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Raman and X-ray scattering experiments have been performed on an aqueous zinc (II) bromide solution with molar ratio [ H 2  0] / [ ZnBr 2  ] =10 at 25 to 140 °C. The intensity of the totally symmetric Zn - Br stretching vibration (ν 1 ) for the dibromozinc(II) complex increased with increasing temperature while that for the tetrabromo complex decreased. A broad band assigned to the symmetric Zn - O stretching vibration ( ν 1  ) for the aqua zinc (II) ion decreased in intensity with increasing temperature. The X-ray diffraction data revealed that the average number of the Zn - Br interactions within the zinc (II) bromo complexes does not change with temperature, whereas the number of Br ··· Br nonbonding interactions within the complexes decreases from 1.8 at 25 °C to 1.5 at 100 °C. From both Raman and X-ray data it is concluded that with increasing temperature the dibromo species is favored, whereas the tetrabromo and aqua zinc(II) species are unstable in the solution. The analysis of the X-ray diffraction data has shown that the mean Zn - Br bond length within the zinc (II) bromo complexes shortens gradually with increasing temperature, accompanied with an increase in the interligand Br ···Br distance. This finding suggests that the Br - Zn - Br bond angle increases with decreasing Zn - Br distance for the lower zinc(II) bromo complexes. The equilibrium shift of the zinc (II) bromo complexes with temperature is discussed on the basis of ion-ion, ion-water, and water-water interactions

Raman Spectroscopic and X-ray Diffraction Studies on Concentrated Aqueous Zinc (II) Bromide Solution at High Temperatures