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e i a C h e m i c a l f s i n e e r i n ss d e r i n e d s" . . . t h e a p p l c a t i o n o I t h e p r l n c i p l e s f t h e p h V s i c as c i e . c e s , o t o g e t h e rw i t h t h e p r i n c i p l e s l e c o f o m i c sa n d o h ! m a f r e l a t i o n st,o f i e l d st h a t p e r t a i nd k e c d y t o p.ocesses proce$ eq!ipmeni ln which m8tler is a.d trearedto effect a changein slate, energycontent, . o f c o m p o s i t i o n . . " ( l J . ' T h i s v e . y v a g u ed e f l . y n i t i o i i s i . t e n t i o n a L lb r o a d a n di n d d n i t e a s t o t h e y e x r e n to f t h e l i e l d , L t i s p r o b a b l ya 5s a r i s f a c r o ra d e r i . i t l o i a s a n y p r a c t i c i n sc h e m l c a l e n g i o e e r w o u d g i v e , l t s h o u l db e n o t e d t h a ! c o n s i d e r a b l e emphasis is placed on the process aod procs$ c q u i p m e n tT h e w o r k o f m a n y c h c m i c ae n g i n e e n , l p w o u l db c t t e rb e c a l l e d r o c e $e i g i n e s i n g . The proce$ may be any co Iection of steps n v o l v l n s c h a n s e si n c h e m i c a c o m p o s i t i o no r L i i v o l v l n sc e r t a i np h y s i c ac h a o s els m a t e r i ab e l n s n l prepared, proce$ed, sepa.ated, or p!ritled The work of mary chemlcalenginee^ nlo ves choosifg s t h c a p p r o p . i a t e t e p si . t h e a p p r o p . i a t e f d e r t o o a n formulate proce$ for accomplsh g a chemica , o m a f u i a c t u r i . so p e r a t i o na s e p a r a r i o n ,r a p u r l l c a t i o n . S i n c e e a c h o t t h e s l e p s c o n s l i i L t i n ga proces k subject to variations, the proces e.g neer musr also spccltythe exaci co.ditions under which eachstep is to be caii ed our. evolves and equipment m!st be As the p.ocess r d e s i O n e t h e w o . k o f r h e c h e m i c ae n g l n e em e r g e s d, a r w i d r t h a i o l t h e m e c h a n l c a ln dc i v i e n g i n e e T.h e . i r a n . i e ro i p r l m a r vr e s p o n s i b i l nfy o m r h e p r o c e $ enqlneerto thc mechanicale.sineer ca. take p ace Mtrslacrorily at various srages the design,so ir ls of

l m p o s s i b l eo d e i i n e a l i x e d e x t e n t t o w h i c h t h e t r $ p o n s i b i l i t ys h o u l db e c a e d t h a t o f a c h e m i c a l e n s i n e e ro r a n a g e a t w h l c h t h e m e c h a n i c a l i e i g i . e e r s h o u l di a k e o v e r r e s p o o s ilbt y i o r e q ! i p . w A t t h e t i m e t h e d e f i n i t i o nq u o t e da b o v e a s presented,the physica scle.ces referred to were pfirnariy che'nhtry 6nd some chsical physics.As t l t e ! n d e r s l a n d 9 o f m a t h e m a t i c a m o d es o l n l c h e m l c a p r o c s s s a d v a n c e sh e v e a t m e n to i t h e l i, s o c h e m i s t f ya i d p h y s l c s I t h e p r o c e s i s e x p f e s s e d In cofsideEbly more mathematica lorrn. l n c r e a s l f s s eo t t h e r m o d y i a m i c s , u l d d y n a m i c s , f u a n d m a t h e m a t l c atle c h n i q ! 6 s u c h a s p r o b a b i l ( V a n d s t a r k r i c s , a t r i x m a n l p u l a t i o na n d c o m p e x m , variab s is chafacle.istlc i modern chomica e o engineerlng pract ce. . most processes be ng c a i r i e do u t o n a h r g e s c ae , h o w e v e .t,h e c h e m h t r Y y h a s b e e n p r e v i o u s w o r k e do ! t , a n d t h e p h y sc a . c h a n g e sn c i d e . t t o p r e p a r a r i oa r d p u r i f i c a t i o n o l i y t h e r e ! c t l o n m i x t ! r ' e sd e m a n dc o n s l d e r a b lm o r e stldy than doesthe chemicareaction. .eq!eni F a p p l l c a i i o no f t h e p r i . c l p l e s o f p h y s i c sa . d o l physical chehislfy is requned in rhe processl.g stepstbat p.oduce physlca chanses, such as vapo. i z a t i o n , c o n d e n e t i o . , o r c r y s t a L L i z a t i oA.s a . proces evolvesinto a planr and the work merses o d w i r h r h a l o f m e c h a n i c a e s i g n e r eh e s c i e n c e r t, mechaiics be.ohes increasingly imporiant. The chemlcal engineers who speciallzein eq! pment must halie thoro!gh and extenslve srounding Ln mecha.ics f materials. o A l l o f a n e n g i n e e r 'w o r k m u n b e q l a f t t a s live, and mathemarlcsis therefo.e a f!ndamenta y l o o l o f t h e e n g l n e e rU n i o r t u n a t e , o u r ! n d c r . s t a n d i n g f m a t h e m a t i cis l a r g e l y e s t r i c t e t o t h e s r d o

a domain of linea. mathematics, nd, eqLally unlortunarely, chem ca molecules seldom be,,dve in accordance with li.ear mathematica rules. , E n e r q y a n d m a t e r i a lb a l a n c ec a l c ! l a ! i o n sw h i c h are fundamenial to any processstudy, can usually w be erpressPd i5 .o idenLe ord pre.rio. il terms of linear marhematics,as long as we omir from our considers atomic a.d nuclear processes r o n s . I n r h e e c o n o m i cs t u d y t o d e t e r m i n e t h e - , , . m o s r p r o f i t a b r e o p e r a r i n gc o n d i r l o n s a n d I n a c c o L n t i n f o r i h e s ae s . e c e i p l s n dd i s t r i b u t i o n f g a o i n c o m et o p r o f i t sa n d c o n s , l r c l u d i n g e p a c e m e n t r '-o f r h e p l a n t m a t h e m a l i c a l c a l c ua t i o n s a r e The existence r contemptaiion f a proce$ o o implies that d mater al ls ro be produced ior which c u s t o m e rw i l l p a y , l t m l n b e d e l v * e d i i a q u a n e t l l y , o f a q u a l i t y ,a n d a t a p r i c ea h i c h a r e a c c e p t . a b l e t o t h e c u s t o m e rS l m u k a n e o u s l yt, m u s t p a y t ior materias, labor, and equipheni lsed in the manutacrufeand rerurn a prcfit over and above all costs. l',,lanymaterials produced by the chemica i n d l s t r y a r e p l a n n e da n d p l a n r sb u i k b e r o r er h r e a l m a r k e t p o t e n r i a lh a s b e e n d e v e t o p e dF o r a . ! o n p l e t e l / n e { p _ o dr c l s o f e e s l r a t e o f r r e ) i / e o f t h e m a r k e t . n u s tb e m a d c ,a n d r h e p l a n r s h o u t d bsc! edin propofiion. Tfe f-ra--e)lioas aloecr o! r.g.ree.in9 p r a c tc e h n o t u s u al y e m p h Nz e d i . l n d e r g r 6 d u a t e r a i n i n gb e c a ! s e f t h e g r e a tq u a n tt y o t t o r e c h . i c a ll n i o r m a t o n a . d l e c h n i q u e sh e s r u d e n ! r T L s i L e d , T l a r t i ! a d l b e q l d l q . ' o L ( r o L r ) ei ( irnp ied by the fact !hat failuresof you.O engineers because ol personnel p.oblcms are at east five i m e s a s f r e q ! e . t a s l a i l ! r f e s e c a u so f i n a d e q ! a ! e b e t e . h n i c a lt r a i . i n q . A l l e n O i n e e 6 u s t r e a l i z e h a r m r th! | dL$ , 1 ri 5 I 'p. dp so4 no r"q I rar t e a m e f f o . r o f a l l p e r s o . f e . V a l u a b l .i n l o i m a r i o n can be obtained irom operato6 oj ihhed w e d ! c a t i o n ab a c k q r o u n d h o h a v eo b s e r v e s l m i t a r d p . o c e s e s .T h e p e A o o w h o h a s " l i v e d " w i r h a n operation has probably obscrved actions and effects and ha5 earnedmethodsof derai ed cofrro that cannot be approached forn6 rheory aLone, by T h e b e s t f g r . e e rn g j o b c a n b e d o n e o n l y w i r h proper regard for a availabe facrs regarde$ of their source, A new proce$ or rhe techntca improvement of an existing one designedwithoLt due regardfor rhe operators k !suatly desiined ro { a i l u r e T h e s l a r ru p o i a n e w p l a n ro r t h e i n s t a r . a rion oI a technlca chanse is ikety ro be mlch a s m o o t h e r n d t h e c o s to f i t m ! c h l e s s f i h e o p e r a t i ing peconnel !ndeGtand the obiectlvs a.d dr o c o r v i n c e d l l h e l rs o u n d n e $ .

SOME BASIC CONCEPTS

Before artemptinq ro describerhe operations rhar comprise a chemlcal processi il is nece$ary to Introduce severa basic concepis that m!sr be unde6tood beiore a descriprionof rh operations

There exkts tor a combinarionsot phasesa con ditlon of zero ner irre.change af praperties ( d s u a l l y n a $ o r e n e r g yi n c h e m i c a p r o c e $ i n q ) c a l i e de q u i i b r i u m , F o r a I s u c hc o m b i n a r i o n . o r s a t - p q u i l i b r i u m h e d i l f e r e n c ei n c o n c e n t r a i i o n f t, o some property berwee. ofe i. the exislinq cotr. dition and onethat wo! d exkr at the equ ibrium c o n d i t i o n i s a d r i v l n gf o . c e , o r a p o t e n i i a d t f f e r ence, tendlfq io alle. the system toward rhe e q ! i b r i o m c o n d i t i o n .T h e t e n d e n c yo t t h e r m a l e.ergy to flow f.om a fegio. of h !h concentratron - hot body - to a reaion of ow co.cenlra tion - cold body k u i v e r s ay l fami iar. S i m i l a d y ,t h e l e n d e . c yo i e t e c f i i c ae n e r g yo f l o w t i t r o m a r e g l o n o f h i s h p o t e n t i a lr o o n e o f t o w p o t e n t i a l i . a c c o r d a n cw l r h O h m t l a w ( / = E / F ) e i s w e l l k n o w n .T h e t e n d e n c y f 6 c e r i c c i d t o f o w o a iro.n an acetic acid.water so ution tnto a. ether phase rn contac! w th t is Less widetv known The d e s c r i p t i o no i r h i s e q ! t t l b r i u m i s c o n s i d e r u b l y m o r e c o m p c a t e dt h a n t h e s t a t e m e n o f e q u , r y t o r t e m p e t u f e s iw h i c h d e s c r i b e r h e e q u i i b r i u m s or enerqy ol mo ecules. luarerla wil i ow lrom a r e go n o r h l g h c o n c e n t r a t t o . a c t i v i r y )! o o . e o f ( o w c o n c e . t r a t i o n ( a c l i v i r y ) ,j u as heat and e l e c t r i c i t yf t o w t r o m h i g h . r o o w c o n c e n r r a r i o . r e g i o n sn t h c s i t ! a t i o n s e n t i o n e d b o v e . i m a T h e e x p r e so n o f r h e e q ! i b r i u m c o n d t i o . s s i a m i l i a r t o a l l i n c o . n c c to . w i t h e i e c t r i c a a n d thennal energy.The concentraror oI slch enersy 6 expresseddifecr y as a votraqe poreniia or a temperature, Accordingly. two bodies al rhe same e e c t r l c a p o t e n t i a l ,o . a i i h e s a m e l e m p e r a t l r e , w i l l b e i n e q u i l i b r i u m r h r e ! a r dr o t h a t o a r r i c u t a . w k r n d o f e n e . g y . F o r t h e e q u i l t b r i u mb e r w e e na liquid and irs vapor, rhe vaporpressu.e cu.ve is r e a s o n a b La m l l i a rT h e c u r v ee x p r e s s d n p r e s s ! r e fy , is u n i t st h e c o n c e n r r a t i oo t v a p o rr h a t t s i n e q u i t i b n rium with rhe pure tiquid when both arc ar a s p e ct e d r e m p e r a t u r e . c a s co f a i q u i d m i x t u r e , t e q L l i b r i u m m u s t e x i s r b e r w e c nr h e t j q u i d p h a s c and Ine vapor phase in regard ro each and elerv c o n s t i t u e n tp r e s e n r .F o r a b i n a r y m t N t u r e ,t h e r e l a t i o n k a r e l a r t v e t y i m p t eo . e d e s c r n q r h e s b c o . c e n t r a t i o no r p a r t i a lp r c $ ! r e o l e a c hc o . s t i r u

&

ent In the vapor phase thar is in equitibrilm with a liq,uid of one particutar composit'on ai the spe( r ed lenperat!re. obvioustv, rhe vaoor w, hp o i d i f l e r e n tc o m p o 5 io n w h e n i r 6 i n q u i l i b n ! m t with different liquid mixtures. The expr;$io.s jor equilibrium i. hutrtcomponenr mixtur;s b*weer the liquid phase and its vapor or berween two liq!id phases having paniat so ubilities become m o r ef l o l v e d . l n e v e t y c s e , t h e c o n di o n m u s r . o e ! r r r e d r f J r i h e p o r e n t i a f o r e d c hc o f * i n r p n i t k i d e r t i c a i . a 1 q u i t i b r i u m h a s eo f 6 p a n i c u t a f p s

Iqo pnd\e, ttdr Jrd I ot il eq I tib,.-r

When two substances phasesnor at equIibrium or afe brought into contacr, there is a rendencyfor a c h a n g eo r a k ep l a c e h a r w i t r e s u t i r a n a p p r o a c h t t t t o w a f d t h e e q u i i b r i u m c o n d t r i o i .T h e d i f I e r e n . e b e r w e e n h e e x i s t i n g o n d i l i o n n dt h e e q u i t i b r i u m r c a c o n d r t i o nk r h e d r i v i n qf o r c ec a ! r n q t h i s c h a n g e . ca. be e\presed in lerms ol c o n c e n r r a r i o no l l h c v a r i o ! s p r o p e ( i e s o ' 5 u b . 5 F 5 r J n c e s o r e ^ a m p t e ,f t i q u i dw a i e ro f t o w e n e r q V c ^ . c e n f i a to n - t h a t n , t o w t e m p e r a r u r_ s e b r o u g h t . c o n r d c w i r h w a r e fv a p o ro f h i g he n e f o v i c o n c e n f f ao n - t h a r i s ,h t g hr e n l p e r a t u r-e e n e r o v t wi be $anslefted from ttre vapor pnase to tiir l i q u i d p h a s e n t i l r h e e f e f o Vc o n c e n ! f a t i o n r h e u s s a m e . b o t h p h a s e st.n t h t s p a n i c u t a r a s e i f r h e c , a m o u n to f q u i d i s t a r g et n c o m p a r i s o n t i h t h e w v a p o r i _ b o t h h a s e s e c o m eo n e b y t h e c o f d e r s a . p b t l o n o f r h e v a p o ra s i t s e n e r q y s n a n s f e ( e d1 ot h e i cold water. The fl.a mirtlre wi| be an increasecl a o o u . t o f l q u i d w a t e . a r a h i q h e rt e m p e r a t l r e t h a o i n i r i a l l y a n d a d e c r e a s ea m o u o t o f w a r e r d v 3 p o r .T h k c o m b l n a t i o n e a c h e s q o i i b r i o mv e r V r e q u c k r y , a r a t e m p e r a t ! r es u c h t h a t t h e v a p o r pre$ure or the warer equatsihe presslre of the v a p o r p h a 5 e .A 5 i m i l a rt i n e o i r e a 5 o . i n o d r j b e c l o l l o w e di n r h e G F o r r w o e r e c r c c ; n d c r e r s chargedto dlfferent con.entrarions Le., vottage), rr rhey are brought inro etcctficat contact, rhe e l e c t r i c a lm * g y w i l l f o w f r o m t h e r e g i o n o f nrgner concentraton to that of tower, Both c.n de.se6 wil be charged ro rhe eme vottaqewhen e q u i i b r i u mi s r e a c h e d . A less familiar ryps of d.ivifg force exisrs when a solurion ot acericacid and water is brouqhr in contact wirh isopropyl dher. The ih;ee j materals wlll lsualy separare.1o rwo tiquid phases, each containi.g some qLantiry of a I three componenrs. The conce.tration of each of rhe lriree s!bstancesin eachoi rhe iwo phaes m!n be k . o w n t o d e s c r i b e h e e q l t t b r i L m c o n d i t i o n _f r

iogeurer, a rransfer anatogous rhar ior eleclricat ro and Inerma energy wi occu.. The resut witlbe d lranster of isopropyl erhe. ioto the wateracid pfas-"and rhe transfer ot both water and acid i.ro I r e e t t e ' p f d d , . 1 . \ p p - t p r d t o e o c nL o n . t l dl ii rqp .^o p bse,, Ttne . ncofven eni and simp e expre$to. Ior the chemical p Lq dl hqcd rf" arolr I pq ot mass in such a phase is . o a r y o ^ \ s od e , S ,d r e o . l V a r i g o r o u sd e f i n i t i o n ,b ! r r h e m o r e 6 c c u r a t e n c a mop comple. iuncrrons f actv ty fuqacirvanc o , r'ee elerg/ d"nd1d 1o.p Kno{ledoeo, uDo p h y sc a c h e ms r r y r h a n i s e x p e d e da t t h i s t i ; e . t . i h e p r e c e d i n g x a m pe t h e m a s s o n c e . r r a t i o n f a e c o c o n p o n e n t h d i f f e r e n t i i e a c h p h a s ea t e q u i | b I n a t r c a s e sd i s c u $ e d a b o v e , i h e p o r e n t i a , l c o . c e . t . a 1 n ) o r a n e { h t ' . g s u b r t a n co f o i N r u r e o e w n e n ( o n p a r e d w r h r h e p o r e n l i a la r r h e e q ! i b . | ! m c o n d i t l o ny i e t d sa d i i f e r e n c en p o l e n t t a l ! h a t i s , a o r ! r f g r o . c e ,t e n d i n g o c h a i g et h e c o n d i t i o n s r o r I n e s y s t e m o w a r d l h e e a u I i b r i u m ,T h e d . i v t . o t f o r c s , o r d i f l e r e n c e i n r h p o t e n t i 6 to f e n e r g y ; s o matrer, witt re.d to prcduce a change at a rate y a r r e c t p r o p o f t i o n a l1 0 t h e d i f f e r e n c ei r o m t h d e q u l i b . i u mp o t e n r i a tT h e r a t ea t w h i c h ! h e s v s t e m . c n a n s e so w a r d e q u i l i b r i u r i k o n e o i t h e m a j o . l !oprcsto be coveredin this book. O b ! o u sy , t h e s e p a . a l i o n t a s o u r i o n , o r o r h e r o p h y s i c a l l V o m o g e n e o um i x r ! r e , r e q u i ; e s r e t e r h s p entrar v6.sier of a consrirue.r to a se.ond ohase that may be physica y separated irom the resid!al ' n i x t ! f e . l l l u s r a l l o n sa r e t h e d e h ! m i d i f i c a r i o n i o 4 t r . 0 y c o n d e n s i n g r b y i r e e z i n ga p a r t o f t h e o morsrurei r the !se oi a tiquid sovent rhat is o nso !b e in rhe unextracred materia. Any hrvo p h a s e t h a t e x h l b hp r e f e r e n t i a ti s t r i b u l i o n f c o n s d o srituefts and rhat can be easityseparatedmay be n v o l e d r n a s e p a r a t r o n o e r a r i o n .T w o s o t i d o p h a s e s a y b e v e r y d i f f i c ut i o s c p d r a r e j t q u i d m a a . d a g a so r s o l i d ! s u a l l y m a y b e a s i t y e p a r a i e d ; s r w o l i q ! i d so l a p p r o x l m a t e e q u a t d e n s i i y n dn o y a ntertacrartension may resistaI practicabteseoara_ t i o n m e a . ss h o n o i a l t e r i . qo n e o f t h e p h a s e s In many of rhe operarionsfor t.ansferrins e.ersy or oarera rrom one phase to another, il is nece$ary to bring rwo streams into conraci to perhit a chanqeroward equitibrium oi enerqyor of

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rons whereexrremety co(osivecondjrtons force lrequenrrepatrs. and n orhe6 ior vanous soe. nc r t u s o n sB k d L 5 eo l r h e q r e a r ep r o d u c i r v i ro f . r v contrnuously operatinq equipment and the resul lant bwer unit 6st, it h usuatty advantageorr io o p e r a t e q u i p m e n r n r i n u o u s t yh i sm e a n t h a r co T. s l r , h o w e v e r , t \ F t w o s J r e d T eb e i l q c o n r d L F o a , e i m e r s n o t a v a r i a b l en r h e a n a y s ko f s u c ha i made to flow in oppositedirections, trafsfer of process, excepr dLringthe rather briei starr!p a.d rnaterial nergyin considerabty or sreateramounts srrutdown periods. The rime rate of transfer oi or is possib e.Sucha flowpatrernis knowoas.ou,.e., reacnonis importanttn Jixingthe nece$ary si:e and capacity equipmeni, the performance of bur is As an illustration, a srream hot mercury if of xpected be the eme today,tomoirow,or nexr lo and a stramof cold warer ar atowedto .each y e a rr i t h e o p e r a t i nc o n d i r i o n s m a i nh e s m e . g re t thermalequilibrium, remperature the attatned can Conditions nor consiant are rhroughour system a d b e p r e d i c t eb y a h e a r ad n c e f d r r e . o g - i . er.f p o r al any time, bot those at a parttcular ooint are , e l a t i v eq u d l t i t i e so ' L h a \ r - e a a s .r t - e i i n n a l temperatures, and their hear capaciries, the tf When smallquantiries materiaare to be oi streams flow simLrltaneousty the eme rnrer frcm processedi is ofieh more convenienr charge h ro p o i n t t o t h e s . m eo u t t e tp o i n t ,i h e e q u i t i bu m t h e e h t i r e l a n r i r yo f m a t e r i a o r h e o q u i p m e . r , q rt temperature definite, h andthe pathisasindrcareo p r o c e sis i n p i r c e a n dr e m o v e p r o d u c r s r , the This i n F i g u r e. l r . l f t h e s t r e a . n s em a d eo f , o w r n l sr t n called batch perarion. a o o p p o s i rd : r e c t : o ns s b r t e r r i l g t - e r c L , y . , u w e s, r T A n o p e r a t i o nh a t i s v a r a n t w t i h l i m e i s t d o w n w a - t h r o L g h 1 J o . l o w 9s r , e a T f 4 d k , , d a 1 spoKen as6 frarsErr or ursteadystate,tn can. or ' o . l t e e n t e - 9 h o r . F e r co - v ir ;s po$ble 1 J st.oan t.asrwith that sooken of whi.h to raEethe temperature the eavin!coot.wdrer c o n d i r i o i s e i n v a f i a nassteadvstete inc h r . o oi r t wirh time quen a streamto a tempe.ature 6bovethat to which the steelpaft for heat rrest,nq and freezn9 ke cu6es rne.cury streamis lowered it teavesthe 3s conrac! n E d o m e s t i c e f r i q e r a r o rr e t u s t r ao n s o l r a r i . g e o u i o n o n ta s i n d i c a r e'o F , g L r e t b . T t - e . 1 L unsteady{t6teoperations. babh operatians, In p c o u n r e r l l o w r i i c i p l ei s J s o : 1 - a l y c h e r , c a l a r m o $ the c i r a engtneennq opeGnois In order to Dermiroreater shutdown e n t i . e y c l e 5a s r a r t . utp a n s i e n tn da transient. a cantinuous ln apefttion,tlle transferof a p.ope.ty th6. woutd be ind-cated t i m e d ! r i n qw h i c h h es t a . i - ! p . a n s i e n tx t s t m a y r t e s b m e r e l y y t h e a t t a i n m e n rf a s i n g e q l i l l b r m o e u be extremely sma in compariso. with rhe steady between leavinq the s!.eams, s t a l e o p e r ao n , A n a l y s so l t . a n s i c no r b a t c h t t o p e . a t r o n su s l a l l y o r e o m p t etx a n o f s r e . d y . h Coniinuo6ed Blich Operrlion m c h s i a t eo p e r a t r o n .e c a ! so i t h s q r e a t es i m p t i c i i y B e r ln rhe no onrv of clenicst p.oce$.g opadrio.s. and the wlde occurence throughout chemical t r r s m o r e e c o n o nc a t l o r a i r G r c o - r n J o r , d n d proces!.9 ol steady.stare oDerarto.s. rhe nltro, steadyoperation of equipmenr,with a min'murn oi d ! c t o r yt r e a t m e nsi n t e r n so f c o n d t i o n r h a t . l o it s dsturbances and shutdowns, This h not atways i o t v a r y w i r h t i n e . A n ay s k o f a t r a . s i e no p e r a . r praclicat io eme sma|.sete operaiions,i. opera_ t on is dlffcre.r lrom ihe steady stareon V in rhe

material,or both. The transfermay be bucom plished with both streams ftowing in rhe eme dne.aionli.e., cocutunt flow). lr cocurcm ftow is used, limit in amountof transfer the thar car uccLr is firmly t by the equitibrium condiriorsthar wi bere.ched betueen two slleansb"rs co |.ac.ed. rhe

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inrrod aio. ot .ie r d t v " . i . o r "o , i " u r r r s v a n d o tis a o t r c"o 5 rr '.ro a , t / s i . o u r o o e " . o . p d pr o r u n d a m e n t a c h a n q et , y i UNtf OTEXATIONS Chemicl p(oce$es may consisrof widety varyins s e q L e r L d s ' s l e o s ,i 5 e o , . p e \ o r w h . h o "r,independent of the materiat being operared !oor and of orher characterisrics of rhe p&tic;t6r synem. In the design of a proce$, each step 1o be u s e d c a n b e s r u d i e di n d t v i d u a l l yf t h e s t e p sa r e i 'eloglized. son. o l-p sr!p" o.e Lt e-i, ! reactio.s, whereasorhers are physicalchanqes. The \e )niili/ o cL4Ticotelo ,ee ,9 oiqr, ,, "res r r a' r r 9 t o t h e p r d . r , p o ! b r e e l i l qL p o c o l p e r p r o . e s i I r o r o ' . i o r a p L \ . c d s l p p s .c d t t a dL I o o e " o l 1 s . a 1 d . t o l f e . r e n , c t . e d c l i o 1 , .i F c 0 ! n ( o p e r a to n s c o f . e p r i . c h e m i c a e . o . e e r i f d i . b a s e do n i h e p h o s o p h vt h a r r h c w i d ; y v d y l . s sequences sleps ca. be reduced!o simple ooera_ or t i o n s o f r e a . t i o n s , h i c h a r e i d e n r i c a ti n f ; n d a . w mentalsreg.rd e5sof rhe matenDl be ng proce$ed, r n 6 p n n c r p t e ,w h c h b e c a m e o b v i o u s r o t h a p i o n e e Bd u r i i g i h e d e v e t o p m e n tf r h e A m e r t c a . o c h e m l c a li n d ! s r r V w a s f i r s r c t e i r t V o r s e n ! e d v b A. D.L rte in t9l5: Any chemici pioc*5, on whdaver5ca dondlccd, hav e be resorved lnro a coordinded5sre. ot whir may b.

iors.or rpp, , dno,_i."tJeI'r" co,rdt"L,cd 4 torr +gr'r'.d. oo*,,e. -ts n" b/, o d rP.r ,o,oq, ol ! r r ' o o e o l o r , . w t ( t , 0 6 o - t F , .L , o t r r o r".rrore5 d ot ^1.f ."nno.b"co,e,ed, i very rreqLenfly chemicat cha.qcs occur i. d m a i e r i ab e i r s d i s r i l t e d r h e a t e d n ; u c h c s e s r h e l o pnyvca opemtron is the primary concrnr afd ii a c r e m r c a c h a . 9 e o c c ! ^ s i m ur a n e o ! s l y , t t r j c o h m o n t V h a n d t e d b y a m o d i l i c a r i o no f r h u ph. c.' p ope' \ oi I r" rd'qb /v1"' !hem,.d r e t e s a f d e q u i t i b r i aa r e k f o w n , r h e s c m a v b e lot 'ero .ot / | oJped i ,ro ,t p u, ,p-dtio T\" r,ocr .L"Ti.r 1 r,,rJ,,.,son..d,.o. . r ( , i c d ., p s r t , r . , o . o L . r rraSrrlrr4dd dd {e Jaoq..oJo L,.",r.!ed o-e t and L s L o t, - n c u . o . o _el'r rg o . , , - r d . p r e o q -1 9 r l p o . r - r ,nn . tre t\p'c"lo ,: )' e-q:-eq Tlcr ho e.o1!e rd srrn oL.sica c,r.ars r- , T-e ir oo-a,,. or Lfc c r d n r q r e / t ) . 5 . r r l o r b e o \ e ro o e d o c c d r ' ir oo l'r ce ol snar 1 p-o.c. me.is n pefcentage yietd frorn chemicalreact o.s i m a i y c a s e s r e t a t t v e t v m a t D e f c e f t a o em a s i p f o v e m e n rn v i e l d . n d v e ( u . o m c r i V llst fi co. s o e r r DV . n o r c e v t e . 3v e p r l c e s i , q o p c r r i o . \ J r , d A l L n i r o p e r a r i o na r e b a s e d p o n p r i . c p t - a s s ! . o r s c e n c et h a t a r e t r a n sa t e d i n t o . d u $ f i a ! . . i . c ! t i o n s _ v e i o ! \ f r e . t so f e . g i n e c r , q T h e i u ; u f . r ! o s , f u r r s r a n . e ,h d sb e e . s r d r t i e d r r e rI v e l v ' r e theory undr the .ame o f , ydra.t|. anjcs ot tirkl mcchsntcs. r has beer an imporrant part ot the work oi civi engi.eere!.der the name oi rr./.,u , i s a . d l so i h a j o r h p o r t a . c ei . s a . i t a r v e . ; i . e e r r . g . P r o be m s o t w a t e r l p p y a n d c o n t r o l h a v c D e e n e tb y e v e r v i v i l i z a t i o n . m c H e a t t r r n s t e r h a s b e e nt h e s l b j e c t o t n r a n v rheoretica lnvesttsationsby physickts a.d inarhe m a r c a . s ; r l h a sp i a y e da m a j o rp a r t i n r h e g c . e . ar on ot pow* trofr fLets,as developedby mecha. cal e.sinee6. Dissiparion f hear in e e.rri.3 o e q ! i p m c n tl s a m a l o rt i m i r a ro n o r t h c p o w e ro ! t p l r o r s u c h m a c hn e r y . p y r o h e t a L r g y a n d t h e h e a l | r e a t n e n t o f m a t e r i a ko l c o n s t r ! c i . . a . . t t o o h f e p r e f f t a d d r i o n i m a j o ra p p t i c a r t o f s r n r o u g h o u ti n d u s t r y io . e f r n d se x a d p t e so t m o s l o r t h e L n i l o p 4 a t i o n si n a D pi c a t i or s r h a ra r e I n I n e p r o v r n c e r o r h e r e f g i n e e r i . qf i e d s . T h e o clremrcalefqi.eer mlst cary o!r ma.y !nil oper

$ pu v4tr n9 mi!i^g. heari,ql r 0 * r n g , a b s o r b i 0 , c o n d e n s n g|, \ t r . ! n 9 i p r e c p , k r i n q sy.rd rinq, nrtr nq d s vhs e ecrutyzi,, Md ro or !^d rol:rively lw or 'hem -. ,nvotvrd , my pin,cui;r procs.. The codprexity ot chomical ensine.rinq rdsutrs noh he veicry of condirans a dc., undn which rhe unir acttonsmui be carred.!t n dtrirent prcms* and from ihe imitdtods a. ro m eriJk or co.nruct'on and d*iqi of spp;idls imposed bv rhp physlcal :nd chcmical ch:6drr or $e rcicrii0 rub naica. (21 The origi.at Inring of the uhir operations q ! o r e d a b o v e n a m e st w e t v a a c r i o n s ,n o t a t o f which are con!dered unit operarions. Addttio.al o.es have been d*ignated sifce rhen, ar a hodesr rare over t h e y e a 6 b u r r e c e . t l y a t a n a c c ee . a r r r q r d r e . F t u r d rrow, heai trd.ster. di5rildron, hum d ficaron ors a b s o r p t i o . , s e d ' m e n r a ro n , c l a $ r n c a i i o . , a q , r a r i ; n and cenrr ruqanon hdve tonq been recog.izpd. . .ecenr yea6 hcrea$ng understandifg of new tech nrquE and adapGhon of od tut setdom uscLj sepdranverechnques hJs ed ro d contnuJ v rncrea!ng nunber ol separartors, procesinq opera

s a t l o n so n m a t e r i a o i w d e l y l a r y i f g p h y s i c aa . d chemlca properties under exiremes of condrrrons d s u c h a s t e m p e r a t L r n d p r e s s u r eT h e u n l t . r p E r arions used to separatem xrures into more or re$ p u r e s L b n a n c e s r e u n i q u et o c h e m i c a le n gn e e r a m i n g . T h e m a t e r i a kb e i n gp r o c e s s e d a y b e n a t ! rally occ!rring mixtures or they may be tho prod ucts of chemicaL reacrions,which vifrually nevr yleld a pure substance. ".. - _.' OFTHE UNITOPEI{ATIONS TNTECRATION E a r l y s t l d i e sr i t h e ! n k o p e . a t i o n s sl . d p e o d e n r a n e p s l a i d a n l m p o r t a n lp a f t o f t h e i o u n d a t l o nf o r the phenomefa growth of the chemidal indlstry. I n a c o m p l e xm a n u f a c t u r e h e i n t e r a c t i o no f t h e i, s s e p r ' o c e e _ gI e e r si o i o , , i d e r r f e r o t o lp , o . " " , y, o r s Y s t e m ,a s a n e n t i t y , s i m u L t a n e o u s c e a r e r o u n d e r s t a n d l . g t t h e l n t e t r e l ao n s o f r h e l ! n d a . t l r m e n t a p r i n c i p l e se a d s o a g r o u p i n q f o p e r a t i o n 5 o m t i o i i t t h e s a m e a t h e m ac a l x p r e s s i . n f a c l i o n s , o o a o d e l . p e ' a t r _ 9 ! a . a b e g e n e . a l i T a r' s o T h e t r a d l t i o n ap s e n t a t i o n t u n i r o p e r a t i o . s l o o h a s b e e n r h e c o l L e c t i o n f a p p r o p r a t et h c o r e tc a l ard practica infornation abo!! each!nt oper a t o n a s a p a c k a g e . n p r e v l o u sl e x l b o o k s e a c h r o p r 6 t i o nh a s b e e n p r e s e n t e dn d e p e n d e fy f r o m t h e o t h e r s . l t i s s e i d o mo b v i o u s i n i . t r d u c t o r y p r e s e n t a t i o n0 r a t s e v e r ao f ! h e u f i r o p e r a to n s s o v e r L a pI t h e i r f o u n d . t o n s a n d a r e q ! t e l f t r i cately rel6tedto each other. The ifte(ela!o.s b e c o m em o . e o b v i o ! s i n m o d o g r a p h s o n e v e r a l o l s r h e ! . i t o p e r a u o f sb e c a u s o t r h e i m p o $ i b t y o f e p r e s e n t i n t h e t h e o r yo n a n y o n e o f $ e o p e r a !o n s g conplerely wirho!t rega.d for the lnfluence of o t h e 6 , S p e c l i i c a l y , e a ! t r a n s f e ri n a f l o w i i g s y r h tem ca.rot be comp etely prescnrcd wirholr coi. j s i d e r u t o n o t r h e f l u i d m e c h a n i c sm a $ t r a n s f e r c a n n o t b e d l v o r c e di r o h h e a t t r a n s f e ra n d f l u i d W l t h i n c r e a s n s n t o h a r i o n h a s c o m eb . o a d e r i o r e c o g n i r l o n i t h e b a s i c s i m i L a r i r l e s ,o n v e r s e t y , C r e c o q n i r i o na n d e l p l o i t a t i o n o l r h e s i m i d r l e s h a v e c o n t r i b u r e dt o a b r o a d e r u n d e r s r a n d i no l g each operation. lt now appcaG thar rhe compart m e n t a l i z a t l o .r f i n f o r m a i i o . b y ! . i t o p e r a t i o n leads to Lnnecesery repetition and waste .f r me a.d that study ol baslc principlcs comhon to a sroup ri the operatirns wl Llead ro a berrer under n a n d i n qo f a l o l r h e m T h s b o o k p . e s e n tL n d e rs i . g t eh e a d i n gtrh o s e s '- oa. operd o.. F".i'o 'in d "nr ,. " i1q generalize.inome.clarure and co.cepts. Th,s p.e se.ration has becn tound to .esuh h rime ecof

o m y I n l e a r n i . s a . d i s b e L i e v e do c o n t r i b u r e t a g r e a t e rb r e a d t ho t ! . d [ t a . d i . q o l a l t h e o p e r allo.s when the i.te(e at ons are underetood Atrilysis theUnil Operationj of The unlt ope.ations ay be analyzed .d 9ro!ped m a u s i . s a f y o n e o f t h r e e p o s s l e m e r h o d sA u n ' r b . operation may be ana yzed using a simplephysica model thal reproducesthe actlon ot rhe operatlon; n m a y b e a n a l y z e d y c . n s i d e r i n qh e e q u i p m e n t . b t u s e d i o r r h e o p e r a t i o n ;o r i r m a y b e a n a y z e d siarting with a mathematio expressionthat de. sfi bes ihe action and is tened using experimenral The physica model is estab ished by carefu study of the basic physical mecha.km. The modeL i s t h e n a p p i e d t o a r e a l s i t ! a t i o n e l t h e rt h r o u g h mathemarcaL xpre$ion or by physica descrip e lion. Eeca!se the model k idealized,some corcct i o n s a r e n e c e $ a r yi n i t s a p p l c a r i o nt o r e 6 lo p e r a t i o n s - h l s a p p r o a c h e l e o p sa n ! n d e B i a n dn g o f T d t h e b a s i ca i . n i l a r i t i ea m o n g t h c p r n c p l e so f t h e s v a ro u s u n r o p e r a f i o n s , T h c g r o u p i n s o ! l d b e m a d ei n t e r m so i t h o s e c o p s a t l o n s a c c o m p L i s h e ds i m i l a r q u l p m e no r l n in e t w h i c h a s i m i a r f u n c r i o no c c u r s .F o r m o s t o i t h e operat ons, the aft preceded a sc entific !nd-PF s t a . d i n g ,a n d e q u p m e n rw a sb u i r a n d o p e r a t e d . o t h e b a s i so i w o e f u l y r c o m p L e t e a s i ck n o w l e d q e . b S o m e i m p r o v e m e r t s i d r e l i n e m e n tc a m e , s e x . s a a p e c t e d ip ! r e l y f f o n t h e a r t a . d t h e e q ! i p m e n t , G . o u p i n go n t h e b a s i s f e q u i p m e n a n d l s f u f c . o t tioning erposes one lo the risk of only perpet!a r i n gt h e m i s t a k e o l t h e p a s t ,A t h o r o u g h! n d e . s s t a n d i n g t t h e b a s i co p e r a t i o n e e . n s L c h m o r e m o s like y to yield lmpfovemenlsin ope.atio.s. The operurio.s co!ld also be qro!ped lo thc fl L i s h io f s i m i l a r i t y f t h e b a s i cm a t h e m a t l c a o r n o u l a r i o no f r h e o p e r a r i o nT h i s m . t h o d o f 9 r o ! p i n q . is unsatlsfactory bcause the perve^lty ot mole oi Because ot culcs in rhen disregardof marhematics. the nofli.earlties i.volved and becauseboundary t c o n d i t i o n s f o n e p h a s e s u a l l y e s p o n do c h a . s e s L r o occurring ln an adjacent phase, h h frequeniLy i m p o s s i b t o f o r m u l a t et h e b o u n d a r yc o n d i l i o n s c ior soLLtionol a mathemarica expresson In man E a c ho f t h e t h r e em o d e so f g r o u p i n g c o u ! b e d used as a basis. The physical model ol rhe tunda mental operatlon h the most stisiactory approach and is used in this presentatio..Whereverpo$ible, rhe physical model is described mathematicaly, and rhe periorman.e is expressdin mathemaricai relarions derived kom lhe fundamental principies.

This formulatlon gives the bsr basis lor undeF s t a n d i n g n d r e f i n i n g h o s eo p e r a t i o . s n w h i c ht h e a t i art is ahead of theory. Thk is true in spire of the tact rhat the modelsare oversimplifiedand that rhe rarhematical formu ation of the behavior of rhe mode cannor be transposedperfectly into a. ex pression rhe behavioroi rhe prototype. of It should be obvious thar there is no univetsal c r i t e . i o nd i c t a i i n q p a d i c u t a r h o t c e f m e r h o do f a c o a n a l y s i a n d t h a t a l l c o n t r b ! t i n q i a c t o 6 s h o ud b e s r e c o g n i z e dn d e c d i n q u p o n a p a r r t c u l a im o d e . i A n y g . o u p i n sr e q L n e ss o m e a r b t t a r yc h o i c ea n d a r w a y s e a v eo f e w i t h s o m eo f i h e o p e r a t i o r sh a r r s r t i l p o o r l y i n t o i h e g e n e r a l s c h e mS !.c h o p e r a t i o n s e m u s tb e n l d i e d i n d i v i d ! a y . Tso MajorPhysicll Models O n e w i d e l y a p p i c a b l e o d e l f o r u n t o p e r a t i o n iss m a device I whch two streansi or phases, are brought togetheri allowed to reach equi ibrium, then separatedand withdrdw.. lr s assumedthat t h e e a v r n gs t r e a m s r e a t e q u i i b r i o m , a n d r h h a nadel ls.alled an equilibriur, sra9e.Eva uarion of the changesin rhe streamsthat mlsr be accom. p l i s h e do a t t a I e q u i l i b r l u m s t a b t i s h * m e a s u e t e a of ultimate performance. Rea equipme.t is evaluated by expressins the chanlesaccomplishedin it a s a f r a c t i o n o r p e r c e . t a g e f r h e c h a n g e sh a t o t w o u l d o c c ! r i n a n e q ! i l i b r i u ms t a g e . . a n o r h e r possiblemodel for vansfer of a property between two st.eams,we visualizethe caff e6 of the prop, e r t y , e v au a t et h e r . u m b e . a n d r a t eo i m i g r a to n , and aiiive at an expfe$ion oI the tute of transfer b e t w e . t h e r w o s t r e a m s n c o n t i . u o u sd o . r a c t This rate of transfer mulrlplied bV the r/he of c o n t a c t \ e l j t n . e x p r e s s o nl o r t h e a m o u n t o f t r a n s i e r a c c o m p l i s h e d .T h e e q u i b r i u m s r a g e model may be expre$ed halhemaricalty in a ll .itediiierence eqLation re atinq enreri.o con c c n t r a t r o no r a n y p r o p e r r yw i r h t h e e q u i l i b r l u m s conccfrrarlons f the properry lr the teaving o s t r c a m s .C r a p h i c a t e c h n i q ! c sl r e q u e n t l yc a n b e u s e dm o r e c o n v e n l e . t l y h a n t h e i i n i l e n i f f e r e . c e r e q L a t i o . . T h e m a d r c m a r l c ae x p r e $ i o . f o r t h e l r a i e o f t r a n s l e r m o d e l i s a d l f f e r e n t i a ie q u a t t o n t h a t c a . s o m e t i m e s c l . r e q r a t e d. g o r o u s y b u t b m o r e i i e q u e n i l ym u s t b e h a n d l e di n r e r m s o f a v e r a O ec o . d i t i o n s .S i n c ea a r q e n u m b e ro l c h e m i c a l proce$ing operatlons are acrually cairied our e i t h e ri n s r a g e o r i n c o n t i . u o l s c o n r a c rr,h e s e w o d r m o d es a r e w i d e y a p p i c a b l e f o r t h e a n ay s i s o f Mosi of tlre u.it operationscan be nud ed on e i t h e ro t t h e r w o b a s e sM a n y o f t h e m a r e c a ( i e d .

oui some|mes io continuousconract equipme.r o a d s o n c , n A i - ) r i o p op o r i p r e 1 r . t . s o r e o p d atons, the advanraqe one or the orher mode ot of a n ay s r s m a y b o b v i o ! s . I m a n y o t h e 6 , t h e chorce is dictated by avaikbility of rhe necesery q l i l b r i l m d a r aa r e a p a r t o l the stock in trade of rhe phvsica chembt and are available ior a larqe number of slbrtaaces under various conditions. To some extenr, the con. verience i. analysish relatedro rhc work of eanir investigatom,in that their resutrs may have ben rnterprered i. a fashion rhal hakos .ne dr rhe other analysk more.onvenienr.Choice of one method oi ana yslsdoes not nece$arily renrict the actla operation to the samenod,a O p e r a t i o ni3 w h r c h* a g e dc o n r a i n g i , r r e q u e . ry n u s e d w l l l b e c o n r d e r e df ' 6 r . T h e m o d e t k r h e device in which rhe rwo incoming strcahs inrer6ci t o a t t a i n e q u l i b r i ! m b e t w e e .r h e s t r o a m s s t h e V a leave the stage.The modet is kiown as an eorl libriun stage antl is a$umed always to yied two prodlct steams ii equilibrium with each other. The qenera zed trearme.t does nor reauire E soeci. f c a t i o no l t h e p f o p e r r yb e i n gr r a n s t e i . e o r o i r h e d nature oi the phases beingcontacted.The pracrical a n a r y s iis b a s e d n r h e i r a c r i o n I r r a n s t ea c c o m . s o o r p l i s h e d i n r h e a c t u a t s r a q ea s c o m p d i e dt o r h e e q u i l i b . i u d r t a g e , r e s e . r a t i ow i t b e i n a sc o m . s P n p etely 9e.fa terms a5po$ibLe,wirho!t regardtc t n e p a r t c u a r n a r u r eo f r h e p h a s e s. a p a ( t c u a r i S i a g e d o n r a c t q m a y b e i t u s t r a r e d s i n gr h e c f u mercu.y a.d water streams discu$ed ear|or Aq shown i. Fig!re l.T, the mercufy and warer conr nuous conract, and heai is rransfetred continuo!sty from the hot str.ah to rhc .old sream. Fo. srdqe orra.r n!. rhe eq! p c m c n l r m o d l t i e da 3 d e r f l b e l j b c o w . t t r h E h o r mercury and cold wate. srreamslscd above as an illustrdtion re mixedlnrimalety .d nrenied to a a a seftler where rhe phasesare separated,the oot flowing streahs w I be at pracitca y rhe sme t e m p e r a t ! r eT h e e q u i i b r i u m t e m p e r a r ! r e a n b e . c predicted by a materia and a. enerqy baa.ce. suppose now thai rwo nixe.seri ers are providcd, o n e o r w h i c h r e c e i v e sh e h o r m e r c u r v a n d t h e t o i h e r o f w h i c h r e c e l v e t h e c o d w a t e r .T h e m e r s c!ry Leavins rhe warmer nixerseliter ftows io rhe coorer m xer settLer, and thewater ea!nrg the cool er mixersettler flows to rhe warmer mirer sefi er. T h c t w o m i x a s e t r l e Bw i l l a c c o m p t i sth e r r a f s l e r h oi nror. hedt thnn the one. f rhe rumber of

mirer senlers increased ,, evenhore eneqy is to equa!o. ror averagecondiriotrs rarher than sotved can be taken f.om the mercu.y.In rhG case, the merclry would be passed throLghrhem i. rhe I n t h s i m pe s tc a s e s ,! i t e ! n u s u a ti n c h e m i c a l q o r d e 1 , 2 , 3 , , . . , , a n dt h e w a t en , . . . , 3 , 2 , 1 . r t procesinq, the raie ol rransporr ts cooslant wirh The ntroduction additionai of stagesdecreasesthe t i m e a d p o s k i o n w i r h i n t h e s y s t e m .T h e d r i ! i n g heat transtered per stagebecaus porentiaL torce may be assLmedto be constant and distri ihe lrom equilibrium diffefence becomes bur the le$, blted ovr a path of fixed tength and of constanr total transferis iocreased. on wodld do rhis No area. The physical propenies of the palh may be partlcuLar operationin the manoer des.ribed, but consranr so rhat rhe propontonality lactor 6 may many transier operatrons use stagecontacring. be assumedto be constant. These a$!mptions are Staqecortacting is a commonway of extracltn! the simplificatio.shat havebeen introducedn t i it o n e c o m p o n e n r o m a l i q u i dm i x t u r e y p r e f e r b a t r i v i n ga t O h m t l a w i n t t s f o r m a s u s u a t y p r e e n t i as l l t i o n o f t h a t c o m p o u no r q r o l p o f c o h l d sented n inrroductory physics couEes. The p o u n d s u c ha s i f t h e r e m o v ao f s l o d gie r m i n g c o u n t e r p a rItn c h e m i c atlr a n s p o r b e c o m e s s l o r o c o m p o n e nitrs m l u b r i c a t i .o i l s , g T h e d n i r o p e r a t i o n n v o l v i nc o . t i n u o l rc o n r a c l is g s i n g d e p e . d u p o n t h e r a t e o f r r a n s f e ra n d a r e , theretore calledrate operatians. rtansletoI a Tle largenumberof properties a materia- suchas of l e c t i c ,m a g n e t l ch e f m a lm a $ ,a n d m o h e n r u m t, , c o . c e i t r a t i o n sl o o w s t h e s a m eb a s l cm a t h e . e n r n a t i c a lx p r e $ i o o f r a t eo l t G i s f e r a s a u . c r i o n f o f c o n c e n t r a t ig r a d l o r t on
force/unit dlstance Fate of tianspo( = !4ins res st6nce/unitof oath area

\1.21 C h e m i c a u b s t a n c s ed o ' n f t n i c em a t h e . s es r n a l r c a q ! a r i o na n dc h e m i c a lq u i t i b r i ! m c o r . e s e is s t a n t r yu p s e t r i n.g a t f o r m u r i o n s f b o ! n d a r y e a o c o n d , t l o nrs a rw o u l dp e r m i r s o r o u s ou r o n s f h | s o E q u a t o n l . l t h e r e f o r e ,a o u 5a v t r a g ea . d a p . v s p r o x r m a t r o n s s tb e u s e dn a r r i v i na t a f a . 5 w e r mu i g I n a n e c o n o r n r cta l n $ h o f r m e . T h e s i m p t i f i . e c a t i o n s s u a l la p p r o a cE q r , a l i o 1 , 2m L r cm o r e u y h n h c l o s e l yh a nt h er i g o r o u s f l u s t o .e q ! a t t o n . t d F o rt h er a t eo p e r a t i o na n a l y s i s m u s r b e b a s e d s, ! p o . l h e d r l v i r i go r c e( a u sn q a . h a n g er,h er m e f d u r i n g h i c h d r i vn q f o r c ei s a o w e dr o a c r , n d w ! a t h e q u a f t t y o f m a t e a l u p o nw h t c h t a c t s T h e r . d i i t u s i o ne q u a r i o n b o v ee x o r e s s eh e t r a n s i e n i a ts b e h a v r o i d l a r q e . u m b e r op r o p e r t t e s u . dte re o f h i n f L ! e n c e l a d r i v l n gl o r c el o r r a n s p o . to t r h e o p r o p e r t y , n c h e m i c a n g i f e e . i n g , 6 s sm o m e n . r e m , tum, a.d therrnalenerqyare rhe threeproperties w h o s er r a n s p o r t t h e m o s ti r e q l e n t i . l o t v e d . s y A s D r . n l o n e d b o v ei , l s u . i v 6 a t r t r ah e s eh r e e a t tr r p r o p e r t e sa o . s w t h a . ! m b e . o j o r h e ^ w i r h , which chehica e.gi.eersare tessfreqLe.ttycon c e n r e dt,e . d t o f o w r . o m r e s i o no f h i g hc o f c e n s l r a t r o nt o r e q i o no f l o w c o n c c . t r a r i oA . c u r a r e s nc p r e d i c t i o .o f t h e a h o l n t o f r h e p r o p e r t yh a t t t ows r'om a donor resioi (so!rce)ro a receiv* r e s i o . h i n k )c a nb e m a d e r t h e d r l ! i n sf o r c er h e i , 3 r e a r r h ep a t h , a n dh eu n i tr e s i s r t v ioy i h e p a r h o r if to { t h e p r o p o r t i o n a l i cy n s r a nu s e di n E q u a r t o n r L 1 ) a r ea c c u r a r e ky o w n T h r o l g h o ! tr h es t L d y ln . of the rate operarions, imporrance a ctear rhe of uddetsranding the meaningol concofrrarion ol cannot be overst.essed. every case,the co.In centrarionexpresses amount of properryper ihe L n i t v o L ! m eo i t h e p h a s e e i n gp r o c e s e dT h e . b

af . Arr a0 ax2

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where | = concentrdtlon i rho propefty 10 be o vansfcrrccl , = d i s t a n c e m e a s u r e di n d k e c t i o n o f transport 6 = proportlona ty constaorfo. a sysrem Th s equatio. is lrequenny ca ed tt. di ftDsion eqdrtb,. lt is a genora expressionthar redlces to O h m t h w i o r e e c t . c a l I l o w f o r s p e cf i e d c o n . d i r i o n s .T h e b r o a d s t L d y o f e l e c r r i c n d m a g . e r i c a t r a n s p o r ih t h e m p o r t a n t " l c l d t h e o r v ' o f r h e . e e c v l c d e n g i n e e rT h e s et w o p h c . o d e n a i o l o w a w e l l e s r a b l i s h e d w s a n d i n v o l v e r e a t i v e L yc o n s i a n t p r o p o f t i o n a l i t yf a c t o ^ ( s u c h a s 6 j . r h e a b o v e e q u a t i o n ) ,S n c e b o u n d a r y c o . d i t i o f s c a n , l ! s u a l l y b e e v a l u a t e da n a l V t i c as o u r o n s a r e f r e q u e n t l y p o s s i b i o r e n g i n e e r i n gc a c u t a io n s . e are lesswelL behavedmaihe Chemical substancs " " m a t i c a l l ya n d t h e p r o p o r i i o n a l i t y c o n s r a n t s a r e , s e l d o m r e a l l y . o n s t a n t ,T h e b o ! . d a r y c o n d i t l o . s a . e m o r e e ! s i v e ; h e n c e , c h e m i c a i . q i n e e r s r e a t y s e l d o mi n p o s i r r o no a p p y m a t h e m a t i c a l le e l a n r a n d r l s o r o . ss o l ! i i o n so f t h e d i f l u s i o ne q L a r i o n!.n o . d e r t o a t r i v ea t a s o ! t i o n o f t h e d i i i u s i o n e q u a t i o n , i t m a y b e s l m p l i l i e di n t o a f i n i t e . i n c r e m e n t

ahount beingtransfefted Ls!aly be expresed can in sohe absoLute unn neasuring that quantity, such as B.itishthermalunits or polnd mo es. tr n also be erpressed termsof the decease ir in concentration the propeftyin a knownamount oi of phasehavinsa known capacity thk prop lor eny, For example, qLaotityof energy a teavin! a synem as hearcan be expressed termsof the ir numberof Btu s or .alories e.ergy_ canaho of it be expresedin termsoi the decrease remper of atore oi a known amounroi rhe phase. These generalizations becomemore meaningfut will as different operatlons anayzed and rhe fians are poded quantitlesare expre$edin rermsoI rhe po$ibleunits.Aecause basicprincipte! various the ol ransport are identical the rhreeproperties, for an analyshwill be oiiered in complele senera y termsbelore specificalion rhe pa.ticular of prop. erty in specific operationi, Unrtedy.Shtc Opention T h ed i t i u s i o n q u a t i o n ,q ! a t i o n. l , k a p pi c a b t e e E l for ransier in on directiononly and thar ts a Iunctionof time, However, tranlfor m6y occurin moretMn onedirefiion, Bigorous $lution requkes knowledge boundary of @nditions interaction a.d o f v a ra b l e sC o m p u r e r c h o u e s a k e o t u t i o n s . q te m s q u l e a c c e s s i b l e , d t h e y u s l a l l ye m po y l i n i t e an d ffereocetechniques. CENIiIt,\ CONSI L DDRATI ONS

menl In qua iry or quanlity. t is rherelore .eces sary thar mathematicaland/or graphicatrechniq!es be availabe to permit rhe pred crion ol any un known answer fo. a particuLar sysiem regarde$ of w h e r h e rt h e ! n k r o w n k a c o m p o s i t i o nq ! a n i i r y , , remperalure, or number of srasesreqlired to ac c o m p l h h6 s p e c i t i e d m o u n to f e n r i c h m e no i a n y a r ALtholgh thls book is devoted exclusve y ro t h e p r i n c i pe s o i t h e u n i t o p e r a t i o n s I c h e m i c a l o englneefing,t should be emphasized rhe prospec. to t i ! e c h e m i c ae n g i n e errh a i u n i t o p e r a t i o na r eo n t y l s o n e s e c t o ro i c h e m i c ae i s i n e e r n s . h e r e a l o b j e c T t v e l s t h e e n q i n e e r i no l t h e m o s re c o n o m i c a l p r o g c e s sT h e ! n i t o p e r a l l o n s r et e c h n l q u els a f f i v l n g , a r , a t t h s p r o c e s sb u r t h e y m u s t n o r b e a o w e d r o crowd out of considerailon the other mportanr s c i e n t i i i c r i n c i p l ets 6 i m u s tb e r e c o q n i z e d . p h The best processcan be designedonly w th p r o p e rr e g a r d o f r h e b a s i c h e m i s t r yk l n e t l c sa f d f c , , i h e f m o d y n a m i c s i i l h a d e q u a t ee c o g .t o n o f t h e w r i m i t a t i o n si m p o s e db y m 6 t e r h k o f c o i s r f ! c t i o n a n d a u x i a r i e st o t h e p l a n t .T h e e q u i p m e nd e s i g n r w i l l i n v o l v e o r k b y e n g i n e e 6i a i n e dl n d h c p t i f e s w f . o r m a y n o t c o v e r e db v t h e c h e m i c a e n o i n e r . T h e ! r m a r e o b j e c r o f t h e e n s i n e en 9 i s i h e a ( . r c ! m ! a t r o n o f a p r o f l t f r o m t h c o p e r a t i o nT h e . l a r g e srt e t u r no f p r o f i t , a i t e f a c o s r s r e a c c o ! n t . a ed ior, demandsull exploiralion f at $e rechf o n i c a l t u c t o r ol n v o l v e d ,I a v o r a b l e u m a n . e a r i o n s h w i t h i n t h e p r o d u c l n gt e a m i a n d a c c ! o r e k i o w . L e d g e f r h e a m o l n t o f p r o d u c rr h a r c a . b e s o d o I o r m a x i m u me v e n r ! a lp r o l i r .

p U n d e n t a n d i nh e b a s i c h y s i c a l r f c p L e s f a n p tg o operution a.d form! ating theseprinclplesnro a expre$ioi are thc liret rei!iremenrs mathematlcal f o r a p p l y i n gh e p r i n c i p i e s i h e ! n i r o p e r a r l o n s , R[FtrRI.:NCES t of pr n e r q i n e e r i n g a c r i c e ,o w e v en,u m e c a v a l u e s h r r mustalways incorporated a practicalafswer be and The samcprobcrn may be me! bVrhedes!n e n g i n e en s p e c i l y i n g ! i p m e n b,y t h eo p e r a t t n g ir eq t e e n gn e e .i n c h e c k l n L h ep e r l o r h a n co l i n s t ae d g e q u r p n r n tr/ b y a n y e n g i n e cn s e e k i nig p r o v e o lr m
2 Lirie ii9lt.ed

1. Con*ruton or rfrc Americannnitur or Chemca A O., R.port to the Carp.nti...t M.t.r., 1, ^ stvet An.t@ety vol,,4, a. .ch.E r1e331,

Part One
Stage Operations

. N . e av d l r h e n . a t p r o c e $ e s e o u - F r h e s e p a . ao l . r o r a s o r d . a t r q r i d , o r a g a sp f a s e , n - o r j c o h . s U L L d . rc o n o o n e r r s . S L c h r o a r , o r s r e o l F l T a d e b v c o n r a c t i l gr f e o f 6 s ew i h . - o r h e r ohare so rrar sone of rhe conponelrs.-e ra.rfeae! rrorn one pfase ro the other, Th+rwo phases are rnen separared 6nd processed i!rther. F E w r a t e i a . s . i r r e - m e d ; r es r r e a r s , 1 d f i n a l a p - o d r c i s i - e f . e o L e r t t yp r r ' f r e o L s i l g a sepa.ar.oorocss, for e<amp . tte ns.Lrdctr.e o. dr, e r c e , a r c o nd r o \ ' d e i s r e m o v e d r o m s f i i , i ! r e c f wirl d r b t c o - t a c l i r g r h e g a sw l h a i q u i o ( s r c l a ! d 0 r e t n 6 n o m i n e s o t u r i o n )t h a r d i s s o e sc a r b o nd d v o . E e b L t 1 0 r d i . . T r e o r - e c a - b o .d o \ i d n i s r l e r r e c o v e r eb y s i m p l yh e a tn ! r h e a m i n e o l u t i o . . d s the tetr ypa-tr:an prcc^re,,rc.rdes rno* r r t r o o e . a ro n s i l v o t ! i - g s e o a . a r i oo , c o T p o n e . r ( , r Dy !ra.sr( ot ma$ between phdses. The separarion o r w h o r ep h d F s , a s i n f i l r r a r i o n , l a v a s o b e r n . d c r u d e d . e r e w e d e s to n t v w i r h r h o f o p e d n o n si n h w t i r c hc o m p o n e n t r a . s f e r b e r w e e n h a s e o c c u 6 r p s e a v n 9 t h e s e p a r a r i o n f h e r e r o q e n e o um.u t t i . o s p h a s e y s t e m so P a r tI t , W i r h i n t h i s c k $ o f s t !ro. cessesrhe choice of Lnir opsrarion to be used depends!pon rhe physicat properties of the mtr. r u r e r o , b e s p a c r e d o b v i o u sy , r h e s e p a r a u o n s easrer I rt s basedupo. a physicat propeny rhit vr es w dery amo.q rhe cohponers ro be seoa The eqLipment used in masstransfer ooer dhons dcpends !pon the ph"sesr. O" pro"es*j d6cu3sedi. chaprer 2. In some cs*, the phascs ". ar,erepeatedtybroughr toqerherand rhen seodrated a s r h e y p a s r h r o u q hr t , e e q u i p m e n t . h e e q ! i T r D n u m n a g e i s r h e p h v r i c a t o d e tu s e dr o . n a t v z e m massrransrer operations in which the phases;re arlernalely contacted a.d separateda number oi

t fer. 'lence, the rc-1 stage opcrat;o-. re,et\ t) r r c s e s e p / a L @ ru @ e s f s . n a r c a l o e d e r c , . L e d oI I r e - o d e t o . a 1 e o u : to . : r n r t a q " , - - e ) e o o e f . n o n s r r e t h e 5 ! b j e c to f t h n e * t s e v e n h a p r e r i . c 'i ofl-e, r/pesof eoLipnenl, rnc rwo phares a . e c o r t l L o L d y c o r r a c t e os o t n a r r h e e \ r e r r ol n a s s t r s . s r e r d e p e . d se r p t i c , i t / r p o l r , . e . a r e or r c n s f e r a n d ! p o n r h e r j m eo f c o n r a c r I r h i s case t F e o l v s , c a r- o o e m * t r c r e r l e t c t o s o , r a r e o r r q r s t r a l s r e . d n d r : n e o f c o r r a c r .- l e r e - r l r o p e r a l o n s - w i |b e c o n s i d * e d i n p a r t s I a . d ll, t. Lnaprer rb flre ma$vafsfr operulo.5drc and r V z e d s. 9 a c o n L j o l o u e c o n r a c ro { l e u m Thc basic ca c! atio.s .equi.ed to .leso. equ pme.! ior the various stagcd op",ot ons uiu olseo upof idenrica co..epts. This secr of con s d e r s t h e g c . * a l c o n . e p t s n v ov e d n r h e d e s a. o r m u r n s r a q s c p a r ao n p r o c e s c sw , e r e r h e v a i , e r ous sEgo oprarions dlfter, edch is dis.u$ed I o{ar DLr whqe@r po$ible thc uperdt,o.s are o e v e r o p e d n J u f f r s d n a n n n , .T h . c a l L U t .ot. i r procduresare i Lstcted wirh exahples irom sDe. c rc srage operations. Chapte. introducsthevarious as tra.sfer 2 m o p c r u lo n s a n d d e s c r i b ers p i c a t e q u i p m c n ts e d y L if t l r c o p e r a r i o . sT h e p h a s p e a t , o . s h i Du n o . w h i ! h r s rne sepaGL prcceses de bas.d are corjsdcred in on Lnaprerr. chaptere rhrolqh 6 deyEtuD aene,dl 4 a melhod of catcutrnon f steaAv tJe srmeJuos o s a t r o . 5 .I n C h d p t e r c e r r d i n m p t i r e L lm e i h o d ,a r e 7 , d E c ! s s e d , a n d C h a p r e r a d e v e t o o sc a t c ! t a t n o methodsIor mutricomponenrstagedoperarions. A compietetabutarion of ttre qeneratnorarion and rts app ication to specilic stagedoprrario.s is gve. at the e.d of Pan L The reader is urged ro r e r e rr o i r o f r E . d n d s r u d vt t c d r e f u v w h t e r e c d r n o t h e f o l l o w i . sc h a p t e 6 .