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The ionization of acids in estuarine waters

Authors:	Frank J Millero

Institution:	The Rosenstiel School of Marine and Atmospheric Science, University of Miami, Miami, FL 33149, U.S.A.

Abstract:	The stoichiometric, $K_{HA}^{1}$ , and apparent, K'_HA, constants for the ionization of a number of weak acids (NH₄⁺, HSO₄^?, HF, H₂O, B(OH)₃, H₂CO₃, HCO₃^?, H₃PO₄, H₂PO₄^?, HPO₄², H₃AsO₄ H₂AsO₄^? and HAsO₄^2?) in seawater at 25°C diluted with water have been fitted to equations of the form (Millero, 1979). In $K_{HA}^{1} = In K_{HA} + AS^{12} + BS$ where In K_HA is the thermodynamic constant in water, S is the salinity, A and B are adjustable parameters. The validity of this equation in estuarine waters has been examined by using an ion pairing model (Millero and Schreiber, 1981). The calculated values of $K_{HA}^{1}$ and K'_HA at S = 35%. are in good agreement with the measured values for all the systems examined. The equation used to extrapolate the measured values to pure water K_HA predicted values that agreed with those determined by using the ion pairing model. The exception was the ionization of HPO₄^2? due to the strong interactions of Ca²⁺ and Mg²⁺ with PO₄^3?. The differences in the predicted values of $K_{HA}^{1}$ in seawater diluted with pure water and average river water were very small for all the acids except HPO₄^2? (the maximum ΔpK = 0.96 in average river water). The larger difference in the $K_{HA}^{1}$ for HPO₄^2? in river waters is due to the strong interactions of Ca²⁺ and PO₄^3?.

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