Matrix isolation studies of some high temperature molecules
Matrix isolation studies of some high temperature molecules
The molecules studied were those present in the high temperature vapours produced by heating KN03, V205 and K2XOq (X = Cr, MO, W). A survey is given of previous applications of matrix isolation to high temperature chemistry. The experimental apparatus employed in this work is described and the method of analysing vibrational spectra is shown. Isotopic substitution is a powerful aid to spectral interpretation and was extensively used. Potassium nitrate vapour was studied in order to determine the geometry of the KN03 molecule, about which some uncertainty exists. It is shown by means of line diagrams that monodentate coordination of the nitrate ion may be distinguished from the bidentate configuration by the qualitative appearance of the 180 isotope pattern. Subsequent experiments on the 180 enriched material show that the molecule is bidentate and this conclusion is confirmed by a subsequent force constant analysis.The vapour produced by heating V205 was investigated. The spectrum produced by the 180 enriched compound is shown to be consistent with the presence of V4010 (Td symmetry), analogous to P4010. The only previous evidence for molecular V4010 was the observation of a parent ion in mass spectroscopic studies. The vaporisation of K2X04 (X = Cr, Mo, W) was also studied. The vapours of all three compounds gave similar spectra, consistent with the presence of K2X04 molecules of Did symmetry. A detailed study of one of these systems (K2WOq) using 1a0 enrichment confirmed this conclusion by means of the agreement between the observed and calculated isotope pattern.
University of Southampton
1980
Price, David Derek
(1980)
Matrix isolation studies of some high temperature molecules.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
The molecules studied were those present in the high temperature vapours produced by heating KN03, V205 and K2XOq (X = Cr, MO, W). A survey is given of previous applications of matrix isolation to high temperature chemistry. The experimental apparatus employed in this work is described and the method of analysing vibrational spectra is shown. Isotopic substitution is a powerful aid to spectral interpretation and was extensively used. Potassium nitrate vapour was studied in order to determine the geometry of the KN03 molecule, about which some uncertainty exists. It is shown by means of line diagrams that monodentate coordination of the nitrate ion may be distinguished from the bidentate configuration by the qualitative appearance of the 180 isotope pattern. Subsequent experiments on the 180 enriched material show that the molecule is bidentate and this conclusion is confirmed by a subsequent force constant analysis.The vapour produced by heating V205 was investigated. The spectrum produced by the 180 enriched compound is shown to be consistent with the presence of V4010 (Td symmetry), analogous to P4010. The only previous evidence for molecular V4010 was the observation of a parent ion in mass spectroscopic studies. The vaporisation of K2X04 (X = Cr, Mo, W) was also studied. The vapours of all three compounds gave similar spectra, consistent with the presence of K2X04 molecules of Did symmetry. A detailed study of one of these systems (K2WOq) using 1a0 enrichment confirmed this conclusion by means of the agreement between the observed and calculated isotope pattern.
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Published date: 1980
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Local EPrints ID: 462750
URI: http://eprints.soton.ac.uk/id/eprint/462750
PURE UUID: 5f795649-bc6a-4868-8207-7359303dc271
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Date deposited: 04 Jul 2022 19:51
Last modified: 04 Jul 2022 19:51
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Author:
David Derek Price
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