STP Resources for Statistical & Thermal Physics

Calculation of the Second Virial Coefficient:

STP SecondVirialCoefficient

FIG. 1: Plot of the second virial coefficient as a function of temperature for the Lennard-Jones
potential.

I.

INTRODUCTION

The STP SecondVirialCoefficient program numerically evaluates the second virial coefficient for the Lennard-Jones potential at various temperatures. The default temperature
range is 0.5 T 5.
STP SecondVirialCoefficient is part of a suite of Open Source Physics programs that model aspects of Statistical and Thermal Physics (STP). The program is distributed as a ready-to-run (compiled) Java archive.

Double clicking the

stp SecondVirialCoefficient.jar file will run the program if Java is installed on your
computer. Additional programs can be found by searching ComPADRE for Open Source
Physics, STP, or Statistical and Thermal Physics.

II.

DESCRIPTION

The pressure equation of state for a dilute gas can be written as

PV
= 1 + B2 (T ) + 2 B3 (T ) + 3 B4 (T ) + . . . ,
N kT

(1)

where P is the pressure, V is the volume, N is the number of particles, T is the temperature,
and k is Boltzmanns constant. The density = N/V , and Bn is the nth virial coefficient.

The second virial coefficient B2 is given by the integral (in three dimensions)
B2 = 2

[1 eu(r) ]r2 dr,

(2)

where = 1/kT and u(r) is the interparticle potential. Except for simple forms of u(r), the
integral must be done numerically.
The program computes the integral for the Lennard-Jones potential at various temperatures. The Lennard-Jones potential is given by
h 12

u(r) = 4

 6 i

(3)

Simpsons rule is used for the numerical calculation. The program uses units such that the
Lennard-Jones parameters /k and are set equal to unity.
Double click on the jar file to run the program. When you click on the Calculate
button, the program numerically evaluates the integral for the second virial coefficient at
various temperatures.
You can change the temperature range of the calculation, Tmin and Tmax . (After you type
in a value, the box remains yellow, which signifies that the program has not incorporated
the new value until you press Enter and then Calculate).

III.

QUESTIONS

1. Describe the qualitative temperature dependence of B2 . Is it positive or negative at

low/high temperatures? Is there a temperature at which B2 equals zero?
2. The Lennard-Jones potential is a reasonable approximation to the interparticle potential for liquid Argon with /k = 119.5 K and = 3.76 1010 m. Given the numerical
results you found in Question 1, what is the temperature at which B2 = 0? This
temperature is called the Boyle temperature.
3. Simple arguments given in most textbooks on statistical mechanics show that B2 has
the approximate form, B2 = b a/kT for potentials that have the same qualitative
behavior as the Lennard-Jones potential, that is, strongly repulsive behavior for small
separations and weakly attractive for large separations. Interpret b and a as fit parameters and determine approximate values for a and b from your results for B2 . Under
the Tools menu, select Data Tool to import your data into the data analysis tool
with Curve Fit.

IV.

INPUT PARAMETERS

Parameter Description
Tmin (Tmax ) Minimum (maximum) temperature of the calculation.
TABLE I: Control parameters.

V.

RELATED CURRICULAR PACKAGES

For further discussion see Chapter 8 of Statistical and Thermal Physics by H. Gould and
J. Tobochnik available on ComPADRE. Other resources are available for Statistical and
Thermal Physics from osp stp.jar or searching ComPADRE for STP, OSP, or Statistical
and Thermal Physics.
c
Harvey
Gould, Jan Tobochnik, Wolfgang Christian, and Anne J. Cox (2009).
10 February 2009.