An evaluation of the apparent dissociation constants of carbonic acid in seawater

Abstract

The internal consistency of five sets of apparent dissociation constants of carbonic acid in seawater obtained by Buch (1951), Lyman (1956), Edmond and Gieskes (1970), Hansson (1973) and Mehrbach et al. (1973) have been tested using the GEOSECS Atlantic data for the total alkalinity, the total CO 2 concentration and the partial pressure of CO 2. As a measure of the consistency for each of the five sets of the dissociation constants with the data, the 77 measured values of the partial pressure of CO 2 have been compared with those calculated from the alkalinity and total CO 2 values determined for these samples. It has been found that: (1) the apparent dissociation constants of Lyman (1956), Hansson (1973) and Mehrbach et al. (1973) appear to be internally consistent with the data, whereas those of Buch (1951) and of Edmond and Gieskes (1970) appear to be markedly inconsistent with the GEOSECS data; and (2) on the basis of a statistical analysis of the data grouped in three temperature ranges, the dissociation constants of Lyman (1956) and of Mehrbach et al. (1973) appear to be most satisfactory.