Kinetic study of Ca({sup 1}S) + N{sub 2}O and Sr({sup 1}S) + N{sub 2}O reactions in the temperature ranges of, respectively, 303--1015 and 303--999 K
- K.U. Leuven, Heverlee (Belgium). Dept. of Chemistry
Metal/N{sub 2}O reactions in incinerators may reduce the emission of the greenhouse gas N{sub 2}O. The study of metal atom/N{sub 2}O reactions allows metal atom/N{sub 2}O reactions in the gas phase to be very exothermic, leading to product molecules being formed in an electronic excited state. When the metal oxides fall back to lower lying states, an intense chemiluminescence can occur. In this way such reactions can be suitable candidates for the development of chemical lasers in which the population inversion is obtained by means of a pure chemical reaction. A kinetic study of the second-order reactions Ca({sup 1}S) + N{sub 2}O(X{sup 1}{Sigma}{sup +}) {yields} CaO + N{sub 2} and Sr({sup 1}S) + N{sub 2}O(X{sup 1}{Sigma}{sup +}) {yields} SrO + N{sub 2} has been carried out in a fast-flow reactor in the temperature ranges of, respectively, 303--1015 and 303--999 K. The alkaline earth metal atoms were thermally generated from the solid metal pellets. Their decays as a function of the added N{sub 2}O concentration were followed by means of atomic absorption spectroscopy (AAS) at 422.7 nm for calcium and 460.7 nm for strontium atoms. Both reactions showed a non-Arrhenius behavior that can best be explained by the presence of two reaction product channels, resulting in a rate constant expressed as the sum of two exponential functions. The best fits over the entire temperature range are given by polynomial expressions. The results will be discussed in view of the literature data on the alkaline earth metal atom + N{sub 2}O reactions. The experimentally derived energy barriers will be compared with the calculated values on the basis of the semiempirical configuration interaction theory (SECI). Reasonably good correlations were obtained between the barrier heights of the reaction and the promotion energy of the metals involved.
- OSTI ID:
- 682145
- Journal Information:
- Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Vol. 103, Issue 27; Other Information: PBD: 8 Jul 1999
- Country of Publication:
- United States
- Language:
- English
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