Polar guest-molecules in natural gas hydrates. Effects of polarity and guest-guest-interactions on the Langmuir-constants

Abstract The effect of partial charges on guest-molecules in hydrates of structure I and II have been examined for H2S, CO2 and SO2 using Monte Carlo-simulations. The simulations indicate that Langmuir-constants for molecules with an average positive charge exposed towards the cavity-walls increases when compared to the corresponding models without charges. The opposite result is observed for molecules with a average negative charge exposed to the cavity-walls. Guest-guestinteractions increases the Langmuir-constants for both types but the effect is relatively larger for H2S than CO2 and SO2

[1]  Michael L. Klein,et al.  Computer simulation studies of the structure I clathrate hydrates of methane, tetrafluoromethane, cyclopropane, and ethylene oxide , 1984 .

[2]  J. D. Bernal,et al.  A Theory of Water and Ionic Solution, with Particular Reference to Hydrogen and Hydroxyl Ions , 1933 .

[3]  N. Metropolis,et al.  Equation of State Calculations by Fast Computing Machines , 1953, Resonance.

[4]  F. Stillinger,et al.  Proton Distribution in Ice and the Kirkwood Correlation Factor , 1972 .

[5]  Michael L. Klein,et al.  Dynamical properties of the structure I clathrate hydrate of xenona) , 1983 .

[6]  Michiel Sprik,et al.  A polarizable model for water using distributed charge sites , 1988 .

[7]  Carolyn A. Koh,et al.  Clathrate hydrates of natural gases , 1990 .

[8]  J. Ripmeester,et al.  Xenon-129 NMR and the thermodynamic parameters of xenon hydrate , 1986 .

[9]  A. Wallqvist.  On the stability of type I gas hydrates in the presence of methanol , 1992 .

[10]  P. Rodger.  Stability of gas hydrates , 1990 .

[11]  M. Klein,et al.  Dynamic properties of the structure II clathrate hydrate of krypton , 1987 .

[12]  J. V. Berkum,et al.  Phase equilibria in SO2 + H2O: the sulfur dioxide gas hydrate, two liquid phases, and the gas phase in the temperature range 273 to 400 K and at pressures up to 400 MPa , 1979 .

[13]  Keith E. Gubbins,et al.  Theory of molecular fluids , 1984 .

[14]  I. R. Mcdonald,et al.  Intermolecular potentials and the properties of liquid and solid hydrogen sulphide , 1989 .

[15]  Jefferson W. Tester,et al.  Use of Monte Carlo in calculating the thermodynamic properties of water clathrates , 1972 .

[16]  Terje Hertzberg,et al.  The influence of gas-gas interactions on the Langmuir constants for some natural gas hydrates , 1993 .

[17]  J. Banavar,et al.  Computer Simulation of Liquids , 1988 .

[18]  John S. Tse,et al.  Thermal expansion of structure I ethylene oxide hydrate , 1987 .

[19]  Gerald D. Holder,et al.  A generalized model for predicting equilibrium conditions for gas hydrates , 1985 .

[20]  Y. P. Handa.  Calorimetric determinations of the compositions, enthalpies of dissociation, and heat capacities in the range 85 to 270 K for clathrate hydrates of xenon and krypton☆ , 1986 .