Infrared absorption spectroscopy and chemical kinetics of free radicals. Progress report, February 1, 1991--March 1, 1994
Rate of reaction of ketenyl radical with O{sub 2} at room temperature was determined as 6.5(6) {times} 10-{sup {minus}13} CM{sup 3} molecules{sup {minus}1} s{sup {minus}1} and an upper bound of 1 {times} 10{sup {minus}13} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1} was estimated for the reaction rate of acetylene with ketenyl. The high resolution spectrum of the {nu}1 acetylenic CH stretch of propargy1 radical (HCCCH{sub 2}) near 3322 cm{sup {minus}1} has obtained and analyzed. Nuclear spin weights demonstrate that the CH{sub 2} hydrogen atoms are in the carbon atom plane. We have attempted to measure the propargy1 recombination rate constant at 296 K; however, the observed rate constant of (1.2{times}0.2) x 10{sup {minus}10} cc-molecule{sup {minus}1}-s{sup {minus}1} may be affected by other reactions. The CH stretch fundamental, {nu}1, of HCCN has been observed, assigned, and analyzed. Analysis of the hot bands associated with bending shows that HCCN is a quasilinear molecule with a very floppy potential function for the HCC bending angle. The barrier to linearity is estimated to be about 100 cm{sup {minus}1}. Rate of the reaction between C{sub 2}H and H{sub 2} has been measured at 295--855 K. The rate constant exhibited a non-Arrhenius form well represented by k = (9.44{plus_minus}0.50) {times} 10{sup {minus}14}T{sup 0.9}exp(-1003{plus_minus}40/T)cm{sup 3}molecule{sup {minus}1}s{sup {minus}1}. The reaction between atomic oxygen and the amidogen radical, NH{sub 2} has been studied at 295 K; the room temperature rate constant was measured as (6.5 {plus_minus} 1.3) {times} 10{sup {minus}1} s{sup {minus}1}. The minor channel leading to NH + OH was observed but accounted for at most about 8% of the NH{sub 2} reacting. The rate constant for the reaction NH+O was determined from fitting the NH time profile to be 6.6{plus_minus}10{sub {minus}11} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}.
- Research Organization:
- Rice Univ., Houston, TX (United States)
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- DOE Contract Number:
- FG05-85ER13439
- OSTI ID:
- 10173812
- Report Number(s):
- DOE/ER/13439-T4; ON: DE94016642; BR: KC0301020
- Resource Relation:
- Other Information: PBD: [1994]
- Country of Publication:
- United States
- Language:
- English
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