Fluid Phase Equilibria,

13 (1983)

91-108

91 in The Netherlands

Ekvier

Science Publishers B.V., Amsterdam -Printed

EXTENSION EVALUATION

OF THE PENG-ROBINSON OF THE VARIOUS

EQUATION

OF STATE TO COMPLEX

MIXTURES:

FORMS OF THE LOCAL COMPOSITION

CONCEPT

Paul M. Mathias and Thomas W. Copeman Air Products & Chemicals, Inc. Box 538, Allentown, PA 18105

ABSTRACT -Density-dependent Prausnitz, equations various local composition (DDLC) mixing rules (Whiting and

1981,

1982 and Mollerup,

1981) offer mixtures.

great promise

to extend

of state to highly

nonideal

In this work we investigate forms. All but the

aspects

and offer two useful (1976)

development results

is done with

the Peng-Robinson

equation

of state,

have general

applicability.

INTRODUCTION Practical broad models to describe phase equilibrium can be divided into two

categories:

equations

of state

and activity-coefficient applied to mixtures

models. containing

Equations

of state have been successfully polar components

,nonpolar and slightly interest, including

at all conditions regions.

of engineering On the other has been hand,

the critical

and retrograde

the mathematical considered

flexibility to model

of activity

coefficient exhibit

models

necessary

systems which

high liquid-phase

nonideality. temperatures moderate

The activity-coefficient where the liquid phase Serious problems models

approach

works well at low reduced incompressible and up to

is relatively arise when

pressures.

these bounds phases

are violated. precludes problems the arise for

,Further, the use of different correct description of mixture

for the various points. 1975).

critical

Additional

supercritical approach

components

(Abrams,

et al.,

The equation-of-state and thus it would

does not inherently to develop

suffer

from these

limitations

be very valuable flexibility Recent promising

equations

of state with the mathematical behavior. on the mixing rules as a

to describe

complex

mixture

research

in equations

of state has focussed flexibility

way to achieve

mathematical

through

a semi-theoretical rules used with

development.

Vidal (1978)

has shown that the standard (1976) equations

mixing

the Soave (1972) to regular Further, mixing

and Peng-Robinson theory

of state are very similar systems.

solution

and thus inadequate have suggested

for "chemical" improvements (Renon

Huron and Vidal

(1979)

to the standard 1968)

rules by applying

the ideas of NRTL model

and Prausnltz,

0378-3812/83/$03.00

0 1983 Elsevier Science Publishers B.V.

92

to but This

the the

excess Huron been

Gibbs

energy

of

the does

Soave not

equation. meet the

The results important

are

promising 1 imit. (1981,

and Vidal pointed investigators for

model out

low-density and Prausnitz

has

by Mollerup have

(1981)

and Whiting proposed

1982); model (DDLC) In theory standard

these to

separately

a physically local

appealing composition

account

mixture

nonideality:

density-dependent

theory. this work we have to the investigated popular density-dependent Peng-Robinson provides but 3-4 the a very (PR) good local-composition equation description of state. of (1981) The

as applied

Peng-Robinson nonpolar

equation systems

asymmetric, .can

DDLC-PR model of magnitude

proposed for highly of

by Mollerup asymmetric proposed

be inaccurate Noting and variety recently systems version

by up to this, Prausnitz of

orders adopted

systems. Dimitrelis of the time a wide other for

we have (1982).

a modlficatlon enables

an idea improved

by

The new model Our

correlations (along in a with computer

complex

mixtures. forms) could of

proposed to

DOLC model expensive

proposed with of a large the

prove

be too

number which,

components. however, retains

Thus we propose several

truncated qualities.

theory

attractive

STANDARD PENG-ROBINSON EQUATION OF STATE According pure fluid is to the Peng-Robinson as a function (1976) of the equation temperature of state the pressure volume as of a given and molar

follows:

P=RT_ v-b

(1)
v(v+b) + b(v-b) dependent dependent ated. Thus, parameters. such that the b is vapor independent pressure of of temperature pure fluid component

a and b are and a is

temperature carrel

the

i s accurately

b a a
B
C

= 0.07780 = ace(T)
=

R Tc/Pc

0.45724
[

R=T,=/P, - fiR) Is + c2(1 - FR)Z different necessary rules. to + c3(l from PR model - j-YR)l that is ] 2 proposed when c2=c3=0. vapor pressure to of focus pressure by Peng The highly on

1 + CI(1 (5)

Equation and polar the Robinson additional

slightly are mixing

origlnally obtained the this

(1976). parameters of

The original

correlate In

substances development

11 ke water

and methanol. Inaccurate

work

we wish vapor

pure

component

93 representation obscures artificially distorts the excess Helmholtz free energy 1973). unchanged shown and

the analysis

of mixture

effects

(Van Ness,

et al.,

For mixtures, but the parameters below:

Peng and Robinson

assumed

that eqn. (1) remains as the mole fraction

a and b are calculated

averages

a = I E xixjaji ij b = Z xibi i

(6)

(7)

a.. is given biiary

by the usual kji

combining

rules which

include

the pair dependent

parameter

aji = (1 - kji) (aiaj)'fl Equations refer to this (1) and (6-8) deflne the "standard" l-Fluid Peng-Robinson (VOW-l) by eqns. model. We model.

form as the van der Waals that the mixing is random

or "conformal"

It should

be noted

rule defined

(6) and (7) do not functions functions are can

imply that the mixture identical) but rather

(all pair radial pair

distribution

that the various basis

radial distribution and Leland, 1972).

be superimposed

on a reduced

(Mansoori

ANALYSIS

OF THE MOLLERUP (1981)

DDLC MODEL his version equation of the density-dependent that local

Mollerup composition compositions surface

derived

Peng-Robinson arise

of state by assuming fn the attractive

local "a" per unit

from differences

parameter

area (q).

Lx
P=RT_ v-b v(v+b) 1 + b(v-b) zxq i i i j j

a ji

/q ji

E ji

1 x. E.. J J' j

(9)

where,

Eji = exp ~~~~~ (I = exp 1 aji/qji ~ 2-&b en

(10)
(11)

RT

94 and,

aji/qj,

(1 - kji) did and

(aiaj/qiqj)lB not employ the universal however, "degree-of-randomness" it is included here

(12)
1981), for

Actually, parameter generality. The

Mollerup

a (Whiting

Prausnitz,

attractive

Helmholtz

energy

corresponding

to eqn.

(9)

is given

by

RT Aa = - Z xiqian
II.

BXjEji

(13)

j [I into the nature and of the DDLC theory is obtained (13) by an

Useful expansion -a A

insight of the

logarithm

exponential

terms

in eqn.

as follows:

= I

Zxiqi i

Exjaji/qji j I

FV

2xiqi i

r Exjafji/qZji \ j have used

- (Exjaj j the simp

/qji)=

1
r'

Fv2

.._._

(14)

2RT

In eqn.

(14)

Fv e -

en

v+
we
L

ifying

notation,

(1 + $ 2)b

2$b

Iv + (I -4)b to

1
J

(IS)

It is interesting same functional (A minor be we

note as

that the

the

first

term

of eqn.

(14)

has

exactly equation qi # q., kji. ; VDW-1 or

the of but To

dependence difference by the all

standard in the

or VDW-1

Peng-Robinson rule when

state. this fix

arises

i-j combining chosen (14) binary as the the

could ideas,

absorbed define and lump

an appropriately first the term of eqn.

parameter, "equivalent"

contribution "nonconformal"

remaining

terms

into

"asymmetric"

contribution. to compare VDW-1 the fugacity Due coefficients complexity of eqn. of the (13) with

It is illustrative those we of its show equivalent the

form.

to the with

equations,

only

comparison

for

a binary

component

1 at

infinite

dilution.

01_!I
-VDW-1

=
-9 2

1) -

(16)

95 a12 [ 912 The right coefficient for negative physically a22 - qz

where,

X =

d
RT

1 -

Fv

(17)

side of eqn. (16) is reduced values

is always

negative

and thus the fugacity effect is obtained

from its VDW-1 value.

(The opposite values

of 0~. However,

only positive

of (I are

meaningful.) it can be shown that the local composition of a system at fixed T, V, g. This effect reduces the

In general,
Helmholtz correct result

energy

is a qualitatively than its

since the DDLC configuration form.

should be more favorable

equivalent

VDW-1

EVALUATION

OF THE MOLLERUP PR-EOS

MODEL

FOR ASYMMETRIC

NONPOLAR

SYSTEMS systems,

The VOW-1 including binary with

provides

a good description asymmetric.

of most nonpolar For example,

those which

are highly correlated

the methane-decane K, even errors It is in

is accurately

over a temperature k2I=O;

range of 311-583 absolute

the default

interaction

parameter,

the average

the K-values extremely capability. proposed case. Figures somewhat methane

of methane

and decane

are 3.5% and 8.8%, rules

respectively.

important

that the DDLC mixing we have conducted

retain this desirable of the model binary as a test

Therefore

an investigation

by Mollerup

(eqn. 9) by using the methane-decane

1, 2, and 3 present chosen

the results

of the investigation. fugacity

We have of

arbitrarily as a function

to show the liquid-phase

coefficient

of composition a decrease

at 310 K and 270 atm. in the fugacity giving

In general, Figure

the 1

DDLC mixing shows

rules cause

coefficient.

that this decreasecan as 3-4 orders

be enormous,

fugacity

coefficients is unity.

too low Figure 1

by as much

of magnitude coefficients values.

when

the q of decane

also presents (1968), large.

the fugacity

with the size parameter local composition

from Bondi is still

q=6, and two higher A non-randomness is shown

The

effect

too

parameter in figure

(o) of 0.2 along with the same decane 2. Figure 3 illustrates to 0.5. These the additional indicate to

size parameters effect

of setting

the binary model

parameter

comparisons parameters

that the Mollerup correlate

requires simple

large and unreasonable system.

this relatively

DEVELOPMENT

OF A NEW DDLC MODEL: of the last section

DEPARTURE

FROM THE GEOMETRIC

MEAN contribution EOS for been reached

The results greatly

show that the "asymmetric" version of the DDLC-PR

over-predicted nonpolar

by the Mollerup systems.

asymmetric,

A similar

conclusion

has already

u: 1.0 kz,- 0.0

q-+-y-0.0
0.2 x(t&aM) OS6 Fig 1. Effect of LC model 310 K and 270 atm. (eqn. 9). Liquid-phase

o.b

of methane-decane

binary

at

10

1
0.0

VOW-l.9'1 (OATAwlnuw 10x)

$;
s
0.1:

U.H

- -xiq=ro___--__---

--

--

_---,/H ,/--

-/_I
#H
All lx%

0.01

:__/-/- ,
u.
40
0.2
I

t*;%l
0.8
I

%(Methano)
9). Liquid-phase of methane-decane binary at

0.4

0.8

Fig 2.

Effect of LC model (eqn. 310 K and 270 atm.

91

-1

ei
i
VOW-~.

q=l

(DATAWITNIN 10%)

-___--__--

LC.qrlO

_____c
__---u
All

u. q=s
l.c.

q*o

,,i

0.k

0.0

0:2

I
x(&a"*)

0:s

Fig 3.

Effect of LC model (eqn. 9). 310 K and 270 atm.

Liquid-phase

of methane-decane

binary at

Fig 4.

Computertime
system.

for calculation

of fugacity

coeffkients

for n-component

98 by Dimitrelis (9) and make occur Prausnitz the rather j-l (1982) who further assumption point that out that models analogous

to eqn.

stringent pair

local ai/qi caused are

compositions # aj/qj. when ji from some They

Inevitably have

In the local

interaction effects rather

whenever are not ji

proposed

that are

composition from jj

interactions "ideal"

different of

ii but

when

different

combination and

ii and

interactions, jiO

referred

to as ji". Since nonpolar the standard

Dimitrelis Peng-Robinson with jiO. We

Prausnitz generally

define produces mean

as an arithmetic results

mean. for

satisfactory should

systems for

kji = 0. the

geometric

be a very

good

first

approximation

assume

that

the

total

molar

internal into as two

energy parts:

of

the

ji and

pair

in a The model.

multi-component "ideal" However, described part the by

fluid

is divideb conformal

ideal

excess.

is entirely "excess" the DDLC

in the

standard

Peng-Robinson local

contribution theory.

causes

non-conformal

compositions

-a U ji -a0 U ji

-a0 U ji a

-aEX + u.. 31
FV

=_._._ al/T

(1 - kji)

T I VP!.!

(19)

-aEX "ji

a = ~ al/T

FV

(-dji)

T I V,N standard However, dji Peng-Robinson in the determines Note data model. we The

(20)

Equation binary

(19)

corresponds kji

to the

usual

parameter set

is retained. The

analysis part 4

have internal

generally energy (i.e., summing rules,

kji = 0.

parameter composition mixture

that that

of the

that d jf the

produces # dfj). ideal

local The

effects. molar

is not

symmetric by mixing

total

internal using

energy the

is obtained and DDLC

and

excess

ji contributions

VDW-1

respectively.

-a0 U

= E Z xjxj ij

-a0 uji

(21)

-aEX U

-aEX = B Xrqi i
x ji j< (22)

99

where

'ji

= x. J

Eji (23)

X 'k Eki k

and Eji = exp

(-dji)Fv

1
by integrating eqns. (18-24) with RT X xiqi rn cri I: xj Eji [j to obtain Helmholtz energy Here we assume that the repulsive of state yields a reasonable

(24)

The Helmholtz respect to l/T.

energy may be obtained Thus,

_a
A

= -

L E xixj (aiaj)'f2 ij

(1 - kji)Fv

1 (25)
requires term athermal (1982) (e.g., model. from

It should be noted that the integration an expression for the athermal Peng-Robinson limit. equation

of the standard contribution

to the total Helmholtz

free energy.

Whiting

and Prausnitr

have shown that the Peng-Robinson athermal term.

repulsive

term resembles

the Flory-Huggins systems

Also we note that highly asymmetric are well described by the standard properties

nonpolar

methane-decane) Expressions eqn. (25).

Peng-Robinson

for all configurational no derived

can easily be obtained

However

properties

are shown in order to save space. viewpoint. It

The above derivation does however

is only valid from a phenomenological that have been made.

state the assumptions limit in addition

The new model meets a and low that is, for an

very important density

to the ones at high temperature (1981) and Mollerup

noted by Whiting effect

and Prausnitz

(1981):

the nonconformal asymmetric

is not necessarily

large (or even nonzero)

system.

This feature allows

the model

to retain the good results accurate correlation of

of the standard

Peng-Robinson

model and facilitates

the phase equilibria

of highly nonideal

polar systems.

DEVELOPMENT

OF AN APPROXIMATE

OR TRUNCATED

DDLC MODEL by eqn. (25) produces model, as shown

The local-composition greatly improved

Peng-Robinson

model defined

correlations However,

over the standard the computational applications

Peng-Robinson

in the next section. unacceptably components. fraction model defined

load might prove to be

high for practical This arises

with a large number of time being consumed 1980.) in mole In the

from the bulk of computer

summation

calculations.

(Also see Boston and Mathias, summations are density

by eqn. (25), these

dependent

and thus

must be redone at each iteration

for the mixture

molar volume.

100 Figure standard calculation opinion, justified impractical the also number includes 4 shows a comparison model of and the average computer (eqn. an time of 25) time for required a single system. of In two) is when 4 our is by the

Peng-Robinson of the

DDLC version in

fugacity increase

coefficients in but computer an

n-component (say, magnitude for

a reasonable by a superior (with of

a factor increase

model,

order

current

computer in the for the

capabilities is greater

process than about

simulation) 15. model for large Figure we

components a comparison that

mixture the

approximate model

or

truncated used

propose. without

We conclude incurring

truncated

may be burden.

systems

a prohibitive

computational

According mixture is

to given

the by

truncated

DDLC model,

the

attractive

Helmholtz

energy

of

-a A

aNC = a Fv 2RT NC Fvz (26)

where the

a is given
NonConformal

by

the

standard is given

Peng-Robinson by

form

(eqns.

6 and

8)

and

term,

aNc =

H 1

xi+

aci

E j

xj tji

(27)

The effects.

parameters Note per

tii thatt binary model (25)

are is pair;

the not

lumped symmetric

contribution (tji # tij)

of

all

the thus

nonconformal the model has 3

and kji. and

parameters The expanding nonconformal

the

third by to eqns. eqn. term

parameter (6, 8,

truncated eqn.

defined

26,

27)

may be derived only the first

by

analogously Denoting this

term.

(14) and retaining -aNC we obtain, as A

-aNC A =--

1 Zxiaci 2RT i

2 xj

P dji (z j xj dji)

1
F, of

I
of

(28)

Notice not Is affect used.

that the

01 and

the

qs

and

as

have since

been only

absorbed the first

in

the

ds,

This

does term

composition the

dependence

nonconformal 3 and over (e.g., 5) has

Further, This has

temperature good

dependence representation

a (eqns. data

been

removed. temperature

facilitated with

a wide

range

temperature-independent

parameters

water-hydrocarbon

systems).

101
The temperature theoretical nonconformal This basis. dependence Mansoori of eqn. (28) may also be justified (1972) on a

and Leland

have shown that the first factor is of order 1/T2.

contribution with

to the compressibility eqn. (28). chosen for eqn.

is consistent

The composition is suggested

dependence

(27) is somewhat

arbitrary.

It

by writing rzz x1 x2

eqn. (28) for a binary, 221

-aNC A

1 = - 2RT

x1 acl d21 + x2 ac2 d12 1 1

(29)

Equations Helmholtz

(28) and (29) always This

give a negative correct but

contribution

to the total the

energy.

is physically of the model.

it

could

restrict

mathematical relatively regressed meaning

flexibility empirical

Therefore, However,

we have chosen we should

the

form of eqn. (27).

note that if the

value

of t is large and negative,

it suggests

that the physical

is lost. and thus dependence it was not possible of eqn. (29) is to

In this work only binary data were analyzed

Further,

for the systems we have (27) and (28) are

the t's have been positive

and thus eqns.

identical. An extremely the standard is especially appealing aspect of the model is that it reduces exactly to it

Peng-Robinson applicable

model when

all the t's are equal systems whfch (e.g., water

to zero.

Thus

to multicomponent polar components

are largely

nonpolar or coal

but have a few important conversion processes).

in petroleum

CORRELATION

OF PHASE

EQUILIBRIUM was correlated for various rules, systems using van der One parameter (d12 and parameter (1968).

Vapor-liquid Waals one-fluid

equilibrium

and local-composition the van der Waals

mixing mfxing

eqn. (25).

(k12) was fit with d21) were fit with

rules and two parameters The non-randomness from Bondi

the local composition and size parameters and average

rules.

(a) was set to unity Table 1 presents

(q) were derived deviations

maximum

K-value

for these an improved higher

two methods. fit to the accuracy,

In each system,
data. while improvement

local composition

mixing

rules enabled

The methanol-benzene was

system was correlated

to a much

less, but St.111 significant, plots of K-value We should deviations

for the other

systems.

Figures

5 and 6 present system.

from data for the form of eqn. 25

methanol-benzene (d12 = d21) did

note the symmetric improvement

not show significant

over the VDW-1 form.

TABLE Correlation of Vapor-Liquid Equilibrium Data

Ref.
Temp. (OC) 12 21 12

Pressure
Mix Parameters k d d Rules %Kl max*

XK2

max

%Kl

avg

%K2

a"g

(Atml

Methanol(l)Benzene(2) Naga ta 1969 60.8-76.7 0.10 0.61 -0.17 LC 1.0

vow-1

-57.0 -7.0

62.1 -14.3

17.1 3.0

Methanol(l)Carbon Dioxide(P) Ohgak i 1976 25-40 0.23 5.7-80.0 VDW-1 LC 0.06

-0.37

14.2 -4.1

27.0 -22.5

2"::

14.8 8.0

Acetone(l)Water(2) Griswold 1952 100 1.1-3.6 VDW-1 LC -0.23

-0.35

-0.02

::::

-49.6 -29.7

22.6 10.6

Isobutylene(l)Methanol(2) Churkin 1976 50 3.1-6.1 VDW-1 LC

0.04 0.0 0.59

33.0 -1.6

16.9 2.5 --

23.9 8.5

* Average

absolute

deviation

in K-value

of component

1.

103 15

1,
A X

x (Methanol)

Fig 5.

Comparison 1969).

of new LC model

(eqn.

25) with

experimental

data

(Nagata,

Fig 6.

Comparison of new LC model data (Nagata, 1969).

(eqn.

25) and VI@1

form with

experimental

TABLE Correlation of Liquid-Liquid Equilibrium Data

System %l d d 12a 12b 21a avg k 12a 12b k d

REP

Temp 0 c

Mix Parameter

Rules

1 2 w

3 avg

1-Butanol(l)Water(e) Hill 1926 5-80 -0.18 -0.1 -0.05 -0.05 0.14 0.12 0.45 0.07 VDW-1 LC LC(tr)4

49.1 1.0 1.2

26.7 0.7 2.6

Benzene (l)Water(e) Tsonopoulos 10-200 -0.08 8::: 0.04 0.74 1.08 -0.15 LC(tr) ZW-' 1982

132.1 0.06 :::

2691.1 :::

Hexane(1) Water(Z) @clpoulos 10-200 -0.24 0.15 0.48 -0.24 0.0 VDW-1 LC LCItr)

"X 2.39 1.35 0.15 16:7

>10000 12.0 12.9

I-Hethylnaphthalene(l)1982 Brady 37-277 -:z 0:31 ZW-' i_C(tr) -0.16 0.01 1.16 1.36 0.21 23.2 1036.0 3.5 '"Z

Water(P)

618

1 =d d T 12b 12 12a +

2 absolute deviation in calculated mole fraction of component 1 in liquid phase 2.

Average

3 absolute deviation

Average

in calculated

mole

fraction

of component

in liquid

phase

1.

4 read "de as et".

For LC(tr),

106

Fig 7.

Correlation of benzene-water Wilson, 1982) with truncated

mutual solubility LC model.

data

(Tsonopoulos

and

0.1

0.01

0.001

0.0001-

o.oooo1

Fig 8.

z.Zrap;lation of I-methylnapthalene-water ., 1982) with truncated LC model.

mutual

solubility

data (Brady

106 Liquid-liquid van der Waals Table for equilibrium one-fluid 2 presents these four and was local correlated composition absolute parameter include to the for a few selected the systems truncated) mole Waals fit using mixing

(including

rules. fractions mixing the

average One (to

deviations was fit

in calculated to the van der

methods.

rule,

parameters and

temperature truncated

dependence) composition with four

were

to

local

composition the

three

local

mixing local in the

rules.

Although

overall

improvement be

is substantial that for

composition k12 regard, local with and d12 the

parameters, parameters local

it should must be

noted

temperature

dependence fit. In this

correlated equation of

an accurate

composition activity parameters the local

state

is analogous It should with the be

to the noted

current that even

composition four binary model) beyond

coefficient (also

models. used

typically

UNIQUAC

activity

coefficient improvement liquid-liquid (temperature with phases The the

composition Peng and

method Robinson use

provides (1980)

a significant for correlation of

methods

like These

equilibria. dependent) for

methods phase. at

separate

interactlon

parameters arises two

each method

No ambiguity end

or discontinuity point where (any)

local

composition

a critical

merge. results with the truncated local composition parameters model are are not particularly temperature against

encouraging dependent. experimental zero.

since Figures data.

the

(three)

interaction

7 and Note

8 present that

a comparison water about

of model

calculations are

tZII for yield

in the the

hydrocarbons accuracy.

nearly

A two-parameter

fit

would

same

CONCLUSION In this theory useful is also van der as work applied we have to the investigated Peng-Robinson for the density-dependent of state. local We composition two approach

equation

propose The the

models

to account to any

nonconformal equation

or asymmetric of state derived

effects. from

applicable Waals

other

generalized

partition

function.

Finally, model high which

the

results DDLC low

of this mixing density

work rules

demonstrate and thus

that meets

an equation the required for

of

state at

employs and

limits activity

temperature models

is promising applications.

as a substitute

coefficient

in practical

ACKNOWLEDGEMENT The D. authors wish for to thank Professors J. M. Prausnitz and F. P. Stein and

Dimitrelis The work

helpful

discussions. paper was sponsored in part of by the International under

reported Company

in this and the

Coal

Refining

United

States

Department

Energy

Contract

DE-AC05-780R03054.

107
List of Symbols

Helmholtz Energy Peng-Robinson parameter, eqn. 1 Second Virial Coefficient Peng-Robinson parameter, eqn. I Binary Interaction Parameter Binary Interaction Parameter Surface Area Size Parameter Number of Moles Pressure Gas Constant Temperature Binary Interaction Parameter Volume Molar Volume Mole Fraction Non Randomness Parameter Temperature Dependent Pure Component Fugacity Coefficient Superscipts a Attractive Contribution Infinite Dilution

Parameter,

eqn.

Subscripts i i Component Comoonent ComPonent Critical i 5 k

i
C

REFERENCES Abrams, 0. S. and Prausnitz,

J. M.,

1975, AIChE

J. 21:116-128. J. M., 1975, Ind. Eng.

Abrams, 0. S., Seneci, F., Chueh, Chem., Fundam., 14:52-54.

P. L., and Prausnitz,

Bondi, A., 1968. Physical Properties of Molecular Glasses, John Waley and Sons, New York.

Crystals,

Liquids,

and

Boston, J. F. and Mathias, P. M., 1980, Phase Equiilibria and Fluid Properties March in the Chemical Industry - 2nd Internation Conference, Berlin. 17-21:823-848. Brady, C. J., Cunningham, Association, RR-62. Churkin, V. N., Gonshov, J. R., and Wilson, G. M., 1982, Gas Processors

V. A.,

and Pavlov,

S. Y.,

1978.

Zh Fiz Khim.

52:488.

"Thermodynamic Properties of Dimitrelis, D. and Prausnitz, 3. M., 1982. Strongly Nonideal Fluid Mixtures from an Extended Quasi-Chemical Theory," American Institute of Chemical paper presented at Fall Annual Meeting. Engineering, Los Angeles, CA, Nov 14-19, 1982. Gmehling, J. and Onken, Dechema, Frankfurt. U., 1981. Vapor-Liquid Equilibria Data Collection,

Griswold, Hill, Huron, A. M.

J. E., J.

and and and

Wong, Malisoff, Vidal,

S.

Y.. W.

1952, M.

Chem. J.

Eng. Am.

Prog. Chem.

Symp. Sot.

Ser.

48:18.

1926, Fluid T. W.,

48:918. 3:255-271. Sot., Faraday

J.,

1979, Jr.,

Phase 1972,

Equilibria, J. Chem.

Mansoori, G. A. and Leland, Trans. II, 68:320-344. Mollerup, Nagata, Ohgaki Peng, , D. I., K. Y., J.,

1981, Fluid
1969, J. Chem. K.,

Phase Eng. 1976, D. 8..

Equilibria, Data, 14:418.

7:121-138.

and

Takashi, Robinson,

J Chem. 1976.

Eng. Ind.

Data Eng.

21:53. Fundam., 15:59-64. 133, Ed:

and

and Robinson, Peng, 0. Y., Newman, S. A., Washington, Reamer, Chem., Soave. H. H., 36:1526. G., 1972, Olds, R. H..

D. B., 1980, DC, 393-414. Sage, 8. H.

in

ACS Symposium

Series

and

Lacey,

W.

N..

1942,

Ind.

Eng.

Chem.

Eng.

Sci.,

27:1197.

Tsonopoulos, Solubilities n-Hexane. Van Ness, 19:238-244. Vidal, J.,

C. and Wilson, G. M., 1982. High Temperature Mutual of Hydrocarbons and Water. I. Benzene, Cyclohexane, accepted for publication in AIChE Journal. H. C., Byer, and S. M., Gibbs, R. E., 1973. AIChE Journal

and

1978,

Chem.

Eng.

Sci.,

33:787-791.

Whiting, W. B. and Prausnitz, J. M., 1981. Equations of State for Strongly Nonideal Fluid Mixtures: Application of The Local-Composition Concept, paper presented at Spring National Meeting. American Institute Chemical Englneering, Houston, Texas, 5-g April 1981. Whiting, W. B. and Prausnitz, J. M., 1982, Fluid Phase Equilibria, 9:119-147.