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The dissociation constants of o -nitroanilinium ion, m -nitroanilinium ion, and 4-chloro-2,6-dinitrophenol in deuterium oxide at 25 °C have been determined by a spectrophotometric method, and an emf method has been used to obtain ( pK  1 + pK  2 )/2 for citric acid in deuterium oxide. In addition, data for the dissociation constants of other weak acids in ordinary and heavy water have been critically examined with a view to clarifying the relationship between the deuterium isotope effect and the intrinsic strength of the acid. The difference Δ pK between the pK value in deuterium oxide and that in water varies linearly with pK above pK = 7. Two stronger inorganic acids (sulfuric and phosphoric) also appear to lie on an extension of this same line. On the contrary, a considerable group of organic acids with pK less than 7 have values of Δ pK that are more or less constant near Δ pK = 0.55. It appears, therefore, that the isotope effect is more complex than has heretofore been assumed.

Deuterium isotope effect on the dissociation of weak acids in water and deuterium oxide