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.limit of Li!lbility!Di~IIIIi:JJK:fl;lrW.o:mully.:. \\[Mt'G dIG pl.ibl'islllZI ~rI.d aII1lhm !lay,,'~ !heir bcM dfm'b in ~nn8·tE1i:'l book,fuel( ~ 00 repre:,;en~atiQns. or Willtnntl~ will! .~~ ~. Ulc <lO~~y i!M ~mp~~ of UItOO!'J!rnt~ gnht~ bo!i~ 8!1d~jtkllkly di~la~m, .ar:ty implie-d\lO\:llll':rrtlie:~ ,Cl'f ~wbilily orfii1ller.s. rot II pnniouln ,,"IUPOS;;, No WIIITIIII\)' IDll.Y be i::n:alI:d QJ wu~~ by aa11::~ rtprt~~.m 'oc v.'IiIl~I'l5!il~ ma[l:l'ws:.. "The advil:~ and m:l1egies ell.nWned ben::inm;l,)' not be S<\Iitable roryour situltoon, 'You !hoold COrisU~l \!/ill!; ~,p!01l'~onall w~ IPP!'Of'J1ia!e, Ne~~f '!bepuIfLisher!Kif :mlOOf 5M11 lit li<l!bll!! fwl!1IQ' 10'S:l of profit Qranyclhet colt1.ll"lmial dm:i .. ges,~ndlldin8 lrut net ~:imili:rl. 10 special, int:ideiIml.~tl.CTtUU, or millet· ~!1!8~-

FQl'; ie~, .ililfillfl'iMliOO GIlII 'll!HodK4: :prodtlcts Md .ser'I'ice5 or fi)r ~~Mi~1 ~fi!.pl~ 'OO!l~' Our Cmtom.erC..u'e :~~iwitbh'lll\(; I!huidl SOOI;::~ at {SOIl) 76M.97·4:.01!!s.idelr.e U:~i.ted Sliltesll.t (l 1:1).572.3993 <Jr' f:u. (ll.1} 5,12.400.2.

W!lcyail~ :ptil!ili~he$ 11$ 'boob in i!I"')1ri~ 01] e~C!clroniei fmmats,. SOI!i"Je OOJllem ilt<at ,~~inprit'lt ma:r' ·1101 be n-lIilalMe .im. el.ecirorlll: fonnat. For imfQIffi::!t!on ;ab(,ut wn~~~!~, ... r;t~i! o~r web site a~ 'i'!WW'.v.i~,~Qill.

lkn!l~ J~im~. 194B-

l'ri~dp'le1 and .modem. ~jut'on.s ofll'WS 1t'IImf~ opcnri~! ~~ ~!!~;-,~ti~,

1'"=' Inc!1:Ides index.

~S~N 97~()4JQ·i !m~;?: (d\;lih)

~.M;\!iUr.l1:isdier. 2:.C~cmfCli'l~smmiiliS' t Titk"

rri :5U.BIW42009 6W'.n4.2J.---ik:2Z

lG , 8 1 6 ~ 4 3 2 l

Copyr'ghtcd rnaleria'

Table of Contents

P'reface toU1e SecQnd edition

x,vll

P,reface' to the First Edition

xix

lNIam;anc: lalum

xxi

1. Fundam,entaiis of IMass Trallllsfer

'1

1.1 IHlROD,U,C7J ON w __ H_ .•. _. " _._. .. __ "............. ]

'1.:2 MOl@CULAR IMAS,S TRANSfl!lR , ..... , ... " ... -n."' .••• " •• ,." •• ,,, •• ,, •• ,, ••• 3

12.1 C(lIlCC!FIlratiow .. ·,- - - "' " H" .. "',. ,;ie

i 22 Ve:lochie-Sl :anG Fluxes ,_ .. ,--_. T- .. --- .. _.- •. _._.- •. _._.- •. _._._,---._.,---._., .. ..-" ..---.". 10

! "2 J. The Maxwell-Ste;f,m R;ebl!OnS ll3 L2. . .4 Fkk"sFirst L .. w fOI: B.ilil!lry Mi:xtlU'es .... ,., .... ,.,.,,, .. ,.,",, .... "" ",,, .. ,,,,., ..... ,., .... ,.~ fi,

1.3 THE IDIFjFUS~ON COEiFFICU:'NT , n

1.3.1 DiffmtOfli Coeffic,lellll§ for Bin<tl]' Jdeal Gas Syst'e'ms ,,, .... ,.,.,,, .... ,,, ....... ,, ... , .... ~8

i,.3.2 nif{i:lij~o!'lJ Coolficii!l!l![~ rot D]~1l1e Liquids .. ,."""' ... "_." "".,.,.,",, •.. ,".",,,,_"",. " ""'., ." :M

[..3.3 nifl'lISi~n Coeffidc.nJts ~o.r Conren:lmted Uqulds .m , :30

i. 3,,4, Effeetiv,e Diffiushiiities in Ml!I]ti.cillli1pOl~ellJ:t Mixru,res ,.,., ".,,, "" , , .. "" ,.,,,,, :3 .~

t4U MoIru'PI.1!Ixan:d!ill!!! Equation ofoCollltinu]l,y " •. , .. , .. "'" ... ,.",,,,, ..... ,,,,,,,, ,,,.,,.,, :37

[,4.:1.: -Sready,,:!itate MQI~clJ]ar Difr-t1s,lQIl in O,ases.""" .om" ".,,,.,.,.,.,,.,., ," , ,. :JS

t4.3 Sw<tdijHSlate Mol~ular D',iffu,~~o~i'l!I, UQltAid:So. o. ";0. ,,,,",,,; "".,,,,, 0';0."" ",'.;'0';' 53

1.5AtEA:lly$_JAIE CUEEtl510N IN SOUDS H.n u u um 56

1.:5" 1 SreO'!.{!.y.:St:Ulil: Bjn-ary MOlec1!J~ar Diffl!lsion iva

pomp!!. So! ids :'!i8

,L5.2 Knud,selll D~fFuSiio:n Xtl[!oroilLl$ Stdid:$ ,," ' ".. 52

15.3Hydrodij'~amic .FJow .or G~L'ls. in .Pot:OlJJ!! S:Olids ,,, ,,,, ,, ,,", 6:-2

Copyrighled rnaterla

vJilii

1 .. 1 AJNAlQGlcS AMONG, MOlECUlA,R liRANSFlcR PI5I'EINIOIMENA ,,,,, .... ,,,,,,,. ,. , , ", ... . ..

PIOB~EMS,

2 .. Convective Mass Transier

91

2.1 INTR.ODl!JCIIQN

91

2:~2 MIASS .. 1ntANSFER CQEFfU::I~E:NT$ """,,, n"'''T'''''" ",,,,, "n", ,.,,, .,.".,,, 92

2.2,1 mfft.l$I,Q~ of A Th_roll~h, Sta.~ifiiml [1,.""""""" .. ,.""."" ,.,." ... "" , ...... , •. ,,, .. ,, 93

L'l.2 EguinloJ3i!' Caull!oo:rdi~sioo ", ...... ,., .... , .... m" .,,""" .""un " """""." """" .. """ .. , .. " "9.5

2:.,3 DI'MIEINSIONAll ANIAIL:YSIS .. """"'" .... ,,, ...... , ", "" .. " ""' .. ,, ""''' """""''''''''',,'' ',,' . 97

'2.:1.] The Bill~ki:t!gh!lm Metil:od ." ... ,., """, .... "' .. ' .. ' ... ' ... '" .... ,' .... ",,, ...... ,,, ' ... "."'.'" ."' .. "." " .. ,.", ..... "", .... ".,,, .. 97

2'.4 fLOW PAST .A, FLAT IP,LAIE: IBOUND.ARY LAYER

THEOR.Y' """"'",,,,,,,,,",,,,,.,.n n.,." n.''' .... ' ... , ...... " ... "" .. "" ... " ..... " ..... " ..... " ..... " "",,',, • [1113

2',,5 M~.SS· AiNID HEAr-TRAiNS FER .AN!AllOGIES

110

2,,6 'C,ON\tE.CTfVE MAS'SwTRANSf6R CORR.eLATIONS .,"'''',''' 119

2;Ji,] Mass-lirnnsftr Cocllih::icnt$ fOT FIMPIj:'!]cs ~'20 2.6.2. Mass·Ti:aJlsfe:r Coofic.i.eJlit5 for Il. Si:nlflie Sriherc " .... ,,, .... ,, .. ", " ... ",,,,,,,, .... ,.,, .....• ~ 21,

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Contents

ix

2.63 .Mass-lfal'lder Cooffit:i:etU~ fer Single: CyUndets g" .• ' •••.•. ,.'.' •.. g •• , •.. g,.,.g ...•. g" •. 1.26

2.6.4 'l'IiId'llJli.elllllifi.ow i:n: (~lro~da'u' :P[pes , , , 1."27

:2 .65 Mass 1'ows,ferio Pacted and! Fhl.idli:2ied Bed$ , *" " " " " "... l33

2 6:6 MallS T1ansferiljl RnII'ow .• EiiDer

Memb:!'a;lle Modilies

2·7 es.1JlMADON nE MULIIC!OJMI!ONENJ MASS~IRANSEER

OOJEFEI,C]ENTS 0 •. 140.

142

REEEBEICES

3. Interlphase .Mlass Transfer

158

158

3.3 I[)IFFU$IIIIOIN BEIWE EIN PHASES

1163

:3 ,3. I ·Two·RCSista!!1ce ·T~C:Oli'j"m , "... ~ M

3 '32 Overall MIl!!!s~Tmll!sfer Coolfickml" 166 :3'3,;] loc;)~ Ma.. .. $- ThaJn\lfur Coefficiemms·

(ic !3ern I CMC

3 .. 4.,.:1 COUtlleOC,tlrren[ flGW g, g, g".,g, _, _;;"; _ ;g;,.,;_;, ;,. ... , , j ; ,., ,., ;"n;., ,., , .. , ... ," ,., , , n'"'''''''' 79

3,.4 . .2 CQcurre;nt: flow ." '''',·n" '''',·n", ,., , ... ,"' .. , , .. , n .. ,.,""',., n" , ''''" , ,.,.,., .. , ,., "''',,,'' , ,., , .,. Ii 92,

;; ,ttlBflrlCiliLeroo_C.&SeS; ""'''","" """0'" "'''",,, "" , .•. , " , , , ]95

3.5 EQUIL!lB!RmM~TAGE O'PERAT[QNS,.g.""g,;"g"""", .. """,g .. , 196.

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PROBliEMS. .202

BEEE.BJEliCES 21&

4., Equ ipmentfoll" G as-lWiqlu id McUiS,'" Transfer

'OperaUo'ns 219

.4.1 I NTROm:::n.llC·T~ON ."., .. ", .. "." ... "., "." .. ,.,',., ... ,.,.,.,', .. , .. ,', .. , .. ,', .. , .. ,"",.", .... ,., .. , .. ,.,., .. '.' .. , ..... ,.,.,.,., ... , "',', ... ' .. 219

4.2.1. 1)pes ·of r.ackilflg .• ,', •.....• ', ......• , , , " •....•..... , , .. , , .. , .. , , .. , , , , , , 220

4.'2,2 Liqllid D:ls>u'ib!llti.O!Il, .. , .. , " .•.. " , ..•.. , , .. , , , .. " " .• , .. , ...•. , .. , .• ' •. , •.. , , , ,. 224

·4,2,3 Liquld, Hio:Jdlu:p •.•. " ..•• , .•....••• , •. , , , '." , .. ,,, •.•... , , •.•.• , , 22'.:5

:4.2.,4 P~!ilure Dr:Qp • ., ., " ," , ' ' •. '"',.' ',,"' , , , , 230

4";2,,,5:Mjl&r.:~ TiIrnnSfer CoeO'icier;ns, . "." ''',. '''''-'''''",,''',,'''''' ,,-,.,," '" ''''''',,'''''' ''''''''",,',,'' H'" '2.36

4.3 GAS::lIIQUI[],OPEiRADOJj4$;GASQJSPERSEID .. , " . to· 242

4,'3..') S'p!!!med! VefiiseJs. CBIJI~ble CO~UIlUlS) .. ."" " " ,,, .. 243

4 .. :),,2 1"r8iy 'lowers .,,, " .. " " '."'" .... , .. , .... , •. , .. ", , •. ,,,,., .. ' .. , .. ,,' .. ' .. " •. , , .. ','.".""""",", .• ,., .• ,'_,,,.,.,.,,, , •.. ,.,., ..• 2-49

4,1.3 Tlra.y D,j!J[O~ ' ' ' ' .. ' •••• '.' .. '" .. ' .. ' .. '" '., .. ' ,' 'm' ' ' ' ' .. ' ' u .. " .. 25:2:,

·~t,,3,.~ ~y Gas·P,n.s~ure :Orop ' .. ' ' .. ' ' .. ' ' .. , " " 256·

4,. j ,,5· ""lee:plng and ~trainme;n:l: , , , , .. , , "" .. , .. , , 258

4.3,,6 "tra, 'leffi:dl1::!lc1( ' ''''''''''H .. ,." •. ,,, .. ' •. """.' •. ,." '., ", •.• ",,,,, " ""., .. '''' :2,60

E:B:08·L!M S !' .. ,' ••••• "".".' "" " " , ,. 261

RiI5'iEE5R15NICES "''',,''''''-'-''-'-'-

.. 281

283

5.1 I NTRODUC:fION '",,..,,,,, """,,, •. , .. ,j •• ,,, """ • "'''' ,, ' •• "'." .. " , " 2:8;3

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Contelnts

xi

5 .. 2 COUNTERCURRENT hUJLTI,S,TAGEEQUIPMENT .. "" ,., 2&4

5.2-. ~ Gropl:li.cnl IDrtI.e:nnimatl.(m, 'oflhe Number {If

idea] 'ftay;s., .. , " " , .. " .. "." " .. ".,."., ".,,, ", ,"" " , , .. ","., ,.,., ".'"." .• , 284,

5 . .'2.:2 '1"raylEcfficie,l1lcies and Real. Trax!> by G~!l!pilical Meth.oos ....... m ..... ' ,., ..... ,. 285

5 '1 3 mlnte, Mh:t!'!,!i"es '286

5.3 'COlJlNI EIB;CUB;IRENI CONJ]]NUOUS,~CONTACI

EQ ILIIIP MIENl" , .. ," ... " .... ".". ",.,.",. ",_.j ._j" __ "> _._ "_.,, _. _".,. ,._,j _ ...... ",_">" ._ n_',_ 292.

,:5..3',1 DHulie So~:~.rttol:l~:;Helliry·:s Law .. " .. "."." " ..... " ".".",." "."." .. "."." ... ". "., ". "."." ". " .... " " ...... "" .... " 298

Ei.,4 THERMAL E.FFECIS [UJRIINiG ABSOR'PTIION AINID SI:RI!pIPING

JUl

,S "..1.1 A,G!.i{l!bllti:c Operation! of Ii 'froy A~e[' . m, , •• , ,"". 3@[,

.:5 ,4.2 .Mi~l"idi;(; Op!fJd1(J~1 of iI. Pa.c:ke4-Bed A~IilM>l'ber ' ", . ., , ' " , _ ' •• " •• ,. :;!{!14

PBoelLEIMS

RE~F'E'REN(;:'E;;S .... "" ........... , .. '",,"

320

6. D istUII,eliliol11

321

16.1 UNTROD'!lJICI~OIN _ '''" ..... " ..... "",.,,''',, .. , .. ,'''' .. ,"'"'' "n"." n" .. , ,,- '''''''- ,,- "",.,.",.,.,""'-''',.,-,-.,.,- 32]

'6.2SIIN'GlE~TAGE OPIERATIO:N:FLASH

VAP'O:R:IIZATI'O:N , .. , ..•. , .. ,., .. , ,., .. " j,.",.,."., " , ,," 322

'6.3 0 IIFEERENljIAlIOISJIU..AJI,OIN .. "',""'" , " ' " ' " 327

Copyrighled rnaterla

xli

6,5.1 'R.ectifYi nl' Secli,on .,,, .. ,,.,, .. ",.".",." " "", ... ,." .. "., .. " ,m "., •••• ,,"" •• ".""" •••• ,,, "." ", ••• ", 3302

6 .. .:5.2 Strip'jtl~iig S~CliDfi, .,." •. ',." .. " ..•. " ", ,.", " ", " " ", , .. " "., ". 33,3

65.3 Feea StlJge!, ;., ,." , .•.....•...•... " " " ; , , 33:5-

6.5.4 N ~rnJbet oifE!()ui Ilibrium S(~geil and Feed"Sla8,e' Location ."'"," ,.,. 338

6.5.5Llmi'l:ing Co.n.d1ti.o:lls .. " ", .... "." ",.",." ... ".",."." ".".".,,, ,,.,,,.,, ".", ",." " ".". '"~ ".",. 338

6.5.6 Wjtn!,l.mR¢fl~)I, !talio' ,.., .,., .. , , .. e= "" •.•• ""." " ., " " " " ••• " " .. ,. , •• " •. ,34!

6.'.7 :Lar.ll\l;l Numb!:",' 0" Sti!ig~!il ,,, ,, , ., ,, , , •. , .•.• 34'

,6,,5.8 U':fiIe of O·penSteam "." .. "." .. " •. "." " .. "." ""." ,,, " " , .. '"~ " " , " , .. , 35· ~,

,6.:5.9 nay Effkie:!!lI;je:l· ,..,.." .. ",', '.',. .. ", .. ' •. ' ' .. ' ' ' '.' ," '.," •. ' ' .. '.,. ' ', " •. ".".,. .• :352

6,6 BINA'RV DISTiLILATION liN 'PACKEID TOWERS " ....... " ... m •• " 360

6,8 FENSKE:·UNDERWOQ'D.:GIII..I..JLAND MEiH:OD .. , .. , , 368

'6.8" W Total 'Refilux~: F~I'l\'!ke Eqllal;iol:l ' " '"'' .". ".' .. " ' "" .. ' .. " ' """. " '"~ " """." "." 368

'0.8.2, Mrul1bniU,m '1te:fiw.;:., Un.dc,nvood. Bql:l!lth,ms " , " •••. " ••. " , , " 372

6.8.1 Cmlililll!]] Conelaticm for N'umberof S:WMS .111 F~lli,.1.e Renu!'! •.••• , 379

6:.9 RM'lOROlJlS, 'CALCUlAT,[ON PROCECiURll!!:S F,OR.

MULIIICOMPONENT D~S'JIILlAlJION

lSI

:6. 9. ~ EQIlHi:b-ri!l.lm. Stag~ Mod!.oGl,,,., .. , , , " , " .. "." .. ".,,, .. ".,."." """"'"l-,",-ju-j _j 382

:6.9-.2 NOi1!9!lii]~b.tirnn. Ra:te.B~d Mod.el , •.•... , ,,', ,. 383

:6.9.3 CW!~mSAA ~ram, •.•. , " , " " "." ,,", " " " " "." 389

,6.9' •. 4 RA'fEF'RAC Prog@1ll '"",. " , , , ......•. , " 397

.6 ,jlO._sA1'cC Ii::II Do[lSIIL.LA1iUlINL,.m.,,,, " " " w ••• 391

'6.11~tlB[l:I!lIry BaJtch D.i:stiUetion, w~th Co.JI;stan:t Re:n~~ ., .. , ...••. , ...• , " •..• 398

6.l0.2D.atcll DistiUilti(ll!! wUh OOfiM:a:n~ mstl!llalC Co:mposwlio,n , , ".,.,.,.".402

6.10.3 Mnltioompcnent Batch D,istiUation , , ,., , .. , ,., " 405

PRO BlEMS, ">, .. " .. ,"", ""''''""""".,, ", .. , ........ ," .. , .. , 'H"" 'H"" ",.,

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Contents

9.5 AP.PUCAIIONS OF' MIEMBRANE-SEPARATION

IP R:O'C:ESSES ", ", ", , , , "." , , " , .. "." .. 538:

9,,;;'''] :D!ia]ys:~s, " .... ".,,, .. '"'" "." ", .. "."." '",,, ,." '",,, .. ".""" ".,,, ",.",.,."."'",, ".,,, ",,,,,.,, .,.., .. "" ,,, 541.

9.5 .. 2 R¢v~r::;c O$!l1O$i~ .. " , ", .........•. "." " " , " , " .. " " " 543

9 .. 5, .. 3 ,Q,;!Ii$ hJ:fT!eatlun , , " , , , 546,

9'" 5.,4 m •. ntliElif:i~tra1io~ and Mlcmfl]tm~'ion •. " .. " .. ,. "., "., , " ., ,., ,.,,, ,.,...546,

REEERENCES

563

566

569

Appendix D IParck:.ed-'Column Design

510

5811

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XVii

Appendix F~2 McCahe~Thie:l;e:V:apor Ifeed

Contents 589

597

599

603

Iln.dex

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The rudea for the firstediliQI), ,of thii!i OOzylwas born OU( of n1,~' experience lcachiilll~ a OOlUfSC on ma . ss-uaasfer operaMons at ~he Chem~c:aJ~ Enginotldl'l,g Departfl1e(nlt of the Un~versHy of &e·no R:i!:l!!l) during, the previous .25 years. TI.ls course is the ~h]rd :in. a. three"ooun:e unit. oper2lions sequenee, The flrsrceurse cevers mf~ml'il:lliYmUarlsf~r (:fiuJd ~unie:l:)" arid! the ~~Cgnd CQt!f5C ,cov~f;Sl:Ieatlrulls~~r, Besidc~sthese two, courses, aaother prcquisite: of'the maS!N.fwtfiife.r oourse ~S,II ~:WQ~ semes~erseque:l'lcc, of clilern:icall cnginooring thllirmodyn.am:bc&"

I decl:dOO lQ wril~ al~;ii:tbQo\;: :foOf a rif~t t,~yl~ Oil m:)~"'t~ti!iir~r (~tati.o!ii~ wi;tn ale ... !;:,l ofpresen:tal.i.on t!:lal was easy to fOllrow bl'~be reader, bUlw.i,tibe'nougl:i depth of oOOVCF1l!g¢ to g,tlllO!Ht~ trutt $h~<kW!WI.!;s.i'f!g tbe book wiU, ~poo,s!JOCC~fl1~ ~QIDip!~,ij(l!) of the Q(I~!:&¢, I~~: abl~ ~Q ~~~ify preruhI,:Jmazy ,de:s;igns {If the most COImnmn ~s"It:aI:l51fe;l' equipment (such as .lIbriorben. s!trippen. d~stnl3t1.iolil coDmnl'ls, liql:iid C;?i:UaCl(lfr~. 0«: .. ). I de¢idcd also to incrn-pornre. from Ute ·VC.ry beginlfli.llg u.f the ~ook~ ·tIitc use of MJlilicad.,!! Qomp!,J!lati.o;n;d ~ool1'hat ls, in my Opi~rllOIll,. ¥cry hclpfll~ owd friendly. The first ,edb.iolll oflihls. book was the :resl!l~t oii'thaJ'I. effort.

Pa:itofm.y objective W;fl:S acihiev·~d. as ~~!"idet!c~d ib1y tlt!~ fQ]kw".itlg ec)1c(.'f!P~ f.IU.m a very lhoi'Ough fCVJeW of tbe n:mt edition, {If my book. wdUen by hof-essm M<llli'k J. McCready, a well·koowillexpen. in ch~micale:ngin.ooring edllC~tlC]l:; "If the topics that are neeckd for a g~\'C.n! 'COll!rSe are :Ifidllded in tlrui1~ 1ext, I would expec:t the C(h.!,~atioft~l e!!,Pe:rh:ooe ~.o go. sII)()iOttHy f.or bOl'b stUid.em 3Ildill:'>]mClor. I th:lnk ~ba.t. s~uden.ts will like ~!h~s lbook, beeause the e,xpl.e.natl:o.llli!! :are dear, the level of d~ffk:Ll:hy is a:ppropr:i:l!t~. and the '[!Xrutlpfe5, and mdl'ided data gili'll the book very mu.c;h ofa 'halldbt;)()]('f]avor, I~s:lrUCl.(lrs wnl find ~hal!,. o'!l'e!l1.,dl., the IlOpWcS are p:Fesented ~r1a. logical order and Ine dis.cu.s!i:iol:l makes sense; there are many examplesand ]0(:; of ~I)nrowo[k probr~ms" (Mclliady,. M. J.,. AIChE J", Vol. 49. No, 1, J:'lIIIl,lary 2(03)".

".Each major seeti.on of the booi. ba.~ Weamjng objectives whJc!hi ce.rta.inly ooneffillIreSU!iJdent~ <1indped:J:aps the ~l1Istruc~or,. A i<e;y feature ofthe OOok, which sep<lJr:illlt$ i~. from th.e QI~~r texts mer1t!o!!1ed abo"'~. is the j!)lCo~tionl of M:~lbc,~d fO,f roth c~mIIpl.c :p:roblcms and home-wo.rk q;uestiol1:s. A [j1bI:ary of Mathcad. progmms for :s;o~vingth.e MnwcU-S:~efan ,~qlll!itioms, pi:1cbdC(iIi.imil cakul.atiOj}S~ sJe'Ve-tra), d~igl~l,binlliJi' dis(m~lio~ pW(lb!em~ by M~C:1be·TIlide methud. <'Ind muUifita,ge c~ro5~ij,rre[!t ¢:~UaotlQI:I ls gJ~VCI:I i.li. die appendices. 11lt!sC p:rqgrnfli'l.iSemable 5tlJdel~ls to obtain 'Uselillso:lutiolls with less effort. as well as 8iI1.ow them to eXf)i'pro I~~I diff~flt variebleserperameters, The wide availahiUty, LOWQQst'" and ease of use. of M~~d allow it lu be th~ moo~rn eql!dv!![~t!lt of 'lJac:t, of ~l1e: en, \lel:ope" caJlo~laltioflS:, whleh Ca!liI be refiillcd •. if ncces5a:ry, 1I!sJng ooH·sc.ah:, process simalators" (McCready, 2003).

However, the smnc; rcvrew-s£ alSQ points (lljit some Hmitati(J!1$of thebook.

Of1~ of' t'h.er:n.ain O:b~ti"'cs 'of liPs ~!W ooHh;:m ~stQn:wedy these Shortc.QIlIl,l!l'lgS of the finn editia n ~O' make i!~nro!l"e, Oliu\I'·ac:t.i ve, as 3. te,,!tIXlok to .01. b:roadc;r a!HJj~nce." Allo.:ncr important o~j,ecli.'I'\c, of tih.c seeend OOith:m is toi.tlC'OIpOJllJOO matt;rial rnilll5d ~() mass transfer-pbanomena (ill b]oiog;ical 8y~1!iem!$" Mt:lny chiemh::al et!gh~eedng

xvII

Copyr'ghted rnaleria'

:xvlU

Pndaceto ~liIe Second Ediiiofl

deparru:m::;nts all over ~ihe wo:rld are cJjilangi:ng t!Je:ir nameso and! ,cumc~la toincrn.we the area of bjoeh~mrcal~ng:inc~ri~gif! th~l:r aff¢:rings. The s«(md OiIhi(Jni:ndl1des ~~rti~ [lent examples suchas eonveetlenand di:ffusi,On of o;(-¥gelll through the txKWy'scirc'u~ ~atary5ysteml,. biO"ianllificia:1 kidlJeys,S:f!pOIl!'art,ion of sugars by cnmmaiogmphy,and pll!ificaUoo o:fi!OOn(Jc~k:lnll13:1iU~oodi~ by affi!f!hy ;aodrovpHot),

As Wi.l!h tht'ifint cdilion,. the fi;rst ro1(l;r ehapters of the 0001',; pmS>el]!ta bask framework For amdy:s.is ~hat lSllppli.C8lbJe, to most mass;·tnmsfe,r opcl'ations., CllltptC:l'S :5 to 7 apply this .commofl methodology to the :maly,s]s 31ild des:~gn of oome of the: rno~t poPijlar ~ype~ or ma~~·tmnf,fi;lr:· QpMati,otls, Chapter 5 CO\iicn gas adb:Sf~rpl;ion aad :!ltritpIlrun,g; Olilapter 6 c01liers distm"ltlQI:I; and Chapter 7 OOlr'ers Hquid I!!JI.lroctcio.n. Cha,pter8, new to t!Ile secendeditlcn, COV,(!r£. h:L!Imidffic3tioi"JJ o~i'3!tiol1s illig~nernl,. ill!!d detil:U~ de£i,l;lti of pac::"~~cooU"g lowerS :specifieaUy, These ope~talions~!111 pairtktiila:" ceeling towe[s~a:reye:ry C1.;1ml11l.(HI 1111 ~riIdllslry. A~sQ, fl"(lm ~e, didact:ic:pohH of view., their rumI.ys;is; and dL'l!lI.tn in\ll:l'~vc ~imlll!:rmeQ~!'imMlj~ iUld! bc~t·tmo8,fer eon$iderndQ~~t Theref(}:!!e. ·tM~~r is e,~PQ~ Lit delaU to the simU<!rH.lies and dJiffe.r~ enees between t!1le..se two transport: phellomel1ia. Cbaprer '9,aruso new, co've:rs mass,· tr<ln:s:fer pll.)(:es!>eS Ils[mg bamers (m,(:rnb~t:s) and! SI:l.Jid wrpti,oo. agents (a&of:jp(~on. •. I;Q!l c~<:~haf!g;e, ~ ~I'IlQ8~!lIphy).

IJII. response to' !!uggestiOills by hofess:or .McC:readYIiM mnler te\'1e:W'C1'S,.

SO:me om~, ]evi:>ions and addilioli'l$ to the :sC\'!:o~d edhiQ-iIi'! are;

•. 10 C~apler 1,. tJheMW!w:el.I.~Ste.fim equetiees (augmen.ted by the steady,,~tD1L;l cOllilinuilly equation for eachcom.ponent) are ml.voo numeric.any U§;Ulg a eomb~~atiio!'l!t)h RllIl1g~·K~u~b~ dif'feren.tiaW eqii!lillion solver (Rkftxetf) aM an ulgcbr<l!1c C<)ualion SOIYef' (Give.n··Hnd),. bolb ~ncluded in M:ewthcad. Thi~ mdfuodal.ogy 15 muCh! more fe:dlMstruml the otl!!presenrreci ~f:! 1i:befin,t editlon (orthogona.l ,coUocati.oo), arulits U1e:(,'):ffl~kM justification is well with.in the 5c-ope ofllble iItlMIl;c:[lla~,ical backgm.uoo req!l!I~red fora. fltSlC:():u.JI'S'e in m:i!!iiS~ transfer o,pemtiol:ls.

~ Chapter] inclll<k.s a sect:iOlll. Olil difflisiOfl in. solids,

• Chapl~r 2 j~h~desa se.c;lio[i! Q"oo~rniary~l:ayer. lhoolj'aoo an ex:am'ple on sjmu]tanoous mass and heallJ'al'lS:rerdLllring :ai~ ll'mmidiflcati:o:n.

~. ChaptGr 6i]ld~ It ~(ln(llfl nl1il!ti~slag¢ batoh distHlati.on.

I wish to ad::now~edl~ gtludlL!llly thecol!triblJltiu!'! (if the l1rtiye.rs~ly of Plre.rto Rico lilt Mayagile:i:; to thi5; pjiojcct My !J!tl!iden~ .in '~he courSe INQU4002 revi!!:wed. thetDteMi. til t!l1eboo:k. f'Ollmd quite 01. few crmrs.and g)llve .eJ!cen!'m~ $t1;g.~ ge~tiQIi~ On wa~~IQ i;mpr'o~e its conteetand p.resen:lation ... .My students are. my SQlI~ ,of moli.l!'a,tirur; they make all th~ efQrt ~Q p~~ this~k wortl!i,rwh~I~!

JtI!hne· Bemtcz; Maya~,Pu:e~Q Rico

Copyr'ghtcd rnaleria'

Tbe! .i;mpollta:nce of the rnaS~Hralilis:Je!i Qpeiralt~ons in chemical processes is prorou,nd There is S\C!l!fCC~YUll.y in.dlll::>trial ~~ tmt ~ Mt t'¢.q't!I~l'¢a pn'lLimi!li3!fY' p1!!r.ificatrio.[1 of mw materiaLs or final separation of produts. T.his Is therealm of mass-transfer opo:lrnlil.)![Is" F1equenUy,. the m~jor pa:rt of~he eost of a, process is tnat fOJ Ib.e s:eparutio"-!i:accom,pli:illi!oo. ~rn, 'I,M :m~i5-'tm!Js[~r {~tiQn~" a good. ~!!;~o!"! fQ;f pracessengineers.and desis;mers to master this s:lIIbjcct The mass-trnn:'lfe:r operadons are [;l£gcly thG! respOIrus[bmty of dwmical ellgimoors. bUI jncmas~ngly prnct:~tio:ners of allie~ ,e!l~i~eeritig disLC;~plii1es ~re.findiiiig tbeffi ~~~ for 'tbe:!r work. 'fiiti!!i·i,~ ~pe:-' c,Ia]]y true for d~Qse engaged i.llC:'l1Ivlrolim,ental eDg.in.eering. whe:re~epar'Hi.(lti processes prcdmmlte:tc,,,

My objective ifru writing th1:$~k. is t.Q pPOvide a me8fiS to mach! undcrgrOO!-, !J<'Ile ~he~~ca~ e:!'lgineerirn.g ·~tuWflts tbe basic prlnc,ipie~ OIf mMS tf,an~fe4' a:~dl;Q!fp,ply these pr11l.'C.iples, aided h'ymooem OOI~plll:at~[fn.aJ tools, ~D tiIl.e desiign ofeq1:dpmenl used j~ ~i.of!~$~s. 'The, fdcafQr it WIIS, bomQut. Qf!Il_Y '~)\perielnce:;; dUri!l!g the last 25 y,ean;:rea.ching mOliss",tTan:'Jfew (lperat:i.OflSC01!!lSeSEll t~eIJn~v,ersity of Puerto .Rico.

'th¢ma.t.cri,aI. ti'¢.iltt:di~ ~h~ book t':ilffilb~ (:(lI\l'~~~O ,a O!l~,"i!r;~SIt;:rCOli~l\;, Chapte:rs are di~ ~mo sections w:ilhc~elldy stated objootlJ~s at ll:Le begimdng. Nl!Ime'rO~sdetaiill;:d ell,ample'S foHow each bri.ef section of t1!(Xil.. AbU!ndan:1 end,.of" chapt.erpr6bl.em~,a~ ~~duded, IllldpoobLem. d¢g~of difficulty ls c:.l~lyl,a:reledf:Qr cae!'t Most of nil,':· prob~C!i!J~ are acco:mpa<nicd by their answers, C'om.pl.!ltcr ~rol.'l.Ilt~ol1 is empltasflied. lbeth in the e_~amlplesal1d in lne end.of-cha:pler problerns, The book uses mostly $] lIlli~s, whiiCih "(ritual.ly ~l~mlinates the: (rutiGus: task af l:!lrut oon"''e:rsions am!1 m'al\iel'l, it "'._readlable" 1m ti:le :inl:eIo<lli,o,tla[ sei.e:IlIHfic and ~eCJl]rli,eal oD.mmuniilY"

FaUoY>'ing the lead of othc,r 1l.1Idm~.sin. the chemical '~nglOO¢rin&ficld :and related. tectmkD~ dlsdp]ine:s,. I decided 1(1)0 mcoq::tOl'3lC tOO use of Math:cad iflto tlti!;:

I:loo"k •. Mi)~1 reader~ win probably lm::ve ;i,worUn.!,!: k:now]edge of MailicoW. (Even ~f the:)' doml"l,lny experience [s that the; basic li:;now~edge n~eded tQ beg I"' IlSlt1.g M:ath.cad c;ffecd'l'cly Cru1, ibccas]]yt9JllJ:ghr: in. .EI twoAu:rur wQrb~op .. ) The use of Mathcadi shl1pillifies mas!l~'I:nms:fer c-41C'u]atiQIlS to a point U1:lt it allows the inslmctctl:" amd ~he ,stude:rU to reooily try ma,my diffe~ent comb.ilrlati'ons afth.e designv:ariablies, :Ell vilal experience for the amalelH'de5~gner.

Th~ M.athcad efiv~OOfimen,t can be u(Oed a!O ·iiJ. sopili:>til¢iltOO :$(:ieIiJtific ,e;iIlcI,dii-' tOft can be ~i~); P!'(}gt4'med to perlOm'ia ,com.plka~ed seq~lice of cal.culatlollS (for e~xantp]e. ~.O ,eillecklbe design .of a. sieve-plate c.tih;lmr. for f1O('1(1:ing" ~SSlt!"e drop, cntrainment, w~eping,and 'ca]c~l:3!ti:!l8, M~h:r¢¢ pl,al.¢ ,r;:ffit;:i~~ci¢s.). {:!!i!'l b~ ~fSed to j;l~'ot resL!lIi:$, anda~ ;,l! wQrd p~-soorto !:l~<lt!lyp.eSWIt :h.Qmeworli; problems. MnthcmJ C;l!'! perRm:n ~;!~(;!l!I<lll~@n1> uS~!1Iga vnr.iety olT'urnlit: systems, a!ild will give a wac;ning s:ignat 'W~I.e:tl. caJllclillillftiQn~. thai are not di!itle!Wskll'lal1yc¢)t'!:!i,j~e!tlt .~lrit;:d, This ,is a most

XiX

Copyr'ghtcd rnaleria'

xxii

liE' E,M~ E

,M(;

EM(il):

Eo EOG

"iI'2~

J

f i:

F

.F F F

- 11

l!'RU)

,PRJ'" f.r . _"l,

(;:11

G,M OID

0;'.

a' ir

G.

lfi

Orp

(Jirn (i:z

'H

R.r::

H

H

H

H~

HErrS,

Nomenclature

e'J:tracti.on factor ddi!ned Jn equ3li,on (7.19),; d:ime:l!ision~ess"

Morp!;u;tc; 5Ui$cfficie.!l_£,Y j[l ~rnt." (If e;!(tiactoom_JOs~ti01l!~ dl~5.jo!'!~!l. Murphree gas·plilose w.ay e:ffi.c:ierl,cy; dimensionLess •.

Murphree gaSi'iPmase uay oeffidency oorrocl@d for emtrammell!l. Q'itemU U'~ emc~ie!'!cy ora ca!l(:ade;;eqJ,}ilibfi~m traysireaL tra:y~, !point gas·,I1Ii1,a,se 1m, cffic;ieiu:y; diimcllsiQn]e!ls.

proponion.n1i:ly coc4'fici~11!1 in cquaion O,~2l).

friCti.Olt factru';: di:mensiomles:s"

:fracHQ:rl'aJ approo,cc}] ((I "(Joeli'IIS 've]oci.ty; d:imensiGlIIles!!:. fractional eXltraotio.l!I; dimerrusiomcss ..

mass;~traru.fct C()C'ffic:iGi1t;. mcil!m,z~,.

molar flow tate of tHe feed to a d:~sHna'l:iolil oohtmn;. ,molts . mass (IQWral,e of the feed loa, liquid ,~tracti{)!}! process; kgI"!!" pru;iCil1g factor; n-~,

fr~fkmal JeQQVe:ry of QQ.mpcm.~nt i la tlJ,e disdllate,; d:i~nsi.O-I1]ess, fractionW ~ovel)' of compon.mt. lin tile res.idue; di.me:nsloniless. Jjql.dd. rroud~ n~mber: dim¢flsiofil~58;.

GalUw numbe., dim.ells~on:le~8.

:superficiaL I]I(Jbr veilochy; mo.l!m~-s ...

:supe,mciaL 1iqllkt·pb~ tnOlar v~LQC;ity; mo1tm2.'~, ~Y1pcrft~dalga\l·iPhu~ :m.ollarr vc1odity; H1oI1mLs" :supemdDL Uquid"mM5 'YclocJtt.y; kglm:l-s, .. supediicm g.as.mass\'clodly;. k.gtm.il~$.

CiWil;Shof tlU~ for mass U:aliblfew::dim.cns:icmlcs5i. u~a:i<l:Lafrlum.beil" fot heat tra:ns:fer; dlim~ll!$i()ll~~SS. Gra'SlZ Dumber.;. dimens:.i(Ulliess.

;ac..-celewatioo dl,l~ to gravity; 9J! mfs2,

dime.nsi.ona~ ,oOllyerskm factor: 1 kg~nVN"s~. Hruuy's law constann :aLm, kPIl,Pa. mowenrh:ilp.y; Jlnl(lt

he~ght of mixing vessel; m.

en.thapl.y Q:f~vapor m:ixrure;Jlkg ..

:height eq~ufval.oot 00 a !l!bw.reti'cal: stag(,il'l fota:gcd ]~qlIjd COCU"aOtiOl1! ooh.linms:;m.

beavy.l.ceyo(itn,p(ini!!),liI! mul1io()~nen1: di~tillatiol'!, :h~liJt {if ,oolu.tiorn;. J~m.ol: ·of 501,utiJolI!.

height of a liquid-phase tralilsfer lI:n~t~ m,

:he'Jght of a ga:s,phase tmes:fer uni,t; m,

Q!v~rol~ ~~gh.t of a g,$-p~ IDl1lsfet yni,t:, ;m, QV~f@U h~~g"ht of al:iq~d.d.!p]liiIse t.mnsferlmlt; m .. convectiv.e' EleDt·tta:nuer coefficic.nt. W/ml..K .. dry.tra.y head l!t;)ss:; em of liquid.

IItqlJh'wefJIl '1:Iead (If clear nqlll~id (jill tray.;. em of ~iq;liIld.

Copyr'ghtcd rnaleria'

N'ome:ncllature

xxiii

Jo, J •. K

K K

K"fJ Kif ,r.:..

k

I~

kl.'

sP'§c~,ific, liq~id .h,oM;"p. m.~hQldl.l!p/:m~ :p~ck:edbed. totil:l. headl,Qsslilmy;, em of ~i.qilld.

wekh.ei,sht; m,

~cu~.:!d ll}s~ d:ue I~ s~rfae.e letf);!iiot!;GHl of liquid. height of l1;V~phase reglolll 01il3, tray~ Ul',

number of d:lmr.ln.s.i,alli~ss groups .Il:ood~ to ooseribc a. s~rll<1tion. Chlih.on-C-o]bufIl j-faelurf:orl!it3Ss tr.atlsfer;. J:imellSiOI!i~ess. eh~~ton.cOnll~m j"',filctQr for heat ~rnnsfer:; di,meml,ionless"

milll~ diffi!l~ku:J! flux of 5P~EieS iwirh [eS~llQ tbef!1Bl'l$"<l!~'£::

V.'.'C. ]<V"'., - iil.v. ;,. k ... ·.'.m~s ..

~!1_.)'~_,~L''''.L _

mola:r dmllSi,oJI fl!U;:Ii of species i willJirespec't 10 ~hemo!!ir"a'\!e:Jilge "'~:locil:y; molfni2;_s,

Besse] ruJltlkm ofthe first lGnd!arnd order zero; dimensioo~e,ss. Besse] fu:nctiorll of the first kindSiltd o.rderone; d!imc!IlSl'O.n1ess. distribmiomc08md.~t; dimclilsfon.less.

IMogl:l d]ffU:SIOI1 coof-r.c:~IiI!I; Clilll~ OLfCm"iS"10rt. parnrncter .inL<ll:l~,U~,r adsorption ~-sallictm;. Pa:-I.

molar SGI~cu vity iPar,mttter~ll!icm e(lI:;cn:lil:lge~ dilmer!s~onle8s.

w~l]I fa~lm' ill! Billet-Seh~l,te!> pre:!J~nl're-drop crl:n:elalions~ d~meills·ion[ess. tliIermar condm::ti;vit.y, W/m-K.

C(j1i'i¥Gltl:hoi~ miiSs-l!1Uisfcr (:,oofideot fOT dirfusion (If ,A, tihrough 8~~fla![ll B I~ d.ililte 8~p~;;e s.o:li.ni.OlI w±th. d:riv.ing force in terms of mciJa. concel'll'mtions;. :ml:s.

convt:cti"le Jtl8s..H~m~f¢r iI;;-ooffidr;l!:!t fUl cq!)~mol!!'!.r ¢O~I!1~cmiffys~on liD g!)~ ph~~e ~soll)!do,n with driving, :lOIQ!;' ln terms oil" mo]ar'oon:O!l1tratiO"n:s;.mls. coill¥ecti.¥e mas&'lmnsfer <X'Ieiffldcl'It for diftUiskm. of Alhrou.g~. St:ag~13fit B illil d]lUrte ga:rph~~ solution wilh dtlviI!g :fooce in terms of pald,d pfe'Si'!Ure;. mQI/IIill~-8-P~.

ovemU oonvectiv,e m8SS·tmns£cr C('J(lffi.cicot t'm diftlls~o!'!()f A~l]gh s~.aglilant lB in clHru~e SOIIl(I(lHSw:illidrl."'hilg:~ h:l terms· of partial preSSIU[CS~ lJIo]lm2·"!'r·Pa.

ctmvecti.'!llc mas~Hfllll~fcr iIXlClffid~!u foJ' eql;Jlmo']ar,c~tcro.iffus±(In ~n gas.pih0i5e ~$()I.1!ltkm.whh drivlng force: in te:mrus of (lEIn~BI~ presflliIre;

m()lfm2~~~Pa.

eonvective maslrtran~fer iCQ(:ifflcKl:lt fQr,aifflJl,~ioJl. of Alhtmlgh ~]agm!:;IIU B m. d]httc liqujd.phrnse: ~llIJtiO!mwith dri"dn,g fOI-allll terms o:fmolru conoel1l:r.U!OI!$~;mfs"

ronvective- mOl!iS4r3nsfer coef!fident fQJ ,equimo~aif cOliJn~e!:diffullii!o~ [n I;~qruid-'pha!le! ~ollltit:mlwjthd!rivLng force i.rn.I~Il11S· ofmo]iu oo!J:lcelllrnt~ons~ mi5:,

Kmud!;enlnl!lmoor, ,diimensl0nrJesi.

:re.a~tiqJl tale ,oornst:a:lllt; linoVm~'-s" mgl~ ftil~U(ID,

Copyr'ghtcd rnaleria'

xxliY

K

--'{'

k

,~

k

Y'

L, L L LK

l·s l...'"

Ls" LO?:

L ... ,

i

J

11.'1 Le

M,~ Mo MTZ

Nomenclature

re~1ncUve faCIl}F f(lr diffusioli! of H'qiujdsin [pQ!XIUS :sQI,idS;, dimension~l1iss. oo~;ve(:li ve mass·;trnrls(cr oooffkie;nt fOJ d:iffusii(lrn of ,I+. tltrou~ SIa,g,llUImll B ill! dilute IlqluM"ph.ais:c sdru:tioll wi.th drlyj]lg fOfCe: ill terms of rnlO're fracriou; moV:m~,

(l\l€;r.lU oon\liecti!,i'ema~$Ht:.msfer (looffide<!1t :for diffij~oo of A tMou~ stagruwt B hI, dl~Ule: c!iOhuiinns wim, driY,ing [moe ]0 terms ofHqlli.d~,ph.ase ro0/1ar fmcLl()ru;,~ mollm'L;s.

(lOlflrvective~·;tr~fer ,m)e;f11Cie:nt for ~:l1~01(llar ,COil mteroif1ful:s:i on in liqui<f..p,b!aiSe so~u;tion Willi driv:tlil,g fQroe in terms ,af:mol!e fracti\lns;, Q1oMmZ=s.

'CO!1!rVe.;:tJr'i"em~s"h~ .. fer coeffiJci,en,t fer diffusion of A through, ~stil\gnallt B ~n dilute iSRs9J>hase sQhlltfuonlw1~h driv~ng force in terms of mole frn,cti01ls; mol/m~,

orvc:mU eonvcctlve mas:s·,]mll~f'cfcoem~l,~n,t far diffusion gf A throu,gn :>U1gna:rl,t ,B in. dilute solut'tOR'S withl driving fOl1Ce, jm, terms orgas-phase molarfracti.ons; Ulol!m1~~,

oOQflIrvcedy¢ mass··U<lflsfet cQefflci.en~; f:0( Clqu:imo.lar c(lll.m:l.e.rdiffu:!iion ,if.l gaslph!ai&C SO]11110111 w.illl. drlvlliIg force in terms of mole fnu:tiOlrls;

moltmZ=s .

.cha~te1iis~:ic lengtl!. m,

molar How ~ale on~e, upnase,; molls, rnength of sClttiing v~ssc];. m.

1i8mJt·!Io!ey co mp<loontin nlJIliiticornpolJeot dliM.iJj~tioll,

mo.lar flow I!'ale anne noooiffl:ls:~l'Ig so~ ... entiin t[i}e' upbase;.mol\ls. mass flo", rat-e ef ~e L-phase:k:gls,.

mass fivw tIlte oft:i1e n()IIdiffu~~g solvent inthe L-p~, kg/so ,efJlfa~nJmemma .. s flowrate,.kgls ...

weir .lengtlJ; m.

cbam.c~riS'l:ic: ]~ngtb~ ru,

tray i1iclme~!i; m.

membrane, ~~C:k:ness; m.

Lewis n,1;!meet;. dilDemlon~ess:,

moJcclilu we~gh.t of SfiC"ies L

.... ' .. 1i""e .. ' "'- ... """~ .. , "m3 O' I .. fC'm3c rr;,"-

'IIJI'4J'~" I,~ Ut: .• ~!hI.IlI~" ~I I r "I j:" " ,', ""uJiIFt.

width of'~¢~il$S·t~:i1fer ~Q!le i.n.f:ixed"bed adwl'pti~m,. m .amQUnt ·ofm.a55;.k;g:.

slope oitllc equ1lihrium.dislriblllltiolrl curv~; diffiCn:o;jQolC$$·, to1al mass nux w.ith respect tQfixed cooro]nm~s; li::_g1m2"6,

ID!;l!S!! t!:Y:;I:;, 0:[ !l;~ote!l i with ~e~pect l'Oifiy;ed COOOO~I1ia1les; kglm~'.s.

number of varia!biies sigllHic3nt lO di~ciFI5<]Qna1.aooly~i$ IQf ~give.n, p,roblc:m. rat£: of masSl!I':a:nSfet fn>m the di.speIWdto tHe continucus phase

hl liquid e:r.;,tfacth;1mkgls.

n~;n;Ibe;r O'f spec[esin a. mixtl!l:re.

Copyr'ghted rnaleria'

Nomenclat.ure

.X;Qr

p~ Pi PB,M

P

P p

Pc

. Pep

Pe" :PI' Po Pr Q Q Q

q

q

e; r

r;.. R R R .R R .... R

III

Re

~mal molar nl!2.X wiith~pect to fixed coordinates; mo!liRl2·s. mola.tfh:lx. off species ~. whhrespect 10 f!!Xed. coo;l'diiltiBles; mol'jm:!,s. !:urnmbcr of '~lJnibril!Jrn5t!l!g,t:l! ill a casc~; di_men5Jo!1!1~~,

mess of Bt,(mass of A. + mass of C) in die. CJi:!H:act liqili!i~s.

numbet of stages in.rectiCYil1!g, section; d~mens:ionless, ..

mass of BI(mass of A,.. mass of C) ~:nllbe raffirmte Hq.uhJs,

rnmmbcr of sta,g,es Ia sldpp.ing seotfo[l~ di:melilsio:nkss.

mllmbcr of~rqjuid'!pbllsc UOI1!sfcr 1J1l!~1:S; di:mcmstcml~s.

number.of g;l£-phase tr.1t1s:tfJfU:fI.llS: dimenstonless,

I)\i~ra]rn f1~!mber of (H!i:pe~·]:lb;a.~ tW<l!nf;f:er UllilS~ diimensoi.ordess. orveralrn number of gas-phase U'IUlSflH' [IfJ!its; djmernsj,Q1lT~-Ils. Qver.llrn nu:mberof lIquid-phase tran~f.er iLudts:; dimJ!!n5li(l!J!less~ Nusse,U !'lU!!I!lben dime:nsi.onle5:s.

Imola:r' Qxyge,n cont.'el:lll1:ation lin tbe all: lealo'.img an aeratiQI:'ILl!!nk:peroellJ.t... Ol(Sgc~. ttMlsfc!" 'li:ffici.¢,!lcy~ IDmlS of !lJ:ili:ygc;n absorbed lily water/total .. I1laSS of 01{yg:e~ SliJppUed

pl:ltl:h., di:SIa;nce, between centers o:ftperforntiOiI!i.in a :sleve plate; m, pillilht~lpre$\li,i!I'e~ (If ~;pedes i; ;ij,Lm, .Pa,kPa., blUr.

lio,gacith:mic mean partial pressuse ofco.mpollcnt H;. a.tm,Pa, kPa, bar. totalpressere; atm, .. Pa,kPa, bar,

permeate Aorw' thrQllgh:a m¢mb!'af!¢;.m.QV~~ .ili!ilpcl~~fPQ~r, ~W,

c..n.u.c"ru pre~surc" Pa, kPa, b.w. Pec;let 1l;l:lmboe'J far mass transfer . Pecl~ number fOf hem. U:,a!l~fef.

Vllpt.JI prcSSUin:, of spc:cjc:-s i;.£lLm •. Pa, kP.1lJ, bar.

power nu.mber definediin equOtiOOl (7-3'7);di:mcn~kl!:'1J~s, Prand!tlJlumber; .(jUw!etlsiol!le~".

¥OlllmelJk now :late. m)/;o;.

net .ra~c of !heating; J/s.

membrane permeml.oe~~ mrs,

memo:r<lJle, Fnneahl~lity~ b!lrn'er, mll:s.

pararnell.!:r· defined by equatiQ);! (6-2.7); dim¢n,_~io~~~~~~. parameter ill Lall,giITIu.1r adsorptkm lsomerm; gig. tank. of lh.ed!irnen'iiomil matrix,. DM:; djme~si.on~ess .. w[u!l~~p.ani.cleradkls; l'Il,

radillS; m.

hleal ga'S CQ!1SUtQ;t;: Jlmol&.K_

renwx. r;uID; mo1es ofref];lilx!mo]es ef distjmall!:, raffinate mEIi5!if:iJ!owrate: kgls .

vcih:l~C: fate of fO.l'l'IiI!alUQ[I ·of A:moles per·tmit voiume- pe!' llI0il time, tetentareflow In a mem.'dl:ra:ne';.rnolJs.

ReYIi!.d~ds rr1llmber;. dimemian]ess.

Copyr·ghtcd rnaleria'

Hi '\i'o]umetne raw of-formation o.fcom:PO!letlt i;. mol1:m"'-s.

S f>u.rt:ace .area.(::ross·,~]onala.rea; m.~,

S stripp.ing f3c,10r. reciprocal of abi§()~JI1:iQn f:actor (/t}i. djtnen~i<mru~ss.

S ntiI.'l:i> flow ralC of th$. SQ1v~nt ent¢rl~Ig a li.quid ~;\~tionpFOCCSS; kg!s.,

Sc Scbm:id~ number; dimensineless,

Sill Sherwood number.; dimemslorn.less.

SR sahr¢:lecdQ1iI:; dime!!'!!'lKm.less;,

S,tD Stanton !i!11,:!m!berfu.r m<1iSS tmrusfuI~ m:m.c{l~loI11css.

StH SWIlWD rlumlberiEorhelli tmnsfe.r;. diim.e-miQnless"

.t tray spacing; m, .

. 1 il!hnc~5. hr,

J~ breflktruolilglrulime, in. fI.:·;.cd.:ood ad$orption~$,

«; :lieSidcnoo time; m1F!,

T ~e;mper.m.l're;. K,

T~ adlabatic saltl!aticm t.emperntuu:~ K.

i'-:.:.Qi

Tb :It011li'Iill Imil:ing point t¢mpcr.(l!1Jure~ K.

T~ critica] (e:mpenllut;':, K.

T~, wel,··:btJJ!b te.mpernlm:e:. K..

u fluidvdod1!.y p~t. ill. i!iUltioli'lfil:'yfi1lit pl.!lJe, paraUcl to the M.!rtace;miS.,

v mass-average \iielocLty For mll!IHomJJ:ponernltrniiXliilre~ .mls.

'Vi "'elocily of !lpeci~'i i; mls.

~l tennimd \Ieilocity (If a ~ni.(OI¢:; nlls ..

V' mow-aJ\i'ero-,ge vcl.oc~ly for m:uUioompo.nent mixt.l:lre;mls~

V vQ[ll!me~ .mJ .•.

'V molar fl()w :rateoftlile V~phase,; mol.e:w:fi,

V~ molar now i!'M.c chic fI(l!Jildiffi1.:!:~.i:lilg OO]VCIiliI: in tile V~plilase;lnol!eS'ii,

'\I' mass fiQwrOl!te of the V~p:hnse;. k.g/s,

'V;{ massfiowra,te of the ool!i.diffusing ~!)I\1l1!m ill! the v .. phase, .kgls.

V" molar v,()IIlIrt\$ <lh ilO~I,lI~~ .a;~. Hqulidat il!'> ~I.oomrlg

pgi;nl;cm}/mol

'Vll ooH1!Ip.mtio; moles ofbolilJupJm.olu$ <)iJ~irl!l~,

Vi> molar YUllllIme ufa Sltlbswnce as llqeld :at its IlOrmalboiJilJig point; ·cmll:mQl.

Vo:' ctit~ca!: voh,:utLe; cm,3fmciL

W rDass,,!I1ow rate:; tgl.s.

W wo:rk.~( unit. mass;. Jlkg,.

W rool<U' flow [!'.a:1eonl:!e :resh:tllletimm a distiHauom. co1umIl:; moll's.

We Wcboe~mllm'bef'denned :h~ ·equation tI-49)~ dlme!lJls:1Qn,les5.

x, mole fmc,11ionl of ~c:ie.') i il'l!eith.c,r liquid Oli' so]~ phase.

Xi ma's:'lfmctiQ~ of species i i!Ji ra!ffina.te ([[quid ,e..xtractThcm).

xB,M' I,ogarithmic mean mulefrec~ion of com:po~tiB, ~!iI liquid Of solldphase,

x roo!artgnlllIco<:nrlimlJt~,

,t" mass of Cimass of A b~1 raffinate ~iqu:ids •.

X m(llle r:a~io 1[1 phase L:. moles of AlmoJI.'l of A-froe L.

Copyr'ghtcd rnaleria'

1

Fundamentals of

Mass 'Transfer

1.1 IINTRODIJCTtO:N

When aJ ~y~t~m ,eootm_L1l5 two or mom com.pt>ne!)ts wbcse ()o~~lJtmrtiof]!s vary immpolitlt to (Xlinm:, thereis OJ. na11l!r.1l tende:n.cyf(W l[UlS.:.'5 to be ~5fe:<Ted~ RlJ!iI!imm,;o:ing th~corn::e!l!u.nlio[l differences w~ltn~l'l the system amd m,o'ii'~,ng i:lltOwaros eqailibrilum. Tfue tmnspo'rt of Qne eompunent fro:m a regi,Q:n (If hi!!!l~r c .... ncellnat~on 1[0 th~[ ofa Lowe:! OOl!ceir!tra~jo[ilJ~S called mass transfer"

,M!lifl.]( of ou.r daily e~!perJeonoes involve masi'Hr:arnfe:r phenemeaa Theinvi!l~ orat~n8 81Qma of:3i CUP' ef Fr:@sh.1y h~wed coff~flalild tilil~ sensuous scent ofa del:icatt'l ptnu:rnc ~othreac;h oornoslrii[s from the seurce by dllffusion througb ,ai,r., ,/\ hmtp or :sugEir addOO to tille cup ,of coffee: Ci\!'c:n,tua][y dissolves aJIld then d!ifWse;s l.mjformly 'librou:gfuollttbe oo¥era£)e. Laundry h3illlging nn.dl.1:r ~he :SUiIru du.ring a breezy day dries fasllxlcau~e: the ffiQj:i<ty~e eVaipo:moof,l and diffli.!~ ~r:!~jb'into th~ ~]:u~v~ly dry molViiflg air;

Mass transfer p]ays inn jm:~rtant role In man.y industrialprocesses. A group 6f oper;a;~ion~ for separating the aompc.]lcm'lts of n1iXlllircs iJs baed on ~:ne; transfer of :maler.ial [rom one bomog,eneotl:s phMe to a:n,Qtille .... These 1:I1er!!liloos-co,ve:red ray lir..e term m(U:Hrnn~/i!r ,opftratlt.in:s-incll:.~ sllclil tecihniq;u.e.s as d!isliUation, ga:sabsorp~!)it, lriilmidific'.1Jt~Qfi, liquid ex,ttactiOi:i~a~OJtitiQ]i •. membmne sep:ll'ations, ami Cltffiieni. The, dJriving. force for tra1f1sfer ill these Qpemi.on~, is a ,o(:ni¢eli,ltiUiot! gradie!tf.m~ch .r~ a tempem~u~ gradient pl<)vicl~ th¢ drlv.ing force !for heat: transfe·!:

DiJ#limrQIl~cfMat~, byp~rtial'\o1!poriz.atio!1!,. ~. li.qjuid mj~JJjJreQfmi~~ible WI~ vo:J..tUe sabstances i!!JW lndlvidual 'cQmpo;r!~~i~Qr;. ~11J!!igme cases, 1l'llQ grqU:pil (If eerapenems, The sepa:mtiolil .of.<II mh;tll::lI:e of ~nel~a,rno\l and '\o¥ai:eif ~nt~ ~;i:S CQ:mp{J!lenit~., of Irqu.id 3Jrinto U1<Iyge:n. rI]tn)'.gen. and argon; .:Jind of ,cr,lIIde: petro]e;um in,lo gasQ~~nc. kero~n¢. tu¢l(1U, l3iIId lUifuricaltl:!'lg S1Q(l\: .a.te: c:l(ample;s Q.fdistill.a:UDIl.

11

Copyr'ghted rnaleria'

2

FundamBlilmlsof IMlass Transfer

Ing(J,l anforpfion a ~olrl!lb]e vaPQr isab8'oroed by_:ms of a.liqllid ~!l wihicllil the: solute gas ls more or less soll~b]e'. from it~ ltIi~,h:l!ro w.llth an .i:ll.crt gas •. The wa:shLf!g '~)famLmonlia f:l1l)rna mil:ture oifammOllJla and! air b~ means ofliqllldi water isa wpka"l !l){"!lIf~e.The solute is sJUbsequenr!:lyreoo:'I'Gred from the liqjuid. by d!istmliltl.oll.and the absol1Ding ]iq!!l~c:I can be eidter' discarded or re~%d. When a rolrl!~ei~ ~ta!lsferred from [ht~Ql venit liquid LO l1Ie: ,gas phase. the opcr;at~on is krioWIl as desorption Oil' ,:rl'ripl'in.g.

[[I IJUmidijioatiQ.n or dehumidification (depanrlrnng Mpon .tru! direotion of U'an!>~ fe,r)11:ie ~Iiq,uiu! p]lase is a pure liquid cClJ!t:llning but ~. (:ornpOl1el1t whi]e d\egas, phase com;ains t:\I,:'O OT.' more sl!lb!S<taflC:~s. UsulIlly litiU;:' inen OJ carrier gM isv:irl,llIaUy ]Ilsolu~b.le ~it th<i ]iqi,i.~d"R(l:mjjv8,1 'of Wacttr vapor f['Q1n air by (iOndensatklii 011 a cold $url'(ioe. and the c.o:ndc!J8:atit)ll of all QJ8i1!:i!!c Va?;:!!; sL!lC~ as ~!i! te~blori:de Otit ,of a s.treOOl of nitregen are ex:a:mpk"s o~' ,deh.umid:ificatioll. In hUJ:rmdification operart.ions ~fle direction of t~rn3f~~ ~s froln tlil~ Hqr~id to Ul~ g:ol!S p.b~~,

The (ld,n:!rptiQ,tz"l~mtion8C~plQh the aMi.ty of cert a in solids p~cfl;renti,i1iUy to eonccmrate spcdfi.cflubfltanccs from sohni0':Il olltoth.eir iSlum:aces" .~:n. this mann.er,. tl1ecompollent.'l of eillher gaseous Of liqlJll.d solrLltL{ms C3!il :00 :separated from each ,olllilc.: ,A few lel'ii.a!miPl¢~ W~IU ,i~l~stf~re the swat v~rr~I:Y (If.'proc~tJic;;lW applici!lti,O\m~ oJadsarpliol1. It ~s, 1:l~.1D dehuimidify a:lrtlOO lOme .. gElSC.s, to remove oojoclionablb OOornlm.d .impu~ rill.!.';1> from. industtial g3se~, to£OCcO,"c:r v.ahtabllll ;sol\'l!nl vapors from rull)t~ mix:l'~s wjth !IiI' artd olhet g;}~e~. ~o reooYve ();ltljecti():r!ab~e W:tea~~ ()(lIar from drink:ing w~~e[,. and mm.l)' otherapp]i.rcati.om,

Liquiii ulf;at,:;U(mis th'l': separntion 'of !he Cl)moti.Fne~:U$ of~ llqui.d :lo]utiQ!!! by (.'()]It,:u;:t w~lh rul()lller ]tlsoiU:MeliqlJi\(t~f the sljJb~l:<linre:s ooflS!HnHing tl1e ongi.mll ~il.l:I· II:km di;snibute themsely;es di ffereIlUybel.wee:n. t!ile t'OVO ]~u,id phases, a ,c;e!litaii:a degree of ,S)eparati.ofll will "csldlLTliIe ,s(]~u;liOrl whkfi i:~ to be ¢cXJttacltld is called thc,/eed,and Ilhe ]i.qllid w.ith \liihieh th.e feed i~ COIl!I:K:~ed jj~ codlled the sol'>''fJm. The SQmve;n,t':.rkh prodi)lt.~ of the ope,r,uio'l] ~!l caUe(l theeNtroct. and the resi.dll!M Hqjuid from whicJlI the selute has been removedis cslled th,e fdjftJUJJ'(I/,.

Meln/Jf-ane se,porutions I~ rnpid!ty j[lc~~l1!g in impomulce.. lngellcral. ~be membrn!le~ ~erve to ,prev,e!1lt j;nte~rmiiTilgl.ing of itrWo uusc]ble phases. They rum p.reve~nt omimu')' hyd!rodiYiAami,c flow, and movement of SUM~"'l.ces tllmugb them is by diffll~ sion, Sepoa:ratio:n of lbe oompo,ne.nM of l:he original ~.o]t!tI,o:nl:ak.e.~ :p.lace, by selecliVleJ],y oo~tromn;, th,c~i!" :p.1ssa,S~ from (line side of IID.e, .I:nembran.e eo th~ other. An t:-!Xamp[~ of amemlo,rane.mediall~(t,liquid-]~q;u:id seprnatio:ti pj;'{Xess: ~$ ,d)YJ/isis. 10 [his !proc¢ss~a colloid i!!i$moY~ f'!!(Inta i~q~id ool~~i(i!,! by cQlI~ac(i"lS tile soh!!ltiion wlth a solvent tbl'ougli illJi jtll~riie;njll'l,g rri.c:rtibralie, wiltliclil :is permeJble~olhe: selutien but not. to the La.:rgc~ CQUoiilil1l.pmti.cks, FOr c~amp]e.aq:ueoos bcc,u.:stlgH solutions col1Jt.n.ining u:ruJ~ :si.redco]loidal mate:ria~1 are freed of the laue. by eonsact w~th wa:1.'eT thoo1!lgba semi~ pewle~b~:¢ fnembr~.n~. Sug!l.rand. Wruel; <.Ii f~i,!~lbT!(fljgll d.e iIlWmhmrn.e tn~t not, ~he, 001- IQ]~.

Copyr'ghtcd rnaleria'

11.2. IMolecular Mass Trans,fer

3

R.e1uming to lfue tum:pof Sllg,a:r :added u) the cup of ooffee;, iJt: ~s. ·e:'Ii'.ident (h!n tb_e timJ.1:requ~red fur (he ~l,:Igar to d[!l~noote iUllifo:rrnJ;y d~pend:~ l!.]JQn whI,Hili'le:r 1E1I~ ~iq~ wid [s ql!..i.esccJJlt o.r whether it is :mec,1umklllly agllated by a spoen, 1 .. gene.aJ, the .mechanism £If msss transfer d:epel1ds: 'L!Ipon the dynamicis of tile sY!item in whiich ]t ()(CU~, Ma:!l~ cantle (ra1!i!il~~d b¥ mndoffl! m(llec!l],aj'm.Qdo~ ilt quj~fl!t.fljlliids,. or ]t can, be, tran!!lferred ironI II. surfaee inte a mo'Ving f!l~i.d, aidCci by the, dy.rlamic, cl:llltilciUMisticsof tM. flow: Th:(lsr. two dis,unct.m.odes oftransport, t11'ole,c-uiar mass trd'luJttr :::md (:lm!Fcctive mMs tranrfe.r., .. are analogous tQ conduction. he::n 1:rlm&fcl" :md eenveetiive healt (:ransfer. Each ·of these m(lde.s of mas~. tmrls(er wi]] 00 desc~ribed aLnd a;1:I0I]y.~ed. The t'i'l'"'O ~h.mIjs:m.s ofton a.c~ s~m{lh.lII:1:eotl~~I.y. Freq,IL!lc<ntlly, wb.cn Otls happens. OtiEirnec!mruSm ,can dbminat_(;) qtl:lntil:ati\'elY:iO that: app.ooxim!llte so.hulOIlS lnvdJvll1g Oll~;Y the domilnantmode can be ii!I!led .•.

1.2 MIOLECUILAIR.IMASS lRANS'FER

kiea.:!'ly ~ 18 ~$ t~ was Oihs:e:rved qu:alitad.vel:y ~!hllt: whenever a g,as mixture conta1ns tw·o or morem.o~eciLi.la~spedes. who&erelali~'e; OOncJtll:l:ii:'.1IIli,Q,il8 viU}' ft{)m point topoint, un alP~ntJ]y natll!ral process results \yhkh rena:s to. dilimrnlsh amy ~1)e-q!laJiti!~$ i~ COlinpt)$ftiQn, T.!t:is maercscopic transport of mass, independent ofa~y cOrl"'eoeti.on effects: within ~~e ,~Y!ltem. i~ def!!!!oo as J:rr,ql¢cr~!{~r dif/u$i().tt"

:~I'I tbe; .specific case, af a gaseo~m~!l.t!L!I,e,lIlog~calex,p~alMlliion of ~~;5 tfllJlliJ.l()rt ph~!lQm.CMI! 'elm ~ dedtllJedf«,m. the. kinet.:ic theory of gases ... Al:my tempcil'OIwrc aoove absol.ute ze~ro~i:nd:h;jdua..l mO~eCil.l~e$ ate in a state of contin!lIal y~lmndQm !llQttOI1,. Within I.m~teigas :m~XLli. .. es, each solu~e rooleclll~e be.bave~ ~liIdepe:ndc:!U. ~'fWi):

Q~bC[80i~tc molcctdc..~, ~moo it ~cJdo._m CiHCOIlf!ters tlu~m. COI~lsio:ns,bc~ween the SOillQle <Iud the isoiw.at molecules are ,eontilill!!ailb'occumn.g" As. ,8. resllIlt, qfth.e comsiolls. :the. soiu]e rnol.oclilesmo'l'e a[{mg os: zi8zag path, wmetiTnes rowmtd,~ !!egi(l]"! of t![gher,cl,lI:'1.' Qeru:ra.uo~. S<)met~:mes ~owanl a: region ():fJowel1 coocentrait'iorn ..

ConlSide.r II by~thetical section pai.511JJ!gflonna~ to tbl.'; C(Jllcc:ntmlion gradient wHlrun. anisa~SiI, 1sobaric gaseeasmixtcre contaJ.l1J[\g soll!llte all.-dsO]\lIent moie·· ,cule8"The two th:im. ,eqmd ·~term:n.ts of volnme aboveall-d below lheseCjtion wi]! eonta~11I U'lc same 'nl!lmber .(If mo~ec~le:s •• as ilt~py]atL\id by .Avopro"'slaw (Wdlly el al., ]9.84).

,Alth.oll!gh ~t is J!(ltpossible to :!i;1:a1l!· wmcb way uy partiCIiJ!.m molecule will lmvo el ~[l a gjvel:l ~1n!Ie:rv a l . .of time. a de[iniJe l1!ymber of ~e:m(l~~uh~$ ill ~helowe!!, dement i(lfv(})llme wHlcr();~s[~e .lrypothetil::.Ellsee'lian frem itiJelo,w. Met t~e same number of !]l{)lecliI]es willl.caw thtl tipper ~lemMtl!n.d cross ~!Ie section from abeve. W!~h the existence ·of a ·conce:I1!I:rM~~1'I pientt, there are :more salute moleeules iln one of the elements of"'QI.~l!me than ~~lh,e Qtl1e:r;aceorui"g~,y,. :a~ iI,lver.all!net transfer frQIll a rng.ilOfi ofhi~iltl: CO[1o(}t'ltration to one of 1.<:Iwer concelltmt1mjJ wiU ~sllh.·Th¢! IiIBt fimN' ·!)f c"iI,C;h :mQicculaIs:pcdcs OOCJtii'$ iin tho ~ction. of a ne,gatirve co.lil.centtatio:n ~ent.

Copyr'ghtcd rnaleria'

Fundam,ental's of Massi:ralnster

The ]aws of mass transfer show tlierehl!lior.ll between the flux of the dlffusi~8 ~,ub~U":t~ and! thtl COllloonllllitiOlil ,gndiCltlt m~pon~lblcfoli tlill~ milss tran~f~. S~IlIt1e diffu:s~:on occ'U:rso[l~ly jill mixtuees, jJbs e'l!'lllusJtioll mustimvo]Vltl an e.M!mi:natloiII. of th.e effect oJ eaCh! component. ,iFo:!' elUfilple, itis afteR desired mknowtbe diffilsionmrtre of a ~pecif.i(: com~!~~ rel:a;Uv-e to the Vll!llocily 'Of tl1.¢ i!njx:ru~ inwhicl! it is moving, Sin.ce each. ,compofl'C.nt may :posscssadiffi!!rcl1!l m.O'o;i~i!ly, the mi:U]J_P;; vc~oci1ly mnsrbe eva!luat~d by averagllliF; the ve~ooitie..s ofal] me components present,

rnn ordeJ!'to estab]~sh a common hasis for future diseussinns, de.finltLo:nsandreJa.~ ~i{)nswhi'ch are ofi~n rtj~d ~~(}e;xplaLin th.cml~ ,of ofunj]Qtlenl", wiillhil1! ·11. !itl_i,~ture 0li_1'S COIlsidcred next,

1 ~2 .. ·1 Coru:::e:n,tratl:ons

L C,o!l'li'crt II oomp;lsHj(l!'! glVll;ll1in ~ fraction ~llIDle f".actioIl. and itrlle reverse,

2. T1'3!1'lsfo.nn 3. mate.ial firoml ,one measllre of ,cO!1lOenJlratl<m to another, [odu.dili[].g mac')l!;fvollJm~ and molC'slvolllme.

11'Oi a mul.ti(,Qmporn;~liIlt mb:.tlIl7Cl, ili~1CO!llCC,BtrnHQI1i ofparuculw!" :species can. he e:w:.pressed ~n many ways_,. A mass CODCentral1on fQr each species, as weU :l:$fQr tile mJx,t"l.l:!ll:, can be de'l1n¢d, FOI: ~pecie", A. the mass cQllcentratio.n, P A' is del1lleda~ the mass orA :per unh volume 0'1 the mi.!Iit!tlre. '111elomi mass oonce:n~mtlon. -or denf.!ty,. p~ is the lotal mass of the miXU~N ,contained in a urut vo1nmc,;Lhat: ~s.

(l··~)

wbc:l1c n is the number of ~:]CS j[l the r.nl:!iliure. The ImlSJjrac1ion, ru~:, is ~h~ mass C(lr!ice:lltntJti~!1!of specie:;; A dii¥id¢d b.'¥ tb~I()t;t~ :rI!3$~ densit.y.

p~ p,.

1(1} '" :~ '-'.1-. -,.~ -. __ '

~- IP

kiP,! .n-

(1.3)

Copyr'ghted rnaleria'

'1.2 Molecular Massi"ransfe:r

5

l1re mt).lar CQl1centfati,{)n of specie~ A.cAI, is de:fi:n.ed $: the nllmber of Mol,@s of A preserupe.r ufli.t voh~mc of tile, :rnllllU,1!Ire. By dc6rdtion, .I mol.€; of a!rly species eentains a massequi.vll1l!lltlO its m;o]ccll~arwej~t;th.cre'fore'. the mass ,cQllCe.nrinllionarld tlte molar conce1ltmtIDolli am related by

(; "" __e.'L ii-' ";;)

.II. M ~,,,,,

~

wJw!e M,iis the malcealar weiglilt of species, A" When ,dcW:ing w~th iii gas pIlase under CQrld~ti.Qns, in wlliet! (lrI¢idea~ g~ law a:wI~e:s:, the ,mzylar concentrat~OI:l iisgilven by

fl,·5)

w~ere P'", lS the palil~a~ ~re~sili!re ofdre speetes A in: tke: miJi:,ulfe, Tis tllile IIbS(llute""m.~ ipeAh!re,allld R is the gascon.staJ],t. nlj~ total molar C(il'i!::e!l!I!(:illOOI,G, is ,~ rota:! :moks ofmix:ture C01I.~ai:ned! ~[1 a ullii.ivdIIiUIiej, that ~s,

(l~)

P

IC~'~

[1.7'

(1·7)

..... n(iill'(lP ~:;, the to.al ~liCsslilre. The m.ole/mctiOl1 fo.rl[quid of~(li~d mj;\tu!~, .lA' and tor g,iISe(]U:S i!TI~tu~. }'Ao' an: tlrem.ol:ar c:oncentrat:iolls of' spec;ie~ Adiiv.ided. by the tQla!l molar loonrenttatiol1:

,eIl

Y· ._ . ...Li:;,

"'-

- c

For 21. gasoous .mixrur:ethat obe,ys the ideal gas.la,w~ the mow ftact,±on" .v~, CUi be wri.t~ ten in le£m~of p~~ure;~"

!J. !!.J.

}'~ "" .' ~., ..

c P

{l,9)

Eqit9!l10Ii. (1~9) is M1. alge:brr.atc representation of Dalton's ~aw ibr g.:lS miixlllre.s:. The sum of the mole fTllC~h)M, by dofiniti011. ilinJllst be 1:

Copyr'ghtcd rnaleria'

8

Fundamsl'1I.tals of Mass Transfer

b) Thecom,pos1li.O!FI 0;[ ~he fresh. wash wh:dion. c\'I:p.resscd in terms of m~l;Mlhcll.ons"

MlI,ltist3.~ wash~fil;g prooccss

Fn:~1\i w~ soludon :24%KNO)

~,[ 62 kg/m,l

SoIutiion

(iii) Cili~'culat~lhe, <liverage mol.«.u.lW' weight, MlI~" of' dIe wash :sohniom, arid. (h~n i~s

tQtrll m.Q~ar den5ii~y,. '

BQ:ji~: 100 kg of:fn:5b wash so,hl!ll.on

compoOOiU,

Mill>S •. kg

KNO", Rp

101.10 lR02

O~23j 4;218

100

Tb.e~fore,

KN03 HzO

(jI,2:17 4,,2~8

U.23714.4f55 :E: 0:(153 0:947

Thtal

4.,,455

Copyr'ghtcd rnaleria'

'1.2 Mol!ec!lHar [Mass iff8nsfer

ExaMple 1..3 Ma.terial .Balances en a .Bio-Artificial Kidney (.Montgolll'cry et al.~ l'!l8)

The [primary r..:mc:tloIllS or ·!:heki.dnt:ys are to remove waste produets. (suehas urea, lIir.ic· ;J~]d.!lif.Ld {:rca1:i:njtl~)iUf!d ~(I ~naLnrt:a,i;_f! Ule€ll,ljd otr!d 8i1hbOliiWOC .inUl.ebi:oOO, Blood censists eftwo pam: bleed cells, .mmdy red {4'5% by vo]umc), .. ndplasrna (55% by vQ.lume},. Urea, uri.c aeid, crcatiininc. and wale. are all feund inthe p:Ja~ma .. Ifth.e kid)" 00)'$ ["aiJ. wastesstan to ~.cccYm}I)[;Ue :and the bod~' becom.e:s Q ... erloo.d~1 w[th fl~~d, .f'O:n1itu:mteliy, p!lt~ents withrella~ f'ailurecan. use a:fl. cJiJ:e:mal. d.ialys]:!Imachiine •. also bown as a .brtMTtifjdl1l J.iJdney. t~) dean the blood. The cJe8!lling of the blood in itJ1C; mi.ficiaJ. kidney is: dillero Ule iliffe:>e:n.ce Ill! toxin cml.CenlfatlollS i)erw,een the blood :md rhe dia~ys~:'l t1ulid .. Sem.ipema.eab!e mem.b:ran.esilil l~e mac!lll[ne sel.ecli."rI'e;ly allo·w toltl,rn;; tQ p.a~iS from th~ ~lQod~o dm diil~Iy.~ls fluid.

Oli!ri!l.gOl! dhdys~8 pKlOedwre~ a patient wa.~ oonnecte<i to the !!T:!lldtim'l for 4 bours, The b]oodi w'as pumped th:rolllgJh. the aril:iifIdal krudlle,y at the mite of J 200 rnUulin, Thep:utia.llly cl¢~!1!!iled "ioodw:a~fetumed~o the p.a[i.ent.'s body, aJlJd the W<l'!il:e!l i!'cm.JJlvcd were collected in the used djalys~:;) fluiod. [)llirj~g th~ prflCf::dum., the paticllt'skid!nc"s were compJetely Inaetlve, A to~al of 1540 g of urinewa'l coli~~cl! with an UOOft OOiIICenLrntl.ofl of 1.3% by weigh.t A sample ohhe hloodplasm'Si was aaaIY1.ed before tbe diamycs;is iU'id fooooro oon~aitru l5's,3mgldL o:fi;lfQ, Th~ £jlCCifi.cgn!!v~ hy of 1he' plasma was measared at 1..02:415. Calc<ulate:

So1uUon

(a) Write~ .EIi. mawr.iai!. balance for urea on 1iheE'lrtifi.daJ. kjd~ey" Basis: "holll's

AssumiQg ~h:lit dIe- rate o~ fru.mI1iilol1 and decom,PQs;]ti:Q:!'l; (If urea ~wi!1!:g th¢ p.~ooure 1$ IlIl:gllg~ble and ~htlt neurea is removoo by the ~at~elll's lGdn.eys:

The muss of !!IreO!in the udae lis .. s~[!1:ply ~54~) x OJJI~ J := :ID.Og. CMcu]ate the mass of urea in lbe cl!i.rty brood by the foUow.ingprooedure:

.. Calc-111M!': the 10111] yo1urn,eof [pWasroa that flo\vs dtrougb t!lro artifid9ilkidney in J. h: .]200'mL:Qt:blood~160.m .. 1[11°55 mL ~f~m~ Idl"c 14h. "'" ~.5:84 dL

rmn I h ml, of blood too nruL

Copyr'ghtcd rnaleria'

FllIndaRilenta~s of Mass Tr:a,nsfer

I' O:llciLIllar~ the ill rea. in jhe diiny blood from dregi!;'t:n plasma cencenrration: ]2$·3 mg of ureal . 1.0 g; ... 115&4 dL of plasma. ~ 2~ ~:.:. . f. ,._

dl, ('!f plasma 11000 mgl ."tt' g, Q, . urea

TI1C: IJ!rcarc-ruo\'w. effie,leneyis. dlcJfI. {20l246) )0::: 100"", 8.1 %.,

(b) Slli,b~ti'~ii:!ting in tbe :i!rnUeriaJ b:3Jan~" the maS~ Qf'iij[-ea in the de:a bloodi:fj f,oil!l!'id (l) be 2'46 - 20 "'" 226 g. Tocalb.date the coaespontiiqg ceneentrarion, ~ne:v"Olume of: plasma .~I11i:ng efI.~r dial.ysi.s must be ca!ciIlI]ntrul Assuming tmtllQ' cells M$ Flillm()ved ~)i' ID~ m@b~m~ d1,lri:f!g ~e: pf(l,"~d~~:. *b~ mass ofpJ~~m",rem;J,i~i!lig, is w.# dm~l1~~ beeweenihe mass (If pli'lsma,eint:e\~~l:Ig ~he al'iiifjc~.d kidne,}! 1II'Id the mass o:f I~rhle: ~!lWl\"t:;d. 'The mm:;sQfpl,asma ,cnt~ri[lg ii~.givtn.~y

L0245 ,8 OfP'lltSmalll00 mL11584 dL ofplasrna,,,. 1,62;280 g of plasma mL ofplas:ma to d!l _

Tb,e~l1liI$sof. plasmaremai.n~ng is .~ 62,280 ~ 1540 = W 60;7408. The'o'O:JUlOO ofp.IMm1l fem.ai:ning~s Uj).740/(t:0245 x 1m) = 1569 dL ot' plasma Th.erefore, Ute urea ennce!1tlfati- -, :'-, I~e fe- a"-;',c -;fa-;- -, :'-. ·(22": X ·]I]II1lfl'l'lc:o;;!"I·", ~'·44 ';-o'dL

_____ • 01:1 n:! l~.!_ __ :I1tLln.ll'lg p. __ smOli.lS F~V. ,.\mvf' . .jV;J ~. _ JmJl:!<'_.

Notice tim! ~Iru the bjo·art[flciaL tilidllcy dte .removal! (;ffi.cien.cy of all tile W3S1~ must btl: Kflpt ]ow I;)fIC311&e: Qnl'le !1;~e~ lQ ffia!:r!1:U!1 :homew~i!!in thepiltier!l'~ lJOOy in all times, If too ma:rl.y\!'!<'l\'i!tes are remaved at o:ne time, death may oceln;:,.

1.2.:2 Velocities and IF~ILJI~es

Your o'~ectives in studyiRg tilisseetiOD. areto be aJDle to:

] . Denne tbc ~Q.uowi.ng terms: !il1.iBi~s-averag.e: velod~y. Inj)1ar...a:\'~rage velecit)'., mass {ormo~ar)f1Il:l!X, and diffUSIon ma$~ (or mQw) fiwl'>.

2. Writc, down an cxpte!!is:ion w c1U!culate fh~ m.:t!l:8: (or molOllr)ml,l;X relative to a fixed coordimate ~'ystem i.1l1 terms of the diffusklUi mass (or molar) flux and the bu]k motion contibUlion,

The ba'S'!c ~!'!1ipjrica~ fcl~arti.Qn, to estima~c ~hc,ratc ofmo]cclli.l~3!I' difl1ssiQn., first pGs(ulated by Fi,ck (U15S), a:lld>accord~ngly~ often referred. 10 as Fick'sJh;st.lmt". qlflan~:ifie,~ the diffusion of compQI:!.~lll A ill ;'lIril i~lb.errn!!L,. j~oo_li~· ~!r;1~t~m, A~oo:rdigS ro Rdi· s la:w~ a sped~~ can bv~ ~ v~kx;:j,t.y rclative ~.Q r!ili'!c. mess Q.;!WI]<lr,·avcl''lgc veloc-

Copyr·ghtcd rnaleria'

1.2 Malecu:lar Massi franst:er

it)' (called diffnS.{ml vei(Jciiry) Of!~Y if gf:id.iootsin tbecl)nC(lturatioll~~i!iitlna ml.ltti~ '(lQ!jl_p(lnr.m!l syslem, the vadousspcci:cswiU :oo.rrtlal.l}'lnoV,eal diH"cre.n!~ vei:OCiJties; fur that 'reason, me'lailllWltion of 8:. characteristic veJocif~' fOr 'l1negns mi:x~ll.!:'e tGqui.ms the· a,venlging of tOOvl.'lillooitics: ,of each species preKe:!1t.

T.he ma~;NlW!,.aJ$'(! rveiociryFor a nlu!l;iromponeintmjxllll~,is defi:n.ed ~Il rerms of the mass densities:

n

"""p'. "v," .£.i- l ~

p

where 'vf (kmlres nl¢abSQbu~ cve:k'IChy of ~pe~i~~ i ~lali:\i'e to the :smtioo3J:)" (loordin~l~ :ax~s" The I'iI!Ims-avera~ ve~kx:]ty ls~evcll!oc.ity that would bemeasueed by a pjtot tube. On the other band" the .m{jI,ar~av.era.gew:loci:tJ fora muU:kompcne,ntmix.ture is: definoo, .!rn terms ohbe m.a]ar CO:i1el!tttrations o:f all OOmpone.illsby

Diffusion rates are most cOllvenieJ:lt~:r described .tll termns of f1m;:es. The malSS ,(0( ,molar) J1~ (itt 3. gi\i~. :~peci¢$ is a \i'~c~Qf '(jU-liiIlJtLty d¢!iiiJUng the a~ijl.U nt ,~f Itlle piir~ tlculer spocies" ~n diUlC:r mails or morae uni.ts,. that pa5SC;5 pc. Jgjv~l1l,l!liJlh time through D unit. areanormal to tlle vector. The flux may ibe defined with .refere.n.Cl!i to CICl!IJldinate.s tlm!1 areRx.ed in space, COCrdil!tl3t,(!S w~k:hare !IllO'Idng wil1rl. rthe;mass-a!o'erag.e ,,'e]od:ty, or ~,Ullate-s whl,Cb .aR moll.inS with nil: IIrI.oIDar:4l:vCnl.g¢ ve,]ocHy,.

Thl'l .lljtt.5'~}lux (If iipGdll-s .i w~lh.respect to coordinates 1hal.w;c filled in space is defl.ned by

n, -pjl'j

[f we sum theccmponcet fluxes;. we obtain the total JIWSS flux, n"'·pv

{1-t3)

Them(}.lat flux of .~.pccies. ~. w~th ~pc::cl to coofdl.n:at:¢~ thatare fixed in spacei i.5 g,~\'Ien

by

Copyr·ghtcd rnaleria'

12

IFundamentals of IMa.ss Trans.fer

O,·l6)

!1!

MId LJI'",,·ij

i::'

The: molardifttl"sit)n fl·ux' ot spe(.\b:'I'l J wHh respect mllhemO]al!'''a¥e~r:age veJlO£o;Jtyis !I1iveuby

~" "" lfI,iV· ,-v), ~ !'~\ I }

(1.t7)

H

i.l[KI 'l:.li ;:: 0

1,,,,,1

".i "'! JIi + Pi\!' "" Jj +!(O'm The mOlar flu,;; Nf is :re~artecl to the mohudif'fus:iorl flux as Nt ""'J;i oF tjlV "'" Jj +y,N

(la]9)

(1-'2.0)

It is importMti to note that tine: rno~ar Hult, N~, d~sc:riOOd by eqI!l3~ion ~ 1.2.0) is ~ r~s~II,Ul!iU of two v,!'!(;ror quanliHes:

J.I

tb~ tl!1oLar dliffIlS:il)D .fl1:ix, J i" teS'tlluog fmm tb~ C:Oti~ cefilnitiOi'lgr:Wi.elit;i:fuhi tent! lS refe~ to ·as· Ute· con " centralion 8'raiJient ctmtributl().n;

the m,Q]arf.'llJ~ oosuillill,g as ro.mpo:n.eni i is ,eanied illl the 'bulk flow of the n'li.l:td~ this flux, term is designated th"" b/jlk mmifIU (f;{ffl'(r,iln~tl'on.

Ei,lf1er or bolt. qll,arnti.ties can. be asignific3J1l~pru1(Jf~he total mQLar :t1i1!1X" Nj• Whenever ¢q'!I.!ation (laiO) i~appUed K) de;scri~e' rnal,;]!: difflilsiuu; the vector mature of the lndi",,~dU!aI, Iluxcs, Ni' mnS!: bc'considered. T.h.e sameapplies for tbf!: mass flll~es ~fI ~q'l1a· ~iot1J (].,.1'9).

ExuDlplt: VI Oxygen Transport i.n th.e Human Body

01.ygel'l ls .importan1i: for [iY.ing. organisms, sino!!:' metaborntC processes in. the body illlvol;!lc oxygen. The transport of oX.ygem in the body is tlile]'efrue crucial tolille. l1!e iIil~i..)I[ld I!l the hlJ:m~!l cJoc:u]atozy ~y~lCJil'l, trnllsporu. o)l~:geml from thehJfI~s to every cell if! tllebody. In fuelru:gcr bloodvessels, most of ~c oxyge,u trons.pon is due to dle- bulk

Copyr'ghtcd rnaleria'

11.2 M!olecldar Miass Tiransfeli'

15

N ··N

!"I' ,I ... - ,

d "".~Y; i.Yj.·; -" b ... rnl

i~! "~Ij

; ·~I.,:2.,···"tl-l

U-21)

These are the .M{trulen".su·jan diiffu;s~:on e<JjU3Jtlons forml:lIHcompone,1iU. systems.

They areOOJililOO aJfi~t th~ EklOUj~hpl!ysic:ist James CI~rk MQ;\w'~~~ alld me IU1.j[rhm SCi.CIIlllSll Josef Stef:m. who were primBil']rny .repcmslbLeEOl' the.]r de¥dop.m.emt arouad 1810. .. It lis important ~~) point eut th.ca. only ljl - 1 af the Max.wcH·StafaA equations am i!l(repe:~de,"Ilt because ~~e d~ mast sum to ... .eru. A~s(l. rma m~mcomp!J._rn~!U jdcal ~s mi:xtllfe a more e:iabor<ILe analysis (!l.3Jll lM~ of lli::ampLte 1.4 lsneeded to show that (Taylor and Kri~hllli:l~ ~993)

For iI. :lthil1ilI)' mi~tllO'l of ]dt:l~ ga~ wheR! rh.0 drhilli'1g force for dH1I't1sioo. is the r:ntilefrncli.cm gradi,eJllt, it is easy to sn.O'w tliI.at .ntiO!l n·27)lredJI!lces to'

(1-2.9)

f'Ornonideal fhJ:~ds the drivin\S force fee dJff~si:o.ll must be dcllncdin l-crHis (lIt ebcm~ leal pote.t:JJt:iali g!a.die!lltsas

di --iTVl" P~i

The $iubscnp~s l',P are· ml emph.'1I.Silie thai the gradient ls to be caI~1iIlated l!J:rlder eon~ulJn wmpetd.l.ulleOlind .iPn:"~~ure OOl:'!dUio;tl:S, We ma_y ~:tp~s's eqJYalie!t! 0-301) !:!l te~!ll.'i Qf.act!vity coeflkJe .. ts, 1'ii" ;and um]e· fmction gmdielli15 as

~i

iii "" '.~. r V.x ~rvJ( .. ~ LJ - li ... j - ·1

j~~

(J·3l)

r' li' ,all:! "(~1ll

.. ~ = .,." .• ' ,',""

I) - .[J 'iI-~~ ax ..

:J'., .• i'.I:

Copyr·ghtcd rnaleria'

Fundamiultals of M'assTli'ans:fer

8. _{l~Ji"~j . fI "'" 0 ~f l::f: j

De ~ymib(l1 I: is mood insquathllli (1 .• :3::2:) to indicate thattbe diff~!el:lt]lali,£!11! wilh res,pe,cl to !ll(lJe, frnctiuJ! ~s to 00 cMtied owt insuch a~n:~r Ilh;U tb¢ mQre fraction~ iI~Wa'J;!S adduiIP'IO 1,.0. Comhming equations (~·26). U·27)., and I( 1·31). weobtaln

0-.33)

~ . .,ji -.-; JOI xN -x 'N

. -.' ... - l:.- ..... 1-1.. ."''j- ~ - 'I-·.· ,'- l I"

:r~&'=.. .. .. =: " , '

~ ,A'Io ,.' ~

i=I~Lf!J i=t CL"u

J' "".1,2'.· .. ··.fl'= I.

wneoo the th,grmQdynamic factor r l~gi:'\i'en!ry! tHnl

r "" ~I.+ "" __ '_I

, ~'''1 ax;

(1·,37)

1.:2:.14 Fiick,~& IFIr&t Law for 8~nary M IduNS

2. Define the Fie" di.ifusivhy and establish lbe~ relation between the Hd, d:ifftlililivj,y a!idlihlt M(lKW¢]].:f.U,efa!i dilf:l:isivhy for a bin'a_ry~ysl¢m,

Copyr"ghtcd rnaleria'

11

A!~ aOOUllhe S~ ~~meU!a( Ma);we[lamJ s:ref~ were dev·elQping their ideas of diffu:Siullil In mu]~icQmpo.lfL:en.l: rni.l~ufes, AdoU fiek and ethers were aUe~mpl~ll,g to uncover the ba:slc diffusion cqumlionsthruughi cxperime:lllta~studics in.·'!i'l)!]v.~rng blmry mix.tures (F~d{. 1855,}. The msu]r of.Fi.ck's work was tile "]aw" thatbears his name. The Fic:k. tI(jumioll fur II ~irlary mixtlire h~lanioo111ilefJJI.a1. j~bati,C' sysrem is

(l~)

where D 12 is the Fid d:ifJut~\!i'ly or dljfusion eottjicient .. Comparilrlg ,equatio:ns (1·:36) and (l·40) We sOe tbat,. to:!' ~ bini'IfY~Y5~iWi, the Fick djfflJ:$j",~~y DimdU!e MS di£hi- 5]vityD arcrelated by

Dii .'" 'D n~. r

.FIJIide",] sYSlelm, r is IJr:lhY'lIld the dlHusivil1es ere identical,

.D.:!! ",.:'1) l:!c far ideal sys~em:s:

(1-41)

(1-42)

-- I' "* ...... ...i... f'~"k d Mil' )I'"ff''' =.,.. "I'

UI.C' ·~oroo.[tlooanu J:'~·&Un~UO!il o I"·.IC .• · :aJl;'_.::i ul,m:~on COl'!h·I.t'c~emts. rs <Jit$~

cussed rntl .I!h.e is'eCIIDt! th!il f(lU(JW~o lheFIct.diffi1Siv.~ty~es two aspects: (1) the s~gl1fifi.ca!nce of 1111. inve..rse dirag coeffiCi.en.t (1)),300 (2) ~!herm.odyrl!lmic, oo!ridea'lity tn. Con.$eijl.l.e!1l1y. the ph.ysicil i~llteq»elami:Ofil of ~he Fick dJiffu!ikllil coefficient is lc:~!i l:!1ln:!ipllre1lj~ tbanoor tbI::. MS diJfll$;i!.vtty.

11.3 THE DIFFUSION Oa6F1FIICHENT

Fic:I('li la w pt:Opani:cmality f-actor. Dj:~ ~Sk:IIDWliil. as l~e .difJu~i:()n coejfidt!1! er dif!usivlty ... hs:fUOOiaJmental. dim.e,lIs:ions, w.hidhareoblaif!oofrum ,eq:l,!latio!1 (1-40'),

~2 '= ,-J 1 -. ~( MX' .'.. . .. '.~ l~~}

= cV'xl" . L; ..... M.! [.f .. It' L Jt

are t[!e;llb:'ClIll~ Itlle foodamenta!l! dimcnsioas oflfrle other transponpfOpeliti.es: ki.ne.mat~ic Viscosity, \I, ad Lhe,!'!!r!<'!1 diffus~V'ity. o:.The:~~ diffusMryis 'usually reported in, i.ii:lits (if c~m1;l!i~ ~fie SI uriills are. rn~l!!. whiieih i:sa f1iGtOf 104 .sma!IIer:.

The diffus.ion o:;.elfkielll depends upon the preS:5iUire, teiiipctatlire. aoo compo· ~itiQO of tht'l $:}'~m. &p¢rimefltfd v,~U!~s fur tht'l diffusiYit~cs of gases,liqu.ids,. and ~oli(l$: are t;lbtl.l~~ il! Appendlx A.. As (l'ne might ,(:xl?~ct f~om iOOl1sideratian. of t'A.e mo'b,Ui1;y of {he malec~lesi ~he- d~f$1Jlsiyjjtie$iilre g~n.e1i!WI.)l' Jljs~!:tQr ~s {iill ~hL': Ii!'!!)g¢ 10.5 x~o"s totO x lO~ m.zls} man fof' ~rquids (ml the ronge 10'"!0 to 1~'m2,s). whk;b. ~n; .higbtl!r lh8:!1th~ V'<l!i~rop1)rtcdfor solids (in WI! :mtl!g;e .~.O-~I,* toU}~(I m2,/s),. IIII ~t..e

- '" -~

absence ·(If e:llperimentiJ. data, semiLbeoreti~<d ¢~s~tO!ll:i have been devel.Qped whicn.

give ap~Jjox:imillio!i!s. :S(lm~limes as va!llid as ex:perimcntru values. due to 1b.e difClcu]· ti~5 ¢JI(;Oin:U~.red i_tl.lhcir :ltlI\ia~tlm!ni:lnl:.

Copyr'ghtcd rnaleria'

Fundamenta,l:s of Mass 'llranlsfer

L EStimate d,]rrusiorn cooff'icieDts: for binary gas isys~em~ rillsing tine Wi:I.keLee CCl;l,Iati.an W.i!10 M!bula:tedval!lIe:!I 0:1" the l..en:nam:dklo:ne.spllr<limeters.

2. Bstimatl':l djffu~klil ~fficiit:-,Dts for bjnal)l ,gru;,!:'yMems 'Illsing diI,e Wl!Lk~ Lee ~,ii8!U.o:n with valiLie;s ,of the l.eii!iW!td·J()Ine~ (l1i:r.:uneteitS estimated f~am ernpi:rical, com~atiOJ:ls:..

;, U~ 11 Mathca~® [Q",,~in~ t\)in'!p~~m'e!)~ <:alc~L~dQln (If din:u~i~"t"! cQeffi(;iCnlS for bInary .gas 5j'StC.oo, l!5~ng the WHk-e-Lec cqiIJllli,QII.

Tne 1heory de$tn:bin,g diffu5:iQIl lin. bi,llat)"g;fl.$ mb::Jtlllfe$ at rnow to mederate preSt' SlliI"CS has ~:n well devc-:iopca Modem \iie:rs~(I!ls of tllle tJmeti.ctbcory of g.~$ have at,lempted to acc(l~mifor the fmroes of attraction ;a:ndrepulsiol!betweell molecure!i," mrscffil:felde:r el al. C~949)"llSi.ng lhe wnard~]\one5, ~~enlial to. eval]Il3ili! the ~nf]uenc.e of lliL~QJ¢.(:ll]it!' fQJC~s~. p~¢:l~n~~d il['J eql!lrtilioo fur t!hl;: djfflJ~iQ!l 'G(I~ffl;ei:E!J1 f~)r g~ pa!lrsof nonpeler, nonreacting meleeules;

(1.-43)

whew

__ [1 tTll

Mtm :;::: 2 '-'-' .. +-_ '-". _. I M,i\ Me

:VAll = dlffulliQfI OO¢£fi.c:icnt,. cm'2/~

Ma, M~ = moL~t1.lar we~,gh!1S of A and B r:: bmlpe:r.tture~ K.

f ~ pre~!);~re, baT

(1:;18 :::: "collisiem diame.ter.," aLennard."Jonespaiim1Lcter:. A

:Oil! = dtif:fti~dOilJ ,e()lli~oi"fl ~!Jtegn~~ dimewkm!e~

The colHs:ioll inite-glial. nl)'~:s. !i fu:ru::tilo:n Qflhe~mpcn>ture and! (If the iQ~eOTlQI~ eo~dru;PQ~otiaJlfi(l~d for one mcd.lX'u]e of.1\. airld OIrI.e' molee!]I,e o~ .IB, lit is uS<1JIaJ1y tilbu;lated Maro._1!~ijJQ!:! '1f'T* ... It,TI€Ali' wlil~~l'e Ki.8 iifle 8QI!tzlmmll constant {1,38 x lO-u, e<EgiKJ and €Al:I :is the ene.rgy Qf I:JlOlecul,lI:rin~emctiolil f011be binary system A and. :8 - 8. Le:nH8JId-IQn.e5.pairumcte~-jn efg. A v~O' ac¢Ilra;~,¢ ap·~o~irnan(llJt 'of SlD c!I!:!bc obtained from (N(lllfi~~{:] ct ai., 1912)

Copyr"ghtcd rnaleria'

1'9

wbere 'P ~KTfEA8' c .. 0 .. 19300 J~ L5:2996

a ~ LOO036 d ... (t4763S e= U6A74

b'~O,1561O e = 1.0358,' h .. 3.89'411

For a binlllY ~:yS:le4tl oompostd of n~~iiifpoJ~ moicculQt pai!!:!! •. t.h¢ :Ui:i~'3ird.-JQfiC$ ~e~ers ,ofl:h~ PiI,te oornlpCIlilentil !'J'!<JJy be eomblned emp.iiiic a Uy by the foUow!Jllg, relations:

These: rc~alio1ils mast Ill'; mod]fied for polar-polruandlpo1:u:-nonpnJarmclJeeular pain;; the pwpmed moo~nc;ati!OJl!5 :Ire dh!!c!:lss.ed by H~JNCh!fe1der 'et al, (1954),

The Lel'mard,~lItmes !p<lrameteir~: Jor fhe pure ,componenl!>"re 1lI~Il;aU'y 'obminoo from 'Y'~scos:ity data, Appendi,x. B I1Ibu]atGS some, of I1t~ data available. In 'l!Me a!Jb.scr!cc ,of c'xperimenral data, the \t.~Jtles of ~hrlp~ete'!'!i fOlT ptl[~ oompone!iLrWlmr), be ~~ti·, mated fmrnttiJe, !'o~IlJO'w,if!g empi:rkal,coIreJlati,ons:

(J ""1.18V~'J fAl'" :;;: tl:5::rb

(1-46) (1-47)

wh~ V.h; I~ (he mol;;w w~ilIme ()~ tlw ~!,lb~wnce as: ~!q;lLI~d ~t!t!l~~1 !;K:Iil~~.g po:!flt, !:~ cm.:;;J8;m.o~, and! Tb :t:5 the rn,Ol'J'Mll boUiml£ po bu. ~empe:ratlne, Molou velames at :nolimal bo.ilill,g pciilll for SQ~cQllIlmonly eneQllin'~~. compounds are listed ~n 'Ta:bJe: .L) . r,o[ otiliU~f corn~tllld:s Hot Wisted lill Ta:fJ:]e l, I, jf a!:eUab~~ value of the ciidc,al volume {'!foe)! is i\vaUEIble, jhe TY,rI :lIn:dCa,lws (l97's) method is rec.ommended:

\II. ",,[t2B5VI,o<t1! .b- ---(;

Olbe:Niisc:" the 3tOnlt-c volumes ofeacb clement present we adI:Jed togelhe. as peor ~!lfle molecular fO:!1T!1!Jla ,of the oompo~nd. 1:ableL2 !iSH;. the C()n:lribtll'~(Ins· for eacifl (If tilr!e COl.lst~II!Ue:nt aiems,

S~v~ral propo!l(;dmet!hoo!!l. for ,~:§Jthnatlng 1)108 in. ]ow,p1'essuro 1::i]!1iuygas sys· tems remain the general form of equation (1.43). wt~h; em.piricaJ! eonstants based on expedmemal d3!M, One of thetm),~1 wide[!y' used :m~thoo!!: •. ~:ti10W!i'! to 00 qu]te g¢~.{l:ral and trenab!c-. was proposed by Wllke, and Lee (1'955):

r3.;03'~ (.' o.~! )".111(1O~~) '1'Yl

I Mia'

D - ,. " , ('~l "'9)'

.,1,# - p.'- -.'M- .. I.e:l:, :~ ,(1, '. - 111"4: "

'.,tSG.IllI"""',i[)'

Copyr'ghted rnaleria'

FllJlndamentals, of Mass Transfer

DAB(T;, P, M}\. Ms' 0" A"0"8,' ~,A!'oi'£IlI!)

W1iJcn tlle ql.ilil!ntiti~:i i!l.pa.r;etlll1h.cses are a$slgn¢dll!'Uffi'lilrical vlIlue,s, the MathcruJro'jik ~jne y.i.eold,s thevalne ofthe diffu:si;viJJty ~d 1>1 the WUke-Lee eql!la.t~Oll. in units of cm21:s. Thas, fortb.eevaIlIiai"llon ofthe d:iffu!iivirly in lids exaaJ!ple, we wrHe

DlliBi(273, r, 76".29 ,4,,48~3. 3.62,.46'7'. 9if) ;:: OJl952 c;m2,/s,

lbe' cxpenmemlat!lj1;ahn: Js ebtained from Appe:rld~IX, A: - c - - c . m'l ~P.a

DMP "" 11).894 --,

5

..•.. ~I" .•. (m~){PaJ(l w) OM -1).894 ')( ')(" ~, )

- I~S,_J bar 10 PEl.

'l

"",·8.94 ><1O ..... ,~ s

The: ~rror of the .estimate, compared to ~he e.xperimell!taI. vllillue"js 6,5%.

E"xamp[e 1~7 C8Ic'l!l~ation of Di'fusivity by the Wilk.e-Lee Equati(fn willa Estimated Values of the Lennard .. J6n:es P.amete~

E!lUlmlte me difflll~iv~ty of aUyl ~bloride· (CJHjCn i~ air at 2,98 K.omdi .~ bart[si!1!g Ut¢ Wilke-Leeequntlofl (~-49'1. The eltperim,entM valu.e mpotted by Lu,eg (1968) is 0,098- ¢m2!~,

So:lutioll

Val'lil¢"~ Qfl~e: U:nn3Jrd·JQmes parameters fo:raUyl.chlorlde (A) are not av.ailah~ei ln Awcnd~x B. Th.e:l'Cctore. Uley mntbloi est~m<lted from eq1!l<litiOWlS (]·46~ W"ld f~4')., From Th:blcc 1.:2. Vb "" (3){14.8) + fS)(3.7) + 2-4Ji, .",. 87.5c:mllmol..An al.remlltiv,e method to e$ti.mate~ Vo!> foraUy] chJoride is iI!ISliflg eq~liIati(lll (l-48)wjjth a v.able 'ofVr; = 234 'G:m.3lmol (Reid. et .111 .• 1987),. The tWO e!ilimale-s a re",jrllJiI~lyidenticam" Fmmequ~ tien (1-46), (J~ ~ $:24 A. Thenormal ooiHog-poiot ~m.Ffll1ll!Jie: fOf :e:ll.y~ oMori&: ts T~ := 3]83K (Reid et Ill, .~987} .. Froml!qll~tio~ (].~47).. fJ,'iK == 366.K. The mn~lidar weight o.fiJlly[cbloride j~ 765, 111e cOfJ'e5iponding",alues. for ~ir are: fJ:a .~ ;1,62 A, :erlr; ~ '97 K.amd Mlj ."'" 29'. Stllbs(~tuting: these values .into tile Mathcadlrouti:ne ofFi\~tlJre 1.3

gives -

Copyr'ghtcd rnaleria'

'P.11

IIJI

-, IN

1:~

.n.

I: §

I~ ~

leil

s. ~j,

'"' 'it-!

IS tl; -
~
.;:a: S 8l
::; ri'
'c:! .~,
A !I.
... .1;;1
,h .. .~ ~ 'or'
~
,- ~ $
1:'['.
~ ..-.I!
III ll_ .t
• ..., «I ;.... - ......

~If

.. i i

'--=.,~ ~I

.Il

~' ~,

..:

::i;

1

+

,"

III
~
..
~
~
if
,;-
!
~ I
~~
~ I
'~ I
=, 23

Copyr"ghtcd rnaleria'

214

IFulildamentals of !Mass Transfer

1.;3~2. emllla.on Coefficients farDlilute Llqu~d&

Your o~Jecdves in study.lng tills section ·ave to be able tD:

1 .. Estimate diffusJo[! cooffidents.fur binary dI~ute :1~qlJi.d .sy&te:m_!iusi[l]g the:

Wl~ike and Cl:Jaflg equilliOil.

2,E!;drn:!ul': dillu5iof;! ~ffi(:je!1t5 for binO'lQ dil!U'~ nil.l~id sYr:item:s, usi~g tbe Hayduk tmd Minl:Jas ~uatiom"

:l.IlJse a Mathcadroulin.e tn imp]ement cruc~l.artiDm of diiffUiSion coeffi.cil!1uS ['Or bjnary diJlJIlt'l nq~l~d S'}lS're~ lli:>j!1g flu': HaylllJik and! Mi~has ~qllali(m.

In (lomLnl~t to the ('~ for S~whe:Iiel om advanced kinetic mwzy to e:M:plai:n mol.ecu.laJ' motilon lis avairnable. theOirie-s .of t.be: structlllr,e of ~lqlllirls and thelr t1':anspott dmrac!{nristic's .aJ:'!'lst~n iUd(l:qUAIi'l Ito allow :.1.. rigorous ttt3ilmru'lt. mjqll~d. d~ffLl<;io:n ~lCie]JU are ~eraJ ~ of ma,gn,]tude s!Jlia'ller tru:m. g.as 1,.tiffIlS~vitres~ :1100 depe:nd 00 cOl1lCeIltratioo. due to 'I'he' cJliIange-s in 'vjscos:ii~ wjtb. concelltratioo and ,chang~:s ilD. Ole d~ ·of ideality ·ijf the s.o~lltion, A:s Uj~mJ;:i!I:~ :ftaCi~io~ ·of ·~~ther CO:fi]pone.fU. i:n.a b~!:iiit~ ry Jllhlit1J!~e apprlQa'ches lI!liIlty, ~lt!e th.eImOdY!Il<tmi'c filcwr r!lppro<l.'i:,hes uoU)" Nld du.~ Flck ili~i'li'jty and·i:JJ.e; MS diffu~~vLzy areeqYill, The dUfuslQlli coeffic.ienls OOWlRed ~:m:le.rlheg, ,oo:nditiorlS <We tbe lnrllnite dW~l!!tii(m di.t1'uslon coefficlents and .aregi'lo'eJI. ~.e

:symoolV'.

The Stdles-EinsfeJ!1I equation ~sa p:u~Ly theoretkal. m.dh.od of esti:matiQS; 'TP,

whmrer:~ isthe iSiollilite (jWtidemd~i!ls anJl ~B is the ~(llveJIt vis:oosilty. 'Ibis equation has boo:n, faidy :SlJCCes·sfulin descrilbintg djffusioo of oolloi.daI pali1l'jcLes: or IM'ge mund mol~ ecllh::;,th:ool.lgb :II! SQrnvetU which 1be~~v¢iS ~5 a eontil'ltunof;t)il!lHve to UI,C diffuLsing Species,

Eqll!1ni.on (~~50) has pmvidedautSefu:l start~RJg potl:'it for :a.muml:icr of ~(im.p.i:ri.cal. c{Jrrel,i!I:ionsa:mllli~ed. ilnto the g~l1~tal fiO:l'tn

T)flu

.i!l!'"'"I1_ /'.'(Y. ).1 leT .... ~)

in wh~ich f{Y;,..,) ~s a function of ~!le m",leclJl~ar vohune .of the od~f:fU:i]llg sol:liue:, f]mp~rjcal correlations Ils~n:g ~e gel1lct'aJ. :form of cqu;U~on, (l-·$~) ~ilivebeenl d~\!e]oped whlcla!)tl.enlpt to predkt me liquid. diffuslun coeJn.:icnt 1n terms of the saline aad solvel!J.rl.pro:penies. Wille and Chl!iliLg (J9SS,) h:a"!!:e P'l',oposed. iI:b.ef~ll()wlng still wiwly 'used cOI::remalion for IIDne;lectro,1y'Le~i!il. 3in. illfilll'~~ly d,ihWle WhUI,Qli!,;

Copyr'ghtcd rnaleria'

1.3 Tlhe Diffus r:on Coeffi:cie'n~:

Dill where ~A!iI

M~ T

1'1.8 VM

25

(J·:52)

'" d~ffil:5:ivHy off A. 11:1 ve')' dHuwsoil.ltioll in :'lOIve:ru B. cm21s ,,;: molec,ul!ar Wiei.g1llt. (If :'Ool'!;'enl B

= l'e!ll!~Ujre. K

,""viwosi.1i)i' of soive']u: .8, cP

;::::; soIU1e molar voruunUl2!1 its normal ooil.ing point, cmjfmol = 75,6 c.m?!:mo] :fur W;a!I(tr acS tiolJlre

;:.association./ut'for of solvent B. dilll:lCI:Jlsklllilcss

'g 2.26 lor walet assoi!j:cnt

= 1.9 for !:'OOlh!m~1 ~ oo]v.e~1 := 1.5 for. eth:all.ol as selvent

"'" ].0 for unassoclated i5()[VGrnJlS (~.~, 1000zem~~ c:thar~ h~ptane)

The value of VIM may be ltte true va'.lu~ or" if!fl.fiDe$~I)" e:,*timated frO'ID eqlJli'l" tiolll (l-4!$)~ 0 r from t]]e data of Table 1.2" e:.t~pt wtum Walle .. is the: diJfll5rulllg solItUe. as noted abovG. The assoeiatlon faow:r: for a solvent c!ln be, estlmated o.nly when dif'fiusivitie:!O ~rnJ ltialso~"''enil M,,:eOOel:l ,experi.menil:ally meas:U!red. There is: also some OOlij~t alxrl!~ th>l!:~bility ,of th¢ Wi&~..cll!!l!ng ~tl;:ltki!l to handle !;;01'I;'e;n1S uf very hlrgh .... iscosity,. say mi} cP or more.

Hayduk and Mltlhas (~.9S2)1 ,eonsidarod, mm)!' ,corrdat~orls for tihe, infinite di:h.~" ~!Qrl b~oory d]W!,l~~()!l coomc~~ot,Byreg~~fi~{ln !Ula~y:$is. th~y Pf'(lp!)sed .s:e\'eral corse:lalloH ccpendi:lIg, t'lrl, the type of SOTII,t~lve4lt sysi'ent

(a) FQr SQ!utC,f hl aqllt!;(}It.'J Jolr~rians:

V~·", L25x 1O-~ (V:·;ir!il ~n,2.92)T',s~!1:~

.. """. 9.58 ~ I. ~12

e .. ,,~~

VkoI

where V~B T

1U.1l V;M

'" dlit1fu:silO'Jty of.A in v'CQ' dl~u.te ,aqIlOOU:S; sQl~lIltiQn, c:m:i:!s """t£m~~:,K

"'V!S~(lS~lty Qfw~~ir) ~~p

::: ~~Iute mol<1!r vQllilme ~itillS ngrn1<l1ID ~HlI!BP'O'j!:U,,~rnll!!OQl

Copyr'ghtcd rnaleria'

26

whe~cr is surtaee teOOt{J!l;l.rt thoe ~lboi]i~g·p(Jiil:lil tempet:Uu.te,. ~11! dyrufcnt. ,If\i':l.I,~ ues of thes'I!!rface:l:ensi!lm are not known. they I:tliaj' '1;)(0, e'sLimaroed ~:yllli); B:!'I)(:kaml !Blrd (1955) correspoooing SIRleS m:ein,o(I (~im:ited to IlOnpolar HquJds)!:

where cr ;; ~ud:ac¢ tetl$iQI'l at tlliJelloOmrual ooiH!l!g.;po:iillt. tcmpemture, d~'~f'Cm

Pc= critical preS~1!~t):, 'bar

Tc :';' critica] te:mper.:uu:re, K

W~~n u~ing the comla.tlQ.n, ~OWfl iH '~Ii!Uh)fl ,( 1 ~S4). th¢ :ari,l,ili,Q~ '!iJ;Q1.Q ~ ... e;ra] IJestriCtiOllS;

L The methnd sheuldnet be used for di!lfu:sian ,m visco1!ls solvents" VarnlleS, ef 118 aoo~ aOOilt 20 cP would da:s~ruf~i' the ~Iv~mt !IS viiJPmIiS,

2, If~ sg]!lL1.c is waJ~. ,81dim~['v,(l1tHl QfVM!:ih~~db¢ uSQd (Vb,t=37.4 ,t;;mNn:wJ),

3. '~f the solute ~s an Qrganic add arid t~ ~ol:\!'emll ~s Ql!her lhao water, ,!:netl!aWlQl, or b:Ulan,('i].Ilt!c add 5t!oulld 00 ooJ'ils:iciC,red a diliJler W:ilb twice lhe e:lripecled va~lIe of VbA,

4. Por llonpol,lC solute-s dllfus:illg il:110 mQ.nohy~ro::\y alcQhQ~s,. the values 'of VWi' sholllM be, n:ndtlpl,ied by <I. fa.c~or equal to 8JJ'l8"where ~jl: ls the scilvent visro£i,t,y inCP.

Example 1.8 CalculaltioR Dr Liquid Diff1ilsivityin Aquoollls So.uUal)

Estimate the dillusi.",'ity of e,lhano] (C~H~p~in a d~'~:Ulte ~oh.l~~jon in. water :at 2S8 K Compare your esumam wim me ,experimental! ¥JlJoe reported il1lAppe'nd~:l A.

Solution

(;'I) me the \Vilk~"Cha;~,gc,orrel,j![!io!'l,. equation (l~52) .. Ca:lcu~!ate tbem.ol:arvoh!lDe of ethaool ... ~si!lig eq~tio!l (! 48) wUh V~=16~7 •. 1 c~m}/mol, (Reb:! et al., 1987):.

The vlsoO$i,t.y oJl]q1il[d! water at :288 KjfS!l:a =1. t53cP(R.e:id et at. 1987},. S\!l~tilitl.lth:l.g ~n equation (1-52) gives

Copyr'ghtcd rnaleria'

1.3 T.he 'Diffuslon Coefficient

!'<l1~1 ,"::I

1,.tIII r."

~I ~

III

.£.. .2..

.... III·~~ -' !!"'Ire

If.." hi

'.-:I,III""'~ '!"ill~ .•.. ~,

Ic"" ....

~I, IJ

~ ~.

I~'" r::.. ....

t.. 1i .:.;.

I~" ~

;0,., ~

~~ ~

....._... ,..,_...

..:l ~

O' b

.

~ ,ga,

r-N:

,d

II

::::::11,;:.

,........, ,......._

~

E4'

i

~ .~

,~

I ~ ........,.

'CQ'" ~ d

!

~

"'"

Q..'"'

III

'0

§

_

I

d II!

.19

FllImdlamentals Of 1M ass T-.:ans,fer

1.;3.3 DJffllilslon Coefflcientsfor CO'.rl cBlnb"alted Uqulds

M·g- ~. ". .. ~"'.c ... ~. fo r _11; .... '. ",.{Io 'no ~in. , ... o-" ............... -oll ~,·.q' ... d lutlons ,.tt~ te ·m, ,p~ ~·o 'c~"""'~

._3''' "II...~~'~ I,I,._ ,r-~~'!r.'''- III;:!!J Jr# L._ • '!r.' ,-.~"'I'IifM,~ ~ ',.~ I v i~'L'VlI!I_ 'it.,. , _ 11,1., ......... i

bine too ~n:filli~ dilution diffusion coclftcierus (:D~l)P <liM (1l11It ~f1 ::l! s:irlgle function ,t:lfcl)~sition. ~ 'WgtWS fotrnlllla ;_~,i1!:co'm_mml&-d! ~y Reid et al, (1981):

'D "'.D~' ·)h('Dfi)'"

.,',. r.~::::.i: \ '- - ~~! ':' "~,, ~:!I ~:'

(l~.56)

Examp,lei.10 Diffusion. Coeffici.enm· in Ole System Acetone~ BeDzeBe mylar and Krishml, 1993),

&t.hoote tOO MS an(!Flck d!.ffu$k~~ ~oeffk;ieollts for an w;:ekme(1~nzene(2)mix;tll'~ oicompos:hi(;fJlx! =0.7808 at298K., The infi~ite d~lutioll d~ftlliIsi.vhi,es at'!!

'1)'0'= 275)(' 10-4 m2!:s

11.· -,. .. " ,

'D'~!=4.15>; lO-'l' m~~ Is

From ·Ow N'lRTI.. ~ualkm. f'()t thJ5 syS<1¢m at tn.", gil!'~1l tempenul!'re and concenlrai!iorJ', the thermoo)'1Damic eoneetien factor r= 0.871. The ,~ocperim:en1al'!j1al'llle £If: Db, iit thj:~ ()onrentratioois 3,3:5 x 104) m'1/s.

Solution

Su.mtirutingin eQ;l!atian (1.:56), we ebtaln

1) li- {2. j'5 x W-!l')iI.!ii~ :;.::~ {-i. IS x~ 1O"~ r1~; "'" .3.192 x l 0·-9' m~ is

D~~ = 1.792 x. U)·~ x 0,871

=1 . .30.xlO~ mlls:

1be~k:OOd value (if ~e' Ficl d.iffi:lslv.ity .is i~1 ,excd[errt1asreem.emt with ~cxpcri~ lhell!~lI] resu1t.

Copyr'ghtcd rnaleria'

1.3 The llilifif,lilsi:on Coefficient:

t. Estimate the. cfIecti'!i'lL'; dlf(usiv]ty of aeomponearin.a milllth~()mpoitetlrt mixtlJ!fe qf ~$ ft((Jm ~ts. bimuy d.1ffL!l£!l:m ·coeffh::i'e!lts with each O[ ~U!, olJi1ell rom,tlilllents, of the mixtlne,

2."E.stimllJle the effec:liv.e diffiLliiivi!y ofa (mitre solute ln ahomogcneoll'S 50JilltW:n of mj~oo solvents room I.tsilmfimte dilution binary diflfuts.lom coefflici~n,ts ,into eaeh of ~he indiJvidua~ sol ... ents,

The MaxweU·Ste£an ~:l:IatioDsf(}I diffus.ion .~n mu~~co:m:pon~.tu: !lysl~ini5 can become \I~ry ,comp]~iC~ted" :aJil.d!lltey are 8ometi:j1Jjell hai:loled by using am'! ~f/f.~{,..-tivg difjutivircy or J)lfe~dob~':ria1]' appnHJ(.:/t. The e:f.fecli,\!'e dilJusi .... Hy IS defined by <l.ssumi.l'Ig tihat[b.e Fate of diffusion ofcom.ponenrt i depends only on. Hs OW,I') composition grnd~(:nt; 't1nat 1::;:"

i"", 1,.2,.··"n

w~cu l)1,<iff is some cbara.c1e.rislh!;, diffusion eoeffieient of species i jn the mru"l~re which must be .s.yn~csiEd. f~m .tI'ro bin:ary MS diH:us1.vh·i£s.

[0 ,g~~, ~!I1e bi:!!aty MS d~f~l!l~]¥l,He!! a:!e' nOm:'!ally &~~y:m,ed jO!k'~d~!U of compos~lio ... With this appro~i matkm. the e:ffec:tlYe di,ff'usi'vity M component i .!ina .. [I'I'um·· compo.IHml gas nuxtu:rc, CRI'!I be derived from tbe Steflu:l~MllXwc-]]equatoro[l 1D Sivc, (Tooybat, 19S{I),

~

N. -,,"" N .'

r, ""l~I"-J

D _~, l\iill ,

,"11ft . -~ .~ .'

L~(y:iN;- Yl~: .)1

_'lrl. J - . J,

~"'I .I.., ....

1>'1 ~

(l·58)

~n ot&r to U$ this equJIJ:i(ln,. :lhe: rellltiOflOOrWGSill the values of ~he N s must be k_~owrt Thj1j. re];'IttG!::!; ~"'led a iWOiStrap com11'ti'on: (Taylor and Kdsilirna, 199.3). Is usnally fi,;.ed by other oQ~~ide'ralio:ns, ~udl.as :reac'1iiolil !J<tojic:hio(m~u:y or energy ball!f:lce~. Conslder, fOfi.1!I~IIDlQe. the gtl$lernl.chemic:al reaction, w.r:iuen as

ow hefl'-e tllile, 'v; are called Slo'ichiometr,ic n~mbers and A:~ ~tl!fids fo:ra chemical fDTIIUda. The sigJll COfl!\lru'!lt~o:n. tmY, is pos~ti:ve. (+) ftJr prod.l!IC;1S amld negartive F} feereaetants

Copyr'ghtcd rnaleria'

Fundamentall:s of Mass Tiransfer

I~Smilrn e:l.at, 1996)'.f'orditIllsio~ with !:Ieterogenoollls ehemieal reacti(lIl,.1!herc;latio'llI.'i belweelll:he flnesarespecUicd by the stui.cll](II:tle:lry oftllcreac't]o!] M d~cribcd by !he fQUow~ng cqu!E!!~iOt1!5,

N! _N2 Nli __ Nt

,_' ':::::iii:i'-.""_~'~.'~~_. _,

v! "l "3, VI

(I-59}

I;!~--r Clirou~Uli!1lct~ ~lJch ~hal NH:] (l) difnlse~ ('0 the 'Cal;'lilys,t surface. aoo N:;! (2.) and H~ (3) d:i,fflusebaCk,a:pp]yi:llg C;qiiuukm, O-·S~9) g·iv,e-s

N! ~-!Nn

N· ·-_·'!N· $ ,_ ,~' "II

Eq-ua:rioli) (l-S8) wgg~i'its tbat the eflleelil~;e dii:ffi:Ulli!i'Hy may vary ~)m"!i,demb:l:y along the diHiliJs.ionpatffil. hut a li:neru: varilltion wit!b. drstance- caJlilisuallybe-iis-sumed (Blrd etal., 1960), Therefore, .rf Dj,~Jf c;h:m£cs s~gn.lfica:nt~yfrom O~ ~nd of the diffll;-

si.on.pathlQ tile Olll'C'J~ the arithmcti.c average of the two 1I'aliues sboald be iIlIsed!.

A oommon :shl1atL(m In 1nlllrlc()mponoent dlffUi!likmho when aU the N'~ e:!(.cept:!"Ii1

:arc, ~ I(ie"all but oompofletlt. I ~~. 5tagna;!U), Equation (1,58) ~!l! ~s

;'''':2.$, '··',.u

0-6])

Examp'le '1.11 Calc-ulaltion of' Effecti.ve 'Diffus-i'vUy in a Multicompo-

Rent GnsM::hJture .

Ammonia 1S beingemeked on a selid caudystooOOIdh.lg to the reaetlon NH3 -7 ~N2 ++ H2

- ,,,,,'

Copyr-ghtcd rnaleria'

1.3Tlhe Diffus i:on Co&ffi:ci8n,t

At one place un lhe 8ppar.aJ,US wihere rilile pressiure is ] baFand: ~!he tempera,tore .is .3001 K. tbe analysis (If tbitgacs ~s. 40% NH3 (n. 20% N::l. (2}.!lnd 40% H;: ,(3) by voium¢, Estlmat(lltnc effoob.lii'{l diffulilvity of ammcnia in the gasco.us .mixture.

So]u~ion

Cru.cula!oo the b~narry diffiu$:ivi;ucs (1:( ammensa ~Il nitmtlcn (2:> 11) and ammonia. 10 ~ydoog~!i! ('D~:'l) u~ing too M.uhcad !!'outioe devel()~d ~!ilExaInpr(l I ,4 Iloim~!~rn""!'I,t the, Wi.I:k.0.Lee:eqllation. Values of t~e Lennasd-Joues pw:ametClS (0: and£lK) are obl:aiim~"dfirom A.ppelildb;;. B. 'The ooma ~eede(J are:

0, .A

M,Slmol

NEil N:;l_ H~

2.900 3.798 2.827

55;8.3 7WA 59.1

]J' Z8 :2

1l!e!:'e:r()re~

'2Jl~~ D AU{300, I. 11,. 28. 2,9,3;798, 558:.3" 71.4) ~" G,n1 cltrV~ '11'13= D'AD{300, I, 17, 2, 2,.9, 2.8:27. 558.3. 59. 7) ~ 0".728 ,cm'2:/s

Fignre 1.5 shows the"mlll'l. of ammonia (1)rowaRI ~bc catalyst suFface,. wh.ere i1 is consamed by chemical reacrien, and the fluxes of mtrogen(2) and hydrogen (3) :pro!ilillce(l by the FellctlOFlrn1gtat:lng away fromlJJlesame :surl'ace.

Figure 1.5 CatalLytlc crack:iw.s, of ammonia (1) into N"J. (2} IIn~. ~ (3),.

As was ~tJ.AlWIl bcfO:!"e.tliestoi.Cbiomtltry of the .macli'o.i:!ifixes thcrelll!tionmip betweenthe h~.d:ivl.d\.!al flU:ii:es,wlnich,. in tnlS partti~i.l.la!t c<1ie. become:; N'"},. = (- If2)N.,

NJ =-, (312)N I ;'N~ +- N2 + N3 ~ - til' SU!hf<titutin;g i~ ·equation (1·58) WI.':: obtain

Copyr"ghtcd rnaleria'

36

Fundamenta~s of M'assTlll'ansifiu

"Je~~s wi,th a m:,1m;M!!' of t~ S:)I~le:ms i!l!v'Olving CO2 led 1.) dey:iatiQ!t$ from e~peri· oomta! Vam~~!i ofU$!liIly Jess d1alI!'1 4% (Reid et rat, 1987).

Ex.ampJe l.13 Cal£U1ution Qf.Efte<:ti.ve Diffu!ijjJyi.ty ofa. IDiilu.te Solute In ,Q. HomogeueousMb:ture of So)"ents

Estiroa~ tJedi:fJ'l,lsioo t'O¢mc::~etnt of !lc~it; acid ~~: \!'~O' Jow cOrt(;¢!ll:ratio~ di.ffili!;:l,ing ~l1ilO ill mixed :s.oJ'!'Icm cO'.ntalni,tlg 40.0 Wit% dbyl ,1I1oonolllTh water-at a tempe,ratu!w of 298.K.

Solu:tbiID

Let: ~ = ocetic' acid. 2, = w,ate;r, and 3= eth.yJ alcohol. Estimate the jinlfini~e dilution d~f~ ills~"(!In (:ooftk'Jel:lt o.hcetic acidbi! Willer a~ 298K us~I1g equation 0·:53),;. Jibe required data. Ill!'e(Reid et al., 198C;): (~) a.t 29.8; K,Pll' C!g 0.894 cP~ (2) V1i.!1, g 111;0 cm)/moL Fro]1J1,eal!la~iOVl O~48.h Vu ~ 62:.4 e,mlltmal. Siu'bsUtuti.ng,in eq~tiolfl O~.53)"

XJ'~2"" ~ .32 X:~'O'~ anl'f s , Elili,male theiillf! ni.le dilu.tion dif:fuskill ,ooefficient of acetic

acid il1 ""tban(l~ a:t c198tL 1'h~ fQ]iuwing d;Ua areav~la1l'le (Re·id,. et at. ]9'87)~

Aoetic ada

Th' K 1~. K

P/!.blU V"cm~/mo~

c

p.@ Z!l8 K. cP

3,90.41 59'4,8 57.9 n'LO

351.4 513.9 6L4 ~6,7;O Ul43

u~ tbe HaydY.k!'!n~ MiiJ!nas CORt:[1!l~Cm for oonaqooOlll,!iSo]utions. Acoomilng to restriction 3 mentioned .aoo¥e" Ithe molar vohl:me· Qflhe a;ceticac;id '00' tie used ~n .e;qU3i. t:ioJ]J (1~S4~ s,bolll{l be VM ~ 2: x 6204 =: ~24.8 ,emflllOOl .. The molar vo],Utnl': of etmn.ol

hi calculated fro:m ,eqJlI.ll!lioo U·48};Vb8 -- 60.9 cm~:lmol .. Using, the Ma,thcad l'UllIitllile, deve~opedill ~iWl!p1~ 1.9 give~

Vi~= .D tel (39'0.4,594.8,.57, 9.',·~ 24.8,35] ,4,$13.,9,61,4.60,9, 2.9S,.i i04S) = [,Ox: JO·~ (:m~

'The~iscos:itYQf a40 WiI:%aqU¢()1!l!l ~WlOl.SQbUi:Qn. ~l 29S ,K. is Ilu= 2,35 C,P(PCOOIl5 and (ieanloplJs, ].969). BefQre s'l!Ibsdrutiing ~[I eq:ljJation of ~ -62). the SO:h!ltiol!l co.mposi. tion mwt be chillintgedfmm mass !n .mdllU'l'nctkms fornlowing a procedll!Ce s~m1~ar eo that ii]l~usua~edi ~n Example 1.2. Aoc'Oroingly.,a 40 wt% :aqIl;lI';QIU e:l!h:uloW ~lu,tio!1 CQrla veru; to 20 .. 1 !l1QJ%. SlJibsdWtif!g j!!,! ¢qll~~iunJ (1·6i) yields

Copyr'ghtcd rnaleria'

31

D ~ ... ~ (l:~" [(0.20<7 I( U H J.(1~l)" • (1- O.2Itl)( 1.32)( O,S94)'"]

= 0.,59'1 x lO-~cm:l:;s

Thoc::\l,[leri:mcl1tall ",ruue, repolJl:cd b~ .Perkins and Geankop]is, (1969) is 00,,,511 x lO~~ cm2!s. Therefore, the error of the estimsteis 3.5%.

1.4 STEA!DY..sTAJE.IM,QILEClUlAR El:I:FFUSllON IIIN F.LUIDS

'1.4.1 Malar IFh!:.Ix. and tihe IEquation of Continluity"

~., Stal[C: thlOl cquiUkm. of C()jUll)lliilty for II. sy5(cm ofvllil'i.fi!ble:co!l1ifl'OOidQft

2, Si!1il_plfy the 'cqrll;MiO:r!llofcu!iJ;tiIituUyEor steady-state djHiL'iion ia o;nc; directlcuin :rectanglil,lali coordinates :and WilihOllIl chemical rea;cHan.

The equal'j'on of c:onHnuoll)' 1'01' compal1:am A ina rn]xuue descriibes, the .cb~ge of CQ!:t,~~I][a~~o!'l orA with :!Ie!lptlct lQ 1i~<fta :f'!:.~ed p!JiJ~u ~!1! sp~ ~~I.1!I.n!1g from mass mmsfc:r of A and dl.e:Itllca~1 .eacti.oFls prOOUclOg A .. ~:n,vecto:, s:vm:oo~ism, the :re8'l!I,ltll:l;~ eqaarion ~s, (B]iI'd~t at" 1960):

The first term in equadon (1.0.3), tlle diliverg{J!lict\! ofthe mo~ar t1UIX vootor,rcpresents the netntte ~frnol!!r efflux. peT unit V'Qh~:r!'!e. In ~m~ulaf .c(Jti)!xh!'l~OO!!i. this lte:rrn can be expanded as

'llie second lenm:J.io 'eq~Hon. O~) .fe\presentil themJJ']al rete 0'1 ~ccuml.l]:uio.n,(JfA l)lt!' uni~'IfO:]um.e .. The term R ... represemts ~h.e \I'QliUmetrkralC~ of fO:nna.tjon of A by cncmi,·

'~1!~ ~~~(i'l)!l (I:!IQ]e~ of ,I\. fQ~~Q[!l:me'"ii~). An ~p(~$~ig!'l simihw ~t) equati{lf! (l~ 1(4) can be WTIHea for each. OQll1pQfLCllll ~f the Mhicure:

38

i~· i.2.·.·"n

ColIsjdcr~ now. soteaciy-;state ,diffusion (no aOCl!!mlil1ru:Lun) W]fuoutchemkal reacUO!ll. 111. tltaJl case.cqU:3ilion (1.66) reduces to

(1.67)

hl,rectangl!~:ar: ('(l(Jroif1l!'!~, with diff~:5iQn, on]yifl tbe ,o;:-<iin."CnOI'l.t;q.il!Ui,oD (1·67) sLfiI1!· plifles tn

(1·68)

This relanon sHpl!1ate!i acenstant mo:1.u nux of eachcom;poncnt in the :m~xt1!l:re and <I, constallil tota~ m:ciJarHu!{. T.herefore, for stc-ady.stale'. on€·dimenscionElI. diffusion W.il1h~ out chernicalreactton.:

i,= 1"2,, ... ,n

~ N"' .. ..,..n.,..~i~t: ,L., -' - j. - ...... -~~...!-

,r-l

1.4.2Stead!y·State Mo!lecular Difllsiarll in Gases,

1. 'Cakul':uc mQ~illnuxe"~ d1llnn,1]: 5'l¢ady·Mare mo~ll[a_J. onc·dim¢!ll8~Ofial, diffi115;!(1Il ~!l g~.

2. Cllkulflle molar fluxes [or steady-state g/3.S00ll:S diffuSl(}n of A through Sl:agnan.tlh :Md fo.!' ~l,!~rn.ol~r '(lol);n.teroiffusilio!it

Consider ~!~Y·~laoo diffij~iotl Q~ly ~~ ~e zdirecti!on witoout chemieal reaetloa iflla billilaty ,gaseous. mixl!tll'e. Far the case of Qlle"-CI[mensi()1iIaill diffus,iOIl,.equatiO.n (l~ 20~ becomes

FbI' a S~~S m:iX~i ~hhet-emperatu:re and!press'l!lreare coil:lstanf. ca:nd D",l1:a:Je eonSI.:l1Il,t. lil1dc;pe;nde!1tof position aJndcornpositio:n. Accordi:n;glO cqunti.olJl (1 .. 69}. nJl t:h.c

1..4 St&ady~tate Molecu.l!ar D~'ff'liIsion in F~uidi$

39

mo.lar fiU!l(~ ·are: aiso (lO~I~~t Bq;u~tiQf1! n·70) :lna,y. thefl"beint:eg_mt¢lj ~ctwe¢ill! the twoooutrr!dary 'OOnd]tlWl5::

at 2: ='<':1 atz =.:1:2

wh~ l ]OOiC3l\!:i'!he lbeginning of the diffusi(l(l path 0'1'1 rugb) and! .2 the ,cnd of the difi'llsi(I!l p~!!h (JA ]Qw).

H()we'ro!e.~b¢fiQre 'eq.t11Uklll (l~JO)1 can be in~egraled., tbe:bootS:lrp relat.io:ol oolwee;1il1 tbe melar nlil:~ of c:ompol1l.c;[J!l A and the total JIKdar firl.l!lI, (N) muU be establisihed! 1I p,rion based Oil! s~QicfutQ,metric or' cl!I.ergy balance oons:ideratioll!sas menmioned be:fooo, 'The !!i~:I:J~ e'Jri;ample w:!U m~~lr;ue the ,f!~m.plesl case: tha(wh.en the: ~:()(a·] molar nux val'ilishes an~l])eoo i~5: 110 buno; IfiOtijnn cootr']bIJition, to the "111)( ,of eiIDer oo.rnpgnenL

Example 1.14 Sf.eady~S;tateEqulm.olar .counterdUTilS.ion

'fhis is <I, si~uatfon frcquel[l.ly e,nCOI:II~lered, ~n bfnary disti~[ation opeTa~i:ons whell the mow l'ato-Itt heat: o:f vapo,rizrLli(),n tilis1mH3I' forooth oompoi1~l'I!ll> .• In this case, fi8 "" ~ N"~ "". cotISlt,rNj ",. N "" 0" Fat alii ideal ga~ fltix:ture.cquaJllOil (l.'70) simrlH~!!s ta

{1·?2)

w~re w,~ I~I, :;:.~ - ,;:;~= Q.,. Noti~tiluU to, ~qu!'!H{)JI (~-72). d~rS!,'~ f(l.r ¢ql)limzyla[ eounterd1Iffiu"suon.,. the driving ·force fgr mass transfer is lincru:, mat i'J. t!J1;i f.l~1'ii 'mcomponerlt .A ~s; di:oocl1y prop<):I'dolla] to llil~ differen.-cein co]!ce!!J_Tt!.rt~"l:! or p!1!r!iat pre$$,1;l~$ betw.eenl.11e; e"tfe~mcs 1>( the d~ffiusi,Q~ path. Th:is result iSA. dh'ect eenseqaeace ,of tbe fiCt thal ~he proces~ d'c:scrilbed ~~.of a PYiw.1y dUtl.L~iQnal rla.u.uc, with IlQ bulk m.otion ilIDn!tdb:utkm. Ap~Ql of' Y.<t, versus posi:timil would 1be a straight nne.

C0!111idet tile ft}Uow~og ol,)!iI'ltri~~ll1l:l(a!In;pl~, A bl,nary gaseotIS milxllure Qf CQmpon.en.1s A and B aJt aprti~:sme of ] :b.ar and te:mpemtllre of :300 K ~rnldc.:rgoes '8teadJY·fSitilit~. eq,uimoJ;n ,OQuJ].wrdiffuslJon al'o:n.g a.l·mm."tbick diffusion path. At oueendohh,e piI&

Copyr'ghtcd rnaleria'

FUf1Idamre:ntals of MassiJi1ransmr

tile mole fhroliion of component Ais 70%.whHe ~u '(be·oth.ew end ,I! IS 20%. Under these '!iJo!:uiitlons, DM = 11 ~ ,emc!,rs; .. cah::I!I~1I!1e the :mohH: flux of comprn1eml A.

S~luHoft

Dfrect suib.stiJution jn~o equ.aUOi:f! (l- 71) yieJds

,. (tOxW4m~l.OX lij~PB,HO.7-'O.2) ,N ~ ~ i[·.·.· ,!I,') 14lTl-pa~)·. (3~)O K) (] .,0 x ~Ir~ m)

. mol.·K '

.. 0,20 m,QVm~..s

,[11 th,e genera] .cMe. ~@ b1!lk rnotlon 'cMmb!lJuo!) 00 (he fl)1.!!~ must ~ ~!i!dlJ.ded, as shown by equation (l ~ 70) .. Separa~:~rlg the vmablesin equatl,an (~~70), gl.ve-s

'l ['N '_yc (N + N )']1 o::!

, -,.j iI! _ - A _. tl,· IQ

' .. hl:' . '=--,

N"I,+N[!' N~ ~ y ..... , (N,. +N~)I·· cD~~

0,·1,;5)

Ddloo the 1110lar jl'fujravllian. "f.J.' ..... ~

T ... =. N_~ N~ 1FN~

I~ (hiis, eK:p!re$~~or:!, N.4gi \'~s tm ~s~ti've d:i~ti()lr! of z, AnyfWux in theo~ite, dLreL':& lion will CM:ry'iII negativ'C; S~gfli. Notice tbat iIlle.m.okl1' flillUi: fmcllon" ... d~pend:s exdu.

(]~76)

Copyr"ghtcd rnaleria'

1.4 St&ady·~StataMoleculali' Dlffust.on iin Fl'u:iids

It wHI be mown 10 ChaplM 2: til:n fQr difflisionJ under tm!l:l[de~U cotldhio!ls. the NUl{ IS usua][y caJcu];uerl as the pmductoot:W'e'e:A an .empirical maSl'Hrnlls£er c:oeff.icl~enl and. a.linear drhdn~ foree, For co.mpariwn. ]ltlf]Wscso. we willlilow manipt:lliU~ ,eqij8!tioJ! (1 .. SO} terewrite it 11i1.IimnS of a }i:fiCrn drivinE: fQ;!lCC" Since

f),p[J) -P .]' [,.p "]

'tV ""! ~t/j· ~. ". -:] 11n I· .~c ..

" A ItT,'J:·.. _. -. . .

~.- I,J _P[J~ p~ P«.

(1-83)

Then

Co.m:;pariClg e(j,uatkms; O~72) a:nd (1~S4}., when aU othercond:iti.o:n!!areeq!J!!a:l,.t!be ratin efthe !t\Q.1~ fllClx ef oompmtent Aund~~ ·~m'!di;tioni'l i(Jf !ltagnant. B (N1j' = O} ~o ~l:Ie eorrc;spondi.ng va111M! un.de-4' cOI1<Htkms of eqlJl!m-.o'lar c(I!,mterdiffusiO:IiI (NB ."" -!'(.}'isgi.liC<llI by Plpv,t'" For very dilutemlX[Iln!S ef oomponeUJ~ A ill S, this ratioapproacbes a. unit vflll!Ie ... Hm; .... e:~'eT, fOf ,corn.centi'al.OO mixr.ures:, thls ratto C,3n be SignificaNdy higher than 1.(1,

For illustration ptIl"p!.lc5eS;, calclilJate- the ftlolarfl.n of oo.lllperJle,r1lt A for the oot1ldirions ,~f .Bxamp1e, 1.14, but. (PI' diffusi.onofA[I\m)ulgli stagllMt B.

S'olu,tion.

C~lcuiate thepDrtl!a~. pressures flf CQ!lUponcriit B at the ends of the d!ift'usio:n patliJ:: Pf!); '''::; 0..·8 ~~; PBI = 0',3 001, SU~liWI!it!!:l: in ~tl!1lt!Q!) (1 ~S.3), P1J.M = 0"5 .I~" ThereFore, us~mg ~he :res<1I!.h QfE~amp~c :U4, we h<livc

Copyr"ghtcd rnaleria'

F1undamenta'is of Mass Tra,nsf1er

Example 1.16 Produdion of Nickel Carbo'nyl: Steady.Sta,te, ODe~ DimensiOol1a1 Hbmry Fr[ux Calculatlon

Nickel c:ubOi'iY] (A} is prodeced by pa;ji;ingcarlJoFi mOi1O'J;l& (D} at 323 K ar.d i a.il:m Olver a ~k~e] Sli:l:b.T]le fonowlll1ij:. feactiQn we$ p];ioe at the ooHti surface;

NiO) ,+ 4CO(g)l-) Ni(CO'4(g)

The: reaction is VCfY mp±d, so dtaJt tille ~nrthlI, proSSll]!@; of CO at the' metal SOOIlC(,) .L$ cssemti<lUy zem, 'Ibegases d:iffll~ tlrnmgh afi.lm.ll,6'25 nun tblek .. M steady·~tate, esli[[l:!'U~ tfie rnte of pr:m.1u.'C'1i:ion, of ni(;liel caroonyl!. ,in rllIO.]elrn::l .of 1i!olid surl'arePeI second, The composition of the blt~k .gas, phase is 50 Illtll% CO. The bin:w-y ga s d~ffll~~v~ ity IlncfuT Ihes:e concl!iU()ES Is D I4.fI :: 20.{!lrrun2h;L

So:h:Jtion.

Figntlro W.7 is ill. iOchermuic diag:!',arn oflfhe diffus:ioflpmces:s. The sto.i.chi.ometry of the, reaction determines the :re]ali.on between ~e, fiU!x£s: from equation (1.59)" N8 ~. - 4N;. and N~ + N~ ~-3NIo.. Calcu1a.te the :mo]adluxfracl!o1i1.-F.t: From ~lJati.('In 0-76),

~'A '~' .•. Nd , . ~ ltIA _ -~! .N )j+Nfj ~3NA s

C1;lllnbini.ng d~is !l'eslJlllt Wilb equation (~-78} give~, IJ!~,

Copyr'ghtcd rnaleria'

t.4Steady-9tate MoleciliIl'ar IDiffusion in F~uid!s

45

.EJ'ulk; gas phase

® __ 50% CO I{B),50% Ni(C04>(A) .. _.= .. ='-'~

(l~!i r~rn

z := 0,625 mit!

32.:3 K

I

,

Figutre :L~7 Schematic diagram fot m,amp.le 1.16.

~Example 1 .. 1.7 MultioomponeDt, Steady~Staw" Gaseous Diffusion in a Ste£anTh.be {Taylo:rand K.dshna,. 1993)

The Ste:fan tube, de,:j~ted ,~he!lIDadcallyilil FiIM,1I1'1t;· 1.8. :Is a ~iIi!P~Cl d(:;yk:c ,~Om,(:tiHlC:i: l,I\,_~d for rneiL~ri,ng diffusien coeffid:erns in binary vapor miatures, In the bcnom of tine: rube is a pool. of quiescent liquid. Theva.po. th::!!t evaporates, from lhis pooo'] dlffus~ es lQ Ilhe top of the moo, A S~. of g~1i IIC!"OSS the: ttlp' of tile tube k,~ps the mo~~('; ~raer tion oftb.c diffusing y,apors, thereta essentially zero, '[he o(llJlpodwl'l Oflhc\ll!Jporal 'IiliIe; vapo.r=H~fU.id interlace, is its equH.ibrilllfll value. Carty Wid Schro(h (1.975) evapo:raleci a, bin:n:y I,iqrtlid mi:Uiilfe: IIilf :lCe'lone (1) and! meLh.::nlo~ (2J in,a Sref:aJ1lJ (l!l:be:. Air (J) was usedas tl;i.t; ('1l:n:,ie~r ,g:a:s. In one ·(If ~~eilre~:.;:per.imel:lfSlht.: ,oollil!f,MJ8itiotl of 111e v,apor at the, liquid intetfaee was}l1 ." 0.319,. Y2 .' '" 0.52:8, :and >'3 "" 0,.153. Thepressl!l!reamd temperature In tbGgas. phase wc.re99,4kPa. ami .328.5 K,.rospectivcly. The I.e;mgith of tille (hffu!ili(KUl path was 0.24 Ill. The MS diffl!!!ilcm ~m~let!ts "rUle Ihree ibioary P<'!I!1> are:

'D u"" 8.48mWl~.ls V IJ= B,12 ~~ f~ .tl"'l '" 1n"9] mm. ~ Is. .LJ;;;~ .7 .•. __ ...

'CatCllihU~ th~ moJ:'U"ftl!l~e.s of Melone aJ!ld mtlthand] •. arul the composition pn:r61.es pred'.¢led by.~h.e Maxwell~Stefaill eqeaeions, COIll,patre your reSiults w]tb the e~perime:n.~.ll data ..

Copyr'ghtcd rnaleria'

46

Air

Screen

Fundamentals, of Mass Tnu'i'lsfer

I

I'~:";d

mixture

Figure 1.8 SChemati:c diageam of a Stefan tube:,

Sofu.tion

!Fw iii muitlecmpanent mil.1!JNre 0'.1 ideal gu8C!i SIt!CbOliS this.l.h.e MM,wCru~I-StefW!. equa-

lions 0 ~3.5) must be snlved simuha.neousl.y tor the fl!liIxes and the composition pro" melli, At (:oo:$ta_n:llmrn~nu'¢ ,a~d p~S~fe dll'! ~0I:a1 molar dens:ityc .and the binary dif~ fusion coc,ffiderusarecomtantFurthen:JIDre, cli.ffu~,iollill clllc S~cfa!~1 tube Ulk(l~ pl<'iWC' ~iIl! on)y one direction, up the l1!1.'OO. Therefore\; the ooll'l.tinll!ity ~,alion :s~mplifle-sto eqlliilion (1.4)9) .. Al!r(3) mHilllscs doWIl the: tlilre as the evaporating, millxtooo diffuses up, butbeeaase a~r dees :not di,i'.8ol¥e in Ule Hqui.d. Hs H!U::\l H)ils zero (~.e •• the diJfiu~o[l

flux Jl of ~he gas. dawJi !:he mbe is exactly balanced bylbe difflli~k)]j~iiiidliced blllk flux x')N ~p tb.c: lure).

'WIth t~ iisS'umptiO!1i8 iibQv~ t~ Maxw~n~S~~f~~ !'¢I(itiofl.~ gh'en, by ,tSqllH~iG!l (1-35)reduoe ~oa. s}'I<>wm of two flest-ordee d±ffercnti,al, 'eql!lflitiOIlS.

(l~85)

slil~bject to theboutrldary coodi:tioDS

2'",,0.

.i"" 1,2

1.4 Staady~tate Mol:ecul'ar Diffusioniin IF~uid$

47

2J. '" YIIN:;: - )'llNII + ')]N~I - 0 -:.vI -Y2)N1

I~I .F12: F I ~l

l{v2.:Yz!!ll - Y'IN'2, + hNj ~(]~}'~, ~ Jz }NO!.

I~I F12· F21:

bqlJAliQr.l f~-87)invQIV¢!ln.at oll!l.y tWQV"..;wiliable oolrlcC1Iitrniio:l1s (y~ andyzl' but nilS(! '~u;!lknolwn flw;cs (NI" N~,. and N~). From equatirut fl~68). w{'; abtill]'Jlfuro~ additiQr.!a:~I;:(l!l!itra:ints;

Eq,uations I{ 1.87) lind {1.88} W.ilhool!Jndruy eondlfions give'Jl by equation (~~86) cOl'ls~i~l:Ile a li{jj#1datY'-jj(:jll~.~ pta'bJem .. Nolic~ lhat ~h.ere are five first-ame. ordiitnat'j" diffcren~iliill, equations ,(ODEs) and oo]y fowl' oolinda~y OOndll:ioi'iil f>~mcd. TOOre..fmt. an addruliomd piece of .L11li'o.rmaLion, ~c; bootstrap rondfution. mnt be spcdm.cd a p,dQ.ri' tocom.pI~rely define ~e; pr(1)l¢m, Before attemptilil!lg to solvl! this: setofequaliom;.we w~n re,1'on'r!!~I,"de n~¢mi!l1 dime!i!!li]o'!'!le~!!·fQrm:, tlefjn¢ a ... ~tor of (1~me~~!Q~l(':S$ depem,tc:m varilll:lle.s,IiI, !i!llIchl1lat

fl-89)

Equaticms (1~81.'and (]A~8) can roe wriUe!i ;in '!.e.~ ili)f~e comj)!m~:iU~ of \!i!!,:C~ t{UU~,

au. . u':luj -(l-"!lL = J,.I~]J.I:I . df} "" U',I !t·t -·IU;lU~.+ ---"'--=-------"---r-_. I~~~'"'"

dU'2 ~ _. _ I _ .!llU~ - (1-1.11 - n1) IJ",.

_- .It.~u~ - u~u~ + -=--=-----'--__;:____;"-"--"-

d.Q _ r~

d~:;t '" 0 dU4! "" Odu~_ "" 0

diJ - • tit} 'tlf1

(] -00)

whe.e Fl. = FuiF!'2 ,and r::: =FxiF~l'

.AII.rul,dlyi,ic41] SQ~;udOIl of ~cmequ~ti.Q!!!i1 fg:t .s~~an dilifflll$l()11 (N~ ~ 0) in a.t:ernary mixture Is a/va:i]able (Clllr:ty and ScfJrodt, 1975),Hj;}w¢¥~r-with ~hL'l (ibjectfvc of

Copyr·ghtcd rnaleria'

IFlllIn,damentals, of Mass Transfer

IEn,ier data:

Na

11-=-

-,,, F~2

'Nj

'g .,-'~

$FJ:2

FOI!.IIM order Ru nge-Kuaa

1.l1,''11,',4, - ~".." " '1'11:$ - r[l- Vl-' u~'~'1

....... ~......,.::."'," 'I

1 ~ i

I

I!:I"I ,'L, ." II, ,'II" IL,'II, , - (,11- iii , ,-, 1I.,.,)',"lI! :

:z '<II ',~ :~ -" ,- -1 ':iI",~

~~~~" + ~~.4- __ -"-_

! ,,:,

o

(I

o

"'" IIL,~ ~ •• ~ .. I J .. '---'

ilI,3L9" In.~:!:* '

irlllClioml[n tem!$ 01 ~ intioalyt!uts: and Runge.Kim. $OIWoo

I

:S1{u;(I,1I4(11,IISO, ;-;;;; i'Idi- 'I .:lei :,I)"]"O,,mn,D

1140 u ~o

The ~ ul Ind ILQ J_1l! t~e &e¢OIId ~dtifllM()Oums, ,m' Sit, ;mddepemd 00 thol, gUK'5 giuII ct lBO, 1~.,lndl 05()

Figure 1.9 Milthcad solul,iOll of; El3Jmple~ 1.1.1.

Copyr'ghtcd rnaleria'

511

~ - ., ' , .

, Shootin.g metbod:

1

I ~Oj;:;;OXI

Known bout:!dJry ~

Ca;~~1 cont:'e~, prde:s

Computationall results:

1.13101= 1.H!i1

-:1 ,ml, l\I~ H\P ;;; 1 ,J'1i co: UI - ~

!II "'

1:-.,- '" "1' Co "O-;l; j!jm.o.t 1

"'.~"','~ "', ..... ,0: ", -,' '

1'""""" :l 1

: .. ,. ,

ConceJMmliDn !)«iNK

Figure 1.9 Mathcad SlJilmJo:liI. of Ex:ample 1.11 (ccmrimJation).

-l rmiI I' M.. ,::; ::U'U! >J: ~o - '--, 'r'

• .,-,:; '2 .

m :'11

)!3 l'" ~ - y 1- '11 it ~ S"=U(iilIo,ii40.~ol:!.)

Experimental results (c.-rty • ..m ~. 1975):

tu,~ I

: 7

lo.::!~J" '(I,~~l ,0.:::32

10',18:5 111Ul

ylop,:,. ,~:':19' .307 .Z>i:l: ,.!~

UA l7

UA)'II;Ull, Oamlpaf1lson o1il'titillits:

Copyr"ghtcd rnaleria'

52

Fundamentals of Mass 1iransfer

E!sUmate the {)V¢r:i!Ur:400 (lfre:<!ctiQn, ;)t $~e;:!dY~:l1tilt¢, 1"~.eMailiwe.H."$te.f.mdiffig::;~Q!:! ,coemC]elll~ are

V.l2 = 7:~ mm 2; If; Xl H == 230mm11s v.~""no, mm1'ls

Solution

EqlUI:tiOI'lS O~85) al]so appl;yru this p:lOb~em~ bOWeNet, there are: three: addil;tiQnal UrWloWitl. quanti,ues:: N~, J'lli,and >:~, Th~ m(J:J~ rr~:ao[l'$ at the .irueli:aolll (z := 3) canlDot be !!ipe~ifie~ ru:trih:1lrilYi. but 3Jrefixe(i by the reacnon srokhi:omnetry. Th;us, the Interface m_n]e fracli(l!'k'i·mt!~tbe, dieoo:rmined simlJ!!:tanecus:ly wiith tbe mo1!arnuxes, The nux of

Copyr'ghtcd rnaleria'

1.4Staad:y~tate MoleclllI'ar IDIHusiom in :Fluiids

53

ethanol 'is determhlCld 1:!!I the rate O'f ch.emi:c8.1 reacliom ail the catalyst. surface .. Fy!:ti!~!i11!.01l~. for cyc:ry ID.o!(! (If ethaJ1o] Ullt~d~ffij~ to the C!Ua~yst .5UJnime, ] mol of ocetElld:ehydc mid 1 mol of hyd:rogen druffl!ise ~Il! ~be cpposilc di:rec4.i.o:n. Thatis, the ibou.rndary condition and 'bootsttap rdation:s are •. respectively.

N~.=kl'J'ni

NZ ."". N:3 ~ -N1

Eqtl~lion5 (1-94) C<l!J] ibe ~pre55Gd ~~ terms of th~ comporu~nts ·of LIte d!imc4ils:ion~css vector ow dependent variiMes: o~ defined in 'eqlliatioo (1·:89)~ as

(1-9S:~

wbere! ~= k,jFrl/The 5l!ooting method .ij:. aga.iIl.imp~em.c1!ltoo using Mathcad to sclve tbe lX.H!liJjJdilry"' ... a:ll!Ie prohl.ern cO!1!iisti!!1gof equ:~no~ (I &90)a!:!d (~.:9.:5;)" 'l"h¢ c()!l~¢d SO]U:liQ:11Ipredh;:.1$an. Qve;miU rste o:freoction N~ ~ OJ!88 m.ol of elluwol1ltl~ .surface arell-' s, and anintcdace composition of K:8!:JWi]% cth:a.noi. 58.3'% ac~taldthydc~ IlIld 32.9% hydrogeR. More details ofd1e so.lutiolil,inc;ludi.llg me: oonlple1e OOIl.OO11till'3UOtl prom!!~. ~. p1'Q!,':id~d .in A~:i!d~x C

1.4.3 Steadiy·State Mo:lecu'lar IDiffusion In IUquids

Your 'O:bjee;tives in studying, this: sedlonare to be .alJ~e tOo:

w. CIl1cUi~3te m.olar flllIl!.e8 during. s~eady-.staic m.ol¢c~l~r, O'Jt¢-dfl:tl'Cl1Isional diffl:l~klll! ~Ili Hql1ids.

2. ealcu~atemdl~fb,lxes WI: steady.,st;lte wHh$ion of A througb st:ng~ant B. :aliLd:l'o.r eqll~malar counterdi.tJu~.ion. both. ill! ~he Uqli!~d phOl!!e;,.

The Inl!egC'ltl()jJj of eqju.at~oJ!1 O.~ ?OJ to put U in the fOffill of eq~iujo .. (l ~n) requ:ireslh.e assemptloa lha]: DAB md f .arre ,cotlstant This: is s~tisfaclnzy fo~ gas mlx~ tares btu. ]l.ot in the case of ~j.qiU~ds •. wnerebotllil.ma)f vary co.lilsi.dcra:b1y with CQnccntnJ.~ tion, Nec ... ~le.s&, it lis c;ustomary to use-equation (1,77) 10 predict m(lmeclu~~ar diffO-· ~oninliq~ld5 wi~ :lin. :rver:lge c 3li!d ·l:helJ.es,t :a.vem:age: value .of Diljf avarul,aib.lc .. !Eq,uatiiOn. (r ~ 77) is cQ:nveni.e:nt~y Wri,t:ttlll for dilute 8o],l)uiOll,cs as

Copyr'ghtcd rnaleria'

w:here Pi and M are,]he SfIhu:loll delilSlrly amd molecllllar we.igb~, respect!ve~y .. As for ll.aS'-e:s. U1Cl: 'Va1~ .of '1' ... mU~ll:l~ ~sm~]~sh~d by th~ p:l'~vamng c.ircumsl1inCt:s. For tbe most comrn.om!lyoccunin~ caLscs, we have, as forgasese

L SiWOO'y .. ..'it!lik: diffu~on of A ilir(llllgh :}tag~MI B

Fbr this; case, N", ~ eonst, NB ;;:: (lio .. "'A.·:;: 1; then equation (~.~961 becoMes

2. Stead,..,suu.~ ,equi:molar 00l!Ullerd:iffU.sion For this case, N~."" - N{jnndi

E?(amp'1e l.:HI Ste9dy~ta.te· M,Olecular Ulffusi611. in Liquids

A c-mysml of ct:!a~eMt!h~le (OlllS04' :SH:P) dissornves ~!:l II. :laIg¢ tank of p.n:e water at 273 K. Bstimatethe :rare at wblcb the cryslEli~ disso~ves by cruculs:ting the nux of CllISo.'~ fmm tile cry-stal sliI!I1'ace, to ~he bulk. sollltkm .. A:~slune that molecular dH'fllsto:n occurs thLfQll!~b. a liquidlillm IJnifg~mlY 00.01 mm tmck ~U;Nou~_tjh:!,g th~ cryMaL At the htnw side; of the: flIm-iIIdjace:n;t to the c;rysw] surfaee-s-the sornutlon is satll!lmtm w~tih CuSO", whire at the outers:ide, of the flIm th~ so~utiolll. is vl!ri!ua1ly plilm water, The sol· ubility of.cllalcantMte ~n wale:r ~t 273- K. j:!O 2~.~g (jf(!fYst='!lVlOO g. ,!:!f water •. ~d the dens1~Y of the oolXsp(lndi,1l1g saturated oo.hn iQ III isl 140 kg/m:l- (Peny Mid. C~dho:n. 19iJ).Thc dirfl'u:slv.iJty of CuSO:. ln dih.ncaqU1!QDS :so]ution ati 273 K can be, c:IltlmQitcd lIS 3.6><. H)~!O m2Js (~ Problem 1.20)1, Tbe dellJS[ty of pllTe .I~ql,'!id water at 273 Kis

,fif'ioi'l:O ~ .. t",,] :7:;;1::;11',,'(;11 ~!!l"'l ,~

Solution

Ibe e;ry.snd dbsolution pITOCe!l5 may be represented 'by ttl€: eqll!atiOJil

Aoco.r4.i:ng]y, fur' each m.ole of cJb.a1c~llthitl!; (molecu1a:r wcrigbt 249.11) that d~sscilves, :I mal. of C:l!I5i04~molecular wC:Jgtlt 1.59 .. 63} and 5 :~I of hydi!1niQ~ W~L'e!, dj{fll:se tbiro~~h the ~iq'Ukl. fil~ foom. Qle s'1I!rtace; o.fthecry.stal. to ~e b':ull!;, of l~e liquid pha:Se:. ·111]515 :5hoV'o'H. scbeIDll!ti\: a Uy~n F~gurc 1.10 (;s,ubstanceA ~8 CluS04Elind substance B is

Copyr·ghtcd rnaleria'

1.4 Steady~tate Diffusion in ,Solids

51

Th.¢; mU(:lUf{l;af th~ sQHdand i~s inruac~1!)r! W~Ul tbe diffusing S,tlbSll~ce: d~errnine !how dm'us:1ol'1 occurs and jherate of mass u::anSptHJI:. The scUds may 00 polymeric, crystalline,orporou!8.

nJn1 dense.nonporous polymeric membnl!ne$ arewideJy used to s.epru'3!~e8$ andllqjlllid mb:ture>. Diffusion of sohiltes through OOnallJ) ~ypes of polymeric solids IS: :!I!oro lik~ difflJ~iufi IlJiUugh liqu,id ~{lltUi!~Jl~ tb8ilillany(~f I:he ,m'lter ~olid-4ig;u!;jQH phenomena, at rneast fO'I the permaent :ll,asesas ool~te5. Co:nsidc •• for eJ.:llmplf;l" two pertlons .of It, g,a!> at d:ifferent presslilres separated 'by a po~y:meric memJlirnme,The ,g~s, disso]ve~il!l 1!l~ solid at ~h~ faG~& c:lC!PQsed t'Q ~f!egas: to an ex~ent II!Isl!Ially d~redly ipmp'!;u~ ti:o.lia.1 ~o thep.reS$U,re, The d,isoo.l¥cd ~ tlw.~ d~ffiiS(:;ll from tb~ higb~ to' iffic [{)w~pre5i' :r.Ul'!C side ~I!l a, maimer dest:rilmble by .Fick'sfmt .Iaw:.

Difftl!!!fi()."l through ;!l(lpp(ln;IlHl CI)!'SI;alline sotids depends rn3:1'.ked~ly on the crysta~llatti.ce s,u!Llchl1<e' and the d.iffi!t~iI!g e:flti:l.y., 'fhe ~b.atl~!Th.50f diff!!l~~Qrn: b~ Cty~lil]!l!le: oo]i;d~ i!i'!cWude (S~adcf and He:1l1oy, -2(06);

L Diirectexchallig:e of tan:i.cepos:h:iol1 by two :ailO11RS or: ~Oll~ •.

Z, Migrnlklf'! of lima]~ ~liJll(!5, thwugh bu~daltilic:-.e spac-es ealled tme,r;,~lit.ial iSilies". 3. MI;gr.al:ion roa 'Viilmmt she h) ~helauioe.

4 .. Migration ,1l1onglanice ~mperfcc1:.lol]'s or~ra1:_1l! ool:mdarie~"

Oiffu.sioll coe;(f:ic-iell:1s ac:t&lc:la!(~d w.i~h tbefir:;l llilree l~echanism ... can 'vary Wl.dt:Jy fi.l:'!d:are almust aLwlIYS at least one order of m~glljtudc :sm!lJ_tcr Ulan diffu_i)!Jon. coeffidcn1!8 ]11 l(lw·''Ii'i~iry liql!li:dJs. As m:ightbcexpected, d:iffusion bythe imJrthi meehan,ism. can bemnch faster dum by IDe oth~r tI1ree mecha!:!ilsmi.

\Vh~n :solid's a!'e.pOrt:lUS, it. iis p!)ss:~bl,e t'() pllOdiC1: the di5us;ivil.y of gascou5; ~A [iiqu.id solute species hi thcporos, InJ this case, an,}" of tile fonowjng mass4nmsrer mechan:is.ms or ,comb~J:I!a!t.ions t'ile~f !'!liB)!' take iP,l::.C-e l(Seaoor and! Hcnley.20(6):

1.. o'rdlll!a!ry molooi!llaJr diffu)lofi tbr(1)lghpores;, wb~chp.re~sel:'lt lO.rtuOu.s pnths arid hinllilt the- n1(Jl,'e<mCl'U of l;aIle .moJccul.cs Wbc~U1cin:ii.:amEr(!1' ismol'C than 10% of the poo.'i dianwtl.'lt.

2. Knl:ldsl:-II d~Iff'I!:si,Qn. wn[chi~vo]v.es· ooUisiQ~;s of diffusing gaseeus molecl!l.Ies: w]th:~he pore walls when I~he pore, diameter aad gas prcsSi;:u'~iU"~ 5u~hthast mit mol.«:'~JlU"mc'UiI! free p a th ]~; la~ ¢omp~. to' tbe !pore diameter;

3. Surfia.ce dift1~siall, ]nVo.livi!~,g the jumping af moleeales, adsorbed on the po.re w.-d~~. from '(me a(J:iQtplion si~e 10 .anolbe;rba:.'5ea on ~u l1ac~ ¢oJI,(:¢nt~;l!tiQJ:'! drivi~[Ig feree,

4. H)!IdrodYr:I!elmjc ;f]bw tbrwgh (If i!lilQtb~, pw:es dri!,l4m by a total pressure Yi!!d~· eillt.

The va8t majority of ti:U'l 5Qid5 u~d lormass"trarnsfer O.l1CJUtIOJllS Me !pow~~ ..

Porous soHCls, are, rusofrequelltiy u~edinc;l!ralyitilic chenUmd rreactors. Because of tlle;ir impO'l"I~llCe~ the fOUOW]fig sections e<Xllio:re wilith greater detail the fOOf n!i!~!!·1rn!1st~r mec:h.<l!nlis:ms ln parous sellds rn~ntiQIili~d abQv~.

Copyr"ghtcd rnaleria'

58

Fundam:anta Is of Massiiransfer

1,,5.1Stoady-State Binary Molecular Dlffu:sion in POR)usSollds

Wilen treat~n\g dfffu:Jl,on, of :sohinesiIl porot!5 mater.iails wb~!'t diftl:ls:!o!J 1L~ eensidered tD occur o:ldy in she flaid imidc' the, pores" H is eammnn to refe.r to. an effeet]Vlt':(H(fl1si'l.4Iy, D.'Il .... , whi.ch isb.aS~.cd o.t1.(rn) tile.'. lDlal c!I'os:i·sectionai area.,.of ~.!IJ.e

,,~,~

porw!i floLid rul'l1e:r 1h~", (~croo·~"fI~Lioord area of the: pore. Ili_ild (2) Q!l!a ~na$gbt ~~,

rath.C!f ~hall the actualpose path, wb~C:h~s l!ISuaJly qui.tc:, 'lrn'IiUOUS,. Inla,bJI:IiOliry system, if P'O<1'El diff!.l$ili;l~l QoCC~ only by ordInary mcleeuler diftiusio:n. Flc!k's law can be used Wlth~HJ: effe.ctive dif~tis;l.vUy ffi:1t can be expressed in. t:enns (If tllcordiiIlary dlft;u&i(llil c;:oefficiell!t, D,,(pii:s

wl1~[¢ II); ~~. m~ fr.:u:ti~n;tl fQfQ$~ty (~ypi~any 0,$) .Qf hlIe is(IUd ~t!d ''Ii' ~$1De' f"O'~·path torl~QS~I.y (I:Ylf~ca!ly 2: to 4}, .. The ,;orluQJiJyis d'el'ined as (he, :rnti.o oftbepare actuci'llle:ngth to the ruength .if!h.epore were straighil ~Il tille, diR(.'ti.:)J:I of diffusion.

For bmary Otix~iiJre:S. diffllsmg ~l'l$idlil:porous ~ids, ~.c a:pp]k;ability ·of t:lCjuatjO!l (I." ~ OO) depends ~ponlti1e \I.i1!;ue of ii, d.imens~O:[lJ]ess rnli(lca]~ed die 'Knudse.11 lI'umlh'lr, Kn, deflncd!lis

Kn=~ d

(l~~Oli)

wheee d is the ~re diameter ,and lis themcan~rcc path of the diffusing, mo]C(nll~cs. Equ"nioll (~~ 1 (0) :app.Uecs when Kn: is less tJilan aJoout OJicS for all 11w dii:f£l1sin8: species ~~ltba~. 19.80),

For liquids" Ithe !.DCa_1iI free, pathi~ COttIttl.or:l!:Y II, few angs-troms:.so ~ifle Knu,dsen n,1l1.moor is amost aI.waysvt!r}' small and djfi'w;i'On .fnsioo the, ~s is usua.uy ouly by ordinary mol.ooL!llar d1ffUSlO:ll. II!! gase.s, lhemean fme patlli'i ,catibe est1mMoofwo:m the (oilll.oiwing (O.j~~~r, ~99?)~

wh,~e l!i:is tlle,Bo~.I:zmallll i'.:onstant: and a".B is ~he collision diam~Ie;rl)f tlil~ diffusiliig species.

E!iti,rg~t~ th~ ~ff~~hc Q:i.ffu~i;Yhy oJ hyd.rogenin etl:liUle In !I. po.wu s solidi w.ilth aa aVCr~ ~se pore size of 4!000 A,4!lJ'% pooo:s;l,ty,. and lDrillosit.y of 2.:5 .. The g,ns :mlxtu:re ~. ata pressU!re of 10alm and a lemperalur.e of .373 K. :For Ibis SYSilem. the oMimity diffiusioll

Copyr'ghtcd rnaleria'

59

coefficie'Jlt.isgi.vc:n. by D;NB'~ {)1.861P lncm.~ls with. totarn pressure P jnartm. {Sead!er and

Herll.etjl., 2(06), _

Saluti.o:n

C1ilcolflki th£ i!l:h'laJilJ fme tum f.om. equation (1-100). Using d_'ai!a from AppGn.illx 13 for bydJruSeifl ~!'!~ elbaiie,arn:l! f>qUo1t]Q!l (145), cMi :: 3.63S A, TheIl,from eql!i.:l!ti(}~ (1- to:!:), l ."", &6.54"'. FtQ.m (:qI1!1lti,Qn. (l- ~ 0 1), Kim "'" 0.022 <: O.G5 .. Therefore. diffusion. in!dde '!h¢~$ occurs Q!i!b' by oWirn:wy!'OOhwl)l]~ di:ffI;lS~!)I;I, Acta tota!~s~!,lreOrw atm,. DAB"" 0,086 .;;rifls, Substhuting the giVeJ11 Y~I1J~cS of PQrosHy1'!Dd~Q]~iI;I(I~iliy :irn ~Ila':ion (:1,100). D:.mm= (H~ ~ 4 cm,O!ls ...

1.5.:2 Knu:dsen Diffus!lt::nlln Porous Salilds

Wheln! th.e Kmu:beI! Irnlmbe-r i~l~ (Kn » 5.,Q)" the mo[cc:ulor mean fi:eeparJlh is muchlar,g.er thiln the tliamneler(l_f:'llu;:~ cWRneliJliwbich the diffus~ng nlOlooldesre::sid!e:. When tihis ~appc!l S,Il\e Moh:c'lllk:~ OOUI:Il;e f:R)1l1I wa.l:l1o waH r.Ji1'tiJC·l' thaD ,conid~_n8 with 'l)fh~ rno.I,ooul~s. Sinoe mol.ccu..larcoUjt)ioH~. are iI!.I!1im:JXl~rt 1I!I'Id~r the:5;C. (:C!!mJl~tioms, each g~s diffi.1:5e·s .indepeooont1y, This mode oftImlsport l~ knewn as· Knud$l!ndiffo - sian .. From the ki,netlc ~beory of gases, .. in a s~rnigilillcyHn.d~ic.al.pore of diameter d and 'e~'c." t. ,' .. ..., K---"":~_-~ d"~I1:~":\i!"rc_ D " t-,-e"ve" I'-,y (T'r-·ba.l 1''''00)

~_., .. g,.I,I .• 1,1.10;; •. _II~~sen_)_u _,s~ " LY,. _ .K,l' .Iii'! .gl .. _ •.• "'.' ,U"'J._ ", .7 __ .

( ')i~

~ d 8.k1'

{) '~- ._-

ir.;-:3 nM,

(1-103)

Foil' Knudsen. di:ft'ililsioo at constanl1m1a] p;resfiu:rre'. wt can 00 mow!'! thiUIhereis abees;~tfo\l!p' oo~djtiQT! gi'V~fi b)i '(Do. 1'99.s.)

(]~105)

This ls kJlowllilis G.r;aham'oS lOll' oJ e]fiIsi<m f'Or KI:l!Il~1iII diffusion u:f a mu,liticompo· lll!nt S}'Shml. III oo~um.t. total p.n:$SU1e' .. For billary 8M mj_:UIJi.N5, equatiQ!l (1.-1 05) simpl~ficSbO

Copyr'ghtcd rnaleria'

Fundamell'1ltalls of M'ass Trans·fer

ED

l) . - ".1

j;'J""''''''--'

"":n t

(l-107)

(l~lOg)

Example 1.2m Knudsen D~tr-usi(fn loP/omus Solid

A mixture of 0'1 (A) OlInd Na (8) d:uffuse151hmU!g~ thepoees of a 2-.I'illln-:t!ni~cik.pi.oce of lmg,lazed poreelaln at 0. total p£eSSlilre of 0.1 atm. and a tl!~mli1l£e of 293 K.. 'fbi! aver" age pme diameter is 0.[ ~m, theporosi~.y ~s. :3R5%. :md itilile ~o:rtull~ity is 4.39.EstilllmlJie tile di:lfusiol1l 'f[u:li;,es ofboll1. cornpo:neoLS wben 'th.e mole frat:li,{Y.Ils of O~ l.1!re 80% .tnd W% on eiiwr side (If tnc porcelain,

Solu;t[oll

Cakula~e the mea!ll free patb from ,eqruati(1I1 (l~102). US1U!(l dlBila f:1'Q1n Appendix B For oxyg~:n. and ~H:ro~~o, ~d 'Grl~Alion. 0-45)., tJ"w ;:: 3.632 A. 'The n, from C"q1.!l!!lio!l (1- l(2)~l := ,6,&(17 A. From eq,liJ::ltion (l~lOM). K_Q = 6,8{)7 :> !LO. Therefore" rranspon ~l1iside ~fle pores ~s, m!lin]y by Knudsen dif£usion. From. eqwnion (] -Im~, D = 0,,] 47 cm~s,FI'(J~ ,eqL.te!~i(J~ (hl07). DK,to,~ = O.Ol~2 cm2ls:: from~q~!ltionl (l-~ .. Hi! = 1;'112, x ~G-J molim'2"!!i. Erom eql,lilti;on (]-I06)1, N8 "" ~NA {3212.8j'-" "" ~lJJ69Nto "" ~1.360 X lO~3 n1o!'!m~"s.

In, th<i HmJgO of .Knl fromrouglruly 0.,02 10 5.0, a tram~ilfi(ln ~an\ge. roth molbcllllar and .Km:.I.dsell diffus]on have ~I:lf]ucnce.andilhctlllx for b~!Ilnrym:i~tums jf!;giv~n by (Trcybal., l$lW)

(D)

"P'.··.l + - .All. ffI. '. . .... _ y .. '

;I D. . ....

, . ·1(.A~.· ".'

I 1) - )

'.. ,.' c!tUff ,

If . "'1+ . - .. _.. .' - "

.... D ~ .'of,

_ K..A'.Ol!

!f'll.rther:, fQr opre-m;:;lild¢dpurc:s, tlile; OOct~WlP !)datio:f! giveR by cquatron, (1-106) fur constant total pres~l.l:re ;:I!pplici'th_1(ll,lighout tile 1RU18~danl nll~ge I'm soHds'Yl':b('I6Cpo1"C dl!lime~et:1'i are on; the G~ of 10 ,!-1m orless {Treybal" 1980).

Copyr'ghtcd rnaleria'

61

Example 1.22 Combined Molecular and Knudsen Diffusion in 3 . . Poraus Solid

Re,pe.al Bx:amp!,e ~ .21 for sn avellige pore d~amele.r ,of 0.3 ,~U:l'il. while thepomsity arid ~D11umity Rlrl1l!ainl ~l:Iel:lange~. At the te;rnperature of 19·3 K and p:resswre of 0.1 atm. D;.~ "" 2:m cm.2ls.

Solution.

Po. IlJ pore diameter 'of 0.,:3 "m, Kn "'" 2.27',. wlil!ic:liI means tlnal Ibot~ mo~.ecldarand KJI!IJ@$Ct! dl:ff!l!::lJoo ~; imJXl~!1J ~d ~~a'Ol!l (]~lO9) m1.!lS!1i be' used: to calculate N.;t. Sllilce the pore dt1l!!lIete!: ~s Je-ss Hm!'l 1Q IAm,~¢ boot$:lmp reladon Qf equlltilioflJ (1..,1,06) app]i.es:

From equation (~-100)"

_, ~14,49(I.4 X ~,ty~ )(10. t30) , . [.·-14,49 (1 + 4.51) - 0.2]

N p.. - 'S.3 W" (29,3)(01.00:2) III) ; -14.49 (l + 4.57) - 0.8 _

. . ~ mol

"" 3.1] x ~O-'--;:m,-··,)

, .. , .. "~ moill

N B =' -L069N"l =~3J,'1x ~O- _. -~-

, m= .. !;

Knudsen di:ffusion is not !know.n for IqiIjd$:. but Important reduetlens in dift'u, sioo ~ws oo~lJr wh~r.(~ mo]ectlfar size of the ,diiftusil~S$ohU~ ~Qm,~ s!g,nifi.c'al1t[ .e]:ati."e UI 1ihe, pO.1t: size of the solid. In ~l:iat ernst" rhe efiecLive, diffu8i""i~y is given 'by (Seade!fEind Henley. 2006)

(~ .• 110)

Copyr'ghtcd rnaleria'

64

fundamentals of Mass Transfer

, _ (1,8 x 1O.{;P;i-s)(8.3 ]4pa-~~IInOI-K) (300'K)( 2,031mQlim;! -.s) (G.,0254m)

,~ "". . (m.380Pa){ sOOPa) .. -

~ 4,462 x lO~II~m~

fb) At 39~ K. the vi SCi)Slty Qf nitrogen is 220 IJP. SllbsHlU~~11!g ~11l 'equ~li.on (1r-113) the newv:a1oos ohcmpcraturo :aJnd 'll'iscosityRl1ld the: value of~, obtained 10 part {a) wh:ile

!.nai!lWiillinglhe (Wtssure ,eond:itlQ:nS lIuchangedyie.lds N~ .... 1.269 mol1m2",s. Tbis cerresponds I!;) <li. volumemcf[ow rale: of' 10.041 :m.~ (measw:w <lit .300' K a:nd .~ atm)jm::!·s.

1.:5.4 uDusly Ga:s" Nladelfor MultJeomponenrl: DiHusl'on

ModeHRlllJllullioOilipcneJflt, gaseous diffusion i,lt 1'Xl!I"O'Li!> media depends 'UPOD the value o~ the K1.1Jl~dS4..'<.n. number" For very ]arg~ pores. 'OoR'cspom:llingm. \!l!![)' small. values of .Kn, the M;l~.weU-Sl¢fan equa;!lQ!1i$ (1-.34)' caa be: used with effe~tic ... l,':' bi~ dif~ ftlsivmecS s~ve~ by

(],-114)

Fbr v~ry ~,miliUpofC1l, cOrr¢$j)QJldi:!'Ig to verylam(l: va:~:1i(::5 of KIl,. K .. 1ul&!c:n diffl,L~iof! prevru~s:l!r!d the, flux of each i!ld!iv~clualco:mpo.n.e,Tl!t LscnlJcul.atedi using eqaatloas (I- 103,}~o (I .. 108), ~nel~tber case, ]f there Is a si,gn.ificant difference il:l total] ]l':I'ie-S;5ure across ~be:so!.id. the liIydrodyna:mi.c flow oon,tribtltiQ:Il mnl be :added.

M0&Lit!:g m,ldilicompOiI1c~u. diff'u,skm. ,inpo;ool!!s media is compl!i.cared wben Ute mem :free pathi ofthem.olecule!i~s on the order ofmagrntllde of tb:cpore diirunelc·1. The difficulties posed. by ~hls, h'll~rm.ed~at~ case may be circllmVmlted by ,affietRod p1iO(XIlJOO by Maxwc;U inI 866. He !!ugg,e!i~ed that ~ihe porous: ma/tenal ire desetibed asa S!lrIp.I>lemenlar:l1' "<lust" spedes cffi1sist~l!ig: of VCr)' 18!l'gem(lLec,u]e~ thi'd !l1'(l k~pt!ifi(itiMless by IlIiI!l unspecifiedl Cixtcm.i.tl forcCi. 'F.hs Chapl1W1:-ffiinog kilietk: ri1eoty j~ then applied to th:~ i"i~W p~eii(jQga~ mixture, wJi~by tlleiii~e~rio:r!be-1wee~n the dust and gas mo·recull,e,s &i:mulatr:.s ~he ]l1teracti.on between. the sOl~d matrix and Ihe~g!ls species, III .11ls way, one is mo~ong~1'" faced with !he pnjbl.am offlull,and comPQ!1;jti<lJ1!'!Iari:a~ tioasaeress :a pam and prob[ruru; ooi:aJtcd 1.0 the SQIM gcQ~.

ne price paid fUflhis simpl~ncllti,QIlI :is tinaii certain ph.ysi.<:a:] fe::alt.l.!I!I'es uf Itbe parous moo.i.lrlmare "1!JiSt.." 0.11':- uf the more ~mportali1!ti:s:sllte~,i:; ·~at die lIIlQdel is filO iOOlger dealing: with dhatlllel~ off:milo sl~~co~p!)!WiQ,g «t idle [poms hi tiliu; :reid meditun,. Tbus, there iis H.Q ~1lL~uctio:n OIf ~be hy~ynantic no~esi;n fbrmid deveiopment ,of tlite eqYilti.on~.nes,e na.ve ~o be addedle:mpir.icaW~y. The wu:rking frum of ehe (lusty itle:ai gas model 'equatio!lsis (Hig[~r tlt at, 2(00)

Copyr·ghtcd rnaleria'

1,,6 DIHusion with !ialnogenso'us. Cl1elil1icallReac::tlon

65

.p .. f7, + .:1.', [1"']', ~. P' ) 'O'b _ .,....~ Y;N.I. - .:Ill" . N .. ·L.

_'.-. ,,}.,._- ,+'--- "Ii' -L ----

RT .', RT . ~;{id .' . l~t ~4 DI(,td

Noti~c; that 'equatiOtl (l·'~I] 5) ca;~. be wri.tter.l for .llW the n rompo.ne~nts, unEi.k:e rhe or.i,g~ jmd MaxweLL"Stc,fllll!lequ:atiolil!S. w:hricb are va!l:idfor o.nly u - 1 co·mpo.n.ents:,. However, 3Ilothe..,r varia!bl@, th.~ total POOSSiUUl, has been, ac!d.e-d. Therefure:, a. bootstmrprela.tion berwufl! the fl'y~e~ i~stin Jle:eded ~o comp.lete the problem fQm1l!.la~ion.

An e'XIPHcit express iOIl1 fbr' ~ne; weal .pressure gradiell'lrt cal!lJ be ,obtained fro1m <lquM.ioo. (l'~ )5) by :summing. wjtb respce.t to all ccmpcrJlct!ts~

(1·]16)

.Equation. (I ~116) can lbe su:hstrutu,led into {I ~ ll::5),wil'i:nel!lfor.n ~ 1 components,to elimi~le the ((IUd :p~S~1[I[f!,l; ~di~!n from 1iI.~ eqlllj~tiM$, 11Ull r¢sIlUi!!;B .r:! ,_ 1 ¢q1IDa:·, tloas are then augmemed wi,lffli equati.an (l ~116)!lnd ~he llOOIStra,pcond.ili,a~. to salve for'tf:J.('; nnuxes and the ~olll!l procSsuro gmdi.¢nt. 'The rosuLtling bornmldary"vMll.op.robLem call be :soh'ell bym(ld~fylflgm.eM!I!IJtc,ad ~nmt de've'loped mill .Examptcs 1,.1/' :and i.ia

1.6 DtFFUSION WITH IHOMOGEiNEOtJSCI-iIEMICAL IR!EACrIION

:I., lXnn~~' '(;Q~ Q·f!"!l):mog(;tl~~S I~MmkaJ ~jtilior!, !Uld ~c:am tnincorporate, i:t ~liI1rolhe, ,oQmrtinui~ty eq;1!IattiJon.

2 .. Define the Damk!OOJe.r number for fmst~rd~r ,ehem:ic:al. oeactl.OIl:,IUI" ;1~!!~!1!! ~~. eff~ Oil! mal:;Ht~U'!!lI~~r t.t'~i.

3. Dedve fhe Kragh m.ooeJ fur ox:ygelil transport :i!:1 skcLcn~ mu~d~ whh Mtehaelis".M~:I'I~cn clilcmicalNacUon. kin~ti.cs.

In mooypnlCCsscs, difflLSiO:l'l.ral.C:s arc a1'cred by nom-ogenoous chemical reaetions . .A homog.eneous reaction is one tlmlrtakes: p]aos in.soh.J!tion .. In tlruat ease, tihe RII. teOOI in eq"U,U1IOlli 0,64), rep:rese:nting ~hevQI~metrk late o.f fiJrrn~ti(lf! of compo:rn¢n~ .A. by cbemkalreactkm. 15 di:ffeR:m from zero, The fn]~bw]n.gex!lm!pl~sm;U:Slratc some ·of tITI;c effects ·ofhornogcmoo"Q ch~rliljcal ~1ii(l!l!$ 011 ll¥l:Ssl:raJlSfc!l' rn.t~s,

Copyr'ghtcd rnaleria'