Infrared spectroscopic and spectroelectrochemical studies in molten sodium chloroaluminates

Author

Paul Anthony Flowers

Date of Award

8-1988

Degree Type

Dissertation

Degree Name

Doctor of Philosophy

Major

Chemistry

Major Professor

Gleb Mamantov

Committee Members

E. Wehry, C. Woods, W. E. Blass

Abstract

Infrared cells suitable for spectroscopic and spectroelectrochemical investigations in molten chloroaluminates have been constructed and applied to several important chemical systems.

The utility of infrared spectroscopy as a direct, quantitative probe of dissolved oxide in molten sodivun chloroaliiminates of basic and acidic compositions has been demonstrated.

Infrared spectra of Ir₄(CO)₁₂ IrCl(CO)₃ in acidic melts under various atmospheres have been obtained. The results indicate that similar hydrido- and deuteridocarbonyl species are produced from either iridium complex under atmospheres of CO:H₂ and CO;D₂, respectively.

The complexation of chloranil by Lewis acidic solvent species has been studied. Infrared results suggest that, in acidic melts, chloranil exists as an adduct with AICI₃ (or Al₂Cl₇-) coordinated at one of the carbonyl oxygens and at the carbon-carbon double bonds.

The infrared spectroelectrochemical behavior of chloranil in basic and acidic sodium chloroaluminates has been examined. An overall twoelectron reduction is observed in the basic melt, while sequential oneelectron reductions are evident in the acidic melt.

Spectroscopic and spectroelectrochemical studies of the reaction between tungsten hexachloride and dissolved aluminum oxychloride have been performed. Results indicate that WCI₅ is oxidized via an EC mechanism in which the one-electron product, WCl₆, is involved in a follow-up chemical reaction with dissolved aluminum oxychloride.

Recommended Citation

Flowers, Paul Anthony, "Infrared spectroscopic and spectroelectrochemical studies in molten sodium chloroaluminates. " PhD diss., University of Tennessee, 1988.
https://trace.tennessee.edu/utk_graddiss/11866