Reaction Of OH Radicals Research Articles

Enhancement of photocatalytic decarboxylation on TiO2 by water-induced change in adsorption-mode

Decarboxylation is an important process in the photocatalytic degradation of organic pollutants. In this study, the adsorption and photocatalytic decarboxylation of acetic acid and trichloroacetic acid were investigated by in-situ diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS), which can distinguish carboxylate groups with different adsorption modes. We found that water molecules promote photocatalytic decarboxylation reaction and the promotional effect of water is attributed to the changed adsorption mode of the carboxylate group by the co-adsorbed water molecules. The IR study shows that degradation of the monodentate-coordinated acetic acids is much faster than that of the bidentate-coordinated one. The kinetic isotope effect studies and analysis of the intermediate products indicates that the degradation of acetic acids originates from the direct oxidation by holes even in the presence of water, rather than from the reaction of OH radicals as generally believed. DFT-based molecular dynamics calculations revealed that the formation of the monodentate-coordinated carboxylate group in the presence of water is attributed to competition between the O atom of the carboxylate group and water for the surface Ti sites. Because of its higher electron density, the monodentate carboxylate group is easier to be directly oxidized by holes than the bidentate group.

Water Ice Radiolytic O2, H2, and H2O2 Yields for Any Projectile Species, Energy, or Temperature: A Model for Icy Astrophysical Bodies

AbstractO2, H2, and H2O2 radiolysis from water ice is pervasive on icy astrophysical bodies, but the lack of a self‐consistent, quantitative model of the yields of these water products versus irradiation projectile species and energy has been an obstacle to estimating the radiolytic oxidant sources to the surfaces and exospheres of these objects. A major challenge is the wide variation of O2 radiolysis yields between laboratory experiments, ranging over 4 orders of magnitude from 5 × 10−7 to 5 × 10−3 molecules/eV for different particles and energies. We revisit decades of laboratory data to solve this long‐standing puzzle, finding an inverse projectile range dependence in the O2 yields, due to preferential O2 formation from an ~30 Å thick oxygenated surface layer. Highly penetrating projectile ions and electrons with ranges ≳30 Å are therefore less efficient at producing O2 than slow/heavy ions and low‐energy electrons (≲ 400 eV) which deposit most energy near the surface. Unlike O2, the H2O2 yields from penetrating projectiles fall within a comparatively narrow range of (0.1–6) × 10−3 molecules/eV and do not depend on range, suggesting that H2O2 forms deep in the ice uniformly along the projectile track, e.g., by reactions of OH radicals. We develop an analytical model for O2, H2, and H2O2 yields from pure water ice for electrons and singly charged ions of any mass and energy and apply the model to estimate possible O2 source rates on several icy satellites. The yields are upper limits for icy bodies on which surface impurities may be present.

Keto-ether and glycol-ethers in the troposphere: reactivity toward OH radicals and Cl atoms, global lifetimes, and atmospheric implications.

Rate coefficients for the gas-phase reactions of OH radicals and Cl atoms with 1-methoxy-2-propanone (1-M-2-PONE), 1-methoxy-2-propanol (1-M-2-POL), and 1-methoxy-2-butanol (1-M-2-BOL) were determined at room temperature and atmospheric pressure using a conventional relative-rate technique. The following absolute rate coefficients were derived: k 1(OH+1-M-2-PONE)=(0.64±0.13)×10-11, k 2(OH+1-M-2-BOL)=(2.19±0.23)×10-11, k 3(Cl+1-M-2-PONE=(1.07±0.24)×10-10, k 4(Cl+1-M-2-POL)=(2.28±0.21)×10-10, and k 5 (Cl+1-M-2-BOL)=(2.79±0.23)×10-10, in units of cm3molecule-1s-1. This is the first experimental determination of k 2-k 5. These rate coefficients were used to discuss the influence of the structure on the reactivity of the studied polyfunctional organic compounds. The atmospheric implications for 1-M-2-PONE, 1-M-2-POL, and 1-M-2-BOL and their reactions were investigated estimating atmospheric parameters such as lifetimes, global warming potentials, and average photochemical ozone production. The approximate nature of these values was stressed considering that the studied oxygenated volatile organic compounds are short-lived compounds for which the calculated parameters may vary depending on chemical composition, location, and season at the emission points.

Atom Tunneling in the Water Formation Reaction H2 + OH → H2O + H on an Ice Surface

OH radicals play a key role as an intermediate in the water formation chemistry of the interstellar medium. For example the reaction of OH radicals with H$_2$ molecules is among the final steps in the astrochemical reaction network starting from O, O$_2$, and O$_3$. Experimentally it was shown that even at 10 K this reaction occurs on ice surfaces. As the reaction has a high activation energy only atom tunneling can explain such experimental findings. In this study we calculated reaction rate constants for the title reaction on a water-ice I$_h$ surface. To our knowledge, low-temperature rate constants on a surface are not available in the literature. All surface calculations were done using a QM/MM framework (BHLYP/TIP3P) after a thorough benchmark of different density functionals and basis sets to highly accurate correlation methods. Reaction rate constants are obtained using instanton theory which takes atom tunneling into account inherently, with constants down to 110 K for the Eley-Rideal mechanism and down to 60 K for the Langmuir-Hinshelwood mechanism. We found that the reaction is nearly temperature independent below 80 K. We give kinetic isotope effects for all possible deuteration patterns for both reaction mechanisms. For the implementation in astrochemical networks, we also give fit parameters to a modified Arrhenius equation. Finally, several different binding sites and binding energies of OH radicals on the I$_h$ surface are discussed and the corresponding rate constants are compared to the gas-phase case.

Theoretical study on the mechanism of the reaction of FOX-7 with OH and NO2 radicals: bimolecular reactions with low barrier during the decomposition of FOX-7

ABSTRACTThe decomposition of 1,1-diamino-2,2-dinitroethene (FOX-7) attracts great interests, while the studies on bimolecular reactions during the decomposition of FOX-7 are scarce. This study for the first time investigated the bimolecular reactions of OH and NO2 radicals, which are pyrolysis products of ammonium perchlorate (an efficient oxidant usually used in solid propellant), with FOX-7 by computational chemistry methods. The molecular geometries and energies were calculated using the (U)B3LYP/6-31++G(d,p) method. The rate constants of the reactions were calculated by canonical variational transition state theory. We found three mechanisms (H-abstraction, OH addition to C and N atom) for the reaction of OH + FOX-7 and two mechanisms (O abstraction and H abstraction) for the reaction of NO2 + FOX-7. OH radical can abstract H atom or add to C atom of FOX-7 with barriers near to zero, which means OH radical can effectively degrade FOX-7. The O abstraction channel of the reaction of NO2 + FOX-7 results in the formation of NO3 radical, which has never been detected experimentally during the decomposition of FOX-7.

Photodegradation and ecotoxicology of acyclovir in water under UV254 and UV254/H2O2 processes

The photochemical and ecotoxicological fate of acyclovir (ACY) through UV254 direct photolysis and in the presence of hydroxyl radicals (UV254/H2O2 process) were investigated in a microcapillary film (MCF) array photoreactor, which provided ultrarapid and accurate photochemical reaction kinetics. The UVC phototransformation of ACY was found to be unaffected by pH in the range from 4.5 to 8.0 and resembled an apparent autocatalytic reaction. The proposed mechanism included the formation of a photochemical intermediate (ϕACY = (1.62 ± 0.07)·10−3 mol ein−1) that further reacted with ACY to form by-products (k’ = (5.64 ± 0.03)·10−3 M−1 s−1). The photolysis of ACY in the presence of hydrogen peroxide accelerated the removal of ACY as a result of formation of hydroxyl radicals. The kinetic constant for the reaction of OH radicals with ACY (kOH/ACY) determined with the kinetic modeling method was (1.23 ± 0.07)·109 M−1 s−1 and with the competition kinetics method was (2.30 ± 0.11)·109 M−1 s−1 with competition kinetics. The acute and chronic effects of the treated aqueous mixtures on different living organisms (Vibrio fischeri, Raphidocelis subcapitata, D. magna) revealed significantly lower toxicity for the samples treated with UV254/H2O2 in comparison to those collected during UV254 treatment. This result suggests that the addition of moderate quantity of hydrogen peroxide (30–150 mg L−1) might be a useful strategy to reduce the ecotoxicity of UV254 based sanitary engineered systems for water reclamation.

Kinetics of gas phase OH radical reaction with thiophene in the 272–353 K temperature range: A laser induced fluorescence study

Absolute rate coefficient for the gas phase reaction of OH radical with thiophene has been measured using the laser photolysis (LP) – laser induced fluorescence (LIF) technique. The kinetics measurements were done over the temperature range of 272–353K and pressure range of 20–30Torr. The bimolecular rate coefficients obtained were pressure independent in the above pressure range and showed Arrhenius type behaviour which were fitted to the expression k(T)=(4.53±0.55)×10−12exp[(250±30)/T]cm3molecule−1s−1. The reaction shows weak negative temperature dependence. These results were discussed with available literature and the tropospheric lifetime of thiophene was calculated.

The OH-initiated oxidation of atmospheric peroxyacetic acid: Experimental and model studies

Peroxyacetic acid (PAA, CH3C(O)OOH) plays an important role in atmospheric chemistry, serving as reactive oxidant and affecting radical recycling. However, previous studies revealed an obvious gap between modelled and observed concentrations of atmospheric PAA, which may be partly ascribed to the uncertainty in the kinetics and mechanism of OH-oxidation. In this study, we measured the rate constant of OH radical reaction with PAA (kPAA+OH) and investigated the products in order to develop a more robust atmospheric PAA chemistry. Using the relative rates technique and employing toluene and meta-xylene as reference compounds, the kPAA+OH was determined to be (9.4–11.9) × 10−12 cm3 molecule−1 s−1 at 298 K and 1 atm, which is about (2.5–3.2) times larger than that parameter used in Master Chemical Mechanism v3.3.1 (MCM v3.3.1) (3.70 × 10−12 cm3 molecule−1 s−1). Incorporation of a box model and MCM v3.3.1 with revised PAA chemistry represented a better simulation of atmospheric PAA observed during Wangdu Campaign 2014, a rural site in North China Plain. It is found that OH-oxidation is an important sink of atmospheric PAA in this rural area, accounting for ∼30% of the total loss. Moreover, the major terminal products of PAA–OH reaction were identified as formaldehyde (HCHO) and formic acid (HC(O)OH). The modelled results show that both primary and secondary chemistry play an important role in the large HCHO and HC(O)OH formation under experimental conditions. There should exist the channel of methyl H-abstraction for PAA–OH reaction, which may also provide routes to HCHO and HC(O)OH formation.

Kinetics of the reactions of OH radicals with n-butyl, isobutyl, n-pentyl and 3-methyl-1-butyl nitrates

The kinetics of the reactions of n-butyl (BTN), isobutyl (IBN), n-pentyl (PTN) and 3-methyl-1-butyl (3M1BN) nitrates with OH radicals has been studied using a low pressure flow tube reactor combined with a quadrupole mass spectrometer. The rate constants of the title reactions were determined under pseudo-first order conditions from kinetics of OH consumption in high excess of the nitrates. The overall rate coefficients, kBTN = 1.0 × 10−13 (T/298)3.36 exp(838/T) (T = 288–500 K), kIBN = 2.8 × 10−14 (T/298)4.09 exp(1127/T) (T = 283–500 K), kPTN = 1.26 × 10−12 (T/298)4.56 exp(45/T) (T = 298–496 K) and k3M1BN = 8.47×10−14 (T/298)3.52 exp(1069/T) cm3molecule−1s−1 (T = 288–538 K) (with conservative 15% uncertainty), were determined at a total pressure of 1 Torr of helium. The yields of the carbonyl compounds, n-butanal (n-C3H7CHO) and isobutanal ((CH3)2CHCHO), resulting from the abstraction by OH of an α-hydrogen atom in n-butyl and isobutyl nitrates, followed by α-substituted alkyl radical decomposition, were determined at T = 300 K to be 0.10 ± 0.02 and 0.15 ± 0.03, respectively. The calculated tropospheric lifetimes of BTN, IBN, PTN and 3M1BN indicate that reaction of these nitrates with OH represents an important sink of these compounds in the atmosphere.

An Experimental Study of the Atmospheric Oxidation of a Biogenic Organic Compound (Methyl Jasmonate) in a Thin Water Film as in Fog or Aerosols

Experiments on the reactions of OH radicals in thin films of water were conducted in a photochemical reactor. The OH radical reactivity of a biogenic molecule (methyl jasmonate) was observed to be much larger in thin films of water than in the bulk aqueous phase. The pseudo-first order reaction rate was enhanced by an order of magnitude on a 38-micron film compared to the bulk liquid. However, the first order rate constant increased by 349%. This has implications in atmospheric systems like fog and mist which have large specific surface areas. The enhanced reactivity is attributable to both the partial solvation and faster diffusion at the air-water interface compared to the bulk liquid.

Highly Oxidized Second-Generation Products from the Gas-Phase Reaction of OH Radicals with Isoprene.

The gas-phase reaction of OH radicals with isoprene has been investigated in an atmospheric pressure flow tube at 293 ± 0.5 K with special attention to the second-generation products. Reaction conditions were optimized to achieve a predominant reaction of RO2 radicals with HO2 radicals. Chemical ionization-atmospheric pressure interface-time-of-flight mass spectrometry served as the analytical technique in order to follow the formation of RO2 radicals and closed-shell products containing at least four O atoms in the molecule. The reaction products were detected as adducts with the reagent ions using acetate, lactate, or nitrate in the ionization process. Observed signals were attributed to a series of C5-products with multiple hydroxy, hydroperoxy, and probably carbonyl groups. H/D exchange experiments supported the product identification. The generation of the detected second-generation products can be mechanistically explained starting from the OH radical reaction of hydroxy hydroperoxide isomers, HO-C5H8-OOH. These isomers represent the dominant products of the initial OH radical attack on isoprene. Dihydroxy dihydroperoxides, (HO)2-C5H8-(OOH)2, were analyzed as the main second-generation products beside the dihydroxy epoxides. A simple kinetic analysis revealed that the observed second-generation products in total (other than dihydroxy epoxides) were formed with an estimated molar yield of 10.0-1.5+2.1 % with respect to converted hydroxy hydroperoxides. A formation yield of 5.8-0.9+1.3 % has been deduced for the main product (HO)2-C5H8-(OOH)2. The detected, highly oxidized isoprene products represent potential secondary organic aerosol precursors. An annual, global (HO)2-C5H8-(OOH)2 formation strength of (16-35) × 106 metric tons is estimated based on product measurements of this study and literature data regarding the formation of the dihydroxy epoxide isomers for an annual isoprene emission of 454 × 106 metric tons of carbon.

Atmospheric Chemistry of 1H-Heptafluorocyclopentene (cyc-CF2CF2CF2CF═CH-): Rate Constant, Products, and Mechanism of Gas-Phase Reactions with OH Radicals, IR Absorption Spectrum, Photochemical Ozone Creation Potential, and Global Warming Potential.

The rate constant for gas-phase reactions of OH radicals with 1H-heptafluorocyclopentene (cyc-CF2CF2CF2CF═CH-) was measured using a relative rate method at 298 K: (5.20 ± 0.09) × 10-14 cm3 molecule-1 s-1. The quoted uncertainty includes two standard deviations from the least-squares regression, the systematic error from the GC analysis, and the uncertainties of the rate constants of the reference compounds. The OH-radical-initiated oxidation of cyc-CF2CF2CF2CF═CH- gives the main products COF2, CO, and CO2, leading to negligible environmental impact. For consumptions of cyc-CF2CF2CF2CF═CH- of less than 54%, the yield of the formation of ([COF2] + [CO] + [CO2])/5 (based on the conservation of carbon) was 0.99 ± 0.02, which is very close to 100%. A possible degradation mechanism was proposed. The radiative efficiency (RE) of cyc-CF2CF2CF2CF═CH- measured at room temperature was 0.215 W m-2 ppb-1. The atmospheric lifetime of cyc-CF2CF2CF2CF═CH- was calculated as 0.61 year, and the photochemical ozone creation potential (POCP) was negligible. The 20-, 100-, and 500-year time horizon global warming potentials (GWPs) were estimated as 153, 42, and 12, respectively.

Kinetics of the photolysis and OH reaction of 4-hydroxy-4-methyl-2-pentanone: Atmospheric implications

This study provides the first kinetic and mechanistic study of the photolysis of 4-hydroxy-4-methyl-2-pentanone (4H4M2P) and the determination of the temperature dependence of the relative rate coefficient for the reaction of OH radicals with 4H4M2P. The UV absorption spectrum of 4H4M2P was determined in the spectral range 200–360 nm. The photolysis frequency of this compound in the atmosphere was evaluated relative to actinometers and found to be J4H4M2Patm=4.2×10−3h−1, corresponding to a lifetime of about 10 days. Using 4H4M2P cross section measurements, an atmospheric effective quantum yield of 0.15 was calculated. The main primary photolysis products were acetone (121 ± 4) % and formaldehyde (20 ± 1) %. A low methanol yield of (3.0 ± 0.3) % was also determined. These results enabled us to propose a mechanistic scheme for the photolysis. Rate coefficients for the reaction of 4H4M2P with OH radicals were determined over the temperature range 298–354 K and the following Arrhenius expression was obtained: kOH+4M4H2P = (1.12 ± 0.40) × 10−12exp(461.5 ± 60/T) cm3 molecule−1 s−1. The lifetimes of 4H4M2P due to reaction with OH radicals has been estimated to ∼2.5 days and indicates that the gas-phase reaction with the OH could be the main loss process for this compound.

Atmospheric degradation of the organothiophosphate insecticide - Pirimiphos-methyl.

The gas phase atmospheric degradation of pirimiphos-methyl (a widely used organophosphate insecticide and acaricide in many European regions) has been investigated at the large outdoor European Photoreactor (EUPHORE) in Valencia, Spain. Its photolysis has been studied under sunlight conditions and its reaction rate constant with OH radicals was measured by the relative rate method. The reaction with ozone was also investigated. The tropospheric degradation of pirimiphos-methyl is controlled mainly by the OH radical reaction. The rate coefficient of the OH reaction with pirimiphos-methyl, k, was measured by a conventional relative rate technique, where aniline was taken as a reference. The resulting value of the OH reaction rate constant with pirimiphos-methyl was k=(1.14±0.2)×10-10cm3molecule-1s-1. The tropospheric lifetime of pirimiphos-methyl with respect to the reaction with OH radicals was estimated to be around 1.6h (283±10) K and atmospheric pressure. Significant aerosol formation was observed in the OH reaction with yields that ranged from 25 to 37%, and with particle diameters below 550nm. This therefore reveals a high human risk due to PM<1, without taking into account the chemical composition of the degradation products. SO2, glyoxal and other oxygenated and nitrogenated compounds were the main degradation products detected.

Rate Coefficients for the Reactions of OH Radicals with a Series of Alkyl-Substituted Amines.

Rate coefficients have been determined at (298 ± 2) K and atmospheric pressure for the reaction of OH radicals with two primary monoalkyl-, one secondary dialkyl-, and five tertiary trialkyl-substituted amines in a large volume photoreactor by the relative kinetic technique. The following rate coefficients (in cm3 molecule-1 s-1 units) have been obtained: (1) 1,2-dimethylpropylamine, CH3C(CH3)HC(CH3)H)NH2, (5.08 ± 1.02) × 10-11; (2) tert-amylamine (tert-pentylamine), CH3CH2C(CH3)2NH2, (0.86 ± 0.17) × 10-11; (3) diethylamine, (CH3CH2)2NH, (7.36 ± 1.47) × 10-11; (4) N,N-dimethylethylamine, (CH3)2NCH2CH3, (7.37 ± 1.47) × 10-11; (5) N,N-dimethylpropylamine, (CH3)2NCH2CH2CH3, (10.97 ± 1.78) × 10-11; (6) N,N-dimethylisopropylamine, (CH3)2NCH(CH3)2, (9.79 ± 1.75) × 10-11; (7) N,N-diethylmethylamine, (CH3CH2)2NCH3, (8.92 ± 1.54) × 10-11; (8) triethylamine, (CH3CH2)3N, (10.86 ± 1.88) × 10-11. The quoted errors are the 2σ deviations from least-squares linear analysis of the kinetic data plus a contribution to take into account uncertainties associated with the reference compounds. With the exception of diethylamine, this study represents the first determinations of the rate coefficients for reaction of the compounds with OH radicals. The results are compared with rate coefficients available in the literature for smaller alkyl-substituted amines and also the values predicted for the compounds investigated by using a structure activity relationship (SAR). With the exception of tert-amylamine, the SAR-predicted OH rate coefficients are in good agreement with the experimental values.

A high-temperature shock tube kinetic study for the branching ratios of isobutene + OH reaction

Isobutene is an important intermediate formed during the oxidation of branched alkanes. It also appears as a byproduct during the combustion of methyl-tert-butyl-ether (MTBE) which is used as octane enhancer in gasolines. To understand better the oxidation kinetics of isobutene, we have measured the rate coefficients for the reaction of OH radicals with isobutene (H2CC(CH3)2) behind reflected shock waves over the temperature range of 830–1289K and pressures near 1.5atm. The reaction progress was followed by measuring mole fraction of OH radicals near 306.7nm using UV laser absorption technique. Three deuterated isotopes, isobutene-1-d2 (D2CC(CH3)2), isobutene-3-d6 (H2CC(CD3)2) and isobutene-d8 (D2CC(CD3)2) were employed to elucidate branching ratios of the allylic and vinylic H-abstraction from isobutene by OH radicals. H-abstraction from the allylic sites was found to be dominant and constituted about 75% of the total rate in the entire temperature range of the current work. The derived three-parameter Arrhenius expressions for site-specific H- and D- abstraction rates over 830–1289K are (units:cm3mol−1s−1):k3,H=6.98×106(TK)1.77exp(−136.6KT)k3,D=4.42×106(TK)1.8exp(−361.7KT)k1,H=6.25×105(TK)2.16exp(−711.6KT)k1,D=3.13×107(TK)1.67exp(−1814KT)The subscript of k identifies the position of H or D atom in isobutene according to the IUPAC nomenclature of alkenes.

Quantum chemical study of the (Z)-2-penten-1-ol (HOCH2–CH = CHCH2CH3) + OH + O2 reactions

ABSTRACTThe mechanism and products of the reaction of (Z)-2-penten-1-ol [(Z)-PO21] with OH radical in the presence of O2 have been elucidated by using high-level quantum chemical methods CCSD(T)/6-311+G(d,p)//BH&HLYP/6-311++G(d,p). The calculations clearly indicate that addition channels contribute maximum to the total reaction and H-abstraction channels can be neglected at temperatures of 220–500 K. The rate constant for the reaction of OH radical with (Z)-PO21 at 298 K is computed to be 1.22 × 10−10 cm3 molecule−1 s−1, which is in stronger agreement with the previously reported experimental values. The kinetic data obtained over the temperature range 220−500 K are used to derive an non-Arrhenius expression: k = 3.69 × 10−13 × exp(1763.7/T) cm3 molecule−1 s−1. For the reaction of (Z)-PO21with OH radical in the presence of O2, the major primary reaction products found in this study are propanal [CH3CH2C(O)H] and glycolaldehyde [HOCH2C(O)H], whereas formaldehyde [HC(O)H], 2-hydroxybutanal [CH3CH2CH(OH)C(O)H] and the epoxide P18 are anticipated to be minor products. The calculated results are consistent with the recent experimental observations.

Atmospheric Chemistry of Tetrahydrofuran, 2-Methyltetrahydrofuran, and 2,5-Dimethyltetrahydrofuran: Kinetics of Reactions with Chlorine Atoms, OD Radicals, and Ozone.

FTIR smog chamber techniques were used to study the kinetics of the gas-phase reactions of Cl atoms, OD radicals, and O3 with the five-membered ring-structured compounds tetrahydrofuran (C4H8O, THF), 2-methyltetrahydrofuran (CH3C4H7O, 2-MTHF), 2,5-dimethyltetrahydrofuran ((CH3)2C4H5O, 2,5-DMTHF), and furan (C4H4O). The rate coefficients determined using relative rate methods were kTHF+Cl = (1.96 ± 0.24) × 10(-10), kTHF+OD = (1.81 ± 0.27) × 10(-11), kTHF+O3 = (6.41 ± 2.90) × 10(-21), k2-MTHF+Cl = (2.65 ± 0.43) × 10(-10), k2-MTHF+OD = (2.41 ± 0.51) × 10(-11), k2-MTHF+O3 = (1.87 ± 0.82) × 10(-20), k2,5-DMTHF+OD = (4.56 ± 0.68) × 10(-11), k2,5-DMTHF+Cl = (2.84 ± 0.34) × 10(-10), k2,5-DMTHF+O3 = (4.58 ± 2.18), kfuran+Cl = (2.39 ± 0.27) × 10(-10), and kfuran+O3 = (2.60 ± 0.31) × 10(-18) molecules cm(-3) s(-1). Rate coefficients of the reactions with ozone were also determined using the absolute rate method under pseudo-first-order conditions. OD radicals, in place of OH radicals, were produced from CD3ONO to avoid spectral overlap of isopropyl and methyl nitrite with the reactants. The kinetics of OD radical reactions are expected to resemble the kinetics of OH radical reactions, and the rate coefficients of the reactions with OD radicals were used to calculate the atmospheric lifetimes with respect to reactions with OH radicals. The lifetimes of THF, 2-MTHF, and 2,5-DMTHF are approximately 15, 12, and 6 h, respectively.

Ab Initio Theoretical Studies on the Kinetics of the Hydrogen Abstraction Reaction of Hydroxyl Radical with CH3CH2OCF2CHF2 (HFE-374pc2)

The hydrogen abstraction reaction of OH radical with CH3CH2OCF2CHF2 (HFE-374pc2) is investigated theoretically by semi-classical transition state theory. The stationary points on the potential energy surface of the reaction are located by using KMLYP density functional method along with 6-311++G(d,p) basis set. Vibrational anharmonicity coefficients, xij, required for semi-classical transition state theory calculations, are computed at the same level of theory. The geometries are re-optimized by M06-2X/6-31+G(d,p) level. Single-point energy calculations are carried out by the CBS-Q combination method. Thermal rate coefficients are computed over the temperature range 200-2000 K and they are shown to be in accordance with the available experimental data. On the basis of the computed rate coefficients, the atmospheric lifetime of HFE-374pc2 is estimated to be about 2 months.

Steam reforming of methane in a synthesis gas from biomass gasification

An experimental and modeling study of the pyrolysis and of the steam reforming of methane in mixtures representative of a gas produced from biomass gasification has been performed. The experimental study has been done in a plug flow reactor under a near atmospheric pressure (1.07 bar), for a residence time of 0.68 s and temperature ranging from 1200 up to 1800 K. Reactants and products were quantified on-line at the exit of the reactor by gas chromatography. The kinetic influence of the different gases present in the synthesis gas (H2O, H2, CO, CO2) on the methane conversion has been investigated. Water steam has shown a very limited impact on conversion, even at the highest temperature, while hydrogen exhibited a strong inhibiting effect on the reforming reaction. Carbon dioxide promoted slightly the reaction, unlike carbon monoxide, which had no kinetic effect. A temperature as high as 1700 K is necessary in these conditions to convert entirely methane. A model derived from that for the combustion of light hydrocarbons was developed with attention to the reactions of unsaturated species with hydroxyl radical OH, which are responsible for the reforming. The main experimental trends are well reproduced. Carbon reforming occurs mainly by reactions of OH radicals with unsaturated C2 molecules, which are soot precursors. Process conditions necessary for high temperature methane reforming would then be favorable to undesirable soot formation.