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Kinetic Analysis of Solid-State Reactions: An Improved Analysis Method

Published online by Cambridge University Press:  10 February 2011

D. P. Smith
Affiliation:
Materials Group, PCS, Cavendish Laboratory, University of Cambridge, Madingley Road, Cambridge, CB3 OHE, UK., dps13@cus.cam.ac.uk
M. M. Chaudhri
Affiliation:
Materials Group, PCS, Cavendish Laboratory, University of Cambridge, Madingley Road, Cambridge, CB3 OHE, UK., dps13@cus.cam.ac.uk
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Abstract

Many reactions of interest occur in the solid state, or with low mobility of the reactants or products, with the result that the physical mechanisms operative during the reaction determine the shape of the reaction rate-time profile; i.e. topochemistry is important. However, often improper account is taken of the physical mechanisms, resulting in erroneous values for the activation energy and kinetic constants.

An improved method of analysis is suggested, allowing the mechanisms of reaction to be determined explicitly. This thus allows the activation energy and kinetic constants to be determined with good theoretical justification. The method has been verified by studying the thermal decomposition of barium azide, where the activation energy was determined to better than 1%. The operative mechanisms so determined are in agreement with visual observations and the literature.

Type
Research Article
Copyright
Copyright © Materials Research Society 1996

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References

1. Wendlandt, W.W., Thermal Analysis, 3rd ed., (Chemical Analysis 19), Wiley, 1985.Google Scholar
2. Galwey, A.K. and and Brown, M.E., Proc. Roy. Soc. London A450 p.501512 (1995).Google Scholar
3. Young, D.A., Decomposition of Solids, Pergamon, Oxford, 1966.Google Scholar
4. Tang, T.B. and Chaudhri, M.M., J. Thermal Anal. 18 p. 247261 (1980)Google Scholar
5. Šesták, J. and Kratochvil, J., J. Thermal Anal. 5 p. 193201 (1973)Google Scholar
6. Tang, T.B., Thermochim. Acta 58 p. 373377 (1982); D.P. Smith, “Characterisation of Peracids”, PhD Thesis, University of Cambridge (1995)Google Scholar
7. Garner, W.E., Chemistry of the Solid State, Butterworths, London, 1955.Google Scholar
8. Tang, T.B. and Chaudhri, M.M., J. Thermal Anal. 17 p. 359370 (1979)Google Scholar
9. Avrami, M.J., J. Chem. Phys. 8 p212224 (1940)Google Scholar
10. Hancock, J.D. and Sharp, J.H., J. Amer. Ceram. Soc. 55 p. 7477 (1972)Google Scholar
11. Fair, H.D. and Walker, R.F., Energetic Materials, Vols I & II, Plenum, New York, 1977 Google Scholar