A thermodynamic model for describing the binding of chloride and alkalis in hydrated Portland cement pastes has been developed. The model is based on the phase rule, which for cement pastes in aggressive marine environment predicts multivariant conditions, even at constant temperature and pressure. The effect of the chloride and alkalis has been quantified by experiments on cement pastes prepared from white Portland cements containing 4% and 12% C3A, and a grey Portland cement containing 7% C3A. One weight percent calcite was added to all cements. The pastes prepared at w/s ratio of 0.70 were stored in solutions of different Cl (CaCl2) and Na (NaOH) concentrations. When equilibrium was reached, the mineralogy of the pastes was investigated by EDS analysis on the SEM. A well-defined distribution of chloride was found between the pore solution, the C-S-H phase, and an AFm solid solution phase consisting of Friedel's salt and monocarbonate. Partition coefficients varied as a function of iron and alkali contents. The lower content of alkalis in WPC results in higher chloride contents in the C-S-H phase. High alkali contents result in higher chloride concentrations in the pore solution.
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