High-temperature photochemistry kinetics studies of the reactions of H(1 sup 2 S) and D(1 sup 2 S) with N sub 2 O

Journal Article · Thu Mar 09 00:00:00 EST 1989 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100342a045· OSTI ID:5040872

Marshall, P; Ko, Taeho; Fontijn, A ^[1]

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1. Rensselaer Polytechnic Institute, Troy, NY (USA)

The H + N{sub 2}O (1) and D + N{sub 2}O (2) reactions have been investigated by using the high-temperature photochemistry (HTP) technique. Empirical fits to the pressure-independent rate coefficients yield k{sub 1}(T) = 4.2 {times} 10{sup {minus}14} exp(-2290 K/T) + 3.7 {times} 10{sup {minus}10} exp(-8430 K/T) and k{sub 2}(T) = 3.5 {times} 10{sup {minus}13} exp(-3600 K/ T) + 5.3 {times} 10{sup {minus}10} exp(-9170 K/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1} over the ranges 410-1230 and 450-1210 K, respectively. The 2{sigma} precision of these results is better than 11% and the 95% accuracy limits are assessed at about {plus minus}25%. The kinetic isotope effect x(T) = k{sub 1}(T)/k{sub 2}(T) decreases from 2.2 at 450 K to 1.3 at 1200 K, behavior contrary to classical transition-state theory which predicts x(T) increasing with temperature. The data are qualitatively consistent with a rate-controlling step that is dominated by tunneling at the lower end of the temperature range.

• OSTI ID: 5040872
• Journal Information: Journal of Physical Chemistry; (USA), Vol. 93:5; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
DEUTERIUM
CHEMICAL REACTION KINETICS
PHOTOCHEMICAL REACTIONS
HYDROGEN
NITROUS OXIDE
EXPERIMENTAL DATA
HIGH TEMPERATURE
ISOTOPE EFFECTS
TEMPERATURE DEPENDENCE
VERY HIGH TEMPERATURE
CHALCOGENIDES
CHEMICAL REACTIONS
DATA
ELEMENTS
HYDROGEN ISOTOPES
INFORMATION
ISOTOPES
KINETICS
LIGHT NUCLEI
NITROGEN COMPOUNDS
NITROGEN OXIDES
NONMETALS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
OXIDES
OXYGEN COMPOUNDS
REACTION KINETICS
STABLE ISOTOPES
400500* - Photochemistry