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The activity coefficients of Fe(III) hydroxide complexes in NaCl and NaClO4 solutions
Authors:Frank J. Millero  Denis Pierrot
Affiliation:a Rosenstiel School of Marine and Atmospheric Science, University of Miami, 4600 Rickenbacker Causeway, Miami, FL 33149, USA
b Cooperative Institute for Marine and Atmospheric Studies, University of Miami, 4600 Rickenbacker Causeway, Miami, FL 33149, USA
Abstract:The osmotic coefficients of FeCl3 at 25 °C from 0.15 to 1.7 m [Rumyantsev et al., Z. Phys. Chem., 218, 1089-1127, 2004] have been used to determine the Pitzer parameters (β(0), β(1) and C?) for FeCl3. Since the differences in the Pitzer coefficients of rare earths in NaCl and NaClO4 are small, the values of Fe(ClO4)3 have been estimated using the differences between La(ClO4)3 and LaCl3. The Pitzer coefficients for FeCl3 combined with enthalpy and heat capacity data for the rare earths can be used to estimate the activity coefficients of Fe3+ in NaCl over a wide range of temperatures (0 to 50 °C) and ionic strength (0 to 6 m).The activity coefficients of Fe3+ in NaCl and NaClO4 solutions have been used to determine the activity coefficients of Fe(OH)2+ in these solutions from the measured first hydrolysis constants of Fe3+ [Byrne et al., Mar. Chem., 97, 34-48, 2005]. The activity coefficients of View the MathML source, Fe(OH)3 and View the MathML source from 0 to 50 °C have also been determined from the solubility measurements of Fe(III) in NaCl solutions [Liu and Millero, Geochim. Cosmochim Acta, 63, 3487-3497, 1999]. These activity coefficients have been fitted to the Pitzer equations. These results can be used to estimate the speciation of Fe(III) with OH in natural waters with high concentrations of NaCl from 0 to 50 °C.
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