Paper 2, Section II, 35A

Statistical Physics
Part II, 2013

(i) The first law of thermodynamics is dE=TdSpdV+μdNd E=T d S-p d V+\mu d N, where μ\mu is the chemical potential. Briefly describe its meaning.

(ii) What is equipartition of energy? Under which conditions is it valid? Write down the heat capacity CVC_{V} at constant volume for a monatomic ideal gas.

(iii) Starting from the first law of thermodynamics, and using the fact that for an ideal gas (E/V)T=0(\partial E / \partial V)_{T}=0, show that the entropy of an ideal gas containing NN particles can be written as

S(T,V)=N(cV(T)TdT+kBlnVN+const)S(T, V)=N\left(\int \frac{c_{V}(T)}{T} d T+k_{\mathrm{B}} \ln \frac{V}{N}+\mathrm{const}\right)

where TT and VV are temperature and volume of the gas, kBk_{\mathrm{B}} is the Boltzmann constant, and we define the heat capacity per particle as cV=CV/Nc_{V}=C_{V} / N.

(iv) The Gibbs free energy GG is defined as G=E+pVTSG=E+p V-T S. Verify that it is a function of temperature TT, pressure pp and particle number NN. Explain why GG depends on the particle number NN through G=μ(T,p)NG=\mu(T, p) N.

(v) Calculate the chemical potential μ\mu for an ideal gas with heat capacity per particle cV(T)c_{V}(T). Calculate μ\mu for the special case of a monatomic gas.