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C H A P T E R2

Diffusion in Dilute Solutions

In this chapter,we considerthe basiclaw thatunderliesdiffusionandits application


to severalsimpleexamples.The examplesthat will be givenarerestrictedto dilute solutions.
Resultsfor concentratedsolutionsare deferreduntil Chapter3.
This focuson the specialcaseof dilute solutionsmay seemstrange.Surely,it would seem
more sensibleto treatthe generalcaseof all solutionsandthen seemathematicallywhat the
dilute-solution limit is like. Most booksusethis approach.Indeed,becauseconcentrated
solutionsare complex,thesebooks often describeheattransf'eror fluid mechanicsfirst and
then teachdiffision by analogy.The complexityof concentrateddiffusion then becomesa
mathematicalcancergraftedonto equationsof energyand momentum'
I haverejectedthis approachfor two reasons.First,the mostcommondiffusionproblems
do take place in dilute solutions.For example,diffusion in living tissuealmost alwaysin-
volvesthe transportof small amountsof soluteslike salts.antibodies,enzymes,or steroids'
Thus many who are interestedin diffusion neednot worry about the complexitiesof con-
centratedsolutions;they can work effectivelyand contentedlywith the simplerconceptsin
this chapter.
Secondand more important,diffusion in dilute solutionsis easierto understandin phys-
ical terms. A diffusion flux is the rate per unit areaat which massmoves. A concentration
profle is simply the variation of the concentrationversustime and position. Theseideas
are much more easily graspedthan conceptslike momentumflux, which is the momentum
per areaper time. This seemsparticularlytrue for thosewhosebackgroundsarenot in engi-
neering,thosewho needto know aboutdiftision but not aboutother transpol'tphenomena.
This emphasison dilute solutionsis found in the historicaldevelopmentof the basiclaws
rnvolved,asdescribedinSection2.L sections2.2and2.3ofthischapterfocusontwosimple
casesof {iffusion: steady-state diffusion into
diffusion acrossa thin film and unsteady-state
.rninfinite slab. This focus is a logical choicebecausethesetwo casesare so common. For
L'xample,diffusion acrossthin films is basic to membranetransport,and diffusion in slabs
rr importantin the strengthof welds and in the decayof teeth. Thesetwo casesare the two
r.xtretnsin nature,and they bracketthe behaviorobservedexperimentally.In Sections2'4
.tnd2.5. theseideas are extendedto other examplesthat demonstratemathematicalideas
Lrsefulfbr other situations.

2.1 Pioneersin Diffusion


2.1.1 ThomasGraham
Our modern ideason diffusion are largely due to two men, ThomasGrahamand
\dolf Fick. Grahamwas the elder. Born on December20, 1805,Grahamwas the son of
i successfulmanufacturer.At 13 yearsof age he enteredthe University of Glasgowwith
:hc intention of becoming a minister, and there his interestin sciencewas stimulatedby
ThomasThomson.

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.

Graham'sresearchon the ditTusionof gases,largelyconductedduring the years 1828to


I 833, dependedstronglyon the apparatusshownin Fig. 2. 1-I (Graham,1829, | 833). This
apparatus,a "diffusion tube," consistsof a straightglasstube, one end of which is closed
with a densestuccoplug. The tubeis filled with hydrogen,and the end is sealedwith water,
as shown. Hydrogendiflises throughthe plug and out of the tube, while air diffusesback
throughthe plug and into the tube.
Becausethe diffusion of hydrogenis fasterthanthe diffusion of air, the waterlevelin this
tube will rise during the process.Grahamsaw that this changein water level would leadto
2.t.2.1d,
a pressuregradientthat in turn would alterthe diffusion. To avoid this pressuregradient,he
continuallyloweredthetubesothatthe waterlevelstayedconstant.His experimentalresults
then consistedof a volume-changecharacteristicof each gas originally held in the tube.
Becausethis volume changewas characteristicof diffusion, "the diffusion or spontaneous
intermixtureof two gasesin contactis effctedby an interchangeof position of infinitely
minute volumes,being,in the caseof eachgas,inverselyproportionalto the squareroot of
the densityof the gas" (Graham,1833,p. 222). Gtaham'soriginal experimentwas unusual
becausethe diffusiontook placeat constantpressure,not at constantvolume(Mason, 1970).
Grahamalso perfbrmedimportantexperimentson liquid diffusion using the equipment
shownin Fig.2.l-2 (Graham,I 850);in theseexperiments, he workedwith dilutesolutions.
In one seriesof experiments,he connectedtwo bottlesthat containedsolutionsat diffrent
concentrations;he waiteil severaldays and then separatedthe bottles and analyzedtheir
contents.In anotherseriesofexperiments,he placeda small bottle containinga solutionof
kno'uvnconcentrationin a largerjar containingonly water. After waiting severaldays,he lE

removedthe bottleand analyzedits contents. r|lllr'

Graham'sresultswere sirnpleand definitive. He showedthat diffusion in liquids was at


leasrseveralthousandtimes slowerthandiflision in gases.He recognizedthat the diffusion p
processgot still slowerastheexperimentprogressed, that "diffusion mustnecessarilyfollow F l ' f r" r .
a diminishingprogression." Most important,he concludedfrom the resultsin Table2.1-1
that "rhe quanritiesdiftised appearto be closely in proportion . . . to the quantity of salt in $sr
the ditTusionsolution" (Graham,1850,p. 6). In other words, the flux causedby difTusion iW .--'
is proportionalto the concentrationdiffrenceof the salt. i!-.]j
:,,lLttiotts 2.1 / Pioneersin Dffision l5

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.

:---'.tudr of Table 2.1-l. Graham's resultsfor liquid difrusion


, ::1\ UI.e

Weight percentof
sodiumchloride Relativeflux

: , , : ' 'l S l E t o 1 r.00


\ :. I. ThiS 2 1.99
3 3.01
-:r r. Jlo\ed ,1 4.00
r .,. :h \\ater,
...j. back Source:Data from Graham(1850).

- . :: 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

true equilibrium and a steadystate,possibly as a result of his studieswith muscles(Fick, lhr

1856).Later,Fick becamemore confidentashe realizedhis hypothesiswas consistentwith


Graham'sresulrs(Fick, 1855b).
Using this basic hypothesis,Fick quickly developedthe laws of diffusion by meansof
analogieswith Fourier's work (Fourier, 1822). He defined a total one-dimensionalflux
./1 as

Jt: Ajr: -AD? (2.1-1)


d7.

whereA is the areaacrosswhich diffusionoccurs,/1 is the flux per unit a;tal.,


c1is concentra-
tion, and z is distance.This is the f,rst suggestionof what is now known as Fick's law. The
quantity D, which Fick called"the constantdependingof the natureof the substances," is,
of course,the diffusion coefficient.Fick alsoparalleledFourier'sdevelopmentto determine
the moregeneralconservation equation

3r'r / d2c, I AA At' \


(2.1-2)
a , : D [ * * A , ' r )

When the area A is a constant,this becomesthe basic equation for one-dimensional GItlN

unsteady-state diffusion, sometimescalled Fick's secondlaw. Jlil5

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

Table 2.1-2. Fick's law for diffu,sionwithout conNection

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.

2.2 SteadyDiffusion Acrossa Thin Film


In the previoussectionwe detailedthedevelopmentof Fick's law, thebasicrelation
for diffusion. Armed with this law,we cannow attackthe simplestexample:steadydiffusion
acrossa thin film. In this attack.we want to find both the diffusionflux andthe concentration
profile. In other words, we want to determinehow much solutemovesacrossthe film and
how the soluteconcentrationchangeswithin the film.
This problemis very important. It is one extremeof diffusion behavior,a counterpointto
diffusion in an infinite slab. Every reader,whethercasualor diligent, shouldtry to master
this problem now. Many will fail becausefilm diffusion is too simple mathematically.
Pleasedo not dismiss this important problem; it is mathematicallystraightforwardbut b,["s
physically subtle.Think aboutit carefully.

2.2.1 The Physical Situation

Steadydiffusion acrossa thin film is illustratedschematicallyin Fig. 2.2-1. On


eachside of the film is a well-mixed solutionof one solute,speciesI . Both thesesolutions
are dilute. The solutediffusesfrom the fixed higher concentration,locatedat z < 0 on the
lefrhand side of the film, into the fixed, lessconcentratedsolution,locatedat z > / on the
right-handside.
We want to find the soluteconcentrationprofile and the flux acrossthis film. To do this,
we first write a massbalanceon a thin layer Az, locatedat somearbitrarypositionz within
the thin film. The massbalancein this layer is

/ 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 -

Becausethe processis in steadystate,the accumulationis zero. The diffusion rate is the


\r tlutictttr - ) / SteadyDiffusion Across a Thin Film 19

.t'iusionflux times the film's areaA. Thus

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:

r-..1I1On z :0, cr: clo (2.2-6)


. : ' r l\ i O n
::rtion z: I, cl : ct! (2.2-1)
.:il and
:.:.rrn.becausethis systemis in steadystate,the concentrations
c16and c17are independent
' lime. Physically,
,u]t to this meansthat the volumes of the adjacentsolutionsmust be much
-
:'rter than the volume of the flm.
t:Jster
. : : . ,i t l l y .
_::J but 2.2.2 Muthematical Results

The desiredconcentrationprofile and flux arenow easilyfound. First, we integrate


- ).2-5 twice to find

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

r3.'rusethe systemis in steadystate,the flux is a constant.


.\s mentionedearlier,this caseis easymathematically.Although it is very important,it
. ,itten underemphasized becauseit seemstrivial. Before you concludethis, try someof
: I: the r' e\amplesthat fbllow to make sureyou understandwhat is happening.
20 2 / Diffusion in Dilute Solutions 2 / SteadyDffisit

.: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 .'

membraneseparates two well-stirredsolutions.Unlike thefilm, themembraneis chemically :r'nneabilitrPs


differentfrom thesesolutions. the diffusion;
Solution As before,we first write a massbalanceon a thin layer Az: - : 1 t r e n c ei ns . ,

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; *

z,: I, ct: HCtt

where 11 is a partitioncoeffcient,the concentrationin the membranedivided by that in the


adjacentsolution. This partitioncoeffcientis a equilibriumproperty,so its useimplies that
equilibrium existsacrossthe membranesurface.
The concentrationprofle that resultsfiom theserelationsis

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-"'

concentrationdrops. Either caseproducesenigmas.For example,at the lefi-hand side of ,|[-


the membranein Fig. 2.2-2(a),solutediffusesfiom the solution at r:y6into the membrane
at hi pher concentration.
This apparentquandaryis resolvedwhen we think carefully aboutthe solute'sdiffusion.
Diffusion often can occur fiom a region of low concentrationinto a region of high con-
centration;indeed,this is the basisof many liquid-liquid extractions.Thus the jumps in
concentrationinFig.2.2-2 arenot asbizarreasthey might appear;rather,they aregraphical
\olution.s 2.2 / Steudt'DiJJusionAcrcssa Thin Film 21

accidentsthatresultfrom usingthe samescaleto representconcentrations insideandoutside


membrane.
This type of diffusion can also be describedin terms of the solute'senergy or, more
exactly,in termsof its chemicalpotential.The solute'schemicalpotentiadoesnot change
acrossthe membrane'sinterface,becauseequilibrium existsthere. Moreover,this poten-
tial, which drops smoothly with concentrarion,as shown in Fig. 2.2-2(c), is the driving
fbrce responsiblefor the diffusion. The exact role of this driving force is discussedmore
completelyis Sections6.4 and1.2.
The flux acrossa thin membranecanbe found by combiningthe foregoingconcentration
profilewith Fick's law:

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.

Example 2.2-2:Porous-membranediffusion Determinehow the resultsof the previous


exampleare changedif the homogeneousmembraneis replacedby a microporouslayer.
Solution The differencebetweenthis caseand the previousone is that diffusion
is no longer one-dimensional;it now wiggles along the tortuouspores that make up the
rnembrane. Rather than try to treat this problem exactly, you can assumean effective
diffusion coefcient that encompassesall ignoranceof the pore'sgeometry.All the earlier
answersare then adopted;for example,the flux is

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

'rh ,..1 0 : A( jrl: - ,/rl.:+r;)- rrAL.z


22 2 / Diftusion in Dilute Solutions

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

of the mobile speciesI in the membrane.A similar


where rl is the rate of disappearance
't-*#
massbalancefbr the immobile product2 gives

, ' d
U - - . . / 1 f / ' 1
47.

But becausethe productis immobile, j2 is zerc,and hence11is zero. As a result,the mass


balancefor speciesI is identicalwith Eq. 2.2-3,leavingthe flux and concentrationprofle
unchanged.
This result is easierto appreciatein physicalterms. After the diffusion reachesa steady
state,the local concentrationis everywherein equilibrium with the appropriateamountof
the fast reaction'sproduct. Becausetheselocal concentrations do not changewith time, the
amountsof the productdo not changeeither.Diffusion continuesunaltered.
This casein which a chemicalreactiondoesnot affect diffusion is unusual.For almost
any other situation,the reactioncan engenderdramaticallydifferent masstransfer. If the
reactionis irreversible,the flux can be increasedmany ordersof magnitude,as shown in
Section I 6.1. If the difTusionis not steady,the apparentdiffusion coefficientcan be much
greaterthan expected,as discussedin Example 2.3-3. However,in the casedescribedin
this example,the chemicalreactiondoesnot affect diffusion.

Example 2,2-4: Diaphragm-cell diffusion One easy way to measurediffusion coef-


cients is the diaphragmcell, shown in Fig. 2.2-3. Thesecells consistof two well-stirred
volumesseparated by a thin porousbarrieror diaphragm.In the more accurateexperiments,
the diaphragmis ofien a sinteredglassfrit; in many successfulexperiments.it is just a piece
of filter paper (seeSection5.5). To measurea diffusion coefficientwith this cell, we fill I
the lower compartmentwith a solutionof known concentrationand the uppercompartment
,F
with solvent. After a known time, we sampleboth upper and lower compartmentsand
measuretheir concentrations.
Find an equationthat usesthe known time and the measuredconcentrationsto calculate
the diffusion coefficient.
\ttlurions 2.2 / SteadyDiJfusionAcross a Thin Film L-')

Solution An exactsolutionto this problemis elaborateand unnecessary. Sucha


solutionis known but neverused(Barnes,1934). The usefulapproximatesolutiondepends
value
on the assumptionthat the flux acrossthe diaphragmquickly reachesits steady-state
(Robinsonand Stokes,1960).This steady-state flux is approachedeventhoughthe concen-
trationsin the upperand lower compartmentsare changingwith time. The approximations
introducedby this assumptionwill be consideredagainlater.
In this pseudosteadystate,the flux acrossthe diaphragmis that given for membrane
diffusion:
I DHI
rrl,grn has /r :| , - l t C r . r o * . r - C lr p p . r )
t t l
the
Here, the quantity H includes the fraction of the diaphragm'sarea that is availablefor
Jiffusion. We next write an overall massbalanceon the adjacentcompartments:
dCt.lu*",
Vtower# - -Ajt
dt

dCr.upp.,
Vuoocr---.::lAjt
.' -\ similar " d

.vhereA is the diaphragm'sarea. If thesemassbalancesare divided bY Vru*",and yuppcr,


-espectively,and the equationsare subtracted,one can combine the result with the flux
tquationto obtain
te mass d ^
- nrnlle : Df(Ct,opp.,- Cl.lo*.,)
tu*.,- Ct.upp",)
;;{Cr

,: .tead) r which
-.nLnt
of A H l I 1 \
: n t e .t h e YR- - - l - r - l
/ \vt"*t''v',,")

:: : rlntost . a geometricalconstantcharacteristicof the particulardiaphragmcell being used. This


, :': If the equationis subjectto the obviousinitial condition
-.l-ferential
.'-:tr\\flil
/ : 0, : C.to*..- Cf.uno.t
Cl.ror..- Ct.upp.,
. -3 nluch
,: -,:lbedin - rheuppercomparrmentis initially filled with solvent,then its initial soluteconcentration
:ll be zero.
Integratingthe differentialequationsubjectto this condition givesthe desiredresult:
, r coeffi- Cl.lo*". - Cl.upp.,
: ( ^-ftDr
:. l-stirred C.,n*.. - C?.uoo"'
,: rriments,
, . . ra p l e c e
-: .. rie fil 'tt \
I / c P ''. ,' ,c. r - L l u P P c r I
.lrrlment D:-ln|
pt C'.'u*",- Cr.upper
.-:r-nts and \ /

,-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 -

the concentrationsin the adjacentcompartmentscan changemuch. As a result,the profle t l _

acrossthe diaphragmwill alwaysbe closeto its steadyvalue,eventhoughthe compartment ci --

concentrationsare time dependent. 'j..lt.thei.-..


Theseideascan be placedon a more quantitativebasisby comparingthe relaxationtime
of the diaphragm,t21o, with that of the comparrmenrs,1l(Dp) The analysisusedhere
will be accuratewhen (Mills, Woolf, and Watts, 1968)
- -D.

trr,t.l,/!:" ( 1
:vai"p,.ogn' +
I
)
| /( p Dr1, ".r \ Vt,,*., Vuppr,
/

This type of "pseudosteady-state


approximation"is common and will be found to underlie
mostmasstransfercoefficients.

Example 2.2-5: concentration-dependent diffusion In all the examplesthus far, we ll


haveassumedthat the diffusion coefficientis constant.However.in somecasesthis is not
true; the diffusion coeffcientcan suddenlydrop from a high value to a much lower one.
Suchchangescan occur for water difTusionacrossflms and in detergentsolutions.
Find the flux acrossa thin film in which diffision variessharply. To keep the problem
simple, assumethat below somecritical concentrationc1., diffusion is tast,but abovethis = t )
concentrationit is suddenlymuch slower.
Solution This problem is best idealized as two films that are stuck together D
(Fi$.2.2-4). The interfacebetweentheseflms occurswhen the concentrationequalsc1..
. Solutions [),isiorrAcrossa Thin Film

:.: :ic diffision


-:::,rgll. TheO-
. J.. \(l that the L0rge
: ' - : . . L n dw i l l n o t d if f u s i o n
- ' h1 rvriting coefficient

\ :.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

- -.. dr. wO - - (Dc r o - c r . )


,/r
. . : . : : - . i.s n o t z(.
. . \e r o n e .
--' risht-handfilm, the concentrationis small, and the diffusion coefficientis large:
: '.:J rroblem
t..
- ,.: -:'!r\e this
l r : - D ?az.
:.-\ tlrgether :,
D (clr_cu)
" 3 . l u a l cs t c . L
_ -
aa
/(r 2 / Difrusionin Dilute Solutions

The unknownposition2,.can be found by recognizingthat the flux is the sameacrossboth


films:
I
t' : o!!r-r-t'
l(c19 - c1,.)

The flux becomes

D ( c ' r o- c r , . )* D ( c r , - c t t )
-
.Il

If the critical concentrationequalsthe averageof c1sand c11,then the apparentdifTusion


coefficientwill be the arithmeticaverageof the two diffusion coefficients.
In passing,we shouldrecognizethat the concentrationprofile shown in Fig' 2.2-4 im' -
+ :rt(,
p l i c i t l y g i v e s t h e r a t i o otfh e d i f f i s i o n c o e f f l c i e n tTs h
. efluxacrossthefilmisconstantand
is proportionalto the concentrationgradient.Becausethe gradientis largeron the left, the
difTusioncoeffcientis smaller. Becausethe gradientis smalleron the right, the diffusion
coefficientis larger. To test your understandingof this point, you should considerwhat
the concentrationprofle will look like if the diffusion coeffcientsuddenlydecreasesas
the concentrationdrops. Such consi<lerations will help you understandthe next and final
examplein this section.
ui

!!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, ]|]:,,

believedto occur becausegaspermeabilityand diffision in skin are variable.Indeed,skin


behavesas if it consistsof two layers,eachof which has a different permeability(Idicula
et at., 1976).Explain how thesetwo layerscan lead to the rashesobservedclinically. !lr]l]rrt[|r i'

Solution This problemis similarto Examples2.2-l and2.2-5,butthe solution trtrlnr{u g:L'r

is very complex in terms of concentration.We can reducethis complexity by defining a |lntlmF[]L,

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

and for layer B, muu:1


f f r
z - Pl;)
pt : Pti +
f{rt.ti..ue -c
ulf
The interfacialpressure iilrhlt(xl.l.;.

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

2.3 UnsteadyDiffusionin a SemiinfiniteSlab


We now turn to a discussionof diffusion in a semiinfniteslab. We considera
volume of solutionthat startsat an interfaceand extendsa very long way' Such a solution
can be a gas,liquid, or solid. We want to find how the concentrationvariesin this solution
as a result of a concentrationchangeat its interface. ln mathematicalterms, we want to
fnclthe concentrationand flux as functionsof position and time'
This type of masstransferis often calledfiee diffusion (Gosting, 1956)simply because
this is briefer than "unsteadydiffusion in a semiinfiniteslab."At first glance,this situation
may seemrare becauseno solutioncan extendan infinite distance.The previousthin-film
examplemademore sensebecausewe can think of many more thin films than semiinfinite
slabs.Thus we might concludethat this semiinfinitecaseis not common. That conclusion
would be a seriouserrol.
The important caseof an infinite slab is common becauseany diffusion problem will
behaveas if the slabis infinitely thick at shorlenoughtimes. For example,imaginethat one
of the thin membranesdiscussedin the previoussectionseparatestwo identical solutions,
so that it initially containsa solute at constantconcentration.Everything is quiescent,at
equilibrium. Suddenlythe concentrationon the leffhand interfaceof the membraneis
rased,as shown in Fig. 2.3-1. Just after this suddenincrease,the concentrationnear this
left interf'acerisesrapidly on its way [o a new steadystate. In thesefirst few seconds,the
concentrationat the right interfaceremainsunaltered,ignorantof the turmoil on the left'
The left might as well be infinitely far away; the membrane,for thesefirst few seconds,
might as *"ll b. infinitely thick. Of course,at largertimes,the systemwill slitherinto the
steidy-statelimit in Fig. 2.3-l(c). But in those first seconds,the membranedoesbehave
like a semiinfniteslab.
This example points to an important corollary, which statesthat casesinvolving an
infinite slab an<la thin membrane will bracket the observed behavior. At short times,
dif1ision will proceedas if the slab is infnite; at long times, it will occur as if the slab
is thin. By focusing on these limits, we can bracket the possiblephysical responsesto
different diflision Problems.

2.3.1 The PhYsical Situation

The diffusion in a semiinfiniteslab is schematicallysketchedin Fig. 2'3-2' The


as
slab initially contains a uniform concentrationof solute cl. At Sometime, chosen
time zero, the concentrationat the interfaceis suddenlyand abruptly increased, although
the solute is always presentat high dilution. The increaseproducesthe time-dependent
concentrationprofile that developsas solutepenetratesinto the slab.
We want to fnd the concentrationprofile and the flux in this situation,and so again we
needa massbalancewritten on the thin layer of volume A Az:

rate of diffusion - f rateof diffusion\


/ soluteaccumulation\ -- / \ (2.3-r)
\ in volumeAAz / \into thelaYeratz ) /
[*:::'l'i1"'
ln mathematicalterms,this is

: A (.i tl-. ,/rl.+r .) 12.3-2)


!o +u rt1
2.3 / UnsteadyDffision in a SemiinfiniteSlab 29

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

We divide by AA: to find tr' ' : "".

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:

/:0, a l l: , cl:cre (2.3-6)


/>0. z:0. cl:cto (2.3-1)
i:@, cl:clx (2.3-8)

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.

2.3.2 Mathematical Solution

The solutionof this problem is easiestusing the methodof "combinationof vari-


ables."This method is easy to fbllow, but it must have been difficult to invent. Fourier,
Graham,and Fick failed in the attempt;it requiredBoltzman'storturedimagination(Boltz- 'rrom r*'
m a n ,1 8 9 4 ) .
:IIlr :".
The trick to solving this problem is to definea new variable q Lr U "*

(2.-r-9)
'/4Dt
The differential equation can then be w ntten as

dt, /(\ dl,, /;t. 1:


. I l : D d, (-- ; t . ,I (2.3-
r0)
ti1 \t / \azl nu
or
,, ,
d ' c r' d r:t
| 1r - n ( 2 . 3r -l ) 'ffius**
Lt<' d<
In otherwords,the partialdiff'erentialequationhasbeenalmostmagicallytransformedinto
an ordinarydifferentialequation.The magic also works for the boundaryconditions;from
F,q.2.3-7,

(:0' cl:cro (2.3-12)


a t
) -l / Unstead) DrJJusionin a Semiinfinite Slab J 1

nd fiom Eqs.2.3-6and 2.3-8,

' l_11 (:oo, cl:ctn (2.3-13)


'\ ith the methodof combinationof variables,the transformationof the initial andboundary
,nditionsis often more critical than the transformationof the differentialequation.
The solutionis now straightforward.One integrationof Eq. 2.3-1I gives
'l-:ll
dc:1 \'
- :ae () 7-14\
d<
. rJnt ls
:erea is an integrationconstant.A secondintegrationand useofthe boundarycondition
.- \
't-5r
cr - clo
-
- r t r
(2.3-
l s)
clc clu
,t. Ol9
:'ft
. , \ l l\ :
) r q
'-6r e r f1 : l : (2.3-t6)
I e "ds
t/ .lo

-R - ir is the errorfunctionof {. This is the desiredconcentrationprofile giving the variation


- rcentrationwith position and time.
1i i a u s e nranypracticalproblems,the flux in the slabis ofgreaterinterestthantheconcentration
... ! :,- ' .: itself.This flux
1 r )r
can againbe foundby combiningFick's law with Eq. 2.3-15:
Ar,
j, : -O'i) : 1/OJ"t, :'l4Dt(crc- cr-) (2.3-t7)
t11

:.rrticularly useful limit is the flux acrossthe interfaceat z - 0:


'I Van- ./rl::o: f Dlrt(c11'-cr!) (2.3-18)
F',urier, - ' .'
lr is the valueat the particulartime / andnot that averagedovertime. This distinction
Boltz-
, -,' ulportantin Chapter13.
- . ::rispoint, I havethe samepedagogicalproblem I had in the previoussection:I must
'.e vou that the appzrentlysimple resultsin Eqs. 2.3-15and 2.3-18 are valuable.
-'" .
I l-g) . , :r'\ultsare exceededin importanceonly by Eqs.2.2-9 and2.2-10. Fortunately, the
.- - :r.rticsmay be difficult enoughto sparkthought and reflection;if not, the examples
r,- .,rrl shclulddo so.

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

concentrationin the liquid.


The difficulties causedby a gas-liquid interfaceare anotherresult of the plethoraof
units in which concentrationcan be expressed.Thesediffculties require concernabout
units, but they do not demandnew mathematicalweapons. The changesrequired for a
urt-
liquid-liquid interfacecan be similarly subtle.

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

and the interfacial flux is

--*:-
,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

where c2 is the concentrationof the solutethat has alreadyreacted,c1 is the concentration


of the unreactedsolutethat can diffuse,and K is the equilibriumconstantof the reaction.If
the reactionis minor, K will be small; as the reactionbecomesirreversible,K will become
verv larse.
- .1/ UnsteadyDffision in a Semiinfinite Slah J-')

- . :.rfiial With thesedefinitions,we now write a massbalancefbr eachsoluteform. Thesemass


- - :.nrllar --,lancesshouldhavethe form

: - : 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
__-

34 2 / Dilfusion in Dilute Solutions

and the interfacialflux is

,/rl::o: V6i r K l l " t ( ( r o- ( r )

The flux hasbeenincreasedby the chemicalreaction.


These effects of chemical reaction can easily be severalorders of magnitude. As
will be detailedin Chaprer5, diffusion coeffcientstend to fall in fairly narrow ranges.
Thosecoefficientsfor gasesare around0.3 cm2/sec;thosein ordinaryliquids clusterabout
l0-5cm2/sec.Deviationsfromthesevaluesofmorethananorderofmagnitudeareunusual.
However,differencesin the equilibrium constantK of a million or more occur frequently.
Thus a fast chemicalreactioncan tremendouslyinfluencethe unsteadydiffusion process.

Example 2.3-4: Determining diffusion coefficients from free diffusion experiments


Diffusion into a semiinfiniteslab is the geometryusedfor the most accuratemeasurement
of diffusion coefficients.Thesemost accuratemeasurements determinethe concentration
Rayleigh interferometer,uses Threr t
profile by interferometry.One relativelysimple method, the
a rectangularcell in which there is an initial step function in refractive index (Dunlop
et al. 1912). The decay of this refiactive index profile is followed by shining collinated
light throughthe cell to give interferencefringes. These fringes record the refractiveindex
v e r s u sc a m e r ap o s i t i o na n dt i m e .
Find equationsthat allow this informationto be usedto calculatediffusion coefficients.
Solution The concentrationproflesestablishedin the diffision cell closely ap-
proachtheprofilescalculatedearlierfor a semiinfiniteslab. The cell now effectivelycontains
two semiinfiniteslabsjoined togetherat z : 0. The concentrationprofile is unalteredfrom
Eq.2.3-15
ct-clg - 7,
:efl ,-
ctx - cto
"/4Dt
wherecle[: (cr-*cr--)/2] istheaverageconcentrationbetweenthetwoendsofthecell.
How accuratethis equationis dependson how exactly the initial changein concentration
can be realzed in practicethis changecan routinely be within 10 secondsof a true step
function.
We must convert the concentrationand cell position into the experimentalmeasured
refractiveindex and cameraposition. The refractiveindex n is linearly proportionalto the
concentratron:
p:4.o1u"n,f/rr.1

where nro1u.n1is the refractiveindex of the solvent. Each position in the camerais propor-
tional to a positionin the diffusion cell:

Z:az,

wherea is the magnificationof the apparatus.It is experimentallyconvenientnot to measure


the positionof one fiinge but ratherto measurethe intensityminima of many fringes. These
minima occur when
n-no
ttx-tto J12
l
iffi*
\ , 1 i l I 1 (r fl , t ).4 / ThreeOther Examoles 35

\\'herer?{ and r?0are the refiactiveindicesat z - oo and z - 0, respectively;./ is the total


numberof interferencefringes,and j is an integercalledthe fringe number. This number
r\ most convenientlydefnedas zero at - 0, the center of the cell. Combining these
iquations,
:-- -..3. As j zi
:- i iilfl9e S. ',""
rl -

. - . .. : 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:

( I ) We want to show how the diff-erentialequationsdescribingdiffusion are derived.


(2) We want to examinethe effectsof sphericaland cylindrical geometries.
(3) We want to supply a mathematicalprimer for solving thesedifferent diffusion
,- ::ht'cell. equations.
'' - r':'rtration
- - ::!re slep :: all threeexamples,we continueto assumedilute solutions.The threeproblemsexamined
'.j\t are physicallyimportantand will be referredto againin this book. However,they are

. :-tJit\Ufed -rroducedlargely to achievethesemathematicalgoals.


- :r.11to the \

2.4.1 Decay of a Pulse (Inplace Transforms)

As a first example,we considerthe diffusion away from a sharppulse of solute


propor- rc that shownin Fig.2.4-l. The initially sharpconcentrationgradientrelaxesby diffusion
:r the z direction into the smoothcurvesshown (Crank, 1975). We want to calculatethe
. rape of thesecurves.This calculationillustratesthe developmentof a differentialequation
.-:riiits solutionusing Laplacetransforms.
:.r nlcasure As usual, our first step is to make a massbalanceon the differential volume AAz as
- 1rlwn:
_r3\.These

/ solute \ / solute \ / solute \


-
l"::r'f:"',) :
I
\
aitfusion
this
inro
volume /
| |
\ this
outof I
airiusion
volume /
Q.4-tl
/
'itr'r'e
36 2 / Diffusion in Dilute Solutions Olt,

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,

0 c'' - D 2c, (2.4-4)


.'
At z.'
This is the samedifferent equationbasic to the free diffusion consideredin the previous
section.The boundarycon<litionson this equationare as follows' First, far from the pulse,
the soluteconcentrationis zero:

/ > 0. : : oQ, cr :0 Q'4-5)

Second.becausediffusion occurs at the samespeedin both directions,the pulse in sym-


metric:
dct
r>0, ':0, -o (2.4-6)
oz
This is equivalentto sayingthat at z : 0, the flux has the samemagnitudein the positive
and negativedirections.
The initial condition for the pulse is more interestingin that all the solute is initially : -
lfilL
locatedatz:0: tLa t ''
M (2.4-1)
/ : 0, cr : -(:)
F@ut
where A is still the cross-sectionalareaover which diffusion is occurring, M is the total *ttrr
amountof solutein the system,and 6(z) is the Dirac function. This can be shownto be a ile*-
), '..lil( )/1.\ : 'Tltrer Otlter Erttrttltle.s
3l

,rronabl
conditionb1,a massbalance:

/- f'M
t,Att::./ M
./ . , iu,.tAdz: (2.4-8)

thisintegration, we shouldremember that(z)hasdimensionsof (length)-r.


rotur this problem,we frsrtakerhet-uptu."
rransfbrm
of Eq.z.+r+withrespectro
,,ll

.."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.

t2.4-6) 2'4'2 steady Dissorution of a sphere (sphericat


coordinates)
i positive our secondexample,which is easiermathematicary,
':herical particle,as shown is the steadydissorutionof
inFig.2.4-2. The sphereis of a sparingly
. initially hat the sphere'ssizedoesnot changemuch. sorubremateriar,
': rulroul.ding However,this materiarquickly dissorvesin
solvent'so that solute'sconcentrationat the
sphere'ssurfceis saturated.
r"ausethe sphereis immersedin a very
-:r-rels largefluid volume,,l..on."nirltion far from
\2.4-7) zero. the
The goal is to find both the dissolution
. rhe total -rere' rate and the concentrationprofile around
Again, the frst stepis a massbarance. the
',ntobea In contrastwith the pi.urou, exampres,
' nlassbalanceis most conveniently
made in sphericalcoordinateso'rigrnating
from the
2 / Dift'usionin Dilute Solutions 2.4/ ThreeOther
38

This basicdiffere

r:Ro.
S o l u t ef l u x
owoy

the sphere werr


rhanged, but tl
E q . 2 . 4 - l 8f i e

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

This basicdifferentialequationis subjectto two boundaryconditions:

r : Ro, ct : ct (sat) (2.4-19)

r:@, ct:0 () 4-)O\

If the spherewere dissolvingin a partiallysaturatedsolution,this secondcondition would


be changed,but the basicmathematicalstructurewould remain unaltered.One integration
of Eq. 2.4-18 yields
dct a
() 4-)1t
dr 12
where a is an integration constant. A secondintegrationgives

() 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)

, : : i u s i o ni s 2.4.3 Unsteady Diffusinn Into Cylinders (Cylindrical Coordinates and


. point by Separatio n of Variable s)
r:lll rlJrt is The final example,probably the hardestof the three,concernsthe diffusion of a
- -1,r)rn .oluteinto the cylindershownin Fig.2.4-3. The cylinderinitially containsno solute.At
:mezero,it is suddenlyimmersedin a well-stirredsolutionthatis of suchenormousvolume
. . r t h el i m i t iet its soluteconcentrationis constant.The solutediffusesinto the cylindersymmetrically.
ri-oblemslike this are importantin the chemicaltreatmentof wood.
We want to find the solute'sconcentrationin this cylinder as a function of time and
t) . 1 - 1 7 ) Jation. As in the previousexamples,the first stepis a massbalance;in contrast,this mass
.,anceis madeon a cylindrical shell locatedat r, of area2r Lr, andof volume 2n Lr Lr.
-re
li \tant, basicbalance
. o l u t ea c c u m u l a t i o n _ solutediffusion - / solutediffusion \
\ / \ (2.4-26)
rl.;1-18) n t h i sc y l i n d r i c asl h e l l/ \ into the shell / \ out of the shell /
40 2 / Dffision in Dilute Solutions

( 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

LPrrLLrc,l : (2trLj), - (2rrL11),',6, Q'4-27)


dt
small:
we can now divide by the shell'svolume and take the limit as ^r becomes
a l a t) 4-)?\
't": -i u'l'
equation
combining this expressionwith Fick's law givesthe requireddifferential
c t_ D _ r , . d ! (2.4-2e)
't
r r r
which is subjectto the fbllowing conditions:
r) 4-30
1<0, allr, ct:0
ct : ct (surface)
(2.4-3r)
/ > 0, r : Ro,
Ac t) l-7)\
r:0, =o lr : o
- : / Three Other Examples 4l

-. 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

r:0, all{. 0:l (2.4-37)


r>0, f :1, 0:0 (2.4-38)
'e
:0. :" - g (2.4-39)
'-:la
oE
:\. tle
:': ihan
r'novice, this manipulationcan be more troublesomethan it looks.
'olve theseequations,we first assumethat the solutionis the productof two functions,
: time and one of radius:
p(r,):
Si:t)J() (2.4-40)
).1-21) Eqs.2.4-36 and2.4-40are combined,the resultingtangleof termscan be separated
. r o nw i t h S G ) f ' ( ' ) :

, - . 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

Thusthepartialdifferentialequation2.4-36hasbeenconvertedinto two ordinarydifferential


equations2.4-42 and2.4-43.
The solutionof the time-dependentpart of this result is easy:

(2.4-44)

wherea'is an integrationconstant.The solutionfor /(6) is more complicated,but straight-


forward:

-r bYo@O (2'4-45)
J G) : alo@t)

where -/sand Is areBesselfunctionsand a andb are two more constants.From F,q.2.4-39


we seethafb :0. From Eq. 2.4-38.we seethat

0: alo@) (2.4-46)

Becaused cannotbe zero,we recognizethat theremust be an entirefamily of solutionsfor


which

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

We now usethe initial conditionF,q.2.4-37to find the remainingintegrationconstant(aa'),,'.


t-f !;

(2.4-4e) Jll ill r

) 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'

This problem clearly involvesa lot of work. The seriousreadershouldcertainly work


one more problemof this type to get a feel for the idea of separationof variablesand for the
practiceof evaluatingintegrationconstants.Even the seriousreaderprobablywill embrace
the ways of avoidingthis work describedin the next chapter. rem-i:
, .\olutk)ns ,rtvection
and Dilute Dffision +)

. 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

In many practicaproblems,both diffusion and convectiveflow occur. In some


(1..1-48) --...speciallyinf-astmasstransferinconcentratedsolutions,thediffusionitselfcausesthe
- :,tion. This type of masstransfer,the subjectof Chapter3, requiresmore complicated
r'- -.rl and mathematical analyses.
ritl (aa'),r'.
:'reis anothergroup of importantproblemsin which diffusion and convectioncan be
: '. :rsily handled.Theseproblemsarisewhen diffusion and convectionoccur normal to
t).4-49) : ". - ther. In other words,diffusion occursin one direction,and convectiveflow occursin
. -':-:c'ndiculardirection. Two of theseproblemsare examinedin this section. The first,
- ..-:f)nacross
a thin fowing f1m, parallelsSection2.2;thesecond,diffusioninto a liquid
ri :l t o ' .\ a less obvious analogueto Section2.3. Thesetwo examplestend to bracketthe
- . :,.ed experimentalbehavior,and they are basic to theoriesrelatingdiffusion and mass
:- .::r coefficients (seeChapterI 3).
(1.4-50)

2.5.1 Steady Diffusion Across a Falling Film

The first of the problemsof concernhere,sketchedin Fig. 2.5-1, involvesdiffusion


- .- a thin, moving liquid film. The concentrations on both sidesof this film are fixed by
(2.4-51) , ::.rchemicalreactions,but the flm itself is moving steadily.I havechosenthis example
' r'ccuSeit occursofien
but becauseit is simple. I hopethat readersorientedtowardthe
-:Lial will wait for later examplesfor resultsof greaterapplicability.
. , solvethis problem,we make threekey assumptions:
,:r.unly work
^ :. .rndfor the . r The liquid solutionis dilute. This assumptionis the axiom for this entire chapter.
.,.il embrace I r The liquid is the only resistanceto masstransfer. This implies that the electrode
reactionsare fast.
A A
++ 2 / Dffision in Dilute Solutions

(3) Masstransportis by diffusionin thez directionandby convectionin thex direction'


Transportby the other mechanismsis negligible.

It is the lastof theseassumptionsthat is most critical. It impliesthat convectionis negligible


in the z direction. ln fact, diffusion in the z direction automaticallygeneratesconvection
in this direction.but this convectionis small in a dilute solution. The last assumptionalso
suggeststhat thereis no difTusionin the x direction. Theremay be suchdiffusion,but it is
assumedmuch slower and hencemuch lessimportantin the x directionfhan convectton.
This problem can be solved by writing a mass balance on the differential volume
W Lx Lz, where W is the width of the liquid film, normal to the plane of the paper:

/ 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 .)

, / soluteflowing in at x minus \ ( 2 . s1- )


r
\ sofute flowing out at r + Lr )
or, in mathematicalterms,
(l
^ (crl{ArA:): [(lrWLx). - (71WAr).*o.l
(tt

, 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.

This can be combinedwith Fick's law to give


r)

0 - D
O-Cl

, 1
(2.s-4)
a 7.-
This equationis subjectto the boundaryconditions

z:0, ('r:clo r?5-5

z: I, cr: clt (2.s-6)

When theseresultsarecombinedwith Fick's law, we haveexactlythe sameproblemas that


in Section2.2. The answersare

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.

2.5.2 Diffusion Into a Falling Fitm


I ' \ - \

The secondproblem of interestis iilustrated


(2.s-6) schematicailyin Fig. 2.5-2 (Bird,
' 'irr' and Lightfoot, r 960).
A thin liquid film flows slowly and wirhour ripptes
'urlce. one side of this firm wets down a
:- -.ent asthat the surfce;the other side is in contactwith a gas,
'h is sparinglysolubrein the liquid. we want
to find out how muchgascrissorves in the
J
(2.5-7) ' ' solvethis problem,we again go throughthe
increasingryfamiliar ritany; we write a
" balanceas a differentialequation,combine this with Fick's
law, and then integrate
'r fnd the desiredresurt.we do this subject
(2.5-8) to four key assumptions:
. r The solutionare alwaysdilute.
i ng. I Mass transportis by 3 diffusion anc.lr convection.
2 / Dilfusion in Dilute Solutions 6/AFinalPerspecti

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

This result is parallelto thosefound in earliersections: '


,rrethe answef\
-r answersapP
l |
- (IVA/r).+r.]
| - t c 1 a , l l : l v ) I : [(WAjr/r): l . T h o s es t u d r
tdt
( 2 . sl -0 ) J think about :
* [ ( l 4 z A z c r u ' ) '- ( W L z c t u . ) , . + 1 . , ]
i masstransfe
the left-handside now conside
when the systemrs at steadystate,the accumulationis zero. Therefore, -"
vary with both z andx' .tetnative vier'
of the equaiionis zero. No otherterms are zero,because71and c1
goesto zero,we find balance.ln t
tf we divide by the volume lv ax az and takethe limit as this volume
. , h i c hl i q u i d
,l
ol1
-
o (2.5-r r) :. -statediffer
0:-;. ^ (lui ,ngwith the
dz. dx
law and set u' equal . equationli
We now maketwo further manipulations;we combinethis with Fick's
second change reflects the assumption of short . .rer is that t
to its maximum vaue, a consnt. This
barely has a chance to cross the interface' and t - nethod use
contacttimes. At such times, the solute
interfacial region' the fluid velocity reaches the , : . c r i b e da :
diffusesonly slightly into the fluid. In this ': of watch
of a constant value is probably not a serious
maximum suggestedin Fig. 2.5-2, so the use - : i d g e .u e
assumption.Thus the massbalanceis
3. \\'erea
,ct
: DA:r-:
(2.5-12l
0 (.r/u-"*) dz'
\ Fina
The left-handsideof this equationrepresents the soluteflow out minusthatin; theright-hand
side is the diffusion in minus the diffusion out' . .rnd:l
This massbalanceis subjectto the following conditions: ' ,,ndtll
(2.5-l3r
. r: 0 . all:, .r :0 :3 lllS:

(2.5-l4r -' Th
r>0. z:0, cr:ct(sat)
-.::er
--t ' 'I - - ( t \ ' ,
(
(2'5-15 : --Ji

with the gasitself, and /


where c1(sat)is the concentrationof dissolvedgasin equilibrium . - '::
threeboundaryconditions
is the thicknessof the falling film in Fig. 2.5-2. The last of these
is replacedwith
(2.5-t6
x>0. z:oo, cl:0
, Solutions ).6 / A Final Perspective
41

This again reflectsthe assumptionthat the film is exposed


only a very short time. As a
:esult,the solutecan diffuse only a short way into the film. Its
diffusion is then unaffected
y the exact location of the other wall, which, from the standpoint
The third of diffusion, might as
n ell be infinitely far away.
The final
This problem is describedby the samedifferentialequationand boundary
conditionsas
Jiffusionin a semiinfiniteslab.The soledifferenceis thatthe quantity
t h ei n s e t x /u^u"replacesthe
lime /' Becausethe mathematicsis the same,the solutionis the
same. The concentration
profileis
ct
: l-erf- (2.s-11)
c 1( s a )t J4Dx f u^r^
rI 5-9t . r n dt h e f l u x a t t h e i n t e r l a c e
is

. 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)

Alternatively,supposewe find thathydrogenhaspenetratedabout0. 1 centimeterinto nickel


Becausethe diffusion coefficientin this caseis about l0-8 cm2lsec.we can estimatehou
long this processhasbeengoing on:

(10-1cm2)
: l: t i m e: lOdays
(10-8 cmzlsec)(time)

This sort ofheuristic argumentis often successful.


A secondimportantperspectivebetweenthesetwo limiting casesresultsfrom compering
their interfacialfluxesgivenin Eqs.2.2-10and 2.3-18:

D
jr : tcr (rhin fitm)
7

i, : f D 1nt Lc1 (rhickslab)

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

ll]ltS 1S Further Reading


:ber - .:nes.C. (1934).P,i'.sics,5.4.
- -r. R. 8., Stewart,W. E., and Lightfbot, E. N. (1960).
TransportPhenomena.New york: Wiley.
- irmann,L. ( 1894).Annalender Physikund Chemie,53,
959.
-.,nk.J. (1975). TheMathematics
of Dffision, 2nd ed. Oxford: ClarendonPress.
. :rop,P J., Steele,B. J.. and Lane, J. E. (1972). ln.. PhysicalMethodso.fChemistry,-,
l:1: lllllfl9S eds.G.Weissberger and B. W. Rossiter.New York: Wiley.
- -1.'nceOf ,.. A. E. (1852). Zetschrftfr RationelleMedicin,2,83.
: .,-:r - statg -.. A. E. (1855a). Poggendorff'sAnnelender Physik,94, 59.
-.. A. E. (1855b).PhilisophicalMagazine,l0,30.
i . llluCh ,. A. E. (1856). MedizinischePlrysik Burnswick.
- 'i\' we -.. A. E. (1903). GesammelteAbhandlungen.W'jrzburg.
r.j '-'lv be .-rier,J. B. (1822). Thorieanal,-iquede la chaleur. Pa,ris.
.ting, L. J. (1956). Advancesin Proein Chemstry,ll, 429.
a:-:lbrane
-.ham, T. (1829).
r i.:iusion Quarterly Journal of Science,Literature and Art,27,74.
',ram, T. (1833).Phiktsophical
: i.r\ e ifl Magazine,2,175,222,351.
-'ram, T. (1850). P/zrlosophicalTransaction.s
::::'rach a of the Rov-alSociett:of London, l40,1.
, - ula. J., Graves.D. J., Quinn, J. A., and Lambersten,C. J. ('|976). In. IJndem-aterPhysiology,
- .\ tar or Vol.5, ed.C. J. Lambersten,p. 355. New York: Academic.
'-.or. E. A. (1970).
. - iJ when Philosophit:alJournal,7,99.
:: i,t\()line 1 i.. R., Woolf, L. A., and Watts,R. O. ( I 968). American Instituteof ChemicatEngineersJoumal,
-:r-n t 4 . 6 7t .
-9oll$
.rnson, R. .A.,and Stokes,R. H. (1960). ElectrolyteSolutions.London: Butterworth.

nickel.
rtehow

nparlng

r:llClents,
: Illes afe
-,r.tntities