Bimolecular Rate Coefficients Research Articles

Contrast and Complexity in the Low-Temperature Kinetics of CN(v = 1) with O2 and NO: Simultaneous Kinetics and Ringdown in a Uniform Supersonic Flow.

Bimolecular rate coefficients were determined for the reaction CN(v = 1) + NO and O2 using continuous wave cavity ringdown spectroscopy in a uniform supersonic flow (UF-CRDS). The well-matched time scales for ringdown and reaction under pseudo-first-order conditions allow for the use of the SKaR method (simultaneous kinetics and ringdown) in which the full kinetic trace is obtained on each ringdown. The reactions offer an interesting contrast in that the CN(v = 1) + NO system is nonreactive and proceeds by complex-mediated vibrational relaxation, while the CN(v = 1) + O2 reaction is primarily reactive. The measured rate coefficients at 70 K are (2.49 ± 0.08) × 10-11 and (10.49 ± 0.22) × 10-11 cm3 molecule-1 s-1 for the reaction with O2 and NO, respectively. The rate for reaction with O2 is a factor 2 lower than previously reported for v = 0 in the same temperature range, a surprising result, while that for NO is consistent with extrapolation of previous high-temperature measurements to 70 K. The latter is also discussed in light of theoretical calculations and measurements of the rate constants for the association reaction in the high-pressure limit. The measurements are complicated by the presence of a metastable population of high-J CN formed by photolysis of the precursor BrCN, and a kinetic model is developed to treat the competing relaxation and reaction. It is particularly problematic for reactions at low temperatures where the rotational relaxation and reaction have similar rates, precluding a reliable determination of the rate coefficients at 30 K. Also presented are important modifications to the data acquisition and control for the instrument that have yielded considerably enhanced stability and throughput.

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.

Generation of 3-aminopropanamide and its cluster formation with nucleation precursors- a theoretical exploration

Aminoamides are formed in the atmospheric environments by the auto-oxidation of the parent diamines. In this work, the oxidation chemistry of diamine (1,3-Diaminopropane, Dap) to the amino amide (3- aminopropanamide, 3-APA) and its new particle formation potential with small atmospheric molecules such as NH3 (A), H2O (W) and H2SO4 (SA) are theoretically investigated using the M062X/6–311++G** theory. The bimolecular rate coefficient of the ·OH initiated H-atom abstraction is computed to be 1.01 × 10−11 cm3 molecule−1 s−1. Further reaction of the peroxy radical intermediate indicates that the pathway involving γ H- shift of the initially formed radical intermediates to be more favourable on kinetic grounds with the effective bimolecular rate coefficient of 3.87 × 10−14 cm3 molecule−1s−1. The thermodynamic barrier associated with the H-shifts involved in this pathway is in the range of 13–20 kcal/mol. The cluster formation of APA with SA is more favourable than the clusters with W and A, wherein the free energy of formation of (APA)(SA) and (APA)(SA)2 are −11.3 and −22.6 kcal/mol, respectively. However, the feasibility of cluster formation with W and A increases with the altitude and becomes spontaneous in the case of water at an altitude of 12 km. The present work indicates that aminoamides like 3-APA can participate in the initial stages of new particle formation events by forming clusters with SA molecules. The scattering parameters and topological analysis of different (Amide)(SA) clusters indicate more scattering properties for the (APA)(SA) cluster, which has an adverse effect on the atmosphere. Furthermore, topological analysis indicates that H-bond formation is more prominent in the (APA)(SA) cluster.

Temperature-dependent aqueous OH kinetics of C2–C10 linear and terpenoid alcohols and diols: new rate coefficients, structure–activity relationship, and atmospheric lifetimes

Abstract. Aliphatic alcohols (AAs), including terpenoic alcohols (TAs), are ubiquitous in the atmosphere due to their widespread emissions from natural and anthropogenic sources. Hydroxyl radical (OH) is the most important atmospheric oxidant in both aqueous and gas phases. Consequently, the aqueous oxidation of the TAs by the OH inside clouds and fogs is a potential source of aqueous secondary organic aerosols (aqSOAs). However, the kinetic data, necessary for estimating the timescales of such reactions, remain limited. Here, bimolecular rate coefficients (kOHaq) for the aqueous oxidation of 29 C2–C10 AAs by hydroxyl radicals (OH) were measured with the relative rate technique in the temperature range 278–328 K. The values of kOHaq for the 15 AAs studied in this work were measured for the first time after validating the experimental approach. The kOHaq values measured for the C2–C10 AAs at 298 K ranged from 1.80 × 109 to 6.5 × 109 M−1 s−1. The values of activation parameters, activation energy (7–17 kJ mol−1), and average Gibbs free energy of activation (18 ± 2 kJ mol−1) strongly indicated the predominance of the H-atom abstraction mechanism. The estimated rates of the complete diffusion-limited reactions revealed up to 44 % diffusion contribution for the C8–C10 AAs. The data acquired in this work and the values of kOHaq for AAs, carboxylic acids, and carboxylate ions available in the literature were used to develop a modified structure–activity relationship (SAR). The SAR optimized in this work estimated the temperature-dependent kOHaq for all compounds under investigation with much higher accuracy compared to the previous models. In the new model, an additional neighboring parameter was introduced (F≥ (CH2)6), using the kOHaq values for the homolog (C2–C10) linear alcohols and diols. A good overall accuracy of the new SAR at 298 K (slope = 1.022, R2=0.855) was obtained for the AAs and carboxylic acids under investigation. The kinetic database (kOHaq values in this work and compiled literature data) was also used to further enhance the ability of SAR to predict temperature-dependent values of kOHaq in the temperature range 278–328 K. The calculated atmospheric lifetimes indicate that terpenoic alcohols and diols can react with the OH in aerosol, cloud, and fog water with liquid water content (LWC) ≥0.1 g m−3 and LWC ≥ 10−4 g m−3, respectively. The preference of terpenoic diols to undergo aqueous oxidation by the OH under realistic atmospheric conditions is comparable with terpenoic acids, making them potentially effective precursors of aqSOAs. In clouds, a decrease in the temperature will strongly promote the aqueous reaction with the OH, primarily due to the increased partitioning of WSOCs into the aqueous phase.

Cost-effective approach for atmospheric accretion reactions: a case of peroxy radical addition to isoprene.

We present an accurate and cost-effective method for investigating the accretion reactions between unsaturated hydrocarbons and oxidized organic radicals. We use accretion between isoprene and primary, secondary and tertiary alkyl peroxy radicals as model reactions. We show that a systematic semiempirical transition state search can lead to better transition state structures than relaxed scanning with density functional theory with a significant gain in computational efficiency. Additionally, we suggest accurate and effective quantum chemical methods to study accretion reactions between large unsaturated hydrocarbons and oxidized organic radicals. Furthermore, we examine the atmospheric relevance of these types of reactions by calculating the bimolecular reaction rate coefficients and formation rates under atmospheric conditions from the quantum chemical reaction energy barriers.

Reaction between Criegee Intermediate CH2OO and Isobutyraldehyde: Kinetics and Atmospheric Implications

AbstractIn the present work, we have investigated the 1,3‐cycloaddition reaction of isobutyraldehyde ((CH3)2CHCHO) with the simplest Criegee intermediate CH2OO using the OH laser‐induced fluorescence (LIF) method in a reaction tube. The experiments were conducted at temperatures and pressures ranging from 280 to 338 K and 5 to 150 Torr. We found that the bimolecular rate coefficient of the reaction is temperature‐ and pressure‐dependent. The measured rate coefficients at 100 Torr are (4.93±0.89), (4.46±0.80), (3.99±0.72), (3.56±0.64), (3.34±0.60), (2.98±0.54), (2.78±0.50)×10−12 cm3 molecule−1 s−1 at 280, 288, 298, 308, 318, 328, and 338 K, respectively. A high‐pressure limit rate coefficient of (4.47±0.80)×10−12 cm3 molecule−1 s−1 was obtained at 298 K by fitting the pressure‐dependent rate coefficients according to the Lindemann mechanism. The Arrhenius plot of the temperature‐dependent rate coefficients results in an activation energy of (−1.86±0.33) kcal mol−1 and a preexponential factor of (1.72±0.31)×10−13 cm3 molecule−1 s−1. In the atmosphere, the reaction of CH2OO with isobutyraldehyde may contribute to the sink of CH2OO in regions where isobutyraldehyde emission is intense under low temperature and low relative humidity conditions.

DFT Insight into the Kinetics and Mechanism of OH⋅‐Initiated Atmospheric Oxidation of Catechol: Addition of 3∑g− O2 and Isomerization of Peroxy Radicals

AbstractAtmospheric oxidation mechanism of predominant catechol‐OH adduct [C6H6O2−OH]⋅ (AD2) by oxygen molecule in its triplet electronic ground state and isomerization processes of catechol peroxy radicals [C6H6O2−OH]⋅−O2 into bicyclic peroxy radicals have been studied at the M06‐2X/aug‐cc‐pVTZ level in conjugation with the RRKM theory. The first step begins via the complexation of [C6H6O2−OH]⋅ with oxygen molecule and formation of two pre‐reactive van der Waals complexes in syn and anti modes. Syn mode addition of O2 is more favorable over the anti mode due to the formation of intramolecular hydrogen bond. Kinetically and thermodynamically, addition of O2 at the C5 position in syn mode, namely peroxy radical AD2‐5OO‐syn, is the most efficient process with bimolecular RRKM rate coefficient 2.80×10−16 cm3 molecule−1 s−1 at ambient conditions. Isomerization (cyclization) of peroxy radical AD2‐5OO‐syn into bicyclic peroxy radicals via the formation of −OO− bridge are strongly endothermic and nonspontaneous processes with high activation energies. Ring closure into the bicyclic peroxy radical AD2‐5,6OO‐syn is the most favorable process with unimolecular RRKM rate coefficient 1.41×10−8 s−1 at ambient conditions.

Aging of α-Pinene Secondary Organic Aerosol by Hydroxyl Radicals in the Aqueous Phase: Kinetics and Products.

The reaction of hydroxyl radicals (OH) with a water-soluble fraction of the α-pinene secondary organic aerosol (SOA) was investigated using liquid chromatography coupled with negative electrospray ionization mass spectrometry. The SOA was generated by the dark ozonolysis of α-pinene, extracted into the water, and subjected to chemical aging by the OH. Bimolecular reaction rate coefficients (kOH) for the oxidation of terpenoic acids by the OH were measured using the relative rate method. The unaged SOA was dominated by the cyclobutyl-ring-retaining compounds, primarily cis-pinonic, cis-pinic, and hydroxy-pinonic acids. Aqueous oxidation by the OH resulted in the removal of early-stage products and dimers, including well-known oligomers with MW = 358 and 368 Da. Furthermore, a 2- to 5-fold increase in the concentration of cyclobutyl-ring-opening products was observed, including terpenylic and diaterpenylic acids and diaterpenylic acid acetate as well as some of the newly identified OH aging markers. At the same time, results obtained from the kinetic box model showed a high degree of SOA fragmentation following the reaction with the OH, which indicates that non-radical reactions occurring during the evaporation of water likely contribute to the high yields of terpenoic aqSOAs reported previously. The estimated atmospheric lifetimes showed that in clouds, terpenoic acids react with the OH exclusively in the aqueous phase. Aqueous OH aging of the α-pinene SOA results in a 10% increase of the average O/C ratio and a 3-fold decrease in the average kOH value, which is likely to affect the cloud condensation nuclei activity of the aqSOA formed after the evaporation of water.

Ozone oxidation of cysteine in optically trapped aqueous micro‐droplets

AbstractThe ozone (O3) oxidation kinetics of cysteine in aqueous micro‐droplets at different acidities is investigated in this study via aerosol optical tweezers coupled with Raman spectroscopy. This study exploits the O3 oxidation of cysteine near the interface of micro‐droplets as a model system to elucidate the oxidation damage of amino acids in biosurfaces. For each optically trapped micro‐droplet, Raman spectroscopy is used to determine its droplet radius, concentrations of solutes, and droplet pH, as well as their time evolutions during the kinetics measurements. The bimolecular rate coefficients of the cysteine + O3 reaction measured in micro‐droplets are around 4 × 105 M−1 s−1 and 2 × 104 M−1 s−1 for pH ≈ 5 and 0.5, respectively. These results agree with the previous bulk measurements, indicating that the observed aerosol kinetics can be solely rationalized via diffusion‐limited kinetics. The results also indicate that a high‐ionic strength could enhance the cysteine + O3 reaction, particularly for the zwitterion form of cysteine. The results imply that when surfactant proteins in lung fluids are exposed to ambient O3, the cysteine residues in proteins will be attacked by O3 at first due to the high reactivity of the thiol moiety in cysteine.

An Experimental and Master Equation Investigation of Kinetics of the CH2OO + RCN Reactions (R = H, CH3, C2H5) and Their Atmospheric Relevance.

We have performed direct kinetic measurements of the CH2OO + RCN reactions (R = H, CH3, C2H5) in the temperature range 233-360 K and pressure range 10-250 Torr using time-resolved UV-absorption spectroscopy. We have utilized a new photolytic precursor, chloroiodomethane (CH2ICl), whose photolysis at 193 nm in the presence of O2 produces CH2OO. Observed bimolecular rate coefficients for CH2OO + HCN, CH2OO + CH3CN, and CH2OO + C2H5CN reactions at 296 K are (2.22 ± 0.65) × 10-14 cm3 molecule-1 s-1, (1.02 ± 0.10) × 10-14 cm3 molecule-1 s-1, and (2.55 ± 0.13) × 10-14 cm3 molecule-1 s-1, respectively, suggesting that reaction with CH2OO is a potential atmospheric degradation pathway for nitriles. All the reactions have negligible temperature and pressure dependence in the studied regions. Quantum chemical calculations (ωB97X-D/aug-cc-pVTZ optimization with CCSD(T)-F12a/VDZ-F12 electronic energy correction) of the CH2OO + RCN reactions indicate that the barrierless lowest-energy reaction path leads to a ring closure, resulting in the formation of a 1,2,4-dioxazole compound. Master equation modeling results suggest that following the ring closure, chemical activation in the case of CH2OO + HCN and CH2OO + CH3CN reactions leads to a rapid decomposition of 1,2,4-dioxazole into a CH2O + RNCO pair, or by a rearrangement, into a formyl amide (RC(O)NHC(O)H), followed by decomposition into CO and an imidic acid (RC(NH)OH). The 1,2,4-dioxazole, the CH2O + RNCO pair, and the CO + RC(NH)OH pair are atmospherically significant end products to varying degrees.

Spectroscopic and Kinetic Studies of the ClSO Radical from Cl2SO Photolysis.

Thionyl chloride (Cl2SO) serves as a common Cl atom source in widespread applications of chlorine chemistry though little is known about the reactivity and spectroscopy of the ClSO radical after a Cl-S bond cleavage. We performed a Pulsed Laser Photolysis experiment to detect ClSO from Cl2SO photolysis at 248 nm in a gas-flow reactor by time-resolved UV-vis transient absorption spectroscopy. A few chemical tests, using I2 and NO2, suggested the structured absorption band between 260 and 320 nm belonged to ClSO radical and that the termolecular ClSO + Cl + M → Cl2SO association reaction occurred. From EOMIP-CCSD/ano-pVQZ calculations, the ClSO band was assigned to the 12A″ ← X2A″ transition involving the π* ← π transition of the SO bond and the vibrational progression to the SO stretching mode of the 12A″ state, with a maximum cross-section = (2.0 ± 0.5) × 10-18 cm2 near 286 nm (1σ uncertainty) and an average spacing of vibrational structure of 658 cm-1. The rapid decay of the ClSO signal monitored near 303 nm could be fit to a second-order kinetic model over 10-90 Torr, which yields an effective bimolecular rate coefficient kCl+ClSO = (1.48 ± 0.42) × 10-11 cm3 molecule-1 s-1 at 292 K and 90 Torr (1σ uncertainty). This fast recombination reaction suggests that Cl-containing SOx species might act as significant Cl atom reservoirs in sulfur oxide-rich environments such as Venus' atmosphere. Moreover, the reported UV spectrum provides a new means for monitoring the ClSO radicals.

Aqueous OH kinetics of saturated C6–C10 dicarboxylic acids under acidic and basic conditions between 283 and 318 K; new structure-activity relationship parameters

Bimolecular reaction rate coefficients (kOH) for reaction of hydroxyl radicals (OH) with adipic, pimelic, suberic, azelaic, sebacic and cis-pinonic acids were measured in aqueous phase for the neutral (pH = 2) and completely deprotonated (pH = 9) forms of the acids listed. Reactions were carried out in bulk solution between 283 and 318 K. Camphoric acid was used as a reference compound for measuring kOH values using a relative rate method, and with hydrogen peroxide (H2O2) as a photochemical source of OH. Concentrations of the reactants were monitored with liquid chromatography coupled with electrospray tandem mass spectrometry (LC-ESI/MS2).The kOH values measured were between 1 and 8 × 10−9 M−1s−1; only adipic and pimelic acids showed a significant pH-dependence to their OH reactivity. The kinetic data acquired and the data reported in the literature for camphoric, glutaric and succinic acids were used to optimize new structure-activity relationship (SAR) parameters. The SAR developed here allowed accurate prediction of kOH values for aliphatic carboxylic acids in the temperature range between 283 and 318 K. The accuracy of the developed SAR was evaluated against the experimental kOH values measured in this work and obtained from the literature data. Moreover, this work is the first to accurately predict the temperature-dependent kOH values for carboxylic acids.

Structure-Dependent Electron Transfer Rates for Dihydrophenazine, Phenoxazine, and Phenothiazine Photoredox Catalysts Employed in Atom Transfer Radical Polymerization.

Organic photocatalysts (PCs) are gaining popularity in applications of photoredox catalysis, but few studies have explored their modus operandi. We report a detailed mechanistic investigation of the electron transfer activation step of organocatalyzed atom transfer radical polymerization (O-ATRP) involving electronically excited organic PCs and a radical initiator, methyl 2-bromopropionate (MBP). This study compares nine N-aryl modified PCs possessing dihydrophenazine, phenoxazine, or phenothiazine core chromophores. Transient electronic and vibrational absorption spectroscopies over subpicosecond to nanosecond and microsecond time intervals, respectively, track spectroscopic signatures of both the reactants and products of photoinduced electron transfer in N,N-dimethylformamide, dichloromethane, and toluene solutions. The rate coefficients for electron transfer exhibit a range of values up to ∼1010 M-1 s-1 influenced systematically by the PC structures. These rate coefficients are an order of magnitude smaller for catalysts with charge transfer character in their first excited singlet (S1) or triplet (T1) states than for photocatalysts with locally excited character. The latter species show nearly diffusion-limited rate coefficients for the electron transfer to MBP. The derived kinetic parameters are used to model the contributions to electron transfer from the S1 state of each PC for different concentrations of MBP. Comparisons of singlet and triplet reactivity for one of the phenoxazine PCs reveal that the rate coefficient kET(T1) = (2.7 ± 0.3) × 107 M-1 s-1 for electron transfer from the T1 state is 2 orders of magnitude lower than that from the S1 state, kET(S1) = (2.6 ± 0.4) × 109 M-1 s-1. The trends in bimolecular electron transfer rate coefficients are accounted for using a modified Marcus theory for dissociative electron transfer.

Gas phase hydroxyl radical reaction with 3,4-Dichloro-1,2,5-thiadiazole in the temperature range of 265–353 K: A kinetic and theoretical study

Kinetic studies for the gas phase reaction of OH radical with 3,4-Dichloro-1,2,5-thiadiazole has been performed using the laser photolysis – laser induced fluorescence technique. The rate coefficients were measured over the temperature range of 265–353 K and at a total pressure of~ 40 Torr of N2. The bimolecular rate coefficients obtained was fitted to the expression k(T)expt=(1.38 ± 0.91) × 10−13 exp[(903 ± 128)/T] cm3 molecule−1 s−1. Theoretical rate coefficients were also evaluated using the energy grained master equation solver which uses energies and structures of transition states and complexes calculated by ab initio method at G4MP2//M06-2X/6-311++G(d,p) level of theory. The reaction shows weak inverse temperature dependence.

A theoretical study on mechanism and kinetics of the C2H3 + C2H3 recombination and the isomerization and dissociation of butadiene

Kinetics and mechanism of the C 2 H 3 + C 2 H 3 recombination and the related isomerization–decomposition of C 4 H 6 have been performed utilizing the CCSD(T)/CBS//M06-2X/aug-cc-pVTZ level of theory together with statistical theoretical VRC-TST and RRKM master equation calculations. The potential energy surface describing the C 2 H 3 + C 2 H 3 reaction was established in detail. The evaluated total high-pressure-limit (HPL) rate constant for the entrance C 2 H 3 + C 2 H 3 → 1,3-butadiene reaction, 0.169 × 10 −10 T −0.508 cm 3 /molecule/s, agrees closely within 0.1 to ~ 2% with the experimental data given by Kawano and co-workers, 0.163 × 10 −10 T −0.5 cm 3 /molecule/s, and the HPL rate constant of the CH 2 CCH + CH 3 → C 4 H 6 reaction can be represented by the expression of 8.51 × 10 −11 exp(165.87 cal.mol −1 /RT) cm 3 /molecule/s, in good agreement with the expression of 6.8 × 10 −11 exp(258.3 cal.mol −1 /RT) cm 3 /molecule/s given by Knyazev and Slagleare, while the HPL rate constants for C 4 H 6 → C 4 H 5 + H presented by the Arrhenius expressions k a = 0.165 × 10 15 exp(-84 kcal mol −1 /RT), k b = 0.62 × 10 15 exp(-85.8 kcal.mol −1 /RT), k c = 0.62 × 10 15 exp(−90.2 kcal.mol −1 /RT), and k d = 0.2 × 10 16 exp(−99.1 kcal.mol −1 /RT) s −1 , are in reasonable accordance with the expressions reported by Hidaka et al. and Leung and Lindstedt, being k a,expt. = 0.5 × 10 15 exp(−87.3 kcal mol −1 /RT), k b,expt. = 0.7 × 10 15 exp(−86 kcal.mol −1 /RT), k c,expt. = 0.42 × 10 16 exp(−92.6 kcal.mol −1 /RT), and k d,expt. = 0.14 × 10 16 exp(−98 kcal.mol −1 /RT) s −1 , respectively. Bimolecular rate coefficients for 16 channels on the PES were calculated at various pressures from 7.6 to 76000 Torr and 300 ≤ T ≤ 2000 K, which rapidly increase with rising temperatures and slightly decrease with rising pressures. The predicted rate constants and the product yields of the C 4 H 6 dissociation reaction are in reasonably satisfactory agreement with the previous theoretical and experimental data without any adjustment from the quantum-chemical calculations. The recommended temperature-/pressure-dependent rate constants can be confidently utilized for modeling C 2 H 3 -related systems under atmospheric and combustion conditions.

Experimental and Theoretical Investigations of the Radical-Radical Reaction: N2H3 + NO2.

The N2H3 + NO2 reaction plays a key role during the early stages of hypergolic ignition between N2H4 and N2O4. Here for the first time, the reaction kinetics of N2H3 in excess NO2 was studied in 2.0 Torr of N2 and in the narrow temperature range 298-348 K in a pulsed photolysis flow-tube reactor coupled to a mass spectrometer. The temporal profile of the product, HONO, was determined by direct detection of the m/z +47 amu ion signal. For each chosen [NO2], the observed [HONO] trace was fitted to a biexponential kinetics expression, which yielded a value for the pseudo-first-order rate coefficient, k', for the reaction of N2H3 with NO2. The slope of the plot of k' versus [NO2] yielded a value for the observed bimolecular rate coefficient, kobs, which could be fitted to an Arrhenius expression of (2.36 ± 0.47) × 10-12 exp((520 ± 350)/T) cm3 molecule-1 s-1. The errors are 1σ and include estimated uncertainties in the NO2 concentration. The potential energy surface of N2H3 + NO2 was investigated by advanced ab initio quantum chemistry theories. It was found that the reaction occurs via a complex reaction mechanism, and all of the reaction channels have transition state energies below that of the entrance asymptote. The radical-radical addition forms the N2H3NO2 adducts, while roaming-mediated isomerization reactions yield the N2H3ONO isomers, which undergo rapid dissociation reactions to several sets of distinct products. The RRKM multiwell master equation simulations revealed that the major product channel involves the formation of trans-HONO and trans-N2H2 below 500 K and the formation of NO + NH2NHO above 500 K, which is nearly pressure independent. The pressure-dependent rate coefficients of the product channels were computed over a wide pressure-temperature range, which encompassed the experimental data.

Kinetics and thermochemistry of the reaction of 1-methylpropargyl radicals with oxygen molecules: Experiments and computations

We have used laser-photolysis/photoionization mass spectrometry to measure the kinetics of the reaction of 1-methylpropargyl (but-3-yn-2-yl, ▪) radicals with oxygen molecules as a function of temperature (T=200−685K) and bath gas density (1.2−15×1016cm−3). The low temperature (T ≤ 304 K) kinetics is dominated by oxygen addition to the ▪ carbon of the radical to form a peroxyl radical, and the measured ▪ bimolecular rate coefficient exhibits negative temperature dependence and depends on bath gas density. At slightly higher temperatures (335−396K), where the redissociation rate of the peroxyl is already observable, we measured the ▪ equilibrium constant as a function of temperature. At even higher temperatures (T=479−685K), the loss rate of 1-methylpropargyl is determined by the addition of oxygen to the terminal ▪ carbon and the reaction is observed to produce methylketene. The high-temperature ▪ bimolecular rate coefficient is independent of bath gas density and the temperature dependence is weakly positive. To explain our experimental findings, we performed quantum chemical calculations together with master equation simulations. By using our experimental data to constrain key parameters, the master equation model was able to reproduce experimental results reasonably well. We then extended the conditions of our simulations up to 2000 K and 100 bar. The results of these simulations are provided in ChemKin compatible PLOG format.

Temperature‐dependent kinetics of the simplest Criegee intermediate reaction with dimethyl sulfoxide

AbstractCriegee intermediates are thought to play roles in atmospheric chemistry, including OH radical formation, oxidation of SO2, NO2, etc. CH2OO is the simplest Criegee intermediate, of which the reactivity has been a hot topic. Here we investigated the kinetics of CH2OO reaction with dimethyl sulfoxide (DMSO) under 278–349 K and 10–150 Torr. DMSO is an important species formed in the oxidation of dimethyl sulfide in the biogenic sulfur cycle. The concentration of CH2OO was monitored in real‐time via its mid‐infrared absorption band at about 1,286 cm−1 (Q branch of the ν4 band) with a high‐resolution quantum cascade laser spectrometer. The 298 K bimolecular rate coefficient was determined to be k298 = (2.3 ± 0.3) × 10−12 cm3/s at 30 Torr with an Arrhenius activation energy of −3.9 ± 0.2 kcal/mol and a weak pressure dependence for pressures higher than 30 Torr (k298 = (2.8 ± 0.3) × 10−12 cm3/s at 100 Torr). The reaction is speculated to undergo a five‐membered ring intermediate, analogous to that of CH2OO with SO2. The negative activation energy indicates that the rate‐determining transition state is submerged. The magnitude of the reaction rate coefficient lies in between those of CH2OO reactions with (CH3)2CO and with SO2.

First direct kinetic measurement of i-C4H5 (CH2CHCCH2) + O2 reaction: Toward quantitative understanding of aromatic ring formation chemistry

The kinetics of the i-C4H5 (buta-1,3-dien-2-yl) radical reaction with molecular oxygen has been measured over a wide temperature range (275–852 K) at low pressures (0.8–3 Torr) in direct, time-resolved experiments. The measurements were performed using a laminar flow reactor coupled to photoionization mass spectrometer (PIMS), and laser photolysis of either chloroprene (2-chlorobuta-1,3-diene) or isoprene was used to produce the resonantly stabilized i-C4H5 radical. Under the experimental conditions, the measured bimolecular rate coefficient of i-C4H5 + O2 reaction is independent of bath gas density and exhibits weak, negative temperature dependency, and can be described by the expression k3 = (1.45 ± 0.05) × 10−12 × (T/298 K)−(0.13±0.05) cm3 s−1. The measured bimolecular rate coefficient is surprisingly fast for a resonantly stabilized radical. Under combustion conditions, the reactions of i-C4H5 radical with ethylene and acetylene are believed to play an important role in forming the first aromatic ring. However, the current measurements show that i-C4H5 + O2 reaction is significantly faster under combustion conditions than previous estimations suggest and, consequently, inhibits the soot forming propensity of i-C4H5 radicals. The bimolecular rate coefficient estimates used for the i-C4H5 + O2 reaction in recent combustion simulations show significant variation and are up to two orders of magnitude slower than the current, measured value. All estimates, in contrast to our measurements, predict a positive temperature dependency. The observed products for the i-C4H5 + O2 reaction were formaldehyde and ketene. This is in agreement with the one theoretical study available for i-C4H5 + O2 reaction, which predicts the main bimolecular product channels to be H2CO + C2H3 + CO and H2CCO + CH2CHO.

Kinetic Studies for the Reaction of syn-CH3CHOO with CF3CH═CH2.

Hydrofluoroolefins (HFOs, CxF2x+1CH═CH2) have great potential to replace hydrofluorocarbons (HFCs) as refrigerants. Here the kinetics for the reaction of syn-CH3CHOO with CF3CH═CH2 (HFO-1243zf), the simplest of HFOs, have been studied in a flash photolysis flow reactor at a total pressure of 50 Torr, by using the OH laser-induced fluorescence (LIF) method. The bimolecular reaction rate coefficients were measured at temperatures ranging from 283 to 318 K. A weak positive temperature dependence was observed, with an activation energy of 1.41 ± 0.12 kcal mol-1. At 298 K, the measured rate coefficient was (2.42 ± 0.51) × 10-14 cm3 s-1, in the vicinity of the previously reported upper limit value for the reaction of CH2OO with CF3CH═CH2.