Rate constants for the reaction, H+D sub 2 r arrow HD+D, over the temperature range, 724--2061 K, by the flash photolysis-shock tube technique
- Chemistry Division, Argonne National Laboratory, Argonne, Illinoise 60439 (US)
Thermal rate constants measured by the flash photolysis-shock tube (FP-ST) technique are reported for the reaction, H+D{sub 2}{r arrow}HD+D, over the temperature range, 724--2061 K. H-atom concentration has been monitored by atomic resonance absorption spectroscopy (aras). The results can be represented by the Arrhenius expression: {ital k}{sub 1}=(3.95{plus minus}0.35){times}10{sup {minus}10} exp({minus}5919{plus minus}95 {ital K}/{ital T}) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}, to within {plus minus}25% over the temperature range. These results are then combined with lower temperature direct determinations, and a three parameter expression is derived which expresses the rate behavior between 256--2061 K: {ital k}{sub 1}=1.69{times}10{sup {minus}17}{ital T}{sup 1.10} exp({minus}3527 {ital K}/{ital T}) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. The experimental results are then compared to theoretical calculations that utilize {ital ab} {ital initio} potential energy surfaces that are presumably the most exact that have ever been determined. Thus, the theoretical to experimental comparison constitutes a stringent test of the {ital ab} {ital initio} surfaces and the dynamical calculations in which they are used. The conclusion from this comparison is that transition state theory supplies a high quality prediction for the rate behavior, being within {plus minus}30% of the experimental data over the entire temperature range.
- Research Organization:
- Argonne National Laboratory (ANL), Argonne, IL
- DOE Contract Number:
- W-31109-ENG-38
- OSTI ID:
- 7006679
- Journal Information:
- Journal of Chemical Physics; (USA), Journal Name: Journal of Chemical Physics; (USA) Vol. 92:6; ISSN JCPSA; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
DECOMPOSITION
DEUTERIUM
ELEMENTS
EXPERIMENTAL DATA
HYDROGEN
HYDROGEN ISOTOPES
INFORMATION
ISOTOPES
KINETICS
LIGHT NUCLEI
NONMETALS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
REACTION KINETICS
SHOCK WAVES
STABLE ISOTOPES
VERY HIGH TEMPERATURE