A spectrophotometric study of aqueous iron (II) chloride complexing from 25 to 200°C

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Ultraviolet absorption spectra of solutions in the system FeC12-HCl-H 2 O with chloride concentrations ranging from 0.01 to 3.4 m and Fe(II) concentrations ranging from 0.005 to 0.025 m have been measured at 25, 50, 100, 150, and 200°C and the equilibrium saturation vapor pressure of the system. Non-linear least squares regression was used to estimate cumulative thermodynamic association constants and molar absorptivities. At 25, 50, and 100°C, only Fe 2+ and FeCl + are detectable, whereas at higher temperatures a minor concentration of a third species, interpreted to be FeCl 0 2 , starts to contribute substantially to total absorbance. Recommended values of the association constants, 1 and 2 , for the equilibria Fe 2+ Cl -1 = FeCl + and Fe 2+ + 2C1 - = FeCl 0 2 , respectively, (and their estimated maximum uncertainty range) are as follows: In combination with published thermodynamic data for the Fe-S-O-H system, the equilibrium formation constants are used to calculate solubilities of selected Fe mineral assemblages in NaCl-rich hydrothermal solutions. The results are in satisfactory agreement with published analytical data from basinal brines and geothermal fluids.

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