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

 

作者: Colin W Clarke,   David N Glew,  

 

期刊: Canadian Journal of Chemistry  (NRC Available online 2000)
卷期: Volume 78, issue 1  

页码: 1-9

 

ISSN:0008-4042

 

年代: 2000

 

DOI:10.1139/v99-219

 

出版商: NRC Research Press

 

数据来源: NRC

 

摘要:

A method has been devised to approximate both the hydrate formula numbernand 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 constantsKp(h–> l1g) have been represented as a function of temperature by a four-parameter equation which yields both values and standard errors (i) for &Dgr;Hot(h–> l1g) and &Dgr;Cpot(h–> l1g) the standard enthalpy and heat capacity changes for D-hydrate dissociation and (ii) forn = rthe 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 pointQ(hs1l1g) 3.392°C; an approximate formula D2S·5.840D2O with SE 0.019D2O is found at upper quadruple pointQ(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-hydra

 

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