The Prediction of Rate Constants from Equilibrium Data for Reactions in D2Osngbnd;H2O Mixtures

摘要

The concentrations of hydrogen and deuterium ions at different fractions of D in the solvent are calculated from the simultaneous solution of the equations CH+·CHDO/CD+·CH2O= 3.76 and CH++CD+= concentration of strong acid. Similarly, the concentrations of hydroxyl and deuteroxyl ions are calculated from the equations COD‐·CH2O/COH‐·CHDO= 0.225 and COH‐+COD‐= concentration of alkali. It is then possible to predict reaction rates for specific hydrogen ion and specific hydroxyl ion catalyzed reactions, in mixtures of H2O—D2O, on the assumption that the rate is proportional to the fraction of D+in the first case and to the fraction of OD‐in the second.