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l-l
l4 2 / Di/Jusionin Dilute Solutions / Pioneers irt Dir
t-r
\c.--=/
D i f f u s i n gg o s
il-
ti
( o)
F i g . 2 . l - 1C
. :
fiee diflsri:
F i g . 2 . l - 1 . G r a h a m ' s d i f f u s i o n t u b e f o r g a s eTs h
. isapparatuswasusedinthebestearlystudyof
diftsion. As a gas like hydrogen difTusesout through the plug, the tube is lowered to ensure
that there will be no Dressuredil'ference.
t+
\/ ' /h
-- Gloss
fi otot'
H( o)
Fig.2.l-2. Graham's diffusion apparatusfbr liquids. The equipment in (a) is the ancestorof
fiee diffusion experiments; that in (b) is a forerunner of the capillary method.
Weight percentof
sodiumchloride Relativeflux
- . :: rnthiS
: .cld to
j ' ' . - t 3 n t .l e 2.1.2 Adolf Fick
: . , : .f - . U l t S The next major advancein the theory of diffusion came from the work of Adolf
' ' . : at u b e .
Eugen Fick. Fick was born on September3, 1829, the youngestof fve children. His
-:- ....Lllel)US father,a civil engineer,was a superintendent ofbuildings. During his secondaryschooling,
:.:'.lr'ritely Fick was delightedby mathematics,especiallythe work of Poisson.He intendedto make
- ---:l:' ltrL)t Of mathematicshis career.However,an older brother,a professorof anatomyat the University
.r.:' ,llllsUOl of Marlburg,persuadedhim to switch to medicine.
I. . . . . I9 " 0 ) . In the spring of 1847, Fick went to Marlburg, where he was occasionallytutored by
-:-.,.Plllnt Carl Ludwig. Ludwig strongly believedthat medicine, and indeedlife itself, must have
'- -
.LltrrnS. a basis in mathematics,physics,and chemistry. This attitudemust have been especially
.--r-::l'ierent appealingto Fick, who saw the chanceto combine his real love, mathematics,with his
.- . ,:J their ehosenprofession. medicine.
. , . : t o nO f In the fall of 1849.Fick's educationcontinuedin Berlin. where he did a considerable
-.,
- . : . r r: . h g irmountof clinical work. In 185t he returnedto Marlburg,wherehe receivedhis degree.His
rhesisdealtwith the visualerrorscausedby astigmatism,againillustratinghis determination
.. .t. riiS ot t o c o m b i n e s c i e n c e a n d m e d i c i n e ( F1i c8k5,2 ) .I n t h e f a l l o f 1 8 5l , C a r l L u d w i g b e c a m e
J irl'iusion professorof anatomy in Zurich, and in the spring of 1852 he brought Fick along as a
..: ' itrlow prosector.Ludwig movedto Menna in 1855,but Fick remainedin Zurich until 1868.
. , , ' 1 . l.. l - 1 Paradoxically,the majority of Fick's scientifcaccomplishments do not dependon diffu-
: . , , r s a l ti n .ion studiesat all, but on his more generalinvestigationsof physiology (Fick, 1903).He did
. irtTusion outstandingwork in mechanics(particularlyas appliedto the functioning of muscles),in
hydrodynamicsand hemorheology,and in the visual and thermalfunctioningof the human
l6 2 / Diffusion in Dilute Solutions
body. He was an intriguing man. However,in this discussionwe are interestedonly in his
developmentof the fundamentallaws of difTusion.
In his first diffusion paper,Fick (1855a) codified Graham's experimentsthrough an
impressivecombinationof qualitativetheories,casualanalogies,and quantitativeexperi- !
ments. His paper,which is refreshinglystraightforward,deservesreadingtoday. Fick's
r
introductionof his basic idea is almost casual: "[T]he diffusion of the dissolvedmaterial
. . . is left completelyto the influenceof the molecularforcesbasic to the samelaw . . . for li
the spreadingof warmth in a conductorand which hasalreadybeenappliedwith suchgreat a
s u c c e s s t o t h e s p r e a d i n geol fe c t r i c i t y " ( F i c k1, 8 5 5 a , p . 6 5 ) .I n o t h e r w o r d s , d i f f u s i o n c a n
be describedon the samemathematicalbasisas Fourier'slaw for heatconductionor Ohm's
law for electricalconduction.This analogyremainsa usefulpedagogicaltool.
Fick seemedinitially nervousabout his hypothesis. He buttressedit with a variety of
argumentsbasedon kinetic theory. Although theseargumentsare now dated,they show ffiT: ;
physicalinsightsthatwould be exceptionalin medicinetoday. For example,Fick recognized rfr:l]c@o ffi
that diffusion is a dynamic molecular process. He understoodthe differencebetweena F,t @: I
When the area A is a constant,this becomesthe basic equation for one-dimensional GItlN
Fick next had to prove his hypothesisthat diffusion and thermal conductioncan be hIr
describedby the sameequations.He was by no meansimmediatelysuccessful.First, he nafl,
tried to integrateEq.2.l-2 for constantarea,but he becamediscouragedby the numerical
effort required. Second,he tried to measurethe secondderivativeexperimentally.Like
IJJ r,
manyothers,he foundthatsecondderivativesaredifficult to measure:"the seconddifference
increasesexceptionallythe efTectof [experimental]errors." Nlffi [lm'
His third effort was more successful.He used a glass cylinder containingcrystalline &iltuf ,&
sodium chloride in the bottom and a large volume of water in the top, shown as the lower
apparatusin Fig. 2.1-3. By periodicallychangingthe water in the top volume,he was able E pmrrr
to establisha steady-state concentrationgradientin the cylindrical cell. He found that this
gradientwas linear,as shownin Fig. 2. 1-3. Becausethis resultcan be predictedeitherfrom
Eq. 2.1-1or from Eq.2.l-2, this was a triumph.
I| )11.t ) I / Pioneersin Diffusion l t
nls
'--
,--:l .in
- E
. -,.1
(!
. '.
.- ., .. ,\ (J
r .-.::lfl o
'6
i-tl1
- o
, *::'.t CL
--
a
, ,ill
Distance,z
. t
Fig. 2 I -3. Fick's experimental results. The crystals in the bottom of each apparatussaturatethe
.-
. - I
adjacent solution, so that a fixed concentration gradient is establishedaong the narrow, lower
: l . t partoftheapparatus. Fick'scalculationofthecurveforthefunnelwashisbestproofofFick's
-\ . law.
-h
For one-dimensionaldiffusion in
- j t : D ,dc'
Cartesiancoordinates az
For radial diffusion in cylindrical
- j r : D ,d c ,
coordinates ar
For radial diffusion in spherical dc,
- j t : D ,
coordinates ar
Nole..Moregeneralequations
aregivenin Table3.2_l.
:le
But this successwas by no meanscomplete. After all, Graham'sdata for liquids an-
JlpatedFq.2.l-1. To try to strengthenthe analogywith thermal conduction,Fick used
Ir - lower apparatusshown in Fig. 2.1-3. In this apparatus,he establishedthe steady-state
- 'ncentrationprofle in the samemanneras before. He measuredthis profile and then tried
JI Dredicttheseresultsusing Eq. 2.1-2,in which the funnel areaA availablefor diffusion
,ned with the distance:. When Fick comparedhis calculationswith his experimental
-r'.ults,he found
- , - : :b e the good agreementshownin Fig.2.l-3. Theseresultswere the initial
: -. . he . r'rilcationof Fick's law.
::Jill
. Lrke
- 2.1.3 Forms of Fick's Inw
J:3ilCe
useful forms of Fick's law in dilute solutionsare shown in Table 2.1-2. Each
- - - ,l t n e r.lurtioncloselyparallelsthat suggestedby Fick, that is, Eq. 2.1-I. Each involvesthe
'rlle phenomenologicaldiffision coefficient.Each will be combinedwith mass
balances
....,ble , analyzethe problemscentralto the rest of this chapter.
'-
, - . h l s One must rememberthat theseflux equationsimply no convectionin the samedirection
-
: i 1lll ',' the one-dimensionaldiffusion. They are thus specialcasesof the generalequations
lr\en in Table3.2-1. This lack of convectionoften indicatesa dilute solution. In fct.
t8 2 / Diffuson in Dlute Solutions
Fig.2.2-1. Difusion across a thin flm. This is the simplest diffusion problem, basic to perhaps
80% of what follows. Note that the concentration profle is independentof the diffusion
coelhcient.
the assumptionof a dilute solution is more restrictivethan necessary,for there are many
concentratedsolutionsfor which thesesimple equationscan be used without inaccuracy.
Nonetheless,for the novice, I suggestthinking of diffusion in a dilute solution.
/ rate ol diffusion \
/ solute \ - / r a t eo d l f l u s t o n \ - . . 1 . . , _ . , _ _ . . . .
I l: | | || O U t o l t n e l a v e rI
\ a c c u m u l a t i o n /\ i n t o t h e l a y e r a t , / \ " " ; ; ; ' , ' i ? ' ' / {N :llu -
0 : A ( j t l . - - / rr . + r . 7 (2.2-1)
):i iding this equationby the film's volume,AAz, andreaffanging,
-/rl')
o:-(rr '-r' r))-)t
\(:+Ar)-zl
hen Az becomesvery small,this equationbecomesthe definitionof the derivative
"
d
0:_;jt (2.2-3)
47.
.erhaps '
,nrbiningthis equationwith Fick's law,
dct
- j t : D () )-4\
'
47.
:r'I11&I!
.' find, for a constantdiffusion coefficientD,
, Juracy.
'1) "
0 : D';',' r? )-51
-
:r. differentialequationis subjectto two boundaryconditions:
ct:albz (2.2-8)
--r On --
..ltlons ;' constantsa andb canbe found from Eqs.2.2-6 and2.2-l, so the concentrationprofile is
. , nt h e 'Z
, nt h e c l : c l o + ( c l /_ c1o) () ) _a\
t
:r' li1s41variationwas,of course,anticipated by the sketchtnFig.2.2-1.
itr this.
The flux is found by differentiatingthis profile:
. \\ithin
dc, D
jt:-D , :;(cro-crr) (2.2-10)
07. I
.:cidentsthatresult
'rembrane.
This type of diff
. ,,lctly,in termsof :
-rossthe membra
,1.which drops .:
(a) (b) (c) :ce responsiblef.
npletely is Secti
Fig.2.2-2. Concentration profiles across thin membranes. In (a). the solute is more soluble in
the membrane than in the adjacent solutions; in (b), it is less so. Both casesconespond to a The flux scroS:;
' . r l ew i t h F i c k ' :
chemical potential gradient like that in (c). i.
. IDH
rI -
r
Exampfe 2.2-l: Membrane diffusion Derive the concentrationprofile and the flux for . is parallelto E.
-'rerhilitrr
a single solutediffising acrossa thin membrane. As in the precedingcaseof a flm, the on'l .'
0 : A ( j t l . - , / rl : + r : )
' , : m P l 2 . 2 - 2 :P o r
This leadsto a differentialequationidenticalwith Eq. 2.2-5:
, : l e a r ec h a n s :
r)
O-Cr Solution
0: D- , n s e ro n - . 1
az'
"' -:.:ne. Rath::
However,this new massbalanceis subjectto somewhatdifferentboundaryconditions:
r ctreficre:
z:0, ct:HCrc - - . r l t h e n; *
ct:H('tl+HlC11 -C,r) l . l - . 1 :\ 1 .
: --'
which is analogous to Eq. 2.2-9.This resultlooksharmlessenough.However,it suggests
^ . . : .'
concentrationprofleslikes thoseinFig.2.2-2, which containsuddendiscontinuitiesat the
interface.If the soluteis more solublein the membranethan in the surroundingsolutions,
then the concentrationincreases.If the solute is less soluble in the membrane.then its ,!L-"'
IDHl
-C11.)
,/t :--(C11y
\ fu)r This is parallelto Eq. 2.2-10. The quantity in squarebrackersin this equationis calledthe
. .r h e permeability,and it is ofien reportedexperimentally.Sometimesthis sameterm is called
.-lllr the permeabilityper unit length. The partition coefficient11 is found to vary more widely
than the diffision coefficientD, so differencesin diffusion tend to be less importantthan
the differencesin solubilitv.
I D-oHf
lr: l-,LltCro-Crr)
t t l
:t the
. rhat rvhereD.s i, u n"*, "effective" diffusion coefficient.Sucha quantityis a flnction not only
of soluteand solventbut also ofthe local seometrv.
Example 2.2-3: Membrane diffusion with fast reaction Imagine that while a solute
:s diffusing steadily across a thin membrane,it can rapidly and reversibly react with
. - !\L\ Ither immobile solutesfxed within the membrane. Find how this fast reaction affects
'-.,ttne :hesolute'sflux.
- .i l o n s . Solution The answeris surprising:The reactionhasno efTect.This is an excellent
:l;'tl ltS :rample becauseit requirescareful thinking. Again, we begin by writing a massbalance
- r J eo f .rn a layer Az locatedwithin the membrane:
rane
/ solute \ / s o l u t ed i f u s i o ni n \ / a m o u n rp r o d u c e d \
*
,lrion. \ a c c u m u l a t i o " i : \ m i n u s t h a r o u ri \ u v c h e m i c a l r e a c r i /o n
: on- Becausethe systemis in steadystate,this leadsto
rrt-s in
nuil!
||nu"tr I
,UllL ), ft":
Porous
Diaphragm fE rems -
'!,!r
fi"-:
tilHflraul riil*r
Fig. 2.2-3. A diaphragm cell for measuring diffusion coefcients. Becausethe diaphragm has ,Jili =
a much smaller volume than the adjacent solutions. the concentration profile wthin the
diaphragm has essentially the linear, steady-statevalue. r
ftrH,*,r'
ff ,un
u
) &l
0:-..--rr
dZ
, ' d
U - - . . / 1 f / ' 1
47.
dCr.upp.,
Vuoocr---.::lAjt
.' -\ similar " d
,: .tead) r which
-.nLnt
of A H l I 1 \
: n t e .t h e YR- - - l - r - l
/ \vt"*t''v',,")
,-an measure the time r and the various concentrations directly. We can also determine
: Jrlculate coeffcient
Seometric factor B by calibration of the cell with a species whose diffusion
ro.uvn.Then we can determine the diffusion coefficients of unknown solutes.
) 1
2 / Diffusion in Dilute Solutions Stead,tDiffusion At
There are two major ways in which this analysiscan be questioned.First, the diffusion
coefficientusedhereis an effctivevalue alteredby the tortuosityin the diaphragm.Theo- clo
reticiansoccasionallyassertthat differentsoluteswill havedifferenttortuosities,so that the
diffusion coefficientsmeasuredwill apply only to that particulardiaphragmcell andwill not
be generallyusable.Experimentalistshavecheerfullyignoredtheseassertionsby writing
| /c9. -cP \
D- - r n 1 ' i h ' u c r ' l u P PI e r
B't - Ct.,pr,,
\C'.'"*", /
S m ol l ----
wherep' is a new calibrationconstantthat includesany torluosityefTects.So far, the exper- diffusion
imentalistshavegottenaway with this: Diffusion coefficientsmeasuredwith the diaphragm coefficient
cell do agreewith thosemeasuredby other methods.
The secondmajor questionaboutthis analysiscomesfrom the combinationof the steady-
stateflux equationwith an unsteady-state massbalance.You may find this combinationto
be one ofthose areaswheresuperfcialinspectionis reassuring,but wherecarefulreflection
is disquieting.I havebeentemptedto skip overthis point, but havedecidedthat I had better
not. Heregoes: trio ra-J C -
The adjacentcompartmentsare much larger than the diaphragm itself becausethey the diffu'ior. -
containmuch more material. Their concentrationschangeslowly, ponderously,as a result
of the transfer of a lot of solute. In contrast, the diaphragm itself contains relatively
little material. Changesin its concentrationprofile occur quickly. Thus, even if this :r film. [ rtc:ir
profile is initially very diffrent from steadystate,it will approacha steadysratebefore
(.
i -
trr,t.l,/!:" ( 1
:vai"p,.ogn' +
I
)
| /( p Dr1, ".r \ Vt,,*., Vuppr,
/
\ :.ii.theexpef-
: : : .: : - . d: i a p h r a g m
: :: I thesteady-
: , , : : b r n a t i o nt o
, . : r : r . i rl e f l e c t i o n z=Q z=zc z=l
- : .::I hadbetter
::g. 1.2-.1.Concentration-dependentdiffusion acrossa thin fiim. Above the concentration t 1,,
: : 'iailusethey ::e drffusion coeffcient is small; below this critical value, it is larger.
: ,-. ., J\ a result
- ' . : : : -r e l a t i v e l y
'- j: tm. a steady-state
massbalanceleadsto the sameequation:
. : 'e. n i f t h i s
: -., -:-,tr'betbre
- - . . : : t ep r o t l e , d j t
'_ - 'rt.Lrtment dz
- -;.ult. the flux j1 is a constanteverywherein the film. However,in the leffhand film
.ri - Lrll tlllle - -': .oncentrationproducesa small diffusion
coefficient:
. -.iJ here
dc,
/ t: - D ,
a?.
. ::.ult is easilyintegrated:
t.: f,
-
.rnderlie I ita, -D I
.ttt
dct
J,,u
- : t h er e s u l t
D ( c ' r o- c r , . )* D ( c r , - c t t )
-
.Il
!!u e]l-:u
Example 2.2-6: Skin diffusion The diffusion of inert gasesthrough the skin can cause M i
,lliirr .,uil.
itching,burning rashes,which in turn can lead to vertigo and nausea.Thesesymptomsare lttfir! [r r, ]|]:,,
new variable: the gas pressurethat would be in equilibrium w'ith the locctlconcentration. ill0tcll'h{r fi
The "concentrationprofles" acrossskin are much simpler in terms of this pressure'even !l|r,[. le. lr"*l
though it may not exist physically. To make theseideasmore specific,we label the two u u-s J
layersof skin A and B. For layer A, uftrv:r nr
!n{rXT r
- Pt go')
P t : P t . g a+s 3, @lg 5!:i:
i(ttti rifrn\E
Pil
ilfullil$h li:t:t1
/ D,qHa\ / DnHa\ M'urii:'-r'
ri"ue
\ ,^ )Ptc"*\ r, /Pt {m:!
-
I ' l t
h - k
can be found fiom the fct that the flux throughlayer A equalsthat throughlayer B.
2.2/ Stead,-DiJJusionAc'rossa Thin FiLm 2l
tn
I P1iP?i
p1p?
Loyer
P1,qos
P2, tissue
. , n
:ll-
G o so u t s i d e
the body
-,:'lJ
:|lr'
. 't]
::.1t
':\
'L.11
z =O z= lA z=lA + lA
Fig. 2.2-5. Gas difiusion across skin. The gas pressuresshown are those in equilibriurn with
the actual concentrations. In the specifc case considered here, gas 2 is more permeable in
layer B, and gas I is more permeable in layer A. The resulting total pressurecan have major
. ifc'
physiologic effcts.
- rll
-,|a
Theseprofiles,which are shownin Fig. 2.2-5,imply why rashesform in the skin. In
. . , .J I particular,thesegraphsillustratethe transportofgas I from the suffoundingsinto the tissue
- i I and the simultaneousdiffusion of gas 2 acrossthe skin in the oppositedirection. Gas I
' , t l, is more permeablein layer A than in layer B; as a result, its pressureand concentration
J.-l gradientsfall lesssharplyin layer A thanin layer B. The reverseis true fbr gas2; it is more
:',\o permeable in layer B thanin A.
Thesedifferent permeabilitieslead to a total pressurethat will have a maximum at the
rnterfacebetweenthe two skin layers. This total pressure,shown by the dotted line in
Fig. 2.2-5, may exceedthe surroundingpressureoutsidethe skin and within the body. If
it doesso, gasbubbleswill form aroundthe interfacebetweenthe two skin layers. These
bubblesproducethe medicallyobservedsymptoms.Thusthis conditionis a consequence of
unequaldifTusion(or, more exactly,unequalpermeabilities)acrossdiffrentlayersof skin.
The examplesin this section show that diffusion acrossthin films can be diffcult to
understand.The difficulty doesnot derivefrom mathematicalcomplexity; the calculation
rs easy and essentiallyunchanged.The simplicity of the mathematicsis the reasonwhy
Jrffusion acrossthin films tends to be discussedsuperfciallyin mathematicallyoriented
books. The difculty in thin-film diffusion comes from adaptingthe same mathematics
ttr widely varying situationswith different chemical and physical effects. This is what is
Jifcult to understandaboutthin film diffusion. It is an understandingthat you must gain
befbreyou can do creativework on hardermasstransferproblems.
28 2 / Diffusion in Dilute Solutions
C o n c e n r o t i o np r o f i l e i n
-4 . !l o m e m b r o n eo l e q u i l i b r i u m
.i-Lrll
.i1'rll
'':
Ir)
..,1l
: .L n l
C o n c e n t r oi fo n p r o fi l e s l i g h l y
.ilg o f e r h e c o n c e n t r o f i o no n
..'rll he lef is roised
I ncreose
lll
'ne
Il \.
rl Limiing concenlrolion
p r o fi l e o f l o r g e f i m e
..'i is
,.: :his
J -ait.
, - I
- .,u.
Fig. 2.3- I . Unsteady- versus steady-statediffusion. At small times, difTusion will occur only
near the lefrhand side of the membrane. As a result. at these small times. the diffusion will be
the same as if the membrane was infinitely thick. At large times, the results become those in
"j an the thin fim.
..:1es.
' j .ib
' .1.
tO
- The
.ifl AS
::10ugh
: sndent
:rln we
1 . 3I-)
Fig.2.3-2. Free diffusion. ln this case,the concentration at the left is suddenly increasedto
a higher constant value. Diflsion occurs in the region to the right This case and that in
Fig.2.2-1 are basic to most diffusion problems.
').3-2)
30 2 / Dilt'usionin Dilute Solutions
Dcr ( j t l , + t , - , r rl . \
: - l - l (2.3-3)
at \(:+a:)-:/
We then let A: go to zero and usethe definitionof the derivative
cr _ /r
_ (2.3-4)
3t 3:
Combining this equation with Fick's law, and assumingthat the diffusion coefficient is
independeo n .e g e t
n lt 'c o n c e n t r a l i o w
^ ^1
d C r' - D d'Ct
' ::2 (2.3-s)
At
This equationis sometimescalled Fick's secondlaw, and it is often referred to as one
exampleof a "diffusion equation."In this case,it is subjectto the following conditions:
Notethatbothcl6Ddct0aretakenasconsta Tnhtesc. o n c e n t r a t i o n c l - i s c o n s t a n t b e c a u s e
it is so fr fiom the interfceas to be unaffctedby eventsthere; the concentrationc1eis
kept constantby adding materialat the interface.
(2.-r-9)
'/4Dt
The differential equation can then be w ntten as
t -r-10) [,r,--nple 2.3-1: Diffusion across an interface The picture of the processin Fig. 2.3-2
nr-- -. ihat the concentrationat z : 0 is continuous.This would be true, for example,if
* " . - ' ( ) t h e r e w aas s w o l l e ng e l ,a n d w h e n z< 0 t h e r ew a sa h i g h l y d i l u t es o l u t i o n .
-- : r\ er. a much more common caseoccurswhen thereis a gas-liquid interfceat
r 3 - l1 ) - = t lrtlinarily,the gas at ; < 0 will be well mixed. but the liquid will not. How will
i::.rcerffect the resultsgivenearlier?
:nlrd into Solution Basically,it will haveno effect. The only changewill be a newboundary
, ' n \ :f r o m
Pro
'1 -l?\ tl
r
-)z 2 / Dffision n Dilute Solutions l{lllnri;n,.'*
wherec I is the concentrationof solutein the liquid, x I is its mole fraction,p ro is its partial ltb nu"^,
pressurein the gas phase,H is the solute'sHenry's law constant,and c is the total molar n
Example 2.3-2: Free diffusion into a porous slab How would the foregoingresultsbe
changedif the semiinfiniteslab was a poroussolid? The diffusion in the gas-filledporesis
much fasterthan in the solid.
Solution This problem involves diffusion in all three directionsas the solute
moves through the tortuouspores. The common method of handling this is to define an
effectivediffision coefficientD.6 and treatthe problem as one-dimensional.The concen-
tration profile is then
('t - cto z.
- : e
('r\-cru " J 4 D , r l
--*:-
,lrlr:o: 1/D.xlnt(crc - c1r)
This type of approximationoften works well if the distancesover which diffusion occurs
are largecomparedwith the size of the pores.
Example 2.3-3: Free diffusion with fast chemical reaction In many problems, the
diffusing solutesreactrapidly and reversiblywith sunoundingmaterial. The surrounding
materialis stationaryand cannotdiffuse. For example,in the dyeing of wool, the dye can
react quickly with the wool as it diffusesinto the fiber. How does such a rapid chemical
reactionchangethe resultsobtainedearlier?
Solution In this case,the chemical reaction can radically changethe process
by reducingthe apparentdiffusion coeflcientand increasingthe interfacialflux of solute.
Theseradical changesstandin stark contrastto the steady-state result,wherethe chemical
reactionproducesno elTect.
To solve this example,we first recognizethat the solute is effectively presentin two
forms: (l) free solutethat can diffuse and (2) reactedsolutefixed at the point of reaction.
If this reactionis reversibleand fasterthan diffusion.
c2: Kct
: - : l.,rf Of
/ a c c u m u l a t i o\ n / d i f f u s i o ni n \ | / a m o u n to r o d u c e d
J' |
bv\
I l - |
, -:' rbout \ inAA: / \ m i n u st h a to u r) \ r e a c t i oi n A A :, " l
/
r -
-:-
IL)f a -
,r thediffusingsolute,thisis
-d t [ A A z c r l: A ( j t l . - , t rl . + r . )+ r l A L z
- _ - - . . - . 1b, e
. :irre r; is therateof productionper volumeof speciesI, the diffusingsolute.By arguments
_ . : : 3 \ 1 5
- r.rogous to Eqs.2.3-2to 2.3-5,this becomes
, .,,lute
d(r rl'('t
' : D
. i : : 1 3a n * u t i ' t
- dI d7'
: .e n -
:r' term on the left-handsideis the accumulation;the first term on the right is the diffusion
" nrinusthe diffusion out; the term 11is the effect of chemicalreaction.
\\'hen we write a similar massbalanceon the secondspecies,we find
-[AAec2] : -rrALz
ot
ocz
At
'1-' do not get a diffusion term becausethe reactedsolutecannotdiffuse. We get a reaction
:::l that has a different sign but the samemagnitude,becauseany solutethat disappears
-. 'peciesI reappears as species2.
-. the To solvethesequestions,we first add them to eliminatethe reactionterm:
. .r' ,.i" .n,o.
'
2c,
,,3 aan I t ' - l -r ' r ) : D -
dt dz'
::.nical
,r i now usethe fct that the chemicalreactionis at equilibrium:
I lLrieSS
. ,r l u t e . 3 i Jl c ,
-(triKcll:D-
Jn l l C a l dt dz.'
:l wo dct D 2 ,t
:-::tiOn. Ar lfK 0:2
.:.ri\ result is subjectto the sameinitial and boundaryconditionsas before in Eqs. 2.3-6,
- --7. and 2.3-8. As a result, the only differencebetweenthis example and the earlier
:oblemis that D/(1 f K) replacesD.
This is intriguing. The chemicalreactionhas left the mathematicalform of the answer
.:,ttlon -:r;hanged,but it has alteredthe diffusion coefficient.The concentrationprofile now is
t , , n .I f
:J()mg ct -cto _ - .-,'-J q i + z- R l l
(r\-(ro
__-
where nro1u.n1is the refractiveindex of the solvent. Each position in the camerais propor-
tional to a positionin the diffusion cell:
Z:az,
. - . .. : 3 r l b o u t
J1 2 uJ4a
l: -:l: -,llUrUOl. .thereZlis the intensityminimum associated with the 7th tiinge. Becausea and t are
, - :'J,l.lentlY.
-'\perimentallyaccessible,measurementsof 210. "/) can be used to find the diffusion
. l:\rCeSS.
D. While the accuracyof interferometricexperimentslike this remainsunrivaled,
- Lrefficient
ic useofthese methodshas declinedbecausethey are tedious.
r\prriments
--
::'-ifl]llt
- -.'nration
:- ' i : 3 r .u s e s 2.4 ThreeOther Examples
The two previoussectionsdescribedifTusionacrossthin films and in semiinfinite
'- - llinated ..lbs. In this section,we turn to discussingmathematicalvariationsof diffusion problems.
: - - . . - :. ' i n d e x . his mathematicalemphasischangesboth the pace and the tone of this book. Up to now,
. e haveconsistentlystressedthe physicalorigins of the problems,constantlyharping on
- - ::lcients.
-ituraleffectslike changingliquid to gas or replacinga homogeneousfluid wth a porous
: , .er'aP- . 'lid. Now we shift to the more common textbook composition,a sequenceof equations
'
: .. ,'.r1113i15 . ,metimesasjarring as a twelve-toneconcerto.
, ,. :::r'J frOm In theseexamples,we havethreeprincipal goals:
rble cond
.-.l:L'gfJII'
. . ' ,e t h r -
P o s i i o nz
: 0 diffuses as
Fig. 2.4- l. Diffusion of a pulse. The concentratedsolute originally located at z
theGaussianprofileshown. T h i s i s t h e t h i r d o f t h e t h r e e m o s t i m p o r t a n t c a s e s , alongwiththose
in Figs.2.2-l and2.3-2.
In mathematicalterms,this is
a
;dlt A A : r ' 1l : A i r l .- A . llr,rr .
t) L-)\
Dividing by the volume and taking the limit as Au goesto zero gives
3r'r }jt r) 4-7t
t 2.
Combining this relationwith Fick's law of diffusion,
,rronabl
conditionb1,a massbalance:
/- f'M
t,Att::./ M
./ . , iu,.tAdz: (2.4-8)
.."0
' t t '-t. ! . t ( t ' _0 , - o ?
a7'
Q'4-g\
':ere
c-1is the transformed concentration.
The boundary conditions are
d|t
z -('l _ _M/A
.li tuses as dz 2D (2.4_10)
: u ith those
a : oc, f't :0
(2.4_r1)
-
;' first of thesereflectsthe properties
' -.ration2.4-9 of the Dirac function, bul the secondis routine.
canthen easily by integratedto give
r14)t
cr : aey'slDz r be-/4 nz
(2.4-t2)
-:re
a and areintegrationconstants.Clearly,
a is zeroby Et1.2.4_11.
UsingEq.2.4-10,
: fnd andhencelr:
(2.4-3)
M/E
';; T,
cl : yro-1tr- 1/ s/ Dz.
(2.4-13)
-
.: inverscLaplacetransformof this function
| 2.4_4) gives
_ M/A,-z2141nt
previous lq; Dt- (2.4-11)
hr'pulse,
l:ch is a Gaussiancurve. You may wish
to integratethe concentrationover the entire
.rcmto checkthat the total
solutepresentisM.
rl.4-5) This solutioncan be usedto solve many
unsteadydiffusion problemsthat haveunusual
' ral
conditions(crank, l9?5). More important,
in sym- ' rollutants, it is often ur. to corelate the dispersion
especiallyin the air, as discussedin Chapter4.
This basicdiffere
r:Ro.
S o l u t ef l u x
owoy
dct
dr
' -':e
a is an inte
c 1: f i -
. :thet$oL'
D i s t o n c ef r o m
s D h e r es c e n i e r \ t - r
asphere.Thisproblemrepresentsanextensionof diffusion
Fig.2.4-2.steadydissolutionof
this dissolutioncanbe
thJoryto a sphericallysymmetricsiuation.In actualphysicalsituations,
'12)
complicated by fiee convectioncausedby diffision (seeChapter
shell of thickness ar
center of the sphere. Then we can make a mass balance on a spherical
shell is like the rubber
located at some arbitrary clistancer from the sphere. This spherical
of a balloon of surface area4T rz and thickness Ar'
earlier:
A mass balance on this shell has the same general fbrm as those used
d i f r u s i o\ n_ l ai[1sio1
/ soluteaccumulation \ _
- ( .,) \2.4-t5)
\ within the shell ) \ i n t ot h es h e l l / \ o u t o l t h es h e l l/
In mathematicalterms,this is
a "
i;, - (4trr2
tru) : o : (4trr2 i),*6, \2.4-r6)
fi6rrt
is
The accumulationon the left-handside of this massbalanceis zero' becausediffusion
this point by
steady,not varying with time. Novices frequently make a seriousefror at
of both terms on the righlhand side. This is wrong. The term r2;1 is
;";""li"g the ,i oit
at (r + Ar) in
evaluateclat r in the first term; that is,-it is r21;r l,). The term is evaluated
the secondtem; so it equals(r * Lr)'(irl'+a').
the Imit
If we divide both sidesof this equationby the sphericalshell'svolume and take
as Ar '+ 0. we find
t d t2.4-17)
0:-,;(r'j1)
rar
is constant'
Combinins this with Fick's law and assumingthat the diffusion coefficient
D d .dct (2.4-18)
o" - --y'-
12dr2 dr
\oltrions 2.4 / Three Other Examples 39
() 4i)\
r
Use of the two boundaryconditionsgivesthe concentrationprofile
. .R 0
cl : tl(sat) - () 4-)11
r
-l \ 1On
,ncanbe The dissolutionflux can then be found from Fick's law:
dc, D R,,
jr:_D, :_jr.1(sat) () 4-)4\
ar
, \ n e S SA r which, at the sphere'ssurface,is
.:rerubber D
lr : -cr(sal) t) 4-)5\
R6
ifthe sphereis twice as large,the dissolutionrate per unit areais only halfas large,though
the total dissolutionrate over the entire surfaceis doubled.
r.-1-l5)
This examplesforms the basisfor suchvariedphenomenaas the growth of fog droplets
.rndthe dissolutionof drugs. It is included here to illustrate the derivationand solution
rf differential equationsdescribingdiffusion in sphericalcoordinatesystems. Different
.oordinatesystemsare also basicto the final examplein this section.
l.:1-I 6)
( c)
z
tr
.
F
z
trj
z
o
P O S I ft o N
Fig.2.4-3.Waterproofngafencepost.Thisproblemismodeledasdiffusioninaninfinite
situation. In reality, the
.yiin.l.r, and so representsan extenslon to a cylindrically symmetrc
because diffusion with the grain is faster than
ends ofthe post must be considered,especially
acrossthe grain.
becomesin mathematicalterms
-. lheseequations,
c1(surface)is the concentrationat the cylinder's surfaceand Rs is the
-. :nder'sradius. The frst of the boundaryconditionsresultsfrom the large volume of
-l\)unding solution,and the secondreflectsthe symmetryof the concentrationprofiles.
Problemslike this are often algebraicallysimplified if they are written in terms of di-
- :rrionlesq variables.
This is standardpracticein many advancedtextbooks.I ofien find
- ' procedure
confusing,becausefor me it producesonly a small gain in algebraat the
- r 3 n s e o f a l a r g e l o s s i n p h y s i c a l i n s i gNh ot .n e t h e l e s s , w e s h a l l f o l l o w t h i s p r o c e d u r e h e r e
lustratethe simplificationpossible.we first definethreenew variables:
('l
dimensionlessconcentratio : ln ' . -0 (2.4-33)
c I (surface)
r
dimensionless
position: f : (2.4-34)
&
Dt
d i m e n s i o n l e s s t i m e : z :.-..- (2.4-3s)
R
liflerential equationand boundaryconditionsnow become
a 0_ l a , l ) e
(2.4-36)
'-4afta6
, - . d R ( r ): K- {. t. tq d . d f ( E- t
J ' 5 t - , .
,1.-+-28) d r d q d
t ds(r) d 1 (t)
"df (2.4-4t)
e(r) dr .fG) d' d
t).4-29) : rrnefxesf and changes,, ./(6) remainsconstantbut g(z) varies.As a result.
I dg(t) )
t) 4-4) \
((r) dt
(1.4-30)
i\ a constant.Similarly, if we hold z constantand let f change,we realize
\2.4-31)
1, n
u , l f tr ts \
t2.4-32) - -, F u . ,
/
2
(2.4-43)
-'r () riq' r/6
A ) 2 / Diffusion in Dilute Solutions
(2.4-44)
-r bYo@O (2'4-45)
J G) : alo@t)
0: alo@) (2.4-46)
Je(a,) : Q (2.4-41) ..
.llllll",,
The most generalsolutionmust be the sum of all solutionsof this form found for different
integralvaluesof n: ll,llf."! f
:
t r . ) : f1 - " ( . 1 , r ' . )J,s 1 a , , , \ e ' l ' ' (2.4-48)
n:l
) and integratefrom f :0
We multiply both sidesof this equationby f Je(cv,,f to t : 1 to
flnd (aa'\. The total resultis then - I
["-
t
o : itI- lrn.,-.)e-o,,' (2.4-50)
L a , , J 1 ( a ], , )
A,i nirrrl
or, in terms of our original variables, I
u-u
@h' -'-
_ | _ )-{ e-DotlRih@,llno)
(2.4-5r)
( t(surface) u , , J 1 ( u , , t ' fR 1 1 l i[],--. --
,t-,
mtul-
This is the desiredresult,though the cy,must still be founclfrom 8q.2.4-41 . 1lr' i'
. Jrferential
Stolic eleclrode
of which solue D i r e c l i o no f
c o n c e n l r o i o ni s diffusion
t2.1-44) r10
:, rut straight-
Moving electrode
i I J-215'l ol which solue
c o n c e n l r o l i o ni s e 1 7
- : Eq.2.4-39
\).4-46)
' . rLrtions
for "o"'nrn,,rl'ou'o
Fig. 2.5- l. Steady diflision in a moving llm. This case is mathematically the same as diffusion
r).1-47) acrossa stagnant 1lm, shown in Fig. 2.2-1. It is basic to the film theory of mass tlanstr
ciescribedin Section I l. L
', ,r Jifterent
2.5 Convection and Dilute Diffusion
/ s o l u t ea c c u m u l a t i o\n -- / s o l u t ed i f f u s i n gi n a t z m i n u s\
\ in WA,r'A.: i \ s o l u t ed i f f u s i n go u t a t . r L z .)
, A z ) - .- ( c ru . ,W A z ) , . + l ' l
* [ ( c r u .W (2.s-2)
The term on the left-handsideis zerobecauseof the steadystate.The secondterm in square
bracketson the right-handside is also zero,becauseneithercl nor ur changeswith x. The
concentrationc1 <loesnot changewith x becausethe flm is long, and thereis nothing that
will causethe concentrationto changein the x direction. The velocity u., certainlyvaries
with how far we are acrossthe film (i.e., with z), but it doesnot vary with how far we are
alongthe film (i.e.,with -r).
After dividing by lVA,rA: and taking the limit as this volume goes to zero, the mass
balancein Eq. 2.5-2 becomes
.I:
^ uJ1
r? 5-31
47.
0 - D
O-Cl
, 1
(2.s-4)
a 7.-
This equationis subjectto the boundaryconditions
cl :t'lnttCti-{lgl7 (2.s-7)
D (2.s-8)
jr:-(.cn-ctt)
I
The flow has no effct. Indeed,the answeris the sameas if the fluid was not flowing. lb uaunl,:
;
' - 1 . t ! ( ,S o l u t i o n s
Convectionand Dilute Diffusion
45
,JlreCIlOn. L i qu i d
s o lv e nt
:r:uli_eible
- :l\ ection
::1\lnalSO
:r.but it is S o l u e g o s
' r. S a t l o n .
,,. r rllume
Li.
C o nv e c li o n
r 5_?\
:l \quare
:r .i..The
:nc that
.r Varies Liquid with
dissolved
r \\e are solulegos
hemass F i g . 2 . 5 - 2u. n s t e a d y - s t a t e d i f f u s i o n i n t o a f a l r i n T
ghf irsma.n a l y s i s t u r n s o u t t o b e
mathematically equivalentto fiee diflusionlseeFig. 2.3-2). rtis basicto the penetratron
theory
of masstransfrdescribedin SectionI 1.2.
.fhisansweristypical
ofmanyproblemsinvolvingdiffusionandflow.
Whenthesolutions
lilute' the diffusion and convection often
are perpendicular to each other and the solution
":aightfbrward. You may armostfeergyppediyou girdedyourserftbr a diffcurtprobrem
(1.5_4) - iound an easyone. Restassuredthat more
diflcutt problemsfollow.
rs again reflectsthe
( 3 ) T h e g a si s P u r e .
.ult, the solutecan di
(4) The contactbetweengas and liquid is short'
the exact location o
example' The third
The frst two assumptonsare identicalwith thosegiven in the earlier be infinitely far au
in the gas only
phase, in the liquid. The final
meansthat therels no resistanceto diffusion lhis problemis des
..rsionin a semiinf
assumptionsimplifiesthe analysis.
shownin the inset
we now make a massbalanceon the differentialvolume IV in width, , t. Becausethe ml
in Fis.2.5-2: p leis
t t
/
massaccumulation :
\ / mass<liffusingin at z minus \ : l -
diffusing out at ^z+ Lz.) c1(sat)
\ w i t h i nW A x A : I \ r-t-tuts
massflowingin at x minus c flux at the inte:
_
- / -l Lx )/ tr., ,l
\ massflowingout at x : Y D
(2.5-l4r -' Th
r>0. z:0, cr:ct(sat)
-.::er
--t ' 'I - - ( t \ ' ,
(
(2'5-15 : --Ji
. t rl . - o : V'Dr^^J,"-cr(sat) ( 2 . 5l 8
-)
Theseare the answersto this problem.
Theseanswersappearabruptly becausewe can adopt the mathematical
resultsof Sec-
rion 2'2. Those studyingthis materialfor the first time often find
this abruptnessjarring.
r. 5r-0 ) Stop and think about this problem. It is an important problem,
basic to the penetration
theoryof masstransferdiscussedin Section 13.2.To supplya forum
' : - r r i n ds i d e for furtherdiscussion,
rveshall now considerthis problem from anotherviewpoint.
. : r. a n dx . The alternativeviewpoint involveschangingthe differentialvolume
on which we make
::'. $e find the massbalance.In the foregoingproblem, we chosea volume
fixed in space,a volume
rhrough which liquid was flowing. This volume accumulated
no solute, so its use led
il.-5-ll) to a steady-state differentialequation. Alternatively,we can choosea differentialvolume
f l o a t i n g a l o n g w i t h t h e f l u i d a t a s p e e d uT- "h*e. u s e o f t h i s v o l u m e l e a d s t o a n u n s t e a d y - s t a t e
-,'lr' equal differentialequarionlike Eq. 2.3-5. Which viewpoint is conect?
n of short The answeris that both are correct;both eventuallylead to the same
" . . ! i e .a n d i t answer.The fixed-
coordinatemethodusedearlieris often dignified as "Eulerian,"
and the movrng-coordinate
:iitchesthe plcture is describedas "Langrangian."The difference
betweenthem can be illustrateclby
I I SenOUS the situationof watchingfish swimming upstreamin a fast-flowing
river. If we watch the
tshfrom a bridge,we may seeonly slow movement,but if we
watch the fish from a freelv
floatingcanoe,we realizethat the fsh are moving rapidly.
(2.5-12)
2.6 A Final Perspective
: rishrhand
This chapteris very important,a keystoneof this book. It introduces
Fick's law for
dilute solutionsand showshow this law can be combinedwith
massbalancesto calculate
concentratlonsand fluxes. The massbalancesare madeon thin shells.
( 2 . 51- 3 ) When theseshells
are very thin, the massbalancesbecomethe ditferentialequations
necessaryto solve the
(.2.5-14) Variousproblems.Thus the bricksfrom which this chapteris built
arelargelymathematical:
shellbalances,diffrentialequations,and integrationsin different
( 2 . 5l-s ) coord-inate systems.
However, we must also see a different and broader blueprint based
on physics, not
." itself,andI mathematics.This blueprint includesthe two limiting casesof'diffusion
acrossa thin flm
.1r\conditions anddiffision in a semiinfiniteslab. Most diffusion problemsfall between
thesetwo limits.
The first, the thin flm, is a steady-stateproblem, mathematically
easy and sometimes
physicallysubtle.The second,the unsteady-state problemof the thick slab,is a little harder
(2.s-t6) to calculatemathematically,and it is the limit at short times.
48 2 / Dffision in Dilute Solutions Final PersJ
In many cases,we can use a simple criterionto decidewhich of the two centrallimits is Further
more closely approached.This criterion hingeson the magnitudeof the Fourier number
s , C . ( 1 9 3 4 ) .f
(length)2 R. B., Stewan
nann,L. ( 189
/ diffusion
- \
I ;. .- . lltime) . l. (1975) T;
\ coelnclent/
r . P J . ,S t e e l
This variableis the argumentof the error function of the semiinfiniteslab, it determines e d s .G . \ \ ;
the standarddeviation of the decayingpulse, and it is central to the time dependenceof r . E . ( 1 8 5 1 r'
diffusion into the cylinder. In other words, it is a key to all the foregoing unsteady-state :. E. ( 185-5r
problems.Indeed,it can be easily isolatedby dimensionalanalysis. : E.( 185-ir
This variablecan be usedto estimatewhere limiting caseis more relevant.If it is much , E . ( 1 8 5 ,'
larger than unity, we can assumea semiinfinite slab. If it is much less than unity, we - E.( l90i
should expect a steadystateor an equilibrium. If it is approximatelyunity, we may be . .( l s : :
, rB
forced to make a fancier analysis. For example,imagine that we are testinga membrane - L. J.(l!:-
for an industrial separation. The membraneis 0.01 centimetersthick, and the diffusion T .r l E l "
coefficient in it is l0 7cm2/sec. If our experimentstake only 10 seconds,we have an T rlS-r-:
unsteady-state problem like the semiinfiniteslab; it they take three hours we approacha r ,l\:,
steady-state situation. trr,l:; -
In unsteady-state problems,this samevariablemay also be usedto estimatehow far or
how long masstransferhasoccurred.Basically,the processis significantlyadvancedwhen
this variableequalsunity. For example,imagine that we want to guesshow far gasoline
has evaporatedinto the stagnantair in a glass-fiberfilter. The evaporationhas beengoing IJ
on about 10 minutes,and the diffusion coefficientis about0. lcm2/sec. Thus
( l e n g t h) 2
- l; length: 8cm
(0.I cm2/sec)(600sec)
(10-1cm2)
: l: t i m e: lOdays
(10-8 cmzlsec)(time)
D
jr : tcr (rhin fitm)
7
Although the quantitiesDll and (Dlrt;l/2 vary differently with diffusion coefficients.
they both have dimensionsof velocity; in f'act,in the lif sciences,they sometimesare
called "the velocity of diffusion." In later chapters,we shall discoverthat thesequantities
are equivalentto the masstransfercoefficientsusedat the beginningofthis book.
\ ..tnons 1A Final Perspective 49
nickel.
rtehow
nparlng
r:llClents,
: Illes afe
-,r.tntities