5. Articulo Hexano-etanol-Acetonitrilo y Agua-Acetonitrilo-Acetato de Etilo

7/28/2019 5. Articulo Hexano-etanol-Acetonitrilo y Agua-Acetonitrilo-Acetato de Etilo

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TERNARY L IQU ID -L IQ U ID AND M ISC IB LE B INARYVA POR -L IQ U ID EQU IL IB R IUM DA TA FOR THE TW OSY ST EM S n-H EXA N E E THA N O L A C E TO N IT R IL EA N D W ATER A C E TO N IT R IL E -E TH Y L A C E TA T E

H iro sh i SU G I and T akash i K A TA Y AM AD e p a r t m e n t o f C h e m i c a l E n g i n e e r i n g , F a c u l t y o jE n g i n e e r i n g S c i e n c e , O s a k a U n i v e r s i t y , T o y o n a k a 5 6 0L iq u i d -l i q u i d e q u i l i b ri u m d at a a r e o b t a i n e d f o r t h e t w o t e r n ar y s y st e m s -h ex an e- e t h an o l -a c e t o n i t r i l e a t 4 0 C a n d w a te r - a c e to n i t r i l e - e th y l a c e t a t e a t 6 0 C . V a p or - l i q u i d e q u i l i b r i a f o rt h e t w o m i s c ib le b in a r i e s o f e a c h t e r n a r y s y st e m a r e a l s o d e t e r m i n ed .T h e m e a s u r e d t e r n a r y l i q u i d - l i q u i d e q u il i b r i a a r e c o m p ar e d w ith t h o s e p re d i c te d f r o m th e c o n -s t i t u e n t b in ary d a t a a l o n e b y u s e o f v ar io us a c t iv it y c o e f f i c i e n t e q ua t io n s .

I n t r o d u c t i o nG o o d p r e d i c t i o n o f t e r n a r y l i q u i d - l i q u i d e q u i l i b r i af ro m c o n s t i tu e n t b in a r y d a ta a lo n e is a d i f f i c u l t p r o b -l e m , b u t i s r e q u i r e d in d e s i g n c a l c u l a t i o n s o f s e p ar a t -in g o p e r a t i o n s . S e v e r a l a t t e m p t s b a s e d o n th erm o-dynamic r e l a t i o n s and a c t i v i t y c oef fic ien t eq ua -t i o n s 6 '7 ) 9 '1 3 ' 1 5 ' 1 6 ) h a v e b e e n m a d e f o r p r e d i c t in g a n dc o r r e l a t i n g t e r n a r y l i q u i d - l i q u i d e q u i l i b r i a . I n p r e -d i c t i o n , g en e r a l l y , t h e p a r a m e t e r s i n a n a c t i v it y c o e f -f i c i e n t e q u a t i o n f o r a c om p le t e l y m i s c i b l e b i n a r y a r ee v a l u a t e d f r o m v ap o r - l i q u i d e q u i l i b r i u m d a t a , w h i l em u tu a l s o l u b i l i t y d a ta a r e u s e d f o r a p ar t i a l ly m is c ib leb in a r y . H ow e v e r , t h e t h r e e b i n a r y d a t a w h i c h c o n -s t i t u t e a t e r n a r y s y s t e m a r e r a r e l y a v a i l a b l e a t t h e s a m et e m p e r a t u re , a n d t h is f a c t l i m i t s p ro g r e s s i n p re d ic t i n gt e r n a r y l i q u i d - l i q u i d e q u i l i b r i a .I n t h i s w o r k , l i q u i d - l i q u i d e q u i l i b r i a w e r e m e a s u r e df o r t h e tw o t e rn a r y s y s t e m s w - h e x a n e - e th a n o l - a c e to n i -t r i l e a t 4 0 C a n d w at e r - a c e to n i t r i l e - e t h y l a c e t a t e a t6 0 C . For th e fo rmer s y s t e m , v a p o r - l i q u id e q u i l i b -r i u m d a t a a t 4 0 C w e r e a l s o d e t e r m in e d f o r t h e tw om is c ib l e b in a r i e s n-hexane-e thanol a n d a c eto n itr ile -e t h a n o l . F o r th e im m is c i b l e b i n a r y s y s t e m 7 2 - h e x a n e -a c e t o n i t r i l e , m u t u a l s o l u b i l i t i e s w e r e d e t e rm i n e d a tt h e s ame temperature. For t h e l a t t e r s y s t e m , v a p o r -l i q u i d e q u i l i b r i a a t 6 0 C w e r e m e a s u r e d f o r t h e tw om is c i b l e b i n a r i e s a c e t o n i t r i l e - w a t e r a n d e t h y l a c e t a t e -a c e t o n i t r i l e . M u tu a l s o lu b i l i t i e s w er e d e t e rm in e d f o rt h e w a te r- e th y l a c e ta te s y s t e m a t t h e s a m e t e m p e r a tu r e .V a r i o u s a c t i v i t y coeff ic ient e q u a t i o n s 1 > 8 '1 2 > 1 8 ) w er eR e ce iv e d D e c e m b e r 2 , 1 9 7 7 . C o r r es p o n d e n c e c o n c er n in g t h is a rt i c le s ho u l db e a d d r e s s e d t o T . K a t a y am a .V O L ll N O . 3 1 9 7 8

u t i l i z e d t o p r e d i c t t h e t w o t e r n a r y l i q u i d - l i q u i d e q u i l i b -r i a f rom t h e c o n s t i t u e n t b i n a r y d a t a , and t h e p r e -d i c t e d e q u i l i b r i a w e r e c o m p a r e d w i t h t h e e x p e r im e n t a ld a t a .1 . E x p e r i m e n t a l1 . 1 V a p o r - l i q u i d e q u i l i b r i aT he exp erim enta l ap para tu s u sed fo r th e m easu re-m e n t o f v a p o r - l i q u i d e q u i l i b r i a w a s a B ro w n s t i l l 3 \T h e v o lu m e o f th e b o i l i n g f l a s k is 2 5 0 c c . T h e d i am e te ro f th e C o t t r e l l p u m p is 1 0 m m . to f a c i l i ta t e m ea s u r e -men t a t lower p r e s s u r e s . A t p r e s s u r e s l o w e r t h a n1 2 0 m m H g, i t w a s d if f i c u l t to o p e r a te th e s t i l l s te a d i ly .T h i s w as t h e m a i n r e a s o n w hy t h e e q u i l i b r i a f o r t h e tw ot e r n a r i e s w e re m ea su red a t d if f e re n t t e m p e r a tu re s.T he eq uilib riu m tem peratu re w as m easu red b y a cali-b r a t e d t h e rm is t e r i n a t h e rm o m e t e r w e l l a n d a W h e a t -s to n e b r id g e o f Y o k o g a w a E l e c t r i c C o . , L td . A d j u s t -m e n t i n p r e s s u r e b y a tw o - l i q u i d m a n o s t a t w a s m a d es o a s t o m a in ta i n t h e t e m p e r a t u re . A f t e r s t e a d y - s t a t ec o n d i t i o n s we r e a t t a i n e d , t h e e q u i l i b r i u m p r e s s u r ew as measured by a calib rated A MPGauge of TokyoA i r c ra f t Instrument Co . , L t d . ( l i m i t o f e r r o r 0 .3m m H g ) , a n d l i q u i d a n d l i q u e f i e d v a p o r s a m p l e s w e r ewi thd r awn f r om l i q u i d a n d vapo r s a m p le r s , r e s p e c -t i v e l y .T he samp les w ere analyzed by a g as ch romatog raphconnected t o a d i g i t a l compu ter H I T A C - 1 0 I I o f

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F ig . 2 A c t i v i t y c o e f f i c i e n t- c o m p o si t i o n c u r v e so f a c e t o n i t r i l e ( l ) - e t h a n o l ( 2 ) s y s t e m a t 4 0 Co f 20cc w as shaken v igo rou s ly in a 30c c te s t tub ei m m e r s e d i n a w a t e r b a t h . T h e w a t e r b a t h w a s r e -g u l a t e d w i t h i n z b O . O F C w i t h a T ak ara T h erm o sta tm o d e l C - 1 1 3 . A f t e r t h e p h a s e s w e r e s e p a r a t e d c o m -p l e t e l y , 2 c c s a m p l e s w e r e w i t h d r a w n f r o m e a c h l a y e rw ith a p reh eated sy r in g e and hypoderm ic n eed le andw e r e i m m e d i a t e l y t r a n s f e r r e d t o 5 c c t a b l e t t u b e s . F o rt h e / 2 - h e x a n e - e t h a n o l - a c e t o n i t r i l e s y s t e m , t h e y w e r ek e p t i n a n a i r b a t h a t a t e m p e r a t u r e a l i t t l e a b o v e t h ee q u i l i b r i u m t empera tur e i n o r d e r t o a v o i d p h a s e -s p l i t t i n g d u e t o c o o li n g . F o r t h e w a t e r - a c e t o n i t r i l e -e t h y l a c e t a t e s y s t e m , e t h a n o l w a s a d d e d f o r t h e s a m ereason . The hom ogeneou s liqu id m ix tu re ob ta in edw as ana lyzed by gas ch rom atog raphy , u s in g the sam em e t h o d a s f o r v a p o r - l i q u i d e q u i l i b r i u m m e a s u r e m e n t s .1 . 3 M a t e r i a l s

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M e rc k U v as ol s pe ctro gr ad e c he m ic als o f m in im u mp u r i t i e s 9 9 . 7 % 9 9 . 7 % a n d 9 9 % , r e s p e c t i v e l y . E t h a n o lw a s s p e c t r o g r a d e o f m i n im u m p u r i t y 9 9 . 5 % o b t a i n e df r o m N a k a r a i C h em i c a l s , L td . A l l o rg a n ic m a te r i a l sw e r e used w i t h o u t f u r t h e r p u r i f i c a t i o n . The w ate ru s e d i n t h e e x p e r i m e n t w a s d e i o n i z e d w a te r d i s t i l l e di n an a l l - g l a s s d i s t i l l a t i o n f l a s k . P h y si c a l p ro pe r t i e so f t h e m a t e r i a l s u s e d i n t h i s w o r k a r e s u m m a r i z e d i nTbe11 . 4 E x p e r i m e n t a l r e su lt s1 ) V a p o r - l i q u i d e q u i l i b r i a : T h e v a p o r - l i q u i d e q u i -l i b r i u m d a t a a t 4 0 C f o r t h e tw o b i n a r y s y s t e m sf t - h ex a n e - e t h a n o l a n d a c e t o n i t r i l e - e t h a n o l a r e p r e -s e n t e d i n T a b l e 2 , a n d t h e d a t a a t 6 0 C f o r t h e t w ob i n a r y s y s t e m s a c e t o n i t ri l e - w a t e r an d e t h y l a c e t a te -a c e t o n i t r i l e a r e i n T a b l e 3 . For ea ch o f t h e f o u rs y s t e m s , a m i n i m u m b o i l i n g a z e o t r o p e w a s fo un d.E s t i m a te d v a l u e s a t e a c h a z e o tr o p e a r e a l s o g iv e n i nT a b l e s 2 a n d 3 . C o l u m n s 4 a n d 5 o f T a b l e s 2 a n d 3s h o w t h e l i q u i d - p h a s e a c t i v i t y c o e f f i c i e n t s , a n d F ig s . 1t o 4 s h o w t h e r e l a t i o n s h i p s o f a c t i v i t y c o e f f i c i e n t s v s .l i q u i d m o l e f r a c t i o n .From t h e e x p e r im e n t a l P-x-ydata , t h e a c t i v it yc o e f f i c i e n t s w e r e c a l c u l a t e d b y

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T a b l e 4 S o l u b i l i t y d a t a f o r th e tw o t e r n a r y s y s t e m s n -h e x a n e ( A ) - e t h a n o l ( B ) - a c e t o n i t r i l e ( C ) a t 4 0 C a n d w a t e r( A ) - a c e t o n i t r i l e ( B ) - e t h y l a c e t a t e ( C ) a t 6 0 CXA XB XA XB XA XB[-] [-] [-] [-] [ -] [-]

/z-Hexane ( A ) - e t h a n o l ( B ) - a c e t o n i t r i l e ( C ) s y s t e m0 . 0 8 5 7 0 . 0 0 0 0 0 . 1 9 6 6 0 . 2 6 8 2 0 . 5 1 1 8 0 . 2 1 4 20 . 0 9 4 3 0 . 0 4 1 0 0 . 2 5 2 5 0 . 2 8 8 4 0 . 5 5 9 5 0 . 2 0 0 50 . 1 0 7 7 0 . 0 9 7 1 0 . 3 0 4 0 0 . 2 8 3 2 0 . 6 0 9 2 0 . 1 7 2 30 . 1 2 1 3 0 . 1 6 1 4 0 . 3 5 2 5 0 . 2 6 8 0 0 . 6 9 3 1 0 . 1 2 5 50 . 1 1 8 1 0 . 2 0 6 0 0 . 3 8 4 5 0 . 2 5 7 8 0 . 7 5 8 7 0 . 0 8 4 8

0 . 1 6 5 7 0 . 2 4 1 4 0 . 4 3 1 5 0 . 2 4 2 2 0 . 9 0 1 5 0 . 0 0 0 0

W a t e r ( A ) - a c e t o n i t r i l e ( B ) - e t h y l a c e t a t e ( C ) s y s t e m. 2 0 4 2 0 . 0 0 0 0 0 . 3 5 1 8 0 . 2 3 5 8 0 . 6 7 3 7 0 . 2 3 1 50 . 2 1 6 4 0 . 0 5 0 0 0 . 3 8 7 8 0 . 2 5 6 8 0 . 7 3 4 1 0 . 2 0 3 40 . 2 2 9 9 0 . 0 9 3 8 0 . 4 6 2 6 0 . 2 7 6 8 0 .7 7 3 7 0 .1 7 4 70 . 2 5 9 2 0 . 1 4 1 5 0 . 5 1 5 4 0 . 2 7 7 7 0 . 8 1 6 4 0 .1 4 8 00 . 2 7 2 4 0 . 1 7 0 1 0 . 5 5 3 6 0 . 2 6 8 4 0 .8 7 7 4 0 . 1 0 4 50 . 2 9 7 1 0 . 2 0 5 8 0 . 5 8 7 7 0 . 2 5 7 6 0 . 9 8 8 2 0 . 0 0 0 00 . 3 2 4 3 0 . 2 1 7 1 0 . 6 2 9 9 0 . 2 4 4 7

T a b l e 5 T i e - l i n e d a t a f o r th e tw o sys tems w -hexane (A)-e t h a n o l (B )-a c e to n i t r i l e (C ) a t 4 0 C a n d w a t e r (A )- a c e to n i -t r i l e ( B ) - e t h y l a c e t a t e ( C ) a t 6 0 CC o m p o n e n t A - r i c h p h a s e C o m p o n e n t C - r i c h p h a s e1 r1 r l l r l lXA XB XA XB_JH M DH [-]w-HexaneA ) - e t h a n o l ( B ) - a c e t o n i t r i l e ( C ) s y s t e m0 . 8 8 3 1 0 . 0 1 6 6 0 . 0 9 6 8 0 .0 8 7 9

0 . 8 6 7 4 0 . 0 2 5 1 0 . 1 0 0 3 0 . 1 2 9 90 . 8 5 4 6 0 . 0 3 3 2 0 . 1 0 5 4 0 . 1 6 2 20 . 8 3 7 2 0 . 0 4 3 3 0 . 1 2 5 0 0 . 1 9 4 20 . 8 1 0 1 0 . 0 5 6 7 0 . 1 3 6 7 0 . 2 1 6 90 . 7 8 2 1 0 . 0 7 7 2 0 . 1 5 2 2 0 .2 3 3 10 . 7 2 7 2 0 . 1 0 8 6 0 . 2 0 5 3 0 .2 6 9 50 . 6 9 1 2 0 . 1 2 6 9 0 . 2 2 4 9 0 . 2 7 4 8

Wate r ( A ) - a c e t o n i t r i l e ( B ) - e t h y l a c e t a t e ( C ) s y s t e m0 . 9 6 8 2 0 . 0 2 1 0 0 . 2 4 9 2 0 . 1 2 7 70 . 9 5 8 4 0 . 0 2 9 9 0 . 2 7 2 6 0 . 1 7 7 40 . 9 4 3 0 0 . 0 4 5 2 0 . 3 4 4 5 0 . 2 3 0 10 . 9 3 0 6 0 . 0 5 7 3 0 . 3 8 7 4 0 . 2 5 7 20 . 9 1 7 1 0 . 0 7 0 6 0 . 4 3 4 0 0 . 2 6 9 70 . 9 0 4 9 0 . 0 8 0 0 0 . 4 7 3 3 0 . 2 7 4 90 . 8 6 2 3 0 . 1 1 5 4 0 . 5 8 4 0 0 . 2 5 8 1

T h e v a p o r - p h a s e f u g a c i t y c o e f f i c i e n t s w e re c a l c u l a t e df r om t h e v i r i a l e q u a t i o n t r u n c a t e d a f t e r t h e s e c o n dt e rm . T he seco nd v i r i a l coefficients f o r pu re com -ponents and t h e cross-coefficients c a l c u l a t e d b y t h eTsonopou l o s c o r r e l a t i o n 1 7 } a r e l i s t e d i n T a b l e s 1 , 2a n d 3 .Fo r t h e a c t i v i t y coefficients o b t a i n e d , t h e c o n v e n -t i o n a l the rmodynamic c o n s i s t e n c y t e s t w as ap p lied .I t i s t h e w e l l - k n o w n a r e a t e s t , b y w h i c h t h e t h e r m o -dynamic c o n s i s t e n c y o f t h e d a t a w as c onfirm ed fo re a c h s y s t e m w it h i n t h e l i m it o f a p r a c t i c a l g u i d e 1 0 } .2 ) L i q u i d - l i q u i d e q u i l i b r i a : T h e s o l u b i l i t y d a t af o r t h e t w o t e rn a r y s y st e m s n -h e x a n e -e th a no l- a c e to n i -t r i l e a t 4 0 C a n d w a t e r - a c e t o n i t r i l e - e t h y l a c e t a t e a t6 0 C a r e l i s t e d i n T a b l e 4 . I n t h e t a b l e , m u t u a l s o lu -b i l i t y d a t a f o r t h e tw o b i n a r y s y s t e m s r c -h e x a n e -

F i g . 5 L i q u i d - l i q u i d e q u i l i b r i a o f - h e x a n e (A )-e t h a n o l ( B ) - a c e t o n i t r i l e ( C ) s y s t e m a t 4 0 C a n d t h ep re d ic te d r e su l t s o f t h e v a ri o us a c ti v it y c oe f f i c ie n te q u a t i o n s

F i g . 6 L i q u i d - l i q u i d e q u i l i b r i a o f w ater (A)-a c e t o n i t r i l e ( B ) - e t h y l a c e t a t e ( C ) s y s t e m a t 6 0 Cand th e p r e d i c t e d r e s u l t s o f t h e v a ri o u s a c ti v i t ycoeff ic ientequations

a c e t o n i t r i l e a t 4 0 C a n d w a t e r - e t h y l a c e t a t e a t 6 0 Ca r e a l s o i n c l u d e d . T h e t i e - l i n e d a t a o f t h e t w o t e r n a r ysy s t e ms a re l i s t e d i n T a b l e 5 . F i g u r e s 5 a n d 6 sh ow t h ee x p e r i m e n t a l d a t a o f t h e tw o t e r n a r y s y s t e m s . I nt h e f i g u r e s , c i r c l e s a r e t i e - l i n e d a t a a n d s o l i d b i n o d a lc u r v e s a r e t h e sm o o t h e d o n e s o f t h e s o l u b i l i t y d a t a i nTbe42 . C o r r e l a t i o n a n d P r e d i c t i o n o f E q u i l i b r i a

The c o r r e l a t i o n o f t h e m e as ur ed v ap o r-liq uide q u i l i b r i u m d a t a w e r e m a d e b y u s e o f v a r i o u s a c t i v i t yc o e f f i c i e n t e q u a t i o n s . T h e s e are t h e W i l s o n e q u a -t i o n 1 9 3 , th e m o d if i e d W i l s o n e q u a t i o n 1 8 5 , t h e t w o -

1 70 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN


5/6

System T a b le 6 P a r a m e t e r s i n v a r i o u s a c t i v i t y c o e f f i c i e n t e q u a t i o n sW i ls o n M od i f i e d 2 - p a r a m e t e rTemp. eq. Wilson NRTL eq.eq.C o m p o n e n t 1 C o m p o n e n t 2 [ C ]-Hexane ethanolA c e t o n i t r i l e e t h a n o l-Hexane acetonitrileA cet onitrile w aterE t h y l a c e t a t e a c e t o n i t r i l eWate r e th y l a ce ta te

A 1 2 A 1 2 T 1 2A n A 2 1 t 2 1

0 . 2 6 9 1 0 . 0 8 1 8 2 ^ 6 7 1 40 .0 4 9 2 0 .4 3 0 8 1 .5 2 5 80 . 4 0 5 6 0 .5 6 7 7 0 .5 4 9 90 . 5 1 8 0 0 .4 1 5 9 0 .8 7 9 9-.1002 1.5525-. 1 6 4 1 1 . 7 8 0 30. 1309 0.4920 0.67500 . 3 5 5 5 0 . 3 5 3 2 1 . 8 5 5 90.7924 0.6326 0. 17910 . 8 2 2 8 1 . 2 0 6 0 0 . 2 3 9 1- 0.2802 4.3581- 0.6039 0. 1464

3 -p a r am e t e rN RTL eq .^12

LEMF UNIQUACeq. eq.r 1 2 ^ 1 2

* " 2 1* " 2 1

0 .4 7 2 7 56 9 0 .4 92 50 . 6 4 60 .1 6 31 . 6 4 4 9 0 . 9 6 6 4 1 . 8 2 2 5

0 . 3 0 0 . 6 9 9 7 0 . 5 3 9 4 0 . 5 4 6 4 1 . 4 6 5 70 . 9 0 4 5 0 . 4 5 6 9 0 . 3 6 5 1

0.20 - - 0.9345 -- 0.9135 -0 . 3 0 1 . 0 7 9 4 0 . 4 6 2 5 0 . 8 4 3 1 0 . 6 1 4 6

1 . 8 8 5 7 0 . 5 8 1 4 0 . 6 4 9 00 . 3 0 0 . 2 2 5 0 1 . 1 6 6 0 . 1 9 3 7 0 . 5 4 6 1

0 . 2 4 1 9 0 . 1 7 6 5 1 . 2 8 3 40 . 2 0 - - 0.6380 0.6174

- 1. 1975 0.4052W il s o n e q u a t i o n 1 9 ) : G E /R T = - x I n ( x l + A 12 x 2 ) - x 2 I n C x 2 + A i * i )M o d i f i e d W il s o n e q u a t i o n 1 8 ) : G E /R T = -x In (x t+ A z l x 2 ) -x 2 In { A 12 x x + x 2 )+ x I n { x + P 2 iX 2)+ x 2 In (p 1 2 x x + x 2 )NRTL equation12) : G E /RT=x1x2LEM F equ atio n 8) : G E /RT=x1x2

r - 2 1 e x p ( - a v 2 1 ) , z - 1 2 e x p ( - ( x t 1 2 )x1+x2Qxp ( - a z21) ' x 2 +x 1 ex p (- aT 1 2 )r 2 1 e x p z - 2 i r 1 2 e xp r 1 2X i+ ^ e x p r s i X s + X i e x p z - 1 2UNIQUAC e quation1) : G E /RT=x1ln-^ +x2ln -2 ' ZXi X '9 I n J L - - \ r q 2 x 2 I n - q 1 x 1 I n ( 0 1 + 0 2 * 2 1 ) - q 2 * 2 I n ( # i r 1 2 + # 2 )

parameter NRT L e q u a t i o n 1 2 } , t h e t h re e -p a ra m e t e rNRT L e q u a t i o n 1 2 ) , th e L EMF e q u a t i o n 8 ) , and theUN I QUAC e q u a t i o n 1 ] . The pa ram eters o f t h e s ee q u a t i o n s , l i s t e d i n T a b l e 6 , w e r e d e t e rm in e d s o a s tom i n im i z e t h e v a l u e o f Z tC r i / ^ e x p t i . - C r i / ^ c a ic .] 2 .I n F i g s . 1 t o 4 , t h e a c t i v i t y c o ef fi ci en t s c a lc u la te db y t h e W i l s o n p a r a m e t e r s i n T a b l e 6 a r e c o m p a r e dw i t h t h e e x p e r i m e n t a l ones . A p p l i c a b i l i t y o f t h eU N IF A Cm o d e l o f F r e d e n s l u n d e t a l . b ) w a s e x a m i n e df o r t h e s e b in a r y s y s t e m s and i t was found t h a t t h emode l g i v e s s a t i s f a c t o r y r e s u l t s , a s s h own i n F ig s .1 t o 3 . I n t h e e t h y l a c e t a t e - a c e t o n i t r i l e s y s t e m , t h ep r e d i c t i o n o f a c t i v i t y c o e f f i c i e n t s c o u l d n o t b e m a d eb y t h e U N I F A C m o d e l s i n c e t h e g r o u p - i n t e r a c t i o nparamete rs be tween e s t e r and n i t r i l e g r o u p s are no tavailable.F ro m t h e m u t u a l s o l u b i l i t y d a t a f o r t h e t w o s y s t e m sf t - h e x a n e ( A ) - a c e t o n i t r i l e ( C ) a n d w a t e r ( A ) - e t h y la c e t a t e (C ), t h e p a r a m e te r s o f t h e m o di f i e d W i l s o ne q u a t i o n , t h e two - pa r ame t e r NRTL e q u a t i o n , t h eLEM F equ a tio n an d th e U NIQ UA Cequa tio n w ered e t e rm i n e d b y s o l v i n g t h e f o ll o w i n g s im u lt a n e o u se q u a t i o n s :

( x A r A ) I = ( -^ A r A ) l l

( x c r c Y = ( x c r c ) u ( 2 )The p aram ete rs o f t h e s e e q u a ti o n s o b t a i n ed a r e a l s ol i s t e d i n T a b l e 6 . I n t h e t a b l e , t h e p a r a m e t e r s o f t h eUN I QUAC e q u a t i o n f o r t h e ^ z -h e x an e -a c e t o n i t r il esys tem are no t g i v e n , a s t h e c om p u te r te ch niq uef a i l e d t o c o n v e r g e . T h e m u t u a l s o l u b i l i t i e s ( x \ -x " )o f t h e r c - h e x a n e ( A ) - a c e t o n i t r i l e ( C ) s y s t e m p r e d i c t e db y u s e o f t h e U N I F A C m o d e l a r e ( 0 . 9 3 3 5 - 0 . 0 6 7 9 ) ,VOL . ll N O . 3 1 9 7 8

w h i c h g i v e a s l i g h t l y n a r r o w e r s o l u b i l i t y r a n g e t h a n t h ee x p e r im e n t a l on e . The UN I FAC mod e l w as n o ta p p l i c a b l e t o t h e w a t e r - e t h y l a c e t a t e s y s t e m s i n c e t h eg r o u p - i n t e r a c t i o n p a r a m e t e r s b e t w e e n w a te r a n d e s t e rg r o u p s a r e n o t a v a i l a b le .The t e r n a r y l i q u i d - l i q u i d e q u i l i b r i a f o r t h e t w os y s te m s w-hexane-ethanol-acetonitrile and w ate r-a c e t o n i t r i l e - e t h y l a c e t a t e w e r e p r e d i c t e d b y t h e v a r i -o u s a c t i v i t y c o e f f i c ie n t e q u a t i o n s w i t h t h e c o n s t i t u e n tb in a r y p a r a m e te r s . T h e c a l c u l a t i o n w a s p e r f o rm e d b ys o l v i n g t h e f o l l o w i n g s i m u l t a n e o u s e q u a t i o n s .

( x t r (y = ( X i r t )u ( 3 )

F o r t h e t e r n a r y l i q u i d - l i q u i d e q u i l i b r i a o f t h e s y s t e m/ 2 - h e x a n e - e t h a n o l - a c e t o n i t r i l e , th e e x p e r i m e n t a l r e -s u l t s a r e c o m p a r e d i n F ig . 5 w i t h t h e r e s u l t s p r e d i c t e db y t h e two-paramete r NRTL e q u a t i o n , t h e L E M Fe q u a t i o n , a n d t h e U N IF A Cm o d e l . T h e p r e d i c t e dr e s u l t ( n o t s h o w n ) b y t h e m o d i f i e d W i l s o n e q u a t i o nw a s a lmos t t h e s am e as t h a t b y t h e t w o -p a ra m e t e rNR T L e q u a t i o n . Th e p r e d i c t e d r e s u l t ( n o t s h o w n )b y t h e N R T L e q u a t i o n w i t h t h e t h r e e p a r a m e t e r s f o rt h e c o n s t i t u e n t m i s c i b l e b i n a r y s y s t e m s g iv e s a n i m -m i s c i b l e r e g i o n a s l a r g e a s t h a t o f t h e U N I F A Cm o d e l .T h is s h o w s t h a t i n p r e d i c t i n g a m u l t i c o m p o n e n t s y s t e mth e three-parameter NRTL e q u a t i o n i s n o t a l w a y ss u p e r i o r t o t h e two -pa r ame t e r o n e . In t h e s y s t e m ,each p r e d i c t e d s e t o f t e r n a r y l i q u i d - l i q u i d e q u i l i b r i as h o w s a l a r g e r i m m i s c i b le r e g io n t h a n t h e e x p e r i m e n t a ls e t , e x c e p t f o r t h a t o f t h e L E M F e q u a t i o n .Fo r t h e s y s t e m w a te r - a c e t o n i t r i l e - e t h y l a c e t a t e ,t h e t e r n a r y l i q u i d - l i q u i d e q u i l i b r i a p r e d i c t e d b y t h e

17 1


6/6

UNIQUAC e q u a t i o n , th e LEMF e q u a t i o n , and them o d i f i e d W i l s o n e q u a t io n a r e s h o w n in F i g . 6 w it h t h ee x p e r i m e n t a l v a l u e s . T h e p re d ic t e d r e s u l t ( n o t s h o w n )b y t h e tw o - p a r a m e te r N R T Le q u a t i o n o r t h e t h re e -p a r a m e t e r N R T Le q u a t i o n l i e s in t h e r e g i o n b e tw e e nth o se o f th e UNIQUACquation and th e m odifiedW i l s o n e q u a t i o n . I n t h e s y s t e m , a l l p r e d i c t e d r e s u l t sg i v e l a r g e r i m m i s c i b l e r e g i o n s than t h e e x pe rim e n ta lo n e .C o n c l u s i o nE x p e r im e n t a l d a t a w e re o b t a i n ed f o r l i q u id - l i q u i de q u i l i b r i a f o r f t -hexane-ethanol-acetoni t r i le a t 4 0 C

a n d w ate r - a c e to n i t r i l e - e th y l a c e ta te a t 6 0 C . V ap o r -l i q u i d e q u i l i b r i u m d a t a w e r e a l s o o b t a i n e d f o r t h e tw om is c ib l e b in a r y s y s te m s o f e a c h te r n a r y s y s te m .I n c o m p a r i s o n w i t h t h e e x p e r im e n t a l d a t a , a p p l i c a -b i l i t i e s o f t h e v a r i o u s a c t i v i t y c o e ff ic i en t e q u a ti o nswe r e t e s t e d in p re d ic tin g th e t e r n a r y l i q u id - l i q u ide q u i l i b r i a f rom t h e c on s t i t u e n t b in ar y d ata a l o n e .Howeve r ,n o s a t i s f a c t o r y r e s u l t s were o b t a in e d f o rt h e s e t e r n a r y s y s t e m s .T h e d a t a p r e s e n t e d i n th i s w o r k w il l b e u s e d t o e x -a m i n e h o w c l o s e l y a n a c ti v i t y c o e f f i c ie n t e q u a t i o n c a np r e d ic t te r n a r y l iq u id - l iq u id e q u i l ib r ia f r o m th e c o n -s t i t u e n t b i n a r y d a t a a l o n e .

A c k n o w l e d g m e n t sT h e a u t h o r s t h an k t h e C o m p u te r C e n te r , O s a k a U n iv e r s i t y ,f o r th e u s e o f i t s f a c i l i t ie s a n d M r . T ak a s h i M u ra y a m a f o r h i sa ss is ta nc e in t h e e x p er im e n ta l m e a s u r e m e n ts .

N o m e n c l a t u r e

1 7 2

t o t a l p r e s s u r eg a s c o n st a n ta b s o l u te t e m p e ra tu r el iqu id m olar vo lum el i q u i d -p h a se m o le f r a c ti o nv ap o r- p ha se m o l e f ra c ti on

[mmHg][ c a l / m o l - K ][ K ][ c c / m o l ][ - ]r j

= l i q u i d - p h a s e a c t i v i t y c o e f f i c i e n t [ - ]

(j> = va po r -ph a se fu ga c ity c o e ff ic ie n t [- ]c a lc . = c a lc u la te d va lu ee x p t l . = e x p e rim e n ta l v al u ei = c ompo n e n t iL = l i q u i d p h a s e

I I=auaion= c om p o ne nt A - ri c h p h a s e= c om p o n e n t C - r i c h p h as e

L i t e ra tu r e C i t e d1 ) A b r a m s , D . S . a n d J . M . P r a u s n i t z : A I C h E J . , 2 1 , 1 1 6 ( 1 9 7 5 ) .2 ) A m e r i c a n P e t r o le u m I n s t i t u te R e s e a r c h P r o j e c t 4 4 , " S e l e c t e dV a lu es o f P ro pe rtie s o f Hyd ro ca rbo ns a nd R ela te d Com -p o u n d s " , T h e r m o d y n a m ic R e s e a r c h C e n t e r , T ex a s A & MU niv . , T e x a s ( 1 9 6 9 ).3 ) B r o w n , I . : A u s t r . J . S c i . R e s . S e r . A - P h y s . S c i . , 5 , 5 3 0 ( 1 9 5 2 ) .4 ) B r o w n , I . a n d F . S m it h : A u s t r . J . C h e m . , 8 , 6 2 ( 1 9 5 5 ) .5 ) F r e d e n s lu n d , A . , R . L . J o n e s a n d J . M . P r a u s n i t z : A IC h EJ ., 2 1, 1 0 8 6 ( 1 9 7 5 ) .6 ) G u f f e y , C . G . a n d A . H . W e h e : i b i d . , 1 8 , 9 1 3 ( 1 9 7 2 ) .7 ) H ir a n u m a , M . : I n d . E n g . C h e m ., F u n d a m ., 1 3 , 2 1 9 ( 1 9 7 4 ) .8 ) M ar in a , J . M . a n d D . P . T a s s io s : I n d . E n g . C h em . , P r o c e s sD es . D ev . , 1 2 , 1 6 7 ( 1 9 7 3 ) .9 ) M a r i n a , J . M . a n d D . P . T a s s i o s : i b i d . , 1 2 , 2 7 1 ( 1 9 7 3 ) .

1 0 ) P r a u s n i tz , J . M .: " M o l e c u l a r T h e r m od y n a m i c s o f F l u i dP h a s e Equ i l i b r i a " , P r e n t i c e - H a l l , Englewood C l i f f s , N. J.(1969) .

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