Internal energy in statistical thermodynamics

The internal energy of a thermodynamic system consisting of non-interacting particles can be represented statistically using the molecular partition function .

It is equivalent to the product of the mean molecular energy and the number of non-interacting particles in the system. From eq320, where , we have:

As mentioned in an earlier article, is the total molecular partition function (i.e. eq257), with contributions from translational, rotational, vibrational and electronic degrees of freedom. Eq360 assumes that all components of , including , are defined using absolute energy levels — for example, the vibrational molecular partition function includes the zero-point energy (i.e. eq290). However, if is instead defined relative to the zero-point energy (i.e. eq292), then we need to add back the zero-point energy term giving:

where .

 

Monatomic ideal gas

For a monatomic ideal gas, each atom is a point mass with no rotational or vibrational degrees of freedom. This implies that there is only a single rotational ground state and a single vibrational ground state, each with energy equal to zero. Therefore, . Furthermore, as explained in the derivation of eq297, for an atom not subjected to extreme temperatures. Hence, eq361 simplifies to:

Substituting eq266 into eq362 and differentiating gives:

Comparing eq363 with eq305, . Substituting , where is the Avogadro constant and is the number of moles, into eq363 yields:

where the universal gas constant is .

 

Diatomic ideal gas

For a diatomic ideal gas, is again given by eq363. is derived by substituting eq275 into and differentiating to give:

Comparing eq364 with eq309, .

For , we substitute eq293 into and differentiating to give:

where .

At high but not extreme temperatures, , which allows us to expand as a Taylor series () to give:

Comparing eq366 with eq313, .

Similar to an atom,  for a diatomic molecule (see derivation of eq297). Hence,

which is consistent with eq316.

The total internal energy of a system of a diatomic ideal gas not subjected to extreme temperatures is therefore:

 

Polyatomic ideal gas

The translational component of the internal energy of a polyatomic ideal gas is again:

As mentioned in this article, each normal mode of vibration of a polyatmomic molecule behaves approximately like a separate harmonic oscillator, with the total vibrational partition function given by eq294:

where for non-linear molecules,  for linear molecules, and is the number of atoms per molecule.

Substituting into of of and differentiating gives:

It follows that at high but not extreme temperatures,

for a linear rotor is derived by substituting eq275 into and differentiating to yield:

for a non-linear rotor (including spherical, symmetric and asymmetric rotors), is derived by substituting either eq280, eq286 or eq287 into and differentiating to give:

Once again, for a polyatomic molecule not subjected to extreme temperatures. Therefore, the total internal energy of a system of a polyatomic ideal gas not subjected to extreme temperatures is:

 

Next article: Equilibrium constant in statistical thermodynamics
Previous article: Statistical thermodynamic derivation of the ideal gas law
Content page of statistical thermodynamics
Content page of advanced chemistry
Main content page

Leave a Reply

Your email address will not be published. Required fields are marked *

Mono Quiz