Enthalpy Relaxation Phenomenon of Heavy Ice

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 115K 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 vapourization, 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 the 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.

[1]  G. P. Johari,et al.  GLASS TRANSITION AND SECONDARY RELAXATIONS IN MOLECULAR LIQUIDS AND CRYSTALS , 1976 .

[2]  S. J. Jones,et al.  Dielectric properties of polycrystalline D2O ice Ih (hexagonal) , 1976, Proceedings of the Royal Society of London. A. Mathematical and Physical Sciences.

[3]  H. Chihara,et al.  ANOMALY IN THE HEAT CAPACITY OF CRYSTALLINE CARBON MONOXIDE AT 18 K ASSOCIATED WITH ORIENTATIONAL ORDERING , 1976 .

[4]  S. Jones,et al.  Study of the low‐temperature ’’transition’’ in ice Ih by thermally stimulated depolarization measurements , 1975 .

[5]  T. Matsuo,et al.  Calorimetric study of the glassy state X. Enthalpy relaxation at the glass-transition temperature of hexagonal ice☆ , 1974 .

[6]  L. Besley,et al.  Vapour pressure of normal and heavy water from 273.15 to 298.15 K , 1973 .

[7]  H. Suga,et al.  Enthalpy Relaxation at Glass Transition Temperature of Heavy Ice Crystal , 1973 .

[8]  N. Fletcher,et al.  Low temperature polarization effects in ice , 1971 .

[9]  Y. Sakabe,et al.  Dielectric Dispersion of NaOH-Doped Ice at Low Temperatures , 1970 .

[10]  P. Bishop,et al.  Electrical Polarization Effects in Pure and Doped Ice at Low Temperatures , 1969 .

[11]  D. Helmreich Elastic Anomalies of Ice at Low Temperatures , 1969 .

[12]  H. Suga,et al.  Phase Changes in Crystalline and Glassy-Crystalline Cyclohexanol , 1968 .

[13]  Elliott H. Lleb Residual Entropy of Square Ice , 1967 .

[14]  V. Moorti,et al.  Interpretation of the Energy of Hydrogen Bonding; Permanent Multipole Contribution to the Energy of Ice as a Function of the Arrangement of Hydrogens , 1967 .

[15]  John F. Nagle,et al.  Lattice Statistics of Hydrogen Bonded Crystals. I. The Residual Entropy of Ice , 1966 .

[16]  H. Engelhardt,et al.  Zur protonischen Leitfähigkeit von Eis-Einkristallen bei tiefen Temperaturen und hohen Feldstärken , 1966 .

[17]  G. Adam,et al.  On the Temperature Dependence of Cooperative Relaxation Properties in Glass‐Forming Liquids , 1965 .

[18]  Claude Jaccard Etude théorique et expérimentale des propriétés électriques de la glace , 1959 .

[19]  K. Pitzer,et al.  The Order-Disorder Problem for Ice , 1956 .

[20]  H. L. Johnston,et al.  Heat and free energy of formation of deuterium oxide , 1940 .

[21]  J. D. Kemp,et al.  The Entropy of Deuterium Oxide and the Third Law of Thermodynamics. Heat Capacity of Deuterium Oxide from 15 to 298°K. The Melting Point and Heat of Fusion , 1936 .

[22]  J. W. Stout,et al.  The Entropy of Water and the Third Law of Thermodynamics. The Heat Capacity of Ice from 15 to 273°K. , 1936 .

[23]  L. Pauling The Structure and Entropy of Ice and of Other Crystals with Some Randomness of Atomic Arrangement , 1935 .