《Physical Chemistry 7ed 物理化学（第七版）》教师用书 Peter Atkins-Julio de Paula -Instructors Solution Manual-Chap20.pdf

20 Statistical thermodynamics: the machinery Solutions to exercises Discussion questions E20.1(b) The symmetry number, σ , is a correction factor to prevent the over-counting of rotational states when computing the high temperature form of the rotational partition function. An elementary interpretation of σ is that it recognizes that in a homonuclear diatomic molecule AA the orientations AA and A A are indistinguishable, and should not be counted twice, so the quantity q = kT /hcB is replaced by q = kT /σ hcB with σ = 2. A more sophisticated interpretation is that the Pauli principle allows only certain rotational states to be occupied, and the symmetry factor adjusts the high temperature form of the partition function (which is derived by taking a sum over all states), to account for this restriction. In either case the symmetry number is equal to the number of indistinguishable orientations of the molecule. More formally, it is equal to the order of the rotational subgroup of the molecule. E20.2(b) The temperature is always high enough (provided the gas is above its condensation temperature) for the mean translational energy to be 3 kT . The equipartition value. Therefore, the molar constant- 2 volume heat capacity for translation is CT = 3 R. V ,m 2 Translation is the only mode of motion for a monatomic gas, so for such a gas CV ,m = 3 R =