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A MODEL FOR ENTHALPY OF VAPORI2AlION USING A NEW ONE PARAMETER EQUATION OF STATE
FOR FLUIDS
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
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
for non-attracting hard spheres. Equation (2) is regarded as one of the best
analytical forms of equation of state for hard spheres.
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
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
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
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
:s 10.20
12.54 10.16
12.43 10.80
13.18 10.17
12.50
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
TABLE 3
Comparison of Experimental AH" (kJ/mole) of Benzene with Values Obtained
from the Models
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
TABLE 5
AH~ For Hfgh Molecular Weight Compounds
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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