2284 I n d . Eng. Cheni. Res.

1990, 29, 2284-2294

Equation of State for Small, Large, Polydisperse, and Associating

Molecules

Stanley H. Huang and Maciej Radosz*

Exxon Research and Engineering Compan), Annandale. IVeu. Jersey 08801

Statistical Associating Fluid Theory (SAFT) has been extended to many real, molecular, and
macromolecular fluids, such as chain, aromatic, and chlorinated hydrocarbons, ethers, alkanols
(aliphatic alcohols), carboxylic acids, esters, ketones, amines, and polymers, having molar mass u p
t o 100000. T h e key result of this work is a n accurate and physically sound equation of state for
predicting density, vapor pressure, and other fluid properties. Practical calculations require three
nonspecific parameters: segment number, segment volume, and segmentsegment interaction energy
(segment energy for short). For chain molecules, the segment volume and segment energy are found
to be nearly constant upon increasing the molar mass, while the segment number is found t o be a
linear function of molar mass. As a result, this equation of state represents a useful, predictive
correlation for many compounds, such as polymers, where no extensive experimental data are available
and where parameters have to be estimated based on molar mass and chemical structure only.
Specific interactions, such as hydrogen bonding, are characterized by two association parameters,
the association energy and volume, characteristic of each site-site pair. These parameters, having
well-defined physical meaning, control the bond strength and hence the degree of association.

Introduction (1975) in the Perturbed Hard Chain Theory (and in more

Molecularly based equations of state not only provide
a useful thermodynamic basis for deriving chemical PO-
tentials or fugacities that are needed for phase equilibrium
simulations but also allow for separating and quantifying
the effects of molecular structure and interactions on bulk
properties and phase behavior. Examples of such effects
are the molecular size and shape (e.g., chain length), as-
sociation (e.g., hydrogen bonding) energy, and mean field
(e.g., dispersion and induction) energy. Ideally, a single
equation of state should incorporate all these effects.
A concept of such an equation of state has recently been
proposed by Chapman et al. (1989, 1990) based on per-
turbation theory. The essence of their approach, referred
t o as the Statistical Associating Fluid Theory (SAFT): is
to use a reference fluid that incorporates both the chain
length (molecular size and shape) and molecular associa-
tion, in place of the much simpler hard sphere reference
fluid used in most existing engineering equations of state.
Chapman et al. (1990) developed Helmholtz energy ex-
pressions accounting for the chain and association effects
based 011 Wertheim's (1984, 1986a,b) cluster expansion
theory.
Wertheim derived his theory by expanding the Helm-
holtz energy in a series of integrals of molecular distribu-
tion functions and the association potential. On the basis
of physical arguments, Wertheim showed that many in-
tegrals in this series must be zero and, hence, a simplified
expression for the Helmholtz energy can be obtained. This
expression is a result of resummed terms in the expansion
series (cluster expansion). The key result of Wertheim's
theory is a relationship between the residual Helmholtz
energy due to association and the monomer density. This
monomer density, in turn, is related to a function 1
characterizing the "association strength".
A reference equation of state used in this work is based
on the SAFT concept that captures the hard sphere, chain,
and association effects. Effects due to other kinds of in-
termolecular forces (dispersion, induction, etc.), usually
weaker, can be included through a mean field perturbation
term. Our mean field term is similar to that proposed by
Alder et al. 11972) and is creatively used in many recent
equations of state, most notably by Beret and Prausnitz
0888-5885190; 2629-2283302.~50/0
recent PHCT versions) and by Chen and Kreglewski (1977)
in their equation of state, also known as BACK and ex-
tended to mixtures by Simnick et al. (1979).
Our goal is to develop a practical but physically sound
equation of state, applicable to small, large, chain, and
associating molecules over the whole density range. While
we are concerned with the quality of fit for various fluid
properties, such as vapor pressures and liquid densities,
our primary concern is the ease and reliability of extrap-
olating to large, often poorly defined and polydisperse
pseudocomponents of real polymer and oil solutions. From
this point of view, the key to success lies in well-behaved
and hence easy to estimate equation of state parameters.
We will define model molecules, bulk fluid properties,
and equation of state parameters to be derived from fitting
real fluids. We will then define our equation of state in
terms of the Helmholtz energy and compressibility factor.
After presenting many correlation results and equation of
state parameters for vapor pressures and liquid densities
of over 100 real fluids, we will show an example of how a
reliable equation of state can be used to estimate critical
constants of large molecules, which cannot be determined
experimentally due to thermal decomposition.
Real Fluids: Nonassociating and Self-Associating
We will treat the effective molecular size (through hard
sphere and chain terms) and molecular association as two
major effects on the bulk properties of real fluids. This
choice can be justified by using a simplified example for
the vapor pressure. It is easy to show that the vapor
can be approximately correlated with respect
pressure (psst)
to temperature ( T )by using a Clausius-Clapeyron type
of equation given below:
In p S a t = A(') - A(Z)/T
where A ( * )is a constant proportional to the enthalpy of
vaporization. A ( 2 )obtained
, from fitting to experimental
vapor pressure data, is log-log plotted against the molar
mass in Figure l a for nonassociating fluids and in Figure
1 b for associating fluids. The data points shown in these
figures are defined in Table I, along with symbols and data
points used throughout this paper.
C 1990 American Chemical Society
 Ind. Eng. Chem. Res., Vol. 29, No. 11, 1990 2285

Table I. Nonassociating and Self-Associatina Real Fluids

o n-alkanes
a n-alkylcyclopentanes fluids data points
v n-alkylcyclohexanes
/ O nonassociating
n-alkanes 0
polypropylene 0
polyethylene 0
pol yisobutylene 0
n-alkylcyclopentanes A
n-alkylcyclohexanes V
benzene derivatives 0
polynuclear aromatics 0
ethers A
ketones r
tertiary amines 4
esters
alkenes
chlorinated hydrocarbons
2 . self-associating
o n-alkanes acids
0 alkllnoii
alkanoia acids alkanols (aliphatic alcohols) 0
lo' t primary amines
O/O
primary amines 4
athen / secondary amines 4
.-E>
. ketones

f 5 -
components only, associating means self-associating and
"':,a Ob)
nonassociating means non-self-associating. We should
;/O note that some non-self-associating molecules can be
cross-associating in mixtures with other molecules.
- In A@) = 5.0237 + 0.72702 In MM The reduced fluid density 7 (segment packing fraction),
the same for segments and molecules, is defined as

where p is the molar density, m is the segment number

(number of segments in each molecule, our first pure
component parameter), and d is the effective segment
diameter that is temperature dependent. This definition
is equivalent to
We will note that A(2)for nonassociating fluids in Figure
l a is a strong, essentially linear function of the molar mass 7 = TpmuO (2)
and that all the points representing hydrocarbons of many where T = 0.740 48 and uo is the segment molar volume in
different structures (chainlike, branched, and ringlike) tend a close-packed arrangement, Le., the volume occupied by
to cluster around the average line. This means that the NA, closely packed segments, in milliliters per mole of
effect of structure, however significant and accounted for, segments. Hence, on the basis of eqs 1 and 2, we can
is much smaller than the effect of molecular size. This is express uo as
true even though we can observe a slight deviation from
the average line for polynuclear aromatics, which can be
explained by a small degree of n-n-induced aggregation. (3)
By contrast, we will note that A@)for associating fluids
in Figure l b shows strong deviations from A(2)for n-al- Since uo is implicitly temperature dependent, because d
kanes. Expectedly, the magnitude of these deviations is temperature dependent, it is useful to introduce a cor-
depends on the degree of association. For example, car- responding, temperature-independent segment molar
boxylic acids and aikanols (aliphatic alcohols), which are volume at T = 0, which will be denoted uw and referred
known to be strongly associated, exhibit greater deviations to as the segment uolume, our second pure component
from the alkane behavior than tertiary amines and ethers parameter:
do. Therefore, we will only treat acids, alkanols, primary
amines, and secondary amines as significantly self-asso- uoo =-
nNAv
u3 (4)
ciating compounds. 61

Model Fluid Properties and Parameters where u is a temperature-independent segment diameter.

Our model pure fluid is a mixture of equi-sized spherical
segments interacting according to a square-well potential.
In addition, we superimpose two kinds of bonds between
these segments, covalent-like bonds to form chains and
association bonds to interact specifically. As a result, our
model molecules can approximate a broad range of mole-
cules, from nonassociating near-spherical (for example,
methane, neopentane) and nonspherical (chain alkanes,
polymers) to associating near-spherical (methanol) and
nonspherical (alkanols). Since this paper deals with pure
Since a characteristic volume, rather than diameter, is
traditionally selected as a pure component parameter, for
example, b in cubic equations of state, V* in the Perturbed
Hard Chain Theory of Beret and Prausnitz (1975), and uW
in the Chen-Kreglewski (1977) equation of state, uoowill
also be used in this work as one of the pure component
parameters. However, while all the volume parameters
were defined by others per mole of molecules, our uoo is
defined per mole of segments.
Temperature dependence of the segment diameter d in
eq 3 is based on the Barker-Henderson approach (1967).
2286 Ind. Eng. Chem. Res., Vol. 29, No. 11, 1990
Specific equations for d and uo given below,
d = o[ 1 - C exp[ s]
] - XA).The
are based on the work of Chen and Kreglewski (1977), who
obtained eq 6 by solving the Barker-Henderson integral
equation for d
d = J d [ l - exp(-u(r)/kT)] dr (7)
0
using a square-well potential; uo/k in eqs 5 and 6 is the
well depth, a temperature-independent energy parameter,
characteristic of nonspecific segment-segment interactions,
which will be referred to as the segment energy, in kelvin,
our third pure component parameter. Similar to Chen and
Kreglewski (1977),we set the integration constant C = 0.12
and use their temperature dependence of u
where e l k is a constant that was related to Pitzer's acentric
factor and the critical temperature (Chen and Kreglewski,
1977; Kreglewski, 1984) for various molecules. Since our
energy parameter is for segments rather than for molecules,
we set e l k = 10 for all the molecules. The only exceptions
are a few small molecules where the e / k values close to
those derived by Kreglewski have been used ( e l k = 0 for
argon; 1 for methane, ammonia, and water; 3 for nitrogen;
4.2 for CO; 18 for chlorine; 38 for CS,; 40 for CO,; and 88
for SO,); larger values of e l k for some of the molecules
treated here as nonassociating may be caused by their weak
self-association.
In addition to the three pure component parameters
characterizing nonassociating molecules, uoo, m, and uo,we
use two association parameters, eAA and K ~ These . asso-
ciation parameters have been proposed for a square-well
model of specific interactions between two sites A
(Chapman et al., 1990). The parameter eAA characterizes
the association energy (well depth), and the parameter K~
characterizes the association volume (corresponds to the
well width rAA).
In general, the number of association sites on a single
molecule is unlimited, but it has to be specified for each
specific molecule. However, we do not specify the location
of association sites. We label these sites with superscripts
A, B, C, etc., to keep track of the specific site-site inter-
actions. Each association site is assumed to have a dif-
ferent interaction with the various sites on another mol-
ecule. Cluster structure limitations, steric hindrance ap-
proximations, and size distributions are explained in detail
elsewhere (Chapman et al., 1990).
In brief, the fraction of clusters of a given size can be
estimated by using general statistical arguments (Flory,
1953). As an example, we shall consider a pure component
system composed of molecules having two sites A and B,
where only AB bonding and only chain clusters are al-
lowed. The fractions of each chain length present (dimers,
trimers, etc.) are functions of X Aand X B (the fractions
of molecules NOT bonded at sites A and B, respectively)
that, in turn, are calculated from the equation of state
described in section 3. Assuming that the activity of a site
is independent of bonding at the other sites on the same
molecule, the fraction of molecules that are present as
monomers is X AXB, or (XA)2 if X A = X B, which is the
case in our example. Similarly, the fraction of molecules
that are present as dimers is given by 2(XA)2(1
general result for the fraction of molecules present as
m-mers is
X(m-mer) = m(XA)2(1- X A ) " - ' (9)
and the average chain length is given by
mave= l / X A (10)
Equation 9 expresses the "most probable distribution" of
Flory (1953), which is in agreement with experimental
results for polymer polydispersity.
Equation of State
The theory results underlying our equation of state are
given in this section in terms of the residual Helmholtz
energy aresper mole, defined as ares(T,V,N) = a(T,V,N)
- aided(T,V,N), where a(T,V,N)and aided(T,V,N) are the
total Helmholtz energy per mole and the ideal gas Helm-
holtz energy per mole a t the same temperature and den-
sity. The residual Helmholtz energy aresis a sum of three
terms representing contributions from different intermo-
lecular forces. The first term aseg accounts for the part of
aresthat represents segment-segment interactions, i.e., hard
sphere and mean-field (dispersion) interactions. The
second term acheinis due to the presence of covalent
chain-forming bonds among the segments. The third term
am accounts for the increment of am due to the presence
of site-site specific interactions among the segments, for
example, hydrogen-bonding interactions. The general
expression for the Helmholtz energy is given by
ares = aseg + a h a h + aassoc
(11)
The segment Helmholtz energy a w , per mole of molecules,
can be calculated from
aseg = ma seg (12)
where sow, per mole of segments, is the residual Helmholtz
energy of nonassociated spherical segments and m is the
segment number. Let us allow ao- to be composed of hard
sphere and dispersion parts, as follows
aoseg = aohs + a disp (13)
As usual, the hard sphere term can be calculated as pro-
posed by Carnahan and Starling (1969)
(14)
where 7 is the reduced density given by eqs 1 and 2.
The dispersion term is a power series initially fitted by
Alder et al. (1972) to molecular dynamics data for a
square-well fluid. This equation, which also provided the
basis for the Perturbed Hard Chain Theory of Beret and
Prausnitz (1975), is given by
Dij are universal constants. In this work, we use Dij's that
have been refitted to accurate PVT, internal energy, and
second viral coefficient data for argon, by Chen and Kre-
glewski (1977).
Both chain and association terms are the same as those
described by Chapman et al. (1990). The chain term, the
 Ind. Eng. Chem. Res., Vol. 29, No. 11, 1990 2287
16 r

12 -
/ O
' O .

t / - m = 0 05096 MM

E
0 10 20 30 40
Molar Mars. kgimole

Figure 2. Segment number m a~ a linear function of molar mass for

n-alkanes and long-chain polymers; PP = polypropylene, P E =
polyethylene, PIB = polyisobutene.

Helmoltz energy increment due to bonding, can be de-

termined from
4
1
.-.chain 1- ,'I

Equation 16 is derived based on the associating fluid 0 1 1 I I I I 1

theory, as explained by Chapman et al. (1990), where the
association bonds are replaced by covalent, chain-forming
bonds.
The Helmholtz energy change due to association is
calculated for pure components from
0 100 200 300
Molar Mass, g/mole
Figure 3. Segment numbers m for n-alkanes and polynuclear aro-
matics, as linear functions of molar mass, set boundaries for other
hybrid classes of hydrocarbons. The branches of diamonds corre-
spond to n-alkyl derivatives of the polynuclear aromatics, e.g.,
methyl-, ethyl-, tz-propyl-, n-butylnaphthalene.

where M is the number of association sites on each mol- Our final equation of state can be presented as a sum of
ecule, X A is the mole fraction of molecules NOT bonded the compressibility factor terms 2, analogous to the
at site A, and LA represents a sum over all associating sites Helmholtz energy terms in eq 11, as given below
on the molecule. - 1 = Zseg + Zchain + z a s s o c
(22)
The mole fraction of molecules NOT bonded a t site A
can be determined as follows where
X A = [ 1 + N A ~ C PBAAB]-l
X (summation over ALL
B
sites: A, B, C, ...) (18)
where NAv is Avogadro's number and p is the molar density
of molecules. Am in eq 18 is the association strength that 5
is approximated as ,9 - T 2

AAB = g(d)"g[exp(tAB/kT) - (19)

AAB is our key property characterizing the association
bonds that depends on the segmental radial distribution
function g(d)seg. Since we approximate our segments as
hard spheres, we approximate g(dIsegas the hard sphere
radial distribution function (Carnahan and Starling, 1969):
1 The equation of state presented above has been used to
1 - -q
2
g(d)"g = g(d)h" = - (20)
(1 - 7d3
The only density dependence in Am is given by g(d)w,and
the only explicit temperature dependence is given by the
tAB/kT,in eq 19. However, we should also note the tem-
perature dependence of d and hence, implicitly, 9.
The temperature-independent segment diameter u, used
in eq 19 to make KAB dimensionless, can be calculated based
on eq 4 as follows
(21)
correlate vapor-liquid equilibria of over 100 real fluids. For
each fluid, the pure component parameters (om, m, and
u"/k for non associating plus tAAand K~~ for associating
fluids) have been regressed from the least-squares mini-
mization using differences in calculated and experimental
vapor pressure and liquid density data. Correlation results
for both nonassociating and associating fluids are presented
in the following two sections.
Segment Parameters for Real Nonassociating
Fluids
For each nonassociating compound, Table I1 lists the
molar mass (MM), temperature range, uW, m, uo/k, percent
2288 Ind. Eng. Chem. Res., Vol. 29, No. 11, 1990
Table 11. Segment Parameters for Real Nonassociating Fluids
AAD%
MM Trange, K uw, mL/mol m uoJk,K PMt diq data source*
nitrogen 28.013 19.457 1.0 123.53 1
argon 39.948 16.29 1.0 150.86 1
carbon monoxide 28.010 72-121 15.776 1.221 111.97 0.68 (6Ia 0.26 (6)O 2
carbon dioxide 44.010 218-288 13.578 1.417 216.08 2.8 (8) 0.86 (8) 3
chlorine 70.906 180-400 22.755 1.147 367.44 1.9 (12) 0.76 (12) 4
carbon disulfide 76.131 278-533 23.622 1.463 396.05 4.5 (12) 1.6 (12) 5
sulfur dioxide 64.063 283-413 22.611 1.133 335.84 1.1 (8) 2.1 (6) 2
n-Alkanes
methane 16.043 92-180 21.576 1.000 190.29 1.4 (10) 0.35 (10) 1
ethane 30.070 160-300 14.460 1.941 191.44 1.8 (15) 1.6 (15) 6
propane 44.097 190-360 13.457 2.696 193.03 2.1 (IO) 1.8 (IO) 7
butane 58.124 220-420 12.599 3.458 195.11 2.3 (12) 2.6 (12) 8
pentane 72.151 233-450 12.533 4.091 200.02 1.9 (12) 3.0 (12) 2, 9
hexane 86.178 243-493 12.475 4.724 202.72 2.3 (14) 3.5 (14) 2
heptane 100.205 273-523 12.282 5.391 204.61 1.8 (14) 3.4 (14) 2
octane 114.232 303-543 12.234 6.045 206.03 1.6 (13) 3.4 (13) 2
nonane 128.259 303-503 12.240 6.883 203.56 0.86 (11) 1.9 (7) 2
decane 142.276 313-573 11.723 7.527 205.46 2.2 (14) 3.5 (14) 2, 10
dodecane 170.340 313-523 11.864 8.921 205.93 0.71 (12) 3.3 (12) 2, 10
tetradecane 198.394 313-533 12.389 9.978 209.40 0.82 (12) 2.8 (11) 2, 10
hexadecane 226.432 333-593 12.300 11.209 210.65 2.1 (14) 3.1 (12) 2, 10
eicosane 282.556 393-573 12.000 13.940 211.25 2.1 (10) 2.6 (10) 2, 10
octacosane 394.77 449-704 12.0 19.287 209.96 1.3 (11) 10
hexatriacontane 506.99 497-768 12.0 24.443 208.74 2.2 (11) 10
tetratetracontane 619.21 534-725 12.0 29.252 207.73 4.8 (10) 10
Polymers
Poly
propylene 15 700 263-303 12.0 822.68 209.96 1.0 (30) 11
ethylene 25 000 4 13-473 12.0 1274.08 216.15 2.1 (24) 12
isobutylene 36 000 333-383 12.0 1823.95 267.44 0.77 (30) 12
n-Alkylcyclopentanes
cyclopentane 70.135 253-483 12.469 3.670 226.70 1.7 (13) 1.1 (5) 2, 10
methyl 84.162 263-503 13.201 4.142 223.25 1.5 (13) 1.3 (5) 2, 10
ethyl 98.189 273-5 13 13.766 4.578 229.04 1.5 (13) 1.6 (6) 2, 10
propyl 112.216 293-423 14.251 5.037 232.18 0.39 (8) 1.4 (6) 10
butyl 126.244 314-458 14.148 5.657 230.61 0.53 (9) 1.1 (5) 10
pentyl 140.272 333-4 83 13.460 6.503 225.56 0.45 (9) 0.94 (4) 10
n-Alkylcyclohexanes
cyclohexane 84.162 283-513 13.502 3.970 236.41 0.68 (13) 1.0 (5) 2, 10
methyl 98.189 273-533 15.651 3.954 248.44 1.3 (14) 3.1 (14) 2, 10
ethyl 112.216 273-453 15.503 4.656 243.16 0.88 (10) 1.4 (6) 2, 10
propyl 126.243 313-453 15.037 5.326 238.51 0.41 (8) 0.99 (4) 10
butyl 140.270 333-484 14.450 6.060 234.30 0.44 (10) 0.90 (4) 10
pentyl 154.297 353-503 14.034 6.804 230.91 0.43 (11) 0.53 (4) 10
Benzene Derivatives
benzene 78.114 300-540 11.421 3.749 250.19 1.4 (13) 2.1 (13) 2
methyl (toluene) 92.141 293-533 11.789 4.373 245.27 2.6 (13) 2.9 (13) 2, 10
ethyl 106.168 293-573 12.681 4.719 248.79 1.2 (15) 3.0 (15) 2, 10
n-propyl 120.195 323-573 12.421 5.521 238.66 1.5 (14) 2.0 (9) 10
n-butyl 134.212 293-523 12.894 6.058 238.19 0.83 (13) 2.1 (9) 2, 10
m-xylene 106.168 309-573 12.184 4.886 245.88 2.1 (14) 2.9 (14) 10
tetralin 132.205 293-673 13.196 5.163 279.17 2.1 (20) 3.9 (20) 13
biphenyl 154.213 433-653 12.068 6.136 280.54 2.5 (12) 2.8 (12) 2
Polynuclear Aromatics
naphthalene 128.174 373-693 13.704 4.671 304.80 1.8 (17) 2.6 (17) 14
I-methyl 142.201 383-551 13.684 5.418 293.45 0.43 (IO) 0.50 (3) 10
1-ethyl 156.228 393-563 12.835 6.292 276.18 0.29 (11) 0.53 (3) 10
1-n-propyl 170.255 403-546 13.304 6.882 266.82 4.2 (6) 2.6 (1) 10
1-n-butyl 184.282 413-566 13.140 7.766 252.11 11.5 (9) 7.0 (1) 10
phenanthrene 178.234 373-633 16.518 5.327 352.00 0.43 (14) 1.6 (11) 15
anthracene 178.234 493-673 16.297 5.344 352.65 0.31 (10) 1.1 (6) 15
pyrene 202.255 553-673 18.212 5.615 369.38 4.9 (7) 16
triphenylene 228.293 573-773 21.271 6.016 379.12 2.2 (11) 16
Ethers
dimethyl 46.069 179-265 11.536 2.799 207.83 1.9 (8) 17
methyl ethyl 60.096 266-299 10.065 3.540 203.54 2.4 (4) 17
methyl n-propyl 74.123 267-335 10.224 4.069 208.13 2.7 (7) 17
diethyl 74.123 273-453 10.220 4.430 191.92 2.4 (10) 2.2 (10) 2
phenyl 170.212 523-633 12.100 6.358 276.13 0.37 (7) 1.5 (7) 2
 Ind. Eng. Chem. Res., Vol. 29, No. 11, 1990 2289
Table I1 (Continued)
AAD 90
MM Trange, K uoo, mL/mol m u o / k ,K PUt uiiq data sourceb
Ketones
dimethyl (acetone) 58.080 273-492 7.765 4.504 210.92 2.3 (10) 1.0 (5) 2, 18
methyl ethyl 72.107 257-376 11.871 4.193 229.99 1.3 (8) 17
methyl n-propyl 86.134 274-399 11.653 4.644 230.40 2.0 (8) 17
diethyl 86.134 275-399 10.510 4.569 235.24 1.4 ( 8 ) 17
Tertiary Amines
trimethylamine 59.111 193-277 14.102 3.459 196.09 0.90 (16) 19
triethylamine 101.192 323-368 11.288 5.363 201.31 0.70 (5) 19
Esters
methanoate
methyl 60.046 225-324 7.548 3.886 215.48 0.61 (8) 0.53 (5) 17
ethyl 74.073 242-348 7.954 4.727 202.72 0.34 (8) 1.0 (6) 17
n-propyl 88.100 262-377 8.671 5.276 203.98 0.71 (8) 1.5 (7) 17
n-butyl 102.127 279-403 10.100 5.460 212.34 2.1 (8) 1.5 (6) 17
ethanoate
methyl 74.073 244-498 7.366 4.918 200.58 3.1 (12) 2.9 (10) 17, 20
ethyl 88.100 273-493 7.897 5.566 196.19 1.5 (12) 3.0 (12) 2
n-propyl 102.127 278-542 8.637 6.106 197.94 1.9 (11) 2.5 (11) 17, 20
n-butyl 116.154 293-413 10.829 5.918 212.11 1.5 (7) 0.82 (5) 17
propanoate
methyl 88.100 261-512 7.991 5.493 199.61 1.7 (11) 3.2 (10) 17, 20
ethyl 102.127 277-538 8.621 6.064 197.45 1.9 (11) 3.1 (11) 17, 20
n-propyl 116.154 293-413 10.332 6.090 207.13 1.3 (7) 1.4 (6) 17
butanoate
methyl 102.127 285-533 8.634 6.176 196.83 1.3 (15) 1.4 (5) 17
ethyl 116.154 298-423 11.273 5.675 214.04 2.9 (8) 1.2 (5) 17
n-propyl 130.181 316-445 10.575 6.713 205.67 2.6 (8) 1.2 (5) 17
Alkenes
ethene 28.054 133-263 18.157 1.464 212.06 2.0 (8) 0.68 (8) 21
propene 42.081 140-320 15.648 2.223 213.90 3.6 (10) 1.5 (10) 22
1-butene 56.108 203-383 13.154 3.162 202.49 1.8 (10) 2.4 (10) 2, 10
I-hexene 84.156 213-403 12.999 4.508 204.71 2.3 (11) 2.8 (11) 2, 10
Chlorinated Hydrocarbons
chloromethane 50.488 213-333 10.765 2.377 238.37 0.75 (7) 0.82 (7) 2
dichloromethane 84.933 230-333 10.341 3.114 253.03 2.2 (7) 0.99 (7) 17
trichloromethane 119.378 244-357 10.971 3.661 240.31 0.25 (7) 1.1 (6) 17
tetrachloromethane 153.823 273-523 13.730 3.458 257.46 1.1 (14) 2.5 (14) 2
chloroethane 64.515 212-440 11.074 3.034 229.58 3.1 (13) 3.4 (13) 17, 20
1-chloropropane 78.542 238-341 11.946 3.600 229.14 0.50 (8) 0.94 (6) 17
1-chlorobutane 92.569 262-375 12.236 4.207 227.88 0.40 (8) 1.2 (6) 17
I-chlorohexane 120.623 306-435 12.422 5.458 225.82 0.33 (8) 1.0 (4) 17
chlorobenzene 112.559 273-543 13.093 3.962 276.72 1.5 (15) 2.7 (15) 2
"Numbers in parentheses indicate number of data points used in the correlation. b ( l )Parameter values are taken from Kreglewski (1984)
without fitting. (2) Vargaftik, N. B. Tables on the Thermophysical Properties of Liquids and Gases; John Wiley & Sons: New York, 1975.
(3) IUPAC. Carbon Dioxide. International Tables of Fluid State; Pergamon Press: Oxford, 1976; Vol. 3. (4) IUPAC. Chlorine. Inter-
national Tables of the Fluid State; Pergamon Press: Oxford, 1985; Vol. 8 (tentative tables). (5) O'Brien, L. J.; Alford, W. J. Ind. Eng.
Chem. 1951,43,506. (6) Goodwin, R. D.; Roger, H. M.; Straty, G. C. Thermodynamic Properties of Ethane from 90 to 600 K and Pressures
to 700 bar. NBS Technical Note 687; NBS: Boulder, CO, 1976. (7) Goodwin, R. D.; Haynes, W. M. Thermodynamic Properties of Propane
from 85 to 700 K and Pressures to 70 Mpa; NBS Monograph 170; NBS: Boulder, CO, 1982. (8) Haynes, W. M.; Goodwin, R. D. Thermo-
dynamic Properties of n-Butane from 135 to 700 K and Pressures to 70 Mpa; NBS Monograph 169; NBS: Boulder, CO, 1982. (9) Das, T.
R., Reed, C. O., Jr. J . Chem. Eng. Data 1977,22,3. (10) Selected Values of Properties of Hydrocarbons and Related Compounds. Research
Project 44 of the American Petroleum Institute and the Thermodynamic Research Center, Texas A&M University: College Station, TX,
Loose-leaf data supplements to 1989. (11) Passaglia, E.; Martin, G. M. J . Res. Natl. Bur. Stand., Sect. A 1964, 68A, 273. (12) Beret, S.;
Prausnitz, J. M. Macromolecules 1975, 8, 536. (13) Kudchadker, A. P.; Kudchadker, S. A.; Wilhoit, R. C. Tetralin; API Monograph 705;
API: Washington, DC, 1978. (14) Kudchadker, A. P.; Kudchadker, S. A.; Wilhoit, R. C. Naphthalene; API Monograph 707; API: Wash-
ington, DC, 1978. (15) Kudchadker, A. P.; Kudchadker, S. A.; Wilhoit, R. C. Anthracene and Phenanthrene; API Monograph 708; API:
Washington, DC, 1979. (16) Kudchadker, A. P.; Kudchadker, S. A.; Wilhoit, R. C. Four-Ring Condensed Aromatic Compounds; API
Monograph 709; API: Washington, DC, 1979. (17) Thermodynamic Tables for non-Hydrocarbons; Thermodynamic Research Center, Texas
A&M University: College Station, loose pages to 1988. (18) Ambrose, D.; Sprake, C. H. S.; Townsend, R. J. Chem. Thermodyn. 1974, 6,
693-700. (19) Boublik, T.; Fired, V.; Hala, E. The Vapor Pressure of Pure Substances, 2nd ed.; Elsevier, Amsterdam, 1984. (20) Perry, R.
H.; Chilton, C. H. Chemical Engineer's Handbook, 5th ed.; McGraw-Hill: New York, 1973. (21) IUPAC. Ethylene. International Tables
of the Fluid State; Pergamon Press: Oxford, 1976; Vol. 2. (22) IUPAC. Propylene (Propene). International Tables of the Fluid State;
Pergamon Press: Oxford, 1980; Vol. 7.

average absolute deviation (AAD%)in vapor pressure (pt, behavior. This is important because the key future
except for polymers) and liquid molar volume (u"q), in- challenge lies in estimating the equation of state param-
cluding the number of data points used in regression, and eters for polydispersed, poorly defined pseudocomponents
data source. The quality of fit for both vapor pressure and of real fluid mixtures, rather than in fine-tuning precise
liquid density is as good as can be usually expected for a predictions (however important) for well-defined pure
reasonable, three-parameter equation of state. However, components. Apart from the expected scatter due to in-
our focus is not on the quality of fit but on the parameter accuracies in experimental data and fitting itself, the pa-
2290 Ind. Eng. Chem. Res., Vol. 29, No. 11, 1990

r Table 111. Correlation of t h e Segment Number m for

Hydrocarbons

L /O'
m = A(1) + A(2'MM
MM range
A(') A(2' in fittine
n-alkanes 0.70402 0.046647 16-619
polynuclear aromatics 2.673 3 0.014 781 78-202
n-alkylcyclopentanes 0.823 60 0.039 044 70-140
n-alkylcyclohexanes -0.010038 0.043 096 84-154
n-alkylbenzenes 0.51928 0.041 112 78-134
1-n-alkylnaphthalenes -2.3190 0.054 566 128-184

0' I I I I I I Table IV. Correlation of t h e Close-Packed Molar Volume

0 100 200 300 mvw for Hydrocarbons
Molar Mass, g/mOle
mum = A") + A(2'MM
Figure 4. Close-packed molar volumes muM for n-alkanes and
polynuclear aromatics, as linear functions of molar mass, set MM range
boundaries for other hybrid classes of hydrocarbons. The branches A(1) ~ 1 2 ' in fittini
of diamonds correspond to rz-alkyl derivatives of the polynuclear n-alkanes 11.888 0.551 87 16-619
aromatics, e.g., methyl-, ethyl-, n-propyl-, n-butylnaphthalene. polynuclear aromatics 5.0117 0.469 42 78-202
n-alkylcyclopentanes 4.2053 0.598 17 70-140
400 n-alkylcyclohexanes 3.6438 0.59961 84-154
n-alkylbenzenes -6.1400 0.62468 78-134
1-n-alkylnaphthalenes -21.619 0.66647 128-184

Table V. Correlation of the Segment Energy u o / kfor

n -Alkanes a n d Polynuclear Aromatics
300
u o / k = A") - A'2) e ~ p [ - A ( ~ ) A l M l

.-E> MM range
-u
X
A") A(2) A'3' in fitting
$- n-alkanes 210.0 26.886 0.013341 16-619
3 polynuclear aromatics 472.84 357.02 0.0060129 78-228

200 Table VI. Correlation of the Segment Energy u o l k for

Other Hydrocarbons
u o / k = A('' - A(2)MM

100
0 100 200 300
Molar Mass, gtmole
Figure 5. Segment energies u o / k for n-alkanes and polynuclear
aromatics as smooth but nonlinear functions of molar mass, set
boundaries for other hybrid classes of hydrocarbons. The branches
of diamonds correspond to n-alkyl derivatives of the polynuclear
aromatics, e.g., methyl-, ethyl-, n-propyl-, n-butylnaphthalene,
rameter values reported in Table I1 are well-behaved and
suggest predictable trends upon increasing the molar mass
of similar compounds.
The segment number m increases with increasing molar
mass within each homologous series practically linearly.
For example, m for n-alkanes is plotted versus molar mass
in Figure 2. It is reassuring to find that a single linear
relationship holds not only for all the small n-alkanes,
which is shown in the insert, but also for macromolecular
chains of varying degree of branchiness, such as poly-
propylene, polyethylene, and polyisobutylene. It is also
reassuring to fmd out that m is essentially a linear function
of molar mass for different homologous series of aromatic
molecules, i.e., upon increasing the side chain length for
alkylbenzenes, alkylnaphthalenes, etc., as shown in Figure
3. The plots in Figure 3 also suggest that the segment
numbers m for all hydrocarbons fall between two bound-
aries set by n-alkanes and plain polynuclear aromatics
(PNA's) and that for a given molar mass m will decrease
with increasing aromaticity. This means that, if there are
no accurate PVT data available, which often is the case,
m can be estimated from molar mass only.
MM range
A'1) A(2) in fittine
n-alkylcyclopentane 239.56 0.085 618 98-140
n-alkylcyclohexanes 278.59 0.313 11 98-154
n-alkylbenzenes 267.39 0.218 25 78-134
1-n-alkylnaphthalenes 425.70 0.941 11 128-184
We note that the effective segment numbers m reported
for hydrocarbons in Table I1 are systematically smaller
than the corresponding carbon numbers. A physical pic-
ture of a n-alkane therefore is that of a chain of overlapping
spherical segments. Hence, the segment volume u" should
correspond to the volume occupied by such segments.
Expectedly, the segment volume uoo for methane is the
largest among alkanes because it corresponds to a single
( m = 1) CH, unit, and it gradually decreases upon in-
creasing the chain length, reaching an asymptotic value
of 12 (set 12.0 for C,,) for long chains.
Since uoo does not vary much with chain length and
remains constant for long chains and since m is a linear
function of the molar mass, the product mum (volume
occupied by a mole of molecules in a close-packed ar-
rangement) is also a linear function of the molar mass, as
shown in Figure 4. As for m alone (Figure 3), n-alkanes
and plain polynuclear aromatics set the boundaries for the
mu" domain for all the hydrocarbons. Apart from testing
these reassuring trends, a practical reason for developing
a correlation for mu- is to provide the basis for estimating
L)", if there are no accurate PVT data available, for a given
m and molar mass.
A similar molar mass correlation can be developed for
the segment energy uo/k, which is shown in Figure 5. As
for m and mu", n-alkanes and plain polynuclear aromatics
 Ind. Eng. Chem. Res., Vol. 29, No. 11, 1990 2291
Table VII. Monomer Fractions XAfor Different Bonding Types
type A approximations XA approximations XA
1 A"#O -1 + (1 + PA)'/^
2PA
-l'+ (1 + 8pA)'12
4pA
-1 + (1 + PA)'/^
PA
-1 + (1 + 1 2 ~ A ) ' / ~
PA
-(I - pA) + ((1 + + 4pA)'12
4pA
-1 + (1 + 1 6 ~ A ) ' / ~
8PA
XA = XB = XC -(1 - 2pA) + ((1 + 2pA)' + 4pA)'I'
XD = 3 X A - 2 6PA

Table VIII. Types of Bonding in Real Associating Fluids" justed when accurate data become available for hybrid
rigorous hydrocarbons, such as aromatic rings with long side chains.
species formula type assigned type The solid lines and curves shown in Figures 3-5 have
been predicted from eqs 26-29. Specific values of the
regression coefficients A(i) are reported in Tables III-VI.
This way we have a useful method for estimating all the
alkanol A 3B 2B equation of state parameters for nonassociating pure fluids
-o:B where no accurate data are available and, especially, for
CH
A
poorly defined pseudocomponents where only average
water B:ij:Hc
4C 3B molar mass and average aromaticity are available. Al-
H O though this method is primarily applied to predicting
amines phase equilibria in mixtures (Huang and Radosz, 19901,
tertiary A 1 non-self-associating this method can also be used to estimate pure component
- N- properties, such as vapor pressures, densities, and critical
I properties.
secondary
-..N- A 2B 2B
HB
Segment a n d Site-Site P a r a m e t e r s for Real
primary 3B 3B
-NL S
Self-Associating Fluids
HA
Vapor pressure and liquid density correlations for
ammonia A ":NOHe 4B 3B self-associating fluids require the use of the am term (eq
HC 17; zero for the nonassociating fluids). Before we can
calculate am, however, we have to define and specify all
set the boundaries for the uo/k domain for all the hydro- the non-zero site-site interactions and hence non-zero A's
carbons. Unlike m and mu", however, although smooth, (eq 19) needed to determine the monomer fractions X A
uo/k is nonlinear with respect to the molar mass. (eq 18). While eq 18 is not X A explicit in general, it can
For the ease of estimating, m, mu", and uof k have been be made X A explicit in many specific cases. Examples of
regressed as simple functions of the molar mass (MM) for one-, two-, three-, and four-site models and A approxi-
many homologous series. For example, mations are provided in Table VI1 along with analytical
X A expressions for each model that can be used in place
m = A(') + A(2)MM for all hydrocarbons (26) of' eq 18.
In order to select a proper expression for X Afrom Table
muw = A(') + A(2)MM for all hydrocarbons (27) VII, one has to assign association sites and non-zero site-
site interactions. Ideally, one should have detailed, in-
u o / k = A(') - A(2) ~ x ~ ( - A ( ~ ) M M ) dependent data from spectroscopy on the association
for n-alkanes and PNA's (28) strength for each site-site interaction. Since such data are
scarce and usually qualitative (we are addressing this
u o / k = A(') - A(2)MM for other hydrocarbons (29) problem in a separate project), one has to make simplifying
approximations aimed at reducing the number of param-
We note that eq 29 is only a linear approximation that is eters that have to be fitted. For example, different hy-
valid up to the MM of a corresponding n-alkane; for higher drogen bonds are assumed to be equivalent, e.g., AAC=
MM values, we set u o / k to be the same as that for a cor- ABC, which means that different sites A and B form
responding n-alkane. This can easily be tested and ad- equivalent bonds with C , or double hydrogen bonds are
2292 Ind. Eng. Chem. Res., Vol. 29, No. 11, 1990
Table IX. Segment and Site-Site Parameters for Real Self-Associating Fluids"
AAD 70
UM,
MM Trange, K mL/mol m ua/k, K elk, K 10*~ Put dig data sourceb
(Model 3B)
ammonia 17.032 200-380 10.0 1.503 283.18 893.1 3.270 1.6 3.2 (10)' 1
water 18.015 283-613 10.0 1.179 528.17 1809 1.593 1.3 (13) 3.2 (13) 1
hydrogen sulfide 34.080 284-369 10.0 1.935 226.38 804.1 0.911 0.69 (14) 1.4 (14) 2
Alkanols (Model 2B)
methanol 32.042 273-487 12.0 1.776 216.13 2714 4.856 0.83 (12) 0.88 (12) 1,3
ethanol 46.069 302-483 12.0 2.457 213.48 2759 2.920 0.86 (10) 0.83 (10) 1
1-propanol 60.096 293-493 12.0 3.240 225.68 2619 1.968 0.16 (11) 1.2 (111 1, 3
1-butanol 74.123 313-493 12.0 3.971 225.96 2605 1.639 0.23 (10) 1.0 (6) 3
1-pentanol 88.150 333-513 12.0 4.642 225.15 2587 1.637 0.32 (IO) 1.1 (5) 3
1-hexanol 102.177 343-573 12.0 5.315 222.88 2556 1.873 0.77 (13) 1.22 (51 3
1-heptanol 116.204 353-573 12.0 6.028 221.62 2579 1.654 0.61 (12) 0.96 (41 3
1-octanol 130.231 373-593 12.0 6.642 220.69 2532 2.001 1.0 (13) 1.0 (4) 3
1-nonanol 144.258 383-613 12.0 7.322 219.18 2516 2.249 1.1 (14) 0.47 ( 4 , 3
1-decanol 158.285 393-633 12.0 8.024 217.14 2448 2.892 2.1 (14) 0.57 (41 3
"propanol 60.096 273-373 12.0 3.249 202.94 2670 2.095 0.27 (11) 0.96 (11) 1. 3
2- butanol 74.123 293-393 12.0 3.933 216.41 2457 1.634 0.32 (11) 1.2 (11, 3
2-methyl-1-propanol 74.123 293-403 12.0 4.028 232.90 2698 0.4032 0.58 (12) 1.4 (121 3
2-methyl-2-propanol 74.123 303-373 12.0 3.966 202.35 2515 1.118 0.21 (8) 0.79 (81 3
phenol 94.114 346-482 12.0 4.103 290.08 1894 4.315 0.24 (9) 0.02 (1I 3
Acids (Model 1)
methanoic 46.025 293-393 15.5 1.341 333.28 7522 0.1625 0.62 (6) 0.49 (5) 3
ethanoic 60.052 313-553 14.5 2.132 290.73 3941 3.926 1.6 (13) 0.69 ( 1 3 ) 1
n-propanoic 74.080 313-463 13.5 3.084 296.03 3400 0.8193 0.25 (9) 0.10 (9) 3
n-butanoic 88.107 333-493 13.0 3.800 268.93 4155 0.3700 0.30 (9) 0.84 (91 3
n-pentanoic 102.134 353-483 12.0 4.719 248.63 4322 0.5103 0.21 (8) 1.0 (8) 3
n-hexanoic 116.161 372-504 12.0 5.482 243.39 4683 0.2352 0.44 (7) 3
n-heptanoic 130.187 385-522 12.0 6.059 241.50 4734 0.2309 0.46 (7) 3
n-octanoic 144.215 399-540 12.0 6.628 240.41 4745 0.2430 0.60 (7) 3
n-nonanoic 158.242 411-557 12.0 7.274 238.97 4798 0.2005 0.44 (7) 3
n-decanoic 172.269 423-572 12.0 7.847 237.10 4906 0.1844 0.60 ( 7 ) 3
benzoic 122.124 405-523 12.0 4.608 272.66 5930 0.3149 0.66 (8) 0.43 14) 3
Primary Amines (Model 3B)
methanamine 31.057 204-413 12.0 2.026 226.86 1045 6.310 0.22 (13) 0.38 (13) 3
ethanamine 45.084 221-433 12.0 2.781 208.61 940.3 10.65 0.27 (13) 0.22 (12) 3
1-propanamine 59.111 243-473 12.0 i3.450 211.36 779.1 17.94 1.3 (13) 1.5 (10) 3
1-butanamine 73.138 265-503 12.0 4.062 210.91 895.4 15.08 2.2 (13) 2.6 (10) 3
1-pentamine 87.165 285-401 12.0 4.773 215.81 746.1 15.15 2.3 (7) 2.0 (7) 3
1-hexanamine 101.192 307-429 12.0 5.476 215.73 722.0 16.63 0.84 (7) 1.7 (6) 3
1-heptanamine 115.219 325-457 12.0 6.153 218.62 553.9 16.57 1.5 (7) 0.99 (3) 3
aniline 93.129 350-673 12.0 4.034 288.10 1269 11.27 2.6 (16) 3.5 (16) 3
Secondary Amines (Model 2B)
dimethylamine 45.084 208-436 12.0 2.637 208.23 1064 15.61 0.73 (12) 4
diethylamine 73.138 240-483 12.0 3.996 212.62 581.3 15.36 3.2 (11) 4
"Numbers in parentheses indicate number of data points used in the correlation. b ( l )Vargaftik, N. B. Tables on the Thermophysical
Properties of Liquids and Gases; John Wiley & Sons: New York, 1975. (2) Sage, B. H.; Lacey, W. N. Some Properties of the Light
Hydrocarbons, Hydrogen Sulfide, and Carbon Dioxide; API Monograph 37; API: New York, 1955. (3) Thermodynamic Tables for non-
Hydrocarbons; Thermodynamic Research Center, Texas A&M University: College Station, TX, loose pages to 1988. 14) Perry, R. H.;
Chilton, C. H. Chemical Engineer's Handbook, 5th ed.; McGraw-Hill: New York, 1973.

assumed to be represented as strong single bonds, e.g.,
between carboxylic groups. Other examples of rigorous
and approximated sets of site-site interactions for self-
associating molecules that are used in this work are given
in Table VIII. The sets defined as rigorous in Table VI11
include all the electron-donor and -acceptor sites on each
molecule.
An example for alkanols will illustrate the use of Tables
VI1 and VIII. Each hydroxylic group (OH) in alkanols,
in principle, has three association sites, labeled A and B
on oxygen and C on hydrogen, as shown in Table VIII.
The association strength A due to the like, oxygen-oxygen
or hydrogen-hydrogen (AA, AB, BB, and CC) interactions
is assumed to be equal to zero. The only non-zero A is due
to the unlike (AC and BC) interactions, which moreover
are considered to be equivalent. Hence, the rigorous type
selected for alkanols in Table VI1 is 3B. Another ap-
proximation is to allow only one site on oxygen (A) and
one site on hydrogen (B). In this case, the assigned type
for alkanols (Table VIII) is 2B, where the only non-zero
interactions AB and BA are equivalent. Although we
tested both types of site assignment for alkanols, 3B and
2B, we felt that the limited experimental data used for
fitting did not justify the use of the rigorous type 3B.
Therefore, we report results for the alkanols of type 2B
in Table IX.
For each self-associating compound, Table IX lists the
temperature range, um, m, uo/k,P l k , KAA, AAD% in vapor
pressure, AAD% in liquid density, including the number
of data points used in regression, and data source. Only
m, u o / k ,c"/k, and K" have been allowed to be adjustable.
The segment volumes uoo have been set equal to 12.0.
except for ammonia, water, and hydrogen sulfide where
it has been set equal to 10.0 and except for small carboxylic
acids where uoo has been made similar to those of corre-
sponding n-alkanes.
Similar to the trends observed for the nonassociating
fluids, the segment number m increases with increasing
molar mass within each homologous series, for example,
for chain acids and alkanols.

E
8
*Oo0
alkanoic acids
. m u m 8
8 '
s-
W
2t
1000 amines
**
0 100 200
Molar Mass, glmole
Figure 6. Plot of the associating energies t / k and segment energies
u o / k versus molar masses of organic compounds in homologous se-
ries. The ratio of the former to the latter is roughly 10 to 1.
The segment energies uo/k are close to 200 K and, hence,
are similar to those derived for nonassociating chain
molecules, as shown in Figure 6. Especially, uo/k for
amines and alkanols essentially matches uo/k for n-al-
kanes. Somewhat larger values for carboxylic acids are due
to the one-site approximation of the double hydrogen
bond. We tested this by allowing two and three sites on
acid molecules and, as a result, obtaining uo/k values that
were very close to 200 K.
Figure 6 also shows the association energies eAA for acids
(one-site approximation), alkanols, and amines. As ex-
pected, the association energies decrease upon going from
acids to amines. The ratios of P / u 0 are also in the rea-
sonable range (of the order of 10).
Example: Critical Constants Can Be Estimated
for Large Molecules
While the critical temperature and pressure are com-
monly used in numerous engineering correlations, such as
those based on cubic equations of state and corresponding
states, they cannot be measured for high molar mass
compounds because of thermal decomposition. Therefore,
there have been various useful empirical methods pro-
posed, such as that of Lee and Kesler (1975), that allow
for extrapolating the critical temperature and pressure to
high molar mass. An alternative, proposed by Mohan and
Peng (1987), is to use a reliable equation of state for such
extrapolation, which at least can be tested on other
properties in the high molar mass range.
Ind. Eng. Chem. Res., Vol. 29, No. 11, 1990 2293
400
too0
Molar Mars. glmole
Figure 7. Critical temperatures for n-alkanes predicted by our
10.000
equation of state falling between those predicted by others.
0 Experimental
o Huang el 01. (19a8)
0 Mohin 6 R n p (1987)
- 99.5 pb Confldence EOS Pndlclion
0
100 2 3 1000 2 3 10,000
Molar Mars, glmole
Figure 8. Critical pressures for n-alkanes predicted by OUT equation
of state agreeing with those of Mohan and Peng (1987).
Mohan and Peng used the Perturbed Hard Chain
equation of state (Cotterman et al., 1986) to extrapolate
the critical properties for long chain alkanes up to poly-
ethylene. As a result, they had to extrapolate all three
parameters C, V*, and T* (Mohan and Peng verified that
the polyethylene density was correctly predicted). By
contrast, the only parameter in our equation of state that
has to be extrapolated is m, which is linear with respect
to MM. Therefore, we found our equation of state to be
particularly suitable for estimating the critical properties
of large molecules.
Like all the analytical equations of state, this one o-
verpredicts the critical temperature and critical pressure.
However, since the differences between calculated and
predicted values have been very consistent for all the
n-alkanes for which there are experimental data, simple
correlations have been developed as follows:
In T, = 1.0169 In T p S- 0.14703 (30)
In P, = 0.89858 In P,"" + 0.18496 (31)
where T, is the critical temperature in kelvin, P, is the
critical pressure in bar, and the superscript eos means
predicted from the equation of state, using a simplified set
of parameters that are specialized for large molecules: m
= 0.05096MM, uoo = 12.0, and uo/k = 210. Equations 30
and 31 are applicable to all the n-alkanes, including
macromolecules, down to about Clo.
Sample results are shown in Figure 7 for the critical
temperature and in Figure 8 for the critical pressure. The
pairs of solid curves shown in Figures 7 and 8 have been
calculated from eqs 30 and 31, respectively. Each pair of
curves corresponds to a 99.5% confidence band. Our
2294 Ind. Eng. Chem. Res., Vol. 29, No. 11, 1990
predicted critical temperatures agree well with the ex-
perimental data and with those predicted by Huang et al.
(1988) but deviate somewhat from those predicted by
Mohan and Peng (1987). Our predicted critical pressures
on the other hand agree well with the experimental data
and with those predicted by Mohan and Peng but deviate
from those predicted by Huang et al. It is worth noting
that, unlike Huang et al.'s, Mohan's and our critical
pressures asymptotically reach zero as the molar mass
increases to infinity, as should be expected (Tsonopoulos,
1987).
Conclusions
The equation of state developed in this work is appli-
cable to small, large, polydisperse, and associating mole-
cules over the whole density range. The equation of state
parameters, segment number, segment volume, and seg-
ment energy, derived for over 100 real fluids, can be readily
extended to other hydrocarbon molecules based on mo-
lecular structure and molar mass only.
The association parameters, also derived in this work
from bulk experimental data, characterize the strength of
specific site-site interactions that lead to molecular asso-
ciation. This way one can separate and quantify the effects
of nonspecific segment properties and specific site-site
interactions on bulk fluid properties.
Our future work on this equation of state will focus on
the phase behavior of binary mixtures and polymer solu-
tions and on the use of spectroscopy for probing molecular
interactions leading to association.
Acknowledgment
This work is an extension of a joint project on associating
fluid theory with the Cornell University group of Professor
Keith E. Gubbins. Helpful comments and stimulating
discussions with Professor Gubbins, John Walsh, and Karl
Johnson are gratefully acknowledged.
Nomenclature
A") = regression constants, each use defined in the text
a = molar Helmholtz energy (total, res, seg, bond, assoc. etc.),
per mole of molecules
a. = segment molar Helmholtz energy (seg), per mole of
segments
C = integration constant in eqs 5 and 6
d = temperature-dependent segment diameter, A
e l k = constant in eq 8
k = Boltzmann's constant = 1.381 X J/K
m = effective number of segments within the molecule (seg-
ment number)
muo" = volume occupied by 1 mole of molecules in a close-
packed arrangement, mL/mol
M = number of association sites on the molecule
MM = molar mass, g/mol
molar = molar with respect to molecules
N = total number of molecules
NA, = Avogadro's number = 6.02 X molecules/mol
P = pressure
P, = critical pressure, bar
psst = saturated vapor pressure
R = gas constant
segment molar = molar with respect to segments
T = temperature, K
T , = critical temperature, K
ulk = temperature-dependent dispersion energy of interaction
between segments, K
u o /k = temperature-independent dispersion energy of inter-
action between segments, K
V = total volume
u = molar volume, uliq = liquid molar volume, mL/mol of bulk
fluid
u0 = temperature-dependent segment volume, mL/mol of
segments
uw = temperature-independent segment volume, mL/mol of
segments
X = mole fraction
XA = monomer mole fraction (mole fraction of molecules
NOT bonded at site A)
2 = P u / ( R T ) ,compressibility factor
K~~ = volume of interaction between sites A and B
AAB = "strength of interaction" between sites A and B, A3
cAB/k = association energy of interaction between sites A and
B, K
7 = (r/6)pnmd3= (aNA,/6)pmd3,pure component reduced
density, the same for segments AND molecules
p = pn/NAv,molar density, mOl/A3
pn = number density (number of molecules in unit volume),
l-3
a =Lennard-Jones segment diameter (temperature inde-
pendent), A
EA= summation over all the sites (starting with A)
Superscripts
A, B, C, D, ... = association sites
res = residual
seg = segment
assoc = associating, or due to association
hs = hard sphere
ideal = ideal gas
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Received for review April 3, 1990
Accepted June 20, 1990