THE

STUDENTS' GUIDE
Quantitative Analysis.
IttTENDHXJ AS

AN AID TO

T>IK

STUDY OP

FRESENIUS' SYSTEM.

BY

H.

CARRINGTON BOLTON,

Ph.D.,

fBOTESSOR or CHEMtSTHV )N TRIHITY COU-IOE, HAKTFORD, COHN.

ILL VSTRA TED.

THIRD EDITION, WITH ADDITIONS AND CORRECTIONS SECOND THOUSAND

NEW

YORK:

JOHN WILEY
1899.

&

SONS

COPVRIG.'tT, iSSl,
Bv H. Carringtos Boltow.

Primed by Braunwonh, Muiiii&

B.irbcr,

Brooklyn. N. V.. U. S. A,

o
p5

to

&
40

"in

-J

< U
o

u
>

>

PREFACE.
A portion of
the following pages originally appeared In
Chemist,

the columns of the American

under the

title:

^'Schemes of Analyses execrtted in the School of Mines, Cohimbia College." Numerous applications for copies in

book form have induced the author to publish the Schemes

under a more general
title.

Since writing the articles the author has been called to

another sphere of labor, and the circumstances which led
to their compilation are explained in the following

para-

graphs, quoted from the prefatory remarks accompanying

the original publication. "

The system

of instruction in Quantitative Analytical

Chemistry, organized in the School of Mines, Columbia

College,

by Dr. C. F. Chandler, has been developed by the

Assistants,

who have had charge

Analysis,

of

the

Laboratory for
Dr.

Quantitative

Mr. Alexis A. Julien,

Paul

Schweitzer, and the writer.

The

practical

examples and the methods of analysis were

originally selected

by

Prof.

Chandler; the latter have been

modified by the Assistants, and from time to time they

have introduced new processes, conforming to the advances

made

in this

department of chemical science.

i.

PREFACE.

The

plan oi

the Students'

Guide

is

similar to that

papers of in the cxcclkiU

Mr. Alexis A. JuUcn entitled

Quantitative Analysis,"
the

"Examples
details,

for

Practice

in

the needs o however, arc the result of observing five years' experience in teaching studeiUs during my
large classes.

The fragmentary
notes
is

character of

many

portions of

the

accounted for by the fact that they are intended

and to indicate to the to serve in part as lecture notes,

student the points to be studied.

Kkesenius'

"

SysUm

of

(American litstmclion in Quantitative Chemical Analysis" New York, edition, by Profs. O.D. Allen and S. W. jolmson
;

S8i)

is

placed in the hands of each student on entering the

laboratory, but

many

students are perplexed by the peculiar,

though systematic, arrangement of this classic worli, and are at a loss to know how to begin work, ivhat io study, and

where
cases.

to

find the information appropriate to particular To aid the student in the study of Fresciiius' work,
it, is

and not to displace

one

of the objects of the

STUnENTS.'

Guide.

It is

then scarcely necessary to state that very

free use has

been made
however,

of

Frescmtis'
in
all

System; acknowl-

edgment

is,

made

cases.

By

occasional
is

references to original papers

the student's

attention

directed to methods, as detailed

by

their authors, with the

hope

of

encouraging the student

in research," H, C. B.

Trinity College,

LIST OF ANALYSES.

List ot Aoilyteis.
i,

BarSc chloHdc,

iJa.

CI, 11,0.

3.
J.

Magnetic

siiSphate,
tiiilphate,

>[!iO, sn,, 11,0.

Amuwnio-ftfi-ic

yO^, Nil.,

l'V,0,j l>y i,yriitiO!i,

;iikI

by pre-

cipUiition

volmiK'lrically,

K, CI,
5. 6. J,

Hj'drodiscdic phosphate,
Silver coin,

KA,Oi Pfii, H,0 by Au, A, Cu, I'b.

direct weight.

Dolomite,
Bronze^
Coal,

CaO. MgO,
Cis,

HiO,, I'cj

),,

CO, by

los

and byUii-ect
S, Z.
volatile

wciglit.

S.
cy.

H,0,
Cu,

matter, fixed carbon,

asli,

S.

10.
It.
12.

Coppfir

fiyrites,

ill

diipricat<3.

Alkalimetry,

Soda A^h, peari ash.

Vinegaf, iiydj'odhloric acid.

Acuiimetryj
Chlorimctr;^,

13,
l.f.

Bkachingr powder.
Pb, Sa, Sb, Zn.

Type

Hiatal,

jj,
16.

;5ir(i;orc,

Zn.
ore,

Chromic iron
Pyrolusite,

Ct,0,.

17.
iS. 19.

MnO,.
SiO,,

Feldspar,
Slag,

A1,0 K,0, Na,0.

SiO., AljOj,

CaO, MgO, FcO, MaO,

iirtd

;o.
St.

liijmatilia,

SiO,, Fc,

Titanifeoiis Iron ore,

Complete analysis.
Fe.

13.

Pig iron.
?!icHol ore,

Mn,
S, Si.

graphite^ combined G, T\

I^, 2^.

Ni. Co.

Ar5cnopyrJt,

A.

vm
Ui(
ij.
oJ Aol]Fi>.

LIST OP ANALVSES.
Constituents IQ t* <l*nntiieA

Guano.
Superpliosphat* of lime,

P,0 CaO, MgO, Fe,0 SiO NHji SO,, organic matter.

P,Oj soluble,
soluble.

!i,0

precipitated,

and

in-

s6.

27,

Water,
Specific gravity of a olid,

CaO, MgO, Na,0,

SiO,, organii:

K,0, SO,, CI,

rrsattcr.

2S.

Heavier, lighter than, and solublti in water, minarais and allo^-s.

39,

*'

"

"

liquid,

By

the lla<k,

by hydrometer, and by

weighinij a solid in the liquid.

30, jt.

Sugar.
Potass ic ferrocyan!c!,

C, H, O.

N
C.

by Willand Varrentrapp's,
iJeSseos* ractliods,
II.

and

32. 33.
3+.

Oil of turpentine,

Urine,
Milk,

Qualit.itive

and quantitative.
sugar, ash.

Water,
sugar,

tjuttcr, casein,

3j.

K aw

Water, crystalli stable grape sugar, ash.

cane

sugai

36. Petroleum,

Fractional distillation, specific grav

Hy,

fire teat.

INTRODUCTORY NOTES.

By means
position of

o Chemical Analysis

we determine

the com-

any substance.
is

The

Analysis object of Qualitative

to determine the

of a body. nature o the constituents

The

Analysis object of Quantitative

of these constituents.

is

to determine the

amount

methods, Gravimetric Quantitative Analysis includes two

attid

Volumetric Analysis.

convert the lcno\vn cousrituIn Gravimetric Analysis we forms as will admit of their ents o a compound into such in by weight. This is done chiefly
exact determination

two ways
1st

By

of a body as separating one of the constituents

fuch

{e.g.,

Cu by

the battery),

2nd,

By

into a converting an existing constituent

{e.g.,

new

form by e^cchange of elements

AgN03+HCl = AgCl

+HNOj).
The forms must
1st
2nd,
fulfil

two conditions:
of

Must be capable
Must be
of

being weighed exactly.

atid fixed composition.

known

3j

INTKODUCTOKV NOTES.

The

on two comidchoice of form of precipitate depends

eratian.'S,

The most

preferable

are

St,

Those most
in

ii\solubIc in the surroundiiig liquid

2ml Those
to

be

which the proportion of the constituenti! determined is very smalt compared with the weight
(t'.j^,,

of the precipitate

In

BaSO,

is

only T3.7 per

cent.).

In Volumetric Analysis the amount of a constituent

estimated by the action of reagents in solutions of
strength and of determined volumes.

is

known

(Sec Notes on Vol-

umetric Analysis,

p.

40).

AND FOR STUDY. WORKS FOR REFERENCE

^
,
\

Svcm
English

^^Z::^..
York, 1881
r^../..
edition.
;

"^JlZ
last

ChemNew Ledcan, Jol. Wile, a.d Son.

of Instruclion

Quantitative

last

German.

QuantUative Chemic.l Analysis.

New
.

York,

last

R,s^, //.

Chimie Analytique. Traits Complet de

2 vols.

fans,

1850-62.

^...

//.,

and yy^/---.

Handbuch der amlytischen Chenne.

_

Leipzig, 1S67.

Mr.
ode
^m...

Lehrbuch

der

cUemisch-analyt.schen

T^^tr^rmpthlUnrmcth

Braunschweig,

last edition.

Sy.ten.atic
last editiotx.

Handbook

of

Volumemc
quantUative

Analysis.

London,

J?a>m>.Me.s.
Analyse.
Crook^s.
last edition,

Leitfaden

ftlr

die

cbemische

Berlin, 1S63.

Seket Methods

in

Chemical Analysis.
,

London,
,

Handtuch der ^o/ley and E. K,ppedition, Untersuchungen. Leipzig, last

techn.sch-chemi.chen

Wshkr
,861.

Also

Gottingen, Beispielen. Die Mineral Analyse in Philadelphia, iramiation by Henry B. Nason.

Outlines of Proximate Organic
Analysis.

1871.

Van
Chem-

PrescoU.

NostTand,

New

York,

last edition.

Caldwell
ical Analysis,

Agricultural QuilitatWe and Quantitative

New

York,

last edition.

Xli

U'ORKS FOE REIEREN.CE

Wankly>r
\Val(;r

^KD FOR STUDY.

last edition.

Ar.alysis.

London,

Mu.s.n. Ankitung .ur Heidelberg, 1S74. wasser.

je,V^v^/..

Analyse Uer Aschex. und Mmet.!-

Notes

on
;

Assaying

and Assay Scheme..

Nev.

York, Wiley
Sforer.

&

Sons

last edition.

First

Outlines

of

Dictionary

of

SoKibilUies of

Chemical Substances.
/lPP^

Cambridge, 1864.
Reactionen der
Stoffe.

Die Chemlsche

wichtigsten anor-

ganiscLn und otgani.chcn

(Tabellen, etc.) Leip.ig,

'Itihchrift fur

Analytisdie Chemic, Frescnius.

Wiesbaden,

1862 to date.

Jahre.btrkht Ubcr die

XS47 to date.

Fortschntte der Chemie.

Giessen,

BuHeHn de
date.

la Soci6t^

Chimkiue de

Paris.

Paris,

1864 to

Chemical Nat^s.

Crookes.

London, 1S60

to date.

American ChevmL

Chandler.

New

York, iS? 0-7 7.

J.

American Journal of Sdaia and Art. New Haven, iSrg to date. Dana.
Journal of Analytical Chcmhtry,
1S87 to date.

D. and E. S.

Edward

Hart.

Easton,

THE

STUDENTS' GUIDE
irt

QUANTITATIVE ANALYSIS.
Amlysis No. I. Baric Chloride.

BaCU + 2H,0.
A, Determination of
See Fies, Quant, Anal., |
795.
141.

Chloriii.
a,

and pages 790 to An^fysts, (References are to Fresenius' QimuUiaiivc

American

edition, tS8i.)
r\

grm. of powdered BaC^-f sH.O and slight excess of dissolve in cold water in a beaker add a and previously acidulated with HNO3; stir well,

Weigh

out 0,8 to

AgNOj
warm.

When

the precipitate of

and the supernatant liquid is slightly acidulated a No. 2 filter; then add boiling water stir, and. with HNO3, to the precipitate in the beaker; pour off through after the precipitate has settled again,
the

has entirely settled, quite clear, pour off through

AgCl

washing by decantation three or filter by four times; then bring the precipitate on the
filter.

Continue

this

means

of a glass rod qv a feather

wash

it

down

into the

point of the filter; wash laistly with a little non-ackhfied water ; cover the funnel with paper ; label properly, and set Weigh a clean porcelain crucible; transtcr aside to dry.

j^

QUANTITATIVE ANALYSIS.

crucible, removing tlie AgCl from the precipitate to this Wrap a clean platipossible. the paper as completely as filter, forming a ^'cradle;" num wire around the rolled-up

burn the
cover
;

filter in

the

cradle over the inverted crucible

fall

do not

let

the ashes

into the crucible.

;

Moisten

the ashes with cone, add a drop o cone.

the contents of

HNO3

(one drop)

heat one minute

HCl; evaporate

cautiously,
until the

and heat

the crucible and cover

AgCI

is

temperature than partly fused, avoiding carefully a higher See Fres., 82, b. Wcish the crucible and necessary.
contents.

For

calculation, see

D.
Fres., 115,
;

AA. Second Method, Compare

Take
into
to 0.2 to 0.5

1,

a,,'?-

grm,

BaCU

+ H,0
(free

dissolve in

warm

water; acidulate with

a "parting flask;" add the flask, and shake well.

precipitate in
tlie

HNOj AgNOj in slight excess; cork When well settled, wash the
from chlorine); pour

flask

by decantation with warm

water,

glass, over a

Invert the flask, covered with a watchweighed porcelain crucible, placed in a large porcelain dish, and filled with water. Withdraw the watchwithout
filtering.

glass carefully, allow the precipitate of

crucible,

AgCl

to fall into the

and remove the parting

flask.

Four the water out

with
filter

of the crucible,

remove the

last portions

paper,

and dry on a water-bath.

weigh.
Note.

Ignite to incipient fusion, and

The

precipitate

settles best in

presence of an

excess of

AgNOj.

B. Determination

of Barimn.

See Frcs., 132,1, i, and loi, I, a. Dissolve i to 1.5 grm. substance in warm water acidulate with HCl dilute to about 250 cc; heat to boiling when boiling hard, add dilute HjSO,, in slight excess boil some minutes and then
; ;
;

CALCULATION OF ANALYSIS.

,
^

15

Test with a settles. keep warm while the precipitate by decantation dropof H^SO,; wash with boiliitg water dry filter wash well then bring the precipitate on a No. 2 crucible burn filter and ignite precipitate in a platinum contents of crucible. a cradle as above, and add ashes to
; ;

Sec

Frcs., 7

'?

precipitate with jVi,/tf._Wash until the filtrate gives no of A*NO When estimating barium in the presence
salts nitrates, chlorides, etc., these

arc sometimes carried

down with

the BaSO^.

Since

it

is

impossible to remove

alone, treat the precipitate these by washing with water Cf. Crookes' acetate. with very dilute HCl. or ammonie

Selea Methods, page 312.

C. Determination of

Watw

(by Ignition)

to 1.5 grms. substance; In a weighed crucible weigh out i small flame, and increase heat very gently at first over a finally, heat to low redness the temperature very gradually operation until the weight then cool, weigh, and repeat the liigh a temperature, remains constant. Caution avoid too substances contain large When else the CI will be expelled. magnesic sulphate, hydrodisodic percentages of water, as water at ioo- C. phosphate, alum, etc., begin to expel the
;

in

an

air-ba.th.

D. Calculation of Analysis-

See Fresenius. page

ments, the
first

79S,

^ilao

196-

Make two

state

to

determine the amount

of the desired

constituent in the precipitate obtained:

, Mol.WUof

1
I
.

precipitate

At. Wt. of the constituent desired

1
\

Actual

weight of
precipitate

[
J

Actual | weight of \
constituent. J

1^

QUANTITATfVE ANALYSIS,

The second statement determines the percentage

desired constituent in the substance taken
Wt. of sii!>
KtAncc taken
Acttial weight

of

tjj

of

contituent

too

''<fffl<s of tl 1

To check work, compare with

when
possible.

theoretical pcrccntasfct

Tfuoretual compasilion of crystulJizcd barium chloride,

Ba 56.15
CI,

= 29.09
14.76

2H,0=

100.00

Use ofFrcscnius' Tables for the calculation of analyses Compare Tabic IH. I- res., page
854,

Examples:

X 0.7= BaOSO, X 0,34335

Fres.,

Fe,0,

= 50,.
also

2Fe,

Consdt Table IV.

pages

%^,6, ei seq..

page J^a

'"',
of

eT-To

f^^

^'-

^'^^SSO,

yielded

we hav^r
'2
'

''"^^''' '^'''^^

^^

precipStaie
"-^^

^^-^

^*^

a3433S
c^o<SS67

*co
.007

^^^^^
* '

.0004

'^^<^ 0.00013

1.2074

041455=50^
0.41455

;^=32.7SpercentSO,

KEI'ORXJjNG

ANALYSES.

E. Reporting

Analyses.
let-

ter

Analyses may be reported on blank forms printed on paper 8" x lo", having following headings
:
, . .

Hakti'okd, !S8 Report of Analysis DliXEKMlNATJON OF GRAMMES TAKEN Metiiod of Analysis These headings are colimin in printed in vertical one horizontal line are placed following headings: Pkecii'ITATes, Actual

OF

Weights, Constituents, Calculated Weights, Percentages, Theoretical Percentages; under each a blank
space
is

left

of

2 1-2 inches.

Under "precipitates"

place
"

formulas of precipitates obtained; under "actual weights"

place actual weighL-i of
'

precipitates; under "constituents

place forniDlcC of constituents to be reported; under "cal-

culated weights
in precipitates;

place the
"

amounts

of constituents existing

percentages" place percentages of in short, the results of constituents actually obtained

under

analyses.

The

last

column, "theoretical percentages," can

pure chemical
salts.

be fdled only

in

the case of few

The words special remarks

from the bottom
processes employed, etc.*

are printed about two inches

of the sheet, leaving

room

for remarks on

Notes
Reactions. (I)
(2)

to the

Analysis of Barium Chloride, -f

-\-

BaCL
BaCI,

H,SO,

-AgNO^

= EaSO, + 2HCI = 2AgCl+ Ba(NO,),.

;

The

chloride of silver precipitate changes color on expos-

ure to light, losing chlorine and forming AgjCl

the change,

however,

is

only superficial, but Mulder says the loss of

weight

is

appreciable.

* Sec scccimcs blaok ai the end of this beok.

(iLrANXri-ATIVE ANALYSI.-,,
iS
is thrown down as AgCJ [^ water, a slight bluish mllkiness maystiU 1,000,000 parts of This cloudiness disappears on adding an excess be seen.

When

one part of silver

of

HO.
Barium sulphate requires more than 400,000 parts of
''

water

for

solution.

The

solubility

is

increased by the preseiiee of NaCl, but HCl produces a sensible increase.

KCIO,

not perceptibly or Ba(NO,)

(Cf. Storcr's Diction.

ary of

Solubilities.)

Barium sulphate thrown down in a solution containing This becomes ferric salts is often contaminated with iron.
evident by the rcddisli
nition.

color of

the precipitate after

ig-

be purified by washing with ammoniuni acetate, or hy solution in cone. HjSO^, and reprecipitation by pouring into water. BaSO^ dissolves In
precipitate
cone.

The

may

H.SO^

in the ratio of 5.7 parts to lOO,

and

in

Nord-

hausen sulphuric acid as 15.9 to roo.

Analysis No.

2.

Magnesic

Sulphate.

MgS0.H-7H,0.
A, Determiuation of Sulphuric Acid.
See Fres.,
stance in
2,50 c.c.
;

132,

I,

i.

Dissolve

to

1.5

grm. of sub-

warm
boil

water, acidulate with

;

HCl,

dilute to about

hard

add

Bad,

carefully, avoiding a large

excess; boil a few minutes; let the precipitate of

settle
;

BaSO,

wash by decantation and on the

I,

filter, aiid

continue

as in Analysis

B,

B. Determination
.

of

Magnesium.

"^^' 104, 2. Dissolve abont 1.2 grm. of substance >n 150 ec. cold water, in a beaker; add 30 c.c. i\H,Cl,

DKTfUOI NATION OF WA'IEK,

I

I9

10

c.c.

NI^HO, and

a slight excess of IINa^PO^.

(Should

add NH^Cl until it a precipitate form on adding NM4HO, Stir the contents of the beaker well, avoiding rcdissolvcs,) touching the sides with the glass rod. Cover, and set aside
for 12 hours, without

warming.
its

Filter

water,

to

whicli

one-fourth

and wash with cold volume of NH^MO has

been added, until the filtrate acidified with HNOj gives only a slight opalescence with AgNO,. Dry thoroughly on increasing the filter, ignite in a platinum crucible, gradually before the heat burn the filter on a cradle until quite white
;

adding the ashes to the contents of the crucible. If the preor two o cipitate or asli is not white, moisten with a drop (See Fres., cone. MNO3, evaporate, and ignite cautiously.
74, b

and

c.)

Weigh

the precipitate as Mg,P,Oj.

C Determination

of "Water.
crucible,

Heat I to 1.5 grni. salt in a weighed platinum and proceed exactly as in Analysis I, C.
Analysis of Maguesic SulpJmte.

Notes

to

amraonio-magnesic phosphate in paragraphs water and saline solutions. Cf. Fres. page 816,

On

the

solubility of

35-35f

15300 parts of pure water.

" "
"

One

44300 part of < 7548 precipitate dissolves in 15600

I

ammoniated
strong
sol.

^vater

"

of

NH.Cl.

"

"

water containing

NH^HO

andNH.Cl.
For
the ammonio-magnesic a discussion of the solubility of vol. phosphate, consult Cladding's letter in Chem. News,
47. P- 71 (!883).

QUANTITATIVE AKALYSIS.
2C
Rcactio>is.--l^y

precipitation

we have:

2MCSO.

+ N1I.,CI + 2NH,H0 + 2HNa,P0,= Mg.(NH.)J',0s + NH.Cl+2Na,S0, + 2H,a

heating

On

we have

(NH,),Mg,P.O.

= Mg,P,0, + 2NH, + M,0.

Theoretical Composition

16.26

MgO
sOj

32.52 5E-22

7H,0

100.00

Amlfsis No.

3.

AMMONtA-I RON -Alum,

Fe,(NHJ,(SOJ,+24H.O.
A- Determination of Sulphuric Acid.
Dissolve
I

gr.

to

1.5

grms. in water, add

c.c, dilute

HCl
in

to prevent ferric hydrate from precipitating ^Vl^^i ''be BaSO.p heat to boiling, add BaClj and proceed exsctlv ;s

Analysis

2,

A.

B. Determination
(Fres.,
(i.)

of

Ammonium,

99,

b, 2,

(-J.)

the salt, if necessary, before weighing, by press ing the powder between folds Diss'^lve of bibulous paper. about 1,5 grms. in a little cold water casserole, ac'd a in a
little

Dry

dilute

to dryness

an excess of PtCl,. Evaporate nearly on a water-bath scarcely heated to boiling. Add

HCl and

01

DETERMINATION OF IRON,
,o to 80
c.c.

21

while still warm; alcohol 10 the casserole The supernatant Uqmd hour.. nor sdr let stand several of PtCl,. should be colored by an excess alter in a small funnel, wash Swedish
;
"

do

(-.

with water thoroughly; dry uilh 'very dilute HCl, then watchthe ftUer and plaee it on the lunncl, then remove lot an air bath ,00^ C exactly-^ dasses with elip; dry in whole. glasses and we.gh the one hour precisely then elose crystalline precipitate on the (.) Brin^' the yellow w^h al means of a clean feather w^h

PI ux-

No

weighed

dry on funnel. Then tran^ ,h;i earefuUy, not too nrueh, Dry and before, and weigh. , ,n -lip, clvv at 100" C. as untU constant calculate results. .vei,h a,a>n, repeating
;

filter

by

composition (M-ija tt.1.,. Precipitate has the determinations, wash with a [In the case of potassium filtrate and ether; also concentrate n.ixture of alcohol and and add to the secondary precipitate wasliHv^".^, lUter from
,

the Lormer.]
)

weighed crucible, burn Transfer the precipitate to a (4 ignite gradually and strongly, a.hes the titer and add the on the first determ. Wei'h the Ft remaming as a check
;

lion, nation.

powadd a little oxalic acid rin the case of potassium, wash residue the crucible, ignite dor to the contents of (See water-bath, ignite, and weigh. with water, dry on
Fres,, 97.
3.

m
.

1-)]

For
p. 8
1

solubility

of
16.

ammonio-platinic chloride, see Fres.

2,

paragraph

U.
I

Detennination

of Iron.
e.)

By /^nhou.-(Ftes.,
in

U3,

i,

Expose
or

l.O

grm. of

the' salt

a weighed covered
Hflfi

platinum,

porcelain

22
crucible, to a
atiire
till all

QUANTITATIVE ANALYSIS.
moderate
is

the water

gradually raise the temperJ expelled; then heat intensely

heat,
be;

fore the

blast-lamp.

and weigh again

11.

the residue as Fe.Oj Test the residue for J-LSO^.

Weigh

heat

By Precipitation. -(Fres.,
I

about

grra. of the salt in question in

c.c.

about 250 to 300 to boilmg, add

pletely, lest

NH.HO

wash hot by decantation. (N.B, Wash out on subsequent ignition a portion

i, a.) Dissolve' a large beaker with of water, acidify with HCl, heat nearly in excess; let settle after stirrin-

113,

NH
of

CI com'
the iron

volatilise as chloride.

One grm.

nearly one gallon of water.)

precipitate separately.

of ferric hydrate requires

filter,

Bring precipitate on thoroughly on funnel, ignite and weigh. Burn

(See Fres., 53
'''''''''
)

dry

filter

and

theXTtfnr"^""'^'^^'^

accordance with

6[(NHJ,S0,]

'^

31-1,0:

'^

oa- SefFr'"'" ^

'^" '^ Makguhkite's Meth-

Pa.es ISO to 204, also Crookes' S.Uc^ Methods, page 73.

distitied^iter

intoabottir'Fm
"P
to the zero

4" i:'^:r-'''''"=^^"*^'^''^^^"'S^^t'^n^J
r , ^'^^^"^^'^^
f

^'^-^

^'P^^"

"^

mark

'^"^^^^^ ^vith this solution

Dissolve exactly o 2 jrrm cleaned with sand n.^

piano-forte wire, previously

and

sufficient

wat'^B:;;

'

^'"'^^^^d' ^ool suddenly "?' ^nder the faucet bui to avoid but ' collapse of flask wait

''Tr

'"'

''''^ ^^"^'

"^^o!
a few

DETERMINATION OF IRON.

23
fall

moments

before allowing the cold water to

upon

it.

The
valve.

flask should

This

is

be provided with a Kronig caoutchouc made by inserting a short <^lass tube through

neck of the flask, and fitting to the projecting the tube a piece of caoutchouc tubing about lo cm. end of slit 4 to 5 cm. long is cut lengthwi.'ic in the long.
a cork in the

caoutchouc tubing, and the open end stopped with a piece The valve is then complete, (Fig. i.) of glass rod.

Fig.

1.

Fio.

The
just

In place of the KrOnig valve, another form may be used. projecting end of the glass tube, fitted to the cork in
the neck of the flask,
is

even with

its

surface.

passed through another cork until Over the end of the cork and

tube a small piece of sheet caoutchouc is fastened by means of pins, the rubber acting as the valve, (Fig. 2.) I laving effected the complete solution of the iron wire in one of

24

QUANTITATIVE ANAI^YSIS,

ing about 300 to 400

these flasks, pour the solution into a large beaker contain, c,c. IIjO, placed upon a sheet of

white paper; wash flask carefully, and add to beaker.

Now

the burette, drop by drop, stininy continually, and continue until the pink hue
tiic

pour

solution of

K,Mn,Oa from

first permanently colors the whole liquid. and calculate a.s follows for the standard

Read the
:

burette

c.c.

used

c.c.

= grms.

Fe

x, or standard.

Repeat the
tained,

titration until
:

two concordant results are obin

Correction

To

allow for the impurities

0.997.

the

iron, multiply the

amount taken by

Reduction of the Ferric Solution. (2.) T:i'\s.%o\vz 4.0 grms, ammonia-iron-alum in water, dilute to exactly 500
c.c.
;

mix

well,

and divide in halves.

Place a piece of amalgamated zinc and a strip of platinum foil in each reduction bottle; pour in the solutions and washings; add a little cone. H,SO and cover the bottles with watch glasses. The reduction requires six to eight hours. If the platinum foils are new, scour them with sdica, rub them with

KHO solution,

then with

and wash

HNO.,

carefully.

Removal

of the polished

and possibly

greasy surface hastens the evolution of hydrogen and consequently the reduction.

Reaction

Fe,(SO,),+Zn+H,SO,=2(FeSO,)+ZnSO,+H,SO,.
(3-) Performance of the Anafysis.Wh^n the reduction ^complete, ascertained by testing a few drops with am^

monium

sulphocyanide, pour the contents of each reduction


DETERMINATION OF
bottle into a large beaker,

IRON,

35

add ILSO4, and K^Mn^Oa from the burette until a permanent pink color is obtained, (See Tlie two determinations, one in eaeh Fres., 112, 2, a.) bottle, should not vary more than 0.2 per cent.
(4.)

Calculation of the Analysis.

No. of

c.c,

used V

Standard =^ a ok amount Fe.

100

wt. of salt taken

per

i ct. 01
,

iron.

IV.

The standard of the solution

in

of

potassium

permanganate may be detcrmiiied

(a.)

several ways.
t.4

Mohrs

Method.
iron.

V^

<i\g\\

out

grm. ammonio-

ferrous sulphate, dissolvu and

of
its

titrate as usual.

One-seventh

weight =:

Ammonio-ferrous sulphate

= FeSO^
is

+ (NHJ,S0., +

6H,0.

In both this and the preceding method the reaction the same.

ioFeSO,+8H,SO,+K,Mn,0,= sFe,(SO,)3+K,SO,+ sMnSO^ + sH.O.

(^.)

Hempcfs Method,
acid,

Weigh
in

out 6.3
of

grms, pure,

dry oxalic

dissolve
-\

one

litre

water,

making

a decinormal
tion,

N
(

solution.
c.c.

Dilute 50
H^SO.,,
:

c.c,

of this solutitrate.

add 6

to

cone.
is

warm and

The

reaction in this case

as follows

5fI,CA + 3H.SO,+ K,Mn,Os= ioCO,-h 3MnS0,+ K,S0,+8H,0.

26

QUANTfTATIVE ANALYSIS.

D Determination of
Water may be determined by
Theoretical composition

Water,

difference.

(N?I,),0=

5.39

Fq^O 16.60
4SO3 33.20
24H,0=:44.8
100.00

Analysis No.

4. Potassium Chloride.
KCl.

imng

Expel hydroscopic moisture carefully by heating and m a porcelain dish over a

the weighing tube.

filling

Bunsen burner, before

A. -Determination of Chlorine.
^-^ actly as ^c^r.f-"f""r Analysis

^i,

^"

"^

^^=^^^^

No.

-"d proceed ex. u ca f

A.
of Potassium-

B.- Determination
JJissolve about Ssllvr^h ^f 0.1;
.,
1

^" ^'

j/rm in d t t.'"'-

'"^ ^"'^^^' -^^^^^^ ^-^^^-^^^ P-ge I. ^ * . UttU ^^1 JitHe cold water in a f-^c:cif
1
.

"

wtt. ^'
p.

^"'"'^ "'""'" """"'"'

"

"' '"'-

chlorid., ,ee Fresenius' (^Z:t^f^ P<;t-io.pla.iio No. ^uiaiysu, 8n, paragraph

8.

DETSRM [NATION OP SODIUM.

Theoretical coviposition
:

2'/

K
CI

5241

47S9
100.00

Analysis No.

5.

HYORODtsoDic
i2H,0.

Phosphate.

Na,HP0,+
A-

Deter minatiOLi

of Sodium.

Cf. Fres., 135, , jJ. Dissolve

c.c.

about

grm.

salt in

200

water

in

a large beaker.

about 0.6 grm. clean piano-forte wire, place 10 (undei a flask, add cone. HCl witli some HNOj, boil hard boiling until excess a hood); when fully dissolved, continue

Weigh

off

of

HNO3
Add

is

removed, then

dilute, and,

if

necessary,

filtej

through a

filter

previously washed

with dilute

HCl

pure FeXl^ to that of the hydrodisoimmediately an excess of NH.HO, dic phosphate, and Heat and let the precipitate stand some hours wash by
this solution of
;

-decantation with

boiling water

very thoroughly.
until

Evap

orate the filtrate with a slight excess of dilute

HCl on
fumes
in

a water-bath
-of

to

dryness,

Heat with care

off;

NH4CI

cease to

come

dissolve

the

residue

through a very small filter Add a few drops platinum preferred. dryness on a water-bath; of dilute HCl; evaporate to ignite very cautiously, not too long, and weigh the NaCL If the residue is not perfectly white and soluble in water
water;
filter

into a small

weighed

dish,

without residue, dissolve,

into another

filter

weighed

dish.

through a very small filter Evaporate and ignite again.

Test residue.

2S

QUANTITATIVE ANALYSIS.

B.
Fres.,
salt
ill

Determination
134,
I,

of Phosphorio Aoid.

b. .

Dissolve
Atiafysis

about

1.2 grtms. of

the

question in cold water; add

excess and

NHJ-IO;
817.

set aside for

in

"magnesia mixture" in twelve hours, and then

No.
2.

continue exactly as

Consult Fres,

Exp, 32,

p.

C Determination
(r)
it

of Water.
place

By igJtilmL~\Vc\gh QwtdJoowlo.S gramme;

weighed crucible,
in

an air-bath, until partially dehydrated; then heat cautiously over a Bunsen burner, ignite eventually to redness, and weigh. (2) By direct wei^hL WQigh. out about 0.7 gramme substance, and introduce it into the weighed ignition bulb by means of a very narrow piece of folded paper. Weigh CaCl, tube, and arrange apparatus, as shown 2*5, in

in a

Fig.

page 61, of Fres. Quani. Analysis (American edition, 188 1),' substituting aspirator for gasometer if more convenient.

Heat cautiously, aspirating continually, and raise the temperature to a low red heat for Three minutes. In driving' the water into the CaCI, tube be careful not to burn the cork Aspirate while cooling, not too rapidly. Weigh CaCl, tube after cooling and the ignition bulb as a check. Consult Fres., 36.
Theoretical Composition
:

When

water

caJculation

is determined by heating to redness, the must be based on two molecules of the salt.

2Na,0

17.33

P,0,= 19.83 2sH,0 = 62.85

roo.oo

SILVER com.

29

t
V

0-

yaANTlTATlVE ANALYSIS.

ANALYSIS OP DOLOMITK.
Note

$t

2. If

it is

" silicates prcsctU,

clesimble to determine the SiOj, in the Ri'sid/w a" must be treated as follows
filter),

Dry and
about
heat.

ignite (with

mix

in a

platinum crucible with

fuse at a red

six parts of

Na.CO, (anhydrous), and

remove the fused mass with boiling water, add on a water-bath, an excess of HCl. evaporate to dryness
Coo!,

completely expelled heat in an air-bath until the HCl is and filter from again moisten with HCl, dissolve in water,
;

the residue.

The

residue which

is dried, ignited,

and weighed.

now pure hydrated SiO The filtrate must be added

is

to " Filtmtc a."

^^^^,

Examine

Fres., 140,

H,

A, a,

and

93, 9-

3. Heat the
" is

filtrate

from " Residue

a,"

add NH^Cl,

and
ted

NH.HO
if

in slight excess.
" is

the

Filtrate a

NH4HO

expelled, filter
105,
I,

(The NH.Cl may be omitHeat until excess of very acid.) quickly, and wash hot. SeeFres.,
partly washed,
dilute

^113, i,a,ad^

a.
" is

Note 4.*' Precipitate b

TTioist,

and then, while

the
filter,

dissolved in a
is

little

warm

HCl on
and

the

solution

reprecipitated by
filter,

NH^HO

the precipitate

brought on the same

ignited.

washed thoroughly, dried, and

Weigh
*'

as

Fe^Oj-fAUO^.

The second

filtrate is

added

to

Filtrate d."

Note 5. Concentrate " Filtrate fi" add some NH^CI unconsiderable exless present already, add (NHJ, 0,0, in Let stand 12 hours in a warm cess, and some NH.HO, Wash partially and filter. Se^ Fres.,% IS4> ^t<^ place.
also ro3,
2, d, a,

>'

AWt'
in

6. Dissolve

the partially washed " Prm/>ttate c"

HCl, reprecipitate with NH^HO and a little (NH,)AO,. Filter and wash hot, add filtrate and washings to " Filtrate c." Dry precipitate on funnel, transfer to crucible, burn filter, add ashes, add a few drops of cone. H,SO^ to contents of

32

QUANTITATIVE ANALYSIS.
low redness, and weigh
3, b, a.

crucible, ignite cautiously to

as

CaSO,.
Note
7.

Compare

Fres., 103,

If

care has been taken to avoid

NH^Cl

in the

preceding steps,

the

undue excess of magnesium may be

thrown down

in "/^///w^^ 6-"

immediately.
:

NI'I^CI must be expelled as follows

Otherwise the Concentrate the liquid,

add 3 grms. of
heat to boiling.

HNO3

for every

to be in the solution,

warm

supposed gently (60 C.) and eventually

grm. of

NH^Cl

Concentrate

''

Filtrate

c" add
2.

NM^HO
See

and NaJdPO^

and proceed as
% 7A-

in

Analysis

B.

Fres,, 104, 2, and

tion.

Notes on the Decomposition of NH^Cl by IINO3 in soluComptes Rendus, October 13, 1851 (Maumene).

J.

Lawrence Smith

in

Also Am. Jour.

follows:

Sci. (2), Vol. 15, note,

American Chemist, Vol. Ill, p. 201. page 240, which is as

:

"The

character of the decomposition which takes

it

place

is

somewhat curious and unexpected

was

first

supposed that equal volumes of CI, N,0, and N were given off, but it is shown that nearly all the NH,HO, with its
is converted into N,0, the liberated the excess of HNO3. little of the ISrH^Cl-}-HN03 does hot undergo the decomposition first supposed, and in this way only can the small amounts of N

equivalent of

HNO^,

HCl mixing with

and CI be accounted
little

for."

"

Some

nitrous or hyper-nitrous
if

acid forms during the

whole process

cone.

HNO3

is

used

or none

if

dilute

HNO3."
on

The
folio Hows

action of

NH.NOj

NH.Cl

is

theoretically as

2{NH,N03;H-NH,C1=5N+C1+6H,0.

ANALYSIS OF DOLOMITE.'

33

The

following are possible reactions

8NlI,Cl

+ ioHNO,=9N,0+8Cl+2iHA
and

2HNO,+2NH,Cl=:N,0+2Cl + 2iN + 5H,0, HN03+NH,Cl-=HCl + N,0-f2HA

2HN03+NH,a=N,O+Cl + NO,+3H,0,
and

HCl+3HN03-=NO + Cl + NOCL + NO,+4Cl + 5H.O.

Note
II.,

8.

d, bb,

Detennination of CO^.-~I. and cc.

out i.o to 2.0 gnns., place

By loss.

Frus..

39,

Weigh
in

the

Geis.sler

apparatus,

fill

the
witii

proper portions of the apparatus

HCl

(dil.)

and with

li.SO.,

(cone.)

respectively.
tiously let the
eral,
till

Weigh apparatus. CauHCl flow on the minboil.

warm

gently, heating at the last

the solution begins to

Cool
details

apparatus and

weigh.

p-or

consult /wj-tv/wj-, as above.

Do

not

,-

nurry this process too much.

JT.

p.^

By

direct weight.

Consult Fres., 139,

II., c.

Arrange apparatus
loops on nails.

as in Fig. 4.

Suspend tubes by wire

a contains soda-lime,
t
/
is

a flask of

about 300

c.c.

capacity.

contains cone. H.SO^. ^ contains pieces of pumice-stone saturated with HjSO^; avoid much liquid in the bend,

cone.

/contains pumice-stone saturated with anhydrousCuSO

34

QUANTITATIVE ANALYSTS.

a strong hot solution of CuS0,,-t-.5H,0, add pieces of pumice-stone, boil hard, evaporate to dryness and The product should be nearly white. ignite well.

N.B.Make

g contains

in

outer tube, soda-lime

;

in

inner tube,

{k\

pumice-stone saturated with II^SO^

both before the absorption and after.

weigh these together

Fig.

4.

Place i.o to

1.5

connect apparatus

Pour a little water through the funnel tube into c, then add gradually HCl, diluted one-half with water. Attach a, and aspirate
;

grms. mineral in c, weigh a is not attached at first.

and

h,

and

gently.
this

Heat cautiously

to

incipient ebullition
let

maintain

a few moments, and

continues.

Weigh

Note

9,

Calculation.

increase of weight gives CO^. Normal dolomite contains

30.4 per cent.

cool while

the aspiration

CaO.

47.8
21.8

"

CO.
MgO.

100.0

Having

estimated

these

constituents,

calculate

the

ANALYSIS OF URONZE.

35

amounts of CaCOj and MgCOj, and report under "Special Remarks," thus

CaO CO, = CaO

:

found

CO,
:

MgO

= iVIgO found CO;, required or N, and M + N must = CO, found, nearly.

:

required or M.

COj

Analysis N&t 8

BrOXze.
Ctt,

To

be determined, Sn, Pb,

Zn,

A. Deterniinatioa
Dissolve about 0.6 grra. bronxe

of Tin.
filings, carefully freed

from accidental impurities, in moderately dilate HNO3, in a flask in the neck of which is placed a small glass funnel. After complete solution (except the SnO,), transfer contents to a porcelain dish, evaporate to dryness, moisten

with

HNOp
91.

add H,0, and

filter

from the SnO,.

Dry

this

residue, ignite in porcelain,

and weigh.

Fres., 126, L, a,

and

B.

DoterrQination

of Lead.

To filtrate from A add dilute H^SO^, evaporate until fumes of HjSO^ appear, or the residue is nearly dry, let the dish cool, then add water, and filter from the PbSO^. See Fres,, g 163, 2, and iiG, 3, a, X Dry, ignite, and weigh precipitate. See Frcs., 83, d.
0.

Determination

of Copper.

The
c.c.

fdtrate from E. should not measure more than 100 Place the solution in a large platinum dish, arran^'e

the Bunsen cells of a galvanic battery, connect the zinc

-5

QUANTITATIVE ANALVSIS.

element with the platinum dish, and the carbon elemen'. with a small piece of platinum foil which is immersed in

Let the battery run four or five hours. Take out a drop of the solution with a pipette, place on a watch Pour out the solution glass and test for Cu with H^S. when the precipitation is completed, and wash thrice with
the liquid.

small quantities of water.

with alcohol twice, dry in

at a very gentle heat,

Tlien wash the copper film the hand, over a Bunscn burner,

and weigh quickly,

for

N.B.

It

is

advisable to test solution

Cu

before

proceeding further.

D. Determination of 2;inc.

Heat the filtrate and washings from C to boiling, add excess of Na^COj, boil a few minutes, wash by dccantation hot, then on filter. Dry, ignite, and weigh as ZnO. Fres,, 1 08, t,a, and 7j.

Analysis No.

9.

Coal.

(Pkoximate Analyses.)

To be determined. Moisture, Volatile and Combustible Matter, Fixed Carbon, Sulphur, and Ash.
A-

Determination

of Moisture.

Pulverize the coal very finely, heat one to two grms. in a

ounce platinum crucible for fifteen minutes at IIS^C. a:r-bath, cool and weigh. Repeat this desiccation in the air-bath, weighing at intervals of ten minutes, until the
lialf

m an

weight

moisture.
It

constant or begins to rise. Loss of weight gives In reporting, give exact temperature at which was determined. N.B. The increase in weight is due
is

it

to oxidation of the coal

generally begins after heating

ANALYSIS OP COAL.
thirty to uincty

37

minutes in the air-bath. Anthracite coai News, Km. may be heated an hour or more. See Ckem.
Repr.,

Vol

V., p. 80.

B.

-Determination of Volatile Combustible Matter.

to

covered, Heat the same crucible with contents, closely three and bright redness over a Bunsen burner, exactly

allowing the crucible one-half minutes, and then without the blast-lamp, exactly three to cool, heat strongly before weigh. The loss and one-half minutes more. Cool and and includes half gives the volatile and combustible matter, See F below. the S in the FeS,.
C-

Determination

of Fixed Carbon.

Bunsen Heat crucible and contents, uncovered, over and the weight is burner, until all carbon is burned off from one to four hours or more. This talces constant.
Loss
in

weight

= iixed carbon, including half

the S.

D Determination of
The
the ash.

the Ash.

difference between the weight last obtained and that Note color of of the crucible gives the weight of the ash.

E.

Determination

of Sulplmr.

Secure a sample of anhydrous NaXOj, shown to be absolutely free from S by the silver test. Weigh out about two grms. coal in fine powder, mix witli about ten grms. NaNOj and ten grms. NaXO, on glazed paper. The sodium salts need not be weighed accurately
;

KNOj may

be used

in place of

NaNO,.

Deflag-

rate in a covered two-ounce platinum crucible, heating O'ver

3$
a

QUANTITATIVE ANALYSIS.
;

Bunsen burner add the mixed coal and sodium carbonate little by little, replacing the cover of the crucible quickly
expect to effect a perfect fusion. Place the crucible and contents in a casserole, add water, and digest until the mass is disintegrated, and the crucible can
each time.

Do not

be removed.
boiling,
If

Add cautiously an excess of HCl, heat to and throw down the ILSO^ with BaCl^ as usual. flocks of SiO, remain insoluble in HCl, evaporate to
water-bath,

dryness on
water,
filter,

heat until

HCl

is

expelled, add

and proceed as above. If the BaSO.^ is reddish after ignition, wash with solution NH^CJijO, and then with pure water, dry, ignite, and weigh again. The BaSO^ may also be purified by solution in cone. H.SO^ and
rcprccipitation with water.

Second Method for Determining SiUphur. VviX two to five grms. powdered coal in a flask holding a litre; add ]00 c.c. HNO, and five grms. powdered KCIO^, heat to boiling, adding more reagents as needed; continue until all
the carbon
is

oxidised.

dryness, add

HCl and

Transfer to a dish, evaporate to water, throw down li^SO^ with

Con.-^ult

BaCl,, and proceed as usual.

Hayes's

article in

Am.

Chem., Feb.,

1875, also Wittstein's article in

Am.

Ckem., April, 1S76.

P-

Calculations.

Theoretically we should deduct half S from the volatile combustible matter (because iron pyrites loses one-half its sulphur at a red heat), one-eighth S from the fixed carbon and three-eighths from the ash. (2FeS become Fe^O^, or 8 X 32 reduces to 8 X 3 4 24.)

Tractically half the amount of sulphur is deducted from the volatile combustible, and half from the fixed carbon; reports should be

made out accordingly

ANALYSIS OF COPPER PYRITES.

39

G,

Estimation
lon^'.

of Carbon and Hydrogen.

Ignite one grm. of

coal with

PbCrO^

in

a hard glass

Pass the IIjO, CO, and MaSO^ formed through two U-tubes, one containing ignited CaC^, and the other a solution of Pb(N03) and through a potash
tube 0.25 metre
bulb,

The

increase in weight of the

first

U-tube gives the

IIjO, and

that of the potash bulb the

One part of carbon in Calculation of Calorific Power. burning yields S.oSo calorific units, and one part of hydrogen
in

COj,

burning 34,460

calorific units.

Hence

to calculate total

calorific units in a coal,

multiply the percentage of

C by

8,080 and divide by 100; also multiply the percentage of by 34,460 and divide by ico. Add the quotients.

(A calorific

unit

is

the

amount

of heat necessary to raise

i"

one grm. of water from 0 to

C.)

See Chem. News,

XXX [V.

p.

233.

1876.

Analysis No.

10.

Copper

Pyrites.

Determination cf Copper.
Pulverize very finely.
it

Weigh out

exactly 2 grms., place

about 300 c.c. capacity and covered with a small funnel, the stem of which is slipped into the neck of Add 20 c.c. cone. HNO3, 5 c.c. cone. HCl, mixthe flask.
in a flask of

ing these in flask under the hood.

Digest some minutes,

boil hard un-

then add cautiously 20

til

c.c.

cone.

H;SO^ and
filter

fumes

of

HjSO^ appear
and wash.

abundantly.

Cool, add water

with caution, dilute not too largely,

from residue {SiO,,

CaSO,,

Test residue for copper before the blow-pipe. Dilute filtrate to 200 c.c. exactly, mix well by pouring into a dry beaker and back agam three or four
etc.),

times

divide in halves by taking out too

c.c.

with a pipette

<jO

QUANTrXATrVE AN'ALVSrS.

and place in a platinum dish previously weighed, (N.B, Volumotric apparatuii as sold is rarely reliable, therefore test pipette and ilasic before measuring as above) Arrange
battery, placing the " battery acid" (one part of H^SO., diluted with 8 to lo of water) in

two

cells of a

Bunsen

the

outer cell and "battery fluid "

the inner.
dish,

Connect the

zitic

and the carbon ( with a piece of platinum ) pole foil which is immersed in the liquid. Cover the platinum dish with two pieces of glass [)Iate, one each side
of the

(KjCr.O^+H^SO^+H^O) in (+) pole with the platinum

platinum

foil,

to prevent loss

by spattering.

Or

use the

spiral described in C/iau. Nezvs, XIX, p. 222 (1869). See also Crookes Sckcl Methods, i>ages 187-200. It is best not to let the battery run all night prepare the solutions on one day and start the battery the next morning. Four hours or more usually suffice for complete
;

cone or

precipitation.

Test a few drop.? of the solution with II,S When precipitation is complete, pour off liquid, wash copper wuh distilled water three or four times (work rapK y) then with strongest alcohol twice; drain the alcohol oft, dry the copper at a very low heat, holding the platinum d:sh m the l^and over a small flame, which must not ouch the dtsh, and weigh immediately. Next treat the
tions should agree to about 0.2 per cent.

and No, 12. Introductory Notea on Volumetric Analysis.

II

Amfyses No.

rrom the determmate action of reagents

in

VOLUMETRIC ANALYSIS.
solutions of

4I

amount of the reacting substance being calculated from the volume of the liquid The first principles and method of procedure have used."
strength, the

known

been foreshadowed
of

in

Analysis No.

3,

III.,

Determination

Iron by Marguerite's method,

eral

ion's

For explanation of genvolumetric methods, see P'rcs. 54, and consult StitHandbook of Volumetric Auulysis, also Mohr's Lchr-

bncli iter c/iauisch-aHalytischen 'fitririuelhodi:

Principles, use,

When
;

volumetric analysis

first

came

into

the standard solutions

were so prepared as to give

results in percentages

thus in Alkalimetry, osio standard

solution of acid was used for potash, another for soda, etc.

The modern system

the proportion

is

based on the

fact that acids

and

alkalies (as well as other reagents) neutralize cacli other in

of their
;

multiples of the same

molecular weights, or of simple consequently standard solutions are

so prepared that one litre contains one-half or the whole of the molecular weight of the reagent weighed in grms.

For example, the molecular weight of HCl being

that of

36.5

and

KHO

56.1, 36.5

grms. of
if

HCl

exactly neutralize

56.1 grms. of

KHO,

and

these respective amounts be

dissolved in one litre of water, the whole of one solution will not only neutralize the whole of the other, but any aliciuot part of one will exactly neutralize a similar aliquot
part of the other.
iettes,)the

And

amount

of reagent

by using graduated vessels, (buused is determined by the

volume of the siluuon. (Before employing burettes, pipettes, and graduated flasks, care should be taken to test
the accuracy of the graduation.)

Standard Solutions.
lar

weight

called

Solutions containing the molecureagent expressed in grms. per litre are normal solutions in the case of di-basic acids
of the
;

(H.SO^,

HoCA

etc.)

and of

" di-acid " alkalies

(NajCOj)

^2

QUANTITATIVE ANALYSIS.
is

one-half the molocular weight of each

taken,

making
are

half

mrmal

solutions.

The standard solutions of the made with the quantities indicated

Oxalic acid

following
:

reagents

ALKALIMETRV.
I-LjSO^ of sp. gr. 1.840 with three or four times its

43

volume

of distilled water

cool

and

dilute to
is

act staodard of this solution sodium carbonate, as below.

3.

one litre. The exdetermined by testing with

Weigh off about 12 Sodium Carbonate Sijlution. heat in a porcelain dish grms. anhydrous C.P. Na^COj
;

to low

redness, stirring until moisture is expelled

place in

a desiccator to cool.
this,
c.c.

Weigh

out accurately 10.6 grms. of

and dissolve
This

in distilled water.

gives a half noirniat solution,

Dilute to exactly 200 each c.c. of which

contains 0.053 grm. of sodium carbonate, as

shown by

this

simple calculation

Na,

--=

46
48

C
O.
Mol. wt. of

=12
==

Na.COs

106

One-half the mol. wt.

=
-=

53
10.6 grms.
;

0.053 grms. This solution serves to standardize the sulphuric acid.

200

c.c.

c.c.

Standardizing- the Sulphuric Acid.

solution, 20, 30, or

Take

of the

Na^COj

40 c.c, accurately measured, place in a wide-mouthed flask of about 300 c.c. capacity add litmus solution, and run in H^SO^ solution from a burette until a wine-red color is obtained boil hard to expel CO;,, and add more acid until the color is permanent. Read off the
;
;

c.c.

used.

Repeat the process.

required
25
c.c.

Suppose 30
solution.

solution

(30

25) water must be added

to

HjSO^

Na.CO^ Then 5 c.c.

c.c.

to every 25

c.c.

of the acid

solution

make

it

normal.

Measure,

therefore,

the

H,SO^
water.

and add the necessary amount of Suppose the HjSO^ solution measures 900 c.c., since 900:=: 25X36, then 36 X 5, or iSo c.c. water must be added. Add the water, mix well, and again determine
solution carefully

44
the Standard
:

QUANTITATIVE ANALYSIS,
one
c.c.

of the

Na, CO, solution should

ex-

In case oi actly Jiciitralize on of the acid should be deterdifficulties the exact standard
c.c. of the

ILSO^

solution.

mined gravimctrically by precipitating 10 or 20 c.c. with BaClj, and calculating from tlie BaSO^ obtained the

amount of HjSO^

in

one ex,

tion of cochineal is

Carminic acid being stronger than carbonic acid, a solusometimes substituted for litmus, in

which case boiling may be dispensed with.

The

dycstufi

tropaeoHne has recently been proposed as an indicator in alkalimetry. Cf. BiK d. chem. Ges. XI, 460 (1878).

Dcci'mrnml Sohtiion of Acid. Call the above normal "No. r;" take 100 c.c. of No. t, put into a litre flask, and dilute to one litre. Call this decUiormal soiution
solution
"

No.

2."

A. Valuation

of

Soda Ash.

{Determination of Na^CO,.)
Place about 12 grms. powdered sample in a platinum
crucible or porcelain dish heat moderately for utes over a Bunsen burner, until all
;

some minexpelled
;

moisture

is

weigh out exactly 10 grm, dissolve in water; dilute to one-hall litre and mix well. Take out 50 c.c, solution (which contains one grm, soda ash), and determine the amount of normal acid needed to neutralize, adding litmus s before, and boiling to expel COj. Suppose 50 c.c. solution soda ash
eool,
;

required 15

c.c.

ard acid

thpn ^^^"

^!f53

x
p.

stand-

',1

100

Tgrm,
Og^.

= 79-5

per cent,
results

Na^CO^.
are

See

Frcs.,

195,

These

appro.ximative and preliminary, and the operation be repeated, finishing with the deci-normal solution
2

only

.below

Take another 50
c.c.

must No.

c,c.

of

run from a burette .2

soda ash solution.;

of .solution

"No.

and then

ACIDIMETRY.
" finish with solution
c,c.

45
in calculating, 10

No

2,"

Of course,
No.
I."

of

No,

2 equals

one

c.c. of "

B-~ Valuation

of Pearl Ash.

Proceed as before; weigh quickly the salt cooled in a In calculating, use desiccator, for it is very hydroscopic.
the factor 0.0691.

The Residual Method of Titmlion.^Thi^ method has

great advantages over the foregoing method, especially when carbonates are in question the sharpness of the end
;

reaction being

much

increased by the

absence of

CO^.
ash

The process

is

as follows:

Super-saturate the soda

;

solution with normal acid in excess

then add normal pot-

point assic hydrate (and decinorraal also) until the neutral is mentioned in the next normal (The is reached.

KHO

paragraph.)

one c.c. alkali, substract Since one c.c. acid the number of c.c. of standard alkali from the number c.c. of standard acid added in the first place, and then calculate
as usual.

ACIDIMETRY.
Generalities.

The value of strong

When

acids, especially

HCl,

HNO3, H,SO

is frequently deduced from the Sec tables in Gravity as determined by the hydrometer. percentages of acids in soluFres., pp. 690, O91, showing

Specific

tions of

different densities.

titration is desirable,

standard

KHO

solution

is

used, and in accordance with

the principles already stated.

Preparation of Standard Alkali. TdkQ about 60 grms.

KHO,

dissolve in

litre of

water, add Ca(I-IO), to throw

down carbonates,
iiormal acid.

boil,

let settle,

mine the exact standard

of

and syphon off. Deterthis with normal and deci-

46

QOANTITATIVI'. ANALVSfS.

A Valuation
Take
5

of HOI.

to 50 c.c. acid,

part, definite volume, take an aliquot as described. the standard

according to strength, dilute lo a add litmus and run in

KHO
X

Ill

calculating

multiply
100,

the

number
this

of

c.c.

of

KHO

added by .0365
ber of
c.c. of

and divide

product by the num-

acid taken

Specific Gravity of the solutirn

as determined by the hydrometer.

Gravity

Example. Took
[.035
;

10

c.c.
i

HCI
c.c.

solution,

having a Specific
i

since

of

water weighs

grm the

weight

of acid

taken

10.35 grms. 8
c.c.

The

acid solution required 8

KHO,

whence

.0365
10.25

100

= 2.84 per cent.

of Vinegar.
titration,

B.

Ajialysis

A.

Determine the acetic acid by

using cochi-

neal solution, or with mcthylaniline violet, as in the

"Witz

method" {Am. Ckc7n.,Yo\. VI, page

method, as follows

12), or use

Mohrs

Add
(in

to a

known
pure
is

quantity of acid a weighed quantity

precipitated

excess) of

dry CaCO,.

After de-

composition

nearly complete in the cold, boil to expel

COj,

of CaCO^ in hot water. CaCOj in excess of normal HCI, and determine the HCI remaining by means of normal KHO, or NaHO and litmus solution. The results with dark
filter,

and wash the excess

Dissolve the

colored vinegars are good.

B, Determine water by drying at lOO" C. to constant weight, and allow for alcohol and acetic acid.

CHLORIMETRV.

47

c.c. Determine akohol by neutralizing about 300 measured and distilling off some vine>^ar with CaCOj Then determine specific gravity by amount, say 150 c.c. the per cent, of alcohol. weighing, and from this calculate

D.

Determine the grape sugar.

(See Analysis No.

33-)

Anafysis No. 13. Chlorimetry.

Constitution of Bleaching Powder.

Bleaching powder
is

formed thus

2CaH,0,

+ 2CU = 2H,0 -f CaClA.CaCl,.

is

The composition of bleaching powder The following are some of the formulse.
"

variously given.

+ H,0,. Watts, CaClO -f CaCl, Ca,0 + 2H,0. 4H.O. Bloxam, CaO C1,0 + CaCl, ^CaO +
Quelques Chimistes
"

CaCl,

Roscoe, CaCljO,.
Muspratt,

CaO

CI,

2H,0.

Fowncs, CaClj Calvert, 2CaCl,

Thorpe,

+ + CaCUO,. CaCl, + CajHr.O.Cl, = CaCl,0, + CaH,0,4CaCl,0,.

3H,0
Kolb, (2CaO,Cl,H,0), CaH,0..
Rose, (CaCL, Ca,0,) CaO,Cl,
Stahlschmidt's theory of
its

+ 4H,0.
formation:
Benefit D.

Chem.

Ges.,

1875:

3CaH,0,

+ 4CI = CaCU 4" CaCl^O,

-{-

CaH.O,

+ 2H,0.

Powder, by Dr. See paper on Constitution of Bleaching Lunge in American Chemist, Vol. V, page 454-

^g

QUANTITATIVE ANALYSIS.

allowed to stand in contact with air and light, it decomposes, CaCl, increasing, and the CaCIO dccreas-

When

uv.

Dry

chloride of lime, at 50"

C, decomposes

thus

(Thoki'K.)

3Ca3H,0,Cl,

= sCaCI, + Ca{C10,), + 3CaH,0, + 6H,0.

water cidoridc of
lime decoraposes

By
thus

the action of

Ca^HoO.Cl,

= Call.O, + CaCl, -^ CaCi.O, + 2H,0.

the
o;

The

value of

commercial article depends wholly

"available chlorine," viz.:
is

upon the amount

the CI in

the hypochlorite, which

thus constantly varying.

The strongest contains 38.5 per cent available chlorine. One or two per cent, of this is present as calcium chlorate,
which
is

without bleaching power.

Action of Acids on Bleaching Powder,

drochloric acid

Action

of

hy

(CaCl,0,

CaCU)

2HCI
:

= 2CaCl, + 2(HC10).

Action of dilute sulphuric acid

(CaCUO,

+ CaCl) + H,SO, = CaSO, + CaCl, +

2(HC10).

Further action of concentrated sulphuric acid

CaSO,

+ CaCl, + 2(HC10) + H.SO^ = 2(CaS0,) + 4CI + 2H,0.

ILORIDE OF LIME.

49

Valuation of Chloride of Lime.

an alkahnc arsen.t^'. Based oa the conversion of s .00 lime. a solution of chloride of into an arseniate by
Penot's

MetlmL

From

Frc.eniiis'

Qmnt.

Analysis,

As,0,

CaCUO,

= As.Gs +

CaCU.

The end

undetermined by KI and starch, turning this mixture blue. decom posed hypochlorite

reaction

is

(,

Prcpamtiou of
n.

^tich
fj.^^COj

250
aq.

c.c.
;

ddute

Starch P/.t.-Bo.1 three grms. one grm. water, add one grm. KI, Moisten paper with to 500 c.c.

Kl

this solution

and dry.
Solution of
..L-.t}^.

ib)

Prcpamtim of

- Dissolve
wah
25

ex
until

actly

4,9s grms. Nai03 +-^aq. (free from S) in 200

pure sublimed As.O,

c.c.

grms

water.

^Bod
j;

Jissolved

and dilute
difficult to

to

one

Utre.

Make a
this
If

s^l^^'""'

Since

it is

weigh out exactly

amount, take
5.0^3 g^"^^-

proportionately. any number and dilate

then
4.95
:

1000=
c.c,

5 -Of

grms.

10127.
c.c.

Add
tion

then 12.7

to the litre.

One

of this solu-

0.00355 CI.

-^l\^ sample well; Process of the Determination. or 60 c.c. water weigh out 10 grms., rub in mortar with 50 Repeat. flask. decant turbid liquid into a litre
(c)

settle;
Fill

up

ro

mark, and mix.

take 50 c.c, run
it

Fill a burette,

into a beaker,

add the

until a drop of the sostandard As,03 solution, stirring

QUANTITATIVE ANALYSIS.
;aon no longer gives Repeat on fresh amount
turbid liquid,
{iL)

a blue

mark on the KI

starch paper.
off

Cautioi: Shake, and draw

Cakulation.

Amoimt taken
represent the number of [French chlorimctrical degrees and 760 m.ra., which one kil. of sample jitrcs o CI at o.^C. Now one litre of CI weighs 3,177 grms.; should yield. Sec foot-note on 100 degrees. hence 31.77 per cent. Qumi. Anal] p. 700 of Fres. amount of ca/dum chloride present may be de-

The

termined by

estimating the hypochlorite as above, and c.c. a slight excess then adding to the second portion of 50
first

of

NHJ-10 and warming.

3

CaClA
AgNOj.

+ 4 NH, = 3CaCl, + 6H,0 + 4N,

HNOj
and determine the
heating
of chlorate

Neutralize the solution with

CI by

The amount

may be determined by

pure a third portion with ammonia, then acidulation with H,S04 and digesting with Zn.

Ca(ClOj).

12H

= CaCl, {- 6H,0.

Again determine the CI by AgNOj, and the increased amount over the second determination gives tjic 01 exist(Thorpe.) ing as chlorate.

TYPE METAL.
(0

51

^t

o " G

^t;

ti

J*
(S4

^ --Si

V
^j
2

3
O
c:

M
R"2

o
'It
.

"

fH

QyWtllTlTATIVE ANALYSIS.

^^f,

_Somc
titi,
H'

of

tho

till

may go
'^"^ '^'^^''^^'

into

solution

as

litratc of

tli*-^

"'^^'^^

'^^'^^

^"^^ ^'^"^

^J^^''''^''
;

in Precipitate c

mixed

witli tlie

sulphide of antimony

in

should be separated by F. W. Clarke's this case they on the solubility of the sulphide method which is based may he found in acid, and details of which
of tin in oxalic

page 249Crookcs' Sckcl Methods,

sec Fres., 165. 4.
- ^l^o

I'O!-

another method

65, 7, a-

Note

->.

On
+

the other hand,

some

of the

antimony

dissolve and remain with Residue a, and lead may refuse to as follows after igniting and weighin which case proceed Sb ? fnse with Na,C03 and sulphur Pl> ? ing tlic SnO, Dissolve in warm water and filter in a porcelain crucible. which may be treated with HNOj from the residue of PbS, To the porcelain crucible and wci:j,hed as PbSO,.
:

in

alkaline solution
precipitate of

add

sliglit

excess of

HCl and

collect

SbSj

+ SnS, +

S on

filter;

dry and remove

to porcelain excess of S by washing with CS transfer dryness, fuse capsule, oxidi/x with UNO, evaporate to .silver dish, dissolve the mass in a mixture with NallO in a uf three

volumes

of alcohol
of

from the antimoniatc

and one of water, and filter For details, see Fres., sodium.

To the solution containing stannatc of sodium, 165, 4, a UCl, saturate with ILS, and treat the precipitated
add SnSj as
usual.

See

Fres., 126,

I, c,

and

9E.

Consult article on the Estimation of Antimony, by E. M. Bartlcy, in American Chemist, Vol. V, page 436; also

paper by Dr. Clemens Winkler, in Fresenius' Zcitschrift

fur

Analj'tischc Ckemic, Heft 2, 1875.

DETERMINATION OF

2IXC.

53

54

QUANTITATIVE ANALYSIS.

CHROMIC IRON

OHtC.

55

tf)

-I

-g

QUANTITATIVE ANALVSIS.

Amfysis No.

17.

Pyrolusite,
method

Determmation of MuOj.
Employ Fresenhis
arul Will's

as described in

edition of 1881, pages 705-709, Fres. Quafif. Analysis, Tiirirmci/iode 215, pp. 617203, A, See also Mohr's
(338 (cd. 1874).

ore, 3.QS5 gi'nis. of acid apparatus if available.

Take

and use Gassier' s carbonic

"

Consult also the following article:

of

On

the Estimation

Manganese in Manganese Ores," by E. Scherer and G. Rnmpf, Chemical News, American RePeroxide of
print. Vol.

VI, page S3, February, 1870.

Analysis No.

18, Feldspar.

A. Determination of Alkalies.
Prof.
[3]
I.

J.

Lawrence Smith's method.

/.

See Am.

Set.

Also Frcs., 140, II, b, Weigh out one grni. Pulverize well in an agate mortar. Mix well in an agate mortar, Jirst, with of the silicate. about one grm of NH^Cl (pure enough to sublime without
269.

residue), and, sirondly, with about eight grms, C. P. precipitated CaCOj add the latter in three or four portions,
;

mixing well after each addition. Transfer the mixture by means of glazed paper to a platinum crucible. Apply the heat of a Bunscn burner to the upper portion of the crucible first and gradually carry the flame toward
the lower part, until the NII^Cl
is

completely decomposed,

DETERMINATION OF ALKALIES.

57
heat before

which ensues
utes.

in four or five minutes.

Then

the blast-lamp, not too intensely, for thirty to forty min-

This operation
facilitated

is

greatly

by using a special
Prof.

apparatus devised for the pur-

pose by
Smith,
Fig5-

J.

Lawrence
in

and
stand

represented

The
its

supports on

rod-G a

cast-iron plate

by a hole large enough to admit the someperforated

what elongated crucible A the bottom of the crucible

projects within the sheet iron

chimney C which by the its place

is

held in

hook
to

N.
the

When
Fic. 5-

heat
of

is

applied

bottom

the crucible

by the

flattened burner F the decomone position proceeds regularly and is completed in about

hour.

Cool the crucible, place

digest the

it

in a porcelain casserole,

and

semi-fused mass with boiling water until thoroughly disintegrated. This may take some hours. Then Ai.O,, Un,0,{?}, filter from the residue (SiO Fe.Oj, of water. etc.), and wash well with about 200 c.c.

CaO,

chlorides All the alkalies of the silicate arc converted into

and are now in the water solution. Add to this solution NH,HO and (NHJ^COj with a few drops of (NHJX.O,. about 50 Evajjorate without filtering, on a water-bath, to small filter a c.c. add a little NH.HO, and filter through platinum dish. Evaporate to dryinto a weighed (No,
2)

riWiUMWfll

Mill

QUANTITATIVE ANALYSIS.
g

ignite very gently to drive off a little ness on a water-bath, If the residue is not perfectly soluble CI and weigh.

NH

in watir
ignite,

filter off, evapor:ite, and quite white, dissolve, gives the weight of the This and weigh again.

by separating it with PtCl, Next determine the K. either manner, or by gravimetric or voland alcohol in the usual CI in the weighed chlorides. umetric estimation of the total page 841, 3. Consult also For calculation, see Fres., and 14. Crookes" Select Methods, pages 13
B.

KG +

NaCI.
.
.

Determination

of SiO A1,0 Fe,0 OaO, and MgO.

six Fuse two grms. mineral with six grms. K^COj add excess o Moisten with water, digest, grms. Na^CU,.

HCl, evaporate
Analysis No.

to

dryness,
filter

expel

HCl

in

air-bath,

add

water and HCl, and

in
7.

from SiO,.

Continue exactly as

SOLUBLE SILICATES.

59

6o

QUANTITATIVE ANALYSIS.

Analysis No.

19.

Iron
P.Os-

Slag.

Ta

be

ddermined:

SiO,

FeO, MnO, Al,Oj, CaO,

MgO,
Puiverizc
finely;

S,

weigh out exactly five grms. mix on glazed paper, by means o a horn spatula, with fifteen grms. anhydrous NajCOj and fifteen grms. K,COp
;

need not mixed slag and fluxes into a two-ounce platinum crucible, and heat over a Bunsen burner until by settling down room is made for more. Heat twenty minutes or more before
fluxes

together with cue grm.

NaNOj.

These

be accurately

weighed.

Put one-third

the

the

blast-lamp.
treat

Cool
boiling

suddenly,
crucible and

place

and

with

water until

in a casserole, thoroughly disinte-

grated.
little

Remove
little,

the

add

excess of

HCl

avoiding loss of liquid by violent effervescence; evaporate to dryness on water-bath, expel HCl
completely by drying (not above 115" C.) in an air-bath. Moisten with water, add HCl, digest, and proceed as pet

by

scheme on following page.

IRON SLAG.
11
.'

61

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rf
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6i
^^i

QUANTITATIVE ANALYSIS. i-S

"
11>

"

y O a ? n h "^

'J

w
'-e

^
'S i?
.*

>

m|. ^ a o
"
CJ

SIS

^^
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tc

8.

-a "
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i;

ba

*'

^
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Q Oh

-v

JXl
Z ^ F
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'T^
ij

5 ^

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=
E?

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li

o
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tixi

"^

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2 n u " "O K
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c
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t-

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cO

u s M " ^

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u
<^

> tU 3

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,

^
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y u

?>

8
o
8

P s o a "
;-!

i:

^."
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a

e1
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tfl

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>-,"

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n

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02
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T-j

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Ct

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T
ii

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ft

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xj

J
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5:0

ES

p
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C

u u

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o ^
a*
rl

1)

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11

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4)

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Si

>? -u

6^
V,

Q
c o S
in

^::

3 O <0 / s

&.9
S5

u *

TITANIPEtlOOS IRON ORE.

63

64

QUANTITATIVE ANALYSIS.

^e13

c u

^
-u
if

.t^>.

O^
1

'^

^
L-

^Jj"
it
.

M ij^

>;

^^

<i '>5

'C

'Si

go

L^

(ii

Co

<,;/<

Si

1^

-a

s::

Q
8
"=
-f'ji
><

o
J3
D

U
CO

lU

jU

o c o * ^ o ^
'^^
flj

'

'~;

TITANU'EKOUS IKON ORE.

65

-3

- /,^
^,

' C (

r^

[jj

w
^

"^

^ ^

*--

^^"w^

^ -?.:,,

_^S:s

cl-^^-w.-i"!^

^-;.*:

-1

2d.

'P.,

e
-^ fl

..r->B^

*!Q^

""Pill > 5
:s-^,:

ty
'-

^ c=

G.S ^B^'-S

-- ^o^ w :i;.^ ^3
*-i-t

l-f^S ?

-*

E c-0 - o E

3
c!

-'^ Aifi -^'S

'J

"

^'-^

::

^>

"*

~
<^,^o

*J

S
C2

J^
'

^.X.'j:

14
t^^
'C

^ U V
0-(i,

0~
*

<i

S o

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te
,

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o o

-.^^ ri ~-^
-=^

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p 'i - ?
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LL<

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G
.S =<

-:;

.; a:
J^;

**

iT

i^

"S *1

O .so

^^ > 5^-

'S "'^.^A -S

in

-_-,-?

= 3

9.

.1^-^
*^ it e,

S
*

^O

"

2.

n
I
I
'g -^ ^^

I
't?

66

QUANTITATIVE ANALYSIS,

Notes to the Preceding Scheme.

/iote
I.

Sampling the ore. Break up

in

an iron mortar

pounds into pieces that will pass through a tin forty or fifty Thoroughly raix the fine and holes. sieve with halHnch Break up about ten pounds of average quality, so
coarse.

that

through a tin sieve with quarter-inch holes, and pulverize in the iron mortai Mix well, take one pound, a brass sieve of 60 meshes to the until it will pass through Mix well, take out about 50 grammes, pul inch.
it'

will pass

linear

pass verize in agate mortar,

through musHn bolting doth,

is

and put into a small

special

bottle, tightly corked, for analysis and

It

determinations.

yet

necessary that every

or a special portion of this required for as needed, in determination should be further pulverized,

the main analysis

powder. an agate mortar, to an impalpable fusion. Thoroughly mix the ore Note 2. Preliminary a third of the and its fluxes on glazed paper, put about the lower portion mixture in a two-ounce platinum crucible, been previously lined with a of whose interior surface has Na,CO and heat over a common Bunsen
thin layer of

violence of the burner with strong flame until the greatest Then add and treat the twoeffervescence has ceased. same precaution. thirds remaining successively and with the until the mass IS: Finally, heat strongly over the blast-lamp more NaXOj, in complete and quiet fusion, adding a little

should

for this not readily fuse. The time required fusion varies fron 30 to 50 minutes. resist this Certain highly aluminiferous ores obstinately known method of attack in such cases mix with the flux a pure precipiweight (two or three grammes) of chemically just before tated silica which has been strongly ignited
it
;

The amount of silica added is deducted from the total amount found in Residue
weighing.

afterwards
d.

NOTES TO THE PRECEDING SCHEME.

Note
3.

6f
the crucible

Removal of the fused mass, Let

below red heat, then chill it suddenly by plunging it into cold water contained in a porcelain caswith boiling serole, lay the crucible on its side and digest The fused mass will generally become detached water. from the crucible and come out in a cake. Then remove
cool until just

the crucible, wash

cone.

it,

treat in a small beaker with a little

particles of the mass,

HCl

to

remove any adhering

and add this solution to that of the Insoluble Residue Should any portion of the fused mass, thicker than a {2). it ought to film, obstinately resist solution in the hot water,
be removed only by patience and long boiling; and no attempt should be made either to dig it out or to dissolve lest by the formation of Aqtia Regla or free CI it in IICl
;

(in the

presence of

NaNOj,

or

Mn^OJ

the crucible be

attacked and injured.

Sefakat!on of SiO^. In order to render the SiOj entirely insoluble, it must be perfectly dehydrated.
Note
5.

Tfce evaporation should be carried to dryness, the residue heated until odors of HCl can no longer be detected, and
the

mass

is

hard and crumbly.

Residue b, temperature somewhat higher than 100 C, in an air-bath.

re-fused with

Since the residue is to be the drying may be completed, at a

Precipitation of BaSO^. Avoid the addition of a large excess of BaCI^ solution. Add only 5 c.c. at first, and then after complete subsidence of precipitate, add a few drops to determine if any HjS04 remains unprecipitated, etc. Then proceed as in Fres., 132, I, i. After
Note
8.

decanting the clear supernatant liquid, boil the precipitate

with water, allow to subside, decant,
liOt water.
filter,

and wash with

These precautions are necessary to dissolve out any other salts of barium, which are always carried

Jown on the
s

first

precipitation.

If

the precipitate of

BaSO^

dark colored after ignition, dissolve in the crucible in

gg

QUANTITAXrVE ANALYSIS,

hot cone. H,SO,, pour into cold water, and collect the pre
cipitate as before.

Naie 9. Separation of SiO,. Evaporate as in Note 5. Then add HCI quite freely and warm for some time before adding any water, as the high heat may have produced

anhydrous Fe.Oj, forming an oxychloride which is very Should the acid slow to dissolve, especially in dilute acid. already added be too dilute, concentrate by evaporation,
add cone. HCI, and digest at a moderate heat. Note II. pRECtP[TATEON OF THE BASIC ACETATES. ^^iV-

combined with Solutions li and cV must be very carefully neutralized with sodium carbonate. (If ammonium carbonate were used, bromide of nitrogen might form in
//-(T/^/

Filtrate g.)

To

neutralize the greater portion of the acid

use crystallized sodium carbonate, and complete the neutralization with a very dilute solution of the carbonate, add-

ing

it

drop by drop, agitating

to dissolve the precipitate,

assumes a deep mahogany-red color. If a permanent precipitate forms, add a little hydrochloric acid, and repeat as above. Then dilute the solution to about i
until the liquid

each gramme of the sesquioxide present, add about 20 grammes sodium acetate dissolved in a small quantity of water, and heat the whole to boiling.
litre for

from ten to fifteen minutes for the complete precipitation of the acetates. The fdtcring should be done rapidly on a ribbed filter, keeping the fluid hot. and
It is sufficient to boil

disturbing the settled

precipitate

as

little

as

possible.

When

available the

advantage.

Bunsen pump may here be used with After the supernatant fluid has been poured
throw on the precipitate and wash
it

through the

filter,

with

boiling water containing a little sodium acetate. Should any basic acetate separate upon concentrating the filtrate,

add some sodium acetate, boil, filter, dissolve the prccip itate in HCI, and unite to the solution of the main body.

NOTliS

TO THE PRECEDING SCHEME.

69

with KCIO3 to oxidize FeO. be In boilinc? Filtrate e heatthe whole of the chlorate by c^u-eful to decompose
incr

with excess of HCl.

1

"Note
in

cipitates of ferric hydrate

and ferric phosphate by decantaand redissolve in hot cone. HNO,. tion two or three times,

Solutkn

r'

Determination of P.O^.-To remove the HCl wash the pro add NHJIO in large excess,

small bulk ( 1 50 c.c. to 100 Evaporate this solution down to and add about 50 partially neutralize with NH.HO,

cc
c

c"

of solution of
is

the solution

ammonium molybdatc in nitric acid. If formed by very acid, ammonium nitrate is

above, otherwise add a small the partial neutralization as the solution, do not bod, aad quantity of the salt. more. Then filter from the yellow let stand 24 hours or

Warm

phospho-molybdate withgranular precipitate of ammonium and wash the precipitate out brin-ing it all on the filter, parts of the precipiwith a solution prepared by mixing 100 gr.=i.2) and 80 parts of tant with 20 parts of HNO, (sp. a small Dissolve the yellow precipitate by pouring water. filter into the through the quantity of dilute the determine the phosphoric acid original beaker, and c.c.) ammoniacal solution by means of mag:nesia mixture (5

NH.HO

in

the usual manner.

Magnesia mixture
If

is

preferably

made

with magnesium chloride.

magnesium phosphate
sium hydrate, add
with

falls

ammoniomixed with flocculent magnethe

crystalline

HCl

until

dissolved and

reprecipitate

NHJ-IO.

precipiReserve the filtrate and washings of the yellow a little more tate, and test for phosphoric acid by adding and allowing of the ammonium molybdate solution, heating pour If a yellow precipitate forms, to stand 12 hours.

through a separate

filter,

dissolve in dilute

NH4HO

and

add
Tf

to the

ammoniacal solution.
yellow precipitate
first

the

obtained was not suf

70
ficiently

QUANTITATIVE ANALYSIS.

washed, a red residue of oxide of iron may remain on the filter, in which case pour dilute HNO3 upon it allow it to pass into the ammoniacal solution, acidulate
that with

HNO3, warm, add more

set aside as before; filter

of the precipitant, and and wash several times with the

diluted precipitant, then dissolve the precipitate on the filter and that adhering to the beaker in as little dilute

NH^HO

as possible.

precipitate of ammonium phosphonot sufficiently constant in composition to admit of directly weighing it in exact analysis it is there-

The yellow granular

is

molybdate

and the phosphoric acid thrown down with magnesia mixture as just detailed. According
fore dissolved in
to

NH,HO

Muntzinger's analysis, after drying at

3-577 percent.
3.963
"
"

loo'^

C,

it

contains

NH^HO
P,Os

92.461

MoO,

100.000

Lipowitz says the precipitate dried at 20" to 30" C. contains 3.607 per cent, of P.Oj,
cent.

P,0,.
3

When

dried at 120''

and Eggertz ^.j to 3.8 per C, Sonnenschein found

of this precipitate sec

about
also

per cent.

For properties

Consult also Finkener's 93, i, foot-note. paper in Bericht d. d. chem. Ges XI, p. 1638 (1878}, and Chem. News, X L VII p. 66 1 ( 88 3), Note II. Washing of Fe,0,3H,0. Wash this precipi,

Fres.,

tate

by boiling up with water and decanting

little
little

until the wa.sh

water shows very

alkaline reaction with litmus paper,

and gives very

precipitate with solution of

AgNOj.
boiling

Then
water.

transfer to

filter,

and wash thoroughly with

Note

16.

Determination of

Mn. (Gibbs'

process.

Am

NOTES TO THE PRECBDISG SCHEME,

Vonr
Sci.
[2]

7'

NI i-lO LceW.

HCl solution add solution of Na,HPO, m large in Lccss and ThenaddcUIutcH.SO,or HCl until the wh.te
XLIV,
p.

216.)

To

the

precipitcite redissolvcs,

heat to boilmg, and add point about an hour, when Lcess Digest near the boiling and gelatinous, becomes precipitate, at first white
the

NH.HO m

Filter and wash crystalline scales. rose-colored and forms the precipitate If tinged red, redissolve with hot water. On ignitwn the preHCl. aad repeat the process,

dilate

cipitato is

Zn is IE Scheme I, Am. Clum., Vol. I, p. 323Determination of Note iS Volumetric

white powder. converted into Mn.P.O,, a nearly separated as in present, it must first be

Fe.

ut

completely free from the KClOj Solution k\ which must be a wide-mouthed reduction used to oxidize Filtrate k, into Carefully let down mto the bottle hoidmg about 250 c. c. a zinc, free from iron, and
bottle

a lump of amalgamated upon it, add about lO c. c. strip of platinum foil resting watch-glass and set aside over cone H SO,, cover with a test the To ascertain if the reduction is complete nio-ht sulpho^yanide. which should solution with ammonium color. e'ive only a trace of pink ^ about 200 c. c., and introduce into a flask holding

Then

fitted

forte

untd complete add dilute H.SO,, and heat and wash out the Cool the flask, pour solution of iron. beaker containing about contents of the flask into a large concentrated II.SO, and 400 c. c. cold water, add a little
wire,
titrate

with a Kronig valve, exactly 0.2

gramme

iron piano-

with a solution of
its

K.Mn.Os
strength.

water) to determine

litres ^^3 grms. ui 2 Repeat, and average

of the reduction'''now nour and wash out the contents cone. H.SO,. and tilmte bottle into a large beaker, add

with the standard

K.Mn.O, as

before.

H the HCl was not

72

QUAlStTITAX/VE AJTALVSIS.
Solution
b"*

properly removed from

the dark brown-red

ferric chloride formed will interfere with the end reaction In such a case re precipitate with of the permanganate.

NI-t^HO, wash thoroughly, and proceed as with SQiittionk'.

Treat Solutian A'
age the results.
Cf.
in

exactly the

same manner, and

3,

aver-

Analysis No.

C. III.

For method
tion, see

of repeating the titration in the arae solup, 74.

CrooUes' Select Methods,

Sundry Suggestion's.
of

i.

Solution a^

may be used

for

duplicating' the determination of S, provided the absence

Fe

is

proved by the proper

tests,
if

Duplicate determinadesired, in the filtrate

tion.s of

Ca and
b^,

Mg

can be made,

from the precipitate formed

Solution
2.

by ammonium hydrate in provided this precipitate be thoroughly washed,

Duplicate determinations of Ti and of

in

Fe can

be

made

Solution

b^

the

Fe can
in

also be estimated volu-

mctrically by dissolving

acid the weighed precipitate

resulting from the treatment of Solution g^\

case, however, the presence of
3.

In the

latter

TiOj

will

impair the

results.

The

purity of the SiOj obtained in Residue

^ may be

tested, after weighing,

by heating with fluoride of ammonium and concentrated sulphuric acid in a platinum crucible, whereby all the SiO, is expelled and is determined by the
loss in weight, the residue

being TiO, probably colored by

Fe,
4.

In fusing Residue

or Precipitate k, hydro-sodium

sulphate

may be
water

substituted for

KHSO+,
it

but since the

for-

mer contains water

until the
is

of crystallization

should be heated
In

expelled before using in fusions.

either case avoid expelling the whole of the H^SO^, or if the mass is heated to redness, partially cool, add cone.
II, SO^

and heat again

at a

lower teaiperature.

In this

NOTES TO THE PRECEDING SCHEME.

73

way the TiO,

will

be held

iti

solution by the excess of acid,

and the resulting acid sulphate will dissolve out readily. For Special Determinations see Notes to Scheme I

in

American Chanist, Vol.

I,

pp.

323

et seq.

Reactions. A full discussion of the many and complex reactions which take place in the preceding scheme for the
analysis of iron ores
i.s

superfluous.

We add
A.

a few remarks and equations which

may

serve

to throw light

The action

upon some

points.

of potassium

permanganate on ferrous
in

sulphate has already been formulated

the notes to Analysis No.
3.

connection with

This action, however, may be regarded as taking place in two stages, as follows
1st stage.

2KMnO,+PI,SO,=K,SO,+2HMnO,.
2HMnO,-f7l-LSO,+ ioFeSO,=2MnSO,. +5(Fe,(SO,)3)+SH,0.
\%

2d stage.

Sobdiofi If

XT^2Xt^ with excess of

in

NHJIO

and the

precipitate dissolved

H^SO^
Note

in

order to remove the

vitiate

larger part of the

HCl which might

18.
it

the results of
of

the titration as indicated in

is

The presence

HCl

injurious also because

exerts a reducing action on the

permanganate as shown

in the

equations following:

and
1^-

2lIMnO,4-l4Ha=2MnCl,+SH,0+loCl, 2FeSO,+H,SO,+2Cl=Fe,(SOj.,+2HCl

When

KClOj

is

employed

in acid solution
c),

as aa

o.xidizing

agent (as in the case of Filtrate

the reaction

which takes place depends upon the acid used and partly upon the strength of said add. Concentrated sulphuric
acid
is

said to act thus

6KC10,+3H,SO,=2HC10,+2CLO,+3K.SO,+2H,0
and
nitiic acid thus:

74

QUANTITATIVE ANALYSIS.

8KCIO3

+ 6HNO3 = 2KCIO, + 6KNO3 + 6C1 + 130

is

The

action of hydrochloric acid on potassium chlorate

variously formulated; Bottger gives the equation (i) and

Odling (2):
(
t

(2)

2KC10,+6Ha=::2Ka+Cl,03+4Cl+3H,0. 4KC10,+ I2HC1=4KC1H-3C10,+9C1-|-6H,0.

of
is

In any of these cases the powerful oxidizing agency

KClOj

evident.

Appendix

to

Aimlysis No.

21.

A. Method
fjrms.
if

for the

Bstimaticn cf Fe and Ti
i

only.

Sample, pulverize, fuse

grm. ore with

in

grms. NaFl-)-i2
Neutralize

KHSO^.
is

Dissolve

large quantity of cold water;

re-fuse.

there

any considerable residue

slight

with

Na^COj until a H,SO^ until the ppt.

Saturate with

precipitate forms, then add

is iilightly

redissolves and the liquid

acid.

H^S
water.

gas,

boil

some
if

hours,

occa-

sionally adding
of

H^S
filtrate

Filter from

the precipitate

TiO,-j-S, dry, ignite, and weigh,

dark colored

re-

add a little KClOj, boil to oxidize Reduce the iron with amalgamated zinc and platlIjS. inum foil, and titrate with KiMn^Oj as usual. As a result
fuse, etc.

To

of the fusion

we have

4NaFl+SiO.+4H^SO^==4NaHSO^-fSiFl,+2fI,0.

PLIGHTS METHOD.
c

75

n
r-

t,

*-

SI

J ^

rf *-

^ ^
cs,

76

QUANTITATIVE

A>.AI,YSIS.

NOTES TO
Note
I.

TIIIC

PRKCEDING SCHEME.
in

77

Care must be taken

dissolving the pig-iron in

all at

HCI+KCIO,
dizcd.

not to add the oxidizing agent

once, nor

some of the iron may remain unoxiShould a small portion of ferrous chloride remain in the solution, the subsequent precipitation of the iron as basic acetate (as in Filtrate f. Analysis No. 21) will be imperfect; instead of an orange red flocculent precipitate
too rapidly, otherwise

resembling ferric hydrate, the iron

pulverulent precipitate,

will fall as

a brick-red

(anhydrous has the property of running through

Note
100'*
2.

ferric oxide?)
fdters.

which

SiOj

obtained' in this manner,

and dried at

C, contains 6 per cent. H,0, which is expelled on ignition, and must be deducted from graphite after the
SiOj
has

been determined.
is

According

to

Allen

(see

Ckemiail News, Vol. XXIX.,

the pig-iron
leticone,

p. 91, Feb,, 1874) the Si of converted by the action of dilute HCl into

3Si0.2HjO.

By fusing

the mixture of leucone and

into solution,

graphite with

KPIO, the former goes

and both

may be

estimated directly,

AA. Determination
Second Method.
232.

of Graphite
Che^yi.
c.c.

and

Silicon.

(Eggektz,

Mix

10

c.c.

HjSO^
is

with 50

News, H^O,

XVI 1 1.,
cool,

p,
5

add

grms. fine borings, boil half an hour, evaporate one-third

and cool

The

reaction

as follows

2Fe,C+8H,SO,^SFeSO,+C,H,+H.
This equation, however, but imperfectly formulates the reaction, the S forming H^S and the P forming PH3. A
large

number

addition to

compounds of C and the CjH^ of the equation

of

H
;

are evolved in

according to Dr.

78

QUANTITATIVE ANALYSIS.
Vol. 129,
\y.

Hahn {Annalm der Chemie mid Parmacie,

1864) they include the following
'Ethjiene,
Gaseotn.
Prop;'Iene,
But^-lene,

57,

C,H..

C,H,. C,H,.

CEnanthene, C^H^,, Caprylene, C,H,^

Liquid.
P;irarnylene,

CH^
etc.

-J

i Am/lene,

Q^^.
etc.

Next add 10

c. c.

HNO3

and

boil 15 minutes.

dFeSO,+8HNOj=2(Fe,(SOj3)+Fe,(NOj6+N,0.
-|-4H,0.
Evaporate on a water-bath until vapor ceases to

come

off

and the mass

is

nearly dry.

Add

75

c, c.

M.O-f-ij

c.

c.

HCl and

boil

15

minutes;

add more
through a
first

HCl
filter

if any Fc,Oj remains undissolved. Miter washed with HCl, dried and weighed; wash

with cold water until no

ings, then with boiling

Dry
the

at

more iron appears in washwater containing 5 percent. HNOj. ioo C, and weigh the residue consisting of SiO,4Ignite
of graphite.
it

graphite.

amount

and weigh again; the loss in weight gives Lest the residue contain someis

thing besides SiO, heating with

well to determine the latter

by

NHjn

and

H,SO which

expels the SiO, in

accordance with the following equation

4NH,FI+SiO,+2H,SO,=SiFl,+2(NH,).SO,+2H,0.
The loss in weight gives the however, Nott 2 of A.

amount

of SiO,;

consult,

<fiAA.-Graphito detmiination according to

Dissolve
5

F.

A. Cair.

'nth hot water, then with

grras. borings in dilute

HCl,

boil, filter,

wash

KHO solution, then

with boiling

DETERMINATION OF TOTAL CARBON.

79

alcohol, {l>) ether and (c) hot water. water, then ^vith (a) determine as in B. Dry and transfer to flask and

volatile combined carbon goes off In this process the together with certain hydrocarbons, and graphite +SiO. remain. The SiO. is removed by the liquid hydrocarbons, out in the alcohol and the the hydrocarbons dissolve boiling water. is removed at last by ether, \vhUe the latter

KHO

B -Detsrmmatlon

of Total Carbon.

Roger's Process. See H. Elliott's modification of London, May, 1869; also Journal of Chemical Society,

Vol. 11, p. 140. Cairns* article in Am. Chem., of a neutral solution To 2.5 grms. of borings add 50 ex. one part of sulphate to S P^rts of of CuSO,! containing minutes; the iron dissolves; water; heat gently for 10 silica, graphite, and comcopper is precipitated, and the bined carbon remain
_

Fe+CuSO,=Cu+FeSO,.
The
order to
volatile

neutral as possible, in cupric sulphate should be as in the form of avoid loss of combined carbon,

hydrocarbons, as shown in

AA.

-o c c CuCl. (I with 50 c.c. strong HCl. boiling, until the copper dissolves

Add

water), part of chloride to 2 parts of and heat for some time nearly to
:

CuCU+Cu=Cu,Cl,.
follows: select a glass tube Prepare an asbestus filter as and 1 8 to 20 cm. in ength. of about 3 to 4 cm. diameter, and place broken Draw out this tube to taper at one end, packed, in the narrowed portion glass and asbestus, lightly Filter the (See^r.... 21S. \ ^' P- 7S90 of the tube. asbestus, wash thoroughly cuprous solution through the

30

QUANTITATIVE ANALYSIS.

with boiling water, and transfer contents of filter to a flask In making this transfer, the carbon, holdiiitr about 200 c.c.
asbestus,

and broken glass

order to use as

may
little

be blown into the flask

too'ether, in

water as possible.

Add

about 3 grms. of CrOj, (or if this is not available, about 5 grras. KXr^Oj), and arrange apparatus as in the determination of COi by direct weight,
to the contents of the flask

Ami/sis No,

7,

note

8, II

(page

34}.

Avoid adding more

little

water than absolutely necessary to transfer the carbon.

Add 30
time.

c.c. to

40

c.c.

concentrated H^SO^,

by

little,

shaking constantly, and closing cock of funnel-tube each

Finally, heat gently to boiling, not allowing

more

than three bubbles of

CO^

gas to pass per second

3C+4Cr034-6H,SO,=:3CO,-h2Cr,(SO,),-|-6H,O.
Boil one minute, attach

aspirate

slowly, three

guard tube of soda lime, and bubbles per second. Weigh the
of CO^. absorbed,

soda-lime tube for the

amount

and calculate

amount

of carbon.

Note~~Tht carbon separated from cast-iron by treatment with .sulphate of copper contains H and O, and cannot therefore be determined by weighing directly. Schutzenbcrgcr and Bourgeois assig.T to it the composition
expressed by the formula C3H,0, and consider it related to graphitic acid. BulleHn de la SocUtk Ckimiqiie dc Paris, Vol, 23. No. 9.
-^

EB.-Other Methods
mJ^i.^Tl?"'^,^''

for

determining Total Carbon.

been devised for deter''"" ^ ^^"^'^h ^^ *i briefly outline, "' rcmarki ema kmg. .'' however, that the foregoing is entirely satii.

^ "'^^^^'^^ '^^^e

DETERMINATION OF TOTAL CAKOON.

I

8i
V..

Method of Alvaroonzalez.

See Am. Chem., Vol.

p_

4jjr.

Place

10 grms. of borings in a beaker and treat

with a solution of cupric sulpliate (40 grms. CuSO^ in 200 Add di200 ^,.c. l"IiO), stirring until the reaction ceases.
lute

HNOj gradually, and

let

stand until the copper has

filter

dis-

solved.

Dilute the solution and

through one of

Rotli-

er's fialf filters (described in Chem. Neivs, Jan. 30, 1874, 100* C. p. 57), wash thoroughly, and dry on funnel at

Detach

ppt.

from

filter

carefully, place in a

weighed cru-

dry at 100 C, and weigh. Ignite and weigh again; the difference between two weighings
cible (thrONY

away

filter),

gives total carbon.

This method is not free from objections, but will answer when great accuracy is not indispensable, and speedy results
are desirable.

Method employed by \."Lo\\nw.PC(i.^^\A^. 'S^^ Chemical Phenomena of Iron Smelting, London, 1872. Digest 3 grins,
2.

borings from 24 to 48 hours with a solution of

e-xcess, collect
filter,

CuSO^

in

the spongy

Cu+C+graphite on an
in

asbestos
in

and burn the carbon

solution.

a stream of oxygen gas, as

the ultimate analysis of organic bodies collecting the

in

CO,

KHO
3.

Cf. Analysis

No.

30.

Method of Regnault and Bromeis. See Crookes' Heat borings in a combustion tube Select Methods, p. 74, with a mixture of plumbic chromate and KClOj, collecting

the
4.

CO,

in

KHO.
also

Methods for the liberation of Combined Carbon are numerous.

{a)
tar

BoussiNGAULT
a thin paste

with 15 to 20

triturates the iron in a porcelain morparts of HgCl^ and sufficient water to

make

Fe+2ligCl,=FeCU4-Hg,Cl,.

g2

QUANTITATIVE ANALVSrS,
dilute with

HCl and warm for an hour; wash and dry. Transfer to a SiO,+C, filter from the boat, and heat in a current of pure H, volatilizing platinum
Then
20(^250
c,c.

the

HgjCL,

Weigh

the C, heat again in a current of O,

burning
(b)

off the C,

and weigh again.

Weyl

dissolves the pig-iron

a galvanic current.

the positive pole of

under the influence of Attach a weighed piece of cast-iron to a Bunscn cell, and suspend it in dilute
being given
off at

HCl.
pole,

The
and

iron dissolves, il

the negative

tlie

carbon
also

is

separated,

Weyl has

devised another

method based upon the

following reaction

Fe,+K,Cr,0,+7(I-r,SO,)=Fe,(SO,)3+Cr,(SOj,

+7tL0+K,S0,.
See Crookes' Sclea Methods,
{c)
]>,

^6.

McCreate
March

s jJfet/iad.

Jottrnal,
of

17, 1877.

See Engineering and Afining The author uses double chloride

dissolve cut the iron, while the copper dissolves in excess of this reagent; he then oxidizes the carbon by means of CrO^ in an apparprecipitated

ammonium and copper to

atus

somewhat similar

to Elliott's, collecting the

CO,

in a

Liebig potash-bulb.
S.

Eggertz ColorimeUic Method.

See Crookes' Select

Methods, pp, 81 to 84; also Britton's paper in the Franklin Institute, Mzy, 1S70.

Journal

oj

C.

Other Methods for the Determination of Sulphur

and Phosphorus.
See Chem.

I.

Eggertz's Method

News. Vol.

XVII.

p.

207.

DETEliMKNATlON OF SULPHUK, ETC.

83

place in a A. Dissolve 10 grms. KCIOj in 200 ex. grms. fine borings, boll and add 60 ex. 500 c.c. fiask, add 5

HA

HCl.

little

by

little,

boiling until the

Fe

dissolves

4KC10j+i2tIC1^4KCl+3C10,+9Cl+6H,0,
and

3Fe+C10.+Cl+4HCl=Fe,a6+2H,0.
of sulEvaporate, dry on water-bath to insure oxidation unnecessary, since SiO^ does Thorough dryness is phur.

not interfere in acid solution with BaSO^. Then add to ex. HCl+30

the precipitation of c.c. H,0, and digest

dissolved.

on water-bath
20
c.c.

until all the

FeXU

is

Then add

and wash thoroughly. Add 2 ex. of a the saturated solution of BaCL (enough to precipitate cooling add 5 c.c. NH.,HO, I-I,SO, from 0.1 grm. S); after Filter, and wash by decantastir and let stand 24 hours. and then thotion with cold water two or three times, ignite, and weigh. If the roughly with hot water. Dry, shows traces of iron after ignition, purify by so-

iW,

filter,

precipitate
lution in

HjSO^. the For the determination of phosphorus dissolve some 140"' C pig-iron in the same manner, and dry at water, anhydrous Fe,0, will remain with the SiO= add
B.
; ;

filter,

fuse residue with a Uttle

KHSO^,

soften with

H,SO

and determine and dissolve in water. Filter from the SiO Add fdtrate to mam it as a check on the main analysis.
one, and determine the
date, as in
2.

P,0;by means of ammonium molyb-

Analysis No. 21.*

Vol. Method of Dh. T. M. Drqwn. See Am. Ckem.,

p.

IV,

425.
5

Treat
the

ex. H,0) containing a solution of K,Mn,0,(i grm. to 200 ceases, Avoid a very rapid evolution of the gas when this
;

H,S

and pass grms. of borings in a flask with HCl, three bottles and PH, formed through a series oi

QUANTITATIVE ANALYSIS,
and then pour the content, ol the Jpirate for some time, with water, and add snfhuent Stleinto a beaker, rinse Filter the colorless sothe K.Mn.O,.

HCl

to

decompose

lution.

add BaCl.

to

throw dow^i the

H,bO and

proceed

as usual.
3

Method employed by

J.

Lowthian Bell.
and pass the gases through a

Dissolve in

HCl

as above,

(lead nitrate super-saturated solution of potassic pUunbate hour, or until the evolution of with KHO), Boil half an
gas has ceased.

Wash

the

PbS

formed, oxidize

it

with

BaSO^ by means of IINOj, and throw down the S as collect on a filter, dry, Ba(NOj),. Let stand 24 hours, This method is said to give higher ignite, and weigh. Compare Fres., p^ercentages of S than that of Eggertz.
I 218,
4.
3-

Method of Arthur H. Elliott. See Am.

I,

Client.,

Vol.
5.

page 376.

Method emfbyed by Y^om^cK 2siA Dietz. See Practical Manual oi Chemical Analysis and Assaying applied London, 1872. Translated by Robert Mallet. to Iron,
Dissolve 3 to 5 grms. borings in HCl in a flask connected with four bottles, the first a condenser, the three following containing solution of AgNOj( I part of nitrate to 20 parta
of water).

and when gas ceases to evolve, aspirate. Pour contents of flask on one filter, and wash the Ag^S, Wash out the flask and cleanse the ends of the tubes wltn bromine water, and expel excess of Br by heat the followBoil,
;

ing reaction ensues

Ag.S+8Br+4H,0=H,SO,+2AgBr+6HBr.
The phosphide
Filter from
is

also converged into phosphoric acti

ppt.

AgBr. and

H,SO,

with BaCi, as U5uai.

DETERMINATION OF IRON MANGANESE, ETC.

6.

8$

llous-nnGhXiiJT for deicnnination of PhosSee Annak's de Chimie et de Physique, June, phorus. in American Chemist, Vol. VI, p. 275. 1 8; 5, and abstract

Method of

7,

l^or additional

methods consult
Neivs,

also papers

Allen,

Chem.

XXIX,

p.

91.
p.

and
147-

by Alfred paper by

Hamilton, Qmn, Nnus, Vol. XXI. Crookes' Sdect Methods, pp. 84-89.

Compare

DDetermination of Iron Manganese,

The
rite's

etc-

iron

may be determined by

difterence or

by Margue-

of pig-iron method, in which case dissolve 0.2 grms. It is advisable to use a as usual. in H.SO^, and proceed the close of the dilute solution of K.Mn.O^ towards

rather

oxidation.

Groups II, iU, For the determination of the bases of pig-iron in HCl, remove and IV, dissolve 10 or 20 grms of and proceed as in Analysts the SiO, by drying thoroughly,
No. 21.

The manganese may be thrown down

in the filtrate,

r,^

trom

means of bromine, or in the the basic acetate of iron by by hydrodisodic phosabsence of calcium, magnesium, etc., 3i8, 6. For other methods phate. See Fres., 109, 3, also articles by Samuel Peters of estimating manganese see

and by William Gah Chem. News, Vol. XXXIII, p, 35, XXXIII, p, 47braith, in Chem. News, Vol, Charles H. Piesse in Chefu. News, See also paper by

Vol.XXIX., pp. 57and no. which silicon exists For testimony as to the condition in E. H, Morton, Cheni. News, in pig-iron, see paper by
Vol.

XXIX.,

p. 107.

86
^
"^
-a 'u

QUANTITATIVE ANALYSIS,

ARSENrCAL NICKEL OKE.

"in

87.

'kJ

"

*<

_i

"fig S-r SLS

a'*s:

s; 73 (w jj to

- F w

o
^'-

y
"
It
.12

="

.&.
1-

-o

rf

- a
-^

^
u O
ii
rt

--<

o n (^

c
rt

'

-^
rt

'^

i;

GO'S- g

... tj TP

t:

" K 5 3 >" (^ ^ S 9-?

fc.

" o QT! _ y E u C )j

a o

Ho a
<5

etts jr

^ ^ o y
i;

id

11

:=: to

o c
I.

1-

i-O

"

^
'

i;

Ji i)

w - ^
-^H

rt
-^

n
rt

-.b-O p;

O ^

o ^ n

B
1:

c ? 2

c M

,;

^g

QUANTITATIVE ANALYSIS.
Analysis No. 25. GUANO,

230 Consult Fres., Quont. Analysis, S2. I, p. A. Cairns, Am. Chcvi., Vol.

also article

by

CaO, MgO, Fe.Oj, ?,0 SO3, To be dettrniined: SiO and volatile matter. .H,0, NHj, total N, organic

A. Determination
Heat
1

of Moisture,

grm. at 100 C. until constant

weight and loss=

H,0[+(NIIJ.CO,].
where great accuracy is required, a correction for the (NHJ^COj counted as water must here be made. Heat the substance in a U tube in a water-bath and a.spirate,
In cases
collecting the

(NH^)jCOj

in

normal ILSO.,.

Titrate with

Subtract (NI-l^),COj found from H,0 determined by heating at 100" C. as above. [-}-(^NH^)iC03]

KHO

as usual.

B. Organic and Volatile Matter.

Determine loss by ignition \n open crucible, and correct
for

H,0, (CO,) and (NH,),C03).

CAmmonia.
Use Schlosings method, Fres., 99, 3, b. Mix the guano with milk of lime and place under bell-jar over a dish of
normal PIjSO^.

A large surface
is

of acid in proportion to

the guano solution

desirable.

Let stand,

cold,

48 hours

or more, and titrate with

(Cf. Analysis No. 11.)

normal

KHO

as in acidimetry,

D,Total Nitrogen.
Use Varrentrapp and
Will's

Heat the guano in a 185. lime, converting it into NH3.

Method, as detailed in Fres., combustion tube with sods

Absorb the NH^ in a standard solution of H.SO^, aspirate and disconnect bulb. Add litmus and titrate with standard KHO.

H Sulphnric
Dissolve in hot HCl, loilow the Scheme F.
filter

Acid. and precipitate with BaCL.or

GUANO.

89

2-i
B 1
a
> u o
<1
T3

u
j.^

<^

d
o
o

o".

3 +
o
S

o c w
a

S S

C S

]>
-o

o^U
-S

"' 3
g-

"

.-t:

-a '5,

^ 3

P-l

*( -o .S

-^
6
!*

o
rr-l

o
4>

o d
.2

o
K
c

19
*:.

QUANTITATIVE ANALYSIS.
90

Ana/p^s No.
To

26.

-Superphosphate of Lime.
Moisture,

be d^Urnnned'.

reduced

(or

reverted)

P,05 P,Os, soluble

and available P.O,.

of Moisture.
of

A. -Determination

Dry

grni. at

loC'and weigh-loss

weight^moisture.

Weigh
4
o-rms.
,

P3O5. B.Determination of Total mix with 2 grm, out I grm. accurately,

KNO, and

crucible, dissolve in Na.COj, fuse in platinum dryness (to dehydrate HNO evaporate in a casserole to Wash thoroughly and SiO,+aq.)> add water and filter.
dilute filtrate
to

500 c.c; take 50

c.c.

of

tliis

solution

l\Oj with (=0.1 grm. of superphosphate) and determine (NH^), MoO^ as usual. Consult Note 12, Analysis No. 21.

C Determination
Digest
I

of Insoluble P.Os.

grm. with about 400 ex. of water in 8 to 10 different portions successively, rubbing the superphosphate Filter and treat residue with water in a porcelain mortar.
(filter

included) with about 50

c.c.

solution of
c.c. of

ammonium
water, and
yo^'C. for

citrate containing

30 grm. of salt to 100

if

carefully neutralized

acid.

Digest at about

40

minutes or longer,
exactly as in B.

filter

and wash.

Dry

residue and fuse

Estimate the I^O^ in same

manner using

100

c.c,

(=0.2 grm. of superphosphate) of the solution

each determination.
of

(500

c.c.) for

D.Determination
(omitting the use of

Reduced and Insoluble PjOs.

grm.) with water as in
citrate),

Leach another sample (i

and fuse as in B.

ammonium

dry the residue

c.c.

Continue as in E, taking 150

of the

solution for each determination.


POTABLE WATER.

9I

E. Calculation.
The reduced PjO, is found by subtracting the PjO; in C from that in D. The soluble PjOs=:B-D and the available P,Oj B-C.
Note.

Reduced or reverted PjOj forms thus

CajP,03+CaH,P,Os^2Ca,H.P.Os.

Consult Bella's Handbitckf pages 802-806.

Analysis No. 27.

Potable Water,
CI; SO^; SiO,;
matter, total

To be delemimed:

K; Na; Mg; Ca;

organic and
solids;

volatile

hardness (soap test); oxy-

gen required to oxidize organic matter (permanganate test).

Quantity required, three to four gallons
demijohns.
;

collect in clean

A. Determination
Measure out 250

of Total Solids
c.c. of

and Lose by
of

Ig-aition-

the water, evaporate to dryness

on

a water bath, in a

weighed platinum dish

in

lOO

c.c. ca-

pacity.

During the evaporation cover the dish with a

paper screen.
weigh.

Dry

an

air

bath

120"-! 30*

C,

and

Weight of residue gives "Total Solids," Ignite gently over a Bunsen burner, moisten with a solution of

CO,

in distilled

II,0, dry on water-bath, heat in air-bath

I20''-130''

C.

as

before and weigh; difference

between

second and

first

ter, also called "

weights gives organic and volatile matLoss by Ignition," For further treatment
11

of residue see F. Compare Chapter " Watir Analysis" 3rd edition, 1874.

of

Wanklyn'a

'''b --Determination litres rite 4 to 6

QUANT TATJ VE ANALYSIS. CaO. HgO. of SiO. Fe.O., A1,0

I

of

water

(according

to

the

ploron
^
h

Zh

SiO. and

dish, washing care^ transfer to platinum dryness, filter from dish, evaporate to the porcelain for Dolomite, Auafysts No, 7. follo^v scheme

of

total

solids)

to small

bulk in

porcelain-

Add HCl

0. Determination of HjSO^.
Take i litre (or less) drops of HCl ^nd determine SO, 200 cc with a few If the water contains usual manner. as BaSO, in the H,SO, (as sulphates) to give a feeble precipsufficient'
itate

of

the water,

boil

down

to

with

BaCl, before concentration,

one^half or one-

quarter litre will suffice.

D. Determination of

CI.

Test the water with AgNO, for CI, and if no cloud otherwise 25 small bulk is formed evaporate i litre to Add a slightly acid solution of AgNO,, to 50 cc. suffice.
;

and proceed as usual.

Second method.
a standard solution
as an indicator.

Determine the CI volumetrically by of AgNO,, using potassium chromate

141,!,
b,
.

See Fres.

E.Determination of
Evaporate 6
finishing on
tilled

Na and E.
the residue with
into
dis-

litres to

dryness in a large porcelain dish,

Boil
filter

a water bath.

water several times,

a platinum

dish

and wash.

Add Ba(HO),
a
little

to filtrate.

Evaporate

to dryness,

heat to low redness, let cool, take

up with water, add

precipitate,

(NH,),COj and
filter,

(NH,)C,04, wash the

water and
if

add

HCl

to

filtrate,

evaporate to dryness, ignite

not clear,
filter,

and weigh.

Dissolve in

svaporate, dry, ignite cautiously,

and weigh again.

This

POTABLE WATEK.
residue of

93

NaCl+KCl must

uble without residue in water.

be perfectly white and solDetermine the CI in the

weighed NaCl-t-KCl and calculate tlie Fres. page 841. Compare Waukfyu, zrd

Na

and

as in

edition,

page 63.

F, To check dotermination of Na and K.

Moisten the weighed " Total Solids" of A with dilute HjSO.,, dry and ignite with a little powdered (NH^)3C03 By deducting from this weight. to constant weight. calculated foi one gallon, the combined weights of SiO
Fe^Os, AI.Oj, CaO, phates), the weights of

MgO

(the latter four reckoned as sulNa,SO^ and K,SO, are obtained.

Test.

G. Dr. Clark's Soap

Consult Sutton's Volumetric Analysis. %Zz,l0: or WankWater Analysis, 3rd edition, page 125. lyn's Principle. \rl^x<l water, so called, destroys much soap
before a lather
uble salts,
viz.
is
:

formed, owing to the formation of

stearates, palmitates,

insol-

and oleates

of cal-

cium and magnesium.

Preparation of Soap Solutions. D\^so\\'C lO grms. of good white Castile soap (which should contain about to 95 12 per cent, of water) in i litre of alcohol 90 from the residue. Let stand and siphon off per cent.

No. !, Label this solution "No. i." Take of solution distilled water, !C0 c.c; of 56 per cent, alcohol, 65 c.c. of 2." Label this soap solution " No 75 c.c, and mix.
;

'Dis^o^^t Preparation of Standard Calcium Solution. evaporate until I grm. of precipitated CaCOj in HCl, c.c. c.c. neutral, take up with water and dilute to 1000 of this solution contains grm. O.ooi CaCOj. burette with SiandardiBation of Soap Solution. ViW a Place ro c.c. of calcium solution soap solution No. 2.
1

QUANTITATIVE ANALYSIS.
J uo(;t{e

Add
f,3^,,

it

to loo c.c. of distilled

in a glass st.<>PP^^'

::;r'arco:tLue

surface of the water. l^inutes on the

calculate.

Lmed

of

sufficient

the burette and shake until a lather addi.^ soap solution consistence to renjajn for Bve
^^^^^i^^^

Read
,

burette and

Repeat.

In certain

amount
c.c.

of

if.;. be made or the loo destroyed by water itself soap solution

cases

allowance should

,,

destroys 0.8

c.c.

soap solution.
as above.

grains per gallon of CaCO,. ligrammes per Utre and of chloride of of the standard solution
" Example. -iocc.

Perfatmance of

Amfysis.-Same

Report

mil-

calcium required 23

c.c.

But 10
of

c.c.

of

CaCU

soap solution solution is equivalent to .oi grm.

of

CaCOj, hence
used
,

c-c.

^^

_ -of

\:a

.00043 gnns

23

I )
if

water under examination require grms. 10 33 c.c. of CaCl, solution, we have 33X. 00043 X per litre of CaCOj. This gives .1419; and .1419X.058318 For the factor .05S318 consult gives grains per gallon.

And

100

c.c.

I,

Calculaiion of Results,

E. Permanganate Test for Organic Matter.

Principle.

Permanganate

of

potassium in solution

oxi-

dizes putrescible organic matter.

PreparaticH of solution

0.320 grms. of permanganate in

solve 0.7875 pure oxalic acid in

Dissolve of fertnanganate, Diswater. I litre of

i

litre of
i

water, weighing

very accurately.

Of

this solution

c.c.=o.oooi grm. oxy

POTABLE WATER,
geii.

95
c,c.

To

standardize the permanganate, take lo

of

oxalic acid aolution; dilute to loO c.c. with distilled water,

add 5 c.c. dilute H,SO^, heat nearly to boiling and run in lo c.c. of from a burette the permanganate solution. Caloxalic acid will require 12 to 15 c.c, permanganate. c.c. of latter in milligrammes of oxygen. value of culate
I

Testing waier,

Take

00

c.c.

potable water add H^SO^,

add standardized permanganate, little by little in the cold, until the water retains a pink tinges after one-half Report amount of o.xygen required to hour's standing.
oxidize organic matter.

ExampL'.

10
of

c.c.

of standard solution of oxalic acid

leqiiired 14 c.c. of solution of

K^MnjOs
is

But 10

c.c.

HjQO^

solution

equivalent to o.ooi

grms. of oxygen, hence

c.c.

used

\
14.

I,

c.c. ^
J

I.

mgm.
(I

= .0713 mgras. =

J
if

oxygen

100 CO. of water under examination required mgms. per 0.8 c.c. of ICMn.Os, we have 0.8 X. 071 3 X lO This matter. litre of oxygen required to oxidize organic gives .5704 milligrammes and .S704X. 058318 gives grains

And

of

oxygen per gallon.

See

I,

Calmlation of Results.

I. Calculation of Results,
grains in a gallon, multi ply the number of milligrammes of each constituent by 0.058318; or use Dr. Wallers Table, published in Am.

To

convert grms. in a

litre into

Report results in two ways: the grains per gallon of uncombined constituents, viz., SiOj, Fe.Oj, AUO3, CaO, MgO, Na,0, K,0, CI, SO,, together with" Loss by Ignition "and "Total Solids;" and secondly
C/wm.,

Vol V,

p.

27S.

QUANTITATIVE ANALYSIS.
96

the bases *u. ^ins oer gallon of

combined with

IS *:r-/wi*.
Combine

he fonowing scheme.

K
K

as
'

K, SO^

excess of

POTABLE WATER.
0.152 grains

97

Na

NajO making
(2)

then a proportion similar

corresponds however to 0.204 grains to f i) wc have

Na,0

SOj

"
=

Amount of Na,0
0.204

Amount
for the

of

SO,

needed

NajO.

62

80

X
hence 0.204
~{-

=: 0.263 gi'sins. 0.263 =^ 0.467 grains NajSO^.

But the water contains 0.340 grains SOj hence we have 0.263 =: 0,077 grains SOj left over to combine 0.340

with CaO.

Accordingly we have the proportion

(3)
f

SO^ CaO
:

Amount of SOj ]
remaining.
J"
:

Amount

of

CaO
J

[needed for the SO^,

80

= 0.0539 grains CaO, hence 0.077 + 0.0539 = 0.130 grains CaSO^.

y

56=

0.077

Proceeding in liice manner the as combined with COj.

0.804
(4)

CaO

remaining

is

regarded

0.0539 = 0.7501 grains CaO

CaO
whence

and

since.
^

CaCO,

= 07501
1.34 grains

Ca CO,.

Collecting the results of the calculation we have (thus far) the following figures for the constituents combined:

NaCl

= 0.354

oaANXrrATtVE ANALVSfS.
98

The
manner

a further following will serve as analyses. of rq^orting similar

example of the

Analysis op Croton

Water

bv Dk. C. F. Chandler.

Grains per gallon. Soda

Potassa
I.ime

0.326
.

0.097
.

0.988

Magnesia
Chlorine

0.524
.

0.243
.

Sulphuric acid
Silica

0,322
.

0.621

Alumina

and oxide of iron

trace

Carbonic acid (calculated) Water in bicarbonates (calculated)

2.604
.

0.532

Organic and volatile matter

0.670
6.927

Less oxygen equivalent to the chlorine

Total
.

.054

6.S73

These acids and bases are probably combined as follows:

Chloride of sodium

....

Grains per galloa

SPECIFIC GRAVITIES OF SOLIDS

AND

LIQUIDS.

09

Analyses No. 28

and No.

29.

Si'ecific
Liquids.

Gkavitiks of

Solids and

A Sp.

gr. of

a solid by direct weight.

" "

Weight

of solid in the air

"

water

=w = w'

Sp. gr.

W
flask.

B. Sp.
Weight
" " " "

gr. of

a solid by the

of solid
flask
"

+ water
-'

"

=w = w' solid = w" +

Sp. gr.

=
(w
of "

+ W) w"
in air

O. Sp.

gr, of

a body soluble in water.

Weight
"

body
"
oil

==

"

oil

Sp. gr. of
"
"

" water

=a =
i

=: W'

The

liquid displaced being

w
a:

w' ^ w"
then
I

Sp. gr.

= w" =

w"'

w
w'"

D.Sp.

gr. of

a body lighter than water and insoltible in it, e.g., Cork.

of cork in air
" lead "
'

Weight
"

"

water

=w = w'
water ==

:uKi corii in

w"

lOO

OUANT[TATIVF. ANALYSIS, ^

Sp. gr.

^__vv"4-w Water and soUibl

in it

a B. -Sp.gr, of

Body

lighter than

Weight

of

body
"

in air
"

naphtha

= =

w
w'

w w' = w"
Sp. gr. of naphtha
" "
"

water
:

=A =
I
:

A w"=
Sp. gr.

w"'

w w

///

ji.

_ Determination

of the Proportion of
Alloy.

two Metala

in an

= S =A Weight of the alloy = Sp. of one of the metals = s" Sp. gr. of the second metal w' Weight of one nietal Weight of the second metal = w"
Sp. gr. of the alloy
gr.
s'

w"
For proofs of
this
Clitmistrj/f p. 74,

= Aw

formula, see Galloivays First Step in

O.

Sp.

gr.

of a liquid by the flask.

Weight

of
" "

aask
" "

and water
"

liquid

=F =w = w'

F
OROANIC ANALYSIS.
lOI

Sp. gr.

w'
;^;zje'
it.

H.-Bp.

gr.

Substance in of a Liquid by weighing a

Weight of substance
(

"

" in liquid

Sp. gr.

of the substance
:

^w = w' =A
gr.

w
or

bp. gr.

(w W) = A sp. = (ww')A
:
1^

Amfysis No.

30. 3

^^^^ 32.

C?^^^V ^wa^j/orir.

of orgamc bodies Introductory Notes. The analysis Proximate Analysis which deals comprises two branches
;

proximate principles of organic bodies with the separation oi

v^ithout altering them,

which and Ultimate Analysis, by composing the of the dements the nature and quantity
organic bodies are determined, analysis is possible No systematic course of proximate animal chemistry is in of the science in the present state for a course o more advanced than vegetable
^
;

this respect

zoo-chemical analysis see article

by Gomp-Besam-

the

Chanie, I. 55^Nenes Handworterbuch der ^f f'^P^f der See also HehUz Lchrhnch maionary, I, 249. Watt's tor Physiological Chemzstry. Zoodicmic and Lehmmis consut organic analysis, general principles of proximate Proximate Organtc Ontlincs

Dr

Albert B. Prescotfs

<'

of

Analysis:
kind.

^^0^
special

useful

manual and the only one

of its

For

bod., methods of analysing organic

articles, consult especially of commercial

" ^^^^^^^ /^^^t^ Unt^rsuchungcn of which Technisdt-chennschcn buck der Kopp is most vahiable. the second edition by Emii

02

QUANTITATIVE ANALYSIS,
of conducting
in

The method
ciently

an ultimate analysis
System,
171-189,
in calling

is suffi.

detailed

Fresenitis*

yet the

following

summary may be

of service

attention

to the chief points.

A. Determination of C, H,

and O,

in Sugar.

Select a very pure well crystallized

candy
better.

will

do,

sample of sugar, rockbut small crystals from a vacuum pan are

powder.
:

Dry

at loo*^ C, in

Provide the following articles

(i)

watch
glass.

The

dried substance in a tared

in

(2) Combustion tube of hard glass drawn out as shown Fres. 174, cleaned and carefully dried.

(3) Liebig potash bulb

Sp. gr. 1.27, or a U-tube

filled

filled

with a with soda-lime.

KHO

solution of

by Thorpe

(4) Chloride of Calcium tube; that of the form described in his Quant. Chcm. Analysis page 347, fig. 80 is

advantageous.
(5) Small U-tube containing potash-pumice in and CaCl3 in the other.

one limb

(6) Rubber tubing.

(7) Fine wire for binding the tubing.

(8) Good corks, free from holes, rolled and pressed. (9) Cupric oxide, granulated preferred, chemically pure, freshly ignited to remove organic matter and moisture, and contained in a corked holder.

platinum boat to contain the substance, (10) or another process be followed, a mixing wire.
(it) Combustion furnace,

if

(12) If oxygen is to be employed, a cylinder of this gas and a system of drying U-tubcs must be provided.

OKGANIC ANALYSIS.

I03

(13) Sundry articles, such as glazed paper, agate mortar, towel, asbestus, a ramrod for cleaning combustion tube. etc.

Process of the Combustion.

(a)

Weigh

the substance (sugar) and preserve in a des;

iccator until ready for use

weigh also the

CaCl^ tube.
fill

KIIO

bulb to-

gether with the U-tube (5),

ib)

Dry

the combustion tube and

with cupric oxide

if

the substance

may be
to be

inserted on a platinum boat

the
it

combustion

is

must be

intimately mixed with

conducted with oxygen, otherwise some powdered CuO

in

the agate mortar and transferred by the glazed paper to the combustion tube. Stir also with the iron mixer. Avoid

introducing moisture,

Connect the apparatus, arranging it as shown in the Test the joints by cut on page 433 of Fresenias' System. apparatus which that bulb of the heating the air in and the combustion tube drive is between the solution
(f)

KHO
if

out a few bubbles of air and let cool,

of the solution
{(f)

an unequal level
tiglit.

is

maintained, the joints are

Conduct the ignition, heating gradually, and beginning at the end next to the CaClj tube do not apply heat
;

to the substance until several inches of

CuO

are red hot.

is

Pass oxygen gas through the tube

ployed.
Frcs.

if

that

method

em-

178.

The combustion

of sugar

may be

completed in about half an hour, other substances require more time, especially those rich in Carbon.
(/) Aspirate air, or pass
slowly.

oxygen through the apparatus

weighed tubes, cool and weigh. From the CO2 and the H,0 found, calculate the C and the H respectively. The O is found by dilTerencc.
(/) Disconnect the

jQ,

QUANTlTA'rJVK ANAf.VSlS.
Theoretical Composit'wii of
Cii

Cane

Stigar.

BKTKRMINA'I'ION OF NITROGEN.

los

Of substances containing 50 percent carbon

take 0,350 grms.

I06
article
;

qUANTITATIVK ANALYSIS.
it

should be heated in a porcelain dish to expel water and ammonia before using.
Operation
of

Fill

the combustion tube about one-third

let it

ful)

warm

soda-lime and

cool

then mix this in

an

agate mortar with 0.2 to 0.4 grms. of the dry ferrocyanide

of potassium,

tube
fi!l

and introduce the mixture again into the and then the tube with the same nearly to the open end. Insert
;

rinse the mortar with a little soda-lime,

a small plug of asbestos loosely, attach the absorption bulb

containing; the sulphuric acid

by a

well-fitting cork,

and

place the tube in the combustion furnace.

the tube at the end nearest the cork,
ally

Begin

to heat

and proceed gradu-

towards the other ^nd.

evolved should bubble quietly through the ab-

The gas

sorption tube, and

when

it

ceases to pass break the

tail-

piece of the combustion tube,

and aspirate gently through

the whole apparatus.

Detach the absorption tube, empty its contents into a beaker, rinse well, add a little litmus, or cochineal solution, and determine, by means of normal KHO, the amount of acid remaining imneutralized by the ammonia. For details of this process see Analysis No. 12,
Theoretical Camposition of Potassitim Ferrocyanide,
*

N
f;::
T.
,^

'7-^

-^^-^
^3-3

37.0

3H.O

J^^
100.0

DETERMINATION OF NITROGEN.
D.

107

Determinatioa

of

from tho Volutns.

Duvias' method modified by Melseiis, Cf. AVfj. 1S4. See also Watts' Dictionary, I. 342.

When
<jr

nitrogen exists
e.

in

an organic substance

in

the form

an oxide,

g. nitro-benzol

CJU

(NO2), Varrentrapp

&
of

Will's

method cannot be employed because the oxides

into ammonia on Dumas' method consists in heating the substance with oxide of copper, and measuring the

nitrogen are not coniplctcly converted

heating with soda lime.

nitrogen evolved by collecting over mercury.

originally devised

The

process

pump

to exhaust the

by Dumas necessitated the use of an aircombustion tube, but this may be

by following Melsens, who introduces hydrosodium carbonate into the tube which gives up carbonic anhydride on heating, and drives out the nitrogen before it.
obviated

For Melsen's process provide the following

(i)

articles

A
(3)

combustion tube 70 cm. long.

(2)

(4)
(5) (6)
(7) (8)

Mercury trough. Graduated cylinder. Copper oxide.

Solution of potassium hydrate.

Hydrosodium carbonate.
Connecting tube. Corks, asbestos, rubber tubing,
etc.

(g)

Combustion

furnace.

In filling the combustion

tube observe

the

following

order: Insert,

cm. of hydrosodium carbonate, then copper oxide mixed 5 cm. of copper oxide, then 15 cm. of with the substance to be analyzed, next add about 28 cm. and of copper oxide, insert a copper spiral 5 cm. long,
first,

15

lastly a

Insert the remaining 2 cm. shown cork with connecting tube, and arrange apparatus as

plug of asbestos

in

in Fig, 93.

page 63;, of Fres. System.

I08

QJTAMTITATIVK ANAI.YSIS.
:

Conduct the operation as follows

Heat
;

a portion of

NaHCOs
of

until all
in

the air

is

expelled
;

test

the with a solution

KHO

an inverted test-tube

then heat

CuO

to red-

ness, arrange the graduated cylinder containing

KHO

solu-

tion over mercury,

until

and heat the mixed

CuO

and substance
in

gas ceases to

come

off; lastly, expel

the nitrogen

the combustion tube by again heating the NalTCO;;, some (Oxalic acid of which must have been left undecomposed.

may
352.)

be substituted for the HNaCO.i,

See Thoype, page

to

Transfer the graduated

it

cylinder

a vessel

of

water, hold

so

that
is

the level of the water within the

equal, then read off the

cylinder and without

the gas in cubic centimeters,

volume of and simultaneously the tem-

perature of the water and the height of the barometer.

CaknlatioH of Results. To obtain the weight of nitrogen from its volume employ the following formula
:

Let

V = Volume
B

of

observed, expressed in cubic centi-

meters.

And

t:= Temperature of the gas.

= Height of the barometer expressed In millimeters.

of aqueous
in

f= Tension
Then
if

expressed

mm.

vapor at the temperature t% of mercury.

:

W = weight of nitrogen we have B W = 001 2566 V

I
.

+.003671''

760

The constant 0,0012566 is the weight in grammes of c. c. of N at o' C and 760 mm. The constant 0.00367 is
Example
:

the coefficient of expansion of gas. In an analysis of

Butvramide

~
:

C,,H:Oj

^'
I

^'^^

fallowing data were obtained

ANALYSIS OF UlUNE.
0.315 grms. of substance gave 43.9
c. c.

IO9

at ("=17''^

and B

= 753-^
/=

'ii"i-

First look out in a table the value of

/at

17. 3.

{Fres.,

page 837, Tabic.)

degree)

We find (calculating for the tenths of

c. c.

I47-

Now V

H-7=73^S f =753.2 mm. B +.00367 X f^^-i.oCsSAnd I

Substituting in equation
:

= 43.9

"im-

w ^ .0012566 V ^^r^^ '\~^ ^^^^ _ .0Oi2 566X43_.9_>iZ38i _ ^.0504 grms. N.

^^^

1.0635^760
i^nd 2:25p4i<_lS?

= 16.00 per cent nitrogen.

Butyramide
5S-2
10.3

0.31S
Theoretical Cotnposition of

C,

Hs

O
j^

18.4
i6.i

100.0

Analysis M>. 33.

Urine.

George B. For brief methods of analysis consult Dr. " Manual of ChemFowler's " Urine Analysis," Thudicura's Sutton's " Systematic ical Physiology." pages 178-192, and Fof Handbook of Volumetric Analysis," part vi. 78HofUltzmann & figures of sedimentary deposits examine
raann's

Pathologischen "Atlas der Physiologischen und

following
to

Harnsedimente." (44 plates.)

The
"Guide

works may also be the Examination of Urine,"

studied:
Attfieid's "

Leggs Chem-

JO
F.

QJJANTITATIVK ANALYSIS.
Hoppc-Seyler's
"

Ilandbuch dcr

Physiol,

and

2ur

Neubaucr & Vogefs " Anleitung Pathol Chem. Analyse," des ilarns;' Qualitative und Quantitative Analyse
Gonip
Jiesariez'
"

istry,"

Lehrbuch der Physiologischen Chemie," Hofmann's "Anleitung zur pages 5;6-s8o, Ultzmatin & Untersuchung des Harns."
Constituents of Urine.
Urine, the secretion of the kidneys, in a healthy individual, is a clear, yellowish, fluorescent liquid of a peculiar
odor, saline taste, with a

mean
:

sp. gr. 1.020.

The

follow-

ing are
1.

its

normal constituents

JVaier.

l-UO.

2.

Inorganic Salts.
IICl,

Mg, combined with H,PO^. ILSO,, CO,, (HNO3,) and SiO^.

Ca,

K, Na,

NH,

'3.

Nitrogenous crystalline bodies.

Urea,
Sugar,

uric

acid,

hip-

puric acid, creatine, creatinine, xanthine,

cystine.
4.

(ammonia,)

Non-nitrogcnotiS organic bodies.

oxalic, formic, malic,

lactic, succinic,

and phenylic

acids, all in small

quantities.

Pigments.

Urochrome, urohaematin.

Alhumenoid. matters.

Matters derived directly from the food.

Besides these, urine may contain, under varying circumstances, as in disease, a large number of
8.

Abnormal constituents. Blood, pus. mucus, albumen,

fibrin, casein, fats, cholesterin,

leucine, tyrosine, allau-

taurine, biUary pigments, glucose, inosite, acetone,

torn,

indigo-blue, melanin,
acid,

butyric acid, benzoic

oxaluric acid, taurocholic acid, glycocholic acid, many others. (See Watts" Dictionary,

and

vol. v. p. 962.)

ANALYSIS OF URINK.

II

These substances do not occur simultaneously in all urine, and many of them but rarely. Only those comraonly determined are considered in the Scheme
(page 112).

Chemical Composition of
Healthy.

XTrino.

(Dalto^.)

Numbers Approximate.
938.00
30.oo
i-^S

Water Urea
Creatine
Creatinine
Urate- of soda
"
\

i-S^

potassia

>
'

l-^O

"

ammonia

Coloring matter and mucus Bi-phosphate of soda

Phosphate
" " "

of

soda
potassa
1-

1 2.

45

magnesia
lime

Chlorides of sodium and potassium Sulphates of soda and potassa

....

7.80
6-9C>

1000.00

Morbid urine may

Albumen,
Sugar,
Bile,

contain, also

(Bright's disease.)

(Diabetes.)

Excess of Urea,
Oxalate of calcium.

in

QUANTITATIVE ANALYSIS.
Action Of ReagontB on Urino. acid urine effects no cliange.

Boilin'^

Boiling alkaline urine

makes

it

turbid

if

rich

earthy

phosphates.

HNO^jOr HCl darkens the

on standing.

color,

and throws down uric acid

KHO

or

NH.,HO throws down

earthy phosphates.
a white ppt. of sul-

BaClj or PbA,
phates.

in acidified urine, yield

AgNOs

white ppt. of chlorides, also coloring matter

and

some organic substances.

Miirexid Test.

Collect

some

of the uric acid

thrown

down by HCl, remove supernatant Hquid, add cone. HNO3, and evaporate to dryness. When cold add a drop of NHiHO. A purplish-crimson color shows formation of murexid

(CeH

NA)-

Reactions of Urea. Hg (NO^Oa throws down a gelatinous white ppt. containing COH^N^ .2HgO.
Boiling with

KHO

converted into

NH^HO

test with

Nessle'r reagent.

HNO;,, nitrate of urea precipitates.

NaClO

or

NaBrO decomposes
Scheme

urea with evolution of

N.

for Analysis of TJrine.

I.

Physical Characters.
Odor.

Certain peculiarities in odor indicate either nature of food or symptoms of disease.

(a)

Viscous or fluid. Color.~W\\Qx\ healthy, urine is amber-colored; bilious, brown or greenish,

(c)

(b) Consisimce.

whea

(d) Specific Gravity.

is

By the urinometer, 1015

4
c.

to 1025

marked H.

S.,

signifying Healthy State.

makes a

difference of about 1 in the reading'.

ANALYSIS OF URINE.
2.

113

Test

witji

Litmus Pa pek, and

note whether acid or

alkaline.
3.

Pour

sample

into a stop-cock funnel,

12 hours.

If a deposit forms, filter,

and let stand and examine the filtrate

and sediment separately. Filtered urine leaves a scum of mucus. (For sedunents, see Schemes, page 117 and 118.)
4.

Determine Total Solids.

to

Evaporate 4 to 6

c.

c,

weighed,

dryness

in

a weighed dish.

Dry

at 115

c.

(In-

accurate).
5.

Ash.

Evaporate 100

c. c.

urine and ignite residue.

6.

Determination of Ukea.
A.

CHjNiO.
Method.
of urea

Lieb ig$
of

Principle

Mercuric nitrate added to a solution

ppt. containing
i

gives a white, gelatinous

molecule urea,

and 2HgO.

(Absence

NaCl

necessary.)

Requirements
{a)
{b)
{/)

Standard solution
Baryta solution.

Hg

(NO3),.

Carbonate of soda

test paper.

Dissolve Standard solution of mercuric nitrate. in strong HNOs, (50 grms.,) 72 grms. pure dry HgO If a yellow evaporate until syrupy, and dilute to i litre.
()

produced by dilution, too little acid is present. It must be evaporated down, fresh acid added, and again di^To test the strength of luted. I c. c, =0.01 grm. urea.
ppt,
is

the mercuric nitrate dissolve 2 grms. cryst. urea in 100 c, c. water, i c, c. mercuric solution should equal o.oi grm. urea.
(^)

Solution of

Ba(NO,).+BaHA-

Mix

part cold

saturated solution Ba(N03X, with 2

solution BalijOa,
[c]

parts cold saturated

and add Soda test paper. Dip a sheet white cone. sol. Na. (CO.,) and dry.

3 parts distilled water.

filter

paper into

"
j[^

QUANTITATIVE ANALYSIS.
24
huiirs,

Process: Collect the urine passed during

and

measure carefully. Place 20 c. c. in a small beaker, add 20 c. c. barium solution, filter from the sulphates and phosOf the filtrate 20 c c. (containing 10 c. c. urine) phates.
are measured
off,

a drop of

AgNQj

added

to precipitate

excess of chlorides, and then standard solution of mercuric

nitrate is

added

until a

drop of the mixed solutions gives a

the test paper.

yellow stain (of mercuric hydrate) on

Byasson adds some of a solution of

KHO (25

grms. to

litre

water) from time to time to partly neutralize the acid set

free.

The

solution

must not be rendered

alkaline.

Calculatioji
c. c.

Amount urine passed in 24 hours : mercuric solution used C each c. c. being equal

=A
in

to 0.01 grm. urea

then

Ax C = grms.
^^

urea passed

24

hours.

Caution:

The

hippuric acids.
sis,"

must be free from phosphoric and Consult Caldwell's " Agricultural Analyurine

page 220.

Urine must contain 2 per cent. urea.

967.

Cf.

Watts' Diet.

vol. V. p.

of Estimathtg Urea. Pour a small quantity of urine into a graduated glass tube one-third full of mercury. Fill the tube with a solution of sodic hypochlorite, close

B.~Daveys Method

tube,

and invert quickly

over a saturated solution of NaCl. while the following reaction

Let stand several hours

:

ensues

CH.N,0-f-3(NaClO)=CO.,-t-2H,0+3NaCl+N,

6o-'^iia

3o^r.i7:i

r ^*'

'"^'^^ ^

ANALYSIS OF URINE.

11$

C.

Hcintz and
c. c.

Ragskys Method.
precipitation with PtCl^.

First determine

ammonia by
with equal

Heat
sule to

2 to

vol.

H^SO^

in a

covered cap-

i8o-2oo.

Cool, dilute with water,

filter,

and defor

termine
loo
c.

NH.

formed by PtCU

Calci'Iate both
;

amounts
by
0.

c,

and take the difference

this multiplied

13425

gives per cent, of urea.

Results very accurate.

D.AfijoJuis Method.
See "American Chemist," V. 431.

Provide the following apparatus glass tube 30 cm. long, subdivided into 30 equal (i)
:

parts,

whose aggregate volume is 55 c. c. The end of the tube is drawn out like a Mohr's burette. capacity. (2) A wide-mouthed gas bottle of 60 c. c. capacity, and long enough to (3) A test tube of 10 c. c.
be slightly inclined when introduced into the gas
bottle.

The

principle of the process

:

is

based upon the following

equation

2(CON2H0+3(CaBr2O,)=3CaBrs-f-2CO3+N4

To make
250
c.
c.

the hypobromite solution take loogrms.

c. c.

NaHO,
and set

H2O, and add 25

bromine

agitate

aside for use.

Process
(r) is

Into a glass cylinder containing water the tube

till

depressed
15

the zero

mark and

surface of water

coincide,

250

c. c.

hypobromite solution (100 grms. NaHO, H2O, 25 c. c. Br) are placed in (2) and the testc. c. is

tube containing the urine

spilling its contents.

The

introduced carefully to avoid flask is closed by a perforated

jl6
Stopper which
tube.

QUANTITATIVE ANAJLVSfS.
is

connected by tubing with the measuring

is

The
tube

urine

now mixed with

is

the hypobromite, and

the disengaged nitrogen

driven into the

measuring tube.
c. c.

The

is

now

levelled to relieve hydrostatic pressure,

off.

and the vobime of nitrogen read

o.
1

Since 55

equal

grm. of urea, a single division corresponds to

^
30

= 0.005
30' bar.)
7.

grm. urea.

(0.15 grm. urea gives 55 c.

c.

nitrogen at 60 Fah- and

Determination of Actual Ammonia. Take 20

and
treat
is

c. c.

filtered urine

The NH3

expelled by milk of lime,

standard acid, in
Frcs. 99, 3 b.
cent.)
8,

by Schlosing's method. and absorbed by the cold under a bell jar. For details see
urine contains 0.078 to 0.143 per

(Human

Determination
I

passed
into
If

distilled water in a porcelain dish. the urine was alkaline add a drop of acetic acid, avoid excess. Allow the coagulated albumen to .settle, filter

24 hours. ounce boiling

in

of Albumen. Measure urine Drop 50 c. c, one c. c. at a time,

through a weighed

filter,

and waslv well

Dry

at 100 C,

and weigh.
9_

Determination of Sugar.

Dilute urine
in

or 10

and apply Fehling's solution as Analysis No. 35, Rmv Sugar.

times,
10.

grape sugar.

See

hltered

Analysis
11.

Determination of Phosphoric Acid. urme add 5 c. c. sodic acetate and ''''' ^'"" ^''''^'^^ '"^ ^""""'^

To 50
titrate

c. c.

with

" ^''^""^^"'^

Determination of Uric Acid.

10
c. c. ijv^i, -.

uruie add

_ To
m

-00 c

HCI

=;t-iiirl ^q stand 4S

k^ hours

,1*

a cool place,

DETERMINATION OF URINK.
filter

117

on a very small weighed

filter.

Wash-water should

If more is not exceed 30 c. c. additional. uric acid for each c. c.

necessary add 0.045

mgm.

removed by coagulation.)
13.
(1)

Dry

at loo'^c.

(Albumen must first be and weigh.

Tests for BilePlace a

little

urine on a white plate, add

HNO3.

peculiar play of colors

if

green, yellow,
is

violet,

&c.

occurs

coloring matter of bile

(2)

present.

If ether. Agitate concentrated urine with boiling will be greenish-yellow. bile is pr'esent the ether solution ppt with alcobaric acetate to urine, treat the
(3)

Add

hol,

decompose

it

dryness.

Water

with HCl, and evaporate the liquid to will dissolve out in the residue coloring
,

matter of the bile. u cr^ vol H.bU^, Pettenkofcrs Tcst.W\\. fluid with one-half (4) add a little powdered cane avoiding rise of temperature Liberation of cholalic sugar mix and add more II.SO,.
; ;

acid produces a purplish-red coloration

iar

this gives a pecul-

absorption spectrum.
for analysis of

See Thudichum's " Manual.

Urinary Sediments.
(Attfield.)
filter.

Scheme

Warm the

and sediment with the supernatant urine,

INSOLUBLE. acid. Phosphates, oxalate of calcium and uric Warm with acetic acid, and filter.
INSOLUBLE. Oxalate of calcium and nric acid. Warm with HCl, and filter.
INSOLUBLE. SOLUBLE. Oxalate of cal
ciuin.

SOLUBLE. Urates of Ca, Na,

and NH.1, chiefly of Na-

soLuin.E.
Pliosphates.

They

.ire

re-depos-

AddNHiHO,
and examine ppt. for PsOs,

ited .as the liquid in cools,. d if sufficient in quantity

mav
ined
acid

be
for

examuric

Apply Uric acid. iTiurexid test.

May
by

CaO
MgO.

and

and
usual

bases
tests.

be

pptd.

by

NIUHO.
jVisCe.

Urates

tnent purpurine.

color are often of a pink or red soluble in alcohol. This is

owing

to the pig-

ri8

QUANTITATIVE ANALYSIS,

Scheme

for

Determination of Urinary Sodimonta by Chemical Testa.

(Attfibld.)

The sediment

is

white;

-wnrm

DETERMINATION OF SUGAR,

119
is

convenient apparatus for the extraction of sugar

described by Prof. S.

W.

Johnson,

in

Am.

J.

of Sci. (3)xiii.

page 196(1877).
D.

Determination
to
little

of total Non-volatile Matter.

Evaporate 10
addition of a

20 g;rms. milk to dryness,

acetic acid,

with

the

and

ignite the residue in a

muffle furnace, at the lowest possible temperature. E-

Dotermination
sum
of
tlie

of Protein Compounds.
butter, sugar,
is

Subtract the
total

and ash from the

chiefly casein.

dry substance, and the remainder

For other methods, see " A Method for the Analysis of Milk," by E. H. von Baumhauer, Am. Chem,^ Vol. VII., 191.
Analysis No.
35.

Raw

Sugar.

A.

Determination

of Moistiure.
until
it

Heat a weighed amount of sugar at 110 Loss ^moisture. longer loses in wciglit.

no

E. Dotermination
Weigh

of Ash.

off ten grms. in a platinum dish.

Either burn the

sugar direct, or add a few drops of cone.

very cautiously in a gas muffle.

H2S04and heat
all

Weigh

the ash.

The two methods do not

the latter
"
is

give results at

concordant

the French method, and the results are called

is

the salts," after subtracting one-ninth, but this

seldom

correct, though the ash burns very white.

C Determination
(i)

of Grape Sugar,

Qualitative

reactions.

Glucose

is

colored

dark-

120

QUANTITATIVE ANALYSIS.
hy-

brown when heated with a strong solution of sodic

drate.
It

dissolves

in

cold

cone.

H,SO, without
mixed with

beinr/

blackened.
If a

[Cane sugar blackens.]

solntion
of

cone,

glucose

is

cobaltic

posits a light-brown ppt.

and a small quantity of fused NaHO, the solution remains clear on being boiled if very concentrated it denitrate,
;

[Cane sugar solutions similarly treated give a violet ppt which turns green on standing].

'

BaH.O. added
a white
ppt.

to

an alcoholic solution of glucose forms

soda is added to a solution of glucose and hen drop by drop a dilute solution of CuSO, a deep b ue hciuKi fonns after some time in the cold, b 't imme;

If a little caustic

,,^^'^^^ ' S^^^^se may be easily deI ^^"^^^^^^.'''" S'^'^^ ^ '-eel tint to the solution cZ'- acetate is Cupnc similarly reduced Pot-i.^Jn c otassio-tartrate of copper acts likewise.
teetcd

,..\

^oZ n

^^^tXZ::T'''- oxide.^^"-e cuprous

"I i-upnc oxicie to
'

win .educe

Preparation of FcIUing^s Solution. Dissolve exactly u6-n orm. , ^ ^'^ ^^'^O, in about ^ 200 c. c. water I^ atntlf T'*" ^"""^ '"'''' ''^ S''^'- "^ P" Rochelle salts

-Hydrate

(CHK NO

:^f^^:^f^^-f^
!
,

^ ^

P-e

sodi-

d-k- On boiling ;th "o precipitate.

^Ponds to 0.0S0

^34639 grms. CnSO. and

'"'"^it

corre-

TuitT ^ ^^^^er, f
'^^'-

^^^^

^^^ should give

DETERMINATION OF GRAPE SUGAR.

121

The

solution of glucose should not contain more than

;

per cent, glucose

iT

stronger, dilute.

Performance of Analysis :
water, (or a dilute solution of NaHO,) the solution the liquid conheat' to boiling and run into gradually, from an accurate taining the glucose, slowly and green Continue until the last shade of bluish burette. filtered, gives no liquid disappears, and a small portion of
flask,

Run

exactly lo
c. c.

c. c.

of the copper solution into a small

add 40

reaction with H->S, nor with

HC^U.O^ and

K^Fe^Cy,,

solution, Since we took 10 c. c, Fehlings glucose, we read off corresponding to 0.050 grms, anhydrous solution taken this shows us the number of c, c. of glucose grms. grape sugar. how much of the substance contains 50

Calculation,

Example.

\i^<t^ 9-

c
;

c,

solution containing glucose

9.5
If solution

.05

= roo

.a:

was

diluted, then

;rX^=per cent

glucose.

cane sugar, by first conThis method may be applied to boiling one to two hours verting it into grape sugar by This is not P^rts water) with dilute H.Sa (I part acid S Milk sugar to formation of caramel.

very accurate, owing but in another proporreduces Fehling's solution direct, 134 milk s"?^"^' tion, 100 glucose

the whole
*Tho

Crystaliaable Cane SugarD. -Determination of syrup, add water so that Weigh out :. grms.* of sugar or and add for about 8oc.c. Dissolve
will

form

depc^^d^^^^^^instrutnent employed. value of

a.

Instruc-

tions usually accompany

siiccharimeter.

122

QUANTITATIVE ANALYSIS.
5 to

syrup

lO

c. c.

basic acetate of lead

to

for
c.

raw sugar
c,
;

less

pour into a Dilute for pure sugar, none. and filter do not beaker, and add piilverizeci bone-black, Dubosq Saccharimeter Fill the tube of a Soleil or wash.
lOO
;

with

this

solution,

perfectly
tint.

full,

insert
details,

the

tube,

and

observe

the transition

For
iii.

sec Atkinson's

translation of Ganot's Physics, 613.

istry, p. 84,

Cf.

Fowncs' Chem-

and Watts' Diet.

673-5.

Analysts of a sample of
Water,

...
.

Raw
.

Sugar.
,

2.07
.

Ash,

1.58 1,82

Grape Sugar,

Cane Sugar

86.00

Analysis No. 37.

Petroleum.

For information as
the
"

to

the composition and refining of

petroleum, the products which

it yields by distillation, and methods of testing kerosene, see Dr. C. F. Chandler's Report on Petroleum Oi!" in the " American Chemist,"

Vol. 11. pp. 409, 446,

and Vol.

III. pp.

20 and 41.

A. Distillation of Petroleum.
The method
nation
of its
in

of examining crude petroleum for determicommercial value, is not that of fractional

its

distillation

true,

scientific

sense, but consists in

wliich separates the liquid into a of aliquot parts, having determinable densities, and flashing points and the value of the sample depends upon the proportion of the light and heavy procertain

process of distillation

number

ducts.

The process
lect a tubulated

of distillation

is

conducted as

follows.

Se-

retort of strong glass, free

from

flaws,

and

DISTILLATION OF PETROLEUM,
of about 500
c. c.

i^t

capacity

connect

this

with a Liebig's

condenser, and arrange

for distilling in the usual

manner.

Through the tubulus of

the retort insert a thermometer.

Provitk ten glass cylinders of 50 to 75 c. c. in capacity, and mark each with a file, so as to show the volume occupied by 25
c. c.

of liquid.

These cylinders are

retort,

to serve as

recipients of the distillate.

Pour 250

c. c.

crude petroleum into the

first,

and apply
Collect

heat very gently at heating until the residue in the retort

increasing gradually, and finally

is

coked.

25

c. c. of the distillate in

the

first cylinder,

and note the

temperature indicated by the thermometer in the retort collect the second 25 c c. in another recipient, note also temperature, and continue in this manner, changing the
recipient for every 2$
tilled over.

c. until

the whole liquid has dis-

B.

Examination

of the Distillates.

Determine the sp. gr. of each distillate by floating in it of each sama small Baumd Hydrometer, note the color by means of Tagliaple, and determine its flashing point description of which are *' Tester," a figure and
bue's

Open

Chemist." found on page 41, Vol. HI. of the "American pour a To test the flashing point, proceed as follows the open into small quantity of the sample to be e.Kamined Light the of water. cup, which is surrounded by a vessel the temperalamp beneath and apply heat very gradually a mmute. should not rise faster than two degrees
: ;

ture

surface The thermometer bulb should dip beneath the vapors From time to time test the inflammable the oil.

of

which

using a small flame, arise from the surface of the oil, and noting simultaneflitting it quickly across the surface, at the moment of ously the height of the thermometer
ignition.

Record

results with each distillate.

J24

QUANTITATIVE ANALYSIS.

The following report of an actual distillaExample. This distillation shows how the rcKults may be reported. with the phenomena technically tion was accompanied called "cracking," by which the heavier hydrocarbons split
up
into lighter ones.
No.
1.

of

(;;,,j.

fr.iclioii.

Colorless,

2.

"

. ..

APPENDIX.
TABLE
I.

ATOMIC THE ELEMENTS, THEIR SYMBOLS, AND

WEIGHTS.
Naoie.
e ^i,i Symbol.
'

Name.

Atomic

^Veifihl.
I*

Aluminium Antimony
Arsenic
Bai'iuni

Molybdenum
Nickel
Nitroiien
.

Mo
Ni

96.
58. 14.

&

N
,

Osmium
Oxygyn
.

Os Pd P
Pt

195.2
16.

Bismuth Uoron Bromine

Cadmium
Caesium Calcium Carbon Cerium
Ciilorinc

Palladium Phosphorus Platinum Potassium

.

106.6
31-

194.S
39-1
104.4-

K
Rh

Rhodium
Rubidium Ruthenium Samarium Scandium
Selenium
Silicon
Silver
.

Rb Ru
Sa
So

85.4
103(?)

Chromium
Cobalt
.

44-

Se
Si
.

79-4
28.

Columbiu Copper

Didymium Erbium
Fluorine

Sodium

Ag Na
Sr

loS. 23.
S7.6>

Stiontium Sulphur

32183.
128.
i?)

Gallium

Tantalum
Tellurium

Ta
Te
.

Glucinum
Gold
.

Terbium
Thallium

Tb
Tl

204.

Hydrogen
Indium
Iodine
.

Thorium
Tin Titanium
.

Th
Sn Ti

232.
118.
SO-

Iridium Iron

Tungsten
.

W
u
Zn Zr

184.

Lanthanum Lend
. .

Uranium
Ytterbium Yttrium
Zinc
.
.

240.
17390.

Yb Y

Lithium

65.2

Magnesium Mancancse
Mercury
.

Zirconium

S9.6

135

126

APPENDIX.

TABLE
PRECIPITATING VALUE OF

II.

COMMON REAGENTS.
recommended
b,

Solutions of reagents being prepared of the strength

by Fresenius (see Fres. Qual. Anal., 17 to 85,

f 1875), the

Johnson's edition

amount of

a reagent required for precipitation

:

may

be

calculated from the following table

One cubic

ccntiintitrc

of

Will precipitate

Dilute sulphuric acid

0.231 grm. Ba.

Barium chloride
Hydrodisodic phosphate

0.033

"
"

SOj.

....

con
0.024
o.oor

MgO,

Magnesia mixture

"
"

Ammonium Ammonium

moiybdate
oxalate

P P

O-

Q.

o.ot6
o.oio

CaO.
"
CI.

Argentic nitrate

TABLE

in.

DIAMETER OF FILTERS AND WEIGHTS OF FILTER ASHES; SWEDISH PAPER.

Fitter

Xo.

APPENDIX.

I=;

TRINITY COLLEGE.
Hartford^
Report of
Analysis of
iSS
-

Determination of

Grammes

taken
Analysis.

Method of

r'-ilcnl'ilnl

Theoretical

Speci.ii

Remarks,

IThK

I. .

reduced

f-cl.

m.r.n 8 b, ,o .c.., d*of th, repoKln^ bh...

Mriliiil

is8

APPENDIX.

OFFICIAL

METHODS OF ANALYSIS
1887-88.

AGRICULTURAL CHEMISTS FOR OF THE ASSOCIATION OP OFFICIAL

METHODS FOR DETERMINING PHOSPHORIC ACID AND MOISTURE.

(1)

Pnparalion of Atw/Zc-. The sample should be well intermixed

portions shall accurately anjd properly prepared, so that separate the substance under examination, without loss or gain of represent
moisture.
(2)

DiUrmination of Moisiure.~-{d)

In potash
to
S

salts,

nitrate of
till

soda, and sulphate of

ammonia

heat

grams

at 130 C,

the

weight is constant, and reckon water from the loss. {!>) In all other secure fertilizers heat 2 ijrams, or if the sample is too coarse to 2 grams each, 5 grams for live hours at 100 in a uniform lots of

steam bath. Phosphoric Acid.^x'xw^ 1 grams on a filter, (3) Water-soluble add a little water, let it run out before adding more water, and repeat
this

treatment cautiously until no phosphate

filter.

is

likely to precipitate in

washings show turbidity after passing the filter When the substance is nearly washed in this clear up with acid. it is transferred to a mortar and rubbed with a rubber-tipped manner
the
If the

pesde to a homogeneous
returned to the
ures not
less
filter

paste

(l>ut

not

further pulverizt-'d), then

filtrate mea-s-

and washed with water untd the

Mi.^ the
k

than 250 cc.

washings.

Take an

aliquot

(usually corresponding to i or

gram

of the substance) and deter-

mine phosphoric acid, as under total phosphoric acid. Wash the residue of the (4) CHratc-imohibte Phosphoric Acid. treatment with water into a 200 cc. flask with 100 cc. of strictly

neutral

citrate solution of 1.09 density, prepared as hereCork the flask securely and place it in a water bath, the water of which stands at 65' C. (The water bath should be of
after directed.

ammonium

such a size that the introduction of the cold flask or flasks shall not cause a reduction of the temperature of the bath of more than 2 C.)

Raising the temperature as rapidly

.is

practicable to 65"

C, which

is

APPENDIX.

129

shakings for thirty subsequently maintained, digest with frequent

solution quickly minulcs from the instant of inscriion, filter the warm ordinary temperaturewith water of (best with fiUcr-pump). antl wash ignite until the the filter and its tontents to a capsule, Tnuisfer

on'anic matter

destroyed, treat with 10 to 15 cc, of concentrated tiame until the phoshydrochloric or nitric acid, digest over a low pass throus^h a dry filti-r. mis, phate is dissolved, dilute to 200 cc, phosphoric acid as under total. take an aliquot and determine citrate-insoluble phosphoric acid is reIn case a determination of
is

quired in non-acidulated jjoods, it is to be without previous washmg with water, of the phosphatic material, except that in case the subprecisely in the way above described, matter (bone, fish, etc.) tlie residue st-mcc contains much animal the pro citrate is to be treated by one of
insoluble in

made by

treating 2

grams

ammonium

cesses described below.

C5)

mal F/wsphoric Add.-\N^\t\y

iollowing methods
:

grams and
;

treat by
cc.

one of

the

(i)

Evaporation with
in acul.

magnesium

nitrate, igniiion.
tratevl nitric

concentrated hydrocldoric about 0.5 f. small quantities at a time

30

cc.

hydrochloric acid. (3 Add acid with a small quantity of and acid, heat, and add cautiously

and solution

(2)

Solution in 30 cc. concen-

gram

of finely pulverised
,

potassium chlorate.
'

Boil gently until

all

dilute to destroyed hydrochloric acid neotralize with ammonia (in case 50 of filtrate grams dry ammonium add about ts has been used as a solvent deagram To the hot solutions for every equivalent). nirate or its molybdic solution. D.ge.t at of that is oresent add 50 cc. with -ionium nurate forgone hour, tilter, and wash 'Hg-ion and ad .on_ of renewed Llution.' (Test the filtrate by ter w th precipitate on the molybdic solution.) Dissolve the more J a ^;^.'^^^^/, \7/''' ammonia and hot water and wash into ^^ with 7^*^ "^;;;^^; ;''J; more than too cc. Nearly neutralize ^^>f P^"^burette add add magnesia mixture from a and ^'-J-^^^"^^'^';' e^ After ^^-n second), stifrin, vigorously

organic matter phosphates are dissolved and all a dry hUer take 200 cc; mix and pass through
;

JpO

luf;C

ju

-^

^^J^_;

ammonia
hours
is

solution ot

usuallv enough),

^^-^^l^^^^^^^ts^^^r.^., l-ilter, wasn wuu ^

,

ignit.

intensely for ten minutes,

and

and weigh. ,vater-soluble phosphoric -' (6) Citrate-soluble Tj "^^^fthe d^rate-soluble. tnecn from the total gives citric insoluble subtracted

APPENDIX.
130

PREPARATION
..^ (,)

O!-'

REAGENTS,

PrepareT6 Prcpau

Anunonium

Citrate

Soluiion.^
.

37o grams of

^^ ^^ ^^^^^^

^^,^,,1^,

neutralize wLth

"^'"^^TfrepareMolymc

4^ gr.ms tdplthesoLion
di "acid in
.

awarm p ace Keep tt,e n,Lxturc gravity 1.20. nitricacid of specific C. deposHs no yel ow heated to 40' or undl a portion evcral day ?o phospho-molybdate. Decant the solution predp'ute of ammoniun. preserve in glass-sloppered vessels. from any sediment, and Nitrate 5'./^.-.-Dissol ve 200 grams
il To Prepare

of molybSolution. ^T^^s^oX.. 100 grams of sp.c.hc gravUy 0.96 or 4-7 cc. of a..mon,a grams or ,,350 cc of thus obtained into ,,sco

Ammonium

of commercial

ammonium

nitrate in

water and bring

to a

volume

ol

''^''\^\?o Prepare
5

recently Magnesia M.r/^r^.-Dissolve 22 grams of

in

Jtcd

calcined magnesia

Jf the latter

Add

little

excess dilute hydrochloric acid, avoiding calcined magnesia in excess, and boil a

few minutes

to precipitate iron,

alumina, and phosphoric actd,

filter,

grams of ammonium chloride, 700 cc. of ammonia make tiie volume of two liters. gravity 0.96. and water enough to 22 grams of calcined magnesia i to grams Instead of the solution of (MgCU, 6H,0) may be used. of crystallized magnesium chloride Washing. One volume ammonia of Ammonia for (5) DiluU volumes of water, or usually specific gravity o.g6 mixed with three ammonia with six volumes of water, one volume of concentrated Yy\sso\\'^ 320 grams of calcined mag(6) Nilrate of Magnesia. then add a little nesia in nitric acid, avoiding an excess of the latter
add
of specific
'80
;

filter from excess of magnesia, calcined magnesia in excess, boil ferric oxide, etc., and bring to volume of two liters,
;

METHODS OF BETERMTNING POTASH.

METHOD OF LINDO AS MODIFIED BY CLADDING.
Superphosphates. ~~^o\\ 10 grams of the fertilizer with 300 cc. add ammonia in slight of water for ten minutes. Cool tlie solution
(1)
;

APPENDIX.
excess, thus precipitating
all

131

phospliate of lime, oxide of iron, and

alumina,

etc.,

make up
I

to 500 cc,

mix

thoroii!>)ily
I

a dry

filter;

take 50 cc. corresponding to

cc. of dilute to whiteness.

to drynfss,

add

ness and

ii;iiiie

and a This full red heal nui^t drops of HCl 5 cc. of a plus a few residue is dissolved in liot wau solution of pure NaCl (containing,' :o grams NaCl to the liter) and an excess of ])latinum solution {4 cc.) arc now added, and the whole evaporated as usual. The precipitate is washed thoroug-lily with The washing should alcohol hy decantation and on fdter, as usual.
phate, no loss
of potasli,
hi; ii:^ed

HjSOi (i to As all tlie need he apprehended by volatilii^ation

until

and filter through gram, evaporate nearly 1), and evaporate to dryjiotash is in lorm of sulis

the residue

perfectly white.
;

t-

be continued

even after the

fdtrate

is

NHiCl
These
away.
filter

solution prepared as above. are

Ten colorless. now run through

is
is

cc.

of the
filter.

the

10 cc. will contain the bulk of the impurities,

and arc thrown

run through the

fresh portion of lo cc.

six*.

NHiCl

now

several times (five or

I'he fdter

then

washed thoroughly

with pure alcohol, dried, and weighed as usual. The platinum solugram metallic platinum in every 10 cc. tion used contains
i

(2) Mitrialcs of J'o!ash~\r\ the analysis of these salts an aliquot portion, containing .500 gram is evaporated with 10 cc. platinum solution phis a few drops of HCl, and washed as before. &>. liMhe analysis of these salts (3) Sulphate of Potash, Kainite,

an aliquot portion containing .500 gram is taken, .250 gram of NaCl added, plus a few drops of HCl, and the whole evaporated with 15 In this case special care must be taken, in the cc. platinum solution. washing with alcohol, to remove all the double chloride of platinum and sodium. The washing should be continued for some time aOer
Twenty-five cubic centimeters of tlie NH^Cl solution are employed, instead of 10 cc, and the 25 cc. pouretl through at least six times to remove all sulphates and chlorides. Wash fin.i!ly with alcohol, dry and weigh as usual. To prepare the washing solution of NH4CI. place in a bottle 500
the filtrate
is

colorless.

cc. H.,0,

TOO grams of

NH.Cl

shake

till

disolved.

Now

pulveri>:e

put in the bottle, and shake at intervals for S or JO grams of K^PtCU, then filter otT liquid into a let seUle over night six or eight hours second bottle. The first bottle is then ready for a preparation of a
;
;

fresh supply

when needed.

1^2

APPENDIX.

ALTERNATE METHOD,
Pulverize
the

prams,
without
In
tills

boil for ten

filtering,
in

take 10 1200 or 300 grams) in a mortar minutes with 200 cc. water, and after cooling, and make up to i.ooo cc, and filter througii a dry paper.
ferlilizer
;

method,

cade the potash

is

contained in organic compounds,

tobacco stems, cottonseed hulls, &c., the substance is to be saturated with strong sulphuric acid and ignited in a muffle to delike

stroy organic matter,

(kaiiiitc),

[f

the

sample have 10
;

to

15

per cent
In

K,0

take 50 cc. of

tlic tiltrate

if

from 2 to 3 per cent K5O (ordiof the filtrate,

eacli case

nary potash

fertilizers),

lake

100 cc.

maKc

the

volume up

to

150 cc, heat to too', and add, drop by drop,

slight
e.Kcess

with constant stirring,

filtering, in the

of bariuni

chloride; without

same manner, add barium hydrate in slight excess .Add 10 Meat, filter, and wash until preci]iitate is free of chlorides. filtrate cc. strong ammonium liydrate, and then a saturated soiu.ion of ammonium carbonate until excess of barium is precipitated. Heat.
i

Add now, in line powder, o.J gram pure oxalic acitl or 0,75 gram ammonium oxalate. Filter, wash free of chlorides, evaporate filtrate
to dryne-ss in a

platinum dish, and, holding-

di.sh witii

crucibie longs,
all volatile

ignite carefully over the free flame

below red heat

until

matter

is

driven

off.

is now digested with hot water, filtered through a. and washed with successive small portions of water until the filtrate amounts to 30 cc. or more. To this filtrate, after adding two drops of strong hydrochloric acid, is added, in a porcelain dish. 5

The

residue

small

filter,

to 10 cc. of

a solution of to
is

grams of

platinic chloride in loo cc. of

water.

the water-bath to a thick syrup, or further treated with strong alcohol washed by decantation. collected in a Gooch crucible or other form offdter,

The mixture

now evaporated on

washed with

strong alcohol, afterwards with

at 100'
It IS

cc. ether,

dried for thirty minutes

C, and weighed.
desirable,
sail,
if

is an appearance of white foreign matter in should be washed, according to the previous method, with to cc. of the half-concentrated solution of NH.Cl, which has been saturated by shaking with K.PtCU. as recommended by Gladding.

there
it

the double

that

The use

of the

factor 0.3056 lor converting

K.PtCU

to

KCI and

0.19308 for converting to

K,0

is

continued.

APl'ENDfX.

133

METHOD FOR THE DETERMINATrON OF NITROGEN.

The Absolute or Cupric Oxide Method.
The apparatus and
reagents needed are as follows
:

APPARATUS.

CombusHon 21;^^ of best hard Bohemian glass, about26 inches long and one-half inch internal diameter. Azotomcter of at least 100 cubic centimeters capacity, accurately
calibrated.

Sprd/igel

Mercury Air Pump. Small Piipir Scoop, easily made from

REAGENTS.
Cupric

stiff

writing-paper.

Oxide (coarse). Wire form

to

be ignited and cooled

before using.

Fine Cupric O^rV*". Prepared by pounding ordinary cupric oxide

ill

mortar. reduced Metallic Coppcr.~-GtAnn\s.iQd copper or fine copper gauze of hydrogen. and cooled in slcam Sodium Bicarbonate. x&G from organic matter. potash in Caustic Potash &/Ki'w?i. Dissolve commercial stick of water so that crystals are deposited on cooling. less than its weight When absorption of carbonic acid ceases to be prompt solution must

be

cliscardt:d.

LOADING TUBE.

Of ordinary commercial

fertilizers

take

to 2

the In the case of highly nitrogenous substances by the amount of nitrogen estimated to be presmust be regulated cupric oxide. (t) About 1 inches of coarse Fill tube as follows ent. cupric oxide to scoop enough of the fine (2) Place on the small ijaper
1

grams for analysis. amount to be taken

analyzed, about having been mixed with the substance to be rinsing watch glass substance, 4 inches of the tube pour on this the with spatula pour of the fine oxide and mix thoroughly with a little
fill,

after

(5^ About 12 little fine oxide. into tube, rinsing the scoop with a ot metallic copper. inches inches of coarse cupric oxide. (4) About 3

APPENDIX.
oxide (anterior layer). (6) Small of coarse cupric fO Aboutsl inches gram of sod.um b.c.rbonatc
p u. of asbestos.
(7)

Eight-tenths to
;

asbestos Cs"\arge. loose plug of

place tab.

.n

furnace, leav.ng

fboutoneinchof
tight.

itprojectinj,;

connect w,th

taking care to smearecl with glycerine,

pump by rubber stopper make conuectioa perfectly

OPERATION.
Exhaust
air

from tube by means of pump.

When

vacuum has
gas under

metallic copper, anterior layer of cupnc that part of tube containing As soon as vacuum bicarbonate of soda. oxide (see 5th above) and carbonic acid gas, shut off the apparatus tiUeci with is destroyed and delivery tube of the pump mercury, and at once introduce the flow of azotometer and just below the surface of into the receiving arm of the
the

mercury been obtained, allow flow of

to continue, light

mercury

seal of the

pass into the air

aMtometer, so that the escaping bubbles will and not into the azotometer, thus avoiding the use-

potasii solution. less saturation of the causlic

or completely the flow of carbonic acid has very nearly delivery tube down into the receiving arm, so that ceased, pass the Light the jets under the bubbles will escape into the azotometer. of oxide, heat gently for a few monicnts to drive out the 12-inch layer Heat moisture that may be present, and bring to red heat.

When

any gradually mixture of substance and oxide, lighting one jet at a time. Avoid too rapid evolution of bul:ibles, which should be allowed lo
escape at rate of about one per second or a little faster. When the jets under mixture have all been turned on,
liglit jets

under layer of oxide

ceased turn out
all

at

end of tube.

When

evolution of gas has

the lights except those under the metallic copper

and anterior layer of o.xidc, and allow to cool for a few moments. Exhaust with pump and remove azotometer before flow of mercury Break connection of tube with pump, stop flow of meris stopped. Allow azotometer to stand at least an cury, and extinguish lights. hour or cool with stream of water until permanent volume and temperature are reached.

Adjust accurately the level of the

eter

KOH
The

solution in bulb to that in

azotometer, note volume of gas, temperature, and height of

barom-

be

make calculations as much diminished by the

;

usual.

labor of calculation

may

use of

the tables prepared by Messrs,

APPENDIX,
Battle

'35

and

Daticy.

of

the

North

Carolina

Experiment

Station

(Raleigh, N. C.).

The above
the

details

are, with

some

modifications, those given in

report of the Connecticut Station for

rSyg

([).

124),

which may

be consulted for details of apparatus, should such details be desired.

Determination dy the Method of Kjeldahl,

keagents and apparatus.
(1)

(a)

Hydrochloric acid whose absolute strength has been determined, by precipitating with silver nitrate an<l weighing the silver chlo-

by sodium carbonate, as described in Fresenius's Quantitasecond American edition, page 680, and (c) by determining the amount netUralixed by the distillate from a weighed quantity of pure ammonium chloride boiled with an excess of sodium
ride, {d)

tive Analysis,

hydrate.
(2) Standard ammonia whose strength, been accurately determined,

relative to the acid, has

(3)

nitrates

"C, P." sulphuric acid, specific gravity 1,83, free from and also from ammoniLtm sulphate, which is sometimes

in the process of manufacture to destroy oxides of nitrogen. Mercuric oxide, HgO, prepared in the wet way. That prepared from mercury nitrate cannot safely be used. (5) Potassium permanganate tolerably finely pulverized. (6) Granulated iiinc. (7) A solution of 40 grams of commercial potassium sulphide in

added
(4)

one

liter

of water.

saturated solution of sodium hydrate free from nitrates, which are sometimes added in the process of manufacture to destroy organic matter and improve the color of the product. That of the Greenbank Alkali Company is of good quality.
(S)
19)

Solution

of

cochineal

prepared

according
edition,

to

Fresenius's

Quantitative Analysis, second

(10)

American

Burettes should, be calibrated

in all

page 679. cases by the user.

well-annealed glass. (11) Digestion flasks of hard, moderately thick, long, with a round, pear-shaped These flasks are about 9 inches bottom, having a maximum diameter of 2] inches, and tapering out gradually in a long neck, which is three-fourths of an inch in diam-

APPENDIX.
the

eter

at

a c. part, aim flared narrowest irt and

225 to /^5o

little

at the edge.

The

is total capacity

flasks oi () DistiUation stopper fiued with a rubber

^"^^^

.'ibe

^^ ,c. capacity, aad above to preve.U the

^^^^^^

^^^^ mechanically duri.g

.vhich
is

is

equally

that the tube

-"-"^^^^f,^ wh.ch

^.'^

f^

rS'condc.sed

shall

be of

^-;"^^^7;;; ",',",,

,y,,,,n^ aad

ammonia

J^td^^: :;^-^--M>- iccurac^ condenser m The chem.Ges., XVIL,

(See Kreus-

^W .ndHe
So es
Tame
stands

okl

Ber. d.

34-)

Jo
1

Ion,
its

supported by consists of a copper tank

is

botton.
is

widening above to 6 inc es. It . and a larger tnbe which goes to the bottom, ^vith a water-supply whose extertin condensu:^ tube., overflow pipe above. The block through seven in nnmber, enter the tank nal diameter is f of an inch, the overthe top. above the level o! boles in the front side of it near through the tank and out and pass down perpendicularly flow holes m the bottom. They through rubber stoppers, tightly fitted into bottom of the tank, and are conproject about \\ inches below tlie tubes of the usual shape, nected by short rubber tubes with glass buib These beakers are which dip into glass precipitating beakers. somewhat narrower below, 6^ inches high, 3 inches in diameter can be made and of about 500 cc. capacity. The titration above, supported on a The seven distillation flasks are directly in them. tank to the wooden frame that supports the

This tank

.6

a wooden on which inches above the work-bench x and 3 .-l-s inches high. 3^ i-hes long

provu^d

Se fro.

front to back,

sheet-iron shelf attached

in front of the latter.
is cut,

Where each

flask is to

stand a circular hole

under with three projecting lips, which support the wire gauze and prethe flask, and three other lips which hold the flask in place on. vent its moving laterally out of place while distillation is going Beiow

Bunsen this sheet-iron siielf is a metal tube carrying seven burners, each with a stop-cock like those of a gas-combustion furprenace. These burners are of larger diameter at the top, wliich
vents smoking

when covered with

fine

gauze

to

prevent the flame

from striking back.

APPENDIX,
(14)

137

holding the digestion flasks consists of a pan of sheet-iron 29 inches long by 8 inches wide, on the front of which is fastt:ned a shelf of sheet-iron as long as the pan, 5 inches wide and 4 inches high. In tliis are cut six holes i| inches in diameter. At the bacl< of the pan is a stout wire running lengthwise of the stand, 3

The stand

for

inches high, with a bend or depression opposite each hole in the The dijjestion flask rests with its lower part over a hole in shelf. shelf and its neck in one of the depressions in the wire frame> tlie

which holds

it

securely

in position.

Heat

is

supplied by low Bunscn

burners below the shelf

applied directly
to

With

a Uttie care the naked Itanie can be

the flask without danger.

THE DETERMINATION.
One gram
tion flask

of the substance to be analyzed

is

brought

into a diges-

with npproximately 0.7

gram
is

of mercuric

oxide and

20

cc. of sulphuric acid.

The

flask

placed on the frame

above de-

scribed heat

of an inclined position and heated below the boiling point The until froihuig has ceased. the acid for from 5 to 15 minutes, or
ill

No further attention then raised till the acid boils briskly. have become a clear liquid, flask is required tiU the contents of the straw color. Th.; whicli is colorless or at least has only a ver>' pale upright, and. while stil! held flask is then removed from the frame, in small is dropped in carefully and
i.'i

potassium permanganate liquid remains <iuantity at a time till after shaking the
hot,

ol

a green or

transferred After cooling, the contents of the flask are purple color. ot potassium this 25 cc. to the distilling flask with water, and to solution, or sutlicient solution are added, 50 cc. of the soda sulphide few pieces oi -ranothe reaction strongly alkaline, and a
to

make

all ammonia has passed the contents of the flask are distilled til! precipitating flask preover into the standard acid contained in the solution can no longer be viously described and the concentrated 20 10 40 minutes. This operation usually requires from

lated zinc

The

flask is at

once connected with the condenser and

safely boiled.

The distillate is then titrated with standard ammonia. greatly The use of mercuric oside in this operation

shortens the

halt rarely over an hour and a time necessary for digestion, wluch is more comdifficult to osidi^e and is in the case of substances most permost cases the use of potassium monly less than an hour. In excepbelieved that in manganate is quite unnecessary, but h is

APPENDIX.
tional c.ses

view of the all merpissiam ^nc.n^^^^-^y^^^^-J^^ the formation of mercuro-0' '^"^ "';: complcldy decomposed by d Mi'cn .. .ot ammonium compound. wlch ^,:ys ^ise to an evolution of soda solution. '' '^ -''''^!^" ", .ij ,? Previous to use, the ^^ ''^^"^ violent bumping,'. iwflmi^en and prevents
.

>.

;s

^H--^^' ^^

vfi

fnr comi)lute oxidiUion,

and

in

sulphide r.mo.es

S;.rtially

re<iace

present which m.ght otherany nit...e. Chat are

"'u^rSCnrmodification must
which nitrogen in substances
use this method
:

be used ibr the determination of to contain nitrates when tt .s des.red

THE NITROGEN OF DETERMINATION OF NlTROGKJ^, INCLUDING of Kjeldahl. Nitrates, by a Modified Method

the substance to be analy;:ed into a Brin- from 07. to 1.4 grams of this 30 cc. of sulphuric acid contamKjeldahl digesting flask, add to and shake thoroughly. Then add ing 2 grams of salicylic acid, shaking the contents of the .radually three grams of zinc-dust, Finallv. add two or three drops of platinic flask at the same time. for holding the solution and place the flask on the stand
chloride

heated over a low flame until all danger raised until the acid from frothing has passed. The heat is then white fumes no longer boils briskly, and the boilinsr continued until
digestion flasks,

where

it is

Add pour ont of the flask. This requires about five or ten mintites. now approximately 0,7 gram mercuric oxide and continue the boil(In case ing until the liquid in the flask is colorless, or nearly so.
become solid before this point more of sulphuric acid.) Complete this o.xidais reached add 10 cc, tion with a little permanganate of potash in the usual way, and proceed with the distillation as described in the method above.
the contents of the flask are likely to

Determination by the Ruffle Method,

preparation of RF-AGENTS.
(i) A standard solution a/ sulphuric acid, half normal, or 19.968 grams SOa per liter. (2) A standard solution of potassium hydrate, half normal, or 27.991 grams KOH per liter.
*DescTib(;c!

by Prof. M, A. ScovcU.

APPENDIX,
I

^39

.^

.vefghfofsoda-H^e

mumg equal part by iLosuiphite .^/i.r..-Pr.pared by .oc!>um and fmdy powdered cry.tall.ed

An

alcoholic solution of cochineal.

,,,,

k^

....r/....-This is prepared by mi.ing '';il''^llr .rf -^///''' granulated sugar and flowers weightof finely powered equal paS by

of sulphur.
(6)

^ rOrdinary granulated soda-lwu.

^

APPARATUS.
^.*-- of hard Bohemian 0) C-..^.A-.. ponit.
glass,

.o inches long and

inch internal diameter, Z)^^ree-l>nll, (>4uck

(3)

drawn

to a

U tubes,

with glass stop-cock.

Aspirator.

PREPARATtON.
(0 Clean and
acid.
fill

the

centimeters of standard tube with lo cubic

,

p:ii

f^,g

tube as follows

' loosely fittng piu o (,v jl^e weighed portion inches of the ^ ' , ,0 t^ '^yP'^^f ^'^^'ely i.ed with from 5 to lo analyzed is mumateiy n . ^^ of the substance to be ""' 'J" " i UJ r .1 c>,o-ir- nntl sulohur mixture. hyposuU grams of the sugar ^"'^ ^"'P ^ ^^f^^-ie^t quantity of the

(I

J^

glared paper, or P-^'^:;; "^^^Xes oVt^^ lo '"^'^^^ ^' phhe mixture to fill about ^' as knee to be analysed,

tube

then add the sub-

^,^ carefully and

If

pour

into the tube

shake

paper or mortar with ture and pour into ^^^^^;^^^'\^\Z\.o.^^^ plug of ignited the tuOe. j^^,^ ^^e 2 inches of the end of

Xof Ue l^^^'^^Zt^tXy^l .o .^^^^

^^-^;V

^^'/J^

f^f

^^

tube rinse off hyposulphite mix;

tube. asbestos at the end of the ^1 1 unUl there is a gas pos.Uon a.d Up on tl^^^^ tube in a l^ori-ntal ^^^^^^^ .^^ ^^.^^ ^^^ of the tu^e. channel all along the top the apparatus is aspirate, and see tube containing the acid,

-^^'^-^

t'S'^^-

tube in the T,, .i rpn-ired combustion the PJ^^P^^" ^ The Combustion.-V\^'^^ t to burn the ^^ ^^ end project .^ .^ ^^^^^^j^^ furnace, letting the open soda-hme port>o by heatmg the Commence ^^^^^^^^ ^^^ cork.
_

to a

full

red heat.

outer end

;^"^""P,f,;,^tm, off that the bubble. of the tube, so

Then

two or three a

APPENDIX.

second,
I

Whrn hen

the v,t he whole Uibe

is

[^rl^^^S^'-toU.

:;;':::dat:l
titrate.

tube...... or a fe. . -rrent o h^nd of the tube, n.d dr.w into a Ueaker wash the contents ... Dptich the U tube and solution, and few drops or the cochineal
o.her
or the

red hot and the evolution of Ihe gas ^ .^^^ ^^ ^^^^^^^ ^^^^^^^^ ^^^^ ^^^^^

U.b

a. .oug

add a

DETERMINATION

I5Y

THE SODA-LlMF. METHOD.

to

draw one end of it glass 14 to 16 inches long, Select a tube of hard is passed other end fit a cork, throu-h which a fine point, and to the
arm

angles, the a tube bent at right

cork closing lightly one

srhss stop-c'ock,
Into the

other end of wlilch passes through a of a 6-inch three-bulbed U tube with

combustion tube first slip a loosely fitting to 2 inches of sodaand then plug of asbestos previously ignited, from 0.7 to 2.8 grams of the substance to be Weigh out lime. glazed paper or porcelain moranalyiied, and mix it on a piece of pulverized soda-lime, and introduce the mixwith some finely

tar

ture into the combustion tube.

The paper or mortar

is

tiien

rinsed

tube. out with a small quantity of soda-lime and poured into the filled up to within i to 2 inches oi the open end The tube is then with granulated soda-lime, then with a plug of ignited asbestos.

free

passage

is

formed

for the

tube in a horizontal position

evolved gases by holding the and tapjjing gently on the table. In-

troduce the prepared combustion tube into the furnace, letting the open end project a little so as not to burn the cork, supporting
the

tube by a clamp.

The tube

is

then gradually heated, com-

mencing
obtain

at the fore part, nearest the cork,

tail.

and progressing slowly

to

towards the
carried

The combustion should be conducted so as

uninterrupted
in

a steady and
out, the acid

flow of gas.
is

the

tube

never

When properly When the colored.

acid begins to
the

the other limb of and start it slowly, then break off the point of the combustion tube and draw a current of air through the apparatus
the

recede

attach

aspirator to

tube,

for a few minutes, in

order to sweep

all

the .ammonia into the acid.

Detach the
ponx-tain basin,
neal,

a beaker or add a few drops of an alcoholic solution of cochithe contents into

alkali

tube and

wash

and

titrate.

The standard acid and

the Ruffle method.

to

be the same

as that

used in

INDEX.
Aeidimcuy,
(

45-

Calorific

power of

coal,

31).

Albumen dctcrminnlion of, in urine, 116. Alkalies, determination of, in potable water,
in feldspar, estimation of, 5*-

C^na

su);ar, analysis of, 101.

determijialion of, jai.

Carbon, estimation
total,

of,

iti

coal, 39,

determination

of, in

pig-iron, 79.

Alkalimetry, 42.
Alloys, dctermiii-ition of

vdlimatc determination

of, in

sugar, toj.

(wo metals

in, too.

Carbonic anhydride, determination by direct

wtiijlit, 3+.

Ahim,

aniinoiiia-iroii, analysis of, 30.

AUiniina, iron ,ina pliospboric acid, 75.

Alv/irgonz.iki,

determination by loss, 33.

car-

determination of

total

Chandler's analysis of Croton Water, 98.

Chloride of lime, valuaiioii
of,

bon, Si< Ammoiiia-iron-alvim, analysis

49'

of, 20.

Ammonia,

deterniinalion

of, in

gunnn, 83,
properties

Chlorimetry, 47. Chlorine, determination

of, 11,

Atnmonio-magncsic
of, 19.

phospbalc,

determination

of, in

potable water, 93.

Chromic
gravimetric determination
of, of,

iron ore, analysis of, 54.

Ammonium,

^.

Clark's soap test for potable water, 93.

Coat, proximate analysis
of, 36.

phospho-molybdate, properties
Analysis, organic, 101.

70.

Cobalt, determination
of,

of, in

nickel ore, 86.

loj.

Analyips, calculations
reporting of,
tj".

15.

Combustions, process of conducting,

Copper,

electrolytic estiiiiaiion of, 33, 39.

of, in

Antimony, determination of, 51. Apjolin's melhod of estimating urea, nj.

Arsenical nickel ore, analysis
of,

estimation

a silver coin, 19.

pyrites, analysis of, 39-

S6.

Ash, estimation

of, in coal, 37.

Davcy's method of estimating urea,

Distillation of petroleum, 1:2.

[14-

B^iric chloride, analysis of, 13.

Dolomite, analysis

of, 30.

Barium, determination
sulphate, properties

Crown's determiiiaiion of sulphur

iron, 83,

in pig-

of, 14.
of, iS.

Bell's determination uf total

iron, 81Bilc, tests for, in urine, 117-

carbon in pig-

EgKcrti' determination of f;rai*'t* ' P'S'

iron, 77.

determination of stdphur and phosphorus

of, 47.
in plc-iron, S2.

Bleachlng powder, constitution

reactions of, 48.

Elliott's

determination of

total

carbon in

valuation

of,

49.
of, 35.

pig-iron, 79-

Broxue, analysis

Butter, determination of, in milk, 118.

Fehling's solution, preparation

of,

no.

Butyramide, estimation of nitrogen

in, 107.

Feldspar, analysis of, 56of Ferrocyamde of potassium, determination

I

Cairns' determination of graphite in pig-iron,

78.

nitrogen
Flight's

in. 105.

Calcium, determination

of, 31.

method of si-p.iratinfj iron, alumina, and phosphoric acid, 75ore, 66.

Calculation of results of analyses, ij.

Fusion of an iron

INDEX.
142
Pearl-ash, valuation of, 4s.
of, ii")Olocosi!, estim.ition sugSf dclcrminalioii

Cmpe

of, iiq.

Penot's metliod for

iirue, 4g.

valu.itioji

of chloride of

GMiihim, (kicrmiiution

of,

in pi-iron, 76.

Permanganate of potassium, stindardixatioD

of, 1$.

Guano,
Hciniz

an-ilysis of, 83.

.in>f

RAgsky's method of esvlmating

urea, 115.

Petroleum, distillation of, lai. Phosphoric acid, determination

determination
of, in

of, 38.

Hematilc, aiislysis Hydrochloric

,icid,

of, 6j.

guano,

8;j.

vsUialion

of, 46.

determination
Flight's

Hydrodisodic pliosphate,

aii.iljsis of, 17.

of, by molybdenum, 65. method of separation from iron,

Hydrogen,

dcteriiiinalion of, in suRir, loj.

ISinsoluble, determination of, in superphos-

Iron and tiunium, determination

basic atntate
of, 53,

of, 74.

phates,

tjO.

6S.

reduced, delctminatioti
phates,
9<J.

oli

in

superphos-

determinalion
31.

of,

in

nmmoiiia-iron-aUim,

Phosphorus, determination
76,
S:!.

of,

in

pig iron,

ore, 63, <lei:rro!nalioti of, in a titaniferous

Pi(;-iron, analysis of, 76,

detcrminiiion determination

of,

by

precipitation, 22-

Potassium chloride, analysis

of, 26.

of, in

hematite, 6j.

ferrocyanidc, f'-terminatioii of nitrogen in,

105.

ore, tilonifcrouii, noalysia of, 63.

slag,

anaKsis

of, 60.
of, 11,

Rravimetrio estimation
71.

of, 16,

volumttric determination

pernian;;anaie, solurioii of, *3.

PyroUisite, analysis of, 56.

Koninck and Diets' determination of sulphur

in pig-iron, 84.

Raw

sugar, analyses

of, itt).

Rcponins
Lead, estimation
Lieblg's
of,

analyses. 17.
of,

in a iilver coin, 19.

iij.

Reverted phosphoric acid, determination

91.

method of cjtimating urea,

of,

Liquids, specific gravity

<^of, ^i.

Litmus solution, preparation

Salamnioniac, aciion of nitric acid on, 32*

Sclilijsitig's

determination of ammonia, SSof, in

Magnesic sulphate, annlysis

Manganese, estimation
Marguerite's
iron, 22.

of, iS.

Sllica,

deicrminauoii
59-

soluble silicates,

Magnesium, separation from calcium,

of, 56.

30.

determination
separation
of.

of, in slag, 6t.

Glbbs' method of estimation, jo.

from

tit.iuiifm,

64.

method

for determination of

Silicates, analysiji of soluble, 59.

Silver coin, analysis of, 29.

Melsens' determination of nitrogen, 107.

Milk, analysis
of,

Slag, analysis of iron, 60.

iiS.
of, in coal, j6.

Moisture, deierniiuation

Molybdenum, use

of, in

estimation of phos-

phoric acid, 69.

Soap test fur potable water, 93. Soda ash, valuation of, 44. Sodium, deternunalion cf, 27. Specific ,i>r.ivities of solids and liquids,
Standard solutions,
4s.

99.

Nickel ore, arsenical, analysis of, S6. Nitrogen, determination of, by Varrenlrapp

Sugar, determination of ash in raw sugar,

119.

and Will's method, 105. Melsens' determination of, 107.

determination

of, in

milk, tiS.

uUtmate analysis

of, 101. of, in

Norma]

solutions, 41.

Sulphur, determination
Sulphuric
01",

pig-iron, Si.

estiniaiion of, In coal, 37.

Organic analysis, loi,

matter in potable water, 94,

acid,
18.

gravimetric

deterroioasion

INDEX.
Sulphoiic
l[on of,
iicid
')3.

'43

in

poLiblc watef, deHnninii-

Vitrrantripp aid Will'l 6timlion of uHRen, tej.

SuiK-tphosphate of lime, analyiU

of, 90.

VintsKar, an.ilyjis ofi 46-

Volatile nultef, cHimilion

tif,

in coal, jj.

VolimioSrksnalysti, itenefil noiesoii, 40.

Tin, dctctmiiniioii
dclerniinalion

of, in

lyiw metnl, 51.

estimilion of nitrosw. urf'

of, in

Lirome, 35,
IV liter analys],

Tttaiiifiirous iron ore, an.ilysLs of, 63.

Titanium, catiinalion
Tilr-ilion, nsaidual

of, in

iron Ofe, 74.

of, 45.

method

cakohiion of rcsolw, 05. by dir! weisht, aStleierininiiitm of, by iKniiioo. J, aS.

dttertwinalioii of,
1

Type

metal, analysis

of, 3".

dcteruiinJlion

rf, is

milk, 118,

Ufe.ijJetdrniinationof, Liebig's niMbwi, 113.

|>otjblc, aji ilyiis of, oi*

Apjohu's method, "SDivsy's mulbod, 114.

Uriii;ir/ linii;nls,
117.

Weyl'a detcrmiiution of
iron, Bj.

total

carbon

in pig-

ac!n:nic for analysis of,

Zinc, dclcrminalioo of, in bronie, jSure, analysis of, jj.

Urine,

.in.alysii of, 109.

compoailloB

of,

nt.

APPENDIX.
AKiiculJural
on;i!jsia, I3B.

chemist*,

official

methods

of

r-hirsphoric aciJ, oflkial

liOD, i>3

method of dewyniin*

Alomic weight! o( dtmsms, table 1. 135, Filters, diimcttrs and wctsht oi ashes, is6.
CbddinK's mcth^^^^^ of dctcrmipiinE potash, Kitldahl'smcThnd nf dctcrmiiiinc nilroEerii
Msiatufe,o(lif:i.il
i;o.

TotaaSi, official

method

of detenninaiion, \yt.

ReagcJiis, prtclpiiatBig value of, is6.

tS5

incihodi of detctminallafi, isB

iif

Report blank, 117. RujUc method of detetmining iutixtn, I^. Soda-lime method of determining nitioecn, 1*1.
Zettflcrs^'s

Nitt'!C<^n."ff"^i'">'''hcd5
Official

Jctcrminatloii,

1^

^heme

for qualjiatu aBiiysis, fold

meihMls

of :isrictiliural chemists,

ista

leg paj;e.