Examination of Possible Non-Arrhenius Behavior in the reactions

1973 ◽  
Vol 51 (13) ◽  
pp. 2147-2154 ◽  
Author(s):  
Thomas C. Clark ◽  
John E. Dove
Keyword(s):  
Bond Energy ◽  
Classical Limit ◽  
Bond Order ◽  
Transition State Theory ◽  
Arrhenius Plot ◽  
State Theory ◽  
Rate Coefficients ◽  
Order Method ◽  
Arrhenius Behavior ◽  
Kinetic Measurements

We present a simplified form of the bond-energy–bond-order method of calculating rate coefficients which can be applied to reactions involving multi-atom reactants. Rate coefficients for the reactions[Formula: see text]are calculated for 300 < T < 1800°K. The Arrhenius plots of the calculated coefficients are curved, but in the temperature range 400–850°K where most kinetic measurements have been made the curvature is not large enough to be readily detected. However deviations from a linear Arrhenius plot should be observable if rate measurements are extended to higher temperatures by, e.g., shock tube experiments. The calculated rate coefficients at 300–1800°K are fitted by the expressions[Formula: see text]in liter mole second units. These expressions contain powers of T which in each case are greater than predicted by the classical limit of transition state theory. For all three reactions there is now some experimental evidence that the predicted curvature does occur. Some consequences of this behavior are examined.

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