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Title: Investigation of some group three halides with various donor molecules including a thermodynamic study of carbonyl bromide and some aluminium halides
Author: Anthoney, Martin Eric
Awarding Body: University of London
Current Institution: Royal Holloway, University of London
Date of Award: 1971
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The Interaction between boron trihalides (bromide, chloride) and benzene derivatives (benzene, m-xylene, mesitylene, hexamethylbenzene) has been studied using the techniques of cryoscopy, vapour pressure measurement, proton magnetic resonance and Raman spectroscopy. No evidence was found to support previous assertions of weak complex formation in solution. The reactions between carbonyl halides (bromide, chloride) and Group three halides (boron, aluminium; chloride, bromide, iodide) have been studied. No complexes could be isolated, in contrast to the system studied previously. No reaction was found using boron halides, but with aluminium halides rapid and extensive halogen exchange occurred at ambient temperatures. Aluminium halides also catalysed the decomposition of carbonyl bromides: [equation] the enthalpy of hydrolysis of carbonyl bromide was measured by adiabatic solution calorimetry [equation] From this was derived [equation] differing significantly from previous values. Estimates have been made of thermodynamic functions for carbonyl iodide. The standard enthalpies of formation of aluminium bromide and aluminium iodide have been determined as [equations] by isoperibol calorimetry of the reactions [equations] Infra-red studies on the complex) have confirmed its structure as dative covalent, with bonding from oxygen to boron. On running the infra-red spectrum at room temperature, there is considerable dissociation of the complex, and also reaction with the potassium bromide windows. Determination of the degree of dissociation has shown that there is only negligible association in the vapour.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Molecular Chemistry