Local coordination about La(3+) in molten LaCl3 and its mixtures with alkali chlorides.

Journal article

The local structure around the La(3+) ions in molten LaCl(3) and its mixtures with alkali and alkaline earth chlorides has been investigated by using extended X-ray absorption fine structure (XAFS) and molecular dynamics (MD) techniques. Such mixtures, which are of current technological interest, are known to be thermodynamically nonideal, and there has been a good deal of work to understand the structural effects factors that contribute to the nonideality. New experimental methods allow observations at the La K-absorption edge at the high temperatures of interest, and the ability of the technique to obtain reliable information even at very low La(3+) concentrations in multicomponent mixtures is demonstrated. Both the mean La(3+)-Cl(-) interionic separation and the mean La(3+) coordination number are found to decrease as the concentration of La(3+) in the mixture decreases. The rate of decrease depends on the identity of the alkali and alkaline earth cations present in the mixtures in a way that parallels the degree of nonideality of the different systems; it is greatest for those alkali cations that coordinate Cl(-) weakly. In dilute mixtures with such cations La(3+) is able to adopt a very stable octahedral coordination geometry but this is inhibited by the presence of more strongly coordinating cations like Li(+) and Mg(2+).

Authors: Okamoto, Y; Suzuki, S; Shiwaku, H; Ikeda-Ohno, A; Yaita, T

• Publication status: Published
• Journal: journal of physical chemistry. A
• Volume: 114
• Issue: 13
• Pages: 4664-4671
• Publication date: 2010-04-01
• DOI: 10.1021/jp910637p
• EISSN: 1520-5215
• ISSN: 1089-5639
• Language: English