Halogen-Catalyzed Decomposition of N2O and the Role of the Hypohalite Radical

Benson, Sidney W.; Buss, Jerry H.

doi:10.1063/1.1744010

Cited by 34 publications

(8 citation statements)

References 4 publications

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“…Blake, Browne, and Burns recently (12) calculated that the depth of the intermolecular potential between Br and 0, is about 1 kcal/mole, while the intermolecular potentials for Br-N, and Br-Kr pairs are about 1.7 and 2.2 kcal/mole deep, respectively. On the other hand, the bond-dissociation energy for ClOO was estimated to be 7 kcal/mole (3) and 8 + 2 kcal/mole (6). Furthermore, we were not able to find a third body dependence, and for this reason the reaction Therefore, present experimental data coupled with previous findings (8) yield the following scheme for BrO decomposition…”

Section: Discussionsupporting

confidence: 37%

“…The latter reaction was also found to be second order with respect to its halogen monoxide. The presently accepted scheme for the C10 decomposition was proposed by Benson and Buss (6) It was generally suspected (3, 6) that BrO decomposition should be similar to CIO decomposition. However, it follows from the work of Burns and Norrish (8) that, unlike ClOO radical, BrOO is unstable.…”

Section: Discussionmentioning

confidence: 99%

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Decomposition of BrO studied by kinetic spectroscopy

Brown¹,

Burns²

1970

Can. J. Chem.

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Kinetics of BrO decomposition was studied between 293 and 673 "K using the technique of kinetic spectroscopy. At 293 "K the reaction rate is second order with respect to BrO and is independent of [Br,], [O,], and total pressure of diluent gas. The activation energy for decomposition obtained from rate measurements between 293 and 450 "K is 0.65 f 0.05 kcal/mole. Above 450 "K this activation energy appears to increase to 4.5 kcallmole. It is shown that, although kinetically the CIO and BrO decompositions are similar, the mechanism for BrO decomposition below 450 "K is much simpler than that of C10. The reaction proceeds, most likely, via one step: 2 BrO -> 2 Br + 0 2 , with Br20, being an activated complex, which has either linear or staggered configuration. CIO and BrO decomposition is compared with H z + I,$ 2 HI reaction.Canadian Journal of Chemistry, 48, 3487 (1970) Introduction Although the kinetics of C10 decomposition have been investigated previously (I-7), a study of BrO decomposition using the flash photolysis technique has not been attempted. On the other hand, the kinetics of BrO formation in flash photolytic experiments has already been studied (8).

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Section: Discussionsupporting

confidence: 37%

Section: Discussionmentioning

confidence: 99%

Decomposition of BrO studied by kinetic spectroscopy

Brown¹,

Burns²

1970

Can. J. Chem.

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“…Clyne and Coxon [14] were able to explain much of the discrepimcies by assuming two competitive ClO decay processes: at high pressures ClO decays viaan unstable intermediate Cl 2 0 2 with a chaperone molecule M involved; at low pressures it decays via the peroxy radical ClOO as proposed by Benson and Buss. [24] This ... complex decay mechanism was studied and appeared to be confirmed by Morris [5].…”

Section: Discussionmentioning

confidence: 76%

Molecular Modulation Mass Spectrometry Kinetic Study of the ClO Free Radical

Johnston

1972

Bulletin des Soc Chimique

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In complex photochemical reactions the effective mechanism may be different at low and at high light intensities, since the ratio of radicals to reactants may approach unity at high light intensities and may be 10−4 or less at low light intensities (such as sunlight). The method of flash photolysis has been highly successful in measuring the spectra and kinetics of free radicals in systems of high light intensities. In this laboratory a method named “molecular modulation spectrometry” has been developed, which measures the spectra and lifetimes of free‐radicals in lowintensity photochemical systems. Previous versions have utilized infrared and ultraviolet spectrometry. In this article the method is extended to ion‐counting mass spectrometry. The molecular‐modulation mass spectrometer was used to re‐investigate the kinetics of the CIO radical at low pressure and at low light intensities. Studies by flash photolysis have shown that the CIO radical decays by simple, second‐order kinetics This study confirms the previous result found in low intensity photolysis of CI2 and O2 that the decay process is complex and dependent on inert gas The change in rate law between high and low light intensities and trends exhibited by the parameters, k′ and k″, show that we still do not have a complete understanding of the mechanism of this reaction.

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“…The exothermicity of reaction (24), i.e., the energy of excitation of the radical HC=CHOOCl*, equals about 25 kcal/mole, provided the energy of the third bond in C2H2 is 65.5 kcal/mole4 and the C-0 bond energy equals about Assuming this radical to undergo decomposition into the same (25) HC=CHOOCl* -+ CH + HC1+ COZ and accounting for reaction (1 2), the total heat liberation in reactions (24) and (25) would be -(AH24 + AHz5) = 50 kcal/rnole…”

Section: (21)mentioning

confidence: 99%

Explosion of acetylene–chlorine mixture at room temperatures initiated by small additions of oxygen: Kinetic study and mechanism

Shtern

Revsin

Соколова

1973

Int J of Chemical Kinetics

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Oxygen added in amounts of O.Ol-O.l% was found to cause the explosion of an acetylene-chlorine mixture at temperatures as low as -78OC. Explosion occurrence and nature depend on the mode of mixing the reactants, the effect of oxygen being associated with concentration limits. The dependence of explosion-inducing oxygen amounts on temperature, pressure, concentrations of reactants, reactor surface type and area, additions of inert gases, and reaction products were investigated. The effect of light on the C2H2 + C12 + O2 was studied. The composition of gaseous products resulting from acetylenechlorine mixture explosion in the presence of minute amounts of oxygen, from a slow reaction inhibited and noninhibited by oxygen, and also from explosion at 400°C in the absence of oxygen, was determined. The results obtained point to the fact that any acetylene-chlorine mixture flash caused by small amounts of oxygen is a branched chain reaction involving activated particles, chain branching presumably being associated with the decomposition of radical CHCl=CHOO*+ CH + HCI + CO2.

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Halogen-Catalyzed Decomposition of N2O and the Role of the Hypohalite Radical

Cited by 34 publications

References 4 publications

Decomposition of BrO studied by kinetic spectroscopy

Decomposition of BrO studied by kinetic spectroscopy

Molecular Modulation Mass Spectrometry Kinetic Study of the ClO Free Radical

Explosion of acetylene–chlorine mixture at room temperatures initiated by small additions of oxygen: Kinetic study and mechanism

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