Reaction Rate Coefficients Research Articles

Elucidating Degradation of Aqueous Organic Redox Flow Batteries by Electrochemical Impedance Spectroscopy

Redox flow batteries, facilitating the dissociation of energy and power, emerge as a promising avenue for electrochemical electricity storage. A shift from vanadium flow batteries to those employing aqueous organic electroactive species is evident due to the latter's advantageous features, such as diverse design possibilities through functionalization, reduced cost, non-toxicity, and improved availability. Despite expectations that organic redox flow batteries can surpass a lifespan of 10 years or 2000 cycles, their practical long-term performance faces challenges arising from electrode, membrane, and organic species degradation. The intricate interplay of various degradation factors during full cell cycling results in observable capacity decay over cycles. Effectively mitigating degradation necessitates the dissection of these factors to identify the limiting component. Electrochemical impedance spectroscopy (EIS) emerges as a potent diagnostic tool capable of pinpointing and disentangling the sources of resistance within an electrochemical device. Through deconvolution of different factors, EIS allows for the quantitative measurement of resistance evolution throughout full cell cycling, reflecting degradation through changes in resistance. Consequently, by monitoring resistance evolution with EIS, the degradation rates of individual factors can be calculated.This study employs an alkaline aqueous organic redox flow battery with 2,5-di-tert-butyl-1,4-dihydroxybenzene sulfate (DHPS) as anolyte and ferrocyanide as catholyte for demonstration. EIS measurements are conducted at various cycles, and three distinct resistance components (charge transfer, ohmic, and mass transport) are identified as functions of cycle numbers. Subsequently, the degradation rates of crucial electrochemical parameters, such as reaction rate and mass transport coefficient, are quantified, providing essential inputs for subsequent modeling endeavors.

Gas-Phase Reaction Kinetic Study of a Series of Methyl-Butenols with Ozone under Atmospherically Relevant Conditions.

Methyl-butenols are a category of oxygenated biogenic volatile organic compounds emitted by plants as part of their natural metabolic processes. This study examines the gas-phase reactions of ozone (O3) with five methyl-butenols (2-methyl-3-buten-2-ol, 3-methyl-2-buten-1-ol, 3-methyl-3-buten-1-ol, 2-methyl-3-buten-1-ol, and 3-methyl-3-buten-2-ol) under atmospheric conditions at a temperature of (298 ± 2) K and pressure of (1000 ± 10) mbar. The experimental values for the gas-phase reaction rate coefficients obtained in this study, by using the relative rate method, are as follows (in cm3 molecule-1 s-1): k(3-methyl-2-buten-1-ol + O3) = (311 ± 20) × 10-18, k(2-methyl-3-buten-2-ol + O3) = (9.55 ± 1.04) × 10-18, k(3-methyl-3-buten-1-ol + O3) = (7.29 ± 0.46) × 10-18, k(2-methyl-3-buten-1-ol + O3) = (4.25 ± 0.29) × 10-18, and k(3-methyl-3-buten-2-ol + O3) = (62.9 ± 6.8) × 10-18. The results are discussed in detail, with particular emphasis on the degree and type of substitutions of the double bond. The determined rate coefficient values are also compared to the available literature data and with estimates of the structure-activity relationship. Additionally, the atmospheric implications toward the tropospheric lifetime and photochemical ozone generation potential for the investigated compounds are provided, which highlight the atmospheric impact of methyl-butenol decomposition into the lower atmosphere.

Atmospheric photo-oxidation of acetic anhydride: Kinetic study and reaction mechanism. Products distribution and fate of CH3C(O)OC(O)CH2O· radical

The rate coefficient for the gas-phase reaction of acetic anhydride (Ac2O) with chlorine atoms at 298 K and atmospheric pressure was experimentally determined (kAc2O+Cl= (1.3 ± 0.4) × 10-12 cm3molec−1s−1), while the rate coefficient for the reaction with the hydroxyl radical was estimated (kAc2O+OH=1.9 x 10-13 cm3molec−1s−1). For the Structure-Activity Relationship method, a value of 0.02 was determined for the −C(O)OC(O) group. The mechanism of photo-oxidation of acetic anhydride initiated by chlorine atoms was determined and CO, CO2, CH3C(O)OH (32 %), CH3C(O)OC(O)C(O)H, and 3-hydroxy-1,4-dioxane-2,6-dione (20 %) were identified as products by infrared spectroscopy. Here we determined for the first time the relative energies of the primary reaction pathways for the CH3C(O)OC(O)CH2O· radical using computational methods, which confirmed our experimental data. Finally, the environmental implications of acetic anhydride emissions were calculated, showing an atmospheric lifetime between 31 and 220 days for the reaction with atmospheric radicals, while its wet deposition lifetime is 1.5 years.

Multi-Level Protocol for Mechanistic Reaction Studies Using Semi-Local Fitted Potential Energy Surfaces.

In this work, we propose a multi-level protocol for routine theoretical studies of chemical reaction mechanisms. The initial reaction paths of our investigated systems are sampled using the Nudged Elastic Band (NEB) method driven by a cheap electronic structure method. Forces recalculated at the more accurate electronic structure theory for a set of points on the path are fitted with a machine learning technique (in our case symmetric gradient domain machine learning or sGDML) to produce a semi-local reactive potential energy surface (PES), embracing reactants, products and transition state (TS) regions. This approach has been successfully applied to a unimolecular (Bergman cyclization of enediyne) and a bimolecular (SN2 substitution) reaction. In particular, we demonstrate that with only 50 to 150 energy-force evaluations with the accurate reference methods (here complete-active-space self-consistent field, CASSCF, and coupled-cluster singles and doubles, CCSD) it is possible to construct a semi-local PES giving qualitative agreement for stationary-point geometries, intrinsic reaction coordinates and barriers. Furthermore, we find a qualitative agreement in vibrational frequencies and reaction rate coefficients. The key aspect of the method's performance is its multi-level nature, which not only saves computational effort but also allows extracting meaningful information along the reaction path, characterized by zero gradients in all but one direction. Agnostic to the nature of the TS and computationally economic, the protocol can be readily automated and routinely used for mechanistic reaction studies.

Gas-Phase Kinetics of a Series of cis-3-Hexenyl Esters with OH Radicals under Simulated Atmospheric Conditions.

The present relative kinetic study reports on the experimentally determined gas-phase reaction rate coefficients of OH radicals with a series of seven cis-3-hexenyl esters. The experiments were carried out in the environmental simulation chamber made of quartz from the "Alexandru Ioan Cuza" University of Iasi (ESC-Q-UAIC), Romania, at a temperature of (298 ± 2) K and a total air pressure of (1000 ± 10) mbar. In situ long-path Fourier transform infrared (FTIR) spectroscopy was used to monitor cis-3-hexenyl formate (Z3HF, (Z)-CH3CH2CH═CH(CH2)2OC(O)H), cis-3-hexenyl acetate (Z3HAc, (Z)-CH3CH2CH═CH(CH2)2OC(O)CH3), cis-3-hexenyl isobutyrate (Z3HiB, (Z)-CH3CH2CH═CH(CH2)2OC(O)CH(CH3)2), cis-3-hexenyl 3-methylbutanoate (Z3H3MeB, (Z)-CH3CH2CH═CH(CH2)2OC(O)CH2CH(CH3)2), cis-3-hexenyl hexanoate (Z3HH, (Z)-CH3CH2CH═CH(CH2)2OC(O)(CH2)4CH3), cis-3-hexenyl cis-3-hexenoate (Z3HZ3H, (Z,Z)-CH3CH2CH═CH(CH2)2OC(O)CH2CH═CHCH2CH3), cis-3-hexenyl benzoate (Z3HBz, (Z)-CH3CH2CH═CH(CH2)2OC(O)C6H5), and the reference compounds. The following reaction rate coefficients (in 10-11 cm3 molecule-1 s-1) were obtained for the OH radical-initiated gas-phase oxidation of cis-3-hexenyl esters: (4.13 ± 0.45) for Z3HF, (4.19 ± 0.38) for Z3HAc, (4.84 ± 0.39) for Z3HiB, (5.39 ± 0.61) for Z3H3MeB, (7.00 ± 0.56) for Z3HH, (10.58 ± 1.40) for Z3HZ3H, and (3.41 ± 0.28) for Z3HBz. The results are discussed in terms of hexenyl ester reactivity and compared with the available literature data and structure-activity relationship (SAR) estimates. The atmospheric implications based on the average lifetimes of the investigated cis-3-hexenyl esters are discussed in the present study. The gas-phase rate coefficients for OH radical reactions are given herein for the first time for cis-3-hexenyl isobutyrate, cis-3-hexenyl 3-methylbutanoate, cis-3-hexenyl hexanoate cis-3-hexenyl cis-3-hexenoate, and cis-3-hexenyl benzoate. The newly determined gas-phase reaction rate coefficients provide new information for existing kinetic databases and contribute to the further development of SAR methodologies useful for predicting the reactivity of oxygenated volatile organic compounds.

Kinetics, products and mechanisms of the OH radicals and Cl atoms reactions with trans-2-octene and cycloheptene

Relative rate coefficients for the gas-phase reactions of OH radicals and Cl atoms with trans-2-octene (k1-OH and k2-Cl) and cycloheptene (k3-OH and k4-Cl) have been determined by in situ Fourier Transform Infrared Spectroscopy (FTIR). The experiments were carried out at 298 ± 2 K and atmospheric pressure (760 ± 10) Torr using synthetic air as bath gas. The following rate coefficients (in units of cm3 molecule−1 s−1) were obtained for the reactions of trans-2-octene and cycloheptene with OH radicals and Cl atoms: k1-OH = (8.51 ± 1.86) × 10−11, k2-Cl = (4.47 ± 1.09) × 10−10, k3-OH = (7.84 ± 1.78) × 10−11, k4-Cl = (5.46 ± 1.01) × 10−10, respectively. This is the first kinetic study for the reactions of trans-2-octene with Cl atoms and the first rate coefficient determination for the title reactions by in situ FTIR spectroscopy. The kinetic data were compared with previously reported values for similar compounds and reactivity trends were developed. Complementary, products identification studies were performed in similar conditions to the kinetic experiments by the in situ FTIR and Gas Chromatography coupled to mass spectrometry (GC-MS). The atmospheric chemical mechanisms were postulated for the first time for both unsaturated compounds. In addition, the atmospheric implications of these reactions were assessed through the estimation of the tropospheric lifetimes, Photochemical Ozone Creation Potential (POCP) and fates of these compounds in the troposphere.

Bridging Model–Data Discrepancies in Mars’ Dayside Ionosphere: Exploring Varying Reaction Rate Coefficients

Measurements of concentrations of neutral and ion species in the upper atmosphere of Mars by the Neutral Gas and Ion Mass Spectrometer (NGIMS) on board the Mars Atmosphere and Volatile EvolutioN mission have served as model input and/or for comparison with model output in numerous earlier studies of the Martian dayside ionosphere. While many models reproduce the altitudinal density profiles of key ion species within a factor of a few, it has proven challenging to achieve a level of agreement within tens of percent for multiple ion species over a wide range of altitudes. We explore means to overcome this issue while keeping with a reduced chemical model and utilizing the assumptions of photochemical equilibrium and that the NGIMS data are devoid of any measurement errors. We entertain, for instance, the idea that the rate coefficient for the charge-transfer reaction between CO2+ and O may vary with altitude as a result of a pressure-controlled internal energy distribution of the CO2+ population.

Dissociative recombination of NS+ in collision with slow electrons

Cross sections and rate coefficients for the dissociative recombination (DR) of the NS+ ion induced by collisions with low-energy electrons are reported for temperatures between 10 and 1000 K, relevant to a large range of interstellar cloud temperatures. Uncertainties are discussed for these rates. Comparisons are made with DR rates for the isovalent NO+ molecular ion which are found to be much faster. The present findings lead to a moderate dissociative reaction rate coefficient, smaller by a factor of 2 than the current estimates reported in the different kinetic databases for a temperature of 10 K. We consider that our rate coefficients obtained through multichannel quantum defect theory for NS+ are likely to be better than those displayed in the different kinetic databases.

High-Temperature Pyrolysis Study of 2-Methyl-2-butanol behind Reflected Shock Wave: Shock Tube and Computational Study.

Pyrolysis of a branched alcohol, 2-methyl-2-butanol (2M2BOH), was carried out behind the reflected shock wave in the temperature range of 1011-1303 K and under pressures varying from 9.3 to 14.6 atm. Qualitative and quantitative analysis of the postshock mixture was performed using gas chromatography-mass spectrometry and gas chromatography with a flame ionization detector, respectively. The rate coefficients for the C-C and C-O bond cleavage reaction pathways were calculated using the variational transition-state theory. The Rice-Ramsperger-Kessel-Marcus/Master equation was employed to calculate the rate coefficients for the H2O-elimination reactions, unimolecular dissociation, and isomerization reaction pathways. The overall decomposition rate coefficient for the 2-methyl 2-butanol (2M2BOH) was estimated to be , where activation energy is given in kcal mol-1. The reaction path analysis was performed, which gives information regarding the contribution of individual intermediate species toward the decomposition of 2M2BOH. A set of reactions was proposed and used to simulate the combustion chemistry of 2M2BOH, which consists of 48 reactions and 39 species. The experimentally measured and simulated mole fractions for the reactant and products showed reasonably good agreement. This work additionally investigates the effect of branching on the decomposition kinetics of long-chain alcohols.

Experimental and chemical kinetic analysis to evaluate CO2 dilution on laminar combustion characteristics of C2H5OH/air blends under normal pressure

Based on a constant volume combustion system, the effect of dilution ratio changes on the laminar combustion characteristics of C2H5OH/air mixture was studied under an initial pressure of 1 bar, initial temperatures of 370 K, 400 K, 450 K, and equivalence ratios of 0.7–1.4. A chemical kinetic mechanism for ethanol-carbon dioxide was established, and the combined physical and chemical effects of carbon dioxide were separated. An independent parameter control method was proposed, introducing virtual species FN2, ICO2, FCO2, and KCO2, to isolate the dilution effect, thermal effect, direct reaction effect, third-body effect, and transport effect. Simulation analysis using the modified chemical kinetic mechanism revealed that various impacts of CO2 reduce the peak progress rate and sensitivity coefficient of key elementary reactions. Furthermore, the dilution effect of CO2 has the greatest influence on the sensitivity coefficients and net progress rates of important elementary reactions. Based on the results of the chemical kinetic simulations, a new global reaction pathway analysis method was created, overcoming the limitations of the Chemkin-pro method. The decomposition pathway of C2H5OH throughout the combustion process was calculated as C2H5OH → SC2H4OH → CH3CHO → CH3CO → CH3 → CH2O → HCO → CO → CO2. Changes in initial temperature and dilution ratio do not alter the main decomposition pathway of C2H5OH. Detailed chemical kinetics and free radical behavior analysis indicate that the LBV of the C2H5OH/CO2/air blends has a linear correlation with [H + O + OH]max.

Hydrogen isotope effects on recombination dominant plasmas in NAGDIS-II

The detachment processes of the hydrogen (H) and deuterium (D) plasmas are comparatively investigated in the linear plasma device NAGDIS-II. The laser Thomson scattering measurements demonstrate that the recombination rate of the H plasma is greater than that of the D plasma as the neutral pressure increases in the molecular activated recombination (MAR) dominant detachment phase. As the recombination process by MAR is strongly dependent on the vibrational and rotationally excited states of the molecule, the rovibrational quantum state populations of the H and D molecules are measured using the Fulcher-α band spectroscopy. The results indicate that the vibrational temperature in the electronic ground state is considerably higher than the rotational temperature during detachment. The reaction rate coefficients for MARs due to charge exchange chains (CX-MAR) and dissociative attachment chains (DA-MAR) are calculated by the collision-radiation model under the measured temperature conditions. It can be observed that the CX-MAR is larger than the DA-MAR for both H and D, and that the CX-MAR of H is larger than the CX-MAR of D at electron temperatures T e above 1 eV. In consideration of the experimentally observed vibrational and rotational excitation temperatures, the reaction rate coefficients of CX-MAR and DA-MAR are increasing in the low T e region. These calculations are in accordance with the experimental results, which indicate that recombination processes due to MAR are more predominant in the H plasma compared to the D plasma. Furthermore, a transition from MAR to electron–ion recombination processes is observed in the D plasma at T e below 0.5 eV.

Causal prior-embedded physics-informed neural networks and a case study on metformin transport in porous media

This study introduces a novel approach to transport modelling by integrating experimentally derived causal priors into neural networks. We illustrate this paradigm using a case study of metformin, a ubiquitous pharmaceutical emerging pollutant, and its transport behaviour in sandy media. Specifically, data from metformin's sandy column transport experiment was used to estimate unobservable parameters through a physics-based model Hydrus-1D, followed by a data augmentation to produce a more comprehensive dataset. A causal graph incorporating key variables was constructed, aiding in identifying impactful variables and estimating their causal dynamics or “causal prior.” The causal priors extracted from the augmented dataset included underexplored system parameters such as the type-1 sorption fraction F, first-order reaction rate coefficient α, and transport system scale. Their moderate impact on the transport process has been quantitatively evaluated (normalized causal effect 0.0423, -0.1447 and -0.0351, respectively) with adequate confounders considered for the first time. The prior was later embedded into multilayer neural networks via two methods: causal weight initialization and causal prior regularization. Based on the results from AutoML hyperparameter tuning experiments, using two embedding methods simultaneously emerged as a more advantageous practice since our proposed causal weight initialization technique can enhance model stability, particularly when used in conjunction with causal prior regularization. amongst those experiments utilizing both techniques, the R-squared values peaked at 0.881. This study demonstrates a balanced approach between expert knowledge and data-driven methods, providing enhanced interpretability in black-box models such as neural networks for environmental modelling.

The reaction of methylidyne with methane: role of the quartet electronic state

The reaction of methylidyne (CH) with methane, which plays an important role in combustion and planetary atmospheres, is characterised with high accuracy coupled-cluster calculations. The reaction on the quartet state potential energy surface (PES) is predicted to lead to direct H-abstraction with a small barrier of 2.2 kcal mol−1, yielding triplet CH2 and CH3. The reaction on the doublet state PES is barrierless, involving an insertion/elimination mechanism that leads to the vibrationally excited (hot) intermediate C2H5, which promptly dissociates to H + C2H4. The results obtained from a statistical chemical kinetics analysis show that the quartet channel makes a negligible contribution to the overall kinetics below 500 K, but becomes important at the higher temperatures characteristic of hydrocarbon flames. Reaction rate coefficients calculated from first principles are in good agreement (within 20%) with experimental values where they are available (200–800 K). For the higher temperatures of combustion environments (where experimental data are lacking), the present study provides high-level results for kinetics modelling purposes.

Gas-Phase Kinetic Investigation of the OH-Initiated Oxidation of a Series of Methyl-Butenols under Simulated Atmospheric Conditions.

Five biogenic unsaturated alcohols have been investigated under simulated atmospheric conditions regarding their gas-phase OH reactivity. The gas-phase rate coefficients of OH radicals with 2-methyl-3-buten-2-ol (k1), 3-methyl-2-buten-1-ol (k2), 3-methyl-3-buten-1-ol (k3), 2-methyl-3-buten-1-ol (k4), and 3-methyl-3-buten-2-ol (k5) at 298 ± 2 K and 1000 ± 10 mbar total pressure of synthetic air were determined under low- and high-NOx conditions using the relative kinetic technique. The present work provides for the first time the rate coefficients of gas-phase reactions of hydroxyl radicals with 2-methyl-3-buten-1-ol and 3-methyl-3-buten-2-ol. The following rate constants were measured (in 10-11 cm3 molecule-1 s-1): k1 = 6.32 ± 0.49, k2 = 14.55 ± 0.93, k3 = 10.04 ± 0.78, k4 = 5.31 ± 0.37, and k5 = 11.71 ± 1.29. No significant differences in the measured rate coefficients were obtained when either 365 nm photolysis of CH3ONO in the presence of NO or 254 nm photolysis of H2O2 was used as a source of OH radicals. Reactivity toward other classes of related compounds such as alkenes and saturated alcohols is discussed. A comparison of the structure-activity relationship (SAR) estimates derived from the available accepted methodologies with experimental data available for unsaturated alcohols is provided. Atmospheric lifetimes for the investigated series of alkenols with respect to the main atmospheric oxidants are given and discussed.

Two Film Approach to Continuum Scale Mixing and Dispersion with Equilibrium Bimolecular Reaction

Reliable reactive transport models require careful separation of mixing and dispersion processes. Here we treat displacing and displaced fluids as two separate fluid phases and invoke Whitman’s classical two-film theory to model mass transfer between the two phases. We use experimental data from Gramling’s bimolecular reaction experiment to assess model performance. Gramling’s original model involved just three coupled PDEs. In this context, our new formulation leads to a set of seven coupled PDEs but only requires the specification of two extra parameters, associated with the mass transfer coefficient and its dependence on time. The two film mass transfer model provides a simple and theoretically based method for separating mixing from dispersion in Eulerian continuum-scale methods. The advantage of this approach over existing methods is that it enables the simulation of equilibrium chemical reactions without having to invoke unrealistically small reaction rate coefficients. The comparison with Gramling’s experimental data confirms that our proposed method is suitable for simulating realistic and complicated bimolecular reaction behaviour. However, further work is needed to explore alternative methods for avoiding the need of a time-dependent mass transfer rate coefficient.

Direct Measurements of Covalently Bonded Sulfuric Anhydrides from Gas-Phase Reactions of SO3 with Acids under Ambient Conditions.

Sulfur trioxide (SO3) is an important oxide of sulfur and a key intermediate in the formation of sulfuric acid (H2SO4, SA) in the Earth's atmosphere. This conversion to SA occurs rapidly due to the reaction of SO3 with a water dimer. However, gas-phase SO3 has been measured directly at concentrations that are comparable to that of SA under polluted mega-city conditions, indicating gaps in our current understanding of the sources and fates of SO3. Its reaction with atmospheric acids could be one such fate that can have significant implications for atmospheric chemistry. In the present investigation, laboratory experiments were conducted in a flow reactor to generate a range of previously uncharacterized condensable sulfur-containing reaction products by reacting SO3 with a set of atmospherically relevant inorganic and organic acids at room temperature and atmospheric pressure. Specifically, key inorganic acids known to be responsible for most ambient new particle formation events, iodic acid (HIO3, IA) and SA, are observed to react promptly with SO3 to form iodic sulfuric anhydride (IO3SO3H, ISA) and disulfuric acid (H2S2O7, DSA). Carboxylic sulfuric anhydrides (CSAs) were observed to form by the reaction of SO3 with C2 and C3 monocarboxylic (acetic and propanoic acid) and dicarboxylic (oxalic and malonic acid)-carboxylic acids. The formed products were detected by a nitrate-ion-based chemical ionization atmospheric pressure interface time-of-flight mass spectrometer (NO3--CI-APi-TOF; NO3--CIMS). Quantum chemical methods were used to compute the relevant SO3 reaction rate coefficients, probe the reaction mechanisms, and model the ionization chemistry inherent in the detection of the products by NO3--CIMS. Additionally, we use NO3--CIMS ambient data to report that significant concentrations of SO3 and its acid anhydride reaction products are present under polluted, marine and polar, and volcanic plume conditions. Considering that these regions are rich in the acid precursors studied here, the reported reactions need to be accounted for in the modeling of atmospheric new particle formation.

Direct Kinetic Measurements of a Cyclic Criegee Intermediate; Unimolecular Decomposition of c-(CH2)5COO.

We report the first direct kinetic measurements of a cyclic stabilized Criegee Intermediate. We have measured the unimolecular reaction rate coefficient of cyclohexanone oxide (c-(CH2)5COO) in the temperature 213-296 K and pressure 7-50 Torr ranges using absorption spectrometry. The c-(CH2)5COO was produced by the photolysis of c-(CH2)5CIBr at 213 nm in the presence of O2. We compare the measured fast c-(CH2)5COO unimolecular rate coefficient, 1998 ± 147 s-1 at 296 K, with the literature calculations for the structurally similar E-nopinone oxide formed in β-pinene ozonolysis. The kuni(c-(CH2)5COO)/kuni(E-nopinone oxide) ratio calculated using transition-state theory and density functional theory agrees well with this comparison. We have also measured the bimolecular rate coefficient of the reaction between c-(CH2)5COO and trifluoroacetic acid at 253 K and 10 Torr and obtained the value (8.7 ± 1.0) × 10-10 cm3 molecule-1 s-1. This very large value agrees with previous kinetic measurements for reactions between stabilized Criegee intermediates and halogenated organic acids.

The chemistry and excitation of H2 and HD in the early Universe

ABSTRACT We have critically reviewed the literature pertaining to reactions that are significant for the chemistry of hydrogen-, deuterium-, and helium-bearing species in the homogeneous early Universe. For each reaction rate coefficient, we provide a fit in the modified-Arrhenius form, specifying the corresponding uncertainty and temperature range. This new network, limited to 21 reactions, should be the most reliable to date. Combined with accurate state-to-state rate coefficients for inelastic and reactive collisions involving H2 and HD, it allows us for the first time to follow the evolution of the abundances of atomic and molecular species, level populations of H2 and HD, and the ortho:para ratio (OPR) of H2, in a self-consistent fashion during the adiabatic expansion of the universe. The abundances of H2 and HD change only marginally compared to previous models, indicating that the uncertainties on the main reaction rate coefficients have essentially been removed. We also find that the adiabatic expansion has a dramatic effect on the OPR of H2, which freezes-out at redshifts z ≲ 50. In contrast, at higher redshifts, the populations of the rotational levels of H2 and HD are predicted to be fully thermalized at the temperature of the cosmic background radiation field, a result that conflicts with some recent, independent calculations. This new network allows the chemistry of primordial gas to be followed during the early phase of collapse towards Population III star progenitors.

Chemical Kinetic Study of the Reaction of CH2OO with CH3O2.

Criegee intermediates play an important role in the oxidizing capacity of the Earth's troposphere. Although extensive studies have been conducted on Criegee intermediates in the past decade, their kinetics with radical species remain underexplored. We investigated the kinetics of the simplest Criegee intermediate, CH2OO, with the methyl peroxy radical, CH3O2, as a model system to explore the reactivities of Criegee intermediates with peroxy radicals. Using a multipass UV-Vis spectrometer coupled to a pulsed-laser photolysis flow reactor, CH2OO and CH3O2 were generated simultaneously from the photolysis of CH2I2/CH3I/O2/N2 mixtures with CH2OO measured directly near 340 nm. We determined a reaction rate coefficient kCH2OO+CH3O2 = (1.7 ± 0.5) × 10-11 cm3 s-1 at 294 K and 10 Torr, where the influence of iodine adducts is reduced. This rate coefficient is faster than previous theoretical predictions, highlighting the challenges in accurately describing the interaction between zwitterionic and biradical characteristics of Criegee intermediates.

Improved Approach for ab Initio Calculations of Rate Coefficients for Secondary Reactions in Acrylate Free-Radical Polymerization.

Secondary reactions in radical polymerization pose a challenge when creating kinetic models for predicting polymer structures. Despite the high impact of these reactions in the polymer structure, their effects are difficult to isolate and measure to produce kinetic data. To this end, we used solvation-corrected M06-2X/6-311+G(d,p) ab initio calculations to predict a complete and consistent data set of intrinsic rate coefficients of the secondary reactions in acrylate radical polymerization, including backbiting, β-scission, radical migration, macromonomer propagation, mid-chain radical propagation, chain transfer to monomer and chain transfer to polymer. Two new approaches towards computationally predicting rate coefficients for secondary reactions are proposed: (i) explicit accounting for all possible enantiomers for reactions involving optically active centers; (ii) imposing reduced flexibility if the reaction center is in the middle of the polymer chain. The accuracy and reliability of the ab initio predictions were benchmarked against experimental data via kinetic Monte Carlo simulations under three sufficiently different experimental conditions: a high-frequency modulated polymerization process in the transient regime, a low-frequency modulated process in the sliding regime at both low and high temperatures and a degradation process in the absence of free monomers. The complete and consistent ab initio data set compiled in this work predicts a good agreement when benchmarked via kMC simulations against experimental data, which is a technique never used before for computational chemistry. The simulation results show that these two newly proposed approaches are promising for bridging the gap between experimental and computational chemistry methods in polymer reaction engineering.