13799-69-4

Upstream product

• 107-71-1 tert-butyl peroxyacetate 
• 109-60-4 1-Propyl acetate 
• 36709-10-1 acetylperoxy radical 
• 2143-58-0 methylperoxy radical 

Downstream Products

• 591-87-7 Allyl acetate 
• 79-20-9 acetic acid methyl ester 
• 540-88-5 acetic acid tert-butyl ester 
• 1608-69-1 N-Acetoxymethyl-N-methyl-formamid 
• 140-11-4 Benzyl acetate 
• 21894-29-1 C₁₃H₁₈NO₃ 
• 108-21-4 Isopropyl acetate 
• 141-78-6 ethyl acetate 

Relevant academic research and scientific papers

Relative rate study of the reactions of acetylperoxy radicals with NO and NO2: peroxyacetyl nitrate formation under laboratory conditions related to the troposphere

A relative rate study has been performed on the reactions CH3C(O)O2· + NO2 + M → CH3C(O)O2NO2 + M (1) and CH3C(O)O2· + NO → CH3· + CO2 + NO2 (2) in an atmospheric flow system in which the relative yields of CH3C(O)O2NO2 (PAN) have been measured as a function of the ratio of reactants [NO]/[NO2]. Over the temperature range 247-298 K, at a total pressure of approx.1 atm, the ratio was independent of temperature, k1/k2 = 0.41 ± 0.03, where the error limits are 2σ. The results are discussed with reference to other relative rate measurements of k1/k2 and to absolute measurements of k1 and k2. The atmospheric implications of the ratio k1/k2 in relation to PAN are briefly considered.

Absolute and relative rate constants for the reactions CH3C(O)O2 + NO and CH3C(O)O2 + NO2 and thermal stability of CH3C(O)O2NO2

A pulse-radiolysis system was used to measure absolute rate constants for the reactions of CH3C(O)O2 radicals with NO and NO2 at 295 K and 1000 mbar total pressure of SF6. When the rate of formation and decay of NO2 using its absorption at 400.5 and 452 nm were monitored, the rate constants k(CH3C(O)O2 + NO) = (2.0 ± 0.3) × 10-11 and k(CH3C(O)O2 + NO2) = (1.0 ± 0.2) × 10-11 cm3 molecule-1 s-1 were determined. Long path-length Fourier transform infrared spectrometers were used to study the rate-constant ratio k(CH3C-(O)O2 + NO)/k(CH3C(O)O2 + NO2) in 6-700 Torr total pressure of N2 diluent at 243-295 K. At 295 K in 700 Torr of N2 diluent k(CH3C(O)O2 + NO)/k(CH3C(O)O2 + NO2) = 2.07 ± 0.21. The results are discussed in the context of the atmospheric chemistry of acetylperoxy radicals.

A reinvestigation of the kinetics and the mechanism of the CH 3C(O)O2 + HO2 reaction using both experimental and theoretical approaches

The kinetics and the mechanism of the reaction CH3C(O)O 2 + HO2 were reinvestigated at room temperature using two complementary approaches: one experimental, using flash photolysis/UV absorption technique and one theoretical, with quantum chemistry calculations performed using the density functional theory (DFT) method with the three-parameter hybrid functional B3LYP associated with the 6-31G(d,p) basis set. According to a recent paper reported by Hasson et al., [J. Phys. Chem., 2004, 108, 5979-5989] this reaction may proceed by three different channels: CH3C(O)O 2 + HO2 → CH3C(O)OOH + O2 (1a); CH3C(O)O2 + HO2 → CH3C(O)OH + O3 (1b); CH3C(O)O2 + HO2 → CH3C(O)O + OH + O2 (1c). In experiments, CH 3C(O)O2 and HO2 radicals were generated using Cl-initiated oxidation of acetaldehyde and methanol, respectively, in the presence of oxygen. The addition of amounts of benzene in the system, forming hydroxycyclohexadienyl radicals in the presence of OH, allowed us to answer that channel (1c) is 1 of reaction (1) has been finally measured at (1.50 ± 0.08) × 10-11 cm 3 molecule-1 s-1 at 298 K, after having considered the combination of all the possible values for the branching ratios k1a/k1, k1b/k1, k 1c/k1 and has been compared to previous measurements. The branching ratio k1b/k1, determined by measuring ozone in situ, was found to be equal to (20 ± 1)%, a value consistent with the previous values reported in the literature. DFT calculations show that channel (1c) is also of minor importance: it was deduced unambiguously that the formation of CH3C(O)OOH + O2 (X 3Σ-g) is the dominant product channel, followed by the second channel (1b) leading to CH3C(O)OH and singlet O3 and, much less importantly, channel (1c) which corresponds to OH formation. These conclusions give a reliable explanation of the experimental observations of this work. In conclusion, the present study demonstrates that the CH3C(O)O 2 + HO2 is still predominantly a radical chain termination reaction in the tropospheric ozone chain formation processes. the Owner Societies 2006.

Temperature-dependent study of the CH3C(O)O2 + NO reaction

The kinetics of the reaction between acetylperoxy radicals and nitric oxide have been examined both by transient IR absorption and by time-resolved UV spectroscopy. The former technique enables measurements of NO loss and NO2 formation, whereas the latter provides data on the decay of acetylperoxy radicals, the secondary formation of methylperoxy radicals, and their conversion into methylnitrite. The two methods give consistent rate constants which are fit by the expression k1 = (2.1-0.8+1.4) × 10-12e(570±140)/T cm3 s-1. The room temperature value of k1 = (1.4 ± 0.2) × 10-11 cm3 s-1 is somewhat smaller than the currently recommended value, which is based on indirect determinations of k1. Measurements of the CH3O2 and NO2 yields indicate that the reaction proceeds exclusively to the products CH3C(O)O and NO2. The negative temperature dependence suggests that the reaction proceeds via an intermediate adduct that rearranges and dissociates into the products.

Kinetics of the cross reactions of CH3O2 and C2H5O2 radicals with selected peroxy radicals

The kinetics of the reactions of selected peroxy radicals (RO2) with CH3O2 and with C2H5O2 have been investigated using two techniques: excimer-laser photolysis and conventional flash photolysis, both coupled with UV absorption spectrometry. Radicals were generated either by photolysis of molecular chlorine in the presence of suitable hydrocarbons or by photolysis of the appropriate alkyl chloride. All such cross-reaction kinetics were investigated at 760 Torr total pressure and room temperature except for the reaction of the allylperoxy radical with CH3O2, for which the rate constant was determined between 291 and 423 K, resulting in the following rate expression: k15 = (2.8 ± 0.7) × 10-13 exp[(515 ± 75)/T] cm3 molecule-1 s-1. Values of (2.0 ± 0.5) × 10-13, (1.5 ± 0.5) × 10-12, (9.0 ± 0.15) × 10-14, -12, (2.5 ± 0.5) × 10-12, and (8.2 ± 0.6) × 10-12 (units of cm3 molecule-1 s-1) have been obtained for the reactions of CH3O2 radicals with C2H5O2, neo-C5H11O2, c-C6H11O2, C6H5CH2O2, CH2ClO2, and CH3C(O)O2, respectively, and (1.0 ± 0.3) × 10-12, (5.6 ± 0.8) × 10-13, (4.0 ± 0.2) × 10-14, and (1.0 ± 0.3) × 10-11 (units of cm3 molecule-1 s-1) for the reactions of C2H5O2 with CH2=CHCH2O2, neo-C5H11O2, c-C6H11O2, and CH3C(O)O2 radicals, respectively. These rate constants were obtained by numerical simulations of the complete reaction mechanisms, which were deduced from the known mechanisms of the corresponding peroxy radical self-reactions. A systematic analysis of propagation of errors was carried out for each reaction to quantify the sensitivity of the cross-reaction rate constant to the parameters used in kinetic simulations. The rate constant for a given cross reaction is generally found to be between the rate constants for the self-reactions of RO2 and CH3O2 (or C2H5O2). However, when the RO2 self-reaction is fast, the cross reaction with CH3O2 (or C2H5O2) is also fast, with similar rate constants for both reactions, suggesting that these particular peroxy radical cross reactions can play a significant role in the chemistry of hydrocarbon oxidation processes in the troposphere and in low-temperature combustion. Relationships between cross-reaction and self-reaction rate constants are suggested.

Time-resolved Spectroscopy and Charge-transfer Photochemistry of Aromatic EDA Complexes with X-Pyridinium Cations

Direct photoexcitation of 1: 1 aromatic EDA complexes with various N-substituted X-pyridinium cations (X = nitro, fluoro, methoxy and acetoxy) is achieved by the specific irradiation of their charge-transfer (CT) absorption bands.Time-resolved picosecond spectroscopy refers to charge-transfer activation by the identification of the aromatic cation radical as the initial transient (T1) formed in a photoinduced electron-transfer together with the X-pyridinyl radical.The homolytic fragmentation of the latter varies with the X-substituent in the order X = NO2 > F > AcO >CH3O, and the addition of X. to the aromatic donors leads to a series of cyclohexadienyl adducts that are identified as longer-lived transients (T2) by time-resolved (nanosecond/microsecond) spectroscopy.The phototransients T1 and T2 together account for the different types of aromatic product (resulting from ring substitution, side-chain substitution and dimerization) that are generated by steady-state CT photochemistry of the aromatic EDA complexes with X-pyridinium cations.

Reactions of some Carboxylic Acid Esters with O(3P) Atoms

The rates of the reactions of methylformate, ethylformate, methylacetate, ethylacetate and propylacetate with oxygen atoms have been measured in a discharge flow system.The measurements were carried out under oxygen atom excess in the temperature range 3003*mol-1*s-1>: - Keywords: Gas phase kinetics / O atom reactions / Carboxylic acid esters / Mass spectrometry / Arrhenius parameters