Aqueous nonelectrolyte solutions. Part XVI. Formula of deuterium sulfide D-hydrate and its dissociation thermodynamic functions

Abstract

A method has been devised to approximate both the hydrate formula number n and the standard thermodynamic functions for hydrate dissociation from the temperature change of the hydrate former fugacity along a univariant three-phase (hl1g) equilibrium line. Thermodynamic equations are derived, their validity discussed, and an iterative method for their solution is described. The univariant (hl1g) equilibrium dissociation of deuterium sulfide D-hydrate (D2S·nD2O phase h) into gaseous deuterium sulfide (g) and liquid deuterium oxide (l1) has been treated to give approximate formulae and dissociation constants at 58 temperatures from 2.798 to 30.666°C. Dissociation equilibrium constants Kp(h–> l1g) have been represented as a function of temperature by a four-parameter equation which yields both values and standard errors (i) for ΔHot(h–> l1g) and ΔCpot(h–> l1g) the standard enthalpy and heat capacity changes for D-hydrate dissociation and (ii) for n = r the approximate formula number of the D-hydrate at each experimental temperature. The formula D2S·6.115D2O with standard error 0.018D2O is found for deuterium sulfide D-hydrate at lower quadruple point Q(hs1l1g) 3.392°C; an approximate formula D2S·5.840D2O with SE 0.019D2O is found at upper quadruple point Q(hs1l2g) 30.770°C. Key words: clathrate D-hydrate of deuterium sulfide, deuterium sulfide D-hyfrate, formula of deuterium sulfide D-hydrate, thermodynamics of clathrate hydrate dissociation, dissociation equilibrium constant of deuterium sulfide D-hydrate, standard enthalpy, and heat capacity changes for dissociation of deuterium sulfide D-hydrate.