illll

ELSEVIER Fluid
Fluid Phase Equilibria
Equilibria 110 (1995) 219 - 230

VAPOR-LIQUID EQUILIBRIA OF BINARY MIXTURES CONTAINING

METH YL T E R T - B U T Y L E T H E R ( M T B E) E) AND/OR SUBSTITUTION
H Y D R O C A R B O N S A T 2 9 8.8 . 15
1 5 K A N D 3 1 3 ..11 5 K

Luis M. Lozano, Eduardo A. Montero, Maria C. Martin and Miguel A.

V illam afi~ i# a~.
a~.

Laboratorio d e Termodimtmica Depto. Ingenierfa Energdtica y Fluidomecd

Fluidomecd nica
E.T.S . d e Ingenieros Industrial
Industriales
es Universidad de Valladolid
Valladolid E-47071 Valladolid
Spain.

~ ~T o w h o m c o r r e s p o n d e n c e s h o u l d b e a d d r e s s e d .

K e y w o r d s : e x p e r i m e n t s , d a t a , V L E l o w p r e s s u r e,
e , h y d r o c a rb
rb o n s , M T B E

ABSTRACT

An up-to-date high accuracy vapor-liquid equilibrium apparatus (Van Ness

t y p e ) f o r b i n a r y a n d t e r n a r y mi x t u r e s h a s b e e n n e w l y b u i l t a n d s u c c e s s f u l l y te te s t e d .
A p r o g r a m o n t h e r m o d y n a m i c c h a ra r a c te
t e r iz
iz a ti
t i o n o f b i n a ry ry a n d t e r n a r y m i x tu tu r e s o f
o x y g e n a t e a d d i t i v e s a n d / o r h y d r o c a r b o n s susu b s t itit u t in
in g t h e ma i n c l a s s e s o f c o n s t i t u e n t s
o f a r e a l g a s o l i n e i s p r e s e n t e d . S o m e o f th th e e a r l y r e s u lt lt s a r e r e p o r t e d , d i s c u s s e d a n d
c o m p a r e d w i t h l i t e r a tu
tu r e d a t a.
a . T h e s e s y s t e ms a r e t h e b i n a r y m i x t u r e s c y c l o h e x a n e +
n - h e p t a n e , b e n z e n e + c y c l o h e x a n e a n d me t h y l t e r t- t- b u t h y l e t h e r ( MT B E ) + n - h e x a n e ,
all have bee n m easured at 313.15 K and the first of them at 298.15 K too.

INTRODUCTION

A p r o g r a m o n t h e r m o d y n a m i c c ha h a r ac
a c t er
e r iz
i z a ti
ti o n o f t e r n a ry ry m i x t u r e s o f
o x y g e n a t e a d d i t i v e s ( e t h e r s,
s, a l c o h o ls
ls ) w i t h h y d r o c a r b o n s ( p a r a ff ff i n s , c y c l o p a r a f f i n s ,
a r o m a t i c s , o l e f i n s ),
), s u b s t it
it u t in
in g t h e m a i n c l asas s e s o f c o n s t i t u e n t s o f a r e a l g a s o l i n e ,
h a s b e e n u n d e r t a k e n b y o u r g r o u p w i t h t h e a im im o f o b ta t a i n in
in g a b e t t e r k n o w l e d g e o f
u n l e a d e d g a s o l i n e s l e a d i n g t o n e w d e v e l o p m e n t s s p e c i f ic ic a l l y a d a p t e d t o t h e
r e q u i r e m e n t s o f a u t o m o b i l e e n g in in e s .
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 f o r s u c h s y s t e ms a r e s c a r c e p r e s e n t l y , s e e f o r
e x a m p l e , W u e t a l. l. ( 19
19 9 1) 1 ) o r B e n n e t t e t al a l . ( 1 9999 3 ),), b u t t h e y a r e i m p o r t a n t i n
d e c i d i n g , f o r e x a mp l e , h o w t h e R e i d v a p o r p r e s s u r e o f a r e a l o r s y n t h e t i c g a s o l i n e
m i x t u r e w o u l d c h a n g e w i t h a d d i ti ti o n s o f v a r io
io u s o x y g e n a t e d c o m p o u n d s a n d m o r e

0378-3 812/95/ (~.50 © 1995 - Elsevi er Science B.V.

B.V. All rights
rights ~ese
~eserved
rved
S S I 0378-3812(95)02756-4
220 L.M. Lozano et al.,
al., / Fluid Phase Equilibria 11
110
0 1995) 219 - 230

g e n e r a l l y i n p r e d i c t i n g t h e v a p o r - p h a s e c o m p o s i ti
t i o n t h a t w o u l d b e i n e q u i l ib
ib r i u m w i t h
d i f f er e n t l i q u i d b l en d s . A l s o , s u ch d a t a ar e n eed ed f o r d e v el o p i n g an d t e s t i n g
eq u at i o n o f s t a t e an d a ct i v i t y co e f f i ci en t m o d el s as w el l as p r e d i c t i v e t h e o r i es t h at
will produce results when no experimental data are available.
P r e v i o u s l y , w e h a v e s t a rtrt e d t h is
is s t u d y m e a s u r in
i n g e x c e s s e n t h a lp
lp i e s u s i n g a H a r t
flow calorimeter in collaboration with Prof. Lichtenthaler's group at the University
o f H e i d e l b e r g ( T u s e l - L a n g e r e t a l.
l . , 1 9 91
91 a n d M a r t i n e t a l .,. , 1 9 9 4 ).
). T h e p u r p o s e o f
t h i s p a p er i s t o p r es e n t an u p t o d a t e h i g h a cc u r a cy s t a t i c v ap o r - l i q u i d eq u i l i b r i u m
(VLE) apparatus newly built and tested according to the design of Van Ness and
c o w o r k er s . ( G i b b s et al . , 1 9 7 2 ; D i E l s i e t al . , 1 9 7 8 ) . E x p er i en c e h as b e e n g ai n ed i n
the past with such equipment as in Villamafi~in et al. (1984) or in Villamafi~in et al.
( 1 9 8 5 ) . A s a c o m p l e m e n t t o th t h e s e t u p , s o m e o f t h e e a r l y e x p e r i m e n t a l r e s u l ts
ts o f
binary mixtures containing methyl tert-butyl ether (MTBE) and/or substitution
hydrocarbons will be reported and discussed as well as the subsequent program of
study.

EQUIPMENT USED

T h e t y p e o f e q u i p m e n t u s e d i s t h e i s o th th e r m a l t o t a l p r e s s u r e c e l l,
l , i n w h i c h s ta t a t ic
ic
eq u i l i b r i u m b et w e en p h a s es i s att att a i n e d . I n p r inin ci p l e , a l l o n e n eed d o af t e r l o ad i n g t h e
ce l l i s t o p l ace i t i n a co n s t an t - t e m p er at u r e b a t h , ag i t a t e t o as s u r e eq u i l i b r i u m ,
m e a s u r e t h e p r e s s u r e i n th th e c e l l, l , a n d s a m p l e th th e p h a s e s f o r a n a ly ly s i s.
s. H o w e v e r , a s a
c o n s e q u e n c e o f D u h e m s t h e o r e m , s a m p l in in g o f t h e p h a s e s i s n o t , i n fa fa c t , n e c e s s a r y .
G i v e n a s e t o f e q u i l i b r iuiu m x , P d a t a a t c o n s ta ta n t T , t h e r m o d y n a m i c s a l l o w s c a l c u l a ti ti o n
o f t h e y - v a l u e s . T h e c a l c u l a ti ti o n s a r e c o m p l e x a n d i t e ra ra t iv
i v e , s u i te
te d o n l y t o c o m p u t e r
c al cu l at i o n . A n ad d i t i o n a l d i f f i cu l t y o f t h e s t a titi c m et h o d i s t h a t , n o t o n l y t h e c el l m u s t
be thoroughly evacuated before the introduction of the liquids, but the liquids
themselves must be degassed.
A s c h e m a t i c d i a g r a m o f th th e s e t u p i s s h o w n i n F i g u r e 1 , i n w h i c h f o u r p a r t s
c a n b e d i s t ini n g u i s h e d : t h e c e ll
ll , t h e i n je je c t io
io n p u m p s a n d t h e t e m p e r a t u r e a n d p r e s s u r e
m e as u r i n g s y s t em s . T h e s t a i n l es s s t e el cel l w i t h i t s m a g n e t i c s t i r r er w as m ad e f o r u s
a t R e n s s e l a e r P o l y t e c h n i c I n s tit i tu
tu t e,
e, T r o y , N e w Y o r k , i t h a s a v o l u m e o f 1 8 0 m l a n d
i t s l i d i n cl u d e s : t h r e e i n j ec t i o n p o r t s a n d m i c r o v al v es , a v acu u m p o r t an d v al v e, an d

ai n cvoap
r poorr apt eosr t a. pI tr e ci si s iiomnmtere ms ed
p e r ai nt u rae c2o5n t1r .o l H( ar
P Tt CS) cbi ee nt ttei fr i cth
th abna t1h mmKo di .n 6o 0u 2r 0r,a nwg he i ch
of
work from 25°C to 60°C using water as thermostating fluid. The initial liquid
co m p o s i t i o n i n j ec t e d i n t h e c el l i s f i x e d b y t h e o p er at i o n , at c o n s t an t t o r q u e , o f t h r ee
1 0 0 m l R u s k a p o s i t iv iv e d i s p l a c e m e n t p u m p s m o d . 2 2 0 0 - 8 0 1 , w i t h a r e s o lu lu t i o n o f 0 . 0 1
ml.
T h e m e a s u r e m e n t o f p r e s s u r e is is n o t d o n e d i r e c t ly ly f r o m t h e v a p o r p o r t o f th th e
c e l l b u t t h r o u g h a d i f fe fe r e n t ia
ia l p r e s s u r e c e l l a n d i n d ic ic a t o r ( D P I ) , R u s k a m o d s . 2 4 1 3 -
7 0 5 a n d 2 4 1 6 - 7 1 1 r e s p e c t i v e l y . B e i n g th th e to to t a l v a p o r p r e s s u r e o f o u r m e a s u r e m e n t s
b e l o w t h e a t m o s p h e r i c p r e s s u r e , w e u s e a s p r e s s u ri ri z i n g g a s a m b i e n t a i r , w h i c h
t h r o u g h a R u s k a v a r i a b l e v o l u m e p r e s s u r e c o n t ro ro l l e r ( V V ) , m o d . 3 8 9 3 - 8 0 1 , a n d t h e
vacuum system allows balancing the vapor pressure in the differential cell. The
 L . M . L o z a n o e t a l .,., / F l u i d P h a s e E q u i l i b r i a 1 10
10 1 9 9 5 ) 2 1 9 - 2 3 0 22

r e a d i n g o f thth i s p r e s s u r e i s d o n e b y a T e x a s I n s t r u m e n t s T I ) p r e c i s i o n p r e s s u r e g a g e
m o d . 1 4 9 p r o v i d e d w i t h a 1 2 5 k P a d if i f f e re
re n t ia
ia l p r e s s u r e B o u r d o n f u s e d q u a r t z c a p s u l e
r o o d . 8 0 1 , t h e ap p ar at u s r es o l u t i o n i n t h i s r a n g e i s 1 . 5 P a. A b s o l u t e p r es s u r e r ea d i n g
i s a s s u r e d b y a v a c u u m s y s te t e m p r o v i d ed e d b y a B a l z e rs rs D U O 0 0 4 B d o u b l e s t a g e
r o t a t o r y p u m p , p r o t e c t e d a g a i n st
s t v a p o r s b y a l iq i q u i d n i t ro
ro g e n c o l d t r a p , b e i n g t h e l e v e l
o f v a c u u m a b o u t 5 x 1 0 3 m b a r ; t h is is v a c u u m l in in e i s a ls ls o u s e d b e f o r e r u n n i n g f o r
e v ac u at i n g t h e r e s t o f t h e i n s t al l at i o n an d f o r d e g as s i n g t h e l i q u i d s .
F i n a l l y , a N P L - c a l i b r a t e d 2 5 o h m I s o t e c h p l a ti t i n u m r e s is
is t a n c e t h e r m o m e t e r i s
u s e d t o m e a s u r e t h e t e m p e r a t u r e o f th th e b a th t h b y m e a n s o f an an A S L - r e s i s t a n c e b r i d g e
m o d . F 1 7 A , a s s u r in i n g a n a c c u r a c y o f 1 r nK nK r e s p e c t t o t h e IT IT S 9 0 . A u x i l i a r y i n d u s tr
tr i al
al
t em p e r a t u r e c o n t r o l l er s T C ) m ai n ta ta i n , thth r o u g h r es is is t an c e t ap es , th th e t e m p er a t u r e o f
the DPI-cell and va por p ressure duct at a temperature higher than that of the cell to
p r e v e n t v a p o r c o n d e n s a t i o n . T h e p u r e l iq i q u i ds
d s c o n t a i n e d inin 1 0 0 0 m l g l a s s b u l b s p l a c e d
over the injection pumps are previously thoroughly degassed using a modified
d i s ti
ti l la
la t io
io n m e t h o d b a s e d o n t h e o n e s u g g e s t e d b y V a n N e s s a n d A b b o t t , 1 9 7 8 .

Pg
TH RMOM T R
DPI

INJECT I ON
TI GAGE VV
PUMPS

BATH PTC

Fig. 1. A schem atic view of the static VLE apparatus.

apparatus.

O n c e t h e r m a l eq u i l i b r i u m i s o b t ai n ed i n t h e b at h at t h e s et t em p e r a t u r e, t h e
evacuated cell is filled with one pure component from the corresponding injection
p u m p , w h e n m e c h a n i c a l e q u i l i b r iu iu m i s o b t a in in e d p r e s s u r e i s r e a d . A r u n c o n s i s t s o f
i n j ec
e c t in
i n g a k n o w n v o l u m e o f th th e s e c o n d c o m p o n e n t in in t o th
th e c e l l,
l, m e a s u r i n g t h e n e w
pressure, further additions are made until we arrive approximately at an equimolar
m o l e f ra r a c t i o n . T h e r e s t o f b i n a r y c o m p o s i t i o n s a r e c o m p l e t e d b y a n e w r u n s t a r ti ti n g
with the second component as the pure one and repeating the process of mixing. In
t h e c a s e o f t e r n a r y s y s t e m s , o n c e t h e s ta ta r ti
ti n g b i n a r y m i x t u re
re i s f o r m e d , t h e t h ir ir d
 L M . L o z a n o e t a L , / F l u i d P h a s e E q u i l ib
ib r i a 1 1 0 1 9 9 5 ) 2 1 9 - 2 3 0

i n j e ct i o n p u m p i n i ti ti a t es th
th e i n co r p o r a t i o n o f t h e t h ir
ir d c o m p o n e n t al o n g a d i l u t i o n l i n e
i n th th e t er n ar y d i ag r a m . S t i r ri ri n g i s a v er y im im p o r t an t o p e r at i o n w h i l e r u n n i n g f o r
h e l p in
i n g e s t a b l is
is h i n g a r a p i d t h e r m o d y n a m i c e q u i li l i b r iu
iu m b e t w e e n b o t h f lu lu i d p h a s e s ,
n ev er t h e l e s s , w h i l e t ak i n g s ev er a l p r e s s u r e rea rea d i n g s t h e s ti ti r r er i s s t o p p ed . T h e
e s t im
i m a t e d u n c e r t a i n ti
t i e s o f t h e d i re
re c t m e a s u r e m e n t s a r e 0 . 5 m K i n t e m p e r a t u r e c o n t r o l, l,
1 m K i n t e m p e r a t u r e m e a s u r e m e n t , 5 P a i n a b s o lu l u t e p r e s s u r e a n d 0 . 0 2 m l i n th th e
injected volumes.

EXPERIMENTAL RESULTS AND CORRELATIONS

A s a t e s t s y s t e m f o r t h e a b o v e b u i l t ap ap p a r a t u s w e h a v e u s e d a r a t h e r c l a s s i c a l
o n e , t h e s y s t e m c y c l o h e x a n e + n - h e p ta ta n e a t 2 9 8 . 1 5 K . T h e p r o g r a m o f
measurements we have started with the total pressure cell includes the oxygenate
additive methyl tert-butyl ether (MTBE), as in our calorimetric measurements, and
g a s o l i n e s u b s t it
it u t io
io n h y d r o c a r b o n s o f d i f fe
f e r e n t c la
l a s s e s:
s : n - h e p t an
an e , n - h e x a n e , b e n z e n e
a n d 1 - h e x e n e . W e p l a n t o d e t e r m i n e s u c c e s s i v e l y a l l t h e p o s s i b l e b i n a ri ri e s a n d
ternaries formed either with pure hydrocarbons or with them with MTBE at 313.15
K . W e r e p o r t a n d d i s c u s s h e r e t h r e e o f t h e s e b i n a ri r i e s : c y c l o h e x a n e + n - h e p ta ta n e ,
b e n z e n e + c y c l o h e x a n e a n d M T B E + n - he h e x a ne
ne .
A l l thth e c h e m i c a l s u ses e d h e r e w e r e p u r c h as as e d f r o m F l u k a C h e m i c A G a n d w e r e
o f t h e h i g h e s t p u r i t y av a i l a b l e, ch r o m at o g r af i c q u al i t y re re ag e n t s ( o f thth e s er i e s p u r i s s .
p . a . ) w i t h s t a tete d p u r i t y o f > 9 9 . 5 m o l . A ll ll r e a g e n t s w e r e t h o r o u g h l y d e g a s s e d .
Vapor pressures of the pure constituents measured in this work and comparable
v a l u e s f r o m l i te te r a t u re
re a r e r e p o r t e d i n T a b l e 1 a n d T a b l e 2 . T h e P ~ v a l u e s i n a ll ll
c a l c u l a ti
ti o n s a r e f i x e d a t a v e r a g e s o f o u r e x p e r i m e n t a l m e a s u r e m e n t s .

TABLE 1

Vapo r Pressures of Pu re C onstit

onstituents
uents at 298.15 K in kPa.

Cyclohexane Heptane

present work 13.007 6.114

6.097
6.099

average value 13.007 6.103

literature value s 13.014 ¢~ 6.095 ('~

13 .0
.027
27 c,~ 6. 09 5 co~
13.004 ~

c,) Calculated from Antoine equation using constants reported

reported in API 44 (TRC).
co Reported by Y oung et al. (197 7).
co~Rep orted by M artin (1983 ).
 L.M. Lozano et aL,
aL, / Fluid Phase Equilibria 110
110 1995) 219 - 230 223

TABLE 2

Vapor Pressures of Pure Constituents at 313.15 K in kPa.

Cyclohexane
Cyclohe xane Heptane Benzene M TB E

pres ent wo rk 24.631 12.344 24.388 59.911

24.631 12.351 24.376 59.914
24.626 12.334 24.383 59.903

ave rag e valu e 24.629 12.343 24.382 59.909

literatur e va lu es 24.6 32 c,
c,)) 12.3 35 ~ ) 24.3 79 ~ ) 59 .9 42 ~b~

t ) Calculated fro m A ntoine equation using constants reported

reported in AP I 44 (TRC).
~b) Calculated fro m Antoine equation using constants reported by A m bro se et al. (1976).

T a b l e 3 g i v e e x p e r i m e n t a l v a l u e s o f t o tata l p r e s s u r e s a n d t h e c o r r e s p o n d i n g
c o m p o s i t i o n s o f t h e li
l i q u id
id a n d v a p o r p h a s e s . D a t a r e d u c t i o n w i ll
ll b e c o m m e n t e d i n
a futher section; for all the binary system s the Margu les equation w ith up to three
p a r a m e t e r s p r o v i d e s s u i ta
ta b l e e x p r e s s i o n o f G E .

U
g - Rr = [ a 2 1x
1 x l + a 12
1 2 x 2 -X
- X x l x 2 ]x
]x x2 1)

TABLE 3

P-x -y D a t a fo r Bi n ary
ary Sy s t ems at 2 5 °C an d 4 0 °C

xl Yl P(k Pa) x1 Yl P(kPa)

H ep t an e(l )+ cy cl o h ex an e(2 ) at 2 9 8 . 1 5 K

0 0 6.114
6.114 0.5480
0.5480 0.7200
0.7200 10 .08 3
0.0455
0.04 55 0.0961
0.0961 6.475
6.475 0.60222
0.602 0.7607
0.76 07 10. 45 2
0.0993
0.09 93 0.1972 6.8755
6.87 0.65066
0.650 0.7949
0.79 49 10. 77 2
0.1494 0.2807 7.245 0.7003 0.8279 11.103
11.103
0.1992 0.3552 7.619 0.7514 0.8602 11.440
11.440
0.2533 0.4280 8.018 0.8081 0.8942 11.810
11.810
0.3019 0.4869 8.370 0.84877
0.848 0.9177
0.9177 12.068
0.351 9 0.542 3 8.732 0.8963 0.9443 12.369
12.369
0.4019 0.5931
0.5931 9.085 0.9480 0.9724 12.674
0.4515
0.45 15 0.6394 9.440 1 1 13.0077
13.00
0.5014 0.6825 9.788
22A L.M. Lozano et aL, / Fluid Phase Equilibria 110 1995) 219 - 230

T A B L E 3 c o n t in
in u e d )

xl Yl P kP a ) xl Yl P kP a )

Heptane 1) +cycloh exane 2) at 313.15 K

0 0 12.344 0.5488 0.7055 19.375

0 0 12.351
12. 351 0. 599 3 0. 7453 19. 995
0.0995 0.186 2 13.676 0.6446 0 . 7 79
79 1 20.513
0.1032 0.1924 13.713 0.6984 0.8171 21.147
0.1532 0.2716 14.397 0.7428 0.8469 21.678
0.2033 0.3436 15.067 0.7999 0.8836 22.338
0.2522 0.4077 15.705 0.8504 0.9146 22.942
0.3014 0.4669 16.331 0.9099 0.9496 23.607
0.3519 0.5230 16.967 0.9512 0.9730 24.064
0.4016 0.5739 17.594 1 1 24.631
0.4504 0.6205 18.202 1 1 24.631
0.4973 0.6624 18.784

Benzene 1 ) + cyclohexane 2) at 313.15 K

0 0 24.632 0.5242 0.5193 27.515

0.0504 0.0727 25.272 0.5503 0.5395 27.502
0.0822 0.1140 25.605 0.6008 0.5791 27.427
0.1570 0.2006 26.276 0.6510 0.6193 27.303
0.1998 0.2449 26.584 0.7014 0.6612 27.122
0.2656 0.3076 26.954 0.7517 0.7054 26.880
0.3213 0.3567 27.195 0.7989 0.7498 26.579
0.3736 0.4004 27.355 0.8489 0.8009 26.199
0.4232 0.4403 27.459 0.8981 0.8569 25.723
0.4504 0.4618 27.498 0.9519 0.9269 25.080
0.5005 0.5009 27.524 1 1 24.388

MTB E 1) + hexane 2) at 313.15 K

0 0 37.267 0.5450 0.6508 52.355

0.0524 0.0966 39.187 0.5481 0.6533 52.428
0.1004 0.1744 40.801 0.5997 0.6947 53.460
0.1493 0.2453 42.368 0.6471 0.7316 54.366
0.1995 0 .3110 43.864 0.6997 0.7718 55.320
0.2494 0.3706 45.301 0.7492 0.8091 56.173
0. 2994 0. 42 56 46. 655 0. 8004 0. 8475 57. 018
0. 3490 0. 4763 47. 930 0. 8485 0. 8836 57. 791
0.3927 0.5183 48.987 0.8939 0.9179 58.455
0.4486 0.5692 50.286 0.9458 0.9575 59.179
0.4944 0.6088 51.292 1 1 59.914
0.4988 0.6125 51.392
 L , M . L o z a n o e t a l . , / F l u i d P h a s e E q u i l i b r i a 1 10
10 1 9 9 5 ) 2 1 9 - 2 3 0 5

R e s u l t s o f th t h e c o r r e la
la t i o n s o f d a t a f o r t h e b i n a r y s y s t e m s , t o g e t h e r w i t h a l l
a n ci l l ar y i n f o r m a t i o n , ar e s u m m ar i zed i n T a b l e 5 . T h e s ec o n d v i r i al co e f f i ci en t s B ~ j
r e q u i r e d t o a c c o u n t f o r v a p o r - p h a s e n o n i d e a li li ti
t i e s c o m e f r o m t h e c o r r e l a t ioio n o f
H a y d e n a n d O C o n n e l l , 1 9 75 75 .

TABLE 4

Summary of Result
Resultss for Binary Systems
Systems at 25°C and 40°C.

C y el
el o h ex
ex an
a n e(
e ( 1 ) C y c l o h ex
e x a n e (1
(1 ) B e n z e n e ( I ) M TB E(1 )
Heptane(2) H e p t a n e ( 2 ) C y c l o h e x a n e (2
(2 ) H e x a n e (2
(2 )
at 298.15 K at 313.15 K at 313.15 K 313.15 K

Pi ~t (kPa ) 13.007 24.631 24.388 59.91 4

P2 ~ (kPa) 6.114 12.351
12.351 24.632 37.267
V1L
V1 L (cm3 /mol) 109 110 91 122
V2L
V2 L (cm3/mol) 147 150 110 134
A122
A1 0.01016 0.07179 0.49043 0.23019
A2zz
A2 0.05819 0.05479 0.44223 0.22342
)~ 0 0 0.03872 0.01248
Bll -2298. -1551. -1310. -1426.
B~22
B~ -296 1. -2520. - 1551. - 1649.
B122
B1 -179 2. -1973. -1426 . -151 3.
rms ~ (kPa) 0.008 0.014 0.005 0.008
max[AP[ (kPa) 0.013 0.028 0.012 0.020

C O M M E N T S O N D A T A R E D U C T IO N

D a t a r e d u c t i o n i s b y B a r k e r s m e t h o d ( B a r k e r , 1 9 5 3 ). ) . A f u n c t ioio n i s c h o s e n ,
establishing the dependence between the excess Gibbs energy and the liquid phase
composition, Margules equation in this work. Its parameters must be determined
u s i n g a s t a t i s t i cal f i t t i n g p r o ced u r e w h i ch ad j u s t s t h e b es t p ar am et er s f o r t h e s el ect ed
l i q u i d m o d el .
As the activity coefficients have an exponential dependence on the excess
G i b b s e n e r g y t h e o b j e c t i v e f u n c titi o n c o n t a in
in i n g t h e s q u a r e d i f f e r e n c e s o f e x p e r i m e n t a l
a n d c a l c u l a t e d v a p o r p r e s s u r e s c o n v e y s u s t o a n o n - li l i n e a r t y p e a d j u s tm
tm e n t , w h o s e
s o l u t io
io n i s d o n e c h o o s i n g t h e M a r q u a r d t s a l g o ri r i th
th m .
O n t h e f l o w d i a g r a m o f F i g u r e 2 w e s t a r t t h e cal cu l at io io n g i v i n g a s i n itit ial
ial d at a
t h e v a p o r p r e s s u r e , t h e l iq
iq u i d p h a s e c o m p o s i t io
io n , t e m p e r a t u r e a n d p r o p e r t i e s o f th th e
s u b s t a n ce s , i n cl u d i n g t h e s e co n d v i r i a l co ef f i c i en t s .
 6 L . M . L o z a n o e t a l .,., / F l u i d P h a s e E q u ilil i b r ia
ia 1 1 0 1 9 9 5 ) 2 1 9 - 2 3 0

F i rst , a b u b b l e-p ressu re cal c u l at i o n i s d o n e u si n g t h e g am m a-p h i ap p ro ac h

(V an N ess, 1 9 82 82 ). T h e resu l t i n g cal cu lat l at ed p re ssu res are th th en u sed b y t h e n o n -l i n ear
M a r q u a r d t s a d j u s t m e n t o b ta ta i n in
in g t h e b e s t f it
it o f,f, i n o u r c a s e , t h e M a r g u l e s e q u a t io io n
p a r a m e t e r s B ( J ). ) . N e x t , a c o r r e c t i o n o f th th e l iq
i q u id
id p h a s e c o m p o s i t i o n h a s t o b e d o n e
t o t a k e i n to t o a c c o u n t t h e v e r y s m a l l a m o u n t o f m a s s d is i s a p p e a r in
i n g w h i l e e v a c u a t in
in g t h e
D P I cel l a ft er e ach p o i n t . T h e n e w x -v al u es feed a n ew i t erat i o n t o g et t h e su i t ed
a d j u s te
t e d p a r a m e t e r s . T h e p r o g r a m a l so so s u p p l ie ie s t h e r e s id
id u a l v a l u e s o f t h e p r e s s u r e ,
w e l o o k f o r t h e s e v a l u e s t o b e t h e m o r e u n i f o r m l y d i s tr t r i b u te
te d o n b o t h s i d e s o f t h e
z e r o l ini n e . T h e p r o g r a m f i n a ll ll y c a lc
lc u l a te
te s t h e t h e r m o d y n a m i c f u n c t io io n s .

I DAT A: P, x, T
_ properties
v V a p o r p h a s e : V i ri
ri a l e q .
L i q u i d p h a s e : M a r g u l e s eqeq .

7 - @ APP ROA CH
BU BB LE - P C A LC
LC .

MA L G RO RQI UT H M R D Margules P ar
ar .
I
O.F. = ~ P ~ , - P ~ ) B J)

no l[ IP .~ -P ,,,I < e? ]

es

MODIFY
MODIFY x?

Fig. 2. D ata reduction flow chart.

 L.M. Lozano et al.,
al., I Fluid Phase Equilibria 110
110 1995) 219 - 230 227

DISCUSSION

O u r r e s u l ts
t s o f th th e t e st
st s y s t e m , c y c l o h e x a n e + n - h e p t anan e a t 2 9 8 . 1 5 K ,
successfully agree with those reported by Martin (1983) measured with a high
a c c u r a c y s t a t ic
i c a p p a r a t u s b a s e d a l s o o n V a n N e s s o r i gi gi n a l d e s i g n . T h e p r e s s u r e
residuals shown in Figure 3 represent the differences between experimental values
o f e a c h a u t h o r a n d v a l u e s c a l c u l a t e d b y t h e i r r e s p e c t iv i v e c o r re
r e l a t io
io n s . I t c a n b e s e e n
t h at
a t b o t h s c at
a t te
t e r p r o p e r ly
l y a r o u n d z e r o a n d y ie ie l d R M S A p = 0 . 0 0 8 k P a a n d m a x ]A ]A p I
= 0 . 0 1 3 k P a f o r o u r r es e s u lt
l t s,
s, a n d R M S A P = 0 . 0 0 8 k P a a n d m a x [ A P I = 0 . 0 1 5 k P a
for Martin's results. The former binary has also been measured at 313.15 K, for it
i s p a r t o f t h e p r o g r a m o f m e a s u r e m e n t s w e h a v e a l re re a d y d i sc
sc u s s e d . N o d a t a f o r d i r e c t
c o m p a r i s o n h a s b e e n f o u n d i n t h e l it it e ra
r a t u re
r e a t th
th a t te
te m p e r a t u r e . T h e s a m e c a n b e s a i d
o f t h e b i n a r y M T B E + n - h e x a n e a t 3 1 3 . 1 5 K , t h e A P r e si si d u a ls
l s b e t w e e n e x p e r im
im e n t a l
a n d c o r r e l a t e d v a l u e s a n d th t h e m a x l A P [ a r e e x p r e s s e d i n T a b l e 4 . A d d i t i o n a ll ll y c a n
be said, for the former system to have a Ap residual at the equimolar pressure of
0 . 0 8 % a n d f o r th t h e l a tt
tt e r o f 0 . 0 1 % .
0.10 i i ~ i i r i ~ 0 . 1 0

t T h i s work I

O_
-0.00 ~. ~a ~, _ _ a . = ~ ° 0 O0
Q ~ n t~ a a

g~

-0.10 , , , , i , , , , I ~ , , I , --0 .10

0.00 0.25 0.50 0.75 1.00

XI

Fig. 3. Com parison for the binary system cyclohexan e + n-heptane at 298.15 K o f Ap residuals
as differences of experimental and correlated
correlated values for the results of this work [] , and th ose of
Martin, 1983, a.

For the benzene + cyclohexane system at 313.15 K com parison is ma de with

recent published results by Zielkiewicz et al. (1990), who critically evaluated them
checking their new static equipment. The P-x-y experimental values and calculated
curves are shown together in Figure 4. The agreement is excellent, as the Ap
residuals of the differences of their respective experimental and correlated values
s h o w i n a m o r e d e t a i le le d w a y i n F i g u r e 5 , g i v in in g b o t h s e t s o f d a t a m a x l A P [ o f 1 0
P a . A p e c u l i a r it i t y o f thth i s s y s t e m c rur u c i a l f o r c o m p a r i s o n i s thth e p r e s e n c e o f a n
azeotrope. We situate it at x~=0.4788 and P~=27.560 kPa. Reducing Zielkiewicz
e t a l.l. 1 9 9 0 e x p e r i m e n t a l v a l u e s w it i t h o u r c o r r e lala t i o n e q u a t i o n , 3 - p a r a m e t e r
M a r g u l e s ' , a z e o t r o p e i s e x h ib i b i te
te d a t x ~ = 0 . 4 7 1 8 a n d P ~ = 2 7 . 5 1 7 k P a . B o t h
p r e d i c t i o n s a r e v e r y c l o s e , p o i n t in
in g o u t th th a t th
th i s w o r k r e p o r t s m o r e e x p e r i m e n t a l
points on that region.
228 L.M. Lozano l al., / F luid hase E qu
quilibria
ilibria 11 1995) 219 - 230

28 .00 . . . . . . . . . . . . . . . . . . . 28.00

27 00 27.00

26.00 26.00
-
0._

{3_

25.00 25.00

24-.00 24.00

23.00 t i i i [ l i i I ~ ~ i i I i r i I 23.00
0.00 O.25 0.50 0.75 1.00
X1 Y1

Fig. 4. P-x-y curves for the system benzen e I) + cyclohex ane 2) at 313.15 K. Experimental
v a l u e s o f t h i s w o r k a r e r e p r e s e n te
te d b y [ 3 , a n d t h o s e o f Z i e l k i e w i c z e t a l . , 1 9 9 0 , b y O . C o r r e l a t e d
c u r v e s f o r t h e l iq
iq u i d p h a s e c o m p o s i t i o n , x ~ , a n d v a p o r p h a s e c o m p o s i t i o n , y ~ , a r e a l s o p l o t te
te d .

0.10 , , , , , , , , , , , , , , , , , , , 0 . 1 0
L
ooo o This work
..... Zielkiewicz et a l.

v A ~ c
_ o .o a a * a ~ a o
-0.00
3-

-0.10 . . . . . . . . . . . . . . . . -0 .10
0.00 0.25 0.50 0.75 1.00
X1

F i g . 5 . C o m p a r i s o n o f P - x d a t a o f t h is is w o r k [ 3 , w i t h t h o s e o f Z i e l k i e w i c z e t a l . , 1 9 9 0 , 4 , f o r t h e
s y s t e m b e n z e n e 1 ) + c y c l o h e x a n e 2 ) a t 3 1 3 . 1 5 K . T h e p r es e s s u r e r e s i d u a ls
ls A P k P a ) a r e d i f f e r e n c e s
b e t w e e n t h e i r r e s p e c t i v e e x p e r i m e n t a l a n d c o r r e l a te
te d v a l u e s .
 L.M. Lozano et aL, / Fluid Phase Equilibria 110 1995) 219 - 230 9

ACKNOWLEGMENTS

O n e o f u s ( M . A . V . ) i s i n d e b te t e d tot o P r o f.f. H . C . V a n N e s s f o r h i s h e lp
lp f u l
c o l l a b o r a t i o n i n t h e b u i l d i n g o f t h e a p p a r a tu
tu s a n d d a t a reduction. Supp ort for this
work came from the DGICYT, Direcci6n General de Investigaci6n Cientffica y
T 6 c n i c a o f th t h e S p a n i s h M i n i s te
te r y o f E d u c a t i o n , P r o j e c t PB-90-0512.

LIST OF SYMBOLS

A12, A21 p ar am et er s i n eq u at i o n ( 1 )
BI1,B22,B12 s eco n d v i r i al c o ef f i ci e n t s
GE excess Gibbs energy
g value of GE/RT for a binary
j co n s t i t u en t i d e n t i f icat
icat i o n : 1 o r
max m a x i m u m v a l u e o f t h e i n d ic ic a te
t e d q u a n t i ty
ty
P t o ta
ta l p r e s s u r e
azeotropic pressure
pi~t v a p o r p r e s s u r e o f p u r e c o n s t it it u e n t i
R u n i v e r s a l g a s c o n s t an t
RMS r o o t m e a n s q u a re re
T absolute temperature
V~L
V~ L m o l a r v o l u m e o f p u r e l iq iq u i d i = 1 , 2
x m o l e f r ac t i o n , l i q u i d p h a s e
Y mole fraction, vapor phase

reek letters

A s i g n i f i es d i f f e r en ce
), p ar am et er i n eq u a t i o n ( 1 )

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