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Reaction Kinetics, Mechanisms and Catalysis

, Volume 110, Issue 1, pp 5–13 | Cite as

Formation and dissociation of gas hydrate in terms of chemical kinetics

  • Valeriy A. Vlasov
Article

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.

Keywords

Gas hydrate Kinetics Phase change Phase equilibria Methane 

List of symbols

Variables

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

Edis

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/(mol n s)

\( k^{\prime} \)

Empirical coefficient, 1/(Pa s)

\( K_0 \)

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

kdis

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

kdis0

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

n

Hydration number

n0

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

ng

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

Greek letters

\( \upalpha \)

Experimental constant, m2/mol

\( \upmu \)

Chemical potential, J/mol

\( \upchi \)

Molar density of gas hydrate, mol/m3

\( \upomega \)

Molar density of water, mol/m3

Subscripts

\( \text{eq} \)

Equilibrium between water, gas hydrate and gas

g

Gas

h

Gas hydrate

w

Water

Notes

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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Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2013

Authors and Affiliations

  1. 1.Institute of the Earth CryosphereSiberian Branch of the Russian Academy of SciencesTyumenRussian Federation

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