Enthalpy Relaxation Phenomenon in a Heavy Ice Crystal

Abstract

The heat capacities of quenched and annealed heavy ice Ih were measured in the temperature range 14 to 300 K by an adiabatic calorimeter. A relaxational thermal anomaly was found at around 115 K and this phenomenon was ascribed to the onset of deuteron ordering in the crystal. The average activation enthalpy of the relaxational process was determined to be (26±5) kJ mol^-1. Residual entropies of the crystal were recalculated on the basis of the present heat-capacity data combined with the revised values for enthalpy of vaporization, saturated vapour pressure, and spectroscopic entropy. They are (3.47±0.41 J K^-1 mol^-1 for the quenched crystal and (3.44±0.41) J K^-1 mol^-1 for a crystal annealed at 102-106 K for 264 h. The characteristics and the origin of the anomaly are discussed in comparison with that of ordinary ice.

This paper has been accepted for publication in full in a forthcoming issue of the Journal of Glaciology.