Electrostriction volume, pressure effects, high

Jenner investigated the kinetic pressure effect on some specific Michael and Henry reactions and found that the observed activation volumes of the Michael reaction between nitromethane and methyl vinyl ketone are largely dependent on the magnitude of the electrostriction effect, which is highest in the lanthanide-catalyzed reaction and lowest in the base-catalyzed version. In the latter case, the reverse reaction is insensitive to pressure.52 Recently, Kobayashi and co-workers reported a highly efficient Lewis-acid-catalyzed asymmetric Michael addition in water.53 A variety of unsaturated carbonyl derivatives gave selective Michael additions with a-nitrocycloalkanones in water, at room temperature without any added catalyst or in a very dilute aqueous solution of potassium carbonate (Eq. 10.24).54... 

It should be mentioned that even in the absence of dipolar, polarizable, or ionic reaction partners, high electric fields may cause shifts in chemical distributions. Such a field effect requires, however, that the solvent phase has a finite temperature coefficient of the dielectric permittivity or a finite coefficient of electrostriction an additional condition is that the chemical reactions proceed with a finite reaction enthalpy (AH) or a finite partial volume change (A V). Electric field induced temperature and pressure effects of this type are usually very small they may, however, gain importance for isochoric reactions in the membrane phase. 

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