Kinetics of the reactions of isopropoxy radicals with NO, NO2, and O2

Balla, R. Jeffrey; Nelson, H. H.; McDonald, J. R.

doi:10.1016/0301-0104(85)80129-4

Cited by 57 publications

(66 citation statements)

References 24 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Indeed, based on the literature room temperature absolute rate constants for the reactions of the methoxy, ethoxy and isopropoxy radicals with 02 (Gutman et al, 1982;Balla et al, 1985;Lorenz et aL, I985;Wantuck et al, 1987;Hartmann et al, 1990) and the values of AHo2, a rate constant of ko~(298 K) = n x 1.6 × 10 -19 e (-°'31 ~Ho0 cm 3 molecule-i s-j…”

Section: Resultsmentioning

confidence: 99%

“…Absolute rate constants for the reactions of alkoxy radicals with 02 are available only for the methoxy (Gutman et al, 1982;Lorenz et al, 1985;Wantuck et al, 1987), ethoxy (Gutman et al, 1982;Hartmann et aL, 1990) and isopropoxy (Balla et al, 1985) radicals. For the other primary and secondary alkoxy radicals, the rate constants for H-atom abstraction by 02 have been assumed to depend only on whether the alkoxy radical is primary or secondary, regardless of the substituents Atkinson, 1990a), although earlier estimation methods did allow for the possibility of a dependence of the room temperature rate constant on the exothermicity of the reaction (Baldwin et al, 1977;Golden, 1979).…”

Section: Oh+rhmentioning

confidence: 99%

See 1 more Smart Citation

Reactions of alkoxy radicals under atmospheric conditions: The relative importance of decomposition versus reaction with O2

Atkinson

Carter

1991

J Atmos Chem

View full text Add to dashboard Cite

The reactions of alkoxy radicals determine to a large extent the products formed during the atmospheric degradations of emitted organic compounds. Experimental data concerning the decompositions, 1,5-H shift isomerizations and reactions with O 2 of several classes of alkoxy radicals are inconsistent with literature estimations of their absolute or relative rate constants. An alternative, although empirical, method for assessing the relative importance under atmospheric conditions of the reactions of alkoxy radicals with 02 versus decomposition was derived. This estimation method utilizes the differences in the heats of reaction, A(AH) = (AH d .... position -AHo,,,actioo), between these two reactions pathways. For A(AH)~ [22-0.5(AHo ...... io,)], alkoxy radical decomposition dominates over the reaction with 02 at room temperature and atmospheric pressure of air, while for A(AH) -> [25 --0.5(AH O .... tion)], the 02 reaction dominates over decomposition (where the units of AH are in kcal mol-t). The utility and shortcomings of this approach are discussed. It is concluded that further studies concerning the reactions of alkoxy radicals are needed.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Oh+rhmentioning

confidence: 99%

Reactions of alkoxy radicals under atmospheric conditions: The relative importance of decomposition versus reaction with O2

Atkinson

Carter

1991

J Atmos Chem

View full text Add to dashboard Cite

show abstract

“…The reaction of i-C 3 H 7 O with NO has been studied by Balla et al [22] while there is no data at all for the reaction of n-C 3 H 7 O with NO. The values obtained in this study are shown in Figure 4 together with the results from ref.…”

Section: The Reaction Of Alkoxy Radicals With Nomentioning

confidence: 99%

“…The values obtained in this study are shown in Figure 4 together with the results from ref. [22], leading to the following Arrhenius expressions:…”

Section: The Reaction Of Alkoxy Radicals With Nomentioning

confidence: 99%

Rate constants for the reactions of C2H5O, i-C3H7O, and n-C3H7O with NO and O2 as a function of temperature

Fittschen

Frenzel

Imrik

et al. 1999

Int. J. Chem. Kinet.

View full text Add to dashboard Cite

show abstract

“…These are well documented only for reactions of methoxy [2-8,lO(a)], ethoxy [5,6,9] and isopropoxy [3,9, i-C3H70 + O2 -HOz + (CH3)zCO [2][3][4][5][6]81 decomposition [2,3,7] isomerization [10(a)] [5,6,91 decomposition [3,7] c91 -A CH3 + cH3cH0} decomposition [3,9, In an ESR study at temperatures >3OO0C at a pressure of -0.3 mbar [7], we have observed the formation of H atoms by the decomposition of CH30 radicals, and for the reaction CH30 + 0 2 , a variation of activation energy with temperature has been observed [8]; these two results might be explained by a tunnel effect.…”

Section: Introductionmentioning

confidence: 97%

Reactions of primary and secondary butoxy radicals in oxygen at atmospheric pressure

Heiss

Maleissye

Viossat

et al. 1991

Int J of Chemical Kinetics

View full text Add to dashboard Cite

The reaction pathways of n-butoxy and s-butoxy radicals have been investigated by TLC and HPLC analysis of end products, particularly peroxides and carbonyl compounds. The butoxy radicals were produced by the pyrolysis of very low concentrations of the corresponding dibutylperoxide in an atmosphere of oxygen and nitrogen, at atmospheric pressure. The decomposition reaction (3) s-BuO + CZHs + CHSCHO and the reaction (2) s-BuO + 0 2 ---f HOz + CH3COC2H6 have been studied, and the ratio k3/k2 has been determined in the temperature range 363-503 K by kinetic modeling of the formation of the observed acetaldehyde and methylethylketone. The rate constant kt obtained was: log,, k3/s-l = (13.8 f : : : ) -(15.0 * 0.9) kcal mo1-'/2.303 R T .A good agreement was observed between experimental data and RRKh4 theory. The implications of the results for atmospheric chemistry and combustion are discussed. At room temperature, the reaction with 02, yielding HOz radicals and methylethylketone is, by far, the main channel for s-BuO radicals. In the field of low temperature combustion, the decomposition of s-BuO radicals producing CzHS and CH3CH0 is the main pathway; the route s-BuO + 0 2 decreases tremendously in importance as the temperature is raised above 393 K.

show abstract

Kinetics of the reactions of isopropoxy radicals with NO, NO2, and O2

Cited by 57 publications

References 24 publications

Reactions of alkoxy radicals under atmospheric conditions: The relative importance of decomposition versus reaction with O2

Reactions of alkoxy radicals under atmospheric conditions: The relative importance of decomposition versus reaction with O2

Rate constants for the reactions of C2H5O, i-C3H7O, and n-C3H7O with NO and O2 as a function of temperature

Reactions of primary and secondary butoxy radicals in oxygen at atmospheric pressure

Contact Info

Product

Resources

About