Reaction Rate Coefficients Research Articles

Identifying the essential roles of light and sonication in dual‐stimuli regulated bulk atom transfer radical polymerization by multiscale simulation

AbstractMore and more attention has been paid to the important roles of external fields in controlled radical polymerization (CRP). However, their essential roles have not been studied thoroughly yet, which hinders the in‐depth understanding of the mechanism and kinetics. Herein, a strategy combining quantum chemical calculations (QCC) and kinetic modeling was adopted to identify the essential roles of light and ultrasonication in the dual‐stimuli regulated bulk atom transfer radical polymerization (ATRP). At the molecular level, the impact of light on Cu‐catalyzed ATRP was investigated. The CuIIBr/Me6TREN has high absorbance at an experimental wavelength of 365 nm (main excitation S0 → D7 accounts for 84.93%). Electron transfer reactions involving Me6TREN are more favorable paths for photochemical reactions, and the mechanism of the copper activation/deactivation pathway is inner sphere electron transfer. At the micro‐scale, a kinetic model based on the method of moment was established with a “series” encounter pair model to consider the influence of ultrasound on diffusional limitation. Simulation results show that the changes of the reaction rate coefficients ka, kda, and kt at high conversion reflect the degree of diffusional limitation by ultrasound. The multiscale modeling strategy applied in this study identifies the essential roles of photo and ultrasonication in dual‐stimuli regulated model systems, which can be extended to other external‐field regulated CRP to improve the mechanistic understanding.

On the increasing competitiveness of UV/Cl to UV/H2O2 advanced oxidation as the organic carbon concentration increases

UV/Cl and UV/H2O2 are advanced oxidation processes (AOPs) used for drinking water treatment and water reuse. This work explored the hypothesis that UV/Cl becomes more competitive to UV/H2O2 at neutral-to-high pH as the concentration of total organic carbon (TOC) increases. Lab experiments and kinetic modelling were used to compare initial pseudo first-order contaminant decay rate coefficients between the AOPs at various pH and TOC conditions. The relative effect of increasing TOC concentrations on UV/Cl vs. UV/H2O2 depended on the pH, contaminant, and organic matter reactivity towards radicals. For example, while the reaction rate coefficients during both AOPs generally decreased with increasing TOC, the UV/Cl reaction rate coefficients for the solely •OH-reactive sucralose decreased 41–138% less than the UV/H2O2 coefficients as the TOC concentration was increased from 0 to 5 mg-C L−1. However, UV/Cl was more affected than UV/H2O2 when targeting caffeine (a contaminant reactive to chlorine radicals). The data were used to define TOC-pH conditions for which either AOP would be more energy-efficient, under a set of standard conditions. The results suggest that UV/Cl may be competitive to UV/H2O2 under a wider range of treatment scenarios than has been conventionally thought based on tests in pure water.

Quantitative structure-activity relationship models for the reaction rate coefficients between dissolved organic matter and PPCPs

To predict PPCPs’ photolysis rate in natural aquatic environment, it is essential to grasp the reaction rates between DOM and PPCPs, yet there are few measured data and no prediction models for this important photochemical parameter. To address this, a reaction rate coefficient (αDOM) was defined to describe the apparent rate of DOM-involved photoreaction for PPCPs. The measured αDOM values for 40 PPCPs in 9 DOM samples varied dramatically, ranging from (−2.1 ± 0.1)× 1010 to (2.2 ± 0.1)× 1011 M−1 s−1. Then the quantitative structure-activity relationship (QSAR) models were developed using chemical and water quality descriptors via the random forest method. We initially separated positive and negative values by a classifier with an AUC value of 0.965, followed by the construction of regression models for positive and negative values, respectively, using a regressor. Positive models achieved satisfactory goodness-of-fit and predictive ability (R2adj=0.92 and Q2ext=0.86), while negative models demonstrated acceptable performance (R2adj=0.71 and Q2ext=0.70). Finally, a comprehensive photolysis model that incorporates the QSAR models for αDOM was established and the significance of water quality parameters was emphasized through sensitive analysis. This model enables more elaborate predictions of PPCPs’ photolysis rates in various water samples, providing valuable assistance for forecasting PPCPs’ environmental fate.

Role of methyldioxy radical chemistry in high‐pressure methane combustion in CO2

AbstractThe combustion chambers of direct‐fired supercritical CO2 power plants operate at pressures of approximately 300 bar and CO2 dilutions of up to 96%. The rate coefficients used in existing chemical kinetic mechanisms are validated for much lower pressures and much smaller concentrations of CO2. Recently, the UoS sCO2 1.0 and UoS sCO2 2.0 mechanisms have been developed to better predict ignition delay time (IDT) data from shock tube studies at pressures from 1 to 260 bar in various CO2‐containing bath gas compositions. The chemistry of the methyldioxy radical (CH3O2) has been identified as an essential combustion intermediate for methane combustion above 100 bar, where mechanisms missing this species begin to vastly overpredict the IDT. The current literature available on CH3O2 is very limited and often concerned with atmospheric chemistry and low‐pressure, low‐temperature combustion. This means that the rate coefficients used in UoS sCO2 2.0 are commonly determined at sub‐atmospheric pressures and temperatures below 1000 K with some rate coefficients being over 30 years old. In this work, the rate coefficients of new potential CH3O2 reactions are added to the current mechanism to create UoS sCO2 2.1 It is shown that the influence of CH3O2 on the IDT is greatest at high pressures and low temperatures. It has also been demonstrated that CO2 has very little effect on the chemistry of CH3O2 at 300 bar meaning that CH3O2 rate coefficients can be determined in other bath gases, reducing the impact of non‐ideal effects such as bifurcation when studying in a CO2 bath gas. The updated UoS sCO2 2.1 mechanism is then compared to high‐pressure IDT data and the most important reactions which require reinvestigation have been identified as the essential next steps in understanding high‐pressure methane combustion.

Stochastic optimization of a uranium oxide reaction mechanism using plasma flow reactor measurements

In this work, a coupled Monte Carlo Genetic Algorithm (MCGA) approach is used to optimize a gas phase uranium oxide reaction mechanism based on plasma flow reactor (PFR) measurements. The PFR produces a steady Ar plasma containing U, O, H, and N species with high temperature regions (3000–5000 K) relevant to observing UO formation via optical emission spectroscopy. A global kinetic treatment is used to model the chemical evolution in the PFR and to produce synthetic emission signals for direct comparison with experiments. The parameter space of a uranium oxide reaction mechanism is then explored via Monte Carlo sampling using objective functions to quantify the model-experiment agreement. The Monte Carlo results are subsequently refined using a genetic algorithm to obtain an experimentally corroborated set of reaction pathways and rate coefficients. Out of 12 reaction channels targeted for optimization, four channels are found to be well constrained across all optimization runs while another three channels are constrained in select cases. The optimized channels highlight the importance of the OH radical in oxidizing uranium in the PFR. This study comprises a first step toward producing a comprehensive experimentally validated reaction mechanism for gas phase uranium molecular species formation.

New Measurements and Calculations on the Kinetics of an Old Reaction: OH + HO2 → H2O + O2.

Literature rate coefficients for the prototypical radical-radical reaction at 298 K vary by close to an order of magnitude; such variations challenge our understanding of fundamental reaction kinetics. We have studied the title reaction at room temperature via the use of laser flash photolysis to generate OH and HO2 radicals, monitoring OH by laser-induced fluorescence using two different approaches, looking at the direct reaction and also the perturbation of the slow OH + H2O2 reaction with radical concentration, and over a wide range of pressures. Both approaches give a consistent measurement of k1,298K ∼1 × 10-11 cm3 molecule-1 s-1, at the lowest limit of previous determinations. We observe, experimentally, for the first time, a significant enhancement in the rate coefficient in the presence of water, k1,H2O,298K = (2.17 ± 0.09) × 10-28 cm6 molecule-2 s-1, where the error is statistical at the 1σ level. This result is consistent with previous theoretical calculations, and the effect goes some way to explaining some, but not all, of the variation in previous determinations of k1,298K. Supporting master equation calculations, using calculated potential energy surfaces at the RCCSD(T)-F12b/CBS//RCCSD/aug-cc-pVTZ and UCCSD(T)/CBS//UCCSD/aug-cc-pVTZ levels, are in agreement with our experimental observations. However, realistic variations in barrier heights and transition state frequencies give a wide range of calculated rate coefficients showing that the current precision and accuracy of calculations are insufficient to resolve the experimental discrepancies. The lower value of k1,298K is consistent with experimental observations of the rate coefficient of the related reaction, Cl + HO2 → HCl + O2. The implications of these results in atmospheric models are discussed.

Elastic and electron capture processes in slow He+–He collision

Aims. The elastic and electron-capture processes of He+ ions with ground helium atoms are very important for studies in astrophysics. It is essential to have reliable state-selective charge transfer, elastic, and transport cross-sections, along with the corresponding reaction rate coefficient data, especially for low collision energies. Methods. We investigated the elastic and non-radiative electron-capture processes in He+(1s)–He(1s2) collisions are investigated employing the full quantum-mechanical molecular orbital close-coupling method. The adopted ab initio adiabatic potentials and coupling matrix elements were obtained by a multi-reference single- and double-excitation configuration interaction approach. Results. We computed the elastic, charge-transfer, and transport cross-sections in the energy range of 0.01–2500eVamu−1 and the reaction rate coefficient in the temperature range of 10–109 K. Good agreement was achieved when compared to the available experimental and theoretical results. Shape resonance, Regge, and Glory oscillations were also found in the elastic and charge transfer cross-sections in the energy region considered here.

Room temperature rate coefficients for the reaction of chlorine atoms with a series of volatile methylsiloxanes (L2‐L5, D3‐D6)

AbstractThe kinetics of chlorine (Cl) atom reactions with a series of volatile methylsiloxanes (VMS) including hexamethyldisiloxane (L2), octamethyltrisiloxane (L3), decamethyltetrasiloxane (L4), dodecamethylpentasiloxane (L5), hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) were investigated in relative rate experiments at room temperature and atmospheric pressure. The experiments were carried out in a 0.2 m3 PFA Teflon chamber, employing proton‐transfer‐reaction time‐of‐flight mass spectrometry (PTR‐ToF‐MS) as the chemical‐analytical tool. The following relative and absolute reaction rate coefficients were obtained using isoprene as reference compound (kVMS/kisoprene; kVMS × 1010 cm3 molec−1 s −1): L2 (0.32 ± 0.02; 1.31 ± 0.21), L3 (0.38 ± 0.00; 1.56 ± 0.23), L4 (0.48 ± 0.01; 1.98 ± 0.29), L5 (0.54 ± 0.03; 2.22 ± 0.34), D3 (0.14 ± 0.02; 0.56 ± 0.13), D4 (0.26 ± 0.01; 1.05 ± 0.16), D5 (0.36 ± 0.02; 1.46 ± 0.22), D6 (0.39 ± 0.02; 1.61 ± 0.25). The following relative and absolute reaction rate coefficients were obtained using toluene as reference compound (kVMS/ktoluene; kVMS × 1010 cm3 molec−1 s −1): L2 (1.59 ± 0.18; 0.95 ± 0.14), L3 (2.25 ± 0.14; 1.35 ± 0.16), L4 (2.38 ± 0.01; 1.43 ± 0.14), L5 (3.57 ± 0.11; 2.14 ± 0.22), D3 (0.87 ± 0.01; 0.52 ± 0.05), D4 (1.48 ± 0.12; 0.89 ± 0.11), D5 (2.02 ± 0.15; 1.21 ± 0.15), D6 (2.54 ± 0.11; 1.52 ± 0.17). Our data confirm that reactions with Cl atoms need to be taken into account when assessing the decomposition of VMS in Cl‐rich tropospheric environments.

The weakening effect of the inhibition of CO2 on the explosion of HCNG with the increase of hydrogen: Experimental and chemical kinetic research

To explore the inhibitory effect of CO2 on HCNG (Hydrogen enriched compressed natural gas) explosion and its chemical kinetic mechanism, the explosion pressure and flame of CO2/HCNG/Air (hydrogen ratio: 0–0.6, CO2 addition: 3 vol%, 6 vol%, and 9 vol%) were tested in a 20 L spherical explosion tank at normal temperature and normal pressure. The experiment results shown that: as the addition of CO2 increases, the inhibition effect on HCNG explosion flame and pressure becomes more obvious. The larger the H2 ratio, the more difficult it is to inhibit HCNG explosion flame and pressure. To explore the chemical kinetics reasons for the above laws, the chemical kinetic parameters (such as free radical formation rate and temperature sensitivity coefficient) of the explosion reaction under the above conditions were calculated by CHEMKIN-PRO. The results indicate that CO2 mainly acts as a stable third body in the reaction system, thereby slowing down the growth of explosion chain reactions. In addition, as the main product of the CH4 oxidation reaction, CO2 has a certain weakening effect on the CH4 oxidation reaction. As the proportion of H2 increases, the elementary reactions such as 3# and 84# that generate ·H radicals are promoted, increasing the concentration of ·H radicals in the reaction system. Therefore, the dominant role of 38# on the temperature rise of the reaction system is enhanced, and the contribution of the CH4 oxidation reaction to the temperature rise of the reaction system is weakened. This is the chemical kinetic reason that CO2 has a weak inhibitory effect on the energy release of the HCNG explosion reaction when the proportion of H2 is large. The research results can provide a theoretical basis for the development of HCNG explosion prevention and control technology.

Comprehensive Theoretical Study on Four Typical Intramolecular Hydrogen Shift Reactions of Peroxy Radicals: Multireference Character, Recommended Model Chemistry, and Kinetics.

Intramolecular hydrogen shift reactions in peroxy radicals (RO2• → •QOOH) play key roles in the low-temperature combustion and in the atmospheric chemistry. In the present study, we found that a mild-to-moderate multireference character of a potential energy surface (PES) is widely present in four typical hydrogen shift reactions of peroxy radicals (RO2•, R = ethyl, vinyl, formyl methyl, and acetyl) by a systematic assessment based on the T1 diagnostic, %TAE diagnostic, M diagnostic, and contribution of the dominant configuration of the reference CASSCF wavefunction (C02). To assess the effects of these inherent multireference characters on electronic structure calculations, we compared the PESs of the four reactions calculated by the multireference method CASPT2 in the complete basis set (CBS) limit, single-reference method CCSD(T)-F12, and single-reference-based composite method WMS. The results showed that ignoring the multireference character will introduce a mean unsigned deviation (MUD) of 0.46-1.72 kcal/mol from CASPT2/CBS results by using the CCSD(T)-F12 method or a MUD of 0.49-1.37 kcal/mol by WMS for three RO2• reactions (R = vinyl, formyl methyl, and acetyl) with a stronger multireference character. Further tests by single-reference Kohn-Sham (KS) density functional theory methods showed even larger deviations. Therefore, we specifically developed a new hybrid meta-generalized gradient approximation (GGA) functional M06-HS for the four typical H-shift reactions of peroxy radicals based on the WMS results for the ethyl peroxy radical reaction and on the CASPT2/CBS results for the others. The M06-HS method has an averaged MUD of 0.34 kcal/mol over five tested basis sets against the benchmark PESs, performing best in the tested 38 KS functionals. Last, in a temperature range of 200-3000 K, with the new functional, we calculated the high-pressure-limit rate coefficients of these H-shift reactions by the multi-structural variational transition-state theory with the small-curvature tunneling approximation (MS-CVT/SCT) and the thermochemical properties of all of the involved key radicals by the multi-structural torsional (MS-T) anharmonicity approximation method.

Imaging concentration fields in microfluidic fuel cells as a mass transfer characterization platform

Microfluidic fuel cells (MFCs) are microfluidic electrochemical conversion devices that are used to power electrical equipment. Their performance relies on improving reactant mass transfer at the electrode interface. In this work, a MFC is developed to implement a novel imaging technique that allows the measurement of reactant concentration fields, featuring formic acid as the fuel and potassium permanganate as the oxidant. The concentration fields were imaged based on transmitted visible spectroscopy, which links the light intensity passing through the MFC to its local reactant concentration. An analytical model was developed to estimate the mass diffusivity and kinetic reaction rate coefficient. For the first time, mass transport and transfer coefficient were simultaneously measured during operation. These parameters estimated using the proposed technique can be implemented in a numerical model to predict the MFC performance and concentration distribution. This work paves the way towards advanced imaging tools for operando mass transfer characterizations in microfluidics and Tafel kinetic characterization in many electrochemical devices.

Radiative magnetodydrodynamic cross fluid thermophysical model passing on parabola surface with activation energy

The proposed work is significantly important due to its applications in manufacturing process of submarine, bullets and aircrafts, and many more engineering and industrial works such as cooling and heating processes and chemical works. The purpose of this article is to scrutinize the flow, heat and mass transferal rate for the boundary layer flow of non-Newtonian fluid with variable fluid characteristics on the radiative paraboloid surface. The non-Newtonian fluid which is under consideration is Cross fluid model which is generalized Newtonian fluid and it acts as a shear thickening and thinning. For the sake of heat and mass transport, we have considered the activation energy and thermal radiation effects. The governing equations of considered fluid model occurred in the PDEs form and then transmuted into ODEs form by using similarity variables. The graphical behavior in terms of velocity field is noted due to viscosity parameter and Hartmann number which shows drops behavior in velocity profile. The impact of thermal radiation and thermal conductivity coefficients is noted here and concluded that both quantities creates enhancement in temperature field. The concentration transfer rate is observing for activation energy, reaction rate coefficient and mass diffusion parameters. Activation energy and mass diffusion coefficient improves the concentration rate while reaction rate diminishes the concentration layer thickness. The result of varying the Weissenberg number upon the skin friction is also analyzed. Also the comparison analyses with published articles are presented.

Isotope Exchange Reaction of OH− Anion with HD at Temperatures from 15 K up to 300 K: Ion Trap Study

This paper presents the results of an experimental study of the reaction of OH− anions with HD molecules leading to the formation of OD− anions. The study’s main goal was to obtain the temperature dependence of the reaction rate coefficient and determine the reaction’s enthalpy. This study was carried out at astrophysically relevant temperatures from 15 to 300 K. The reaction was studied using a temperature-variable cryogenic linear 22-pole radio-frequency ion trap. The rotational temperature of the OH− anions in the ion trap was characterized by near-threshold photodetachment spectroscopy. At 15 K, the measured reaction rate coefficient is 5 × 10−10 cm3 s−1. With increasing temperature, the reaction rate coefficient decreases monotonically to 5 × 10−11 cm3 s−1 at 300 K. Comparing with the previously determined rate coefficient of the reverse reaction of OD− anions with H2, we obtained the temperature dependence of the equilibrium constant. The enthalpy and entropy of the title reaction were determined in the studied temperature range as ΔH = (−23.9 ± 0.7 ± 2.6sys) meV and ΔS = (−8.5 ± 1.2 ± 1.4sys) J mol−1 K−1, respectively.

Monte Carlo simulation of ion kinetics in nitrogen and oxygen plasmas under non-uniform electric field conditions

The kinetics of N4+ and O− ions was numerically studied in nitrogen and oxygen plasmas in a highly non-uniform electric field. Mean ion energy and reaction rate coefficients in a background gas at pressures from 1 to 10 Torr were calculated through a Monte Carlo simulation. The ion characteristics followed the local reduced electric field at high pressures, whereas nonhydrodynamic effects leading to a nonlocal dependence of the mean ion energy and rate coefficients on the field were obtained at low pressures. As a result, the rates of N4+ ion dissociation, electron detachment from O− ions, and charge exchange in collisions between O− and O2 lagged the local field value. The non-local effect on the ion rate coefficients was more profound when the field decreased in space. We suggested a simplified method of describing ion rates in spatially varying electric fields on the basis of the Monte Carlo simulation of these rates for uniform electric field conditions and mean ion energy calculations in non-uniform fields. This method is similar to the local-mean-energy approximation utilized for describing electron swarm parameters in varying electric fields. The results of the simplified method were compared with the results of the direct Monte Carlo simulation.

Radiative efficiencies and global warming potentials of agricultural fumigants

A rounded assessment of the environmental impacts of fumigants used within the agricultural sector must consider the potential climate impacts of their release into the atmosphere. Within policy settings, the 100-year Global Warming Potential (GWP100) is the most commonly used metric. While GWP100 values are available for the widely used fumigant sulfuryl fluoride, no estimates are available for 4 alternative fumigants: ethyl formate, cyanogen, hydrogen cyanide and phosphine. Existing laboratory measurements of the infrared spectra and reaction rate coefficients of these gases are used to produce new estimates of their radiative efficiencies and atmospheric lifetimes, and the first estimates of their GWP100 and other climate emission metrics. Although uncertainties are considerable, their GWP100 values are estimated to be no more than 2% of the GWP100 value of sulfuryl fluoride. These new estimates will enable informed estimates of the climate impact of the use of these fumigants, which must account for the differing usage and release rates to achieve the same fumigant efficacy.

Atmospheric distribution of HCN from satellite observations and 3-D model simulations

Abstract. Hydrogen cyanide (HCN) is an important tracer of biomass burning, but there are significant uncertainties in its atmospheric budget, especially its photochemical and ocean sinks. Here we use a tracer version of the TOMCAT global 3-D chemical transport model to investigate the physical and chemical processes driving the abundance of HCN in the troposphere and stratosphere over the period 2004–2016. The modelled HCN distribution is compared with version 4.1 of the Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE-FTS) HCN satellite data, which provide profiles up to around 42 km, and with ground-based column measurements from the Network for the Detection of Atmospheric Composition Change (NDACC). The long-term ACE-FTS measurements reveal the strong enhancements in upper-tropospheric HCN due to large wildfire events in Indonesia in 2006 and 2015. Our 3-D model simulations confirm previous lower-altitude balloon comparisons that the currently recommended NASA Jet Propulsion Laboratory (JPL) reaction rate coefficient of HCN with OH greatly overestimates the HCN loss. The use of the rate coefficient proposed by Kleinböhl et al. (2006) in combination with the HCN oxidation by O(1D) gives good agreement between ACE-FTS observations and the model. Furthermore, the model photochemical loss terms show that the reduction in the HCN mixing ratio with height in the middle stratosphere is mainly driven by the O(1D) sink with only a small contribution from a reaction with OH. From comparisons of the model tracers with ground-based HCN observations we test the magnitude of the ocean sink in two different published schemes (Li et al., 2000, 2003). We find that in our 3-D model the two schemes produce HCN abundances which are very different to the NDACC observations but in different directions. A model HCN tracer using the Li et al. (2000) scheme overestimates the HCN concentration by almost a factor of 2, while a HCN tracer using the Li et al. (2003) scheme underestimates the observations by about one-third. To obtain good agreement between the model and observations, we need to scale the magnitudes of the global ocean sinks by factors of 0.25 and 2 for the schemes of Li et al. (2000) and Li et al. (2003), respectively. This work shows that the atmospheric photochemical sinks of HCN now appear well constrained but improvements are needed in parameterizing the major ocean uptake sink.

A systematic analysis of chemical mechanisms for ethylene oxidation and PAH formation

Accurate prediction of soot formation and evolution remains a formidable challenge due to the complex interaction between gas-phase composition and solid-phase particles. Recent studies have shown that the choice of gas-phase mechanisms is of primary importance in affecting predictability. In this work, a systematic analysis of ethylene (C2H4) combustion mechanisms denoted as KAUST, Stanford, Aachen, Polimi, ABF, DLR/UT, Naples, Caltech, and SJTU, which have been widely used in the soot community, is performed to investigate their differences in fundamental chemistry, polycyclic aromatic hydrocarbon (PAH) chemistry, and soot prediction. It is found that the nine mechanisms exhibit large differences even in predicting canonical combustion properties (e.g., ignition delay time, laminar flame speed, and extinction strain rate), indicating significant variations in the fundamental chemistry. This is due to the fact that although most mechanisms share very similar dominant fuel-oxidation reactions, there are notable differences in the rate coefficients of sensitive reactions used in these mechanisms. Owing to the uncertainties in the fundamental chemistry, the predictions of C2H2 from the nine mechanisms show significant differences, which contributes to the differences in soot precursor prediction, in conjunction with the difference in benzene (A1) formation pathways demonstrated by the element flux analysis of the C atom. Furthermore, it is found that PAHs containing two rings play a dominant role in soot formation for most mechanisms. Moreover, it is observed that while Caltech and SJTU significantly under estimate soot formation, they reasonably reproduce its sensitivity to strain rate. These results indicate that despite substantial advances in the development of C2H4 oxidation and PAH formation chemistry, the various existing mechanisms lead to significant differences in predicting soot concentrations which can be traced back to considerable differences in both fundamental chemistry and PAH chemistry. This suggests that the fundamental chemistry should be calibrated or improved before further development of PAH chemistry and soot models.

The determination and prediction of the apparent reaction rates between excited triplet-state DOM and selected PPCPs

To determine and predict the reaction rate between 3DOM* and PPCPs in various water bodies, this study defines a reaction rate coefficient (α3DOM∗) to describe the reaction between 3DOM* and PPCPs. As the values also included the inhibition effect of DOM's antioxidant moieties, the calculation of α3DOM∗ is inconsistent with that of a bimolecular rate constant via the steady-state kinetic method. The α3DOM∗ values of 12 selected PPCPs were determined in two DOM solutions and ten DOM-containing water samples collected from typical surface water bodies in Beijing. The Pearson coefficients between nine predictors including the absorbance ratio (E2/E3), specific absorption coefficient at 254 nm (SUVA254), fluorescence index (FI), biological index (BIX), humification index (HIX), pH, total organic carbon (TOC), total fluorescence intensity (TFI) and TOC normalized TFI (TFI/TOC) and α3DOM∗ were examined. Correlation patterns for sulfonamides, β-blockers and diclofenac supported the electron transfer pathway, and was distinctly different from those appeared for FQs where quenching effect played a main part. TFI and TFI/TOC were recognized as the most useful surrogates in empirically predicting α3DOM∗. For PPCPs that went through the electron transfer pathway, α3DOM∗ could be well fit to the Rehm-Weller model assuming a proportional relationship between TFI and △Get. For FQs, α3DOM∗ was found to linearly correlated with TFI/TOC. The α3DOM∗ values determined in this study enrich the database of PPCPs photolysis parameters, and the correlation analysis provides reference for forecasting PPCPs fate in the aquatic environment.

OH reaction rate coefficients, infrared spectra, and climate metrics for (E)‐ and (Z)‐ 2‐perfluoroheptene (2‐C7F14) and 3‐perfluoroheptene (3‐C7F14)

AbstractIn this work, perfluoroheptene 2‐ and 3‐C7F14 stereoisomer specific gas‐phase OH reaction rate coefficients, k, were measured at 296 K in ∼600 Torr (He bath gas) using a relative rate (RR) method. Gas‐chromatography (GC) with electron capture detection (ECD) was used for the separation and detection of the stereoisomers. Rate coefficients for (E)‐2‐C7F14, (Z)‐2‐C7F14, (E)‐3‐C7F14, and (Z)‐3‐C7F14 were measured to be (in units of 10−13 cm3 molecule−1 s−1) (3.60 ± 0.51), (2.22 ± 0.21), (3.43 ± 0.47), and (1.48 ± 0.19), respectively, where the uncertainties include estimated systematic errors. Rate coefficients for the (E)‐ stereoisomers were found to be systematically greater than the (Z)‐ stereoisomers by a factor of 1.6 and 2.3 for 2‐C7F14 and 3‐C7F14, respectively. Atmospheric lifetimes with respect to OH radical reaction for (E)‐2‐C7F14, (Z)‐2‐C7F14, (E)‐3‐C7F14, (Z)‐3‐C7F14 were estimated to be ∼33, ∼56, ∼36, and ∼86 days, respectively, for an average OH radical concentration of 1 × 106 molecule cm−3. Quantitative infrared absorption spectra were measured as part of this work. Complimentary theoretically calculated infrared absorption spectra using density functional theory (DFT) are included in this work. The theoretical spectra were used to evaluate stereoisomer climate metrics. Radiative efficiencies (adjusted) and global warming potentials (GWPs, 100‐year time‐horizon), were estimated to be 0.12, 0.19, 0.12, and 0.23 W m−2 ppb−1 and 1.9, 5.1, 2.1, 9.3 for (E)‐2‐C7F14, (Z)‐2‐C7F14, (E)‐3‐C7F14, (Z)‐3‐C7F14, respectively. Atmospheric degradation mechanisms are discussed.

Theoretical kinetics investigations of the reaction HO + SO ↔ H + SO2 on an accurate full‐dimensional potential energy surface

AbstractThe reaction HO + SO → H + SO2 (Rt) and its reverse (R‐t) play an important role in environment and the combustion of sulfur‐containing fuels. However, their kinetics is of high uncertainty as its reaction profile is complicated with multiple deep complexes and channels. In this work, the kinetics and mechanisms of Rt and R‐t are studied comprehensively based on a newly developed full‐dimensional accurate potential energy surface (PES) with the aid of machine learning. This highly accurate PES is interfaced with the software Gaussian. Then reliable information, including the energy, structures, and vibrational frequencies of the stationary points, as well as the minimum energy path and variational analysis can be efficiently determined. The variational transition state theory (VTST) and Rice−Ramsperger−Kassel−Marcus (RRKM) theory are employed to obtain the rate coefficients of each elementary reaction. The temperature‐ and pressure‐dependent rate coefficients of Rt are derived by the RRKM‐based master equation with hindered rotor and free rotor model considered. In addition, the effect of isotope substitution for the hydrogen is investigated on the reaction kinetics. Meanwhile, the quasi‐classical trajectory (QCT) calculation is performed on the PES‐2020 to obtain the temperature‐dependent reaction kinetics.