CO H2 Reaction Research Articles

Dynamics of the reaction CH2I + O2 probed via infrared emission of CO, CO2, OH and H2CO.

The reaction CH2I + O2 has been widely employed recently for the production of the simplest Criegee intermediate CH2OO in laboratories, but the detailed dynamics of this reaction have been little explored. Infrared emission of several products of this reaction, initiated on irradiation of CH2I2 and O2 (∼8 Torr) in a flowing mixture at 308 or 248 nm, was recorded with a step-scan Fourier-transform spectrometer; possible routes of formation were identified according to the observed vibrational distribution of products and published theoretical potential-energy schemes. Upon irradiation at 308 nm, Boltzmann distributions of CO (v ≤ 5, J ≤ 19) with an average vibrational energy of 32 ± 3 kJ mol-1 and OH (v ≤ 3, J ≤ 5.5) with an average vibrational energy of 29 ± 4 kJ mol-1 were observed and assigned to the decomposition of HCOOH* to form CO + H2O and OH + HCO, respectively. The broadband emission of CO2 was simulated with two vibrational distributions of average energies (91 ± 4) and (147 ± 8) kJ mol-1 and assigned to be produced from the decomposition of HCOOH* and methylene bis(oxy), respectively. Upon irradiation of samples at 248 nm, the emission of OH and CO2 showed similar distributions with slightly greater energies, but the distribution of CO (v ≤ 11, J ≤ 19) became bimodal with average vibrational energies of (23 ± 4) and (107 ± 29) kJ mol-1, and branching (56 ± 5) : (44 ± 5). The additional large-v component is assigned to be produced from a secondary reaction HCO + O2 to form CO + HO2; HCO is a coproduct of OH. The branching between CO and OH is (50 ± 5) : (50 ± 5) at 308 nm and (64 ± 5) : (36 ± 4) at 248 nm, consistent with the mechanism according to which an additional channel to produce CO opens at 248 nm. Highly internally excited H2CO was also observed. With O2 at 16 Torr, the extrapolated nascent internal distributions are similar to those with O2 at 8 Torr except for a slight quenching effect.

First-Principles Study of the Reaction Mechanism of CHO + H on Graphene Surface.

Many organic molecules observed in the interstellar medium are considered to be formed on dust grains and populated into the gas phase. We analyzed the reaction of HCO + H on a graphene surface using ab initio molecular dynamics simulations as a case study of the formation and desorption of organic molecules on interstellar dust particles. During the reactions of chemisorbed CHO (chemisorbed at the C atom) with free H, CO was generated and efficiently desorbed from the surface. These results suggest that the reactions, of which the reactant forms a covalent bond with the surface while the product does not, cause efficient desorption of the product upon reaction. In such reactions a repulsive force between the product and the surface would be generated and accelerate translation of the product in a specific direction. In addition, it was also shown that the branching ratio of the reactions between radical species on the surface would be affected by the form of the adsorption on the surface, e.g., when a free H reacted with the CHO chemisorbed at the C atom, CH2O was not generated.

Co-optima fuels combustion: A comprehensive experimental investigation of prenol isomers

Carbon monoxide time-histories, ignition delay times, and laminar burning velocity measurements are reported for the oxidation of 3-methyl-2-buten-1-ol (prenol) and 3-methyl-3-buten-1-ol (isoprenol). These prenols are fuel candidates outlined by the U.S. Department of Energy’s Co-Optimization of Fuels and Engines (Co-Optima) program. The laminar burning velocity measurements were conducted for two fuels with synthetic air within a constant-volume spherical combustion chamber at initial conditions of 428 K and 1 atm for a range of equivalence ratios from 0.75 to 1.50. The laminar burning velocities of the two fuels were found to be similar, and the maximum value occurred at an equivalence ratio near 1.0. Carbon monoxide time-histories and ignition delay times were recorded behind reflected shockwaves in a double-diaphragm, heated shock tube over the temperature range 1269–1472 K near 9.4 atm with a mixture of 0.05% fuel/0.35% O2/99.6% Ar. Comparisons with predictions of a detailed chemical kinetic mechanism from the literature were provided. Current model predictions overpredicted both the ignition delay time and the max CO yield; however, the model captured the profile of CO formation well. Detailed uncertainty and sensitivity analyses were carried out to identify important reactions that need attention for accurate prediction of these fuel’s chemistry. Further investigation into the rate of C3H3 + O2 = CH2CO + HCO reaction was suggested based on current experiments. The experimental data and analysis presented here is critical in the development, validation and improvement of kinetic models of these promising Co-Optima fuels.

Molecular dynamics of combustion reactions in supercritical carbon dioxide. Part 4: boxed MD study of formyl radical dissociation and recombination.

Fossil fuel oxy-combustion is an emergent technology where habitual nitrogen diluent is replaced by high pressure (supercritical) carbon dioxide. The supercritical state of CO2 increases the efficiency of the energy conversion and the absence of nitrogen from the reaction mixture reduces pollution by NOx. However, the effects of a supercritical environment on elementary reactions kinetics are not well understood at present. We used boxed molecular dynamics simulations at the QM/MM theory level to predict the kinetics of dissociation/recombination reaction HCO• + [M] ↔ H• + CO + [M], an important elementary step in many combustion processes. A wide range of temperatures (400-1600K) and pressures (0.3-1000atm) were studied. Potentials of mean force were plotted and used to predict activation free energies and rate constants. Based on the data obtained, extended Arrhenius equation parameters were fitted and tabulated. The apparent activation energy for the recombination reaction becomes negative above 30atm. As the temperature increased, the pressure effect on the rate constant decreased. While at 400K the pressure increase from 0.3atm to 300atm accelerated the dissociation reaction by a factor of 250, at 1600K the same pressure increase accelerated this reaction by a factor of 100. Graphical abstract Formyl radical surrounded by carbon dioxide molecules.

Dynamical interference in the vibronic bond breaking reaction of HCO.

First-principles treatments of quantum molecular reaction dynamics have reached the level of quantitative accuracy even in cases with strong non-Born-Oppenheimer effects. This achievement permits the interpretation of puzzling experimental phenomena related to dynamics governed by multiple coupled potential energy surfaces. We present a combined experimental and theoretical study of the photodissociation of formyl radical (HCO). Oscillations observed in the distribution of product states are found to arise from the interference of matter waves-a manifestation analogous to Young's double-slit experiment.

The sensitizing effects of NO2 and NO on methane low temperature oxidation in a jet stirred reactor

Abstract The oxidation of neat methane (CH 4 ) and CH 4 doped with NO 2 or NO in argon has been investigated in a jet-stirred reactor at 107 kPa, temperatures between 650 and 1200 K, with a fixed residence time of 1.5 s, and for different equivalence ratios (Φ), ranging from fuel-lean to fuel-rich conditions. Four different diagnostics have been used: gas chromatography (GC), chemiluminescence NO x analyzer, continuous wave cavity ring-down spectroscopy (cw-CRDS) and Fourier transform infrared spectroscopy (FTIR). In the case of the oxidation of neat methane, the onset temperature for CH 4 oxidation was above 1025 K, while it is shifted to 825 K with the addition of NO 2 or NO, independently of equivalence ratio, indicating that the addition of NO 2 or NO highly promotes CH 4 oxidation. The consumption rate of CH 4 exhibits a similar trend with the presence of both NO 2 and NO. The amount of produced HCN has been quantified and a search for HONO and CH 3 NO 2 species has been attempted. A detailed kinetic mechanism, derived from POLIMI kinetic framework, has been used to interpret the experimental data with a good agreement between experimental data and model predictions. Reaction rate and sensitivity analysis have been conducted to illustrate the kinetic regimes. The fact that the addition of NO or NO 2 seems to have similar effects on promoting CH 4 oxidation can be explained by the fact that both species are involved in a reaction cycle interchanging them and whose result is 2CH 3 + O 2 = 2CH 2 O + 2H. Additionally, the direct participation of NO 2 in the NO 2 + CH 2 O = HONO + HCO reaction has a notable accelerating effect on methane oxidation.

Full dimensional potential energy surface and low temperature dynamics of the H2CO + OH → HCO + H2O reaction.

A new method is proposed to analytically represent the potential energy surface of reactions involving polyatomic molecules capable of accurately describing long-range interactions and saddle points, needed to describe low-temperature collisions. It is based on two terms, a reactive force field term and a many-body term. The reactive force field term accurately describes the fragments, long-range interactions among them and the saddle points for reactions. The many-body term increases the desired accuracy everywhere else. This method has been applied to the OH + H2CO → H2O + HCO reaction, giving a barrier of 27.4 meV. The simulated classical rate constants with this potential are in good agreement with recent experimental results [Ocaña et al., Astrophys. J., 2017, submitted], showing an important increase at temperatures below 100 K. The reaction mechanism is analyzed in detail here, and explains the observed behavior at low energy by the formation of long-lived collision complexes, with roaming trajectories, with a capture observed for very long impact parameters, >100 a.u., determined by the long-range dipole-dipole interaction.

Isotope exchange reactions involving HCO+ with CO: A theoretical approach

Aims. We aim to investigate fractionation reactions involved in the 12C/13C, 16O/18O, and 17O balance. Methods. Full-dimensional rovibrational calculations were used to compute numerically exact rovibrational energies and thermal equilibrium conditions to derive the reaction rate coefficients. A nonlinear least-squares method was employed to represent the rate coefficients by analytic functions. Results. New exothermicities are derived for 30 isotopic exchange reactions of HCO+ with CO. For each of the reactions, we provide the analytic three-parameter Arrhenius-Kooij formula for both the forward reaction and backward reaction rate coefficients, that can further be used in astrochemical kinetic models. Rotational constants derived here for the 17O containing forms of HCO+ may assist detection of these cations in outer space.

Mechanisms of carbon monoxide hydrogenation yielding formaldehyde catalyzed by the representative strong mineral acid, H2SO4, and Lewis-Brønsted superacid, HF/AlF3.

The mechanism of the CO + H2→ H2CO reaction catalyzed by acidic systems was investigated theoretically using the ab initio MP2 and CCSD(T) methods and the aug-cc-pVDZ basis set (the effects of the surrounding solvent molecules were approximated by employing the polarized continuum solvation model). Two representative acids were chosen to verify the usefulness of such catalysts in this process: sulfuric acid (as a strong mineral acid) and HAlF4 (as a superacid). Detailed mechanisms in both gas and liquid phases proceeding either along a concerted path or according to a stepwise route were investigated and discussed. The most important findings include the observation that both acids seem to catalyze the carbon monoxide hydrogenation in a qualitatively similar way but only the HAlF4 superacid is predicted to effectively reduce the activation barriers to render the whole process plausible.

State-of-the-Art Thermochemical and Kinetic Computations for Astrochemical Complex Organic Molecules: Formamide Formation in Cold Interstellar Clouds as a Case Study.

We describe an integrated computational strategy aimed at providing reliable thermochemical and kinetic information on the formation processes of astrochemical complex organic molecules. The approach involves state-of-the-art quantum-mechanical computations, second-order vibrational perturbation theory, and kinetic models based on capture and transition state theory together with the master equation approach. Notably, tunneling, quantum reflection, and leading anharmonic contributions are accounted for in our model. Formamide has been selected as a case study in view of its interest as a precursor in the abiotic amino acid synthesis. After validation of the level of theory chosen for describing the potential energy surface, we have investigated several pathways of the OH + CH2NH and NH2 + H2CO reaction channels. Our results show that both reaction channels are essentially barrierless (in the sense that all relevant transition states lie below or only marginally above the reactants) and once tunneling is taken into the proper account indicate that the reaction can occur under the low temperature conditions of interstellar environments.

SYNTHESIS OF FORMAMIDE AND RELATED ORGANIC SPECIES IN THE INTERSTELLAR MEDIUM VIA CHEMICAL DYNAMICS SIMULATIONS

ABSTRACT We show, by means of direct dynamics simulations, how it is possible to define possible reactants and mechanisms leading to the formation of formamide in the interstellar medium. In particular, different ion–molecule reactions in the gas phase were considered: NH3OH+, NH2OH , H2COH+, and NH4 + for the ions and NH2OH, H2CO, and NH3 for the partner neutrals. These calculations were combined with high level ab initio calculations to investigate possible further evolution of the products observed. In particular, for formamide, we propose that the NH2OH + H2CO reaction can produce an isomer, NH2OCH , that, after dissociative recombination, can produce neutral formamide, which was observed in space. The direct dynamics do not pre-impose any reaction pathways and in other reactions, we did not observe the formation of formamide or any possible precursor. On the other hand, we obtained other interesting reactions, like the formation of NH2CH . Finally, some radiative association processes are proposed. All of the results obtained are discussed in light of the species observed in radioastronomy.

Quantitative HNO detection behind shock waves

Knowledge about the high temperature kinetics of HNO, which represents a key species in NOx flame chemistry, is scarce. Using the very sensitive absorption based frequency modulation (FM) spectroscopy, HNO has been measured behind shock waves for the first time. The UV photolysis of glyoxal/NO mixtures at λ=193 nm served as an HNO source with stable HNO concentration plateaus generated via the fast initial formation of HCO radicals followed by the reaction HCO + NO → CO + HNO. FM line shapes of three selected transitions of the A˜1A′′(100)−X˜1A′(000) band of HNO have been recorded and their pressure broadening coefficient has been determined. By analyzing HNO and HCO concentration-time profiles measured under very similar reaction conditions it was possible to confirm an HCO/HNO formation mechanism and to determine the HNO absorption cross section. The expression log[σc(HNO,p=0bar,295K<T<1800K)/cm2mol−1]= 5.86 – 1.62×10−3×T/K+2.74×10−7×T2/K2 with an uncertainty of ± 40% in σc is recommended for the RR3(4) rotational line at ν˜=16173.86 cm−1 (618.2816 nm). The capability to perform quantitative HNO measurements behind shock wave make possible direct rate constant studies of bimolecular HNO reactions in future experiments.

THE H2 + CO H2CO REACTION: RATE CONSTANTS AND RELEVANCE TO HOT AND DENSE ASTROPHYSICAL MEDIA

ABSTRACT A theoretical thermochemical and kinetic investigation of the thermal H2 + CO ↔ H2CO reaction was performed for a temperature range from 200 to 4000 K. Geometries and vibrational frequencies of reactants, product, and transition state (TS) were obtained at CCSD/cc-pVxZ (x = T and Q) levels and scaling factors were employed to consider anharmonicity effects on vibrational frequencies, zero-point energies, and thermal corrections provided by these methodologies. Enthalpies Gibbs energies, and rate constants for this reaction were determined by including a complete basis set extrapolation correction for the electronic properties calculated at CCSD(T)/cc-pVyZ (y = Q and 5) levels. Our study indicates that enthalpy changes for this reaction are highly dependent on temperature. Moreover, forward and reverse (high-pressure limit) rate constants were obtained from variational TS theory with quantum tunneling corrections. Thus, modified Arrhenius’ equations were fitted by means of the best forward and reverse rate constant values, which provide very reliable estimates for these quantities within the temperature range between 700 and 4000 K. To our knowledge, this is the first kinetic study done for the forward H2 + CO H2CO process in a wide temperature range. Finally, these results can be used to explain the formaldehyde abundance in hot and dense interstellar media, possibly providing data about the physical conditions associated with H2CO masers close to massive star-forming regions.

Numerical simulations of steady perforated-plate stabilized Syngas air pre-mixed flames

Numerical investigations of steady, laminar premixed Syngas-air flames are presented in this paper. Three-dimensional simulations were performed to examine the impact of operating conditions on steady state characteristics of perforated burner flame. A detailed H2CO reaction mechanism having 12 species and 38 reactions was used for combustion modelling. The three dimensional simulation results are validated against the 1D flat flame result using PREMIX. Effects of inlet velocity, fuel composition and equivalence ratio on flame stability were examined. A clearly identified recirculation zone was present above the top surface of the burner plate in the case of 50% H2-50% CO Syngas mixture. The strength recirculation zone was diminishing with the increase in percentage of hydrogen in the Syngas mixture, and the flame has stabilized closer to the top surface of the burner plate. The flame stand-off distance is found to decrease with increase in inlet velocity. Effect of increase in H2 fraction in Syngas has less effect on flame height at higher H2 fractions.

Numerical analysis of knock during HCCI in a high compression ratio methanol engine based on LES with detailed chemical kinetics

In this study, knock during HCCI (homogeneous charge compression ignition) was studied based on LES (large eddy simulation) with methanol chemical kinetics (84-reaction, 21-species) in a high compression ratio methanol engine. The non-knocking and knocking combustion of SI (spark ignition) and HCCI engines were compared. The results showed that the auto-ignition spots were initially occurred near the combustion chamber wall. The knocking combustion burnt faster during HCCI than SI methanol engine. The HCO reaction rate was different from SI engine, it had two obvious peaks, one was positive peak, and another was negative peak. Compared with the SI methanol engine, in addition to the concentration of HCO, the concentrations of the other intermediate products and species such as CO, OH, CH2O, H2O2, HO2 were increased significantly; the reaction rates of CH2O, H2O2, and HO2 had negative peaks, and whose values were several times higher than SI methanol engine.

Glyoxal Oxidation Mechanism: Implications for the Reactions HCO + O2 and OCHCHO + HO2.

A detailed mechanism for the thermal decomposition and oxidation of the flame intermediate glyoxal (OCHCHO) has been assembled from available theoretical and experimental literature data. The modeling capabilities of this extensive mechanism have been tested by simulating experimental HCO profiles measured at intermediate and high temperatures in previous glyoxal photolysis and pyrolysis studies. Additionally, new experiments on glyoxal pyrolysis and oxidation have been performed with glyoxal and glyoxal/oxygen mixtures in Ar behind shock waves at temperatures of 1285-1760 K at two different total density ranges. HCO concentration-time profiles have been detected by frequency modulation spectroscopy at a wavelength of λ = 614.752 nm. The temperature range of available direct rate constant data of the high-temperature key reaction HCO + O2 → CO + HO2 has been extended up to 1705 K and confirms a temperature dependence consistent with a dominating direct abstraction channel. Taking into account available literature data obtained at lower temperatures, the following rate constant expression is recommended over the temperature range 295 K < T < 1705 K: k1/(cm(3) mol(-1) s(-1)) = 6.92 × 10(6) × T(1.90) × exp(+5.73 kJ/mol/RT). At intermediate temperatures, the reaction OCHCHO + HO2 becomes more important. A detailed reanalysis of previous experimental data as well as more recent theoretical predictions favor the formation of a recombination product in contrast to the formerly assumed dominating and fast OH-forming channel. Modeling results of the present study support the formation of HOCH(OO)CHO and provide a 2 orders of magnitude lower rate constant estimate for the OH channel. Hence, low-temperature generation of chain carriers has to be attributed to secondary reactions of HOCH(OO)CHO.

Unique active site structure for C2 oxygenated compound formation in CO–H2 reaction over ordered mesoporous CeO2 supported Rh catalysts

Inside ordered mesopores of ceria, thin silica overlayers were formed on the ceria surface, which can make alkali metal cations highly dispersed as Si–O–(alkali metal)+. When nanoparticles of Rh were impregnated into these modified ceria mesopores, unique tilted CO adsorption sites (RhCOalkali metal+) were formed, which might stabilize reaction intermediates of C2 oxygenated compounds and which might enhance their selective formation in CO–H2 reaction under mild conditions.

Catalytic NO activation and NO–H2 reaction pathways

Kinetic and isotopic data on Pt clusters and activation free energy barriers from density functional theory (DFT) on Pt(111) are used to assess the elementary steps involved in NO–H2 reactions. Pt clusters 1–10nm in diameter gave similar turnover rates, indicating that these elementary steps are insensitive to surface-atom coordination. N–O cleavage occurs after sequential addition of two chemisorbed H-atoms (H*) to NO* which are quasi-equilibrated with H2 and NO co-reactants. The first step is equilibrated and forms HNO*, while the second addition is irreversible and forms *HNOH*; this latter step limits NO–H2 rates and forms OH* and NH* intermediates that undergo fast reactions to give H2O, N2O, NH3, and N2. These conclusions are consistent with (i) measured normal H/D kinetic isotope effects; (ii) rates proportional to H2 pressure, but reaching constant values at higher pressures; (iii) fast H2–D2 equilibration during catalysis; and (iv) DFT-derived activation barriers. These data and calculations, taken together, rule out N–O cleavage via NO* reactions with another NO* (forming O* and N2O) or with vicinal vacancies (forming N* and O*), which have much higher barriers than H*-assisted routes. The cleavage of N–O bonds via *HNOH* intermediates is reminiscent of C–O cleavage in CO–H2 reactions (via *HCOH*) and of O–O cleavage in O2–H2 reactions (via OOH* or *HOOH*). H*-addition weakens the multiple bonds in NO, CO, and O2 and allows coordination of each atom to metal surfaces; as a result, dissociation occurs via such assisted routes at all surface coverages relevant in the practice of catalysis.

Kinetic analysis of co formation under oxy-combustion conditions

The paper reports the results of numerical computations concerning the formation of CO in the kinetic flame during natural gas oxy-combustion. The effect of temperature, reagent residence time and the composition of an atmosphere containing CO2 with 21 and 29 vol % O2 on the variation of CO concentration in the flame was examined. The oxy-combustion process was conducted with a 25 % excess oxygen. The analysis of reactions in flames at temperatures of 1500 K and 1800 K was performed within the Chemked II program using the combustion mechanism proposed by Mendiara & Glarborg, which includes 779 reactions. The computation results have confirmed that the rate of the key reactions responsible for the production of CO in the flame depends on the flame temperature and the oxy-combustion temperature. The peak CO concentrations are higher for the oxidizing mixture containing 29 vol % O2. After attaining a maximum, the CO flame concentration drops faster for an atmosphere richer in oxygen. The longer the time of reagent residence in the flame region, the lower the CO concentration. In different atmospheres and at different combustion temperatures, an identical CO level can be achieved in wet combustion gas. Irrespective of the temperature and atmosphere of oxy-combustion, most CO is produced as a result of the reaction OH + CO HCO2. The reduction of oxygen in the oxidizing atmosphere at flame temperatures of 1500 and 1800 K lowers the CO production in the dominant reactions responsible for CO formation. The contribution of individual reactions in the CO production for the identical atmospheres is different with varying temperature. In the case of the reaction HCO + O2 HO2 +CO, the temperature increase reduces the CO production. A reverse dependence of CO production on temperature characterizes the reaction H2 + CO + M CH2O + M. In addition, change in temperature changes the order in which the dominant reactions occur. Within the residence time equal to 100 ms, two periods of intensified CO production and consumption can be identified. The peak concentrations of H, OH and O radicals in the flame attain a maximum within the same time; as time goes by, the highest concentration is achieved by OH radicals. The presence of considerable levels of CO2 in the combustion substrates has an inhibiting effect on the natural gas oxidation process.

The H + CO ⇌ HCO reaction studied by ab initio benchmark calculations

The title reaction has been calculated using complete active space self-consistent field and internally contracted multi-reference configuration interaction, including Davidson correction, calculations. Dunning's correlation consistent atomic basis sets, together with several complete basis set extrapolation schemes, were employed. Core-valence and scalar relativistic effects were also taken into account, as well as anharmonicity of the vibrational modes. Core-valence correlation appears to have a large impact on the calculated frequencies, spectroscopic constants, and on the energetics. In particular, the best estimate for the HCO (DCO) formation barrier height at 0 K, 4.54 ± 0.14 (4.43 ± 0.14) kcal mol(-1) is larger than previous theoretical works and well above the usually accepted value of 2.0 ± 0.4 kcal mol(-1), measured at room temperature. Inclusion of temperature and entropy at 298 K does not seem to be able to solve this discrepancy. The present theoretical barrier height is therefore the recommended value. The exo-ergicity of the HCO (DCO) dissociation reaction, predicted to be -13.36 ± 0.57 (-14.72 ± 0.57) kcal mol(-1), is slightly below the experimental value. Finally, all tested density functionals fail to reproduce accurately both the formation and dissociation barriers.