The structure of aqueous solutions of some dihydrogen orthophosphates by laser Raman spectroscopy

Upprättat; 1987; 20090511 (ysko)
Powdered crystals and pure, aqueous solutions of ammonium, sodium, and potassium dihydrogen orthophosphates in concentrations ranging from 0.01M to supersaturated were investigated at 30°C using laser Raman spectroscopy between 700 and 1350 cm-1. With increasing solute concentration, the peak position of the 875 cm-1 P-(OH)2 symmetric strech band increased. Extreme asymmetry in the 1075 cm-1 P=O2 symmetric stretch band developed to lower energy. The integrated intensity ratio of the 875 cm-1 band to the 1075 cm-1 band envelope remained constant. These observations are consistent with anion-anion association via hydrogen bonds. Deconvolution of the spectral bands showed only 40% and 20% of the phosphates exist as monomers in saturated potassium and ammonium solutions, respectively, and that anion association does not cease at the dimer. The spectra provided no evidence of quasi-crystalline entities in solution. The necessary breaking and reforming of hydrogen bonds during the growth process can explain rapid z-direction growth, growth activation energy, and the rate-limiting surface growth mechanism.

Ingår i:Journal of Crystal Growth: Elsevier BV84:4, s. 577-5880022-02481873-5002

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