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Fluid Phase Equilibria 136 1997.

3747

Pressure and temperature dependence of excess thermodynamic


quantities of LennardJones binary mixtures
Fumio Kawaizumi
a

a, )

, Masaharu Ohba b , Takahito Fukuyama a , Hiroyasu Nomura

School of Engineering, Nagoya Uniersity, Chikusa-ku, Nagoya-shi, 464-01, Japan


b
Kawaijuku, Chikusa-ku, Nagoya-shi, 464, Japan

Abstract
The PY-integral equation has been applied for the model system consisting of monatomic molecules A and
B obeying the LennardJones potential law so as to establish the molecular basis for interpretation of excess
thermodynamic quantities of solutions. The potential parameters used are sA A s 1.0 and sB B s 0.9283, as well
as A A s 1.0 and B B s 0.8. These parameters are set as sA Ar sB B . 3 s A Ar B B . The critical parameters of
these fluids are known to be Pc , Tc . s 0.129, 1.32. for species A and 0.129, 1.06. for species B and
calculation has been carried out in the region where pressure and temperature are simultaneously below the
critical values. The formalism proposed recently by Ohba and Nomura J. Phys. Chem., 99, 12355 1995.. has
been adopted and the excess thermodynamic quantities such as excess volume V E , excess enthalpies H E , and
excess specific heat capacities Cp E have been evaluated. Pressure dependence was one order of magnitude
smaller than the case of temperature dependence and that the change of temperature from 0.95 to 1.0 gives rise
to far more remarkable effect on the excess quantities than for the temperature change from T s 0.8 to 0.9. The
components contributing to the partial molecular enthalpy and the specific heat capacity have been evaluated.
q 1997 Elsevier Science B.V.
Keywords: Statistical mechanics; Method of calculation; Equation of state

1. Introduction
Very often the results of solution calorimetry on binary system are given in terms of the excess
thermodynamic quantities. The excess thermodynamic quantity Y E is defined as Y E s Y exp y Y ideal
and for binary system Y E s x 1Y1 q x 2 Y2 . y x 1Y10 q x 2 Y20 ., where the symbols Yi and Yi 0 refer to
some appropriate partial molar quantity and thermodynamic quantity of pure component, respectively,
and x i is the molar fraction of component i. Many workers have discussed the solutesolvent
)

Corresponding author.

0378-3812r97r$17.00 q 1997 Elsevier Science B.V. All rights reserved.


PII S 0 3 7 8 - 3 8 1 2 9 7 . 0 0 1 0 9 - X

F. Kawaizumi et al.r Fluid Phase Equilibria 136 (1997) 3747

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interaction on the basis of variation of Y E with composition. However, the quantity Y E is obtained
by subtracting the large quantity from the one with similar magnitude and it occurs that if some
anomalies with regard to the liquid properties exist in one component in neat state of the binary
system, large part of the anomalies may not be observed in the values of Y E.
The purpose of this work is to establish the molecular basis for interpretation of the excess
thermodynamic quantities by applying the integral equation theory of solution. In our previous paper
w1x, we demonstrated that the enthalpy of LennardJones binary mixture in the supercritical fluid
region calculated by the integral equation theory was in excellent agreement with the results w2x
obtained by the Monte Carlo MC. method.
The most essential advantage of the integral equation theory over the molecular dynamics MD. or
MC method is that the contribution of various factors to the heat capacity as well as each enthalpic
term out of three steps of dissolution process are evaluated far easily than for the case of MD or MC.
This point is shown below. The system investigated in this work is a simple system consisting of two
kinds of monatomic molecule and we are interested in to how much extent the excess thermodynamic
properties can be interpreted in a quantitative way in terms of as small numbers of molecular
parameter as possible.

2. Formalism and calculation


For ease of comprehension, the following expressions given in our earlier work w1,3x are
reproduced here. The partial molecular enthalpy H NkT, P , N X is given in our previous paper w3x as
follows:
H NkT , P , N X s pVk y U 1 q U 2 q U 3

1.

where
U 1 s Vk
UC s

UC

2.

V
s

Nt

ri r jH u i j g i j d r

2 rt

3.

is1 js1

U2s

riH u k i g k i d r (
is1

and
U3s

ri r j Hu i j g i jN T , P , N d r
k

5.

is1 js1

The contribution pVk y U 1 refers to the formation of a cavity whose volume is Vk . The term U 2 is
related to the process in which the solute molecule is inserted into the cavity and then the solute
molecule interacts with solvent molecules around the solute molecule. Finally, the last term U 3 shows
the contribution from the perturbation of solvent structure around the solute molecules arising from

F. Kawaizumi et al.r Fluid Phase Equilibria 136 (1997) 3747

39

solutesolvent interaction.
By differentiation of enthalpy with respect to temperature, we have the heat capacity for which the
following expression was given earlier w1x.
CprNt s Cp1 q Cp2 q Cp3

6.

where
Cp1 s

1
2 rt

Cp2 s y

ri r jH u i j g i jTP , N d r

7.

is1 js1
s

1
2 rt

ri r jH u i j a P g i j d r

8.

is1 js1

and
Cp3 s Pa Prr t

9.

The term Cp1 refers to the contribution from the structural change with temperature, Cp2,
contribution from thermal expansion of the system as a whole, and the third term Cp3 is related to the
external work. In Eq. 6., the kinetic energy contribution, 3k Br2, where k B is the Boltzmann

Fig. 1. Comparison of theoretical results with the data for argon. a. V P Relation, b. T P relation.

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F. Kawaizumi et al.r Fluid Phase Equilibria 136 (1997) 3747

constant, is disregarded.
The model system consists of monatomic molecules A and B obeying the LennardJones potential
law. The potential parameters used are sA A s 1.0 and sBB s 0.9283, as well as A A s 1.0 and
BB s 0.8. The LorentzBerthelot rule is used for mixture of two species A and B. These parameters
are set as sA Ar sBB . 3 s A Ar BB in order to eliminate the apparent effects due to the increase of
interaction with mere increase in dimension of the model sphere. The critical parameters of these
fluids are Pc , Tc . s 0.129, 1.32. for species A w4x and 0.129, 1.06. for species B. As our main
concern is the excess thermodynamic quantities of ordinary liquid mixtures, the parameters used for
calculation should correspond to those of the state of binary liquid. No simple criteria for binary but
one-phase mixed liquid are available. However, it is reasonable to assume that if pressure and
temperature set for calculation are simultaneously below the critical values for both components under
consideration, then one stable liquid phase of LennardJones fluid would be formed.
2.1. Verification of calculation procedure
To examine how much extent our calculation procedure can reproduce the actual liquid state, we
have evaluated the PV diagram for one component liquid. In the calculation, the Maxwell rule was
applied for the sigmoidal area in the PV diagram to estimate the gasliquid coexisting region. Final
result of this examination process is represented in Fig. 1 in reduced form of the PV and PT
relation of our calculation in comparison with the experimental data for argon. Fig. 1 demonstrates
clearly the validity of our calculation procedure of the thermodynamic property of liquid system.
2.2. Result of calculation
The states investigated are shown in Fig. 2 by the symbol =. Some examples of the calculated
results for the excess quantities V E , H E , and Cp E are given in Figs. 35 for their pressure and
temperature dependence, respectively. The absolute magnitude of the excess quantities decrease
regularly with the increase of pressure, while all excess quantities investigated become negatively

Fig. 2. P T Phase diagram of the system and the states studied. The symbols ' and B indicate the phase boundary
between gas and liquid calculated by integral equation theory.

F. Kawaizumi et al.r Fluid Phase Equilibria 136 (1997) 3747

41

Fig. 3. Pressure dependence of excess thermodynamic quantities V E , H E, and CPE T s 0.8..

large with the increase of temperature. The rapid increase of the excess quantities from the state
T s 0.95 to 1.0 in Fig. 4 and from 0.9 to 0.96 in Fig. 5 is noteworthy and this fact must be discussed
on the basis of the relation in which region of the liquid phase the state investigated is located. The

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F. Kawaizumi et al.r Fluid Phase Equilibria 136 (1997) 3747

Fig. 4. Temperature dependence of excess thermodynamic quantities V E , H E , and CPE P s 0.1..

rapid increase of excess quantities in Figs. 4 and 5 mentioned above is ascribed to the variation of the
respective quantity of the B-component due to its approach to phase boundary from the state T s 0.95
to 1.0 at P s 0.1 in Fig. 4 and from T s 0.9 to 0.96 at P s 0.08 in Fig. 5. To date excess quantities

F. Kawaizumi et al.r Fluid Phase Equilibria 136 (1997) 3747

43

Fig. 5. Temperature dependence of excess thermodynamic quantities V E, H E , and CPE P s 0.08..

have generally been concerned with those states which are far from the critical point but recently
measurements of the thermodynamic quantities near the critical point have been done w5x. Figs. 4 and
5 suggest that in discussing the excess quantity data near the critical point, the conventional

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F. Kawaizumi et al.r Fluid Phase Equilibria 136 (1997) 3747

Fig. 6. Partial molecular enthalpy of component B of its infinite dilution.

interpretation of the excess thermodynamic quantity may not be acceptable.


In Figs. 35 the scale of ordinate of Fig. 3 for V E and Cp E is one order smaller than for the
corresponding illustration of Figs. 4 and 5, while the difference is not so large for the case of H E. If
the molecular parameters for argon A A s 1.712 = 10y21 J and sA A s 3.42 = 10y10 m are adopted,
then the units in the scale for H E and V E in Figs. 35 are 1.0 kJ moly1 and 24 cm3 moly1,
respectively. The order of magnitude of these values is in good agreement with the experimental
results, for example, G E s q0.084 kJ moly1 and V E s y0.52 cm3 moly1 for the mixtures of argon
and krypton at 116 K w6x.
It is interesting to note that the present calculation shows the slightly negative enthalpic values,
while the LorentzBerthelot mixtures are believed to have small but positive excess enthalpic values.

Fig. 7. Cp of equimolar mixture.

F. Kawaizumi et al.r Fluid Phase Equilibria 136 (1997) 3747

45

Fig. 8. Each term contributing to Cp given in Fig. 7.

The calculated results of H NkT, P , N X for component B at infinitely dilute state is given in Fig. 6,
which clearly shows that the effect of pressure variation plays only a minor role. Each term in the
right hand side of Eq. 1. has found to vary linearly with temperature or pressure and their magnitude
is in the following order:

F. Kawaizumi et al.r Fluid Phase Equilibria 136 (1997) 3747

46

yU 2 ) yU1 4 pVk ) U 3 f 0
H NkT, P , N X

is actually determined by the balance of negative contribution of U 2 and positive and a


little smaller contribution of yU1. Very trivial contribution of U 3 is understandable in view of the
model system of monatomicmonatomic molecules obeying LennardJones potentials investigated in
this work. In such system, the structural change after introduction of solute into solvent media is
small. But neglect of U 3 for evaluation of H E is not always allowed, for in some cases the order of
magnitude of H E and U 3 is similar.
Finally, the results for Cp are illustrated in Figs. 7 and 8. Fig. 7 is associated with Cp and each
term of contribution to Cp expressed in Eq. 6. for equimolar mixture of the components A and B. In
accordance with the result for H NkT, P , N X , the contribution Cp1 which is related to the structural change
is very small and Cp is determined by the balance of the Cp2 and Cp3 terms.

3. List of symbols
Cp
g
H
U
V
Vk
Y
aP

Heat capacity.
Radial distribution function.
Enthalpy.
Internal energy.
Volume.
Partial molar molecular. volume of species k.
Thermodynamic quantity.
Thermal expansibility.

3.1. Subscripts
excess
exp
ij
t
T, p, N X
0

Thermodynamic excess quantity.


Experimental.
Sphere i and sphere j.
Total.
Parameters held constant during the partial differentiation.
Pure state.

3.2. Superscripts
Nk
0
E
r
and s

Number of species k for which partial differentiation is carried out.


Pure state of component.
Thermodynamic excess quantity.
Number density of species.
Parameters in LennardJones potential.

F. Kawaizumi et al.r Fluid Phase Equilibria 136 (1997) 3747

References
w1x
w2x
w3x
w4x
w5x
w6x

F. Kawaizumi, Y. Amakasu, M. Ohba, H. Nomura, J. Mol. Liq. 65r66 1995. 377380.


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J.B. Ott, L.R. Lemon, J.T. Sipowska, P.R. Brown, J. Chem. Thermodyn. 27 1995. 10331045.
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