Physica 139 & 140B (1986) 148-150

North-Holland, Amsterdam

EFFECT OF PRESSURE ON THE INTERNAL ENERGY OF LENNARD-JONES MIXTURES

Koichiro N A K A N I S H I

Department of lndustrial Chemistry and Division of Molecular Engineering, Kyoto University, Kyoto 606, Japan
Molecular dynamics calculations have been carried out for Lennard-Jones fluid mixtures simulating an athermal solution.
The excess internal energies of mixing U z have been obtained as a function of molar composition at 120 K and reduced
number densities between 0.5 and 1.5. The pressure range involved is from essentially zero up to 4(I 000 atm. The U ~ values
at constant density (volume) show a large pressure dependence. They change sign from positive to negative as the pressure
increases. Thus, the mixture is probably not athermal except for some limited situation.

1. Introduction

0"12 = (0.'11 -{- 0"22)/2 = 0.'Argon '

T h e present study is a part of extensive c o m p u ter simulation projects for m o d e l fluid mixtures
interacting with L e n n a r d - J o n e s (LJ) potential
[1,2]. In particular, the following two p r o b l e m s
are investigated here. We will deal with an
athermal-like mixture of LJ fluids. This can be
d o n e by assuming an appropriate c o m b i n a t i o n of
the values of the potential p a r a m e t e r s for the two
c o m p o n e n t s . First, we want to see w h e t h e r or not
such a quasi-athermal model mixture is really
athermai. Secondly, we will discuss the effect of
pressure on the internal e n e r g y of this LJ mixture
at constant t e m p e r a t u r e and volume.

m I = m 2 = mArgon.
H e r e LB refers to the well-known L o r e n t z Bertheiot rule for unlike interactions. These assignments to potential p a r a m e t e r values need a
c o m m e n t : in accordance with the definition of the
solubility p a r a m e t e r , 6, as the square-root of the
ratio of the energy of vaporization E to the m o l a r
v o l u m e V [3], both the c o m p o n e n t s 1 and 2 have a
c o m m o n value of e/o- 3. In o t h e r words, they are
assumed to have the same value of "microscopic
cohesive energy density ( M C E D ) " . It is thus
expected to behave as an athermal mixture.

3. Method of calculation
2. Models
The model fluids used in this study are those
molecules which interact with a L e n n a r d - J o n e s
12-6 potential and can be characterized by two
parameters, e and 0... In addition, one must
specify the molecular mass m of each molecule.
The mixture a d o p t e d here m a y be called the
L B _ 2 _ 2 ~/3 model which has the following
p a r a m e t e r values:

e l l / k = 169.42 K, 0.'11 : 3.797 A.,

e22/k = 84.71 K, 0..22 = 3.013 ,~,
E'12 = ( E l l

X E22) I/2 =

E'Argon ,

We have carried out conventional N E V ensemble molecular dynamics calculations to obtain the
internal energy, pressure and m a n y other static
and dynamic properties of the present model
mixture and its c o m p o n e n t s . Some details of the
calculation m a y be s u m m a r i z e d briefly as below.
T h e total n u m b e r of molecules is either 108 or 256
and the equimolar and two other mixtures have
been used. T h e t e m p e r a t u r e of the system is set to
120 K and the volumes of the system are determined from constant reduced n u m b e r densities p
which are b e t w e e n 0.5 and 1.5. The equations of
m o t i o n have been solved by a difference m e t h o d
based on Verlet's algorithm [4]. The time step is
1 x 10 14s and the numerical integration of the

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K. Nakanishi / Internal energy of Lennard-Jones mixtures

equation of motion is extended up to 15 500 steps.

The ensemble data from the final 5000 steps were
used for averaging.

4. Results and discussion

The internal energies of the L B - 2 - 2 '/3 model

at 120 K were obtained as a function of the molar
composition at p values of 0.5, 0.75, 1.0, 1.3 and
1.5. These p values are based on the ~r value for
c o m p o n e n t 1 which is fairly large c o m p a r e d with
that of c o m p o n e n t 2. Since the p value used
exceeds unity where the internal energy value of
c o m p o n e n t 1 tends to increase in the positive
direction, it is necessary to monitor the radial
distribution function ( R D F ) for possible solidification. The R D F of c o m p o n e n t 1 possesses the
characteristics of an a m o r p h o u s solid state for
p > 1.1. Table I shows the effect of density and
pressure on the internal energy of c o m p o n e n t 1.
The internal energies of mixtures are plotted
against the mole fraction of c o m p o n e n t 2, x, for
each value of O in fig. 1.
The U versus x relation is convex to the x-axis
for p values between 0.5 and 1.0. This means a
positive deviation from the ideal solution law,
namely, endothermic mixing of two components.
This deviation increases with an increasing value
of p. However, a reversal of this tendency can be
seen at p = 1.3 and a remarkably deep minimum
in U value can be seen at p = 1.5. We define
excess internal energy U z as
U E =U(x) -U,(1

- x) - U 2 x ,

where U, and U: are the internal energies of pure

c o m p o n e n t 1 and 2 at a c o m m o n p value. The U E
values as a function of x at each p are given in
table II. In accordance with the results in fig. 1,
U E increases from a small positive value at
p = 0.5 (essentially zero pressure) with increasing
p, but changes sign somewhere between p = 1.0
and 1.3 and becomes a large negative value at
p = 1.5. This indicates that, when high pressure
fluids (sometimes one c o m p o n e n t is an amorphous solid) are mixed in a vessel of constant

149

Table I
Effect of pressure on the internal energy of c ompone nt 1 at
120 K.
R e duc e d numbe r
density "~ O

Pressure
p(atm)

Potential energy
- U/lO-~4 erg mol -z

0,50
0.75
1.00
1,10
1.20
1.30
1.40
1.50

- 190
-270
510
3100
7300
14 000
25 000
42 000

9.07
12.65
17.46
17.70
16.80
14.14
9.31
1.82

as b~
as
as
as

~ Based on the o" value for the c ompone nt 1.

b~ A m o r p h o u s solid state as judged from R D F .

volume, the heat of mixing depends largely on the

pressure and an exothermic mixing will be observed even for nonpolar liquids.
Finally we can conclude from the present calculation that the present model mixture is probably not athermal except for some limited situation. This means that an equality in M C E D does
0

//

\ i../ , i

//

"

~ // ii

kll~ ~,,O i" ,- ," i ~ Z"

"
.~

",','e'

/ i ,,,o"

-10

l/m;
--

-15

I%,

/1~

1
I

0.5
X

Fig. 1. Internal energies of L B - 2 - 2 ~'3 model as functions of

molar composition and reduced numbe r density at 120 K.

150

K. Nakanishi / Internal energy of Lennard-Jones mixtures

Table II
Excess internal energies of mixing U E for L B - 2 - 2 ~/3 model at 120 K
x

0.25

0.50

0.75

0=0.50

UE(kJ mol ~)
P(atm)

0
- 190

+0.13
- 120

+0.16
-45

+0.19
30

0
75

p = 0.75

UE(kj mol ~)
P(atm)

0
-270

+0.37
-290

+0.46
-160

+0.37
-67

0
67

P = 1.00

UE(kJ mol J)
P(atm)

0
510

+0.79
450

+0.83
270

+0.60
6

0
90

p = 1.30

UE(kj mo1-1)
P(atm)

0
14 000

-1.07
2300

0
270

p = 1.50

UE(kJ mol 1)
P(atm)

0
42 000

-2.80
21 000

-4.20
6700

-2.60
2100

0
760

not necessarily warrant

the formation

of an ather-

real mixture.

References
[1] K. Nakanishi and K. Toukubo, J. Chem. Phys. 70 (1979)
5848.

[2] P. Gierycz and K. Nakanishi, Fluid Phase Equilibria 16

(1984) 255.
[3] J.H. Hildebrand, J.M. Prausnitz and R.L. Scott, Regular
and Related Solutions (Van Nostrand Reinhold, New
York, 1970).
[4] L. Verlet, Phys. Rev. 159 (1967) 98.