The thermodynamics of ammonium scheelites. III: An analysis of the heat capacity and related data of deuterated ammonium perrhenate ND4ReO4

An analysis of the heat capacity of deuterated and undeuterated NH4ReO4 has been carried out in which the effects of the anisotropy of the thermal expansion have been considered, an approach hitherto not used for ammonium compounds. In the ammonium scheelites, the axial thermal expansion coefficients are very large, but of opposite sign, and as a result the volume of the scheelite lattice is nearly independent of temperature. It is shown that the correction from constant stress to constant strain results in a major contribution to the heat capacity of this highly anisotropic lattice. The difference between the experimental and calculated values of heat capacity, referred to as ΔCp, is expressed as the sum of the contributions from the anisotropy and the rotational heat capacity. The results of the analysis show that the rotational contribution is much smaller then previously thought. However, the exact contribution of the anisotropy cannot be calculated at this time because the elastic constants are not known. In calculating the heat capacity, maximum use has been made of external optical mode frequencies derived from spectroscopic measurements.