Abstract
This chapter deals with elementary reactions in solutions. The effect of the solvent on reaction rates is illustrated with the Menschutkin reaction. Diffusion-controlled and reaction-controlled limits are discussed. The diffusion rate constant is related to diffusion coefficients with Fick’ first law of diffusion, and the diffusion coefficients are related to the solvent viscosity with the Stokes–Einstein equation. The effect of charges is discussed in relation to the solvent dielectric constant. The origin of spin-statistic factors in diffusion-controlled reactions is presented. Reaction control is interpreted on the basis of the Transition-State Theory. The effects of internal pressure, electronic charges, ionic strength and hydrostatic pressure are presented with illustrative examples. Finally, the use of photoacoustic calorimetry to measure transient volume changes is presented.
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