Experimental studies of Cl-atom reactions at high temperatures: Cl + H{sub 2} {yields} HCl + H from 291 to 1283 K
- Rensselaer Polytechnic Inst., Troy, NY (United States)
A method is presented for producing Cl atoms for kinetic experiments above 750 K. Combined with a low temperature Cl-atom production technique, rate coefficients for the title reaction have been obtained over a wide temperature range. The Cl atoms were generated by flash photolysis of CCl{sub 4} for the low-temperature measurements and by pulsed laser photolysis of NaCl for the high-temperature measurements. The relative Cl-atom concentrations were monitored by time-resolved resonance fluorescence. The data are well fitted by the expression k{sub 1}(291--1,283 K) = 4.4 {times} 10{sup {minus}11} exp({minus}2568 K/T) cm{sup 3}/molecule, with 2{sigma} precision limits of {+-} 9 {+-}16 %, depending on temperature, and corresponding 2{sigma} accuracy limits of about {+-} 26 %. There is good agreement between the rate coefficients measured here and those from previous low-temperature studies, leading to the recommendation k{sub 1}(200--1,283 K) = 2.3 {times} 10{sup {minus}16} (T/K){sup 1.63} exp({minus}1592 K/T) cm{sup 3}/molecule s, with a suggested 2{sigma} accuracy limit of {+-}28% for the combined data. A transition state theory calculation base don a semiempirical London-Eyring-Polanyi-Sato (LEPS) potential energy surface gives excellent agreement with the combined experimental results. Extension of their previous recommendation for the reverse reaction to lower temperatures leads to k{sub 2}(200--1,200 K) = 6.6 {times} 10{sup {minus}16} (T/K){sup 1.44} exp({minus}1241 K/T) cm{sup 3}/molecule s, with 2{sigma} accuracy limits within {+-}25 %. There is excellent agreement between the present data and the predicted expression from that reaction and equilibrium data.
- OSTI ID:
- 93526
- Report Number(s):
- CONF-940711-; TRN: IM9537%%271
- Resource Relation:
- Conference: 25. international symposium on combustion, Irvine, CA (United States), 31 Jul - 5 Aug 1994; Other Information: PBD: 1994; Related Information: Is Part Of Twenty-fifth symposium (international) on combustion; PB: 1838 p.
- Country of Publication:
- United States
- Language:
- English
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