Atmospheric chemistry of acetone: Kinetic study of the CH3C(O)CH2O2+NO/NO2 reactions and decomposition of CH3C(O)CH2O2NO2

Sehested, Jens; Christensen, Linda; Nielsen, Ole John; Bilde, Merete; Wallington, Timothy J.; Schneider, William F.; Tyndall, Geoffrey S.

doi:10.1002/(sici)1097-4601(1998)30:7<475::aid-kin4>3.0.co;2-p

Cited by 31 publications

(36 citation statements)

References 49 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…2While there are no literature data concerning k 3 , our measured value of k 3 is very similar to the rate constants of reactions of other alkyl with NO such as[29],Ϫ11 k(CH COCH ϩ NO) ϭ (2.6 Ϯ 0.3) ϫ 10 3 2 [16], Ϫ11 k(HC(O)CH ϩ NO) ϭ (2.5 Ϯ 0.3) ϫ 10 2 and the high-pressure limit of k(CH ϩ NO) ϭ 3 cm 3 molecule Ϫ1 s Ϫ1 [25]. Ϫ11 (1.68 Ϯ 0.10) ϫ 10 Combining the branching ratio and k /(k ϩ k ) 1a 1a 1b…”

supporting

confidence: 67%

Absolute rate constants for F + CH3CHO and CH3CO + O2, relative rate study of CH3CO + NO, and the product distribution of the F + CH3CHO reaction

Sehested

Christensen

Nielsen

et al. 1998

Int. J. Chem. Kinet.

Self Cite

View full text Add to dashboard Cite

Using a pulse-radiolysis transient UV-VIS absorption system, rate constants for the reactions of F atoms with CH 3 CHO (1) and CH 3 CO radicals with O 2 (2) and NO (3) at 295 K and 1000 mbar total pressure of SF 6 was determined to be Ϫ10 k ϭ (1.4 Ϯ 0.2) ϫ 10 , k ϭ 1 2 By monitoring the for-Ϫ12 Ϫ11 3 Ϫ1 Ϫ1(4.4 Ϯ 0.7) ϫ 10 , and k ϭ (2.4 Ϯ 0.7) ϫ 10 cm molecule s . 3 mation of CH 3 C(O)O 2 radicals ( Ͼ 250nm) and NO 2 ( ϭ 400.5nm) following radiolysis of SF 6 /CH 3 CHO/O 2 and SF 6 /CH 3 CHO/O 2 /NO mixtures, respectively, it was deduced that reaction of F atoms with CH 3 CHO gives (65 Ϯ 9)% CH 3 CO and (35 Ϯ 9)% HC(O)CH 2 radicals. Finally, the data obtained here suggest that decomposition of HC(O)CH 2 O radicals via C9C bond scission occurs at a rate of

show abstract

supporting

confidence: 67%

Absolute rate constants for F + CH3CHO and CH3CO + O2, relative rate study of CH3CO + NO, and the product distribution of the F + CH3CHO reaction

Sehested

Christensen

Nielsen

et al. 1998

Int. J. Chem. Kinet.

Self Cite

View full text Add to dashboard Cite

show abstract

“…Also included in the mechanism was the formation of acetonyl peroxy nitrate by the reaction sequence where reaction d was assumed to be rapid, and for the forward and reverse pathways of reaction e the known rate coefficients k e ) 6.4 × 10 -12 cm 3 molecule -1 s -1 and k -e ) 10 s -1 were used. 4,5 The results of the calculations show that reaction c has indeed an effect on the dissociation quantum yield and its pressure dependence, which determines the quenching coefficient k M / k D . On the other hand, the (temporary) formation of acetonyl peroxy nitrate has no significant influence, because the comparatively long irradiation times favor decomposition.…”

mentioning

confidence: 95%

Photodissociation of Acetone in Air: Dependence on Pressure and Wavelength. Behavior of the Excited Singlet State

Emrich¹,

Warneck²

2005

J. Phys. Chem. A

View full text Add to dashboard Cite

Page 9436. The quantum yield for the photodissociation of acetone in air is subject to a Stern-Volmer type pressure quenching, which increases with increasing wavelength in the spectral region 280-337 nm. 1,2 By combining our own data with those of Gierczak et al., 1 we were able to show 2 that the quenching coefficient k M /k D , that is, the ratio of the rate coefficients for collisional quenching by carrier gas molecules M and dissociation of the photoexcited acetone molecule declines exponentially with excitation energy above the dissociation threshold. In the semilogarithmic plot chosen to demonstrate this behavior, all the existing data fell reasonably well on a straight line except our point at 330 nm. The experiments had utilized the yield of peroxy acetyl nitrate (PAN)sderived from CH 3 CO + O 2 in the presence of NO 2 as scavengersto determine the photodissociation quantum yield. At 330 nm, in contrast to experiments at other wavelengths, the degree of NO 2 photodissociation relative to that of acetone was undesirably high, because of the low absorption cross section of acetone. Photodissociation of NO 2 leads to side reactions, for example, the reaction of NO with CH 3 O 2 (formed from CH 3 + O 2 ), which is followed by further reactions that ultimately generate OH radicals. Therefore, the experimental data at 330 nm had required corrections to account for the additional reactions. Corrections were made by means of computer calculations based on a rather extensive reaction mechanism given in our paper. We have recently recognized that the mechanism is incomplete, in that it disregarded the reaction of acetone with NO 3 radicals, which also are a byproduct of NO 2 photolysisThe rate coefficient for this reaction, k c ) 8.5 × 10 -18 cm 3 molecule -1 s -1 , is fairly small, 3 and for this reason we had omitted the reaction. Moreover, most of the NO 3 radicals associate with NO 2 to form N 2 O 5 , and the equilibrium set up between NO 3 and N 2 O 5 favors the latter species. The only loss reaction included previously for NO 3 radicals was that with NO. Owing to the rather high concentration of acetone, however, reaction c must be included in the mechanism. Consequently, it was added to the list of reactions and new calculations were made. Also included in the mechanism was the formation of acetonyl peroxy nitrate by the reaction sequence where reaction d was assumed to be rapid, and for the forward and reverse pathways of reaction e the known rate coefficients k e ) 6.4 × 10 -12 cm 3 molecule -1 s -1 and k -e ) 10 s -1 were used. 4,5 The results of the calculations show that reaction c has indeed an effect on the dissociation quantum yield and its pressure dependence, which determines the quenching coefficient k M / k D . On the other hand, the (temporary) formation of acetonyl peroxy nitrate has no significant influence, because the comparatively long irradiation times favor decomposition. The calculations lead to the following corrected linear correlation for the inverse (corrected) quantum yield at 330...

show abstract

“…Under these conditions, the rate constant for the disappearance of peroxynitrate (k obs ) does not quite reflect the value of k 2 and, therefore, it must be corrected by multiplying the factor {1 + k À2 [NO 2 ]/k 3 [NO]}. This correction has been extensively used [26][27][28][29][30][31] and, in our system, led to a correction of less than 3% in k obs .…”

Section: Thermal Stability Of Dmppnmentioning

confidence: 99%

Chlorine initiated photooxidation of (CH3)3CC(O)H in the presence of NO2 and photolysis at 254nm. Synthesis and thermal stability of (CH3)3CC(O)OONO2

Henao¹,

Argüello²,

Malanca³

2015

Journal of Photochemistry and Photobiology A: Chemistry

View full text Add to dashboard Cite

Atmospheric chemistry of acetone: Kinetic study of the CH3C(O)CH2O2+NO/NO2 reactions and decomposition of CH3C(O)CH2O2NO2

Abstract: Pulse radiolysis was used to study the kinetics of the reactions of CH 3 C(O)CH 2 O 2 radicals with NO and NO 2 at By monitoring the rate of formation and decay of NO 2 295 K.10 cm molecule s . istry of acetone and the long range atmospheric transport of

Cited by 31 publications

References 49 publications

Absolute rate constants for F + CH3CHO and CH3CO + O2, relative rate study of CH3CO + NO, and the product distribution of the F + CH3CHO reaction

Absolute rate constants for F + CH3CHO and CH3CO + O2, relative rate study of CH3CO + NO, and the product distribution of the F + CH3CHO reaction

Photodissociation of Acetone in Air: Dependence on Pressure and Wavelength. Behavior of the Excited Singlet State

Chlorine initiated photooxidation of (CH3)3CC(O)H in the presence of NO2 and photolysis at 254nm. Synthesis and thermal stability of (CH3)3CC(O)OONO2

Contact Info

Product

Resources

About