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- Cerreta, M.K., et al.
(author)
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The structure of aqueous solutions of some dihydrogen orthophosphates by laser Raman spectroscopy
- 1987
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In: Journal of Crystal Growth. - : Elsevier BV. - 0022-0248 .- 1873-5002. ; 84:4, s. 577-588
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Journal article (peer-reviewed)abstract
- 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.
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