Atmospheric chemistry of benzaldehyde: UV absorption spectrum and reaction kinetics and mechanisms of the C6H5C(O)O2 radical

Caralp, F.; Foucher, Virginie; Lesclaux, R.; Wallington, Timothy J.; Hurley, M. D.

doi:10.1039/a903088c

Cited by 45 publications

(67 citation statements)

References 23 publications

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“…A closer inspection of the table shows that there is a systematic decrease in activation energy when an oxygen atom is present between the terminal and the carbonyl carbon atoms (compare rows 1 and 2, 3 and 4, and 5 and 6). This is in agreement with results obtained and reported by Caralp et al [6]. It can also be seen that activation energies are larger for fluorinated counterparts (compare rows 1 and 3 and 2 and 4).…”

Section: Methodssupporting

confidence: 95%

“…In this paper, we report a calculated value obtained through the fitting of the concentration-time profiles reported in that work for the trifluoromethoxycarbonyl peroxy nitrate and products experimentally determined at 298 K. This fit leads to a value of 40 s −1 , which is smaller than the values obtained by other workers. Other decarboxylation reactions have been studied, for example, by Maricq et al [13,16], Wallington et al [11], and Caralp et al [6], who determined the rate constants for CF 3 COO and C 6 H 5 COO radicals and concluded that the rate constants are significantly higher, around 5 × 10 4 s −1 . Our value for k 7 has to do mainly with the adjustment of the relative concentrations of CF 2 O and CF 3 OC(O)O 2 C(O)OCF 3 and does not affect the kinetic parameters obtained for the thermal decomposition of the peroxy nitrate despite the difference with the value reported for decarboxylation of other radicals [6,11,13,16].…”

Section: Methodsmentioning

confidence: 97%

“…These limits encompass our experimental value. Data reported for similar peroxy nitrates taken from the literature [1,4,6,11,24] are listed in Table III. As can be seen, all reported activation energies fall within a range of 9 kJ mol −1 .…”

Section: Methodsmentioning

confidence: 99%

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Thermal decomposition of trifluoromethoxycarbonyl peroxy nitrate, CF₃OC(O)O₂NO₂

Manetti¹,

Malanca²,

Argüello³

2008

Int J of Chemical Kinetics

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The thermal decomposition of trifluoromethoxycarbonyl peroxy nitrate, CF3OC(O)O2NO2, has been studied between 278 and 306 K at 270 mbar total pressure using He as a diluent gas. The pressure dependence of the reaction was also studied at 292 K between 1.2 and 270 mbar total pressure. The rate constant reaches its high‐pressure limit at 70 mbar. The first step of the decomposition leads to CF3OC(O)O2 and NO2 formation, that is, CF3OC(O)O2NO2 + M ⇆ CF3OC(O)O2 + NO2 + M (k1, k−1). Reaction (−1) was prevented by adding an excess of NO that reacts with the peroxy radical intermediate and leads to carbonyl fluoride (CF2O), carbon dioxide (CO2), nitrogen dioxide (NO2), and small quantities of CF3OC(O)O2C(O)OCF3. The kinetics of reaction (1) was determined by following the loss of CF3OC(O)O2NO2 via IR spectroscopy. The temperature dependence of the decomposition follows the equation k1(T) = 1.0 × 1016 e−((111±3)/(RT)) for the exponential term expressed in kJ mol−1. The values obtained for the kinetic parameters such as k1 at 298 K, the activation energy (Ea), and the preexponential factor (A) are compared with literature data for other acyl peroxy nitrates. The atmospheric thermal stability of CF3OC(O)O2NO2 and its dependence with altitude is discussed. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 831–838, 2008

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Section: Methodssupporting

confidence: 95%

Section: Methodsmentioning

confidence: 97%

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Thermal decomposition of trifluoromethoxycarbonyl peroxy nitrate, CF₃OC(O)O₂NO₂

Manetti¹,

Malanca²,

Argüello³

2008

Int J of Chemical Kinetics

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“…Lightfoot et al, 1992;Noziere et al, 1994;Caralp et al, 1999). Similarly, the subsequently-formed aromatic acyl-oxy radicals are assumed to decompose to yield CO 2 and phenyl type radicals (Caralp et al, 1999), followed by addition of O 2 to yield phenyl peroxy radicals, F-O 2 :…”

Section: Aromatic Aldehydesmentioning

confidence: 99%

“…Noziere et al, 1994;Caralp et al, 1999;Calvert et al, 2002), the reactions are assumed to lead to overall abstraction of the aldehydic hydrogen atom, followed by addition of O 2 , leading to the production of aromatic acyl peroxy radicals, -C(O)O 2 (where is a phenyl or an alkyl-substituted phenyl group):…”

Section: Aromatic Aldehydesmentioning

confidence: 99%

Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part B): tropospheric degradation of aromatic volatile organic compounds

et al. 2003

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Abstract. Kinetic and mechanistic data relevant to the tropospheric degradation of aromatic volatile organic compounds (VOC) have been used to define a mechanism development protocol, which has been used to construct degradation schemes for 18 aromatic VOC as part of version 3 of the Master Chemical Mechanism (MCM v3). This is complementary to the treatment of 107 non-aromatic VOC, presented in a companion paper. The protocol is divided into a series of subsections describing initiation reactions, the degradation chemistry to first generation products via a number of competitive routes, and the further degradation of first and subsequent generation products. Emphasis is placed on describing where the treatment differs from that applied to the non-aromatic VOC. The protocol is based on work available in the open literature up to the beginning of 2001, and some other studies known by the authors which were under review at the time. Photochemical Ozone Creation Potentials (POCP) have been calculated for the 18 aromatic VOC in MCM v3 for idealised conditions appropriate to north-west Europe, using a photochemical trajectory model. The POCP values provide a measure of the relative ozone forming abilities of the VOC. These show distinct differences from POCP values calculated previously for the aromatics, using earlier versions of the MCM, and reasons for these differences are discussed.

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Photodissociation Dynamics of Benzaldehyde (C₆H₅CHO) at 266, 248, and 193 nm

Bagchi

Huang

et al. 2011

Chemistry An Asian Journal

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The photodissociation of gaseous benzaldehyde (C(6)H(5)CHO) at 193, 248, and 266 nm using multimass ion imaging and step-scan time-resolved Fourier-transform infrared emission techniques is investigated. We also characterize the potential energies with the CCSD(T)/6-311+G(3df,2p) method and predict the branching ratios for various channels of dissociation. Upon photolysis at 248 and 266 nm, two major channels for formation of HCO and CO, with relative branching of 0.37:0.63 and 0.20:0.80, respectively, are observed. The C(6)H(5)+HCO channel has two components with large and small recoil velocities; the rapid component with average translational energy of approximately 25 kJ mol(-1) dominates. The C(6)H(6)+CO channel has a similar distribution of translational energy for these two components. IR emission from internally excited C(6)H(5)CHO, ν(3) (v=1) of HCO, and levels v≤2, J≤43 of CO are observed; the latter has an average rotational energy of approximately 13 kJ mol(-1) and vibrational energy of approximately 6 kJ mol(-1). Upon photolysis at 193 nm, similar distributions of energy are observed, except that the C(6)H(5)+HCO channel becomes the only major channel with a branching ratio of 0.82±0.10 and an increased proportion of the slow component; IR emission from levels ν(1) (v=1) and ν(3) (v=1 and 2) of HCO and v≤2, J≤43 of CO are observed; the latter has an average energy similar to that observed in photolysis at 248 nm. The observed product yields at different dissociation energies are compared to statistical-theory predicted results based on the computed singlet and triplet potential-energy surfaces.

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Atmospheric chemistry of benzaldehyde: UV absorption spectrum and reaction kinetics and mechanisms of the C6H5C(O)O2 radical

Cited by 45 publications

References 23 publications

Thermal decomposition of trifluoromethoxycarbonyl peroxy nitrate, CF₃OC(O)O₂NO₂

Thermal decomposition of trifluoromethoxycarbonyl peroxy nitrate, CF₃OC(O)O₂NO₂

Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part B): tropospheric degradation of aromatic volatile organic compounds

Photodissociation Dynamics of Benzaldehyde (C₆H₅CHO) at 266, 248, and 193 nm

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Atmospheric chemistry of benzaldehyde: UV absorption spectrum and reaction kinetics and mechanisms of the C6H5C(O)O2 radical

Cited by 45 publications

References 23 publications

Thermal decomposition of trifluoromethoxycarbonyl peroxy nitrate, CF3OC(O)O2NO2

Thermal decomposition of trifluoromethoxycarbonyl peroxy nitrate, CF3OC(O)O2NO2

Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part B): tropospheric degradation of aromatic volatile organic compounds

Photodissociation Dynamics of Benzaldehyde (C6H5CHO) at 266, 248, and 193 nm

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Product

Resources

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Thermal decomposition of trifluoromethoxycarbonyl peroxy nitrate, CF₃OC(O)O₂NO₂

Thermal decomposition of trifluoromethoxycarbonyl peroxy nitrate, CF₃OC(O)O₂NO₂

Photodissociation Dynamics of Benzaldehyde (C₆H₅CHO) at 266, 248, and 193 nm