Abstract
The rapid increase of the first and second apparent dissociation constants of carbonic acid with salinity results in a remarkable pH distribution in an estuary. On going down-stream, instead of a gradual continuous increase in pH from fresh water values of 7·0 to 7·5 to a marine value of 8·2, the pH shows a certain minimal value at low salinity. With high pH fresh water a sharp decrease at low salinity is observed. Depending on the alkalinity ratio of the fresh river water and the sea water, the carbonate ion concentration in an estuary can remain surprisingly low up to relatively high salinities. This phenomenon might affect the shell growth of certain molluscs. In order to obtain the proper dissociation constants for brackish waters of low chlorinities, a practical adjustment of well known data for pure water and sea water is made: pK 1′ ( for 0 ⩽ Cl ⩽ 9‰) = 3404·71 T + 0·032786T − 14·8435 − 0·08921Cl 1 2 pK 2′ ( for 0 ⩽ Cl ⩽ 0·005‰) = 2902·39 T + 0·02379T − 6·4980 − 0·7531Cl 1 2
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