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Fluid Phase Equilibria, 52 ( 1989) 3 l-38

Elsevier

Science

SAFT:

Publishers

Equation-of-State

W.G. CHAPMANls2,

2.

ExxonResearch

School

of Chemical

and Engineering

Printed

in The Netherlands

Solution Model for Associating Fluids

K.E. GUBBINSl,

1. Cornell University,

31

B.V., Amsterdam

G. JACKSONl,
Engineering,

Company,

M. RADOSZ2

Ithaca,

Corporate

NY

14853,

Research,

USA

Annandale,

NJ 08801,

USA

ABSTRACT
An equation-of-state
Statistical

Associating

model

has been developed

Fluid Theory

(SAFT).

for predicting

The agreement

found to be excellent at all the stages of model development;


spheres,

and

equilibrium

non-associating

chains.

The

model

has

phase

with molecular

for associating

been

shown

to

equilibria,

based

simulation

data

spheres, mixtures
reproduce

on the
has been

of associating

experimental

phase

data for a few selected real pure compounds.

INTRODUCTION
Associated

fluid mixtures

like and

unlike

molecules,

molecular

properties

of the clusters

the bulk fluid properties


statistical

mechanical

defined site-site

interactions
Especially

hydrogen-bonded

molecules of components
and

donor-acceptor

(size, energy, shape) are very different


One way to account

such as the perturbation

and the bulk fluid behavior


pertinent

is Wertheims

theory,

Since effective

from the monomeric

for such association

to quantify

[Cummings

contribution

but also clusters of

clusters.

effects is to use

the relationship

19843, [Cummings

molecules,

between well

19861, [Andersen],

which provides the basis for

our

model of

fluids.

Wertheim
molecular

not only monomeric

are also very different.

methods,

and [Wertheim].
associating

contain

for example

derived

distribution

his theory

functions

the next section, Wertheim

by expanding

and the association

the Helmholtz
potential.

showed that many integrals

expression

for the Helmholtz

expansion

series (cluster expansion).

energy can be obtained.

resummed

cluster expansion

Specifically,

using perturbation

in a series of integrals
arguments

explained

of
in

in this series must be zero and, hence, a simplified

This expression

the Helmholtz
theory.

energy

Based on physical

is a result of resummed

energy can be calculated

terms in the

from Wertheims

32

The

key result

the residual
is related

energy

to a function

mixtures

of spheres

1988B].

of Wertheims

Helmholtz

This

Statistical

characterizing

and

paper

terms

accounts

for that

part

interactions.
segments,

The

presence

ps

which

ps

is short

=a

where

the

site-site

achain

ASSOCIATION

bonded

theory

Carlo

of associating

in this section

is due

LJ segments.
specific

in terms

from

fluids,

termed

between

density,

in turn,

has been extended

simulations

of the residual

different

[Chapman

SAFT

third

interactions

of covalent

aassoC

among

for the Helmholtz

the

to

1988A,

which stands

accounts

is given

energy
The first

for

bonds

for the increment


for

ares which
term

such as, Lennard-Jones

chain-forming

segments,

energy

forces.

interactions,

presence
term

Helmholtz

intermolecular

segment-segment
to the

The

example,

seg

(LJ)

among

the

of ares due to

hydrogen

bonding

below.

(1)

+ achai(p;d,m)

density

TERM

FOR

our

analysis

We

start

for

mixtures

of

PURE

number

the

associating

symbols

are defined

below.

association

components.

term,
The

first

for pure

Helmholtz

self-associating

energy

change

due

compounds
to

association

and,
is

from

%M

(general)

of association

at site A, and C

and the other

COMPONENTS

from

for pure components

M is the

+ aassoc(p,T;d,cAB,,AB)

of molecules,

s =g [hXA
-$1 +
where

model

Wertheims
Monte

monomer

for

p is the molar

calculated

against

to use relationship

This

aassoc

Seg(rn+p,T;o,c)

second

strength.

tested

represents

a chai

term

The genera1 expression

seg +

=a

and

contributions

of ares which

second

of

interactions.

is defined

representing

for example

association

molecules,

is an easy
density.

ENERGY

of state

of three

expansion

Theory.

HELMHOLTZ

The equation

the

cluster

and the monomer

an equation-of-state

Fluid

is a sum

the

chain

presents

Associating

RESIDUAL

resummed

due to association

represents

sites

on each molecule,

a sum over all associating

XA is the mole

fraction

of molecules

NOT

sites on the molecule.

The mole fraction

of molecules

AB

NOT

-1

1
where

N,,

is Avogadros

number

bonded

at site A can be determined

(SUmmatiOn
werALL sites:
and

p is the

molar

density

A, 8.

as follows

c...)

of molecules.

AA

in equation

(3) is the

33
association

strength

AAB = 4,FAB Tr2

defined as

g(r)seg dr

(4)

where FA6 is given by

FAB = exp(cAB/T)

The integral

- 1

(5)

in equation

A+~ = d3 g(d)

(4) can be approximated,

icAB [exp(cAB/T)

which is our key property


equation

(6)

distribution

depends

function

1988A, 1088B], as follows

(6)

the association

on two segment

as the hard sphere r&a!

in [Chapman,

- ;1

characterizing

g(d).

as explained

properties,

Since we approximate

distribution

function

bonds.

The association

the segment
our segments

diameter

strength

d, and

AAB given by

the segment

as hard spheres, we approximate

radial
g(d)

[Carnahan]:

= s3 a

a g(d)hs
.s@)sg

(7)

where 1 is the reduced density defined as

,,=%lpd3,
6

(8)

where p is the molar density of molecules.

The association
association

strength

energy,

cAB

AAs
,

the only explicit temperature

ASSOCIATION
Extension
calculated

given by equation

and volume,

dependence

on two parameters

dependence

is given by the $/T,

in equation

characterizing

in AAs is given by g(d)

the
and

(6).

TERM FOR MIXTURES


to multicomponent

mixtures

is straightforward.

The Helmholtz

as an average which is linear with respect to mole fractions

where X Ai, the mole fraction

energy of association

is

Xi

of molecules i NOT bonded at site A, is given below


B.

X* =

(6) also depends

n AB. The only density

AiBj

(c, over ALL sites on molecule j:


Bj

Aj,

-1

1
Bj,

(10)
Cj...,

c,

over

all components)

34

As we can see, XAi depends

Pj =

'j

on the molar

density

pj

(11)

Pmixture
AiBj

and on the association

strength

CHAIN

AiBj

AAiB
= (dij)3 gij(dij)seglcAiBj

/T)

(12)

- 1

TERM
The

equation

increment

of the Helmoltz

energy

due to bonding,

on the other

hand,

can be determined

from

(13)

.chain
m

where

mi is the number

correlation
sphere

Xi

(1

mi)

function

contact.

are replaced

(13)

~(gii(dii)h)

of spherical

for the

segments

interaction

(13) IS
. d erived

Equation

by covalent,

in molecules

of two

chain-forming

based

spheres

of component

i, and gii is the hard

i in a mixture

on the associating

of spheres,

fluid

theory

evaluated

where

sphere

pair

at the

hard

the association

bonds

bonds.

RESULTS
The

equation

of state

is a result

of a systematic

associating

mixtures

were carefuly
elsewhere

verified

The

1988A],
single

version
the

[Jackson].
sites

against

This

in Figure

tested

initial

with

agreement

energy
simplified

simulation

in Figure

2 is believed

in Figure

compounds
argon

(acidic

equation

vapor

pressure

3. Representative

developed

results

spheres

Since

and

detailed

pure

for two-site

have

been

reported
here.

to be in an excellent

fluids
of a

to

of the model

are shown

was found

systems

chains,

versions

results

of hard-core
factor

theory,

nonassociating

comparisons

spheres,

simulations

of Wertheims

the prototype

1m] , only sample


[J OS

[Joslin],

hard-sphere

and for other

[Chapman
fluid

properties,

with
such

of monomers.
associating

fluid

of [Dickman]

to be satisfactory
and saturated
pressure

are shown

by Twu

an extension

for the compressibility

of the

vapor

acid and methanol)

of state,

Carlo

was obtained

extension

computer

Representative
shown

agreement

and the fraction

the

data.

[Jackson],

is illustrated

shown

associating

for the associating


Monte

section,

of this development

simulation

(NVT)

agreement

simple

stages

1988B],

of the theory,

1. Similar

as, the configurational


The

molecular

canonical

in the previous

from

At the early

1986, 1987, 1988A,

initial
with

described

development,

of chains.

[Chapman

agreement

model

density

saturated

in Figures

to chain

dimers,

for our equation

liquid
and

for

theory

results
liquid

tetramers,
of state

(1).

and

has also
octamers.

been
The

model.

for a chain
density

4 and 5. These

[1980], for aseg in equation

molecules

alkane

results

results

(n-octane)

are

for self-associating

were obtained

using

an

35
r-

ir-

IF

5
_i-

3-

/
0/
1
0.0

0.1

0.2

0.3

0.4

Reduced Density

Figure 1. The compressibility factor 2 = P/(pRT)

f or a hard sphere system with one attractive site as a

function of reduced density (q). The results of Monte Carlo simulations are represented by the circles, the
solid curve represents theoretical predictions obtained from numerical integration which are essentially the
same aa those obtained from the approximated model, for cAA = 7T, ,AA

0.1

0.2

0.3

= 1.485E4

[Jackson].

0.4

Reduced Density
Figure 2. The comprwsiblity

factor, from Monte Carlo simulations of [Dickman] (pointa) and from theory

(solid curves), for varying chain lengths of 2, 4, 8, as a function of reduced density 11(equation 8).

-11
20
25

30

35

104/T
600

300

I
.002

I
.003

.004
Density

I
.005

ho

.006

[Mole/cc]

Figure 3. n-Octane vapor pressure and liquid density, experiment.4 (squarea [Anonymous]) and m
predicted (solid curves).

37

-0

I
.

650

..
%

\
.\
t
t

...

I-

l.

2.5
1000/T [K]

,005

.Ol

,015

Density [Mole/cc]

gigwe 4. Acetic acid vapor pressure and liquid density, experimental (points [Anonymous]) and model
predicted (solid curves).

.Ol
lOOO/T[k]

.02

Density [Mole/cc]

Figure 5. Methanol vapor pressure and liquid density, experimental (points


predicted (solid curves).

[Anonymous]) and model

38
REFERENCES

Andersen, A.C.,
Anonymous,

1981. J. Chem. Phys., 59: 4714; ibid 1974, 61: 4985.

1986. Physical Sciences Data, Thermodymanic


Hydrocarbons

Data for Pure Compounds,

25 Part A:

and Ketones, Elsevier, New York.

Carnahan,

N.F., K.E. Starling, 1969. J. Chem. Phys. 51: 635.

Chapman,

W.G.,

1988A. Theory and Simulation

of Associating

Liquid Mixtures, Ph.D. Dissertation,

Cornell University.
Chapman,

W.G.,

K.E. Gubbins,

C.G. Joslin, C.G. Gray, 1987. Pure & Appl. Chem., 59: 53.

Chapman,

W.G.,

K.E. Gubbins,

C.G. Jo&n,

Chapman,

W.G.,

G. Jackson, K.E. Gubbins,

C.G. Gray, 1986. Fluid Phase Equilibria,

Cummings,

P.T., G. Stell, 1984. Molec. Phys., 51: 253.

Cummings,

P.T. L.J. Blum, 1986. J. Chem. Phys., 84: 1833.

Dickman,

R., C.J. Hall, 1988. J. Chem. Phys., 89: 3168.

Jackson, G., W.G.


Jo&n,

29: 337.

1988B. Molec. Phys., in press, (Chain Molecules).

Chapman,

C.G., C.G. Gray, W.G.

K.E. Gubbins,
Chapman,

1988. Molec.

K.E. Gubbins,

Twu, C.H., L.L. Lee, K.E. Starling, 1980:Fluid

Phys. 65: 1.
1987. Molec. Phys., 62: 843.

Phase Equilibria, 4: 35.

Wertheim,

M.S. J. Stat. Phys. 1984, 35: 19; 1984, 35: 35; 1986, 42: 459; 1986, 42: 477.

Wertheim,

M.S. J. Chem. Phys. 1986, 85: 2929; 1987, 87: 7323.

Acknowledgements
This
Institute.

work was partially

supported

by the National

Science

Foundation

and the Gas Rese

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