Characterisation of high temperature metal halides by mass spectrometry and matrix isolation infrared spectroscopy
Characterisation of high temperature metal halides by mass spectrometry and matrix isolation infrared spectroscopy
This thesis describes the characterisation of some high temperature transition metal and rare earth halide molecules using mass spectrometry and argon matrix isolation infrared spectroscopy. Details of experimental procedure and relevant background theory are given.
New mixed halide species CoBrCl and NiBrCl were seen in the vapour over mixtures of the appropriate dichloride and dibromide at ~800K. The infrared spectra in argon showed the v(Co-Cl) of CoBrCl at ~ 460cm-1 and the v(Ni-Cl) of NiBrCl at ~ 480 cm-1. The computer program "SOTONVIB" was used to estimate the force constants for these as linear molecules.
Some rare earth tribromides and trichlorides were prepared from their respective oxides and found to form a small proportion of dimers at temperatures up to 1200K in the vapour phase. Matrix isolation studies gave the following monomer v3 frequencies (cm-1): LaBr3, 234; CeBr3, 235; PrBr3, 232.2; NdBr3, 236.2; DyBr3, 244.5' HoBr3, 243.2; LaCl3 318.4; and HoCl3, 339. Some v1 frequencies have been tentatively assigned, however, no firm conclusions about geometry have been reached. Enthalpies of sublimation of some of the species seen in the mass spectra were also measured.
The mass spectrum of the vapour over a mixture of HoCl3 and CsCl revealed a CsHoCl3+ ion, assigned as a fragment of the ternary species CsHoCl4.
Rare earth trichlorides and tribromides both of the same metal and of different metals were mixed and the new mixed halide species LaBr2Cl, LaBrCl2, NdBr2Cl, HoBr2Cl and HoBrCl2 were observed in the vapour phase. A range of mixed dimers was also found to be present.
CrCl3 was verified as having its v3 vibration, in an argon matrix, at ~495cm-1, contrary to recent work claiming otherwise using a system which included Mo in contact with the sample. The reaction of CrCl3 with Mo metal was studied and a molybdenum chloride was produced.
University of Southampton
1998
Spittle, Peta Jean
(1998)
Characterisation of high temperature metal halides by mass spectrometry and matrix isolation infrared spectroscopy.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
This thesis describes the characterisation of some high temperature transition metal and rare earth halide molecules using mass spectrometry and argon matrix isolation infrared spectroscopy. Details of experimental procedure and relevant background theory are given.
New mixed halide species CoBrCl and NiBrCl were seen in the vapour over mixtures of the appropriate dichloride and dibromide at ~800K. The infrared spectra in argon showed the v(Co-Cl) of CoBrCl at ~ 460cm-1 and the v(Ni-Cl) of NiBrCl at ~ 480 cm-1. The computer program "SOTONVIB" was used to estimate the force constants for these as linear molecules.
Some rare earth tribromides and trichlorides were prepared from their respective oxides and found to form a small proportion of dimers at temperatures up to 1200K in the vapour phase. Matrix isolation studies gave the following monomer v3 frequencies (cm-1): LaBr3, 234; CeBr3, 235; PrBr3, 232.2; NdBr3, 236.2; DyBr3, 244.5' HoBr3, 243.2; LaCl3 318.4; and HoCl3, 339. Some v1 frequencies have been tentatively assigned, however, no firm conclusions about geometry have been reached. Enthalpies of sublimation of some of the species seen in the mass spectra were also measured.
The mass spectrum of the vapour over a mixture of HoCl3 and CsCl revealed a CsHoCl3+ ion, assigned as a fragment of the ternary species CsHoCl4.
Rare earth trichlorides and tribromides both of the same metal and of different metals were mixed and the new mixed halide species LaBr2Cl, LaBrCl2, NdBr2Cl, HoBr2Cl and HoBrCl2 were observed in the vapour phase. A range of mixed dimers was also found to be present.
CrCl3 was verified as having its v3 vibration, in an argon matrix, at ~495cm-1, contrary to recent work claiming otherwise using a system which included Mo in contact with the sample. The reaction of CrCl3 with Mo metal was studied and a molybdenum chloride was produced.
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Published date: 1998
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Local EPrints ID: 463239
URI: http://eprints.soton.ac.uk/id/eprint/463239
PURE UUID: c837a221-3ff2-4c00-ba7b-4342423446ac
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Date deposited: 04 Jul 2022 20:48
Last modified: 04 Jul 2022 20:48
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Author:
Peta Jean Spittle
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