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Energy transport effects on rapid bimolecular chemical reactions

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  • Keizer, Joel
  • Peacock-Lopez, Enrique

Abstract

Mass diffusion is known to affect the rate of rapid bimolecular chemical reactions in solution. Rate constants are decreased with respect to their collisional values, an effect which can renormalize the bare rate constant by a factor as large as 100. In this paper we explore the added effect of the thermal diffusivity on rapid reaction rates. This effect arises from the coupling of energy fluctuations to density fluctuations either through the activation energy for reaction or from the heat of reaction. Calculations presented here, using statistical nonequilibrium thermodynamics to calculate the nonequilibrium radial distribution function, show that this effect vanishes in dilute solution. In more concentrated solutions the effect remains negligible unless the diffusion constant is much larger than the thermal diffusivity. Even then the effect is only of the order of 10% of the size of mass diffusion effects in concentrated solutions.

Suggested Citation

  • Keizer, Joel & Peacock-Lopez, Enrique, 1987. "Energy transport effects on rapid bimolecular chemical reactions," Physica A: Statistical Mechanics and its Applications, Elsevier, vol. 147(1), pages 61-76.
    • Handle: RePEc:eee:phsmap:v:147:y:1987:i:1:p:61-76
    DOI: 10.1016/0378-4371(87)90097-5
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    References listed on IDEAS

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    1. Keizer, Joel & Medina-Noyola, Magdaleno, 1982. "Spatially nonlocal fluctuation theories: Hydrodynamic fluctuations for simple fluids," Physica A: Statistical Mechanics and its Applications, Elsevier, vol. 115(3), pages 301-338.
    2. Theodosopulu, M. & Résibois, P., 1976. "Kinetic approach to the long-time behaviour in fluids," Physica A: Statistical Mechanics and its Applications, Elsevier, vol. 82(1), pages 47-71.
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