Modified Arrhenius Expression Research Articles

Mechanistic and kinetic insights of the formation of allene and propyne from the C3H3 reaction with water.

Allene (H2C = C = CH2) and propyne (CH3-C≡CH) are important compounds in the combustion chemistry. They can be created from the reaction of proparyl radicals with water. In this study, therefore, a computational study into the C3H3 + H2O potential energy landscape has been carefully conducted. The computed results indicate that the reaction paths forming the products (allene: CH2CCH2 + •OH) and (propyne: HCCCH3 + •OH) prevail under the 300-2000K temperature range, where the latter is much more predominant compared to the former. However, these two products are not easily formed under ambient conditions due to the high energy barriers. In the 300 - 2000K temperature range, the branching ratio for the propyne + •OH product declines from 100 to 86%, whereas the allene + •OH product shows an increase, reaching 14% at 2000K. The overall bimolecular rate constant of the title reaction can be presented by the modified Arrhenius expression of ktotal = 1.94 × 10-12 T0.14 exp[(-30.55kcal.mol-1)/RT] cm3 molecule-1s-1. The total rate constant at the ambient conditions in this work, 2.37 × 10-34 cm3 molecule-1s-1, was found to be over five orders of magnitude lower than the total rate constant of the C3H3 + NH3 reaction, 7.98 × 10-29 cm3 molecule-1s-1, calculated by Hue et al. (Int. J. Chem. Kinet. 2020, 4(2), 84-91). The results in this study contribute to elucidating the mechanism of allene and propylene formation from the C3H3 + H2O reaction, and they can be used for modeling C3H3-related systems under atmospheric and combustion conditions. All the geometric structures of the C3H3 + H2O system were optimized by the B3LYP method in conjunction with the 6-311 + + G(3df,2p) basis set. Single-point energies of these species were calculated at the CCSD(T)/6-311 + + G(3df,2p) level of theory. The CCSD(T)/CBS level has also been used to compute single-point energies for the two major reaction channels (C3H3 + H2O → allene + •OH and C3H3 + H2O → propyne + •OH). Rate constants and branching ratios of the key reaction channels were calculated in the 300-2000K temperature interval using the Chemrate software based on the transition state theory (TST) with Eckart tunneling corrections.

Kinetics and mechanism of the gas-phase reaction of the hydroxyl radical with meta-aminotoluene compound.

An ab initio investigation into the potential energy landscape of the meta-aminotoluene + •OHreaction has been conducted in this study. The calculated results reveal that the reaction channel leading to the product (NHC6H4CH3 + H2O) prevails under the 300-1700K temperature range, while the reaction path forming the product (NH2C6H4CH2 + H2O) dominates in the higher-temperature region (T ≥ 1800K). Within the specified temperature range, the product branching ratio for the former declines from 48 to 30%, while the latter shows an increase, reaching 29%. The overall second-order rate constants of the titled reaction obtained at the pressure 760Torr (N2) can be illustrated by the modified Arrhenius expression of ktotal = 1.46 × 10-13 T0.58 exp[(-0.759kcal.mol-1)/RT] cm3 molecule-1s-1 and ktotal = 1.86 × 10-22 T3.24 exp[(-5.086kcal.mol-1)/RT] cm3 molecule-1s-1, covering the temperature range of T = 300-600K and T > 600K, respectively. The total rate constant at the ambient conditions in this work, 1.43 × 10-11 cm3 molecule-1s-1, has been found to be roughly one order of magnitude lower than the available experimental data, ~ 1.2 × 10-10 cm3 molecule-1s-1, measured by Atkinson et al., Rinke et al., and Witte et al., or the theoretical value, 4.4 × 10-10 cm3 molecule-1s-1, and calculated by Abdel-Rahman and co-workers for the aniline + •OH reaction. The structures of reactants, transition states, intermediate states, and products of the meta-aminotoluene + •OHreaction are calculated with the aug-cc-pVTZ basis set and the methods DFT/B3LYP and CCSD(T). The rate constants and branching ratios in the 300-2000K temperature range are calculated with the statistical theoretical TST and RRKM master equation computations including tunneling corrections, with potential energy surface constructed by the CCSD(T)//B3LYP/aug-cc-pVTZ approach.

Gas-phase molecular formation mechanisms of cyanamide (NH2CN) and its tautomer carbodiimide (HNCNH) under Sgr B2(N) astrophysical conditions

Context. Cyanamide (NH2CN) and its tautomer carbodiimide (NHCHN) are believed to have been key precursors of purines and pyrimidines during abiogenesis on primitive Earth. The detection of guanine and cytosine in meteorites and comets provides evidence of their nonterrestrial formation. Although NH2CN has been found in several molecular clouds, NHCHN has only been detected in Sgr B2(N). Their possible molecular formation mechanisms in the gas phase and therefore their respective molecular precursors remain an open subject of investigation. Aims. The main objective of this paper is to determine which reactions can produce NH2CN and HNCNH in the amounts observed under the astrophysical conditions of Sgr B2(N). The determination of their most likely precursors could serve to provide new insights into possible routes to purine and pyrimidine synthesis, and by extension to nucleosides, under the astrophysical conditions of dense molecular clouds. Methods. Initially, we proposed 120 reaction mechanisms, 60 being dedicated to NH2CN formation and the remaining 60 to HNCNH. These mechanisms were constructed using 25 chemical species that were identified in outer space. We calculated the molecular energies of reactants and products at the CCSD(T)-F12/cc-pVTZ-F12 and MP2/aug-cc-pVDZ levels of theory, and defined the values of thermodynamic functions using the Maxwell-Boltzmann statistical quantum theory. Via an extensive literature review on the abundances of reactants and products in Sgr B2(N), in addition to a detailed kinetic study for a range of 20–300 K, we identify the most likely reaction mechanisms for both cyanamides of those proposed previously and presently. Results. From the 120 analyzed reactions, only nine for NH2CN and four for HNCNH could thermodynamically account for their synthesis in Sgr B2(N). The kinetic portion of our study shows that Ra60 (CH3NH2 +·CN → NH2CN +·CH3), with a modified Arrhenius expression of kT = 1.22 × 10−9 (T/300)−0.038 exp− (−147.34/T) cm3 mol−1 s−1, is the most efficient reaction at low temperatures (<60 K). Above 60 K, no reaction with known reagents in Sgr B2(N) is efficient enough. In this way, Ra37-2 (·HNCN +·NH2 → NH2CN +3NH) appears to be the most likely candidate, showing a modified Arrhenius constant of kT = 2.51 × 10−11 (T/300)−32.18 exp− (−1.332/T) cm3 mol−1 s−1. In the case of carbodiimide production, Rb18 (·H2NC +·NH2 → HNCNH +·H) is the most efficient reaction, fitting a rate constant of kT = 4.70 × 10−13 (300/T)−3.24 exp− (36.28/T) cm3 mol−1 s−1 in Sgr B2(N). Conclusions. The detected gas-phase abundances of cyanamide (NH2CN) in Sgr B2(N) can be explained as: Ra60 (·CN +·CH3NH2) from 20 to 60 K; Ra5: (·CN +·NH2) from 60 to 120 K; and Ra37-2 (·HNCN +·NH2) from 120 to 300 K. The carbodiimide (HNCNH) synthesis could proceed via Rb18 (·H2NC +·NH2). Moreover, the presence of·HNCN and·H2NC in Sgr B2(N) are predicted here, making them viable candidates for future astronomical observations. The foreseen column density for the cyanomidil radical is ~1016 cm2 s−1 at 150 K or higher, while for amino methylidine, the value is a few 1013 cm2 s−1 at 100 K.

Theoretical study on the mechanism and kinetics of the oxidation of allyl radical with atomic and molecular oxygen

The C3H5O and C3H5O2 potential energy surfaces accessed by the oxidation reactions of allyl radical with atomic and molecular oxygen have been mapped out at the CCSD(T)-F12b/cc-pVTZ-F12//ωB97XD/6-311G(d,p) level of electronic structure theory to unravel the reaction mechanism. Temperature- and pressure-dependent reaction rate constants have been evaluated using variable reaction coordinate transition state and RRKM-Master Equation theoretical kinetics methods. The C3H5 + O reaction is found to be fast in the 300-2500 K temperature interval, with the total rate constant of 1.8-1.0 × 10−10 cm3 molecules s−1 independent of pressure in the considered 30 Torr – 100 atm range. Acrolein + H formed by a simple O addition/H elimination mechanism via the CH2CHCH2O association complex are predicted to be the major reaction products with the branching ratio decreasing from 61% at 300 K to 44% at 2500 K. Other substantial bimolecular products include C2H3 + formaldehyde (32%-26%) formed through the C-C bond β-scission in CH2CHCH2O and two minor products C2H4 + formyl radical HCO and allene + OH, where the latter, formed via direct H abstraction by O from the central carbon atom of allyl, becomes significant only at high temperatures above ∼1500 K. The C3H5 + O2 reaction studied in the 200-2500 K temperature range shows a peculiar kinetic behavior characteristic for a bimolecular reaction with a low entrance barrier, shallow association well, and high ensuing isomerization and decomposition barriers to bimolecular products. This behavior is described in terms of three distinct temperature regimes: the low-temperature one with slightly negative dependence of the rate constant, the intermediate one where the rate constant sharply drops, and the high-temperature regime with an Arrhenius-like rate constant. The rate constant is relatively high (10−13-10−12 cm3 molecule−1 s−1) in the low-temperature regime when the reaction produces the peroxy association complex CH2CHCH2OO, but slow at higher temperatures when it leads to bimolecular products. Under combustion relevant conditions, the C3H5 + O2 rate constant is by 5 to 3 orders of magnitude lower than that for C3H5 + O, but since O2 concentrations in flames could be as much as 3 orders of magnitude larger than O concentrations, C3H5 + O2 cannot be ruled out as a significant allyl radical sink. Above 1500 K, the C3H5 + O2 reaction can form vinoxy radical + formaldehyde (40%-15%) via the five- or four-membered ring closure and opening mechanism starting from the initial peroxy intermediate, acrolein + OH (41%-49%) via the H shift from the attacked carbon to the terminal oxygen followed by the immediate O-O bond cleavage, and allene + OH (18-25%) via the H migration from the central CH group to the terminal O atom accompanied or followed by the C-O bond rupture. Modified Arrhenius expressions fitting the computed rate constants for both reactions have been generated and proposed for kinetic models.

Kinetics of the Gas-Phase Reaction of Hydroxyl Radicals with Dimethyl Methylphosphonate (DMMP) over an Extended Temperature Range (273-837 K).

The kinetics of the reaction of hydroxyl radical (OH) with dimethyl methylphosphonate (DMMP, (CH3O)2CH3PO) (reaction 1) OH + DMMP → products (1) was studied at the bath gas (He) pressure of 1 bar over the 295–837 K temperature range. Hydroxyl radicals were produced in the fast reaction of electronically excited oxygen atoms O(1D) with H2O. The time-resolved kinetic profiles of hydroxyl radicals were recorded via UV absorption at around 308 nm using a DC discharge H2O/Ar lamp. The reaction rate constant exhibits a pronounced V-shaped temperature dependence, negative in the low temperature range, 295–530 K (the rate constant decreases with temperature), and positive in the elevated temperature range, 530–837 K (the rate constant increases with temperature), with a turning point at 530 ± 10 K. The rate constant could not be adequately fitted with a standard 3-parameter modified Arrhenius expression. The data were fitted with a 5-parameter expression as: k1 = 2.19 × 10−14(T/298)2.43exp(15.02 kJ mol−1/RT) + 1.71 × 10−10exp(−26.51 kJ mol−1/RT) cm3molecule−1s−1 (295–837 K). In addition, a theoretically predicted pressure dependence for such reactions was experimentally observed for the first time.

The Role of Methylaryl Radicals in the Growth of Polycyclic Aromatic Hydrocarbons: The Formation of Five-Membered Rings.

The regions of the C13H11 potential energy surface (PES) related to the unimolecular isomerization and decomposition of the 1-methylbiphenylyl radical and accessed by the 1-/2-methylnaphthyl + C2H2 reactions have been explored by ab initio G3(MP2,CC)//B3LYP/6-311G(d,p) calculations. The kinetics of these reactions relevant to the growth of polycyclic aromatic hydrocarbons (PAH) under high-temperature conditions in circumstellar envelopes and in combustion flames has been studied employing the RRKM-Master Equation approach. The unimolecular reaction of 1-methylbiphenylyl proceeding via a five-membered ring closure followed by H elimination is predicted to be very fast, on a submicrosecond scale above 1000 K and to result in the formation of an embedded five-membered ring in the 9H-fluorene product. The 1-/2-methylnaphthyl + C2H2 reaction mechanism involves acetylene addition to the radical on the methylene group followed by a six- or five-membered ring closure and aromatization via an H atom loss. Despite of the complexity of the C13H11 PES, these straightforward pathways are dominant in the high-temperature regime (above ∼1000 K), with the prevailing products being phenalene, with a significant contribution of 1H-cyclopenta(a)naphthalene, for 1-methylnaphthyl + C2H2, and 1H-cyclopenta(b)naphthalene and 3H-cyclopenta(a)naphthalene, for 2-methylnaphthyl + C2H2. The methylnaphthyl reactions with acetylene represent a clean source of the three-ring PAHs, but they are relatively slow owing to the high entrance barriers of ∼10 kcal/mol, with the rate constants of about an order of magnitude lower as compared to those for naphthyl + allene and σ-aryl + C2H2. The 1-methylnaphthyl + C2H2 and 2-methylnaphthyl + C2H2 reactions represent prototypes for PAH growth by an extra six- and five-membered ring on a zigzag edge or a corner of PAH and the generated modified Arrhenius expressions are recommended for kinetic modeling of PAH expansion by the mechanism of acetylene addition to methylaryl radicals.

Ab initio kinetics of OH-initiated oxidation of cyclopentadiene

This work computationally reports a detailed kinetic mechanism of the OH-initiated reaction of 1,3-cyclopentadiene (CPDN), a key intermediate during the oxidation processes of aromatic and acyclic compounds, in the wide range of T = 298 – 2000 K and P = 0.76 – 7600 Torr. The temperature- and pressure-dependent behaviors of the title reaction were simulated using the RRKM-based Master Equation rate model on the potential energy profile explored at M06-2X/aug-cc-pVTZ level. The model reveals that the OH-addition on Cα of CPDN to form adduct 5-hydroxycyclopent-2-en-1-yl dominates at low temperatures (e.g., T ≤ 1000 K at 760 Torr), while the direct H-abstraction channels from Cα and Cβ of CPDN become predominant at high temperatures (e.g., T > 1000 K at 760 Torr). The observed U-shaped temperature-dependent behaviors and slightly positive pressure dependence at low temperatures (e.g., T ≤ 1000 K &P = 760 Torr) of the total rate constants are described by a double modified Arrhenius expression as ktot(T) = 1.61 × 109 × T−6.67 × exp[-1627.6 K/T] + 3.87 × 10-17 × T2.08 × exp[-2519.9 K/T] (cm3/molecule/s) for T = 298 – 2000 K &P = 760 Torr. Discrepancies in ktotal(T, P) between the early calculations and measurements in low- and high-temperature regimes are also resolved. Also, the thermodynamically consistent mechanism is provided to advance modeling and simulation of any CPDN-related applications.

Direct H abstraction by molecular oxygen from unsaturated C3–C5 hydrocarbons: A theoretical study

AbstractPotential energy surfaces for the H abstraction reactions by molecular oxygen from unsaturated closed‐shell C3–C5 hydrocarbons, including allene and propyne (C3H4), propene (C3H6), diacetylene (C4H2), vinylacetylene (C4H4), 1,3‐butadiene (C4H6), butene isomers (C4H8), cyclopentadiene (C5H6), and cyclopentene (C5H8), which were earlier identified among the main pyrolysis products of jet fuel components, have been explored at the CCSD(T)‐F12/cc‐pVTZ‐f12//ωB97XD/6‐311G** + ZPE(ωB97XD/6‐311G**) level of electronic structure theory. The results of the ab initio calculations were then utilized in transition state theory calculations of the reaction rate constants. The H abstraction reactions by O2 appeared to be most favorable from the allylic sites and from allene and propyne forming the propargyl radical, with the reactions involving the cyclic allylic sites in cyclopentadiene and cyclopentene exhibiting the lowest reaction endothermicities and barriers. They are followed by the reaction of O2 with cyclopentene producing cyclopent‐1‐en‐4‐yl and the reactions with vinylacetylene and 1,3‐butadiene forming the resonantly stabilized i‐C4H3 and i‐C4H5 radical products. The H abstractions from primary and secondary vinylic sites as well as from acetylenic sites are significantly less favorable and unlikely to compete. The calculated rate constants have been validated against the previous experimental and theoretical results for propene and butene isomers. All considered reactions of H abstraction by O2 are predicted to be rather slow, with their rate constants at 1500 K being on the order of 10–17‐10–16 cm3 molecule–1 s–1 and exhibiting a well‐defined Arrhenius behavior. Modified Arrhenius expressions for the reaction rate constants both in forward and reverse directions and Evans–Polanyi relationship between the activation and reaction energies have been generated and proposed for kinetic combustion models. The H abstractions by O2 forming the resonantly stabilized radicals were concluded to likely contribute to the initiation of oxidation of the unsaturated C3–C5 species produced in the pyrolysis of the important components of jet fuels.

Predictive Combustion Kinetics of OH Radical Reactions with a C5 Unsaturated Alcohol: The Competitive H-Abstraction and OH-Addition Reactions of 2-Methyl-3-buten-2-ol.

2-Methyl-3-buten-2-ol (MBO232) is a potential biofuel and renewable fuel additive. In a combustion environment, the consumption of MBO232 is mainly through the reaction with a OH radical, one of the most important oxidants. Here, we predict the intricate reactions of MBO232 and OH radicals under a broad range of combustion conditions, that is, 230-2500 K and 0.01-1000 atm. The potential energy surfaces of H-abstraction and OH-addition have been investigated at the CCSD(T)/CBS//M06-2X/def2-TZVP level, and the rate constants were calculated via Rice-Ramsperger-Kassel-Marcus/master equation (RRKM/ME) theory. The decomposition reactions of the critical intermediates from the OH-addition reactions have also been studied. Our results show that OH-addition reactions are dominant below 850 K, while H-abstraction reactions, especially the channel-abstracting H atoms from the methyl groups, are more competitive at higher temperatures. We found that it is necessary to discriminate H atoms attached to the same C atom, as their abstraction rates can differ by up to 1 order of magnitude. The calculated results show good agreement with the reported experimental data. We have provided the modified Arrhenius expressions for rate constants of the dominant channels. The kinetic data determined in this work are of much value for constructing the combustion models of MBO232 and understanding the combustion kinetics and mechanism of other unsaturated alcohols.

Study of the CN(X2Σ+) + N(4S) Reaction at High Temperatures: Potential Energy Surface and Thermal Rate Coefficients.

Reactions involving C and N play an essential role in the chemistry around the surface of a hypersonic spacecraft during its atmospheric re-entry. The collision of CN with other molecules and atoms has particular interest in aerothermodynamic modeling. This work focuses on the study of the CN + N → N2 + C reaction in the triplet manifold 3A″ of CN2. A high-level full-dimensional potential energy surface for this system is developed from ab initio calculations at the MRCI-F12 + Q level of theory. This surface is employed in quasiclassical trajectory calculations, and thermal rate coefficients from 100 to 20,000 K are computed. The rates for the formation of N2 are compared with the available experimental data, and good agreement is found. At low and intermediate temperatures, the N2 formation is more efficient than the N-exchange process, while at high temperatures, the rates for both processes are comparable. Finally, analytically modified Arrhenius expressions for the reaction rates of N2 formation and N-exchange are reported.

Reaction Rate Coefficient of OH Radicals with d 9-Butanol as a Function of Temperature.

d9-Butanol or 1-butan-d9-ol (D9B) is often used as an OH radical tracer in atmospheric chemistry studies to determine OH exposure, a useful universal metric that describes the extent of OH radical oxidation chemistry. Despite its frequent application, there is only one study that reports the rate coefficient of D9B with OH radicals, k1(295 K), which limits its usefulness as an OH tracer for studying processes at temperatures lower or higher than room temperature. In this study, two complementary experimental techniques were used to measure the rate coefficient of D9B with OH radicals, k1(T), at temperatures between 240 and 750 K and at pressures within 2–760 Torr. A thermally regulated atmospheric simulation chamber was used to determine k1(T) in the temperature range of 263–353 K and at atmospheric pressure using the relative rate method. A low-pressure (2–10 Torr) discharge flow tube reactor coupled with a mass spectrometer was used to measure k1(T) at temperatures within 240–750 K, using both the absolute and relative rate methods. The agreement between the two experimental aproaches followed in this study was very good, within 6%, in the overlapping temperature range, and k1(295 ± 3 K) was 3.42 ± 0.26 × 10–12 cm3 molecule–1 s–1, where the quoted error is the overall uncertainty of the measurements. The temperature dependence of the rate coefficient is well described by the modified Arrhenius expression, k1 = (1.57 ± 0.88) × 10–14 × (T/293)4.60±0.4 × exp(1606 ± 164/T) cm3 molecule–1 s–1 in the range of 240–750 K, where the quoted error represents the 2σ standard deviation of the fit. The results of the current study enable an accurate estimation of OH exposure in atmospheric simulation experiments and expand the applicability of D9B as an OH radical tracer at temperatures other than room temperature.

Mechanism and kinetics of the oxidation of 1,3-butadien-1-yl (n-C4H5): a theoretical study.

Ab initio CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311G(d,p) calculations of the C4H5O2 potential energy surface have been combined with Rice-Ramsperger-Kassel-Marcus Master Equation (RRKM-ME) calculations of temperature- and pressure-dependent rate constants and product branching ratios to unravel the mechanism and kinetics of the n-C4H5 + O2 reaction. The results indicate that the reaction is fast, with the total rate constant being in the range of 3.4-5.6 × 10-11 cm3 molecule-1 s-1. The main products include 1-oxo-n-butadienyl + O and acrolein + HCO, with their cumulative yield exceeding 90% at temperatures above 1500 K. Two conformers of 1-oxo-n-butadienyl + O are formed via a simple mechanism of O2 addition to the radical site of n-C4H5 followed by the cleavage of the O-O bond proceeding via a van der Waals C4H5OO complex. Alternatively, the pathways leading to acrolein + HCO involve significant reorganization of the heavy-atom skeleton either via formal migration of one O atom to the opposite end of the molecule or its insertion into the C1-C2 bond. Not counting thermal stabilization of the initial peroxy adducts, which prevails at low temperatures and high pressures, all other products share a minor yield of under 5%. Rate constants for the significant reaction channels have been fitted to modified Arrhenius expressions and are proposed for kinetic modeling of the oxidation of aromatic molecules and 1,3-butadiene. As a secondary reaction, n-C4H5 + O2 can be a source for the formation of acrolein observed experimentally in oxidation of the phenyl radical at low combustion temperatures, whereas another significant (secondary) product of the C6H5 + O2 reaction, furan, could be formed through unimolecular decomposition of 1-oxo-n-butadienyl. Both the n-C4H5 + O2 reaction and unimolecular decomposition of its 1-oxo-n-butadienyl primary product are shown not to be a substantial source of ketene.

Impact of activation energy on hyperbolic tangent nanofluid with mixed convection rheology and entropy optimization

The present work numerically examines the entropy generation in the transport of hyperbolic tangent nanofluid over a stretchable surface with nonlinear Boussinesq approximation. Impacts of viscous dissipation, Joule heating, strength of uniform magnetic field along with modified Arrhenius expression is accounted. Under the significance of Buongiorno’s model, thermophoresis and Brownian effects are considered. The dimensionless form of mathematical system is obtained by adopting similarity variables. Consequence of flow parameters are explored through graphs. More, drag coefficient, heat transfer rate and Sherwood number are presented with tables and bar charts. Here, we noted that power law index parameter declines the fluid motion and entropy generation increases with diffusion variable.

Combination Reactions of Propargyl Radical with Hydroxyl Radical and the Isomerization and Dissociation of trans-Propenal.

Ab initio investigation for the ground-electronic potential energy surface (PES) of the CH2CCH + OH combination and the trans-CH2CHCHO isomerization and decomposition has been performed at the UCCSD(T)/CBS(TQ5)//M06-2X/aug-cc-pVTZ level of theory. Thermal and microcanonical rate constants, as well as branching ratios in the 300-2000 K temperature range have been predicted based on optimized structures and vibrational frequencies of species involved using statistical theoretical VRC-TST and RRKM master equation computations. The calculated results are in good agreement with the prior reported data, particularly as an accurate scaling of the energy barriers was carried out. Based on the view of PES and kinetic-predicted values, the reaction paths leading to C2H2 + CO + H2, CH3CH + CO, C2H4 + CO, C2H3 + HCO, and C3H3O + H are the prevailing product channels for the C3H3 + OH bimolecular reaction under the considered 300-2000 K temperature range. Among those products, CH3CH + CO is the most dominant one in the low-temperature condition; however, C2H2 + CO + H2 becomes the most favorable product in the high-temperature region. Alternatively, the C3H4O dissociation processes leading to C2H2 + CO + H2, C2H3 + HCO, C2H4 + CO, and CH2C + CH2O constitute the major paths, in which, C2H2 + CO + H2 is the most critical one with the ∼62% and ∼59% branching ratios at E = 148 and 182 kcal/mol, respectively. The overall second-order rate constants of the bimolecular reaction C3H3 + OH → products obtained at the pressure 760 Torr (Ar) can be illustrated by the modified Arrhenius expression of k(T) = 1.36 × 10-13T1.26 exp[(-1.12 ± 0.43 kcal mol-1)/RT] and/or k(T) = 3.77 × 1017T-7.58 exp[(-18.82 ± 0.20 kcal mol-1)/RT] cm3 molecule-1 s-1, covering the temperature range of 300-1300 and/or 1300-2000 K, respectively. The total high-pressure limit rate constant for the C3H3 + OH → CH2CCHOH barrierless processes is in good agreement with the k(T) = 8.30 × 10-10 T-0.1 cm3 molecule-1 s-1 literature data. Moreover, microcanonical rate constants for the C3H4O isomerization and dissociation are in excellent accordance with the previously predicted values given by Chin and Lee. The present study supplies a thorough insight into the mechanisms and kinetics of the C3H3 + OH combination as well as the C3H4O multistep isomerization/dissociation pathways.

Conversion of acenaphthalene to phenalene via methylation: A theoretical study

Ab initio calculations of the C13H10 and C13H9 potential energy surfaces related to the reaction of 1-acenaphthyl and methyl radicals and secondary isomerization of C13H9 primary radical products have been performed at the chemically accurate G3(MP2,CC)//B3LYP/6-311G** level of theory to unravel the mechanism of conversion of acenaphthalene to phenalene or phenalenyl radical + H. The computed energetics and molecular parameters were utilized in Rice-Ramsperger-Kassel-Marcus Master Equation (RRKM-ME) calculations of reaction rate constants and relative product yields. The 1-acenaphthyl + CH3 reaction is predicted to proceed by a fast radical-radical recombination mechanism and to predominantly produce collisionally stabilized 1-methylacenaphthalene B1 or a C13H9 benzylic radical A1 + H with exothermicities of 106.8 and 25.2 kcal/mol, respectively. The A1 + H channel is preferable at higher temperatures, whereas the stabilization of 1-methylacenaphthalene is favored at higher pressures. The radical A1 can nearly irreversibly interconvert to phenalenyl radical AP via a 22.7 kcal/mol exothermic isomerization process involving formal insertion of the CH2 group into a CC bond of the five-member ring leading to the expansion of this ring to a six-member ring. The rate constants for the H addition reaction to phenalenyl radical to form phenalene and the reverse H loss from phenalene were also computed and the strength of the weakest CH bond in the CH2 group of phenalene is evaluated as 62.2 kcal/mol. The analysis of the reaction kinetics allowed us to deduce a mechanism for the conversion of 1-acenaphthyl radical to phenalene or phenalenyl radical + H via methylation involving the formation of A1 via a well-skipping channel or stabilization and dissociation of (or H abstraction from) B1 followed by isomerization of A1 to phenalenyl AP, which can add an H atom producing phenalene. Rate constants for the significant elementary reactions are fitted to modified Arrhenius expressions and are proposed for kinetic modeling of the expansion of a five-member ring on a zigzag edge of PAH to a six-member ring by methylation.

Conversion of methane to benzene in CVI by density functional theory study

A density functional theory (DFT) study was employed to explore the mechanism of the conversion of methane to benzene in chemical vapor infiltration (CVI) based on the concluded reaction pathways from C1-species to C6-species. The geometry optimization and vibrational frequency analysis of all the chemical species and transition states (TS) were performed with B3LYP along with a basis set of 6–311 +G(d, p), and Gaussian 09 software was used to perform the study. The rate constants were calculated by KiSThelP according to the conventional transition state theory (TST), and the Wigner method was applied to acquire the tunneling correction factors. Then the rate constants were fitted to the modified Arrhenius expression in the temperature range of 800–2000 K. As for the barrierless reactions calculated in this paper, the rate constants were selected from the relating references. Through the energetic and kinetic calculations, the most favorable reaction pathway for benzene formation from methane was determined, which were mainly made of the unimolecular dissociation. The conversion trend from C1-species to C4-species is mainly guided by a strong tendency to dehydrogenation and the pathways from C4-species to C6-species are all presumed to be able to produce C6H6 molecule.

Reactions of β-hydroxypropyl radicals with O2 on the HOC3H6OO• potential energy surfaces: A theoretical study

Although addition reactions of β-hydroxypropyl radicals with O2 are important steps in the reaction pathways of propylene oxidation at low temperature, there is a lack of available accurate rate constants for these reactions in the literature. To obtain complete reaction channels and relatively accurate rate constants over a wide range of temperatures and pressures, a systematic method, which combines the high level ab initio calculation, the conventional transition state theory (TST), the variational transition state theory (VTST) and Rice-Ramsberger-Kassel-Marcus/Master-Equation theory (RRKM/ME), was used to investigate these reactions. The CCSD(T)/cc-pVTZ method was applied to calculate potential energy surfaces. High-pressure limit rate constants of barrierless reactions and those reactions with tight transition states were obtained using the VTST and the TST, respectively. RRKM/ME theory was used to compute rate constants in the fall-off range for pressure-dependent reactions. Take CC•COH as an example, the peroxy adduct of CC•COH with O2 can further react to form more stable products, and subsequent reactions include H-shift reactions, HO2 elimination reactions, OH elimination reactions and Waddington reaction. In these reactions, Waddington reaction is one of the most competitive advantage paths, as it has the lowest barrier. This conclusion is similar to that of those reactions about O2 with products from OH addition to ethylene or isobutene. Rate constants of relevant reactions were fitted to the form of a modified Arrhenius expression, and were implemented into the existing mechanism to simulate concentration profiles of main species of propylene oxidation in a jet-stirred reactor. The results show that predicted results of the revised mechanism are closer to the experimental data than those of the original mechanism. Our calculated rate constants over a wide range of temperatures and pressures for these reactions are transferable and can be applied to a wider range of oxidation conditions.

On the universality of ignition delay times of distillate fuels at high temperatures: A statistical approach

Ignition delay times (IDTs) of fuels provide very important macro-information about the fuel reactivity and autoignition behavior. IDTs constitute a key metric for fuel/engine co-optimization studies. Chemical kinetic modeling pursuits rely on experimental IDTs as their primary validation target. There have been extensive works in literature on measuring, calculating, modeling and correlating IDTs of a wide range of hydrocarbons, oxygenates, mixtures of pure components and real fuels. Recently, some studies employed a simplified ignition model at high temperatures, comprising of a fast fuel decomposition step and a rate-determining small molecule oxidation step. This description suggests that high-temperature IDT is mainly controlled by the ignition of fuel fragments and is rather weakly dependent on the initial fuel composition. In this work, we study the validity of the hypothesis that IDT of multi-component fuels is weakly dependent on fuel composition under specific thermodynamic conditions. If so, high-temperature IDTs of practical fuels may be described by a universal Arrhenius type correlation. By combining experimental observations and chemical kinetic simulations, we determine the ranges of key parameters (temperature, pressure, equivalence ratio, composition) under which a universal IDT assumption is valid. We conclude that, for fairly random composition and within a P-T-ϕ constraint, IDTs of gasolines and jet fuels may be predicted with a high degree of certainty by the following modified Arrhenius expressions (P = 10–80 bar, P0 = 1 bar, ϕ = 0.5–2, fuel/air mixtures, units are ms, bar, K, mol, kcal):τgasoline=6.76*10−7(P20)−1.01φ1.13−1759Texp(29.39RT),forT>1000−0.073.ln(PP0)+φ−0.0338+0.0938τjetfuel=4.46*10−7(P20)−1.21φ2.04−2596T*exp(29.33RT),forT>1000−0.0371.ln(PP0)+φ−0.00727−0.0995

Scission of the Five-Membered Ring in 1-H-Inden-1-one C9H6O and Indenyl C9H7 in the Reactions with H and O Atoms.

Quantum chemical G3(MP2,CC)//B3LYP/6-311G(d,p) calculations of the C9H7O potential energy surface were utilized to investigate the mechanism of the 1-H-inden-1-one (C9H6O) + H and indenyl (C9H7) + O reactions and were combined with Rice-Ramsperger-Kassel-Marcus Master Equation (RRKM-ME) calculations to predict temperature- and pressure-dependent reaction rate constants and product branching ratios. The most favorable reaction pathways for C9H6O + H lead to the bimolecular C8H7 + CO products, which are slightly endothermic with respect to the reactants. The reaction begins with H addition to the ortho or meta C atoms in the five-membered ring, C9H6O + H → w2/w3, and then proceeds by isomerization to w1, (w3 →) w2 → w1. From thereon, the w1 → w9 → w8 → p1 and w2 → w8 → p1 pathways lead to ortho-vinyl phenyl + CO, whereas w1 → w10 → w11 → p2 and C9H6O + H → w10 → w11 → p2 produce styrenyl + CO. The results of the RRKM-ME calculations showed that only the well-skipping C9H6O + H → C8H7 (p1/p2) + CO mechanism is relevant under combustion conditions. A comparison with a smaller prototype 2,4-cyclopentadienone + H → C4H5 + CO reaction demonstrated that the H atom is a less efficient destroyer of a cyclopentadienone-like moiety when this moiety is linked to an aromatic or a PAH structure. The C9H7 + O reaction begins with highly exothermic barrierless addition of the oxygen atom to the radical site in the five-membered ring of indenyl producing w1 and then, the reaction mostly proceeds by β-scission in the five-membered ring, which may be preceded by H migration to w2 or w10, and completes by the CO loss forming the highly exothermic C8H7 radical products. Modified Arrhenius expressions for the rate constants of all reactions pertinent to the formation of C8H7 + CO from C9H6O + H, C9H7 + H, and unimolecular decomposition of benzopyranyl have been generated and suggested for combustion kinetic modeling. It is concluded that the oxidation reactions of a five-membered ring with atomic oxygen remain fast in the presence of attached or surrounding six-membered rings.

Temperature and Pressure Dependent Rate Coefficients for the Reaction of Ketene with Hydroxyl Radical.

The reaction of ketene with hydroxyl radical is drawing growing attention, for it is found to constitute an important step during the combustion of hydrocarbon and oxygenated hydrocarbon fuels, e.g., acetylene, propyne, allene, acetone, gasoline, diesel, jet fuels, and biofuels. We studied the potential energy surface (PES) of this reaction using B2PLYP-D3/cc-PVTZ for geometry optimization and composite methods based on CCSD(T)-F12/cc-PVTZ-F12 for energy calculations. From this PES, temperature- and pressure-dependent rate coefficients and branching ratios at 200-3000 K and 0.01-100 atm were derived using the RRKM/ME approach. The reaction is dominated by four product channels: (i) OH addition on the olefinic carbon of ketene to form CH2OH + CO, which is the most dominant under all conditions; (ii) H abstraction producing HCCO + H2O, which is favored at high temperatures; (iii) OH addition on the carbonyl carbon to form CH3 + CO2, which is favored at low pressures and high temperatures; and (iv) collisional stabilization of CH2COOH, which is favored at high pressures and low temperatures. With increasing temperatures, the overall rate constant koverall exhibit first negative but then positive temperature dependency, with its switching point (also the minimum point) at ∼400 K. Both product channel CH2OH + CO and HCCO + H2O are independent of pressure, whereas formation of CH3 + CO2 and collisional stabilization of CH2COOH are highly pressure dependent. Fitted modified Arrhenius expressions of the calculated rate constants are provided for the purpose of combustion modeling.