Structure of the methyl radical

Carbon-13 hyperfine splittings equal to 41±3 gauss have been observed in the paramagnetic resonance of a mixture of C¹²H₃ and C¹³H₃ radicals produced by x-irradiation of CH₃I at 77°k. The observed splitting provides strong evidence that CH₃ is a planar molecule.     

Breath water-based doubly labelled water method for the noninvasive determination of CO2 production and energy expenditure in mice

ABSTRACT

We explored a novel doubly labelled water (DLW) method based on breath water (BW-DLW) in mice to determine whole body CO₂ production and energy expenditure noninvasively. The BW-DLW method was compared to the DLW based on blood plasma. Mice (n?=?11, 43.5?±?4.6?g body mass (BM)) were administered orally a single bolus of doubly labelled water (1.2?g H₂¹⁸O kg BM^?1 and 0.4?g ²H₂O kg BM^?1, 99 atom% (AP) ¹⁸O or ²H). To sample breath water, the mice were placed into a respiration vessel. The exhaled water vapour was condensed in a cold-trap. The isotope enrichments of breath water were compared with plasma samples. The ²H/¹H and ¹⁸O/¹⁶O isotope ratios were measured by means of isotope ratio mass spectrometry. The CO₂ production (RCO₂) was calculated from the ²H and ¹⁸O enrichments in breath water and plasma over 5 days. The isotope enrichments of breath water vs. plasma were correlated (R²?=?0.89 for ²H and 0.95 for ¹⁸O) linearly. The RCO₂ determined based on breath water and plasma was not different (113.2?±?12.7 vs. 111.4?±?11.0?mmol?d^–1), respectively. In conclusion, the novel BW-DLW method is appropriate to obtain reliable estimates of RCO₂ avoiding blood sampling.     

Gas‐phase oxidation of CH2 = C(CH3)CH2Cl initiated by OH radicals and Cl atoms: kinetics and fate of the alcoxy radical formed

Relative kinetics of the reactions of OH radicals and Cl atoms with 3‐chloro‐2‐methyl‐1‐propene has been studied for the first time at 298 K and 1 atm by GC‐FID. Rate coefficients are found to be (in cm³ molecule^?1 s^?1): k₁ (OH + CH₂ = C(CH₃)CH₂Cl) = (3.23 ± 0.35) × 10^?11, k₂ (Cl + CH₂ = C(CH₃)CH₂Cl) = (2.10 ± 0.78) × 10^?10 with uncertainties representing ± 2σ. Product identification under atmospheric conditions was performed by solid phase microextraction/GC‐MS for OH reaction. Chloropropanone was identified as the main degradation product in accordance with the decomposition of the 1,2‐hydroxy alcoxy radical formed. Additionally, reactivity trends and atmospheric implications are discussed. Copyright © 2015 John Wiley & Sons, Ltd.     

When hydrogen is slower than methane to ignite

Hydrogen (H₂) is known to be the fastest fuel to ignite among all practical combustion fuels. In this study, for the first time, longer ignition delay times (IDTs) for the H₂ and H₂ blended CH₄ mixtures were measured compared to those for pure CH₄. This work investigates the ignition characteristics of H₂, CH₄, and 50% CH₄/50% H₂ mixtures using a rapid compression machine at pressures ranging from 20 to 50 bar and at equivalence ratios (φ) from 0.5 to 2.0 in air in the temperature range 858–1080 K. The experimental IDTs are simulated using a newly updated kinetic mechanism, NUIGMech1.3, and good agreement is observed. At lower temperatures the IDTs of H₂, CH₄, and the 50% CH₄/50% H₂ mixtures are similar to one another, and the IDTs of the 50% CH₄/50% H₂ mixtures are longer than those for pure CH₄ at temperatures below 930 K. At temperatures below 890–925 K, depending on the operating pressure and equivalence ratio, the hydrogen mixtures are the slowest to ignite, with IDTs being 2.5 times longer than those recorded for CH₄ at a pressure of 40 bar at 890 K for φ = 1.0, and at 875 K for φ = 2.0. At low temperatures alkyl (Ṙ = ĊH₃ and Ḣ) radicals add to O₂ producing RȮ₂ radicals, which then react with HȮ₂ radicals forming ROOH (H₂O₂ and CH₃OOH) and O₂. For H₂, the self-recombination of HȮ₂ radicals leads to chain propagation which inhibits reactivity, whereas for CH₄, the reaction between RȮ₂ (CH₃OȮ) and HȮ₂ leads to chain branching, increasing reactivity. Furthermore, CH₃OOH decomposes more easily to produce CH₃Ȯ and ȮH radicals than does H₂O₂ to produce two ȮH radicals. Thus, mixtures containing higher H₂ concentrations are slower to ignite compared to those with higher CH₄ concentrations at low temperatures.     

ESR spectroscopics study of radicals formed from methoxycarbonylcholine picrate hemihydrate

Abstract

The electron spin resonance of γ-irradiated single crystals of methoxycarbonylcholine picrate hemihydrate, C₇H₁₆NO₃ ⁺ · C₆H₂N₃O₇ ^? · ½ H₂O has been observed and analyzed for different orientations of the crystal in the magnetic field. The crystals have been investigated between 70 and 350 K. The spectra were found to be temperature independent and the radiation damage centers are attributed to – ?[Obar]OCH₃ and –CH₂CH₂O? radicals. The g and hyperfine coupling constants were found to be almost isotropic with an average, g = 2.0060, a _H1 = 4.4G for –CH₂CH₂O?, g = 2.0050, a _H2 = 3.5G for –CH₂CH₂O? and g = 2.0045, a _H = 3.5 G for –?[Obar]OCH₃. These values indicate a long-range coupling between the unpaired electron and H protons.     

Semiempirical molecular orbital calculations of anisotropic 1H, 13C and 19F hyperfine coupling constants in hydrocarbon and fluorocarbon radicals

The anisotropic hyperfine coupling constants (AHCC) from the electron spin resonance (E.S.R.) spectra of a variety of atoms in organic radicals have been calculated by means of semiempirical molecular orbital wavefunctions in the INDO approximation. Hyperfine tensors involving ¹H, ¹³C and ¹⁹F nuclei are obtained for the ?H, ?H₃, CH₃?H₂, (CH₃)₃? hydrocarbon radicals, malonic acid radical, ?H₂F, ?F₂H, ?F₃ and CF₃?H₂ radicals. The calculated values are compared with available experimental, non-empirical and semiempirical values for these radicals. All integrals of the operator entering the electronic contributions have been evaluated over Slater type orbitals. The introduction of deorthogonalized wavefunctions gives generally better calculated results. In particular, the tensor components of the ¹⁹F AHCC are in good agreement with the experimental results without the necessity of readjusting the effective nuclear charges.     

Mechanism for sonochemical reduction of Au(III) in aqueous butanol solution under Ar based on the analysis of gaseous and water-soluble products

When an aqueous Au(III) solution containing 1-butanol was sonicated under Ar, Au(III) was reduced to Au(0) to form Au particles. This is because various reducing species are formed during sonication, but the reactivity of these species has not yet been evaluated in detail. Therefore, in this study, we analyzed the effects of Au(III) on the rates of the formation of gaseous and water-soluble compounds (CH₄, C₂H₆, C₂H₄, C₂H₂, CO, CO₂, H₂, H₂O₂, and aldehydes), and the rate of Au(III) reduction as a function of 1-butanol concentration. The following facts were recognized: 1) for Au(III) reduction, the contribution of the radicals formed by the pyrolysis of 1-butanol was higher than that of the secondary radicals formed by the abstraction reactions of 1-butanol with ·OH, 2) ·CH₃ and CO acted as reductants, 3) the contribution of ·H to Au(III) reduction was small in the presence of 1-butanol, 4) aldehydes and H₂ did not act as reductants, and 5) the types of species that reduced Au(III) changed with 1-butanol concentration.     

Application of benzophenones to elucidate the photochemical reaction pathways of hydrogen peroxide with dimethylsulfoxide

Benzophenone ((C₆H₅)₂CO) and decafluorobenzophenone ((C₆F₅)₂CO) were applied to elucidate the photochemical reaction pathway of hydrogen peroxide (H₂O₂) with dimethylsulfoxide (DMSO). When a solution of benzophenone in DMSO was excited with the 355 nm laser light, three transient species were observed in the time-resolved electron paramagnetic resonance spectra: benzophenone ketyl (C₆H₅)₂COH^⋅, methyl^⋅CH₃, and methylsulfinic methyl^⋅CH₂SOCH₃ radicals. However, when decafluoro-benzophenone was used with DMSO, only ketyl and methylsulfinic methyl radicals were observed under the same experimental conditions. When the reaction of benzophenone and DMSO was carried out in the presence of H₂O₂, different time profiles of^⋅CH₃ radicals were observed. In the reaction of decafluorobenzophenone-DMSO-H₂O₂, the time profiles of the radicals were not affected by the presence of H₂O₂. Thus, these results verify that^⋅CH₃ radicals are regenerated in a cyclic pathway, in which^⋅CH₃ radicals attack H₂O₂. The regeneration pathway allows us to observe f-pair polarization throughout the lifetime of^⋅CH₃ radicals, which last several microseconds, an order of magnitude longer than theT ₁ relaxation time of^⋅CH₃ radicals.     

Structures and thermochemistry of methyl ethyl sulfide and its hydroperoxides: HOOCH2SCH2CH3, CH3SCH(OOH)CH3, CH3SCH2CH2OOH,and radicals

Hydroperoxides and the corresponding peroxy radicals are important intermediates during the partial oxidation of methyl ethyl sulfide (CH₃SCH₂CH₃) in both atmospheric chemistry and in combustion. Structural parameters, internal rotor potentials, bond dissociation energies, and thermochemical properties (ΔH_f^o, S^o and C_p(T)) of 3 corresponding hydroperoxides CH₂(OOH)SCH₂CH₃, CH₃SCH(OOH)CH₃, CH₃SCH₂CH₂OOH of methyl ethyl sulfides, and the radicals formed via loss of a hydrogen atom are important to understanding the oxidation reactions of MES. The lowest energy molecular structures were identified using the density functional B3LYP/6‐311G(2d,d,p) level of theory. Standard enthalpies of formation (ΔH_f^o₂₉₈) for the radicals and their parent molecules were calculated using the density functional B3LYP/6‐31G(d,p), B3LYP/6‐31 + G(2d,p), and the composite CBS‐QB3 ab initio methods. Isodesmic reactions were used to determine ?H_f^o values. Internal rotation potential energy diagrams and rotation barriers were investigated using the B3LYP/6‐31G(d,p) level theory. Contributions for S^o₂₉₈ and C_p(T) were calculated using the rigid rotor harmonic oscillator approximation based on the structures and vibrational frequencies obtained by the density functional calculations, with contributions from torsion frequencies replaced by internal rotor contributions. The recommended values for enthalpies of formation of the most stable conformers of CH₃SCH₂CH_2, CH₂(OOH)SCH₂CH₃, CH₃SCH(OOH)CH₃, and CH₃SCH₂CH₂OOH are ?14.0, ?33.0, ?37.2, and ?32.7 kcal/mol, respectively. Group additivity values were developed for estimating properties of structurally similar and larger sulfur‐containing peroxides. Groups for use in group additivity estimation of sulfur peroxide thermochemical properties were developed.     

Structure and dynamics of radicals in zeolite matrices: ESR and theoretical studies

Amine radical cations of the type R₃N^·+ and [R₃NCH₂]^·+, R=CH₃, C₃H₇, and nitric oxide, NO, have been used to probe the bonding to the surface and the dynamics of the radicals trapped in the confined space of cages or channels in the zeolite. Regular continuous-wave electron spin resonance (ESR) was employed to study the internal motion of the cation radicals formed by γ-irradiation of amines and related ammonium ions, introduced during the synthesis of the zeolites Al-offretite, SAPO-37, SAPO-42 and AlPO₄-5. The ESR spectra of [(CH₃)₃NCH₂]^·+ radical cation in several studied systems changed reversibly with temperature, indicating dynamical effects. Free rotation about the >N?CH₂ bond of the [(CH₃)₃NCH₂]^·+ species was found to occur in the temperature range of 110 to 300 K, while the rotation about the >N?CH₃ bonds was hindered. The observations confirm the theoretical prediction on the basis of density functional theory calculations, which indicate that the corresponding barriers are of the order of 0.3 and 7 kJ/mol, respectively. The radical cations of the type R₃N^·+ with R=C₂H₅, C₃H₇ were found to undergo a different type of dynamics, involving a two-jump process of the methylene hydrogens next to the nitrogen. A cage or channel size effect on the stability and molecular dynamics was inferred in some cases. Pulsed ESR was employed to study the (NO)₂ triplet-state dimers in Na-A type zeolite, with the purpose to resolve the interaction with surface groups, and to elucidate the role of the zeolite on stabilizing the triplet rather than the usual singlet state. Measurements performed at 5 K gave rise to Fourier transform spectra that were assigned to the dimer species interacting with one or more²³Na nuclei, with approximative parameters A(²³Na)=(4.6, 4.6, 8.2) MHz and Q(²³Na)=(?0.3, ?0.3, 0.6) MHz for the hyperfine and nuclear quadrupole coupling tensors, respectively. The values are of similar magnitude as those determined for the NO?Na⁺ complex. The stability of the triplet-state structure was attributed to unusual geometric structure imposed by the zeolite matrix, with the N?O bonds along a line as in [O?N?Na⁺?N?O], which according to UHF ab initio calculations has a triplet ground     

Carbon-13 NMR Spectra of Some Group VIIB Transition Metal Thiocarbonyl and Selenocarbonyl Complexes

Recently, we reported the discovery of the first examples of transition metal selenocarbonyl complexes, (n⁵-C₅H₅) Mn (CO)₂ (CSe) and (n⁶-C₆H₅CO₂CH₂(CO)₂ (CSe).¹ These complexes are particularly interesting because, unlike CO and CS, the diatomic CSe molecule has so far eluded isolation even at very low temperatures,² and so these complexes represent the stabilization of a chemically unstable species through coordination to a metal (cf. metal carbene complexes). We have also synthesized several thiocarbonyl complexes of the same type,^3,4 as well as the analogous rhenium selenocarbonyl complexes.⁴ While many detailed studies of the ¹³C nmr spectra of transition metal carbonyls have appeared in the literature over the past few years, there have been no such studies for the closely related thiocarbonyls and selenocarbonyls, although a few isolated data have been reported recently for metal thiocarbonyls.^5,6 In this communication, we report the ¹³C nmr spectra of the isoelectronic series of complexes, (n⁵-C₅H₄R) M(COI)₂ (CX) (M = Mn, R = H, CH₃; M = Re, R = H; X = O,S, Se).     

Investigation of the kinetics of OH∗ and CH∗ chemiluminescence in hydrocarbon oxidation behind reflected shock waves

The temporal variation of chemiluminescence emission from OH^?(A² Σ ⁺) and CH^?(A² Δ) in reacting Ar-diluted H₂/O₂/CH₄, C₂H₂/O₂ and C₂H₂/N₂O mixtures was studied in a shock tube for a wide temperature range at atmospheric pressures and various equivalence ratios. Time-resolved emission measurements were used to evaluate the relative importance of different reaction pathways. The main formation channel for OH^? in hydrocarbon combustion was studied with CH₄ as benchmark fuel. Three reaction pathways leading to CH^? were studied with C₂H₂ as fuel. Based on well-validated ground-state chemistry models from literature, sub-mechanisms for OH^? and CH^? were developed. For the main OH^?-forming reaction CH+O₂=OH^?+CO, a rate coefficient of k ₂=(8.0±2.6)×10¹⁰ cm³?mol^?1?s^?1 was determined. For CH^? formation, best agreement was achieved when incorporating reactions C₂+OH=CH^?+CO (k ₅=2.0×10¹⁴ cm³?mol^?1?s^?1) and C₂H+O=CH^?+CO (k ₆=3.6×10¹²exp(?10.9 kJ?mol^?1/RT) cm³?mol^?1?s^?1) and neglecting the C₂H+O₂=CH^?+CO₂ reaction.     

Pulsed ESR and molecular motions

The possibilities of applying three different pulsed ESR techniques have been considered: 1. Phase relaxation measurements by electron spin echo (ESE) affords the estimation of the correlation time of the motion in the region up to 10^?5 s. The results of theoretical and experimental analysis of the effect of methyl group rotation in nitroxide radicals have been proposed. 2. The method of pulsed saturation involving detection of ESE signal allows the range of the measured times to be extended up to the values of about 10^?2 s. The rotation of CH₂ group in the CH₂CO₂ ^? radical and that of the CH₃ group in the CH₃CHCO₂ ^? radical have been investigated. 3. The method of pulsed saturation combined with pulsed scanning of H₀ allows the analysis of the rotationally induced redistribution of the pulsed saturation throughout the ESR spectra of the radicals. This version of pulsed ESR has been used to study the mobility of nitroxide spin labels.     

CH3OH在ZnO(0001)表面的光催化解离

本文利用266 nm波长的激光及程序升温脱附的方法研究了甲醇在ZnO(0001)表面的光催化反应. TPD结果显示部分的CH₃OH以分子的形式吸附在ZnO(0001)表面,而另外一部分在表面发生了解离. 实验过程中探测到H₂,CH₃^·,H₂O,CO,CH₂O,CO₂和CH₃OH这些热反应产物. 紫外激光照射实验结果表明光照可以促进CH₃OH/CH₃O^·解离形成CH₂O,在程序升温或光照的过程中它又可以转变为HCOO^-. CH₂OH_Zn与OH_ad反应在Zn位点上形成H₂O分子. 升温或光照都能促进CH₃O^·转变为CH₃^·. 该研究对CH₃OH在ZnO(0001)表面的光催化反应机理提供了一个新的见解.     

ESR of Gamma Irradiation and Ultraviolet Photolysis Products in Some Tetrasubstituted Ammonium Compounds

Abstract

The electron spin resonance of gamma and ultraviolet irradiated tetrabutylammonium halides [CH₃(CH₂)₃]₄NX (X=I,Cl,Br), tetrabutylammonium hydrogen sulfate [CH₃(CH₂)₃]₄NHSO₄, tetrabutylammonium periodate [CH₃(CH₂)₃]₄NIO₄, and ultraviolet photolyzed tetramethylammonium iodide, (CH₃)₄NI, and tetramethylphosphonium iodide, (CH₃)₄PI have been investigated between 140 and 350 K. The gamma and ultraviolet irradiation damage centers in tetrabutylammonium compounds were attributed to CH₃—CH^…—CH^…—CH₂, radicals, and ultraviolet photolysis damage centers in tetramethylammonium and phosphonium iodides were attributed to ?H₃ radicals. The g values of both radicals are found to be isotropic and g = 2.0030 and 2.0037 respectively to the methylallyl and the methyl radicals. The hyperfine coupling constants of the free electron to the protons in the radicals are reported and discussed.     

The catalytic effects of H2CO3, CH3COOH,HCOOH and H2O on the addition reaction of CH2OO + H2O → CH2(OH)OOH

The addition reaction of CH₂OO + H₂O → CH₂(OH)OOH without and with X (X = H₂CO₃, CH₃COOH and HCOOH) and H₂O was studied at CCSD(T)/6-311+ G(3df,2dp)//B3LYP/6-311+G(2d,2p) level of theory. Our results show that X can catalyse CH₂OO + H₂O → CH₂(OH)OOH reaction both by increasing the number of rings, and by adding the size of the ring in which ring enlargement by COOH moiety of X inserting into CH₂OO···H₂O is favourable one. Water-assisted CH₂OO + H₂O → CH₂(OH)OOH can occur by H₂O moiety of (H₂O)₂ or the whole (H₂O)₂ forming cyclic structure with CH₂OO, where the latter form is more favourable. Because the concentration of H₂CO₃ is unknown, the influence of CH₃COOH, HCOOH and H₂O were calculated within 0–30 km altitude of the Earth's atmosphere. The results calculated within 0–5 km altitude show that H₂O and HCOOH have obvious effect on enhancing the rate with the enhancement factors are, respectively, 62.47%–77.26% and 0.04%–1.76%. Within 5–30 km altitude, HCOOH has obvious effect on enhancing the title rate with the enhancement factor of 2.69%–98.28%. However, compared with the reaction of CH₂OO + HCOOH, the rate of CH₂OO···H₂O + HCOOH is much slower.     

The 13C bicarbonate method: an inverse end product method for measuring CO2 production and energy expenditure

We reconsider the principle of the ¹³C bicarbonate (NaH¹³CO₃) method (¹³C-BM) for the determination of the CO₂ production to obtain an estimate of energy expenditure (EE). Its mathematical concept based on a three-compartmental model is related to the [¹⁵N]glycine end product method. The CO₂ production calculated by the ¹³C-BM, R_aCO₂(¹³C) is compared to the result from the indirect calorimetry, RCO₂(IC). In an interspecies comparison (dog, goat, horse, cattle, children, adult human; body mass ranging from 15 to 350?kg, resting and fasting conditions) we found an excellent correlation between the results of ¹³C-BM and IC with RCO₂(IC)?=?0.703?×?R_aCO₂(¹³C), (R²?=?0.99). The slope of this correlation corresponds to the fractional ¹³C recovery (RF(¹³C)) of ¹³C in breath CO₂ after administration of NaH¹³CO₃. Significant increase in RF(¹³C) was found in physically active dogs (0.95?±?0.14; n?=?5) vs. resting dogs (0.71?±?0.10, n?=?17; p?=?.015). The ¹³C recovery in young bulls was greater in blood CO₂ (0.81?±?0.05) vs. breath CO₂ (0.73?±?0.05, n?=?12, p?<?.001) and in ponies with oral (0.76?±?0.03, n?=?8) vs. intravenous administration of NaH¹³CO₃ (0.69?±?0.07; n?=?8; p?=?.026). We suggest considering the ¹³C-BM as a ‘stand-alone’ method to provide information on the total CO₂ production as an index of EE.     

EPR Study of γ-Irradiated UHMWPE Doped with Vitamin E: Assessment of Thermal Effects on the Organic Radicals During Vitamin E Diffusion

Thermal effects on ultra-high-molecular-weight polyethylene (UHMWPE) residual radicals during the vitamin E diffusion process were studied in detail. Electron paramagnetic resonance (EPR) technique showed a significant reduction in concentrations of radiation-induced primary (alkyl (–CH₂– ^?CH–CH₂–), allyl (–CH₂–^?CH=CH–CH–CH₂–) and polyenyl (–^?CH–[CH=CH–] _m –) with m > 3) radicals for both control and vitamin E-doped samples. The concentrations of radiation-induced primary radicals (RIPRs) were found to decrease proportionally with the heat/diffusion time. While the EPR spectra of the control samples showed only polyethylene (PE) radicals, the spectra of vitamin E-doped samples were found to exhibit vitamin E radicals in addition to PE radicals. Of particular interest, the heat involved during vitamin E diffusion plays a significant role in reducing the radiation-induced primary radicals of UHMWPE. For 120 min of heat/diffusion time, the available quantity of primary radicals in control samples were found to be ~7.5 % of initial radicals. The leftover amounts of these primary radicals for vitamin E-doped samples were approximately ~10.0 %. In addition to this, EPR power saturation techniques were also used to assess the effects of initial heat/diffusion treatment on the oxygen-induced residual radicals (OIRRs): R₁ (–^?CH–[CH=CH–] _m –) with m > 3 and R₂ (^?OCH–[CH=CH–] _m –) with m = 2 or 3. It was found that the concentration of OIRRs also decreases proportionally with initial heat/diffusion time. The remaining amount of OIRRs relative to leftover RIPRs after heat/diffusion was found to be approximately 4.0 % in controls and was still found to be 10.0 % in vitamin E-doped UHMWPE. This may indicate that vitamin E slows down the oxidation processes, which may contribute to the strong oxidation resistance of vitamin E-doped UHMWPE.     

Dilution effects analysis of opposed-jet H2/CO syngas diffusion flames

This paper reported the analysis of dilution effects on the opposed-jet H₂/CO syngas diffusion flames. A computational model, OPPDIF coupled with narrowband radiation calculation, was used to study one-dimensional counterflow syngas diffusion flames with fuel side dilution from CO₂, H₂O and N₂. To distinguish the contributing effects from inert, thermal/diffusion, chemical, and radiation effects, five artificial and chemically inert species XH₂, XCO, XCO₂, XH₂O and XN₂ with the same physical properties as their counterparts were assumed. By comparing the realistic and hypothetical flames, the individual dilution effects on the syngas flames were revealed. Results show, for equal-molar syngas (H₂/CO = 1) at strain rate of 10 s^?1, the maximum flame temperature decreases the most by CO₂ dilution, followed by H₂O and N₂. The inert effect, which reduces the chemical reaction rates by behaving as the inert part of mixtures, drops flame temperature the most. The thermal/diffusion effect of N₂ and the chemical effect of H₂O actually contribute the increase of flame temperature. However, the chemical effect of CO₂ and the radiation effect always decreases flame temperature. For flame extinction by adding diluents, CO₂ dilution favours flame extinction from all contributing effects, while thermal/diffusion effects of H₂O and N₂ extend the flammability. Therefore, extinction dilution percentage is the least for CO₂. The dilution effects on chemical kinetics are also examined. Due to the inert effect, the reaction rate of R84 (OH+H₂ = H+H₂O) is decreasing greatly with increasing dilution percentage while R99 (CO+OH→CO₂+H) is less affected. When the diluents participate chemically, reaction R99 is promoted and R84 is inhibited with H₂O addition, but the trend reverses with CO₂ dilution. Besides, the main chain-branching reaction of R38 (H+O₂→O+OH) is enhanced by the chemical effect of H₂O dilution, but suppressed by CO₂ dilution. Relatively, the influences of thermal/diffusion and radiation effects on the reaction kinetics are then small.     

Termolecular chemistry facilitated by radical-radical recombinations and its impact on flame speed predictions

Recent theoretical studies have shown that termolecular chemistry can be facilitated through reactions of flame radicals (H, O, and OH) or O₂ with highly-energized collision complexes (either radical or stable species) formed in exothermic reactions. In this work, radical-radical recombination reaction induced termolecular chemistry and its impact on combustion modeling was studied. Two recombination reactions, H + CH₃ + M → CH₄ + M and H + OH + M → H₂O + M, were analyzed using ab-initio master equation analyses guided by quasiclassical trajectory results. The dynamics results and the master equation calculations indicate that CH₄^? and H₂O^? (formed in the two radical-radical reactions outlined above) react rapidly with flame radicals and O₂ at rates that are competitive with collisional cooling. The addition of these processes into conventional combustion modeling requires two modifications: the inclusion of the new nonthermal termolecular reaction rates and the simultaneous reduction of the competing recombination reaction rates. The former is described with newly derived Arrhenius expressions based on quasiclassical trajectories, and the latter is achieved by perturbing the recombination reaction rate during the simulation. Kinetic modeling was used to gauge the impact of including this nonthermal chemistry for H₂/CH₄-air laminar flames speeds. Inclusion of this nonthermal chemistry has a noticeable impact on simulated flame speeds. The procedure developed here can be utilized to properly quantify the effects of such nonthermal reactions in macroscopic kinetic models.