Simple and Accurate Approximation for the Centrifugal Factor in RRKM Theory

Waage, E. V.; Rabinovitch, B. S.

doi:10.1063/1.1672828

Cited by 20 publications

(8 citation statements)

References 16 publications

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“…This effect has been described in detail recently by Waage and Rabinovitch [41] [42]. For a loose model, for which Z+/Z = 6, then Fo, the correction factor to kE, defined as is approximately 0.54; for Z+/Z of only 2, FO is 0.86.…”

Section: B Centrifugal Efectsmentioning

confidence: 93%

Some aspects of theory and experiment in the ethane–methyl radical system

Waage

Rabinovitch

1971

Int J of Chemical Kinetics

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A critical examination has been made of some aspects of the thermal decomposition of ethane and the reverse recombination reaction. The experimental Arrhenius A-factors for ethane are, in general, smaller than those which are calculated from thermodynamic quantities together with the observed rate constants for methyl recombination. Theoretical calculations also illustrate a discrepancy between the experimental work on recombination and decomposition. The experimental shapes of k/k, falloff curves and the pressure region of falloff are compared with the predictions of RRKM theory for various models.

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Section: B Centrifugal Efectsmentioning

confidence: 93%

Some aspects of theory and experiment in the ethane–methyl radical system

Waage

Rabinovitch

1971

Int J of Chemical Kinetics

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“…Steps (5) and (13) represent collisional stabilization of these energetic species in terms of the strong collision hypothesis, while step (6) for DMS-di and step (14) for ES-di count all possible decomposi-tion pathways. The decomposition paths believed to be of major importance are indicated by steps (7) through (12) for DMS-di and steps (15) through (19) for ES-di. Steps (10) through (12) and steps (17) and (18) are proposed to proceed through molecular elimination.…”

Section: Mechanismmentioning

confidence: 99%

“…Reaction (14) for the total rate constant for the decomposition of chemically activated ethylsilane-d3 is proposed to consist of five contributors, steps (15)- (19). The bond rupture processes, steps (15) and (16), for the production of ethyl radicals and deuterium atoms are considered later via RRKM calculations.…”

Section: Total Rate Constantsmentioning

confidence: 99%

“…The insertion reactions, steps (2) and (3), involve only the singlet species. Steps (5) through (19) describe the fate of the chemically activated molecules produced in steps (2) and (3). Steps (5) and (13) represent collisional stabilization of these energetic species in terms of the strong collision hypothesis, while step (6) for DMS-di and step (14) for ES-di count all possible decomposi-tion pathways.…”

Section: Mechanismmentioning

confidence: 99%

“…The final reaction, step (19), is postulated as the most likely reaction to make up the total rate constant for the decomposition of chemically activated ethylsilane-d3. Investigation of this reaction and experimental confirmation of the rate constant is not feasible since ethene is produced in reactions between methylenes [16].…”

Section: Total Rate Constantsmentioning

confidence: 99%

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The decomposition kinetics of chemically activated methyl‐d₁‐methylsilane‐d₂ and ethylsilane‐d₃

Richardson

Simons

1978

Int J of Chemical Kinetics

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The decomposition kinetics of chemically activated methyl-dl -methylsilane-dz (DMS-dj) and ethylsilane-d3 (ES-d;) from the Si-D and C-H insertion reactions of CH2 ('AJ with methylsilane-d3 have been studied. The total rate constants for decomposition of chemically activated DMS-dz and ES-d3 have been measured. The individual rate constants for molecular elimination of CHsD, CHzDz, and Dz from DMS-d; and for molecular elimination of CH3CHzD and Dz from ES-dl have been measured. All of the above rate constants exhibit the expected kinetic isotope effect when compared to those found previously in the undeuterated system. RRKM theory calculations of the rate constants for the expected C-Si and Si-D bond rupture processes, based on energetics and activated complex models deduced previously for the undeuterated system, were carried out. In the case of DMS-d; the RRKM theory calculations of rate constants for the bond rupture processes combined with experimental rate constants for the molecular elimination processes gave a total rate constant for decomposition in agreement with the measured value. The results of a high-pressure study of the CH3DKHzDz ratio from chemically activated DMS-d3 decomposition were consistent with complete randomization of internal energy up to a pressure of 4 atmospheres (lifetime of -1.7 X lo-" sec). This is not an unexpected result in light of earlier work.

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Specific Rate Constants of Unimolecular Processes II. Adiabatic Channel Model

Qüack

Troe

1974

Ber Bunsenges Phys Chem

598

266

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The rate of unimolecular processes is calculated by means of a statistical adiabatic channel model. The rates are mainly determined by the maxima of the channel energies. The channels are constructed by correlating reactant and product states; the channel energies are computed by a simple interpolation procedure. The coupling between the various vibrational‐rotational motions is taken into account. The influence of parameters of the potential surface on channel energies and on rate constants is studied. Numerical results for the NO2, CH4, CD4, C2H6 and C2D6 dissociation – recombination kinetics are compared to experimental data. The statistical adiabatic channel model gives similar results as minimum local entropy models. Both these approaches lead to stronger curvatures of k(E) and smaller activation energies for the thermal rate constant k∞ than the corresponding RRKM calculations.

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Simple and Accurate Approximation for the Centrifugal Factor in RRKM Theory

Cited by 20 publications

References 16 publications

Some aspects of theory and experiment in the ethane–methyl radical system

Some aspects of theory and experiment in the ethane–methyl radical system

The decomposition kinetics of chemically activated methyl‐d₁‐methylsilane‐d₂ and ethylsilane‐d₃

Specific Rate Constants of Unimolecular Processes II. Adiabatic Channel Model

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Simple and Accurate Approximation for the Centrifugal Factor in RRKM Theory

Cited by 20 publications

References 16 publications

Some aspects of theory and experiment in the ethane–methyl radical system

Some aspects of theory and experiment in the ethane–methyl radical system

The decomposition kinetics of chemically activated methyl‐d1‐methylsilane‐d2 and ethylsilane‐d3

Specific Rate Constants of Unimolecular Processes II. Adiabatic Channel Model

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The decomposition kinetics of chemically activated methyl‐d₁‐methylsilane‐d₂ and ethylsilane‐d₃