Inorganic Molten Salts Research Articles

Lewis acid-base interactions in inorganic oxyacids, molten salts and glasses—III: Co-ordination studies of thallium, lead and bismuth in sulfate/chloride/bromide glass systems

The behaviour of the basicity indicator ions Tl +, Pb 2+ and Bi 3+ are studied in model glasses having anion compositions: chloride-sulfate, bromide-sulfate and chloride-bromide. Changes in the co-ordination spheres of these metal ions with glass composition are detected spectroscopically from the s- p nephelauxetic effect. When the ligands are chloride and bromide, all three metal ions form mixed coordination spheres, but for chloride-sulfate or bromide-sulfate mixtures, Pb 2+ and especially Bi 3+ tolerate mixed co-ordination spheres much less readily. Highly polarizing cations in the glasses severely modify competitive ligand behaviour of the constituent anions. The presence of network structures in glasses is shown to give rise to more than one Lewis basicity value, and for measuring basicity it is necessary to know the extent to which the probe ion enters the network. The results also indicate how the modification of an anion's basicity seems to be dependent on the degree of “hardness” of the anion.

Establishment of an optical scale for Lewis basicity in inorganic oxyacids, molten salts, and glasses

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTEstablishment of an optical scale for Lewis basicity in inorganic oxyacids, molten salts, and glassesJ. A. Duffy and M. D. IngramCite this: J. Am. Chem. Soc. 1971, 93, 24, 6448–6454Publication Date (Print):December 1, 1971Publication History Published online1 May 2002Published inissue 1 December 1971https://doi.org/10.1021/ja00753a019RIGHTS & PERMISSIONSArticle Views1316Altmetric-Citations357LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (828 KB) Get e-Alerts Get e-Alerts

Dispersion and Absorption of Ultrasonic Waves in Molten Zinc Chloride

Among the inorganic molten salts, liquid zinc chloride is unusual in that it has a high shear viscosity which makes it possible to study its viscoelastic properties by high-frequency sound-propagation techniques. Longitudinal ultrasonic-absorption and velocity measurements were made in the frequency range 5–95 and 5–45 Mc, respectively. Shear-elasticity measurements were obtained in the frequency range 43–118 Mc. The viscosity range covered was 3 60 poise. A single relaxation time was observed for the absorption at each temperature investigated. The data demonstrate the existence of a volume viscosity and the simultaneous presence of both shear and structural-relaxation processes. The ratio of the compressional viscosity to the shear viscosity is 0.8 and was found to be nearly independent of temperature. The activation energies for the shear and compressional flows are approximately equal. Both the longitudinal and sear-dispersion data can adequately be described by a single and the same relaxation time at a given temperature. The variation of the relaxation time with temperature is in accordance with the rate theory. The shear modulus and the relaxational part of the compressional modulus increase exponentially with decreasing temperature. (This work supported by the U. S. Atomic Energy Commission.)

Raman Spectra and Ionic Interactions in Molten Nitrates

A simple experimental assembly designed for use with a conventional Toronto-type source and capable of use at temperatures up to 700°C is described for the Raman technique. Application to the series of molten inorganic salts Li, Na, K, Cs, Rb, and Ag/NO3, and selected mixtures of these, is reported. The Raman frequencies, relative intensities, depolarization ratios, and vibrational force constants are discussed. A regular variation of the Raman frequencies and force constants which correlates with the change in the polarizing power of the cationic environment is noted. The results are examined in the light of current views on the structure of molten salts.