Reaction Rate Coefficients Research Articles

Cost-Effective Implementation of Multiconformer Transition State Theory for Alkoxy Radical Unimolecular Reactions.

Alkoxy radicals are important intermediates in the gas-phase oxidation of volatile organic compounds (VOCs) determining the nature of the first-generation products. An accurate description of their chemistry under atmospheric conditions is essential for understanding the atmospheric oxidation of VOCs. Unfortunately, experimental measurements of the rate coefficients of unimolecular alkoxy radical reactions are scarce, especially for larger systems. As has previously been done for peroxy radical hydrogen shift reactions, we present a cost-effective approach to the practical implementation of multiconformer transition state theory (MC-TST) for alkoxy radical unimolecular (H-shift and decomposition) reactions. Specifically, we test the optimal approach for the conformational sampling as well as the best value for a cutoff of high-energy conformers. In order to obtain accurate rate coefficients at a reduced computational cost, an energy cutoff is employed to reduce the required number of high-level calculations. The rate coefficients obtained with the developed theoretical approach are compared to available experimental rate coefficients for both 1,5 H-shifts and decomposition reactions. For all but one of the reactions tested, the calculated MC-TST rate coefficients agree with experimental results to within a factor of 7. The discrepancy for the final reaction is about a factor of 15, but part of the discrepancy is caused by pressure effects, which are not included in MC-TST. Thus, for the fastest alkoxy reactions, deviation from the high-pressure limit even at 1 bar should be considered.

Theoretical study on the formation of Criegee intermediates from ozonolysis of pentenal: An example of trans-2-pentenal.

In this study, we investigated the reaction mechanism and kinetics of ozone with trans-2-pentenal using density functional theory (DFT) and conventional transition state theory (CTST). At 298K and 1atm, the gas-phase reaction mechanisms and kinetic parameters were calculated at the level of CCSD(T)/6-311+G(d,p)//M06-2X/6-311+G(d,p). Both CC and CO bond cycloaddition as well as hydrogen abstraction were found. The calculations indicated that the main reaction path is 1,3-dipole cycloaddition reactions of ozone with CC bond with the relatively lower syn-energy-barrier of 3.35kcalmol-1 to form primary ozonide which decomposed to produce a carbonyl oxide called a Criegee intermediate (CI) and an aldehyde. The subsequent reactions of CIs were analysed in detail. It is found that the reaction pathways of the novelty CIs containing an aldehyde group are extremely similar with general CIs when they react with NO, NO2, SO2, H2O, CH2O and O2. The condensed Fukui function were calculated to identify the active site of the chosen molecules. At 298K and 1atm, the reaction rate coefficient was 9.13×10-18cm3 molecule-1 s-1 with atmospheric lifetime of 1.3 days. The calculated rate constant is in general agreement with the available experimental data. The branching ratios indicated that syn-addition pathways are prior to anti-addition. The atmospheric ratios for CIs formation and the bimolecular reaction rate constants for the Criegee intermediates with the variety of partners were calculated. Our theoretical results are of importance in atmospheric chemistry of unsaturated aldehyde oxidation by ozone.

Radical addition and H abstraction reactions in C2H2, C2H4, and C2H6: A gateway for ethyl- and vinyl-bearing molecules in the interstellar medium

Context. Recent interstellar detections include a significant number of molecules containing vinyl (C2H3) and ethyl (C2H5) groups in their structure. For several of these molecules, there is no clear experimental or theoretical evidence that supports their formation from simpler precursors. Aims. We carried out a systematic search of viable reactions starting from closed-shell hydrocarbons containing two carbon atoms (ethane, C2H6; ethylene, C2H4; and acetylene, C2H2), with the goal of determining viable chemical routes for the formation of vinyl and ethyl molecules on top of interstellar dust grains. Methods. We used density functional theory calculations in combination with semiclassical instantem theory to derive the rate coefficients for the radical-neutral surface reactions. The effect of a surface was modeled through an implicit surface approach, profiting from the weak interaction between the considered hydrocarbons and the dust surfaces. Results. Our results show that both H and OH radicals are key in converting acetylene and ethylene into more complex radicals that are liable to continue reacting and to form interstellar complex organic molecules. The relevant reactions, for example OH additions, present rate constants above 101 s−1 that are likely competitive with OH diffusion on grains. Similarly, H atom addition to acetylene and ethylene is a very fast process, with rate constants above 104 s−1 in all cases, and is greatly enhanced by quantum tunneling. Hydrogen abstraction reactions are less relevant, but may play a role in specific cases involving the OH radical. Reactions with other radicals NH2 and CH3 are likely to have much less impact on the chemistry of ethyl- and vinyl-bearing molecules. Conclusions. The effective formation at low temperatures of four radicals (C2H3, C2H5, C2H2OH, and C2H4OH) through our proposed mechanism opens the gate for the formation of complex organic molecules, and indicates a potential prevalence of OH-bearing molecules on the grain. Following our suggested reaction pathway, we explain the formation of many of the newly detected molecules, and propose new molecules for detection. Our results reinforce the recent view on the importance of the OH radical in interstellar surface chemistry.

On the chemistry mechanism for low-pressure chlorine process plasmas

A chemical reaction mechanism of chlorine plasma under low-pressure conditions that is widely used in the literature is validated against the experimental data of Y. Wang and J. K. Olthoff [J. Appl. Phys. 85, 6358 (1999)] for an inductively coupled plasma reactor. The model used in the present study is a self-consistent two-dimensional fluid plasma model coupled with Maxwell’s equations. The quantities of interest in the plasma are the fluxes and energy distribution functions of Cl2+ and Cl+ ions. We find that the charge exchange reaction between Cl+ and Cl2 that is typically included in chlorine plasma reaction mechanisms results in poor predictability of the model compared to experiments. Neglecting this reaction allows for a correct prediction of the dominant ion species in the low-pressure chlorine plasma and dependence of their fluxes on the gas pressure. Additionally, neglecting the charge exchange reaction allows for a rather accurate prediction of ion energy distribution functions at the grounded electrode. Overall, we conclude that the rate coefficient of the charge exchange reaction between Cl+ and Cl2 reported in the literature significantly exceeds what may in fact explain the role of this process in a low-pressure plasma discharge.

The Reaction of HO2 and CH3O2: CH3OOH Formed from the Singlet Electronic State Surface

High-level coupled-cluster calculations in combination with two-dimensional master equation simulations were used to study the HO2 + CH3O2 reaction, which plays an important role in the oxidation of methane and hydrocarbons in the Earth’s atmosphere and low-temperature combustion. The main reaction pathways taking place on the lowest-lying triplet and singlet potential energy surfaces (PES) were characterized. Interestingly, methyl hydroperoxide (CH3OOH), the sole product, could be produced from both the triplet and singlet PESs, with a ratio of roughly 9:1. Formaldehyde is not made as a primary product, but can be formed via secondary chemistry. The formation of methyl tetraoxide (MTO) from the singlet PES is unimportant. The calculated reaction rate coefficients were found to be practically pressure-independent for p ≤ 760 Torr and can be given by k(T)=2.75×10−13×e+1.75 kcal mol−1/RT (in cm3/s), an expression useful for kinetics modeling over the range T = 200–800 K. The rate constant has a slight negative Arrhenius energy dependence of about −1.75 kcal mol–1, falling about a factor of 30 from 200 K to 800 K.

New Stable and Fast Ring-Polymer Molecular Dynamics for Calculating Bimolecular Rate Coefficients with an Example of OH + CH4

The accurate and efficient calculation of the rate coefficients of chemical reactions is a key issue in the research of chemical dynamics. In this work, by applying the dimension-free ultrastable Cayley propagator, the thermal rate coefficients of a prototypic high dimensional chemical reaction OH + CH4 → H2O + CH3 in the temperature range of 200 to 1500 K are investigated with ring polymer molecular dynamics (RPMD) on a highly accurate full-dimensional potential energy surface. Kinetic isotope effects (KIEs) for three isotopologues of the title reaction are also studied. The results demonstrate excellent agreement with experimental data, even in the deep tunneling region. Especially, the Cayley propagator shows a high calculation efficiency with little loss of accuracy. The present results confirmed the applicability of the RPMD method, particularly the speed-up using a Cayley propagator, in theoretical calculations of bimolecular reaction rates.

Formation of phosphorus monoxide through the [Formula: see text] reaction.

Phosphorus is a key and vital element for a diverse set of important biological molecules, being indispensable for life as we know. A deeper comprehension of its role in astrochemistry and atmospheric chemistry may aid in finding answers to how this element became available on Earth. The PO molecule is one of the main reservoirs of phosphorus in the interstellar medium (ISM), and a better understanding of the mechanisms and rate coefficients for its formation in the ISM is important for modelling its abundances. In this work, we perform multireference configuration interaction calculations on the formation of PO via the [Formula: see text] reaction, analyzing its potential energy surface and rate coefficients for the global reaction on both doublet and quartet states. We also perform DFT (M06-2X) and CCSD(T) calculations, in order to compare the results. We found that the OPO system possesses a high multiconfigurational character, making DFT and CCSD methodologies not suitable for its potential energy landscape calculation. The rate coefficients have been calculated using the master equation system solver (MESS) package, and the results compared to recent experimental data. It is shown that the quartet state contributes for temperatures higher than 700K. The computed rate coefficient can be described by a modified Arrhenius equation [[Formula: see text]] with [Formula: see text], [Formula: see text] and [Formula: see text] K.

Evaluating the Atmospheric Loss of H2 by NO3 Radicals: A Theoretical Study

Molecular hydrogen (H2) is now considered among the most prominent substitute for fossil fuels. The environmental impacts of a hydrogen economy have received more attention in the last years, but still, the knowledge is relatively poor. In this work, the reaction of H2 with NO3 radical (the dominant night-time detergent of the atmosphere) is studied for the first time using high-level composite G3B3 and modification of high accuracy extrapolated ab initio thermochemistry (mHEAT) methods in combination with statistical kinetics analysis using non-separable semi-classical transition state theory (SCTST). The reaction mechanism is characterized, and it is found to proceed as a direct H-abstraction process to yield HNO3 plus H atom. The reaction enthalpy is calculated to be 12.8 kJ mol−1, in excellent agreement with a benchmark active thermochemical tables (ATcT) value of 12.2 ± 0.3 kJ mol−1. The energy barrier of the title reaction was calculated to be 74.6 and 76.7 kJ mol−1 with G3B3 and mHEAT methods, respectively. The kinetics calculations with the non-separable SCTST theory give a modified-Arrhenius expression of k(T) = 10−15 × T0.7 × exp(−6120/T) (cm3 s−1) for T = 200–400 K and provide an upper limit value of 10−22 cm3 s−1 at 298 K for the reaction rate coefficient. Therefore, as compared to the main consumption pathway of H2 by OH radicals, the title reaction plays an unimportant role in H2 loss in the Earth’s atmosphere and is a negligible source of HNO3.

Green synthesis of copper oxide and manganese oxide nanoparticles from watermelon seed shell extract for enhanced photocatalytic reduction of methylene blue

In the current study, copper oxide (CuO) and manganese oxide (MnO) nanoparticles (NPs) were synthesized through a simple, cost-efficient, and green method using watermelon seed shell extract as a stabilizing and reducing agent. The synthesized CuO and MnO NPs were characterized by using scanning electron microscopy (SEM), Energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR) and Ultraviolet spectroscopy (UV). The particle sizes of CuO and MnO NPs were determined to be in the range of 15–97 and 6–51 nm, respectively, by TEM and XRD analysis. The photocatalytic performance of the CuO and MnO NPs used as catalysts were investigated for the photocatalytic reduction of methylene blue in an aqueous solution. In the photocatalytic reduction of methylene blue, sodium borohydride (NaBH4) was used as the reducing agent. The CuO and MnO NPs were capable to remove 96.58% (in 70 min) and 96.60% (in 140 min) of methylene blue from aqueous media, respectively. Besides, the kinetics of the photocatalytic reaction was investigated by a pseudo-first order model, and the reaction rate coefficient for methylene blue with CuO and MnO NPs were calculated as 0.0426 and 0.0235 min−1, respectively. The results demonstrated that the synthesized CuO and MnO NPs through the green method were promising catalysts to improve the photocatalytic reduction performance of methylene blue.

Membrane assisted transport of thorium (IV) across bulk liquid membrane containing DEHPA as ion carrier: kinetic, mechanism and thermodynamic studies

Abstract Extraction and carrier mediated transport of thorium (IV) ions through bulk liquid membrane containing di-2-ethylhexyl phosphoric acid (DEHPA) in kerosene as metal ion carrier. The feed comprised of thorium (IV) ions solutions containing various concentrations of hydrochloric acid, while sulfuric acid solutions of different concentrations are used as a stripping agent. Various parameters about thorium (IV) ion extraction and transport were investigated: the feed solution acidity, initial metal ions aqueous solution concentration, carrier concentration and stripping agent concentration. More than 85% thorium (IV) is recovered in 960 min using 0.2 M DEHPA/kerosene as carrier and 1.5 M H2SO4 as stripping agent from the 0.0001 M HCl solution containing 50 mg L−1 thorium (IV) as feed. Assuming a consecutive, irreversible extraction and back-extraction (stripping) reactions a simple kinetic model was proposed for estimating the reaction rate constant or reaction rate coefficient under the investigated experimental conditions. The activation energy values of extraction and back-extraction reactions were calculated to be 29.94 kJ mol−1 and 20.55 kJ mol−1, respectively, which indicates that the extraction process was controlled by the mixed regime (both kinetic and diffusion), and the back-extraction process was mainly controlled by diffusion process.

Modeling the formation of disinfection byproducts in chlorinated swimming pool water: Role of body fluid analog

Abstract The recirculation of pool water and the continuous input of pollutants and disinfectants in swimming pools intensifies the accumulation of disinfection byproducts (DBPs), which have received increasing attention. Trihalomethanes (THMs) are the most common DBPs found in swimming pool water. Developing a predictive THM model is an efficient and promising way to optimize the chlorine dosage and guarantee water safety. Because the main components of swimmer inputs and their respective quantities have been formalized and determined through body fluid analogs (BFA), the model development can rely on the chlorination of BFA components and mixtures. In this study, a well-established second-order reaction chlorine decay model with a variable reaction rate coefficient was expanded to describe the chlorine consumption in swimming pool water. The THM model with a variable formation coefficient was first developed based on the identical assumption of the chlorine model, that is, the reactivity of the reactants decreases as the reaction progresses. The results showed that uric acid exhibited the fastest initial rate coefficient for chlorine decay. Although citric acid showed a considerably high specific THM formation potential (μmol-THM, species/mg productive chlorine consumption), urea and humic acid (HA) were attributed to the fast-reacting THM formation precursors. The rate coefficients of urea and HA were higher than that of citric acid. For the mixture, the (overall) reaction rate coefficients were formulated as a function of the rate coefficient of the individual substance and the concentration of the substance remaining in the water. This concept was tested using BFA and BFA with HA. The model accurately described the chlorine consumption and THM concentrations (R2 > 0.96).

Chemical kinetics and mechanism of BOH (1A') reaction with CH2 (3B1)

This study focuses on the possibility of the reaction of BOH (1A') with CH2 (3B1) through a general description of the reaction mechanism at CCSD(T)/aug-cc-PVTZ//MP2/aug-cc-pVTZ and CCSD(T)/aug-cc-PVTZ//B3LYP-D3/aug-cc-PVTZ levels of theory. The reaction mechanism and kinetics were studied in the gas phase in a broad range of temperature (300 to 3000 K) and pressure (0.1 to 2000 Torr). The steady-state approximation and RRKM calculations (RRKM-SSA) were employed to evaluate the reaction kinetics and calculate Arrhenius parameters. We found that the rate coefficient of the title reaction is independent of pressure and temperature-dependent. The major product of the reaction at 400 K is cyc-CH(O)B + H2 and the most stable specie on the potential energy surface is CH3BO. The total rate constant expression for the title reaction in the temperature range of 300 to 3000 K is kTotal=1∙97×10-11×T0∙15exp(-11∙95kJmol-1/RT).

Capture theory models: An overview of their development, experimental verification, and applications to ion-molecule reactions.

Since Arrhenius first proposed an equation to account for the behavior of thermally activated reactions in 1889, significant progress has been made in our understanding of chemical reactivity. A number of capture theory models have been developed over the past several decades to predict the rate coefficients for reactions between ions and molecules-ranging from the Langevin equation (for reactions between ions and non-polar molecules) to more recent fully quantum theories (for reactions at ultracold temperatures). A number of different capture theory methods are discussed, with the key assumptions underpinning each approach clearly set out. The strengths and limitations of these capture theory methods are examined through detailed comparisons between low-temperature experimental measurements and capture theory predictions. Guidance is provided on the selection of an appropriate capture theory method for a given class of ion-molecule reaction and set of experimental conditions-identifying when a capture-based model is likely to provide an accurate prediction. Finally, the impact of capture theories on fields such as astrochemical modeling is noted, with some potential future directions of capture-based approaches outlined.

A shock tube experiment and an improved high-temperature diisopropyl ketone model by Bayesian optimization

Ignition delay times (IDTs) for di-isopropyl ketone (DIPK) were measured at pressures of 6 and 10 atm, equivalence ratios (ϕ) of 0.5, 1.0, and 2, and over a temperature range of 1100 - 1500 K. In the DIPK sub-model proposed by Barari et al., DIPK⇔IC3H7+IC3H7CO (R2) was erroneously written as DIPK⇔IC3H7+ IC4H7O and the consumption paths of dimethyl ketene (DMK) are missing. A DIPK sub-model was proposed on the basis of Barari model by correcting these errors, reassigning the rate coefficients of the DIPK unimolecular decomposition reactions (R1, R2), H-abstraction reactions by O˙H (R3, R4), fuel radical isomerization reaction (R5), and β-scission decomposition reactions (R5-R10) using the analogy method, and adopting the theoretical calculations of the H-abstraction reactions by H˙, C˙H3, and HO˙2 (R11-R16) provided by Allen et al.. The rate coefficients of R1-R10 were globally optimized by the Bayesian optimization algorithm using the experimental IDTs and profiles of DIPK and DMK. The optimized model well predicts not only the IDTs and profiles of DIPK and DMK, but also the laminar flame speeds and the profiles of many intermediates (propyne, propylene, and methyl ketene) and small species (H2, CO, CH4) during the pyrolysis of DIPK. The calculation using the method of Chen et al. shows that no optimized reaction violates the collision limit. The sensitivity and rate of production analysis were used to discuss the DIPK unimolecular decompositions, DIPK H-abstraction reactions, DIPK radicals isomerization and β-scission reactions, and the optimization of the DIPK sub-model.

The role of highly vibrationally excited H2 initiating the nitrogen chemistry

The formation of hydrides by gas-phase reactions between H2 and a heavy element atom is a very selective process. Reactions with ground-state neutral carbon, oxygen, nitrogen, and sulfur atoms are very endoergic and have high energy barriers because the H2 molecule has to be fragmented before a hydride bond is formed. In cold interstellar clouds, these barriers exclude the formation of CH, OH, NH, and SH radicals through hydrogen abstraction reactions. Here we study a very energetically unfavorable process, the reaction of N(4S) atoms with H2 molecules. We calculated the reaction rate coefficient for H2 in different vibrational levels, using quantum methods for v = 0−7 and quasi-classical methods up to v =12; for comparison purposes, we also calculated the rate coefficients of the analogous reaction S (3P)+ H2(v) → SH + H. Owing to the high energy barrier, these rate coefficients increase with v and also with the gas temperature. We implemented the new rates in the Meudon photodissociation region (PDR) code and studied their effect on models with different ultraviolet (UV) illumination conditions. In strongly UV-irradiated dense gas (Orion Bar conditions), the presence of H2 in highly vibrationally excited levels (v ≥ 7) enhances the NH abundance by two orders of magnitude (at the PDR surface) compared to models that use the thermal rate coefficient for reaction N(4S) + H2 → NH + H. The increase in NH column density, N(NH), across the PDR is a factor of ~25. We investigate the excitation and detectability of submillimeter NH rotational emission lines. Being a hydride, NH excitation is very subthermal (Trot ≪ Tk) even in warm and dense gas. We explore existing Herschel/HIFI observations of the Orion Bar and Horsehead PDRs. We report a 3σ emission feature at the ~974 GHz frequency of the NH NJ = 12 − 01 line toward the Bar. The emission level implies N(NH) ≃ 1013 cm−2, which is consistent with PDR models using the new rate coefficients for reactions between N and UV-pumped H2. This formation route dominates over hydrogenation reactions involving the less abundant N+ ion. JWST observations will quantify the amount and reactivity of UV-pumped H2 in many interstellar and circumstellar environments.

New insights into the oxidation chemistry of pyrrole, an N-containing biomass tar component

Pyrrole, the smallest molecule with a nitrogen atom in the heterocycle ring, is an important tar component from coal and nitrogen-rich biomass devolatilization. Understanding the combustion chemistry of pyrrole can help to elucidate the pollutant formation chemistry from fuel nitrogen, thus enabling cleaner biomass energy utilization technologies. Experimental measurements were performed in a jet stirred reactor coupled with time of flight molecular beam mass spectrometry using synchrotron vacuum ultraviolet beam as photon ionization source, and gas chromatography-mass spectrometry to provide comprehensive measurements of 31 species including nine C4 and C5 N-containing compounds. Based on the evidence from the experiments and aiming to improve the kinetic model performance, possible formation routes are proposed with OH addition as the entrance reaction. Reaction rate coefficients for the OH addition channel as well as those for key H-atom abstraction reactions (H, OH, CH3, and HO2) were calculated by quantum chemical methods and updated in the model. The updated model can qualitatively predict the identified C4 N-containing species and perform reasonably well for a large set of experimental data considered for validation, overall improving the performance of the previous model. The influence of the investigated reactions on the predictions of fuel reactivity and pollutant formation motivates further investigations of N-containing fuel chemistry.

Theoretical study about the hydrogen abstraction reactions on methyl acetate on combustion conditions

Methyl acetate is considered a prototype molecule to study biodiesel ignition and combustion and is seen as a possible fuel or fuel additive. For this reason, methyl acetate decomposition paths have been investigated in recent years. In the present study, hydrogen abstraction reactions on methyl acetate by OH(2Π), HO2(2A'), H(2Σg), O(3P), and O2(3Σg) were conducted, and the effect of methodology and anharmonic corrections on the rate coefficients were evaluated. The M06-2X and B3LYP-D3 functionals with the cc-pVDZ, cc-pVTZ, aug-cc-pVDZ, and aug-cc-pVTZ basis set were used for methodology evaluation and the CCSD(T)/cc-pVTZ//M06-2X/aug-cc-pVTZ for the rate coefficients calculation and literature comparisons. The rate coefficients were calculated in the range of 250-3500K, including tunneling corrections, methyl-hindered rotations, and anharmonic effects calculated by the VPT2 method. The methodology analysis showed that the B3LYP-D3 functional leads to lower activation energies for all elementary reactions studied, and the double-zeta basis is insufficient to calculate precise rate coefficients. The inclusion of anharmonic corrections consistently lowered the rate coefficients of all elementary reactions studied and changed the Arrhenius plot profile with the temperature. Significant anharmonic effects were observed at higher temperatures, being the reaction with O2(3Σg) the most affected by this correction. Differences superior to 105 cm3 molec-1s-1 in the rate coefficients were observed in some cases.

High accuracy barrier heights, enthalpies, and rate coefficients for chemical reactions

Quantitative chemical reaction data, including activation energies and reaction rates, are crucial for developing detailed kinetic mechanisms and accurately predicting reaction outcomes. However, such data are often difficult to find, and high-quality datasets are especially rare. Here, we use CCSD(T)-F12a/cc-pVDZ-F12//ωB97X-D3/def2-TZVP to obtain high-quality single point calculations for nearly 22,000 unique stable species and transition states. We report the results from these quantum chemistry calculations and extract the barrier heights and reaction enthalpies to create a kinetics dataset of nearly 12,000 gas-phase reactions. These reactions involve H, C, N, and O, contain up to seven heavy atoms, and have cleaned atom-mapped SMILES. Our higher-accuracy coupled-cluster barrier heights differ significantly (RMSE of ∼5 kcal mol−1) relative to those calculated at ωB97X-D3/def2-TZVP. We also report accurate transition state theory rate coefficients {k}_{infty }(T) between 300 K and 2000 K and the corresponding Arrhenius parameters for a subset of rigid reactions. We believe this data will accelerate development of automated and reliable methods for quantitative reaction prediction.

Investigation of the combustion process of activated fuel in an automotive diesel engine

BACKGROUND: Intensive development of the transport sphere and the extension of the fleet of tractors and cars, as well as the tightening of standards and requirements in the field of exhaust gas emissions have resulted in increased requirements for the combustion process. This problem can be solved by improving the working process in the engine by preheating the fuel to 300 C in the high pressure fuel supply system. Under external thermal influence, the conditions of mixture formation are improved, an increase in the rate of preflame reactions and a positive change in the dynamics of the combustion process are observed. When potential energy of hydrocarbon molecules increases in the activated complex system, energy is redistributed among active molecules. Along with this, the rate coefficient of a chemical reaction increases due to the concentration of foci of hydrocarbon molecules that have reached the energy barrier.
 The object of research is the process of diesel fuel combustion at preliminary external influence on it.
 AIMS: The aim is to study the combustion process of a motor-tractor diesel engine upon fuel activation. Development of a scheme of individual phases of the activated diesel fuel combustion of depending on the temperature at heating.
 METHODS: Theoretical study and analysis of the combustion process of thermally preprepared fuel for an automotive diesel engine. Theoretical determination of the dependence of the rate of formation and concentration of toxic components and dispersed particles on the rate constant of direct and reverse chemical reactions, as well as on the activation temperature of fuel at emission in exhaust gases.
 RESULTS: The actual coefficient of molecular change of the working mixture increases when diesel fuel is activated. The rate of formation of total nitrogen oxides and hydrocarbons increases by 1.79% and 3.66%. The proportion of unburned carbon in the combustion process on activated fuel varies within (24) %.
 CONCLUSIONS: Theoretically, a scheme for changing individual phases of the activated fuel combustion process by time and temperature has been developed. Fuel heating accelerates the pre-flame preparation in the liquid phase, shortens the duration of the rapid gorenje phase. The concentration of toxic indicators depends on the constant of the chemical reaction rate and the activation temperature of the fuel.

Gas-Phase Ozone Reaction Kinetics of C5-C8 Unsaturated Alcohols of Biogenic Interest.

Unsaturated alcohols are volatile organic compounds (VOCs) that characterize the emissions of plants. Changes in climate together with related increases of biotic and abiotic stresses are expected to increase these emissions in the future. Ozonolysis is one of the oxidation pathways that control the fate of unsaturated alcohols in the atmosphere. The rate coefficients of the gas-phase O3 reaction with seven C5-C8 unsaturated alcohols were determined at 296 K using both absolute and relative kinetic methods. The following rate coefficients (cm3 molecule-1 s-1) were obtained using the absolute method: (1.1 ± 0.2) × 10-16 for cis-2-penten-1-ol, (1.2 ± 0.2) × 10-16 for trans-2-hexen-1-ol, (6.4 ± 1.0) × 10-17 for trans-3-hexen-1-ol, (5.8 ± 0.9) × 10-17 for cis-3-hexen-1-ol, (2.0 ± 0.3) × 10-17 for 1-octen-3-ol, and (8.4 ± 1.3) × 10-17 for trans-2-octen-1-ol. The following rate coefficients (cm3 molecule-1 s-1) were obtained using the relative method: (1.27 ± 0.11) × 10-16 for trans-2-hexen-1-ol, (5.01 ± 0.30) × 10-17 for trans-3-hexen-1-ol, (4.13 ± 0.34) × 10-17 for cis-3-hexen-1-ol, and (1.40 ± 0.12) × 10-16 for trans-4-hexen-1-ol. Alkenols display high reactivities with ozone with lifetimes in the hour range. Rate coefficients show a strong and complex dependence on the structure of the alkenol, particularly the relative position of the OH group toward the C═C double bond. The results are discussed and compared to both the available literature data and four structure-activity relationship (SAR) methods.