Direct measurements of the rate constants of the reactions NCN + NO and NCN + NO2 behind shock waves

The high-temperature rate constants of the reactions NCN + NO and NCN + NO(2) have been directly measured behind shock waves under pseudo-first-order conditions. NCN has been generated by the pyrolysis of cyanogen azide (NCN(3)) and quantitatively detected by sensitive difference amplification laser absorption spectroscopy at a wavelength of 329.1302 nm. The NCN(3) decomposition initially yields electronically excited (1)NCN radicals, which are subsequently transformed to the triplet ground state by collision-induced intersystem crossing (CIISC). CIISC efficiencies were found to increase in the order of Ar < NO(2) < NO as the collision gases. The rate constants of the NCN + NO/NO(2) reactions can be expressed as k(NCN+NO)/(cm(3) mol(-1)s(-1)) = 1.9 × 10(12) exp[-26.3 (kJ/mol)/RT] (±7%,ΔE(a) = ± 1.6 kJ/mol, 764 K < T < 1944 K) and k(NCN+NO(2))/(cm(3) mol(-1)s(-1)) = 4.7 × 10(12) exp[-38.0(kJ/mol)/RT] (±19%,ΔE(a) = ± 3.8 kJ/mol, 704 K < T < 1659 K). In striking contrast to reported low-temperature measurements, which are dominated by recombination processes, both reaction rates show a positive temperature dependence and are independent of the total density (1.7 × 10(-6) mol/cm(3) < ρ < 7.6 × 10(-6) mol/cm(3)). For both reactions, the minima of the total rate constants occur at temperatures below 700 K, showing that, at combustion-relevant temperatures, the overall reactions are dominated by direct or indirect abstraction pathways according to NCN + NO → CN + N(2)O and NCN + NO(2) → NCNO + NO.     

Kinetics of the NCN + NO reaction over a broad temperature and pressure range

Rate coefficients for the reaction (3)NCN + NO → products (R3) were measured in the temperature range 251-487 K at pressures from 10 mbar up to 50 bar with helium as the bath gas. The experiments were carried out in slow-flow reactors by using pulsed excimer laser photolysis of NCN(3) at 193 or 248 nm for the production of NCN. Pseudo-first-order conditions ([NCN](0) ? NO) were applied, and NCN was detected time-resolved by resonant laser-induced fluorescence excited near 329 nm. The measurements at the highest pressures yielded values of k(3) ～ 8 × 10(-12) cm(3) s(-1) virtually independent of temperature and pressure, which indicates a substantially smaller high-pressure limiting value of k(3) than predicted in earlier works. Our experiments at pressures below 1 bar confirm the negative temperature and positive pressure dependence of the rate coefficient k(3) found in previous investigations. The falloff behavior of k(3) was rationalized by a master equation analysis based on a barrierless association step (3)NCN + NO ? NCNNO((2)A″) followed by a fast internal conversion NCNNO((2)A″) ? NCNNO((2)A'). From 251-487 K and above 30 mbar, the rate coefficient k(3) is well represented by a Troe parametrization for a recombination/dissociation reaction, k(3)(T,P) = k(4)(∞)k(4)(0)[M]F(k(4)(0)[M] + k(4)(∞))(-1), where k(4) represents the rate coefficient for the recombination reaction (3)NCN + NO. The following parameters were determined (30% estimated error of the absolute value of k(3)): k(4)(0)[M=He] = 1.91 × 10(-30)(T/300 K)(-3.3) cm(6) s(-1)[He], k(4)(∞) = 1.12 × 10(-11) exp(-23 K/T) cm(3) s(-1), and F(C) = 0.28 exp(173 K/T).     

Rate coefficients and equilibrium constant for the CH2CHO + O2 reaction system

The kinetics of the CH2CHO + O2 reaction was experimentally studied in two quasi-static reactors and a discharge flow-reactor at temperatures ranging from 298 to 660 K and pressures between 1 mbar and 46 bar with helium as the bath gas. The CH2CHO radicals were produced by the laser-flash photolysis of ethyl vinyl ether at 193 nm and by the reaction F + CH3CHO, respectively. Laser-induced fluorescence excited at 337 or 347.4 nm was used to monitor the CH2CHO concentration. The reaction proceeded via reversible complex formation with subsequent isomerization and fast decomposition: CH2CHO + O2 <= => O2CH2CHO --> HO2CH2CO --> products. The rate coefficients for the first and second steps were determined (k1, k-1, k2) and analyzed by a master equation with specific rate coefficients from the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. Molecular and transition-state parameters were obtained from quantum chemical calculations. A third-law analysis led to the following thermodynamic parameters for the first step: Delta(R)S degrees 300K(1) = -144 J K(-1) mol(-1) (1 bar) and Delta(R)H degrees 300K(1) = (-101 +/- 4) kJ mol(-1). From the falloff analysis, the following temperature dependencies for the low- and high-pressure limiting rate coefficients were obtained: k1(0) = 5.14 x 10(-14) exp(210 K/T) cm(-3) s(-1); k1(infinity) = 1.7 x 10(-12) exp(-520 K/T) cm(-3) s(-1); and k2(infinity) = 1.3 x 10(12) exp[-(82 +/- 4) kJ mol(-1)/RT] s(-1). Readily applicable analytical representations for the pressure and temperature dependence of k1 were derived to be used in kinetic modeling.     

Thermal decomposition of NCN(3) as a high-temperature NCN radical source: singlet-triplet relaxation and absorption cross section of NCN((3)Σ)

The potential of the thermal decomposition of cyanogen azide (NCN3) as a high-temperature cyanonitrene (NCN) source has been investigated in shock tube experiments. Electronic ground-state NCN(3Σ) radicals have been detected by narrow-bandwidth laser absorption at overlapping transitions belonging to the Q1 branch of the vibronic 3Σ+?3Π subband of the vibrationally hot 3Πu(010)?3Σg?(010) system at = 30383.11 cm(-1) (329.1302 nm). High-temperature absorption cross sections σ have been directly measured at total pressures of 0.2?2.5 bar, log[σ/(cm2 mol(-1))] = 8.9?8.3 × 10(-4) × T/K (±25%, 750 < T < 2250 K). At these high temperatures, NCN(3Σ) formation is limited by a slow electronic relaxation of the initially formed excited NCN(1Δ) radical rather than thermal decomposition of NCN3. Measured temperature-dependent collision-induced intersystem crossing (CIISC) rate constants are best represented by kCIISC/(cm3 mol(-1) s(-1)) = (1.3 ± 0.5) × 1011 exp[?(21 ± 4) kJ/mol/RT] (740 < T < 1260 K). Nevertheless, stable NCN concentration plateaus have been observed, showing that NCN3 is an ideal precursor for NCN kinetic experiments behind shock waves.     

Atmospheric chemistry of ethyl propionate

Ethyl propionate is a model for fatty acid ethyl esters used as first-generation biodiesel. The atmospheric chemistry of ethyl propionate was investigated at 980 mbar total pressure. Relative rate measurements in 980 mbar N(2) at 293 ± 0.5 K were used to determine rate constants of k(C(2)H(5)C(O)OC(2)H(5) + Cl) = (3.11 ± 0.35) × 10(-11), k(CH(3)CHClC(O)OC(2)H(5) + Cl) = (7.43 ± 0.83) × 10(-12), and k(C(2)H(5)C(O)OC(2)H(5) + OH) = (2.14 ± 0.21) × 10(-12) cm(3) molecule(-1) s(-1). At 273-313 K, a negative Arrhenius activation energy of -3 kJ mol(-1) is observed.. The chlorine atom-initiated oxidation of ethyl propionate in 980 mbar N(2) gave the following products (stoichiometric yields): ClCH(2)CH(2)C(O)OC(2)H(5) (0.204 ± 0.031), CH(3)CHClC(O)OC(2)H(5) (0.251 ± 0.040), and C(2)H(5)C(O)OCHClCH(3) (0.481 ± 0.088). The chlorine atom-initiated oxidation of ethyl propionate in 980 mbar of N(2)/O(2) (with and without NO(x)) gave the following products: ethyl pyruvate (CH(3)C(O)C(O)OC(2)H(5)), propionic acid (C(2)H(5)C(O)OH), formaldehyde (HCHO), and, in the presence of NO(x), PAN (CH(3)C(O)OONO(2)). The lack of acetaldehyde as a product suggests that the CH(3)CH(O)C(O)OC(2)H(5) radical favors isomerization over decomposition. From the observed product yields, we conclude that H-abstraction by chlorine atoms from ethyl propionate occurs 20.4 ± 3.1%, 25.1 ± 4.0%, and 48.1 ± 8.8% from the CH(3)-, -CH(2)-, and -OCH(2)- groups, respectively. The rate constant and branching ratios for the reaction between ethyl propionate and the OH radical were investigated theoretically using quantum mechanical calculations and transition state theory. The stationary points along the reaction path were optimized using the CCSD(T)-F12/VDZ-F12//BH&HLYP/aug-cc-pVTZ level of theory; this model showed that OH radicals abstract hydrogen atoms primarily from the -OCH(2)- group (80%).     

Kinetics and mechanism of the NCN + NO2 reaction studied by experiment and theory

The rate constant for the NCN + NO 2 reaction has been measured by a laser photolysis/laser-induced fluorescence technique in the temperature range of 260-296 K at pressures between 100 and 500 Torr with He and N 2 as buffer gases. The NCN radical was produced from the photolysis of NCN 3 at 193 nm and monitored by laser-induced fluorescence with a dye laser at 329.01 nm. The rate constant was found to increase with pressure but decrease with temperature, indicating that the reaction occurs via a long-lived intermediate stabilized by collisions with buffer gas. The reaction mechanism and rate constant are also theoretically predicted for the temperature range of 200-2000 K and the He and N 2 pressure range of 10 (-4) Torr to 1000 atm based on dual-channel Rice-Ramsperger-Kassel-Marcus (RRKM) theory with the potential energy surface evaluated at the G2M//B3LYP/6-311+G(d) level. In the low-temperature range (<700 K), the most favorable reaction is the barrierless association channel that leads to the intermediate complex (NCN-NO 2). At high temperature, the direct O-abstraction reaction with a barrier of 9.8 kcal/mol becomes the dominant channel. The rate constant calculated by RRKM theory agrees reasonably well with experimental data.     

Shock Tube Measurements of the Rate Constant of the Reaction NCN + O2

The rate constant of the comparably slow bimolecular NCN radical reaction NCN + O₂ has been measured for the first time under combustion relevant conditions using the shock tube method. The thermal decomposition of cyanogen azide (NCN₃) served as a clean high‐temperature source of NCN radicals. NCN concentration–time profiles have been detected by narrow‐bandwidth laser absorption at cm^?1. The experiments behind incident shock waves have been performed with up to 17% O₂ in the reaction gas mixture. At such high O₂ mole fractions, it was necessary to take O₂ relaxation into account that caused a gradual decrease of the temperature during the experiment. Moreover, following fast decomposition of NCN₃ and collision‐induced intersystem crossing of the initially formed singlet NCN to its triplet ground state, an unexpected and slow additional formation of triplet NCN has been observed on a 100‐μs timescale. This delayed NCN formation was attributed to a fast recombination of ¹NCN with O₂ forming a ³NCNOO adduct acting as a reservoir species for NCN. Rate constant data for the reaction NCN + O₂ have been measured at temperatures between 1674 and 2308 K. They are best represented by the Arrhenius expression . No pressure dependence has been observed at pressures between 216 and 706 mbar.     

Thermal decomposition of ClOOCl

ClOOCl was prepared in situ in a temperature controlled photoreactor (v = 420 L) by photolyzing OClO/N2 mixtures in the wavelength range 300-500 nm at temperatures between 242 and 261 K and total pressures between 2 and 480 mbar. After switching off the lights, excess NO2 was added, and IR and UV spectra were monitored simultaneously as a function of time. By spectral stripping of all other known UV absorbers (in particular, other chlorine oxides and chlorine nitrate), we determined rate constants k-1 of the reaction ClOOCl (+M) --> ClO + ClO (+M) from the first-order decay of the residual UV absorption of ClOOCl at 246 and 255 nm. k-1,0 = [N2] x 7.6 x 10(-9) exp[(-53.6 +/- 6.0) kJ mol(-1)/RT] cm3 molecule(-1) s(-1) (2sigma) was derived for the low-pressure limiting rate constant. Application of Troe's expression for the limiting low-pressure rate constants of unimolecular decomposition reactions leads to E0 = Delta(r)H0(0)(ClOOCl-->ClO+ClO) = 66.4 +/- 3.0 kJ mol(-1). k-1,0 started to fall off from the pressure proportional low pressure behavior at p approximately 30 mbar; however, reliable extrapolation to the high pressure limit was not possible. The decomposition rate constants of ClOOCl were directly measured for the first time, and they are higher, depending on temperature and pressure, by factors between 1.5 and 4.2 as compared to experimental data on k-1 by Nickolaisen et al. [J. Phys. Chem. 1994, 98, 155] which were derived from the approach of ClO to thermal equilibrium with its dimer ClOOCl. Combination of the present dissociation rate constants with recommended temperature and pressure dependent data on the reverse reaction (k1) demonstrate inconsistencies between the dissociation and recombination rate constants. Summarizing laboratory data on k1 and k-1 above 250 K and field measurements on the ClO + ClO <= => ClOOCl equilibrium in the nighttime polar stratosphere close to 200 K, the expression Kc = k1/k-1 = 3.0 x 10(-27) exp(8433 K/T) cm3 molecule(-1) is derived for the temperature range 200-300 K.     

Predicted thermochemistry and unimolecular kinetics of nitrous sulfide

The geometry of N(2)S was obtained at the CCSD(T)/aug-cc-pV(T + d)Z level of theory and energies with coupled-cluster single double triple (CCSD(T)) and basis sets up to aug-cc-pV(6 + d)Z. After correction for anharmonic zero-point energy, core-valence correlation, correlation up to CCSDT(Q) and relativistic effects, D(0) for the N-S bond is estimated as 71.9 kJ mol(-1), and the corresponding thermochemistry for N(2)S is Δ(f)H(0)(°)=205.4 kJ mol(-1) and Δ(f)H(298)(°)=202.6 kJ mol(-1) with an uncertainty of ±2.5 kJ mol(-1). Using CCSD(T)/aug-cc-pV(T + d) theory the minimum energy crossing point between singlet and triplet potential energy curves is found at r(N-N) ≈ 1.105 ? and r(N-S) ≈ 2.232 ?, with an energy 72 kJ mol(-1) above N(2) + S((3)P). Application of Troe's unimolecular formalism yields the low-pressure-limiting rate constant for dissociation of N(2)S k(0) = 7.6 × 10(-10) exp(-126 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 700-2000 K. The estimated uncertainty is a factor of 4 arising from unknown parameters for energy transfer between N(2)S and Ar or N(2) bath gas. The thermochemistry and kinetics were included in a mechanism for CO/H(2)/H(2)S oxidation and the conclusion is that little NO is produced via subsequent chemistry of NNS.     

Kinetics of elementary steps in the reactions of atomic bromine with isoprene and 1,3-butadiene under atmospheric conditions

Laser flash photolysis of CF(2)Br(2) has been coupled with time-resolved detection of atomic bromine by resonance fluorescence spectroscopy to investigate the gas-phase kinetics of early elementary steps in the Br-initiated oxidations of isoprene (2-methyl-1,3-butadiene, Iso) and 1,3-butadiene (Bu) under atmospheric conditions. At T ≥ 526 K, measured rate coefficients for Br + isoprene are independent of pressure, suggesting that hydrogen transfer (1a) is the dominant reaction pathway. The following Arrhenius expression adequately describes all kinetic data at 526 K ≤ T ≤ 673 K: k(1a)(T) = (1.22 ± 0.57) × 10(-11) exp[(-2100 ± 280)/T] cm(3) molecule(-1) s(-1) (uncertainties are 2σ and represent precision of the Arrhenius parameters). At 271 K ≤ T ≤ 357 K, kinetic evidence for the reversible addition reactions Br + Iso ? Br-Iso (k(1b), k(-1b)) and Br + Bu ? Br-Bu (k(3b), k(-3b)) is observed. Analysis of the approach to equilibrium data allows the temperature- and pressure-dependent rate coefficients k(1b), k(-1b), k(3b), and k(-3b) to be evaluated. At atmospheric pressure, addition of Br to each conjugated diene occurs with a near-gas-kinetic rate coefficient. Equilibrium constants for the addition/dissociation reactions are obtained from k(1b)/k(-1b) and k(3b)/k(-3b), respectively. Combining the experimental equilibrium data with electronic structure calculations allows both second- and third-law analyses of thermochemistry to be carried out. The following thermochemical parameters for the addition reactions 1b and 3b at 0 and 298 K are obtained (units are kJ mol(-1) for Δ(r)H and J mol(-1) K(-1) for Δ(r)S; uncertainties are accuracy estimates at the 95% confidence level): Δ(r)H(0)(1b) = -66.6 ± 7.1, Δ(r)H(298)(1b) = -67.5 ± 6.6, and Δ(r)S(298)(3b) = -93 ± 16; Δ(r)H(0)(3b) = -62.4 ± 9.0, Δ(r)H(298)(3b) = -64.5 ± 8.5, and Δ(r)S(298)(3b) = -94 ± 20. Examination of the effect of added O(2) on Br kinetics under conditions where reversible adduct formation is observed allows the rate coefficients for the Br-Iso + O(2) (k(2)) and Br-Bu + O(2) (k(4)) reactions to be determined. At 298 K, we find that k(2) = (3.2 ± 1.0) × 10(-13) cm(3) molecule(-1) s(-1) independent of pressure (uncertainty is 2σ, precision only; pressure range is 25-700 Torr) whereas k(4) increases from 3.2 to 4.7 × 10(-13) cm(3) molecule(-1) s(-1) as the pressure increases from 25 to 700 Torr. Our results suggest that under atmospheric conditions, Br-Iso and Br-Bu react with O(2) to produce peroxy radicals considerably more rapidly than they undergo unimolecular decomposition. Hence, the very fast addition reactions appear to control the rates of Br-initiated formation of Br-Iso-OO and Br-Bu-OO radicals under atmospheric conditions. The peroxy radicals are relatively weakly bound, so conjugated diene regeneration via unimolecular decomposition reactions, though unimportant on the time scale of the reported experiments (milliseconds), is likely to compete effectively with bimolecular reactions of peroxy radicals under relatively warm atmospheric conditions as well as in 298 K competitive kinetics experiments carried out in large chambers.     

A kinetic study of Mg+ and Mg-containing ions reacting with O3, O2, N2, CO2, N2O and H2O: implications for magnesium ion chemistry in the upper atmosphere

Reactions between Mg(+) and O(3), O(2), N(2), CO(2) and N(2)O were studied using the pulsed laser photo-dissociation at 193 nm of Mg(C(5)H(7)O(2))(2) vapour, followed by time-resolved laser-induced fluorescence of Mg(+) at 279.6 nm (Mg(+)(3(2)P(3/2)-3(2)S(1/2))). The rate coefficient for the reaction Mg(+) + O(3) is at the Langevin capture rate coefficient and independent of temperature, k(190-340 K) = (1.17 ± 0.19) × 10(-9) cm(3) molecule(-1) s(-1) (1σ error). The reaction MgO(+) + O(3) is also fast, k(295 K) = (8.5 ± 1.5) × 10(-10) cm(3) molecule(-1) s(-1), and produces Mg(+) + 2O(2) with a branching ratio of (0.35 ± 0.21), the major channel forming MgO(2)(+) + O(2). Rate data for Mg(+) recombination reactions yielded the following low-pressure limiting rate coefficients: k(Mg(+) + N(2)) = 2.7 × 10(-31) (T/300 K)(-1.88); k(Mg(+) + O(2)) = 4.1 × 10(-31) (T/300 K)(-1.65); k(Mg(+) + CO(2)) = 7.3 × 10(-30) (T/300 K)(-1.59); k(Mg(+) + N(2)O) = 1.9 × 10(-30) (T/300 K)(-2.51) cm(6) molecule(-2) s(-1), with 1σ errors of ±15%. Reactions involving molecular Mg-containing ions were then studied at 295 K by the pulsed laser ablation of a magnesite target in a fast flow tube, with mass spectrometric detection. Rate coefficients for the following ligand-switching reactions were measured: k(Mg(+)·CO(2) + H(2)O → Mg(+)·H(2)O + CO(2)) = (5.1 ± 0.9) × 10(-11); k(MgO(2)(+) + H(2)O → Mg(+)·H(2)O + O(2)) = (1.9 ± 0.6) × 10(-11); k(Mg(+)·N(2) + O(2)→ Mg(+)·O(2) + N(2)) = (3.5 ± 1.5) × 10(-12) cm(3) molecule(-1) s(-1). Low-pressure limiting rate coefficients were obtained for the following recombination reactions in He: k(MgO(2)(+) + O(2)) = 9.0 × 10(-30) (T/300 K)(-3.80); k(Mg(+)·CO(2) + CO(2)) = 2.3 × 10(-29) (T/300 K)(-5.08); k(Mg(+)·H(2)O + H(2)O) = 3.0 × 10(-28) (T/300 K)(-3.96); k(MgO(2)(+) + N(2)) = 4.7 × 10(-30) (T/300 K)(-3.75); k(MgO(2)(+) + CO(2)) = 6.6 × 10(-29) (T/300 K)(-4.18); k(Mg(+)·H(2)O + O(2)) = 1.2 × 10(-27) (T/300 K)(-4.13) cm(6) molecule(-2) s(-1). The implications of these results for magnesium ion chemistry in the atmosphere are discussed.     

Studies of the kinetics and thermochemistry of the forward and reverse reaction Cl + C6H6 = HCl + C6H5

The laser flash photolysis resonance fluorescence technique was used to monitor atomic Cl kinetics. Loss of Cl following photolysis of CCl4 and NaCl was used to determine k(Cl + C6H6) = 6.4 x 10(-12) exp(-18.1 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 578-922 K and k(Cl + C6D6) = 6.2 x 10(-12) exp(-22.8 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 635-922 K. Inclusion of literature data at room temperature leads to a recommendation of k(Cl + C6H6) = 6.1 x 10(-11) exp(-31.6 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) for 296-922 K. Monitoring growth of Cl during the reaction of phenyl with HCl led to k(C6H5 + HCl) = 1.14 x 10(-12) exp(+5.2 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 294-748 K, k(C6H5 + DCl) = 7.7 x 10(-13) exp(+4.9 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 292-546 K, an approximate k(C6H5 + C6H5I) = 2 x 10(-11) cm(3) molecule(-1) s(-1) over 300-750 K, and an upper limit k(Cl + C6H5I) < or = 5.3 x 10(-12) exp(+2.8 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 300-750 K. Confidence limits are discussed in the text. Third-law analysis of the equilibrium constant yields the bond dissociation enthalpy D(298)(C6H5-H) = 472.1 +/- 2.5 kJ mol(-1) and thus the enthalpy of formation Delta(f)H(298)(C6H5) = 337.0 +/- 2.5 kJ mol(-1).     

Ab initio study on the oxidation of NCN by O (3P): prediction of the total rate constant and product branching ratios

The reaction of NCN with O is relevant to the formation of prompt NO according to the new mechanism, CH+N2-->cyclic-C(H)NN- -->HNCN-->H+NCN. The reaction has been investigated by ab initio molecular orbital and transition state theory calculations. The mechanisms for formation of possible product channels involved in the singlet and triplet potential energy surfaces have been predicted at the highest level of the modified GAUSSIAN-2 (G2M) method, G2M (CC1). The barrierless association/dissociation processes on the singlet surface were also examined with the third-order Rayleigh-Schr?dinger perturbation (CASPT3) and the multireference configuration interaction methods including Davidson's correction for higher excitations (MRCI+Q) at the CASPT3(6,6)/6-311+G(3df)//UB3LYP/6-311G(d) and MRCI+Q(6,6)/6-311+G(3df)//UB3LYP/6-311G(d) levels. The rate constants for the low-energy channels producing CO+N2, CN+NO, and N(4S)+NCO have been calculated in the temperature range of 200-3000 K. The results show that the formation of CN+NO is dominant and its branching ratio is over 99% in the whole temperature range; no pressure dependence was noted at pressures below 100 atm. The total rate constant can be expressed by: kt=4.23x10(-11) T0.15 exp(17/T) cm3 molecule(-1) s(-1).     

Atmospheric chemistry of two biodiesel model compounds: methyl propionate and ethyl acetate

The atmospheric chemistry of two C(4)H(8)O(2) isomers (methyl propionate and ethyl acetate) was investigated. With relative rate techniques in 980 mbar of air at 293 K the following rate constants were determined: k(C(2)H(5)C(O)OCH(3) + Cl) = (1.57 ± 0.23) × 10(-11), k(C(2)H(5)C(O)OCH(3) + OH) = (9.25 ± 1.27) × 10(-13), k(CH(3)C(O)OC(2)H(5) + Cl) = (1.76 ± 0.22) × 10(-11), and k(CH(3)C(O)OC(2)H(5) + OH) = (1.54 ± 0.22) × 10(-12) cm(3) molecule(-1) s(-1). The chlorine atom initiated oxidation of methyl propionate in 930 mbar of N(2)/O(2) diluent (with, and without, NO(x)) gave methyl pyruvate, propionic acid, acetaldehyde, formic acid, and formaldehyde as products. In experiments conducted in N(2) diluent the formation of CH(3)CHClC(O)OCH(3) and CH(3)CCl(2)C(O)OCH(3) was observed. From the observed product yields we conclude that the branching ratios for reaction of chlorine atoms with the CH(3)-, -CH(2)-, and -OCH(3) groups are <49 ± 9%, 42 ± 7%, and >9 ± 2%, respectively. The chlorine atom initiated oxidation of ethyl acetate in N(2)/O(2) diluent gave acetic acid, acetic acid anhydride, acetic formic anhydride, formaldehyde, and, in the presence of NO(x), PAN. From the yield of these products we conclude that at least 41 ± 6% of the reaction of chlorine atoms with ethyl acetate occurs at the -CH(2)- group. The rate constants and branching ratios for reactions of OH radicals with methyl propionate and ethyl acetate were investigated theoretically using transition state theory. The stationary points along the oxidation pathways were optimized at the CCSD(T)/cc-pVTZ//BHandHLYP/aug-cc-pVTZ level of theory. The reaction of OH radicals with ethyl acetate was computed to occur essentially exclusively (～99%) at the -CH(2)- group. In contrast, both methyl groups and the -CH(2)- group contribute appreciably in the reaction of OH with methyl propionate. Decomposition via the α-ester rearrangement (to give C(2)H(5)C(O)OH and a HCO radical) and reaction with O(2) (to give CH(3)CH(2)C(O)OC(O)H) are competing atmospheric fates of the alkoxy radical CH(3)CH(2)C(O)OCH(2)O. Chemical activation of CH(3)CH(2)C(O)OCH(2)O radicals formed in the reaction of the corresponding peroxy radical with NO favors the α-ester rearrangement.     

Kinetic studies on the temperature dependence of the BrO + BrO reaction using laser flash photolysis

The BrO self-reaction, BrO + BrO → products (1), has been studied using laser flash photolysis coupled with UV absorption spectroscopy over the temperature range T = 266.5-321.6 K, under atmospheric pressure. BrO radicals were generated via laser photolysis of Br(2) in the presence of excess ozone. Both BrO and O(3) were monitored via UV absorption spectroscopy using charge-coupled device (CCD) detection. Simultaneous fitting to both temporal concentration traces allowed determination of the rate constant of the two channels of , BrO + BrO → 2Br + O(2) (1a); BrO + BrO → Br(2) + O(2) (1b), hence the calculation of the overall rate of and the branching ratio, α: k(1a)/cm(3) molecule(-1) s(-1) = (1.92 ± 1.54) × 10(-12) exp[(126 ± 214)/T], k(1b)/cm(3) molecule(-1) s(-1) = (3.4 ± 0.8) × 10(-13) exp[(181 ± 70)/T], k(1)/cm(3) molecule(-1) s(-1) = (2.3 ± 1.5) × 10(-12) exp(134 ± 185 /T) and α = k(1a)/k(1) = (0.84 ± 0.09) exp[(-7 ± 32)/T]. Errors are 1σ, statistical only. Results from this work show a weaker temperature dependence of the branching ratio for channel (1a) than that found in previous work, leading to values of α at temperatures typical of the Polar Boundary Layer higher than those reported by previous studies. This implies a shift of the partitioning between the two channels of the BrO self-reaction towards the bromine atom and hence directly ozone-depleting channel (1a).     

Falloff curves for the Reaction CH3 + O2 (+ M) --> CH3O2 (+ M) in the pressure range 2-1000 bar and the temperature range 300-700 K

The reaction CH(3) + O(2) (+M) --> CH(3)O(2) (+M) was studied in the bath gases Ar and N(2) in a high-temperature/high-pressure flow cell at pressures ranging from 2 to 1000 bar and at temperatures between 300 and 700 K. Methyl radicals were generated by laser flash photolysis of azomethane or acetone. Methylperoxy radicals were monitored by UV absorption at 240 nm. The falloff curves of the rate constants are represented by the simplified expression k/k(infinity) approximately [x/(1 + x)]F(cent)(1/{1+[(log)(x)/)(N)(]2}) with x = k(0)/k(infinity) F(cent) approximately 0.33, and N approximately 1.47, where k(0) and k(infinity) denote the limiting low and high-pressure rate constants, respectively. At low temperatures, 300-400 K, and pressures >300 bar, a fairly abrupt increase of the rate constants beyond the values given by the falloff expressions was observed. This effect is attributed to a contribution from the radical complex mechanism as was also observed in other recombination reactions of larger radicals. Equal limiting low-pressure rate constants k(0) = [M]7 x 10(-31)(T/300 K)(-3.0) cm(6) molecule(-2) s(-1) were fitted for M = Ar and N(2) whereas limiting high-pressure rate constants k(infinity) = 2.2 x 10(-12)(T/300 K)(0.9) cm(3) molecule(-1) s(-1) were approached. These values are discussed in terms of unimolecular rate theory. It is concluded that a theoretical interpretation of the derived rate constants has to be postponed until better information of the potential energy surface is available. Preliminary theoretical evaluation suggests that there is an "anisotropy bottleneck" in the otherwise barrierless interaction potential between CH(3) and O(2).     

A consistent model for the thermal decomposition of NCN3 and the singlet– triplet relaxation of NCN

The thermal decomposition of cyanogen azide (NCN₃) and the subsequent collision‐induced intersystem crossing (CIISC) process of cyanonitrene (NCN) have been investigated by monitoring excited electronic state ¹NCN and ground state ³NCN radicals. NCN was generated by the pyrolysis of NCN₃ behind shock waves and by the photolysis of NCN₃ at room temperature. Falloff rate constants of the thermal unimolecular decomposition of NCN₃ in argon have been extracted from ¹NCN concentration–time profiles in the temperature range 617 K <T< 927 K and at two different total densities: k(ρ ≈ 3 × 10^?6 mol/cm³)/s^?1=4.9 × 10⁹ × exp (?71±14 kJ mol^?1/RT) (± 30%); k(ρ ≈ 6 × 10^?6 mol/cm³)/s^?1=7.5 × 10⁹ × exp (‐71±14 kJ mol^?1/RT) (± 30%). In addition, high‐temperature ¹NCN absorption cross sections have been determined in the temperature range 618 K <T< 1231 K and can be expressed by σ /(cm²/mol)= 1.0 × 10⁸ ?6.3 × 10⁴ K^?1 × T (± 50%). Rate constants for the CIISC process have been measured by monitoring ³NCN in the temperature range 701 K <T< 1256 K resulting in k_CIISC (ρ ≈ 1.8 ×10^?6 mol/cm³)/ s^?1=2.6 × 10⁶× exp (‐36±10 kJ mol^?1/RT) (± 20%), k_CIISC (ρ ≈ 3.5×10^?6 mol/cm³)/ s^?1 = 2.0 × 10⁶ × exp (?31±10 kJ mol^?1/RT) (± 20%), k_CIISC (ρ ≈ 7.0×10^?6 mol/cm³)/ s^?1=1.4 × 10⁶ × exp (?25±10 kJ mol^?1/RT) (± 20%). These values are in good agreement with CIISC rate constants extracted from corresponding ¹NCN measurements. The observed nonlinear pressure dependences reveal a pressure saturation effect of the CIISC process. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 45: 30–40, 2013     

Experimental and modeling study of the ion-molecule association reaction H3O+ + H2O (+M) --> H5O2(+) (+M)

Experimental results for the rate of the association reaction H3O+ + H2O (+M) --> H5O2(+) (+M) obtained with the Cinetique de Reactions en Ecoulement Supersonique Uniforme flow technique are reported. The reaction was studied in the bath gases M=He and N2, over the temperature range of 23-170 K, and at pressures between 0.16 and 3.1 mbar. At the highest temperatures, the reaction was found to be close to the limiting low-pressure termolecular range, whereas the limiting high-pressure bimolecular range was approached at the lowest temperatures. Whereas the low-pressure rate coefficients can satisfactorily be reproduced by standard unimolecular rate theory, the derived high-pressure rate coefficients in the bath gas He at the lowest temperatures are found to be markedly smaller than given by simple ion-dipole capture theory. This result differs from previous observations on the related reaction NH4(+) + NH3 (+M) --> N2H7(+) (+M). This observation is tentatively attributed to more pronounced contributions of the valence part of the potential-energy surface to the reaction in H5O2(+) than in N2H7(+). Falloff curves of the reaction H3O+ + H2O (+M) --> H5O2(+) (+M) are constructed over wide ranges of conditions and represented in compact analytical form.     

Atmospheric chemistry of (Z)-CF3CH═CHCF3: OH radical reaction rate coefficient and global warming potential

Rate coefficients, k, for the gas-phase reaction of the OH radical with (Z)-CF(3)CH═CHCF(3) (cis-1,1,1,4,4,4-hexafluoro-2-butene) were measured under pseudo-first-order conditions in OH using pulsed laser photolysis (PLP) to produce OH and laser-induced fluorescence (LIF) to detect it. Rate coefficients were measured over a range of temperatures (212-374 K) and bath gas pressures (20-200 Torr; He, N(2)) and found to be independent of pressure over this range of conditions. The rate coefficient has a non-Arrhenius behavior that is well-described by the expression k(1)(T) = (5.73 ± 0.60) × 10(-19) × T(2) × exp[(678 ± 10)/T] cm(3) molecule(-1) s(-1) where k(1)(296 K) was measured to be (4.91 ± 0.50) × 10(-13) cm(3) molecule(-1) s(-1) and the uncertainties are at the 2σ level and include estimated systematic errors. Rate coefficients for the analogous OD radical reaction were determined over a range of temperatures (262-374 K) at 100 Torr (He) to be k(2)(T) = (4.81 ± 0.20) × 10(-19) × T(2) × exp[(776 ± 15)/T], with k(2)(296 K) = (5.73 ± 0.50) × 10(-13) cm(3) molecule(-1) s(-1). OH radical rate coefficients were also measured at 296, 345, and 375 K using a relative rate technique and found to be in good agreement with the PLP-LIF results. A room-temperature rate coefficient for the O(3) + (Z)-CF(3)CH═CHCF(3) reaction was measured using an absolute method with O(3) in excess to be <6 × 10(-21) cm(3) molecule(-1) s(-1). The atmospheric lifetime of (Z)-CF(3)CH═CHCF(3) due to loss by OH reaction was estimated to be ~20 days. Infrared absorption spectra of (Z)-CF(3)CH═CHCF(3) measured in this work were used to determine a (Z)-CF(3)CH═CHCF(3) global warming potential (GWP) of ~9 for the 100 year time horizon. A comparison of the OH reactivity of (Z)-CF(3)CH═CHCF(3) with other unsaturated fluorinated compounds is presented.     

Reaction mechanism and kinetics of the NCN+NO reaction: comparison of theory and experiment

The rate constants for the NCN + NO reaction have been measured by laser photolysis/laser-induced fluorescence technique in the temperature range of 254-353 K in the presence of He (40-600 Torr) and N2 (30-528 Torr) buffer gases. The NCN radical was produced from the photodissociation of NCN3 at 193 nm and monitored with a dye laser at 329.01 nm. The reaction was found to be strongly positive-pressure dependent with negative-temperature dependence, as was reported previously. The experimental data could be reasonably accounted for by dual-channel Rice-Ramsperger-Kassel-Marcus calculations based on the predicted potential-energy surface using the modified Gaussian-2 method. The reaction is predicted to occur via weak intermediates, cis- and trans-NCNNO, in the 2A" state which crosses with the 2A' state containing more stable cis- and trans-NCNNO isomers. The high barriers for the fragmentation of these isomers and their trapping in the 2A' state by collisional stabilization give rise to the observed positive-pressure dependence and negative-temperature effect. The predicted energy barrier for the fragmentation of the cis-NCNNO (2A') to CN + N2O also allows us to quantitatively account for the rate constant previously measured for the reverse process CN + N2O --> NCN + NO.