Hydrogen rotational heat capacity 2026-10-18
Let and for the conditional distributions of parahydrogen and orthohydrogen, with . Differentiating the normalized Boltzmann factors gives . Thus the rotational heat capacity at constant volume per molecule of a composition frozen at isAt conversion equilibrium, the law of total variance adds a nonnegative contribution from the changing species populations:The last term is the contribution from conversion. Compare the first two terms with a frozen sample at the same instantaneous composition; a frozen sample generally has different weights too. This formula follows directly from the variance of a mixture: subtract the overall mean inside each species, expand the square, and the cross terms vanish because each conditional deviation has zero mean. It also proves nonnegative rotational heat capacity in either model.
For an original worked example at , summing the allowed ladders gives , , and . The calculated rotational heat capacities are and for frozen normal hydrogen. The contrast is large because changing species accesses the to separation, whereas fixed species must use the larger to or to separations. These are model numbers at a chosen dimensionless temperature, not measured hydrogen data.
Both rotational heat capacities approach zero as , although frozen normal hydrogen retains nonzero rotational internal energy. Both approach as within the rotor model. The high-temperature limit is a formal limit with all other excitations suppressed; actual molecular hydrogen eventually needs molecular vibration, nonrigidity, and dissociation. Multiplying the per-molecule result by the Avogadro constant gives rotational molar heat capacity in units of the molar gas constant . A dilute classical ideal gas additionally contributes from translation to its heat capacity at constant volume.
