Application of RRKM theory to the reactions OH + NO2 + N2 → HONO2 + N2 (1) and ClO + NO2 + N2 → ClONO2 + N2 (2); a modified gorin model transition state

Rate constants as a function of both temperature and pressure were calculated for the title reactions using RRKM theory in conjunction with a modified Gorin transition state. The modification introduces a hindrance parameter which accounts for repulsive interactions between the rotating fragments. At the highest stratospheric pressures (∼50 torr) and at stratospheric temperature (∼220°K), the extent of “falloff” from first-order [N2] dependence is ∼70% for reaction (1) and ∼35% for reaction (2).

[1]  M. Zahniser,et al.  Chlorine nitrate: Kinetics of formation by ClO+NO2+M and of reaction with OH , 1977 .

[2]  J. Troe.  Theory of thermal unimolecular reactions at low pressures. I. Solutions of the master equation , 1977 .

[3]  R. Zellner.  Fall-Off Curves for the Reaction ClO + NO2( + N2) ClONO2 (+N2) , 1977 .

[4]  M. Quack,et al.  Unimolecular Processes V: Maximum Free Energy Criterion for the High Pressure Limit of Dissociation Reactions , 1977 .

[5]  W. Demore,et al.  Rate constant for formation of chlorine nitrate by the reaction ClO + NO2 + M , 1977 .

[6]  C. Mead.  Mixing character and its application to irreversible processes in macroscopic systems , 1977 .

[7]  M. Quack,et al.  Unimolecular reactions and energy transfer of highly excited molecules , 1977 .

[8]  M. El-Sayed,et al.  Isotope separation using the effect of resonant microwaves on the rate of triplet state photochemistry in solids , 1976 .

[9]  R. A. Perry,et al.  Rate constants for the reactions of the OH radical with NO2 (M=Ar and N2) and SO2 (M=Ar) , 1976 .

[10]  Ian W. M. Smith,et al.  Rate measurements of reactions of OH by resonance absorption. Part 5.—Rate constants for OH + NO2(+M)→ HNO3(+M) over a wide range of temperature and pressure , 1976 .

[11]  M. Quack,et al.  Complex Formation in Reactive and Inelastic Scattering: Statistical Adiabatic Channel Model of Unimolecular Processes III , 1975 .

[12]  H. Johnston.  Pollution of the stratosphere. [Role of supersonic transport] , 1975 .

[13]  G. W. Harris,et al.  Reaction of hydroxyl radicals with NO, NO2 and SO2 , 1975 .

[14]  Kenneth M. Evenson,et al.  Laser magnetic resonance study of the gas phase reactions of OH with CO, NO, and NO2 , 1974 .

[15]  J. Margitan,et al.  Gas phase recombination of OH with NO and NO2 , 1974 .

[16]  W. Tsang.  Comparisons between experimental and calculated rate constants for dissociation and combination reactions involving small polyatomic molecules , 1973 .

[17]  S. Stein,et al.  Accurate evaluation of internal energy level sums and densities including anharmonic oscillators and hindered rotors , 1973 .

[18]  D. C. Tardy,et al.  Theory of Unimolecular Reactions , 1973 .

[19]  I. Smith,et al.  Rate measurements of reactions of OH by resonance absorption. Part 2.—Reactions of OH with CO, C2H4 and C2H2 , 1972 .

[20]  B. Rabinovitch,et al.  Centrifugal effects in reaction rate theory , 1970 .

[21]  R. H. Miller,et al.  Infrared spectra of isotopic halogen nitrates , 1967 .

[22]  H. Johnston,et al.  Energy Transfer Processes in the Unimolecular Decomposition of Nitryl Chloride1 , 1956 .