Beruflich Dokumente
Kultur Dokumente
Elsevier
Science
SAFT:
Publishers
Equation-of-State
W.G. CHAPMANls2,
2.
ExxonResearch
School
of Chemical
and Engineering
Printed
in The Netherlands
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
Fluid Theory
(SAFT).
for predicting
The agreement
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
INTRODUCTION
Associated
fluid mixtures
like and
unlike
molecules,
molecular
properties
of the clusters
mechanical
defined site-site
interactions
Especially
hydrogen-bonded
molecules of components
and
donor-acceptor
is Wertheims
theory,
Since effective
to quantify
[Cummings
contribution
clusters.
effects is to use
the relationship
19843, [Cummings
molecules,
between well
19861, [Andersen],
our
model of
fluids.
Wertheim
molecular
methods,
and [Wertheim].
associating
contain
for example
derived
distribution
his theory
functions
by expanding
the Helmholtz
potential.
expression
expansion
resummed
cluster expansion
Specifically,
using perturbation
in a series of integrals
arguments
explained
of
in
This expression
the Helmholtz
theory.
energy
Based on physical
is a result of resummed
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,
simulations
of the residual
different
[Chapman
SAFT
third
interactions
of covalent
aassoC
among
the
to
1988A,
which stands
accounts
is given
energy
The first
for
bonds
ares which
term
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
COMPONENTS
from
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
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
an equation-of-state
Fluid
is a sum
the
chain
presents
Associating
RESIDUAL
resummed
due to association
represents
sites
on each molecule,
XA is the mole
fraction
of molecules
NOT
of molecules
AB
NOT
-1
1
where
N,,
is Avogadros
number
bonded
(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
defined as
g(r)seg dr
(4)
FAB = exp(cAB/T)
The integral
- 1
(5)
in equation
A+~ = d3 g(d)
icAB [exp(cAB/T)
(6)
distribution
depends
function
(6)
the association
on two segment
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
radial
g(d)
[Carnahan]:
= s3 a
a g(d)hs
.s@)sg
(7)
,,=%lpd3,
6
(8)
The association
association
strength
energy,
cAB
AAs
,
ASSOCIATION
Extension
calculated
given by equation
and volume,
dependence
on two parameters
dependence
in equation
characterizing
the
and
(6).
mixtures
is straightforward.
The Helmholtz
energy of association
is
Xi
X* =
AiBj
Aj,
-1
1
Bj,
(10)
Cj...,
c,
over
all components)
34
Pj =
'j
on the molar
density
pj
(11)
Pmixture
AiBj
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 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
[Joslin],
hard-sphere
[Chapman
fluid
properties,
with
such
of monomers.
associating
fluid
of [Dickman]
to be satisfactory
and saturated
pressure
are shown
by Twu
an extension
of the
vapor
of state,
Carlo
was obtained
extension
computer
Representative
shown
agreement
the
data.
[Jackson],
is illustrated
shown
associating
section,
of this development
simulation
(NVT)
agreement
simple
stages
1988B],
of the theory,
1. Similar
molecular
canonical
in the previous
from
At the early
initial
with
described
development,
of chains.
[Chapman
agreement
model
density
saturated
in Figures
to chain
dimers,
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
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
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]
38
REFERENCES
Andersen, A.C.,
Anonymous,
25 Part A:
Carnahan,
Chapman,
W.G.,
of Associating
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.,
Cummings,
Cummings,
Dickman,
29: 337.
Chapman,
K.E. Gubbins,
Chapman,
1988. Molec.
K.E. Gubbins,
Phys. 65: 1.
1987. Molec. Phys., 62: 843.
Wertheim,
M.S. J. Stat. Phys. 1984, 35: 19; 1984, 35: 35; 1986, 42: 459; 1986, 42: 477.
Wertheim,
Acknowledgements
This
Institute.
supported
by the National
Science
Foundation