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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

Show that the Lennard-Jones potential reaches its minimum value at r=r0, and that its value at this minimum is -u0. At what value of rdoes the potential equal zero?

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.)

Modify the ising program to compute the total magnetisation (that is, the sum of all the s values) for each iteration, and to tally how often each possible magnetisation value occurs during a run, plotting the results as a histogram. Run the program for a 5 x 5 lattice at a variety of temperatures, and discuss the results. Sketch a graph of the most likely magnetisation value as a function of temperature. If your computer is fast enough, repeat for a 10 x 10 lattice.

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.

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