DOI: 10.1063/1.1676654. High-Temperature Vaporization and Thermodynamics of the Titanium Oxides. VII. Mass Spectrometry and Dissociation Energies of TiO(g) and TiO2(g)

High-Temperature Vaporization and Thermodynamics of the Titanium Oxides. VII. Mass Spectrometry and Dissociation Energies of TiO(g) and TiO2(g)

10.1063/1.1676654

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

Two experiments of the successive vaporization type, five mass spectrometric vaporization experiments, and two isomolecular exchange reaction experiments were undertaken to resolve discrepancies in the thermodynamics of the titanium—oxygen system. The first two types of experiments confirmed that Ti3O5(s) is the congruently vaporizing phase. The second type of experiment showed that the principal reaction accounting for the congruent vaporization is Ti3O5(S)=TiO(g)+2TiO2(g). In the third type of experiment, measurements on the isomolecular exchange reaction TiO(g)+Sc(g)=Ti(g)+ScO(g) showed that the dissociation energy of TiO(g) is smaller than that for ScO(g) and on the basis that D0o(ScO) is 160.4±2.0 kcal/mole, D0o(TiO) becomes 156.9±2.2 kcal/mole, or 6.80±0.10 eV. This result may be combined with earlier vapor pressure measurements on Ti3O5(s) and the congruency condition to yield D0o(TiO2)=311.7±1.8 kcal/mole, 13.52±0.08 eV, or very nearly twice D0o(TiO). One of the two previously discussed discrepancies in the thermodynamics of the titanium oxides appears to have been resolved, and the likely resolution of the other is discussed.

Bibliography

Hampson, P. J., & Gilles, P. W. (1971). High-Temperature Vaporization and Thermodynamics of the Titanium Oxides. VII. Mass Spectrometry and Dissociation Energies of TiO(g) and TiO2(g). The Journal of Chemical Physics, 55(8), 3712â3729.

Authors 2

Peter J. Hampson (first)
Paul W. Gilles (additional)

References 31 Referenced 45

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Dates

Type	When
Created	21 years, 7 months ago (Feb. 4, 2004, 5:07 p.m.)
Deposited	1 year, 6 months ago (Feb. 9, 2024, 4:13 a.m.)
Indexed	2 months, 4 weeks ago (June 7, 2025, 2:45 a.m.)
Issued	53 years, 10 months ago (Oct. 15, 1971)
Published	53 years, 10 months ago (Oct. 15, 1971)
Published Print	53 years, 10 months ago (Oct. 15, 1971)

Funders 0

None

BibTeX

@article{Hampson_1971, title={High-Temperature Vaporization and Thermodynamics of the Titanium Oxides. VII. Mass Spectrometry and Dissociation Energies of TiO(g) and TiO2(g)}, volume={55}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.1676654}, DOI={10.1063/1.1676654}, number={8}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Hampson, Peter J. and Gilles, Paul W.}, year={1971}, month=oct, pages={3712–3729} }

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  "abstract": "<jats:p>Two experiments of the successive vaporization type, five mass spectrometric vaporization experiments, and two isomolecular exchange reaction experiments were undertaken to resolve discrepancies in the thermodynamics of the titanium\u2014oxygen system. The first two types of experiments confirmed that Ti3O5(s) is the congruently vaporizing phase. The second type of experiment showed that the principal reaction accounting for the congruent vaporization is Ti3O5(S)=TiO(g)+2TiO2(g). In the third type of experiment, measurements on the isomolecular exchange reaction TiO(g)+Sc(g)=Ti(g)+ScO(g) showed that the dissociation energy of TiO(g) is smaller than that for ScO(g) and on the basis that D0o(ScO) is 160.4\u00b12.0 kcal/mole, D0o(TiO) becomes 156.9\u00b12.2 kcal/mole, or 6.80\u00b10.10 eV. This result may be combined with earlier vapor pressure measurements on Ti3O5(s) and the congruency condition to yield D0o(TiO2)=311.7\u00b11.8 kcal/mole, 13.52\u00b10.08 eV, or very nearly twice D0o(TiO). One of the two previously discussed discrepancies in the thermodynamics of the titanium oxides appears to have been resolved, and the likely resolution of the other is discussed.</jats:p>",
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