Gas-phase Reactions Of Hydroxyl Radicals Research Articles

Gas-Phase Kinetic Investigation of the OH-Initiated Oxidation of a Series of Methyl-Butenols under Simulated Atmospheric Conditions.

Five biogenic unsaturated alcohols have been investigated under simulated atmospheric conditions regarding their gas-phase OH reactivity. The gas-phase rate coefficients of OH radicals with 2-methyl-3-buten-2-ol (k1), 3-methyl-2-buten-1-ol (k2), 3-methyl-3-buten-1-ol (k3), 2-methyl-3-buten-1-ol (k4), and 3-methyl-3-buten-2-ol (k5) at 298 ± 2 K and 1000 ± 10 mbar total pressure of synthetic air were determined under low- and high-NOx conditions using the relative kinetic technique. The present work provides for the first time the rate coefficients of gas-phase reactions of hydroxyl radicals with 2-methyl-3-buten-1-ol and 3-methyl-3-buten-2-ol. The following rate constants were measured (in 10-11 cm3 molecule-1 s-1): k1 = 6.32 ± 0.49, k2 = 14.55 ± 0.93, k3 = 10.04 ± 0.78, k4 = 5.31 ± 0.37, and k5 = 11.71 ± 1.29. No significant differences in the measured rate coefficients were obtained when either 365 nm photolysis of CH3ONO in the presence of NO or 254 nm photolysis of H2O2 was used as a source of OH radicals. Reactivity toward other classes of related compounds such as alkenes and saturated alcohols is discussed. A comparison of the structure-activity relationship (SAR) estimates derived from the available accepted methodologies with experimental data available for unsaturated alcohols is provided. Atmospheric lifetimes for the investigated series of alkenols with respect to the main atmospheric oxidants are given and discussed.

Kinetics of the Gas-Phase Reaction of Hydroxyl Radicals with Dimethyl Methylphosphonate (DMMP) over an Extended Temperature Range (273-837 K).

The kinetics of the reaction of hydroxyl radical (OH) with dimethyl methylphosphonate (DMMP, (CH3O)2CH3PO) (reaction 1) OH + DMMP → products (1) was studied at the bath gas (He) pressure of 1 bar over the 295–837 K temperature range. Hydroxyl radicals were produced in the fast reaction of electronically excited oxygen atoms O(1D) with H2O. The time-resolved kinetic profiles of hydroxyl radicals were recorded via UV absorption at around 308 nm using a DC discharge H2O/Ar lamp. The reaction rate constant exhibits a pronounced V-shaped temperature dependence, negative in the low temperature range, 295–530 K (the rate constant decreases with temperature), and positive in the elevated temperature range, 530–837 K (the rate constant increases with temperature), with a turning point at 530 ± 10 K. The rate constant could not be adequately fitted with a standard 3-parameter modified Arrhenius expression. The data were fitted with a 5-parameter expression as: k1 = 2.19 × 10−14(T/298)2.43exp(15.02 kJ mol−1/RT) + 1.71 × 10−10exp(−26.51 kJ mol−1/RT) cm3molecule−1s−1 (295–837 K). In addition, a theoretically predicted pressure dependence for such reactions was experimentally observed for the first time.

Kinetics of the gas-phase reaction of hydroxyl radicals with trimethyl phosphate over the 273-837 K temperature range.

The kinetics of the reaction of hydroxyl radical (OH) with trimethyl phosphate (CH3O)3PO (TMP) (reaction (1)) OH + TMP → products (1) was studied at the bath gas (He) pressure of 1 bar over the 273–837 K temperature range. Hydroxyl radicals were produced in fast reactions of electronically excited oxygen atoms O(1D) with either H2O or H2. Excited oxygen atoms O(1D) were produced by photolysis of ozone, O3, at 266 nm (4th harmonic of Nd:YAG laser) over the 273–470 K temperature range and by photolysis of N2O at 193 nm (ArF excimer laser) over the whole temperature range including the elevated temperature range 470–837 K. The reaction rate constant exhibits a V-shaped temperature dependence, negative in the low temperature range, 273–470 K (the rate constant decreases with temperature), and positive in the elevated temperature range, 470–837 K (the rate constant increases with temperature), with a turning point at 471 K. The rate constant could be fairly well fitted with the three parameter modified Arrhenius expression, k1 = 7.52 × 10−18 (T/298)9 exp(34 367 J mol−1/RT) cm3 per molecule per s (273–837 K). Previously, only one indirect experimental measurement at a single (ambient) temperature was available. The temperature dependence over an extended temperature range obtained in this study together with the peculiar V-shaped temperature dependence will have an impact on the modelling of the flame inhibition by phosphates as well on the further understanding of the mechanisms of elementary chemical reactions.

Gas-Phase Reaction of Hydroxyl Radical with p-Cymene over an Extended Temperature Range.

The kinetics of the reaction of OH radicals with p-cymene has been studied in the temperature range of 243-898 K using a flow reactor combined with a quadrupole mass spectrometer: OH + p-cymene → products. The reaction rate constant was determined as a result of absolute measurements, from OH decay kinetics in excess of p-cymene and employing the relative rate method with OH reactions with n-pentane, n-heptane,1,3-dioxane, HBr, and Br2 as the reference ones. For the rate coefficient of the H atom abstraction channel, the expression k1b = (3.70 ± 0.42) × 10(-11) exp[-(772 ± 72)/T] was obtained over the temperature range of 381-898 K. The total rate constant (addition + abstraction) determined at T = 243-320 K was k1 = (1.82 ± 0.48) × 10(-12) exp[(607 ± 70)/T] or, in a biexponential form, k1 = k1a + k1b = 3.7 × 10(-11) exp(-772/T) + 6.3 × 10(-13) exp(856/T), independent of the pressure between 1 and 5 Torr of helium. In addition, our results indicate that the reaction pathway involving alkyl radical elimination upon initial addition of OH to p-cymene is most probably unimportant.

Rate Coefficients for the Gas-Phase Reactions of Hydroxyl Radicals with a Series of Methoxylated Aromatic Compounds.

Rate coefficients for the reactions of hydroxyl radicals (OH) with a series of oxygenated aromatics (two methoxybenzene and five methoxyphenol isomers) have been obtained using the relative kinetic method in 1080 and 480 L photoreactors at the University of Wuppertal, Germany. The experiments were realized at 295 ± 2 K and 1 bar total pressure of synthetic air using in situ Fourier transform infrared spectroscopy for the chemical analysis. The following rate coefficients (in units of cm(3) molecule(-1) s(-1)) were determined: methoxybenzene (anisole), (2.08 ± 0.21) × 10(-11); 1-methoxy-2-methylbenzene, (4.56 ± 0.50) × 10(-11); 2-methoxyphenol (guaiacol), (5.40 ± 0.72) × 10(-11); 3-methoxyphenol, (6.93 ± 0.67) × 10(-11); 4-methoxyphenol, (5.66 ± 0.55) × 10(-11); 2-methoxy-4-methylphenol, (7.51 ± 0.68) × 10(-11); 2,3-dimethoxyphenol, (7.49 ± 0.81) × 10(-11); and 2,6-dimethoxyphenol (syringol), (8.10 ± 0.98) × 10(-11). The rate coefficients for the reactions of OH with 2,3-dimethoxyphenol and 1-methoxy-2-methylbenzene are first time measurements. The rate coefficients determined in this work are compared with previous determinations reported in the literature and also with the values estimated using a structure-activity relationship method. A comparison is performed between the OH rate coefficients obtained for methoxylated aromatics with those of other substituted aromatics in order to understand the influence of the type, number, and position of the different substituents on the reactivity of aromatics toward OH. In addition, a comparison is made between the OH and Cl rate coefficients for the compounds. The principal atmospheric sink of these methoxylated aromatic compounds during daytime is their reaction with OH radicals. The corresponding lifetimes for reaction with OH radicals and Cl atoms are 2-8 and 11-50 h, respectively.

Kinetic study of the gas-phase reactions of hydroxyl radicals and chlorine atoms with cis-3-hexenylformate

Recently, it has been demonstrated that grass and cut grass are important sources of C6 esters’ emissions into the atmosphere. The esters emitted as part of the wound defense mechanisms are responsible for the smell of freshly cut grass and are also highly photochemically reactive. Thus, these grass emissions should be included in models of urban photochemical pollution so that accurate smog predictions can be obtained. In this work, we have carried out a kinetic study of the gas-phase reactions of chlorine atom and hydroxyl radical with cis-3-hexenylformate (HCO2CH2CH2CH=CHC2H5) for the first time. This was performed in a Teflon static reactor at room temperature and atmospheric pressure of nitrogen or air using gas chromatography with flame ionization detection. Kinetic rate coefficients obtained for cis-3-hexenylformate were (in units of cm3 molecule−1 s−1) (2.45 ± 0.30) × 10−10 and (4.61 ± 0.71) × 10−11 for chlorine and hydroxyl radical reactions, respectively. The reaction between the ester and chlorine atoms is very fast, approaching the collision-controlled regime; nevertheless, the rate constant for the reaction with hydroxyl radical is lower. In addition, the rate coefficients for the reactions of cis-3-hexenylformate with different atmospheric reactive species were estimated through a Quantitative Structure–Activity Relationship model in which High Occupied Molecular Orbital energy of the formate is used as a theoretical molecular descriptor. Tropospheric lifetimes, based on the homogeneous sinks of the cis-3-hexenylformate, are estimated from the kinetic data obtained in the present work. The relatively short atmospheric lifetimes of the ester indicate that the compound will be oxidized near its anthropogenic origin source.

Gas-Phase Reaction of Hydroxyl Radical with Hexamethylbenzene

Aromatic hydrocarbons are important components of polluted ambient air. The reaction of OH radicals with hexamethylbenzene (HMB) is a prototype system to study ipso addition leading eventually to dealkylation. We have investigated the OH + HMB and OD + HMB reactions between 323 and 433 K using a discharge fast-flow reactor coupled to a time-of-flight mass spectrometer with single-photon VUV photoionization (10.54 eV). The H atom abstraction channel has been found to be equal to (13.7 ± 4.4) % at 330 K leading to (11.1 ± 3.6) % at 298 K, higher than predicted by commonly used structure-reactivity relationships. The back dissociation rate constant has also been measured and has been found to be smaller than the rate of other aromatic hydrocarbons, in good agreement with density functional theoretical calculations. The dealkylation channel, leading to pentamethylphenol (PMP) + CH(3), is always found to be the minor channel, estimated inferior to 2% at 298 K.

Rate constant and secondary organic aerosol yields for the gas-phase reaction of hydroxyl radicals with syringol (2,6-dimethoxyphenol)

Syringol (2,6-dimethoxyphenol) is a potential marker compound for wood smoke emissions in the atmosphere. To investigate the atmospheric reactivity of this compound, the rate constant for its reaction with hydroxyl radicals (OH) has been determined in a simulation chamber (8 m3) at 294 ± 2 K, atmospheric pressure and low relative humidity (2–4%) using the relative rate method. The syringol and reference compound concentrations were followed by GC/FID (Gas chromatography/Flame Ionization Detection). The determined rate constant (in units of cm3 molecule−1 s−1) is ksyringol = (9.66 ± 1.11) × 10−11. The calculated atmospheric lifetime for syringol is 1.8 h, indicating that it is too reactive to be used as a tracer for wood smoke emissions. Secondary Organic Aerosol (SOA) formation from the OH reaction with syringol was also investigated. The initial mixing ratios for syringol were in the range 495–3557 μg m−3. The aerosol production was monitored using a SMPS (Scanning Mobility Particle Sizer). The SOA yields (Y) were determined as the ratio of the suspended aerosol mass corrected for wall losses (M0) to the total reacted syringol concentration assuming a particle density of 1.4 g cm−3. The aerosol formation yield increases as the initial syringol concentration increases, and leads to aerosol yields ranging from 0.10 to 0.36. Y is a strong function of M0 and the organic aerosol formation can be expressed by a one-product gas/particle partitioning absorption model. To our knowledge, this work represents the first investigation of the rate constant and SOA formation for the reaction of syringol with OH radicals. The atmospheric implications of this reaction are also discussed.

Kinetic study of the OH-initiated photo-oxidation of four unsaturated (allyl and vinyl) ethers under simulated atmospheric conditions

Using the relative rate technique, rate constants for the gas-phase reactions of hydroxyl radicals with n-propyl vinyl ether (k1), 2-chloroethyl vinyl ether (k2), allyl ether (k3) and allyl ethyl ether (k4) have been measured. Experiments were carried out at (298 ± 2) K and atmospheric pressure using N2 and ultra pure air as bath gas. Using isoprene, 1-methyl-1-cyclohexene, 2-methyl-2-butene, 3-buten-1-ol and 2-methyl-2-propen-1-ol as reference compounds, the following rate constants were derived: k1 = (11.0 ± 0.4) × 10−11, k2 = (9 ± 1) × 10−11, k3 = (6.8 ± 0.7) × 10−11 and k4 = (4.2 ± 0.7) × 10−11, in units of cm3 molecule−1 s−1. This is the first experimental detcermination of k2–k4. The rate constants obtained are compared with the previous literature data for corresponding alkenes reactions with OH and the observed reactivity trends are discussed. The atmospheric implications of the results are considered.

Computational note on the structure and vibrational spectra of organic micropollutants: 1-Ethylnaphthalene and 2-ethylnaphthalene

2011 Elsevier B.V. All rights reserved. Polycyclic aromatic hydrocarbons (PAHs) constitute a class of widespread and persistent carcinogenic and mutagenic hazards [1]. However, it is well-known that in many different environments PAHs are prevalently formed by alkylated mixtures [2]. Microbial biodegradation pathways of alkylated PAHs are significantly affected by position of substituents [3]. For instance, in aqueous systems the biodegradation rate of 2-ethylnaphthalene (2-EN) is predicted to be ca. four times higher than that of 1-ethylnaphthalene (1-EN) [3]. In addition, the rate constant for the gasphase reaction of hydroxyl radical with 2-EN was estimated to be greater than that with 1-EN [4]. Therefore the ability to discriminate these isomers is of great environmental interest. Previous studies revealed that vibrational spectroscopies can be useful to distinguish alkyl-naphthalene isomers [5–7]. In this work, we report the structure, energetics, IR and Raman spectra of ethylnaphthalene isomers obtained in the gas-phase by using DFT and ab initio methods. All calculations were carried out by Gaussian 03 program [8]. Molecular structures of possible rotamers (Fig. S1, Supplementary data) were optimized using B3LYP functional with 6-31G⁄ basis set. Table S1 in the Supplementary data reports the relative stability of the rotamers obtained by HF, MP2 and B3LYP methods. At all levels of calculation 1-EN(a) and 2-EN(a) (Fig. 1) are predicted to be the most stable aand b-substiAll rights reserved. alysis, Monitoring and Miniria 8, Catania 95125, Italy. tuted rotamers, respectively. Interestingly, 1-EN(a) is 1–2 kcal/mol less stable than 2-EN(a) owing to stronger alkyl-hydrogen steric repulsions (Fig. 1). Selected geometrical parameters of 1-EN(a), 2-EN(a) and naphthalene are collected in Table S2. The results for naphthalene show that the calculated values are in good agreement with the experimental ones. The largest geometrical differences between 1-EN(a) and 2-EN(a) are found for C1–C9 and C2–C3 bond lengths (0.01 A). Vibrational wavenumbers, IR and Raman spectra of 1-EN(a) and 2-EN(a) were calculated under the harmonic approximation at the B3LYP/6-31G⁄ level, confirming that both these rotamers are equilibrium structures. Wavenumber values were corrected by a single scaling factor of 0.9594 [9]. In agreement with the experimental UV Raman spectra excited at 233 nm [10], the high and middle spectral zones (Figs. S2–S5 of the Supplementary data) are not much informative to discriminate the investigated isomers. Differently, the low-energy IR spectral zone (Fig. 2) is dominated by a strong absorption band located near 800 cm 1 and assigned to out-of-plane C–H bending deformation (Fig. S6). This transition is red-shifted by 33 cm 1 on passing from 2-EN(a) to 1-EN(a), and concomitantly it increases in intensity by a factor of two. Additionally, the low-wavenumber Raman spectral region (Fig. 3) is characterized by an isolated peak near 700 cm 1 attributed to rings breathing vibration (Fig. S6), which on going from 2-EN(a) to 1-EN(a) is shifted downward by 70 cm . Thus the low-energy IR and Raman spectral regions can be useful to identify ethylnaphthalene isomers. Note also that, calculated depolarization ratios for the natural and plane-polarized lights (Table S3) increase by ca. 20% on passing from 1-EN(a) to 2-EN(a). Fig. 1. Lowest-energy structure of 1-ethylnaphthalene and 2-ethylnaphthalene. Fig. 2. Simulated B3LYP/6-31G⁄ IR spectra (Lorentzian lineshapes, half-height of 10 cm ) of ethylnaphthalene isomers. Fig. 3. Simulated B3LYP/6-31G⁄ Raman spectra (Lorentzian lineshapes, half-height of 10 cm ) of ethylnaphthalene isomers. A. Alparone, V. Librando / Computational and Theoretical Chemistry 965 (2011) 244–245 245

Rate Constants for the Gas-Phase Reactions of OH and O3with β-Ocimene, β-Myrcene, and α- and β-Farnesene as a Function of Temperature

The rate constants for the gas-phase reactions of hydroxyl radicals and ozone with the biogenic hydrocarbons β-ocimene, β-myrcene, and α- and β-farnesene were measured using the relative rate technique over the temperature ranges 313-423 (for OH) and 298-318 K (for O₃) at about 1 atm total pressure. The OH radicals were generated by photolysis of H₂O₂, and O₃ was produced from the electrolysis of O₂. Helium was used as the diluent gas. The reactants were detected by online mass spectrometry, which resulted in high time resolution, allowing large amounts of data to be collected and used in the determination of the Arrhenius parameters. The following Arrhenius expressions have been determined for these reactions (in units of cm³ molecules⁻¹ s⁻¹): for β-ocimene + OH, k = (4.35(-0.66)(+0.78)) × 10⁻¹¹ exp[(579 ± 59)/T]; for β-ocimene + O₃, k = (3.15(-0.95)(+1.36)) × 10⁻¹⁵ exp[-(626 ± 110)/T]; for β-myrcene + O₃, k = (2.21(-0.66)(+0.94)) × 10⁻¹⁵ exp[-(520 ± 109)/T]; for α-farnesene + OH, k(OH) = (2.19 ± 0.11) × 10⁻¹⁰ for 23-413 K; for α-farnesene + O₃, k = (3.52(-2.54)(+9.09)) × 10⁻¹² exp[-(2589 ± 393)/T]; for β-farnesene + OH, k(OH) = (2.88 ± 0.15) × 10⁻¹⁰ for 323-423 K; for β-farnesene + O₃, k = (1.81(-1.19)(+3.46)) × 10⁻¹² exp[-(2347 ± 329)/T]. The Arrhenius parameters here are the first to be reported. The reactions of α- and β-farnesene with OH showed no significant temperature dependence. Atmospheric residence times due to reactions with OH and O₃ were also presented.

Rate Coefficients for the Gas-Phase Reaction of Hydroxyl Radicals with 2-Methoxyphenol (Guaiacol) and Related Compounds

2-Methoxyphenol (guaiacol) and its derivatives are potential marker compounds for wood smoke emissions in the atmosphere. To investigate the atmospheric reactivity of this type of compounds, rate coefficients for their reactions with hydroxyl (OH) radicals have been determined at 294 ± 2 K and 1 atm using the relative rate method with gas chromatography for chemical analysis. The rate coefficients (in units of cm³ molecule⁻¹ s⁻¹) are: 2-methoxyphenol, (7.53 ± 0.41) × 10⁻¹¹; 3-methoxyphenol, (9.80 ± 0.46) × 10⁻¹¹; 4-methoxyphenol, (9.50 ± 0.55) × 10⁻¹¹; 2-methoxy-4-methylphenol, (9.45 ± 0.59) × 10⁻¹¹; and methoxybenzene, (2.20 ± 0.15) × 10⁻¹¹. The estimated atmospheric lifetime for 2-methoxyphenol is ~2 h, indicating that it is too reactive to be used as a tracer for wood smoke emissions. The reactivity of the methoxyphenols is compared with other substituted aromatics and interpreted in relation to the type, number, and positions of the different substituents on the aromatic ring. The atmospheric implications of the reactions are also discussed.

ChemInform Abstract: Relative Rate Constant Measurements for the Gas-Phase Reactions of Hydroxyl Radicals with 4-Methyl-2-pentanone, trans-4-Octene, and trans- 2-Heptene

The relative OH reaction rates from the simulated atmospheric oxidation of 4-methyl-2-pentanone, trans-4-octene, and trans-2-heptene have been measured. Reactions were carried out at 297 ± 2 K in 100-liter FEP Teflon®-film bags. The OH radicals were produced from the photolysis of methyl nitrite. The measured rate constants (×1011 cm3 molecule−1 s−1) were as follows: 6.77 ± 0.50 for trans-4-octene, 1.40 ± 0.07 for 4-methyl-2-pentanone, and 6.70 ± 0.23 for trans-2-heptene using an absolute rate constant of 2.63 × 1011 cm3 molecule−1 s−1 for the reaction of OH with propene; the principal reference organic. © John Wiley & Sons, Inc.

Kinetic study of the OH reaction with some hydrochloroethers under simulated atmospheric conditions

Using the relative rate technique, rate constants for the gas-phase reactions of hydroxyl radicals with 2-chloroethyl methyl ether ( k 1), 2-chloroethyl ethyl ether ( k 2) and bis(2-chloroethyl) ether ( k 3) have been measured. Experiments were carried out at (298 ± 2) K and atmospheric pressure using synthetic air as bath gas. Using n-pentane and n-heptane as reference compounds, the following rate constants were derived: k 1 = (5.2 ± 1.2) × 10 −12, k 2 = (8.3 ± 1.9) × 10 −12 and k 3 = (7.6 ± 1.9) × 10 −12, in units of cm 3 molecule −1 s −1. This is the first experimental determination of k 2 and k 3 under atmospheric pressure. The rate constants obtained are compared with previous literature data and the observed trends in the relative rates of reaction of hydroxyl radicals with the ethers studied are discussed. The atmospheric implications of the results are considered in terms of lifetimes and fates of the hydrochloroethers studied.

OH-Initiated Degradation of Unsaturated Esters in the Atmosphere: Kinetics in the Temperature Range of 287−313 K

The kinetics of the gas-phase reactions of hydroxyl radicals (OH) with methyl methacrylate (k(1)), butyl methacrylate (k(2)), butyl acrylate (k(3)), and vinyl acetate (k(4)) have been investigated for the first time as a function of temperature using the relative technique. The experiments were performed in a 1080 L quartz glass photoreactor over the temperature range (T = 287-313 K) at a total pressure of 760 +/- 10 Torr synthetic air using in situ FTIR absorption spectroscopy to monitor the concentration-time behaviors of reactants. OH radicals were produced by the 254 nm photolysis of hydrogen peroxide (H(2)O(2)). The following Arrhenius expressions (in units of cm(3) molecule(-1) s(-1)) adequately describe the measured rate coefficients as a function of temperature: k(1) = (1.97 +/- 0.95) x 10(-12) exp[(921 +/- 52)/T], k(2) = (1.65 +/- 1.05) x 10(-11) exp[(413 +/- 34)/T], k(3) = (4.4 +/- 2.5) x 10(-13) exp[(1117 +/- 105)/T], and k(4) = (4.06 +/- 2.02) x 10(-12) exp[(540 +/- 49)/T]. All of the rate coefficients display a negative temperature dependence and low pre-exponential factor, which supports an addition mechanism for the reactions involving reversible OH-adduct formation. The rate coefficients (in units of cm(3) molecule(-1) s(-1)) determined at room temperature (298 K) were as follows: k(1) = (4.30 +/- 0.98) x 10(-11), k(2) = (6.63 +/- 1.42) x 10(-11), k(3) = (2.17 +/- 0.48) x 10(-11), and k(4) = (2.48 +/- 0.61) x 10(-11). The results are compared with previous values of the rate coefficients reported in the literature, which were mainly measured at room temperature. The reactivity of the various unsaturated esters toward the OH radical is discussed in terms of structure activity relationships and parallels are drawn with the OH-radical activities of structurally similar compounds. Using the kinetic parameters determined in this work, residence times of the esters in the atmosphere with respect to their reaction with OH have been determined and are compared with other possible degradation pathways. Possible atmospheric implications of the various degradation pathways studied are discussed.

Temperature-Dependent Kinetics Study of the Gas-Phase Reactions of OH with n- and i-Propyl Bromide

An experimental, temperature-dependent kinetics study of the gas-phase reactions of hydroxyl radical with n-propyl bromide, OH+n-C3H7Br-->products (reaction 1), and i-propyl bromide, OH+i-C3H7Br-->products (reaction 2), has been performed over wide ranges of temperatures 297-725 and 297-715 K, respectively, and at pressures between 6.67 and 26.76 kPa by a pulsed laser photolysis/pulsed laser-induced fluorescence technique. Data sets of absolute bimolecular rate coefficients obtained in this study for reactions 1 and 2 demonstrate no correlation with pressure and exhibit positive temperature dependencies that can be represented with modified three-parameter Arrhenius expressions within their corresponding experimental temperature ranges: k1(T)=(1.32x10(-17))T1.95 exp(+25/T) cm3 molecule(-1) s(-1) for reaction 1 and k2(T)=(1.56x10(-24))T4.18exp(+922/T) cm3 molecule(-1) s(-1) for reaction 2. The present results, which extend the current kinetics data base of reactions 1 and 2 to high temperatures, are compared with those from previous works. On the basis of the present data and available data from previous studies, the following bimolecular rate coefficient temperature dependencies can be recommended for the purpose of kinetic modeling: k1(T)=(1.89x10(-19))T2.54exp(+301/T) cm3 molecule-1 s-1 for reaction 1 in a temperature range 210-725 K, and k2(T)=(2.83x10(-21))T3.1exp(+521/T) cm3 molecule(-1) s(-1) and k2(T)=(4.54x10(-24))T4.03exp(+860/T) cm3 molecule(-1) s(-1) for reaction 2 in temperature ranges 210-480 and 297-715 K, respectively.

Daytime tropospheric loss of hexanal and <I>trans</I>-2-hexenal: OH kinetics and UV photolysis

Abstract. The ultraviolet (λ=250–370 nm) photolysis and the OH-initiated oxidation of hexanal and trans-2-hexenal, which are relevant atmospheric processes, have been investigated at room temperature and as a function of temperature (T=263–353 K), respectively. This kinetic study as a function of temperature is reported here for the first time. Absolute absorption cross sections (σλ) were obtained using a recently built system operating in the UV region. The obtained σλ allowed the estimation of the photolysis rates (J) across the troposphere. Kinetic measurements of the gas-phase reaction of hydroxyl radicals (OH) with hexanal and trans-2-hexenal were performed by using the laser pulsed photolysis/laser-induced fluorescence technique. Rate coefficients kOH for both aldehydes were determined at temperatures between 263 and 353 K at 50 Torr in helium or argon bath gases. The temperature dependence of kOH for both aldehydes was found to be slightly negative. The tropospheric lifetime of hexanal and trans-2-hexenal due to the chemical removal by OH radicals has been estimated across the troposphere. The loss rate due to the OH chemical removal was compared with the estimated photolysis rates. Our results show that OH-reaction is the main loss process for these aldehydes in the troposphere, although photolysis is not negligible for hexanal.

OH reaction rate constants and UV absorption cross-sections of unsaturated esters

Absolute rate coefficients have been determined for the gas-phase reactions of hydroxyl radicals with methyl acrylate ( k 1), methyl methacrylate ( k 2) and ethyl acrylate ( k 3). Experiments were performed using two different techniques, the relative rate method and the pulsed laser photolysis-laser induced fluorescence technique. The kinetic data obtained were used to derive the following Arrhenius expressions in the temperature range 253–374 K (in units of cm 3 molecule −1 s −1): k 1 = ( 2.0 ± 0.8 ) × 1 0 - 12 exp [ ( 553 ± 51 ) / T ] , k 2 = ( 2.5 ± 0.8 ) × 1 0 - 12 exp [ ( 821 ± 55 ) / T ] , k 3 = ( 2.3 ± 0.8 ) × 1 0 - 12 exp [ ( 580 ± 65 ) / T ] . At 298 K, the reaction rate constants obtained by the two methods were in good agreement. In addition, the UV absorption spectra for the three unsaturated esters have been determined at (298±2) K and the absorption cross-sections in the wavelength region 215–298 nm were reported. The results are presented, discussed and used to estimate the atmospheric lifetimes for the studied esters.

Linear free energy relationships on rate constants for the gas-phase reactions of hydroxyl radicals with PAHs and PCDD/Fs

Polyparameter linear free energy relationships (LFERs) on rate constants ( k OH) for gas-phase reactions of hydroxyl radicals with polycyclic aromatic hydrocarbons (PAHs) and polychlorinated dibenzo- p-dioxins and dibenzofurans (PCDD/Fs) were developed. Quantum chemical descriptors and partial least squares (PLS) regression were used for model development. Acenaphthylene was found to be an outlier and was excluded in the final model development. The cumulative variance of the dependent variable explained by the PLS components and determined by cross-validation ( Q cum 2 ), for the optimal model, is 0.97, indicating good robustness and predictive power of the model. The main molecular structural factor governing k OH values of PAHs and PCDD/Fs is molecular ability to donate electrons, as described by the energy of the highest occupied molecular orbital ( E HOMO), the average of net atomic charges on hydrogen atoms ( q H + ), and the average of net atomic charges on carbon atoms ( q C). PAH and PCDD/F molecules with high E HOMO and low q H + and q C values tend to have high log k OH values. The LFER model indicates the temperature dependence of log k OH is weak.

Kinetic Studies on the Reactions of Hydroxyl Radicals with a Series of Alkoxy Esters

Rate coefficients for the gas-phase reactions of hydroxyl radicals with a series of alkoxy esters of structure RC(O)O(CH2)nOR‘, where R = H, CH3, R‘ = CH3, C2H5, and n = 1−2, have been determined with use of relative and absolute rate methods. Relative rate measurements were performed in a Teflon reaction chamber at 298 ± 2 K and atmospheric pressure. Absolute rate measurements were made with pulsed laser photolysis−laser induced fluorescence over the temperature range 263−372 K at pressures of ∼100 Torr. The kinetic data are used to derive Arrhenius expressions for the reactions and tropospheric lifetimes for the alkoxy esters. The reactivity of the alkoxy esters is discussed in light of the current understanding of the atmospheric chemistry of oxygenated organic compounds.