Vibrational Spectral Studies of Solutions at Elevated Temperatures and Pressures. IV. Raman Spectra of Aqueous Zinc Nitrate Solutions

Authors: Irish, D. E.1; Jarv, T.2

Source: Applied Spectroscopy, Volume 37, Issue 1, Pages 1-87 (January/February 1983) , pp. 50-55(6)

Publisher: Society for Applied Spectroscopy

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Abstract:

Raman spectra of 5.196 m aqueous zinc nitrate solution have been measured at a pressure of 11 MPa and temperatures ranging from 25 to 300°C. A band at 386 cm−1, assigned to the hexaaquazinc(II) cation, decreases in intensity and increases in frequency as the temperature rises. These observations are consistent with the replacement of water molecules in the primary solvation shell of Zn2+ by a nitrate ion. Changes in the spectrum of nitrate ion support this interpretation. Evidence is also presented which suggests that the octahedral configuration around Zn2+ is being changed to a tetrahedral configuration. Estimates are made of the populations of inner sphere and outer sphere nitrate; from the plots of log Q m vs 1/T estimates are made of ΔH and ΔS for the ion association. The plots are remarkably linear over 275 degrees of temperature.

Keywords: High temperature aqueous chemistry; Raman spectroscopy; Zinc nitrate

Document Type: Research Article

DOI: http://dx.doi.org/10.1366/0003702834634109

Affiliations: 1: Guelph-Waterloo Centre for Graduate Work in Chemistry, Waterloo Campus, Department of Chemistry, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 2: Guelph-Waterloo Centre for Graduate Work in Chemistry, Waterloo Campus, Department of Chemistry, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1; present address: Ontario Hydro, Kipling Complex, 800 Kipling Ave., Toronto, Ontario M8Z 5S4

Publication date: January 1, 1983

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