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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 freqeuncy 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

Raman spectroscopy Zinc nitrate High temperature aqueous chemistry

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References

Swaddle

T. W.

, Chem. Can. 32, 21 (1980).

Irish

D. E.

and Brooker

M. H.

, in Advances in Infrared and Raman Spectroscopy, Clark

R. J. H.

and Hester

R. E.

, Eds. (Heyden, London, 1976), Vol. 2, Ch. 6, p. 212.

Waters

D. N.

, in Molecular Spectroscopy, a Specialist Periodical Report (The Chemical Society, London, 1979) Vol. 6, Ch. 2, p. 46.

Bradley

D. J.

and Pitzer

K. S.

, J. Phys. Chem. 83, 1599 (1979).

Sze

Y. K.

and Irish

D. E.

, J. Solution Chem. 7, 395 (1978).

Bulmer

J. T.

Irish

D. E.

, and Ödberg

, Can. J. Chem. 53, 3806 (1975).

Sze

Y. K.

and Irish

D. E.

, J. Solution Chem. 7, 417 (1978).

Al-Baldawi

S. A.

Brooker

M. H.

Gough

T. E.

, and Irish

D. E.

, Can. J. Chem. 48, 1202 (1970).

Sze

Y. K.

and Irish

D. E.

, J. Solution Chem. 8, 395 (1979).

10.

Irish

D. E.

Jarv

, and Ratcliffe

C. I.

, Appl. Spectrosc. 36, 137 (1982).

11.

Bulmer

J. T.

Irish

D. E.

Grossman

F. W.

Herriot

Tseng

, and Weerheim

A. J.

, Appl. Spectrosc. 29, 506 (1975).

12.

Jarv

Bulmer

J. T.

, and Irish

D. E.

, J. Phys. Chem. 81, 649 (1977).

13.

Murphy

W. F.

and Bernstein

H. J.

, J. Phys. Chem. 76, 1147 (1972).

14.

Davis

A. R.

and Irish

D. E.

, Can. J. Chem. 46, 943 (1968).

15.

Jarv

, Ph.D. thesis, University of Waterloo, Waterloo, Ontario, Canada, 1980.

16.

Janz

G. J.

and Muller

M. A.

, J. Solution Chem. 4, 285 (1975).

17.

Chang

T. G.

and Irish

D. E.

, J. Solution Chem. 3, 161 (1974).

18.

Fuoss

R. M.

, J. Am. Chem. Soc. 80, 5059 (1958).

19.

Swaddle

T. W.

and Fabes

, Can. J. Chem. 58, 1418 (1980).

20.

Angell

C. A.

and Gruen

D. M.

, J. Am. Chem. Soc. 88, 5192 (1966).

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

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