Microcanonical ensemble treatment next up previous
Next: Relation to thermodynamic entropy Up: The ideal gas Previous: The ideal gas

Microcanonical ensemble treatment

Consider a system of N particles in a cubic box of volume tex2html_wrap_inline545 .

The particles are assumed not to interact with each other. Thus, the Hamiltonian in Cartesian coordinates may be taken to be

displaymath29

where we are assuming that all particles are of the same type.

The microcanonical partition function is

displaymath34

Since the Hamiltonian is independent of the coordinates, the 3N coordinate integrations can be done straightforwardly. The range of each one is 0 to L. Thus, these integrations give an overall factor tex2html_wrap_inline551 :

displaymath43

To do the momentum integrals, we first change variables to

eqnarray50

Substitution into the partition function gives

displaymath56

The 3N dimensional integral can now be seen to an integration over the surface of a sphere defined by the equation

displaymath64

Therefore, it proves useful to transform to 3N dimensional spherical coordinates, tex2html_wrap_inline557 , where

displaymath70

Then

displaymath75

where tex2html_wrap_inline559 is the 3N-1 solid angle integral over the 3N-1 angles. The partition function now becomes:

displaymath81

At this point, we use an identity of tex2html_wrap_inline565 -functions:

displaymath87

to write

eqnarray90

We will also make use of the fact that N is large, so that we may take tex2html_wrap_inline569 . Using the general formula for an n dimensional solid angle integral:

displaymath104

where tex2html_wrap_inline573 is the Gamma function:

displaymath108

which satisfies

eqnarray113

Thus, the solid angle integral is

displaymath118

and the partition function finally becomes

displaymath123

The entropy S(N,V,E) is given by

displaymath130

Note that the term tex2html_wrap_inline577 since tex2html_wrap_inline579 , which is negligibly small compared to the term proportional to N and tex2html_wrap_inline583 . Thus, we can neglect it. Now, we can simplify tex2html_wrap_inline583 using Stirling's approximation

displaymath135

which is valid for N very large. Also, note that

displaymath137

so that

displaymath140

Substituting these approximations into the expression for the entropy, we obtain

displaymath142

We could also simplify the tex2html_wrap_inline583 using Stirling's approximation, however, let us keep it as it is for now, since, as we remember from our past treatment of the microcanonical ensemble, this factor was included in the partition function in an ad hoc manner, in order to account for the indistinguishability of the particles. We will want to explore the effect of removing this term. Without it, the entropy is the purely classical entropy

displaymath150

Other thermodynamic quantities can be easily obtained. For example, the temperature is

displaymath157

or

displaymath162

which is the result we obtained from our analysis of the classical virial theorem. The pressure is given by

displaymath165

or

displaymath169

which is the famous ideal gas law. This is actually the equation of state of the ideal gas, as it expresses the pressure as a function of the volume and temperature. It can also be written as

displaymath172

where tex2html_wrap_inline591 is the constant density of the gas.

One often expresses the equation of state graphically. For the ideal gas, if we plot P vs. V, for different values of T, we obtain the following plot:

   figure177
Figure 1:

The different curves shown are called the isotherms, since they represent P vs. V for fixed temperature.

The heat capacity of the ideal gas follows from the expression for the energy

displaymath193

From our previous analysis of the virial theorem, we can conclude that each kinetic mode contributes k/2 to the heat capacity.


next up previous
Next: Relation to thermodynamic entropy Up: The ideal gas Previous: The ideal gas

Mark Tuckerman
Thu Feb 20 00:47:55 EST 2003