Reaction of methoxy radicals with oxygen. I. Using dimethyl peroxide as a thermal source of methoxy radicals

Using dimethyl peroxide as a thermal source of methoxy radicals overthe temperature range of 110–160°C, and the combination of methoxy radicals and nitrogen dioxide as a reference reaction: a value was determined of the rate constant for the reaction of methoxy radicals with oxygen: is independent of nitrogen dioxide or oxygen concentration and added inert gas (carbon tetrafluoride). No heterogeneous effects were detected. The value of k₄ is given by the expression In terms of atmospheric chemistry, this corresponds to a value of 10^5.6 M^?1·sec^?1 at 298 K. Extrapolation to temperatures where the combustion of organic compounds has been studied (813 K) produces a value of 10^7.7 M^?1·sec^?1 for k₄. Under these conditions, reaction (4) competes with hydrogen abstraction or disproportionation reactions of the methoxy radical and its decomposition (3): In particular k₃ is in the falloff region under these conditions. It is concluded that reaction (4) takes place as the result of a bimolecular collision process rather than via the formation of a cyclic complex.     

Thermal reaction of CH2O with NO2 in the temperature range of 393–476 K: FTIR product measurement and kinetic modeling

The thermal reaction of CH₂O with NO₂ has been investigated in the temperature range of 393–476 K by means of FTIR product analysis. Kinetic modeling of the measured CH₂O, NO, CO, and CO₂ concentration time profiles under varying reaction conditions gave rise to the rate constants for the following key reactions: (1) and (2) The error limits shown represent only the scatter (±1 σ) of the modeled values. In the modeling, the total rate constant for the CHO + NO₂ reaction, k₂ + k₃, was not varied and the value reported by Gutman and co-workers (ref. [8]) was used for the whole temperature range investigated here. The proposed reaction mechanism, employing these newly established rate constants, can quantitively account for nearly all measured product yields, including the [CO]/([CO] + [CO₂]) ratios reported by earlier workers.     

H2S-promoted thermal isomerization of butene-2 CIS to butene-1 or butene-2 trans around 500°C

H₂S increases the thermal isomerization of butene-2 cis (B_c) to butene-1 (B₁) and butene-2 trans (B_t) around 500°C. This effect is interpreted on the basis of a free radical mechanism in which buten-2-yl and thiyl free radicals are the main chain carriers. B₁ formation is essentially explainedby the metathetical steps: whereas the free radical part of B_t formation results from the addition–elimination processes: . It is shown that the initiation step of pure B_c thermal reaction is essentially unimolecular: and that a new initiation step occurs in the presence of H₂S: . The rate constant ratio has been evaluated: and the best values of k₁ and k_1', consistent with this work and with thermochemical data, are . From thermochemical data of the literature and an “intrinsic value” of E_?3 ? 2 kcal/mol given by Benson, further values of rate constants may be proposed: is shown to be E₄ ? 3.5 ± 2 kcal/mol, of the same order as the activation energy of the corresponding metathetical step.     

The kinetics of the thermal bromination of CF3I. Determination of the bond dissociation energy D(CF3−I)

The kinetics of the thermal bromination reaction have been studied in the range of 173–321°C. For the step we obtain where θ=2.303RT cal/mole. From the activation energy for reaction (11), we calculate that This is compared with previously published values of D(CF₃?I). The relevance of the result to published work on k_c for a combination of CF₃ radicals is discussed.     

The oxidation of CFClCFCl and CF2CCl2

The oxidation of CFClCFCl and CF₂CCl₂ were studied at room temperature by chlorine- and oxygen-atom initiation. The chlorine-atom initiated oxidation of CFClCFCl yields CCl₂FCF(O) as the exclusive product. Its quantum yield is ～420, which gives k_3a/k_3b=210 where reactions (3a) and (3b) are The O(³P)? CFClCFCl reaction gives CClFO with a quantum yield of 0.80, polymer, and small amounts of an unidentified product which is probably cyclo-(CFCl)₃. Thereaction paths are with k_9a/k₉=0.80. The overall reaction of O(³P) with CFClCFCl proceed one fifth as fast as the O(³P)-C₂F₄ reaction. When O₂ is also present, the same free-radical chain oxidation occurs by O(³P)initiation as by chlorine-atom initiation. The chlorine-atom initiated oxidation of CF₂CCl₂ gives CF₂ClCCl(O) as the major product, with quantum yields ranging from 42 to 85. Smaller amounts of CF₂O and CCl₂O are produced in equal amounts with quantum yields of ～3.5. The reactions responsible for the products are The O(³P)-CF₂CCl₂interaction yields CF₂O and with quantum yields of 1.0 and ～0.85, respectively. In thepresence of O₂ the radical chain products are observed, but the mechanism is different than that for other chloroolefins.     

Determination of the mechanism of the oxidation of the trichloromethyl radical by the photolysis of chloral in the presence of oxygen

The photooxidation of chloral was studied by infrared spectroscopy under steady-state conditions with irradiation of a blackblue fluorescent lamp (300 nm < λ < 400 nm, λ_max = 360 nm) at 296 ± 2 K. The products were hydrogen chloride, carbon monoxide, carbon dioxide, and phosgen. The kinetic results reveal that the reaction proceeds via chain reaction of the Cl atom: The results lead to the conclusion that mechanism (B) is confirmed to be more likely than mechanism (A), which was favored at one time by Heicklen for the mechanism of the oxidation of trichloromethyl radicals by oxygen molecules: The ratio of the initial rates of CO and CO₂ formation gave k₇/k₆ = 4.23M^?1, and the lower limit of reaction (5) was found to be 3.7 × 10⁸M^?1 sec^?1.     

Reaction of NO with hypochlorous acid

The reaction between NO(g) at concentrations between 0.1 and 1.0 Torr in 1-atm N₂ and aqueous solutions of NaClO has been studied over the pH range of 6–12 and hypochlorite concentrations between 0.01 and 1.0M. A very rapid and efficient reaction occurs leading to the production of about 30%–40% of the NO as NO₂ and with conversions of NO up to 98% at about 1-sec contact time. It is shown that a fast chain reaction initiated by the endothermic step can account for the data. The very exothermic reaction NO + ClO^? → NO₂ + Cl^? is shown to be at least 30-fold slower than i. The overall reaction seems very promising as a method of reducing NO and NO₂ emissions from the exhausts of industrial plants.     

On the gas-phase free radical displacement reaction CH3 + CD3COCD3 → CD3 + CH3COCD3

The gas-phase free radical displacement reaction has been studied in the temperature range of 240–290°C and at 140°C with the thermal decomposition of azomethane (AM) and di-tert-butylperoxide (DTBP), respectively, as methyl radical sources. The reaction products of the CD₃ radicals were analyzed by mass spectrometry. Assuming negligible isotope effects, Arrhenius parameters for the elementary radical addition reaction were derived: The data are discussed with respect to the back reaction and general features of elementary addition reactions.     

Addition of trichloromethyl radicals to tetrachloroethylene

The gamma-radiation-induced free-radical chain reactions in liquid CCl₄? C₂Cl₄? c? C₆H₁₂ mixtures were studied in the temperature range of 363–448°K. The main products in this system are chloroform, hexachloropropene and chlorocyclohexane. These products are formed via reactions (1)–(5): with G values (molec/100 eV) of the order of magnitude of 10² and 10³ at the lowest and highest temperatures, respectively. Values of k₂/k₁ were determined from the product distribution. In turn, these values gave the following Arrhenius expression for k₂/k₁ (θ = 2.303RT, in kcal/mol): From this result and the previously determined Arrhenius parameters of reaction (1), k₂ is found to be given by .     

Influence of butadiene-1,3 on ethanal pyrolysis at 495°C

At 495°C and a low extent of reaction, ethanal pyrolysis is slightly inhibited by the addition of small quantities of butadiene-1,3, whereas it is accelerated by more important quantities. The inhibiting effect is interpreted in terms of a free-radical chain mechanism in which the main chain carriers of ethanal pyrolysis (CH₃.free radicals) reversibly add to butadiene-1,3 and yield penten-2-yl (R.) free radicals. These free radicals either react in a metathetical step: or in terminating steps. But butadiene-1,3 also gives rise to new initiation steps: which account for the accelerating effect. Process (i₃) seems to be more important than process (i₂) in the experimental conditions, but its nature could not be identified. The results are consistent with literature data and the following value of k₆: (4.57T in cal/mol).     

The kinetics of the Diels–Alder addition of cyclopentadiene to acetylene and the decomposition of norbornadiene

The title reactions have been investigated in a static system. The addition of acetylene to cyclopentadiene (CPD) results in formation of norbornadiene (BCH), cycloheptatriene (CHT), and toluene (T), while BCH decomposition produces CPD, C₂H₂, CHT, and T. Kinetic studies, comprising both product–time evolution and initial pressure variation, support a mechanism These reactions are almost certainly homogeneous and molecular in nature. Least mean square analysis of the data yield for temperatures of 525–656°K, log k_?1 (1./mole·s)=7.51±0.05? (24.19±0.15 kcal/mole)/RT ln 10, and for temperatures of 584–630°K,      

Kinetics of the reactions Br2 + HCN,BrCN + I−, S(CN)2 + I− in aqueous acid solution

Spectrophotometric methods have been used to obtain rate laws and rate parameters for the following reactions: with k_a, k_b, E_a, E_b having the values 85±5 l./mole · s, 5.7±0.2 s^?1 (both at 298.2°K), and 56±4 and 66±2 kJ/mole, respectively. with k_c=0.106±0.004 l./mole ·s at 298.2°K and E_c=67±2 kJ/mole. with k_d=(3.06 ±; 0.15) × 10^?3 l./mole ·s at 298.2°K and E_d=66±2 kJ/mole. Mechanisms for these reactions are discussed and compared with previous work.     

Effect of olefins on the thermal decomposition of propane part I. The model reaction

Study of the thermal decomposition of propane at very low conversions in the temperature range 760–830 K led to refinement of the mechanism of the reaction. The quotient V/V characterizing the two decomposition routes connected with the 1- and 2-propyl radicals proved to depend linearly on the initial propane concentration. This suggested the occurrence of intermolecular radical isomerization: in competition with decomposition of the 2-propyl radical: The linearity led to the conclusion that the selectivity of H-abstraction from the methyl and methylene groups by the methyl radical is practically the same as that by the H atom. The temperature-dependence of this selectivity ( μ = kCH₃/kCH₂) was given by Further evaluation of the dependence gave the Arrhenius representation for the ratio of the rate coefficients of the above isomerization and decomposition reactions. Steady-state treatment resulted in the rate equation of the process, comparison of which with measurements gave further Arrhenius dependences.     

Induced heterogeneity,a novel technique for the study of gas-phase reactions. Part I. Determination of the arrhenius parameters for C?C bond scission in propane

It is shown that, by deliberate activation of the reaction vessel, heterogeneous reaction at the wall can be made to dominate chain termination in a complex gas-phase reaction. For a homogeneous process, characterized, as is often the case, by multiple terminations, this has the effect of simplifying the mechanism and allowing explicit solution of the relevant steady-state equations so that the rate constants of some individual steps can be evaluated without assumption as to the values of those of others. The pyrolysis of propane, in the vicinity of 500°C, has been used as an example of this approach. Enhancement of the wall activity leads to the reaction (1) providing, almost exclusively, chain termination. As a result, rate constants for the initiation step (2) can be directly determined. The results of this study provide the Arrhenius equation In combination with current thermochemical values this result gives k_?1 = 10^13.40 cm³/mol·s which, in turn, implies, via the geometric mean rule, k_Et-Et = 10^12.9 cm³/mol·s for ethyl–ethyl recombination, in good accord with the most recent determinations and compatible with the newly proposed value of the enthalpy of formation of ethyl. The first-order wall constant k₈ has been evaluated as k₈<10^4.2 s^?1. This appears to be the first occasion on which a wall constant has been evaluated from data for a high-temperature complex gas reaction.     

Shock tube study of cyanogen oxidation kinetics

Mixtures of cyanogen and nitrous oxide diluted in argon were shock-heated to measure the rate constants of A broad-band mercury lamp was used to measure CN in absorption at 388 nm [B²Σ⁺(v = 0) ← X²Σ⁺(v = 0)], and the spectral coincidence of a CO infrared absorption line [v(2 ← 1), J(37 ← 38)] with a CO laser line [v(6 → 5), J(15 → 16)] was exploited to monitor CO in absorption. The CO measurement established that reaction (3) produces CO in excited vibrational states. A computer fit of the experiments near 2000 K led to An additional measurement of NO via infrared absorption led to an estimate of the ratio k₅/k₆: with k₅/k₆ ? 10^3.36±0.27 at 2150 K. Mixtures of cyanogen and oxygen diluted in argon were shock heated to measure the rate constant of and the ratio k₅/k₆ by monitoring CN in absorption. We found near 2400 K: and The combined measurements of k₅/k₆ lead to k₅/k₆ ? 10^?3.07 exp(+31,800/T) (±60%) for 2150 ≤ T ≤ 2400 K.     

Reaction kinetics of NH in the shock tube pyrolysis of HNCO

The high temperature kinetics of NH in the pyrolysis of isocyanic acid (HNCO) have been studied in reflected shock wave experiments. Time histories of the NH(X³Σ^?) radical were measured using a cw, narrow-linewidth laser absorption diagnostic at 336 nm. The second-order rate coefficients of the reactions: (1) were determined to be: cm³?mol^?1?s^?1, where f and F define the lower and upper uncertainty limits, respectively. The data for k_1a are somewhat better fit by:      

Rate data for O + OCS → SO + CO and SO + O3 → SO2 + O2 by a new time-resolved technique

Pulsed laser photolysis of O₃ in a large excess of N₂ has been used to generate O(³P) atoms in the presence of OCS. By observing chemiluminescence from the small fraction of electronically excited SO₂ formed in the reaction of SO with O₃, rate constants of (1.7 ± 0.2) × 10^?14 and (8.7 ± 1.6) × 10^?14 cm³/molecule sec have been determined at 296 ± 4 K for the reactions and In addition, it has been shown that any reaction between SO and OCS has a rate constant 10^?14 cm³/molecule sec.     

Oxidation of S and SO by O2 in high-temperature pyrolysis and photolysis reaction systems

The reaction of S atoms with O₂ was studied behind reflected shock waves applying atomic resonance absorption spectroscopy (ARAS) for concentration measurements of S and O atoms. S atoms were generated either by laser-flash photolysis (LFP) of CS₂ or by the high-temperature pyrolysis of COS, respectively. The concentrations of O₂ in the mixtures ranged between 50 ppm and 400 ppm, and those of the S precursors, CS₂ and COS, between 5 and 25 ppm. The rate coefficient of the reaction was determined from the observed decay of the S absorption signals for temperatures 1220 K ? T ? 3460 K. The measured O-atom concentration profiles in COS/O₂/Ar reaction systems were evaluated, using simplified kinetic mechanism, to verify the given rate coefficient k₅. In experiments with the highest value of the [O₂]/[COS] ratio the measured O-atom concentrations were found to be sensitive to the reaction: The fitting of the calculated O-atom profiles to the measured ones results in mean value of: which is to be valid for the temperature range 2570 K ? T ? 2980 K. A first-order analysis of the observed S absorption decay in LFP shock wave experiments on CS₂/Ar gas mixtures resulted in a rate coefficient of the background reaction (R4): for temperatures 1260 K ? T ? 1820 K. © 1995 John Wiley & Sons, Inc.     

Rate constants for abstraction of hydrogen from ethylene by methyl and ethyl radicals relative to abstraction from propane and isobutane

A method is described for the measurement of relative rate constants for abstraction of hydrogen from ethylene at temperatures in the region of 750 K. The method is based on the effect of the addition of small quantities of propane and isobutane on the rates of formation of products in the thermal chain reactions of ethylene. On the assumption that methane and ethane are formed by the following reactions, (1) measurements of the ratio of the rates of formation of methane and ethane in the presence and absence of the additive gave the following results: Values for k₂ and k₃ obtained from these ratios are compared with previous measurements.     

Kinetics and mechanism of the reaction H + CH3ONO

The reaction of hydrogen atoms with methyl nitrite was studied in a fast-flow system using photoionization mass spectrometry and excess atomic hydrogen. The associated bimolecular rate coefficient can be expressed by in the temperature range of 223-398°K. NO, CH₃OH, CH₄, C₂H₆, CH₂O, and H₂O are the main products; OH and CH₃ radicals were detectable intermediates. The mechanism was deduced from the observed product yields using normal and deuterated reactants. The primary reaction steps were identified as followed by a rapid unimolecular decomposition of CH₂ONO into CH₂O and NO. Since the extent of reaction channel (1b) could not be determined independently, only extreme limits could be obtained for the individual contributions of the two channels of reaction (3) which follows the generation of CH₃O radicals: The most probable values, k_3a/k₃ = 0.31 ± 0.30 and k_3b/k₃ = 0.69 ± 0.30, support the previous results on this reaction, although the range of uncertainties is much greater here.