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- W1979330490 abstract "The shock tube technique with D- and H-atom atomic resonance absorption spectrometric (ARAS) detection has been used to measure rate constants for two isotopic modifications of the most fundamental chemical reaction, H + H2 → H2 + H: D + H2 → HD + H (1) and H + D2 → HD + D (2). Hydrogen atoms were produced from the thermal decomposition of either C2D5I or C2H5I. Ethyl iodide decomposition above ∼1150 K is fast, and the product ethyl radicals decompose even faster, giving ethylene and hydrogen atoms. This clean source of atoms then allows for first-order analysis of both reactant and product hydrogen atoms for determining rate constants. The rate constant results can be described by the Arrhenius expressions k1 = 3.17 × 10-10 exp(−5207K/T) cm3 molecule-1 s-1, over the temperature range 1166−2112 K, and k2 = 2.67 × 10-10 exp(−5945K/T) cm3 molecule-1 s-1, over the temperature range 1132−2082 K. These new results are compared to earlier results and supply additional values for evaluating the rate behavior for both reactions over the very large temperature range ∼200−2200 K. These evaluations are then compared to recent quantum mechanical scattering calculations of the thermal rate behavior that are based on a new and quite accurate potential energy surface (i.e., globally accurate to ∼0.01 kcal mol-1). Within experimental error, there is now complete convergence between the experimental evaluation and the new theory, bringing to completion a 75-year effort in chemical kinetics and dynamics. This is the first completely solved problem in chemical kinetics." @default.
- W1979330490 created "2016-06-24" @default.
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- W1979330490 date "2003-12-19" @default.
- W1979330490 modified "2023-09-23" @default.
- W1979330490 title "New Rate Constants for D + H<sub>2</sub> and H + D<sub>2</sub> Between ∼1150 and 2100 K" @default.
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- W1979330490 doi "https://doi.org/10.1021/jp030848k" @default.
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