Role of Solvation and Desolvation in Polymer "Catalysis". 7. The Influence of High Pressures on the Alkaline Hydrolyses of Neutral and Cationic Esters Catalyzed by Macroions

Article abstract of DOI:10.1021/j100230a026

The alkaline hydrolyses of electrically neutral esters and positively charged esters are influenced by macroions under high pressures up to 2000 bar.The polyelectrolytes used are sodium poly(styrenesulfonate) (NaPSS) and poly(trimethylvinylbenzylammonium chloride) (PMVA).All of the volumes, enthalpies, and entropies of activation of the reactions examined increase on the addition of hydrophobic macroanions (NaPSS), whereas they decrease on the addition of the hydrophobic and cationic macroions (PMVA).The significant role of the hydrophobic hydration effects of macroions, i.e., the formation of the "iceberg" water structure around the hydrophobic reactants and macroions, is demonstrated for the observed rate acceleration and deceleration with PMVA and NaPSS, respectively.