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Formation and dissociation of gas hydrate in terms of chemical kinetics

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Abstract

Based on the general theory of chemical kinetics, a theoretical model was developed for the formation and dissociation of a gas hydrate. An expression is derived for the driving force of the formation and dissociation. The presented theory was compared with other well-known theoretical models and, from the available experimental data, the temperature dependence was determined for the methane hydrate formation and dissociation rate constants.

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Abbreviations

A :

Affinity, J/mol

c :

Molar concentration of gas close to the interface, mol/m3

E :

Activation energy of the gas hydrate formation reaction at an interface, J/mol

E dis :

Activation energy of the gas hydrate dissociation reaction at the interface, J/mol

f :

Fugacity of the gas, Pa

K :

Kinetic parameter, mol/(m2 Pa s)

k :

Rate constant of the gas hydrate formation reaction at the interface, m3n+1/(moln s)

\( k^{\prime} \) :

Empirical coefficient, 1/(Pa s)

\( K_0 \) :

Pre-exponential factor in the Arrhenius equation, m3n+1/(moln s)

k dis :

Rate constant of the gas hydrate dissociation reaction at the interface, m/s

k dis0 :

Pre-exponential factor in the Arrhenius equation, m/s

n :

Hydration number

n 0 :

Amount of methane, used in the formation of the hydrate, mol

n g :

Amount of the gas, mol

\( n_{\text{H}} \) :

Amount of methane present in the hydrate, mol

\( n_{\text{h}} \) :

Amount of gas hydrate, mol

\( n_{\text{w}} \) :

Amount of water, mol

\( p \) :

Pressure, Pa

\( R \) :

Gas constant, J/(mol K)

\( R_{\text{dis}} \) :

Rate of the gas hydrate dissociation reaction at the interface, mol/(m2 s)

\( R_{\text{form}} \) :

Rate of the gas hydrate formation reaction at the interface, mol/(m2 s)

\( r \) :

Rate of change of moles of the substance at the interface during the gas hydrate formation/dissociation reactions, mol/(m2 s)

\( S \) :

Interfacial area, m2

\( T \) :

Temperature, K

\( t \) :

Time, s

\( Z \) :

Compressibility factor

\( \upalpha \) :

Experimental constant, m2/mol

\( \upmu \) :

Chemical potential, J/mol

\( \upchi \) :

Molar density of gas hydrate, mol/m3

\( \upomega \) :

Molar density of water, mol/m3

\( \text{eq} \) :

Equilibrium between water, gas hydrate and gas

g:

Gas

h:

Gas hydrate

w:

Water

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Acknowledgments

This work was supported by the Russian Foundation for Basic Research (project No. 10-05-00270) and the Council on Grants of the President of the Russian Federation (Grant NSh-5582.2012.5).

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Authors and Affiliations

  1. Institute of the Earth Cryosphere, Siberian Branch of the Russian Academy of Sciences, P.O. Box 1230, 625000, Tyumen, Russian Federation

    Valeriy A. Vlasov

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Vlasov, V.A. Formation and dissociation of gas hydrate in terms of chemical kinetics. Reac Kinet Mech Cat 110, 5–13 (2013). https://doi.org/10.1007/s11144-013-0578-x

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