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Title: The characterisation of chemical species in high temperature lamps
Author: Jenkins, Delyth Myfanwy
ISNI:       0000 0001 3589 9771
Awarding Body: University of Southampton
Current Institution: University of Southampton
Date of Award: 1993
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This thesis describes the application of matrix isolation infrared spectroscopy and transpiration techniques to study the chemistry of high temperature lamp systems. Methods used to investigate the chemistry of tungsten halogen and metal halide lamps are reviewed. Matrix isolation techniques and the apparatus developed for the in-situ study of high temperature species are described; the species are formed by passing a reactive gas mixture over a heated metal filament and then trapped for study by matrix isolation infrared spectroscopy. Some theoretical aspects of infrared spectroscopy are discussed, in particular the use of isotopic substitution to determine the shapes of matrix isolated species. The use of spectroscopic data and statistical thermodynamic methods to estimate the bulk thermodynamic properties of vapour phase molecules are also described. The reaction of W or Mo with O₂/X₂ (X = Cl, Br) or CO₂/Cl₂ gas mixtures gives MO₂X₂ as the primary reaction product. Smaller amounts of MOX₄ are also formed, although MoOBr₄ is not detected. Monomeric MO₃ and O₃, together with a number of other features believed to be due to polymeric metal oxide species, are observed following the reaction of W or Mo with O₂/I₂ mixtures. Matrix isolation infrared spectra of the products of the reaction of Cl₂ with W can be interpreted in terms of the formation of WCl₅ and WCl₆. MoCl₅ (C₄v symmetry) is detected in corresponding Mo/Cl₂ experiments and a further absorption band at 433cm⁻¹ is attributed to MoCl₄ (Td symmetry) on the basis of observed Mo and Cl isotope patterns. No metal bromides or iodides are detected when these halogen vapours are passed over heated W or Mo filaments. The principal products of the reaction of Cl₂ or Br₂ with Ta or Nb are the MX₅ pentahalides and, for Nb, a smaller amount of the oxyhalides NbOX₃. The oxyhalides ReO₃X (C₃v symmetry) are formed when Cl₂ or Br₂ is passed over heated Re filaments.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Metallic component corrosion