Non-Complexing Anions for Quantitative Speciation Studies Using Raman Spectroscopy in Fused Silica High-Pressure Optical Cells under Hydrothermal Conditions

Applied Spectroscopy - Tập 69 Số 8 - Trang 972-983 - 2015
L. Applegarth1, Christopher Alcorn1, Katherine Bissonette1, John A. Noël1, Peter R. Tremaine1
1University of Guelph, Department of Chemistry, Guelph, Ontario, N1G 2W1, Canada

Tóm tắt

This paper reports methods for obtaining time-dependent reduced isotropic Raman spectra of aqueous species in quartz capillary high-pressure optical cells under hydrothermal conditions, as a means of determining quantitative speciation in hydrothermal fluids. The methods have been used to determine relative Raman scattering coefficients and to examine the thermal decomposition kinetics of the non-complexing anions bisulfate (HSO4−), perchlorate (CIO4−), perrhenate (ReO4−), and trifluoromethanesulfonate, or “triflate” (CF3SO3−) in acidic and neutral solutions at temperatures up to 400 °C and 30 MPa. Arrhenius expressions for calculating the thermal decomposition rate constants are also reported. Thermal stabilities in the acidic solutions followed the order HSO4− (stable) > ReO4− > CIO4− > CF3SO3− with half-lives (t1/2) > 7 h at 300 °C. In neutral solutions, the order was HSO4− (stable) > CF3SO3− > ReO4− > CIO4−, with t1/2 > 8 h at 350 °C. CF3SO3− was extremely stable in neutral solutions, with t1/2 > 11 h at 400 °C.

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Applied Spectroscopy

Tập 69 Số 8

972-983

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