Fluid Phase Equilibria, 18 (1984) 231-243 237

Elsevier Science Publishers B.V.. Amsterdam - Printed in The Netherlands

A MODEL FOR ENTHALPY OF VAPORI2AlION USING A NEW ONE PARAMETER EQUATION OF STATE
FOR FLUIDS

G. NATARAJAN and D. S. VISWANATH

Chemical Engineering Department, University of Missouri-Columbia,
Columbia, MO 65211

(Received January, 1984)

ABSTRACT
Natarajan, G. and Viswanarh, D.S., 1984. A model for enthalpy of vaporization using a new one parameter equation of
state for fluids. Fluid Phase Equilibria, 18: 237-243.

An equation of state for a real fluid is presented and compared with the
existing models such as the Carnahan-Starling equation of state. The proposed
equatfon Is used in computing enthalples of vaporizatfon of benzene from boiling
point to a temperature of 0.95 T,. It has also been used to compute AH" for
several hydrocarbons at 298.15K. The present model for calculating AH" has been
compared wfth other models due to Yosfm-Owens, Wilhelm-Battino, Reiss and
co-workers, Camahan-Starling, and Muller-Prausnitt.

INTRODUCTION
Molecular theory of fluids and the theoretical development of equations of
state for real fluids have not developed to a stage of application to real flufds
due to the severe mathematical difficulties. However, the recent advances fn
computing capabflftles have enabled successful computer experiments through
molecular dynamfcs and Monte Carlo calculations. The results of such experiments
have made significant contrlbutions in the theoretical understanding of dense
fluids. In this work utillzlng the perturbation technique and the recent Monte
Carlo results an equation of state in closed form Is derived and tested
exhaustively to check Its abflity to predict compressibility and enthalpies of
vaporization.
Usfng different approaches Thiele (1963) and Werthefm (1963) arrived at a
closed form solution for the Percus-Yevick equatfon and showed

ZHS - Pv/Nkt - (l+y+y2)/(I-y)3 (1)

y = b/4v = (l/6) (~4 (vo/v); b = (2/3)x No3

0378-3812/84/$03.00 0 1984 Elsevier Science Publishers B.V.

238

for the compressibility of non-attracting hard spheres. The same result was
obtained using scaled-particle theory by Reiss, et al. (1959). Carnahan and
Starling (1969) studying the different virial expansions slightly modified the
Ree-Hoover expansion to arrive at the relation

= Pv/NkT = (l+y+y2-y3)/(1-y)3 (2)

zcs

for non-attracting hard spheres. Equation (2) is regarded as one of the best
analytical forms of equation of state for hard spheres.

NEW EQUATION OF STATE

The Percus-Yevick solution represents the hard sphere fluid with good success.
However the agreement is poor when tested for real fluids and therefore more
realistic potentials such as the Lennard-Jones 12-6 potential are required for
better representation. Since the rigid sphere approximation holds good at high
temperatures, a perturbation technique can be employed for real fluids with hard
sphere potential as the reference. The perturbations due to density and temperature
can be estimated from the repulsive part of the potential function. This scheme was
originated by Zwanzig (1954) and later used by several workers' (Smith and Alder,
1959; Frisch, et al., 1966; Mcquarrie and Katz, 1966; Barker and Henderson, 1967 1.
Following this technique Levesque and Vet-let (1969) showed that

P/pkT = (P/pkT)Hs +BodJ fI(pd=) + BL (pd")' f2(pd=) (3)

where

3
fI(pd ) = c i-I b i (pd3)i ; f2( d3) = C j-l cj(pd3)j (4)

The numerical value of the constants in equation (3) evaluated by the Monte Carlo
method (Levesque and Verlet, 1969) are bI = - 5.851, b2 = - 5.757 and b7 = - 5.966.
As most of the b values are of the same order of magnitude, we take hi's are equal
and consider only the first order correction. Substftuting the compactness factor y
for pd3, the series in y is seen to be -y ln(l-y). With these substitutions
equation (3) becomes

P/pkT = P/(pkT)HS + 2.071116 y In (l-y) (5)

The constant 2.071116 in equation (5) is obtained using an average value of b =

-5.858 and notfng that the b, values estimated by Levesque and Verlet (1969) are

based on the virial volume b,/4 where as the volume used in compactness factor y is
the hard sphere close packing volume No3/K The value of B is taken as unity as
 239

the attractive part is strongly dependent on y and is a weak function of

temperature. Utilfzfng equation (l), equation (5) becomes

ZhV = (l+y+y*)/(l-y)3 + 2.071116 y In (l-y) (6)

In arriving at equatfon (6), equation (1) rather than equation (2) is utilized as
our results fn calculating enthalpies of vaporization of varfous substances at
198.16 K (Table 2) showed equation (1) to be better. Further it has been found
that the Carnahan-Starling equation is very inaccurate for a mixture of hard
spheres whereas equation (1) gives accurate results. Also, in a strfct
mathematical sense, - Q/(1-y)13 in equatfon (2) is by itself a correction term to
the exact hard sphere equation (1).

RESULTS
A comparison of the compressibility values predicted by different models with
the exact calculations of Alder and Wainwright (1960) is shown in Table 1. All the
models perform to the same degree of accuracy with the present model slightly
better than the other two models. However a better criteria to test the
theoretical models is to calculate other thermodynamic properties which involve
differentfatfon and/or integration of the model equation. Estimation of a property
like enthalpy of vaporization requires an equation of state and properties of
liquid and vapor states. Equation (6) combfned with the relation hHV = /pdv gives

AH, = RT Iln{(v9/ve)/(l-y)I + {3y(2-~1/2(1-~)*1

+ 2.071116 {(l-y) In (l-y) + ~11 (7)

The results of equation (7) have been compared with the values of Yosfm and Owens
(1970) based on equation (1) and the values of Wflhelm and Battino (1973) based on
equation (2) are shown In Table 2. AHv was estimated usfng equation (7) and
experimental values of ve and molecular diameters reported by Wilhelm and Battino

TABLE 1
Comparison of Compressfbilfty Equations

v/v0 zNv zcs 'HS 'AW

:s 10.20
12.54 10.16
12.43 10.80
13.18 10.17
12.50

1:7 8.50 8.56 9.01 8.59

5.86 5.83 6.03 5.89

ro:o
5.: 2.93
1.36 3.03
1.36 3.06
1.36 3.05
1.36
240

TABLE 2
Comparison of AHv (kJ/mole) at 298.15 K for Hydrocarbons

Hydrocarbon Expt. AH, NV % Dev. AHV HS % Dev. AH, C5 % Dev.

, , s

n-Hexane 31.551 30.407 3.63 29.630 6.09 29.166 7.56

n-Heptane 36.551 34.807 4.77 33.943 7.14 33.348 8.76
n-Octane 41.488 39.007 5.98 38.069 a.24 37.346 9.98
n-Nonane 46.442 43.461 6.42 42.444 8.61 41.566 10.50
n-Oecane 51.367 47.389 7.74 46.321 9.82 45.327 11.76
n-Dodecane 61.287 56.439 7.91 55.235 9.87 53.880 12.09
n-Tetradecane 71.170 64.513 9.35 63.234 11.15 61.632 13.40
3-Methylheptane 39.836 37.794 5.12 36.676 7.43 36.189 9.15
2.3-Oimethylhexane 38.794 37.536 3.24 36.609 5.63 35.908
2,4-Dimethylhexane 37.769 36.436 3.53 35.529 5.93 34.863 ;:z
2,2,4-Trimethyl-
pentane 35.133 34.798 0.95 33.911 3.48 33.278 5.28
Cyclohexane 33.037 33.537 -1.51 32.679 1.08
Methylcyclohexane 35.359 33.592 -0.66 34.705 1.85 X5 5*$
Benzene 33.849 33.711 0.41 32.873 2.88 32:320 4:52
To1 uene 37.991 37.497 1.30 36.598 3.67 35.945 5.38
m-xylene 42.656 41.461 2.80 40.502 5.05 39.741 6.83

TABLE 3
Comparison of Experimental AH" (kJ/mole) of Benzene with Values Obtained
from the Models

Temp. Expt. Data Present Yosfm-Owens Wilhelm- Refss, Muller-

K Battino et. al. Prausnftt

351.74 30.831 30.524 29.727 29.301 33.951 30.207

360.46 30.495 30.017 29.229 28.826 33.738 30.256
365.66 30.205 29.713 28.931 28.541 33.600 30.259
371.61 29.868 29.365 28.590 28.214 33.431 30.238
375.35 29.489 29.145 28.375 28.008 33.319 30.253
376.95 29.465 29.051 28.283 27.919 33.270 30.201
385.45 28.851 28.550 27.794 27.449 32.996 30.106
393.99 28.552 38.043 27.299 26.974 32.697 29.970
399.25 27.898 27.728 26.993 26.679 32.505 29.866
406.25 27.514 27.307 26.583 26.284 32.233 29.706
419.75 26.521 26.482 25.781 25.509 31.663 29.328
439.47 25.071 25.237 24.573 24.340 30.712 28.533
455.25 23.846 24.191 23.561 23.355 29.826 27.835
459.07 23.436 23.929 23.307 23.108 29.592 27.643
477.75 21.766 21.572 21.998 21.832 28,291 26.662

Average absolute
per cent dev. 1.29 3.09 4.10 17.04 7.67
 241

(1973) as a function of temperature. Vg employed was the ideal gas volume as the
introduction of second virial did not improve (AH,,)prediction for any of the
mdels coatpared in this paper. Table 3 shows the predfcted AH, values as a
function of temperature for benzene. The experimental data are those collected in
our laboratory (Natarajan and Viswanath, 1983) and these values agreed with the
published data of Todd and co-workers (1978) within f 0.5 percent. In this
coatparison we have also fncluded the values predicted by models due to Reiss, et
al. (1959) and Muller-Prausnftz (1979). The method of Rdss. et al. uses a

TABLE 4

Statistical Analysis of Enthalpy of Vaporization: A Comparison

Compound Present Wilhelm Yosim- Reiss Muller- Temp.

Battino Owens et al. Prausnitz Range (n)

Benzene 3 1.29 4.10 3.09 17.04 7.67 351.79 to

a 1.56 1.71 1.54 6.05 7.21 477.75 (15)

Toluene 5 2.86 6.14 5.18 8.24 11.02 379.63 to

a 1.14 1.74 1.58 5.48 5.37 521.13 (16)

p-xylene a 6.06 9.26 a.40 4.90 10.40 411.49 to

a 2.33 2.52 2.35 5.76 5.53 557.25 (14)

a: average absolute percent deviation from experimental data obtained in

our laboratory; a: standard deviation; n: number of data points considered
in the temperature range.

TABLE 5
AH~ For Hfgh Molecular Weight Compounds

Tep. Lit. Muller-

Colnpound Da.ta Present Prausnitz

Quinoline 510.75 z-2 a 45.3 41.0

553.15 42.9 38.6
593.15 42:5 40.4 36.2
633.15 40.0 37.7 33.5
653.15 36.1 32.1
Anthracene 613.47 39.Ob
56.6 53.3 43.8
622.97 55.8 52.5 43.0
639.97 54.3 51.2 41.9
652.97 53.1 50.2 41.1
Phenanthrene 652.00 5a.2*c 51.8 42.3

a: Viswanath (1979); b: Kudchadker. et al. (1979); c: Muller-Prausnftz (1979).

*This value appears to be higher as a value of 53.0 kJ/mole is quoted by
Kudchadker, et al. (1979) which is in better agreement with the present model.
242

temperature dependent thermal expansfon coefficient and the semi-empirfcal method

of Muller and Prausnitt employs several adjustable parameters. Table 3 Is extended
into Table 4 to show a statistical analysis for benzene, toluene and p-xylene. A
detailed analysis for toluene, p-xylene and other compounds will be published
elsewhere. This model is tested further for Its ability in predicting @Iv values
for high molecular weight, two or more ring compounds. The results are compared
with the Muller-Prausnitz method developed for high molecular weight compounds.
The results presented in Table 5 show the superiority of the present model compared
to the Muller-Prausnitt method.

LIST OF SYMBOLS
AW Alder-Wafnright
b hard sphere closed packed volume, m3 mol-I
constants in eqn. (4)
bi
C. constants in eqn. (4)
d Camahan-Starling
d molecular diameter, m
a functfon in eqn. (3) and (4)
fl
a function in eqn. (3) and (4)
f2
HS Hard Sphere
enthalpy of vaporization, kJ mole-’
AHV
f integer in eqn. (4)
j integer in eqn. (4)
k Boltzmann constant, J deg"
N Avogadro Number, mole-'
-2
P pressure, N m
R gas-law constant, J deg"
T temperature, k
-1
V volume, m3 mole
-1
volume at close packing, m3 mol
vO
-1
vapor volume, m3 mole
?I
lfquid volume, m3 mole-l
VR
Y compactness parameter (y = aNa3/ti Ye)
z compressibility factor (2 = Pv/pkT)
f3 = l/kT
P particle densfty (p = N/v)
u collision dfameter, m
 243

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