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Effect of Solvent on Free Radical Reactions

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Liquid-Phase Reaction Rate Constants
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Abstract

Solvent viscosity has a substantial influence on the elementary reactions for which the rates are diffusion-limited. Such reactions include recombination of atoms and reactions between free radicals that have rate constants on the order of 109 or 1010 liter/mole·sec. A decrease in the diffusion coefficient of iodine atoms with increasing viscosity was demonstrated in [422]. Often used to calculate k is the Stokes-Einstein formula D = kT/3πησ, which is substituted into the formula k = 4·10-3πσ D N to give k = 8 R T/3000 η. For atoms, this formula is, strictly speaking, inapplicable, as is evident from Table 96: The product kη/T changes from solvent to solvent instead of remaining constant.

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© 1974 IFI/Plenum Data Company

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Denisov, E.T. (1974). Effect of Solvent on Free Radical Reactions. In: Liquid-Phase Reaction Rate Constants. Springer, Boston, MA. https://doi.org/10.1007/978-1-4684-8300-0_9

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  • DOI: https://doi.org/10.1007/978-1-4684-8300-0_9

  • Publisher Name: Springer, Boston, MA

  • Print ISBN: 978-1-4684-8302-4

  • Online ISBN: 978-1-4684-8300-0

  • eBook Packages: Springer Book Archive

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