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Consider a gas of "hard spheres," which do not interact at all unless their separation distance is less than r0, in which case their interaction energy is infinite. Sketch the Mayer f-function for this gas, and compute the second virial coefficient. Discuss the result briefly.

Short Answer

Expert verified

The second order virial expansion is,

P=2r03N3

Step by step solution

01

Step 1. Given information

The expression for Mayer's f function is,

f(r)=e-u(r)-1

The factor,

=1kTc

Here,

k=Boltzmann constant

Tc= Critical temperature

Thus, the Mayer's function=

f(r)=eu(r)kT-1

u(r)= potential energy due to interaction of any pair of molecules.

Considering the gaseous molecules are "hard hemispheres". If the separation between them ris more than the intermolecular separation r0then potential energy is,

u(r)=0

Ifr<r0, then the potential energy is,

u(r)=

02

Step 2. The second virial coefficient is,

B(T)=-20r2f(r)dr

=-20r0r2f(r)dr

=-20r0r2e-m(r)kT

=-20r2e-0

=-20r0r2dr

=2r033

From the equation we can say that the second virial coefficient is independent of temperature.

The second order virial expansion term,

P=NB(T)V

Substituting the B(T)=2r033in the equation,

P=NV2r033

=2r03N3

Thus, the second order virial expansion is,

P=2r03N3

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Most popular questions from this chapter

Consider an Ising model in the presence of an external magnetic field B, which gives each dipole an additional energy of -BB if it points up and +BB if it points down (whereB is the dipole's magnetic moment). Analyse this system using the mean field approximation to find the analogue of equation 8.50. Study the solutions of the equation graphically, and discuss the magnetisation of this system as a function of both the external field strength and the temperature. Sketch the region in the T-B plane for which the equation has three solutions.

In this problem you will use the mean field approximation to analyse the behaviour of the Ising model near the critical point.

(a) Prove that, when x1,tanhxx-13x3

(b) Use the result of part (a) to find an expression for the magnetisation of the Ising model, in the mean field approximation, when T is very close to the critical temperature. You should find MTc-T,where(not to be confused with 1/kT) is a critical exponent, analogous to the f defined for a fluid in Problem 5.55. Onsager's exact solution shows that =1/8in two dimensions, while experiments and more sophisticated approximations show that 1/3in three dimensions. The mean field approximation, however, predicts a larger value.

(c) The magnetic susceptibility is defined as (M/B)T. The behaviour of this quantity near the critical point is conventionally written as T-Tc- , where y is another critical exponent. Find the value of in the mean field approximation, and show that it does not depend on whether T is slightly above or slightly below Te. (The exact value of y in two dimensions turns out to be 7/4, while in three dimensions 1.24.)

The Ising model can be used to simulate other systems besides ferromagnets; examples include anti ferromagnets, binary alloys, and even fluids. The Ising model of a fluid is called a lattice gas. We imagine that space is divided into a lattice of sites, each of which can be either occupied by a gas molecule or unoccupied. The system has no kinetic energy, and the only potential energy comes from interactions of molecules on adjacent sites. Specifically, there is a contribution of -u0to the energy for each pair of neighbouring sites that are both occupied.

(a) Write down a formula for the grand partition function for this system, as a function of u0, T, and p.

(b) Rearrange your formula to show that it is identical, up to a multiplicative factor that does not depend on the state of the system, to the ordinary partition function for an Ising ferromagnet in the presence of an external magnetic field B, provided that you make the replacements u04and 2BB-8. (Note that is the chemical potential of the gas while uB is the magnetic moment of a dipole in the magnet.)

(c) Discuss the implications. Which states of the magnet correspond to low density states of the lattice gas? Which states of the magnet correspond to high-density states in which the gas has condensed into a liquid? What shape does this model predict for the liquid-gas phase boundary in the P-T plane?

Modify the ising program to simulate a one-dimensional Ising model.

(a) For a lattice size of 100, observe the sequence of states generated at various temperatures and discuss the results. According to the exact solution (for an infinite lattice), we expect this system to magnetise only as the temperature goes to zero; is the behaviour of your program consistent with this prediction? How does the typical cluster size depend on temperature?

(b) Modify your program to compute the average energy as in Problem 8.27. Plot the energy and heat capacity vs. temperature and compare to the exact result for an infinite lattice.

(c) Modify your program to compute the magnetisation as in Problem 8.28. Determine the most likely magnetisation for various temperatures and sketch a graph of this quantity. Discuss.

Use the cluster expansion to write the total energy of a monatomic nonideal gas in terms of a sum of diagrams. Keeping only the first diagram, show that the energy is approximatelyU32NkT+N2V20r2u(r)e-u(r)drUse a computer to evaluate this integral numerically, as a function of T, for the Lennard-Jones potential. Plot the temperature-dependent part of the correction term, and explain the shape of the graph physically. Discuss the correction to the heat capacity at constant volume, and compute this correction numerically for argon at room temperature and atmospheric pressure.

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