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a, )
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.
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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.
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
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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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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.
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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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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
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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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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:
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yU 2 ) yU1 4 pVk ) U 3 f 0
H NkT, P , N X
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
3.2. Superscripts
Nk
0
E
r
and s
References
w1x
w2x
w3x
w4x
w5x
w6x
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