Hostname: page-component-7bb8b95d7b-cx56b Total loading time: 0 Render date: 2024-09-18T18:45:57.202Z Has data issue: false hasContentIssue false
  • English
  • Français

Toward Quantitative Thermodynamics and Kinetics of Pyrolysis of Bulk Materials at High Temperature and Pressure

Published online by Cambridge University Press:  10 February 2011

G. K. Williams  and
T. B. Brill
G. K. Williams
Affiliation:
Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716
T. B. Brill
Affiliation:
Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716
Get access

Abstract

An evaluation was made of whether T-jump/FTIR spectroscopy could be used to determine the decomposition kinetics (Ea and ln A) and thermochemical (ΔHd) constants of an energetic material at high temperature and high heating rate. Polystyrene peroxide was chosen because of its known, simple, decomposition process. The kinetic constants are reasonable for O-O bond homolysis as the rate determining step: Ea = 39 kcal/mol, ln (A, s−1 ) = 21.5. Significant uncertainty exists, however, in the estimation of ΔHd.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 418: Symposium GG – Decomposition, Combustion, and Detonation Chemistry of Energetic Materials , 1995 , 163
Copyright
Copyright © Materials Research Society 1996

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

1. Brill, T. B., Arisawa, H., Brush, P. J., Gongwer, P. E. and Williams, G. K., J. Phys. Chem. 99, p. 1384 (1995).Google Scholar
2. Brill, T. B., J. Propul. Power 11, p. 740 (1995).Google Scholar
3. Wenograd, J., Trans. Farad. Soc. 57, p. 1612 (1961).Google Scholar
4. Merzhanov, A. G., Combust. Flame 11, p. 201 (1967).Google Scholar
5. Semenov, N. N., Z. Phys. 48, p. 571 (1928).Google Scholar
6. Brill, T. B., Brush, P. J., James, K. J., Shepherd, J. E. and Pfeiffer, K. J., Appl. Spectrosc. 46, p. 900 (1992).Google Scholar
7. Rastogi, R. P., Kishore, K. and Chaturvedi, B. K., AIAA Journal 12, p. 1187 (1974).Google Scholar
8. Kishore, K., J. Therm. Anal. 21, p. 15 (1981).Google Scholar
9. Kishore, K. and Ravindran, K., Macromolecules 15, p. 1638 (1982).Google Scholar
10. Kishore, K., Gayathri, V. and Ravindran, K., J. Macromol. Sci. Chem. A19, p. 943 (1983).Google Scholar
11. Kishore, K. and Mukundan, T., Nature 324, p. 130 (1986).Google Scholar
12. Cais, R. E. and Bovey, F. A., Macromolecules 10, p. 169 (1977).Google Scholar
13. Kishore, K., J. Chem. Eng. Data 25, p. 92 (1980).Google Scholar
14. Kishore, K. and Ravindran, K., J. Anal. Appl. Pyrolysis 5, p. 363 (1983).Google Scholar
15. Brownlee, R. T. C., Cameron, D. G., Topsom, R. D., Katritzky, A. R. and Sparrow, A. J., J. Mol. Struct. 16, p. 365 (1973).Google Scholar
16. Nakanaga, T., Kondo, S. and Saëki, S., J. Chem. Phys. 76, p. 3860 (1982).Google Scholar
17. Coates, A. W. and Redfern, J. P., Nature 201, p. 68 (1964).Google Scholar
18. Barrett, K. E. J., J. Appl. Polym. Sci. 11, p. 1617 (1967).Google Scholar
19. Shepherd, J. E. and Brill, T. B., 10th International Detonation Symposium, Office of Naval Research, Arlington, VA 1993, pp. 849–855.Google Scholar
20. Thynell, S. T., Gongwer, P. E. and Brill, T. B., J. Propul. Power, submitted.Google Scholar
21. Rogers, R. N., Anal. Chem. 44, p. 1336 (1972).Google Scholar
22. Williams, G. K. and Brill, T. B., Combust. Flame 102, p. 481 (1995).Google Scholar
23. Hiatt, R. in Organic Peroxides, Vol. III, Swern, D., Ed. (John Wiley & Sons, Inc., New York, 1972), pp. 1–66.Google Scholar
24. Benson, S. W. and Shaw, R. in Organic Peroxides, Vol I, Swern, D., Ed. (John Wiley & Sons, Inc., New York, 1970), pp. 106–140.Google Scholar
25. Brill, T. B., Brush, P. J., Patil, D. G. and Chen, J. K., 24th Symposium (International) on Combustion. The Combustion Institute, Pittsburgh, PA 1992, pp. 1907–1914.Google Scholar