The apparent solubility product K′sp of calcite in seawater was measured as a function of temperature, salinity, and pressure using potentiometric saturometry techniques. The temperature effect was hardly discernible experimentally. The value of K′sp at 25°C was 4.59·10−7 mole2/(kg seawater)2 at 35‰S, 5.34·10−7 at 43‰S, and 3.24·10−7 at 27‰S. The apparent partial molal volume was found to be −34.4 cm3 at 25°C and −42.3 cm3 at 2°C from a linear fit of log(K′sp P/K′sp 1). These results were used in conjunction with field data to calculate the degree of saturation in the oceans and showed undersaturation at shallower depths than previously reported.
The apparent dissociation constants of carbonic acid in seawater are independent of pH for the range 6.5–8.5. These constants, therefore, can be used in the study of geochemical and biochemical processes in the oceans. The arbitrary nature of the pH of seawater does not affect its value in oceanographic practice.
The apparent (stoichiometric) solubility product of calcite in artificial seawater of salinity 35‰ was measured by a saturometer technique. The value of the apparent solubility product was found to be (4·59 ± 0·05) × 10−7 moles/(kilogram of seawater)2 at 25°C with a temperature coefficient of −0·0108 × 10−7/°C between 2 and 25°C. These values are significantly smaller than those found by MacIntyre (1965) and other workers. The effect of these results on the saturation of the oceans with respect to calcite is examined.