Temperature dependence of the reactions of HO2 with NO and NO2

Mixtures of N₂O, H₂, O₂, and trace amounts of NO and NO₂ were photolyzed at 213.9 nm, at 245°–328°K, and at about 1 atm total pressure (mostly H₂). HO₂ radicals are produced from the photolysis and they react as follows: Reaction (1b) is unimportant under all of our reaction conditions. Reaction (1a) was studied in competition with reaction (3) from which it was found that k_1a/k₃^1/2 = 6.4 × 10^?6 exp { z?(1400 ± 500)/RT} cm^3/2/sec^1/2. If k₃ is taken to be 3.3 × 10^?12 cm³/sec independent of temperature, k_1a = 1.2 × 10^?11 exp {?(1400 ± 500)/RT} cm³/sec. Reaction (2a) is negligible compared to reaction (2b) under all of our reaction conditions. The ratio k_2b/k₁ = 0.61 ± 0.15 at 245°K. Using the Arrhenius expression for k_1a given above leads to k_2b = 4.2 × 10^?13 cm³/sec, which is assumed to be independent of temperature. The intermediate HO₂NO₂ is unstable and induces the dark oxidation of NO through reaction (?2b), which was found to have a rate coefficient k_?2b = 6 × 10¹⁷ exp {?26,000/RT} sec^?1 based on the value of k_1a given above. The intermediate can also decompose via Reaction (10b) is at least partially heterogeneous.     

Constraining the mechanism and kinetics of OH + NO2 and HO2 + NO using the multiple-well master equation

Several recent experimental studies have provided substantial new constraints for the mechanisms on the HNO3 potential energy surface. These include observations of biexponential OH decay over short time scales from OH + NO2, which constrain key properties of the short-lived HOONO intermediate, observations of both conformers of the HOONO intermediate itself, isotopic scrambling data for 18OH + NO2, and observations of HONO2 production from the HO2 + NO reaction. We combine all of these recent data in a master-equation simulation of the system. This simulation is initialized with computational values for both stable species (wells) and transition states, but parameters are then adjusted to fit the observations. All parameters are kept within limits defined by experimental and theoretical uncertainty, and all converge away from their bounds. The primary fitting is carried out on the OH kinetic data-we first fit the biexponential kinetics, then address the isotopic scrambling. Isotopic scrambling is shown to be rapid but not complete at low pressure, while at least two parameter sets are shown to be consistent with the biexponential data. Of these two parameter sets, one is far more consistent with recent observations of trans-HOONO decay, isotopic scrambling, and HONO2 production from HO2 + NO. This we regard as the most probable potential energy surface for the reaction. On this PES, cis-trans isomerization for HOONO is slow but isomerization of trans-HOONO to HONO2 is rapid. This has significant implications for observed HOONO behavior and also HONO2 formation in the atmosphere from both HO2 + NO and OH + NO2.     

Reflected shock tube studies of high-temperature rate constants for OH + NO2 --> HO2 + NO and OH + HO2 --> H2O + O2

The motivation for the present study comes from the preceding paper where it is suggested that accepted rate constants for OH + NO2 --> NO + HO2 are high by approximately 2. This conclusion was based on a reevaluation of heats of formation for HO2, OH, NO, and NO2 using the Active Thermochemical Table (ATcT) approach. The present experiments were performed in C2H5I/NO2 mixtures, using the reflected shock tube technique and OH-radical electronic absorption detection (at 308 nm) and using a multipass optical system. Time-dependent profile decays were fitted with a 23-step mechanism, but only OH + NO2, OH + HO2, both HO2 and NO2 dissociations, and the atom molecule reactions, O + NO2 and O + C2H4, contributed to the decay profile. Since all of the reactions except the first two are known with good accuracy, the profiles were fitted by varying only OH + NO2 and OH + HO2. The new ATcT approach was used to evaluate equilibrium constants so that back reactions were accurately taken into account. The combined rate constant from the present work and earlier work by Glaenzer and Troe (GT) is k(OH+NO2) = 2.25 x 10(-11) exp(-3831 K/T) cm3 molecule(-1) s(-1), which is a factor of 2 lower than the extrapolated direct value from Howard but agrees well with NO + HO2 --> OH + NO2 transformed with the updated equilibrium constants. Also, the rate constant for OH + HO2 suitable for combustion modeling applications over the T range (1200-1700 K) is (5 +/- 3) x 10(-11) cm3 molecule(-1) s(-1). Finally, simulating previous experimental results of GT using our updated mechanism, we suggest a constant rate for k(HO2+NO2) = (2.2 +/- 0.7) x 10(-11) cm3 molecule(-1) s(-1) over the T range 1350-1760 K.     

对流层中的OH与HO2自由基的研究进展

OH与HO2自由基是大气中重要的氧化剂,研究它们的化学反应性质及对其进行实地测量,对深入理解大气氧化过程和了解区域乃至全球大气自净能力有重要意义.自工业革命以来,每年有数千万吨的自然和人为污染物进入对流层,这些物质会严重影响·OH的生成和消除,因此·OH的浓度可能在全球范围内发生大的变化.本文总结了国内外近年来有关·OH与HO2·的最新研究成果,目前比较一致的结论是由于人类活动的影响,全球·OH的浓度比工业革命前降低了.但是在一些污染地区,由于氮氧化合物对·OH的负反馈作用,一定程度上弥补了·OH的净损失.在最近20年中,·OH在对流层中的浓度基本稳定在106cm-3.本文还介绍了实验室研究方法及外场测量技术的进展,提出了尚待解决的一些问题.     

Multichannel RRKM-TST and CVT rate constant calculations for reactions of CH2OH or CH3O with HO2

The kinetics and mechanism of the gas-phase reactions between hydroxy methyl radical (CH(2)OH) or methoxy radical (CH(3)O) with hydroproxy radical (HO(2)) have been theoretically investigated on their lowest singlet and triplet surfaces. Our investigations indicate the presence of one deep potential well on the singlet surface of each of these systems that play crucial roles on their kinetics. We have shown that the major products of CH(2)OH + HO(2) system are HCOOH, H(2)O, H(2)O(2), and CH(2)O and for CH(3)O + HO(2) system are CH(3)OH and O(2). Multichannel RRKM-TST calculations have been carried out to calculate the individual rate constants for those channels proceed through the formation of activated adducts on the singlet surfaces. The rate constants for direct hydrogen abstraction reactions on the singlet and triplet surfaces were calculated by means of direct-dynamics canonical variational transition-state theory with small curvature approximation for the tunneling.     

Absolute rate constants for the self reactions of HO2, CF3CFHO2, and CF3O2 radicals and the cross reactions of HO2 with FO2, HO2 with CF3CFHO2, and HO2 with CF3O2 at 295 K

The kinetics of the self-reactions of HO₂, CF₃CFHO₂, and CF₃O₂ radicals and the cross reactions of HO₂ with FO₂, HO₂ with CF₃CFHO₂, and HO₂ with CF₃O₂ radicals, were studied by pulse radiolysis combined with time resolved UV absorption spectroscopy at 295 K. The rate constants for these reactions were obtained by computer simulation of absorption transients monitored at 220, 230, and 240 nm. The following rate constants were obtained at 295 K and 1000 mbar total pressure of SF₆ (unit: 10⁻¹² cm³ molecule⁻¹ s⁻¹): k(HO₂+HO₂)=3.5±1.0, k(CF₃CFHO₂+CF₃CFHO₂)=3.5±0.8, k(CF₃O₂+CF₃O₂)=2.25±0.30, k(HO₂+FO₂)=9±4, k(CF₃CFHO₂+HO₂)=5.0±1.5, and k(CF₃O₂+HO₂)=4.0±2.0. In addition, the decomposition rate of CF₃CFHO radicals was estimated to be (0.2–2)×10³ s⁻¹ in 1000 mbar of SF₆. Results are discussed in the context of the atmospheric chemistry of hydrofluorocarbons. © 1997 John Wiley & Sons, Inc.     

Direct determination of the rate constant of the reaction NO + HO2 → NO2 + OH with the LMR

The rate of the reaction was determined in an isothermal discharge flow reactor with a combined ESR–LMR detection under pseudo-first-order conditions in HO₂. The rate constant was identical in experiments with two different HO₂ sources: F + H₂O₂ and H + O₂ + M. The absolute rate constant at T = 293 K was measured as In the range 2 ≤ p mbar ≤ 17 no pressure dependence for k₁ was found.     

Ab initio calculations to the reactions of HF and HCl with Si(OH)4 and (HO)3SiOSi(OH)3: Modeling of SiO2 etching reactions

The local mechanisms of dissociative chemisorption and reactive etching are investigated by molecular models modeling ?SiOH groups and ?SiOSi? bridges at SiO₂ surfaces. The elementary reaction paths for the reactions of HF and HCl with Si? O bonds of the models, Si(OH)₄ and (HO)₃SiOSi(OH)₃, are calculated by the Hartree–Fock method. The local transition-state structures are nearly plane quadrangles with neighboring pentacoordinated silicon and tricoordinated oxygen atoms. For the reaction and activation energies, the electron correlation is considered by the Møller–Plesset perturbation theory. The results agree with experimental findings. © 1994 John Wiley & Sons, Inc.     

A systematic computational study on the reactions of HO2 with RO2: The HO2 + CH3O2(CD3O2) and HO2 + CH2FO2 reactions

A systematic theoretical study of the reactions of HO2 with RO2 has been carried out. The major concern of the present work is to gain insight into the reaction mechanism and then to explain experimental observations and to predict new product channels for this class of reactions of importance in the atmosphere. In this paper, the reaction mechanisms for two reactions, namely, HO2 + CH3O2 and HO2 + CH2FO2, are reported. Both singlet and triplet potential energy surfaces are investigated. The complexity of the present system makes it impossible to use a single ab initio method to map out all the reaction paths. Various ab initio methods including MP2, CISD, QCISD(T), CCSD(T), CASSCF, and density function theory (B3LYP) have been employed with the basis sets ranging from 6-31G(d) to an extrapolated complete basis set (CBS) limit. It has been established that the CCSD(T)/cc-pVDZ//B3LYP/6-311G(d,p) scheme represents the most feasible method for our systematic study. For the HO2 + CH3O2 reaction, the production of CH3OOH is determined to be the dominant channel. For the HO2 + CH2FO2 reaction, both CH2FOOH and CHFO are major products, whereas the formation of CHFO is dominant in the overall reaction. The computational findings give a fair explanation for the experimental observation of the products.     

Theoretical study on the kinetics of OH radical reactions with CH3OOH and CH3CH2OOH

The mechanisms and kinetics studies of the OH radical with alkyl hydroperoxides CH(3)OOH and CH(3)CH(2)OOH reactions have been carried out theoretically. The geometries and frequencies of all the stationary points are calculated at the UBHandHLYP/6-311G(d,p) level, and the energy profiles are further refined by interpolated single-point energies method at the MC-QCISD level of theory. For two reactions, five H-abstraction channels are found and five products (CH(3)OO, CH(2)OOH, CH(3)CH(2)OO, CH(2)CH(2)OOH, and CH(3)CHOOH) are produced during the above processes. The rate constants for the CH(3)OOH/CH(3)CH(2)OOH + OH reactions are corrected by canonical variational transition state theory within 250-1500 K, and the small-curvature tunneling is included. The total rate constants are evaluated from the sum of the individual rate constants and the branching ratios are in good agreement with the experimental data. The Arrhenius expressions for the reactions are obtained.     

Experimental and ab initio study of the HO2.CH3OH complex: thermodynamics and kinetics of formation

Near-infrared spectroscopy was used to monitor HO2 formed by pulsed laser photolysis of Cl2-O2-CH3OH-N2 mixtures. On the microsecond time scale, [HO2] exhibited a time dependence consistent with a mechanism in which [HO2] approached equilibrium via HO2 + HO2.CH3OH (3, -3). The equilibrium constant for reaction 3, K(p), was measured between 231 and 261 K at 50 and 100 Torr, leading to standard reaction enthalpy and entropy values (1 sigma) of delta(r) = -37.4 +/- 4.8 kJ mol(-1) and delta(r) = -100 +/- 19 J mol(-1) K(-1). The effective bimolecular rate constant, k3, for formation of the HO2.CH3OH complex is .10(-15).exp[(1800 +/- 500)/T] cm3 molecule(-1) s(-1) at 100 Torr (1 sigma). Ab initio calculations of the optimized structure and energetics of the HO2.CH3OH complex were performed at the CCSD(T)/6-311++G(3df,3pd)//MP2(full)/6-311++G(2df,2pd) level. The complex was found to have a strong hydrogen bond (D(e) = 43.9 kJ mol(-1)) with the hydrogen in HO2 binding to the oxygen in CH3OH. The calculated enthalpy for association is delta(r) = -36.8 kJ mol(-1). The potentials for the torsion about the O2-H bond and for the hydrogen-bond stretch were computed and 1D vibrational levels determined. After explicitly accounting for these degrees of freedom, the calculated Third Law entropy of association is delta(r) = -106 J mol(-1) K(-1). Both the calculated enthalpy and entropy of association are in reasonably good agreement with experiment. When combined with results from our previous study (Christensen et al. Geophys. Res. Lett. 2002, 29; doi:10.1029/2001GL014525), the rate coefficient for the reaction of HO2 with the complex, HO2 + HO2.CH3OH, is determined to be (2.1 +/- 0.7) x 10(-11) cm3 molecule(-1) s(-1). The results of the present work argue for a reinterpretation of the recent measurement of the HO2 self-reaction rate constant by Stone and Rowley (Phys. Chem. Chem. Phys. 2005, 7, 2156). Significant complex concentrations are present at the high methanol concentrations used in that work and lead to a nonlinear methanol dependence of the apparent rate constant. This nonlinearity introduces substantial uncertainty in the extrapolation to zero methanol.     

Theoretical study of reactions of N2O with NO and OH radicals

The reactions of N₂O with NO and OH radicals have been studied using ab initio molecular orbital theory. The energetics and molecular parameters, calculated by the modified Gaussian-2 method (G2M), have been used to compute the reaction rate constants on the basis of the TST and RRKM theories. The reaction N₂O + NO → N₂ + NO₂ (1) was found to proceed by direct oxygen abstraction and to have a barrier of 47 kcal/mol. The theoretical rate constant, k₁ = 8.74 × 10⁻¹⁹ × T^2.23 exp (−23,292/T) cm³ molecule⁻¹ s⁻¹, is in close agreement with earlier estimates. The reaction of N₂O with OH at low temperatures and atmospheric pressure is slow and dominated by association, resulting in the HONNO intermediate. The calculated rate constant for 300 K ≤ T ≤ 500 K is lower by a few orders than the upper limits previously reported in the literature. At temperatures higher than 1000 K, the N₂O + OH reaction is dominated by the N₂ + O₂H channel, while the HNO + NO channel is slower by 2–3 orders of magnitude. The calculated rate constants at the temperature range of 1000–5000 K for N₂O + OH → N₂ + O₂H (2A) and N₂O + OH → HNO + NO (2B) are fitted by the following expressions: in units of cm³ molecule ⁻¹s⁻¹. Both N₂O + NO and N₂O + OH reactions are confirmed to enhance, albeit inefficiently, the N₂O decomposition by reducing its activation energy. © 1996 John Wiley & Sons, Inc.     

Water-catalyzed gas-phase hydrogen abstraction reactions of CH3O2 and HO2 with HO2: a computational investigation

The gas-phase hydrogen abstraction reactions of CH(3)O(2) and HO(2) with HO(2) in the presence and absence of a single water molecule have been studied at the CCSD(T)/6-311++G(3d,2p)//B3LYP/6-311G(2d,2p) level of theory. The calculated results show that the process for O(3) formation is much faster than that for (1)O(2) and (3)O(2) formation in the water-catalyzed CH(3)O(2) + HO(2) reaction. This is different from the results for the non-catalytic reaction of CH(3)O(2) + HO(2), in which almost only the process for (3)O(2) formation takes place. Unlike CH(3)O(2) + HO(2) reaction in which the preferred process is different in the catalytic and non-catalytic conditions, the channel for (3)O(2) formation is the dominant in both catalytic and non-catalytic HO(2) + HO(2) reactions. Furthermore, the calculated total CVT/SCT rate constants for water-catalyzed and non-catalytic title reactions show that the water molecule doesn't contribute to the rate of CH(3)O(2) + HO(2) reaction though the channel for O(3) formation in this water-catalyzed reaction is more kinetically favorable than its non-catalytic process. Meanwhile, the water molecule plays an important positive role in increasing the rate of HO(2) + HO(2) reaction. These results are in good agreement with available experiments.     

Some observations on the kinetics and thermochemistry of the reactions of HO2 radicals with aldehydes and ketones

The rapid, gas phase equilibrium addition of HO₂ radicals to CH₂O to form the peroxy radical HOCH₂OO^? is in agreement with the known thermochemistry of these species. The recent study of the similar addition of HO₂^? to ketones shows no significant reaction, which is again in agreement with known thermochemistry. All these reactions are notable for significant dipole attraction between the reactants ranging from 3 to 7 kcal/mol. The thermochemistry shows that the hydroperoxyl alkoxy species, the primary possible adduct, is not favored by the free energy change for direct addition. This and the observed kinetics favor a concerted addition, H‐atom transfer, as the transition state for the reactions. Kinetic estimates for forward and reverse reactions are in good agreement with observations. A thermochemical examination of the step‐wise addition of HO₂^? to the carbonyl shows that the reaction proceeds through a concerted, cyclic transition state involving simultaneous H‐transfer, 3 + 2 cyclo‐addition of HO₂^? to the carbonyl group. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 509–512, 2001     

Gas-phase reactions of azulene with OH and NO3 radicals and O3 at 298 ± 2 K

Azulene, which is isomeric with naphthalene, was studied to determine whether it behaves like a polycyclic aromatic hydrocarbon or an alkene in its gas-phase reactions with OH and NO₃ radicals and O₃. Using relative rate methods, rate constants for the reactions of azulene with OH and NO₃ radicals and O₃ of (2.73 ± 0.56) × 10^?10 cm³ molecule^?1 s^?1, (3.9) × 10^?10 cm³ molecule^?1 s^?1, and <7 × 10^?17 cm³ molecule^?1 s^?1, respectively, were obtained at 298 ± 2 K. The observation that the NO₃ radical reaction did not involve NO₂ in the rate determining step indicates that azulene behaves more like an alkene than a polycyclic aromatic hydrocarbon in this reaction. No conclusive evidence for the formation of nitroazulene(s) from either the OH or NO₃ radical-initiated reaction of azulene (in the presence of NO_x) was obtained.     

Pressure-dependent OH yields in alkene + HO2 reactions: a theoretical study

The major bimolecular product of alkyl + O(2) reactions is alkene + hydroperoxyl radical (HO(2)), but in the reverse direction, the reactants are reformed to a very limited extent only. The most important products of the alkene + HO(2) reactions are alkylperoxy radical (ROO(?)), hydroxyl radical (OH) + cyclic ether, and the corresponding hydroperoxyalkyl ((?)QOOH) species. Moreover, abstraction of allylic hydrogens can compete with the addition, further complicating the possible outcome of this reaction type and its effect on low-temperature combustion chemistry. In this paper, six alkene + HO(2) reactions and the reaction between an unsaturated oxygenate and HO(2) are studied based on previously established potential energy surfaces. The studied unsaturated compounds are ethene, propene, 1-butene, trans-2-butene, isobutene, cyclohexene, and vinyl alcohol. Using multiwell master equations, temperature- (300-1200 K) and pressure-dependent rate coefficients and branching fractions are calculated for these reactions. The importance of this reaction type for the combustion of unsaturated compounds is also assessed, and we show that, to get reliable results, it is important to include the pressure-dependence of the rate coefficients in the calculations.     

UV absorption spectra of HO2 and CH3O2 radicals and the kinetics of their mutual reactions at 298 K

We report results of a flash photolysis study of the UV, spectra of HO₂ and CH₃O₂ radicals, obtained by using a calibration technique based on the reaction Cl+NO→NOCl. We also report preliminary results from our study of the kinetics of the reaction CH₃O₂+HO₂→products at room temperature and near atmospheric pressure. Our results are consistent with the only previous direct determination of the rate constant of the second reaction: k₁ = (6.4 ± 1.0) × 10⁻¹²cm₃ molecule⁻ s⁻¹. From the same study we derive rate constants for the self-reaction of HO₂ and CH₃O₂ radicals, which agree with recommended values.     

Kinetics and products of the gas-phase reactions of divinyl sulfoxide with OH and NO3 radicals and O3

Using relative rate methods, rate constants for the gas-phase reactions of divinyl sulfoxide [CH 2CHS(O)CHCH 2; DVSO] with NO 3 radicals and O 3 have been measured at 296 +/- 2 K, and rate constants for the reaction with OH radicals have been measured over the temperature range of 277-349 K. Rate constants obtained for the NO 3 radical and O 3 reactions at 296 +/- 2 K were (6.1 +/- 1.4) x 10 (-16) and (4.3 +/- 1.0) x 10 (-19) cm (3) molecule (-1) s (-1), respectively. For the OH radical reaction, the temperature-dependent rate expression obtained was k = 4.17 x 10 (-12)e ((858 +/- 141)/ T ) cm (3) molecule (-1) s (-1) with a 298 K rate constant of (7.43 +/- 0.71) x 10 (-11) cm (3) molecule (-1) s (-1), where, in all cases, the errors are two standard deviations and do not include the uncertainties in the rate constants for the reference compounds. Divinyl sulfone was observed as a minor product of both the OH radical and NO 3 radical reactions at 296 +/- 2 K. Using in situ Fourier transform infrared spectroscopy, CO, CO 2, SO 2, HCHO, and divinyl sulfone were observed as products of the OH radical reaction, with molar formation yields of 35 +/- 11, 2.2 +/- 0.8, 33 +/- 4, 54 +/- 6, and 5.4 +/- 0.8%, respectively, in air. For the experimental conditions employed, aerosol formation from the OH radical-initiated reaction of DVSO in the presence of NO was minor, being approximately 1.5%. The data obtained here for DVSO are compared with literature data for the corresponding reactions of dimethyl sulfoxide.     

UV absorption spectrum of CF3CFClO2 and kinetics of the self reaction of CF3CFCl and CF3CFClO2 and the reactions of CF3CFClO2 with NO and NO2

The ultraviolet absorption spectrum of CF₃CFClO₂ and the kinetics of the self reactions of CF₃CFCl and CF₃CFClO₂ radicals and the reactions of CF₃CFClO₂ with NO and NO₂ have been studied in the gas phase at 295 K by pulse radiolysis/transient UV absorption spectroscopy. The UV absorption cross section of CF₃CFCl radicals was measured to be (1.78 ± 0.22) × 10^?18 cm² molecule^?1 at 220 nm. The UV spectrum of CF₃CFClO₂ radicals was quantified from 220 nm to 290 nm. The absorption cross section at 250 nm was determined to be (1.67 ± 0.21) × 10^?18 cm² molecule^?1. The rate constants for the self reactions of CF₃CFCl and CF₃CFClO₂ radicals were (2.6 ± 0.4) × 10^?12 cm³ molecule^?1 s^?1 and (2.6 ± 0.5) × 10^?12 cm³ molecule^?1 s^?1, respectively. The reactivity of CF₃CFClO₂ radicals towards NO and NO₂ was determined to (1.5 ± 0.6) × 10^?11 cm³ molecule^?1 s^?1 and (5.9 ± 0.5) × 10^?12 cm³ molecule^?1 s^?1, respectively. Finally, the rate constant for the reaction of F atoms with CF₃CFClH was determined to (8 ± 2) × 10^?13 cm³ molecule^?1 s^?1. Results are discussed in the context of the atmospheric chemistry of HCFC-124, CF₃CFClH. © 1994 John Wiley & Sons, Inc.     

Kinetics of the reaction HO2 + NO2(+M) = HO2NO2 using molecular modulation spectrometry

Rate constants for the reaction HO₂ + NO₂(+ M) = HO₂NO₂(+ M) have been obtained from direct observations of the HO₂ radical using the technique of molecular modulation ultraviolet spectrometry. HO₂ was generated by periodic photolysis of Cl₂ in the presence of excess H₂ and O₂, and k₁ was determined from the measured concentrations and lifetime of HO₂ with NO₂ present. k₁ increased with pressure in the range of 40–600 Torr, and a simple energy transfer model gave the following limiting second- and third-order rate constants at 283 K: k₁^∞ = 1.5 ± 0.5 × 10^?12 cm³/molec·sec and k₁^III = 2.5 ± 0.5 × 10^?31 cm⁶/molec·sec. The ultraviolet absorption spectrum of peroxynitric acid was also recorded in the range of 195–265 nm; it showed a broad feature with a maximum at 200 nm, σ_max = 4.4 × 10^?18 cm².