagentshas been used
to removeoxygenfronr gas streams.When vaporsof a solventcan be tolerated,
the wet methodshave the advantageof being quick and easyto set up. Recipes
for the preparationof somecommon oxygen-removing
solutionsare listedin Table 3.3. The gas is bubbled through thesesolutionsusing a simplegas scrubber
or a more sophisticatedself-regenerating
system(Fig. 3.2). Solutionscontaining
Toble 3.3. Recipes for Oxygen-Removing Solutions

Solution
Preparation
Chromoussulfate(aqueous)
Alkaline pyrogallol(aqueous)
Sodium hyposulfate(aqueous)
Sodium anthraquinonesulfonate
(aqueous)
Benzophenoneketyl (oil)
A fresh solution0.4 M in chrome alum and 0.05

M in sulfuric acid is contactedwith liehtly
anralgantatedZn
15 g pyrogallicacid in 100 mL of 50% aqueous
KOH
4 8 g N a 2 S 2 O 14,0 g N a O H , a n d l 2 g
anthraquinonesulfonatein J00 mL H2O
2% sodium anthraquinonesulfonatein 1.5 M
NaOH is contactedu'ith zinc metal
I g Na dispersedin mineral oil plus 4 g
benzophenonein 1L of mineral oil
A m ol g o m o t e d
F i g . 3 , 2 . A s e l f - r e g e n e r a t i n g a s s c r u b b e r . T h e i n c o m i n g g a s c a u s e st h e s o l u t i o n t o p e r c o l a t e
t h r o u g h t h e a m a l g a m a t e dz i n c .
)URIFICATION
OF GASES
75
:he chromous ion have a more favorablerate of oxygenabsorptionthan many

,rther solution scavengers.lSignificant concentrationsof foreign gases,other
ihan the solvent,are introducedby some of these solutions.For example, the
.'hromousion reactsslowlywith waterto evolvehydrogen,and alkaline pyrogalIol is claimed to evolveCO.
havethe obviousadvantage
For many applications,the dry oxygenscavengers
rrfnot introducing solventvaporsinto the gas stream.Also, someof the dry scavr.ngersare capableof achievingextremelylow oxygenpartial pressures.Generally, a column of dry oxygenscavengeris usedfor long-termapplications,such
as the purification of the inert gas for permanentSchlenkor glove-boxinstallations. In thesecases,the greater inconvenience
of settingtheseup comparedto
liquid systemsis more than offsetby the long-termstabilityand high capacityof
the dry columns.
AlTable 3.4 summarizessomeof the most common dry oxygenscavengers.
though a heated tube containing bulk metal, such as copper turnings, is still
occasionallyused,the bulk-metal oxygenscavengers
havebeenlargelydisplaced
mda t e r i a l s . T h e s e h i g h l y d i s p e r s e dm e t a l o r
by high-surface-area-supporte
nretal oxide materials react rapidly with residualoxygenand thereforecan be
usedat or near room temperature,which is a tremendousconvenience.
The procedurefor making highly activesupportedcoppermetal is availablein the literature,2and materialsof this generaltype are availablecommercially.3The commercial materials, Ridox and BTS Catalyst,are provided in pellet form, which
reducesbackpressurein the flowing streamof inert gas. With a spacevelocityof
6,000h ' Ridox shouldyield purified gaswith lessthan 1 ppm of oxygenat room
temperaturewhen the feed stream contains as much as 5000 ppm of oxygen.
Literature on the BTS Catalystindicatesa lower but acceptablerate of oxygen
removalfor particleswhich are 2-3 mm in diameter. Ideally, the BTS Catalyst
shouldbe crushedand screenedto the appropriatesize,althoughmany research
workersdo not take the trouble to do this. The Ridox particlesare smallerin size
and appropriatefor useas supplied.One kilogram of BTS Catalystor Ridox will
removeup to 4 L of oxygenat atmosphericpressureand room temperature.Although this capacity can be increasedsignificantlyby heating the material to
150'C, this is rarely done. A column at room temperature(which is packedwith
a 700 X 50-mm bed of the scavenger)will sufficefor purifying a dozenor more
large high-pressurecylindersof gas.
are somewhatself-indicating.The color
Supported-copperoxygenscavengers
of the oxidized material is dull green, whereasthe activereducedform is dark
brown to black. Fig. 3.3 illustratesthat the rate of oxygenscavengingdecreases
as these materials take up oxygen. If oxygenlevelson the order of I ppm are
required, the oxygen removal efficiencyshould not be allowed to drop below
l H . W . S t o n e J, . A n t . C h e t n .. l o c . .5 8 , 2 5 9 1( 1 9 3 6 ) .
r F . R . M e y e ra n d G . R o n g e ,A n g e u . .C h e r n . . 5 2 ,6 3 7 ( 1 9 3 9 ) .
r R i d o x i s a v a i l a b l ef r o n r F i s h e rS c i e n t i f i cC o . , 7 l I F o r b e sA v e . , P i t t s b u r g h ,P A 1 5 2 1 9 ;B T S C a t a l y s t
l o r p . , 2 5 5 O s e r A v e . , H a u p a g e ,N Y . 1 1 7 8 8 .
i s m a r k e t e db y F l u k a C h e n r i c aC
Ioble 3.4. MiscelloneousDryOxygenScovengers

Agent
Na-K (67-81% K by weight)
Na or K supportedon glasswool
CoO
MnO on silica gel

Crr* in silica gel
Palladizedor platinized
asbestos(or "Deoxo" unit)
SupportedCu (BTS catalyst
or Ridox)
Ba, Ca, Ca-10% Mg alloy, La
Mg, Th, or Zr
Brass,Cu, Ce, or U
Li
Description
Liquid aboveOoCand may be used in a U-tube
gas bubbler. RemovesOz, HzO, and Hg
vapor."
Similar to above.SupportedNa is preparedby
embeddingthe metal chunks in glasswool,
e v a c u a t i n ga. n d h e a t i n gt o 3 0 0 o C . b
Removes02 at room temperature. Prepared by
slowlyheating CoCOj to 340oC in vacuo. Not
easilyregenerated.'
Removes02 at room temperature.Easily
regenerated.Seetext for preparation.
Preparedby adsorptionof a Cr+l solutionon
silica gel followedby reduction at 500oCin H2.
Efficient, low-capacity02 absorptionat room
temperature.'1
Removestracesof 02 from H2 at room
temperature,removes02 from inert gasesat
room temperature.
70"C required for catall'ticremovalof 02 from
an H2 stream,30-.10"Crequiredfor catalltic
removal of O2 frorn CO stream.
Removalof 02 from Ar stream at 300, 650, 475.
500, 600, 400. and 600oCrespectively."
Also
removalof 02 and N2 at 400, 650, 500, 800,
640, 800, and l,000oC respectively.'
Removalof 02 from Ar or N2 stream at 500, 600,
300, 200"C respectively.''
Similar to Ca. RemovesN2 and 02 but reacts
u i t h q u a r t zo r g l a s s . /
" E . R . H a r r i s o n , J . S t i . I r t s t r . .2 9 . 2 9 - 5( 1 9 5 2 ) .
/ ' H . H . S t o r c h ,J . A n t .
C h e n t .S o c . . 5 6 , 3 7 4 ( 1 9 3 4 ) ;E . R . H a r r i s o n J, . S c i . I n s t r . ,3 0 , 3 8 ( 1 9 5 3 ) ,
s u p p o r t e dK .
' H . A . P a g e la n d E . D . F r a n k , J . A n t . C h t ' t t t . S o c . , 6 3 1
, 468(lq4l).
J R . L . B u r u e l l . J r . . p r i v a t ec o m n r u n i c a l i o n .
' D . S . G i b b s , H . J . S v e c .a n d R . E . H a r r i n g t o n I, n d . E n g . C h e r n . . 4 8 , 2 8 9( 1 9 5 6 ) n
l o t et h a t h o r M g
r e a c t s* i t h V y c o r o r f u s e d s i l i c a t u b i n g .
/ P . A . F . W h i t e a n d S m i t h ( G e n e r a l R e f e r e n c e sp) p . 4 8 , 2 2 2 .
76
77
PURIFICATION
OF GASES
j
c
a
o
o
E
o
c
o
o0
S t a n d a r dc c o f o x y g e n p e r g r a m o f R i d o x
Fig.3.3. OxygencapacityofRidoxattwodifferentflou'rates.A,spacevelocity3000hr;B.space
velocity6000hr.(AdapteduithpermissionofthecopyrightownerfromFisherScientificCo.,Bulletinl99B/8-021-01.)
95%. At this level of oxygen impurity in the exit stream, the capacity of the
Ridox scavengerwould be L25 cmr of oxygenper gram of scavengerat a space
v e l o c i t yo f 3 , 0 0 0 h - ' .
Ridox and BTS Catalystare supplied in the oxidized form and must be reducedat elevatedtemperatureswith hydrogenbefore use. This processmust be
done with some care to avoid the excessively
high temperaturesthat causethe
supportedcopper particlesto sinter, thus decreasingthe efficiencyof the catalvst. The regenerationstepfor Ridox is carriedout by wrappingthe column with
heatingtape and heating to 200oC in a streamof nitrogen. The bed is then reducedby the introduction of hydrogengas diluted with the nitrogenstream.The
hydrogencontent of this gas should be about 5% by volume. (The gas mixture
7B
PURIFICATION
INERT
GASESAND THEIR
can be formed by monitoring the hydrogenand nitrogenflow rateswith paraffin

oil bubblers on the inlet lines. The outlets of thesebubblers are joined by a Tt u b e a n d t h e c o m b i n e ds t r e a mi s c o n d u c t e dt o t h e t o p o f t h e c o l u m n . )S i n t e r i n g
of the supportedcopperwill occur if the temperaturewithin the column exceeds
250'C during this processor if the hydrogenconcentrationexceeds6 % . Alternatively, the regenerationmay be performedwith 5% hydrogenin nitrogenfrom a
high-pressurecylinderof mixed gas. The temperatureconditionsare the sameas
thosealreadymentioned.Temperaturesaround l50oC are recommendedfor the
regenerationof the BTS Catalyst.The effluent gas from the column should be
conductedthrough a paraffin oil bubbler, and from there to an efficient hood
having no open flames. Large amounts of water are producedin the processof
regeneratingthese materials. The bulk of the liquid water is convenientlydiscarded by way of a valve at the bottom of the column, as illustratedin Fig. 3.4.
When the reductionis complete,the last tracesof moistureare removedby evacuating the heated column or by continuing to purge dry hydrogenor nitrogen
through the heatedcolumn and gentlyheatingthe baseof the column with a hair
dryer. Care must be taken to avoid exposingthe regeneratedcolumn to a sudden
influx of air, since this rvitl causesevereoverheating.These supportedoxygen
scavengers
cannot be regeneratedif they are exposedto gas streamscontaining
organicor metalloid halides,halogens,mercury, sulfides.phosphine,or arsine.
In addition, amnroniaand nrostaminesare tenrporarypoisonsin the sensethat
they reduceor eliminate the oxygentake-up, but the supportedoxygenscavenger can still be regeneratedand subsequentlyusedin the absenceof thesematerials.
Manganous oxide is another convenientoxygen scavengerrvhich has been
used for the regenerationof inert atmospheresof dry boxesfor a long time.r s
Recently,it has been shownthat a silica gel-supportedform of MnO is capable
of removingoxygendown to the parts per billion range, and that this material
has little tendencyto polymerizeolefins.bTheseproperties,as well as the easeof
regeneration,make MnO very attractivefor the ultrapurificationof inert gases,
catalyticreactions,and
the purification of olefinsto be usedin oxygen-sensitive
more routine applications.There is evidencethat the MnO is poisonedby metal
carbonylsat room temperature.
A procedurefor the preparationof finely divided MnO is to alternatelayersof
v e r m i c u l i t ea n d m a n g a n o u so x a l a t ei n a c o l u m n s i m i l a rt o t h a t s h o r v ni n F i g .
3.4. Initial activationis performedby heatingthe evacuatedcolumn to 330oCfor
6 h. The resultinggreenMnO is pyrophoricand must not be exposedto a sudden
inrush of air. The predominantreactionwith oxygen,Eq. (2), resultsin a brownb l a c k p r o d u c t ;s o v i s u a li n s p e c t i o no f t h e c o l u m n r e a d i l yi n d i c a t e si t s d e g r e eo f
rT. L. Bro*n, D. W. Dickerhoof, A. Balus.
D.
a n d G . L . M o r g a n . R o , . . ! c i .l r s r r . . 3 3 , 1 9 1 ( 1 9 6 2 ) .
5 P .A . F . W h i t e a n d S . E . S m i t h ( g e n e r arl e f e r e n c e sp) ,. 1 9 9 .
n B . H o r v a t h , R . M o s e l l e r , E . G . H o r v a t h , a n d H . L . K r a u s su .nZo.r g . u l l g . C h e m . , l I 8 , l ( 1 9 7 5R
) i.
M o e s e l l e rB, . H o r v a t h ,D . L i n d e n a u ,E . G . H o r v a t h ,a n d H . L . K r a u s s .Z . N u t u r l i r s c h . . 3 l b . 8 9 2
( I976).
PURIFICATION
OF GASES
79
Teflonin
glassvalve
F i g . 3 . 4 . O - x - v g esnc a v e n g ecr o l u n t n .T h e c o l u n r ni s p a c k e di v i t h R i d o x o r B T S C a t a l v s t .T h e h e a t .
i n g t a p e a n d t h e r n t o c o u pl e u i r e a r e u s e dd u r i n g r e g e n e r ai to n . W a t e r u h i c h c o l l e c t sd u r i n g r e g en e r a .
t i o n c a n b e b l e d o u t t h r o u g h t h e v a l v ea t t h e b o t t o n r .
exhaustion.Sincefine particlesof manganeseoxide sloughoff of this material, a

large plug of glasswool is recommendedin the exit of the column.
6MnOfOr:2Mn3Oa
()r
Manganous oxide supported on silica gel also is a very clean and efficient
oxygen scavenger.6
The following recipe was designedfor small quantities of
fine-meshmaterial to be usedin the ultrapurificationof helium; it may be scaled
up and larger-meshsilica gel may be used for packing large columns. A l0S-g
quantity of 60-70 mesh silica gel is washedwith 1.5% nitric acid, followed by
distilled water, and dried at 100oCovernight. A 32-g portion of Mn(NOr)z is
PURIFICATION
INERT
GASESAND THEIR
dissolvedin 85 mL of water. With constantstirring. 3-mL portionsof this solution are added slowlvto the dry silicagel over a period of approximatelyI h. At
t h e e n d o f t h i s p r o c e s st h e s i l i c ag e l s h o u l ds t i l l a p p e a rt o b e d r y . W a t e r r e n r o v a l
and partial oxidation of this material are perfornledby heating it overnight at
1 0 0 " Ct o p r o d u c ea b l a c k m a t e r i a l ,w h i c h i s f u r t h e ro x i d i z e da t 3 0 0 ' C i n o x y g e n
for I h. CAUTION: Nitrogen oxides are evolvedduring both of thesesteps,and
theseshould be vented in a good hood after absorption in base. If the oxidation
w a sn o t d o n ei n a g l a s st u b e , t h e b l a c k s o l i di s p a c k e di n t o a P y r e xt u b e a n d t h e n
r e d u c e di n a h y d r o g e ns t r e a ma t 3 7 0 ' C f o r I h , y i e l d i n ga p a l e - g r e e ne, x t r e n r e l y
air-sensitivesolid. The consumptionof the MnO b.ytracesof oxygenin an inertgas streamis evidentby a sharp line of den.rarcation
betweenthe green.reduced
form and brown-black, oxidized material. When regenerationis necessary,the
last-mentionedreduction step is performed. As with the regenerationof supportedcopper.water is evolvedin the regenerationstep.This must be eliminated
b e f o r et h e c o l u m n i s c o n n e c t e di n s e r i e sr v i t h a d e s i c c a n t .
F. Nifrogen Scovengels.
The removal of nitrogen from an argon or helium stream is often done with hot titanium sponge.Great care should be taken
to removeH2O from the gas streambeforeit contactsthe titanium. Noneof these
ntaterialscan be regenerated,so the chargeof nitrogengetterhas to be replaced
periodically.Commercial nitrogen getter units are availablefrom Vacuunr AtmospheresCorp. With a helium stream it is possibleto adsorb nitrogen onto
molecularsievesat liquid nitrogen temperature, - 196oC,and therebyachieve
low levelsof nitrogen. The molecular sievescan be reactivatedperiodicallyby
warming to room temperature and, if water has been coabsorbed,heating to
4 0 0 ' C t o r e m o v et h i s m a t e r i a l .
puRtFrcATroN
3,3 INERT-GAs
sysTEMs
Desiccants,oxygenscavengers,
low-temperatureadsorptiontraps, and the like
are generallycombinedto form purification systems.Systemsof this type usedin
conjunction with recirculating purifiers for glove boxes have already been describedin Chapter2. This sectionwill provideadditionalexamplesrangingfrom
schemesfor the routine purification of inert gasesto the ppm rangeto the ultrapurification of helium to the ppb range.
A. Purificolionof o LoborotoryIned-GosSupply. A typicalarrangentent for drying and deoxygenatingan inert gas from a high-pressurecylinderis
shownin Fig. 3.5. The pressureregulatorshouldideallybe of the two-stagetype,
having an outlet control range of 0-15 or 0-30 psig to permit precisecontrol of
the gas inthe2-4 psig range.The valvesfollowingthe needlevalvein Fig. 3.5 are
usedto isolatethe columnsfrom the atmospherewhen a tank is being changed,
and alsoto permit flushing air from the regulatorand gasline after a new tank is
84
INERT-GAS
PURIFICATION
SYSTEMS
Desiccant
rl
1l'
rli
t,l
Pressure
regulatot
'l'
f';
F i g . 3 . 5 . I n e r t - g a ss u p p l yw i t h g e n e r a lp u r p o s ep u r i f i c a t i o nt r a i n . G a s c o n t a m i n a t i o ni s a v o i d e db y
conducting the gas through metal tubing. Where a flexible connection is desired, a short lenglh of
p o l y ( v i n y lc h l o r i d e )t u b i n g i s u s e d .M e t a l b e l l o w sv a l v e sa r e i n c l u d e di n t h e i n l e t l i n e t o
heavy-walled
k e e p a i r o u t w h i l e c h a n g i n gc y l i n d e r s ,a n d t o a l l o w a i r t o b e p u r g e d f r o m t h e v a l v e sa n d r e g u l a t o r
a f t e r i n s t a l l i n ga n e w c y l i n d e r .
attached.This last featuregreatlyextendsthe lifetime of the desiccantsand oxygen scavenger.Supportedcopper or MnO is the most convenientoxygen-scavenging material, and molecular sieves4A or 5A are suitable desiccants.The
amount of rubber or poly(vinyl chloride) tubing in the purified gas stream
shouldbe kept to an absoluteminimum. Where it is needed,heavy-walledpoly(vinyl chloride)tubing or Teflon tubing is preferredbecausethey displaylow gas
permeabilityand do not degraderapidly. The columnsare generallyarrangedso
that the oxygenscavengingcolumn can be isolatedand regeneratedwithout exposingthe desiccantto the water which is producedin regeneration.It is possible
to regenerateboth the oxygenscavengerand molecularsievecolumnssimultaneouslyby wrapping them all with heatingtape. Alternatively,a singlelargemixed
bed of oxygen scavengerand molecular sievedesiccantcan be used, with the
regenerationstep being carried out long enoughat 370oCto eliminateall water.
As noted earlier, theseoxygenscavengers
are self-indicating,so it is easyto
determinewhen regenerationis necessary.However,there do not appearto be
82
INERT
GASES
AND IHEIRPURIFICAIION
convenientindicators for moisture. The commonry

used cobalt-dopeddesic_
cants,which changefrom brueto nearrycolorressupon
becomingsaturated.are
insensitiveto lou' levelsof moisture and therefore
not useful in"thesecolumns,
exceptas a precautionagainsta worst-casesituation.
The qualitativetestsdiscussedin chapter 2 are often used for checking
a laboratoryinert-gassystem.
For example,the experimentalistmay exposea smau
quantity of aruminum arkyl' titanium tetrachroride,or other sensitivemateriar
to the jas as a prerudeto
performingan experiment.In rargeinstalrations,
continuousmonitoringby oxygen and moisture metersntay be justified.
B. ulllopurificqtion of Herium. Arthough
the parts per miilion range for
impurities obtainabrein systemsdescribedin
the precedingsectionmeet or exceed the requirementsfor the vast majority of raboratory
Jperations,there are
situationsin which far higher purity is needed.For
e*ample,a highly activeheterogenouscatalystmay havea low concentrationof
surface-actiue"rit.s
which are
readilypoisonedby the steadyflow of a slightlycontaminated
inert-gasstreamin
aflow reactor. In appricationsrequiring very row revels
of impuriti a sequence
of a low-temperatureadsorbent,suchai moiecurar
sievesor silicager,ptus sirica
gel-supportedMno will produceherium with reactive
impuritiesii th. purt, pe.
billion range. one such purification train is ilrustrated
inFig. 3.6. The row-temperatureadsorptiontraps reducewater and hydrocarbons
tJ very row reversand
substantiallyreduce the reverof nitrogen, whereas
the Mno trap reducesthe
oxygento the low ppb lever.The purification
train and ail subsequentconnec-
l-1e
----->
F i g . 3 . 6 . U l t r a p u r i f i c a t i o nt r a i n f o r
h e l i u m . ( A ) G l a s s t r a p c o n t a i n i n gs i l i c a g e l w h i c h
is main.
t a i n e d a t - 1 9 6 . C b y i m n r e r s i o ni n a l i q u i d
D e w a r ; ( B ) g l a s s t r a p c o n t a i n i n gM n O , i m p r e g .
n a t e d s i l i c a g e l n r a i n t a i n e da t r o o n l t e m p e r a t u r e i
( C ) N u p r o b e [ o u , s' a r ' e s , n . , o u n ' t " do n
a sturdy
n t e t a lp l a t e l ( D ) S u a g e l o c kf i t t i n g s w i t h T e f l o n
f e r r u l e s :( E ) c o p p e ro r s t a i n l e s s _ s t eteulb i n g . A
sec_
o n d l o w - t e m p e r a t u r et r a p ( A ) c a n f o l l o u , t r a p ( B )
t o e n s u r ec o m p l e t eH l O r e m o v a l .
B3
DETECTION
OF IMPURITIES
tions must be very secureto preservethe purity of the gas stream.No rubber or
plastictubing should be used. All valvesshould be of the metal bellowsor diaphragm type (seeChapter 10) and joints either soldered,welded,or of the swage
rype.
3,4 DETEcToN
oF TMPURITTEs
A seriesof qualitativeand quantitativetestsfor water and oxvgenimpurities is
given in Section2.3.F. Of the two, moistureis far easierto detectquantitatively
than oxygen.
One of the easiestand most versatilewaysto detectoxygenquantitativelyin
an inert-gassourceis to use MnO-impregnatedsilica gel (describedin Section
3 . 2 . E )i n w h i c h t h e m a n g a n e s e
l o a d i n gi s k n o w n . A c o l u m n o f t h e M n O / S i O 2
nraterialis packed into one arm of a U-tube of known inner diameterand activated. After activation, a known florv rate of inert gas is passedthrough the
MnO/SiO2 column. The distancethe line of demarcationbetweenthe black,
oxidizedmaterial and the pale-green,reducedn.raterialtravelsin a giventime is
then measured.Using Eq. (3), the amount of oxygenin the inert-gasstreamcan
be determined:
5 8 0 d 2 l p ( w t% M n )
O2(inppm):fr
(3)
whered is the inner diameter of the glasstubing (in mm), / is the distancethe
line of demarcationtraveled(in mm), p is the densityof the MnO/SiO2 (in g/cc).
F is the inert-gasflow rate (ccltime), and t is the elapsedtime. As an example,if
the MnO/SiO2 recipedescribedin Section3.2.E u'ereused(resultingin a nrang a n e s el o a d i n go f a p p r o x i m a t e l y8 % ) i n a 6 - m m - i . d .t u b e w i t h a n i n e r t - g a sf l o w
r a t eo f 1 0 0c c l m i n , a n d a s s u m i n gt h e d e n s i t yo f t h e M n O / S i O 2i s 0 . 2 g / c c . i f t h e
line of demarcationtravels 5 mnt in I h the inert gas contains about 28 ppm
oxygenby volume. Much lower levelsof oxygen,such as in the ppb range,could
be accuratelydeterminedby lowering the Mn loading, increasingthe inert-gas
flow rate, and observingthe progressive
oxidationof the MnO/SiO2 for a longer
period of time.
REFERENCES
GENERAL
C o o k , G . 4 . , E d . , 1 9 6 1A r g o n , H e l i u n t u n d R o r e G u s e s , I n t e r s c i e n c eN, e u ' Y o r k . T h e p u r i f i c a t i o n
a n d h a n d l i n g o f r a r e g a s e si s d e s c r i b e dh e r e .
W h i t e , P . A . F . , a n d S . E . S m i t h , l 9 b 2 I n e r t A t n t o s T t h e r e sB, u t t e r s o r t h . L o n d o n . T h i s b o o k
p r e s e n t sa n e x c e l l e n td i s c u s s i o no f i n e r t - g a sp u l i f i c a t i o n , $ i l h e m p h a s i so n t h e p u r i f i c a t i o no f
g l o v e b o xa t n r o s p h e r e sf o r l a r g e p l u t o n i u m - h a n d l i n gf a c i l i t i e s . S i n c e t h e a p p e a r a n c eo f t h i s
b o o k b e t t e r m e t h o d so f s u p p o r t i n gM n O h a v e b e e nd e v e l o p e da n d v a r i o u so t h e r a d v a n c e sd i s c u s s e di n t h e p r e s e n tc h a p t e r h a v e b e e n m a d e . N e v e r t h e l e s st h, i s b o o k p r o v i d e su s e f u lg e n e r a l
i n f o r n r a ti o n .
PURIFICATION
OF
SOLVENTS
AND
REAGENTS
This chapter describesthe removal of water and atmosphericgasesfrom some

comnron solventsand the purification of some common laboratory reagents
which are susceptibleto contaminationby moistureand oxygen.Equipment designsand proceduresare introducedhere as needed,but most of this material is
d e s c r i b e di n o t h e r s e c t i o n so f t h i s b o o k : g e n e r a li n e r t - g a st e c h n i q u e s( 1 . 1 , 1 . 3 1 . 5 ) , c o n v e n t i o n adl i s t i l l a t i o n( 1 . 2 ) , d e s i c c a n t (s3 . 2 . B ) ,f r e e z e - p u m p - t h a w
deg a s s i n g( 5 . 3 . A ) , a n d t r a p - t o - t r a pd i s t i l l a t i o n( 5 . 3 . D , 8 ) .
4,4 soLVENT
PURtFtcATtoN
A . G e n e l o l M e l h o d s o f P u r i f i c o f i o n . B e c a u s et h e s o l v e n t o f t e n i s
presentin largeexcessover most reagents,it is important to achievelow levelsof
reactiveimpurities in the solvent.Distillation, purging u,ithan inert gas,adsorption, washing,reactionwith oxygenor water getters.and freeze-pump-thawdegassingare the most common purification methods.
B. Distillofion ond Purging. The great efficiencyof fractional distillation
for the removal of water from hydrocarbonand chlorocarbonsolventsis often
not well appreciated.The physicalorigin of this good separationis in part the
largepositivedeviationof the water vapor pressurefrom Raoult'slaw becauseof
the lack of affinity of water for theseliquids. Typically, the distillationof a simple hydrocarbonsolventwith a column of 100platesand discardingthe first two
84
SOLVENIPURIFICATION
B5
fractionswill reducethe water contentto levelsacceptablefor most work. Oxyqen removalfrom solventswhich do not react with oxygenis readily achievedby
r'vacuationor purging with an inert gas. The former method is most convenient
for materialsbeing handled on a vacuum systemand is describedin Chapter5.
'fhe
purging of solventswith an inert-gasline is readily accomplishedusing the
rrrangementsillustrated in Fig.4.l. These methods work well with saturated
aliphatic,aromatic, and chlorinatedhydrocarbons.Purging methodsare not effectivewith ethersand olefinswhere peroxideformation occursthrough chemical interaction.In thesecases,chen.rical
nreansor adsorbentsare neededto purify the solventprior to distillation.
Water can be removedfrom solventsby meansof adsorbC. Adsotbenfs.
ents. Molecular sievesand alumina are the most common adsorbentsused to
rttain very low moisture levels.These adsorbentsshould be activatedprior to
use. as describedin Chapter 3. The purification can be carried out in a batch
nranner with the molecular sievesor alumina introduced into a solvent container. After standing and allowing the adsorbentto settle,the solventmay be
Jrawn off. Much lower levelsof impurities can be achievedby taking advantage
,rf the multiple-stagepurification with a column of adsorbent(seeFig. 1.27).
fhe column is filled with activatedadsorbent,then purged with inert gas. The
F i g . 4 . 1 . A p p a r a t u sf o r p u r g i n g s o l v e n t sw i t h i n e r t g a s . ( a ) A l o n g n e e d l ea t t a c h e dt o a n i n e r t - g a s
s o u r c ei s d i r e c t e dt h r o u g h t h e s i d e a r ma n d i n t o t h e s o l v e n t .A s l o r vi n e r t - g a sf l o r vr u n s t h r o u g h t h e
s i d e a r n rt o a v o i d b a c k - d i f f u s i o no f a i r i n t o t h e f l a s k . ( ) S o l v e n tp u r g e u s i n g a s e p t u ma n d a d o u b l e n e e d l ea r r a n g e m e n t .
86
AND REAGENTS
PURIFICATION
OF SOLVENTS
degassedand predried solventis then admitted to the column, slowlyat first. It

is best to discardor recyclethe first few milliliters of material, and not to exceed
the capacityof the column for impurities. A guide to the capacityof activealumina for water is given in the literature,rAlumina effectivelyremovesperoxides
from alkenesand ethers, but water is adsorbedmore stronglythan peroxides.
Thereforepredrying of the solventin a batch manner rvith molecularsievesis
advisable.
One problem associatedwith usingsolid adsorbentsto dry solventsis disposal
of the usedadsorbent,especiallyif large quantitiesof solventare dried. Usually
the adsorbentcan be reactivatedby careful heating in a stream of inert gas or
under vacuum. (If the adsorbentwas usedto dry olefinsor other peroxide-containing solvents,any peroxidesmust first be destroyed;seeSection4.1.D.) Reactivating Iargequantitiesofadsorbent, however,can bejust as difficult as proper
disposal.
D. Preputificotion of Solvenls. Somesolventpurification procedurescall
for some type of wash. For example, saturatedhydrocarbonsare often washed
with concentratedH2SOato removealkenes.Thesewashingproceduresare generally done first, sincethey usually involvethe use of an aqueoussolutionor a
substancethat containssignificantamounts of water. Unlike the following procedures,washescan be done in the presenceof air. sincefurther treatmentusually involvesa step designedto eliminateoxygen.
Bulk water is removedfrom organicsolventsby meansof a separatoryfunnel.
Before distillation from a highly active desiccant,very wet solventsshould be
dried with materialssuch as MgSOaor molecularsieve4A. The solventis then
degassedand chargedinto the still pot along u'ith the appropriatedrying agent.
If ethersor olefinsare being purified, they shouldbe testedfor peroxidesbefore
drying. CAUTIONT Peroxides are strong oxidizing agents which may react explosivelywith strong reducing agentssuch as LiAlH4 or alkali metals. Peroxides
also can be extremely shock sensitive.
The presenceof peroxidesin an organic liquid may be detectedby the developnrentof an intensebrown color u'hen a feu' drops of aqueoussodium iodide
s o l u t i o na r e m i x e d w i t h a f e u ' m i l l i l i t e r so f t h e l i q u i d . A m o r e q u a n t i t a t i v e
method involvesadding 1 mL of the liquid to an equal volume of a l0% sodium
iodide in glacial acetic acid solution. A yellow color indicatesa low peroxide
concentration,whereasa brown color indicatesa high peroxideconcentration.
If the concentrationof peroxideis not too great, the materialcan be salvaged
by shaking with aqueousferrous sulfate. In the caseof a u'ater-solubleether,
solid CuCl may be usedto removetracesof peroxides.2
Large amountsof peroxides may be renrovedby storing the liquid over activatedalumina or by running
the liquid through an activatedalumina column. CAUTION: Do not allow the
r M . L . M o s k o v i t zA
, n t . L a h o r u t o r y '1, 2 , 1 4 2( 1 9 8 0 ) .
) O r g u t t i cS l r r t i r r e s e 4
s .5 . 5 7 ( 1 9 6 5 ) .
PURIFICATION
SOLVENT
B7
alumina to dry completely. The adsorbedperoxidesmay be removedby washing

the alumina with an aqueous ferrous sulfate solution.
E. Highly Aclive Desicconls ond Oxygen Scovengers.
Alrhough the
abovemethodsare sufficientlyrigorousfor many purposes,there are indications
that these proceduresstill leavetrace quantitiesof oxidizing impurities in the
solvent.For example,freeze-pump-thawtechniquesdo not removeall of the oxygenfrom benzeneasjudged by NMR Z1 determinations.rFor greaterpurity it is
common to employ distillation in conjunctionwith chemicalmeansfor the removal of tracesof moisture,oxygen,and oxidizing impurities. A typical solvent
distillationsetupis illustratedin Fig. 4.2. This particular still is not designedfor
high distillation efficiency,but rather as a meansof separatingthe solventfrom
the purifying agents.In this designthe reservoirfor the distilled solventis situated abovethe still pot. The vapor path also permitsexcessdistillateto return to
the pot. Thesefeaturesminimize the amount of attentionrequiredfor the distillation.
It is important to give the still pot an initial chargewhich substantiallyexceedsthe volume of the upper reservoirso that the still pot will not go dry. It is
very important to avoid letting the heatedstill pot go dry. The heatedflask may
crack and the solid contentsin the pot may decomposeto contaminatethe syst e m . I n s o m ec a s e sa n e x p l o s i o nm a y o c c u r ( e . g . w h e n L i A l H 4 i s u s e d ;s e eb e low). A metal catch pan should be positionedunder each distillation apparatus
t o c o n t a i na n y s p i l l sw h i c h m a y o c c u r u p o n s o l v e n tr e m o v a l .E a c h s t i l l s h o u l d
also be vented to a fume hood.
Someof the rigorousdrying and deoxygenatingagentswhich havebeen used
i n c l u d eL i A l H 4 , s o d i u m w i r e o r s h o t , s o d i u m - b e n z o p h e n o nNea, - K a l l o y , a n d
CaH2. CAUTION: These strong reducing agentspresentan explosion hazard in
the presenceof chlorocarbonsor reducible organic compounds. Of theseagents.
solid Na and CaH2often have unfavorableratesof reactionwith impurities and
thereforeare not highly effectiveeven at the reflux temperatureof the solvent.
Although the liquid Na-K alloy and solubleLiAlH.r are often usedfor the purification of solvents,the authorsdiscouragetheir use in their laboratoriesbecause
there is significantrisk of explosionif thesematerialsare not handledcarefully.
Lesstreacherousdehydratingagentsare available.There are many examplesof
explosionswhen LiAlHa hasbeenusedto dry ethers,especiallytetrahydrofuran.{
Both peroxidesand CO2 have been discussedas the possibleorigins of these
explosions,and a dry or nearly dry still pot has also been implicated. If LiAlH.r
must be used to dry ethers, the peroxidesshould be removedfirst, the ether
should be predried and degassed,and, in the distillation from LiAlH4, the still
pot should never go dry. In addition, a sturdy shield should be usedto protect
laboratory personnelfrom the still. Sodiunr-potassiunr
alloy likewiseis somer J . H o n r e r ,A . R . D u d l e y ,a n d W . R . M c W h i n n i e .J . C l t e n . S o c . ,C h e n t .C o n t n t . . 8 3 9( 1 9 7 3 ) .
alnorgunic St'rt&eses, 12, 317 (1970).
BB
PURIFICATION
AND REAGENTS
OF SOLVENTS
,/.
Fig. 4.2
I n e r t a t m o s p h e r es o h e n t s t i l l .
what treacherous.becausesuperoxidebuildup on the surfaceof this liquid metal

c a n l e a d t o s p o n t a n e o uisg n i t i o n .
Sodium-benzophenone
representsa good conlpromisebetweeneaseof use
and safety.As mentioned,the solventshould be prepurified to removemost of
the water and oxygen,and the still pot should be purged with an inert gas. Sodium wire with a cleansurfaceis then introducedalong with a small amount (ca.
IMPURITIES
DETECTING
B9
5 g/L) of benzophenone.The pot is stirred vigorouslywith a stout stirring rod to

break the residualsurfacefilm on the wire. If the solventis relativelypure, a blue
color may begin to form in the solution around the sodium. In the more usual
case,it may be necessary
to stir for sometime to initiate the formation of the blue
color. With purging, the pot is then attached to the still, and the solvent is
brought to reflux temperature.The solventshould turn a deep blue or green,
marking the formation of the sodium-benzophenone
and the exhaustionof water and oxidizing species.The distillation is then carried out. If good gradesof
starting solventsare used, the pot can be replenishedwith prepurified solvents,
with perhaps the addition of some additional benzophenone.The principal
ketyl are the extra trouble of initiating its
drawbacksof sodium-benzophenone
formation and the introduction of tracesof benzeneinto the dried solvent.
4,2 sorvENT
sToRAGE
Freshly distilled solventsare readily contaminatedand, in the case of ethers
which are suppliedwith peroxideinhibitors, the purification step leavesthe solvent susceptibleto rapid peroxideformation. Therefore,it is necessaryto provide the proper meansof solventstorage.It is possibleto minimizethe amount of
fresh solventwhich must be stored by using the distillation setup illustrated in
Fig.4.2, which has a reservoirthat may be tapped when needed.A simple sidearm flask (seeFig. 1.3) is satisfactoryfor short-termuse when solventpurity is
not highly critical. Solventmay be removedfrom sucha flask by syringethrough
the open joint while a flush is maintained on the equipment, or a septum sidearm may be used. Much better exclusionof the atmospherecan be achievedby
meansof a Teflon valveclosure,such as illustratedin Fig. 4.3. The advantages
of this designare the excellentisolationof the solventby the Teflon-tippedvalve
and the lack of contaminationof the solventby stopcockgreases.This type of
solventstoragetube is ideal for usewith a vacuum systemand is alsosatisfactory
for removalof solventby syringewhile an inert-gasflush is maintainedfrom the
sidearmof the valve.
TMPURTTTEs
4,3 DETEcTTNe
Peroxidedetectionin organicsolventswas previouslydiscussedin Section4. 1. D.
It is imperative that solventssuspectedof peroxide contaminationbe tested,
since an extreme explosionhazard resultswhen peroxidesare concentratedin
the still pot during distillation.
The detectionof water in solvents,especiallyin trace quantities,can be troublesome. A method employing infrared spectrometryhas been developedby
Barbetta and Edgell for the detectionof water in solventsat the submillimolar
90
AND REAGENTS
PURIFICATION
OF SOLVENTS
F i g , 4 . 3 . S o l y e n ts t o r a g et u b e s r v i t h T e f l o n v a l v e s .( a ) T h e O - r i n g j o i n t o n t h e s i d e a r ma l l o * s a t t a c h m e n t t o a v a c u u m l i n e e q u i p p e d w i t h O - r i n g j o i n t s . ( b ) S a n r eb a s i c d e s i g n a s i n ( r ) r v i t h a
s t r a i g h ts i d e a r m .T h i s d e s i g ni s e a s i l yc o n n e c t e dt o a S c h l e n kl i n e v i a T y g o n o r o t h e r f l e x i b l et u b i n g
that fits overthe sidearm.
level.sIn this method, the intensewater fundamentalabsorptionband at 3,590

cm-rwas used to monitor the water content of a varietyof solvents,including
acetonitrile.THF. and Dvridine.
4,4 puRrFrcAnoN
oFspEcrFrc
sotvENTs
A. Wolel.
Purging rvith inert gas or pumping on this solventwill rid it of
dissolvedoxygen.Dissolvedsaltsmay be removedby distillationor by utilizing a
commerciallyavailabledeionizingsystem.
B. Soturoled Hydrocorbons.
Purging and freeze-pump-thawmethods
are effectivein degassingparaffins. Distillation u'ith the eliminationof the first
fractionsproducesdry solvent.Molecular sievesnrayalsobe usedto removewater. Distillation from sodium-benzophenone
ketyl is highly effectivein obtaining
very low levelsof water and oxygen. Commercialgrades of hydrocarbonsare
often contaminatedwith olefins, which can be eliminatedby severalwashings
: A . B a r b e t t aa n d W . E d g e l l .A p p l . S p e c t . , 3 2 . 9 3( 1 9 7 8 ) .
SOLVENTS
PURIFICATION
OF SPECIFIC
94
with concentratedsulfuric acid, separationfrom the acid, washingwith water,

and, after preliminary drying with molecular sieves4A or 5A, subjectingthe
solvent to fresh desiccant or one of the drying proceduresoutlined above.
The methodslistedfor saturatedhydrocarC. Aromolic Hydtocorbons.
bons may be usedwith benzene.Thiopheneand similar sulfur-containingimpurities are removedby sulfuric acid washes.Very-high-puritybenzenemay be prepared by fractional crystallizationfrom ethanolfollowed by distillation.
Toluene and xylenesare purified in the same manner as benzene;however,
thesesolventsshould be kept cool (at or below room temperature)during sulfuric acid treatment due to their greaterreactivitytoward sulfonation.
Molecular sievesprovidea good meansof drying these
D. Chlolocolbons.
materials. CAUTION: Strong reducing agents,such as metal hydrides, Na, and
Na-K, react violently with halogenatedhydrocarbonsand should never be used
to dry thesematerials. Chloroform generallycontains 1% ethanol to suppress
phosgeneformation. This may be removedby shakingwith concentratedH2SOa,
separatingfrom the acid, washingwith water, predryingwith molecularsievesor
silicagel, drying with molecularsieve44, and distilling, taking the centralfraction. This material must be useddirectlyor storedstrictlyout of contactwith the
atmosphere.Methylenechlorideis lessreactivethan chloroformand is not prone
or dried with molecular
to phosgeneformation. It may be distilled from PaO16
sievesand distilled under an inert atmosphere.(Note that tracesof phosphine
are introduced into a material by the use of P4Oro.)
E. Elhels. Diethyl ether is availablein very dry grades,which for most purposescan be used directly from the freshly opened can. Similarly, purified
grades of tetrahydrofuran are availablewhich are often sufficientlydry to be
used directly (Fisher). When extremelysensitivematerialsare handled, diethyl
ether and tetrahydrofuranare often distilledfrom LiAl&. However,great care
must be taken first to removeall peroxidesand neverto let the still pot go dry
(seethe generaldiscussionin Section4.1). Sodium-benzophenone
ketyl is also
effectivewith etherswhich are peroxidefree, and it has the advantageof being
safer than LiAlHl. A small amount of benzeneis introduced into the solvent
ketyl is used.
when sodium-benzophenone
F. Nifliles. Acetonitrile is a convenientsolventfor many ionic compounds,
but it is extremelydifficult to dry to much better than millimolar in water. In
addition, degradationproductsof the solvent,ammonia and aceticacid, may be
present.Stronglyacidic or basic drying agentsreact with this solventand strong
reducingagentsare ruled out. One recommendedprocedureis first to predrythe
solventwith molecularsievesor silicagel if largequantitiesof water are present,b
. u r e u r r d A p p l . C h e r r r . .1 3 . 4 2 9 - 4 1 3( 1 9 6 b ) .
" J . F . C o e t z e eP
92
AND REAGENTS
PURIFICATION
OF SOLVENTS
then to stir or shakethis material with calcium hydride, which will removeboth
aceticacid and water. The predried acetonitrileis then distilled at a high reflux
ratio from PaOle(lessthan 5 g/L) under an inert atmosphere.A gel may form in
the distillation flask. and care should be taken to leavebehind the bulk of the
solventand residuesin the distillation flask. The solventis then refluxed over
calcium hydride and distilled under an inert atmosphereusing a high reflux ratio and a good fractionatingcolumn. The middle fraction is collected.Acrilonitrile is an impurity which will contaminatethe product if this distillation is not
efficient.
As an alternativeto this procedure!someworkers advocatestirring acetonitrile with calcium hydride, distilling it under a dry inert atmosphere,and passing it through a highly activatedalumina column under a dry inert atmosphere.
The removal of tracesof water from methanol and ethanol is
G. Alcohols.
difficult. Calcium turnings, magnesium turnings activated with iodine, and
lump calcium hydride are sometimesusedto removetracesof water from methanol. However,theseactivemetalsmay contain somenitride and give rise to contamination by ammonia. These same drying agents may be used with higher
alcohols.A column of dry molecularsieve4A is alsoeffectivein removingwater
from ethanol and higher alcohols.
H. Acefone.
Acetoneis very difficult to dry, sincemany of the usual drying
agentscausereaction, including MgSOa.Storageover molecularsieve4A yields
relativelydry acetone.High-purity acetonemay be obtained by saturatingthe
solventwith dry NaI at room temperature,decantingand cooling to -l0oC,
isolatingthe crystalswhich form (Nal-acetonecomplex),warming the crystalsto
r o o m t e m p e r a t u r ea
, n d d i s t i l l i n gt h e r e s u l t i n gl i q u i d .
4,5 puRrFrcATroN
oF soMEcoMMoNLyusED
GAsEs
A. Acelylene.
This gasis sold in cylinderscontainingacetone,which maintains a low pressureof acetylene.Therefore,acetoneis the principal contaminant and may be removedby passingthe gas through an aqueoussolution of
N a H S O 3 . T h e g a s s t r e a m i s t h e n d r i e d w i t h m o l e c u l a r s i e v e s .W h e n s m a l l
amounts of acetone-freeacetyleneare needed,it is convenientto generatethe
gas from calcium carbide and water. Again, the resulting acetylenestream is
d r i e d r v i t h m o l e c u l a rs i e v e s .
CAUTION: Acetylene is thermodynamically unstable with respectto the elements and it may explode spontaneouslyat high pressures.The gas should never
be handled above 15 psig pressure.If water addition to calcium carbide is used
to generateacetylene,the generator must be kept cool and the acetyleneallowed
unrestricted flow from the generator.
PURIFICATION
OF SOMECOMMONLYUSEDGASES
YJ
This good low-temperatureor high-pressuresolventmay be

B. Ammonio.
purchased in a fairly dry state. The last traces of water can be removed by condensingthe ammonia onto sodium on a vacuum line, allowingthe blue color of
dissolvedsodium to develop,and trap-to-trap distilling of the resulting ammonia into a metal cylinderor into a reactionvessel.The experimentalistshouldbe
thoroughlyfamiliar with vacuum line operationsbefore attempting this procedure. The major pitfall is bumping the ammonia with a suddenpressurerise,
which can propel stopcocksat great speedsor burst the glassapparatus.One
other potential problem is contaminationof the vacuum line with sodium resulting from a fine spray which forms as the ammonia evaporates.A generousplug
of glasswool above the drying tube reducesthis last problem, and a pressure
releasebubbler (seeFig. 1.2) will reducethe chancesof pressurizingthe vacuum
system.
C. Bolon Holides. These compoundsare best handled and purified on a
vacuumsystem.Siliconestopcockgreasereactswith the boron halides,and most
hydrocarbongreasescontain unsaturatedhydrocarbonswhich are polymerized
by theseLewis acids.A halogenatedstopcockgrease,Teflon-in-glassvalves,and
Viton O-rings all give satisfactoryperformancewith the boron halides. Boron
trifluoride is availablein cylindersand may be freed from residualatmospheric
gasesby trap-to-trap distillation in the vacuum system.For very critical applications, further purification can be achievedby the formation of the benzonitrile
adduct at 0oC in a vacuum system;this adduct is then evacuatedto removevolatiles such as the weaker acid SiFa.The BF3 is recoveredfrom its benzonitrile
Adjacentto the trap containingthe adduct is
adduct by thermal decomposition.T
a trap cooled to -78oC (Dry Ice), and this is followed by a trap cooled to 196'C (liquid Nz). About 20 torr of dry nitrogen is introducedinto this train of
three traps; the first trap containing the adduct is warmed to about 60oC with
hot water and the valve leading to the adjacent, -78o trap is cracked open
s l i g h t l y ,w h i l e t h e v a l v eb e t w e e nt h e - 7 8 ' a n d - 1 9 6 o t r a p i s o p e n e d .I n t h i s
w a y b e n z o n i t r i l ec o l l e c t si n t h e - 7 8 ' t r a p a n d B F 3 , i n t h e - 1 9 6 ' t r a p . W h e n
the decompositionof the adduct is complete, the purified BF3 is trap-to-trap
distilled to a storagebulb.
The contaminants in commercial boron trichloride usually are HCI and
COC|2,as well as oxychlorideswhich have some volatility. The oxyhalidesare
readily removedby one or two trap-to-trap distillationsin a clean vacuum system. Most of the HCI can be removedby holding the BCl3at - 78oCand pumping away the volatilesfor a brief period (someBCI: is sacrificedin the process).
Phosgene,which may be detectedby its gas-phaseinfrared absorptionat 850
cm r, is very difficult to remove.Liquid boron tribromide is generallysupplied
in sealedampules.If it is straw colored,dibromine is a likely impurity, and this
-H.
C . B r o w n a n d R . B . J o h a n n s e nJ. . A n t . C h e n t . S o c ., 7 2 , 2 9 3 4 ( 1 9 5 0 ) .
PURIFICATION
AND REAGENTS
OF SOLVENTS
can be removed by shaking the compound with mercury. Hydrogen bronride

may be removedby trap-to-trap fractionation in which the BBr.ris collectedat
-45oC and the HBr at - 196'C.
D. Colbon Dioxide. Water is generallythe main contaminant in carbon
dioxide,especiallyif Dry lce is usedas the sourceof this gas.Trap-to-trapsublimation of the carbon dioxidethrough an interveningactivatedsilicagel trap on a
high-vacuumline effectivelyremoveswater. Low-boilinggasessuch as nitrogen
or oxygenare removedif the sublimation is done under dynanricvacuunt.
E. Colbon Monoxide.
The most troublesomeimpurity in carbon monoxide generallyis oxygen,which may be removedby passingthe gasoversupported
copper(e.9., Ridox) or supportedMnO, both of rvhichare discussedin Chapter
3. It is reported in the literature that CO does not impair the performanceof
MnO, but experiencein the authors' laboratory indicatesthat MnO that has
been exposedto CO is not readily regenerated.
F. Efhylene. Oxygen is a very troublesomeimpurity for many studiesand
can be removedby passingthe ethyleneover supportedMnO or supportedcopper.
G. Hydrogen.
Oxygenmay be reducedto the low parts per million rangeby
means of a platinum-metal catalyst,which combinesthe residualoxygenwith
hydrogen.The ultrapurificationof hydrogencan be achievedby diffusionof the
gas through a heated palladium thimble. Commercialunits are availablethat
a r e b a s e do n t h i s p r i n c i p l e . E
H. Hydlogen Holides. Water can be removedfrom HCI and HBr by trapto-trap distillation in a vacuum systent.If thesegasesare handled at 100torr or
below, a trap held at -78oC may be usedto condensewater. An activated-carbon trap can be usedto rentoveany halogenimpuritiesin thesegases.Performing the transfer under dynanricvacuum will also removeany lorv-boilinggases
not condensableat liquid nitrogen temperatures.
The purification of HI is complicatedby the well-knownequilibrium between
i t s e l fa n d h y d r o g e na n d i o d i n e ,E q . ( t ) .
2 H I ( g ) = H z ( g )* I z ( g )
(l)
The attainment of equilibrium is very slow at room temperature. Residual

iodine can be removedby passingthe gas over red phosphorousor shaking it
with mercury. The gas may be then be passedthrough a trap at -78'C to cons A v a i l a b l ef r o m M a t h e s o nG a s
P r o d u c t s .P . O . B o x 8 5 . E a s t R u t h e r f o r d . N J 0 7 0 7 3 .
ANHYDROUS
METALHALIDES
95
d e n s em o i s t u r e ,a n d c o n d e n s e di n a s e c o n dt r a p a t - 1 9 6 " C .A h i g h v a c u u ml s
maintainedon the exit of the secondtrap to removehydrogen.
l. Sulfur Dioxide. This compound is a usefulreactantand lou'-temperature
solvent.The commercial compressedgas rnay be condensedat liquid nitrogen
temperatureand atnrosphericgasespumped away.Moisture is removedby passdispersedin glasswool.
ing it through a trap containing PaO16
4.6
METAL
HALIDEs
ANHYDRoUS
Thesevery useful starting materialsoften are reactiveu'ith atmosphericnroisture. Simple dehydration by the application of heat is not effectivewhen the
metal ion is small and,/or irr a high oxidation state becausehydrogenhalide is
eliminatedand ntetal oxyhalidesor hydroxyhalidesresult. Severalgeneralmethods are available for the removal of oxygen-containingligands from metal
for the purificationof commercialhalidesare not
halides;but elaborateschenres
attractive,becausethe direct synthesisfrom pure starting materialsis generally
may be consulted
lessdifficult. The cumulative indicesof Inorganic Syrttheses
for thesesyntheticprocedules.
Commercialgradesof aluminurn chlorideand aluminurn bromide are generally contaminated*'ith hydloxylic impurities. Somepurificationcan be achieved
b y s u b l i m i n gt h e r r r a t e r i ailn a g l a s sa p p a r a t u su n d e r v a c u u m .B e t t e rp u r i f i c a tion can be accomplishedby mixing good-qualityhalide(e.g. that sold by Fluka)
w i t h a l u m i n u m w i r e a n d l % - b y - w e i g h ts o d i u m c h l o r i d ep r i o r t o t h e s u b l i m a tion. The function of the NaCl is to fornr molten NaAlCll. which has an affinity
for ionic impurities.eA secondsublimation is sometimesnecessaryto remove
fine particlesof alunrinum if the first sublimation was performed too rapidly.
T h e p u r e s ts a m p l e so f a l u m i n u m h a l i d e sa r e o b t a i n e db y d i r e c ts y n t h e s i s .
A variety of transition metal chloridesand other chloridescan be dried by
m e a n so f t h i o n y lc h l o r i d e .r v i t ht h e e v o l u t i o no f S O 3a n d H C l . r 0T w e n t yg r a n r so f
the finely divided metal chloride is placed in 50 rnl- of freshly distilled SOCI2.
When the evolutionof gashas ceased,the mixture is refluxedfor l-2 hours. and
then excessthionyl chloride is distilled from the reaction flask under reduced
pressure.Residualthionyl chloride is renrovedfrom the product in a vacuum
desiccatorcontaining KOH. The halide should be transferredand stored in a
nroisture-freeatmosphere.Halides which have been successfullydried by this
. o C l 2 .a n d
m e t h o d i n c l u d e : L i C l , C u C l 2 .Z n C l 2 , C d C l 2 ,T h c l i , C r C l . r ,F e C l . r C
NiCI,.
. n t . C h e n t .S o c . . l 0 l , 3 2 3( 1 9 7 9 ) s: e ea l s oD . W . S e e g m i l l e r ,
" J . R o b i n s o na n d R . A . O s t e r y o u n g . . / A
( 1 9 7 0 ) ,f o r a r c c r v s t a i i i z a t i o tne c h . n d L . A . K i n g . l r o r g Nut'|. Chen. Zer.. 6, 8t'J5
G . W . R h o d e sa
nique.
r('4. R. Pray. lnorgunic Jl'nt,/rt'sc.r.
5. r 5 3 ( 1 9 5 7 ) .
96
AND REAGENTS
PURIFICAIION
OF SOLVENTS
REFERENCES
GENERAL
B r a k c r . W . . a n d A . L . M o s s n r a n .1 9 8 0 ,M u t h t ' s o r tG u s D u t u B o o k , 6 t h e d . . M a t h e s o nD i v . S e a r l e
t e t h o d so f
M e d i c a lP r o d u c l s L
, y n d h u r s t ,N . J . . 0 7 0 7 1 .A l t h o u g ht h i s v o l u m ed o e sn o t p r e s e n m
p u r i f i c a t i o n .i t d o e sp r o v i d ei n f o r m a t i o nu ' h i c h i s u s e f u li n t h e h a n d l i n go f g a s e s .s u c h a s t a b u l a t i o n s o f p h y s i c a lp r o p e r l i L ' s i.n f r a r e d s p e c t r a( s o m e t i n r e ss h o u i n g i m p u r i t i e s r i h i c h a r e n o t
i d e n t i f i e da s s u c h ) .s a f e t yi n f o r m a t i o n a
, n d h a n d l i n gi n s l r u c t i o n s .
. . r T r e r i l r e n t uI n
D o d d , R . E . , a n d P . L . R o b i n s o n . l 9 - 5 , {
l o r g u r t i t ' C h e r n i s t r yE' ,l s e v i e r ,A m s t e r d a m .
P r o p e r t i e sa n d m e t h o d s o f p r e p a r a t i o na n d p u r i f i c a t i o n f o r m a n y i n o r g a n i c c o n r p o u n d sa r e
g i v e nh e r e .
, i l e v - l n t e r s c i c n c eN, e u Y o r k , p .
G o r d o n , A . G . a n d R . A . F o r d . 1 9 1 2 . T h e C h e n t i s t s C o r n p u n i o nW
429-439.
generall.vdescribespurification nrethodsin conjunction with
The seriesentitle<lInorgunlc S.r'rrrftest,s
s l n t h e t i c p r o c c d u r e s .C u n r u l a t i v ei n d i c e ss h o u l d b e c o n s u l t e di n v o l u n r e s1 0 , 1 5 , 2 0 , a n d t h e
n r o s t r e c e n l i s s u e .V o l u n r e s l - 1 7 r v e r ep- L r b l i s h e db l M c G r a u ' - H i l l , N c - $Y o r k ; V t i l u n r e sl 8 t o
p r e s e n ta r e p u b l i s h e db y W i l e 1 , N e * Y o r k : b a c k v o l u m e sa r e a v a i l a b l ef r o m K r e i g e r P u b l i s h i n g
C o . . B o x 9 5 4 2 . M e l b o u r n e .F l a . . - 3 2 9 0 1 .
J o l f r . W . L . , 1 9 7 0 . . S . r l t f t e s u/ st t d C h u r o c t e r i : u t i o rot l l n o r g u r r i t C o n t p o u n d s ,P r e n t i c e - H a l l .E n g l e u ' o o dC l i f f s .N . J . .p . l l 4 - 1 2 1 .
L a g o * ' s k i ,J . J . . F , d . , T h e C h e t n i s t r ro- . l N o n - A q u e o u sS o / r ' t r r I s ,A c a d e m i c . N e w Y o r k . T h i s s e r i e s
c o n t a i n sd e t a i l e da c c o u n t so f t h e p u r i f i c a t i o n ,p r o p e r t i e s .a n d h a n d l i n gr r f s o n r en r a j o rs o l v e n t s :
, y d r o g e nh a l i d e s a. n r i d e sa, n d a m m o n i a ;V o l . 3 ( 1 9 7 0 ) s, u l f u rd i o x i d ea n d a c e t i c
Vol. 2 (1967)h
a c i d l V o l . 4 ( 1 S 7 6 ) .t e t r a n r e t h v l u r e ac .y c l i cc a r b o n a t e sa. n d s u l f o l a n e V
: o l . 5 A ( 1 9 7 8 ) ,t r i f l u o r o a c e t i ca c i d , h a l o s u l f u r i ca c i d s . i n t e r h a l o g e n si.n o r g a n i ch a l i d e sa n d o x y h a l i d e s .
P e r r i n . D . D . , W . L . F . A r n r a r e g o .a n d D . R . P e r r i n , 1 9 8 0 ,P u r i J ' i t u t i o rot - /L u b o r u t o n ' C h e n i c u l s ,
2 n d e d . , P e r g a m o n ,L o n d o n . T h i s b o o k i s b r o a d e r b u t l e s si n c i s i v et h a n t h e o n e l i s t e d a b o v e .
G e n e r a lp u r i f i c a t i o nt e c h n i q u c sa r e d i s c u s s e da, n d v e r y b r i e f d i r e c t i o n sa r e g i v e nf o r t h e p u r i f i c a t i o n o f a w i d e v a r i e t vo f o r g a n i c sa n d i n o r q a n i c s .
R i d d i c k , J . A . , a n d W . B . B u n g e r . 1 9 7 0 ,O r g c n t i cS o / v e r r t sT, e c h n i q u e so l C h e n t i s t r y .V o l . 2 . 3 r d
e d . , W i l e y - l n t e r s c i e n c eN, r - r vY o r k . A l e r r g o o d s u m n l a r yo f t h e v a r i o u st e c h n i q u e sr e p o r t e df o r
t h e p u r i f i c a t i o no f i n d i v i d u a l s o l v e n t sa l o n g* i t h s o n r ep h y s i c a ld a t a a n d r e f e r e n c e tso t h e o r i g i nal literature.
PART
Vocuum Line
Monipulotions
VACUUMLINEDESIGN
ANDOPERATION
When properly handled, a vacuum line is a true joy to use becauseit providesa
closedreactionvesselwith excellentexclusionof air, quantitativeretentionof all
reactionproducts,and a readymeansfor the transferand quantitativemeasurement of gases.
Vacuum lines are employedin problemsrangingfront the simpletransfer of
volatilesubstancesto the extendedseriesof operationsinvolvedin the synthesis,
purification, and characterizationof new compounds.This chapterpresentsan
overviewof the designof glassvacuum systems.Followingchaptersgive greater
d e t a i l o n i n d i v i d u a l c o m p o n e n t ss u c h a s p u m p s ( C h a p t e r 6 ) , m a n o m e t e r s
(Chapter7), joints and valves(Chapter 8). and metal vacuum systems(Chapter
l0). The presentalsodescribesthe basicoperationsfor the transferand purificagases,the quantitativePVT (pressuretion of condensableand noncondensable
volunre-temperature)
nleasurementof gases.and the characterizationof condensablegasesby vapor pressure.More specializedoperationsare describedin
Chapter 9.
5.4
GENERAT
DESTGN
A. TypicolSysfemS.A simplesystem
for thetransfer
of samples
to aninfrared gas cell or to a NMR sample tube consistsof a fore pump, diffusion
pump, trap, and manifold (Fig. 5.1). At the other extremeis a general-purpose
chemical vacuum line, u'hich permits the separationof volatile compounds.
transfer of noncondensablegases,and storageof reactivegasesand solvents
(Fig. 5.2). When attack of stopcockgreaseis a seriousproblem, grease-freede-
100
AND OPERATION
VACUUMLINEDESIGN
T h e r mo c o up le
vocuum
gouge
( o r M c L e o dg o u g e )
F i g , 5 . t . S i m p l ev a c u u n tl i n e . A l i n e o f t h i s s o n m i g h t b e u s e dt o t r a n s f e rv o l a t i l es a m p l e st o i n f r a r e d g a s c e l l s ,N M R t u b e s . e t c . I t m i g h t a l s o b e u s e df o r l o a d i n gt u b e sf o r s e a l e d - t u b er e a c t i o n sa n d
for vacuumsublinrations.
signs basedon O-ring joints and glassvalveswith Teflon stemsare frequently

used (Fig. 5.3). Each stopcock,valve,or joint adds to the cost and to potential
sitesfor leakage,so the vacuum line design should be the simplestpossibleto
servcthe intended uses.
B. Moior Componenls.
The extendedarray of glass tubing in a typical
vacuum systemrequiresproper support to minimize breakage.A rigid lattice is
essentialto reducethe differential movementof variousglasscomponents.For
large vacuum systemsthe lattice is generallyfirmly mounted on a sturdy low
bench as illustrated in Fig. 5.4. Horizontal bars increasethe rigidity of the lattice, but they should not be usedfor clampingapparatus.NOTE: It is important
to clamp the vacuum line parts only to vertical bars, because a clamp may
swivelaround a horizontal bar and thus not provide reliable support. Heavy permanent items, such as mercury-filledToepler puntps or Mcleod gauges,are
preferably mounted on the bench and supported in a bed of plaster of Paris.
When the vacuum line is first assembledand carefully but firmly clamped in
place, it is good practiceto annealsegnlentsof tubing betu'eenadjacentclamps
to relievestresson the apparatus.
T h e f u n c t i o n a lu n i t s i n t h e g e n e r a l - p u r p o svea c u u m l i n e i l l u s t r a t e di n F i g .
5 . 2 a r e f a i r l y t y p i c a l :( l ) a s o u r c eo f h i g h v a c u u m ,( 2 ) a h i g h v a c u u mm a n i f o l d ,
and (3) various working manifolds. These working manifolds may contain a
train of U-traps for the separationof volatiles,or a seriesof containersfor the
storageof either gasesor volatile liquids. In addition to U-traps, the working
DESIGN
GENERAL
,10,1
F i g . 5 . 2 , M u l t i p u r p o s e h i g h - v a c u u ms y s t e m .B u l b s f o r g a s s t o r a g ea r e a t t h e t o p o f t h e f i g u r e .
D i r e c t l y b e l o u t h e s ei s t h e h i g h - v a c u u n rm a n i f o l d , r v h i c hi s a t t a c h e dt o a t r a p a n d p u m p s a t s i t e I
a n d c o n n e c t e dt o a h i g h - v a c u u mg a u g e a t 2 . T h e * o r k i n g m a n i f o l d i n t h e c e n t e r o f t h e f i g u r e i s
a t t a c h e dt o a t r a i n o f U - t r a p s a n d t o v a r i o u si n l e t s .I t i s a l s oc o n n e c t e dt o a T o e p l e rp u m p a t 3 . G a s e s
a n d v o l a t i l e l i q u i d s a r e i n t r o d u c e dt h r o u g h t h e i n l e t s a t t a c h e dt o t h i s m a n i f o l d , a n d l a r g e r e a c t i o n
v e s s e l os r s p e c i a la p p a r a t u sa r e f r e q u e n t l ya t t a c h e dt o t h e l a r g ej o i n t . A t t h e b o t t o n l o f t h e f i g u r e i s a
n r a n i f o l du ' i t h s o l v e n ts t o r a g ev e s s e l sa t t a c h e d ;i t i s a l s oc o n n e c t e dt o a g r a d u a t e dt r a p w h i c h a l l o w s
n r e a s u r e m e not f t h e v o l u m e o f s o l v e n tb e f o r e i t i s t r a n s f e r r e dt o t h e n r a i n u o r k i n g m a n i f o l d . S t a n d a r d h i g h - v a c u u m s t o p c o c k sa r e e m p l o y e d e x c e p t o n t h e s o l v e n t a n d g a s s t o r a g eb u l b s , w h e r e
g r e a s e l e sns e e d l ev a l v e sa r e u s e d .
manifold generallyhas sitesfor attaching reaction vessels,gas inlets, and the

like. This working manifold usually includesone or more mercury-filledmameasurementof gaseous
nometersfor the PVT (pressure-volume-temperature)
reactantsor products,or for vapor pressuremeasurements.The main high-vacuum manifold is usually equipped with a high-vacuumgaugeso the initial degree of evacuationcan be measured.This gauge is also valuable for locating
102
AND OPERATION
VACUUMLINEDESIGN
F i g , 5 , 3 . W a v d a - D y eg r e a s e l e svsa c u u m l i n e . T h i s a p p a r a t u sn r a k e se x t e n s i v eu s eo f m e t a l b e l l o w s
t u b i n g a n d O - r i n g s e a l s .T h u s t h c r e a c t i o nv e s s e l sf,i l t e r s ,a n d o t h e r i t e n r sc a n b e t i l t e d a n d m a n i p u l a t e d l i k e S c h l e n ku a r e , a n d h i g h v a c u u n rc o n d i t i o n sc a n b e a c h i e v e df o r t h e r e m o v a lo f a t m o s p h e r i c
g a s e sa n d f o r b a k i n g o u t r e s i d u a lm o i s t u r e .T r a p - t o - t r a p d i s t i l l a t i o no f v o l a t i l es o l v e n t ss u c h a s N H r
o r S O zi s r e a d i l , va c c o n r p l i s h e w
d i t h t h i s a p p a r a t u s .T h i s v e r s i o ni s n o t d e s i g n e df o r t h e n r e a s u r e n r e n t
o f v o f a t i l e so r t r a p - t o - t r a p s e p a r a t i o n .( R e p r o d u c e df r o m A . L . W a y d a a n d J . L . D y e , J . C h e n r .
E d u c . 6 2 . 3 5 6 ( 1 9 8 5 )b y p e r n r i s s i o no f t h e c o p y r i g h to w n e rt h e D i v i s i o no f C h e m i c a lE d u c a t i o no f t h e
A n t e r i c a nC h e n r i c a lS o c i e t v . )
leaksin the system.A Toepler pump is generallyattachedto the vacuum line if

gasesare to be manipulated.The Toeplerpump is not an absononcondensable
lute necessityfor transferring noncondensable
gasessuch as CO and CH4. As
d e s c r i b e di n S e c t i o n 5 . 6 . 8 , l o w - t e m p e r a t u r ea d s o r p t i o np r o v i d e s a s i m p l e
method for transferring these gases.
The mechanicalfore pump is a heavyitem which setsup considerablevibration. This vibration disrupts the menisciof mercury manometersand is otherwiseundesirable.To minimize the transferof vibrationsto the vacuum line. the
fore pump generallyis mounted on the floor (rather than on the bench of the
vacuum rack) and the connectionbetweenthe fore pump and the vacuumsystem
is made with heavy-walledvacuum tubing or flexible corrugatedmetal tubing.
Detailson pumps, manometers.vacuumgauges,specialapparatus,and leak
testing are given in Chapters 6-10. It is the purposeof the remainder of this
gases,trapchapterto describethe transferof condensableand noncondensable
to-trap fractional separationof volatiles,and the use of vapor pressurein the
characterizationof volatilecompounds.Theseoperationsare basicto practically
a l l c h e m i c a lv a c u u ml i n e w o r k .
INITIAL
EVACUATION
103
Electncol
o u t Ie l
F i g . 5 . 4 . T y p i c a l l a t t i c e .G l a s sa p p a r a t u si s c l a n p e d t o t h e v e r t i c a lr o d s , u h i c h a r e s p a c e da t 1 0 -t o
l 2 - i n . i n t e r v a l s .O n e o r t w o h o r i z o n t a lr o d s a r e g e n e r a l l yi n c l u d e dt o i m p a r t r i g i d i t y . W h e n t h e r a c k
i s l a r g e , t h - i n . - d i a m e t e r s t e e l o r s l a i n l e s s - s t e er ol d s a r e p r e f e r r e dt o a l u m i n u n r l o d s b e c a u s et h e
l a t t e r d o n o t a f f o r d a r i g i d l a t t i c e . F r a n t e sa r e c o n s t r u c t e df r o r n p i p e ( a b o u t 2 - i n . d i a m e t e r ) .w c l d e d
a n g l ei r o n , w e l d e d H - b e a m , b o l t e d F l e x i - f r a m e ,o r s i m i l a r r i g i d m e m b e r s .T h e v a c u u m l i n e l a t t i c e
s h o u l d b e g r o u n d e db y r u n n i n g a c o p p e rw i r e f r o n r t h e l a t t i c et o a $ a t e r p i p e . I t i s a d v a n t a g e o u tso
c o v e rt h e b e n c h w i t h T r a n s i t e o r a s i m i l a r h e a t - r e s i s t a nst u r f a c e ,s i n c et h i s f a c i l i t a t e sg l a s s b l o u ' i n g .
T h e d i m e n s i o n sg i v e n a r e t y p i c a l o f a r a t h e r l a r g e r a c k - A h o o d e dv a c u u m r a c k i s o c c a s i o n a l l -uts e d
t o h e l p c o n t a i n r e a c t i v eo r p o i s o n o u ss u b s t a n c e rse l e a s e di n a m i s h a p . T o p r o v i d et h e r e q u i r e dr i g i d i t y . i t i s s o m e t i m e sn e c e s s a r tyo b r a c e t h e t o p o f t h e v a c u u m r a c k t o a w a l l .
5.2 tNrTrAL
EVAcuAloN
A good initial vacuum is necessarybecausenoncondensable
foreign molecules
will impedethe movementof the condensablematerial. when largequantitiesof
relativelyunreactivegasesare being handled (for example, BF:). it is usually
satisfactoryinitially to evacuatethe systemto 10 r torr. Small quantitiesof gas
and highly reactivegasesrequire a better initial vacuumfor their transfer( t0-'tl0-s torr), and most preparativechemical vacuum systemsare designedwith
this degreeof vacuum in mind. Mercury exertsa pressureof approximatetyl0 3
torr at room temperature,so mercuryvapor is presentthroughouta vacuum line
which is equippedwith mercury manontetersand other mercury-containingapparatus. Sincemercury vapor is condensableand relativelyunreactive,its presenceoften can be ignored.
To start a vacuum systemsuch as that illustratedin Fig. 5.1, the clean main
trap is fitted in place with an evencoat of stopcockgreaseon the joint. A Dewar
partially filled with liquid nitrogen is raisedaround this trap, and the fore pump is
immediatelyturned on. CAUTIoN: oxygen from the atmospherewill condensein
a trap held at liquid nitrogen temperature; therefore, it is important never to leave
a trap cooled to liquid nitrogen emperatureexposedto the atmosphere for a significant length of time. when the line has pumped down to lessthan 1 torr, the
404
VACUUMLINEDESIGN
AND OPERATION
stopcocksare turned to route the gasthrough the diffusionpump, and the heater
on the diffusion pump is then turned on. (If the diffusionpump is water cooled,
the water shouldalsobe turned on.) The progressof the evacuationis followedby
meansof an electronicvacuum gaugeor a Mcleod gauge. If possible.the line
should be evacuatedfor severalhours beforeuse(overnightis preferablefor a large
vacuumsystem)to permit the desorptionof moistureand a thoroughcheckon the
performanceof the line. If the line doesnot pump down rapidly, the most likely
sourceof leaks is poorly greasedstopcocks.Sometimesthe offending stopcockor
joint can be turned to work out the leakagepath in the grease.Details on the
proper greasingof stopcocksand joints are given in Chapter8, and methodsfor
hunting leaksare describedin Chapter7.
5,3 MANrpuLATroN
oFvorATtrE
uoutDsANDcoNDENsABTE
GASES
A. Fteeze-Pump-Thow Degossing. Liquids which have been exposedto
the atnrosphereor to inert gasescontain appreciableamountsof dissolvedgases
t h a t s h o u l db e e l i m i n a t e db e f o r eu s e .I f s m a l l q u a n t i t i e so f l i q u i d a r e i n v o l v e d ,
gasessuch as oxygenand nitrogen may be eliminatedby meansof the transfer
processdescribedin Section5.3.C. In the more common situationof needingto
d e g a sa l a r g e v o l u m e o f l i q u i d , t h e f r e e z e - p u m p - t h a tue' c h n i q u ei s e m p l o y e d .
T h i s i s a c c o m p l i s h e db y c o o l i n g t h e s a m p l e t o l i q u i d n i t r o g e nt e n r p e r a t u r e ,
pumping on the sampleat this temperature,closingthe stopcockor valveso the
s a m p l ei s i s o l a t e df r o m t h e v a c u u m ,a l l o w i n gt h e s a m p l et o m e l t , t h e n r e f r e e z i n g
i t a n d p u n r p i n ga w a y a n y n o n c o n d e n s a b g
l ea s e sw h i c h b o i l e do u t o f t h e m a t e rial. This processis generallyrepeatedseveraltimes. Note that ice and frozen
methylenechloride, may break glassapparatuswhen they are thawed.The easiest course of plevention is to use a round-bottomed container which is onefourth full or less.Another effectivemeasureis to warnr the tube rapidly so that
a film of liquid forms betweenthe container and the mass of the frozen solid.
With experience,the latter techniquecan be effectivein very difficult situations
s u c h a s a w a t e r - f i l l e dt h i n - w a l l e dN M R t u b e .
B. Ihe llonsfer of Condensoble Goses. Condensable
gasesare conveniently separatedand transferredin a vacuum line by vaporizationand condensation. Prior evacuationof the systemand a suitablylow temperatureare necessary
to quantitatively transfer the material. The vapor pressurecorrespondingto
"quantitative" condensationof a compound will depend on the volume of the
systemand the quantity of material being transferred;as a generalrule, a maximum vapor pressureof 10-3 torr is satisfactory.For simple transferoperations,
liquid nitrogen (bp - 196"C) is the most commonly used refrigerant.
C. Exomple:Tronsferof o CondensobleGos. Suppose

wewishto
transfer the HCI from a 1-L glassbutb into a trap on the vacuum system(Fig.
MANIPULATION
AND CONDENSABLE
GASES
OF VOLATILE
LIOUIDS
105
F i g . 5 . 5 . T h e t r a n s f e ro f H C i f r o n r a b u l b i n t o a t r a p b i c o n d e n s a t i o nS
. e e S e c t i o n5 . 3 . C f o r a
d c s c r i p t i o no f t h e t r a n s f e r p r o c e d u r e .
5.5). The bulb is attachedto the vacuum line by meansof a carefullybut lightly
g r e a s e dt a p e r j o i n t , a n d i s h e l d i n p l a c eb y s p r i n g s ,c l a m p s ,o r r u b b e r b a n d s .
T h e s y s t e m ,e x c l u s i v eo f t h e b u l b , i s e v a c u a t e dt o a t l e a s t l 0 3 t o r r p r e s s u r e
( s t o p c o c kV c l o s e da n d I I , I I I , a n d I V o p e n ) .T h e U - t r a p i s c o o l e dw i t h a D e w a r
of liquid nitrogen,and then HCI is admitted by slowlyopeningstopcockV. Stopcock lV is generally left open at this point becausethe HCI is quantitatively
trapped at the boiling point of liquid nitrogen, - l96oC, and the open stopcock
allowsany contaminating"noncondensable"gasessuch as oxygenand nitrogen
to be renroved. CAUTION: Avoid pressurizing a vacuum line. Failure to keep
the pressure below one atmosphere may result in stopcocks popping out with
high velocityor explosionof the glassapparatus.In the examplejust given, the
bulb may have been of lL capacity and filled with 1 atm of HCl. If this were
condensedinto a smaller U-trap, followed by closingstopcocksIII and IV, the
liquid nitrogen would have to be maintained around the trap to prevent the
buildup of excessivepressure.
D. Trop-fo-Trop Froctionotion.
Compoundsof significantlydifferent volatility can be separatedby passingthe vaporsthrough a seriesof traps, each of
which is cooled to a temperaturewhich will condenseone of the components.
Judgedby the standardsof ordinary distillation, trap-to-trap distillation is very
inefficient.Thereforethe processis usefulonly when there is a largedifferencein
the vapor pressuresof the componentsbeing separated.A rough estimateof the
separationefficiencymay be gained from vapor pressuredata (assumingthe
compoundsdo not strongly interact in the condensedstate). If. at a particular
temperature,the ratio of vapor pressuresof tu'o compoundsis l0{ or greater,an
106
AND OPERATION
VACUUMLINEDESIGN
excellentseparationshould be possible;a ratio of 103will usuallylead to a good

separation;and a ratio of 102will permit fair separation.The separationis influencedby the rate of the trap-to-trap distillation: (l) the finite vapor pressureof
the lessvolatile component will lead to its accumulationalong with the more
volatile component;and (2) if flow rates becometoo high and the more volatile
component is in substantialexcess,the more volatile gas will entrain the less
volatile componentand sweepsomeof it through the low-temperaturetrap. In
order to achieveefficient separation,the first factor leadsone to favor a quick
distillation, while the secondleadsto the choiceof a slow distillation.
Each separationproblem presentsits own peculiarities,so there is no single
best procedurefor trap-to-trap fractionation.For example,if the componentof
primary interest is a minor constituentmixed with a more volatile compound,
the entrainment problem may be serious.To reduceentrainment,the mixture
may be passedthrough severalcold traps, and each trap should be deeplyimmersedin the cold bath to afford maximum contactwith the cold surface.Sometimes entrainment is minimized by the inclusionof glasshelicesor indentations
(Vigreaux)in the trap. However,a principal origin of entrainmentappearsto be
the formation of microcrystallitesin the gas phaseand theseare sweptthrough
the trap by the secondcomponent.Low flow ratesand large-diametertubing in
the traps minimize this mechanicalentrainment.To achievea low flow rate, the
volatilizationof the mixture is often moderatedby placing a chilled but empty
Dewar around the sampletube as illustratedin the following example.The use
of two or more traps cooled to the same temperatureallows the crystallitesto
volatilizebetweentraps and increasesthe chancethat the componentwill condenseon the walls of the next trap.
As alreadypointed out, it is possibleto monitor the purity of the fractionsby
methodssuch as vapor pressure(seebelow) or gas phaseinfrared spectroscopy
(Chapter9). In planning an experiment,solventsand reactantsare often chosen
such that their vapor pressuresfacilitate the separationof reactants,products,
and solvent. For compounds of similar volatility, more advancedseparation
t e c h n i q u e sa r e r e q u i r e d , s u c h a s f r a c t i o n a l c o d i s t i l l a t i o n ,l o w t e m p e r a t u r e
column distillation, or gas chromatography,all of which are describedin Chapter 9.
E. Exomple: Seporolion of BFgond CH2C|2. Boron trifluoride (bp
- 1 1 0 . 7 ' C ) i s r e a d i l ys e p a r a t e df r o m m e t h y l e n ec h l o r i d e( b p 4 0 . 7 " C ) a s i l l u s trated in Fig. 5.6. Inspectionof the vapor pressuredata in Appendix V reveals
that BF3exerts75 torr at - 126"C, whereasextrapolationof the vapor pressure
data for CH2Cl2to this temperature(log P vs. l/T plot) indicatesa vapor pressureof lessthan l0-3 torr for this component.Therefore,the reactionmixture is
slowlypassedthrough a trap cooledto - 126'C (methylcyclohexane
slushbath,
see below), which retains the methylene chloride, and into another trap at
- 196"C(liquid nitrogen),which retainsthe boron trifluoride. The rate of trans-
MANIPULATION
OF VOLATILE
LIQUIDS
AND CONDENSABLE
GASES
126" slush
rt
ll
Reoction
mtxture
CH2Clz
conoenses
107
\Liquio
nrtrogen
( - 1 9 6" C )
8Fs
condenses
B F 3o n d C H 2 C l 2
Fig. 5.6. Schematic representation of trap-to-trap fractionation for a BFr-CH:CI2 mixture. See
S e c t i o n5 . 3 . E f o r a d e s c r i p t i o no f t h e s e p a r a t i o np r o c e d u r e .
fer of the gasesthrough the traps is moderated by placing a chilled Dewar

around the tube containingthe reactionmixture. (This is accomplishedby initially condensingthe mixture in the left containerat liquid nitrogen temperature, pouring the liquid nitrogen out of this Dewar, and replacingthe chilled
Dewar around the sampletube.) After the distillationis complete,the individual
traps can be isolatedto retain the components.The recoveryof BF3 should be
quantitative.This may be verifiedby expandingthe gas into a calibratedvolume
attachedto a manometer,followedby pressuremeasurementand calculationof
the molespresentby the ideal gas law. Finally, purity checksmay be performed
by vapor pressuremeasurement,gas-phaseinfrared spectroscopy,
andlor mass
spectrometry. This sequenceof separation, quantitative measurementof volatiles, and physical identification of components affords a powerful method of
studyingreactionsinvolving at leastone volatile substance.
F. PVT Meosuremenl of Goses. One of the primary advantagesof the
vacuum line manipulation of gasesis the easewith which quantitativemeasurements are made. If the problem simply requiresdispensingmeasuredamounts
of gas, a proceduresuch as the following may be employed.The ideal gas law is
sufficientlyaccuratefor most chemicalwork if the compoundsare well removed
from their condensationtemperaturesand pressures.For example,the van der
Waals equation of statefor CO2indicatesthat 1 mmol of this gas in 25 mL will
exert749.7torr pressureversusthe idealgasvalueof 748.4torr. This disparityin
pressuresamountsto a 0.2Voerror, which is lessthat the other errorsinvolvedin
routine PVT measurements,and is perfectlyadequatefor most chemicalproblems.
108
VACUUMLINEDESIGN
AND OPERATION
G. Exomple:Colibrotion of o Bulb ond PVTMeosuremenlof o

GOS. In this examplewe are interestedin obtaining a known quantity of gas,
using as our gas sourcea storagebulb attachedto the vacuum system.First it is
necessary
to have at hand a calibratedvolume. If a bulb of known volume is not
available,an evacuatedgas bulb of the type shownin Fig. 5.5 is weighed,filled
with water (if it is large) or mercury (if it is very small), and reweighed.The
volume is then determined using the weight differenceand the density of the
liquid at the ambient temperature.
The clean,dry, calibratedbulb is attachedto a vacuumsystem,suchas site A
on the line illustratedin Fig. 5.2, and evacuatedto 10 3 torr or lower. Gas may
be admitted to the calibratedbulb by isolatingthe working manifold from vacuum and openingthe stopcocksand valvesleadingto one of the upper gas storage bulbs, C, while the pressureis monitored by manometerD. When the desired pressureis reached,the valve on the storagebulb is turned off, pressure
and temperaturemeasurementsare made, and then the stopcockon the calibrated bulb is turned off . At this stagewe know the pressure,temperature,and
volume of the gas in the calibrated bulb, which permits the calculationof the
number of molesvia the ideal gas equation.
Beforethe gas in the calibratedbulb can be dispensedit is necessary
to eliminate the gas which fills most of the working manifold and the manometer.This
may be accomplishedby condensingthe excessgas back into the storagebulb
and closingoff that bulb. The gas which is containedin the calibratedbulb attachedat site A can now be condensedinto any of the evacuatedtraps on the line
or into an evacuatedreactionvessel,which might be attachedat site B.
H. Exomple:Colibrofionof o Tropond Meosuremenlof o GosSomple. In contrastto the previousexample,the objectivehere is to measurethe

anlount of an entire gas sample, such as the BF-j recoveredin the trap-to-trap
d i s t i l l a t i o nd i s c u s s eidn S e c t i o n5 . 3 . E . I n t h i s t y p eo f m e a s u r e m e nat m a n o m e t e r
is includedin the calibratedvolume.and it is necessary
to accountfor the change
of volumeas the mercurylevelchangesu'ith changesin pressure.As describedin
C h a p t e r7 a c o n s t a n t - v o l u mgea s b u r e t c a n b e u s e d ,b u t t h i s i s s o m e w h a ct u m bersonre.So the sin.rplerproceduredescribedhere is more frequentlyused.
Supposethat we wish to calibratethe volumeof trap E connectedto manometer D on the vacuum line in Fig. 5.2. A known quantity of a gas, such as CO2,is
condensedinto trap E using the calibratedbulb and the techniquesjustoutlined
in Example 5.3.G. The stopcocksare then turned so that trap E communicates
with the central manometerD but is isolatedfrom the rest of the vacuumsystem.
At this point, the cold trap is removedfrom E, the trap is allowedto come to
room temperature,and the pressureand room temperatureare measured.The
volume of the manometer-trap combination is determined from the known
moles of gas, the pressure,and the temperature,using the ideal gas law. The
processis repeatedwith successively
larger samplesof CO2,and a plot of volume
versuspressureis constructedfrom the data. Sincethe bore of the manometeris
of constant diameter, this plot should be a straight line. It also is possibleto
LOW.IEMPERATURE
BATHS
409
determine the variation of volume with pressureby previouslymeasuringthe

inside diameter of the nlanometertubing. The volume-versus-pressure
plot is
enteredinto the laboratory notebookfor future use.
we can now determinethe total molesof gas in a sampleby condensingthis
gas into trap E, measuringthe pressureon manometerD, measuringthe room
temperature.and using the volume-versus-pressure
plot to determinethe volume of the gas so that the ideal gas equation can be applied.
5.4 row-TEMPERATURE
BATHS
A . L i q u i d N i l r o g e n o n d L i q u i d A i r . L i q u i d n i t r o g e ni s t h e m o s tc o m m o n l y
usedrefrigerantfor the manipulationof condensablematerialson a vacuumsystem becauseit is easyto use. inexpensive,and will not supportcombustion.Furt h e r m o r e ,i t s b o i l i n g p o i n t i s l o w e n o u g h , - 1 9 6 o C ( 7 7 " K ) , t o l o w e rt h e v a p o r
pressureof most materialsbelow l0 I torr, which is necessary
for the quantitative transfer of corrdensiblentaterialson the vacuulll systent.
CAUTION: Skin contact with liquid nitrogen may lead to a frostbite burn.
An occasionaldroplet of nitrogen, such as is encounteredwhen filling a Dewar,
often does not freeze the skin becauseof an insulating film of gaseousnitrogen
which forms immediately. However, the skin is readily frozen if the liquid nitrogen is held on a spot by clothing which is saturatedwith the refrigerant, or by any
other means which leads to extended eontact.
CAUTION: The releaseof large quantities of liquid nitrogen in a confined
spacedisplacesair and can lead to asphyxiation. The areas where liquid nitrogen is dispensedor handled in significant quantities should be well ventilated.
In most large metropolitanareasliquid nitrogenis readilyavailablecommerc i a l l y . I t m a y b e d e l i v e r e da s t h e l i q u i d f r o m t h e D e w a r o n a t r u c k t r a i l e r t o a
large storageDewar on site. More commonly, it is deliveredin medium-size
pressurizedor atmospheric-pressure
Dewarswhich can be movedinto the laboratory (Fig. 5.7). As illustratedin that figure, liquid nitrogenis u'ithdrarvnfronr
the pressurizedDewar by meansof a valveand spigot.much as one drawsu'ater
from a tap. The differencebetweenfilling a vesselu'ith water or a small Dewar
with liquid nitrogen is that the delivery tube and small Dewar must cool to
- 1 9 6 " c b e f o r el i q u i d c a n b e c o l l e c t e dI.n i t i a l l yo n l y c o l d g a sw i l l
i s s u ef r o m t h e
deliverytube. After the liquid starts to flou' it will be rapidly volatilizedin the
small receivingDewar until that Dewar is cooledto the boiling point of nitrogen.
S i m i l a r l y .I i q u i d i s g e n e r a l l yd r a r v nf r o n r m e d i u m - s i z a
e t n r o s p h e r ipcr e s s u r eD e wars by applicationof a small positivepressureof nitrogengas (about l-3 psig).
w h i c h f o r c e st h e l i q u i d o u t o f a d i p - t u b e .A g a i n t h e r e i s a n i n i t i a l c o o l - d o w ' n
period as the dip-tube is initially insertedinto the Deu'ar and the deliverytube
and receivingDewar are cooled.
The Dewarsusedon a vacuum systemare generallyof the r.r'ide-mouthed
variety, with capacitiesranging from r,/rto I L, although larger Dewars are some-
1,10
VACUUMLINEDESIGNANDOPERATION
Lrqurd-level
indicator
D e w a vr a c u u m
Rupturd
ersk
Rupturedisk
N 2g a s +
LiquidN2
(a)
(b)
F i g . 5 . 7 . L i q u i d n i t r o g e n s t o r a g eD e u ' a r s .( a ) A t m o s p h e r i c - p r e s s u rD
e euar. Liquid nitrogenis
d r a w n f r o n t t h e D e u a r b v a p p l y i n ga s m a l l p c t s i t i v e
p r e s s u r eo f n i t r o g e ng a s t o t h e i n l e t o n t h e s l e e v e
o f t h e m e t a l d i p - t u b e , f o r c i n g l i q u i d n i t r o g e no u t t h e d i p - t u b e .( D ) S c h e m a t i cd r a w i n g o f a p r e s s u r i z e d s t o r a g eD e w a r . S p i g o t sa r e g e n e r a l l yp r o v i d e df o r b o t h l i q u i d a n d g a s w i t h d r a w a l .
times used on the main traps of a vacuum system.Becauseof the cooling time
and the lossesof nitrogen involved in drawing liquid nitrogen front a storage
Dewar, it is common to employ a 3-5 L dispensingDewar when the vacuunl
systemis in operation(Fig. 5.8). This dispensingDewar then requiresonly occasionalfilling, and it can be of a narrow-mouth design,which reducesevaporation losses.To further reduce losses,a looselyfitting cap or cork is generally
placed over the mouth of a Dewar containing liquid nitrogen, and a Dewar
which has a U-trap or storagetube protruding from its mouth is generallycovered rvith glass u'ool. This loose cap also greatly reducesthe condensationof
oxygen(bp - l8J'C) in the Dewar. CAUTION: It is very important neverto seal
a Dewar of liquid nitrogen, becausethe insulation on a Dewar is never perfect;
so the liquid is constantly boiling and a sealedDewar will eventually explode.
Liquid air is a potential substitutefor liquid nitrogen but is not commonly
usedbecausethe vaporsr.r'illsupport combustionand there is ordinarily little or
no price advantagein its use.
B. Slush Bofhs. Liquid nitrogenand Dry Ice are convenientand inexpensive
refrigerants.But, as shou'nin the examplesin this chapter,a wider rangeof lo$'temperaturebaths is necessary
for trap-to-trapfractionationof gasesand for the
characterizationof a substanceby vapor pressuremeasurements.A convenient
constant-temperature
slush bath consistsof a nrixtureof a frozen compoundin
e q u i l i b r i u mw i t h i t s l i q u i d . T h e b a t h i s m a d e i n a c l e a nD e w a r n o m o r e t h a n
BATHS
LOW-TEMPERATURE
444
Fig.5,8. Laboratory-size
l i q u i d n i t r o g e nD e w a r s .( o ) C r o s ss e c t i o no f a w i d e - m o u t h e dg l a s sD e w a r .
These range in capacity from l,/r to I L or larger, and are generally used to cool traps on vacuunl
s y s t e m s(.b ) C r o s ss e c t i o no f a m e t a l D e w a r . T o m i n i m i z e l i q u i d n i t r o g e nl o s s e sa, l o o s e - f i t t i n gc a p i s
u s u a l l yp l a c e do v e r t h e m o u t h o f t h e D e w a r .
three-quartersfull with the pure liquid and placed in a good hood. Freshly
drawn liquid nitrogen is slowly added while the liquid is rapidly stirred rvith a
stout stirring rod. There is a tendencyfor a hard frozenring to form around the
sidesof the Dewar at the surfaceof the liquid. The addition of liquid nitrogen
should be slow enough and the stirring adequateto minimize the size of this
frozen ring, which in an extreme casewill preventthe slush bath from fitting
around a trap. Liquid air or liquid nitrogen which has condensedoxygenfronl
the air should not be usedto nlake slushbaths of combustiblecompounds.The
consistency
of the final product should be similar to a thick malt. If the slushis
too thick it cannot be penetratedby a trap, and if it is too thin it will not hold a
constanttemperaturefor long. A list of convenientmaterialsfor slush baths is
g i v e ni n T a b l e 5 . 1 .
Many slushbaths havepoor lastingproperties,which makesit advantageous
to precoolthe trap. This is accomplishedby cooling the trap with liquid nitrogen, removingthe Dewar of liquid nitrogen, and placing the slush balh below
the trap. The stirring rod is then usedto swab a spot on the trap with the slush.
At first the bits of slushwill freezeon the trap, but as the trap warms the frozen
slushwill melt. At this point the slushbath is raisedaround the trap. The liquids
from a slush may be reused.
412
VACUUMLINEDESIGN
AND OPERATION
Ioble 5.4. Compoundsfor CryostoficBolhs

T e n r p ." C "
+ 6.55
+5.53
0.00
Temp, oC"
Conrpound
Cyclohexane
Benzene
Water/'
- 8.6
- r5.2
-22.95
- 30.82
Methyl salicl'late
Benzyl alcohol
Carbon tetrachloride
Bromobenzene
-37.4
-15.2
-5r.5
Anisole
Chlorobenzene
Ethyl nralonate
- 57.5
Chloral
- 63.5
- 83.6
Chloroform'i
Ethyl acetate
- 95.0
- 96.7
-1ll
- 1il.95
- l 18.9
- 126.59
-
IJJ
- r38.3
- r39
- 160.0
Compound
Toluene
Methylenechloride
Trichlorofluoro methane
( F r e o n - lI . b p 2 3 . 8 " C ) '
Carbon disulfide
Ethyl bronride
Methylcyclolrexane
DichlolofIuoromethane
( G e n e t r o n - 2 1b. p 8 . 9 ' C ) '
Ethyl chlotide
C H C l r . 1 9 . 7 %b y u ' e i g h t
C 2 H < B r 4. 4 . 9 %
t r a n s - C 2 H 2 C l123, . 8 %
c 2 H C l . r 2, 1 . 6
isoPentane
" M o s t o f t h e s cv a l u e sa r e t a k e n f r o n r J . T i n r l e r n r a n s . P i l n ' s r c o - c h c n t i cCaol n s t u t t t so l ' P u r e O r p u r t i t

CotnpoutttlsV
, o l s . I a n d 2 , E l s e v i e r ,A n t s t e r d a n r .1 9 5 0a n d 1 9 6 - 5 .
i ' P u r ec r u s h c d i c c i n c o n t a c t u i t h d i s t i l l c d u a t e r .
' T h e s ef l u o r o c a r b o n sh a v e l o u t o x i c i t ya n d a r e n o n f l a n r m a b l e T
. h e l i q L r i dn r a yb e s t o r e df o r r e u s ei n
a s t o p p e r e dD e u a r i n a f r e e z e r .
' i R e a g e n t - g r a d ce h l o r o f o r m c o n t a i n s a s i g n i f i c a n t q u a n t i t y o f a l c o h o l , u ' h i c h l o w e r s t h e n r e l t i n g
pornt.
C. Dry lCe BOlhS. In contrastto the fixed temperatureof slushbaths, a Dry

Ice bath is sonrewhatless reliable becausethe equilibriunl temperature is a
strongfunction of the partial pressureof CO2abovethe bath. For example,one
test in which Dry Ice was freshly powderedin air had a temperature8oC below
the normal sublimationtemperatureof - 78.5"C. In anothertest, l0-h standing
was requiredfor a Dewar of Dry Ice to attain - 78.5oC.1However,a small electric heaterburied in the Dry Ice producedenoughCO2to expelthe air and attain
the normal sublimationtemperaturein a matter of minutes.The temperatureof
an equilibratedDry Ice bath at any barometricpressuremay be found using the
expressionfor sublimation pressure:
rogP:e.81137
itk
' R . B . S c o t t , i n T e m p e r u t u r e , I t s M e a s u r e n e n t u n d C o n t r o l , V o l . l , R e i n h o l d ,N e w Y o r k ; 1 9 4 1 ,p .
212.
MANIPULATION
OF NONCONDENSABLE
GASES
413
whereP is in torr and t in degreesCelsius.GenerallyDry Ice is used in a bath

containingacetoneor anotherlow-meltingliquid to aid thermal conductionand
promote equilibration.
pRopERTy
AsA cHARAcTERrsnc
5,5 vApoRpREssuRE
Vapor pressures,which are readilydeterminedon a vacuum line, providea convenientand sensitivemeansof identifyinga volatilecompoundand/ or checking
its purity. The sampleis condensedat liquid nitrogentemperatureand all of the
residualgasesare pumped out of the system.If the compoundhas beenexposed
to the atmosphereimmediatelyprior to the measurement,it shouldbe degassed
by severalfreeze-pump-thawcycles.
The trap or tube attached to the vacuum systemcontaining this sample is
maintained at the desiredlow temperatureby means of a slush bath, and the
pressureis read on a mercury manometer.The samplemust be largeenoughso
that liquid is presentwhile the measurementis being performed.The presence
of an impurity of different volatility can be detectedby the disparitybetweenthe
known vapor pressureand the observedvalue.Another effectivemeansof checking the purity is to removeby condensationa significantportion of the sample
into a trap for temporarystorageand then redeterminethe vapor pressure.If the
secondvapor pressureis different from the first, impurities are presentin the
sample.Vapor pressuredata for somecommon compoundsat convenientslush
bath temperaturesare given in Appendix V.
5.6 MANrpuLATroN
oF NoNcoNDENsABLE
GAsEs
Liquid nitrogen is the coldestinexpensiverefrigerantavailable.The two lowertemperaturerefrigerants,liquid hydrogenand liquid helium, are expensive,difficult to handle, and the former is dangerousbecauseof the productionof explosivevapor. Thus gasessuch as Hz, Nz, 02, CO, and CHa,which havehigh vapor
pressuresat liquid nitrogen temperature, - 196'C, require specialmethodsfor
their transfer. The two most commonly usedtechniquesfor these"permanent"
gasesare a reciprocatingmercury pump (Toepler pump) and low-temperature
adsorptionon high-surface-areasolids. The Toepler pump is very predictable
and, when it is operating properly, quite trustworthy. However,it is expensive
and complicated,and if mishandledit can fail spectacularly.Low-temperature
a d s o r p t i o ni s c h e a p , v e r s a t i l e ,a n d e a s yt o i m p l e m e n t , b u t r e q u i r e sc a r e f u l
checkingto avoid erroneousresults.
A. Ioepler Pump. The principlesof operationof a Toepler pump are outlined in Fig. 5.9, where it will be noted that a systemof internal check valves
permits gas from the vacuum systemto enter the upper chamber, and subsequentlyto be compressedand expelledinto a gasburet. The systemmay be man-
414
VACUUM LINEDESIGNAND OPERATION
To
vocuum
lrne
F i g . 5 . 9 . T o e p l e rp u m p a n d g a s b u r e t . I n t h i s i n s t a l l a t i o na " c o n s t a n t - v o l u m e "m a n o m e t e ri s u s e d
f o r m e a s u r i n gt h e p r e s s u r e .S t o p c o c kB a l l o w st h e a t t a c h m e n to f a s a m p l i n gb u l b o r a l a r g ee x p a n s i o n b u l b f o r u s ew i t h l a r g ev o l u n r e so f g a s . S t o p c o c kA i s u s e df o r i n i t i a l e v a c u a t i o no f t h e c a l i b r a t e d
v o l u n r ea n d s a m p l eb u l b s . l t i s c l o s e dd u r i n g t h e o p e r a t i o no f t h e p u m p . W h e n a g a s i s t o b e m e a s u r e d ,t h e n r e r c u r yl e v e l si n t h e r i g h t a r m o f t h e T o e p l e rp u m p a n d i n t h e l e f t a r m o f t h e m a n o m e t e r
a r e a d j u s t e dt o l e v e l s( C ) f o r w h i c h t h e g a s v o l u m e h a s b e e n c a l i b r a t e d .A n e x c e l l e n tv e r s i o no f t h i s
p u m p i s m a n u f a c t u r e db y t h e R o d d e r I n s t r u m e n t C o . , L o s A l t o s , C a l i f .
ual, but most often it is controlledby meansof contactswhich sensethe mercury

level. These are connectedto a relay and solenoidvalve which control the air
pressurein the bottom chamber. On the inlet cycle, the gas being pumped is
distributed betweenthe vacuum systemand the upper chamber of the pump.
Thus the fraction of gas removedper cycle is equal to the volume of the upper
Toepler pump chamber V, divided by the volume of the vacuum systemV, plus
the volume of the upper chamber.The fraction of gas remaining in the vacuum
line after /r cyclesis
r: [r -
-l
v, ),
V,,+ V,]
from which it is easyto estimatethe number of cyclesnecessary

to collectthe gas
"quantitatively." The completeness
of gas collectionalso can be judged by failure of gas to bubble through the outlet valveon the compressioncycle,or by the
lack of pressurechangefor the collectedgas over severalcollectioncycles.
The primary modesof failure of this type of pump are leakagepast the internal check valvesor sonle mishap which leadsto a sudden rush of air into the
upper or lower chamber. The first problem impairs the pumping action and is
MANIPULATION
OF NONCONDENSABLE
GASES
445
most commonly causedby poor check valve design or dirt on the check valves.
The inrush of air from operator error or a malfunction results in a surge of mercury which may break the apparatus and create a shower of mercury.
B. Low-Iempetofule
Adsorplion.
This method provides a convenient
methodof transferringand separatingsomepermanentgases.The utility of lowtemperaturegas adsorptionwas recognizedby Dewar in 1875,but the applications describedhere are in part basedon the selectivityof certain solidswhich
were not recognized until fairly recently.2Since the adsorption of one gas can
affect that of others, materialswhich are condensableat - 196'C are first removed by the conventionalcondensationproceduresdiscussedearlier in this
gasesare then adsorbedon a suitablesolidsurface
chapter.The noncondensable
at low temperature.Molecular sieve4A,at - l96oC will stronglyadsorbHu, Oz,
N2, CO, CHa, and similar "permanent gases." Silica gel at this sametemperature adsorbshydrogenonly lightly and the othersstrongly.Thus it is possibleto
separatehydrogen quantitatively from the other permanent gasesby an adsorption trap of silicagel followedby anotherof molecularsieves;or. in placeof the
molecularsieves,one may use a Toepler pump to collectthe hydrogen.It is important to cool the adsorbentsbefore they are exposedto the gas mixture, because cooling silica gel in contact with hydrogen from room temperature to
-196oC leadsto the retentionof a small amount of the hydrogenin the silica
gel. Heat flow is not efficient between the particles, so it is necessaryto wait
patientlyfor the trap to cometo the desiredtemperature.In this connection,it is
desirableto avoid traps with very large cross sections,which are especiallyslow
to come to temperature.
This simple techniquecan be applied to a varietyof transferoperations,and
it often servesto replacethe more cumbersomeand expensiveToepler pump.
The solid adsorbentshould be sievedto eliminatefinesor large particles.Particlesof about 50 mesh(0.3-mm diameter)are ideal, and theseshouldbe contained
in a suitableU-trap or other trap designwith a small plug of glasswool on the
inlet and outlet to preventthe adsorbentparticlesfrom being sweptinto the vacuum line (Fig. 5.10). Before use, the freshly packed trap is heated to about
300oCwhile being evacuatedto a high vacuum. The initial evacuationand heating must be done slowlyto avoid sweepingthe adsorbentout of the trap by the
copious quantities of adsorbed gasesand water vapor which are evolved.
Low-temperatureadsorption is also useful for the quantitative transfer of
gasesinto specialapparatus.For example,a small quantity of activatedmolecular sievein a freeze-outtip on an infrared cell may be usedfor the identification
of methane;or, when placed in a freeze-outtip on a manometerand calibrated
volume,the molecularsievespermit the measurementof the quantity of noncondensablegas.
2The principfes of selectiveadsorption by zeolitesare discussedin D. W. Breck, Zeolite

lgloleculur
S r e v e sW
, iley, New York; 1974.
11
VACUUMLINEDESIGNANDOPERATION
e d s o r p t i o n .( o ) S o l i d a d s o r b e n t l
F i g . 5 . 1 0 . 1 ' r a p d e s i g nf o r g a s m a n i p u l a t i o nb y l o u ' - t e m p e r a t u r a
( b ) T e f l o n - g l a s sv a l v e( 4 m m ) : ( c ) g l a s sw o o l p l u g s ; ( d ) O - r i n g c o n n e c t o r s( 9 n r m ) ; ( e ) g r o u n d - g l a s s
s t o p c o c ko r 1 ' e f l o n - g l a svsa l v eo n h i g h - v a c u u ml i n e ; ( D t o h i g h v a c u u m m a n i f o l d . T h e t r a p m a v b e
t o i n t o n a h i g h - v a c u u ml i n e t o a n o t h e ra t t a c h m e n tp o i n t w i t h o u t e x p o s m o v e df r o n r o n e a t t a c h n r e n p
i n g t h e a d s o r b e n t( a n d a n y g a s s a m p l ec o l l e c t e di n t h e t r a p ) t o a t n r o s p h e r i cg a s e s .
5,7 sAFETY
As with most scientificapparatus,improper handling of the vacuum line can be
hazardous.Appendix I presentsa detailed listing of laboratory hazards, and
Section7.1.E describesthe correct handling of mercury. This brief sectionu'ill
serveas a reminderof potentialsafetyproblemswhich are encounteredin the use
of a vacuum system.Sincethere alwaysis the possibilityof explosionor implosion of pressurizedor evacuatedglassware,eyeprotectionshould be worn at all
times around a vacuum line. Other hazards include; explosionof glassware
which is inadvertentlypressurizedby the uncontrolled\\'arming of condensed
gasesin a small volume;implosionof evacuatedstoragebulbs and Dewars(these
items should be surroundedwith tape or a specialplasticcoatingto contain flying glass);exposureto mercury, which is a cumulativepoison (spills should be
promptly and thoroughly cleanedup); asphyxiationby nitrogen gas (liquid ni-
SAFEIY
4 -7
trogen should not be handled in a small, poorly ventilatedroom); and frostbite

from the contact of skin with low-temperaturerefrigerants.
CAUTION: Since electricity is used to run equipment such as vacuum
pumps, gauges,and Tesla coils, proper care must be exercisedwhen using and
maintaining this equipment. Individual items should be grounded through a
three-prong plug, and vacuum racks must be properly grounded, for example,
by means of a copper wire between the vacuum rack and a water pipe.
REFERENCES
GENERAI
Angelici,R.J.,1977,SynthesisundTechniqueinlnorgunicChentistn-,2nded.,Saunders,Philadelp h i a . T h i s b o o k p r o v i d e sa u s e f u le x e r c i s ei n v a c u u m l i n e p r a c t i c ef o r t h e n e u ' c o n r ct.or t h e f i e l d .
n h e r t t i e , 3 r de d . . E n k e V e r l a g ,
B r a u e r . G . . E d . , 1 9 8 1 .H u t t d h u t h t l e r P r e p u r u t i v e nA n o r g c t r t i s c h eC
S t u t t g a r t . T h e f i r s t c h a p t e l i n c l u d e ss o m e i n f o r n r a t i o no n v a c u u n rl i n e t e c h n i q u e .a n d v a r i o u s
s \ ' n t h e s etsh r o u g b r ) u t h i s l h r c r ' - v o l u n r es e t i l l u s t r a t et h e a p p l i c a t i o no f r a c u u r ) 1s Y s t e n rtso i n o r '
. h e E n g l i s he d i t i o n o f t h e s e c o n dc d i t i o n o f t h i s b o o k i s o f s o m eu s e ,b u t i t
ganicpreparationsT
is not up-to-date.
J o l l y , W . L . , 1 9 7 0 , T h e S y n t h e s i su n d C h u r u c t e r i z u t i o nt t f I n o r g a t i c C o t n p o u n d s .P r e n t i c e - H a l l ,
E n g l e * o o d C l i f f s , N . J . A n e x c e l l e n t ,c o n c i s ei n t r o d u c t i o nt o c h e m i c a lv a c u u m l i n e t e c h n i q u e .
u i t h s o m ee x p e r i m e n t sw h i c h r v i l l p r o v i d eg o o d e x e r c i s e tso t h e n e w c o n r e tr o c h e m i c a lv a c u u n l
Ii n e s .
M e l v i f f e . H . . a n d B . G . G o u e n l o c k , 1 9 6 4 .E x p e r i n r e u t u l v l e t h o d si n G u s R e a c t i o t r sM
, acnrillan,
l e t h o d sf o r g a s - p h a s e
L o n d o n . P r i m a r i l y d e v o t e dt o e x p e r i m e n t a m
k i n e t i c s t u d i e s ,b u t t h e p r i n c i p l e sa n d a p p a r a t u sa r e o f i n t e r e s ti n g e n e r a lc h e m i c a lv a c u u n l l i n e t e c h n o l o g v .
M o o r e , J . H . . C . C . D a v i s , a n d M . A . C o p l a n , 1 9 8 3 ,B u i l d i n g S c i e n t i l i cA p p a r u t u s , A d d i s o n - W e s l e y , R e a d i n g ,M a s s . , A g o o d , p h y s i c a l l yo r i e n t e dr e f e r e n c eo n l a b o r a t o r yt e c h n i q u e .C h a p t e r s3
a n d 4 c o v e rg l a s s b l o w i n ga n d v a c u u m a p p a r a t u s ,r e s p e c t i v e l ) .
O ' H a n fo n . J . 4 . , 1 9 8 0 ,A U s e r ' sG u i d e t o V a t u t r t r rT e c h n o l o g l ' W
. i l e y . N e u Y o r k . A p r a c t i c a lg u i d e
t o t h e g e n e r a la r e a o f v a c u u r nt e c h n o l o g ya n d r e l a t e d p r i m a r i l y t o s e m i c o n d u c t o ra n d o p t i c s
technology.
S a n d e r s o n ,R . T . , 1 9 4 8 , V u c u u r r tl g l u n i p u l a t i < uotJ V o l u t i l eC < t t r 1 t < t u r t dWs i,l e y . N e u Y o r k . A g o o d
b u t s o n r e r v h aot u l - o f - d a t ed i s c u s s i o no f v a c u u m l i n e t e c h n i q u e s .
S t o c k . 4 . . 1 9 6 4 ,H y d r i d e s o . l ' B o r o nu n d S i l i c o n , C o r n e l l U n i v e r s i t yP r e s s .I t h a c a . N . Y . l n c o n n e c t i o n u ' i t h t h i s p r e s e n t a t i o no f h i s p i o n e e r i n gr e s e a r c ho n b o r o n h v d r i d e s ,S t o c k d e s c r i b e st h e
c l r e m i c a lv a c u u n l l i n e t e c h n i o u e s* h i c h h e i n v e n t e d .
Pumpsfor Rough
ond HighVocuum
This chapter is primarily devotedto pumps for high vacuum-operation(10-310-s torr), which is the vacuum range of greatestinterestin chemicalvacuum
lines.In addition, rough-vacuumsystems(760-0.1torr) are discussedin connection with their use in manipulating mercury-filledapparatus,such as Toepler
pumps and Mcleod gauges.
6,4 RoueH-vAcuuM
sYsTEMs
A. Applicofions for Rough Vocuum.
In the descriptionof the operation
of a Toepler pump given in Chapter 5, mercury was transferredfrom a lower
reservoirto an upper pumping chamberby the useof pressuredifferentials.The
upper chambercommunicateswith the high-vacuumline and the lowerreservoir
with a rough-vacuumsystemor the atmosphere.Mercury is pulled from the upper chamber into the lower reservoirby meansof a rough vacuum appliedto the
lower reservoir,and on the other stroke, mercury is forced into the upper chamber by admitting air to the lower reservoir.There are other typesof equipment
where mercury is added to or withdrawn from the vacuum systemby similar
means,including the constant-volume
gas buret (Chapter7) and varioustensimeters(Chapter 9).
B . D e s i g n o f E q u i p m e n l . S i n c e t h e r o u g h - v a c u u ms y s t e mm a y h a v e a
practical vacuum limit of I torr to severaltens of torr, equipnlent must be designed and filled with mercury to take into account the disparity in pressures
betweenthe high-vacuumside and the mercury reservoir.The reservoirmust be
,t.lI
HIGH-VACUUM
PUMPING
SYSIEMS
119
placed low enough so that the apparatus can function properly with a differential in the mercury heights on the high-vacuumand reservoirsides.It is also
important to bear this differentialin mind when filling apparatuswith mercury.
C. Rough-Vocuum Sysfem. A relativelyinexpensivesingle-stagepump
(seeSection6.2) will servewell for most rough-vacuumapplications.It is important to protect this pump, by means of an uncooledtrap of appropriate size,
from the possibleinrush of liquid mercurywhich may occur during an accident.
To avoid the buildup of toxic mercuryfumes in the work area, the exhaustfront
the pump is conducted to a hood. The rough-vacuummanifold may be constructedfrom glass,copper,or polyethylenetubing. The latter, more robust materials are often preferredbecausethe rough-vacuummanifold often is placed
belowthe main vacuum systemand is thus vulnerableto itemsthat are dropped.
A typical rough-vacuumsystemis illustratedin Fig. 6.1.
6,2 HGH-vAcuuM
PUMPTNG
sYsTEMs
A. Rofory Oil-Seoled Pump Designs. All of the commercialoil-sealed
pumpsarebasedon a rotorinsidea cylindrical
mechanical
stator.Theseindivid-
R u b b e rv a c u u m t u b i n g
Solenoid
valve
To Toepler
pump
Exhaust
to
hood
F i g . 6 . 1 . R o u g h - v a c u u ms y s t e m .F r e q u e n t l yu s e d i t e n r ss u c h a s t h e T o e p l e r p u m p a n d c o n s t a n t v o l u m e m a n o m e t e ra r e o f t e n c o n n e c t e dp e r m a n e n t l yi n t o t h e r o u g h - v a c u u n rs y s t e m .A l s o , o n e o r
t w o o u t l e t s ,w i t h v a c u u m t u b i n g a t t a c h e d ,a r e i n c l u d e d f o r g e n e r a lu s e , T h e m a n i f o l d g e n e r a l l yi s
c o n s t r u c t e df r o m r i g i d p l a s t i co r m e t a l t u b i n g .
120
PUMPSFORROUGHAND HIGHVACUUM
ual stageswill be discussedbelow. Of greatestimportanceis not the designof

thesestages,but rather whether the pump has a singlestageor two stagesconnected in series.A well-constructedsingle-stagepump is capableof attaining
about 0.01 torr, but a more practical limit is on the order of I torr, This type of
pump is useful in rough-vacuum systems.Two-stage pumps generally are
quoted to attain between10 3 and 10-a torr, althoughpumping speedsare slow
near thesepressurelimits. Two-stagepumps are generallypreferredfor backing
diffusion pumps in high-vacuumsystems.
There are three common designsfor the internal workingsof rotary oil pumps
and theseare illustrated in Fig. 6.2. All employ a rotor which revolvesinside a
cylindrical stator; a sealbetweenthe fixed and moving parts is maintainedby a
thin film of oil. Of the three designs,the internal-vanepump is by far the most
common in the laboratory;it is generallyusedto back a diffusion pump in highvacuum systems.Internal-vane pumps generally make relatively little noise
when operating at high vacuum. The rugged and easilyrepairedexternal-vane
pump is mainly availablein small pump sizesand finds its greatestuse in rough
pumps. These pumps appear to stand up to a hostileenvironmentbetter than
the internal-vanepumps, but they have the disadvantageof producing a loud
clanking sound when operating at their vacuum limit. The rotary-plunger
pumps are used in high-vacuum applicationsand are fairly common in large
vacuum systems.Very good pumps are availablein all three designs.
For many yearsthe connectionbetweenthe pump and motor was made with a
V-belt, but "direct-drive" pumps are becomingcommon. The latter are more
compact, smootherrunning, and perhaps a bit quieter and more reliable. On
the other hand, the semiflexiblecouplerbetweenthe motor and pump shaft can
F i g . 6 . 2 . I n t e r n a l - v a n e ,e x t e r n a l - v a n e a, n d p l u n g e r - t y p er o t a r y v a c u u m p u m p s . I t w i l l b e n o t e d
t h a t t h e i n t e r n a l - v a n ep u m p i n v o l v e sa r o t o r c o n c e n t r i cw i t h t h e d r i v e s h a f t , b u t w h i c h i s o f f - c e n t e r
with respect to the stator. By contrast, the external-vane and rotary-plunger pumps have a rotor
which is asymmetric with respect to the shaft: however, the shaft is centered in the stator. All three
involve closetolerances,so the high-vacuum performance is impaired by particles of dirt or corrosive
gases.Some pumps are partially constructed from soft die-cast metal, which is eroded by mercury.
Specialcorrosion-resistantpumps and inert flourinated pumps are used in the semiconductorindustrv.
HIGH.VACUUM
PUMPINGSYSTEMS
124
wear out, and when this does happen, the coupler is more difficult to replace
than a belt.
Many vacuum pumps are suppliedwith a gas ballast valvewhich is designed
to preventthe condensationof moistureand similar condensablematerials.This
valve bleedsa small amount of air into the pump and as a result the ultimate
vacuum and pumping speedof the pump suffer.There is no occasionto usethis
featureon a pump on a typical chemicalhigh-vacuumline, and it rarely, if ever,
is used in typical laboratory rough-pumpingsystems.
B. Troubleshooling
ond Mounfingo MechonicolPump. It will be
noted in Fig. 6.2 that gasfrom a rotary pump is exhaustedthrough an immersed
flapper valve.For this valveto make a good sealit must be coveredwith oil. One
common cause of the loss of ultimate vacuum performancein these types of
pumps is a low oil level, and this should be the first item to be checkedwhen a
pump is not performing well. A telltale sign of low oil is a changein the soundof
the pump.
With a little experiencethe experimentalistbecomesused to the sound of a
properly operating pump, and any deviationin this sound is a sign of trouble.
The distinctivesound when there is a small leak in the system,or a low oil level
(the soundsare often similar), or the slapping sound characteristicof a worn
belt, is a tip-off that remedialaction is necessary
beforethe problem getsworse.
A vacuum pump should be scrupulouslyprotectedfrom corrosivevaporsand
materialswhich will be absorbedin the pump oil or condensein the pump. For
most laboratoryoperationsa low-temperaturetrap is employedfor this purpose,
and in the caseof fluorine handling systemsa soda-limetrap is usedto neutralize
the corrosivegases.Despite these precautions,the pump oil does eventually
break down and becomecontaminated.Regular oil changesshould be scheduled for a pump at about yearly intervalsfor a well-protectedpump and more
often for pumps which are not well protected.
pumps are now widely used in the semiconductor
Specialcorrosion-resistant
industry. Often theseare equippedwith pump oil purifiers and are neverturned
off when contaminantsare present.Thesepumps are expensiveand under harsh
conditionsthey break down much more often than a well-protectedconventional
pump.
As mentioned in Section5.1.B, the transmissionof vibration from the mechanicalpump to a vacuum rack decreases
the accuracyof manometerreadings.
To minimize this problem, it is generallybest to mount the pump on the floor
below a vacuum rack and to connect the pump to the systemwith a short length
of heavy-walledrubber tubing, Tygon tubing, or flexible metal tubing.
C. Diffusion Pump Design ond Operolion.
The pumping speedof a
two-stagemechanicalpump generallydrops veryrapidly below 10 I torr. By contrast, Fig. 6.3 showsthat a typical diffusion pump has good pumping speedbelow this pressure.Therefore,a tandem arrangementof a diffusion pump with a
422
100
10
1
o
-i
Mechonrcol
0.1
1O-7
10-6
to-s
1O-4
1O-3
i)-z
1O-r
B torr
F i g . 6 . 3 . C o m p a r i s o no f t h e p u m p i n g s p e e do f a t y p i c a l t w o - s t a g em e c h a n i c a p
l ump with a singles t a g ed i f f u s i o n p u m p .
rotary fore pump is commonlyemployedfor the evacuationof high-vacuumsystems.

The designof a diffusion pump is illustratedin Fig. 6.4. Thesepumps operate
by boiling mercury or a low-vapor-pressure
oil and conductingthe vaporsout of
a nozzle.This nearly unidirectionalstreamof vapor moleculescollideswith gas
moleculeswhich have diffused into the pump from the systembeing evacuated.
As a result of thesecollisions,momentum is imparted to the gasmoleculesin the
direction of pumping. The vapor is then condensedand returned to the boiler,
and unwantedeffluent gas is removedby the mechanicalfore pump. Frequently
the diffusion pump is designedwith two or more nozzlesin seriesto allow operation of the pump at a high fore pressurewithout sacrificingultimate vacuum.An
oil pump is fasterthan a mercurypump of comparablesizebecauseof the higher
collisionalcross sectionof the large oil moleculesand the higher velocitiesof
thesehigher boiling materials.An oil diffusion pump requiresperiodicrepracement of the fluid, whereasa mercury pump can operate many years without
attention. Among the commonly used fluids for diffusion pumps presentedin
Table 6.1, the siliconeoils are the most popular in chemicalsystems.Becauseof
increasedawarenessof the health hazardsof mercury, oil diffusion pumps have
becomethe standard in most laboratories.when a mercury diffusion pump is
employed,it is highly advisableto include a cold trap (-78'c is satisfactory)
betweenthe diffusion pump and the fore pump to reducethe amount of mercury
vapor reachingthe atmosphere.
The rate of boiling of the pumping fluid is determinedby trial and error. The
useof too low a rate of boiling will reduceboth the pumping speedand the limiting fore pressure.In general,the heaterinput should be high enoughso that the
123
PUMPINGSYSTEMS
HIGH.VACUUM
+
tl
C
F i g . 6 . 4 . C r o s s - s e c t i oonf a m e t a l d i f f u s i o np u m p . T h e u p p e r s t a g ei n t h i s p u n r p h a s a w i d e a n n u l a r
o p e n i n g ( A ) w h i c h p r o v i d e sa g o o d u l t i m a t e v a c u u n l . T h e l o u e r s t a g eh a s a s n l a l l a n n u l a r o p e n i n g
( A ' ) s o t h e p u n t p u i l l o p e r a t ea g a i n s ta h i g h f o r e p t e s s u r e (. B ) H i g h - v a c u u n rc o n n e c t i o nt o t h e l o u t e m p e r a t u r et r a p a n d v a c u u n rl i n e . ( C ) C o n n e c t i o nt o r o t a r y o i l - s e a l e dp u m p . T h i s p u m p i s c o o l e d
b y m e a n s o f w a t e r t u b e s ( D ) . A i r - c o o l e dv e r s i o n sh a v e f i n s i n p l a c e o f t h e s et u b e s a n d a f a n i s i n s t a l l e dt o b l o w a i r o v e r t h e s ef i n s . ( E ) E l e c t r i c a l l vh e a t e do i l r e s e r v o i r .
vapor is condensingbelowthe nozzleat a brisk rate. Ifthe boiling rate is too fast,
the pumping efficiencygoes down becauseof backstreamingof the pumping
vapors. Bumping, or eruptive boiling of the fluid, has an adverseeffect on the
pumping action and is to be avoided.The sourceof bumping is an inversionin
the vapor pressureof the fluid, owing to cooling of the surfaceof the fluid by
evaporationwhile heat is appliedfrom below.Becauseof its low thermal conductivity and high heat of vaporization,oil is much more susceptibleto bumping
than is mercury. Heaterswhich protrude into the pumping fluid are generally
most effectivein reducing bumping.
124
Toble6.'l. Comporisonof Fluidsfor DiffusionPumps

Type
Mercury
Apiezon A
Apiezon B
Apiezon C
Silicone702
Silicone704
Silicone705
Octoil
Octoil S
Metal
Hydrocarbon
Hydrocarbon
Hydrocarbon
Silicone
Silicone
Silicone
Ester
Ester
Vaporpressure
at 25"C(mm)
2x103
2 x 10-s
4 x 10-?
l0E
l0 6 - l0-lr
l0-e - l0 r0
2xl0r
2 x lO-s
Resistanceto
Air Oxidation
Best
Poor
Poor
Poor
Better
Better
Better
Fair
Fair
D . M o t c h i n g l h e F o t e P u m p o n d D i f f u s i o n P u m p . A d i f f u s i o np u m p
has a critical pressureabovewhich it doesnot operate.Therefore,the fore pump
must be capableof achievingthis limiting pressurein a reasonabletime period.
Furthermore, the fore pump should be capableof removing at least as many
molesof gasper unit time as the diffusion pump delivers.The throughput (speed
in volume per unit time X pressure)is proportional to the speedon a molar
basis;so a match of the pumps is obtainedwhen S1P1: SzPz.In this equation,
52 is the speedof the diffusion pump at the appropriatehigh vacuumP2,P1is the
limiting fore pressurefor the diffusion pump, and Sqis the pumping speedof the
mechanicalpump at this pressure.Generally,the pump manufacturersprovide
the information necessaryfor approximatethroughput calculations.
E. COld Trops. In addition to the fore pump and the diffusion punlp, a third
activepumping elementin most chemicalvacuum systemsis a liquid nitrogencooledtrap situatedbetweenthe main high-vacuummanifold and the diffusion
p u m p . T h i s t r a p p u m p s t h e s y s t e mb y r e m o v i n gc o n d e n s a b l e sa.n d i t s e r v e st o
protectthe diffusion and mechanicalpumps from corrosivevapors.It is undesirable to accumulatelarge quantitiesof condensablesin this trap and it is poor
practiceto usethe trap to discardunwantedcondensables
in the vacuum system.
(These unwanted materials should be condensedinto a tube attached to the
working manifold and renoved to a hood.) Even a slight buildup of condensableseventuallycausessome lossof vacuum. As the liquid nitrogen levelfalls.
the ntaterialcondensednear the top of the trap will volatilize;while most of it is
immediatelyrecondensedin the lou'er portion of the trap, a small amount diff u s e sb a c k i n t o t h e v a c u u ml i n e . T h u s . w h e n t h e v a c u u mi s c r i t i c a l .t h e D e w a r
shouldbe kept full of liquid nitrogen. Specialtrap designspreventthis problem
by condensingthe vapors at the bottom of the liquid nitrogen reservoirrather
125
HIGH.VACUUM
PUMPINGSYSTEMS
than the top.' However,thesetraps are cumbersomeand difficult to clean. so

they are not commonly used on chemicalvacuum lines.
A trap designwhich allowsperiodic cleaningis highly desirablefor chemical
vacuum systems.Two such designsare illustratedin Fig. 6.5, wheresomeof the
desirablefeaturesare described.
To avoid oxidation of
F. Alrongemenf of the Pumping Componenls.
the pumping fluid, the hot diffusion pump should not be exposedto large quantities of air. Therefore,an arrangementof stopcocksis usedto bypassthe diffusion pump when large arnountsof air are being pumped. This bypassfeature
also makes it unnecessary
to wait for the diffusion pump to cool down when the
main trap must be removedfor cleaningor when the vacuumsystemis turned off
( o)
(Dl
Fig.6.5, Main traps. (a) This trap is long enoughto extendto the bottonrof a l-L De*ar and
s u f f i c i e n t l ys m a l l i n d i a m e t e r t o a v o i d e x c e s s i v d
e i s p l a c e m e n ot f l i q u i d n i t r o g e n .T h e s ef e a t u r e sa l l o w t h e t r a p t o r e m a i n p a r t i a l l v i m m e r s e di n l i q u i d n i l r o g e na f t e r s t a n d i n go v e r n i g h t .T h e a r r a n g e m e n t o f i n l e t a n d o u t l e t s h o u ' nh e r em i n i m i z e sc l o g g i n go f t h e t r a p b e c a u s cm o s t o f t h e c o n d e n s a t ei s
d e p o s i t e do n ( h e l a r g eo u t e r t u b e r a t h e r t h a n t h e s n r a l l e ri n n e r t u b e . ( ) A U - t r a p i s a d v a n t a g e o uisf
t h e r e i s a l i k e l i h o o do f c o n d e n s i n gs i g n i f i c a n tq u a n t i t i e so f p y r o p h o r i co r h i g h l y t o x i c c o m p o u n d s ,
b e c a u s ea f i n i t e a m o u n t o f m a t e r i a l i s a l w a y sc o n d e n s e do n t h e c e n t e rt u b e o f t r a p ( a ) . T o r e m o v ea
t r a p s u c h a s ( b ) f r o m t h e l i n e , o n e s h o u l d f i l l i t w i t h n i t r o g e na n d q u i c k l y t a k e i t t o a h o o d , w h e r ea
s l o $ ' s t r e a n or f n i t r o g e nn r a yb e p a s s e dt h r o u g h i t t o n r o d e r a t et h e r e a c t i o nu ' h i c hw i l l o c c u rw h e n t h e
c o n t e n t so f t h e t r a p w a r m u p a n d v o l a t i l i z e .B a l l j o i n t s f a c i l i t a t et h e r e m o v a lo f a U - t r a p .
r A . J o r d a n , , /S. c i . l n s t r . , 3 9 . 4 4 7 ( 1 9 6 2 ) ; H . W . J o n e s , R e v . . l c i . / r s r r . . 3 5 , 1 2 4 0 ( 1 9 6 4 ) . T r a p s o f t h i s
t y p e . h a v i n g i n t e r n a l l i q u i d n i t r o g e nr e s e r v o i r sa. r e a v a i l a b l ef r o m E c k & K r e b s S c i e n t i f i cL a b o r a t o r y G l a s sA p p a r a t u sl n c . . 2 7 - 0 94 0 t h A v e . . L o n g I s l a n dC i t y , N Y l l 1 0 l .
126
and the fore pump is vented to the atmosphere.This bypassmay be accomplished with one two-way stopcock in conjunction with a conventionaloff-on
stopcock.as illustrated in Fig.6.6. Also, a specialthree-waystopcockis available which combinesthesetwo functions.2To maintain good pumping speedin
the system,large-diametertubing and large stopcocksshould be usedon items
leadinginto th; diffusion pump. Items connectingthe diffusionpump outlet and
the mechanicalfore pump can be of smaller diameter becausethe pressureis
higher in this section.
G. Exomple: Initiol Pump'Down ond Venling the Pumping

SySfem.
Initial evacuationof the system is accomplishedby attaching all
F i g . 6 . 6 . P u m p s , t r a p s , a n d b y p a s s .( A ) M e c h a n i c a lf o r e p u m p l ( B ) s h o r t l e n g t h o f v a c u u m t u b r h e n f o r e p u n r p i s t u r n e d o f f ; ( D ) d i f f u s i o np u m p ; ( E ) c o l d t r a p
i n ! ; ( C ) s t o p c o c kf o r v e n t i n gs y s t e n w
(G)
a t - l g 6 o C ; ( F ) . ( H ) s t o p c o c kw h i c h a l l o u , t h e d i f f u s i o n p u m p t o b e i s o l a t e da n d b y p a s s e d ;
p
u
m
p
s
'
a
n
d
f
r
o
m
t
h
e
t
r
a
p
n
r
a
n
i
f
o
l
d
n
l
a
i
n
o
f
t
h
e
i
s
o
l
a
t
i
o
n
s t o p c o c kw h i c h a l l o w s
2 l t e m 8 5 5 5 f r o m E c k & K r e b s ( s e ef o o t n o t e l ) .
HIEH-VACUUM
PUMPINGSYSTEMS
127
traps, starting the fore pump, and evacuatingthe vacuum line. At this point a
Dewarcontainingliquid nitrogenis slowlyraisedaround the main trap (E in Fig.
6.6), the stopcocksare turned to route the gasesfrom the main trap (E) through
the diffusion pump (D), and on to the fore pump. The diffusion pump is turned
on and the systemallowedto pump down.
To shut the systemoff, stopcocks(F) and (H) are turned to isolatethe diffusion pump and to establishstraight communicationbetweenthe main trap (E),
and the fore pump; also, the main valveto the vacuum system(G) is closed.The
foltowing set of operationsis then carried out in sequenceand without delays
betweeneachstep:the fore pump is switchedoff , stopcock(C) is openedto bring
the systemto atmosphericpressure,the liquid nitrogen-filledDewar on trap (E)
is lowered,and trap (E) is removedand placed in a hood. The diffusion pump
heatercan then be switchedoff. The reasonfor carryingthesestepsout in fairly
rapid sequenceis that oncethe fore pump is turned off , oil may back up into the
evacuatedsystemif the flapper valvein the pump fails. In addition. if trap (E) is
left at liquid nitrogentemperaturefor very long, it will condenseoxygenfrom the
atmosphere;so it is important to remove the liquid nitrogen and discard the
contents of the trap soon after the systemis vented. CAUTION: It is important
never to leave a trap which is cooled by liquid nitrogen open to the atmosphere.
The condensedliquid oxygen presentsan explosion hazard in contact with oxidizable materials and sudden warming or bumping of an oxygen-filledtrap will
pressurizethe system, with potential breakage or explosion.
If pyrophoricmaterialsare presentin trap (E), it may be safestto isolatethis
trap from either pump by stopcock(F), and carry out a trap-to-trap distillation
of the material into a tube attached to the vacuum system. If this tube is
equippedwith a stopcock,it can later be ventedinto a nitrogenstreamin a hood.
Alternatively,a U-trap of the type shownin Fig. 6.5 may be usedand the procedures describedin that figure caption may be followed.
H. Limitolion of Pumping Speed by the Apporolus.

The time required
to reducethe vacuum in a line below l0 I torr is often limited by the stopcocks
and tubing in the line and not by the pumps. In this situation,little advantageis
gained by the use of a large fore pump-diffusion pump combination, and, as
describedpreviously,the increasedvibration of a larger mechanicalpump may
lead to inaccurate manometer readings. The major limitations on pumping
speedoccur at pressureswhere the mean free path of a moleculeexceedsthe
small dimensionsof the system.Under theseconditionscollisionswith the walls
becomemore frequent than intermolecularcollisions.For example,the mean
free path of oxygenat l0-r torr and 25oC is about 5 cm, which is much larger
than the usual tubing diameter.
It is instructiveto considerthe formula for the number of moleculesper second. g, streamingfrom one end of a cylindricaltube of diameterd and lengthI
to the other,Eq. (l).
428
._
"
Nd3r
3L
(P,
"2"un
\ 'lr=
P,\
JT,l
(1)
P1 and Z' are the pressureand temperatureat one end and P2 andT2refer to the
other end, M is the molecularrveightof the gas,R is the gas constant,and N is
A v o g a r d o ' sn u m b e r . T h i s e q u a t i o na p p l i e si n t h e a b o v e - m e n t i o n e(dm o l e c u l a r
flow) region, which commencesat about 10-2 torr. of particular importanceis
the direct proportionalitv of the flo*' to the cube of the tube diameter. Thus,
large-diametertubing and large-borestopcocksimprove the pumping speedat
low pressures.As with a serieselectricalcircuit, the total impedance(proport i o n a l t o 1 / q ) i s e q u a l t o t h e s u n ro f t h e i n d i v i d u a li m p e d a n c e sE, q . ( 2 ) .
lll
q-u:
^*
Q\
Therefore, one small-borestopcockor a length of small-boretubing will predominatein the determinationof the impedanceof the system.The analogylvith
electricalcircuitry also holds for the parallel arrangementof impedances.Thus,
if there are two or more connectionsbetweena manifold and the sourceof vacu u m , t h e i m p e d a n c eq i s g i v e nb y E q . ( 3 ) .
4:Qrlqz
(3)
To take advantageof this effect, and also to be able to pump severalsectionsof

the line at once, it is advantageousto designthe main high-vacuummanifold
( e . g . , F i g . 5 . 2 ) a n d t h e m a i n t r a p u ' i t h l a r g e r - d i a m e t e r t u b i nagn d l a r g e r s t o p cocksthan are found in the working manifolds.
GENERAT
REFERENCES
l - h e r ea r e n t a n yg o o d b o o k so n ( h e s c i e n t i f i ca n d t e c h n i c a la s p e c t so f v a c u u n ra n d o n l v a f e w a r e c i t e d
here.
D u s c h n r a n .S . , 1 9 6 2 ,S c i e n t i l i cF o u n d u t i o r t so l V u c u u t t tT e c h n i q u e . 2 n de d . . r e v . b y J . M . L a f f e r t y
e t a l . , w i l e y . N e w Y o r k . P u m p s f o r h i g h v a c u u m a n d u l t r a h i g h v a c u u n la r e d i s c u s s e di n s o m e
d e t a i l , a n d e q u a t i o n sf o r t h e k i n e t i c b e h a v i o ro f g a s e sa r e p r e s e n t e d .
Holland, L. . w. steckelmachera
, n d J . Y a r w o o d . 1 9 7 4 .v t t c u u r t tM s n u u l , E . a n d F . N . S p o n . L o n d o n ( i n t h e U . S . : H a l s t e dP r e s sd i v . o f J o h n W i l e y & S o n sI n c . ) . A v e r y u s e f u lg e n e r a lr e f e r e n c e ,
c o v e r i n gp r i n c i p l e so f g a s f l o u , m a t e r i a l so f c o n s t r u c t i o n ,s e a l a n t sa, n d c o m m e r c i a le q u i p m e n t .
R o t h , A . . 1 9 8 2 ,V u c u u m T e c h n o l o g v , 2 n de d . , N o r t h - H o l l a n d ,A m s t e r d a m .T h i s e x c e l l e n t c, o m p r e h e n s i v eb o o k c o v e r ss i n t i l a rm a t e r i a ll o t h e a b o v ev o l u n r e sa n c li t d o e sn o t n e g l e c tr o u g n - v a c u u n r
a n d h i g h - v a c u u mr e g i o n s .
W i s s f e r ,G L . a n d R . W . C a r l s o n .E d s . . 1 9 7 9 ,V u c u u n t S c i e n c e
ond Technologv,Yol.l4 of Methods
o l ' E x p e r i n t e n t u l P h v s i c s ,L . M a r t o n a n d c . M a r t o n , E d s . A c a d e m i c .N e u y o r k . A n e x c e l l e n t
m u l t i a u t h o r v o l u m ec o v e r i n ga l l n t a j o r a s p e c t so f v a c u u mt e c h n o l o g yT
. h e e m p h a s i si s o n p h y s i c a l a p p l i c a t i o na n d u l t r a h i g h v a c u u m , b u t t h e r e i s p l e n t y o f u s e f u l i n f o r m a t i o n f o r c h e n r i c a l
applications.
O ' H a n l o n , J . F . . 1 9 8 0 ,A l J s e r sG u i d e t o V u c u u t t tT e c h n o l o g l ,W
. iley, New York. This book is orie n t e d s o m e w h a tt o s e m i c o n d u c t o ra n d o p t i c sa p p l i c a t i o n s .I t h a s v e r y u s e f u ls e c t i o n so n r e s i d ual gas analysis.
PRESSURE
AND FLOW
MEASUREMENT
AND
LEAKDETECTION
The measurenrentof pressuresis quite important in vacuum line rvork, where

determinationsare performed routinely in the medium- or high-vacuumrange
to estimatethe initial vacuunrin a system,and in the l-760-torr range to meaFlow measurementand control is comsuregaseswhich are being n-ranipulated.
monly employedin catali.ticflow reactors,in reactorsfor the growth of electrical
and optical materialsfrom gas-phasereagents,and in gaschromatographicanalytical systems.Leak detectionis related to thesetopics and is of major inrportance in troubleshootingvacuum and gas-handlingsystems.The implententation of these pressureand flow measurementsand techniquesfor leak testing
will be coveredin this chapter.
(.r-760ToRR)
7 ,4 MANoMETRY
A. Melcuty Monomefels for Routine Work. The pressure-volume-temperaturemeasurementof gasesis the backboneof quantitativechemicalvacuum
line work. For thesemeasurementsan error of a few percentis frequentlysufficient and may be attained by a simple U-manometerattachedto a calibrated
volume and read with an "inexpensive"cathetometer.
The manometersillustrated in Figs. 7 .l and 7.2 are convenientfor use in
conjunctionwith a chemicalvacuum system.The simple U-manometerin Fig.
7.1 minimizesthe amount of mercury usedand thereforeminimizesthe massof
the manometer.The bubbler manometerillustratedin Fie. 7.2 usesmore mer129
430
PRESSURE
AND FLOWMEASUREMENT
AND LEAKDETECTION
I
Co 420 mm
Copillory
(o)
(b)
F i g . 7 . 1 . T h e d i m e n s i o n sf o r a U - m a n o m e t e r .( a ) U - m a n o m e t e rb e f o r e i t i s f i l l e d w i t h m e r c u r y .
T h e d i m e n s i o n ss h o u n g i v e a r a n g eo f p r e s s u r e su p t o 1 a t m . U s i n g c a p i l l a r yt u b i n g i n t h e l o w e rp a r t
o f t h e m a n o m e t e rr e d u c e st h e v o l u m e o f m e r c u r y r e q u i r e d . ( ) M e r c u r y - f i l l e dU - m a n o m e t e r .T h e
p r o c e d u r ef o r f i l l i n g t h e m a n o m e t e ri s a s f o l l o u ' s .F i r s t , t r i p l e - d i s t i l l e dm e r c u r y i s f i l t e r e d d i r e c t l y
i n t o t h e m a n o m e t e ru n t i l t h e m e r c u r y c o l u m n i s a b o u t 4 2 5 m m h i g h i n b o t h l e g s( i . e . , a b o u t 5 - 1 0
m m a b o v et h e u n i o n w i t h t h e c a p i l l a r yt u b i n g i n t h e r e f e r e n c el e g ) . B o t h s i d e so f t h e m a n o m e t e ra r e
t h e n e v a c u a t e da n d g e n t l y f l a m e - d r i e d .T h e e v a c u a t e dr e f e r e n c es i d e i s s e a l e do f f a t p o i n t A , a n d
m e r c u r yi s f o r c e d i n t o t h e s m a l l u p p e r U b y p r e s s u r i z i n gt h e m e a s u r i n ga r m . T h i s t r a p s a n y r e s i d u a l
g a s i n t h e s m a l l u p p e r c h a m b e r .T o r e t a i n t h i s r e s i d u a lg a s p e r m a n e n t l y ,a v a c u u m i s e s t a b l i s h e di n
t h e r e f e r e n c ea r m b y g e n t l et a p p i n g o r h e a t i n ga t p o i n t B w h i l e e v a c u a t i n gt h e m e a s u r i n ga r m . T h i s
final processmay be repeated on occasion to ensure a good referencevacuum.
cury but provides pressurerelease,and is thereforedesirablefor applications

where excesspressuremight build up inadvertently,as, for example,in the introduction of gasesfrom a compressed-gas
cylinder or in chemicaloperations
with low-boilingsolvents,such as liquid ammonia. Filling instructionsfor both
manometersare given in their respectivefigure captions.Accurate manometry
requires a clean mercury surface, so either manometer should be filled with
freshly filtered triple-distilled mercury, and the interior of the manometer
,134
(,|-760TORR)
MANOMETRY
T o v a c u u ml i n e
- 850mm
/'"
s p r a yt r a pa n o
atmosphere
(or vacuum)
F i g . 7 . 2 . A v e r s a t i l eb u b b l e r m a n o m e t e r .T h e b u b b l e r m a n o m e t e ri s s e c u r e l ym o u n t e d b y t h e r e s . h e l e v e lo f
e r v o i r a n d a t t a c h e dt o t h e v a c u u n rs y s t e m .I t i s t h e n e a s i l yf i l l e d b y t h e f o l l o w i n gp r o c e s s T
t h e b o t t o m e n d o f t h e v e r t i c a lt u b e d i p p i n g i n t o t h e r e s e r v o i ri s m a r k e d o n t h e o u t s i d eo f t h e r e s e r v o i r . N e x t , a c a l c u l a t e da m o u n t o f m e r c u r y i s f i l t e r e d i n t o t h e r e s e r v o i r .W i t h t h e v a l v eb e t w e e nt h e
two arms open, a vacuum is s/ox'{t'drawn on the manometer. The mercury level must not drop belos'
, r e l s eb u b b l e su ' i l l e n t e r t h e v e r t i c a lt u b e a n d s h o o tn r e r c u r yt h r o u g h t h e
the mark on the reservoiro
v a c u u m s y s t e m .I f t h e m e r c u r y l e v e l i n t h e r e s e r v o i rc o m e sc l o s et o t h e n r a r k , t h e m a n o m e t e ri s
b r o u g h t u p t o a t n l o s p h e r i cp r e s s u r ea n d m o r e m e r c u r y i s a d d e d . W h e n t h e p r o p e r a m o u n t o f m e r c u r y i s p r e s e n ti n t h e f u l l y e v a c u a t e dm a n o m e t e r ,t h e m e r c u r yl e v e ls h o u l db e a b o u t 1 0 m m a b o v et h e
m a r k o n t h e r e s e r v o i r ,a n d t h e u p p e r m e n i s c u ss h o u l d b e i n a r e g i o n o f t h e m a n o m e t e rs u i t a b l ef o r
m e a s u r e n l e n t .a s i l l u s t r a t e d . O n c e t h e m a n o n l e t e r i s p r o p e r l y f i l l e d a n d e v a c u a t e d .t h e v a l v e i s
c l o s e dt o i s o l a t et h e r e f e r e n c ea r m a t h i s h v a c u u m .
should be clean and dust-free.The proportions of these manometersand the

amount of mercury should be arrangedsuch that pressuresfrom zero to somewhat over 760 torr can be spannedby the manometerwithout gas being forced
around the bottom of the U-manometeror out of the bubbler on the bubbler
manometer.To minimize errors arisingfrom capillarydepression,the two arms
of the manometershould be of the samediameterin the regionof the menisci(a
minimum internal diameter of 8 mm is preferable).
132
AND FLOWMEASUREMENT
AND LEAKDETECTION
PRESSURE
B. Monomeflic
Meosulemenls.
The ideal gas law is generally sufficiently accurateto measurethe amount of gas at the subatmosphericpressures
encounteredin vacuum line work. When the gas is being measuredin a U-trap
with an attachedmanometer,the volumeof the systemwill changewith pressure
becauseof the varying heights of the mercury level. One way of avoiding this
complication is to employ a manometerin which the mercury level can be adjusted to a fixed height in the measuringarm by introductionof mercuryfrom a
reservoir.However,this is cumbersome,so the usual practiceis to calibrateone
leg of a simple manometer(Fig. 7.1 or 7.2). This processhas been describedin
S e c t i o n5 . 3 . H .
To achieveacceptableerrorsarisingfrom capillarydepressionof the mercury,
the manometerarms should be constructedfrom glasstubing having the same
internal diameter, preferablynot lessthan 8 mm. When the interior surfaceof
the manometer adsorbsvapors or becomesdirty, the meniscuson the exposed
leg of the manometeroften will not havethe sameheight as that on the reference
side. lf this condition arisesand if small pressuresare being measured,it may be
necessary
to make a capillary depressioncorrectionas indicatedin the next secin routine work (i.e., in the 100-700torr
tion. Such correctionsare unnecessary
p r e s s u r er e g i o n )u s i n g a c l e a nm a n o m e t e r .
Ordinarily, the largesterror in manometerycomesin measuringthe differential mercury column height. A cathetometer(Fig. 7.3), is routinely usedfor this
process,but a meter stick attachedto the manometerprovidessufficientaccuracy for rough measurements.The cathetometerconsistsof a telescopewith a
crosshairwhich is alignedwith the top of the mercurymeniscus.This telescopeis
mounted on a calibrated vertical scaleequippedwith a supplementaryvernier
scalefor accurate interpolation of the readings.Before use, the cathetometer
must be leveledso the travel of the telescopeis indeed vertical. Similarly, if a
manometeris read by meansof an attachedmeter stick, the manometermust be
strictly vertical.This can be accomplishedat the time of constructionby using a
bubble levelor a plumb line. It is good practiceto mount all manometerson a
true vertical.
Whether the meniscusheight is measuredwith a cathetometeror a meter
stick, it is important to have good illumination of the meniscusand to do the
illumination in a consistentmanner throughout a set of measurements.A sheet
of white paper behind the manometeroften providesgood definition of the meniscus.Under many lighting conditions,illumination of this paper from behind
may further improve the visibility of the meniscus.
C. Monomelers fot High Acculocy Work. For a mercury manometer
with one arm evacuated,the pressureis givenby P : hdg, where is the differencein the height of the mercury columns,d is the densityof mercury, and g is
the accelerationdue to gravity. In the old set of pressureunits the pressurewas
reportedin mm of Hg. This pressureunit was definedfor mercuryat 0oC, where
its densityis 13.5951g/cmr, and the accelerationdue to gravity irgo : 980.665
133
MANOMETRY(,r.760TORR)
Focus
nt
odJUstme
Level
/ 'T.rae-l cv-se:a i-ol n-np'qscrew

vernlel
\ _' r r n e - o o l u s T m e n T
e l e v o t i o ns c r e w
Colibrotrons
L e v e l r n gs c r e w s
F i g . 7 . 3 . C a t h e t o m e t e r .T h i s t y p e o f c a t h e t o m e t e ri s u s e d i n r o u t i n e m a n o m e t r y . I t i s l i g h t i n
w e i g h t a n d m a y b e m o v e d e a s i l yf r o m o n e s i t e t o t h e n e x t . A s t u r d y t h r e e - l e g g e d
platform *hich is
t h e s a n r eh e i g h t a s t h e v a c u u n rl i n e b e n c h n r a yb e u s e dt o b r i n g t h ( }c a t h e t o m e t etro t h e p r o p e r h e i g h t
f o r t h e o b s e r v a t i o no f m a n o m e t e r so n t h e v a c u u m l i n e .
cnl/sec2.More recently,the torr pressureunit has conle into wide use, and to
within 7 x l0-l percentthe torr is equal to the mm of Hg. (Further definitions
of the various pressureunits may be found in Appendix VI.) Precisework requires the correctionof the mercury height by a factor of g/gs (whereg is the
local value for the accelerationdue to gravity), and a secondfactor oI dt/dy,
which is the density of mercury at the measuringtemperaturedivided by the
densityat 0oC. Valuesfor the ratio d,/ds are givenin Appendix VI, and the local
434
AND FLOW MEASURFMENT

PRESSURE
AND LEAKDETECTION
value of g/90 may be determined from the data given in the CRC Handbook oJ
Chemistry and Physics.
If the manometer arms are not of equal diameter or if their interior surfaces
are coveredby different adsorbedmolecules,the menisciin the two arms will be
different and a capillary depressionerror is introduced. The accuracyof this
correctionis low. so it is best minimized by employinglarge-boretubing and the
purest available mercury. Despite these precautionsthe menisci are rarely of
identicalheight. A table of capillarydepressioncorrectionsis givenin Appendix
VI. Further discussions
of precisionmanometryare availablein the literature.r'2
D. Generol Propedies of Melcury.
No other liquid rivals mercury as a
general-purposemanometric liquid. However,mercury is not without its drawbacks: it is toxic, and it is attacked by strong oxidizing agentssuch as NO2,
halogens,and oxidizing fluorides. In addition, it reactswith tin tetrachloride
and with a few organometalliccompounds,such as dimethylcadmium.Mercury
amalgamatesand appreciablydissolvesmany metals, such as the alkali and alkaline earth metals,Zn, Cd, Sn, Pb, Bi, Ga, Au, and Tl. Tracesof thesemetals
influence the surfacetension and glass-wettingtendencyof mercury. Copper,
Ag, Pt, and AI are somewhatlesssoluble,but they are solubleenough (about
10-3% by weight) so as to affect the surfacetension. Finally, there is a group
composedmostly of transition metals that are quite insoluble(5 X 10-s% or
l e s s ) :C r , C o , F e , M o , N i , S b , T i , W , a n d V . r
E. Reducing Exposule lo Metcury.
Elementalmercuryvapor and dust of
mercurycompoundsare absorbedthrough the respiratorytract, skin, and digestive tract. The current acceptablethresholdlevelin the United Statesfor continuous exposureto mercury in the air is 0.05 mg,/m3,which correspondsto a partial pressureof 4 X 10-6 torr. Since the vapor pressureof mercury is on the
order of 2 X l0-3 torr at room temperature,it is clear that an enclosed,poorly
ventilatedroom containing exposedmercury would vastly exceedthe accepted
limits. The hazardsof working with mercury are minimized by adopting good
housekeepingpractices.The laboratoryshould be well ventilated,mercuryvesselsshould be closed,and spills shouldbe thoroughlyand promptly cleanedup.
After all traces of visible mercury have been picked up, the area of the spill
should be treated with zinc dust or charcoalwhich has been treatedwith a solution of iodine. lt is particularly undesirableto heat mercuryin the open, so care
must be taken to clean it from glassapparatusbeforeglassblowingand to keep
mercury off warm surfaces,such as mechanicalpumps.
Mercury dropletshavea great tendencyto roll, making it difficult to cleanup
r G . W . T h o n r p s o n . T e c h t i q u e s oOl r g a n i c C h e n r i s t r y , 3 r d e d .V. o l . I , I ' t . l , A . W e i s s b e r g e E

r ,d . .
I n t e r s c i e n c(eN e w Y o r k : 1 9 5 9 ) ,p . 4 1 0 .
r A . F . G e r m a n n J . P h 1 , sC. h e m . , 1 9 , 4 3 7( 1 9 1 5 ) .
,
r P . P a s c a l ,E d . . .N o u v e u u T r u i t e d e C h e n r i eM i n e r a i e . V o l . 5 , ( P a r i s :M a s o n e t C i e , 1 9 6 2 ) ,p . 5 l O f f .
(1.760
TORR)
MANOMETRY
135
spills. A vacuum pickup devicefor mercury can be constructedfrom a vacuum

filtration flask with its sidearmconnectedto an aspirator,as illustratedin Fig.
7.4a. Another meansof picking up small globulesof mercury is a spiral of copper wire, as shownin Fig. 7 .4b. A varietyof mercurypickup devicesis available
from laboratorysupply houses.
When it is received,mercury is generallycovered
F. Cleoning Melcury.
with a scum which can foul manometers,Toepler pumps, and similar apparatus. This scum can be removedby a simple filtration procedure.A standard
filter paper is folded to fit an appropriatefunnel and a pinhole is piercedin the
tip. The hole must be large enough so that mercury dropletswill run through,
but small enoughso that the last drop and its associatedscum are retainedby its
surfacetension.This type of filtration processis routinelyperformedbeforefilling an apparatus.
Mercury that has been contaminatedby metallic impurities is cleanedby a
nitric acid wash to removemost electropositive
metals,and it is then distilledto
S p r r o lo f
o m o l g o m o t e dw i r e
T o v a c u u ms o u r c e
(a)
F i g . 7 . 4 . M e r c u r y p i c k u p d e v i c e s (. a ) V a c u u m p i c k u p d e v i c e .C o l l e c t e dm e r c u r yi s t r a p p e d i n t h e
flask for recycling or disposal. () Amalgamated copper wire pickup device.The wire is first cleaned
i n n i t r i c a c i d , t h e n d i p p e d i n t o a s o l u t i o no f m e r c u r i c n i t r a t e t o g i v e a t h i n c o a t i n go f m e r c u r y .
Droplets of mercury readily cling to the spiral and may be shaken off into a mercury wastecontainer.
136
PRESSURE
AND FLOWMEASUREMENI
ANO LEAKDETECTION
remove nonvolatileimpurities. These servicesare availablecommerciallyand

thereforewill not be describedfurther.
G. Bourdon Gouges.
As an alternativeto mercury manometersthere is a
variety of gaugesbased on mechanicalor electricalpressuretransducers.This
sectionpresentsa descriptionof purely mechanicalgaugeswhich still find usein
this electronicage.aThe metal Bourdon gauge(Fig. 7.5) is fashionedaround a
s e m i c i r c u l a rt h i n - w a l l e d m e t a l t u b e w i t h m e c h a n i c a ll i n k a g e t o a p o i n t e r .
Fused-quartzspiral gaugesare also available.In this case,a thin spiral is sensitive to a pressuredifferential, and the deflectionis balancedwith air pressurein
the surroundingenvelope.The air pressureis then measuredwith a manometer.
H . E l e c t r o n i c P r e s s u r e T l o n s d u c e r s . E l e c t r o n i cp r e s s u r et r a n s d u c e r s
equippedwith digital pressurereadoutprovidea convienientand fairly compact
Bourdontube
Closedend
Mechanicalink
Appliedpressure
F i g . 7 . 5 ' A n r e t a l B o u r d o n g a u g e .T h e t h i n B o u r d o n t u b e i s s e n s i t i v et o t h e p r e s s u r ed i f f e r e n t i a l
b e t w e e nt h e s u r r o u n d i n g a t m o s p h e r ea n d t h e g a s c o n t a i n e dw i t h i n t h e t u b e . T h e t u b e d e f l e c t sa n
i n d i c a t i n g n e e d l eu ' h i c h a l l o w s a d i r e c t p r e s s u r ed e t e r m i n a t i o nf r o m t h e c a l i b r a t e ds c a l e .
rBourdon and spiral gauges
w i t h d i a l r e a d o u t a r e a v a i l a b l ef r o m W a l l a c e & T i e r n a n , 2 5 M a i n S t . .
B e l l e v i l l e .N J 0 7 1 0 9 .W a r d e n q u a r t z s p i r a l g a u g e sa r e a v a i l a b l ef r o m R u s k a I n s t r u m e n t C o r p . , B o x
3 6 0 1 0 , H o u s t o n , T X 7 7 0 3 6 ; T e x a s I n s t r u m e n t s I n c . , D i s p l a y s y s t e m s ,B o x 1 4 4 4 , H o u s t o n , T X
7700t.
MEDTUMAND H|GH-VACUUM
(10'1-,10-6
MEASUREMENTS
TORR)
137
methodfor pressuremeasurementin a varietyof environments.Although a wide

variety of designsare available,the most common units are based on capacitance or inductancedetectionof the displacementof a diaphragm (Fig. 7.6).s
The specificationson the gauge should be carefully matched to the range and
accuracywhich are required. Someattention must be paid to long-termdrift in
the gauge,especiallywhen the gaugeis exposedto changesin temperatureand
mechanicalvibration. The portion of the gaugewhich is exposedto the gas can
be made from a variety of materials,includine fluorine-resistantmetals.
7 .2 MEDTuM(,to-''-.t0-6
ANDHtcH-vAcuuM
MEAsuREMENTS
ToRR)
Gaugeswhich are sensitivein this range are primarily used to determine ultimate vacuum on a systemand to hunt leaks.This pressurerange is measurable
by a variety of gaugetypes ranging from the manually operatedmercury-filred
Mcleod gauge to variouselectronicgauges.
A. Mcleod Gouges.
This gauge provides a simple and reliable way of
measuringpressuresgreater than l0 " torr. It works on the principle of conrpressinga large volume of low-pressuregas into a small volume wherethe pressure is great enoughto be measuredwith a mercury column. Gas which is cont a i n e d i n t h e u p p e r b u l b o f t h e g a u g ei l l u s t r a t e di n F i g . 7 . 7 i s c o m p r e s s e idn t o
t h e u p p e r c l o s e d - e n cd a p i l l a r y .a n d t h e h e i g h td i f f e r e n t i abl e t w e e nt h e m e r c u r y
in this closedcapillary and an adjacentopen-endcapillaryis relatedto the origi-
F i g . 7 . 6 . E l e c t r o n i c p r e s s u r et r a n s d u c e r .T h i s s e n s i n gu n i t i s b a s e do n t h e n r e a s u r e m e not f t h e
c a p a c i t a n c eb e t u e e nt h e d i a p h r a g n rD a n d s e n s o r sS . P , i s t h e p r e s s u r eb e i n g n r e a s u r e da n d P " i s a
referencepressurewhich may be a high vacuum.
i D i a p h r a g n rg a u g e sw i t h d i g i t a l
r e a d o u t a r e a v a i l a b l ef r o m M K S l n s t r u n r e n t sl n c . , 2 2 T h i r d A v e . .
B u r l i n g t o n ,M A 0 1 8 0 3 ;V a l i d y n eE n g i n e e r i n gC o r p . , 8 6 2 6 w i l b u r A v e . , N o n h r i d g e ,C A 9 l 3 2 g l
D a t a n r e t r i c sD r e s s l e rI n d u s t r i e sI n c . , 3 4 0 F o r d h a m R d . , W i l m i n g t o n , M A 0 1 8 8 7 ;F l u i d p r e c i s i o n .
l n c . , I l 0 M i d d l e s e xS t . , C h e l n r s f o r dM
, A 01863.
138
PRESSURE
AND FLOW MEASUREMENT
AND LEAKDETECTION
To vocuum
3ystam
Ralcrence
c0prllofy
Coprllory
(r'lh ctoscdcnd)
8o
Arr ond
Y o c u u mI n l t l
lor odiusfmGnt
of mercury
htrCht
Hg rcservoir
F i g ' 7 ' 7 ' T h e M c l e o d g a u g e .T h e p r i n c i p l e so f o p e r a t i o n

f o l l o u , .L e t t h e u n k n o u , np r e s s u r er n a
s v s t e nb
l e P w h e n t h e H g l e v e li s b e l o u ' p o i n t l . L e t t h e v o l u n r e
o f t h e b u l b a n d c l o s e dc a p i l l a r ya b o v e
I be V' uhich is knoun. When the mercuryis allo*ed
to rise past point l. the gas rs trapped and
f i n a l l y c o n l p r e s s e di n t o t h e c a p i l l a r y . S u p p o s et h a t u ' h e n
t h e m e r c u r yi n t h e r e f e r e n c ec a p i l l a r yi s a t
0 , t h e n r e r c u r - iyn t h e d e a d - e n d e dc a p i l l a r vi s B m m b e l o u 0 ( i . e . ,
t h e p r e s s u r eo f t h e c o n r p r e s s egda s
i s B n l m ) ' S i n c et h e i n i t i a l p r e s s u r e - v o l u mper o d u c t e q u a l s
t h e f i n a l p r e s s u r e - v o l u mper o d u c t ,p V =
, t r r ' t, h e v o l u m e i n t h e c a p i r r a r yr s i l l b e t h e h e i g h tB t i m e st h e a r e ao f t h e L - a p i l a r yb o r e l . T h u s p :
1 t r / v = B 2 ( A/ w . S i n c e, 4 a n d v a r e k n o u n a r r d B i s n r e a s u r e dt,h e o r i g i n a r p r e s s u r e( p )
m a 1 ,b e
c a l c u l a t e d 'M o s t c o n r n r e r c i agl a u g e sa r e p r o v i d e du i t h
a c a l i b r a t e ds c a l eu . h i c hp r e s e n t sp r e s s u r e s
d i r e c t l y ' A l t e r n a t i v e l y ,i t i s p o s s i b l et o d c v i s ea l i n e a r s c a l e
for the Mcleod gauge. In one such
n r e t h o dt h e n r e r c u r yh e i g h t i n t h e c l o s e dc a p i t a r y i s a r u a y sa d j u s t e d
t o t h e s a n l ep o i n t ( 8 , , ) ,a n d ( h e n
t h e d i f f e r e n c ei n n r e n i s c u sh e i g h t sb e t u . e e nt h e t s , o c a p i l l a r i e s
i s n r e a s u r e d( B ) . F o r t h i s c a s et h e
p r e s s u r eb e i n g n r e a s u r e d| e p : p t , n i v : ( B t i A / v ) a B .
A s i n t h e p r e v i o u se x a m p r e .t h e q u a n t i t y i n
p a r e n t h e s e rse p r e s e n t st h e g a u g ec a l i b r a t i o nc o n s t a n t .
nal pressurein the vacuum system.Further detailson the operation

of this gauge
are explainedin the caption to Fig. 7 .7.
A clean gauge and pure mercury are essentiarfor reliableoperation
because
_
the presenceof impurities causesmercury to cling to the capilrarywalls.
This
ntay lead to unreliablereadingsand a tendencyfor the mercurycolumn
to break
up in the capillary' If the mercury corumn in the capiilaryis bioken
by gas bubbles, the pressurereadingsare highly inaccurate.In any case,
the capilrarytubing is tapped to settlethe mercurybeforea pressuremeasurement
is obtained.It
is very important to run the mercury rntoothryinto the upper
chamber. If the
mercury surgesinto this chamber, it may break the apparatusand
showerthe
surroundingarea with mercury. The Mcleod gaugesintendedfor
the high-vac-
(,IO-1-,IO{
MEASUREMENTS
TORR)
MEDIUM-AND HIGH-VACUUM
,139
uum rangeare generallybulky and contain a largequantity of mercury.Because

of its mass,the gaugeis generallymountedon the benchof the vacuum line. The
reservoiris well supportedby a cork ring and/ or plasterbaseinsidea pan which
is deep enough to catch the mercury in the event of a mishap.
The Mcleod gauge is not suitable for the determination of pressuresof easily
condensedgases,such as water vapor, and it has the additional disadvantageof
being slow and sometimesclumsyto operate.Becauseof this naturally slow response,the electronicvacuum gaugesare superiorfor tracing leaks.
The tilting Mcleod gauge (Fig. 7.8) is a simple, inexpensive,and portable
gaugewhich may be usedto measurepressuresdown to about 10-l torr. These
gaugesare very useful for checking rough vacuum systems,Schlenk systems,
and for the calibration of thermal conductivityvacuum gauges.
B. Thelmol Conduclivity Gouges.
Included in this categoryis a seriesof
similar gaugeswhich go under a variety of names: Pirani, thermocouple,and
thermistor gauges.These simple and relativelyinexpensivegaugescontain a
heatedelement, and the temperatureof that elementis detectedby meansof a
thermocoupleor thermistor (Fig. 7.9). Direct readoutin pressureis providedby
meansof a calibrateddial. It is common for theseunits to be calibratedoverthe
1-10-3-torr range; however,at either end of the scalethe readingsare approximate. A gaugeof this type is usefulfor measuringthe pressurein the antechamber of a glovebox, for monitoring the fore pump pressurein large vacuum sys-
Reference
coprllory
R e s e r v ori
Copillory
( w r t h c l o s e de n d)
F i g . 7 . 8 . T i l t i n g M c L e o d g a u g e .T h e g a u g er o t a t e sa r o u n d t h e c e n t e rs e c t i o n .T h i s c e n t e rs e c t i o n
a l s o c o n t a i n sa n i p p l e ( e x t e n d i n go u t f r o m t h e b a c k o f t h e d r a w i n g ) w h i c h m a y b e a t t a c h e dt o t h e
v a c u u m s y s t e mt h r o u g h a h o s e .F o r a m o r e p e r m a n e n ta r r a n g e m e n tt,h e c e n t e rs e c t i o ni s a t t a c h e dt o
a v a c u u m l i n e b y m e a n so f a s t a n d a r dt a p e r j o i n t a n d t h e b a s ei s d i s c a r d e d .I n i t i a l l y , t h e g a u g e i s
r o t a t e d s o t h a t t h e m e r c u r y r u n s i n t o t h e r e s e r v o i r .W h e n p r e s s u r ee q u i l i b r i u m i s e s t a b l i s h e dw i t h
the system being measured, the gauge is rotated back so that gas is compressedinto the dead-end
capillary and the top of the mercury in the referencecapillary coincideswith the top end of the deade n d c a p i l l a r y . G e n e r a l l y ,t h e g a u g e i s p r o v i d e dw i t h a s c a l ew h i c h m a y b e r e a d d i r e c t l yi n t e r m s o f
p r e s s u r eT
. h e s eg a u g e sc o v e rt h e m e d i u m - v a c u u mr a n g e ,b u t g e n e r a l l yd o n o t e x t e n di n t o t h e h i g h vacuum region.
140
AND FLOWMEASUREMENT
PRESSURE
AND LEAKDETECTION
T o v o c u u ms y s ' f e m
T h er mo c o u pel
To
p o w er
supply
mrcroomme.rer
F i l om en l
F i g . 7 . 9 . S e n s i n ge l e m e n t f o r t h e t h e r m o c o u p l ev a c u u m g a u g e .T h e t h e r m o c o u p l ei s i n c o n t a c t
w i t h a h e a t e df i l a m e n t a n d m e a s u r e si t s t e m p e r a t u r e .A v a r i a n t i n v o l v e sa t h e r m i s t o rw h i c h s e r v e s
b o t h a s a h e a t i n g a n d a s e n s i n ge l e m e n t .
tems, and for chemicalvacuum systemsin which high vacuum is not required.
The thermal conductivityof a gas is dependentnot only on the pressure,but also
on the heat capacity, molecular weight, and accommodationcoefficient(efficiency of energy transfer with a surface) of the gas being measured. Furthermore, the accommodationcoefficientwill vary if the surfaceis coatedwith foreign matter. Therefore, these gaugesare generallynot suitable for accurate
pressuremeasuren.rent,
but this is of little consequencein their most frequent
application as sensorsof the generaldegreeof vacuum in a system.
One of the most troublesomeaspectsof the thermal conductivitygaugesis the
altered responsecausedby the pyrolysisof thermally unstablemoleculeson the
hot sensingelement.To minimize this problem, the gaugeshouldbe turned off,
or the sensingtube isolated,when thermally sensitivecompoundsare handled.
The calibration of the gaugecan be checkedperiodicallywith a tilting Mcleod
gaugeand the sensingtube replacedwhen the unit getsbadly out of calibration.
The sensinghead is generallyconstructedfrom metal with a tube inlet. This
sensormay be attachedto a glassvacuum systemby the use of vacuum wax to
securethe inlet tube insidea glasstube on the vacuumsystem.To facilitatemaking a good seal,the latter tube should havean insidediameterjust slightlylarger
than the outsidediameterof the tube on the sensor.Often the tube on the sensor
has pipe threadsand this may be attachedto a pipe thread-to-swage
union. As
describedin Chapter 8, a swagejoint fitted with a Teflon ferrule can be attached
to glasstubing of appropriate diameter.
C. lonizolion Gouges.
This rather broad classof gaugesincludes coldcathodeionizationgauges(sometimescalled Penninggauges)and thermionicor
hot-cathodevacuunl gauges(one highly efficient versionis called the BayardAlpert gauge).Thesegaugesare ntainly used in the pressurerange below l0-l
torr, and the thermionic gaugesextend into the ultrahigh vacuum range (10 r2
torr). The operationof thesegaugesis basedon a common principle: the measurementof the positiveion current from gas moleculeswhich havebeenionized
by electronimpact.
(.10.1-,I0-6
MEDIUM.AND HIGH.VACUUM
MEASUREMENTS
TORR)
441
In the cold-cathodegauge,a glow dischargeis initiated by a very-high-voltage

starting pulse and is maintainedby an applied high voltage.A schematicof the
sensinghead is shownin Fig. 7.10. A magneticfield is employedin this sensorto
confine the electronsto a spiral path and thus increasethe probability of collision with gas molecules.The sensitivityto variousgasesvarieswith the nature of
the gas,with the sensitivityfor helium and hydrogenbeing low and that for mercury and polyatomicmoleculessuch as acetonebeing high. In its most common
application,judging the initial degreeof evacuationof a system,the factor of 30
or so in sensitivityto various common gasesis of little importance.
The cold-cathodegaugeis a good choicefor measuringthe initial vacuum in
chemical high-vacuum systemsbecausethe pressurerange is appropriateand
the gauge is robust. Standard commercial units are availablefor measuring
pressuresin the approximaterange of l0 2 to 10 7 torr, and the rangeof most
interestfor syntheticchemical systemsextendsfrom this upper limit to about
10-6 torr. The sensingelement collectsdebris from the fragmentaionof polyatomic molecules,and thereforeit is necessary
to turn off the instrumentor isolate the sensingelementwhen significantpressuresof polyatomicmoleculesare
present.Fortunately,the gauge is tolerant to a fair amount of depositand the
sensinghead can be cleanedby scrapingout or dissolvingthe deposits.The re-
F i g . 7 . 1 0 . C u t a w a yo f a c o l d c a t h o d e( P e n n i n g )g a u g e .T h e u i r e a n o d e( A ) i s c o n n e c t e dt h r o u g h a
c e r a m i ci n s u l a t o r( l ) t o t h e h i g h - v o l t a g el e a d ( H ) . U n d e r t h e i n f l u e n c eo f t h e m a g n e t i cf i e l d c r e a t e d
b 1 ' M , t h e e l e c t ( r n st r a v e l a l o n g s p i r a l p a t h b e t $ e e n t h e b o d l ' a n d t h e a n o d e . T h e c u r r e n t , u h i c h
a r i s e sf r o m c l e c t r o n sa n d p o s i t i v ci o n s o f t h e i o n i z e dg a s n r o l e c u l c si,s r e l a t e dt o t h e p r e s s u r e .T h e
o p e n e n d ( C ) i s a t t a c h e dt o t h e v a c u u m s y s t e m .
142
AND LEAKDETECTION
AND FLOWMEASUREMENT
PRESSURE
sponseof the ionizationgaugeis fast, which makesit an excellenttool for tracing

leaks. The sensingelement for a cold-cathodegauge is generallycontainedin
either a glassor metal envelope.If a unit with a glassenvelopeis used,it may be
sealeddirectly to the vacuum systemand cut off from the systemwhen the time
comesfor cleaning.Metal headsmay be waxedto a largetubular openingon the
vacuum system,or attached by an O-ring joint, such as a Cajon Ultra-Torr
u n i o n ( s e eS e c t i o n8 . 1 . B ) .
In the cold-cathode gauge a steady-stateconcentration of electrons is maintained by electron impact on the moleculesbeing measured.By contrast, the
primary source of electrons in hot-cathode gauges, such as the Bayard-Alpert
gauge,is a hot filament. Theseelectronsare accelefatedtoward a positivegrid,
and in this region moleculesare ionized by electronimpact. The positivegrid
collectsthe electronsand permits positiveions to passthrough to an electrode
which is biasednegativewith respectto the filament. This positiveion current is
then relatedto pressure.Thesetypesof gaugeshaveexcellenthigh-vacuumsensitivity and are routinely used in high-vacuumand ultrahigh-vacuumsystems.
For chemical systemswhere there may be a moderatelyhigh background of large
molecules,the hot-filamentgaugesare fairly readilyfouled, and if exposedto air
the hot filament is burned out. For thesereasons,the hot-cathodegaugeis preferred for clean, very-high-vacuumsystemsand is rarely used for vacuum lines
primarily devotedto syntheses.
Both the thermionic and cold-cathodegaugesexert a significant pumping
action on a vacuum systemdue to the breakdown and depositionof molecular
ions createdby electronimpact. Thesegaugesare pfone to degasdepositedmaterial when turned off, or soon after they are turned on.
D. ReSidUol GOS AnOlyzerS. A residual gas analyzeris basicallya small
mass spectrometerwhich provides a method of identifying the foreign gas in a
vacuum chamber as well as judging its pressure.Thesedevicesare widely used
on ultrahigh-vacuumapparatusto judge the nature of the backgroundgas and
to detect the sourceof contamination. They also are usedto diagnosethe performance of a variety of apparatus employed in modern thin-film researchand
technology,such as vacuum evaporators,plasma etching devices,and the like.
The residual gas analyzeris indespensablein the ultrahigh-vacuumapparatus
employedfor the study of chemistryon singlecrystalsurfaces,wherethe nature
of contaminant gasesis important. This type of apparatus is also useful for
desorptionof moleculesfrom surfaces,and
studyingthe temperature-dependent
to identify gaseousproducts in chemicaland catalyticsystems.
Typical residualgas analyzersemploy electronimpact to generateions and a
quadrupole "mass filter" to obtain the mass-to-chargeratio of these species.
Mass rangesfor theseanalyzersvary: 2-80 atomic massunits for small units; l500 on larger, more expensivegas analyzers.Electron impact ionizationof the
gas is achieved using a hot filament as the source. Many instruments are
equippedwith a secondfilament which can be switchedinto usein the eventof a
failure of the first. When a robust detectorof moderatesensitivityis needed,a
LEAKDETECTION
143
Faradaycup is usedto collections and thus providea direct measureof the ion
current. For higher sensitivityand rapid response,an electronmultiplier detector is employed.In this devicethe acceleratedions impingeon a surfacewith the
emissionof secondaryelectrons.Theseare multiplied by a cascadealongeither a
channelor set of plateshaving a large potential gradient.
The residualgas analyzersensinghead is generallysuppliedon an ultrahighvacuum flange which can be readily accommodatedon most metal vacuum apparatus.
7 .3 LEAK
DETEcnoN
A. Sflofegies. Leaks are a ubiquitousproblem with vacuum systems.They
come in two varieties:real and virtual. A real leak involvesan opening in the
vacuum chamber. Examples are a pinhole or hairline crack in the glass,or a
stopcockin which the greasehas channeled.Virtual leaks, on the other hand,
are containedwithin the vacuum systemand might include such things as the
outgassingof stopcockgreaseor O-rings which have absorbedsolventvapors.
The walls of a glass apparatus present a large virtual leak as the moisture is
desorbedfrom the freshly evacuatedapparatus. A knowledgeof the prior use of
the apparatuswill often permit one to spot a virtual leak. Alternatively,the outgassingof condensablematerialscan be verifiedby cooling a sectionof the vacuum systemwith liquid nitrogen while the pressureis checkedwith a vacuum
gauge. Another method of differentiatingreal and virtual leaksis to pump out
the sectionto be tested,isolatethe section,and measureand recordthe pressure
as a function of time. The rate of pressurerisefor a real leak is constant,whereas
the virtual leak will tend to leveloff as the effectivevapor pressureof the outgassing material is reached.The following sectionswill be devotedprimarily to the
ddtectionof real leaks.
It is important to conduct the searchfor leaksin a thorough and methodical
fashion,as outlined in Table 7.1. The examplesgivenhere are for a glasssystem
with greasedstopcocksand joints, but the readershould have little difficulty in
applying the samestrategyto other typesof apparatus.In many instancesthere
may be a suspectsitewhich a quick checkwill revealto be the sourceof the leak.
If, however,there is no obvioussource,a methodicalcheck shouldbe inititated.
For any system.the vacuum pump shouldbe checkedfirst to ensureit is delivering the appropriatevacuum. In a typical preparativevacuunlsystem,stopcocks,
valves,and joints are the most common sourcesof leaks. Freshlygreasedjoints,
particularly those which have been greasedtoo heavily, are likely to develop
leakagepaths which generallytake the form of dendritic channels.Old greased
joints or those which have been subjectedto solventvapors may developleaks
when turned, becausethe greasefilm is too thin. Theseleakagepaths are generally evident in the form of fine striationswhich extend around the diameter of
the stopcockbut interconnectat various points. Thus a visual inspectionof the
greasedjoints and stopcocksmay turn up the sourceof the leak. Once a suspect
144
PRESSURE
AND LEAKDETECTION
AND FLOWMEASUREMENT
Toble7.'1.Summoryof fhe Sfrofegyfor Locofingond ConfrollingLeoks

Prelintinun, Survevo.f \ra1t.t
Preliminary visual check of any greasedstopcocksand valves.(Look for striationsor
channelsin the grease.)
Methodicul SeurchJor Leuk
I
correct
Check pumping systemto be sure it is achievinga good vacuum. If necessary,
problem with fore pump, diffusion pump, or cold trap.
z-
Pump out entire systemand turn off stopcocksor valvesto isolateeverysystentpossible.
J.
After a short wait, open sectionto the vacuumgaugeand note whetheror not there is a
large pressurerise.
When a suspectsectionis located,punrp it out, isolateit from the pump and measure
the pressurerise at regular time increnrents.A steadypressurerise indicatesa real
leak. A levelingoff of pressurerise with time indicatesa virtual leak.
5 . Inspectgreasedstopcocksand joints in the vicinity of the leak, and turn the stopcock
or joint while noting the pressure.Run a Tesla coil over glass-blownjoints to locate
pinholes. Inspect O-ring contact on glassware.Squirt CH,OH on suspectedparts
while noting pressureon an ionizationgauge. Use a halogenor helium leak tester(a
necessityon metal systenrs).
6. Clean systemandlor bake it out if virtual leaks are indicated.
F i x i t t ga L e u k
l. Regreasefaulty stopcocksor joints.
2. Clean O-rings and/or replaceO-rings on leaky O-joints or valves.
3. Tighten Swagelokjoints or remake the joint with new tubing and ferrules.
4. Troubleshootthe seat, packing, or bellowson metal valves.
5. Repair pinholesin glassor poorly welded or brazed metal parts.
joint or stopcockis found, its potential role as a leakagesite can be checkedby

rotating it slightlywhile checkingan electronicvacuumgaugefor fluctuationsin
the vacuum. Often O-ring joints or glassvalvescontainingO-ring sealsare potential sitesof leakage,but here the problem is more difficult to spot visually.
If visual inspectionof the most suspectjoints or stopcocksfails to revealthe
leak, a systematicisolationof parts of the vacuum systemis in order. For a vacuum line of conventionaldesign(e.9., a line approximatingthat in Fig. 5.2), it is
generallybest to turn off all stopcockswhich interconnectthe various parts of
the vacuum system.As a result, the high-vacuummanifold is isolatedfrom the
pumps and the rest of the line, and it is checkedby determining if there is a
steadypressurerise in that section.If this sectionappearsto be intact, but it
LEAKDETECTION
A AE.
does not pump down well when reopenedto the pumps, the vacuum sourcers
suspect.In the eventthat the vacuum sourceand main manifold are not at fault,
each sectionof the vacuum systemis then openedto the high-vacuummanifold,
with an eyeon the pressuregaugeto indicatethe leaking section.Once the general region of the leak is identified, this part of the apparatus is thoroughly
checkedto pinpoint the leak. A visual check ofjoints and stopcocksmay again
be in order, or the searchmay be conductedwith one of the devicesmentioned
below.
B. Leok Defecfion Using o Teslo Coil. Pinholesare a major sourceof
leaks, particularly in newly constructedglassware.One of the common devices
for locating these leaks is the Tesla coil, which providesa high-voltage,highfrequencyspark dischargein air. The probe of the Tesla coil is touched to the
glass apparatus at various spots until a glow dischargeis initiated inside the
vacuum chamber. The probe is then passedover the suspectparts of the glassware, and the presenceof a pinhole is revealedby an intenseblue spark which
jumps through the hole. The Tesla coil should neverbe usedaround thin glass,
such as bread-seals,since it will puncture holes in the apparatus.Similarly. it
may punctureO-ring materialsand generallyis not usefularound greasedjoints.
The Tesla coil is also ineffectivearound metal parts, which simply serveas a
ground.
The color of the glow dischargeinside the apparatusis characteristicof the
gasespresentand of some help in locating the leak. For example,if the atmospherein the vacuum systemis primarily ntercury,a light blue glow is seen;but
if there is an air leak, the dischargetakes on a more purple color. When the
pressurein the systemdrops below approximately10 3 torr, the glow discharge
cannot be sustained,and this is sometimesuseful as a crude indication of the
degreeof vacuum.
C. [eok Defeclion Using Vocuum Gouges.
R e f e r e n c eh a s a l r e a d y
been made to the use of an electronicvacuum gaugein hunting leaks. A coldcathodegaugeis particularly useful becauseit has rapid responseand operates
well in the presenceof small leaks. Becauseof this rapid response,acetoneor
methanol can be squirted on the suspectedarea. If a hole is present,a momentary pressuredrop will be observedbecausethe acetoneor methanolmolecules
are slowerthan air to diffuse through the hole. Sometimesa helium stream is
directed on the suspectedleak; in this casea pressurerise is noted when the
helium passesover the site of the leak, becausehelium diffusesmore rapidly
t h a n a i r . I t a l s o i s s o m e t i m e sp o s s i b l et o u s e a p u t t y l i k e m a t e r i a l , s u c h a s
Apiezon Q, to cover temporarily a suspectedleak.
If the leak path is tortuous, these techniquesdo not work rvell and a leak
detectormay be more suitable. For example, leaks in swage-typefittings (Section 10.3.C) and valvesof various types may be difficult to detect using these
methods.
146
PRESSURE
AND FLOW MEASUREMENT
AND LEAKDETECTION
D. Leok Delection UsingHeliumor HologenLeok Deteclors. Commercial leak testers have high sensitivityand are very useful with metal vacuum
systems.Only two common types, one based on halogenatedcompoundsand
one basedon helium, will be coveredhere.
The halogenleak tester is widely used in refrigerationapplications,but it is
sufficiently sensitivefor many types of chemical vacuum systems.The apparatus
is filled with a halogenated hydrocarbon and the probe of the tester is passed
over the suspectedarea. The gas that is collectedby the probe is passedover a
hot platinum wire with the resulting formation of positiveions which are collectedand measuredwith a microammeter.
Helium leak testershavefar higher sensitivitythan thosebasedon halogens.
In this case,helium is detectedby a small mass spectrometerset on mass4. In
the leastsensitivemode the apparatusis filled with helium and the suspectsites
are "sniffed" with a probe connectedto the vacuum chamberof the massdetector. In a more sensitivemode the leak detectoris connectedto the vacuum system often as the solepump on the system.A streamof helium is then passedover
the suspectsitesfor the leak. An audible and/or meter signalis usedto indicate
the amount of helium reachingthe massdetector.Sincethe natural background
at mass 4 is very low, thesetesterscan be highly sensitiveand very specificin
pinpointing leaks.The helium leak testeris, however,fairly complexand expensive, since it includes, in addition to the mass spectrometer,a vacuum system
complete with liquid nitrogen trap, diffusion pump, fore pump, and often a
large roughing pump.
E. Leok DelecfionUsingResiduolGosAnolyzers. Theresidual

gasanalyzer,which has been describedin Section7 .2.D, is an excellentdevicefor locating both virtual and real leaks. Most of these instrumentscan be scanned
through the low molecularweight massrange. This massspectrumallowsready
discrimination between virtual leaks from solventsand the like, versus real
leaks, which show up with high peakscorrespondingto the atmosphericgases.
The location of the specificsite of leakagemay be accomplishedby settingthe
instrumenton mass4 and passinga smalljet of helium overthe suspectedareas.
7 .4 FLowMEAsUREMENT
When working with apparatussuch as catalyticflow reactors,the measurement
and control of gas flow becomesas important as the measurementof pressure
just describedfor vacuum line work. Some of the more common methodsfor
measuring and controlling gas flow in gas-handlingsystemswill now be discussed.
Gas flow is usually quoted in terms of velocity(cmls) or "mass flow" (standard cm3/s).Velocitymay be measuredby a venturi tube pointing into the flowing stream with a pressuretransduceror manometerconnectedto the venturi
tube. The two schemeswhich are more attractivefor small-scaleapparatusare
147
FLOWMEASUREMENT
the rotameter, which is basedon a "float" which is bouyed by the stream of gas,
and a variety of thermal methods based on thermal conductivity or heat capacity. The thermal methods are readily adapted to digital output and automatic
flow control. Although the temperature of the operating sensorelement is not
high (generallyunder 100"C), thermally sensitivecompoundscan be pyrolyzed
in this type of flow meter.
A variety of flow meter deA. Flow Meosutemenl by Displocemenf.
positive
signsare basedon the
displacementof a small amount of easilyvisualized material which doesnot alter the flow rate. A simple and easilyconstructed
mass flow meter of this type, the soap-film meter, is based on timing the displacementof a soapfilm up a buret tube (Fig. 7.11). This type of flow meter is
often placed at the exit of a gas chromatograph or small flow reactor. It is very
Buret
R u b b e rb u l b
F i g . 7 . 1 1 . S o a p - f i l mf l o w m e t e r . S o a p s o l u t i o ni s p o u r e d i n t o t h e r u b b e r b u l b s o t h a t t h e s o l u t i o n
l e v e l i s j u s t b e l o w t h e l e v e l o f t h e s i d e a r m . A f t e r a t t a c h i n gt h e f l e x i b l e t u b i n g t o t h e f l o w i n g g a s
s o u r c e ,t h e r u b b e r b u l b i s g e n t l y s q u e e z e dT. h i s a l l o w st h e f l o w i n g g a st o p e r c o l a t et h r o u g h t h e s o a p
s o l u t i o n ,p i c k i n g u p a t h i n f i l m o f s o a pw h i c h w i l l t r a v e lu p t h e b u r e t . B y n o t i n g h o w l o n g i t t a k e sf o r
the film to travel between two points on the buret, the flow may be determined.
448
AND LEAKDETECTION
AND FLOWMEASUREMENT
PRESSURE
usefulfor occasionalmeasurements.but cumbersomeif the flow must be monitored frequently.

B. Flow Meosutemenl by Orifice Areo. The simplestand most popular
laboratorymassflow gaugeis the rotameter,which consistsof a float in a vertical
taperedtube with the larger diameterat the top and the gas inlet at the bottom
(Fig. 7.12). The float maintains a constantpressuredifferentialon the gasflowing past it, and as the float rides higher a larger annular openingis availablefor
the gas. Graduations on the side of the glassor clear plastic tapered tube are
thus relatedto the flow rate. Thesegraduationsare calibratedfor a specificgas
(often dry air); a calibration chart is neededfor other gases.The calibration of a
rotameteris dependenton the pressurein the system.If true "massflow" (molar
flow) is required, a pressurecorrectionis necessary.
C. FlowMeosurementby PressureDrop ocrosson Orifice. Another

common schemefor the measurementof flow is basedon the determinationof
the pressuredrop on either side of a constriction,such as an orifice or venturi.
Either a liquid-filled differentialmanometeror a pressuretransducerwith associateddigital readoutmay be usedfor this pressuremeasurement.The flow rates
determinedby these meters are in units such as cmr/s, and it is necessaryto
make a correctionfor total pressureto converttheseto standardcm3/sor mol/s.
A popular seriesof massflow metersis availablewhich is basedon the useof a
thermal sensorin a side stream (Fig. 7.13). Generally,these flow meters are
F i g . 7 . 1 2 . R o t a m e t e rf l o w m e t e r . T h e b a l l i s b o u y e db y g a s f l o u u p t h e c o n i c a lt u b e . A g r a d u a t e d
scale is provided for visual measurement of the flow rate.
FLOWCONTROL
149
F i g . 7 . l 3 . S c h e n r a t i co f a m a s s f l o w n l e t e r . T h e f l o s ' i s p r o p o r t i o n a lt o ( 2 , - I , ) I . T h i s t 1 ' p eo f
n r e t e ri s o f t e n e m p l o y e di n a n e l e c t r i c a l l yc o n t r o l l e df l o u ' r e g u l a t o r .Z , a n d T , a r e t e n r p e r a t u r ! ' s e n sors:Hisxheater.
suppliedwith a digital readout calibratedfor the massflow of one specificgas.

Thermally sensitivecompoundsmay be pyrolyzedon the therrnalelement,and
the small sensorchannel can be blocked by the decompositionproducts. The
calibration on these meters is dependenton the heat capacityof the gas being
handled and, to a somewhatlesserextent, on the viscosityof the gas. The caliin handline different
bration factor can be electronicallvalteredfor convenience
gases.6
7 ,5 FLowcoNrRoL
A. Flow Confrolwifhoul Feedbock.
F l o w c a n b e c o n t r o l l e db y m e a n so f
a needlevalve ifthe pressuredrop acrossthe valveis constant.The pressureon
the upstreamsideoften can be held constantwith a single-or two-stagemechanical diaphragm regulator(Section10.l.B). If the streamof gas doesnot experience a variable constrictionafter the needlevalve,the abovecombinationprovides a simple and convenient means of providing a steady flow. Often an
arrangementsuch as this is used in conjunctionwith a rotameteror electronic
m a s sf l o w m e t e r ( F i g . 7 . 1 4 ) .
i ' F l o * ' n r e t e r sb a s e do n t h e r n r a ls e n s o r sa n d e l e c t r o n i cf l o s ' c o n t r o l l e r sa r c a v a i l a b l ef r o m t h e f o l l o w i n g c o m p a n i e s :M K S a n d D a t a n l e t r i c s ,l i s t e di n f o o t n o t e5 : B r o o k sI n s t r u m e n t sD i v . , E m e r s o nE l e c t r i c C o . , 4 0 7 W . V i n e S t . , H a t f i e l d , P A 1 9 4 4 0 ;T e l e d y n eH a s t i n g s - R a y d i s tH
. ampton, VA 23661:
T y l a n l n c . . 2 3 3 0 1S . W i l m i n g t o n A v e . , C a r s o n ,C A 9 0 7 4 5 ;U n i t I n s t r u m e n l sI n c . , 1 1 4 0E . V a l e n c i a
D r . . F u l l e r t o n .C A 9 2 6 3 1 .
4(n
AND LEAKDETECTION
PRESSURE
AND FLOWMEASUREMENT
F i g . 7 . 1 4 . C o m b i n a t i o n o f t \ r ' o - s t a g ep r e s s u r er e g u l a t o r ( P ) , s h u t o f f v a l v e ( S ) , f l o w c o n t r o l v a l v e
( F ) , a n d r o t a m e t e r( R ) . O i s t h e q a s o u t l e t .
D. Flow Confrol wifh Feedbock.

More positivefeedbackcontrol of the
flow rate is neededfor applicationssuchas flow reactorsfor the epitaxialdeposition of semiconductorfilms, and catalltic flow reactors.Severalelectronicflow
controllersare available.One of the most commonly used versionsis basedon
the massflow meter with a thermal sensingelement,mentionedabove,and feedback control to a valve,which typically is either actuatedthermally or magnetically.bSome of thesevalveshave rather small orificeswhich can be cloggedby
the decompositionof reactivemolecules,for exampleSiHaand Ga(CH:):, which
may react with traces of oxygen. As with the flow meters based on the same
principle, thesecontrollersregulatethe molar flow, independentof total pressure. A calibration factor is necessary
for different gases.but this can be determined from the ratio of heat capacitiesfor gasesof similar nature. A large
change in the character of the the gas-say, hydrogen in place of nitrogenrequiresexperimenta.lrecalibration.
GENERAL
REFERENCES
B e n e d i c t ,R . P . , 1 9 8 4 ,F u n d u n t e n t a l so l T e n t p e r a t u r t ' P
, r e s s t t r ea, n d F l o u ' M e u s u r e m t ' n t s . 3 r de d . ,
W i l e 1 . N e u ' Y o r k . P a r t I l o f t h i s b o o k . e n t i t l e d " P r e s s u r ea n d I t s M e a s u r e m e n t , "p r e s e n t sa n
e x c e l l e n to v e r v i e uo f t h e c o n c e p t a n d s t a n d a r d so f D r e s s u r ea, n d t h e u s e o f m e c h a n i c a la n d
GENERAL
REFERENCES
45.1
electronic transducers to measure pressure. "Flow and Its Measurement" is reviewed in Part
I I I , i n c l u d i n gc h a p t e r so n t h e c o n c e p to f f l o w r a t e a n d t h e o r e t i c a rl a t e sf o r c o n s t a n t - d e n s i tayn d
c o m p r e s s i b l ef l u i d s i n c l o s e d - c h a n n ef il o w .
I n t r o d u c t i o n t o H e l f u n M a s s S p e c t r o m e t e rL e q k D e t e c t i o n , l 9 8 0 , V a r i a n A s s o c i a t e sP
, alo Alto.
This reference presents a good overview of the fundamentals and methods of leak detection,
followed by a detailed discussionof the helium leak detector.
L e a k D e t e c t o r M a n u a l , 1 9 8 1 , G e n e r a l E l e c t r i c C o . , L y n n , M a s s . T h e m a n u a l f o c u s e so n h a l o g e n
leak detector methods developedby this company.
O'Hanfon, J. F., 1980, A Users Guide to Vacuum Technologt,,Wiley, New York. This book is a
good source of information on vacuum gaugesand residual gas analyzers.
T h o m p s o n ,G . W . , 1 9 5 9 .T e c h n i q u e s o .Of r g u n i c C h e m i s t r y .V o l . l . P a r t l , 3 r d e d . , A . W e i s s b e r g e r ,
E d . . l n t e r s c i e n c eN
. ew York.
STOPCOCKS,
JOINTS,
AND VALVES
This chapter describesthe various stopcocks,valves,and joints used in glass

vacuum and inert-atmospheresystems.Although greasedstopcocksand joints
are familiar and straightforwardin design,their use on high-vacuumsystems
requiresmore than the usual amount of attention to detail. The newerO-ringsealedjoints and valves,which are taking the place of greasedstopcocksand
joints in many applications,are also discussedhere. Metal bellowsvalvesare
more leak-tight than glassvalvesor stopcocks,but their use on glassapparatus
requiresspecialdesignswhich are outlined at the end of this chapter.
8.'l JorNrs
A. Slondold Toper ond Boll Joints. These joints (Fig. 8.1) have been
usedfor many yearson vacuum and inert-atmospheresystems,and the availability of a variety of syntheticgreasesand waxeshas extendedtheir utility. Of the
two, the ball-and-socketjoint permits more flexibility in the orientationof the
two halves.When this flexibility is important, this type of joint is obviouslyto be
preferred, even though the ball joint is somewhat more prone to leak than a
standardtaper joint. Both metal ball joints and metal standardtaper joints are
available,rand theseitems provide one meansof joining metal and glassapparatus,
rMetal ball joints, metal standard taper joints, and O-ring joints with a step tooled into the groove
are available from Kontes Glass Co., P.O. Box 729, Vineland, NJ 08360. The first two items are also
a v a i l a b l ef r o m A c e G l a s s C o . , P . O . B o x 6 8 8 . V i n e l a n d , N J 0 8 3 6 0 .
,52
153
JOINTS
ik
n
rd
PT
mma
V,,
Ffl
lBmm=\
l.+
9mm-l-r-'i I
'+ommfr
)r (l-
1l
5 24/40
tl
r\l
J 1Bl9
F i g . 8 . 1 . S t a n d a r dt a p e r ( 3 ) a n d s p h e r i c a lj o i n t ( $ ) . W h e n t h e j o i n t s a r e l u b r i c a t e dw i t h g r e a s e ,
t h e y m u s t g e n e r a l l yb e h e l d t o g e t h e r .S p r i n g so r r u b b e r b a n d sa r e f r e q u e n t l ye n t p l o y e do n s t a n d a r d
t a p e rj o i n t s , w h i l e a s p r i n g - l o a d e dc l a m p ( i l l u s t r a t e dh e r e )o r a s c r e wc l a m p ( i l l u s t r a t e di n F i g . 8 . 3 ) i s
u s e dw i t h b a l l j o i n t s . T h e m e t h o d u s e df o r s p e c i f y i n gj o i n t s i z e si n t h e U n i t e d S t a t e si s i l l u s t r a t e d .
a n d i t i s d e s c r i b e di n d e t a i l i n N a t i o n a l B u r e a u o f S t a n d a r d s ,C o m m e r c i a lS t a n d a r dC S 2 l - 3 9 .
Teflon sleevesare availablewhich may be usedto replacegreaseas a sealing

agent in standardtaperjoints. Thesesleevesare usefulon still pots and in other
harsh but not highly demanding situations;however,it has been the authors'
experiencethat they are not suitablefor high-vacuumapplicationsor in situations requiring very good exclusionof the atmosphere.To achievegood vacuumtight performance with standard taper joints, the greasemay be applied in several thin stripeswhich run parallel to the direction of the male joint (Fig. 8.2).
The joint is then worked togetherwith an oscillatingmotion which squeezes
out
the pockets of air and leads to a thin, uniform film. Good-quality stopcock
greasecontaininga minimum of volatilesand uncontaminatedby dirt or dust is
essential,becausevolatilesoutgasbadly and particlesinterrupt the film and produce leaks. The film of greasemust be thin becausethe pressuredifferential
acrossthe joint will pull channels in a thick film. Silicone and hydrocarbon
greasesare the most popular; the chemicaland physicalcharacteristicsof these
and other common greasesare given in Table 8.1.
In general,stopcockswhich have been disassembled
should be cleanedthorbefore
are
regreased
reassembled.
Hydrocarbon
oughly
they
and
solventswill
removemost greases.When the glasswareis being cleanedrigorously, hydrocarbon residuescan be removed in an acid-dichromatecleaning bath. Residues
from silicone stopcock greaseare much more tenacious.Thin films of such residues can be removed by means of alcoholic KOH (methanol nearly saturated
with KOH). Ground-glassitems, and particularly fritted items, should not be
left in the alcoholic KOH bath for extended periods, sincethis cleaning solution
slowlyetchesglass.
When a joint is only occasionallyopened and flexibility at the joint is not
^qA
AND VALVES
JOINTS,STOPCOCKS,
F i g . 8 . 2 . A p p l i c a t i o no f g r e a s et o j o i n t s a n d s t o p c o c k s (. a ) G r e a s ei s a p p l i e d i n s e v e r atl h i n s t r i p e s
t r ' h i c hr u n p a r a l l e lt o t h e d i r e c t i o no f t h e m a l ej o i n t . A w o o d e ns p l i n t m a v b e u s e dt o a p p l y t h e g r e a s e
to avoid contamination by moisture or dust on fingers. () The joint is worked together with an
o s c i l l a t i n gm o t i o n a n d s l i g h t s t e a d yp r e s s u r e .
needed,it is generallypreferableto use wax insteadof grease.Wax makes a

much more permanentjoint than greasebecauseit doesnot flow out of the joint
and is somewhat less sensitiveto solvent vapors. Two excellent waxes are
Apiezon W, a black hydrocarbonwax, and Kel-F 200, a colorlesschlorofluorocarbon of low vapor pressureand good resistanceto chemicalattack. The characteristicsof these waxes are given in Table 8.2. Both halvesof the joint are
heatedto somewhatabovethe melting point of the wax using a small gasburner
flame or heat gun. A stick of the wax may then be rubbed on the male joint,
preferably in stripes as describedabove. The two warm parts are joined and the
wax is worked into a uniform film by oscillatingthe joints and pushing the two
parts together.usuallywith additional heatingof the outer joint. Temperatures
well abovethe melting point causebreakdownof the wax; this is particularlytrue
of DeKhotinsky-typewaxes, which polymerizewhen heated too strongly. To
open a waxed joint, it is heated uniformly and gently to just abovethe melting
point and disassembled.It is most satisfactoryto cleanoff old wax with the appropriate solventand apply fresh material beforethe joint is reassembled.
B. O-Ring Joinfs. The major difficulty with greasedand waxedjoints is their
failure to hold vacuum when exposedto solvents,heat, and somechemicals.For
many applicationsO-joints overcomethese limitations. A successfulglass Oring joint which is in wide use is illustratedin Fig. 8.3, whereit may be seenthat
both halvesof the joint are identical. They mate with an O-ring fitted into a
groove,and the two parts are held in placewith a clamp. The two halvesof these
Toble8.'1. SomeCommon Greosesfor Vocuum Apporolus
Brand and Type
Approximate
Vapor
Pressure
(nrm,at
room temp.)
Application
Approximate
Usable
Range("C)
Hydrocarbons
Apiezon L
Apiezon M
Apiezon N
Apiezon T
l0-r0
l0 7
l0 6
l0
Ground joints
Ground joints
Stopcocksand joints
Stopcocksand joints
Max.
Max.
Max.
Max.
Halocarbon
25-55
< l0 '"
Stopcocksand joints
Max. ca. 30
Silicone
Dow Corning Hy Vac
< l0 6
Stopcocksand joints
Ca. -20to
100
30
30
30
I l0
>
Resistance
to Organic
Solvent
Vapors
ChemicallyAttacked by
Poor
Poor
Poor
Poor
Reactivehalidessuch as
BCl.1,and very strong
oxidizing agentssuch as Ol
Poor
Strong reducing agentssuch

as alkali metals, and strong
nucleophilessuch as alkyl
phosphines
Fair
Tends to cake after long

exposureto NH.1gas
Reactivemetalloid fluorides
like BF.
" M a n - ys a m p l e so f t h i s g r e a s ec o n t a i n ss o m e l o w - n l r l c c u l a r - w e i g hvt o l a t r t e sa n d s i l i c ag e l . H a l o c a r b o nP r o d u c t s ,8 2 B u r l e w sC o u r t , H a c k e n s a c k ,N J 0 7 6 0 1 .
(rr
atr
,156
AND VALVES
JOINTS.STOPCOCKS.
Toble8.2. SomeCommon flord Woxeslor Vocuum Apporolus

Approximate
Maximum
Usable Temp.
Temperature
for Application
Resistanceto Organic
Solvents
Brand and Type
(" c)
Apiezon W'
(hydrocarbon)
80
100
Hydrocarbons and nonpolar

solvents-poor
Lower alcohols-good
Sealstix
(improved
DeKhotinsky)
100
140
Hydrocarbons-good
Alcohols,acetone,ethyl
acetate,and dioxane-poor
40
90
Kel-F20tr
( ' c)
Hydrocarbons and nonpolar

solvents-poor
Lower alcohols-good
'Available from most scientific suppliers.

6 C e n t r a lS c i e n t i f i cC o . , C h i c a g o , I L , a n d m a n y o t h e r s c i e n t i f i cs u p p l i e r s .
'MinnesotaMining and ManufacturingCo., St. Paul, MN.
O
tol
Itlta
ll
'---.\-
E+ffi
#
(ne)
qv
,<---:r
ilil
(c)
( )
Fig. 8.3. Cross-sectionof a Urry-type glass O- ring joint and two types of screw clamps. (c ) An Oring. () Cross sectionof a Urry-type O-joint. Note the ridge which is tooled into the groove. (c) Two
t y p e s o f j o i n t c l a m p s . T h e u p p e r o n e i s m a n u f a c t u r e db y A . H . T h o m a s C o . . P h i l a d e l p h i a ,P A
19r05.
O-ring joints are identical, which givesflexibility in apparatusdesignand use.

Although thesejoints are nominally standardizedso those made by the various
manufacturerswill take the same sizeO-rings and clamps,there are important
differencesin the way the O-ring grooveis tooled. Somecommerciallyavailable
O-ring joints have a groove for the O-ring which has a simple rounded cross
section.This type of joint is much more prone to leak than joints made with a
JOINTS
4F'7
ridge or steptooled into the the O-ring groove.rThe stepor ridge provideshigher
pressureon the O-ring and thus givesa better sealthan the designsin which the
pressureis distributed more uniformly over the groove. Since O-rings are manufactured from elastomericmaterials, they are subjectto the absorptionof solventswith attendant swelling.In addition to the undesirablechangesin dimensionsthis causes,swellingalso leadsto a lossin strengthand, in extremecases,
disintegrationof the O-ring may result. The problem is considerablylessserious
than for greasesand waxes,and it is often possibleto choosean O-ring material
which is only slightly affectedby the solventsor chemicalsbeing handled.To aid
in this selectiona summary of elastomerpropertiesis given in Table 8.3, and a
more extensivediscussionof elastomersis givenin Appendix III. The bulk of the
laboratoryapplicationsis servedby two typesof O-ring materials:hydrocarbon
rubbers, such as ethylene-propylene
rubber or butyl rubber, and halocarbon
rubber, such as Viton. The former withstandspolar solventsand strong reducing agents,whereasthe latter holds up to nonpolar solvents,oxidizing agents,
and Lewis acids. Teflon O-rings and Teflon-coatedO-rings are available,but
most of theseare not sufficientlycompliant to provide reliable leak-tight seals.
The Solv-Sealis a variant on the aboveO-joint designwhich reducescontact
As illustratedin Fig. 8.4, this joint consistsof a pair
of the O-ring with solvents.2
of O-rings fitted to the outside of a Teflon cylinder and a pair of glassjoints
which mate with this seal. The cylinder fits inside the glassparts and the parts
are clamped togetherwith a standardcompressionclamp of the type illustrated
in Fig. 8.3. The vacuum sealis made at the concentricO-rings,but the supporting Teflon cylinder also mates with the glass parts sufficiently well to reduce
contactbetweenthe O-rings and solvents.As with the standardO-ring joint describedabove,the symmetryof the two halvesof the Solv-Sealjoint and the ability to positivelyclanrpthe two halvestogethermake thesejoints especiallyversatile. Both types of O-ring joint are very useful in the Schlenk-type
inert-atmosphereglassware(see Chapter 1), and on high-vacuum systemsin
which organic solventsare handled extensively.
There is a variety of O-ring fittings which attach to straightglasstubes (Fig.
8.5). The outer body of thesefittings is constructedfrom metal or plastic and
containsa threadednut which either directlyor indirectlycompresses
an O-ring
betweenthe outer wall of a tube and the inner wall of the fitting.r Thesefittings
providegood vacuum-tight performanceand are especiallyusefulfor attaching
NMR tubes and storagetubes to a vacuum systemso they may be sealedoff.
They are also convenientfor joining metal and glasstubing and find application
in situationswherethe two parts of an apparatusmust rotate while a leak-tight
sealis maintained (for example.the vacuum line filtration apparatusdescribed
2 S o l v - s e aal sr e a v a i l a b l ef r o m F i s c h e ra n d P o r t e rC o . L a b - C r e s tD i v . . C o u n t yL i n e R o a d , W a r m i n s i ,
ter. PA 18974.
yfhe
concentric O-ring fittings are available from Crawford Fitting Co., 29500 Solon Rd., Solon,
O H 4 4 1 3 9 ( u n d e r t h e t r a d e n a m e o f C a j o n U l t r a - T o r r f i t t i n g s ) ; a n d K o n t e s G l a s s C o . ( a d d r e s si n
f o o t n o t e l : i t e m s K - 1 7 9 9 0 0a n d K - 1 7 9 9 1 0 ) .
(rl
@
Ioble 8.3. Properfiesof some Eloslomerso'D

Chemical Reactivity
SolventSensitivity
Polar
Elastomers Hydrocarbons Organics
Butyl Rubber
Buna N
EPR
Chloroprene
Silicone
Vitono
Solvent code/
P,P
G,P
P,P
F-,P
P,P
G,G
1.2
F,G,P,F.F
P,P,P.P,P
F,G,P,F,F
P,P,F,P,P
P,P,P,F,P
P,P,P,P,P
3,4,5,6,7
Strong
Chlorinated
Alcohols Hydrocarbons Oxidants
G,F
G,G
G,F
G,F
F,F
G,G
8,9
P
FtoP
P
P
P
G
P,F
P,P
P,F
P,P
P,F
G,G
l 0 , ll
Strong
Reductants
;
t2
Covalent
Halides
Conc.
Sulfuric
Approximate"
Usable
Temp.
Range("C)
G,P
G,P
G,P
P,P
F,G,G
r3 , 1 4
F
P
F
P
P
G
-54, 150"
-54, 120'
-54, t50'
-54, 150'
-80,230'
-50, 300'
"G : Good, F : Fair, P : Poor. All ratings are for room temperature.
'Adapted in part from data supplied by E. L duPont and by Parker Seal Co.
' F o r t h e d r y O - r i n g i n a i r . T h e l o w - t e m p e r a t u r el i m i t s a r e o n l y a t t a i n a b l ew i t h s p e c i a lf o r m u l a t i o n s .
r l , r r - h e x a n e 2l . b c n z e n e ;3 , p y r i d i n e ; 4 . a c c t o n e ;5 , d i e t h y l e t h e r ; 6 , e t h y l a c e t a t c ;7 , n i t r o m e t h a n e ;8 , n r e t h y la l c o h o l ;9 , r - h e x y l a l c o h o l ; 1 0 , b r o m i n e ; I l ,
5 0 9 o c h r o m i c a c i d ; 1 2 . N a i n l i q . N H , ; 1 3 , s t a n n i cc h l o r i d e : 1 4 , s u l f u r c h l o r i d e .
Fig' E.4. Solv-sealjoint' A pair of o-rings form the seal between

the Teflon cylinder and glass
j o i n t s . T h e c y l i n d e r f i t s i n s i d et h e g l a s sp a r t s . A c o m p r e s s i o n
c l a m p ( s e ef i g . g . J c ) h o l d s t h e j o i n t
tpgether.
t)loss or m e t 0 t
?uDlng
(b)
Fig. 8.5. A cutaway illustration of O-ring coupling devices.(a.) The body and knurled nuts
are
made of metal (cajon union). (b). Body and compressionnuts made of plastic (Kontes).
{59
160
JOINTS,STOPCOCKS,
AND VALVES
in Chapter 9). Fittings such as the Cajon Ultra-Torr require tubing of closely
matching diameter.
Still another O-ring joint design is based on a glass fitting with an inner
threada(Fig 8.6).
C. Swoge-Type Fitlings. These fittings are widely used for joining metal
tubing, but they can alsobe usedwith glasstubing. Swagejoints are describedin
d e t a i l i n S e c t i o n 1 0 . 3 . C , w h i c h s h o u l d b e c o n s u l t e df o r d e t a i l s . A l t h o u g h
thesefittings are used successfullyfor glass-to-glass
seals,the aforementioned
O-ring joints are generallymore satisfactorybecausethey are easierto tighten
and lesslikely to lead to stresson the glasswhen they are installed.The major
application of swage-typefittings is in joining metal and glassparts: for example, to attach a metal gas deliveryline to a glassapparatus,or to attach metal
valvesto a glasssystem.A taperedTeflon ferrule is usedto form the sealbetween
the fitting and the glasstube. Sincethe complianceof this ferrule is not great, it
is essentialto use a ferrule of the correct dimensionsto match the glasstubing.
This may require the use of medium-walledtubing, which is sized in English
units, to mate the standard swagejoints, which are generallysuppliedwith dimensionsin English units. It is alsopossibleto obtain fittings and ferrulesmade
to metric dimensionsswhich will mate directly with the appropriate-sizestan-
B u s hi n g
T h r e a d e dg l a s s
O-ring
Fig. E.6. Ace threaded connector. This connector providesan O-ring sealbetweena threaded glass
t u b e a n d a n i n n e r t u b e w h i c h m a y b e g l a s s ,p l a s t i c ,o r m e t a l .
aThreaded O-ring connectors are available
from Ace Glass Co. (addressin footnote l).
sSwage-typefittings to metric and English
dimensionsare availablefrom Crawford Fitting Co. under
the trade name Swagelok (address in footnote 3).
sToPcocKs
461
dard walled glass tubing, which is also made to metric dimensions.To avoid
cutting the ferrule or cracking the glasstube insidethe swagefitting, it is bestto
finish the glasstube with a clean cut perpendicularto the tube axis, and to remove the sharp edge with very light sanding or a very light fire polish. Because
Teflon tends to cold flow, it is sometimesnecessaryto retightenthesejoints.
8,2 sToPcocKs
The proper selectionand maintainanceof stopA. Vocuum Sfopcocks.
cocks is important becausethey are a primary sourceof leaks in vacuum or inertatmosphere systems.Close tolerances are necessary,and therefore most highvacuum stopcockshave the plug and shell individually lapped together and
numbered to avoid mismatch. Hollow-plug vacuum stopcocksseemto give the
best performance. The common patterns for such stopcocksare shown in Fig.
8.7. For those shown in Fig. 8.7a through 8.7d, the plug is held in the stopcock
by the vacuum on the back side of the stopcock,thus reducing leakage.These
types of stopcocks are only useful on vacuum systems.It is important to avoid
Fig. 8.7. Hollow-plug vacuum stopcocks.The hollow plug is firmly seatedin types (a), (), and (c)
as long as the lower section is at reduced pressure. Stopcock (d) has a hollow plug with an oblique
tube in the center; when the plug is turned by 180", the lower section may be evacuated. Subsequently, only occasionalevacuationof the vacuum cup is necessary.Type (e) doesnot have provision
for evacuation of the plug and is therefore more liable to leak. Prolonged exposureof any of these
stopcocks to solvent vapors erodes the grease and introduces leaks. (Adapted from Catalog C-64,
Eck and Krebs Co., Long Island City, NY lll0l.)
162
AND VALVES
JOINTS,STOPCOCKS,
pressurizingthese stopcocks,becausethe plug is then loosenedand in an extreme casecan becomea projectile.It should be noted that the vacuum cup on
the stopcockillustrated in Fig. 8.7d can only be evacuatedthrough the lower
sidearm.This factor requiresthat the stopcockbe orientedwith that arm pointing toward the sourceof vacuum.
Proper application of greaseis evenmore important with stopcocksthan with
joints, becausestopcocksgenerallyhaveshorterleakagepathsthan dojoints and
the frequent actuation of the stopcockresultsin a more demanding situation.
The barrel and plug shouldbe cleanand lint free. Four even,longitudinalstripes
of greaseare appliedto the plug and it is insertedin the open position(Fig. 8.2).
By applicationof pressureand small oscillationsto the plug, the greaseshould
form a continuousthin film. Large stopcocksmay requireevacuationto achieve
a continuousfilm of grease.Permanentstriationsrunning around the stopcock
and barrel may be due to minute particles of dirt or uneven or insufficient
grease.For a reliable, vacuum-tight seal these striationsmust be eliminated;
however,one must avoid the temptation to solvethis problem by the use of excessgrease. NOTE: If a stopcock is greased too heavily, the greaseextrudes into
the orifice and clogs the opening. Furthermore, the thick film of grease will
break down under vacuum by the formation of channels.A guide to the choiceof
the optimum stopcockgreaseis given in Table 8.1.
It is bestto evacuatea freshlygreasedsystemat leastseveralhours beforeit is
to be used and to work in the stopcocksby occasionallyturning them. When
high vacuum is required, it is usuallyadvantageous
to evacuatethe systemovernight and to flame the glass,exclusiveof stopcocksand joints, to desorbmoisture.
It is important to minimize the exposureof stopcocksand valvesto volatile
organicsolventsat room temperaturebecausethe vaporsdissolvein the stopcock
grease.The presenceof solvent vapors acceleratesthe tendencyfor stopcock
greaseto be squeezedout of the stopcock;and on long standingin the presence
of solventvapors,the stopcockgreasewill literally washout of the joint or stopcock. Once the greasehas absorbedsolventvapors,high vacuum may be unattainable becausethe solventvaporsoutgasfor a long time.
When the greasefilm has becomeextremelythin, either by the influenceof
long standing or of solvents,the leak-freeoperationof the stopcockwill be impaired. This is generallyevidentby the appearanceof striationsin the stopcock
greaseor by the suddencloudy appearanceof the greasefilm when the stopcock
is turned. In this event,thorough cleaningand regreasingare in order. When the
greasebecomestoo thin, it is possiblefor the stopcockto stick in the shell. A
seizedstopcockcan be freed by heatingthe shellwith an air-gasflame and pulling the plug out with a twisting motion. This operationshouldbe carriedout in a
smooth, rapid sequence.A bushy medium- hot flame is used and the stopcock
shell is heatedevenlyfor perhaps 15 seconds.The shell is graspedwith a cloth
towel or gloved hand to stabilizeit and the plug is simultaneouslyturned and
pulled out with the other hand. As describedfor joints in Section8.1.A, stopcocksshould be thoroughlycleanedbeforethey are regreasedand reassembled.
SIOPCOCKS
163
B. Lopping Slopcocks.
Even though commercialvacuum stopcocksmay
be lapped by the manufacturer,it is occasionallynecessary
to repeatthe process
in the laboratory. A stopcock for which a striation-free film of greasecannot be
attained, or one in which the greaseconsistentlyfails prematurely,are candidatesfor relapping.In the extremecase,a poorly matchingplug and shellwill be
evidentfrom a tendencyfor the plug to bind when it is turned. Sometimesstopcocksdistort when they go through an annealingoven, and this is very often the
casewhen a repair is made very closeto the stopcock.Finally, if one memberof a
lappedpair is broken, the substitutepart will haveto be lappedwith the remaining part. Before the operation is started, grease must be thoroughly removed
from both parts, not only on the mating surfacesbut also in the orifices. To
provide an indication of the progressof the grinding operation, the plug and
barrel are both marked with four or more pencil lines running the length of the
ground glass.
If the stopcockis badly warped, it is necessary
to start with coarsegrit, such
as 1SO-mesh
corundum. A small portion of grit is made into a pastewith glycerin
or a 50-50 mixture of water and glycerin.This thin pasteis appliedto the plug in
a smooth,evenlayer. The glycerinis not essential,but it is highly recommended
becauseit reducesthe tendencyfor the parts to seize.The two parts are ground
together by an oscillating motion; the plug is then removed,turned by about
one-fourthof a revolution,and replaced.The grinding is continuedwith care to
replenishthe grit and lubricant before the plug becomesdry. If the parts become
dry or are forced, the plug may seizein the shelland ruin the job. Progressof the
rough lapping should be followed by noting the disappearanceof the pencil
marks. Excessivegrinding with the coarsegrit must be avoidedbecausethis
causesa mismatch of the orifices in the plug with those in the shell. When the
rough grinding is complete,the parts are washedthoroughlyto removethe last
tracesof grit, and the roughnessof the surfacesis reducedby repeatingthe processusing a fine grit and the water-glycerinlubricant. Either 600-meshcorundum or abrasivepolishing alumina is satisfactoryfor the finishing operation.
The latter has the advantagethat it can be removedeasilyand thoroughlyfrom
the apparatus by a quick sodium hydroxide rinse followed by water and acid
rinses.
C. Slopcocks fol Plessure ond Vocuum.

In a typical Schlenksystem,
the apparatusis repeatedlyexposedto a small positivepressureand to vacuum.
This causesstopcocksto become dislodged; therefore, satisfactoryperformance
requiresgood stopcockretainers.An excellentretainer designis illustrated in
Fig. 8.8. This particular retainer requiresthe use of the stopcockproducedby
the same manufacturer.b
6An excellent stopcock and retainer design for use with Schlenk systemsis available front Kontes
G l a s s C o . ( a d d r e s si n f o o t n o t e 1 ) .
464
AND VALVES
JOINTS.STOPCOCKS.
t
/___
r--=+
tl
tl
/\
e-F
E*\
ffiffi
\o.,.ing
ffi
g
4I
(b)
Fig. 8.8. Retainer stopcocksfor vacuum and pressure.This style of stopcock(Kontes Inc.) is especially useful on a Schlenk manifold where both vacuum and small positive pressuresof inert gas are
u s e d .( a ) T h e r e t a i n e ri s b e i n g s n a p p e do n t o t h e b a s eo f t h e s t o p c o c kp l u g . ( ) T h e k n u r l e d n u t h a s
b e e n t i g h t e n e dt o h o l d t h e p l u g i n p l a c e .
D. Metering wilh Sfopcocks.

Stopcocksare not very satisfactoryfor regulating the flow of gases,but improved flow control can be achievedby notching
the orificeson the plug, as illustratedin Fig. 8.9. This is accomplishedby drawing the corner of a three-corneredfile acrossthe orifice in the direction which is
at right anglesto the plug.
8.3 vALVES
A. Gloss Volves. A few of the manydifferentstylesof glassvalveson the
marketare illustratedin Fig. 8.10.The generaldesignconsists
of a glassbody
housingeithera glassor plastic(Teflonor Kel-F)stem.Whenthe stemis con-
Fig. E.9. Notched stopcock plug. A triangular file drawn acrossthe orifice at right angles to the
length of the plug will notch the orifice. This may then be used to better control gas flow, such as an
i n e r t - g a sf l o w w h i l e w o r k i n g o n a S c h l e n km a n i f o l d .
165
VALVES
T e f l o ns t e m
O-ring
G l o s sb o d y
ond seol
(o)
(b)
F i g . E . 1 0 . T e f l o n - g l a s sv a l v e s .A n u m b e r o f v a r i a n t s o f t h i s b a s i c d e s i g n a r e o n t h e m a r k e t . A
" s t r a i g h t t h r o u g h " f l o w p a t t e r n s h o w n h e r e f o r v a l v e( a ) ; ( b ) i s a " r i g h t - a n g l e d " d e s i g n .T y p e ( a )
u s e sa t h r e a d e dT e f l o n s t e m u ' o r k i n g i n a t h r e a d e dg l a s sb o d y . l n t y p e ( b ) t h e s t e m d o e sn o t r o t a t e ,
s o w h e n t h e c a p a n d T e f l o n n u t a r e t u r n e d , t h e s t e m i s f o r c e d u p o r d o w n . B o t h s t y l e sa r e a v a i l a b l e
w i t h a n O - r i n g o n t h e t i p o f t h e s t e m . A l s o , s o m e m a n u f a c t u r e so f f e r e x t e n d e dt i p s , s h o w n i n ( o ) ,
w h i c h p e r m i t g a s f l o w c o n t r o l . ( l l l u s t r a t i o n ( b ) r e p r o d u c e db y p e r m i s s i o no f t h e c o p y r i g h to w n e r ,
K o n t e s I n c .)
structedfrom Teflon, a direct Teflon-to-glasssealprovidesgoodgascutoff at the

seat.The sealbetweenthe glasshousingand the stem is generallyachievedwith
O-rings, although there are at leasttwo designson the market (Quick-Fit and
Young) in which the seal is Teflon-to-glass.Although they are generallynot as
leak-tight as conventionalstopcocks,thesegrease-freevalveshave the tremendous advantagethat they may be used in the presenceof liquid solventsor with
solventvaporscloseto their condensationtemperature.The Stockmercuryfloat
valve,which formerly providedthe most satisfactoryglassvacuum valvefor use
in the presenceof solvents,has been almost completelyreplacedby thesenewer
glassvalves.
In severalvalve designs,the seal at the seat is made by meansof an elastomeric O-ring on the tip of the valve stem. Leak tests indicate that this design
offersno improvementin sealingoverthe valvesin which there is a direct Teflonto-glassseal at the seat. Furthermore, an O-ring at this point is vulnerableto
solvents;so it is the opinion of the authorsthat a direct Teflon-to-glass
sealat the
seatis preferablefor generaluse. When a valveis subjectto temperaturefluctuations, an O-ring on the tip of the stem is an advantage.Teflon has a much higher
expansioncoefficientthan glass,so a valvewith a Teflon stemordinarily should
not be cooled. If cooling is necessary,the sealat the seatcan be maintainedby
tightening the valve as it cools.If the valvehas an O-ring on the seat,it should
not be cooledbelow the brittlenesstemperatureof the elastomer.
The major leakagepath in thesevalvesis past the sealbetweenthe glassbody
and the valvestem, and the variousproductson the market vary widely in their
466
ANDVALVES
JOINTS,
STOPCOCKS,
leak rate at this point. A visual indication of a potential leaky valve is poor Oring contact with the shell or, in those designsusing a Teflon contact, uneven
contact betweenthe Teflon and the glassbody. In general, it is desirablefor the
O-ring to be under high compressionagainstthe glassbody. If there is only a
thin line of contact, the chancesare great that the valvewill leak badly. Some
improvement in performance is achievedwith a light coat of stopcockgreaseon
the O-ring, but this measureis defeatedin the presenceof solvents.Most valve
designsprovide protection of the O-ring seal on the stem by means of a Teflon
wiper machined into the stem, or a Teflon O-ring adjacent to the elastomericOring.
Sincethe Teflon-to-glasssealat the seatof the valve is much more dependable
than the O-ring-to-glasssealat the stem, the valveshouldbe attachedto a piece
of apparatusin the orientationwhich best utilizesthe seatseal. For example,if
the valveshown in Fig. 8.10a is usedon a portablegas bulb, the seatsealon the
valveshould be closestto the bulb. Any leakageinto the bulb would then haveto
occur past the seatseal.If the bulb were attachedto the other arm on the valve,
the bulb would be exposedto the relativelypoor stem seal.Any leakagepast the
stem seal would then contaminatethe contentsof the gas bulb.
The excellent performance of
B. Mefol Volves in Gloss Apporofus.
metal diaphragmsand metal bellowsvalveshas prompted their use in glasssystems. The various types of metal valvesare discussedin detail in Chapter 10;
therefore,this sectionwill addressthe problemsof compatibilityof metal valves
and glass apparatus. The union of metal valves to glass apparatus can be
achievedeasily by means of the swage-typeconnectorsdescribedin sections
8.1.C and 10.3.C. Becausemetal valvesare generallyheavy and more robust
than the glasstubing they are connectedto, the metal valvesmay imbalancea
'l
lo f,Fq
Rl
Gl o s s
TuOrng
A n g l e- r r o n
brocket
boltedto
volve
--l
g l o s st u b i n g
(b)
M o u n t s f o r m e t a l v a l v e su s e di n c o n j u n c t i o nw i t h g l a s ss y s t e m s(.a ) T h e v a l v e sa r e r i g i d l y
Fig. 8,1l
m o u n t e d o n a m e t a l f r a m e w o r k . ( b ) A s e m i f l e x i b l el o o p o f g l a s si s i n c l u d e d t o r e d u c em e c h a n i c a l
strainwith bulky parts.
' ( t t ' g ' 3 l g ) 3 u r q n 1s s e 1 3r a l a u e r p

-llrus Jo dooy u .ro 3urqn1 s.r\olleqIeleru Jo qlEuayuoqs e Jo suueru q uapds
sse13aql o] uorlJeuuoJ elqrxelJrres esn o1 sr sped sse13aql 01 sseJlsJo uors
-srrusueJlar.{leJnpeJol eJnseeuJeq}ouv '{JeJ tunnJe^ aql ol ,{1pl1os
pelunou
sr uJnl ur qJlr.{^\'}aIcBJq llaru o} a^le^ or{i lloq o} sr sr.ualqoJdeseql azrlulurru
o1 qceordde lereua8lseq eql 'pelenlr? ro pellelsur sr e^le^ eql ueq^\ Eurqnl
sse;8aql uo ssoJlsqJnru ool 1nd o1.{cuapuale eq eu araql pue snleruddessu;3
L9'
S]AIVA
VACUUM
SPECIALIZED
LINEEQUIPMENT
AND
OPERATIONS
In Chapter5 the basic designand operationsof a vacuum line werepresentedto

providea conciseintroductionto chemicalvacuum line techniques.This chapter
describesa varietyof more specializedoperationswhich may be consultedas the
reader's needs dictate. Familiarity with the basic vacuum line operationsdescribedin Chapter 5 is assumed.Someof the topics presentedhere are usedfor
the quantitative characterizationof chemical reactions:tensimeters(Section
9.1.A) and tensimetric titrations (9.1.C); or propertiesof compounds:vapor
pressuresabove room temperature (9.1.E), molecular weight determinations
( 9 . 1 . F ) , m e l t i n g p o i n t s ( 9 . 1 . H ) , a n d s p e c t r o s c o p idce t e r m i n a t i o n (s9 . 1 . I . ) A n other group of techniquesis employedfor separations,either for isolation of
products or for analytical purposes: low-temperaturefractional distillation
( 9 . 2 . 8 ) , v a c u u m l i n e f i l t r a t i o n ( 9 . 2 . A ) , a n d g a s c h r o m a t o g r a p h (y9 . 2 . C ) .T h e
long-term storageof gasesand solventsis describedin Section9.3. Sealedtube
reactionsare describedin Section9.4. Finally, a pair of miscellaneous
topicsare
given in Section9.5: sampling alkali metals(9.5.A) and generationof dry gases
(9.5.8).
9,4 cHARAcTERtzATtoN
A. Tensimeters. A tensimeteris an apparatususedto isolatea volatilesample on a high-vacuumsystem,and to characterizethe sampleby measuringthe
equilibrium vapor pressure.The tensimeteris usedin a varietyof important de,r68
169
CHARACTERIZATION
terminations, such as vapor pressuremeasurementson pure substances,gasand resolutionequilibrium measurements,gas-solutionkinetic measurements,

lated purposes such as molecular weight determinations and tensimetric
titrations. Becauseof the wide variety of applications,scoresof designshave
appearedin the literature. This sectionprovidesthree examplesof tensimeter
designsand discusses
the main parameterswhich must be consideredin the design of new systems.
The apparatusillustratedin Fig. 9.I providesa simple, portable,and greasefree systemfor the wide varietyof applicationsmentionedin the introduction to
this section.To achieveportability, this apparatusis built with approximately
10-mm-tubing, which enablesthe determinationof pressureswith acceptable
accuracy for most purposes and yet limits the volume of mercury so that the
Somple
F i g , 9 . 1. M u l t i p u r p o s et e n s i m e t e r S
. i n c et h e s t a n d a r dt a p e rj o i n t i s p o s i t i o n e dc l o s et o t h e m a n o n l e t e r , t h e j o i n t i s c l o s et o t h e b a l a n c ep o i n t o f t h e a p p a r a t u s .T h e t e n s i m e t e ri s b e s t s u p p o r t e db y
c l a n t p i n ga t t h e t a p e rj o i n t a n d b y r e s t i n gt h e b o t t o m o f t h e t e n s i m e t e ro n a p i e c eo f f o a m i n a s n r a l l
d i s h u h i c h i n t u r n i s s u p p o r t e db y a r i n g c l a m p . T h e b r a c e b e t w e e nt h e l e f t a r m o f t h e m a n o m e t e r
a n d t h e j o i n t i s h e l d i n p l a c ew i t h e p o x yc e m e n ta n d a d d ss t a b i l i t yt o t h e a p p a r a t u s .T h e t e n s i m e t e ri s
f i l l e d w i t h m e r c u r y i n t h e s a m em a n n e r a s a U - m a n o m e t e r( s e eF i g . 7 . I c a p t i o n ) .T o m i n i m i z e t h e
v o l u n t eo f m e r c u r y , c a p i l l a r yt u b i n g i s u s e df o r t h e b o t t o m a n d p a r t o f t h e l e f t l e g .
\70
AND OPERATIONS
VACUUMLINEEOUIPMENT
SPECIALIZED
apparatusis easily portable. The demountablesample tube permits the introduction of nonvolatilesolids.This sampletube is attachedto the apparatuswith
an O-ring joint (rather than a greasedjoint), therebypermitting long-termmeasurementsin the presenceof solventvapors. The apparatusis equippedwith a
Teflon-glassneedlevalvewith the seattoward the interior of the tensimeter.As
explainedin Section8.3.A this orientationof the valvereducesleakageinto the
interior of the tensimeter.Also note that the main standardtaper joint is positioned closeto the manometer,and thus closeto a point of balancefor the apparatus. This feature, as well as the crossbrace, make the apparatusreasonably
sturdy and easyto handle.
The volunreinside this tensimetervarieswith pressure.Therefore.in situations which require a knowledgeof the number of molesof gas, it is necessary
to
constructa calibrationcurverelatingthe internalvolumeof the tensimeterto the
nlercurylevel.The procedurefor calibratinga manometerand attachedvolume
h a s b e e nd e s c r i b e di n S e c t i o n5 . 3 . H .
Another type of tensimeterpermits the mercury level to be manipulated so
that a constantgas volume is achieved.One such constant-volumetensimeteris
illustrated in Fig. 9.2. This apparatus is sufficiently unwieldy that it is best
treated as a permanentitem of equipment,with the mercury reservoirwell supported by a fixed plasterbaseand the inlet tube fused to the vacuum system.In
the version shown here, the sample tube is also fused to the apparatus, thus
reducing leakagewhich is inevitablewhen joints are used. Owing to the lack of
leakagepaths, this apparatus is usefuIin situationswhere very long equilibration times are necessary.Sincethe apparatusis fixed, it is possibleto use largediameter tubing in the manometerand thus obtain great accuracyin the pressure measurements,if this is necessary.
Vapors can be transferredinto or out of the apparatusby applying a rough
vacuum to the reservoirwhich drawsmercuryout of the U and into the reservoir.
After the volatile materialsare condensedinto the apparatus,they are isolated
from the vacuum systemby bringing the mercury reservoirto atmosphericpressure and slowlybleedingmercury into the U. If it is important to know the gas
volume in the apparatus,the mercury levelis adjustedto some referencepoint.
such as A in Fig 9.2. for which the volume of the apparatushas previouslybeen
determined.
Electronic manometersprovide a convenientmethod of pressuremeasurement in a tensimeter,and the general arrangementmay be very simple (Fig.
9.3). The one problenr which must be anticipated is long-term zero pressure
drift, which can be encounteredwith an electronicpressuregauge.Drift is minimized by maintaining a constanttemperatureon the pressuretransducerand by
avoiding mechanicalvibration at the transducer.
B. Thermol Tronspirotion. In most tensimetry,it is correctlyassumedthat

the pressureat the manometeris equal to the pressurein the samplecontainerto
171
CHARACTERIZATION
T o h r g hv a c u u ml r n e
tr
S e a l o f l -$(
It l
Sample
tube
- 850mm
B a l lb e a r i n g
S a m p l et u b e '
tensrmeter
seal
Breakseal
Sample
Gr o un d ' g l as s
Teflon needlevalve
To atmosphere
--.>
Mercury reservoir
T o r o u g hv a c u u m l i n e
F i g . 9 . 2 . C o n s t a n t - v o l u m et e n s i m e t e r .T h e s a m p l et u b e ( e n l a r g e dv i e w . u p p e r l e f t ) i s l o a d e d* i t h
s o l i d i n a d r y b o x o r b y s u b l i m a t i o nf r o m t h e v a c u u m l i n e . T h e t u b e i s e v a c u a t e d s, e a l e d ,* e i g h e d .
then glassblown to the tensimeter. After evacuating and flame-drying the tensinreter, the mercury
l e v e l i s r a i s e d a n d t h e b r e a k - s e a lc r a c k e d . S i n c e t h e m e r c u r y s e r v e sa s t h e c u t o f f t o t h e v a c u u m
m a n i f o l d , t h e s a m p l e i s n o t e x p o s e dt o g r e a s e ,s t o p c o c k s o
, r j o i n t s . T h i s d e s i g ni s d e s i r a b l eu h e n
v e r y l o n g e q u i l i b r a t i o nt i m e s a r e n e c e s s a r yT. h e m e r c u r y l e v e li s a d j u s t e da t t h e v o l u m e - c a l i b r a t e d
r e f e r e n c ep o i n t , s u c h a s A o n t h e d i a g r a m , i f i t i s i m p o r t a n t t o k n o w t h e g a sv o l u m ei n t h e a p p a r a t u s .
which it is connected.However,at low pressures,wherethe diameterof the connectingtubing is small relativeto the mean free path of the gas molecules,the
pressuresin the two chambersare related by P"/P6 : (To/Tr)t'2.1
rThermal transpiration is discussedin many books on vacuum technology. See, for example: S.
D u s h m a n , S c i e n t i J i cF o u n d a t i o t r so f V a c u u n t T e c h n i q u e , 2 n de d . , r e v . b y J . M . L a f f e r t ye t a l . ( N e *
York: Wiley, 1962).
172
AND OPERATIONS
VACUUMLINEEOUIPMENT
SPECIALIZED
To vacuumsvstem
Fig. 9.3. Tensimeter based on an electronic pressuretransducer. The sample with a microstirring
bar is immersed in a constant-temperaturebath. The pressuretransducer (P), is connected to the
g l a s sa p p a r a t u sb y a g l a s s - t o - m e t asl e a lo r a S w a g e l o kf i t t i n g . S i s a m a g n e t i cs t i r r e r .
C. Exomple: Stoichiomefry of
Inleroction by Tensimefric
TifloliOn. This techniqueprovidesa convenientmethod for followingthe stoichiometryof a reactionbetweena gas and a solutionor pure liquid. Also, similar
techniquescan be applied to the study of gas-liquid equilibria and gas-solid
equilibria. In a tensimetrictitration, measuredamounts of a gaseousreactant
are addedto a solution. After eachaddition a pressuremeasurementis made. A
plot of these pressuresversusthe moles of added gas is then inspectedfor the
break-point, which representsthe stoichiometryof interaction(Fig. 9.4).
A typical arrangementof componentsin a tensimetrictitration is presentedin
Fig. 9.5, which showsthe previouslydiscussedtensimeterand a calibratedbulb
attachedto a vacuum line.2The samplecontaineron the tensimeteris fitted with
a small reciprocatingstirrer which consistsof a thin glass rod connectedto a
glass-encased
headlessnail or glass-encased
bundle of soft iron wire. This stirrer
is driven by an external solenoid,the field of which is switchedon and off by a
current-interruptingdevice,the detailsof which are laid out in Fig 9.6. The size
of the calibratedbulb is chosenso that it will containthe desiredamount of gas
for each addition at a pressurewhich is convenientand accuratelymeasured
(e.g., 100-500 torr). The calibration procedureand stepsused dispensinggas
from such a bulb are describedin Section5.3.G.
r E x a m p l e so f t e n s i m e t r i ct i t r a t i o n s m a y b e f o u n d i n J . J . R u p p a n d D . F . S h r i v e r ,I n o r g .
C h e n t . ,6 . ,
755(1967).
473
CHARACTERIZATION
150
I
100
E
E
50
10
20
MoleratioBF:/FezCpz(C0)q
F i g . 9 . 4 . T y p i c a l t e n s i m e t r i ct i t r a t i o n c u r v e .T o t a l p r e s s u r ei n t h e t e n s i m e t e ri s p l o t t e d a g a i n s tt h e
m o l e r a t i o o f B F r a d d e d t o r e a c t a n t . I n t h i s c a s et h e s o l v e n tw a s t o l u e n ew h i c h w a s m a i n t a i n e da t
- 7 8 ' C f o r e a c hp r e s s u r em e a s u r e m e n tT. h e h o r i z o n t a lp o r t i o n o f t h e p r e s s u r ec u n , eo r i g i n a t e sf r o m
t h e l o w t o l u e n ev a p o r p r e s s u r ea t t h i s t e m p e r a t u r e .A b o v e t h e l : 1 r a t i o o f r e a c t a n t s ,e x c e s sB F l i s
present and the pressure increasessteadily with each addition of BF-r.
The sequenceof operations(assumingthe initial solid is not air sensitive)

would be to load the sampletube with a weighedamount of reactivecompound
and the stirrer, to attach this tube to the tensimeter,and to pump out the air in
the tensimeter.The sample tube is cooledto liquid nitrogen temperatureand
solventis then condensedinto the sampletube from a storagecontaineron the
vacuum line. The main valve on the tensimeteris then closedand the sample
containerallowedto warnl so the solid may dissolve,perhapsrvith the aid of the
stirrer. A constanttemperatureslushbath is next placedaround the sampletube
as illustrated in Fig. 9.5 and an initial pressuremeasurementis taken on the
manometer.Next, the first alloquotof the reactivegas is transferredfrom a storagebulb elsewhereon the vacuum systeminto the calibratedbulb usingthe techn i q u e so u t l i n e d i n S e c t i o n5 . 3 . G ( t h e b u b b l e r m a n o m e t e rs h o w ni n F i g . 9 . 5 i s
used for the pressuredeterminationrequired for this process).This gas is con-
,"."W
m0nometer
D e w o rw i t h
consr0nlr e m p e r ol u r e
slush
S O l u t r Oonf
somple
F i g . 9 . 5 . A p p a r a t u s f o r a t e n s i m e t r i ct i t r a t i o n . T h e b u b b l e r m a n o m e t e ri s u s e d t o m e a s u r ea l i quots of the reactive gas.
- Com
Motor
_
ll,
\l
| n/'
lHl
--
ro sorenoid
"o,r, 4+Microswirch
F i g . 9 . 6 , D e t a i l s o ft h e s o l e n o i d s t i r r e rI f. t h e s o l e n o i d i s w o u n d w i t h 2 l bo f 2 2 - g a u g m
e agnetwire,
i t w i l l w i t h s t a n d 1 1 5 V i n i n t e r m i t t e n tb u r s t s .T h e c u r r e n t i n t e r r u p t e r .s h o w na b o v e .i n v o l v e sa c a m
w h i c h o p e n sa n d c l o s e sa m i c r o s w i t c h .
174
CHARACTERIZATION
175
densedinto the sample tube, which has again been cooled to liquid nitrogen
temperature,the contentsof the tensimeterare isolatedby meansof the tensimeter valve, and the sample is again warmed to the slush bath temperaturewith
stirring. When the pressurein the tensimeterhas becomesteady,the pressureis
recorded. Additions of gas and pressuremeasurementsare continued in this
fashion, and eventually a plot of pressureversusmoles of added gas can be constructedas illustratedin Fig. 9.4. Often the equilibrationtimes stretchout in the
vicinity of the break-point if the reactantsandlor products are only partially
soluble. Slow equilibration times also result from slow gas diffusion when the
vapor pressureof the solventis great. In general,it is best to choosethe solvent
and the temperaturefor the measurementso that the solventvapor pressureis
low.
D. Exomple:Stoichiometryof Inferoction by DifferentiolGos Abtitrationisin

utilityof thetensimetric
sotplionMeoSuremenl. Thegreatest
observingreactionswhich are favored at low temperatures.If, however,the
product has a negligibledissociationpressureat room temperature,it is simpler
and often quite satisfactoryto add an excessof reactivegas to the solutionin the
tensimeter,to stir the solution, and to monitor the pressureuntil no nroregas is
absorbed.The solventand excessreactivegas can then be condensedinto the
vacuum system,separatedby trap-to-trap distillation as describedin Section
5.3.D, and excessreactivegas measuredby its pressure,volume. and temperature in a trap on the vacuum line (see Section5.3.H). Another check on the
stoichiometryof the interactionis providedby the weightgain of the sampletube
and its contents. Assuming that the product is air sensitive,the weight after
reactionis determinedby filling the tube with nitrogen,quickly removingit from
the tensimeter,capping it with a small tared plug, and weighingthe tube and
plug.
Sincea volatile liquid
E. Vopor Pressules obove Room Tempelofute.
will distill to the coldestpoint in an apparatus,it is necessary
to thermostatthe
entire tensimeter systemwhen vapor pressuresare determined aboveroom temperature. Two different designsare presentedin Fig.9.7 which n.reetthis requirement; alternativelyan immersibleglassBourdon pressuretransducermay
be used. The apparatus in Fig. 9.7.b \s suitablefor the measurementof gasphaseequilibria as well as vapor pressures.The first and simplestdesignof the
is operatedin the followingmanner: On
two (Fig. 9.7.a), calledan isoteniscope,r
a vacuumsystem,liquid is condensedinto the terminal bulb. A few hundred torr
of an inert gas is introduced, the valve is turned off, the apparatus removedfrom
the vacuum system,and the frozen liquid is allowed to melt. The part of the
liquid in the terminal bulb is now tipped into the lower U, and inert gas in the
regionbetweenthe bulb and the U is removedby gentlepumping on the system,
r A . S m i t h a n d A . W . C . M e n z i e sJ. . A m . C h e n r .S o c . . 3 2 r8 9 7 , 9 0 7 , 1 4 1 2( 1 9 1 0 ) .
176
SPECIALIZED
VACUUMLINEEOUIPMENT
AND OPERATIONS
Fig. 9.7. Tensimeters for vapor pressuresabove room temperature. (c) Isoteniscope.() An im
mersible tensimeter.
with perhaps some warming of the bulb with one's fingers to promote gentle
boiling rather than bumping. The apparatusis next attachedto a manometer
and surgebulb equippedwith a stopcockthrough which inert gasor vacuum can
be applied.The isoteniscope
is immersedin a constant-temperature
bath, and at
eachgiven temperaturethe liquid levelon the two sidesof the lower U is evened
up by adjusting the inert-gas pressurein the external manometer-surgebulb
combination. When a null point is reachedfor the liquid levelsin the lower U,
the vapor pressureof the liquid is indicatedby the pressureon the externalmanometer. The presenceof the inert gas in this manometer system prevents the
rapid distillation of liquid out of the isoteniscope.
The apparatusin Fig. 9.7.b is the simplestto operatebecausethe entire manometersystem,the sample,and its vapor are immersedin the constant-temperature bath. The mercury reservoir permits the removal of mercury from the Umanometerportion of the apparatus,and the material to be measuredis then
condensedinto the terminal bulb. While this material is still condensedand
there is a high vacuum in the system,the mercury is reintroducedto the U, thus
isolatingthe sample.The apparatusis immersedin a constant-temperature
bath
to the levelof the wavy lines. With a vacuum on the upper portion of the apparatus the vapor pressurescan be measured directly. If vapor pressuresbeyond
the range of the immersible manometermust be measured,the mercury in the
CHARACTERIZATION
477
thermostatedapparatuscan be usedas a null indicator as describedabove,with

an external manometer and supply of gas connectedat the upper joint.
Many other methodsfor vapor pressuremeasurementsmay be found in the
literature and in generalthesemay be adaptedfor air-sensitivecompounds.a-7
F. Moleculol Weight Delerminolions.
In principle, any standard
method of molecular weight determinationmay be adapted for use under airfree conditions,and thosewhich involveinert-atmospheretechniqueshavebeen
coveredin Section 1.5.F. This sectionwill cover molecular weight determinations which require the use of a vacuum system.
Vapor densityprovidesa useful meansof molecularweight determinationfor
substanceswhich exert a high vapor pressureat or near room temperature.In
the simplest case, an evacuatedbulb of known volume is tared, filled with a
measuredpressureof the gas at a known temperature,and is reweighed.These
pressure,temperature,and volume data yield the molesof gas (if the ideal gas
law is assumed)and the additional weight data permit the calculationof the
number of grams per mole.
The high surfaceareaof the bulb and small weightof the gasreducethe accuracy of this determination becausethe large surface can pick up significant
weightby adsorptionof moisturefrom the atmosphereand from fingerprints.To
minimize these sourcesof errors, the bulb may be wiped with a lint-free cloth
moistenedwith water or alcohol before each weighing. The inaccuracyintroduced by the adsorptionof atmosphericmoistureon the surfaceof the bulb can
be minimized by using another bulb of the same size as a counterweightand
treating both bulbs in an identicalmanner. The two bulbs are allowedto equilibrate with the atmospherein the double-panbalanceenclosurefor about onehalf hour before weighing.
Liquid samplescan be weighedin a small, grease-free
bulb and then transferred completelyto an apparatussuch as the one shown in Fi1.9.7.b, where the
sample is completely volatilized and the pressure,volume, and temperature
measuredat an elevatedtemperature.Other methodsfor volatilesubstancesinclude the gas densitybalance8and effusion measurementso.
The molecularweightsof nonvolatilesubstanceswhich havea high solubility
in a solventwith a high vapor pressureare convenientlymeasuredon the vacuum
{ D . E . M c l a u g h l i n a n d M . T a m e r e s ,J . A n t . C h e n r .S o c . , 8 2 ; 5 6 1 8 ( 1 9 6 0 ) lD . E . M c l a u g h l i n , M .
Tameresa
. n d S . S e a r l e sI,r . , J . A n t . C h e n t . S o c . , 8 2 ; 5 6 2 1( 1 9 6 0 ) .
s G . W . T h o m p s o n a n d D . R . D o u s l i n , i n A . W e i s s b e r g e ar n d B . W . R o s s i t e r ,E d s . , T e c h n i q u e so J
C h e m i s t r y ,W i l e y - I n t e r s c i e n c e1. 9 7 1 ,V o l . l , N o . 5 , p . 2 3 .
6W. Swietowlawski,Ebulliometric Measuremenls. (New York: Reinhold. 1945).
'G.
W . T h o m p s o n a n d D . R . D o u s l i n , i n T e c h n i q u e so J C h e n t i s r 4 , ,A . W e i s s b e r g e ra n d B . W .
R o s s i t eE
r d s . , W i l e y I n t e r s c i e n c e1,9 7 2 , Y o l . I , p t . 4 , p . 2 3 .
n H . L . S i m o n s ,C . L . S c h e i r e r .a n d H . L . R i t t e r . R c y . S c i . I n s t r . , 2 4 : 3 6 ( 1 9 5 3 ) .
' g L .K . N a s h ,A n a l . C h e m . , 2 0 ; 2 5 8 ( 1 9 4 8 ) ;D . P . S c h o e m a k e a
r n d C . W . G a r l a n d , E x p e r i m e n t si t t
Physical Chemistry, (New York: McGraw-Hill, 1962). p. 102.
478
spEctALtzED
vAcuuM LINEEeutpMENT
ANDopERATIoNS
line by the vapor pressuredepressionof the solvent.Assumingthe solution behavesideally, Raoult's law can be usedto calculatethe mole fraction of solutein
the solution:
P :
PoXro1""n,
Xsotute:1-Xrolu.nt
In principle, only the weightsof the soluteand solventusedto preparethe solution, and the vapor pressureof the solutionP, would haveto be determinedat a
known temperature.To reduceerrors,the vapor pressureof the pure solventPo
is simultaneouslydetermined,with both solutionand pure solventtubesthermostated in the sameconstant-temperature
bath. Very good data can be obtained
by using two of the tensimetersillustratedin Fig. 9.1. A more specializedapparatus, which utilizes a differential manometer,is shown in Fig. 9.8. To obtain
the best resultsusing either apparatus,it is important to make carefulmeasurementswith a cathetometer,and to employ as high a temperatureas practicalso
Solenoid
S l u s h- ,
both \
F i g . 9 . 8 . A p p a r a t u sf o r t h e d e t e r n r i n a t i o no f m o l e c u l a rw e i g h t sb - t ' v a p o r - p r e s s u dr ee p r e s s i o nT. h e
bottom of the differential manometer (D) may be frozen with Dry Ice to keep the mercury from
s l o s h i n gw h e n s o l v e n ti s a d d e d o r r e m o v e d ,o r w h e n t h e s a m p l et u b e i s a t t a c h e d .T h e s o l e n o i du s e d
t o s t i r t h e s a m p l et u b e i s d e s c r i b e di n F i g . 9 . 6 . V a n d V ' a r e g r e a s e - f r e vea l v e s .
CHARACTERIZATION
179
that Po is large and the difference betweenP and Po is magnified. Under these
conditions, it is quite important to recognizethat a correction may be necessary
for the quantity of the solventin the gas phase,sincefor high temperaturesand
largevolumesthe amount of solventin the solutionmay be significantlyreduced.
For molecularsubstances,a wide varietyof solventsare useful-for example,
methylenechloride, pentane,dimethyl ether, and trimethylamine.Liquid ammonia is alsofrequentlyused.With l:1 electrolytes,ammonia hasthe advantage
that the primary speciesare ion pairs, whereassolventsof lower dielectricconstant generallylead to higher and lessdefinite degreesof aggregation.Correction for nonidealitycan be made by determiningthe apparentmolecularweight
as a function of concentrationand extrapolatingto infinite dilution.
The isopiestic(isothermaldistillation) method for the determinationof molecular weightsis closelyrelated to the vapor pressuredepressionmethod.l0A
weighedamount of standard is introduced into one leg of an apparatusand a
weighedportion of the unknown is placedin the other leg. Solventis introduced
into the apparatus,which is then evacuatedand thermostated.The solventwill
distill from one solution to the other until the vapor pressures(and therefore
mole fractions) of the two have equalized.If the solutionsare ideal, or if the
deviationsfrom ideality are similar, equilibrium will occur when the mole fraction of the known equalsthat of the unknown.
A simpleisothermaldistillationapparatusis illustratedin Fig. 9.9. While not
specificallydesignedfor air-sensitivecompounds,the apparatusmay be loaded
in a dry box. After introduction of samplesand solvent,it is sealedoff under
vacuum and allowedto equilibrate,with the apparatusarrangedso the liquid is
in the large bulbs in order to afford a maximum area of exposedsolvent.The
apparatusis periodicallytipped so the two solutionsflow into the calibratedlegs.
When no changein volume is observedfrom one time to the next, the relative
volumesof the solutionsare, to a good approximation,proportionalto the moles
of solutein the two legs.
Since equilibration sometimestakes days or weeks.the isopiesticmethod is
not suitablefor unstablecompoundsor compoundswith appreciablevolatilities.
Also, long equilibration times require leak-freeand grease-freeapparatus.Another designfor an isothermaldistillation apparatusis given in Fig. 9.10.
G. Iempelofule
Defelminotions.
In vacuum line work it is frequently
necessary
to measurelow temperatures.While the mercury-in-glass
thermometer is convenient, it does not extend below the freezing point of mercury,
-38.9". Pentane-in-glass
thermometershavea similar convenience
and may be
useddown to about - 150"C, but they are only usefulfor rough work (an error of
5"C is common). For more precisedeterminations,a calibratedthermocoupleor
thermistor, or a vapor pressurethermometer,is useful.
The vapor pressurethermometerconsistsof a manometerwith one arm exroG. L. Beyer, in Techniques oJ Chenistry, A. Weissbergerand B. W. RossiterEds.. Wiley
Intersc i e n c e ,1 9 7 2 ,V o l . 1 . p t . 4 , p . 1 8 3 .
480
AND OPERAIIONS
VACUUM LINEESUIPMENT
SPECIALIZED
Fig. 9.9. Signer-typeisopiesticmolecular weight apparatus. The sample, standard, and solventare
introduced through the upper tubes, which are then sealedoff after freezingthe solutions and evacua t i n g t h e a p p a r a t u s .T h e a p p a r a t u si s a l l o w e d t o s t a n d i n t h e p o s i t i o n s h o w n t o a l l o w m a x i m u m
exposureof the solution to the vapor. Volumes of the standard and unknown solutions are found by
tipping the apparatus so the calibrated legs are filled.
posedto the vapor of a pure substancewhich is condensedin the probe (Fig.

9. I 1). Providingthat somecondensateis present,the temperatureof the probe is
found by comparisonof the observedvapor pressurewith tabulateddata for the
thermometricmaterial. The vapor pressurethermometerillustratedin Fig. 9.11
is similar to Stock'sdesign.tr.tzMore compactdesignshaveappearedin the literture,l3'tlbut some sacrificein accuracyseemsinevitablewith these.
Any substancewhich may be obtained pure and for which accuratevapor
pressuredata are availablemay be usedfor vapor pressurethermometry.Stock
recommendeda convenientseriesof compoundsand, in collaborationwith Hennig and others,he obtainedaccuratevapor pressuredata for thesecompounds.ls
Thesedata wereobtainedon a temperaturescalefor which 0'C : 273.1K; however,more recentdata on severalof the compoundsshowit would be difficult to
improve on Stock's vapor pressuretables. When high accuracyis desired,the
usual precautionsinvolvedin precisemanometry(Chapter7) must be observed.
Thermistors, or "thermally sensitiveresistors," are semiconductorswhich
havehigh negativetemperaturecoefficientsof resistance.There is no simple reI r A . S t o c k ,Z . E l e k t r o c h e m i e , 2 9 : 3 5 4 ( 1 9 2 3 ) .
r r A . S t o c k . H y d r i d e s o J B o r o n a r d S i l i c o n ,( l t h a c a , N . Y . : C o r n e l l U n i v e r s i t yP r e s s ,1 9 3 3 ) ,p . 1 9 0 .
rrA. Farkas and L. Farkas, Ind. Eng. Chent. (Anal. Ed.), 12:296 (t940).
I ' S . C . L i a n g , R e v . ^ S c iI.n s t r . , 2 3 ' , 3 7 8 ( 1 9 5 2 ) .
l s F . H e n n i g a n d A . S t o c k ,Z . P h . , - s i k . , 2 2 7 ( 1 9 2 1 ) .
\
484
CHARACTERIZATION
F i g . 9 . l 0 . A p p a r a t u sf o r t h e d e t e r m i n a t i o no f m o l e c u l a rw e i g h t so f a i r - s e n s i t i v ceo m p o u n d sb y t h e
i s o t h e r m a ld i s t i l l a t i o nt e c h n i q u e .T e m p e r a t u r ef l u c t u a t i o n so f t h e t w o s o l v e n t sa r e m i n i m i z e di n t h i s
illustration by a Dewar filled with water. This apparatus is used in the following manner. In a dry
box the sample is placed in a tared tube through sidearm A, the sidearm is then sealedoff, the tube
a n d r e m n a n t o f t h e s i d e a r ma r e w e i g h e d ,a n d t h e t u b e i s a t t a c h e dt o t h e a p p a r a t u sb y g l a s s b l o w i n g
a t B . A w e i g h e dp o r t i o n o f a s t a n d a r di s i n t r o d u c e di n t o t h e o t h e r b u l b , a n d t h e f i l l i n g t u b e i s s e a l e d
off. After evacuation, opening of the break-seal, and reevacuation,a measuredportion of solvent is
distilled into both arms of the apparatus. The processof equilibration is followed by periodic ren r o v a la n d m e a s u r e m e not f t h e s o l v e n tf r o m o n e a t m . T h e s o l v e n tm a y b e m e a s u r e dv o l u m e t r i c l yi n
t h e l i q u i d o r g a s s t a t e s ,o r b y w e i g h t .
lationshipbetweenthe resistance
R and the temperature7. However,the following empirical resistance/temperature
relationshipis quite useful:r
Rr:R.',.0f-r(i-*)]
whereRo is the resistanceat a temperatureTo,Rr is the resistanceat a temperature T, and .B is a constant.
Low-ten.rperature
thermistorsare usually made from nonstoichiometriciron
oxides and have a resistancesensitivityof around 15% per Kelvin at 20 K.17
Thermistorsact as ohmic conductorsat any fixed temperature.Therefore,one
advantageof using a thermistor is that ordinary copper wiring may be used to
build the circuit; reference junctions and special extension wires are not
needed.r8Thermistorsare generallyquite stableto long-termfluctuationsafter
a n i n i t i a l a g i n gp e r i o d .
r b S .D . W o o d , B . W . M a n g u m , J . J . F i l l i b e n ,a n d S . B . T i l l e l t . J . R e s .N B S , 8 3 ; 2 4 7 ( 1 9 7 8 ) ,
rrT. J.
Q u i n n ( g e n e r a lr e f e r e n c e s )p, . 2 2 3 .
r 6 R . P . B e n e d i c t( g e n e r a lr e f e r e n c e s ) .
482
AND OPERATIONS
VACUUMLINEEOUIPMENT
SPECIALIZED
is filled as describedin the caption to

Fig. 9.11. The vapor-pressurethermometer. The manometer
t
h
r
o u g h a j o i n t a t t a c h e da t p o i n t A ' A
o
u
t
g
a
s
s
e
d
a
n
d
e
v
a
c
u
a
t
e
d
r
s
t
h
e
n
Fig. 7.1. The manometer
off undervacuum at point
pure compound is condensedinto the pfobe, and the apparatus is sealed
must be taken not to
care
room
temperature,
below
boil
which
A. For thermometric compounds
overfill the apparatus.
which are
Thermocouples consist of two dissimilar electrical conductors
constituting
wires
joined to form a measuring junction, with the free ends of the
betweenthe meaihe referencejunction. When a temperature difference exists
free ends of the
the
,uring and reiere.tcejunctions, an emf is produced between
can be used
device.This emf , which is a function of the temperaturedifference,
junction
reference
junction if the
to determine the temperature at the measuring
in
is
shown
circuit
temperature is known. A schematicof a typical thermocouple
Fig.9.12.
situation is the
The most common thermocouple type used in a laboratory
and a useType J iron/constantan thermocouple' Low cost' high thermopower'
183
CHARACIERIZATION
Cu
MaterraB
l
Measunng
lunctron
lce bath
r e f e r e n c ej u n c t i o n
F i g , 9 . 1 2 . T y p i c a l t h e r m o c o u p l ec i r c u i t . T h e i c e w a t e r b a t h m a y b e p r e p a r e di n a D e w a r f o r e x t e n d e du s eo f t h e c i r c u i t .
ful temperaturerangeof -200-760oC contributeto the popularityof the Type J

thermocouple.Below 0oC, rust and embrittlement may become a problen.re
Therefore, it is a good practice to remove the referencejunction from the ice
water bath and dry it thoroughlywhen the thermocoupleis not being used.
When using a measuringjunction at a remote site relativeto the reference
junction, it is important to usethe proper extensionwire betweenthe junctions.
Usually, a wire with the samecompositionas the thermocouplewire itself, but
not made to such a high specification,is used.
H. Melling Point Determinolions.
The melting point, or more correctly
in a standardmelting point
point,
a
may
be
determined
the triple
of volatilesolid
is
line into a capillary
after
from
vacuum
block or bath
the solid sublimed
the
and sealedoff under vacuum. To avoid sublimation of the sample during the
determination,the capillary must not protrude fron'rthe melting point block or
bath.
Stock devisedthe apparatusillustrated in Fig. 9.13 to obtain melting points
of volatile and reactivesubstancesbelow room temperature.This particular apparatus overcomesthe problem of poor visibility of the sample,which is being
maintainedat a low temperature.The apparatuscontainsa glassplungerwhich
has an iron core on the top and a glass cross at the bottom. The plunger is
slippedinto a tube which allowsmoderateclearance.In operation,the tube with
plunger is evacuated,the plunger is lifted by a hand magnet, and a ring of the
sampleis distilled into the apparatusbelow the cross.The plunger is loweredso
that the crossrestson the frozen ring, and a bath of cold liquid is placedaround
the tube and allowedto warm slowly.The temperatureof the bath may be measured with a vapor pressurethermometerand the top of the plunger observed
''T. J.
Q u i n n ( g e n e r a lr e f e r e n c e s )p, . 2 6 4 .
184
AND OPERATIONS
SPECIALIZED
VACUUMLINEEQUIPMENT
,ll
F i g . 9 . 1 3 . S t o c k - t y p em e l t i n g - p o i n ta p p a r a t u s .A , t u b e ; B , m a g n e t i cc o r e l C . g l a s sc r o s sr e s t i n go n
t h e b o t t o m ( l e f t d r a w i n g ) , p o i s e da b o v et h e r i n g o f f r o z e n s o l i d ( r i g h t d r a w i n g ) ; D , t i p o f p l u n g e r
w h i c h i s o b s e r v e d iE , h a n d m a g n e t u s e dt o r a i s e p l u n g e r .
through a cathetometer.The nlelting point correspondsto the temperatureat

which the plunger beginsto move.
Visual observationof melting points may be made in the apparatusillustrated
i n F i g . 9 . 1 4 .T h e s a m p l e ( sa) n d a m e r c u r y - i n - g l a st hs e r m o m e t ear r eh e l db y s u p ports constructedfrom thin-walled brass tubes. The bath is cooled below the
freezing point of the samplesand stirred by a motor-drivenstirrer. The apparatus may be placed in a warm water bath, and the rate of warming may be
controlledby the extent of evacuationof the jacket. If the substancefreezesas a
solid phasewhich is difficult to distinguishfrom the liquid, it is illuminatedfrom
behind by light which is passedthrough a Polaroidfilm and then viewedthrough
a crossedPolaroid.
l. Specfloscopic Delerminofions.
Gas-phaseinfrared spectraprovide a
useful adjunct to vapor pressuremeasurementsin the identificationof volatile
materials.The cell illustratedin Fig. 9.15 allowsthe sampleto be quantitatively
returnedto the vacuum line after the spectrumhas beenobtained,so the process
is completelynondestructive.The primary problem with a gas cell is to obtain a
vacuum-tight seal betweenthe window material and the cell body; this may be
accomplishedwith Glyptal paint or with wax. If the latter is used,it is necessary
to warm and cool the alkali halide windowsslowlyto avoid crackingthem due to
thermal stress.For this purposean infrared lamp is handy. The most satisfactory method of attaching windows is O-rings becausethis allows the easy removal of the windowsfor cleaningand polishing.
A r r- d / l v e n
stirrer\
Fig.9.l4.
A p p a r a t u s f o r t h e r i s u a l o b s e r v a t i o no f m e l t i n g p o i n t s
.)
r e e z e- o u l
rrp
Alkoliholide
windows
S i d ev i e w
End view
i s i n c l u d e db e t w e e nt h e n l e t a l r e t a r n F i g . 9 . 1 5 . A g a s - p h a s ei n f r a r e d c e l l . N o t e t h a t a t h i n g a s k e t
orving to unever'ltightening o{ the
breakage
windov
reduce
helps
to
This
irr! ptut. and e windou..
nuts.
,t85
18
SPECIALIZED
VACUUMLINEEOUIPMENT
AND OPERAIIONS
A versatilelow-temperatureinfrared cell is presentedin Fig. 9.16.20It is suitable for mull or pressed-diskinfrared spectraof solids,solid stateinfrared spectra of condensedvapors, and spectra of products from solid-gasreactions.
Mulled or powderedsamplesare supportedbetweenalkali halide windowsin the
copper block B, which is cooledby refrigerantin the cold finger A. Beforethis
refrigerantis added, the cell must be evacuatedthrough the needlevalve.When
the cell is usedfor low-temperaturespectraof condensables,
the vaporsare bled
through the needlevalve and squirted directly onto one surfaceof a cold alkali
h a l i d ep l a t e h e l d i n b l o c k B ,
The cell illustratedin Fig. 9.17 has provenvery usefulin the determinationof
visible and ultraviolet spectrafor air-sensitivesolutions.Despite its simplicity,
this cell is quite versatile.To introducean air sensitivesolution,the cell is evacuated and filled with dry nitrogen through the O-joint, the stem of the needle
valve is removedwhile a stream of nitrogen is maintainedthrough the cell, the
solution is injectedby meansof a syringeequippedwith a long needle,and the
stem is replaced.When the needlevalve is closed,the solution may be tipped
18/9 O-r ng
lo nt
Needle
V OI V E
40/54
-
KBr drsk
Nletol
end plote
B
C o p p e br l o c f
KBrdrsk
F i g . 9 . 1 6 . L o w - t c n r p e r a t u r ei n f r a r e d c e l l ( c r o s s - s e c t i o n )A. n i n d i u n r g a s k e t b e t s e e n t h e * ' i n d o r v
a n d c o p p e rb l o c k g r e a t l yi n c r e a s e tsh e e f f i c i e n c yo f h e a t t r a n s f e r .I f t h e t e m p e r a t u r eo f t h e u ' i n d o u i s
t o b e n r e a s u r e d* i t h a t h e r n r o c o u p l et.h e l e a d sm a 1 ' b ep a s s e dt h o u g h p i n h o l e si n t h e u p p e r O - r i n g .
U n d e r c o n t p r e s s i o no f t h e i o i n t , t h i s t y p e o f e l e c t r i c a l e a d - t h r o u g hi s v a c u u n r - t i g h t T
. h r e a d e dr o d s
u s e dt o c l a n r p t h e e n d p l a t e sh a v e b e e n o m i t t e d f o r c l a r i t y . A s p r i n g h o l d s t h e K B r d i s k i n p l a c e .
: o T h i sc e l l i s s i m i l a r t o o n e d e s c r i b e db y E . L . W a g n e r
a n d D . F . H o r n i g . J . C h e n t .P h v s . , l 8 ; 2 9 6
( 1950).
187
CHARACTERIZATION
l-cm
eprece
c u v et t e
Reservoir
Fig, 9.17.
Evacuable cell for visible spectroscopy.
into the cuvetteand the spectrum may then be run. If a measuredportion of

reactivegas is to be added to the solution, the contentsare frozen in the reservoir, the cell is evacuated,and the gasis distilledinto it. When this cell is usedin
it is necessary
to replace
conjunctionwith most visible-ultravioletspectrometers,
with
light-tight
cover
cover
a
specially
constructed,
the usual cell compartment
needle
The
cylindrical
reservoir
provides
accommodate
the
valve.
which
spaceto
is an important feature of the cell becausethe cuvette,which has a squarecross
section,is easilybroken by frozen solutions.
Commercial cylindrical quartz cells can be adapted for gas-phasework as
illustratedin Fig. 9.18. Sucha cell finds usein the near infrared for the determination of overtonevibrational frequencies,and also in visible and ultraviolet
spectroscopy.A much lessexpensivecell which is adequatefor most gasesmay
be constructedfrom Pyrex along the lines of the cell shownin Fig. 9.18. Quartz
windowsmay then be attachedby epoxyresin. A cell which is filled from a conventional vacuum line will generallycontain nercury vapor which absorbsat
2$7 ^. Once the origin of this absorptionis recognized,it causeslittle difficulty
becauseof its narrow bandwidth.
are described
Many specializedspectralcellsdesignedfor reactivesubstances
in the literature, and referencesto someof theseare given in Table 9.1.
is well suitedfor the study of air-sensitiveliquids
Laser Raman spectroscopy
becausethe sample may be containedin an all-glasscell.2rSuch a cell is much
easierto load on a vacuum line and to maintain leak-freethan is an infrared cell.
Also, such a tube is easierto heat or cool than the typical IR cell.
2 r D . P . S t r o m m e n , a n d K . N a k a m o t o , L u b o r a t o 1 , R u n t u n S p e c t r o s c o p . yW, i l e y I n t e r s c i e n c eN
. ew
Y o r k . 1 9 8 4 .C h a p t e r 2 .
488
SPECIALIZED
VACUUM!INEEOUIPMENT
AND OPERATIONS
F i g . 9 . 1 E . A q u a r t z g a s c e l l . T h e a d a p t e r w i t h j o i n t , s t o p c o c k .a n d f r e e z e - o u ts i d e a r m i s u ' a x e d
o n t o t h e t a p e r j o i n t o f a c o m m e r c i a lc e l l .
Severalmethods may be used to attach an NMR tube to a vacuum system.

The O-ring union, illustratedin Fig. 8.5, permits attachmentof standardNMR
tubes to a vacuum outlet. Once the NMR tube has beenfilled with an air-sensitive sampleon the vacuum system.it is necessary
to bring the tube up to atmospheric pressurewith inert gas, remove the tube, and quickly stopper it. Recently. a small in-line valve has been introduced rvhich has a provisionfor an
O-ring sealwith a speciallyconstructedNMR tube.22This valveallowsthe NMR
tube to be sealedbeforeit is disconnectedfrom the vacuum line. and the valveis
left on the tube during data collection.Owing to its symmetricdesign,the valve
doesnot interferewith the spinner.
The best exclusionof air is achievedby glassblorvingan NMR tube onto a
joint so that the joint may be attachedto the vacuum line when volatile compounds are to be sampled.The sample,solvent,and referenceare distilled into
the tube, which is then sealedoff under vacuum. A symmetricsealhelpsto avoid
erratic spinning. A highly volatile reference,such as tetramethylsilane,may be
s t o r e di n a s m a l l " s o l v e n tc o n t a i n e r "( F i g . 9 . 1 9 )a n d m e a s u r e di n t h e g a sp h a s e .
The large expansioncoefficientof many solventscan crack the sanrpletube
when the sampleis warmed from the liquid nitrogentemperature.To reducethe
chanceof breakage,the tube is withdrawn slowlyfrom liquid nitrogenand. as it
is removed,the sampleis thawedwith the fingers;it is particularlyimportant to
usethis processwith the thin-walledvarietyof NMR tube. The expansioncoefficient also has to be taken into account so that there is sufficientdead spaceto
accommodatethe sample when it has warmed to room temperature. If high
pressuresare anticipated,a checkis made of the strengthof the tube by immersing it in a warm water bath before it is insertedinto the NMR probe.
2 z T h ei n - l i n e v a l v e a n d a s s o c i a t e dN M R t u b e
i s m a n u f a c t u r e db y J . Y o u n g L t d . , l l C l o v i l l e R o a d ,
A c t o n . L o n d o n W 3 8 B S , U . K . I n t h e U n i t e d S t a t e so n e s u p p l i e r i s R . J . B r u n f e l d t C o . . P . O . B o x
2 0 6 6 . B a r t l e s v i l l eO
. K 74005.
Toble9.'1.Relerenceslo lnfroredond Visible-Ultroviolef

Cellsfor AirsensiliveCompounds
Description
I nJrured
Vacuum-tight infrared cell for liquids
Reference
A. B. Burg and R. Kratzer, Inorg. Chem.,
1, 725 (1962).
Infrared cell for carbon suboxidepolymer R . N . S m i t h , D . A . Y o u n g , E . N . S m i t h ,

a n d C . C . C a r t e r ,I n o r g . C h e m . , 2 , 8 2 9
( 1963)
Pressure-tightcell for infrared spectra of
liquids
D. C. Smith and E. C. Miller,./. Opt. Soc.

A m . , 3 4 , 1 3 0( 1 9 4 4 ) .
Method of attaching dissimilarwindow

materialsto a vacuum-tightlowtemperaturecell
E. Schwarz,J. Sci. Instr., 32, 445 (t955);

V . R o b e r t sJ. . S c i .I n s t r . , 3 1 , 2 5 1 ( 1 9 5 4 )
lnfrared spectra of adsorbed species
R . P . E i s c h e n sS
, . A . F r a n c i s ,a n d W . A .
P l i s k i n ,J . P h y s .C h e n r . , 6 0 ,1 9 4( 1 9 5 6 ) ;
M. Courtoisand S. J. Teichner,"/.
C a r a l y s i sI,, l 2 l ( 1 9 6 5 ) .
C. Tessier-Youngs
et al.,
Organometallics,2, 898 (1983).
A l l - g l a s sc e l l f o r t h e i n f r a r e d1 < 4 . 7 p )
spectra of gases.
F. A. Cotton and L. T. Reynolds, .4nr.

"/.
Chent.Soc., 80, 269 (1958).
Low-temperaturenear-infraredand
v i s i b l ec e l l sf o r l i q u i d a n r r n o n i a
solutions.
W. J. Peer and J. J. Lagowski,J. Phvs.

, . C. Fohn,
C h e n t . , 8 4 ,l l l 0 ( 1 9 8 0 ) E
R . E . C u t h r e l l ,a n d J . J . L a g o u ' s k i ,
I n o r g . C h e n t . .4 , 1 0 0 2( 1 9 6 5 ) .
Heated infrared cell for solidsin a

controlledatmosphere
T. Wydevenand M. Leban, Anal. Chenr..

3 9 , 1 6 7 3( 1 9 6 7 ) .
Lo\4'-temperature
liquid infrared cells
R . G . S t e i n h a r d t .P . A . S t a a t s .a n d H . W .
Morgan, Rer,..lci. hstr., 38, 975 (1967)
Silverchloride window-to-bodyseals
J. F. Harrod and H. A. Poran, Rcv. .lci.

l r r s r r ., 3 8 . l 1 0 5 ( 1 9 6 7 ) ;A . G u e s ta n d
C . J . L . L o c k . R e r ' . S c i .I n s t r . , 3 9 . 7 8 0
( r968).
Optical matefialsand variousinfrared

c e l ld e s i g n s .
R. G. J. Miller, 1965,Luboratory Methods

in Irt/rured Spectroscopv,Heyden and
S o n sL t d . . L o n d o n .
Protectiveholder for KBr presseddisks
P. A. Saatsand H. W. Morgan, p,oi.

Spectry., 22, 576 ( 1968).
Visible-Ultruviolet
L o u ' - t e m p e r a t u rvea c u u n r - t i g hvt i s i b l e u l t r a v i o l e ct e l l f o r s o l u t i o n s .
R . N a k a n e .T . W a t a n a b e .O . K u r i h a r a ,
and T. Oyama, Bull. Chem. Soc.Juputt,
3 6 ,r 3 7 6( r 9 6 3 ) .
L o w - a n d h i g h - t e n r p e r a t u rgea s t i g h t
v i s i b l e - u l t r a v i o l ceet l l .
Y. Hirshbergand E. Fischer,Rey. Sci.

l r r s l r . . 3 0 , 1 9 7( 1 9 5 9 ) .
489
190
AND OPERATIONS
SPECIALIZED
VACUUMLINEEQUIPMENT
r8/9 J
F i g . 9 , 1 9 , S o l v e n ts t o r a g ec o n t a i n e r . S o l v e n ti s d i s t i l l e d i n t h r o u g h t h e s i d e a r m , w h i c h i s t h e n
s e a l e do f f u n d e r v a c u u n r .T h e c o n t a i n e ri s a t t a c h e dt o t h e v a c u u m l i n e t h r o u s h a l 8 / 9 b a l l i o i n t o r
O-ring joint.
Sampling for ESR work is often more complex than for NMR becausethe
high sensitivityof the ESR spectrometerrequirescareful exclusionof paramagnetic impurities or their progenitors.Also, the radical is generallyextremelyreactiveand presentin low concentrations,so that exclusionof tracesof moisture
and air is important. Frequently,paramagneticlow-valentmetal complexesand
anion radicalsare producedby alkali metal reduction;a typical cell for the generation and samplingof such speciesis illustratedin Fig. 9.20. Avarietyof other
sampling methodshave been described.23
9,2 sEPARAToNs
A. Vocuum Line Filltotion. For their work on the diammoniateof diborane, Parry, Schultz, and Girardot2adeviseda versatilevacuum line filtration
apparatuswhich is useful when small quantitiesof solid are handled and when
the solventis sufficientlyvolatile to be distilled on the vacuum line. The filter is
attachedto the vacuum systemthrough a standardtaper joint which allowsit to
be rocked or inverted (Fig. 9.21). Prior to filtration, any volatile contentsare
frozen down and the apparatusis thoroughly evacuated(Fig. 9.2la). By inversion of the apparatus,the solution is then poured onto the frit, and the solvent
vapor pressureis employedto effect a "suction" filtration by closingthe stopcock in the equalizingarm and coolingthe lower tube (Fig. 9.21b). The precipitate is washedby distillation of the solventfrom the lower receiverinto the upper
portion of the apparatus(with the stopcockin the sidearmopen) and repetition
r r C . P . P o o l e ,J r . , E l e c t r o n S p i n R e s o n o n c e(,N e w Y o r k : I n t e r s c i e n c e1. 9 6 7 ) ,C h a p t e r l 5 ; J . L . D y e ,
J . P h y s .C h e n t . 8 1 , 1 0 8 4( 1 9 8 0 ) .
2 { R .W . P a r r y ,D . R . S c h u l t z ,a n d P . R . G i r a r d o t ,J . A n t . C h e n t . . S o c . , 8 0I; ( 1 9 5 8 ) .
494
SEPARATIONS
1 0 /3 0
24/40 |
A l k ol i
metol
S o m p l eo d d i t i o n
tubeSr
2-mm
copillory
S2
ESR
t ub e
S o l v e n td i s t i l l e d
into this orm
R eo c t i o n
Front view
S i d ev i e w
F i g . 9 . 2 0 . A p p a r a t u sf o r t h e g e n e r a t i o na n d s a m p l i n go f a n i o n r a d i c a l s .T h e s a m p l ei s a d d e dt o t h e
p u r g e d a p p a r a t u s , S r i s s e a l e do f f , a n d t h e a p p a r t u s i s e v a c u a t e d .C h u n k s o f s o d i u n r a r e m e l t e d
t h r o u g h t h e c a p i l l a r ya n d t h e n s u b l i m e di n t o t h e r e a c t i o nt u b e . S o l v e n ti s d i s t i l l e di n t o t h e s i d e a r m
f r o m t h e v a c u u n l l i n e , a n d t h e a p p a r a t u si s t i p p e d s o t h a t t h e r e s u l t i n gs o l u t i o ni s p o u r e d o n t o t h e
sodium mirror in the reaction zone. The resulting solution of radical is poured into the 5-mm ESR
t u b e , f r o z e n d o w n , a n d s e a l e do f f a t S 2 .T h e r a d i c a l g e n e r a t i o na n d c o l l e c t i o nc a n b e c a r r i e do u t a t
r e d u c e dt e m p e r a t u r eb y i m m e r s i n gt h e t u b e i n a n a p p r o p r i a t es l u s h b a t h .
of the suction filtration (Fig.9.2lb). The condensationof solventin the upper

portion of the filter can be accomplishedby wrappingpart of the upper tube with
glasswool and pouring small quantitiesof liquid nitrogen into the glasswool.
When the filtering and washing operationsare complete,the solventmay be
removed under vacuum. The apparatus is filled with nitrogen, capped, and
taken into a dry box for the transfer of solids. This set of operationsis easily
carried out when using solventswhich exert lessthan 1 atm pressureat room
temperature;in this casethe major precautionis slow removalof the solventto
avoid splatteringof solid in the filtrate. However,solventswhich boit belowroom
temperature require much more skill in handling becausethey are liable to
bump and blow the apparatusapart. The chanceof bumping may be reducedby
a rocking motion imparted to the apparatuswhen the solventis volatilized.Also,
pressurizationof the apparatusis minimized by alwaysleavingit open to a bubbler manometer. Even though the design presentedin Fig. 9.21 avoidsdirect
contact of the liquid with stopcockgrease,the presenceof solventvapors may
lead to the eventualerosionof the grease.This can be minimized by working
192
AND OPERATIONS
SPECIALIZED
VACUUMLINEEQUIPMENT
Fig.9.2l
V a c u u m l i n e f i l t r a t i o n a p p a r a t u s .( c ) A s o l u t i o nr e a d y t o b e f i l t e r e d ; ( b ) a p p a r a t u si n v e r t e d a n d b o t t o m r e c e i v e rc o o l e d t o b r i n g a b o u t s u c t i o n f i l t r a t i o n . T h e p r e c i p i t a t ei s w a s h e db y
o p e n i n gt h e s t o p c o c k ,a l l o * ' i n gt h e b o t t o m t u b e t o w a r m , a n d c o o l i n gt h e t o p $ ' i t h g l a s su ' o o ld i p p e d
i n l i q u i d n i t r o g e n . T h e c o n r p o n e n t sa r e h e ' l dt o g e t h e r b y s p r i n g so r r u b b e r b a n d s . A g r e a s e - f r e e
v e r s i o no f s i m i l a r d i m e n s i o n sm a , vb e c o n s t r u c t e db , vn r a k i n gt h e f o l l o u i n g s u b s t i t i o n s3 2 4 r , 1 0s t o p c o c k - v a l v e ;S l 4 l J S - r / t _ i n .C a i o n O - i o i n t .
fairly rapidly and maintaining the solventbelow room temperature,or by using

the O-ring versionof this apparatus.which is describedin the caption to Fig.
9.2t.
When a large quantity of solid is handled, a scaled-upversionof the vacuum
line filter may be used;but if the quantity is too large, it becomesunwieldy.The
vacuum line filter design by Wayda and Dye, Fig. 5.3 is the best choicewhen
large quantitiesare handled. Many specializedvacuum line filters are described
2b
in the literature.2s
z s G .D . B a r b a r a s C
, . D i l l a r d , A . E . F i n h o l t ,T . W a r t i k , K . E . W i l z b a c h ,a n d H . l . S c h l e s i n e e r . J .
A n t . C h e n r . . l o c . ,7 3 ; 4 5 8 5( 1 9 5 1 ) .
roA.B. Burg and R. Kratzer,Inorg. Chenr., l:725 (1962).
SEPARATIONS
493
B. Low-Tempeloture Floclionol Distillotion. A versatile lorv-temperat u r e d i s t i l l a t i o nc o l u m n h a sb e e nd e s i g n e db y D o b s o na n d S c h a e f f e r . 2 ' Iits s u i t able for the separationof small anounts of compoundswhich have appreciable
v o l a t i l i t i e si n t h e - 1 6 0 - 0 ' C r a n g e .T h e c o l u m n( F i g . 9 . 2 2 )i s e v a c u a t e da. n d t h e
sampleto be distilledis condensedin the lowerU-trap. A streamof cold nitrogen
gas is maintainedthrough the centertube, and the U-tube is warmed so that the
sampleis introducedto the column. The temperatureof the column is controlled
by varying the boil-off rate of liquid nitrogenfrom a Dewar (Fig. 9.23). When a
sufficientlyhigh temperatureis reached,the first componentwill slowlymoveup
the column and may be collectedover a period of time at liquid nitrogentemperature in the upper U-trap. Ordinarily. a good separationis obtainedfor conrponentsu'hich boil 15' apart. A number of other designsare presentedin the liter2q
ature for low-temperaturedistillation columns.28
A closelyrelated techniqueis the "fractional codistillation" method of Cady
'rrThe amount and boiling rangeof the componentswhich may
and Siegrvar1fi.l0
be handled by this technique are comparableto those describedabovefor the
low-temperaturedistillation column. Essentially,a gas chromatographyapparatus is employed with the column replacedby a t/+ or r/rl-in.copper U-tube
packed with approximatelyS0-meshmetal powder. The mixture to be separ a t e d ,w h i c h m a y b e a s m u c h a s 2 m L o f l i q u i d f o r t h e l a r g ec o l u m n ,i s d i s t i l l e d
o n t o t h e i n l e t s i d eo f t h e U - t u b e a t l i q u i d n i t r o g e nt e m p e r a t u r ea, n d a s u i t a b l e
helium flou' rate is then established.The liquid nitrogenis poured from the Dew a r a n d t h e D e w a r i s r e p l a c e da r o u n dt h e U - t u b e .A s t h e c h i l l e dD e r v a ra n d U tube u'arm up, the componentsprogressthrough the colunrnand then thlough a
thermal conductivitydetector,which is followedby cold traps for the collection
of fractions.A simpleversionof this apparatusis illustratedand explainednrore
fullyin Fig.9.24.
Gas chromatographyhas been employedfor
C. Gos Chromofoglophy.
the separationof reactivecompoundsranging from boron hydridesto interhalogens. For manv reactiveliquids, conventionalinstrumentation(Fig. 9.25) has
been employed.However,gasesgenerallyrequire an inlet systemwhich is rrrore
involvedthan the familiar syringeinjectionport routinely usedfor organiccontpounds.
There is no lack of books and articles dealing with the major facetsof gas
chronratography;for examples,seethe generalreferenceslist at the end of this
chapter. Furthermore,most chemistsare familiar with the technique,and many
r - A . N o r n r a r ra n d R . S c h a e f f e r ,p r i v a t e c o m n r u n i c a t i o n .
r r J . R . S p i e l n r a na n d A . B . B w g , I n o r g . C h e t n . , 7 : 1 1 3 9( 1 9 6 3 ) .
: u D . J . L e R o y , C u n . J . C h e n t ., 2 8 , 4 9 2 ( 1 9 5 0 ) ;A . A . C o n r s t o c ka n d G . K . R o l l e f s o nJ, . C h e n . P l t l ' s . .
l 9 : 4 , 1 I( l 9 5 l ) .
r ( ' G .H . C a d y a n d D . P . S i e g r v a r t hA.t r u l . C I r c m . .J l ; b l 8 ( 1 C 5 9 ) .
l H . w . M y e r sa n d R . F . P u t n a m .A n u l . C h e m . . 3 4 ; 6 t r ' l( 1 9 6 2 ) .
194
SPECIALIZED
VACUUM
L I N E E Q U I P M E N TA N D
OPERAilONS
C o l dg o s
/'E
Pe^lone in
gloss thermometer
I
To vocuum lrne
Cold N2
S om p l e
collected here
C o o l o n tg o s ,
1 5 m mO D
S o m p l et u b e
8mmOD
VOCUUM
C 0 . 1 7m
2 mgop
t h r o u g hw h i c h
the moteriod
l istills
D e w or j o c k e t
2 5 m mO D
Exponsiob
nellows
Coolontveni
L
1 0m mI D '
Somple
N 2o u t
to J
(b)
F i g . 9 . 2 2 . L o w - t e m p e r a t u r ef r a c t i o n a l - d i s t i l l a t i o nc o l u n r n .( c ) N o r m a n ' s m o d i f i c a t i o n o f a d e s i g n
b y D o b s o na n d S c h a e f f e r (. ) A n a l t e r n a t ec o l u m n d e s i g n( J . D o b s o n . P h . D . t h e s i s . I n d i a n a U n i v e r s i r v .I 9 6 7 ) .
commercialinstrumentsare available.Therefore.this sectionwill focuson inlet

systems,particularly inlets which serveas an interfacebetweena gas chromatograph and a vacuum system.Also, a brief accountwill be givenof the conditions
and equipmentwhich havebeen used successfully
in the separationof somereactiveinorganic substances.
An inlet systemfor quantitativervork must presenta represeiltatilesampleto
the carrier gas stream in the chromatograph,This can be a problem with highly
To Vorioc
ColdN2+
Soleiy plug
Glosswoolor
e x p o n d e dp l o s t r c
Insul0lron
Heoter
F i g . 9 . 2 3 , A t t a i n m e n t o f l o w t e m p e r a t u r e sb y b o i l i n g n i t r o g e n . I n m a n y a p p l i c a t i o n ss u c h a s t h e
stifl in Fig. 9.22, the Variac is set to provide a convenient steady-stateboil-off temperature. When
closetemperature control is desired, a commercial control with a thermocouple or thermistor sensor
m a y b e u s e dt o c o n t r o l t h e h e a t i n p u t .
To bridge
T o v o c u u mI n e
H e s u p py
2-mm
copillory
iubrng
S om p l e
Insuloiron
/4Ot"/A UU Coppel ruDe

f lled wrih powdered metol
F i g . 9 . 2 4 . F r a c t i o n a lc o d i s t i l l a t i o na p p a r a t u s .I n t h i s d e s i g n( d u e t o S . M . W i l l i a m s o n ) ,t h e s a m ple is distilled into U-tube A and then carried by a helium stream into the upper left leg of the metal
t u b e , w h i c h i s c o o l e dw i t h l i q u i d n i t r o g e n .W h e n t h e l i q u i d n i t r o g e ni s p o u r e do u t a n d r e p l a c e db y a
chilled Dewar, the fractions are carried through the column by the helium stream and collected in
trap B when they appear in the detector. (Only one trap for fraction collecting is illustrated.)
.t95
196
AND OPERATIONS
VACUUMLINEEOUIPMENT
SPECIALIZED
Deteclor
o
.9
o
O
lrne
Fig. 9.25. Schematic of a gas chromatograph. The flow control generally consistsof a standard
p r e s s u r er e g u l a t o rp l u s a n e e d l ev a l v e .G a s p u r i f i c a t i o ni s s o m e t i m e sn e c e s s a r yp, a r t i c u l a r l yu ' i t h a i r a n d m o i s t u r e - s e n s i t i vceo m p o u n d s .A s h o r t c o l u m n o f m o l e c u l a rs i e v e sh e l d a t - 7 8 ' C i s f r e q u e n t l y
a d e q u a t e .T h e t r a p s ( f o r t h e c o l l e c t i o no f f r a c t i o n s )a n d f l o u n r e t e ra r e o p t i o n a l . T h e d a s h e dl i n e s
i n d i c a t ep o i n t s a t w h i c h c o m m u n i c a t i o nw i t h t h e v a c u u m l i n e i s p o s s i b l e .
volatile substances,becausepartial condensationof a multiconlponentsysten

will lead to a different relativeconcentrationof the componentsin the gas phase
than in the liquid phase.The following procedureis recommendedfor obtaining
a representativesample of a liquid containinghighly volatilecomponents:32
'l . The liquid phaseis made homogeneous,
2. A portion of the tiquid phaseis isolatedfrom the bulk of the liquid without
changein composition(i.e., without boiling).
3. The isolated portion is completetyevaporatedinto a suitable container
again without changein composition.
4. The vapor is made homogeneous.
Similarly, it is advantageousto obtain a gas samplefrom a homogeneouspolycomponent mixture by isolating a segmentof the homogeneousgas phase by
meansof a valve(s)and then removing all of this samplefor analysis.
Volatile reactiveliquids presentfew problemssincethey generallycan be distilled from the vacuum line into a tube equippedwith a serum bottle cap (Fig.
9.26). Nitrogen is then admitted to the tube, and the sample is taken with a
syringe. Another scheme involves an inlet with a capillary tube or ampule
breaker.33-3s
This method is potentiallyuseful for vacuum line work, sinceit is
relativelysimple to fill and sealoff a sampletube attachedto the vacuum line.
When slight contaminationof a gas sampleby air is not objectionable,syringe
techniquesmay be used. In order to minimize contaminationby air. a syringe
I V . D i e b l e r a n d F . L . M o h l e r . J . R e s . N B . i . 3 9 1 1 4 9( 1 9 4 7 ) .
r r M . D i m b a t , P . E . P o r t e r , a n d F . H . S t r o s s ,A r r o 1 .C h e m . , 2 8 : 2 9 0 ( 1 9 5 6 ) .
u S . W . S . M c C r e a d i ea n d A . F . W i l l i a n r sJ, . A p p l . C h e n t . , 7 : 1 7 ( 1 q 5 7 ) .
r s J .W e n d e n b u r g a n d K . J u r i s c h k a ,J . C h r o n n t o g . , l 5 l 5 3 8 ( 1 9 6 4 ) .
197
SEPARAIIONS
>.
Serumbottle
- cop
F i g . 9 . 2 6 . L i q u i d s a m p l i n gt u b e . T h e g a sv o l u m eo f t h i s a p p a r a t u si s k e p t s m a l l t o m i n i m i z e d e p l e t i o n o f t h e m o r e v o l a t i l ec o m p o n e n ti n t h e l i q u i d p h a s e .
with a Teflon- or rubber-tippedplunger is employed,36

the syringeis flushedwith
carrier gas, and the pressureof the gas sampleis adjustedto slightlymore than 1
atm beforethe aliquot is rvithdrawn.While veryconvenient,this approachis not
appropriatefor highly reactivegasesor situationsin which rapid, accuratesampling is desired.
The common method of gas samplingis to employa loop of tubing which may
be cut in or out of the carrier gas stream.The loop is filled with a gassampleand
then switchedin serieswith the carrier gas sourceand column. The loop may be
filled by evacuatingit and then either admitting the sampleat a measuredpressure from the vacuum line or distilling the entire samplefrom the vacuum line
into the loop (Fig. 9.27). Obviously,this processrequiresthe useof valveswhich
will hold a high vacuum. The valve requirementsare less stringent when the
sampling operation is performed by flushing the sample gas through the loop
(Fi9.9.27). This approach is well adapted to the analysisof commercialgas
streamsand is useful in the laboratoryfor samplingthe output of flow reactors.
However.it is not convenientfor most vacuunl Iine work.
A wide varietyof valvesmay be usedto achievethe aforementionedgas injection. Specialvalvesare availablewhich provide synchronousswitching of the
sampleinto the gas stream.One type involvesa body attachedto the carrier gas
'Ihe
passagesin this body open on a flat, polishedsurline and sample loop(s).
face. A rotor with passageways
which will interconnectthose on the body is
pressedfirmly againstit. By turning the rotor, the gas stream may be switched
betweendifferent ports. One of the most satisfactorydesignsfrom the standpoint of leak-tight performanceis based on a spring-loadedcone of graphiteimpregnatedTeflon which rotates in a metal body.37The porting is schematically illustrated in Fig. 9.28. Another type of valve involvesa shaft bearing a
r b S .H . L a n g e r a n d P . P a n l a g e s A
, n a l . C h e n t . . 3 0 ; 1 8 8 9( 1 9 5 8 ) .T e f l o n - t i p p e dg a s t i g h ts y r i n g e sa r e
m a n u l a c l u r e db y t h e H a m i l t o n C o n r p a n y ,W h i t t i e r . C A . " D i s p o s a b l e " s v r i n g e sw i t h r u b b e r ' - t i p p e d
p l u n g e r sa r e n r a n u f a c t u r e db v B e c t o n , D i c k i n s o n , C o . , R u t h e r f o r d , N l .
r - T h e s ev a l v e sa r e m a n u f a c t u r e db y V a l c o a n d a r e a l a i l a b l e f r o m s u p p l yh o u s e so f c h r o m a t o g r a p h i c
e q u i p m e n t . s u c h a s S u p e l c o ,I n c . , S u p e l c oP a r k , B e l l e f o n t e ,P A 1 6 8 2 3 .
AND OPERATIONS
VACUUMLINEESUIPMENT
SPECIALIZED
198
Injectrng
C o rr t e r
+Column
Somple >
tn
Corrrer
g o s-x- x
+Column
+Colu mn
.tl
s".i,{l-l
nU\
\,
lVonometer
Corrre/
Column
in
Fig.9.27.
Some configurations for gas sampling.
.""ffi,.ffi,.
Lo00
LooP
Fig. 9.28.
Loop
LooP
Gas inlet valve. Schematic of cone-typeor disk-type valve'
seriesof O-rings in grooves.This fits inside a cylinder from which passageways

is altered by sliding the Oextend. Communication betweenthe passageways
out.
ring bearing shaft in or
before discussing some individual systems,it is worth pointing out that an
ordinary analytical chromatograph will handle sampleswhich are very close to
t/a-\n.'
the scaleencounteredin vacuum line work (up to 1 to 3 mmol with a
diametercolumn). Therefore,the usual analyticalchromatographis potentially
useful for the purification of products or reactants for small-scalevacuum line
preparative wrk. For preparative work or for subsequentcharacterization of
iheiractions, the gas from the chromatograph is led through a small collection
Efficiency is improved
manifold where individual components are trapped.3s'3q
trap'
in
the
material
similar
wool
or
by including looseglass
r s J .H a s l a m . A . R . J e f f s ,a n d H . A . W i l l i s , , A n a l y s r ,8 6 ' 4 5 ( 1 9 6 1 ) '
i q C . M . D r e w a n d J . R . M c N e s b y ,i n D e s t y ,E d . , G a s C h r o m a t o g r o p h .1y9 5 8 ,( L o n d o n : B u t t e r w o r t h ,
1958),p. 216; G. Guiochon and C. Pommier, Gus chromatographv in Inorganics and organometalircs.Ann Arbor Sci. Pub., 1973.
SEPARATIONS
499
Permanentgasesmay be separatedby gas-solidchromatography.For example, oxygen,nitrogen, and hydrogenmay be separatedby a column packedwith
Linde 5A or 13X Molecular Sievesand detectedby thermal conductivity.40'1r
Permanentgasessuch as H2, 02, N2, CO, and CHa. as well as carbon dioxide,
terminal alkenesand straight-chainalkanesup to pentaneare well separatedby
a temperature-programmedcolumn consisting of a carbon molecular sieve
The separationof H2, N2, CO, CO2,NO, and N2O is possicalledSpherocarb.42
A more thorough
ble on speciallyactivatedsilicagel at reducedtemperatures.a3
review of the separation of light gasesis given by Littlewood,aaand by Thompson.asThe fairly strongoxidizingagentNO2can be separatedfrom CO2,air, and
other nitrogen oxidesby using ordinary materialsof constructionfor the chromatograph.a6However, very strong oxidizing and fluorinating agentsrequire the
useof nickel, Monel, Teflon, and Kel-F as constructionmaterials,and Kel-F oil
For example,a chroon a powderedTeflon supportfor the column packing.aT'48
matograph of this sort was used for the separationof Cl2, ClF, ClF3, HF, and
UFu.otA thermal conductivitydetectoremployingnickelaTor Teflon-protected
has been used.The gas-densitydetector,wherethe heat filamentsdo
elementsa8
and flame ionization have also been
not come into contact with the samples,ae'so
used for strong fluorinating agents.
A number of metal and metalloid halides have been separatedwith rather
conventionalarrangements.For example, Keller and FreiserseparatedSnCla,
TiCl4, Nbcls, and TaC15at 200'C using a coppercolumn packedwith squalane
on Chromsorb P (a modified diatomaceousearth).srA variety of chlorosilanes
have been separatedusing siliconeoil plus diethyl phand methylchlorosilanes
and thermal conductivitydetectors.s2
thalate as the stationary-phase
In his study of methyl-ethyllead alkyls, Dawson found that pretreatmentof
the ChemsorbW support with sodium hydroxidereducedthe interchangeof alkyl groups between the lead species.SE-30 silicone rubber was used as the sta-
a O SA. . G r e e n ,A n a l . C h e n t . , 3 l ; 4 8 0 ( 1 9 5 9 ) .
a l G . G n a u c k , Z . A n a l . C h e m . , 1 8 9 : 1 2 4( 1 9 6 2 ) .
a 2 A v a i l a b l fer o m A n a l a b s , T h e F o x b o r o C o m p a n y . 8 0 R e p u b l i cD r i v e , N o r t h H a v e n . C T 6 0 4 7 3 .
arl. Marviflet and J. Tranchant, in R. P. W. Scott, Ed., Gas Chrontatography, /960 (London: Butt e r w o r t h , 1 9 6 0 ) ,p . 3 2 1 .
{aA. B. Littlewood, Gas Chromatogruphv (New York: Academic, 1962), pp. 372ff..
{sB. Thompson (general references).
a o JM
. . T r o w e l l ,A n a l . C h e m . , 3 7 ; l l 5 2 ( 1 9 6 5 ) .
a ] A . G . H a m l i n , G . l v e s o n ,a n d T . R . P h i l l i p s ,A n a l . C h e n t . , 3 5 12 0 3 7 ( 1 9 6 3 ) .
a E R .A . L a n t h e a l u m eA, n a l . C h e m . 3 6 ; 4 8 6 ( 1 9 6 4 ) .
,
4qJF
. . E l l i s , C . W . F o r r e s t ,a n d P . L . A l l e n , A n a l . C h i m . A c t a , 2 2 t 2 7 ( 1 9 6 0 ) .
s o T . R . P h i l l i p s a n d D . R . O w e n s i n R . P . W . S c o t t , E d . , G a s C h r o n t a t o g r a p h l .1- .9 6 0 ( L o n d o n :
B u t t e r w o r t h , 1 9 6 0 ) ,p . 3 0 8 .
s l R . A . K e f f e r a n d H . F r e i s e r ,i n R . P . W . S c o t t , E d . , G a s C h r o m a t o g r a p h y ,/ 9 6 0 ( L o n d o n : B u t t e r w o r t h , 1 9 6 0 ) ,p . 3 0 8 .
s 2 G .F r i t z a n d G . K s i n s i k Z . A n o r g . C h e m . , 3 0 4 ; 2 4 1 ( 1 9 6 0 ) .
,
200
AND OPERATIONS
VACUUMLINEESUIPMENT
SPECIALIZED
tionary phase and, in line with previouswork, electroncapture detectionwas

found to give high sensitivityfor the lead alkyls.ss
The gas chromatographicseparationof many hydridesmay be accomplished
with relative ease. For example, Borer and Phillips resolved 2l silanes up
through Si6H16and 5 germanesthrough Ge.rHroon a column of siliconeoil on
Celite.slThis sametype of column has been usedto separatethe boron hydrides
while paraffin oil was used as the stationaryphase in
through pentaborane,ss
anotherstudy.sbThe borane samplesof Borer, Littlewood,and Phillips included
the unstablecompoundsBaHl6and BsH". In order to checkfor decomposition,
they perfotmed severalrepeatedpassesof their samplesthrough the chromatograph and this revealedslight decompositionof BsH11.A check of this sort appearsadvisablewheneverunstablecompoundsare handled.Thermal conductivity detectorshave been usedwith all of thesehydride compounds;however,less
thermally stablehydridescreatedepositsin the detector,which impairs its function. An interestingtechniquewhich circumventsthis problem and increasesthe
sensitivityof detectioninvolvesthe use of a furnace on a quartz capillary tube
which is placedbetweenthe exit of the column and the detector.Completepyrolysisof the hydride occursin this tube to yield hydrogen,which is then detected
by thermal conductivity. Highly purified nitrogen u'as used as the carrier gas,
and the best separationof SiHa,GeHa,AsH3, and PH3was obtainedwith a silic o n eo i l s t a t i o n a r yp h a s e . s -
9,3 sToRAGE
oFGAsEs
ANDsoLVENTs
Small quantitiesof gasesare most convenientlystoredin glassbulbs, which are
selectedto be free from thin spotsand are well annealed.Despitetheseprecautions, there is the chanceof implosionwhen the bulb is evacuated;the resulting
hazard of flying glassmay be avoidedby wrapping the bulb with tape. enclosing
it in a wire mesh cage, or coating it with a tough plastic paint.ssThe requirementsfor a stopcockor valveon a storagebulb are much more stringentthan for
ordinary use becausecontinual exposureto the gas may break down stopcock
grease.A Teflon-glassvalvedoesnot suffer from this disadvantage,but when it
is usedon a storagebulb, the seatsideof the valveshouldretain the gas sincethe
stem side is more subjectto leakage(Fig. 9.29).
Large quantitiesof gas and solventswith high vapor pressuresmay be stored
srH.J. Dawson,
3\ 542(1963).
Ir.,Anal.Chent.,
s a K .B o r e ra n d C . S . G . P h i l l i p s ,P r o c . C h e m . . 9 o c . 1
, 8 9 .( 1 9 5 9 ) .
s s K .B o r e r ,A . B . L i t t l e u ' o o da, n d C . S . G . P h i l l i p s J, . I n o r g . N u c l .C h e m . , 1 5 ; 3 1 6( 1 9 6 0 ) .
: n J .J . K a u f n r a n ,J . E . T o d d . a n d W . S . K o s k i , , 4 r a l . C h e n t . , 2 9 t1 0 3 2 ( 1 9 5 7 ) .
s r G . G . D e v y a t y k h ,A . D . Z o r i n , A . M . A m e l c h e n k o ,S . B . L y a k h m a n o v .a n d A . E . E z h e l e v aA. k a d .
N o r l < . , S S S R( E n g l i s ht r a n s . ) ,1 5 6 ;S 9 1( 1 9 6 1 ) .
: s A v a i l a b l ef r o m A c e G l a s s C o m p a n y , V i n e l a n d , N J .
201
SIORAGEOF GASESAND SOLVENTS
Cooted
\Freeze-out
T o m o r n m o n r of l d
tip
F i g . 9 . 2 9 . T y p i c a l a r r a n g e n r e n ot f g a s s t o r a g eb u l b s .
i n 2 0 0 - m L s t a i n l e s s - s t e ec ly l i n d e r sf i t t e d w i t h p a c k l e s sv a l v e sa n d m o u n t e d
firmly on an angle iron frame. The tank may be attachedto a small manifold
(equippedwith a mercurybubbler manometer)through a glassbellowsor a loop
of 6-mm glasstubing to take up any slight differentialmovement(Fig. 9.30).
It is convenientto store frequently used solventsin containersdirectly attachedto the vacuum line. The valverequirenrentsare evenmore stringentthan
for gas storage,becausethe attack of stopcockgreaseby organic solventvapors
is a certainty.Therefore,Teflon-stemmedvalvesare generallycalledfor. A good
solventstoragecontainermay be constructedfrom a distillationflask. As shown
in Fig. 9.19, the solventmay be fractionallydistilled directly into the sidearmof
,,Glossloop
:_pockless
F i g . 9 . 3 0 . S t o r a g eo f g a s e si n m e t a l t a n k s . T h e v a l v ei s b o l t e d d i r e c t l yt o t h e s t e e lf r a m e . w h i c h i s
rigidly mounted.
202
VACUUMLINEEQUIPMENT
AND OPERATIONS
SPECIALIZED
this flask. The solventis then frozen down, the flask is evacuated,and the sidearm is sealedoff. Inclusion of a drying agent, such as calcium hydride, in the
flask ensuresthat the solventwill remain anhydrous.
The long-termstorageof liquids and gasesis bestaccomplishedin an ampule
or bulb fitted with a break-seal.Once the sample is sealedoff in such a container, leakageis no problenr as it would be if a stopcockor valve were used.
Furthermore,this practiceis economicallysound,sincea break-sealis much less
expensivethan a stopcockor valve.
9,4 sEALED
TUBE
REAcnoNs
The difficultiescreatedby stopcocksand valvescan usuallybe minimized. However,it is occasionallynecessary
to completelyeliminatethesesourcesof leakage
and contaminationby the useof break-sealsand vacuum seal-offs.Typical situationsin which sealedtube techniquesare widely usedare quantitativehydrolysis and oxidation reactionswhich require elevatedpressuresand temperatures,
precisephysical measurementson highly reactiveorganometalliccompounds,
long-term storage of reactive samples, and nonaqueous reactions under high
pressure(for example, SOzor NH: at room temperature).Each pieceof apparatus must be constructedto meet a specificneed, so it is not possibleto outline
an apparatuswhich is of generaluse. Nevertheless,
severalexampleswill be presentedhere which serveto indicate the approach.
B r e a k - s e a l (sF i g . 9 . 3 l ) a r e c o m m o n l yu s e d o n s e a l e dr e a c t i o na n d s t o r a g e
tubes becausethis type of seal allows recoveryof volatile materials. The type
illustrated in Fig. 9.31c may be openedin an apparatuswhich containsan offcenter arm which may be rotated to break the small tube (Fig. 9.32a). Among
the many variants of this designof tube opener, one by Mahler and Velmey is
constructedfrom al,/4-in. stainless-steel
needlevalvewhich is drilled out to receivethe break-sealso that the valve stem may be screweddown on the small
tube (Fig. 9.32b).seThe break-sealand vacuum systemare connectedto this
Seollhrougn
{ lornt
II
[-!
I
Fig,9,3t.
tl
rl
Break-seals.
s q W .M a h l e r a n d H . V F e f m e y ,R e y . S c i . I n s t r . , 3 3 , ' t 1 2 7 ( 1 9 6 2 ) .
203
TUBEREACTIONS
SEALED
T o v o c u u ml t n e
T o s e o l e dt u b e
v
(b)
Fig.9.32. Tubeopeners.
modified valve by Swagelokfittings in which a Teflon front ferrule is used (see

Chapter4). The break-sealsillustratedin Fig. 9.31b and c are openedby means
iron rod actuatedby
of a magnetic hammer which consistsof a glass-encased
meansof a hand magnet.
The reaction tube illustrated in Fig. 9.33c is useful for hydrolysisreactions
and other situationsin which considerablepressuremay build up in the tube
becausethe break-sealusedhere withstandshigh pressures.The procedureinvolvesdistillation of the compoundand outgassedwater (or HCI-watermixture)
into the tube on the vacuum line. It is then sealedoff under high vacuum (Ap-
F i g . 9 . 3 3 . T y p i c a l s e a l e dt u b e d e s i g n s
204
VACUUMLINEEQUIPMENT
ANDOPERATIONS
SPECIALIZED
pendix II) and allowed to warm to the appropriate temperature. When high
pressuresare anticipated.everyprecautionmust be taken to avoid endangering
explosionshieldor a small metal
laboratorypersonnel.In general,a safety-glass
containmentshield around the tube should be used,and the experimentshould
be arranged so that the tube can be cooled to a low temperaturebefore it is
handled. The break-sealis easilybroken by clumsy handling, so it is protected
by an openjoint. Glassapparatusunder pressuremust alwaysbe treatedas dangerous;however.somerough guidesare given in Appendix II for the minimization of breakage. It is quite important for a glassbomb tube to be smoothly
blown and well annealed.
After hydrolysisor similar reaction, the tube is cooledin liquid nitrogen to
reducethe pressureof the gasesand openedwith a specialdevice(Fig. 9.32). If
noncondensablegasesresult, they are collectedwith the Toepler pump or low
temperatureadsorptionfor measurementand identification.
If the weight gain of the contentsof the tube is of interest. the break-seal
describedabove(Fig. 9.31a) is inconvenientbecausethe broken parts are not
easyto collect and weigh. In this casethe break-sealsillustrated in Fig. 9.316
and c are more useful. The former is availablecommerciallyat low cost, and
either type is easilyconstructed.Thesebreak-sealsare broken open by meansof
iron rod or, if it will not reactwith the gasesunder study. a clean
a glass-encased
ball bearing.The breaker is raisedwith a hand magnetand allowedto fall on the
thin break-seal.The tube shown in Fig. 9.33c is useful for studying gas-solid
reactionswherethe reactionhas to be allowedto standfor a long time or whereit
requires heating. A typical procedureinvolvesweighing the tube and a small
s t o p p e r , i n t r o d u c i n g t h e s o l i d , o u t g a s s i n gu n d e r h i g h v a c u u m , r e w e i g h i n g .
reevacuating,distilling a measuredquantity of reactivegas back into the tube,
and sealingthe tube off under vacuum (Appendix II). When the reactionis complete, the tube is attachedto the vacuum line, the spaceabovethe break-sealis
evacuated,and, after the gas in the tube has beencondensed,the tube is opened
by meansof the magnetichammer. The tube is allowedto warm very slowlyby
means of a chilled Dewar to prevent the solid and glass particlesfront being
carried into the vacuum systemby a sudden surge of gas. After the gas is collected,dry nitrogenmay be admitted to the tube, and the tube removedfrom the
vacuum line while the magnetichammer is quickly removedand a small rubber
stopperis usedto sealthe open end. Both parts of the tube are then weighedin
order to calculatethe weightgain of the solid. In addition, the recoveredgas may
be measuredand identified.
The trap-to-trap condensationof compounds with low volatility is ahvays
troublesome, and the situation is aggravatedif the compound evolvessmall
quantities of less condensabledecompositionproducts. When these casesare
encountered,the sample is best collectedin a U-tube (Fig. 9.33b) becauseit
allowsthe distillation of the compound through one leg while a high vacuum is
maintained on the other. Both arms of this tube must then be sealedto isolate
the sample.
S e a l e d - t u b em a n i p u l a t i o n s h a v e b e e n e m p l o y e d i n p h y s i c a l s t u d i e s o n
TUBEREACTIONS
SEALED
205
Grignard reagentswhere traces of oxygen and stopcockgreasemay lead to erroneousresults.60'br

As illustrated in Fig. 9.34, the apparatusis designedwith a
specificsequenceof operationsin mind.
Reactionsof liquefied gases,such as NH-r and SO2, may be carried out in
sealedtubes at room temperature. Liquid ammonia exerts approximately 10
atm pressureat room temperature,so a tube diameterlarger than l5 mm should
be avoidedand the previouslymentionedsafetyprecautionsmust be observed.
Franklin and his studentscarried out many acid-baseand metathesisreactions
in multileggedtubessuch as thoseillustratedin Fig. 9.35.62The reagentsmay be
chargedinto the legs, the solventintroducedon the vacuum line, and the tube
sealedoff. The reaction betweentwo or more solutionsis accomplishedby tipping the tube. If a solid is formed, the supernatantliquid may be decantedand
the leg containingthe solid may then be cooledin an ice water bath to accumulate ammonia for washing the solid. Some workers prefer to use multilegged
of this sort with a small pressurestopcockfitted to the inlet tube, in which
vessels
F i g . 9 . 3 4 . A p p a r a t u s u s e df o r t h e p r e p a r a t i o na n d s a m p l i n go f G r i g n a r d r e a q e n t sf o r N M R s p e c t r o s c o p y .T h e a p p a r a t u sw a s e v a c u a t e dt h r o u g h J 1a n d t h e M g b a k e d . E x c e s se t h e r a n d a l k y l h a l i d e
w e r e d i s t i l l e d o n t o t h e m e t a l , a n d t h e a p p a r a t u sw a s s e a l e do f f a t S r . U p o n w a r m i n g t o 0 ' C a n d
s h a k i n g ,a r a p i d r e a c t i o no c c u r r e d .T h e a p p a r a t u sw a se v a c u a t e da t J , . t h e b r e a k - s e aB
l w a sb r o k e n ,
a n d e t h e r a n d e x c e s sa l k y l h a l i d e w e r e r e m o v e d .F r e s hd r y e t h e r a n d t h e t e t r a m e t h y ls i l a n es t a n d a r d
w e r e d i s t i l l e d i n , t h e a p p a r a t u sw a s s e a l e do f f a t S , , a n d a s m a l l p o r t i o n o f t h e s o l u t i o nw a s f i l t e r e d
t h r o u g h t h e f r i t F i n t o t h e N M R t u b e , w h i c h u a s s e a l e do f f a t 5 2 .( A d a p t e df r o m D . F . E v a n sa n d J .
P . M a h l e r , J . C h e n r ." l o c . , 1 9 6 2 ,5 1 2 5 . )
n o A .D . V r e u g d e n h i lal n d C . B l o m b e r g ,R e c . T r u v . C h i n . , 8 2 : 4 5 3 ( 1 9 6 3 ) .
n l D . F . E v a n sa n d J . P . M a h l e r .J . C h e n t . . i o c . .1 9 6 2 :5 1 2 5 .
n r E . C . F r a n k l i n . T h e N i t r o g e n S y s t e not J ' C o n t p o r i a d (sN e u Y o r k : R e i n h o l d , 1 9 3 5 ) .
206
VACUUMLINEEQUIPMENT
AND OPERATIONS
SPECIALIZED
//l\/t[\
#
/\
U\JUUUUU
(o)
(b)
(c)
Fig. 9.35. Sealed tubes for the observation of reactions in liquefied gases.Liquid phasesmay be
decanted from one leg to the next.
casethe tube is easilyopened to sample gasesor removethe solvent.63Of course,

the tube may alsobe fitted with a break-sealthrough which gaseousand volatile
productsmay be removed.This was the approachtaken by Stock, who included
a slightly constricted portion in the middle of the tube with a wad of glasswool to
serveas a filter.
9.5 MrscELLANEous
TEcHNteuEs
A. Sompling Alkoli Mefols. Of the alkali metals, lithium is in some respectsthe most difficult to handle. It reactsslowlywith nitrogen;so when purity
is important, it should be handled in an argon atmosphereor in a vacuum. In
addition, the molten metal reactswith Pyrex, causingit to crack.
For rough applicationsit is satisfactoryto cut and weighsodiumor potassium
chunks under a hydrocarbon. CAUTION: Halogenated hydrocarbons should
not be used because they present a serious explosion hazard in the presence of
alkali metals. In the case of potassium, the oxidized layer should be carefully
scraped from the surface before the metal is cut, becausean explosion may result
if this crust is embedded in the metal. For many, purposesweighed quantities of
pure sodium may be introducedin sealed,thin-walledglassbulbs which may be
broken with a glass-encased
magnetichammer to releasethe metal. Thesebulbs
are preparedas follows. A thin glassbulb is blown onto a joint so that there is a
constricted region between the bulb and the joint (Fig. 9.36). The bulb is
weighedand its volume is measuredfor a subsequentbuoyancycorrection.A
chunk of metal of the approximatedesiredweight is placedin the apparatusso it
restson the constriction,and the bulb is attachedto a vacuum line and evacuated. When a high vacuum is attained, the constrictionand region aboveit are
flamed gently so that the metal melts and runs down into the bulb. The crust of
oxide is left behind in this process.The bulb is sealedoff under vacuum at the
constriction.After the top part is cleaned,it is weighedalong with the bulb, and
brW.C.JohnsonandW.C.Fernelius,./.
C h e n t . E d u c . , 6 : 4 4 1( l g 2 i l . l n t h i s r e f e r e n c e a n d f o o t n o t e
6 3 , t h e p r o c e d u r e sw h i c h a r e d e s c r i b e dd o n o t i n v o l v et h e u s e o f a v a c u u m l i n e .
207
TECHNIQUES
MISCELLANEOUS
--i;
\a
ll
llI
tel
l'l
.i'7
lllt
lltd
OV
F i g . 9 . 3 6 . P r e p a r a t i o no f w e i g h e ds a m p l e so f p u r e a l k a l i m e t a l . O n t h e l e f t t h e s o d i u n t i s b e i n g
m e l t e d u n d e r v a c u u m b y m e a n s o f a c o o l f l a m e . O n t h e r i e h t t h e b u l b h a s b e e n s e a l e do f f u n d e r
a buoyancycorrectionis then appliedto give an accurateweightfor the metal in

the bulb. Sodium, which is sealedoff in this manner, is usefulfor quantitative
work on the vacuum line sinceno extraneousgasesor solid impurities are introd u c e dw i t h t h e s a m p l e .
The sodium-potassiumalloy (45-90 weight %K) is molten at room temperature and cesium melts at 28.5o, so both of theseare easilyhandled as liquids.
For example,a hypodermicsyringeis convenientfor their transfer.The sodiumpotassium alloy is made by heating the two metals together while they are protectedby a high-molecular-weighthydrocarbon.
With the exceptionof lithium, the alkali metals may be distilled in an allglass, high-vacuum apparatus to yield a very pure sample. Finally, a novel
methodfor the quantitativeintroductionof small amountsof sodium into a glass
apparatusis the electrolysisof the metal through glass.oa
B. Genelofion of Dry Goses. Directionsaregivenbelowfor the preparation andlor purificationof severalusefulgases.

Oxygen.oo A tenfold excessof potassiumpermanganate(calculatedon the basis of 2KMnOa : MnO2 * K2MnOa * Or) is placed in a glassbulb which is
sufficientlylarge to allow doubling of the volume of solid as the reaction proceeds.A plug of glasswool is placed abovethe sample to avoid contamination of
the vacuum systemby solid particles.The sampleis heatedto 100oCwhile it is
evacuatedovernightunder high vacuum. After this initial bake-out,the sample
is left open to the vacuum pump while the temperatureis raised to approximately 200oC, where oxygen production commences.The vacuum pump is
closedoff briefly so that oxygenevolution can be roughly estimated. Evacuation
is continued until 5-10% of the theoreticalquantity of oxygen has been disH W . L . J o fl y . J . P h y s .C h e n t . , 6 2 ' , 6 2 9( 1 9 5 8 ) .
208
SPECIALIZED
VACUUMtINE EQUIPMENT
AND OPERATIONS
carded. The oxygen sample is then collectedwhile the solid is heated above
200'C (but not in excessof 230'C).
Methane. ResearchGrade (about 99.65 mote % pure) and CP (about 99.0
mole 7o pure) methaneare availablein cylinders.The removalof CO2, Oz, Nr.
and higher hydrocarbonsfrom methaneby adsorptionon charcoalhas been described in the literature.6s
Ethylene. This gas is availablefrom the Matheson Company in CP (99.0%
pure) and ResearchGrade (99.9 To pure). Oxygen may be removedby passing
the gas through a tube containing MnO.
sulfur Dioxide. High-purity sulfur dioxide is availablein cylinders.It may be
further purified by passingit over Pao,6to removewater and degassing.In their
precisework on the vapor pressureof SO2,Giauque and Stephensonprepared
this gas by the reaction of concentratedsulfuric acid with sodium sulfite.66It was
then passedthrough water to removeSO3,through PaO16
to removethe water,
and finally subjectedto severaltrap-to-trapdistillations.followingby degassing.
Ammonia. The major contaminantsin the "anhydrous ammonia" available
from the Matheson Company in cylindersare water, oil, and noncondensable
gases.Most of these impurities are removed by passingthe NH3 through a trap
h e l d a t - 2 2 " C a n d c o n d e n s i n gi t a t - 1 9 6 ' C u n d e r v a c u u n t .T h e w a t e r i s r e moved by distilling the ammonia into a tube which contains a small lump of
sodium. The tube is warmed slightlyto n.reltthe an'rmoniaand form a blue solution, and the resultingdry ammonia is punrpedaway.A fairly largeplug of glass
wool must be included betweenthis tube and the vacuum systemto avoid contaminating the line with a fine spray of sodium metal. The gas is condensedat
-196'C under high vacuum to removehydrogenand other noncondensables.
GENERAL
REFERENCES
Temperolureond TempeloluteMeosuremenf
Benedict, R. P., 1984,Fundantentals o;f Temperuture, Pressure,and Flov' Measurements,3rd ed.,
Wiley. New York.
Quinn, T. J. , 1983, Tenrperuture, Academic, London. A comprehensivereviewof thermometry over
t h e t e m p e r a t u r er a n g e0 . 5 - 3 0 0 0 K . T h e b o o k i n c l u d e sc h a p t e r so n r e s i s t a n c e
t h e r m o m e t r va n d
thermocouples, and is extensivelyreferenced.
o : J . H . E i s e m a na n d E . A . P o t t e r .
" / . R e s . N a r . B u r . S t d . , 5 8 ; 2 1 3 ( 1 9 5 7 ) ;H . H . S t o r c ha n d P . L .
G o l d e n ,J . A m . C h e n t . , . l o c . ,5 4 , 4 6 6 2 0 9 3 2 \ .
6 6 W .F . G i a u q u e
a n d C . C . S t e p h e n s e n",/ . . 4 n r C h e n t .S o c . , 6 0 ; l 3 B 9 ( 1 9 3 8 ) .
G E N E R ARLE F E R E N C E S
209
Schooley,J. F., Ed., 1982, Tentperuture-lts Meusurentent und Control in Scienceund Industry,
V o l . 5 , A m e r i c a n I n s t i t u t e o f P h y s i c s ,N e u Y o r k . A n e x c e l l e n ts o u r c eo f s t a t e - o f - t h e - a rtth e r m o m e t r y c o m p r i s e do f p a p e r sf r o m t h e S i x t h I n t e r n a t i o n a lT e n r p e r a t u r eS y m p o s i u m .T o p i c s
w h i c h a r e c o v e r e di n c l u d e t e m p e r a t u r es c a l e sa n d f i x e d p o i n t s , r a d i a t i o n , r e s i s t a n c et,h e r m o c o u p l e , a n d e l e c t r o n i ct h e r m o m e t r y ,t e m p e r a t u r ec o n t r o l , a n d c a l i b r a t i o nt e c h n i q u e s .P r e c e d i n g v o l u m e si n t h e s e r i e sd a t e b a c k t o 1 9 3 9 .
Gos Chromotogrophy
K e s z t h e l y i ,C . P . , 1 9 8 1 , i n P . T . K i s s i n g e ra n d W . R . H e i n e m a n , E d s . , L a b o r a t o r y T e c h n i q u e si n
Electrounulyticul Chentistry, Marcel Dekker, New York. Vacuum line design and experimental
m e t h o d sf o r e l e c t r o c h e m i c ael x p e r i m e n t a t i o n .
M c N a i r , H . M . . a n d E . J . B o n e l l i , l 9 6 9 , . B a s i cG a s C h r o n t u t o g r u p h , - , S t he d . , V a r i a n A s s o c i a t e s ,
lnc.
T h o m p s o n , 8 . , 1 9 7 7 , F u n d . a n t e n t a lqs f G u s A n u l y s i sb y G u s C h r o n n t o g r u p h y ,V a r i a n A s s o c i a t e s .
I n c . , P a l oA l t o , C A .
40
Metol Sysfems
Glassapparatusoften is widely usedfor the constructionof laboratoryapparatus

becauseit is relatively inert, light. transparent, and easy to clean. However,
metal apparatus has decided advantagesin some applications.For example,
metals are mechanicallymore robust than glass, many metals are resistantto
reactivefluorides,and metal valvesand joints can be much more leak-tightthan
their glass counterparts.Becauseof thesequalities,metal is used for the constructionof high-pressureapparatus,fluorine-handlingvacuum lines, and veryhigh-vacuumsystems.In addition, metal is a popular materialfor gas-handling
manifolds and flow reactorsfor catalysisresearch.
The first part of this chapteris devotedto the proper handling of gascylinders
and compressed
gases.This sectionshouldbe requiredreadingfor anyoneworking with compressedgasesfor the first time. The constructionof apparatusfrom
seamless
tubing is describednext, and the designand characteristics
of common
metal components,such as valvesand joints, are presented.The chapter ends
with detailsof somegeneral-purpose
metal apparatusfor catalltic reactorsand
fluorine chemistry.Attention also is directedto Appendix IV for detailson the
propertiesof metals.
'10.'l coMPREssED
GAsEs
A. Sofe Hondling of Cylindels.
Severalpopular cylindersfor the containment of compressedgasesrange from the size often used for nitrogen or oxygen
(about 9 in. in diameter by 52 in. high, exclusiveof the valve and cap) to the
lecturebottle (2 in. in diameter by l5 in. long) which is used to dispensesmall
amountsof reactivegases.In the United States,the cylindersizesvary from one
2tio
GASES
COMPRESSED
241
supplier to the next; however, there is fairly uniform adoption of valve outlet
fittings as perscribedby the CompressedGas Association.A typical compressed
gas valve and fitting for large cylinders consistsof an emergencypressurerelease
fixture, an on-off valve, and the outlet fitting. CAUTION: Never tamper with
the emergency pressure release fixture. Unfortunately, the emergency pressure
release fitting sometimes has a hexagonal outer contour and therefore can be
loosenedby means of a wrench. The valve assemblyis the most vulnerable part
of the cylinder and it can be broken off if a cylinder is accidentallydropped. A
pressurizedcylinderwhich has broken open is very dangerousbecauseit is propelled like a rocket. CAUTION: To minimize the chance of a cylinder being
ruptured by falling, the cylinders should always be strapped in place when the
protective cap is removed, and the cap should be replaced before the cylinder is
moved to another location. Of course, a cylinder should never be deliberately
dropped, evenwhen the protectivecap is in place.
Some of the common high-pressurecylinder fittings are illustrated in Fig.
10.1.Many of thesehaveas their sealingsurfacesa conein the outlet and a coneshapedor rounded nipple on the connectingpiece.Thosefittings, which do not
have gaskets,require firm tightening to achievea gastightseal.For a few gases
which are deliveredat lower pressure,the connectionis made by meansof flat
surfaces,one of which contains a washer of lead or other soft metal. NOTE:
Left-handed threads are used on flammable gas cylinder fittings, for example,
H2e propane, and CO. The connector for these flammable gasescan be identified by means of V-shaped indentations on the edges of the hexagonal nut (Fig.
f0.f .b). It may seemto the user that the wide variety of outlets is a nuisance;
however,they servethe beneficialpurposeof avoiding accidentalconnectionof
the wrong gasto an apparatus,and they avoidthe possibilityof using a regulator
for a flammablegas on a cylindercontainingoxygenor anotheroxidizingagent.
Trapped gas or oil residuesfrom a flammable gas are likely to explodeif suddenly compressedwith high-pressureoxygen.
The CompressedGas Associationspecifiestwo typesof outletson lecturebotttes(Fig. 10.2),dependingon whetheror not the gas is corrosive.A lead washer
is insertedbetweenthe tank outlet and the connectorfitting. Thesegasketsgenerally last for only a few cyclesof assemblyand disassembly,so a good stock
should be kept on hand. Theseare readily made using two hole punchesof appropriatediameterand a sheetof r/ro-in.-thicklead. As with the largertanks, the
outlet valveon the standardlecturebottle is of the on-off type and is not suitable
for the control of gas. Both pressureregulatorsand needlevalvesare available
which will mate with the lecturebottle fitting. A needlevalveis the most generally usefulmeansof gas regulationbecauselecturebottlesare most often usedto
dispensesmall quantitiesof gas for chemicalreactions.In place of the lecture
bottle, somechemicalsupply housesprovidegasesand highly volatileliquids in
small welded steelcontainers(about 3 in. in diameter and 5 in. high) that are
light and easyto handle. In general,thesecylindersare used for low pressure
and relatively noncorrosivegases, and are fitted with a needle valve outlet
equippedwith a swageor pipe thread fitting. The valvethat is suppliedon the
212
METALSYSTEMS
I
8?5
t3 l6
(a)
CONNECTION
-T
TJ .825' 830"
13/16', | 3 / r 6 "
1_r
l(b)
OUTL E1
CONNCTION
----r-845"
1t8
-..J
ffi"
7ta
ll:l
(c)
I
OUTLET
L,..,r-_T_
- . ^ ^ I^. U.J V
-.'l
1"
"ll-__r W A S H E
(d)
F i g . 1 0 . 1 . S o m ec o m m o n h i g h - p r e s s u r et a n k f i t t i n g s . T h e s e a li n t h e t o p t h r e e f i t t i n g s i s m a d e b y
c o n t a c tb e t w e e nt h e n i p p l e i n t h e c o n n e c t i o na n d t h e s e a ti n t h e o u t l e t . N o t e t h e c o n e - s h a p e dr,o u n d ,
a n d b u l l e t - s h a p e dn i p p l e sf o r ( , r ) , ( ) , a n d ( c ) r e s p e c t i v e l yT. h e b o t t o m c o n n e c t i o n( d ) i s s e a l e db y
m e a n so f a f l a t s o f t - m e t a lg a s k e t .N e v e ra t l e n r p tt o m i x o u t l e t a n d c o n n e c t i o n sb e t u e e nt h e v a r i o u s
d e s i g n s .N o t e t h e g r o o v e so n t h e c o n n e c t i o nn u t s f o r c o n n e c t i o n s( 6 ) , ( c ) , a n d ( d ) . T h i s g r o o v ei n d i c a t e sa f i t t i n g w i t h l e f t - h a n d e dt h r e a d s .( R e p r o d u c e db y p e r n r i s s i o no f t h e c o p y r i g h th o l d e r , M a t h e s o n G a s P r o d u c t s .l n c . )
tank often is satisfactoryfor controllingthe gas outlet, but if there is any doubt,
an additional needlevalve (see Section 10.5) or pressureregulator should be
added.
B. Sofe Delivery of Goses. The vast majority of compressedgas cylinders
are supplied with efficient on-off valveswhich provide no significant flow or
pressurecontrol. CAUTION: It is necessaryto equip a compressedgas cylinder
with some means of controlling the pressureand/or flow of the gas being deliv-
243
COMPRESSED
GASES
OUILET
I
5625
9/16
.561l
.5524
9/16',
OUTLET
+l
LEAOWASHER
--T(b)
5/16" 32
ffi
Ett
Fig, 10,2. Fittings for lecture bottles. Both fittings are designed to seal by means of a soft lead
washer, which must be replaced frequently. Fitting (c) is for noncorrosivegasesand (b) is for corrosive gasses.(Reproduced by permission of the copyright holder, Matheson Gas Products, Inc.)
ered. The choice of pressureversusflow control is basedon the nature of the

experimentbeing performed. The deliveryof gas to a closed,low-pressuresystem requiresthe useof pressurecontrol by meansof a diaphragmregulator(Fig.
7.14). For example, the deliveryof nitrogen or argon to an inert atmosphere
Schlenk-typeapparatus(Chapter 1) dictatesthe useof a good pressureregulator
which will deliver about 3 psig of gas. Similarly, the oxygenfor a glassblowing
torch is suppliedvia a diaphragmregulator.The leastexpensivepressureregulators are fitted with only one stageof regulation.This resultsin a slow changein
the outlet pressureas the tank pressuredecreases.Much better regulation is
obtained with two-stageregulators.Another point which requiresattention in
the choiceof a regulator is the output regulationrange. A different regulatoris
chosenfor high-pressureoutlets (to fill high-pressurereactors)than for general
use. The general-usemodels listed by many distributorshaveoutput regulation
in the 0-75 or 0-50 lb/in.2 range, which is not optimum for someof the most
common laboratory applications.The best choicefor inert-gaslines and glassblowing torchesis a regulator designedfor a 0-15 lb/in.2 output. As described
below, corrosiveand high purity gasesrequire specialregulators.
If gas is to be deliveredto a reactionflask which has an unobstructedoutlet, a
simple flow control valve on the high-pressurecylinder will provide adequate
regulationof the gas delivery.In this casea needlevalveis attachedto the cylinder, or to a pressureregulatorwhich in turn is attachedto the cylinder.It alsois
possibleto deliver gas to a closedsystem,such as a vacuum line, with a flow
control valve. In this casethe pressurewithin the apparatusmust be carefully
monitored by means of a manometer and the systemshould also be equipped
with a meansof pressurerelief, suchas a mercurybubbler manometer(Fig.7 .2).
When reactivegasessuch as HCI or BF3 are handled, the regulatoror valve
should be constructedof a metal which is corrosionresistant.The sas distribu-
214
METALSYSTEMS
tor's cataloggenerallyIiststhe appropriatevalvematerial.r For example.a needle valve controller for the delivery of hydrogen halides or metalloid halidesfrom
a lecture bottle should be constructedfrom Monel. whereasbrass valveswill
suffice for unreactivegasessuch as Freons, sulfur hexafluoride,and the like.
The combination of mechanical action of the valve. the corrosive action of the
gas, and moisturefrom the air can readily leadto corrosionand seizureof valves
or regulators. Therefore, it is good practice to purge out the valve after each use.
In the caseof a lecture bottle needlevalve. this entails removal of the needle
valveand flushing it with a streamof inert gas. Someof the commerciallyavailable regulators and fittings for corrosivegasesare equipped with a purging inlet
so the system can be purged with inert gas before and after the reactive gas is
dispensed.
When very-high-puritygasesare handled, specialpressureregulatorswith
metal diaphragmsare desirableto avoid contaminationby atmosphericgas diffusion through elastomeric materials on conventionalregulators. Similarly,
metal or glass delivery lines are preferred over rubber for the delivery of highpurity gas.
10,2 cuTnNeANDBENDTNG
TUBtNc
Seamlesscopper and stainless-steel
tubing are usedfor a varietyof gas delivery
and reactor systemsin the laboratory, and it is a tremendous convenienceand
time saver if the researchworker is able to perform simple fabrication and repairs. Seamlesstubing of r/.r-in.O.D. or larger is fairly rigid; therefore,when
high flexibility is needed,a loop of r/s-in.seamlessstainless-steel
tubing may be
used. An evenbetter choicefor low-pressureapplicationswhich requireflexible
metal tubing is thin-walled corrugatedstainless-steel
tubing. The methods of
joining corrugatedtubing to apparatuswill be describedin this section.
Seamlesscopperor stainless-steel
tubing may be cut with a hacksawor, more
conveniently,with a tubing cutter by the processillustratedin Fig. 10.3. In either case,the cut should be squareand cleaniffittings are to be usedon the tube
ends. Any burr on the tube can be removedwith a file or the specialrouting
blade attached to most tubing cutters. When bent on a sharp radius, tubing
tends to collapse. To reduce this problem, a hand-operated tubing bender is very helpful (Fig. 10.3). Sturdy, tightly coiled spring sets may be purchasedfor bendingtubing. The spring is slippedoverthe outsideof the tube and
removedafter the bend is completed.It is also possibleto minimize kinking by
packing the tube with sand and corking the ends. The advantageof theselatter
two methodsare that the bend can be made with any radius around the circumferenceof a pipe or bar of suitable size. If the exact radius is not critical, the
tAirco Rare and Specialty Gas Catalog, Airco,575 Mountain Ave., Murray Hill, NJ 07974',Linde
Specialty Gasesand Related Products, Union Carbide Corp., Linde Div., Box 444, Somerset,NJ
08873; Matheson Gas Products, Matheson Gas Products, P.O. Box 1587, Secaucus,NJ 07094.
215
JOINTS.
AND FITTINGS
TUBING.
Cutlrng wheel
Stotroncry
b e n d r n gf o r m
0t0cx
C o mp r e s s r o nf y p e
Roto
\Siotronory
p r e s s u r ed i e
Drowtype
(c)
F i g . 1 0 . 3 . C u t t i n g a n d b e n d i n gt u b i n g . ( c ) S i d e v i e w o f a t u b i n g c u t t e r . ( ) T h e t u b i n g c u t t e r i n
u s e :T h e h a n d l e i s t u r n e d u n t i l t h e c u t t i n g w h e e ls l i g h t l yp e n e t r a t e st h e m e t a l t u b i n g . ( b ) T h e c u t t e r
is then rotated around the tubing. The handle is retightened and the processis repeated until the
tubing is conrpletelysevered.(c) Two designsfor tubing benders. (Reproduced bv permission of the
copyright holder, Crau'ford Fitting Co., Cleveland, Ohio.)
tubing bender is generallypreferred.Large-diametertubing is not easilybent,

and sharp turns are impractical in any diameter tubing, so in these casesan
elbow fitting is used.
Thin-walled corrugatedtubing can be crushedby swage-typefittings. Sometimes this type of tubing is fitted by the supplier with heary-walledend tubes
which can be connectedby conventionaltechniques(Section10.3)to an apparatus. If the tubing is not so equipped,it is necessary
to havethick-walledtubing
brazed or weldedto the ends. One manufactureralso providesheavy-walledinsertswhich can be slipped inside the thin-walledtubing to provideadded rigidity.2
',l0,3 TUBTNG,
ANDFTTTTNGs
JorNTs,
A. Soldel ond Weld Fittings. Copperelbows,T's, and oossesaremanufacturedto be soldered
or brazedto coppertubing(Fig. 10.4).Whensoftsolder
2 C r a w f o r dF i t t i n g C o . , 2 9 5 0 0 S o l o n R d . , S o l o n , O H 4 4 1 3 9 .
216
METALSYSTEMS
uu
lt
NH
:)
(o)
(b)
F i g . 1 0 . 4 . T w o s o l d e rf i t t i n g s . ( a ) C r o s s - s e c t i oonf a n e l b o w . ( ) A T - f i t t i n g . ( R e p r o d u c e db y p e r m i s s i o no f t h e c o p y r i g h th o l d e r . C r a w f o r d F i t t i n g C o . . C l e v e l a n d ,O h i o . )
is used, the insideof the fitting and outsideof the tubing are tinned with solder
and the hot parts are slippedtogether.An acid-typeflux, for example,l0% HCI
plus l0% ZnCl2 in water, aids in the tinning process.Similarly, hard solder
(brazingor silversolder)joints can be used.Solderedjoints are compactand can
be very leak-tight, but they are permanentand the solderingprocessintroduces
impurities andlor oxidation of the tubing; therefore.the apparatusshould be
thoroughly cleanedbefore it is used. Weld fittings, similar in generaldesignto
the solderfittings, are availablein a variety of materials.2
B. Flote Fittings. This type of fitting (Fig. 10.5)is one of the oldestmeansof
making a removabletubing joint. As shownin the figure, annealedtubing with a
smoothlycut end is flared by clamping it into a flaring tool and tapping the inner
die on this tool with a mallet. If the metal is not annealedor if the flaring process
is roughly performed, a crack may developon the flared edge, renderingthat
surfaceuseless.The flared tubing forms a joint betweena nut and a coneof the
flared tubing. Considerabletorque is neededto obtain a leak-tight seal. The
flare fitting is cheap and works well with copper.but it is more trouble to make
than swage-typefittings and is not practical with many hard metals. To overcome thesedisadvantages,a variety of swage-typefittings havebeen developed
under trade names such as Swagelok.Gyrolok. and Tylok.
F i g , t 0 . 5 . C r o s s - s e c t i o on f a f l a r e d t u b i n g f i t t i n g . A n n e a l e dt u b i n g i s f l a r e d b y m e a n so f a s i m p l e
f l a r i n gt o o l , a n d t h i s f l a r e dt u b i n g i s c o m p r e s s e d
a g a i n s ta n i p p l e f i t t i n g b y m e a n so f a t h r e a d e dn u t .
247
AND FITTINGS
TUBING.
JOINTS,
C. Swoge-Iype Fitlings. These popular connectorsare availablein various metalsand plastics,and they are usefulfor joining similar or dissimilarmaThe common swagetubing
terials, such as metal to plastic or metal to glass.2'3
couplerhas four parts: the body, into which the tube is placed,two ferrules,and
a packing nut (FiB. 10.6).In general,the tubing shouldbe softerthan the fitting
so that during the tightening processthe ferrulessink into the tubing and at the
same time the end of the tubing is butted tightly into the body. In the caseof
stainlesssteel,hardenedtubing should be avoidedbecauseit is not sufficiently
ductile to conform to the ferrules and body. In general,brassfittings are used
fittings with stainless-steel
tubing, Monel
with copper tubing, stainless-steel
with Monel, and so on. The joint is assembledas illustratedin Fig. 10.6 and the
nut turned down finger tight. By meansof a wrenchon the body and anotheron
the nut, further tightening by lt/e revolutionscompletesthe assembly.These
typesof fittings can be openedand closed;however,the ferrulesare not removable. When a fitting is reassembled,a fraction of a revolution is sufficientto
complete the seal. The swage-typefittings begin to leak if opened numerous
times, and the flare joint describedaboveor the modified flange-typejoints describedbelow are preferredwhen frequent opening is necessary.
joints also are convenientfor joining metal apparatusto glassapSwage-type
paratus. In this case, the body of the joint may be made of any metal and a
Teflon or graphite front ferrule is employed.The ferrule deformson compresto
sion to make the seal.BecauseTeflon will cold-flow,it is sometimesnecessary
retightenthesejoints. A graphite front ferrule is preferredwhen elevatedtemperaturesare employed,as in the caseof heatedgas chromatographycolumns.
In either case,the backing ferrule is generallychosenas a harder material than
the front ferrule, for example, nylon or metal in the caseof a Teflon front fer-
io)
(b)
Fig. 10.6. Swage-typefittings. (d) T-fitting () Cross-sectionshowing the front ferrule A and the
b a c k f e r r u l e B . ( R e p r o d u c e db y p e r m i s s i o no f t h e c o p y r i g h th o l d e r , F . J . C a l a h a n ," S w a g e l o kM a n u a l , " C r a w f o r d F i t t i n g C o . , C l e v e l a n d ,O h i o . )
r H o k e I n c . , I T e a n a k i l l P a r k , C r e s k i l l ,N J 0 7 6 2 6 .
218
METALSYSTEMS
rule, or metal in the caseof a graphitefront ferrule. It is critical to employtubing

which makes a precise fit with the Swagefitting and ferrules. Unfortunately,
most swage-typejoints availablein the United Statesare made to English standards, whereasthe standard-walledborosilicateglasstubing is manufacturedto
metric specifications.Becausethe toleranceson ordinary glasstubing are not
highly precise,it is possibleto find the occasionalpieceof standard-walledtubing which will match a swagefitting with English dimensions.The better solution is to employ medium-walledtubing, which is manufacturedto English dimensions.It is important to have a squarecut and no sharp edgeson the end of
the glasstube, becausesharp or jaggededgeswill cut or scratchthe soft ferrule
materialsand irregular edgesare likely to break. It is possibleto achievea satisfactory edgeby meansof a clean break and a very light fire polish, but the preferred method is to cut the tube end on a diamond saw and removethe edgeby
very light grinding on a water-cooledsandingbelt or similar grinding surface.
Most gas chromatographysupply housesalso stock one-pieceferrulesmade
of Teflon, graphite, or Vespel (a polyimide). The upper working temperature
quotedfor eachof theseis 250, 450, and 350'C, respectively,and all of theseare
quite usefulfor connectingglasstubing to metal fittings. The Vespeland graphite ferrules have the advantageover Teflon that they do not cold-flowand they
givegenerallybetter performanceon joints that are heatedand cooled.Vespelis
more mechanicallyrobust than graphite. New ferrules made from a Vespelgraphitecompositecan be usedup to around 400oand haveevenbetter mechanical propertiesthan Vespel.
D. Flonge lubing Conneclols.
Recently,metal tubing connectorshave
becomeavailablein which inner and outer packing nuts are employedto hold
two flangestogether.2In somedesignsan O-ring sealis made betweenthesetwo
flanges,and in others a metal gasket is employed(Fig. 10.7). Theseflange fittings are attachedto tubing by solderingor welding, so they are lessconvenient
to install initially than the swage-typefittings, but they are easilyassembledand
disassembled
and are preferablewhen the systemis openedoften. Sincethe ends
of the fitting are flat, thesetypes of fittings can be usedwhere a component must
be removedthat is in line with the entranceand exit tubes. This is not possible
with standardswageor flared connectors.The Cajon VCR fitting, which is available in stainlesssteelor Monel, givesgood servicein fluorine vacuumsystems.In
this application, flat gasketsof copper or nickel can be used.
E. Miscelloneous lubing Connecfols.
The varietyof tubing couplersis
enormousand a comprehensivelist would be out of place in this book, but several additional typeswill be mentionedhere which are useful in the laboratory.
Metal standard taper and metal ball joints are available,and these will mate
with correspondingground-glassjoints to provideone meansof connectingparts
made of dissimilar materials.aAs with glass standard taper joints, the seal is
{ K o n t e sG l a s sC o . . P . O . B o x 7 2 9 . V i n e l a n d . N J 0 8 3 6 0 .
249
TUBINGAND PIPEJOINTS
HEAVY.WALLED
(b)
F i g . 1 0 . 7 . F l a n g e t u b i n g c o n n e c t o r s (. a ) C a j o n V C O O - r i n g s e a l e df i t t i n g l ( b ) C a j o n V C R m e t a l
gasketed flange fitting. (Reproduced by permission of the copyright holder, Markad ServicesCo.)
made with greaseor wax. Another useful type of joint is based on an O-ring
which is compressedbetweenthe insideof the joint and the outer dianleterof a
tube. Plastic annular O-ring fittings of this type, designedprimarily for glass
a p p a r a t u sa, r e d e s c r i b e di n S e c t i o n8 . 1 . B . F i g . 8 . 5 . S i m i l a r l y ,a n a n n u l a rO - r i n g
joint, which was originally designedfor a metal apparatus.is illustratedin Fig.
8.5. This joint is equally serviceablewith plastic or glass tubing. As with the
swage-typeconnectors,glasstubing must be chosenwith an outside diameter
which conformsto the dimensionsof the fitting. This generallydictatesthe use
of medium-walledtubing with fittings made to English dimensions.Also, the
ends of the glasstubing must be preparedas describedfor the swagejoint, so
that the O-ring is not damaged. These annular O-ring sealsare generallynot
satisfactoryfor pressuresabove1 atm. One usefulfeatureof this type of joint is
that the tube inside the fitting may be rotated without breaking the seal.
40.4 HEAVv-wALIED
TUBTNG
ANDptpEJotNTs
Many of the fittings describedabovemay be employedwith heavy-walledtubing
or metal pipe. Somefittings which are more specializedfor this purposeare describedhere.
zzv
METALSYSTEMS
A. Cone Joinls. The cone-typefitting, illustrated in Fig. 10.8, was designedfor usedwith heavy-walledtubing for high-pressureapparatus.sA special
tool or lathe is employedto shapethe tube end into a cone. In one modification
the outsideof the tube is threadedto receivea small collar. When the gland nut
is tightenedagainstthis collar, the cone is forced againstthe conical inner surface of the body. Since the two parts have a slightly different cone angle, the
contact area is small and good leak-tight performance is achieved.At one time
theseconejoints were often used on vacuum systenrsfor fluorine handling becausethe joint can be made and broken repeatedly.Horvever,flangejoints have
generallysupersededthe conejoints in this applicaton.
B. Pipe Joints. Good joints suitablefor vacuumor pressureapplicationscan
be made by meansof tapered pipe thread joints in heavy-walledtubing. Unlike
all of the joints discussedso far, the sealis made in the threadsof this joint. The
threadedportions of both the male and female pipe joint are tapered, and as a
result the inner and outer threads are wedged into each other when they are
screwedtogether(Fig. 10.9). To achievea good sealthe male pipe threadsare
wrapped with two layersof Teflon pipe tape, which servesthe role of sealantand
Body,
Collor
Glond Cold-worked
ruornq
F i g . 1 0 . E . C o n e h i g h - p r e s s u r jeo i n t . l n t h i s p a r t i c u l a rd e s i g nt h e h e a v y - w a l l e d
t u b i n g i s b e v e l e do n
t h e e n d a n d t h r e a d e dt o r e c e i v ea c o l l a r . T h e g l a n d n u t t h r u s t sa e a i n s tt h e c o l l a r a n d f o r c e st h e c o n e e n d e dt u b e i n t o t h e b o d v .
F i g . 1 0 . 9 . N o r m a l p i p e t h r e a d e dj o i n t . N o t e t h e t a p e r e d t h r e a d so n b o t h t h e n t a l e a n d f e m a l e
c o m p o n e n t s .U n l i k e m o s t o t h e r j o i n t s . t h e s e a li s f o r m e d i n t h e t h r e a d e dp o r t i o n o f t h e j o i n t .
s A u t o c l a v eE n g i n e e r s ,I n c . . E r i e , P A .
TUBINGAND PIPEJOINTS
HEAVY.WALLED
224
a lubricant for the threads. NOTE: The use of Teflon tape should be confined to
pipe threads. It makes no $ense to use Teflon tape on the threads of flared,
flange, or swage-type fittings because the seal is not made at the threaded portion of those fittings.
The commonly usedtaperedpipe thread in the United Statesis designatedas
Normal Pipe Thread (NPT), whereasthe designspecifiedby the International
StandardsOrganization is designatedas an ISO tapered pipe thread. Tapered
pipe-threadedjoints can be openedoccasionally.If frequent opening is necessary, other joints, such as the ISO parallel-threadedpipe joint, are preferred.
When pipe-threadedjoints are specifiedwithout any further qualifier in the
United States,it is generallyunderstoodthat the fitting is NPT. The ISO parallel
pipe thread is basedon parallel threadsand an O-ring or other gasketbutt-type
seal. NOTE: Neither ISO fittings nor standard threaded fittings should be
screwed into tapered pipe threads.
C. Bolled Flonge Closures. The flangejoint is widely usedto link largediametertubing and to provide accessto the interior of reactionor vacuum vessels (Fig. 10.10). Typically, the flanges are bolted together and are sturdy
enoughto withstand this pressurewithout appreciabledistortion. The bolts are
spacedevenlyaround the flangeto distributethe load evenlyon the gasketmaterial. Very often one of the flanges is cut with a grooveto take an O-ring or sometimes a metal V-ring. The joint is designedso that there is significantbut limited
compressionon the O-ring. The limit is achievedby metal-to-metalcontact of
the flanges.The grooveis larger than the width of the O-ring, to permit radial
expansionof the O-ring when it is under compression.The generalstrategyin O-
F i g . 1 0 . 1 0 . O - R i n g s e a l e db o l t e d f l a n g ec l o s u r e .T h i s t y p e o f j o i n t i s u s e df o r l a r g ed i a m e t e ro p e n i n g s .T h e g r o o v et o r e c e i v ea n O - r i n g s e a li s m a c h i n e ds o t h a t t h e d e p t h E i s 8 0 % o f t h e O - r i n g w i d t h
a n d F i s I 3 5 % o f t h e O - r i n g w i d t h . T h e e x t r a c l e a r a n c ei s o n t h e i n s i d eo f t h e g r o o v ef o r a p p l i c a t i o n s
i n w h i c h t h e a p p a r a t u si s t o b e p r e s s u r i z e da n d o n t h e o u t s i d eo f t h e g r o o v ew h e n t h e a p p a r a t u si s t o
be evacuated.
222
METALSYSTEMS
ring groove design is to specifythe depth of grooveto be 80% of the width of the
O-ring and the width of the grooveto be 135% of the O-ring width. As illustrated in Fig. 10.10, the designof the groove differs for vacuum and pressure
applications.
For ultrahigh-vacuumand many high-pressureapplications,O-rings do not
provide the required degreeof seal,so metal gasketsare employed(Fig 10.11).
Annealed copper or soft aluminum gaskets are the most common, and the
flanges are machined with opposing circular ridges or steps which provide a
small area of contact with the gasket and thereby a high force per unit area.
Flangesof this type are commerciallyavailable.6To maintain alignment of the
two halves.guide pins are sometimesincorporatedinto one flange with holesin
the opposingpart.
40,5 vALVEs
Becausethey involve moving parts, valves are generally more troublesome in a
vacuum or pressuresystemthan arejoints. Furthermore,valvesare readilydamaged if improperly handled and they are often designedfor a specific purpose.
Becauseof these factors, the intelligent use of valvesrequires a knowledgeof
their constructionand mode of operation. For example,a meteringvalveand a
cutoff valve have different internal design, although they may look identical
from the outside.Similarly, the nature of the seatmaterial and the way in which
the seal is made around the valve stem are often essentialinformation in the
choice of the proper valve and the maintenance of a metal system.
A. Volve Seols ond Sfems. Valves which are intended for fine gas flow
control are designedwith a long needlelikestem and a gently taperedseat(Fig.
10.12a).Although these"metering valves"givegood flow control, they do not in
general give a positive shutoff . When the valve is designedfor positive shutoff a
V/
7)
| 600
f9
@
Fig. l0.ll.
M e t a l g a s k e t s e a l e db o l t e d f l a n g e c l o s u r e s .A s o f t m e t a l g a s k e t , g e n e r a l l ym a d e o f
a l u m i n u n r o r c o p p e r , i s c l a m p e d b e t w e e nk n i f e e d g e s( a ) o r s t e p p e df l a n g e s( ) .
b V a r i a n V a c u u m A c c e s s o r i e sV, a r i a n A s s o c i a t e sP
, aloAlto, CA.
VALVES
223
blunt stenrtip and simple seatis employed(Fig. 10.12b).Cutoff valvesare available for which some degree of flow control is achieved by means of a fairly
sharply tapered conical tip. However,if good flow control and positiveshutoff
are required, a metering valve and a cutoff valve in seriesare generallycalled for.
This type of configuration has alreadybeen discussedin connectionwith high
pressurecylinders.One of the most commonetrors in the useof small valvesis to
shut them too tightly. A good shutoff valveis designedso that there is fairly large
force per unit area between the stem and seat; therefore, if the valve is overtightened,the seatand/ or stemis distortedand the valvewill not seatproperlyin
subsequentuse. Similarly, meteringvalvesare often delicateand not designedto
be overtightened.In somevalvedesigns,wear on the seatand stem tip is minimized by meansof a "floating tip" which permits the valvestem to rotate independentlyof the tip. Thus, as the valveis tightened,the tip is not ground into the
seat.
B. Pocked Volves. Some of the least expensiveand most common valves
have a sealingmaterial (packing) compressedbetweenthe valve stem and the
valvebody. For valvesusedin laboratoryapparatusthis sealis generallyaccomplished by meansof an O-ring (Fig. 10.12a),or a Teflon washer.Compression
on the O-ring is determinedby the groove dimensionson the stem and inside
diameterof the valvebody. If a leak developsalong the stem, the valvemust be
disassembled,
cleaned,and the O-ring replaced.The situationis differentwith a
Teflon packing washer. In this casethe packing is causedto pressagainstthe
stem and the valvebody by meansof the packing nut (Fig 10.13).This packing
nut may require occasionaltightening to maintain proper contact with the valve
stem and body. Clearly,it is important to identify the valvetype in order to remedy a leak past the stem. In dealingwith O-ring packedvalves,it also is important to recognizethe chemical sensitivityof the O-ring and, if necessary,to
changethe O-ring to match the compoundsbeing handled. (SeeChapter5 and
Appendix III for information on the solventsensitivityof variouselastomers.)
Another variation in the design of packed valvesis the relative position of the
threadswhich actuatethe valvestem and the packing material. With the O-ring
valvesit is common to positionthe threadsso they are protectedfrom liquids or
gasesinsidethe valveby the O-ring seal(Fig l0.l2a). However,with Teflon and
similar packing materials, which must be maintained under pressureby the
packing nut, it is more common for manufacturersto thread the valve stem inside of the packing material. This arrangementis undesirablewhen highly corrosiveliquids are being handled, becauseexposureof the threadedsurfacesto
the corrosivematerial is likely to seizeup the valve.SomeTeflon-packedvalves
are availablein which the threadsare protectedby the packing (Fig. 10.13).
C. Diophlogm ond Bellows Volves. For high-vacuumapptications,rhe
leakageof a packed valve is sometimesunacceptable.so diaphragm or bello*s
valvesare employed.In thesevalvesthe packing is eliminatedby using a flexible
metal diaphragm or bellows sealed to the valve stem and the body (Fig.
224
METALSYSTEMS
(o)
F i g . 1 0 . 1 2 . T w o v a l v ed e s i g n s .( a ) A n O - r i n g s e a l st h e v a l v es t e m t o t h e b o d y .
10.12b).The diaphragm or bellowsflex as the stem is actuatedand thus permit

the transmissionof the throttling action of the valvewithout the useof packing.
A varietyof designsare possible;in somevalvesthe diaphragmsand valvestems
may be replacedbecausethe diaphragm or bellowsis attachedto the valvebody
by meansof a demountablesealinvolvinga gasketor O-ring. In valvesdesigned
for very-high-vacuumperformance,the diaphragm or bellowsis sealedto the
body by brazing or welding.
D. Boll, Plug, ond Gote Volves. The valvesdiscussedaboveoften introduce considerablerestrictioninto the systembecauseof small orificesand tortuousflow patterns.Suchrestrictionsare not seriousfor most applicationsat 1 atm
pressureor above,but they may be unacceptablefor vacuumapplications,where
small-diameteropeningsare a seriousimpediment (seeChapter 6). Ball and
225
VALVES
(b)
F i g . 1 0 . 1 2 ( ) . A m e t a l b e l l o w sa t t a c h e da t o n e e n d t o t h e b o d y a n d a t t h e o t h e r e n d t o t h e s t e m
f o r m s a h i g h l y l e a k - t i g h t b u t b u l k i e r a n d m o r e e x p e n s i v es e a l . ( R e p r o d u c e db y p e r m i s s i o no f t h e
copyright holder, Markad ServicesCo.)
plug valves,which provide large orificesand straight lines of flow (Fig. 10.14),
In the ball valve,a smoothball, with
bear a strongsimilarity to glassstopcocks.2
a large hole along one axis and a handle attachedalong an orthogonalaxis, is
surrounded by a spherical cavity and an elastomer seal. A 90o rotation of the
valvebody will closeor openthe valve.The plug valveis similar, but in this casea
cylindricalplug is usedand the plug is equippedwith O-ring seals.Both typesof
valvescan be manufacturedwith closetolerancesand are suitablefor mediumand sometimeshigh-vacuum applications. The more expensivegate valve is
T e Jl o n
pockrng
Needle
F i g . 1 0 . 1 3 . A h i g h p r e s s u r ev a l v ew i t h T e f l o n p a c k i n g . T h e t h r e a d so n t h e v a l v es t e m ( n o t s h o w n )
are above the Teflon packing and are thus protected from corrosive materials. The packing nut
t i g h t e n st h e T e f l o n p a c k i n g w a s h e r a g a i n s tt h e n e e d l ev a l v e s t e m a n d t h e v a l v e b o d y . O c c a s i o n a l
t i g h t e n i n go f t h e p a c k i n g n u t i s r e q u i r e d t o m a i n t a i n a g o o d s e a l .
Fig. 10.14. A metat ball valve. This type of valve shown here in a 3-way version, provides a large
unobstructed aperature. (Reproduced by permission of the copyright holder, Markad ServicesCo.)
226
TYPICALMETALSYSIEMS
227
availablewith a bellowsclosurealong the stem. This type of valveis often used

betweena diffusion pump and an associatedmetal high-vacuumsystem.
E. Mounfing Volves. It is often desirableto mount a valvesecurely,so that
when it is actuatedthere is no mechanicalstresson the connectionbetweenthe
valveand the tubing. For example,if a valveis attachedto small-diametertubes
joints, repeatedflexing of thesejoints can open up leaks.
by meansof swage-type
mounting
holes on the valvebody are provided by the manufacOccasionally,
turer for bolting the valveto apparatus.The secondcommon fixture is a bulkhead connector,which consistsof threadson the outsideof the valvebody and a
pair of nuts on this threaded section.To use this mount, the valve handle is
generallytemporarily removedand the valveis mounted by meansof thesenuts
through a hole in a sturdy sectionof sheetmetal, as illustratedin Fig. 10.12b.
Gate valvesare generallyequippedwith bolted flange conectorsso that they can
be connectedto large-orificetubing.
'10.6 PREssURE
eAueEs
The measurementof pressurefrom a few torr to l0a torr in an all-metal system
can be accomplishedby meansof a metal Bourdon or diaphragm gaugewith a
dial readout. Although a bronzechamberis the most common, thesegaugesare
availablewith more corrosion-resistant
metals.and someare availablewhich are
accurateto 0.5 torr.7
Various types of pressuretransducerswith digital readout are availablewith
metal interior construction.Thesehavebecomequite popular for fluorine-handling systemsand the like. A descriptionof someof the common typesis givenin
Chapter 7.
40,7 ilPrcALMETAL
sYsTEMs
A. Fluotine Hondling Syslems. Fluorine is thermodynamicallycapableo{
reactingwith most materialsof construction,but the reactionrate may be extremely slow below certain critical temperatures.The slow rate of corrosionof
many metals occurs becauseof the formation of a passivefluoride film. Some
generalizationson the resistanceof various materialsto fluorine are given by
Peacock.sFluorine which is free from hydrogenfluoride may be handled in borosilicateglassfor periodsof up to a few hours and temperaturesup to 200oC
without extensiveattack; fused silica is suitablefor longer periodsand slightly
highertemperatures.However,surfacemoistureon the glass,which is extremely
T A m e r i c a nC h a i n a n d C a b l e C o . , H e l i c o i d G a u g e D i v . , 2 3 0 P a r k A v e . , N e w Y o r k . N Y .
R . D . P e a c o c k , i n A d y a n c e si n F l u o r i n e C h e n i s t r y ' ,M . S t a c e y ,J . C . T a t l o w , a n d A . G . S h a r p e ,
E d s . , V o l 4 , ( W a s h i n g t o nD C : B u t t e r u , o r t h .1 9 6 5 ) ,p . 3 1 .
228
METALSYSTEMS
hard to eliminate,catalyzesthe reactionof fluorine with theseglasses,and therefore, glassis rarely usedfor fluorine handling. Coppermay be usedup to 500'C,
while nickel and Monel are usefulto about 800"C. Fluoriteand ceramicalumina
are resistantto 1,000oC,but the latter becomesporous even though it is not
erodedby fluorine. Stainlesssteeland brasshavebeen usedoccasionallyto contain fluorine at room temperature, but they are less desirablethan Monel,
nickel, or copperfor laboratoryapparatus.Passivatedaluminum is satisfactory
for fluorine handling even at temperatures somewhatabove room temperature,
but it has the practical disadvantageof not being readily soldered.Mixtures of
fluorine and hydrogen fluoride are more reactivethan either component, and a
fair number of fluorine derivatives,such as ClF3, are more reactivethan F2. For
these highly reactive fluorides, nickel or Monel are the preferred metals of construction.
The strongestand leastporousjoints are made by inert-gaswelding (seeAppendix IV), but serviceablesilver solderjoints are possible.Lead gaskets,soft
solderjoints, and brazedjoints may be usedwith fluorine and most all gaseous
fluorinating agents,but are unsatisfactorywith liquid BrF3. Soft solder(lead-tin
solder)is very sensitiveto HF. Junctionsbetweendissimilarmetals,suchas copper and nickel, are subjectto electrolyticcorrosionwhen exposedto liquid fluorinating agentswhich also are electrolJtes,such as BrF3 and F2-HF.
Most metal systemsare passivatedby conditioningwith fluorine andlor volatile fluorides prior to use. It is often desirableto precedethe conditioningstep
with a hydrogen reduction of the interior of the apparatusbecausethe mixed
oxyfluorideof an element,which might be producedfrom oxide coatingsin the
apparatus,are frequently similar in volatility to the simple binary fluorides. A
typical reductionand conditioningcycleinvolvesfilling the previouslyevacuated
systemwith closeto 1 atm of hydrogen, after which the traps, tubing, and other
heat-resistantitems are heated with a gas-airflame. The systemis then evacuated and heatedagain to expel moisture.To passivatethe apparatus,a mixture
of 5-10% fluorine in an inert gas is first introduced,and nickel or Monel parts
are heated.The gas is replacedby fluorine somewhatbelow I atm of pressure,
and nickel and Monel parts are heated to a dull red until the pressuredrop
ceases.Sometimesthis passivationis followed by another treatment with a
highly reactivefluorine compound, such as ClF3, which is introducedfor a few
hours to conditionparts which cannotbe heated,suchas Teflon packedvalvesor
fluorocarbon reaction vessels.The disadvantageof this last passivationstep is
that ClF3 is strongly adsorbed on the walls of the apparatus, and extensive
pumping is neededto removeit from the system.As a generalrule, the conditioning should include a fluorinating agentwhich is at leastas strongas any that
subsequentlywill be handled. Somematerials,such as stainlesssteel,platinum,
and gold, do not form a protective fluoride film and therefore cannot be conditioned.
Two typical metal vacuum systemsfor fluorine compoundsare illustratedin
Fig. 10.15. In either systemthe vacuum pumps are protectedfrom the vacuum
To pump
(o)
F i g , 1 0 . 1 5 . M e t a l v a c u u m s y s t e m sf o r h a n d l i n g f l u o r i n e a n d r e a c t i v ef l u o r i d e s .( a ) A d e s i g nu s e d
extensivelyat Argonne National Laboratory constructed of nickel tubing and Monel valves(A) u'ith
c o n e j o i n t s ( i l l u s t r a t e d i n F i g1.0 .l 3 ) ; ( D ) n i c k e l U - t r a p ; ( E ) M o n e lB o u r d e n g a u g e ( 0 - l 0 0 0 t o r r () F
; )
1 3 0 - m L n i c k e l r e a c t o rc a n ( F i g . 1 0 . 1 7 ) ;( G ) 1 , 5 0 0 - m Ln i c k e l s t o r a g eo r n r e a s u r i n gc a n , ( H ) 8 5 - m L
n i c k e l c a n , ( J ) b r a s sv a l v e :( K ) s o d a - l i m et r a p t o p r o t e c tv a c u u m p u m p s ; ( L ) M o n e l v a l v e .( R e p r o duced by permission of the copyright holder, The University of Chicago Press,Irom Nobel Gus Comp o u n d s ,H . H . H y m a n ( E d . ) , C h i c a g o ,1 9 6 3 . )
( ) A l e s sm a s s i v ev a c u u m s y s t e m :( A ) K e l - F o r T e f l o n r e a c t i o nt u b e s( i l l u s t r a t e di n F i g . 1 0 . 1 6 ) ;
( B ) F l a r ef i t t i n g f o r t h e r e a c t i o nt u b e l ( C ) n i c k e le x p a n s i o nc a n ; ( D ) c a l i b r a t e dn i c k e l c a n l ( E ) M o n e l
B o u r d o ng a u g e ;( G ) t o s o d a - l i m et r a p s a n d p u m p s l ( H ) t o s a m p l i n gc e l l s .M o n e l b e l l o w sv a l v e s( V ) ,
M o n e l S w a g e l o kj o i n t s , a n d n i c k e l t u b i n g a r e u s e d f o r t h e m a i n c o m p o n e n t si n t h e v a c u u m l i n e .
( R e p r o d u c e d f r o m T . A . O ' D o n n e al n d D . F . S t e u ' a r t l r o r g . C h e n t . 5 , l 1 3 4 ( 1 9 6 6 ) , b y p e r m i s s i o n o f
t h e c o p y r i g h th o l d e r , T h e A m e r i c a n C h e n r i c a lS o c i e t y . )
229
230
METALSYSTEMS
line by meansof a sodalime trap. Kel-F or Teflon reactiontubes are convenient

becausetheir translucencepermits the observationof the contents.Details of the
reactiontube are given in Fig. 10.16.The tube can be machinedfrom Kel-F bar
stock or it can be fashioned from heat-formable and -sealableTeflon FEP. The
metal reaction can illustrated in Fig. 10.17 is preferredwhen the reactantsdo
not have to be observedand when modest pressuresof reactantsare desired. For
the manipulation of HF solutions,apparatusmade from Kel-F or Teflon is desirable.A reactionvesselis illustratedin Fig. 10.18and a cell for spectroscopy
is
s h o w ni n F i g . 1 0 . 1 9 .
lry'onel
C o n eh i g h fitting
1 t /1 6 - 1 4
thre o d
Reoc'tion
tube
(b)
I s ue ' f f
*-5/C
>
4f
lVetol nut
or 3/e" 45'
f l o r ef i i t i n g
Trop
(o)
(c)
F i g . 1 0 . 1 6 . P e r f l u o r o c a r b o nr e a c t i o n t u b e a n d f l a n g e - f i t t i n g s . )( a ) D e t a i l e d c r o s s - s e c t i o o
nf t h e
c o m p o n e n t s ;( b ) a n d ( c ) t w o a d a p t a t i o n so f t h e b a s i c d e s i g n . T h e f l u o r o c a r b o nt u b e m a y b e m a chined from Kel-F; alternatively, Teflon FEP tubing may be heat molded to form a flange and heat
c r i m p s e a l e da t t h e b a s e .
S w o g el o k
fitting
Bellows
Welded
nackeI
(o)
1 / q" N P T M o n e l p l u g
I
It
a
HokeM-327
7a"OD tube
% " O D , 3 / 6 "I D M o n e lf u O e
4"
W e l d i n s i d eo n d o u t s r d e
D e e pw e l d o n d m o c h i n et o l O D
/r
tI
O . O 6 5w ol l
I
I
D e e D w e l d o n d m o c h r n et o I
OD
--rFr"-f
(b)
Fig. 10.17. Detail of two different nickel reaction cans. Design (b) is convenientfor the addition or
r e m o v a lo f s o l i d s .I R e p r o d u c e db y p e r m i s s i o no f t h e c o p y r i g h th o l d e r ,T h e A m e r i c a nC h e m i c a lS o c i e t y . F r o m W . E . T o l b e r g , R . T . T e w i c k , R . S . S t r i n g h a m ,a n d M . E . H i l l , I n o r g . C h e n t . , 6 , 1 1 5 6
( 1e67).
l
231
232
METALSYSTEMS
T r a pl l l
Tovacuum
throughcorrugated
T e f l o nf l e x l i n e
Trap I
Trap ll
F i g . 1 0 . 1 8 . A s s e m b l yf o r t h e m a n i p u l a t i o n o f H F s o l u t i o n s .M o n e l S u ' a g e l o ku n i o n s a r e u s e d t o
j o i n U - t r a p s c o n s t r u c t e df r o m T e f l o n F E P t u b i n g . A r i g i d K e l - F o r M o n e l t u b e m u s t b e p l a c e di n s i d e
t h e T e f l o n t u b i n g t o m a k e i t s u f f i c i e n t l yr i g i d t o h o l d a s w a g e - t y p es e a l . S i m i l a r S w a g e l o ka t t a c h ments are made to the valves. IReproduced by permission of the copyright holder, The American
C h e m i c a l S o c i e t y .F r o r n K . 0 . C h r i s t e , C . J . S c h a c k , a n d R . D . W i l s o n . / r r o r g . C h e m . . 1 6 . 8 4 9
( t 9 7 )7. 1
Sincefluorine and most volatile fluorides are corrosiveand highly toxic. the
vacuum rack for a fluorine handling systemgenerallyis placedin a hoodedenclosure(Fig. 10.20)and the fluorine tank is often enclosedin a separateenclosure which can be manipulated remotely(Fig. 10.21).
B. Flow ReOcfors. Laboratory-scalecataly.ticreactors and reactors for the

reactionof solidswith gasesare often constructedfrom metal. One of the principal objectivesin the use of laboratory-scalecatalytic reactors is the determination of rate data which can be associatedwith specificphysical and chemical
processesin a catalytic reaction. Descriptions are available for these kinetic
analysesas they relate to reactor designsand reactionconditions.q
e E . G . C h r i s t o fl e l , C a t a l . R e v . , 2 4 1 5 9( 1 9 8 2 ) ;L . K . D o r a i s w a m ya n d D . G . T a j b l , C u t a l . R e v . , 1 0 ,
1 7 7 ( 1 9 7 4 ) ;L . L . H e g e d a sa n d E . E . P e t e r s o n ,C a t a l . R e v . , 9 , 2 4 5 ( 1 9 7 4 ) .
F i g . 1 0 . 1 9 . S p e c t r o s c o p ic e l l f o r H F s o l u t i o n s .A l l i n t e r n a lp a r t s a r e K e l - F , T e f l o n , o r , i n t h e c a s e
of window material, sapphire or silver chloride. A commercial Teflon valve may be substituted for
t h e c u s t o m K e f - F v a l v e s h o w n h e r e . ( R e p r o d u c e df r o m H . H . H y m a n a n d J . J . K a t z N o n a q u e o u s
s o l v e n t s l s t e m s , T . c . w a d d i n g t o n E d . , p . 4 7 ( 1 9 6 5 )b y p e r m i s s i o no f A c a d e m i c p r e s sI n c . )
233
F l u o r e s c e n It q h f
l n o p p o sf e s l o e
S l i d r n gs o t e r Y gloss doors
G l o s se n d
windows
-/
Electilcol
outlet
.'-o
/9
\l-Laboratory Planning;t'orchemFig. 10.20. Hooded vacuum rack. (Reproducedfrom D. R. Ward,

istryandChenicalEttgitteering,H.F.Lewis'(ed.)(1962)bypermissionofthecopyrightholder'
V a n N o s t r a n d R e i n h o l dC o ' , I n c . , N e w Y o r k ' )
234
N
c)
(rr
steel shott
Lelt sade
od; weld to
F ront
Too
Side I top tlonges

't"x 1" ongle sleel
l4 holes diom r/a l

drill to moich
door I llonges
a-a
0oor
2 door hondles
t/d x'l t/j' steet
etoining bor
I ock stop
Box purge to
nitrogencYlinder
Centeringbrocket
Purge lrne to
nitroqen cylinder
l/r'diom hole
for nitrogen line
R e t o i n i n g b o r . 1 / d i o m s t e e l ;
locote to hold cylinder
o g o i n s l c e n t e r i n gb r o c k e t
Safety enclosure for a high-pressure fluorinc tank
f l o n g e s i 14 w o s h e r s
I ' 1 4 f h u m b n u fs
F
I
t -2"
l4bolts 516'squore
I ntee '/4 v o l v e s
Hoke M
ongleI stem
lengths o0tronol
l/<'copper tubing
B flored tittinqs
Fig. 10.21.
L_.
Geor supporis
Dlote l,/i'sieel
To NoF scrubber
Cc r i r r O g e
2 " d r o m b e v e lg e o r s
Pillowblock
Ll_r
l1r
I I 1?',
I l#'
l t;o'
Connectrng.sleeve
t o gp h o l ee t / 2z \xtt/ /2z
l/ T
Eoltom hole ttti't r/e"
I
c e n t e r i n q' / |
|
brocket
|
|
Verticol geor short

e n d m i l l e dt o
1/i'xt/'squore x2"
5'- 6"I
Loose sleeve
T- wrench
\U
\r
zPortition
l9
15 'h
tII
Bockstop
Centering brocket
1t' \ 1t/i ongle steel
Right side
Box- lj' steel

oll- welded
construction
diom s/ri'
Centerrng
-brocket instoll
to fit cylinder
necX
4" diom ducl lo

exhousl sysien
236
METALSYSTEMS
REFERENCES
GENERAL
B r o k e r , W . , a n d A . L . M o s s m a n , M u t h e s o n G a s D a t u B o o k , M a t h e s o nG a s P r o d u c t s ,P . O . B o x
1 5 8 7 ,L y n d h u r s t , N J 0 7 0 7 1 .A g e n e r a ld e s c r i p t i o no f t h e h a n d l i n g o f c o m p r e s s e d
g a s e si s g i v e n
along with information on fittings and properties of specific gases.
Calahan, F.1., Swagelok Tube Fittirtg und Installatiott Manual, Crawford Fitting Co., Cleveland.
Proceduresfor forming and joining metal tubing are described.
C a n t e r f o r d ,J . H . , a n d T . A . O ' D o n n e l l , 1 9 6 8 ,i n H . B . J o n a s s e na n d A . W e i s s b e r g e rE
, ds., Iecftn i q u e so f I n o r g a n i c C h e n t i s t 1 ' ,V o l . 8 , W i l e y , N e w Y o r k , p . 2 9 1 . G e n e r a lt e c h n i q u e sf o r f l u o rine handling.
Hagennrulfer, P., Ed., 1985, Inorganic Solid Fluorides, Academic, Ne* York. Chapter 2 of this
book, "Preparative Methods," gives an extensivelyreferenced account of synthetic methods
used in inorganic fluoride research. Severalapparatus are pictured and described in detail.
H y m a n , H . H . , E d . , N o b l e G a s C o n t l > o u n d s , l 9 6 3 ,U n i v e r s i t yo f C h i c a g o P r e s s ,C h i c a g o . M a n y
c h a p t e r sc o n t a i n e x p e r i m e n t a ld e t a i l .
Guide to So.feHandling qf CompressedGases,Matheson Gas Products. P.O. Box 1587, Lyndhurst,
NJ 07071. The safe handling, transporting, and storageof compressedgasesare described.
Moore, J. H., C. C. Davis, and M. A. Caplan, 1983,Building ScientiJicAppurdlr/.r, Addison-Wesl e y , R e a d i n g ,M a s s . I n c l u d e sc o v e r a g eo f m e t a l w o r k i n ga n d t h e c o n s t r u c t i o no f a p p a r a t u sf r o m
metal components.
S t e e r e ,N . V . E d . , 1 9 7 1 ,H a n d b o o k o J L a b o r u t o r y , . l c / e n ,T, h e C h e m i c a l R u b b e r C o . P r e s s ,C l e v e l a n d . C o n t a i n sa c h a p t e r o n c o m p r e s s e dg a s c y l i n d e r sa n d c y l i n d e rr e g u l a t o r s .
W e i n s t o c k ,8 . , R e c o r d o J C h e m i c u lP r o g r e s s 2, 3 . 2 3 ( I 9 6 3 ) . A p p a r a t u sf o r t h e s v n t h e s i sa n d c h a r a c terization of xenon fluorides is oresented.
Sofety
Many air-sensitivecompoundsare very strongreducingor oxidizing agents,and

thereforecare must be used in their manipulation to avoid explosionsand fires.
Careful planning and executionof experinrentscan nrinimizethe dangerof reactive compoundslike diborane.However,there is an unfortunatetendencyto forget mundane hazardssuch as the fire and explosionhazardsof organic solvent
vaporsor hydrogengas. The chemistalso shouldbe sociallyresponsibleby never
discardinghighly toxic materials down the drain and by chemicallyscrubbing
noxiousgasesfrom gas streamsbefore the gas is allowedto go into a hood.
1.4 coMBUsTrBLEs
The explosionlintits for vapor-air mixtures are the nraximum and ntinimum
concentrationsof vapor betweenwhich a flame will propagatethrough the mixture. Large quantitiesof flammable solventsand gasesmust be handled in wellventilatedareasso that the vaporsare dilute. Laboratoryrefrigeratorspresentan
explosionhazard becausethe storageof highly volatilesolventsand volatilesolutions in them may lead to the buildup of the solventvapor concentration.The
usual householdrefrigerator is equipped with a thermostat and a light switch
which may spark and ignite solventvapors. Explosion-proofrefrigeratorsare
commerciallyavailable.
High pressuresof oxygennray spontaneouslyignite nrany combustiblematerials such as hydrocarbongreasesand oils. Therefore,regulators,gauges,and
other oxygen-handlingsystemsshould be strictly oil-free.
237
238
SAFETY
1.2 UNsTABLE
coMPouNDS
A large number of compoundsare unstablewith respectto spontaneousdecomposition. Only a few of the most important will be listed here.
'1. Acetylene may spontaneouslyexplode if its pressureexceedsl5 psig.
Commercial acetylenecylindersare filled with a porous material soakedin
acetonewhich maintains a safe acetylenepressureby dissolving the gas.
Acetyleneshould never be passedthrough a vacuum pump, which will
compressthe gas.
2. Acetylidesof heavymetals are often explosive.
3. Azides, diazo compounds,and fulminates are frequentlyexplosive.
4. Nitrogen chlorides, bromides, and iodides are endothermiccompounds
which may detonate.
5. Organic peroxidesare liable to detonate.Exposureof ethers,alkenes,and
alkynesto air and light leadsto peroxideformation. Distillation of these
solventsposesan increaseddanger due to the concentrationof peroxides
in the still pot as the distillation proceeds. When present in small
amounts, the peroxide is removedbefore distillation by the use of reducing agentssuch as ferrous sulfate in acidic aqueoussolution. Peroxides
may be detectedby the addition of a few drops of aqueous10oloKI solution to a few mL of the ether. The presenceof a peroxideis revealedby the
appearanceof the brown triiodide color.
6. Liquid or solid ozone is explosive.
7. Perchloratesalts of metal complexesare liable to detonate.Perchlorate
has been a popular counter ion for metal complexes,but saferions, such
as tetrafluoroborateor hexafluorophosphate,
can generallytake its place.
1,3 soMEDANeERous
MTxTUREs
Undiluted mixtures of strong oxidizing agentswith strong reducing agentsare
potentiallydangerous,as are mixtureswhich leadto unstablecompounds.A few
of theseare listed below.
1 . Perchloric acid forms explosive mixtures with organic compounds and

easilyoxidized inorganiccompoundssuch as ammonia.
2.
Nitric acid with organic compoundsand ammonium nitrate with metal

powdersor organic materialsare potential explosives.
3 . Ammoniacal silver(I) solutionsmay form an explosivecomponentafter

4.
long standing or in the presenceof strong base.

In the presenceof air, mercury and anhydrousliquid ammonia form an
explosivecompound, as doesyellow mercuric oxide with ammonia.
WASTES
DISPOSAL
OF REACTIVE
239
5. Activated charcoalwith nitrates, chlorates,liquid air, or liquid oxygen

forms explosivemixtures.
6. Liquid air or liquid oxygenwith organic matter is very dangerous.
7. Active metals, such as the alkali metals, alkaline earths, and finely divided aluminum, may explodewhen mixed with chlorinatedhydrocarbons, such as chloroform and carbon tetrachloride.
8. Potassium permanganatewith sulfuric acid yields the explosivecompound permanganicacid.
9. Decaborane(and possiblysomeother boron hydrides)in the presenceof
carbon tetrachloride, and possibly other halogenatedhydrocarbons,
forms a very shock-sensitivehigh explosive.
'l0. Similarly, an explosivematerial resultswhen alkyl phosphinesare mixed
with halogenatedhydrocarbons.
'l'1. Sodium amide (NaNHz),forms an explosivecompound upon prolonged
exposureto the air.
12. The distillation of ethers from lithium aluminum hydride occasionally
leads to an explosion.The exact causeis not known, but CO2 may be
involved. The danger can be minimized by predrying the ether with calcium hydride and then using a minimum amount of LiAlHa for final distillation. Also, the distillation should be performed behind a blast
shield, and the still pot should neverbe allowedto go dry. Frequently,a
safebut powerful desiccant,such as benzophenoneketyl or sodium-potassium alloy, may be used in place of LiAlHa.
'13. The reaction of potassium with atmospheric oxygen leads to a surface
layerof potassiumsuperoxide.When this oxidizinglayer is embeddedin
the metal, an explosionmay result. Therefore,the oxidizedsurfacelayer
must be scrapedoff beforethe metal is cut. Presumablya similar problem existswith rubidium and cesium.
'14. Dimethyl sulfoxideis reportedto form an explosivemixture with BeHq-2
and with diborane. It is probable that other boron hydridesand hydroboratesbehavesimilarly.
'l 5. N2O4with some chlorinated hydrocarbonsand olefins forms shock sensitive compounds.
1,4 DrsPosAL
oF REAcTTvE
wAsTEs
Lithium aluminum hydride wastes may be destroyed by passing nitrogen
through a water bubbler, an empty trap to catch the water, and then into the
flask containing the waste. Alternatively, hydride wastesmay be covered with
rags and burned in an open area. Aluminum alkyls may be burned in the open,
or a dilute solution of the alkyl in a hydrocarbon may be run into agitated water
in a vesselwhich is blanketedwith nitrogen.Variants of thesemethodsare effec-
240
SAFETY
tive with a wide variety of compoundswhich are decomposedby water or alcohols. Alkali metal residuesmay be destroyedby isopropylor /-butyl alcoholand
then flushed down the drain with water. Since potassiumis more difficult to
destroycompletelyby alcoholsthan is sodium, extra care must be used when
disposingof potassium.
Nitrogen halides are destroyedwith cold base. Azides and fulminates may
often be destroyed with acid, while heavy metal acetylidesare decomposedby
ammonium sulfide. The removal of peroxidesby reduction has been described
above.
1.5 HrGH-PREssuRE
GAscYLTNDERs
Proceduresfor safehandling of pressurizedgasesare given in Chapter 10.
1,6 AsPHYXTATToN
BYrNERr
GAsES
An atmosphereof inert gaseswill not support life; therefore,good ventilationis
required.
1.7 EXTTNGUTsHTNe
FtREs
Carbon dioxide fire extinguishersare widely used in laboratoryfire fighting because the CO2 does not damage apparatus or causeelectrical shorts. Furthermore, carbon dioxide is effective against a wide variety of fires and is not toxic.
The National Fire Protection Associationadopts the following classificationof
fires:
ClassA fires occur with wood. paper, fabric, and similar solids. Water and
wet fire extinguishersare recommendedbecausethey are effectivein quenching
burning embers.
ClassB fires occur with liquid hydrocarbonsand similar combustibleliquids.
Foam, dry-chemical,halocarbon,and CO2extinguishersare recommended.
ClassC fires occur in live electricalequipment. Clearly, water and wet-type
fire extinguishersmust be avoided.
ClassD fires involve strong reducing agents such as active metals (magnesium, titanium, zirconium, and alkali metals),metal hydrides,and organometallics. Specialdry-chemicalfire extinguishersare availablefor thesefires (e.g.,
Ansul Co.). Sand is also useful for small fires of this type. Water should be
avoided becauseit promotes the fire by liberation of hydrogen or hydrocarbons.
REFERENCES
GENERAL
244
REFERENCES
GENERAL
B r e t h e r i c k . L . , 1 9 8 5 , H a n d b o o k o f R e a c t i v eC h e m i c u l H a z a r d s , 3 r d e d . . B u t t e r s , o r t h s ,B o s t o n .
C h e n r i c a lh a z a r d s .u i t h r e f e r e n c e sf o r 4 . 9 0 0 c o m p o u n d s .
K e i t h . L . H . , a n d D . B . W a l l e r s , E d s . , 1 9 8 5 ,C o n r p e n d i u n o
t . fS u I e t J , D n u S h e e t s J o rR e s e u r c ha n d
I n d u s t r i a l C h e n t i c a l s , 3 V o l , V C H P u b l i s h e r s .D e e r f i e l dB e a c h , F l o r i d a . H e a l t h h a z a r d s ,f i r s t
a i d , r e c o m m e n d e ds t o r a g e ,a n d r e f e r e n c e sf o r 8 6 7 c h e m i c a l s .
Prudettt Practicesfor Hundling Hazardous Chenticals in Laborutories, National Academy Press,
W a s h i n g t o n , D . C . , 1 9 8 1 .G e n e r a l l a b o r a t o r yp r a c t i c ef o r h a z a r d o u sm a t e r i a l s ,e l e c t r i c a lh a z a r d s , l a b o r a t o r yv e n t i l a t i o n , s t o r a g eo f c h e m i c a l s .d i s p o s a lo f c h e m i c a l s ,a n d t h r e s h o l d l i n l i t
v a l u e sf o r c h e m i c a l s u b s t a n c e s .
S a i . N . I . , E d . . 1 9 8 4 ,D u r t g e r o u sP r o p e r t i e so . l ' l n d u s t r i a lM a t e r i a l s . 6 t h e d . . R e i n h o l d ,N e u Y o r k .
P h y s i c a lp r o p e r t i e s ,f i r e a n d e x p l o s i o nh a z a r d s .t o x i c i t y , a n d i n c o n r p a t i b i l i t yf o r a b o u t 2 0 , 0 0 0
chemicals.
S t e e r e ,N . V . , E d . , 1 9 7 1 ,H a n d b o o k o f L a b o r a t o r y ^- t d l e t r , T
, h e C h e m i c a lR u b b e r C o . , C l e v e l a n d ,
Ohio.
GLASSAND
GLASSBLOWING
Even though the servicesof a professionalglassblowermay be available,it is

often much more efficientfor the chemistto construct,modify, and repair small
glass items, and most chemistsinvolved in vacuum line work are capable of
much more. In addition to the advantageof efficiency, glassblowingaffords an
agreeablediversionwhich is doubly rewarding when an aestheticallypleasing
apparatusis produced.As an aid to the designof glassapparatus,this appendix
presentsinformation on the properties of some common laboratory glasses,followedby instructionsfor somebasicglassblowingoperations.Theseinstructions
should be supplemented,if possible,by observingan experiencedglassblower.
The beginner will find practice necessaryto developthe manual dexterity and
judgment which are required in glassblowing.
ll,4 PRoPERnEs
oFGLAssEs
The glassesin general laboratory use contain SiO2 andlor B2O3as the glassforming constituentand frequently a metal oxide modifier, which is added to
lower the viscosityof the glassor to impart other desirablecharacteristics.Glass
is an amorphous substancewhich may be viewed as a highly viscousliquid.
Thus, unlike a pure crystallinesubstance,it does not display a sharp melting
point, but despitethis, it is convenientto speakof temperaturesaround which
recognizable changes in properties occur: The strain point correspondsto the
temperatureat which internal stressis largelyrelievedin 4 h; more precisely,it
242
243
PROPERTIES
OF GLASSES
correspondsto a viscosityof 1014spoise(P).r At the annealingpoint (10t3.0P),

internal stressis substantially relieved in 15 min. The deformation point corresponds to a temperature at which viscousflow neutralizesthe effect of thermal
expansion(about l0rr-10r2 P). The soJteningpoint has an involveddefinition,
but roughly speakingit correspondsto a temperatureat which a small heated
rod will slowly elongate under its own weight. This correspondsto a viscosityof
approximately1070P.
Glassis generallyannealedat a temperaturebetweenthe strain point and the
annealing point and is worked above the softeningpoint. The relationshipof
thesetemperaturesis brought out more clearlyin Fig. II.1, whereit may be seen
that fused quartz is the most refractory of the common laboratory glasses,and
Vycor, a96Yo silica glassmanufacturedby Corning GlassWorks, is somewhat
lessso. Becauseof the high softeningpoints of thesetwo glasses,they must be
worked with a hydrogen-oxygenflame and, unlike borosilicateglass,they are
generallyblown while in the flame. The ability of theseglassesto withstandhigh
temperaturesleads to their use in combustiontubes and similar applications.
The maximum temperaturefor continuoususe is about 900"C for Vycor, while
t I
$
|..
o Q
I
] ^ ,
\ - + " 'o r np o r n t
\l
-\SL.
o
612
o
o
o
oi^
;L;;
t-
,.]
;
lol-tf 11n_s_pqq|.
400
600
800 1000 1200 1400 1600

T em o er o t u r e .o C
Fig. II.l.
Viscosity-temperature curves for some common laboratory glasses.The numbers in parenthesescorrespond to Corning designations.(Adapted from Corning Glass Works, Corning, Ny,
Bulletin B-83, 1957.)
'These are tentative designationsspecified by the American Society

For Testing Materials.
GLASSAND GLASSBLOWING
244
continuousheating of fused quartz aboveabout 1000'C will lead to failure due

to devitrification(crystallization).Also, becauseof their high strengthand very
low coefficientof expansion,theseglassescan withstand considerablethermal
shockwithout breaking. For example,a red-hot tube can be plunged into water
without cracking. Another important property is their transmissionof ultraviolet and near-infraredradiation (Fig. II.2); accordingly,fused quartz and, to a
lesserextent, Vycor are often employed in cell windows and reaction vesselsfor
photochemicalwork. Finally, the high strengthof fused quartz leadsto its frequent use in fibers for the suspensionof galvanometerparts, as the helical spring
for weighing small samples,and for spiral gauges.
The majority of chemical glasswareis constructedfrom borosilicateglass,
which has the advantagesfor routine use of a reasonablylow coefficient of expansionand a convenientsofteningtemperaturefor glassblowing.In addition to
the oxidesof siliconand boron, theseglassescontainsmall amountsof the oxides
of aluminum, sodium, and potassium.The trade designationsfor the glassused
in most laboratoryequipmentare Pyrex7740(CorningGlassWorks) and Kimax
K-33 (Owens-Illinois).They are very similar in compositionand are compatible
with each other, but cannot be fused directly to flint glassor fused quartz. Although the softeningtemperatureis 820'C, it is unwiseto useborosilicateglass
s_
c
9
E
c
o
400
500
W o v el e n g t hm, i l l i m i c r o n s
100
.{o
6
oqo
E
c
o
F
1.O
20
5U
40
50
W o v el e n q t h , m i c r o n s
Fig. II.2. Transmission of Pyrex, Vycor, and fused quartz. Transmission curves for 2-mm-thick
s a m p l e so f ( a ) f u s e d q u a r t z ( G E t y p e 1 0 2 ) , ( b ) V y c o r ( C o r n i n g 7 9 1 0 - n o t e t h a t t h i s i s a s p e c i a l l y
controlled grade; the more common 7900 has an ultraviolet cutoff similar to 7740), and (c) Pyrex
( C o r n i n g 7 7 4 0 ) . ( A d a p t e d f r o m d a t a s u p p l i e db y C o r n i n g G l a s s W o r k s a n d G e n e r a l E l e c t r i c C o . )
Certain glassesand types of fused quartz are available which lack the infrared absorption at about
2.7 microns.
AND MATERIALS
EOUIPMENT
245
above500"C, especiallyif evacuatedor under stress.2Unlessotherwisestated,

the piecesof apparatusdescribedin this book, as well as the glassblowingoperations which follow, apply to Pyrcx7740or Kimax K-33. Becauseof its poor resistanceto thermal shockand low softeningtemperature,flint glassis not desirable
for most laboratory apparatus. The junction of dissimilar glassesis generally
performedthrough a graded sealcomposedof rings of compatibleglasseswhich
have a smooth variation in expansioncoefficientand melting point. The very
useful Pyrex-to-quartzgraded sealsare availablecommercially.Also, a serviceceable union may be made betweenPyrex and the high-temperature-resistant
ramics,3
The tensilestrengthof glassis influencedby a sufficientnumber of variables,
so it is difficult to specifyvalueswhich will apply to laboratoryconditions.It is
decreasedby surfacescratches,moisture,and many solvents.Also, the strength
for glassunder continual load. As a result, strengthsgreaterthan 1 X
decreases
106lblin.2 and as low as 19 lb /in.2 havebeendetermined.It has beensuggested
that a value of 1,000 lb/in.2 is reasonablefor annealedglass.aAccordingly,this
valuecan be usedto calculatethe valuesfor the bursting pressuresof glasstubes.
Any glass tube under pressuremust be treated as dangerousbecauseof the
highly variabletensilestrengthof glass.Valuescalculatedfor sealedtubes are of
limited value becausetestshave shown that the weak point is usuallythe glass
seal.s
ANDMATERTALS
ll.2 EoUTPMENT
An amazing variety of glass apparatus can be constructedby using simply a
torch and low-pressurenatural gas and oxygensupplies.Also, a pair of didyntium-tinted glassesis a necessityto elim'inatethe yellowglare of sodium emission
which occurswhen borosilicateglassis heated.
A nrorerepresentativegroup of equipmentfor use in the laboratoryincludes
the following items, someof which are illustratedin Fig. II.3:
Hand torchband oxygenpressureregulator
Didyntium glasses
Glass knife or three-corneredfiles
r A . W . L a u b e n g a y e rl ,r r l . E n g . C l t e n t . , 2 .l 1 7 4 ( 1 9 2 9 ) , d e s c r i b e s s o m e e x p e r i m e n t s w h i c h g i v e a n
i n d i c a t i o no f t h e u s e f u l t e m p e r a t u r er a n g e f o r P y r e x .
r J . A . A f e x a n d e rF, u s i o r t . 3 .5 ( 1 q 5 6 ) :E . R . N a g l e .F u s i o t t . 1 0 . 2 J( 1 9 6 J ) .
r P r o p e r t i e so . l S e l e c t t r lC o n t n t e r t i u lG l r r s s e sB
, u l l e t i n B - 8 3 . C o t n i n g G l a s sW o r k s . C o r n i n g . N . Y .
5 J .T a n a k a . J . C h e n t . E d u c . . 5 0 . 4 9 7 8( 1 9 7 2 ) .
n S u r f a c e - n r ihxa n d t o r c h e sa r e a v a i l a b l ef r o m B e t h l e l r e mA p p a r a t u s ,l n c . , F l a l l e r t o w n ,P a . I n t e l n a l . r a n g eo f t i p s i s a l s o
m i x h a n d t o r c h e sa r e a v a i l a b l ef r o n r m o s t l a b o r a t o r yo r w e l d e r ' ss u p p l yh o u s e s A
r e q u i r e dw i t h t h e i n t e r n a l - m i x t o r c h e s .
246
Swiveland blowhose
Tweezers
Tapered graphite rods (hexagonalor circular crosssection)
Set of plain and one-holestoppersand corks
Glassfiber paper and/or aluminum foil
Polariscope,or two piecesof polaroid film and a flashlight
Caliper scale
A pair of rollers mounted on a stand
A small fireproof bench top or table
A reasonablydust-free cabinet stockedwith a variety of standard wall
tubing,
heavy-walledcapillary tubing, and rod
A ring stand and clamps with woven-glass-covered
fingers
Surface-mix bench burner for large items
clean glassis used for glassbrowingbecauseforeign matter is easiryincorporated into molten glass.Aside from the obviousbad effectsthis can have
on the
surfaceand characterof the glass, specksof dirt are a frequent source
of pinholes' To avoid picking up foreign matter, it is desirabreto usefreshryprepared
surfacesfor making joints and to minimize contact of thesesurfaceswith
anything but glassor cleanglass-workingtools. In this connection,tubinq
shouldbe
s t o r e di n a c a b i n e tt o a v o i d t h e a c c u m u l a t i o no f d u s t .
@
@
4?
ryh
tl
il
F(
|.l\
t\
---2-1
.4'-/J
-t-'1
CAL-/J
a,-JP
vc=
Fig' II'3'
S o m e g l a s s b l o w i n gi m p l e m e n t s .A n i n t e r n a l - m i x h a n d t o r c h
a n d a s e r i e so f t i p s a r e
s h o u n i n t h e u p p e r l e f t . I n t h e u p p e r r i g h t i s a s e t o f r o l l e r s .F r o m
t o p t o b o t t o m i n t h e c e n r e ra r e a
b r a s s ' s h a p i n gt o o l , a t a p e r e d c a r b o n r o d o n a h a n d l e , a g l a s sk n i f e
with tungsten-carbide
cutting
e d g e s .a n d a v e r n i e rc a l i p e r s c a l e .A t t h e b o t t o m a s w i v e la n d b l o w h o s e
a r e i l l u s t r a t e da t a s l i g h t l v
larger scalethan the other items. The short length of tubing
on this swivel may be connecteddirectl!
t o a n i t e n r o r i t m a y b e a t t a c h e db y m e a n so f a o n e - h o l es t o p p e rr v i t h g l a s s
t u b e . I n e i t h e r c a s ef r e e
r o t a t i o n o f t h e i t e m a n d s i m u l t a n e o u sb l o w i n g a r e p o s s i b l e .
247
ANNEALING
ll.3 sEeuENcE
oFoPERAIToNs
Molten glassresemblesvery thick molasses,so it tends to sag and flow under the
influence of gravity. Therefore, wheneverpossible,the piecesbeing worked are
rotated to avoid the pileup of glass. When clamping is necessary,the effects of
saggingmay be minimized by clamping tubes in a verticalfashionand placing a
tube with thick walls aboveone that has thin walls.
In general, it is best to finish a piece without interruption and to anneal it
immediatelywith the hand torch. An evenwall thicknessis alwaysdesirablebecausethin glassis weak, while lumps are frequentlystrained.Beforean intricate
apparatus is constructed, the sequenceof work is planned so that it is always
possibleto apply pressure(blow) on a joint that is being constructed.Occasionally it is necessaryto blow a temporary hole in an apparatus to serveas a place to
attach a blowhose.For example, supposea bulb with an attachedstopcockis
being constructed from a round-bottom flask and a stopcock. A small hole is
first blown into the bottom of this flask (Fig. II.4c), and either a blowhosewith a
swivelis attached or elsea temporary length of tubing is attached. Either of these
provides a mechanism for sealing off the neck and then blowing another hole
which will match the stopcock(Fig. II.4). After the stopcockis attached, it
provides an opening for blowing while the temporary hole is being sealed(Fig.
ll.4c). Details of glassblowing operations involved in the construction of this
bulb are presented in the following sections.
ll.4 ANNEALTNe
In the processof working glass,the thermal gradientsintroduce strainswhich
must be relieved if reliable serviceis expectedfrom the glassware.The most sat-
-+
Swivel
ond
blow hose
To swivel
ond
blowhose
S w iv e I
ond
0low nose
(c)
Fig. II.4. Some steps in attaching a stopcock to a flask T h i s s e q u e n c ea l l o w st h e g l a s st o b e b l o r v n

at each stage.
248
isfactory procedure involvesthe use of a glassblower'sannealing oven, which

provides gradual and well-controlledwarming and cooling cycles. However,
large and intricate parts must be annealedwith the bench torch immediately
after constructionand then placed in an annealingoven. A muffle furnace will
servewell as an annealingoven. For most laboratory items of moderatethickness,the furnace and contentsare allowedto warm from room temperatureto
570"C; this temperatureis maintainedfor half an hour, and then the furnace is
turned off and allowedto cool slowly. Many small parts may be adequatelyannealedwith the bench torch alone. A cool, bushy flame is used, and attainment
of the annealingtemperatureis judged by the appearanceof the yellow sodium
flame. Strains tend to concentrateon either side of a sectionwhich has been
worked, so a generousarea should be annealed.After the glasshas been thoroughly and evenlyheatedto the annealingtemperature,the flame temperatureis
gradually reduced. Some glassblowersrecommendthat the last bit of heating
shouldbe done with a sootyflame; however,it is doubtful that such a cool flame
is worthwhile.For largeparts, it is handy to havea Fisherburner availableto use
in the annealingprocess.After the glasshas cooled,strainsmay be locatedas
light streakswhen the apparatusis viewedbetweencrossedPolaroids.
When a large apparatusis mounted on a lattice, strainsare inevitablyintroduced by the clamping operation. This is partly avoidedby using a minimum
number of clamps. Also, all heavyitems, such as thosewhich contain appreciable quantitiesof mercury, must be individuallysupported.The clamp fingersare
bestcoveredwith wovenglasssleeves
or a layerof glassfiber paper. Thesecovering materialshavea degreeof resiliencyand allow the useof a torch in the vicinity of the clamp for the purposeof making repairsor alterations,and for flaming
out and annealingthe apparatus.After a vacuum line has been assembled,but
before it is evacuated,the glass is softenedand annealedat selectedpoints to
removestrains introducedby the clamping.
ll.5 cuTnNGGLASS
TUBTNe
Glass is generallybroken and not cut. Small-diametertubing is conveniently
broken by making a scratch about one-fourth of the way around the tube and
then grasping the tube on either side of the scratchand simultaneouslypulling
and bending. The nature of the scratch is quite important; it should be made
with a sharp tool and with a smooth, firm motion, so that the glasscrackles.
Sawing at the glass with the corner of a dull file producesa rather ineffective
scratch.The breaking operation is facilitated if the scratchis moistened.With
large tubing or with a permanentlyclamped piece,this method cannot be used,
and in thesecasesthe finite thermal expansioncoefficientof Pyrex is utilized to
producea strain around the scratch.The simplestprocedureis to heat the end of
a small-diameterglassrod until it is white hot and then quickly touch this to the
glassjustbeyondthe scratch.Ifthe resultingbreak is not sufficientlylong, it can
be led around the tube by touching the hot rod just beyondthe end of the break.
ENDSAND FIRECUIOFFS
TEST.TUBE
z4Y
A variant of this technique is to extend the scratch about three-fourths of the way
around the glassand then to direct a small but very hot flame at right anglesto
the tube so that it grazesthe tubing along the middle of the scratch.While a
smooth,cleanbreak can be producedby the foregoingmethods,a more satisfactory surface for subsequent glassblowing is often produced by a fire cutoff,
which is describedin SectionII.7. It is sometimeshandy to smoothup a jagged
end or removeglassby brushingthe end with a metal screen.However,this practice is not recommendedif the end is going to be glassblown,becausemetal
particlesadhereto the glass.
eLAssTUBTNG
ll,6 BENDTNe
Simplebendscan be made by evenlyheatinga broad sectionof tubing and allowing the free end to sag under its own weight. For this purpose a large flame is
used which is sufficiently hot to surpassthe softening point, but not hot enough
to melt the glass.A bend may also be made by evenlyheatingthe desiredlength
of tubing to the softening point and then removing it from the flame and making
the bend. Kinks or very sharp bendsshouldbe avoidedbecausethey break easily
under strain. It is sometimesnot possibleto avoid somecollapseof a tube when a
bend is made, but its shape is restoredby stopperingone end of the tubing,
heating the sectionto be re-formed to the working point in a large flame, and
then gently blowing on the open end of the tubing just after the flame is removed.With a little practice,one can combinethe bendingand blowing into one
continuousoperation.
ll.7 rEsT-ruBE
ENDs
ANDFIRE
cuToFFs
Both ends of a tube are graspedand rotated in a hot flame until the glassbecomesmolten (Fig. II.5c). The tube is then pulled apart in the flame, and excess
glass is removed from one half by melting the unwanted glass and pulling it out
with a piece of cool rod or tubing (Fig. II.5). This should leavea completely
closed tube, free of excessglass. The closed end is now heated in a hot flame
until it becomesmolten, and during this heating, the saggingof glass is preventedby constantlyrotating the tube (Fig. II.5c). As the tube is being rotated,
it is removed from the flame and gently blown out to give a hemisphericalend of
uniform thickness(Fig. II.5d). Timing is important in this processbecauseif the
end is blown out immediately after heating, any thin regions will blow out first;
but with the correct delay, thick sectionswhich cool the slowestwill be preferentially blown out to yield a uniform wall thickness.Failure to rotate the glass
constantly is a common error, which leads to uneven heating of the end and a
lopsided product. Another error is to heat the closedend too long, which leadsto
an excessiveaccumulationof glass.
When one is forced to work close to the end of a tube, it is not possible to
250
/
-Ftr
tI\,,
K
(a,
,
(d)
Fig. II.5. Construction of a test-tube end. (c) A small section of the tube is melted and
the halves
pulled apart. () A small hot flame is used to melt excessglass, which is then pulled off with
a cold
piece of glass. (c) The end is heated evenly, removed from the flame when it is molten
but before
excessglass accumulates, and gently blown. (d) A finished product. The end should be hemispheri_
c a l a n d t h e w a l l t h i c k n e s su n i f o r m .
grasp both ends as decribed above. In this situation another piece of tubing or a
rod is sealedto the end of the tube to serveas a handle.A verycrudejunctionwill
suffice since the handle is temporary.
The preliminaries to produce a fire cutoff are the same as for a test tube end.
Instead of gently blowing the molten glass into a hemisphere, a more vigorous
putf is given to produce a large, thin bulb. Just as with the test tube end, even
heating is necessaryto ensure a well-shapedopening (Fig. II.6). If properly
blown, the thin glass is easily brushed off by use of glassrod or another piece of
glass tubing to leave an even opening with a slight flare and a thin edge.
(b)
(o)
Fig. II.6.
A fire cutoff. (a) A large, very thin bulb is btown out. () The thin glass is brushed away
254
END.TO.END
SEALS
ll.8 END-Io-END
sEArs
The end-to-end seal is a very common operation in constructing glass equipment. The processis aided if the ends to be joined are smoothly broken or are
evenlyblown out; and it is usually desirable to start with freshly broken or firecut piecesbecausethis minimizesthe chanceof incorporatingdirt into the joint.
When the joint is to be made offhand, the torch is clamped and a free end of
one of the tubes is stoppered; the tubes are then grasped in either hand and
rotated in a hot and rather large flame (Fig. II.7a). This processrequires some
dexterity, sincethe rotation must be even and the ends must not touch but must
becomethoroughly molten. The heating is carried on at an evenbut quick pace
to avoid a large accumulation of molten glass around the two ends. Next, the
pieces are removed from the flame and pressedtogether. This is generally followed by a gentle pull and simultaneous blowing to thin out the ring of glass
which has formed at the junction (Fig. ll.7b). Here again, it is necessaryto develop somedexterity so that the piecesare initially joined in a concentricfashion.
If the initial union is badly skewed or if a continuous hole-free seal is not
achieved, a smoother final product is generally obtained and time is saved by
starting over, rather than attempting to patch up the joint.
The pulling-out and blowing operations described above are not absolutely
essential,becausethe next step is to smooth out the joint. This may be accomplished in severalways. Generally, the part is rotated in a hot flame until the
glass in the joint is thoroughly melted; it is then removedfrom the flame and
gently pulled to thin out the thick glass and blown to restorethe glass to its
correct diameter. Close coordination of the rotation rate for each hand is necessary to avoid twisting the glass during the heating. When unwieldy parts are
ffi
(c)
Fig. II.7. Construction of an end-to-end seal. (a) A large hot flame is used to create an even molten
rim on both piecesof glass.() The two ends are joined, which leavesa small ridge of glassthat must
be worked in. (c) The finished product should have a reasonably uniform wall thickness and no
vestigesof the ridge.
252
encountered,a sightly different approach may be taken. In this case,the welt of

glass at the junction is worked in by heating a small segment of the glass to a
molten state and then blowing it out to the correct radius. One then moveson to
the adjacent segmentand works it in. A final heating of the joint to the softening
point, alignment, and blowing may be necessary;but the above processdoes
avoid a continuousbelt of molten glass,which may be hard to handlebecauseof
the bulky nature of the apparatus.
An end-to-end seal may also be made by firmly clamping one of the parts,
preferably in a vertical direction, and lightly clamping the other so that the edges
are aligned but do not quite touch. One hand is used to steady the lightly
clamped piece and the other directs the hand torch around the two ends to give
continuous molten edges.The lightly clamped piece is then pressedinto the
other, and the parts are worked together as describedabove. If the glasssagstoo
much toward the lower component, the part may be inverted and additional
smoothing performed.
When the two tubes to be joined are of different diameters,the task is slightly
more difficult. In this case,a test tube end is formed on the larger tube; then a
very small flame is directedin the centerof this end, and only a small holewith a
diameterwhich matchesthe small tube is blown out. To allow better control of
the hole sizeand to yield a lip which facilitatesthe subsequentsealing,it is helpful to perform this blowing-out operationin two stages(Fig. II.8).
(b)
(c l
Fig. II.E. Preparation of a large-diametertube for an end-to-end sealwith a smaller tube. (a) A test
tube end is formed on the large tube, and a small molten spot is createdon the end with a small hot
f l a m e . ( ) A b u l g e i s b l o w n i n t h e e n d . ( 6 ) T h e e n d o f t h i s b u l g e i s m e l t e da n d b l o w n c o m p l e t e l yo u t .
T h e d i a m e t e ro f t h i s o p e n i n g s h o u l d m a t c h t h a t o f t h e s m a l l t u b e .
253
RINGSEALS
When an end-to-end seal is made with heavy-walledcapillary tubing, the

end(s)of the capillary tubing is blown out to producean openingwith a normal
wall thickness.It is convenientto accomplishthis in two stages,as illustratedin
Fig. II.9. Subsequently,the seal is made in an ordinary manner.
ll,9 r-sEALs
A round hole is blown in the side of a tube by first blowing a bulge and then
concentratingthe flame on the end of this bulge and blowing it out. This twostep operation gives a round hole and leavesa lip which is convenientfor the
subsequentsealingoperation(Fig. IL10). The two edgesto be sealedare heated
evenlyto the molten state,joined, and then worked in like the end-to-endseal.
When a T-seal is made by joining a small tube to the side of a large one, care
must be taken to avoid sudden cooling and reheating of the joint before it is
finished and completelyannealed.If this is not done, considerablestrain developsbecauseof the unsymmetricalconfigurationaround the axis of the large
tube.
11,4
0 RTNG
sEALs
There are two common waysof making ring seals.One of theseis illustratedin
Fig. II.l1, whereit may be seenthat a test tube end is formed on the outer tube,
:---
-_--]r\l
Y_/
(b)
F i g . I I . 9 . P r e p a r a t i o no f c a p i l l a r y t u b i n g f o r a n e n d - t o - e n ds e a l .( a ) A t u b e t r l o w no u t t o n o r m a l
w a l l t h i c k n e s s .( b ) T h e s a m e t u b e w i t h t h e e n d b l o u ' n o u t .
II
tl
g
tl
IV
tl
|t l | "---l
t^l
(o)
(b)
Fig. II.l0.
C o n s t r u c t i o no f a T - s e a l ./ a ) A b u l g e i s b l o w n i n t h e s i d eo f t h e t u b e . ( ) T h e e n d o f t h e
b u l g e i s h e a t e da n d b l o w n o u t 1 0 l e a v ea s m a l l l i p . ( c ) A j u n c t i o n i s m a d e i n a m a n n e r s i m i l a r t o t h e
c o n s t r u c t i o no f a n e n d - t o - e n ds e a l .
254
A s b es l o s
@
(b)
ffi
(c)
Fig. II.ll.
Some steps in making a ring seal. (a) The formation of a seal between the inner and
outer tubes. () A bulge is blown, which createsan extension of the inner tube. (c) The end of the
bulge is blown out. This piece is now sealedto a tube of the same diameter as the inner tube.
and a smallertube is then slipped insideand held centrallyby glasspaper. This

inner tube is butted firmly againstthe test tube end, and a sealis made between
the two tubes by playing a small and rather hot flame on the outside of the test
tube end in the region wherethe two tubes touch. When the sealis made, a very
small flame is directed in the center of the seal, and the glassis blown out by
applying pressurethrough the inner tube. This is best accomplishedby first
blowing a bulge and then heating the end of the bulge and blowing it out. The
resulting lip is then immediatelysealedto a tube with a diametersimilar to the
inner tube, and the joint is annealed.
The secondmethod (Fig. IL12) involvesblowing a hole in the test tube end of
a large tube. This hole should be just large enoughto allow the central tube to
slip through it; and it may be necessaryto use a tapered carbon rod on the hot
glassto obtain the correct sizeopening. A small annular bulge is then blown in
the small-diametertube in the region in which the seal is to be made, and this
tube is slipped though the hole so that the bulge is on the outside.The concentricity of the tubes is ensured by severalturns of glass paper around the central
tube or by an appropriately bored cork. A small, hot flame is directed at the
bulge where it contacts the hole, and the parts are rotated until the glassis molten. The small tube is then pushedtoward the larger one to make the seal and
then pulled back and blown to createa uniform wall thickness.
Ring sealsare particularly susceptibleto breakagefrom thermal strains, so it
255
SEALS
METAL-TO-GLASS
(c '
Fig. II.12. Secondmethod for the construction of a ring seal. (c) Test tube end on a large-diameter
tube has a small-diameter fire cutoff. () A small tube with a bulge is inserted. (c) The two tubes are
sealed.
is best to make the complete seal without interruption and to anneal the final
product carefully before it is allowed to cool.
ll,44 cLosED
crRcurTs
It is sometimes necessaryto make a seal between two stationary tubes. Each
particular case will require a slightly different solution, but one approach is to
soften and stretch one pieceof glassso that it meetsthe other, and then make the
seal by heating the glass at the joint, pulling it together over any small gaps with
a small pieceof glassrod. It is also possibleto join two tubeswhich do not meet
by filling the spacebetweenthem. When this is done, the flame is directedprimarily onto the glassrod which is being usedas filler and not on the open edges,
becausethese tend to sag away from the joint if they are strongly heated. The
same situation is encounteredwhen a hole is beins filled.
sEALsT
ll. 42 METAL-ro-eLAss
A small tungstenelectricallead (1/8-in. diameteror less)can be sealeddirectly
to Pyrex by the following procedure. A short length of Pyrex tubing is found
TDetailedinformation on glass-to-metalseals may be found in the following references:J. H. Part r i d g e , G / a s s - t o - M e t aS
l e a l s , ( S h e f f i e l d ,U , K . : T h e S o c i e t yo f G l a s s T e c h n o l o g y ,1 9 4 9 ) t W . H .
Kohl, Materials and Techniquesfor Electon Zres, (Neu York: Reinhold, 1960): Chapter 13; F.
Rosebury.Handbook oJ Electron Tube and Vacuum Techniques( Reading, Mass: Addison-Wesley.
1 9 6 5 ) .p p . 5 4 f f .
256
which will just slip over the wire and which is sufficientlyshort to leaveadequate
bare wire on either end for electricalconnections.The tungstenwire is heated
white hot, cooled, sanded until it is bright, and then carefully oxidized by
quickly passingit through a flame. The oxide coatingshould be thin enoughto
give the appearanceof gun-metalblue. The small pieceof tubing is slippedover
this tungstenwire and heatedto collapseit onto the wire. If the sealis properly
made, the tungsten-glassinterfacewill have a copperlikeappearanceand few
bubbles.The glasssheathmay then be sealedinto a hole in the apparatus.Generally, the hole is blown with a small lip which may be softenedand then collapsedonto the glasssheathby tweezersor a carbon rod.
One of the most satisfactorymetal-to-glasssealsinvolvesan Fe-Ni-Coalloy
called Kovar. The coefficientof expansionof this alloy is closeto that of Pyrex,
to which it can be directly bonded; however,an evenbetter match in expansion
coefficientsis obtained with a specialborosilicateglass(Corning7052, Kimble
EN-l or K-650). A variety of tubes is availablecommerciallyinvolvinga Kovar
tube sealedto a Pyrextube through one or more intermediateglasses.The propertiesof Kovar are discussedin Appendix IV under iron (SectionIV.l.E).
Copper-to-glassseals (Housekeeperseals)and stainless-steel-to-glass
seals
e Thesesealsare somecan be made and the directionsmay be found elsewhere.8
what strainedand are generallynot suitableif the joint is exposedto wide temperature variations.
It is possibleto solder most metals directly to glassby use of indium metal
(mp 155'C) or an indium alloy such as In 95 % Ag 5 % (mp about 145"C).The
heatedglassis rubbed with the molten solderto wet the surfaceand then heated
in contact with the metal, which was previously"tinned" with the solder.r0
A number of low-meltingglasseshavebeen speciallyformulated for "soldering" glassto glass.metal, or ceramics."In general,the coefficientof expansion
for the solderglassshould nearly match that of the items being bonded.
ll.'13 HEALTNe
cRAcKsANDPTNHoLES
Occasionallya crack will developin an apparatusbecauseof mechanicalshock
or internal strainswhich were not completelyremovedby annealing.Providing
the glassis not shatteredor the part is not under a large, externallyproduced
strain, the crack may be healedby gentleheating. The area around the crack is
first slowlyheated,and then the soft flame (somewhathotter than an annealing
W . G . H o u s e k e e p e r , JA. n r . I n s t . E l e c . E n g . . 4 2 , 9 5 1 ( 1 9 2 3 )a; l s o E . L . W h e e l e r , S c i e n t i J ' i c G l a s s b l o v , i n g ,( N e w Y o r k : l n t e r s c i e n c e ,1 9 5 8 ) .p p . l 6 2 f f .
' q S . O . C o l g a t e a n d E . C . W h i t e h e a d . R e v . . l Icui .s t r . , 3 3 .l l 2 . 2 ( 1 9 6 2 ) : J . E . B e n b e n e k a n d R . E .
Honig,Rev. Sci.Instr., Jl, 460 (1960).
r o R .B . B e l s e r .R e y . S c i . I n s t r . , 2 5 . 1 8 0 ( 1 9 5 4 ) .
I r S o l d e rG l a s s K i t , O w e n s - l l l i n o i sC o . , T o l e d o , O H I
Q u a r t z C e n r e n tB i n d e r , A r n e r i c a nT h e r m a l
F u s e dQ u a r t z C o . , M o n t v i l l e , N J .
257
TUBINGUNDERVACUUM
SEALING
flame) is movedgraduallytoward the crack. In many casesthis processwill lead

to the disappearanceof the crack. If, however,the crack doesnot heal, it will
slowlyopen up as the glass sagsaway from the crack. A pieceof cane (smalldiameterglassrod) may then be used to unite the open edgesof the crack and
somefinal blowing will be necessary
to obtain a smoothseal.A pinholeusuallyis
sealedby melting the spot with a small hot flame and pulling away a small
amount of glasswith a glassrod.
lrlr.44sEAUNG
ruBrNeUNDER
vAcuuM
Operationssuch as the collectionof a samplein a sealedvial or the performance
of reactionsin sealedtubes require the ability to sealoff tubing under vacuum.
This is easilyaccomplishedif a thickenedsectionof glasswith a moderateinside
diameter (about 5 mm) was included in the apparatus(Fig. IL l3c). The thickenedsectionshouldbe sufficientlylong so that the adjacentthinner tubing is not
softenedduring the seal-offoperation.The inner wall of the constrictedportion
should be free from foreign matter, and throughout the sealingoperation the
To
v o cu u m
p um p
To
pump
Thickened
sectlon
To
pump
.ll,
T-7
\/
-LL
fth
\/
t^J
(b)
vi\
Y4\
ntl
r)
l/'7\
(cl
V a c u u m s e a l - o f f .( a ) T h e t u b e i s e v a c u a t e d I. f a v o l a t i l es u b s t a n c ei s b e i n g s e a l e di n t o
Fig. II.l3.
t h e t u b e , t h e l o w e re n d o f t h e t u b e i s i m m e r s e di n l i q u i d n i t r o g e n .( 6 ) T h i c k e n e ds e c t i o nc o l l a p s e db y
a s o f t f l a m e . ( c ) A h o t f l a m e i s p l a y e do n t h e c o l l a p s e ds e c t i o n ,a n d t h e s e a l e dt u b e i s p u l l e d a w a y .( d )
Not shown. The tube end is gently annealed.
258
GLASSAND GLASSBTOWING
vesselis pumped on to remove gaseswhich boil out of the glass. A seal may be
made by directing a soft flame evenly around the middle of the constricted section. To avoid sucking a hole in the glass, care is taken to move the flame off a
section as it begins to collapse. After the tube has been collapsed in an even
fashion, one is left with a small, nearly solid section, which may still contain a
threadlike opening betweenthe two halves.Next, a small, very hot flame is directed around the nearly solid section, and while the flame is on the glass, the
tube is separatedfrom the apparatus by pulling it away. Finally, the sealedend
is annealed with care to avoid further collapseof the tube.
REFERENCES
GENERAT
Barr, W. E. , and V. J. Anhorn, 1959, Scientific Glassblowing, Instruments Publishing, Pittsburgh.
Heldman, J. D., 1946, Techniques of Glass Manipulation in Scientific Research, Prentice-Hall,
Englewood Cliffs, N.J.
Laborutory GlassBlowing with Corning Glasses,l96l , Bulletin, B-72, Corning Glass Works, Corning, N. Y.
Moore, J. H., C.C. Davis, and M. A. Coplan, 1983,Building Scientific Appararzs, Addison-Wesley,
Reading, Mass. Glassblowing is covered in Chapter 3.
Parr, L. M., and C. A. Hendley, 1956, Laboratory Glassblowing, G. Newnes, London.
Wheefer, E. L., 1958, Scientific Glassblowing, Interscience, New York, Available from E. L.
W h e e l e r ,P . O . B o x 4 8 3 3 , C h i c o , C A 9 5 9 2 7 .
PLASTICS
AND
ELASTOMERS
Many recent improvements in apparatus have resulted from the availability of
new high-polymer materials. These substancesexhibit a wide range of physical
and chemical properties. Therefore, it is frequently necessaryto exercisecare in
the choice of the rubber or plastic to be used for a particular application.
Rubbers and plastics have a much more limited range of useful temperatures
than do metals or glass. Most polymeric materials undergo a low-temperature
transformation to a brittle glassystate which often limits their utility at reduced
temperatures. In addition, plastics lose their strength at high temperatures.
Small changes in formulation may significantly alter the usable temperature
range of a polymer material, so the glasstransition temperaturesand maximum
usable temperatures quoted in this appendix are only approximate.
Elastomers and, to a lesserextent, plastics tend to swell in the presenceof
solvents.Frequently, this swelling is accompaniedby a loss in strength. In addition, some plastics are dissolvedby certain solvents,and all-polymeric materials
may be chemically destroyed.It is in the areasof solventand chemical resistance
that most problems are encountered in the laboratory.
The permeability of high-polymer materials to atmosphericgasesand solvents is much greater than for metal or glass. This is often a significant factor
when air-sensitivecompoundsare being handled or when a high vacuum is desired. It is evident from Table III.1 that permeabilities may vary greatly from
one material to the next. The rate of permeation decreaseswith an increased
cross section of the plastic or elastomer, becausethe amount of gas which will
pass through a membrane of thickness d is given by the equation
q:QA(+),
259
260
PLASTICS
AND ELASTOMERS
where,4 is the membrane area, Pr - Pz is the difference in partial pressuresof a

particular gas on the two sides of the membrane, / is the time, and Q is the
permeability.rValuesare presentedin Table III.1 for the permeabilityQ of various materials to atmospheric gases. In most cases,the permeability increases
with temperature; and it may be decreasedby greater cross-linking or greater
crystallinity.
From the data in Table III.l it may be seen that cellophane and cellulose
acetate have very large permeabilities to water; also, the solubility of water in
these materials is great, so they are clearly unsuited as moisture barriers. Of the
elastomerslisted, silicone rubber has the highest permeability to air.
pRopERTTES
ANDFABRtcAIoN
lll, 4 pLASTrcs:
GENERAL
Most plastics may be classifiedas thermosetting or thermoplastic. At the molecular level the former are characterizedby a three-dimensionalcross-linkednetwork. These thermosetting plastics soften progressivelyas heat is applied, but
they do not exhibit a true melting point, and often the maximum usabletemperature is higher than for a comparable thermoplastic. The thermoplastics,which
are composed of high-polymer chains without cross-links, exhibit reasonably
well-defined softening ranges and are often more susceptibleto solventsthan
similar thermosetting polymers.
The method of fabrication for plastic items is influenced by whether or not
one is dealing with a thermoplastic or a thermosetting plastic. In general, the
first group may be heat-sealed,heat-molded, and solvent-cemented,but these
possibilitiesare not availablefor the thermosetting resins. Both groups generally
can be machined.
Irradiation of thermoplastics leads to cross-linking and thus imparts the
properties of a thermosetting plastic. Tubing which has been expandedafter the
radiation treatment has a "memory" of its former sizeand will shrink to its original size when heated. Shrinkable tubing is available in a number of different
plastics.2
Heat-sealingis routinely used in the "bagging" operationfor the disposalof
radioactive and/or highly poisonous materials from a glove box. The general
approachin heat-sealingis to heat the film to the melting temperatureand press
the molten surfacestogether. To accomplish this, a tool with a heated Tefloncoated roller is availablecommercially, and an accessoryheat-sealingtip is available for many electric solderingguns.
It is possibleto weld substantialpiecesof thermoplasticby the use of a hot-
rWhile reasonably accurate for the permeation of simple nonpolar gases,this equation is less suitable for water vapor, so the permeability data quoted for this substanceare of qualitative signific a n c eo n l y .
2 R a v c h e ml n c . . M e n l o P a r k . C A 9 4 0 2 5 .
AND FABRICATION
PLASTICS:
GENERALPROPERI|ES
261
gastorch (Fig. IILl).3 Theseoperateby electricallyheating air or nitrogen;this

hot gas is directed on the seamto be welded while a rod of the sameplastic is fed
into the molten seam (Fig. III.2). This procedureis effectivefor joining poly(vinylidine chloride) (Saran), rigid polyvinyl chloride, and polyolefins.The
heat gun is also usefulfor joining metal or glasstubing to plastictubing, such as
To construct a vacuum-tightjoint, the glassor metal tubing is
polyethylene.a
trealeaabovethe melting point of polyethylene,and the polyethylenetube is softened and slipped over it. The joint is heatedwith the hot-air gun, and the polyethyleneis worked into the joint with a cold metal tool. A satisfactoryend-to-end
,.ui -uy be made with polyolefinand similar thermoplastictubing. The endsof
the two parts to be joined are evenly melted with the hot'air gun and then
pressedtogether. while still molten, the welt of plastic at the seal is pinched
iogetherwith pliers or tweezers,and the resultingthin, circular band of plasticis
later trimmed away. Thermoplastictubing may be sealedoff by a simple crimp
seal. This involvesrotating the plastic tubing in the jet of hot air until an even
molten ring results. This sectionis then crimped together with tweezersor pliers'
and the two halvesare cut apart at the seal.For small'diametertubing, a "test
tube end" sealmay be achievedby drilling a shallowhole of the samediameter
as the tube in a metal plate. This plate is then heatedon a hot plate to the melting point of the plastic, and the end of the plastictube is forced into it' A removable collar of glass or metal tubing may be slipped over the plastic tube to prevent bulging abovethe seal and a film of talc or silicone stopcockgreasemay be
used to preventsticking to the heatedmold. A simple alternatemethod of joining and sealingthermoplastictubing such as Kel-F or polypropylene,is illustrated in Fig. III.3. The plastictubing (1) is forcedtogetherinsidea glasstubing
mold (2), which is gently heated by a cool flame (4), and a rod is insertedto
shapethe interior of the weld (3). This is an excellentprocedure,since it proequipmentis readilyavailablein the
ducesclean,strongweldsand the necessary
laboratory.s
To bend thernroplastictubing, a btoad area of the tubing is evenlyheatedin
the hot-air streamand then bent. Just as with glasstubing, unevenheatingleads
to a sloppy bend. A much more satisfactorybend can be obtained by heating the
tubing in hot water or air, bending it with a metal-tubingbender(Appendix lV),
and. while it is still in the bender, quenching the tubing in a stream of cold
water. Also, a flare, which is suitablefor joints, may be constructedby heating
the tube end in hot water or air, shapingthe end with a flaring tool (Appendix
IV), and quenching.
Sheetsof thermoplastic material may be hot-formed into a variety of smooth
shapesby heating the sheet in an oven to a temperature at which it becomes
plia-ble. The sheet is then bent over a form. In the laboratory this method is
rPlastic welding torches are available from tool suppliers.
a W h e nw e l d i n gp o l y e t h y l e n ea n d p o l y p r o p y l e n ec, l e a n .f r e s h l yc u t s u r f a c e ss h o u l db e p r e p a r e d 'a n d
nitrogen should be used in the torch becausea thin film of oxide prevents a satisfactorybond.
s N e i l B a r t l e t t k i n d l y s u p p l i e d a d e s c r i p t i o no f t h i s t e c h n i q u e '
o.
25
25
30
30
Butyl rubber, vulcanized
20
25
Fluorocarbon polymers:
Teflon (polytetrafluoroethylene)
Teflon FEP (tetrafluoroethylene

hexafluoropropene copolymer)
Ethylene-propylenerubber
Silicone rubber
Thiokol B, vulcanized
25
7.2
r.6
13
48
42
40
16
t.7
30
25
30
2s
25
25
25
H2
25
2l
25
Temp
"C
Neoprene,vulcanized(polychloroprene)
Buna N, vulcanized
Buna S, vulcanized
Butadienerubber, vulcanized
Natural rubber, vulcanized
Elastomers
Ethylcellulose,plasticized
Cellulose nitrate
Cellulose acetate, plasticized
Cellophane(celluloseacetate)
Celluloseand cellulosederivatives
Polymer
4.5
1.3
0.3
91
(air...
4.0
23
19.2
17
3.8
0.78
l.95
26.5
0.0021
Oz
1.9
....11)
(270)
3.3
1.2
7.9
6.5
6.2
1.0
0.28
0.12
8.4
0.0032
N2
l0
4.7
5.1
3 .r
460
25.8
130
139
122
30
2.38
2.2r
41.0
0.0047
COr
Ioble lll.'1.PermeobilifyO lin {0-r0 cm2/(s-torr)l

for SomeCommon PolymericMoleriolso
65
4,400
6,100
910
2,300
I 1.000-35.000
47-169.000
HIO
o.
(.)
(4)
25
(ls)
0.3
5xl0-r
I.l
3.95
0.51
2.3
1.4
25
25
30
30
30
25
30
25
30
30
25
0.045
0 038
0.040
20
25
30
30
25
0 . 1I
9x10-4
0.29
1.36
0.18
0.44
0.3
0.01r
0 009.5
0.005
1.5
0.03
8.8
16.7
2.1
9.2
8.0
0 .r 5
0.088
0.21
r.300
I3-330
130-260
920-r,300
2r-66
40-4,000
< 0.3
* T h e s ed a t a a r e t a k e n f r o m H . Y a s h u d a , " P o l y m e r H a n d b o o k , "
J . B r a n d u p a n d E . H . I m m e r g u t ( e d s . ) ,V l 3 f f , I n t e r s c i e n c ep u b l i s h e r s ,N e w y o r k ,
1 9 6 6 ;G . J . v a n A m e r o n g e n ," E l a s t o m e r sa n d P l a s t o m e r s , "R . H o u w i n k ( e d . ) , v o l . I , p p . 3 l O f f , E l s e v i e rP u b l i s h i n gC o m p a n y ,A m s t e r d a m , 1 9 5 0 1
R.p.
Bringer, paper presented at Societyof AerospaceMaterials and ProcessEngineers, St. Louis, May 7-9, 1962 (fluorocarbon data, in part),
Ethylene
p r o p y l e n er u b b e r : " N o r d e l a n E n g i n e e r i n gP r o f i l e , " E . l . d u P o n t d e N e m o u r sa n d C o . , E l a s t o m e r C h e m i c a D
l ept., Wilmington, DE., and Du pont
bulletin T-38 (Teflon FEP).
Poly(methyl methacrylate)
Acrylics:
Pliofilm, plasticized; rubber hydrochloride
Saran; polyvinylidene chloride
Polyvinyl chloride
Polystyrene
Polypropylene
Polyethylene,high density
Polyethylene,Iow density
Olefin polymers:
Myhr Ipoly(ethyleneterephthalate)]
Polycarbonatepoly(4,4' -isopropylidene
diphenylenecarbonate)
Nylon 6 [poly(6-aminocaproic acid)l
Polyamidesand polyesters:
Kel-F, crystalline (polychlorotrifluoroethylene)
264
AND ELASTOMERS
PLASTICS
.f---------1
i
)
/-,tFig. III.l.
Lop fillefweld
P l a s t i cw e l d i n g t o r c h .
D o u b l eV b u t i
weld
Corner
weld
{o)
(b)
Metal clamPtngstrrPS---.
a-
aPrast,cl
\nz/ ,z
vilw
A-JIP
t--------------T
tl
,-Hot ptate
ll
(c)
Fig. III.2.
Plastic welding practice. (a) Some typical welds. () Technique for feeding rod into
weld. With the rod bent back into a 45o angle, it is easyto heat and the rod is forced into the seam.
The torch should be fanned between the rod and the parts being welded, with somewhat greater
concentration on the latter. (c) An edge seal accomplishedon a hot plate.
suitable for the construction of simple, smooth shapesand is particularly successful with poly(methyl methacrylate) sheet stock.
As mentionedearlier, many thermoplasticmaterialsdissolveor becometacky
in the presenceof a solvent, and this providesthe basisof solventcementing. The
edgesto be joined should be well mated; one of the edgesis then soakedfor
about 5 min in the solvent. The part is removed from the solvent, and excess
liquid is allowedto drip off. While still damp, the part and its mate are lightly
PLASIICS
CELLULAR
265
F i g . I I I . 3 . J o i n i n ga n d s e a l i n gt h e r m o p l a s t i ct u b i n g . ( a ) E n d - t o - e n ds e a lb e t w e e nt u b e so f i d e n t i c a l
diameter; (b) end-to-end seal between tubes of different diameter: (c) closed-endsea!.
clamped together. When clear plastic is used, the joint should be transparent
and nearly bubble free. Solvent sealing is especiallyuseful in the fabrication of
parts from cast poly(methyl methacrylate) sheet stock.
Most of the common machining operationscan be performed on plastics
which are not too soft or too brittle to withstand working. Plasticsdo not dissipate heat as effectivelyas metals, so care has to be taken to avoid overheating.In
the caseof Teflon, poisonousfumes may be given off by the excessivelyheated
plastic; and many of the thermoplasticscan be heated to the point that they flow
and gum up. In general,overheatingcan be avoidedby employingsharp drills
and cutting tools and by appropriateadjustmentof working rates.Heat dissipation can be increasedby drilling with an in-out motion, and inert coolants,such
as water or water-oil emulsions.mav be used.
Plnsrcs
lll.2 cELLUTAR
At one time or another practically every plastic and elastomerhas been processedin a cellular form. Only two of the most commonly encounteredfoamed
plastics will be considered here: styrofoam and foamed polyurethane. Both of
266
PLASTICS
AND ELASTOMERS
thesematerials have low thermal conductivity and are very useful as low-temperature insulators.
While unaffected by water, styrofoam is dissolvedby many organic solvents
and is unsuitablefor high-temperatureapplicationsbecauseits heat-distortion
temperature is around 77oC. Molded styrofoam objects are produced commercially from expandable polystyrenebeads, but this processdoes not appear attractive for laboratory applications becausepolyurethanefoams are much easier
to "foam in place." However, extruded polystyrene foam is available in slabs
and boards which may be sawed,carved. or sandedinto desiredshapesand may
be cemented. It is generally undesirableto join expanded polystyreneparts with
cementsthat contain solventswhich will dissolvethe plasticand thus causecollapseof the cellular structure. This excludesfrom use a large number of cements
which contain volatilearomatic hydrocarbons,ketones,or esters.Somesuitable
cementsare room-temperature-vulcanizing
siliconerubber (seebelow) and solvent-freeepoxy cements. When a strong bond is not necessary,pol)ryinyl-acetate
emulsion (Elmer's Glue-All) will work.
Urethane foams may be rigid, semirigid, or flexible dependingon the ingredients and their proportions. The rigid urethane foams generallyswell in the presence of organic solventssuch as benzene,carbon tetrachloride, and acetone;
however,exposureto thesesolventsand subsequentdrying has little effect on the
foamed plastic. Some of the flexible foams are more solventsensitive,but this
doesnot preclude the use of most cements.Flexible expandedurethanetubing is
commerciallyavailablein a variety of sizes.6It providesa simple and efficient
method for the insulation of tubing which carries refrigerants. For example, it
has proven successfulfor the insulation of liquid nitrogen lines.
Foamed-in-placepolyurethaneis preparedby allowinga polyol Ipoly(ethylene
glycol), polyesteralcohols,etc.] to react with a diisocyanatein the presenceof an
amine catalyst. The gas which creates the foam may be a dissolved material,
such as a Freon, which volatilizes during the exothermic polymerization reaction.? A second method involves the use of water in the reaction mixture; this
hydrolyzespart of the isocyanateto produce an amine and CO2 gas. The Freonformed material is preferred for the insulation of low-temperature apparatus
becausethe thermal conductivity of the foam is greatly reduced at low temperatures by the condensationof the Freon in the cells. It is probable that the longterm effectivenessof this phenomenon must be maintained by surrounding the
foamedplastic with an airtight enclosurewhich will preventdiffusion of air into
and Freon out of the cells.
bPolyurethaneand polyvinyl foamed tubing for insulation are available from refrigeration supply
houses.
TThe ingredients for the preparation of polyurethane foam
are available from many companies, including the Perlon Corp., Lyons, IL, and American Latex Products, Hawthorne, CA.
PROPERTIES
OF SPECIFICPLASTICS
267
plAsTrcs
lll.3 pRopERIrEs
oFspEcrFrc
A. ACrylics. This group of clear thermoplastic materials is frequently encountered under the trade name Plexiglas(Rohm and Haas). The most common
member of the series,poly(methyl methacrylate),has a softeningpoint of l24oC,
at which temperature sheet stock, rods, and tubing may be formed into special
shapes.In addition, the plastic may be machined;however,carehas to be taken
to avoid overheating. Cast poly(methyl methacrylate)sheetstock may be bonded
by means of a solvent such as methylene chloride or 1,2-dichloroethane.
Giauque and co-workers used a cement composedof equal volumes of methyl
methacrylate monomer and dichloromethane. This is used exactly like the pure
solvent cements. After the lightly clamped parts had dried for a few hours, the
joint was further cured and annealed by heating the part to 50oC for about 1
day. It was found that a joint of this sort gavereliable vacuum-tight performance
at liquid helium temperature.s
Ploslics. Polyvinyl chloride is often fabriB. Chlotinoled Hydtocorbon
cated into sheets and tubing. Some formulations are reasonablytransparent.
Generally, plasticizersare included in the formulation to increasethe flexibility,
and tubing of this sort is a familiar laboratory item under the Tygon trademark.
A number of formulations are available, but one of these, Tygon R-3603, is recommended for general laboratory use. It makes a good seal with glass tubing
and is claimedto havea vapor pressureof 10-7 mm at 21'C. The amount of gas
desorbed by polyvinyl chloride is very low in comparison to rubbers. Furthermore, the data in Table III.1 show that polyvinyl chloride has a lower permeability to atmospheric gasesthan rubber, so healy-walled Tygon tubing is to be preferred to rubber when a flexible vacuum connection is required. While this
tubing is less susceptibleto deterioration than most rubber tubing, it tends to
stiffen and become milky in appearanceafter long exposureto water. It is essentially inert with aqueous acids and alkalies but is attacked by most organic solvents,as well as Cl2, HCl, and BCl3.The R-3603formulation becomesbrittle at
-45oC and loses much of its strength around 93"C. Rigid polyvinyl chloride
pipe is availablefrom hardware and plumbing suppliers.It is easilycut with a
saw and may be joined to elbows, T's, and other fittings by means of a special
cement. The grade which is made to carry drinking water has a low content of
volatiles and has been found suitable for rough- and medium-vacuum systems.e
Polyvinylidinechloride (Saran)is a tough plasticwhich is extensivelyused in
laboratorydrainpipes.This form of the plastic is rigid, but flexible transparent
films are usedwidely in food packaging.Polyvinylidinechloridebecomesbrittle
at l0"C and losesmost of its strengthat77oC.It has unusuallylow permeability
8 W . F . G i a u q u e , T . A . G e b a l l e , D . N . L y o n , a n d J . J . F r i t z , R e v . S c i .I n s t r . , 2 3 , 1 6 9 ( 1 9 5 2 ) .
e R . L . H a r t m a n , R e v . . S c i .I n s t r . , 3 8 , 8 3 ! ( 1 9 6 7 ) .
268
AND ELASTOMERS
PLASTICS
to gasesand is chemically attacked by only very strong oxidizing or reducing

agents.The solventresistanceis fairly good, and thereforesolventbonding is not
easy. Both edgesto be bonded should soak in the solvent (preferably warm) for
an extendedperiod of time before they are joined. Cyclohexanone.
o-dichlorobenzene,and dioxane are suitable for solvent bonding. Epoxies form string
bonds to vinylidine chloride, and welding or heat-sealingis quite successful.
C. Epory Resins. The epoxy resins are thermosetting plastics which have
great strength and the ability to form tenacious bonds with most surfaces.Furthermore, the cured resin is resistantto many solventsand chemicals.(Some
epoxy resins are decomposedby acetic acid, and all are attacked by very strong
oxidizing agents.)Becauseof this combinationof properties,epoxycementsare
frequently used to bond metal, glass,wood, and plastics.
Epoxy resins tend to outgas under vacuum, primarily through the slow desorption of moisture and low-molecular-weightorganic material. However,good
epoxy cements which are compounded without filler materials or solventshave
acceptable outgassing rates for high-vacuum applications.r0Another property
which must be anticipatedfor some applicationsis the high thermal expansion
coefficient of the cured resin. Becauseof this property, a glass tube which contains a solid plug of the cured resin will often break when heated or cooled.
The basic ingredient in the epoxy resin is a viscouspolymer which generally
contains two epoxide groups
o
(-o -cH 2 -cH - iH- l
per molecule.The further polymerizationof this resinto a hard infusiblemassis
brought about by mixing it with a curing agent (also called a hardener or a catalyst)just prior to application. The curing agentsvary in compositionand mode
of action, but one common type involvestertiary amines which catalyzethe attack of one epoxide group on the next to interlink the original resin through
-O-(CH2-CH(R)-O),
groups. Reactivecuring agents,such as primary and
secondaryamines and alcohols, are also employed and are incorporated into the
polymer during the cure. The proportions of resin to curing agent recommended
by the manufacturer should be followed with reasonableaccuracy to avoid an
incompletely cured product or an excessivelyfast and exothermic cure which
' o T h eA r a l d i t e r e s i n s( e . g . , A r a l d i t e I a n d l 0 l ) m a n u f a c t u r e db y C i b a P r o d u c t sC o r p . , S u m m i t . N J .
and the Epon Adhesivesmanufactured by Shell Chemical Co., Pittsburgh, PA, are widely used in
v a c l l u m a p p l i c a t i o n s .K . S . B a l a i n a n d C . J . B e r g e r o n ,R e v . S c i . I n s r r . , 3 0 , 1 0 5 8( 1 9 5 9 ) ,f o u n d t h a t
S t y c a s t2 8 5 0G T , m a d e b y E m m e r s o na n d C u m m i n g I n c . , C a n t o n , M A , g a v ea s e a lw h i c h w a s s u i t a b l e f o r v a c u u m a n d p r e s s u r ea p p l i c a t i o na t l o w t e m p e r a t u r e sW
. . R . R o a c h .J . C . W h e a t l e y ,a n d A .
C . M o t a d e V i c t o r i a , R e v . . 9 c i ./ r r s r r . , 3 5 , 6 3 1 ( 1 9 6 4 ) u s e d E p i p o n d 1 0 0 - A ( F u r a n e P l a s t i c s ,4 5 1 6
B r a z i l S t . , L o s A n g e l e s ,C A ) f o r t h e c o n s t r u c t i o no f v a c u u m - t i g h t ,l o w - t e m p e r a t u r ee l e c t r i c a l - f e e d
t h r o u g h s .I t s h o u l d b e n o t e d t h a t t h e o p a q u ee p o x yc e m e n t sw h i c h a r e s o l d i n h a r d w a r es t o r e so f t e n
c o n t a i nf i l l e r s .
PLASTICS
PROPERIIES
OF SPECIFIC
269
leavesno time for application. The uncured resin and hardenershould be handled in a well-ventilatedarea, and contact with the skin should be avoidedbecausethe aminesemployedin the hardenerare toxic skin irritants, and the resin
may cause dermatitis or an asthmalike condition with sensitiveindividuals.
"One-component"epoxy preparationsare also availablein which the catalystis
activatedby the applicationof heat.rr
D. FluorocolbOn Polymets. Four different fluorocarbonsaccountfor the
bulk of the laboratory applications:polytetrafluoroethylene,
Teflon PTFE; poly(chlorotrifIuoroethylene),KEL-F; tetrafluoroethylene-hexafluoropropylene
copolymer, Teflon FEP; and tetrafluoroethylene-perfluorovinylether copolymer, PFA. These polymersare inert with most chemicalsand solventsat room
temperatureand exceptionallyinert with oxidizing agents.They also have an
exceptionalresistanceto temperatureextremes.However,they are decomposed
by liquid alkali metals,solutionsof thesemetalsin liquid ammonia, and carbanion reagentssuchas butyllithium. Teflon retainssomeof its complianceat liquid
hydrogentemperature.The maximum temperaturewhich is recommendedfor
continuousserviceis 260'C for Teflon PTFE and PFA. and about 200"C for
Kel-F and Teflon FEP.
Teflon is an opaque, flexible solid with a waxy feel. It has a self-lubricating
quality which makes it a useful material for the packing in valves.However,it
tends to cold-flow, and must be well supportedon all sidesif it is to be used
under pressure.For this reason,Teflon O-rings have not been particularly successfulin high-vacuumapplications;but other typesof gasketswhich are supported better, such as simple flat gasketsbetweenflanges, are serviceable.The
flexibility and tendencyof Teflon to cold-flow may lead threaded parts in Teflon
to strip when they are under much force. Conventional Teflon PTFE can not be
heat-moldedor heat-sealed,and cementingis not very satisfactory.The principal method of fabrication in the shop is machining. Teflon FEP is similar in
most respectsto the conventionalmaterial; however,it is more transparentand
may be readilyheat molded and heat-sealed.Both typesof Teflon tend to outgas
when used in high-vacuumapparatus.
Kel-F is a somewhatmore rigid plastic than the Teflons and has much less
tendencyto cold-flow.Therefore,it will bear a continuousload and is preferable
to Teflon for threaded items. As with Teflon FEP, Kel-F may be heat-formed
and sealed(330 to 400 'C). It is somewhatmore susceptibleto swellingthan the
Teflons when it is contactedwith halogenatedand aromatic hydrocarbonsat
elevatedtemperatures.Also, it is slightly more susceptibleto oxidation at elevated temperature. However, at room temperature it gives satisfactoryperformancein the presenceof solventsand strongfluorinating agents.Kel-F is useful
in vacuum apparatusand is an excellentseatmaterial for metal valves.Porous,
s i n t e r e df i l t e r d i s k s o f K e t - F a n d T e f l o n a r e a v a i l a b l ec o m m e r c i a l l v . r 2
The
r r C i b a P r o d u c t sC o r p . S u n r m i t , N J .
r r P a l lT r i n i t v M i c r o C o r p . , C o r t l a n d , N Y .
270
PLASTICS
AND ELASTOMERS
former may be heat-sealedinto Kel-F apparatus. When heated in air, the toxic
gasesCOF2 and HF are evolvedabove400oC for Teflon PTFE and above350oC
for Teflon FEP. When machining either of these polymers or heat-sealingthe
latter, care should be taken to avoid overheating, and good ventilation is advised.
E. Nylon. The most common member of this group of polyamide plastics is
nylon 66 (polyhexamethylenediamineadipic polyamide), which has high
strength and a very low tendency to cold-flow. It has a self-lubricating quality
and is used for small bearings, gears, cams, and threaded parts. It has a greater
tendency to outgas under vacuum than most plastics. It is easily machined and
may be cementedwith epoxy resinsbut not with solvents.It is dissolvedby phenol and phenolic compounds and by concentrated acids. Nylon should not be
used for long periods above 149oCin the air, and it softensrather sharply about
100"C abovethis temperature.
F. Polyeslet Resins. Polyesterresins are made by the esterification of polyhydrolylic alcoholswith polybasiccarboxylic acids. High-molecular-weightpolyesterswith OH end groups are used in conjunction with isocyanatesto produce
many of the urethane plastics. When the polyester contains some unsaturated
sites, polymerization may take place to cross-link the polyestersand produce a
thermosetting plastic. This cure is initiated by a catalyst, such as an organic
peroxide, and acceleratorsare also included to promote the action of the catalyst. Fiberglass-reinforcedpolyesteritems have high impact resistanceand good
chemical and thermal resistance. Therefore, this material is used in the construction of fume hoods, dry boxes, and tanks for chemicals.The ingredientsfor
making polyester-reinforceditems are available from boat shops.
Clear polyestersheet stock and rods are availablel3and, like reinforced polyester plastic, may be drilled, sawed,and machined. This clear plasic is harder
than poly(methyl methacrylate) and much more solventresistantthan either poly(methyl methacrylate)or polystyrene.As with all thermosetting plastics, it may
not be heat-formedor solvent-bonded.However,bonding with epoxycementsis
satisfactory.This plastic is claimed to give continuous serviceat 80oC and intermittent serviceup to 150"C.
Transparent polyesterfilms such as Mylar (Du Pont) are much stronger than
most other plastic films. However,Mylar is not as resistantto oxidizing agents
and basesas are polyolefinfilms.
G. Polyolefins. The thermoplastichydrocarbonspolyethyleneand polypropylene are flexible, inexpensivematerials with good chemical resistance.Two
types of polyethylene are available: low density and high density. The former
containsbranchedpolymer chains which impart flexibility. The maximum usar 3 As e r i e so f m a t e r i a l s
o f t h i s n a t u r e i s p r o d u c e du n d e r t h e H o m a l i t e t r a d e n a m e b y G - L I n d u s t r i e s ,
I n c . , T h e H o m a l i t e C o r p . ( a s u b s i d i a r y . )l,l B r o o k s i d eD r . , W i l m i n g t o n , D E .
OF SPECIFICPLASTICS
PROPERTIES
271
ble temperature is about 80"C. High-density polyethylenecontains linear chains

and is more rigid, higher melting, less permeable,and more solventresistant
than the conventional material. The maximum usable temperature, about
120"C, is strongly dependenton the syntheticdetails. Polypropyleneis similar
to, but slightly more brittle than, high-density polyethylene.Polypropylenealso
is useful at higher temperatures than polyethylene.
All the polyolefinswill swellin the presenceof aromatic,aliphatic,and chlorinated hydrocarbons; this swelling increaseswith temperature, and at sufficiently
high temperatures dissolution results. They are attacked by strong, warm oxidizing agents, but are resistant to strong reducing agents like sodium in liquid
ammonia. Since they are not dissolvedby solventsaround room temperature,
polyethyleneand polypropylenecannot be solvent-bonded.Also, adhesivesdo
not generallyadherewell; however,as describedearlier in this appendix, heatsealing is very successful.
The aliphatic polyolefins are translucent to visible light and contain some
strong absorptions in the medium-infrared, but they are transparent through
most of the far-infrared and are therefore used as cell-window material for farinfrared spectroscopy.The use of low-density polyethylenein vacuum systems
has been describedby Duncan and Warren, who note that a l/s-in. wall thickness is sufficient to prevent collapse of tubing up to t/z-in. They found it relatively easy to evacuatetheir system to 10-6 torr after an outgassing period of
severaldays.raIn addition to the releaseof previously dissolvedgases,the vacuum is impaired by the permeation of the plastic by atmosphericgases;however,
theseauthorsclaim that this factor is not too serioussincea vacuumof 10-{ torr
could be maintained on their polyethylene system when it was left overnight
without pumping.rs Polyethylene is not desirable for low-temperatute traps
partly becauseof its low thermal conductivity and also becauseof its high brittlenesstemperature,which is about -50-- 120" and -37-- 120"C for low-density and high-density polyethylene,respectively.If a polyethyleneitem contains
internal stress, it is liable to break below the brittleness temperature.
Polystyreneis an inexpensivetransparent plastic which is often used in industry for the fabrication of parts by injection moulding. However, the tougher
acrylic plastics are preferable for the construction of laboratory apparatus. Polystyrene is soluble in many organic liquids and, if strain free, may be solventbonded by the use of chlorinated hydrocarbons, benzene, or toluene. Special
impact-resistant grades are available which are less susceptibleto solventsand
thus a little harder to solvent-bondthan the conventional material. Polvstvrene
also may be welded.
raJ.F. Duncan and D. T. Warren, Brit. J. Appl. Phys., 5,66 (1954).

rsFrom calculations based on permeability data and some laboratory tests, the authors believethat
the pressurerise quoted here is lessthan can be expectedwith low-densitypolyethylene.The permeability data in Table III.I show that considerableimprovement is possibleby using high-densitypolyethylene.
272
PLASTICS
AND ELASTOMERS
lll.4 ELAsToMERs
are generallymuch more
It will be noted from Table III.I that the elastomersr
permeableto gasesthan are plastics.Also, there is a greatertendencyfor elastomers to swell in the presenceof solvents.In addition to the basic polymer, most
finished-rubberproducts contain fillers, such as carbon black, and curing and
vulcanizingagents,such as sulfur. Other additivesmay be includedto improve
the flexibility (plasticizers)and decreasedamageby oxidation. The sulfur which
is used as a vulcanizing agent can lead to contaminationof chemicalsystems.
For this reason some sulfur-freerubber goods are available.It should also be
noted that siliconerubber is generallyvulcanizedwithout the use of sulfur.
lll,5 pRopERTrEs
oFspEcrFrc
ELAsToMERs
A. Buno N (Nifiile Rubbel). This rubber is a copolymerof butadieneand
acrylonitrile.As the nitrile content is increased,the resistanceto hydrocarbons
increases,but the low-temperatureflexibility decreases.
In general,nitrile rubber swellsmore in the presenceof polar solventsthan nonpolar solventsand is
not usuallysuitablein contactwith ketones,nitro compounds,and halogenated
hydrocarbons.lt is resistantto dilute inorganic acids and alkalies.The brittlenesstemperature of formulations which contain low percentagesof acrylonitrile
(about 20%) is about -55oC, while 36 % acrylonitrileleadsto an increasein
brittlenesstemperature to -27oC. On the other hand, softenersmay be included in the formulation which allow the brittlenesstemperatureto be reduced
to about -54"C for the high-nitrile-contentrubber. Use above120"C is not recommended. Nitrile O-rings and gasketsare extensivelyemployedfor applications which require resistanceto hydrocarbons.From the data in Table III.l it
willbe noted that the permeabilityof Buna N to moistureis high, but Buna N Orings are used with successon vacuunl systems,and both static and dynamic
sealsare possiblebecausethis rubber has good resistanceto abrasionand coldflow.
B. Butyl Rubber. Butyl rubber is a copolymerof isobutylenewith a small
amount of isoprene. The outstanding characteristicsof this rubber are its low
permeabilityto gases,high strength,and resistanceto oxidation. Becauseof the
low permeability,butyl rubber O-rings are useful in high-vacuumservice,and
butyl rubber glovesare desirable for use in inert-atmosphereglove boxes. Butyl
rubber tends to stiffen rapidly as the temperature is lowered so that it losesmuch
of its resilienceabovethe brittlenesstemperature,which is about -45oC. Use
aboveabout 100oCis not recommended.Butyl rubber swellsexcessively
in conrAdditional information on the properties of specificelastomersmay be found in J. Brandup and E.
H . I m m e r g u t , E d s . , P o l y m e rH a n d b o o k , 2 n d e d . , ( N e w Y o r k : W i l e y . 1 9 7 5 ) .
PROPERTIES
OF SPECIFIC
ELASTOMERS
273
tact with aliphatic, aromatic, and chlorinated hydrocarbons.Its resistanceto

ketonesis satisfactory,and contact with siliconeoils and greasesdoesnot lead to
swelling.It is attackedby hydrogensulfide, halogens,and basesbut is
excessive
reasonablyresistant to acids.
Neopreneis a polymer of 2-chloroC. Neoprene (Polychloloprene).
1,3-butadiene.It has good resistanceto aliphatic hydrocarbons(not as good as
Buna N, however).Much more swelling is noted with halogenatedhydrocarbons, aromatic hydrocarbons, and carbon disulfide, but satisfactory performanceis possiblein the presenceof thesesolvents.This rubber may be exposed
to all concentrated acids except nitric without extensive damage. Neoprene
swellsexcessivelyin the presenceof ketones. The brittle temperature is a sensitive function of the amount of monomer other than chloropreneused in formulating the rubber; also, plasticizersare sometimesadded to lower the brittle
point, which is ordinarily about -40"C. The upper usefultemperatureis about
150oC;however,it is inadvisableto heat neoprenegasketsabove90"C, since
they tend to take a permanent set around this temperature. Neopreneis still used
as an O-ring and gasketmaterial in high-vacuumsystems,but other elastomers
have taken its place in most vacuum and laboratory applications.
Rubbel.
D. Ethylene-Ptopylene
Ethylene-propylene rubber, as the
name implies, is a copolymerof ethyleneand propylene.This particular rubber
has verygood resistanceto polar organiccompoundslike ketones,ethers,acetic
acid, and amines.It alsowithstandssiliconeoils and greases,dilute acids,alkalies, and metal solutionsin liquid ammonia. However,it swellsconsiderablyand
losesits strength in aliphatic, aromatic, and chlorinated hydrocarbons.It is
claimed to be serviceablefrom -54 to 149"C. This elastomer is very attractive
for general laboratory O-ring ware. It also has good abrasion resistanceand tensile strength, so ethylene propylene rubber O-rings are suitable for dynamic
seals.The permeabilityof this rubber is fairly high (Table III.I).
E. Fluolocorbon Rubber. The most familiar rubber in this seriesis VitonA (DuPont), which is a copolymerof hexafluoropropylene
and 1,1-difluoroethylene. This material is the best generalelastomerfor O-rings and gasketsto be
used in high-vacuumwork. It will withstandtemperaturesfrom -29 to 205"C;
and it is resistantto acids and halogenated,aromatic, and aliphatic hydrocarbons, and many metalloidhalideslike BClj. However,it swellsand breaksdown
in contact with oxygenated and basic solventssuch as ketones, ethers, esters,
amines, and ammonia. Acetic and chlorosulfonicacids also attack Viton-A.
This rubber is not recommendedfor continuoususe in aqueousbasic media. It
will be noted that Viton-A and ethylene-propylene
rubber complement each
other rather well, sincethe former is resistantto hydrocarbonsand many oxidizing agentsbut attacke.dby certain polar organic solvents,while the latter rubber
has the opposite characteristics.
274
AND ELASTOMERS
PLASTICS
A fluoroelastomer manufactured by Du Pont called Kalrez, has mechanical

properties and resistanceto oxidants which are similar to those of Viton. In contrast with Viton, Kalrez has good resistanceto polar moleculessuch as amines,
ethers,ketones,and esters.Kalrez is unique among the elastomersin its toleranceto both polar and nonpolar solvents.The cost of O-rings made from Kakez
is very high, but for certain critical applications this cost can be justified because
of the outstanding range of solvent tolerance.
F. Notulol Rubber.
Natural rubber products have low resistanceto hydrocarbonsand relativelyhigh permeabilityto gasesand moisture.Natural-rubber
goods are often more flexible than those made of synthetic rubber and have excellent tensile strength.
G. SilicOne Rubbel.
Siliconerubber hasoutstandingflexibility at low temperatures coupled with good resistanceto heat (about -95-230"C). Brief service up to 300oC is possible for most silicone rubbers. Plasticizersare not used
with this rubber, which is a contributing factor to the very low weight loss of
silicone rubber in high vaccum. These rubbers are generally resistant to nitric,
acetic, and hydrochloric acid but are attacked by concentratedH2SOa,concentrated base, and HF. Resistanceto aliphatic, aromatic, and chlorinated hydrocarbonsis variable.The principal weaknesses
of siliconerubber are high permeability to gasesand poor resistanceto tearing and abrasion.
Room-temperature-vulcanizing
silicone rubber (General Electric and Dow
Corning) is available at hardware stores and is very useful as an adhesiveand
sealant. Atmospheric moisture is necessaryto effect the cure, so broad areasof
impermeable materials should not be cemented with these preparations. The
uncured material evolves acetic acid, and the cured material appears to lose
someweight in high vacuum; but if usedwith moderation, it can be considereda
satisfactoryvacuum sealant for most chemical vacuum systems.
REFERENCES
GENERAL
Data sheetson the solvent resistanceof various plastics and rubbers are available from the primary
manufacturers. In addition, a number of O-ring manufacturers publish information on the
solvent and chemical resistanceof elastomers used in O-rings, For example, the Parker Seal
Company, 17325Euclid Ave. , Cleveland, OH, publishes a Seal Compound Manual which contains this information.
Diels, K., and R. Jueckel (H. Adam and J. Edwards, trans.), 1966,Leybold Vacuum Handbook,
Pergamon, New York. This is an English translation of the secondGerman edition. It contains
information on the gas desorption and mechanical properties of plastics and elastomers.
Evans, V., 1966, Plastics as Corrosion-resistantMaterials, Pergamon, New York.
Newmann, J. A., and F. J. Bockhoff, 1959, Welding of Plastics, Reinhold, New York.
SPI PlasticsEngineering Handbook, 1976,4th ed., Van Nostrand Reinhold, New York. This book is
concetned with the commercial production of plastic items. However, it contains some information which is useful for the fabrication of plastic items in the laboratory or shop.
METALS
When metal apparatus is designedfor chemical applications, it is usually necessary to consider corrosion and heat resistanceas well as easeof fabrication. In
this appendix these topics ate discussedat a level which should help the experimentalist to specify the correct materials and construction procedures.No details of shop practice are given. The interested reader may pursue this topic in
the general referencescited at the end of this appendix, and in Chapter 10.
Except for a few very hard and very soft metals, intricate shapesmay be machined from heavy metal stock. Parts with thin metal cross sectionsfrequently
can be constructed from tubing or sheet stock which may be bent and formed
into a variety of shapes.
Permanentjoints may be formed by soldering or welding. Soldersmelt below
the melting temperature of the parts being joined, and must wet the surfacesof
theseparts if a bond is to be achieved.A flux is employedto promote this wetting
process,and the residual flux must generallybe removedbefore the parts may be
used. For example, a borate flux is frequently employed for hard soldering
(brazing and silver soldering). This flux forms an adherent glassydeposit which
will slowly outgas in vacuum. Welding is performed by melting the parts to be
joined at the seam and simultaneouslymelting a "filler" rod of the sameor very
similar material into the seam. Arc or gas welding may be used with most
metals, but the least porous welds are obtained by inert-gaswelding (Heliarc). In
this process,an electric arc createsthe elevatedtemperature, while a stream of
helium or other inert gas blankets the molten area. When possible, inert-gas
welds should be specified for vacuum apparatus. When the apparatus is large
enough to be welded from the inside, this mode of welding should be specified
becauseit avoids the presenceof rifts and voids which may slowly outgas. Of
necessity,small items must be welded from the outside, but this is often quite
acceptablebecausethe material is thin. When it is not thin, a bevel should be
275
276
METALS
provided so that the seam is thoroughly penetrated. Somegood and bad welding
practicesare illustrated in Fig. IV.1. Often an oxide film or scaleis left by welding or soldering; this should be removed from parts which are used in high vacuum becausemetal oxides slowly outgas, becauseof the desorption of moisture.
The fabrication from seamlesstubing is describedin Section10.1.
lV,4 PRoPERnEs
METALs
oFsPEcrFrc
A. Aluminum. Aluminum(mp 660"C),is a tight,softmetalwith fair resistanceto corrosionby laboratoryfumesexcepthydrogenhalidevapor.It hasexcellentelectricaland thermalconductivity.Many aluminumalloysare used;
somemay be softenedby heatingto 550'C and quenchingin water.The metal
subsequently
work-hardens
or hardensuponstandingfor a fewhours(that is, 24
ST and 14ST alloys),andall aluminumalloysareeasilymachined.
Thesealloys
+__,
l-
r----rt'------l
vo cuum
tr
tJ
Vocuum \
--]
L-J
Yl"iiJl
:l tr-
"';\1*1
---tl
*9
vn::::)J_
Ira
--S"
\rConlinuousweld
Q T r o p p e dv o t u m e
lncorrect
-l
#jjI{
Vocuum 5
-l
u"j"r^fL ,
+=
=-
Nlntermrtient weld
Dirf trop
I
Correct
Fig, W.1.
Welding practice for vacuum apparatus. Note that the general approach is to weld on
the inside and avoid dead spaceswhich may present leaks that are extremely hard to locate.
PROPERTIES
METALS
OF SPECIFIC
277
consistof more than 90% aluminum. Copper, magnesium,silicon, and transition metals are the most common alloying agents.Pure aluminum and most aluminum alloysmay be welded,but the techniqueis not easy.Aluminum soft solders are generally unsatisfactory,but certain aluminum-containingeutectics
make suitablehard solders.Electrodepositionon aluminum is not practical,but
a tenaciousoxide coating may be formed by the anodizing process,which involveselectrolyticoxidation. The resultingcoatingmay be dyed(e.g., black dyes
are frequently used on parts used in spectroscopicwork).
The chemicalresistanceof aluminum is fair, but any chemicalwhich destroys
the protective oxide coating will lead to rapid corrosion; therefore, strong acids,
alkalies,and mercury must be kept out of contactwith aluminum.
B. Coppet.
Copper (mp 1,083"C), is a moderatelysoft metal which has a
high electrical and thermal conductivity. Electrolyticcopper, 99.9% pure, is
usedfor electricalwire; and free-cuttingalloys,containingsmall amountsof sulfur or tellurium, are commonly usedfor sheetor bar stock. Copper may be machined, brazed, and soldered.However,becauseof its toughness,it is much less
easyto machine than brass. It tends to work-hardenbut may be annealedby
heating, followed by rapid quenching.
Copper is amalgamatedby mercury and attackedby strongoxidizing agents,
such as nitric acid, chlorine, and fluorine. However,the bulk metal forms a protectivefluoride coating and is suitablefor apparatususedwith fluorine and oxidizing fluorides.The presenceof ammonia promotesthe air oxidationof copper,
so copper and brassfittings should be avoidedaround NH3. Copper is attacked
by many sulfur-containingsubstancesand is slowlyattackedby most strong acids in the presenceof oxygen.
Alloys of copper and zinc are called brass, while bronzesare composedof
copper and tin. These alloys are generallyeasily machined, brazed, and soldered. Their chemical resistanceis somewhatbelow that of copper. For example, brass is slowly attacked by fluorine and oxidizing fluorides. Brazedjoints
are much strongerthan soft solder, and when used on well-matchedsur{aces,
the brasstendsto penetratethe joint and form a good. vacuum-tightseal.On the
other hand, the highly fluid nature of molten brassmakesit more difficult to fill
gaping holeswith brazing rod than with soft solder.
C. Gold. Gold (mp 1,063'C), is a soft, inert metalwith good electricaland
thermal conductivity.It is easilyplated onto metalsand vacuumevaporatedonto
various surfaces.Except for fused KOH and similar bases,strong oxidizing
agentslike aqua regia, and strong fluorinating agents,gold is chemicallyinert.
D. Indium. Indium (mp 157'C), is a soft metal which wets many surfaces
and retainsits ductility at very low temperatures.This combinationof properties
makes indium an excellentgasket material betweendissimilar materials. For
example, a gasket made of indium wire will give a vacuum-tightseal between
278
MEIALS
quartz and metal from room temperature to below 4 K. Indium is also used in
some special-purposesolders.It is attackedby cold dilute mineral acids, halogens, and other oxidizing agents, but is not affected by solutions of KOH.
E. lrOn. Iron (mp 1,535oC),is softer and somewhatmore corrosionresistant
than the commonly encountered alloys. Cast iron contains a separateiron carbide phase as well as carbon dissolvedin iron; in addition, other elementssuch
as silicon, manganese,sulfur, and phosphorus are generally present. Gray iron
and severalother grades of cast iron contain graphitic carbon as a secondphase
dispersedthoughout the casting. The presenceof graphitic phasesleadsto slow
outgassing, which may be objectionable for certain exacting vacuum requirements. Iron castings may be somewhat porous becauseof rifts and voids in the
granular structure. Such a casting is not suitable for vacuum work. Iron and
steel are not amalgamated or appreciably dissolvedby mercury; so iron or steel
containers are used to transport mercury, and steel is used in some mercurydiffusion pumps.
Steelcontainssome carbon, about2To, but considerablylessthan cast iron,
which contains over 5 % . Steel tends to becomebrittle at low temperatures, so it
is not recommenced for high-pressure cylinders which will be cooled to liquid
nitrogen temperature.
Slight variations in the constituents of iron or steel make them resistant to
strong bases,nitric acid, and so on, but the judicious choice of irons and steels
for specific chemical resistanceis not practical in the laboratory.
Stainless steels are iron-based alloys which contain more than l2To chromium. A common compositioncontains l8% Cr and 8% Ni, and is designated
as either 18:8 or type-304stainlesssteel.Unlike ordinary carbon steel,the stainlesssteelsin the 300 seriesdo not become brittle at low temperatures. Stainless
steel has a rather low thermal conductivity.It may be welded, brazed, or soldered and is machinable with somedifficulty. Type 303 is the easiestto machine.
While the chemical resistancevaries somewhat, stainlesssteel is fairly resistant to most acids and bases, is not amalgamated by mercury, and is generally
resistantto oxidizing agents.While it can be used in fluorine handling, Monel
and nickel are much better for this purpose. The resistanceof stainlesssteel to
atmospheric corrosion is an advantagein vacuum work becausea corroded surface tends to outgas.
Certain alloysof iron, nickel, and cobalt (Kovar, Fernico,etc.) havethermal
expansioncurveswhich nearly match those of borosilicateglasses,and a good
bond may be formed between the two. Kovar is similar to carbon steel in its
chemical properties. For example, it oxidizes when heated in air and is not wet
by mercury. It may be machined,welded.copperbrazed,and soft soldered.Silver solders should not be used with Kovar since they may causeembrittlement.
At low temperaturesKovar undergoesa phasetransformation,and the change
in expansioncoefficient below this temperature may be sufficient to causefailure
of a glass-to-Kovar seal. The transformation temperature usually is below
PROPERTIES
OF SPECIFIC
METALS
279
-78.5'C. The exact transformationtemperaturevariesfrom one batch of the

metal to the next and somesamplesof Kovar havetransformationtemperatures
below - 196"C. Another significantpropertyof Kovar is its low thermal conductivity.
F. Leod. Lead (mp 328'C), is a soft metal which finds use in gaskets,soft
solder,and radiation shields.While lead tank liners are usedin someindustrial
processes,
this metal is not attractivefor laboratorycontainers.
G. Nickel. Nickel (mp 1,453"C),finds its primary usein the constructionof
apparatusto handle fluorine and volatilefluorides.In this situationthe metal is
renderedpassiveby a fluorine coating. Nickel plating is easilyperformed and
provides a means of imparting corrosion resistance.The metal may be machined, silver soldered.copperbrazed, or welded.However,the weld should be
performedon clean surfacesbecausethe presenceof impuritiescontaininglead,
sulfur, phosphorus,and variouslow-meltingmetalsleadsto embrittlementand
failure at the weld.
Monel is a type of alloy containing about 70To nickel, with the remainder
mainly copper. Except for susceptibilityto nitric acid, Monel is generallysuperior to stainlesssteelin corrosionresistance.Monel is similar to stainlesssteelin
machinabilityand is welded like pure nickel.
H. Pollodium. Palladium (.np 1,552'C), is soft and ductile but workhardens.At elevatedtemperatures,the diffusionof hydrogenthrough palladium
is rapid, which forms the basisof a methodfor the purificationof hydrogen.The
best performanceis obtained from a palladium-silveralloy containing about
18% silverbecause,unlike pure Pd, this alloy doesnot undergoa phasetransition in the presenceof hydrogen.Palladium is not as inert as platinum and is
attacked by sulfuric and nitric acids.
l . P l o l i n u m . P l a t i n u m( m p 1 , 7 6 9 ' C ) ,i s a m a l l e a b l ea n d d u c t i l em e t a l w i t h
high chemicalresistance.Becauseof this resistance,it finds usein somelaboratory ware. lt is attackedby aqua regia, and, at somewhatelevatedtemperatures,
by sulfur, phosphorus,halogens,and cyanide(in the presenceof air). The coefficient of expansionfor platinum nearlymatchesthat of soft glass(flint glass),and
an adequatesealbetweenplatinum wire and soft glassmay be obtained.
J . S i l v e r . S i l v e r( m p 9 6 1 ' C ) , h a s t h e h i g h e s te l e c t r i c aal n d t h e r m a lc o n d u c tivity of any metal. It is used in making electricalcontactsand in the construcand both chemical
tion of some laboratory ware. It is easilyelectrodeposited,
and evaporationcoatingwith silverare possible.Silveris generallylessresistant
to attack by oxidizing agentsthan is platinum or gold. However,it is resistantto
fused alkaliesand fused alkali-peroxidemixtures.Therefore,it is usedto nrake
2BO
METALS
cruciblesfor NaOH-Na2O2fusions. At elevatedtemperaturesoxygen diffuses

through silver, and this property is occasionallyusedto purify oxygen.
Two types of silver solder are available.The soft-silversoldersare generally
alloysof silverwith lead, which, like the common tin-lead soft solders,melt below 400"C. The soft-silversoldershavethe advantageover the Sn-Pb varietyof
greaterresistanceto creepunder load. The hard-silversoldersgenerallycontain
copper as the primary alloying constituent.Thesesoldersgenerallymelt above
600'C. One common type of silversolder,AWP 355, is resistantto fluorine and
many fluorides.
(Tantalum mp 2,996'C). is an extremelychemicallyresistant
K. Tonlolum.
metal which is hard but ductile. Becauseof its high melting point and good corrosion resistance,tantalunr is frequentlyused as a containerfor high-temperature melts. It is attackedby HF and other fluorides,as well as sulfur trioxide and
nitrogen oxides.
L . T u n g s l e n . T u n g s t e n( m p 3 , 4 1 0 " ) ,h a s t h e h i g h e s tm e l t i n gp o i n t a n d l o w est vapor pressureof the nretals.The commonlyavailableform of the metal contains trace impurities which impart brittleness.Tungsten wire is occasionally
fibrous and therefore somewhatporous along the axis of the wire. Very pure
forms have some ductility. Tungsten is oxidized in air but is otherwisefairly
chemicallyinert. Mineral acids have little effect. The expansioncoefficientis
similar to Pyrex, so tungsten is frequently used in electricallead-throughsfor
glassapparatus.It is not wet by mercury.
REFERENCES
GENERAL
H o k e C o r r o s i o nC h a r t , H o k e I n c . . I T e n a k i l l P a r k . C r e s s k i l l ,N J . A c o m p a c tt a b u l a t i o nf o r c o m m o n
m e t a l sa n d p l a s t i c s .
L e e , J . 4 . , 1 9 5 0 ,M a t e r i u l s o l C o , r s t r u c t i o t r , l o C
r h e m i c a lP r c c e s sI n d u s t r i e s . M c G r a w - H i l l , N e u
Y o r k . I n f o r n r a t i o no n t h e c o r r o s i o nr e s i s t a n c e
o f n r a t e r i a l sa r r a n g e da c c o r d i n gt o t h e c o r r o s i v e
agenr.
M e t t l s H u n d b o o . 9 t he d . . V o l s . l - 8 . A m e r i c a nS o c i e t yf o r M e t a l s .1 9 7 8 - 8 5 .
M o o r e , J . H . , C . C . D a v i s , a n d M . A . C o p l a n . 1 9 8 3 ,B u i l d i n g S c i e n t i J i cA p p u r a r a s , A d d i s o n - W e s l e y , R e a d i n g .M a s s .
O b e r g . E . . F . D . J o n e s .a n d H . L . H o r t o n , l 9 l t 4 . M u c h i n e n " s H a n d b < n k . 2 2 n d e d . , T h e l n d u s t r i a l
P r e s s .N e r vY o r k . A r e f e r e n c eb o o k o n m a c h i n es h o p p r a c t i c ea n d p r o p e r t i e so f m e t a l s .
T r e s e d e r ,R . S . , I 9 8 0 , N A C E C o r r o s i t t t E
t n p i t t e e r ' sH u r t d b o o k . N a t i o n a l A s s o c i a t i o no f C o r r o s i o n
E n g i n e e r s ,H o u s t o n .
W t l d i n g H u r t d b o < t k , 5 t he d . . A n r e r i c a nW e l d i n g S o c i e t y ,N e r vY o r k , 1 9 6 7 .C o n t r i n s u s e f u ls e c t i o n s
o n t h e p r i n c i p l e so f u ' e l d i n ga n d u ' e l d i n gs p e c i f i cm e t a l s l i k e n i c k e l a n c ls t a i n l e s ss t e e l .
VAPORPRESSURES
OF PURE
SUBSTANCES
Vapor pressuredata are important in the identification,separation,and general

manipulationof known compoundson the vacuum line and for the characterization of new compounds.This appendixwas preparedwith theseapplicationsin
mind. It is introduced with a discussionof the use and limitations of several
analy'ticalexpressionsfor the representationof vapor pressuredata. A description of a least-squares
treatmentof vapor pressuredata for fitting to the Antoine
equation is then presented.Finally, a table of vapor pressuresat convenient
slush bath temperaturesis presentedtor 479 compounds.
REpREsENTATToN
V,'1 ANALvTTcAL
oF vApoR pRESSURE
DATA
Most of the widely usedvapor pressureequationshaveas their basisthe Clapeyron ecuation
dP
AH
dT
TAV
(1)
which is an exact thermodynamicexpression.AH is the molar heat of vaporization, and AV is the changein molar volume betweenthe condensedand gaseous
p h a s e s I. f i t i s a s s u n r e d
p h a s ei s n e g l i g i b l e
t h a t ( l ) t h e v o l u m eo f t h e c o n d e n s e d
, nd (3)the
b y c o m p a r i s o nt o t h a t o f t h e g a s ,( 2 ) t h e g a se x h i b i t si d e a lb e h a v i o r a
28tl
282
VAPORPRESSURES
OF PURESUBSTANCES
latent heat of vaporization is constant over the temperature interval of interest,

Eq. (l) may be integratedto yield the simple relationship
rogP:-ffir*u
(2)
or
_A
(3)
logP:;*u
When convertingto the absolutetemperaturescale ?, it is important to recognize the conventionOoC : 273.15 K. The constantsA and B in Eq. (3) are
determinedempiricallyfrom experimentaldata by plotting log P versus| / T and
taking the slopeas -A and the interceptat | /T : 0 asB. Equation (2) is found
to yield a fairly accuratefit to vapor pressuredata for highly volatilesubstances
and is often perfectlyadequatefor moderatelyaccuratedata below the boiling
point.
The heat of vaporizationvaries slowly with temperatureand eventuallybecomeszero at the critical temperature.In addition, the assumptionswhich were
used to approximateAV (ideal gas behavior and negligiblevolume of the condensedphase)are inaccurateat high pressures.However,the assumptionsare
adequatefor data of moderateprecision(about + lYo) in the I -760-torr range,
and in these cases the heat of vaporization may be determined from the .4
parameteras indicatedin Eq. (3). Of course,different,,4and B parametershave
to be determinedfor each particular phase(e.g., for the liquid, and for each
solid phase,if more than one exists).lf A andB are known for one phaseand the
heat of transition(fusionor solid-statetransition)is known, the heat of vaporization and its equivalent,the,4 valuefor the secondphase,may be calculated.The
new valueof B is then found by taking advantageof the fact that the vapor pressuresfor the two phasesare identical at the transition temperature.
When accuratevapor pressuredata are plotted as log P versus1,/T over an
appreciablepressurerange,it is usuallyfound that there is somecurvatureto the
plot. This defect in Eq. (3) is largely overcomeby an empirical modification
proposedby Antoine:
B
(4)
logP:A-
t+c
The introduction of a third constantC leadsto an improvedequationwhich has

been testedin somedetail and found to be the bestthree-parametervapor pressure equation for general use.r'2Usually the temperatureterm in Eq. (4) is in
degreesCelsius.Becauseof its simple form and generallygood accuracy,this
equation has been chosenfor use in someof the most extensivecompilationsof
l C . W . T h o m s o n .C h e n r .R e v . , 3 8 , I ( 1 9 4 6 ) .
rM. Kh. Karupet'yanta
s n d K u a n g - Y u e hC h ' u n g .C h e n t .A b s . , 5 3 . l 7 6 l 3 d ( 1 9 5 9 ) .
ANALYTICAL
REPRESENTATION
OF VAPORPRESSURE
DATA
283
vapor pressuredata (seebelow).Equation(4) is found to give

a generallysuitable
fit between30 torr and 3 atm, and it givesa much better fit
between50 and 760
torr' Thomson notesjh{ the accuracyis poor when the reduced
temperature
exceeds0.75 (?..d : T/T*). However,it is often much simpler
to usea second
Antoine equationabovethis temperature,adjustedso that
the two coincidenear
?."a : 0.75, rather than fit the entire set of vapor pressure
data with a singre,
more complex expression.The drawbacksof the equation in
the high-pressure
region are of little consequencein vacuum line work, where
pressuresgreater
than an atm are seldomattained. The deviationswhich
occur telo* l0 torr are
of more importance becauseit is often necessaryto extrapolate
data very far into
the low-pressureregionto estimatethe temperaturewhich
must be usedto trap a
component effectively. under these conditions, an
extrapolation based on
Eq. (3) is generallyreriabreand can be readily accomplishedgraphicaily.
The c value in Antoin-e'sequation appearsto be the teast
ciiticat parameter,
and someworkers use a fixed value of 230 for all compounds.
However,Thomson has found that there is a correlationbetweenc and the
boiling point of a
substance.For elements which yield monatomic vapors,
and foi subtances
which boil below - l50oC the correctionleadsto
C :
264 - 0.034 16
where/5 is the normal boiring point in degreescelsius.

For other compoundshe
finds
C :
240 - 0.19 r,.
The relationshipsare not exact, so if the data are good

it is better to determine
C directly.
Another rather simpresemiempiricarmurtiparameter
equationhas beenused
to fit vapor pressuredata:
-A
logP=f+BT+CT2+D
(s)
Multiplying through by ? and rearrangingleadsto

TtogP -
-A
+ DT + BT2 + cT3
The parameters.4through D in this equation are easily

fit by meansof a leastsquaresroutine. In severaltest casesit wasfound that
the ur" of fou. parameters
in Eq' (5) gives a slightly poorer fit to vapor pressure
data than does the threeparameterAntoine equation.
It appearsthat the variation of the heat of vaporization
with temperatureis
one of the primary sourcesof inaccuracyof Eq. (2),
and the extra empirical
parametersin Eq. (4) introducea variationof afl with
temperature.In a somewhat different approach, it is assumedthat the heat
of vaporizationis a rinear
function of temperature,and the remainingassumptions
invorvedin the deriva-
284
OF PURE
SUBSTANCES
VAPORPRESSURES
tion of Eq. (2) are retained.With theseapproximationsthe Clapeyronequation

may be integratedto yield the Kirchoff equation
logP:
(6)
+*B-ctogT
Nernst proposeda somewhatmore elaborateequation,which may be written
togP:
(7)
+*B-CtogT*DT
He found that C frequentlyis closeto 1.75,and it is the practiceof someworkers

to usethis valuefor all substancesand vary only,4, B andD . While Eqs. (6) and
(7) give a better fit to the vapor pressuresof somecompoundsthan the Antoine
equation, the accuracyis more often not quite as good. Also, the estimationof
vapor pressuresby the extrapolationof Eqs. (6) and (7) beyondthe highestpressure of the original data appearsto lead to more error than one would obtain
upon extrapolationof the Antoine equation. Finally, Eqs. (6) and (7) are much
more difficult to usewhen one wishesto find the temperaturecorrespondingto a
given pressure.
Many other vapor pressureequationshave been used; the interestedreader
may refer to Partington'streatisefor someof these.3One of the most successful
equationsfor the faithful reproductionof vapor pressuresfrom low pressuresto
the critical pressurewas devisedby Frost and Kalkwarf.a
l o- g p : A + B = * C l o g T + +
I
t'
This equation is appropriatefor iterativecomputer calculation.Simplifications

have been proposedby Thodos.s
pRocEDURE
V ,2 LEAsI-souAREs
FrrTtNG
FoRTHE
ANToINE
EOUAIION
When precisevapor pressuredata are available,it is desirableto employ a leastsquaresfitting procedureto the Antoine equation.The formulation of this problem is availablein detail in the literature and will be summarizedhere.b
rJ. R. Partington, An Adtunced Treutise
on PhysicatChentistry, Vol. 2 (London: Longmans, Green,
l9sl), pp.265ff.
{ A . A . F r o s ta n d D . R . K a l k u a r f , C h e n . P h y s . , 2 l
J.
,264 (1953).
5R. C. Reid and T. K. Sherwood.
T h e P r o p e r t i e so J G u s e su n t t L i q u i d s , 2 n d e d . ( N e w Y o r k : M c G r a w - H i l l , 1 9 6 6 ) ,C h a p . 4 . R e f e r e n c e sa n d a d i s c u s s i o no f t h e F r o s t - K a l k w a r fe q u a t i o n n r a y b e
f o u n d h e r e .A l s o , a r a t h e r c o m p l e t ec o m p a r i s o no f v a r i o u sr e d u c e de q u a t i o n si s p r e s e n t e dT. h e s ea r e
m o s t u s e f u la t h i g h p r c s s u r e s .
o C . B . W i t l i n g h a me t a l . , J . R e s . N a t . B u r .
9td.,35,219 (1945).
FORTHEANTOINE
EQUATION
FITTING
PROCEDURE
LEAST.SQUARES
A.
Detivolion of Equolions.
285
Equation (4) may be rearrangedto the form

(8)
(A-togP)(C+t)-B:0
If the left side of Eq. (8) is multiplied out and a changeof constantsmade. this
equation becomes
(9)
ut*h*clogP-rlogP:0
- (AC - B), and C: -C.

w h e r ea : A , b
S i n c eE q . ( 9 ) i s l i n e a r i n t h e c o n s t a n t sa , b , a n d c , d a t a m a y f i t t o t h i s e q u a t i o n u s i n g l e a s ts q u a r e s .T o r e d u c er o u n d i n ge r r o r s , i t i s e a s yt o m a k e i n i t i a l
, hichwill be
e s t i m a t e so f a , b , a n d c b y u s i n g E q . ( 9 ) . T h e s ei n i t i a l e s t i m a t e sw
b6, and c6, m] be calculatedfrom threeexperimentalpoints, preferacalleda1y,
bly spreadout overa substantiaIpressurerange.This resultsin the generationof
three simultaneouslinear equationsof the form of Eq. (9).
S u b s t i t u t i n ge s ,b s , a n d c 1 i1n t o E q . ( 9 ) g i v e s
Fo:
a o t+ o + c o l o g P - r l o g P :
(10)
which may be added to and subtractedfrom Eq. (9) to obtain

(11)
at**7logP*Fo:g
w h e r e a : ( a - a i , 0 : ( b - b d , ? = ( c - c o ) ,a n d F p i s d e f i n e d i nE q . ( 1 0 ) .
E q u a t i o n( l l ) i s t h e f o r m o f t h e A n t o i n ee q u a t i o nu s e dt o s e t u p t h e n o r m a l
e q u a t i o n sf o r t h e l e a s t - s q u a r ecsa l c u l a t i o n :
aE(ti)2
-t
BDti
* " y D r il o g P i :
E76ti
qDtt
+ 0(1)
* ' y El o g P i :
L.f'n
(12)
a D t i l o g P ' * B D l o gP i * 7 I ( l o g P i ) 2 : L . f s l o g P i
: estt + lr{r+ c0 log Pt - ti log Pi .
where.l'iy
Theseequationsare solvedsintultaneouslyfor a, 6, and'y, the resultingvaluesusedto find a, b, andc, and finally thesevaluesare usedto find,4, B, ard C.
The entire procedureis easilycarried out on a hand-heldcalculator,as demonstratedin the examplebelow. If many calculationsneedto be done, thesecalculations can be done on a computer.
B. ExompleColculofion:Ihe AnfoineEquotionfor Woter. TableV.1

fists the vapor pressuredata for water from 20 to 80oC. Valuesof as, b6, and c6
are calculatedfrom the data at 20, 50, and 80oC by solvingthe following three
simultaneousequations:
a o ( 2 0 )* b s * c s l o g ( 1 7 . 5 3 5:) 2 4 . 8 7 8
a o ( 5 0 )* b 0 * c o l o g ( 9 2 . 5 1 ) :
98.309
ao(80)* b0 I co log(355.1) : 204.028
286
VAPOR
PRESSURES
OFPURE
SUBSTANCES
ao:
bo :
co:
8'07577
154.140
-233.761
Next, the summationsappearingin Eq. (12) are found for alr of the data points.
This leadsto the set of three simultaneousequations:
a(87,420) + P(1s50) + {3224,87) - - 19.2937

a(1550) +B(1)
+ ^ y ( 6 0 . 1 9 4 0 )-:0 . 1 0 9 8 6
a ( 3 2 2 4 . 8 7+) 0 ( 0 0 . 1 9 4 0
+ ) y ( 1 2 1 . 5 3 6 ) :- 0 . 5 1 1 0 9
e : -0.00307
0 : 0.00002
^Y= 0'07716
From this we obtain
o : 8.07270
b : 154.140
c : -233.684
Finally,reversing
the first changeof constants
yieldsthe Antoineconstants
A : 8.07270
B : 1732.32
C : 233.684
and, therefore,the Antoineequation
logP:8.07270-
1732.32
t + 233.684
By comparingthe secondand third columnsof rabre v.r. it is seenthat the

agreementbetweenthe experimentaland calculatedwater vapor pressurevatues
is quite good.
V,3 coRRELAnoN
ANDEsTtMATtoN
oFvApoRpREssuREs
occasionallyone has availablea singlevapor pressurepoint-for example,the
normal boiling point-but wishesapproximatevapor pressuresat other temperatures. some of the simplestschemesare basedon Eq. (2). If the compound is
not likely to self-associate
through hydrogenbondsor other specificinteractions,
the Trouton constant(aH,.uo/T:6,,,1in
) is approximately2l catlmolo. Substitution
of this value into Eq. (2) showsthat the vapor pressureis relatedto normal boiling point T5 by Eq. (13).
: +.0(r logP",n,
+)
(13)
AND ESTIMATION
OF VAPORPRESSURES
CORRELATION
287
of woler
Ioble V.t. ExperimenfolondColculofed Vopor Pressure
P".o(torr)
20
22
24
26
28
30
32
34
36
38
40
^1
AA
4b
48
50
52
54
56
58
60
62
64
66
68
'70
72
74
76
78
80
17.535
19.827
22.38'7
25.209
28.349
31.824
35.663
39.898
44.563
49.692
55.324
61.50
68.26
75.65
8 3 . 7I
92.51
102.09
112.51
r2 3 . 8 0
136.08
149.J8
163.77
179.31
r9 6 . 0 9
214.t7
233.7
254.6
277.2
301.4
JZ / .-'t
355.r
P."1,(torr)
t7.541
19.836
22.389
25.224
28.366
3r . 8 4 3
35.684
39.919
41.584
4 9 . 71 2
s5.343
61.51
68.27
75.66
83.72
92.5r
r02.08
112.48
123.78
136.04
149.32
I63.69
179.21
195.98
2r4.06
233.5
254.5
2'77.0
301.2
327.2
355.0
While very approximate,this relationshipis usefulfor order-of-magnitudeestimation of vapor pressures,u'hich is often adequatein establishingtrial conditions for trap-to-trapfractionation.For this purpose,a family of curvesbasedon
E q . ( 1 3 ) i s p r e s e n t e di n F i g . V . 1 .
Another useful approximation is the Ramsay-Youngrule, which statesthat
for two relatedsubstances,the ratio of the temperaturesat which they exert the
samevapor pressureis constant.TThat is,
-The
n a t u r e o f t h e a p p r o x i m a t i o ni n v o l v e dh e r e i s d e s c r i b e db y S . G l a s s t o n e ,T e x t b o o kt t l P h v s i c u l
C h e n t i s t r y , 2 n de d . ( P r i n c e t o n ,N J : V a n N o s t r a n d ) .p . 4 5 4 .
288
VAPOR
PRESSURES
OFPURE
SUBSTANCES
/T
'\
/T
(j1)p:('o
\p,
\ rB /
\rBl
Vapor pressuredata often can be found for a substancesimilar to the one for
which a singlevapor pressureis available,and the tabulationby Stull (seebelow)
is handy for this purpose,sincethe data are given at a seriesof fixed pressures.
A better estimateof vapor pressuresfor a varietyof organic compoundscan
be made by means of the correlationsof Hass and Newton. This procedureis
easiestto use if the normal boiling point is known, but it may be used in an
iterativefashionif the vapor pressureis known at an arbitrary temperature.The
descriptionis availablein the Handbook of Chemistryand Physics,so it will not
be repeatedhere.8
Finally, we note a simple but crude rule which is usefulfor quick estimates:
For every l0oC rise in temperaturethe vapor pressureapproximatelydoubles.
350
,Z-
300
co
-a
250
(c
-l
,--
{'/
200
150
100
50
z2
_l
ffi
)<
,6
'z
-/
50
100
150
200
zso
300
350
400
450
500
Ta,oK
F i g . V . l . A p p r o xi m a t e r e l a t i o n s hi p s b e t w e e nt h e v a p o r p r e s s u r ea t a n a r b i t r a r yt e m p e r a t u r ef a n d
the boiling point Is.
8 H . B . H a s s a n d R . F . N e w t o n , H u n d b o o k o l C h e n r i s t n , u n t lP h t , s i c s . 6 4 t he d . , ( C l e v e l a n d .O h i o :
C h e m i c a lR u b b e r P u b l i s h i n gC o n r p a n y ,1 9 8 3 - 8 1 ) ,p . D - 1 8 9 .T h i s i n f o r m a t i o ni s p r e s e n t e di n e a r l i e r
e d i t i o n sa n d i s i n d e x e du n d e r : " b o i l i n g p o i n t s , c o r r e c t i o nt o s t a n d a r dp r e s s u r e . "
TABLEOF VAPORPRESSURES
289
oFvAPoRPREssuREs
V .4 TABLE
The followingtable of vapor pressuredata (pages290-31I) is suppliedas an aid
to the planning of experimentsand identificationof compounds.When vapor
pressuredata are employedas a criterion of purity. the investigatormay wish to
evaluatethe original work critically and obtain a preciseinterpolationof this
data to the temperatureof interest;therefore,referencesare includedat the end
o f t h e t a b l e ( p a g e s3 1 2 - 3 1 3 ) .M o s t o f t h e v a p o r p r e s s u r etsa b u l a t e dh e r e w e r e
calculatedon a digital computer using parametersfrom the referencescited. In
t h e s ec a l c u l a t i o nO
s o C: 2 7 3 . 1 5K . S i n c em a n y o f t h e o r i g i n a lr e p o r t sm a y h a v e
employedslightly different valuesfor the ice temperature,a small error is sometimes introduced.Calculatedvalueswhich knowinglyrepresentan extrapolation
When an analyticalexpresor are otherwisesuspectare enclosedin parentheses.
sion was not availableor the given analy.ticalexpressionwas obviouslyerroneous, the original data werefit to Eq. (9) by leastsquares.The slushbaths which
c o r r e s p o n dt o t h e g i v e nt e m p e r a t u r ea r e m e t h y l c y c l o h e x a n-e ,1 2 6 . 5 9 ' ;c a r b o n
d i s u l f i d e ,- 1 1 1 . 9 5 ' ;e t h y la c e t a t e -, 8 3 . 6 ' ; c h l o r o b e n z e n e- ,4 5 . 2 " ; c a r b o nt e t r a c h l o r i d e ,- 2 2 . 9 " ; i c e w a t e r ,0 ' C . A l l t e m p e r a t u r e gs i v e ni n t h e t a b l e a r e i n
degreesCelsiusand pressuresare torr. A subscripts meansthe condensedphase
is a solid.
\o
o
tris(trifluoromethyl)arsine(CFr),As
Beryllium:
Beryllium borohydrideBe(BIIn)2.. .
Diethylberyllium (C2H5)2Be
Bismuth:
Trimethylbismuthine(CI{e)aBi.. . ..
A r s e n i c p en t a f l u o r i d e A s F r . . . .
Arsenictriehloride .{sClr. . . . . .
Arsenietrifluoride AsFr.. . . . ..
Arsine AsHr.
l)imethylarsine (CI{r)zAsI{. . .
Methyldichloroarsine CH rAsClr
Methyldifl uoroarsine CII:AsFr.
Trimethoxyarsine As(OCIIT)r. .
Trirnethylarsine (CHr)rAs. . . . .
S t i b i n eS b t I r
Antimony pcntachloride SbCl5

Antimony pentafluoride (SbFs)
Triethylstibine (CrI{s)rSb. . .
Trimethylstibine (CI{r)3Sb. . .
Aluminum:
Aluminum borohydrideAl (BII{) 3
Trimethylaluminum (C[Ir)rAl .
Antimony:
Compound
Tobleof vopor pressures
,'-
.JD
1.6
2l
l5r
AD
l6
2.6
30
58
i). t
629
:J) ( l 0 )
87
22
2.0
1)8
187
,,
178
l6
4t)
3ir
l-t5.etl-zz.75l
Vapor pressure, torr
- t e o . s : rt rl _r . u-s$l . 6
Tenperalure, oC
492
l0
87
l0
295
55r
109
3.8
1.2
luu.oo
l07 l
- 85.8
6
LB
9r.3"
194
LB
LB
LB
LB
LB
2
,)
LB
504
(33.3)
l"
-79.8
-16
- 5.9
- 116.9
2.8
8.3
-98
-62.0
-88
-64.5
l5
mp("c)
LB
LB
LB
LB
LB
- 52.8
1 3 13
622
-62.3
3 7. 1
134.5
7 6 .I
14',2.6
1 6 1. 4
806
(-18 4)
459
r24 7
bp("c)
.o
l)ihydroxyrnethylboran
CcH 3 B ( O H) : l
Dimethylamine-borane
I
(cH3)rNrIBI{3.
I
l)inrethylarninodihorlnr.
I
.
1
BzHrN(CIIr)2.. .
crHr(BClr),
1 , 2 - B i s ( d i f lu o r o b o r y l ) e t h a n e
CzH,(BFr)2.
1 , 2 - B i s( d i f l u o r o b o r y l ) e t h e n e
(BFz)zCzHz.
Bis (dimethylarnino)borane
BH(N(CH3)r)2.
.
Bis (dimethylanrino)chloroborane
( ( C H r ) r N ) r B C.l . . . .
1 , 2 - B i s( d i m e t h y l b o r y l ) e t h a n e
(B(CH3)r),CrH(.
Bis (perfluorovi nyl ) chloroborane
(CzFrtzBCl
Borane carbonl'l BII3CO. . . . . . .
BorazinoBrN3ll6.
Boron tribromide BBrr.
Boron trichloride B('lr
B o r o n t r i f l u o r i d cR F a . . . . .
Bromodiborane BzI{ rl}r .
l ) i b o r a n e( 6 ) B r l l 6 . . . . . .
I)iboron tetrachloride BrCl{. . . .
I)iboron tetrafluoride BrFn. . . . .
Boron:
1 , 2 - B i s( d i c h l o r o b o r y l ) e t h a n e
(BClr)rcrH.
1 , 2 - B i s( d i c h l o r o b o r y l ) e t h e n e
75
:JT}I
r)<
I l"
2.5
qar
6. ii
378
,tl
50
60
2lt
9.9
ll
l4l
4.:l
175
27
t7
44
ilir
l9
476
ll
l2
l,
8.5
380
25
69
'262
42
5.8
507
9.4
,2
r56
6.1
l3
50.3
90.9
124
-99.9
16.0
-93
(65 5)
-34
co.100
)J. J
100.5
-64.0
-47.5
- i)t)
- 104
- 165.5
-92.6
-46
- 107
tl
16
ll
LB
t2
LB
LB
13
LB
l4
7
29
20
10
98
LB
-57.5
- 137.0
-82
-31 5
- 130
- 28.5
r46
1 0 5 7.
l5
(35)
( 144)
(t42)
t\)
H e x a b o r a n e (l 0 ) 8 6 I I r o .
I\Iethoxydimeth ylborane
(CHr)zBOCHr
N-Methylborazine BrI{rNrHrCII3 .
l)imethylpropenylborane
Cr[Is(CHr)zB.
1,3,2-I)ioxaborolane (CIIzO) rBII .
1,3,2-Dithiaborolane (CIITS)rBII . .
l)imethylphosphine-trimethylborane
(CHr)'PIIB(CIl3r3.
1Qfl.1,PIIBHI
l)imethylphosphine-dimethylborane
(CH3),PHBI{(CHr)r.
N,N'-l)imethylborazine
B3H3N3(CH3)2.
D i m e t , h y l d i b o r a n e( C H r ) z B r I { , . . . .
I)imethylfluoroborane B(CII3)rF. .
I )i m ethyl phosph i ne-bo rane
B,B'-I)imethylborazine
Brll (CH3)rNrIIr. . .
I)imethylarsine-borane
(CIlr)zAsllBIIr... .
Di m eth yl am inod ic hlorobo ran e

(CH3),NBCl,
Compound
T emperalure,
t2
6.0
bt)
87
|4
1)6
0.7
Li)
,)i
( 4 e ) /')')|
ll0
657
/.ltl,)i
L:)
ta
(76)
5.8
-/,5.el1-es.75l
- t e 6 . l e l -I I t . s s-8e.6
,.*,
l
Ioble of vopor pressures(Conlinued)
84
(242)
(01)
4.1
3l
:t6
l8
2l
(84)
')
LB
l1)
rr.l
, )|
2'2
22
I,ts
LI}
I,B
,4')
(174)
I8
I,B
l9
I,B
20
-62 :l
mp("c)
( 108,)
-2 6
(107)
(8,:r.5)
( 1 1 23 )
bp("c)
\o
19
Ba(CzllrrrNrHr.
TrinrethoxyboraneB(OCH3)r. . . . .
T r i m e t h y l a m i n e - b o r a n e ( C I I r ) 3 NB I l
Tri nr ethy ltrrsine-boran e
(CIIr)rAsBIIr
Trimethylborane B(CI{r) r
B, R', B " -'l rimet h ylborazine
Br(CIIr)rNrIlr
I\Iethyldifluoroborane BCHrFr. . . . . .
trIeth1'ldivinylboranc (C.H').CIlrB.
NI eth yl phos ph ine-bo r an e
CH3PH:BII3
B-Nlonomethylborazine
83ll:cH3N3IIr.
Pentrborane(9) BsII,. .
P c n t u b o r a n e ( Il ) B 5 I l r .
P e r f lu o r o v i n y l d i c h l o r o b o r a n e
CrFrBCl:.
P e r f lu o r o v i n y l d i f l u o r o b o r a n c
C,F3BF2
P h o s p h o r u s t r i f lu o r i d e - b o r a n e P F , B I I
T e t r a l r o r a n e (l 0 ; B n I I ' o
Tetraborane(8) carbonyl BoHrCO. .
Tetraboron tetrachloride B{Cl4. . . .
Tetranrethoxl'diboron B:(OCIIT)r .
Tetramcthyldiborane (CIIr){BrIJ? .
Triethoxl'trorane B (OCzH r)r
(C:Hrtr... ...
Triethylborene
B, I)', B" -T riethylborazine
.t
18
,7
6.1
l5
lrl
40
I
47
(3
l0
388
20
65
52
4.9
l8
3.1
2a
( rl 3 )
(31)
154
_20,l
(l2e)
10,
(173)
663
-14
(-62.2)
l8
(5e 6)
(140)"
( 130)
6 8 .6
ll8
102
48
(87)
(57)
(63)
158
2)
1-63
(l.5)"
30
146
0.9
t4
49
t:) I
IJ
,,
(219)
70
209
170
(2)
(344)
31.5
-tot s
94
-46.4
-ot
-26
-72 5
-96
- 1 1 6 I.
- 120
- I14.5
- 108
-59
-46.8
-122
- 130.5
LB
32
33
t5
l6
l5
28
LB
30
LB
3l
32
',7
ll
18
25
,24
20
2l
.o
5
Chlorofornr CHClr.
Chloromcthane CHrCI
Chlorotrifluoromethane CF3Cl. . . . .
Dibromomethane C I{:Brz
I)ichlorodifluoromethane CFzClz. . .
I)ichlorofluoromethane CIIClrF. . . .
I)ichloromethane C I{:Clz.
One carbon:
Bromomcthane CIITBT
. .
C a r b o n d i o x i d eC O z . .
C a r b o n t e t r a b r o m i d eC B r r . . . . . . . .
Carbon tetraehloride CClo. . . . .
..
C a r b o n t e t r a f l u o r i d eC F { . . . . .
Carbonyl chloride COClr.
Carbonyl fluoride COFz. .
Chlorodifluoromethane CHClFr. . . .
Trimethylboroxine Br(CIIr)rOr. . . . .
Trimethyldiboranc (CI{r)rBzHr. . . .
Tris (dimethylamino)borane
B(N(CII3)-)a
Tris(pcrfluorovinyl)borane (C?Fr)rR
Trivinylborane (C:IIr) rB.
Cadmium:
l)imethylcadrnium (CI{:):Cd.,
Compound
-'
1)l
2a
3.9"
1':"
3tt
7l
(2 9l
9.6
8.3
(t5)
2.7
36
376
(2 2) ( 5 1 )
8.2
40
iss
.),
lu
531
(138)
ll
60
aoJ
:^^
66r
9.8
50
(64)
(4 8) 2 l
r22
38
Vaprtr pressure, torr
(435)
45
lnt
l"
(0.8),
105.7
36
3.6
-/.o,
191.9
76.7
- 128
7.6
- 83.4
-40.8
6l .7
-24.22
-81 .2
96.95
-29.9
8.9
3 9 .8
152
(104.5)
(55)
4.3
23
(235)
JJ
45.5
(7e)
bp("c)
80
- 2s.751
o.oo ss.oo
tt.o
I
l-,,0.u,
|
Temperature, "C
( 2 6 ) 56
200
/:)r
t24
(4 6) (()2)
617
( 3 .1 )
o2
279
107
667
,'7
- 1 2 6 . 5 t1)1] 1
-. s l l -
Tobleof vopor pressures(Confinued)
ll
2l
34
20
LB
Rel.
- 135
-95.
90.
MCA
LB
LB
_t,
LB
- 183.
LB
-t27. 8
D
- l14
LB
- 160
35
-63.
D
-97 . MCA
- r8l.
LB
-52.
MCA
- 160
LB
- 9 3 . t) M C A
mp("c)
N
9
(rr
CF3CFCI'.
l, l-Dibromoethane CrHrBrr
1,2-I)ibromoethane CzHrBrr
1 , 2 - D i c h l o r o -1 , 2 - d i f i u o r o e t h y l e n e
CtFtClt
l. l-Dichloroethane CzHrClz
1,2-Dichloroethane CzHrClz
I , 1-Dichlorotetrafluoroethane
Trichlorofluoromethene CClrF. . . . .
Trifl uoroiodomethane CFrI .
Trifluoromethane CHFr.
Trifluoromethyl hypofluorite CFrOF
Two carbon:
Acetaldehyde CHsCHO.
Acetic acid CH3COOH.
...
A c e t y l c n eC r H r .
Bromoethane CzHsBr.
Bromoethylene CzHrBr
l-Chloro-1, l-difl uoroethane CzH rClF
Chlorocthane C:HtCl .
C h l o r o e t h y l e n eC z l l r C l . . . .
Chloropentafluoroethane CrClFr. . . .
Chlorotrifluoroethane CrH2ClFi. . . .
Difluoromethane CHrFr.
Fluoromethane CHrF.
Formaldehyde CH:O. .
Formic acid HCOOH
Iodomethane CHrI. .
M e t h a n eC H r . . .
Nlethanol (CH3OH)
13
76
t26
l4
coJ
12"
IJ
28
1.1
67"
1.9
ll4
251
207
(12)
z8
(7.1)
l.l
(87)
,.t
te
( 2 . 6 ) (47)
l3
t52
(, ,\ (46)
t4
l8l
59
574
3l
331
76r"
1 l
1ii
( l 5 ) (27)
260
24
( 1 0 m m a t - 1 9 6 .5 )
''''"1.
26
l9
266
(4e
.)
108
l9
(tl
.
..
.c
(468)
424
"l
2S
302
140
iuor ( 1 6 3 )
157
444
(1 6 4 )
109
103
753
at
42
646
20.6
228
7S
26
12
(469)
l5
t25
428
406
- 112
57.28
83.5
-27 .9
1 0 80.
l3l 4
- r3.37
-39.2
20.4
117.9
- 84.
38.4
1 5 .8
-9.8
12.27
- 161.5
64.7
23.77
-22.5
-82.4
-95.0
r00.6
42.43
- 51.6
-78.4
-19.1
LB
38
ot
MCA
MCA
MCA
MCA
MCA
D
MCA
35
LB
-97
MCA
-35.7
D
- 1 3 6 . 4 MCA
- 1 5 3 .8
D
-99.4
LB
- 158
4l
-63
MCA
9.79
D
40
- 123
MCA
1 6 . 7 MCA
-80.8
39
- 1 1 8 . 6 MCA
- 139.5
D
- 147
< -215
-111
- r82.5
-97.7
- 1 4 1. 8
-ot
8.4
-66.5
t\)
\o
o.
F l u o r o e t h a n eC r l l i F .
Ilcxafluoroethane
CrFe.... .
Iodoethano C:HsI . .
Tetrafluoroethylene CrFr... . .
l, 1,2-Trichlorotrifl uoroethane
C:ClrFr.
l, l, l-Trifl uoroethane CHTCFT
Three carbon:
A c e t o n eC r H o O .
Cyclopropane CrHr. . .
M e t h y l a c e t a t eC r I l r O r . . . . .
.l\lethyl aeetylene CrH,. . . .
Methyl ethyl ether CsHaO. . . .
P r o p a d i e n eC r H n . . .
z - P r o p a n a lC r H r C H O . . . . . . . .
Propane C.Ha. . .
1,2-I)ichlorotetrafluoroethane
CzClrF,.
l,l-l)ifluoroethane CzHrF:. . .
l, l-I)ifluoroethylene CHrCFr .
Dimethyl ether CzIIoO
E t h a n eC r H o . . . . . . . . .
B t h a n o lC r H s O H . . . . .
EthyleneCrHo... ...
Ethylene oxide CzHnO. . . .
Compound
Temperalure, "C
(l 3)
42
30
(7.1)
(1 e)
106
(12)
(2 8)
76
(45)
l8
4tt3
b/t,
62
2l
o,t
l5
459
156
,,
I
176
54
7.1
4l
93"
r52
(48)
660
5.
48r
3.4
437
30
260
20
534
87
2U3
28
r68
l6
l8
ll
172
20
r02
554
6l
o/
4l
l2
680
318
211
/r9t\
334
r36
60
- 1e 6. ss
o .o oI s5 .0 0
1rl1.ssl- as.o
l- r ,u.ntl- ee.zsl
Ioble of vopor pressures(Confinued)
56.5
-33.I
57.8
-23 2
7.4
-34.5
4 8 .0
-42.l
47.57
-47 .6
-37 .7
-78.3
72.3
-76.3
r0.7
30
-24.7
- 85.7
-24.8
- 88.6
78.29
- 103.8
bp("c)
I ta
_ I
- r87.
- 136
-80
-94.
- 126.
- 98.
- 102.
-35
- 169
- lll
- 138
- 183
-94
- tt7
mp("c)
LB
LB
LB
D
MCA
D
MCA
D
35
40
LB
MCA
LB
MCA
36
35
MCA
40
MCA
D
N{CA
Ref.
\o
h)
Tetrahydrofuran CrH a().

lrazs-2-Butene CnHa. .
Five carbon:
CyclopentaneCrHro. .
C y c l o p e n t e n eC s l l e . . .
2,2-Dimethylpropane CsII rr
(neopentane)
CyclobutaneC,Hr....
Dimethylacetylene CrH o
Diethyl ether (CrHs)zO.
1,2-Dimethoxyethane CrHroO:. . .
1 , 4 - l ) i o x a n eC r l l a O z
Divinyl ethcr ColloO
Furan CnHrO.
Isobutane CnHto. .
2-Methylpropene CrI{ s.
Methyl z-propyl ether CrllroO. . .
Octafluorocyclobutane CrFr. . . .
2-ButanoneC,IIaO....
l-ButeneC.Ha........
c z ' s - 2 - B u t e n eC r I I e . . . . .
l-PropanoC
l aH'OH....
2-Propanol CTHzOII.. .
2-PropenalC3II{O... . .
Propene C,Hu . .
Four Carbon:
1 , 2 - B u t a d i c n cC r l l o . . . . .
1,3-Butadiene C,He. . . .
n-Butanal CsHzCHO. . .
n-ButaneCnHro...... .
(2 0)
10
I'
( 5. 3 )
(7.0)
( 9 .l )
87
(17)
19
l3
164
(8 7) 1 2 6
( 4 .1 )
4.0. l0l,
( 6 .l )
I
94
I
(8 3) 123
( 1 .1 ) I J
2 . 5 " 50
(2 e)
(7.3)llr
ion
31
39
280
It
(72)
70
484
391
(34)
376
..
DI
299
i.l
380
244
167
80
r78
350
1.2
( 6 6 ) (27)
t\
r30
t07
48
734
3t7
380
163
(457)
(145)
(234)
2r5
534
65
3S
(672)
604
100
t12
lrunl
2l
45
185
t 7. 4
q(t
658
460
30
3l
496
3.3
8.3
(8e)
9.5
49.26
44.2
r0.85
-4.41
74.8
- 0.5
79.6
-6.26
3.72
12.g
26.97
34.6
85.2
l0l. t
27.8
3 1 .I
- 1 1. 7 3
- 6.9
3 9 .I
-6.6
ca.63
0.88
97.2
82.6
52.5
-47.7
- 16.55
-93.88
- r 3 5 .1
- 85.6
- 1 5 9. 6
- r40.4
D
D
LB
LB
D
D
MCA
-40.2
LB
43
-ios.o D
- 1 3 6 .1 9
D
- 108.9
D
- 9 6 . 4 MCA
- r 3 8 .4
D
- 85.9
LB
- r 8 5. 4
D
- r 3 8. 9
D
-50
LB
-32.26
D
- I 1 6 . 3 MCA
-69
42
LB
10
- 1 2 6 . 2 |M C A
I
- 8 8 . 5 MCA
-87 .7
LB
- 185.25 D
\o
n - O c t a n eC r H , r . .
Styrene CaHe. .
2,2,4-Trimethylpentane
(isooctane)
CslI 1g
Six carbon:
B e n z e n e ( C eI I o ) .
C h l o r o b e n z e n eC o I I r C l
C y c l o h e x a n eC r H r , . .
C y c l o h c x a n o n eC o H r o O
C y c l o h e x e n eC u H t o . .
Diethyleneglycol dimethyl ether
CuH',Or.
Di-n-propyl ether CoI{rrO
n - H c x a n eC r H , , . .
Seven carbon:
B e n z a l d e h y d eC t H . O .
n - H e p t a n eC r H t o . .
1\{ethylcyclohexane CzH r r
Toluene CrHr. . .
Eight carbon:
Cyclooctatetrene (CrHr)
2-Methyl-1,3-butadiene CslI g
(isoprene.l
2 - N l e t h y l h u t a n eC s l l r z . . .
n-Pcntane CrII rr. .
Compound
Temperature, "C
(2 e)
l3
( l .r
(1,5
(29
(2.3) (ll)
(2 7) 12
(l 3) (67
45
,^
( 6. 0 ) 25
t':'
24,
(le8)
259
183
..'.n,
(63)
87
50
(2 2) (12)
(1.0)
l4
(l6)
Vapor pressure, tom
49
99.2
140.56
r25.67
t45.2
( 7 .8 )
t4
(6.0)
46
46
28
179
9 8 .4
100.9
110.6
t62
89.5
68.7
(4)
70
l5l
( 1 e. )
8 0 .r
131.7
80.7
155.6
82.98
34.07
2 7. 9
36.07
bp("c)
95
(l2)
98
4.6
89
(550)
688
512
- 1 s 6 . 5 e 1 - 1 1 r-.8sss.l 6 l - t 5 . p t l - e e .o.oo
z s l p,.oo
I
D
D
D
R"l.
42
LB
D
- 107
-30
-56.8
-4.
D
D
D
-26
LB
-90.61 D
-126
D
-94
D
-64
-122
-93
5.
D,J
- 4 5. 2 1
6
D
-45
LB
-rffi.5
D
- 145
- 159.9
-r29.7
mp('c)
19
\o
<t
I ) i m e t h y l g e r m a n e( C l I 3 ) r G e I I r . . . .
F l u o r o g e r m a n eG e F H r .
G e r m a n eG o H n . .
(iermanium tetrachloride GeCln. . . .
(iermanium tetrafluoride (ieFo. . . .
Nlethylchlorogermane C H rGeI{zCl. .
Methyldichlorogermane CH rGeIICl,
Nlethylgermane CH rGeIIr.
Trichlorofluorogermane (leFClr. . . .
Trichlorogerrnane Ge HCl3.
T r i g e r m a n e C e a H s ..
Halogen
BromineBrr.........
IJromine pentafluoride BrFs. .
Bromine trifluoridc BrFr. . .
Chlorine Clr .
Germanium:
Bromogermane GeBrHr.
Chlorogermane GeClHr
Chlorotrifluorogermane [.ieFrCl. . . .
l)ichlorogerrnane fieOl: H:.
I)ifluorodichlorogermane GeF:Clr. . .
l ) i g e r m a n e C l e r l l e.
I ) i m ethylc h lorogerm an e
(CHr)rGcllCl
m-XyleneCrHro..
o-Xylene CrH,o. .
p.Xylene C.Hro
Gallium:
Triethylgallium (CzHs)rfla
Trimethylgallium (CHr)rGa
48
D<
44
182
(2 4)
83
(1 5)
(5 3)
44
48
453
2a
4.9
(2 8)
66
l3t)
1.3
(ll)
24
2t5
407
7.7
(le0)
(36)
87
13,
ll
24
(n3l
(435)
100
(3e)
26
(2 8)
JO
3l
358
(s.7)
(27e)
(623)
58.8
40.9
125.8
-34.1
(8e 4)
- 0.6
(15.6)
(-e3)
8 5 .8
( - 35),
( 7 0 .e )
( 11 3 . 2 )
(-35.1)
37
74
111.1
( 31 )
(28)
-21
6 9 .5
-0
(247)
133
272
689
(8e)
39
87
234
t 4 2. 4
5 5 .6
1 3 9 .I
r 4 4. 4
1 3 8 .3 5
653
l0
,o,
o<
6.8
218
1.5
65
( s 7 ) (30) (r20)
(470)
\t . t )
(s e) (337),
l8
l0l
21
79
(26)
(8 2)
(6 6)
(8 8)
(l o
(l J
-7 .1
-60.6
8.8
- r0l
- 106
- l0l
-62
- 158
-50
_76
- 149
-22
- 165
-50
ca. - 109
-32
-52
-66
-68
-52
-82
_16
45
45
46
7S
LB
47
45
45
45
LB
LB
LB
LB
LB
44
44
LB
44
LB
LB
D
D
D
MCA
MCA
I\(CA
MCA
-47.87
-25 18
r3.26
o
o
(.)
l)ioxygen difluoride FzOr. . .

FluorineF2.....
Ilydrogen bromide HBr. . .
Hydrogen chloride HCI . . .
I l y d r o g e n f l u o r i d eI I F . ,
Hydrogen iodide HI
Iodine heptafluoride IF7.
Iodine monochloride ICI
Iodine pentafluoride IFr.
Oxygen difluoride Fz0. . .
Indium:
Trimethylindium (CIIr) rln
Chlorine dioxide CIO: .

Chlorine dioxygen fluoride ClOrF. .
Chlorine fluoride ClF. .
Chlorine pentafluorideC1F5..... .
Chlorine trifluoride ClFr. . .
Chlorine trioxygen fluoride CIOrF
(perchlor5'l fluoridet
l)euterium chloride ])Cl. . . .
l)euterium fluoridc I)F
I ) i c h l o r i n eh e p t o x i d e ( C l : O ' ) . . . . . . .
I ) i c h l o r i n eo x i d o ( ' l z O .
('ontpountl
20
45
o.t
2.0"
30"
38"
28"
124
7.9
t'20
|.4
28,
:,.
173
(1 7)
50
498
1.7"
299
3
173
90
l9
5.0
69
47
190
34
104
179"
l3l
146
5.l)
246
139
D.' J
,tD)
155
Tentperature, "C
4.O
580"
696
ao
385
451
at 30"
'7'
26
,'7
25.00
r35.8
-56
- 188
-66.7
-85
19.5
- 35.6
6
97.8
102
- 144.9
88.4
LB
- 1 4 7 . 7 MCA
- tt4 .7 MCA
- 8 3 . 6 MCA
- 9 r . 7 MC
- 1 2 0. 6 M C A
- 1 6 3 . 5 N{CA
- 2 1 9 . 6 MCA
-/
MCA
- tt4 .2 M C A
- 8 3 . 4 MCA
- 5 0 . 9 I\ICA
6 . 0 MCA
r 3 . 9 MCA
9 . 4 MCA
-223.8 MCA
-46.7
-84.8
18.6
84
,1
-59
MCA
-l15
MCA
- 1 5 5 . 6 MCA
- r03
78
- 7 6 . 3 MCA
mp("c)
10.9
-5.7
-90
-14
1 1. 8
bp\"c)
G,
Ethylamine C?II5NH,
( 1 , 2 - d i a m i n o e t h a n e )E t h y l e n e d i a m i n e
c,H4(NHr),
Fluorine nitrate NOrF.
H y d r a z i n eN z H n . . . . . . .
Hytlrogen azide HNr
Hydrogen cyanide HCN. .
N{ethylamine CHTNHz
Lead:
Tetraethylplumbane (C:Hs)rPb. . . .
Tetramethylplumbane (ClI3) 4Pb
Nitrogen:
Acetonitrilc CIITCN
AmmoniaNHr ..
AnalincC6H7N.
BenzonitrileCTlIbN
Carbonyl cyanide CO(CN),
cis-Difluorodiazinc N:Fr .
Cyanogen bromidc CNBr.
Cyanogen chloride CNCI . .
Cyanogen fluoride CNF. . .
I ) e u t c r o a m m o n i aN I ) 3 .
f ) i c . v a n o g e nC z N z . .
Diethylamine (CrHs)rNH
I)imethylamine (CHr)rNH
N,N-I)imethylforamide CTHTON . .
l,l-l)imethylhydrazine (CHr):N'IIz.
1,2-l)imethylhydrazine (CHr)rNzHz.
Dinitrogen pentoxide NrOr. .
Dinitrogen tetroxide NrOn. . .
s .z "
r57
l0
,,
494
408
95
731
26
(1.5)
.JO,'
19"
4 . 7 " 163"
40
44
lOt
112
9.3
( 2 .e )
5.5,
707
l9
179
'.,-
6.9
1.7
183
265
263
366
a!
4l
l6
70
562
456
31
28
76
t4
512
742
12
70
413.
4.
235
rtn
0.8
0.8
124
(e6)
0.4
30
-27 .5
LB
LB
25.7
-6.45
JO
tt7 .2
-44
113.5
(81 6)
LB
MCA
1 . 5 MCA
-80
MCA
- 1 3 .2 9
49
- 9 3 . 5 NICA
.1)
- l8l
-45.7
LB
- 7 7 . 7 NICA
-6
184
LB
l9l
LB
-38
65
LB
- 105 7
<-195
48
5r.8
LB
-5.2
t2.5
LB
-72.9,
LB
-31.05
- 7 4 . 3 IUCA
-21.3
-27.9
LB
-50
55.7
8l
-92.2
6.88
80
-60.5
149
D
-58
LB
LB
4l
MCA
- 9 . 3 T{CA
2r.2
-81
16.58
MCA
183
(ll0)
(,)
Methyl hydrazine CHrN:Hr.

N-Methylhydroxylamine
C H3NHO H
O-Methylhydroxylamine CH:ONHz .
Methyl isothiocyanate CH3NCS. . . . .
Methyl thiocyanate CHISCN...
.
Nitric acid HNOr.
Nitric oxide NO. . . .
Nitroethane CrH5N02
Nitrogen trichloride NClr. .
Nitrogen trifluoride NFr. . .
Nitromethane CH3NO,
Nitrosyl chloride NOCI . .
Nitrosyl fluoride NOF. .
Nitrous oxide NrO.
Nitryl chloride NO2CI
Nitryl fluoride NOrF. .
Phenyl isocyanate C6H5NCO
PiperidineCtHrtN.
Pyridine CrH'N.
Pyrrole C.HrN.
Tetrafluorohydrazine NrF.. .
Tetramethylhydrazine (CHn).Nr. . . .
trons-Difluorodiazine NrFr. . .
Triethylamine (CrHr)rN.
Compound.
Temperature, "C
t.7
14,
(478)
l0
393
4.6"
175
1.6
s.z
8.9
I'
573
1.6
345
9.0
2.6
2l
8.1
4.1
(2.0
495
37
84
8.
2.6
l4
- t 26.6slr t t.sll-s.e.6 - /+s.e

l -ze.zsl
o.oo
I
I
(l l)
26
32
20
(50)
6.5.
293
24,
t2
63
-72.4
165.5
106
115
l3l
co. -73
73
- 1r1.4
89.5
_ r5.3
-5.4
-59.9
- 8 8. 4 8
r0r
ll9
1 3 2. 9
83
-151.8
114
(71)
- 129.06
115
4 8 .r
bp("c)
Rel
LB
LB
LB
:.' :
JJ.C
LB
-51
LB
- 4 1 . 6 MCA
- 1 6 3. 6 MCA
-90
LB
_27
MCA
- 2 0 6 . 8 MCA
-29
LB
- 5 9 . 6 MCA,
- r 3 2 . 5 MCA
- 9 0 . 8 MCA
- 145 MCA
_:::
MCA
LB
LB
LB
LB
50
LB
-172
48
-114.7
8l
42.5
,np("C)
(.,
o
(.)
Trifluoroacetonitrile CFrCN
Trifluoronitrosometh&neCFINO. . . .
Trimethylamine (CHr)aN
Trimethylhydrazine(CH:)rNrH. . . . .
Oxygen:
Deuterium oxide DzO.
OzoneOs.
Water HzO.
Phosphorus:
1,2-Bis(trifluoromethyl)diphosphine
PzHz(CFr)2.
BromodifluorophosphinePBrFr. . . . .
ChlorodifluorophosphinePClFr. . . . .
DibromofluorophosphinePBrrF. . . . .
DichlorofluorophosphinePClrF. . . . .
PFzI. .. . . . .
Difluoroiodophosphine
DifluorophosphinePF:H
acid HPOzFr. . . .
Difluorophosphoric
Dihydrogen phosphorustrifluoride
PH2F3.
D i m e t h y l p h o s p h i n(eC H s ) z P H . . . . .
D i p h o s p h i n eP r H . . . .
Hydrogen phosphorustetrafluoride
PHF{..
Methylphosphoryl chloride fluoride
CH3POCIF.
Methylphosphoryl difl uoride
CHsPOF'
;r-Oxo-bisdifluorophosphine(PFr)rO.
P h o s p h i nPe H r . . . .
PhosphoruspentabromidePBrr.. . . .
3.6
7.l
32
(4.4)
<q
(2)
12
t2l
556
34
4.L
ot
1.5
47
l9
207
rt7
20
2l
/ft
8.0
163
(2 0) l 1
184
567
lll
.l
cc
55
54
54
LB
MCA
56
- 1 3 3 . 8MCA
1 0 3 . 7MCA
-36.9
(ee.7)
-18.3
36
(8.5)
-l
-22.8
-99
-52
(130.7)
( -3e)
3.8
20.9
59
MCA
- 1 3 3 . 8M C A
- 1 6 4 . 8MCA
_ 1 1 5 MCA
_r44
MC
-93.5
52
-124
53
- 9 6 . 5 MCA
(e.2)
224
...
32
(6e.5)
-16
-47.3
78.3
13.9
(26.7)
-64.6
I16.4
51
LB
82
LB
3 . 8 2MCA
-251
MCA
0 . 0 API
-117.1
-72
-r44.4
(l .6)
640
334
7T
r09
32
448
243
710
:li1l
r00
24
43
1 0 1. 4
- 1 1 1. 3
2l
r96
-ol-t
-84.5
29
o
o
5
Phosphoryl trichloride POCI3. .

..
Phosphoryl trifluoride POF3. . . . . . .
Tetrafluorodiphosphine PrFo... . . . .
Tetrakis (trifl uoromethyl ) cyclotetraphosphinePn(CFr)n.
Trifluoromethylphosphorus
tetrachloride CFBPCIn
Trimethylphosphate
(CH aO)gPO .
PhosphoruspentafluoridePFr. . .. . . .
Phosphorustribromide PBrr.. . . . . . .
P h o s p h o r ut sr i c h l o r i d P
e Clr.. ..... .
P h o s p h o r ut sr i f l u o r i d e
PFr. . .......
Phosphorylbromide chloridefluoride
POBTCIF.
Phosphorylbromide dichloride
POBrClz
Phosphoryl bromide difluoride
POBrFz.
Phosphorylchloridedifluoride
POCIF,,
Phosphoryldibromidefluoride
POBrzF.
Phosphoryl dichloride fl uoridc
POCI,F.
Compound
Tobleof vopor pressures(Continued)
ra+
48"
7.6,
8.1
4.8
367
.)a
84
l2
672
240
68
3.0
199
60
t4
6.6
9.4
Vapor pressure, tom
Temperalure, "C
(104)
191
t3
(.e)
(135)
52.9
105.5
-39.5
(-6.2)
lr0
3.1
32.1
136
7S
g2
582
9.9
100
- 84.5
r73.2
76.r
l0r .2
bp("c)
MCA
MCA
MCA
MCA
MCA
MCA
ne|.
-52
66.4
58
LB
- 8 0 . 1 MCA
l . l MCA
- 3 9 . 1 N,ICA
-86.5
57
- r r 7 . 2 MCA
- 9 6 . 4 MCA
- 8 4 . 8 MCA
l3
-93.8
-40.5
-92
- l5l .5
mp("c)
o
(rl
(^,
Bromodichlorofl uorosilane SiClr BrF

B r o m o s i l a n oS i l l r B r
Bromotrifl uorosilanc Si FrRr
i-Butylsilane (i-C4Hr)SiIl3.
a-Butylsilane (n-CrI{g)SiIIr.......
C h l o r o s i l a n eS i l I 3 C l .
I)ibromochlorofl uorosilane SiIlrrCl F
Dibromodifluorosilane SiFrBr:. . . . .
I )i b r o m o s i l a n e S i I I : B r z
I ) i c h l o r o d i f l u o r o s i l a n eS i F r C l r . . . . . .
I ) i c h l o r o s i l a n eS i I l r c l r .
Trimethylphosphine (CII3)3P.. . .
Tris (trifl uoromethyl) phosphine
(CFr)rP.
I , 2 , 3 - T r i s( t r i f f u o r o m e t h y l )t r i p h o s phinePrll:(('Fr)r...
Iladon:
lladon Itn.
Selenium:
Carbon diselenide CScr. . .
Carbonyl selenide COSe. .
I l y d r o g e n s e l e n i d eI I 2 S e . . . . . . . . .
I\lethylselenol CH rSelI
S c l e n i u m h e x a f l u o r i d cS c F e . . . . .
Seleniumtetrafluoride SeFa... .
Selenyl fluoridc Sr'OF, .
Silicon:
A l l y l t r i c h l o r o s i l a n eC r I I s S i C l 3 . .. . . .
1 , 2 - B i s( t r i c h l o r o s i l y l ) - e t h a n c
(sicl3)rcrII4
(4.l),
r-
.)<
1 ti"
t)
2.1
(46)
a;>
8{)
26;
149
83
65li
(7 l) (32)
( 4 . 2 ) l'), \
tt t)
393
:-t.4 22
( 3 . 6 ) (.i,2) ( r 6 7 )
l3
3.0
44
4 ltt
ir9
198
3.ll
6.2
l7
24
2;4
5t"
6;-r4
( 1. 4 ) ( 2 5 )
(21)" (217)"
( 3 .3 )
l3
i)48
c0
73
(452)
(7e)
tioet
2r6
.>a
4.4
3.6
400
I l)
t4'2
2l{)
(322)
(242)
f\43
( r. 3 )
la
16
4.2
l8
459
7 4 .I
-32.2
(8.3)
l I
-41.8
(48.6)
(56.4)
- 30.4
59.3
(2o2)
(116.8)
-46.3,
105
t26
1 2 l. 8
-21 .9
-62.O
ca. 123
(17.3)
38.4
MCA
lrt
-98
-67
-70
- 139
-tte t
- ll2
-94
-70.5
60
LB
6l
LB
62
62
6l
LB
LB
LB
LB
6l
60
-45.5
LB
-124
LB
- 6 5 . 7 MCA
LB
- 3 4 . 8 TICA
- 9 . i r I\(CA
MCA
l5
-71
59
o
o.
(.)
Si-MethyldisilazaneH NSi H $i H:C H

MethylailaneCHrSiHr.
Methyltrichloroailane CH$iClr. . . .
Diethyldichlorosilane (CrH')sSiCl'. .
Diethylsilane (CrHu)zSiH:.
Dimethylc hlorofl uorosilane
(CH3)'SiCIF.
Dimethyldichlorosilane (CH r)rSiCls.
Dimethyldifluorosilane (CHr)rSiFr. .
Dimethylsilane (CH')zSiHr.
D i s i l a n e S i z H o ..
l)isiloxane (SiHr)rO.
Ethyldichlorosilane CzHsSiHCl'. . . .
E t h y l s i l a n e C r l l 5 S iH i .
Ethyltrifluorosilane CrHiSiFl
Ethnylsilane C'HSiH..
Hexafl uorodisilane SizFc
Hexamethyldisiloxane (CHr)uSi,O. .
Iododisilane SirHsI
Methylchlorofl uorosilane CH3SiHCI
Methyldichlorofl uorosilane
CH,SiCI,F.
Methyldichlorosilane CHsSiHClr. . .
Methyldifluorosilane CHTSiHF'. . . .
Compound
4.8
Toble of vopor pressures(Conlinued)
58
23
195
( 2 .6 )
II
(475)
l4
(le)
83
263
71"
(l4)
(182)
( 6 . 2 ) (e7)
( 3 . 7 ) 44
I.ir
t.4
l2
(2.3)
( 3 . 4 ) (67)
t?
253
18
195
l5
193
(4 8)
189
227'
150
544
643
429
iioj iiir i iozr
60
74
47
nu.
(37)
75.5
(- 13.7)
-5.4
-22.4
-19.r
3 4. 0
-56.8
(66.4)
25.4
(40.e)
8]
1'o2
s9.2
-r5.2
t22
38
ruln]
36.2
70.5
2.1
-20.1
14.5
500
r42
t7r
43
1t.ro']
(13)
254
bp("c)
(2 6)
83
o.oo st.oo
I
1.7
8.3
l3
3.3
(267) (722)
JOU!
51
ll
239
686
548
563
lt
(sle)
325)
746
Temperalure, "C
_l?i
-o.z
-r79.7
- r50
-r32.5
- r43.6
mp("c)
LB
60
LB
LB
6l
60
LB
60
LB
6r
6l
61
60
62
LB
63
LB
LB
6,4
LB
60
62
Rel.
(.)
.
.
SzFtoOr
Bis (trifluoromethyl)disulfide (CFr) rS'
(CF3)rS..
Bis(trifluoromethyl)sulfide
Carbon disulfideCSz.. . .
Carbon selenosulfide
CSSe.. .
Vinyltrichlorosilane CzHrSiClr. . .
Sulfur:
Bis (pentafl uorosulf ur) peroxide
T e t r a s i l a n eS i { H r o . .
Tribromofluorosilane SiFBr:. . . . .
Tribromosilane SiHBrr.
Trichlorofluorosilane SiFCl3. . . . . .
Trichlorosilane SiHCls.
Trifluorochlorosilane SiFaCl. . . . .
Trimethylchlorosilane (C H r)rSiCl
Trimethylfl uorosilane (CH3) rsiF .
Trimethylsilane (CHr)3SilI.. ..
Trisilane SirHa. .
Yinylsilane CzHaSiHr.
Methyltrifluorosilane CH3SiF3. .
SilaneSiH.
Silazane(SiH3)rN
Silicon tetrabromide SiBrr... . . .
Silicon tetrachloride SiClr. .. . . .
Silicon tetrafl uoride SiFr
Silylcyanide SiHTCN
Silylphosphine SiHrPH,
Tetramethylsilane (CHr)rSi. . . . .
l3
18,
304
1.3
l9
lg
9
5 . 0 a;t
r83
l5
5
240
(e 6) 40
t27
( t . 2 ) ( 6 .5 ) (26)
(4.6)
(1.it)
177
70
,,
LU
76
388
594
96
8.1
26
8.8
472
218
1.7
ato
ot
4l
506
(276)
;;
109
l).v
2;
(4.7) 2l
12t
(2 0) 3 7
22r
4.1
67
28
6.5
(24)
(280) (73)
56
t7
1.5
77
24
( 4. 8 )
no
350
JD
4.1
t.l
28
49
1r,
(l.e)
760
-30.2
(8e)
362
305
529
oo
28it
234
598
4 7. 3
( 8 .3 )
-t9
49.4
(34.6)
(e0.6)
83.7
rt2
12.6
3l .8
-70
5 7. 6
16.4
(6.7)
it2.9
ca. -22.6
(r0e)
33
86
32
(738)
250
52
153
5 7. 3
- 95,
49.6
12.l
26.2
315
7.6
237
-lll.9
LB
LB
LB
61
LB
60
LB
62
6l
62
6r
LB
6l
6l
LB
60
LB
LB
LB
62
-lll.95
-85.2
65
66
66
D
LB
-111
"
-ii '
- 135.9
-tr7.4
- 1 7 9 .l a
_,:,
32
<_135
- l0l.7o
- 99.5f
ca. -90
-82.5
_74
- t2l
-126.5
_ 185
- l0.6
5
-68.8
(^t
Carbon subsulfideCrSr. . .
Carbonyl sulfide COS.
D i e t h y ls u l f i d e( C z H r ) : S . . . . . . . . .
DihydrogendisulfideHrSr... . . . . . .
Dimethyl disulfide(CHr)rS,
Dimethyl sulfide (CHr)zS . .
Disulfur decafluorideSrF'o. . . . .. . .
Disulfur dichlorideSzClz..
Disulfur difluorideSrFr. . .
EthanethioC
l zHrSH.
Hydrogensulfide HzS
MethanethiolCH'SH.
Nitrogen sulfur fluoride NSF. . . .
Nitrogen sulfur trifluoride NSFr. . . .
Pentafluorosulfurhypofluorite SFsO
Peroxydisulfuryl difluoride SgOoFz..
l-PropanethiolCaHsSH
Pyrosulfuryl difluoride SzOrFz.. . . .
Sulfinyl bromide SOBrr.
Sulfinyl ehlorideSOClr..
Sulfinyl chloridefluorideSOCIF.. . .
Sulfinyl fluorideSOFz.. .
Sulfur dichlorideSClz.
Sulfur dinitrogen difluoride SNrFz. .
Compound
Temperature, "C
to
4.0
2tl
2.1
64
45
D.J
213
263
57
au
(3 2)
7.6
( 1. 3 )
51
I;)
160
710
44
2.0
47r
159
58
184
l.l
463
r54
296
6.3
r20
ino
9.5
05/
1.9
485
lb/
23r
6 7 .I
6 7. 7
51
140
75.6
t2.3
-43.9
59
-11.1
- 2 7. r
_35
76
r09.7
3 7. 3
2 8 .9
137.6
-91
35.0
-60.3
5.96
co. 3
9 2 r.
-50.2
25.00 bp("c)
32
111
( 6 . 7 ) to
( 7. 2 ) (36)
(2.2) t2
46
6 . 1 28
98
307
482
lI)
200"
(3.0) 61
l.J
- 1p6.lsl-1r t.sll - ffi.6 - 45.p

1l- ee.rslo.oo
|
|
Rrt.
MCA
MCA
PI
67
67
68
68
API
MCA
- 5 2 . 2 MCA
MCA
MCA
MCA
-78
MCA
- 108
MCA
-lli
I
-t2l
-89
-72.6
- 86.0
-55.4
-112
-o.D
-80
MCA
- 1 2 0 . 5M C A
-tzl
API
_o9
0 . 4 LB
- r38.2
J
- 104.0
D
- 8 9 . 8 MCA
-84.72
D
-98.3
D
mp("c)
(.)
o
.o
r.7
I .0"
8.7
1.0
l9
293
724
4.6
54
69
tf
2l
(4i
39
40
45"
2t
218
(18)
80
260
139
140
74"
233"
-38.4"
59.0
-2t.7
9l-r
448
428
69.4
-55.4
-48.5
(121)
8 4 .1 6
-38
-53
78.0
t24
(4.6)
82
494"
543
240
56
( 1 . 5 ) (20)
48
(4 8)
3.4,
6.0"
8.5
8.4
9.9
o .a "
- 10.0
-63.9
-40
Tin:
S t a n n a nSe n l l n . . .
(CI{r)oSn. . .
Tetrameth-t'lstannane
T i n t e t r a t ' h l o r i dS
enCl.
D'
l.t
601
416
(le2)
(r47)
(l
t4
l4l
( 8 . 7 ) (e8)
4.9,
1 3 " 186,
6 . 1 68
2.l.
Sulfur dioxidc SOz.. . .

Sulfur hexafluorideSF6.. .
Sulfur tetrafluoride SFo
S u l f u r t r i o x i d eS O 3 ( a s, t a b l e ) .. . . .
Sulfur trioxide SOr (, mctastable)
Sulfur trioxide SOr (r, metastable)
Sulfur trioxide SO, (liq.)
Sulfuryl bromide fluorideSO:BrF.
Sulfuryl chlorideSOzCI:.
S u l f u r y lf l u o r i d eS O z F z..
Sulfuryl tetrafluorideSOF{.. . . . . .
Tetrahydrothiophene(CHr)rS. . . .
T h i o p h c n eC o H o S .
TrifluoromethanethiolCFTSIL . . . .
Trifl uoromethylsulfuryl fl uoride
CF3SO'F.
Trimethylenesulfide (CHr)rS. . . .
Tellurium:
I)itellurium decafluorideTerFro.. .
Hydrogentelluridc II1Te. .
Tellurium hexafluorideTeF6.. . . . .
Thallium:
T r i e t h y l t h a l l i u m( C , H 5 ) 3 T l. . . . .
T r i m e t h y l t h a l l i u m( C H : ) r T l. .
.
;-
-49.7
. 1)
-63
LB
LB
LB
LB
LB
-33.7 MCA
_46
NICA
- 3 7 . 8 MCA
.,:",
LB
LB
MC
MCA
MCA
IlICA
MCA
I\{CA
MCA
40
MCA
- 5 4 . 1 MCA
- 1 3 5 . 8 T,,IC
_99.6 MCA
-97
LB
-38.2
t)
( - l5e)
69
-50.5
- 124
62.2
32.5
16.8
-/o.i)
(.,
Transition metal:
Cromyl chloride CrOrClr.
Cobalt nitrosyl tricarbonyl
Co(CO)rNO.
llafmium borohydrideHf (BHr)r. .
Iridium hexafluoride IrFo. . . .
Iron dinitrosyl dicarbonyl
.
F e ( C O ) , ( N O2) .
fron pentacarbonylFe(CO)5.
Iron tetracarbonyl dihydride
Fe(CO),H,
Molybdenum hexafluorideMoF5. . . .
Nickel tetracarbonylNi(CO),. . . . . . .
Osmium hexafluorideOsFo..
Platinum hexafluoridePtF6.... . . . . .
e eFs...... . . .
R h e n i u mh e x a f l u o r i dR
Rhenium oxypentafluoride ReOFs. . .
Titanium tetrachlorideTiCl4. . . .. . .
eF....... ..
T u n g s t e nh e x a f l u o r i dW
Vanadium tetrachlorideVCI{. .. .. . .
Zirconium borohydride Zr(BH)t. . . .
Uranium:
e Fa. . . . .....
U r a n i u mh e x a f l u o r i dU
Compound
Temperature, "C
4.7,
1.8
U.l"r
o.0,
, .9rr
, .4rr
43
2.5
373", '
1.8
1.0
,9
26or
172,1
I 10,
8.2,
:, .' D:
394
313.,
112,,
546
109.
(11)
(DD/J
t7
168,,
r35
84"
oo.or
r23
34
43
47.5
69.14
33.8
73
(138)
L 7. r
152
r05
107.6
26
30
/.o
60,r
2.0
4.8
116
7 7. 8
118
53.6
20
bp("C)
95
15"
226,,
,a
4.3
2 . 1 , 17,
...
37",
3.9,
rr
lgrr
n.0tt
6.1
37,r
43,
-.61_$.se
1e
1 ._zo.oo
- 126.ssll l I pt.oo
r 1r.sll
Tobleof vopor pressures(Conlinued)
LB
LB
70
(-r12)
LB
LB
70
7l
70
72
70
73
LB
70
LB
LB
-70
1 7. 4
-22
3 3. 4
6 1. 3
18.7
40.8
_23
2.0
_26
28.7
6,{.I
LB
LB
l8.4
-21
28.8
43.8
LB
Ret.
_95
np("c)
(.)
Diethylzine (CzHs)zZn.. . . .
Dimethylzinc (CHs)zZn.. ..
Di-n-propylzinc (C zHt) tZn . .
Xenon Xe.
Xenon difluoride XeF:. . .
Xenon hexafluorideXeF6.
Xenon tetrafluoride XeFl .
Xenon oxygen tetrafluoride XeOFr
9.1
.1)
l6
37r
.t)
At 23"
9<
to
4.5"
29"
r23
1.9
0.6,
2.6
"
0.3,
7.9
(117.6)
43.8
(139.4)
-30
-29.2
-81
r2g
46
rt7
_28
-lll.9
2
LB
2
MCA
74
75
74
76
312
OF PURESUBSTANCES
VAPORPRESSURES
Referenccs for table of vapor Pressurcs:

D to Dreisbach'sbooks,
,4p1 refers to the American Petroleum Institute Tables,
./toJordan,sbook,MC,4totheManufacturingChemistsAssociationTables,arrd
sourcesare given in this
.LB to LancloltBornstein. The conipletecitntionsto these
references (f)
follorving
the
Data'
ln
Pressure
aopendix under Solrces of Vapor
(\"9)
br
Eq
fit
was
data
original
the
that
nieâns
I' Am'Chem' Soc',62:3425(1940)'
1. Burg and Schlesinger,
2. Bramfordet al., "J.Chent.Soc',1946:468'
3 . B e r k ae t a l . ,J . I n o t g ' N u c LC h e m ' , 1 4 : 1 9 0( 1 9 6 0 ) ( f) '
(
4. Shermanand Ciauque,I ' Am. Chem' Soc, 77:2154 1955)'
1953:1565'
Soc
Chem.
,
5. Benettet al., ,J.
(
6. Schlesinger,et al.' J. Am' Chem Soc, 62t3421 1940)'
(
'
1954
76:3293
Soc.,
)
Chem'
Am.
7. llrw et ;1., /.
8, Ceron et al., J. Am.Chem' Soc''8l:6368 ( f959 )'
)
9. Burg and Sandhu,lnorg. Chem',1:1467.(l^9-61
10. Urr| et al., /. Am. Chem.Soc.,76:5299 ( 1954) '
(1960)'
11. Staffordand Stone,I. Am. Chem. Soc.,82:6238
Press,Ithaca, N'Y',
i. S,""1, "Hydrides of Boron ancl Silicon," Cornell University
1933.
(1532)'
13. Pohlandand Harlos,Z. Anorg.AIIgetn Chen',207:242
(1956)'
Chem
Phys.
,6Oz9Il
14. Wirth anrl Palmer,!'
Table 39D'
15. Holtzman et al., "Proclirctionof Boranesand Related Research,"
1967'
York,
New
AcademicPress,Inc.,
16. Alton et al.. J. A.rn.Chem. Soc, 81:3550 ( 1959)
17. Burg and Randolph,l. Ant.Chem soc',7I:345I ( 1949)'
f 8 , B u r g a n d S c h l e s i n g eJr.,A m . C h e n ' S o c ' , 5 8 : ' 1 0(9f 9 3 6 ) '
et al., /. Am. Chen. Soc' 6O:1296(1938)'
19. Schi-esincer
2O. Burg, I.-Am' Chem. Soc, 62:2228 ( 1940)'
2L, Pariow et al., I. Am. Chen' Soc.79:5091( 1957)'
22. Egan et al., lnorg. Chem., 3:1024 ( 1964) '
2 3 . B u r e a n d K r a t z e rl,n o r g . C h e n ' , 1 : 7 2 5 ( f 9 6 2 ) '
2 4 . S p i e l m a na n d B u r g ,l t t o r g .C h e m , 2 : 1 I 3 9 ( 1 9 6 3 ) '
2S. Wirth and Patmer,J. Phys. Chem., 6O:914( 1956)'
2 6 . B u r g a n d S c h l e s i n g eI r. , A m . C h e n S o c, 5 5 : 4 0 0 9 ( 1 9 3 3 ) '
27. Parryand Bissot,J Am Chem. Soc,78:1524 ( 1956)'
28. Burg and Spielman,J. Am. Clrcm.Soc, 8l:3479 (1959)
2 9 . F i n c h a n d S c h l e s i n g eI r. ' A m .C h e n . S o c ' , 8 O : 3 5 7(31 9 5 8 ) '
30. Brotherton,et al., J. Am. Chem. Soc.,82:6245(1960)'
31. Wirshburnet al., Adc ht Chertt.,\et ,23"129 ( 1959)
, h e m .B e r . , 5 4 : $ f ( f 9 2 1 ) '
3 2 . S t o c ka n d Z e l d e r C
33. Haworth and Hohnstedl,l. An. Chen Soc.,82:3860(i960)'
, 3 : 9 5 3( 1 9 5 1 ) '
. o c .7
3 4 . B u r g a n d R a n d o l p hI, A n . C l r c n r S
35. Benningand McHarness,lnd. Eng. Chem.,32:197(19'10)'
3 6 . C . F . F u r u k a w ae t a l . ,J . R e s .N a f B u r ' S t d . , 5 1 : 6 9( 1 9 5 3 ) '
37. Bankset al., "1.Chem' Soc.,1948:2188.
38. Ducllel et al., /. An. Chem. Soc.,7O:3986( 1918) (f )'
( 1 9 4 7 )( f ) .
3 9 . S t u l l ,l n d . E n g . C h e n . , 3 9 : 5 1 7
( 1955).
47:1449
Eng.
Chen
Ind.
et
al.,
,
40. Mears
41. Boothet al., /. Am. Chen. Sor:.,55:2231 ( 1933)'
42. C. Kubas, rrnptrblishedobsenations, Northwestern Universitv, 1968; Anstrl
Co. Data Sheet.
SOURCES
OF VAPORPRESSURE
DATA
313
43. Kolski and Schaeffer,l. Phys.Chem.,64:1696 (1960).

44. Dennisand Judy, I. Am. Chem. Soc.,5l:232I (f929).
45. Ambergerand Boeters,AgneroChem.,73:'114( 196l ).
46. Sravastavaand Onyszchuk,Proc. Chem. Soc., 196l:205.
47. Fischer and Weidemann,Z. Anorg. Allgem. Chem.,213:106 ( 1933).
48. Colburnet al., /. Am. Chem.Soc.,8l:6397 ( 1959).
49. Giauqueand Ruehrwein,I. Am. Chem.Soc.,6L:2626( 1938).
50. Colburn and Kennedy, l. Am. Chem. Soc.,8O:5004 ( 1958).
51. Pace and Bobka, I. Chem. Phys., 35:454 ( 1961).
52. Budolph and Parry,lnorg. Chem.,4:1339( 1965).
53. Rrrdolphet al., Inorg. Chem.,5:L464(1966).
54. Holrnesand Storey,lnorg. Chem.,5:2146(1966).
55. Zeffert et al., /. Am. Chem. Soc.,82:3843 ( 1960).
56. Rudolph et al., J. Am. Chem. Soc.,88:3729 ( 1966).
57. Lustiget al., /. Arn.Chem.Soc.,88:3875 (f966).
58. Matrler and Burg, I. Am. Chem. Soc.8O:616I ( 1958).
59. Burg and Peterson,lnorg. Chent.,5:943( 1966).
6t0. Jenkins,lnd. Eng- Chem., 46:2367 ( Igil ).
61. Stock,Z. Elektrcchemie,32:Ml ( 1926).
62. Tannenbaumet al., I. Am. Chem. Soc.,75:3753 ( 1953).
63. Ebsworthand Frankiss,J. Chem. Soc.,1963:661.
64. Ward and MacDiarmid,I. Am. Chem. Soc.,82:215I ( 1960).
65. Merrill and Cady, I. Am. Chem. Soc.,8399B ( l96f ) ( f ) .
6i6. Brandt et al., /. Chem. Soc.,1952:2198.
67. Glemserand Richert,Z. Anorg.Allgem.Chem.,307:313(1961) (f )
68. Drrdley et al., ,1.Am. Clrcm. So.,78:1553 ( 1956) .
69. Dinney and Pace,J. Chem.Phys.,32:805 (l%O).
7O. Cady et al., ,1.Chem. Soc.,1961:I563.
71. Anderson,I. Chem. Soc.,l93O:1653.
72. Weinstocket al., /. Am. Chem.Soc.,83:4310 (1961).
7 3 . C a d y e t a l . ,/ . C h e n t . 9 o c . , 1 9 6 1 : 1 5 6 8 .
74. Schreiner et al., bstracts of Papers, l53d ACS Meeting, April 1967, Sec. R,
no. 127.
75. Weinstocket al., Inorg. Chern.,5:2189( 1966).
76. Chernick et al., "Noble Gas Compounds," p. 106, University of Chicago Press,
Chicago, 1963.
77. Lamb and Roper,I . Am. Chem. Soc.,62:806 ( 1940) .
78. Pihpovich et al., Inorg. Clrem.,6:1918 ( 1967).
79. Finholt et al., ,I. Ant. Chem. Soc.,69:2692(1947) (f ).
8 O . A s t o ne t a l . , . l .A m . C h e n . S o c . , 6 l : 1 5 3 9( 1 9 3 9 ) .
81. Pohlandand Mehl, Z. Physik.Chem.,A164:48 (1933).
82. Astonet al., .I. Am. Chem. Soc.,66:l l7l ( 1944) .
SOURCES
OFVAPORPRESSURE
DATA
Boubfik, T. and H. E. Vojitech, 1984, The Vapor Pressureso.fPure Substances,Physical.9crences
D a t a . Y o l . 1 7 . 2 n d e d . . E l s e v i e r .A m s t e r d a m .
Dreisbach, R. R. , I 955, Physical Properties of Chemical Compounds, Vols. I , 2. and 3 (Advancesin
C h e m i s t r yS e r i e s ,N o s . 1 5 , 2 2 a n d 2 9 ) . A m e r i c a nC h e m i c a lS o c i e t y ,W a s h i n g t o n ,D . C . A n t o i n e
p a r a m e t e r sa r e g i v e n f o r o r g a n i c c o m p o u n d si n t h e s eb o o k s ; f r e q u e n t l yt h e s eh a v eb e e n t a k e n
from other compilations.
314
VAPORPRESSURES
OF PURE
SUBSTANCES
Gmelin Handbook oJ Inorganic Chemistry, Springer-Verlag, Berlin, While not specificallydevoted

to vapor pressures,equations and referencesto data are available in this multi-volume compendium.
Jordan, T. E., 1954, Vupor PressureoJ'Organic Contpound.s,Interscience,New York. Vapor pressure equations, tabulations, and graphs for organic and organometallic compounds. This book
contains a fair number of errors and inconsistencies.
S t u l l , D . R . , 1 9 4 7 ,I n d . E n g . C h e n t . , 3 9 , 5 l 7 , 1 6 8 4 .R e p r o d u c e d w i t hm i n o r c h a n g e si n H a n d b o o k
of Chemistry and Phvsicsand in Chemicul Engineers' Handbook, Stull presentstabulations of
temperatures corresponding to vapor pressuresfrom l-760 torr for 1,500 compounds. In addition, short tables of data are given for the I -60-atm region. Even though 40 years old, this is a
v a l u a b l ec o m p i l a t i o n .
Wilhoit, R., and B. Zwolinski, 1971, Handbook o.f Vapor Pressuresand Heats of Vaporization o.f
Hydrocarbons and Related Contpounds, College Station, TX: Texas A & M.
PRESSURE
AND
FLOW
CONVERSIONS
Conversionfactors for various pressureunits and flow units are given in Table
V I . 1 . T a b l e V I . 2 l i s t sv a l u e so f t h e r a t i o d , / d o f t h e d e n s i t yo f m e r c u r ya t a t e m peraturet divided by the densityof mercury at 0'C) overthe temperaturerange
0-99'C. Capillary depressioncorrectionsfor mercury in glasstubes are given in
Table VI.3. The completesetof correctionsfor a pressuremeasurementis made
as follows:
P(mm):
h.u,(g/gd@,/di + C,-
Cl
where fto5,is the observeddifferencein height of the two mercurvcolumns,9/96

is a correctionfor the local accelerationdue to gravity (whereg is the local value
of the accelerationdue to gravity and 96 : 980.665cm/s2). d,/d()is a correction
for the densityof mercury(seeTable VI.2), C" is the capillarydepressioncorrection for the upper column of mercury (seeTable VI.3), and C1 is the capillary
depressioncorrectionfor the lower column (seeTable VI.3).
315
toble Vl.,l. ConversionFoclorsfor Pressure

Unilsond FlowUnifs
Pressureunits: I atm :
:
:
:
:
:
:
760 torr
1 . 0 1 3 2 5b a r
1 0 1 , 3 2 5P a ( N m 2 )
1 , 0 1 3 , 2 5 0d y n e / c m 2
1 0 3 3 . 2 3g / c m 2
14.6960lb/in.2
760 mm (Hg at 0"C)
F l o u ' u n i t s :I L / s : 0 . 0 6 m j l m i n
: 2 . 1 1 8 8 0f t r l m i n
: 15.850342gal/ntin
316
1.000000
0.998188
0.996381
0.994580
0.992782
0.990989
0.989200
0.987415
0.985634
0.9838s6
0.9998t8
0.998007
0.996201
0.994399
0.992602
0.9908
r0
0.989021
0.987237
0.985456
0.983679
0.999637
0.997826
0.996021
0.994219
0.992423
0.990630
0.988842
0.987059
0.985278
0.983501
0.999456
0.997645
0.995840
0.994040
0.992244
0.990452
0.988664
0.986880
0.985r 00
0.983323
3
0.999275
0.997465
0.995660
0.993860
0.992064
0.990273
0.988486
0.986702
0.984922
0.983146
0.999094
0.997284
0.99s480
0.993680
0.99r 885
0.990093
0.988307
0.986524
0.984744
0.982968
0.9989r
2
0.997r 03
0.995300
0.993501
0.99r705
0.989915
0 . 9 8 82r 8
0.986346
0.984566
0.982791
0.99873
l
0.996923
0.995r20
0.993320
0.991526
0.989736
0.987950
0.9861
68
0.984389
0.9826
r4
0.998550
0.996742
0.994939
0.99314r
0.991347
0.989557
0.987771
0.985990
0.98421
I
0.982436
0.998369
0.996562
0.994759
0.992961
0.99168
0.989379
0.987593
0.985812
0.984033
0.982259
'These density ratios are based on the densitiesgiven by P. H. Bigg, Brit. J. Appl. Pfrys. 15, I I I I (1964). This referenceshould be consulted for valuesin the
,
r a n g e - 2 0 t o O o Ca n d 1 0 0 t o 3 0 0 ' C , a l o n g w i t h e s t i m a t e de r r o r s .
30
40
50
60
70
80
on
ln
0
t0
OC
dt/do
Ioble V1.2.Rotioof lhe Densityof Mercuryof TemperotureI Dividedby the Densifyol OoCo
TobleV|.3. CopilloryDepressionCoreclion for Mercuryin GlossTubeso

Tube
diameter
(mm)
0.2
2
3
4
5
6
7
8
9
l0
ll
l2
l3
IA
IA
t5
l6
l7
l8
19
20
2.52
1.14
0.63
0.39
0.26
0 .l 8
0.13
0.10
0.08
0.06
0.04
0.03
0.03
0.02
0.02
0.01
0.01
0.01
0.01
Meniscusheight, mm
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
4.51
2.r3
r.22
0.76
0.51
0.37
0.26
0.20
0.t2
0.1l
0.08
0.07
0.05
0.04
0.03
0.02
0.02
0.01
0.01
2.93
r.73
l.l0
0.75
0.53
0.38
0.29
0.21
0.16
0.13
0 .t 0
0.07
0.06
0.05
0.04
0.03
0.02
0.02
2.12
1. 4 1
0.96
0.69
0.50
0.38
0.28
0.20
0.16
0.13
0.10
0.08
0.06
0.05
0.04
0.03
0.02
2.47
t.64
1.15
0.82
0.61
0.45
0.34
0.26
0.20
0.16
0.12
0.09
0.07
0.06
0.04
0.03
0.03
1.84
1.30
0.94
0.70
0.52
0.39
0.31
0.24
0.18
0.14
0 . 11
0.09
0.07
0.0s
0.04
0.03
1.42
1.04
0.78
0.59
0.45
0.35
0.27
0.2r
0.16
0.r2
0.l0
0.08
0.06
0.05
0.04
1.13
0.84
0.64
0.49
0.38
0.29
0.23
0.r8
0.14
0.11
0.08
0.07
0.05
0.04
0.90
0.69
0.53
0.41
0.32
0.25
0.19
0 .1 5
0.12
0.09
0.07
0.06
0.04
'From G. W. Thomson. Techniquesqf Organic Chemistry, Vol. I Pt. 1 3rd

ed., A. Weissenberg,
,
,
E d . , I n t e r s c i e n c eN
, e w Y o r k , 1 9 5 9 ,o . 4 1 0 .
3.18
INDEX
Acetone,purification,92
Acetylene:
generation,92
purification,92
Acrylic plastics,267
Alcohols,purification,92
Alkali metals,sampling,206-207
Aluminum:
gaskets,222
generalproperties,276-277
to fluorine,228
resistance
Aluminumcompounds,vapor pressureof,
290
Ammonia:
purification,93
vapor pressureof, 301
Ampule:
opening,34-35
sealing,32-34
Analysis:
gaschromatography
in, 199-2N
hydrides,27,30,200
in,27,30
hydrolysis
pyrolysisin, 200
Annealing:
glass,243
plastic,267
Antimony compounds,vapor pressureof, 290
Antistaticdevices,65-66
Antoine equation,282
Aprezon:
diffusion pump oil, 122-124
Q sealant,145
vacuumgrease,155
vacuumwax, 156
Argon, saeInert gas
purification,91
Aromatic hydrocarbons,
Arseniccompounds,vapor pressure,290
Baggingradioactivewastes.61-62
Bendingtubing:
glass,249
metal,274-215
plastic,26l
Berylliumcompounds,vapor pressureof, 290
vaporpressure
of,290
Bismuthcompounds,
Boron compounds,vapor pressureof,297-294
Boron halides,purification,93-94
Borosilicateglass:
ir-visible-uvtransmission,
244
resistance
to fluorine,227-228
tensilestrength,245
thermalproperties,242-245
seeao Glassblowing
Brass:
generalproperties,27'7
resistance
to fluorine, 228,277
Break seals,202-204
Bubblermanometer,129-l3l
Bubblers,8-12
Buna-N,272
Buret, gas,27, 29-30, 108
Burstingpressureof glasstubing,245
Butyf rubber,272-273
319
320
Cadmiumcompounds,vapor pressureof, 294
Calibrationof volume, l0g_i09
Cannula,seeSyringetechniques
Carboncompounds.vapor pressureof:
one carbon,291-295
two carbon,295_296
three carbon,296-297
four carbon,297
five carbon,29i-2g|
six carbon,298
sevencarbon,298
eightcarbon,Z9B-299
Carbondioxide:
purification,94
as refrigerant,112-ll3
vaporpressureof, 112_113.294
Carbondisulfide,vaporpressureof, 307
Carbonmonoxide,purification,94
Cariustube, seeSealedtube reactionvessels
Cathetometer,I3Z-133
Cellularplastics,265-266
Centrifuge
tube,cappable,
4l
Cesium,sampling,
207
Chlorocarbons,
purification,9l
Clapeyron
equation,2gl
Codistillation,
193,195
Columnchromatography,
37_3g
Conditioningfluorineapparatus,22g
Conductance
of tubingrowardgases,127_1Zg
Copper:
gaskets,
222
generalproperties.2'/7
resrstance
to fluorine,Z2g,277
Cryoscopyapparatus,3g, 39
Crystallizarion,
35-37
Cvlinder,withdrawalof liquidfrom, 20_21
Degasing:
freeze-pump-thaw,
l0.l
l i q u i d s , 8 51, 0 4
Desiccants,
70-72, g5-gg
Diffusionpump:
designof, 121-123
fluidsfor. 124
Distillation:
fractional,low-temperature,
193_195
rnertatmosphere,
12_13,g7_gg
trap-ro-trap,
105_107
Droppingfunnel,8, 30
Dry box, seeGlove box
D r y I c eb a t h s 1
, 12-113
Drying agents,70-72. 85-86
Dryingglassware,
l1
INDEX
Elastomers,
seeRubber
End-to-end
seals:
glass,251-253
plastic,26t,265
Epoxy resins, 268-269
Esr samplepreparation,190_191
Ethers,purification,
9l
Erhylene:
purification,94,20g
vaporpressureof, 296
Ethylenepropylenerubber,273
Explosionhazards:
acetylene,92
dangerousmixtures,239_239
liquidair, 10.103,127
liquid oxygen,10, 103,127
o r g a n i vc a p o r s1, 1 , 2 3 7
perchlorates,
Tl, 23g
peroxides,
36-87,239
pressurized
glassware,
11, 105,ll0
slushbath,lll
unstablecompounds,23g
Feed-throughs,
electrical,throughglass,255_
256
Filtercannula,22-23
Filtration:
fluorinecompounds,232
underinert gas,22-23,30_32.
35, 3g_41
of liquefiedgases,
35, 39_41,102,190-192
low temperarure,35, 39_41, 102,1g0_Ig2
vacuumline, 190-192
Fire curoff, 249-250
Fire extinguishers,
240
Flint glass,2,15
FIow reactors,232
Fluorine:
conditioningapparatuswith, 22g
corrosionof variousmaterialsby,2?7_22g
cylinderenclosure,235
precaurionin handling,232
pressuremeasurement,137,227
vacuumline manipulation, 227_232
Fluorocarbon:
grease,155
plasticapparatu
s, 269-270
polymers,generalproperties,269_270
rtbber,273-274
sealingcompoun<i,145
wax, 154,156
Fractionaldistillation,ree Distillation
Frirre,30, 32, 40
Friftedfunnel,30,32
INDEX
Fusedquartz:
244
ir-visible-uvtransmission,
to fluorine,227
resistance
thermal properties,243-244
Fusedsilica,seeFusedquartz
Gallium compound,vapor pressureof, 299
Gas:
cylinders, 166,210-212
generation,207-208
generator,automatic,25-26, 28
26-27, 29
measurement,
samplingtube, 26
separation,115,105-107,190-200
storage,2m-202
transferof:
25, 27, 104-105
condensable,
24-26, 113-116
noncondensable,
seeao Inert gas
Gas chromatograPhY:
gasinlet valves,197-198
209
generalreferences,
hydrides,200
permanentgases,199
preparative,198
reactivehalides,199
sampling,194-198
Gauge:
Bourdon,136
cold-cathode,140-142
diaphragm,137
electronicpressuretransducer,136-13'l
high vacuum,140-143
hot-cathode,142
ionization,140-142
Mcleod, 13'7-139
mediumvacuum,137-140
Philips,seeGauge,cold-cathode
Pirani,139-140
spiral,136
thermalconductivitY,139-140
thermionic,140, 142
thermocouple,139
Germaniumcompounds,vapor pressureof,
299
Glass,propertiesof , 242-245
Glassblowing:
annealing,247-248
bendingtubing,249
closedcircuits,255
cuttingtubing,248-249
end-to-endseal,251-253
equipmentfor, 245-246
321
fire cutoff, 249-250
healingcracks,256-257
healingpinholes,255
seals,255-256
metal-to-glass
ring seals,253-255
sealingevacuatedtubing,257-258
of operations,247
sequence
test-tubeends,249-250
T-seals,253
Glove bag, 45-46,62-63, 64
Glove box:
antichamberdoors,52-53
commonoperationsin, 65-66
51-56
contaminationof atmosphere,
evacuable,63
gloves,59-61
hazardousmaterialscontainment,61-62
54-56
of atmosphere,
maintenance
materialsof construction,63-64
monitoringimpurities,56-59
pump-and-fill,48
purging,49-51
Gold,27'7
Grease,vacuum,153-155
Halogencompounds,vaporpressureof.,299300
plastics,260
Heat-sealing
Helium, ultrapurification,82-83. Seealso
Inert gas
High vacuum:
definitionof, 118
140-142
measurement,
Hot-tubereactions,42-43
Hydride wastes,disposalof,239
Hydrocarbons,saturated,purification,9091
Hydrogen,purification,94
Hydrogenchloride:
purification,94
Hydrogenfluoride:
corrosionof glassby, 227-228
plasticapparatusfor, 230,232
cellsfor, 233
spectroscopic
Hydrogenhalides,purification,94-95
Hydrogeniodide:
purification,94-95
Hydrolysis:
analysisby,26-30
apparatusfor, 27-30
322
Implosionof evacuatedbulbs,200
Indium, 277-278
Indium compounds,vaporpressureof, 300
Inert gas:
detectionof impuritiesin, 56-59, g3
impuritiesin commercial,6g_69
purification,69-80
purificationsystems,80-g3
Infraredcells:
gas,184-185
liquid, 23-24
low temperature,186
specialized.
l39
Infrared transmissionof glass and qtartz,244
Iron,278-279
IR samplepreparation,23-24
Isoteniscope,
175-176
Joints:
ball-and-socker,
l5Z-154
conehigh pressure,220
flange,218-219,221-Z2Z
flare,216
greasefor, 155
greasrng!
153-154
knife edge,222
O-ring,154,156-160
pipe thread, 220-221
Solv-Seal,
157,159
standardtaper,152-154
swage,217-218
wax for, 156
Kabez,274
Kel-F,generalproperries,269-270. Seealso
Fluorocarbon
Kimax glass,seeBorosilicateglass
Kirchoff vapor pressureequation,2g4
Kovar:
genralproperties,278-279
seals,256
Lead,279
Lead compounds.vapor pressureof, 301
Lead-throughs,
seeFeed-throughs,
electrical,
throughglass
Leak detectors,145-146
Leaks:
dry box, 51-52
locating:
in glassapparatus,
143-146
in metal apparatus,146
real,143
repairof, 144
INDEX
virtual, 14,3
Liquid, transfer:
betweenflasks,22-23
from metaltanks,20-21
Liquid air, 109-ll0
Liquid nitrogen,109-110
Lithium,sampling,
206
Low-temperature
baths,109-113
Low-temperarure
distillarion,193-lg5
Manganese
oxide:
finely divided,prepararion,7g-79
supported,
preparation,
79-g0
Marlifold:
fluorine, 228-230
glass,high vacuum,100-102
for inert gasand vacuum,9-10
roughvacuum,119
Manometer:
designs,129-131
reading(s),
132
correction
of, 132-134,
315,317_3lg
Medium vacuumrmeasurement,13j-140
Meltingpoint determinations,
lg3-1g5
Mercury:
capillarydepression
of, 132,134,315.3lg
cleaning,135-136
cleaningup spills,134-135
densityof, 315.317
generalproperties,134
manometers,129-l3l
solubilityof metalsin, 134
toxicity,134
trappingvapor,722
Metal alkyl wastes,disposalof,239_240
Metalhalides,anhydrous,
purification,
95
Metaltubing:
bending,214-2t5
cutting,214-215
flarefitting,216
O-ring fitting, 159,2t8-2t9, Z2\-ZZ2
sofder fitting, 215-216
swagefitting,217-2lg
weld fitting, 215-216
Methane:
purificationof, 208
Molecularsieves:
gaschromatography
with, 199
low temperatureadsorptionon, j2_.13,
I 1-s_116
wateradsorption,
70-73.85-g6
INOEX
Molecularweightdetermination:
boilingpointelevation,
38
freezingpoint depression,
38-39
isothermal
distillation.179,180
vapordensity,177
vapor pressuredepression,177-179
Monel:
resistance
to fluorine,228
Mylar.270
Naturalrubber,274
Needlesizes,syringe,19
Needlevalves:
metal, ?22-224
Teflon-in-glass,
164-165
Neoprene,273
Nernstvapor-pressure
equation,284
Nickel:
resistance
to fluorine,228,279
Nitrile rubber,272
Nitriles,purificationof , 91-92
Nitrogen:
impuritiesin, 68-69
l i q u i d ,1 0 9 - l 0
purification,69-80
reacrivity,
68, 206
scavengers,
80
seealso Inert gas
Nitrogencompounds,vapor pressureof, 301303
Nmr samplepreparation,
23-24,188
Nylon,270
Oil, diffusionpump. 122,121
O-ring:
chemicalresistance
of, 1-58-1-59,
272-274
joint, 156-157
properties
of elastomers
for, 158
solventresistance
of, 157-158
Outgasing:
of asbestos,
5l
of cloth.51
of corrodedmetal,51
of elastomers.1.13
of glass.1,13
of paper,5l
of stopcockgrease.1.13,162
of wood,51
Oxygen:
detectionof, 56-59
preparation.207-208
323
removal:
from inert gases,74-80
from solvents,8T-89
Oxygencompounds,vapor pressureof, 303
Palladium,279
Perfectdisplacement
of, 49-50
Perfectmixing,49-50
Permeability:
dry box gloves,52-54, 59
glovebags,52-54
plasticsand elastomers,259-260, 262-263
Peroxides:
detectionof, 86
removalof, 86-87
Phosphorus
compounds,vapor pressureof,
303-305
Pinholes:
detection
of, 145
repair.257
joints,220-22.
Pipe-thread
Plasticizers,
16,267
Plastics:
bending,26l
cellular, 265-266
fabrication,260-261.264-265
machining,
26,5
permeability, 259-260, 262-263
thermoplastic,260-261, 264-265
thermosetting,260
welding. 260-261, 264
seealso genericname of specific plastics
Plastictubing:
bending.261
crimpseals,261
end-to-end
seals,261-26-5
end seals,265
Platinum,279
Polyamideplastics,270
Polychloroprene,
273
Polyesterresins,270
Polyethylene,
270-271
Polyfluorocarbons, 269-270
Polymerpressurebottle, 230
Poly(methyl
methacrylate),
63,261,
267
Polyolefins,270-271
Polypropylene,
270-271
Polystyrene,271
Polyurethane,
foamed,266
Polyvinylchloride,267
Polyvinylidinechloride,26'7-268
Pop-bottle
techniques,
41-42
324
INDEX
Potassium,
sampling,206_207
Pressure:
definitionof unirs,316
measurement,
129_134.
136_143
Pumpingspeed:
calculation
of pump_down
rimefrom. {g
olrruslon
pumps,122
limitationby appararus,l2j_I2g
mechanical
pumps,120_122
rhroughputcalculationwith, 12.1
_
Pumps:
arrangement
of, 127
diffusion,l2l_124
mechanical,122, lZ4, 126_127
Toepler,ll3_l15
Purgingair from apparatus:
drybox,49_51
initial purge,7_g
open vessels,g_9
Schlenkware,30_31
synnges,l0_11
Pyrex,seeBorosilicategiass
Pyrolysis,analysisby, 2-00
Quartz,seeFusedquartz
Rack for vacuumline, 103
Radon,vaporpressureof, 305
Ramanspectroscopy,
lg7
Reactionvessels:
for anionradicalgeneratron,
190_19i
for fluorine, 230_231
hotrube,42-43
rnertatmosphere,
30
sealedrube, 43_44
vacuum_line
filtration, 102, lg0_1g2
for vaporpressuretitrations, 16g,
lj2_l:/3
_
Reactivewasres,disposalot, 239_240
Ketflgerants:
Dry lce. 112-t13
Iiquidnitrogen,109_ll0
liquid nitrogenboil_off,193,195
slushbaths, 110_112
Residualgasanalyzers,142_143
Ring seal, 253-255
Roughvacuum:
apparatus,
llg_119
definitionof, 11g
Rubber:
generalproperties,272_27
4
permeability,262_263
sepra,14_17
genericnameol specificrubbers
^t:l :lto
Kuotdlum.sampling,
207
Safety:
disposalof reactivewastes,239_240
extrnguishing
fires,240
implosionof evacuatedbulbs,200
seealsoExplosionhazards
Sampling:
alkali metals,206_207
gasmixrures,197_l9g
volatileliquid mixrures,196-197
Saran,267-269
Schlenkware:
assembly,
3l_32
basicpieces,30
H-rube,39_41
purglngair from, 31
rube,30_32
Sealedtube reacrionvessels,42_43,
202_206
Sealingevacuatedtubing. ZS7_25g
Seals:
glass:
end-ro-end,251_253
graded.2.15
ring, 253-255
gfass-to-meral.
255-256
glassT, 253
plastic.end-to-end,
265
Seleniumcompounds.
vaporpressure
ol, 305
Jepta,rubber,l4_17
Serumbottlecap,ree Septa,rubber
Shortcircuit,4g-50
Siliconcompounds,
vaporpressureof, 305_
307
Silicone:
diffusionpump oil, 122,124
grease,155
rubber,274
Silver,279-280
S l u s hb a t h s l,l 0 - l l 2
Sodalime ftap. Z2g_230
Sodium.sampling,206_207
Soft glass,seeFlint glass
Soldering:
glass,256
metal,I 15-116, 228,275_2.76
Solid,transferof, 3l_3-5
Solvents:
cryoscopy,112
detecting
g9_90
impurities,
purification,84-g9. 90_92
storage,89,200_202
Solv-Seal,
157,i59
Spacevelocity,70
Stainless
steel:
generalproperties,27g
325
INDEX
to fluorine.228,278
resistance
Steel,278
Stirrers:
reciprocating.174
rotary,S
Stockvalve,165
Stopcocks:
designof, 161
greasing,
162
improvingfine control,164
lapping,163
retainer.163-164
Storage:
gas,200-202
solvent,89.200-202
Styrofoam.265-266
36-37
Sublimation.
Sulfurcompounds,vapor pressureof, 307309
Sulfurdioxide:
purificationof, 95, 208
vapor pressureof. 309
Swagefitting, 21'7-218
13-24
Syringetechniques.
Tantalum,280
Teflon:
generalproperties,
269
l53
sleeves,
tape. 220-221
seealsoFluorocarbon
Telluriumcompounds,vapor pressureof,
309
Tensimeters.
168-175
Teslacoil, i45
Test-tubeends:
glass,249-250
plastic,26l
Thalliumcompounds.vapor pressureof,
309
170-17I
Thermaltranspiration.
Thermistor,180-181
Thermocouple,
182-183
Thermometer:
mercury-in-glass,
179
pentane-in-glass,
179
vaporpressure,
179-180
Thermoplastics
, 2ffi-261, 264-265
plastics,260,265
Thermosetting
17-18
Three-needle
technique,
Throughput,124
vaporpressure
of,309
Tin compounds.
4
Titration, tensimetric,172-17
T o e p l e pr u m p ,1 1 3 - l l 5
Transrtron
metalcompounds,
vaporpressure
of, 3 l0
Traps:
fluorocarbon.232
glass.124-125
gasadsorption,I l5for low-temperature
116
metal,229
soda-lime,228-230
volumecalibration
of, 108-109
Trap-to-trap
distillation,105-107
T-seal.253
Tubing:
metal,ste Metal tubing
plastic,seePlastictubing
Tungsten:
generaIproperties,
280
to glassseals,255-256
Tygon,267
Ultraviolet:
cells,2,1
transmission
of glassand quartz.244
U-manometer,129-131
vaporpressure
of. 310
Uraniumhexafluoride,
Vacuumgauge,seeGauge
Vacuumline:
100-i03
arrangement
of components.
generalpurpose,99-100
greaseless,
l02
latticefor. 103
335
metal,22'7-232,
plastic,119
simple,99-100
Valves:
attachingto apparatus,225,227
ball.224-226
bellows,223-225
223-224
diaphragm.
gate.224-225
needlevalves,222-224
packedmetal,223
Teflon. 233
164-166
Teflon-in-glass,
Vapor pressure:
by, 113
characterization
correlations,286-288
estimation,286-288
113
measurement,
289-311
of pure compounds,
tabulations,290-311
179-180
thermometry,
titrations.1'72-175
326
Vapor pressureequation:
Antoine,282
four-parameter,283
Frost-Kalkwarf,284
Kirchoff,284
derivation,285
least-squares,
Nernst,284
two-parameter.282
Vibration:
effecton gauges,137
reductionof,102,121
Visible:
cells,24
of glassand quartz,244
transmission
Viton-A, 273
Vycor:
244
ir-visible-uvtransmission.
thermalproperties,243-244
INDEX
Wastes:
bagging.62
radioactive,
reactive,disposal,239-240
Water:
detection,56-58, 89-90
purification,90
removal:
from inert gases,70-73
from solvents,85-89
vapor pressureof, 287,303
Wax,vacuum,153-154,156
Weighingtubes,micro, 31-32,34
Welding:
metal,275-2'16
plastic,260-261,264
Xenon compounds'vapor pressureof' 311
Zinc compound,vapor pressureof, 311

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I

QD6l.557 l9rJ6 542

PART2 VACUUM LINEMANIPULATIONS

APPENDIXIII PLASTICSAND ELASTOMERS

V.l Analy'ticalRepresentationof Vapor

Toble '1. Comporisonof lnert-Almosphere

Exclusionof Air Quantities"

Rapid and easymanipulation

B. Plonning lhe Expeliment.

there will be countercurrentdiffusion of atmosphericgases.An estimateof the

where,4is the cross-sectional

D. PUrging Sylinges. Syringes

:hrough inlet 2, with no flow from inlet 1, preventsair contaminationduring the

B. Septo ond Olher Closules. Rubber septamay be attachedin a variety

siliconerubber, sandwichedbetweenthin sheetsof Teflon. The siliconerubber

Ioble '1.'l SpeclrolSignoluresof lmpuriliesfrom SfopcockGreoseond

Reto ne. wosher

Assembled hypodermic syringe in metal pipette holder.

E. Exomple:Wifhdrowolof Highly Reoclive liquids from Mefol

F. Liquid llonsfer Connuloe.

used imnlediately,it should be rinsed u'ith degassedsolventimmediatelyafter

-:: through it from a syringeneedle attachedto a tube and low pressuregas

of a reaction.For example,the analysisof activehydridesand alkyl compounds

tig. 1.19. A gas buret for the measuremeno

evolutionhas ceased.the water levelsare again matched.and both a buret and

^.-.-Fig. 1.23. Weighing pigswith caps'

F i g ' l . 2 4 . O p e n i n g a s c a | c d r n l p u | c ' l . J ) T h e n e c k o | ' t h e a n r p u l c i s c a r e fnue| c| rks' cl noerret gdauss i n g

and other glassblowing operationsare givenin Appendix Il. When an evacuated

materialspresentis that impurities createdby partial reactionwith adventitious

liquids may be carefullyremovedby syringeand crystalsshakenfrom the tube in

,f theseO-ring joints are identical.When moderatequantitiesof solidsare being

!entional designs,a complete set of common operationsfor synthesisand,/or

\ completemethodologyfor the manipulation and reactionof air-sensitive

F i g , 1 . 3 1 . H e a v y - w a l l e dc e n t r i f u g e - t u b er, u b b e r c a p l i n e r , a n d c a p . ( " P o p b o t t l e " r e a c t o r . )T u b e s

f' W . C . J o h n s o na n d C . A . H a s k e w ,I n o r g . S y n t h . . l , 2 b ( 1 9 3 9 ) .p r e s e n td e t a i l so f t h e g a l l i u n rc h l o ride synthesis.

his chapter describesthe principlesof inert-atnrosphere

glove bags with integral polyethyleneglovesare much more convenient(Fig.

F i g . 2 . 1 . P o l v e t l t r ' l c ngcl o v eb a g . S e v e r a sl i z c sa r e a v a i l a b l e .i n c l u d i n gg l o v eb a g su ' i t h t * o p a i r s o f

flush of inert gasthrough the box is often employedto ntinimizeimpuritiesin the

small punlpabletransfer lock is generallyattachedto a largebox to facilitatethe

Sincethe pumping speedof a mechanicalpump doesnot vary greatlyat modera t e p r e s s u r e s( e . g . , F i g . 6 . 3 ) . i t i s r e a s o n a b l et o a s s u m ea n a v e r a g ec o n s t a n t

B. Pulging. Figure 2.2 illustratesthree simplemodelsfor flushing air from a

In contrastto perfectdisplacement,Eq. (4) demonstratesthat perfectmixing

gen through the walls is significant. For an average-size

ning the glovesin and out during routine manipulations.Commercialunits are

rure metersare availablewhich operatein the parts per million range.8These

2,4 GLovEBox HARDwARE

tionsmay be nearlysimultaneous.Once the systemis up to latm of pressure,the

O-ring (do not

Unfortunately,the working distancefor commercialstereomicroscopes

F i g ' 2 ' 1 3 ' C o n t m e r c i a lm e t a l g l o v eb o x . A n a l u m i n u m g l o v eb o x w i t h

debris from the materiarsbeing handred, and it can be nicked if improperry

B. Exomple: Tronsferof Moferiols through on Evocuoble Air

material, causesmall crystallographic-size

: : n o n , C . J . , l 9 6 3 , " G l o v e B o x T e c h n i q u e s , "i n H . B . J o n a s s e na n d A . W e i s s b e r g e re. d s . , f e c f t n i q u e o f I t t o r g u n i c C h e n t i s t r y ,V

\c'\'engradesranging from "extra dry" (which is quoted to be 99.9% pure) to

adsorbent.In general,the purificationprocessis fasterfor finer particlesand for

Good capacity;regenerateat 400'C in

Fair capacity;regenerateat 500"C in

Silica gel (narrou

Fair capacity;regenerateat 300'C

Limited capacity;especiallyin the

perthrough a drying tube. The regenerationof these moleculaf sievescan be

c.Low-TemperolureTroppingondAdsolptionofWolel.Alowtemperaturetrap is an effectivemeansof reducingthe moisturein a gasto a very