Characterizing methane and nitric oxide interaction in oxygen-free outwardly propagating spherical flame

Co-firing methane (CH₄) and ammonia (NH₃) has attracted growing concerns as a feasible greenhouse gas reduction strategy in gas turbine-based power generation, which raises the need to better understand the interaction of methane and nitric oxide (NO) under flame conditions. In this work, laminar flame propagation of CH₄/NO mixtures at initial pressure (P_u) of 1 atm, initial temperature (T_u) of 298 K and equivalence ratios of 0.4–1.8 was experimentally investigated using a constant-volume combustion vessel. Laminar burning velocities (LBVs) and Markstein lengths were experimentally determined. A kinetic model of CH₄/NO combustion was developed with rate constants of several important reactions updated, presenting reasonable predictions on the measured LBVs of CH₄/NO mixtures. The modeling analyses reveal that the reduction of NO can proceed through two mechanisms, i.e. the hydrocarbon NO reduction mechanism and non-hydrocarbon NO reduction mechanism. Among the two mechanisms, the non-hydrocarbon NO reduction mechanism which includes reactions NO+H = N+OH, NO+O = N + O₂ and NO+N = N₂+O has a higher contribution to NO reduction at the equivalence ratio of 0.6, while the hydrocarbon NO reduction mechanism with hydrocyanic acid (HCN) as the key intermediate plays a more important role at the equivalence ratio of 1.8. NO+H = N+OH and CH₃+NOHCN+H₂O are found to be the two most sensitive reactions to promote the flame propagation, while the LBVs measured in this work are demonstrated to provide strong constraint for these reactions. Furthermore, previous CH₄/O₂/NO oxidation data measured in flow reactor and rapid compression machine were also simulated, which provides extended validation of the present model over wider conditions.     

Acetaldehyde oxidation at elevated pressure

A detailed chemical kinetic model for oxidation of CH₃CHO at intermediate to high temperature and elevated pressure has been developed and evaluated by comparing predictions to novel high-pressure flow reactor experiments as well as shock tube ignition delay measurements and jet-stirred reactor data from literature. The flow reactor experiments were conducted with a slightly lean CH₃CHO/O₂ mixture highly diluted in N₂ at 600–900 K and pressures of 25 and 100 bar. At the highest pressure, the oxidation of CH₃CHO was in the NTC regime, controlled to a large extent by the thermal stability and reactions of peroxide species such as HO₂, CH₃OO, and CH₃C(O)OO. Model predictions were generally in good agreement with the experimental data, even though the predicted temperature for onset of reaction was overpredicted at 100 bar. This discrepancy was attributed mainly to uncertainties in the CH₃C(O)OO reaction subset. Predictions of ignition delays in shock tubes and species profiles in JSR experiments were also satisfactory. At temperatures above the NTC regime, acetaldehyde ignition and oxidation is affected mainly by the competition between dissociation of CH₃CHO and reaction with the radical pool, and by reactions in the methane subset.     

Mid- and long-wave infrared absorption cross sections for acetonitrile

Infrared absorption cross sections for acetonitrile (methyl cyanide; CH₃CN) have been determined in the 880–1700 cm^?1 spectral region from spectra recorded using a high-resolution FTIR spectrometer (Bruker IFS 125 HR) and a multipass cell with a maximum optical pathlength of 19.3 m. Spectra of acetonitrile/dry synthetic air mixtures were recorded at 0.015 cm^?1 resolution (calculated as the Bruker instrument resolution of 0.9/MOPD) at a number of temperatures between 203 and 297 K and pressures appropriate for atmospheric conditions. Intensities were calibrated using three composite acetonitrile spectra recorded at the Pacific Northwest National Laboratory. These absorption cross sections will provide an accurate basis for upper tropospheric/lower stratospheric retrievals of acetonitrile in the mid-infrared spectral region from ACE satellite data.     

Reactions and anion desorption induced by low-energy electron exposure of condensed acetonitrile

Thermal desorption spectrometry (TDS) and electron stimulated desorption (ESD) are employed to investigate mechanisms responsible for the formation of C₂H₆ in electron irradiated multilayer films of acetonitrile (CH₃CN) at 30 K. Using a high sensitivity time-of-flight mass spectrometer, we observe the ESD of anionic fragments H⁻, CH₂ ⁻, CH₃ ⁻ and CN⁻. Desorption occurs following dissociative electron attachment (DEA) via several negative ion resonances in the 6 to 14 eV energy range and correlates well with a “resonant” structure seen in the TDS yield of C₂H₆ (i.e., at mass 30 amu). It is proposed that C₂H₆ is formed by the reactions of CH₃ radicals generated following DEA to CH₃CN which also yields CN⁻. Between 2 and 5 eV, a second resonant feature is seen in the C₂H₆ signal. While DEA is observed in the gas phase at these energies, no anion desorption occurs since anionic fragments likely have insufficient kinetic energy to desorb. Since the CH₂ ⁻ ion has not been observed in gas-phase measurements, we propose that it is formed, along with HCN (that is detected in TDS) when dissociation into CH₃ ⁻ and CN is hindered by adjacent molecules.     

Oxidation of ethyl methyl ether: Jet-stirred reactor experiments and kinetic modeling

Larger ethers such as diethyl ether (DEE) and di-n-propyl ether (DPE) have different oxidation behavior (double-NTC behavior) compared to the simplest dimethyl ether (DME). Such phenomena are interpreted with different reactions and processes in different ether kinetic models, which also predict different formation pathways of oxidation intermediates such as acids. To gain further insights into the oxidation kinetics of linear ethers, ethyl methyl ether (EME), which has a nonsymmetrical structure, was studied in this work. Oxidation experiments of 1% of EME were performed in a jet-stirred reactor at 1 atm, a residence time of 2 s, an equivalence ratio of 1, and over a temperature range of 375–850 K. The intermediates were analyzed with photoionization molecular-beam mass spectrometry. To explain the oxidation behavior of EME, a detailed kinetic model was also constructed. The oxidation of EME spans a wider temperature range than DME, but no obvious double-NTC behavior was observed as DEE. Based on the model analysis and profiles of critical intermediates such as ketohydroperoxides (KHPs) and CH₃O₂H, the low-temperature oxidation behavior of EME was explained by the chain-branching reactions of the fuel itself and the oxidation intermediates. Abundant species such as aldehydes, acids, esters, and fuel-specific dione species were detected and could be well reproduced by the current model. In particular, acids are produced by the decomposition of KHPs and subsequent reactions of the intermediate CH₃CHO. Esters and dione species are mainly formed via fuel-related pathways.     

Raman spectra of acetonitrile in imidazolium ionic liquids

Raman spectra of dilute solutions of acetonitrile in ionic liquids reveal the characteristic features of ionic liquids' polarity. This is accomplished by investigating the Raman bandshape of the ν (CN) band, corresponding to the CN stretching mode of CH₃CN, which is a very sensitive probe of the local environment. The amphiphilic nature of the CH₃CN molecule allows us to observe the effect of electron pair acceptor and electron pair donor characteristics on ionic liquids. It has been found that the overall polarity of nine different ionic liquids based on 1‐alkyl‐3‐methylimidazolium cations is more dependent on the anion than cation. The observed wavenumber shift of the ν (CN) band of CH₃CN in ionic liquids containing alkylsulfate anions agrees with the significant different values previously measured for the dielectric constant of these ionic liquids. The conclusions obtained from the analysis of the ν (CN) band were corroborated by the analysis of the symmetric ν₁ (CD₃ ) stretching mode of deuterated acetonitrile in different ionic liquids. Copyright © 2010 John Wiley & Sons, Ltd.     

Force field calculations of acetonitrile using CNDO/force method

The redundancy-free internal valence force field (RFIVFF) of acetonitrile is reported using CNDO/force method. The initial force field is set up by taking the interaction and bending force constants from CNDO force field and transferring stretching force constants from the force fields of chemically related molecules. The final force field is obtained by refining the initial force field using vibrational harmonic frequencies of CH₃CN,¹³CH₃CN, CH₃ ¹³CN, CH₃C¹⁵N, CD₃CN and CD₃ ¹³CN. The final force field thus obtained is found to be excellent on the basis of frequency fit and potential energy distribution.     

Formation of combustible gases during interaction of tungsten and zirconium with supercritical fluid H2O/CO2

Oxidation of bulk samples of tungsten (923 K) and zirconium (773 and 873 K) by H₂O/CO₂ supercritical fluid (molar ratio [CO₂]/[H₂O] = 0.17–0.26) at a pressure of about 300 atm is investigated. Oxidation produces monoclinic WO₃, monoclinic W₁₉O₅₅, monoclinic ZrO₂, H₂, CO, CH₄, and carbon (on the surface of tungsten oxide). Differences in oxidation mechanisms for tungsten and zirconium are revealed. CO₂ molecules take part in the oxidation of tungsten only after oxide formation in reaction with H₂O. Zirconium is oxidized fully, and oxidation of tungsten terminates in the formation of the oxide layer at the metal surface.     

Solvent‐dependent structural dynamics of 2(1H)‐pyridinone in light absorbing S4(ππ*) state

The B‐band resonance Raman spectra of 2(1H)‐pyridinone (NHP) in water and acetonitrile were obtained, and their intensity patterns were found to be significantly different. To explore the underlying excited state tautomeric reaction mechanisms of NHP in water and acetonitrile, the vibrational analysis was carried out for NHP, 2(1D)‐pyridinone (NDP), NHP–(H₂O)_n (n = 1, 2) clusters, and NDP–(D₂O)_n (n = 1, 2) clusters on the basis of the FT‐Raman experiments, the B3LYP/6‐311++G(d,p) computations using PCM solvent model, and the normal mode analysis. Good agreements between experimental and theoretically predicted frequencies and intensities in different surrounding environments enabled reliable assignments of Raman bands in both the FT‐Raman and the resonance Raman spectra. The results indicated that most of the B‐band resonance Raman spectra in H₂O was assignable to the fundamental, overtones, and combination bands of about ten vibration modes of ring‐type NHP–(H₂O)₂ cluster, while most of the B‐band resonance Raman spectra in CH₃CN was assigned to the fundamental, overtones, and combination bands of about eight vibration modes of linear‐type NHP–CH₃CN. The solvent effect of the excited state enol‐keto tautomeric reaction mechanisms was explored on the basis of the significant difference in the short‐time structural dynamics of NHP in H₂O and CH₃CN. The inter‐molecular and intra‐molecular ESPT reaction mechanisms were proposed respectively to explain the Franck–Condon region structural dynamics of NHP in H₂O and CH₃CN.Copyright © 2015 John Wiley & Sons, Ltd.     

Generation of CW cold CH3CN molecular beam by a bent electostatic quadrupole guiding: Monte-Carlo study

A new kind of continuous-wave (CW) cold molecular beam, methyl cyanide (CH₃CN) beam, is generated by a bent electrostatic quadrupole guiding. The Stark shift of rotational energy levels of CH₃CN molecule and its population distribution are calculated, and the dynamic processes of electrostatic guiding and energy filtering of CH₃CN molecules from a gas source with room temperature (300 K) are simulated by Monte Carlo Method. The study showed that the longitudinal and transversal temperatures of output cold CH3CN beam could be about ～2 K and ～ 420 mK, and the corresponding guiding efficiency was about 10^?5 as the guiding voltage was 3 kV. Furthermore, the temperature of the guided molecules and its guiding efficiency can be controlled by adjusting the guiding voltages applied on electrodes.     

Theoretical study on the mechanism and kinetics of atmospheric reactions NH2OH + OOH and NH2CH3 + OOH

Mechanism and kinetics of NH₂OH + OOH and NH₂CH₃ + OOH reactions were studied at the B3LYP and M062X levels of theory using the 6-311++G(3df, 3pd) basis set. The NH₂OH + OOH and NH₂CH₃ + OOH reactions proceed through different paths which lead to different products. Transition state structure and activation energy of each path were calculated. The calculated activation energies of hydrogen abstraction reactions were smaller than 25 kcal/mol and of substitution reactions are in the range of 50–70 kcal/mol. The rate constants were calculated using transition state theory (TST) modified for tunneling effect at 273–2000 K.     

Generation of CW cold CH3CN molecular beam by a bent electostatic quadrupole guiding: Monte-Carlo study

A new kind of continuous-wave (CW) cold molecular beam, methyl cyanide (CH₃CN) beam, is generated by a bent electrostatic quadrupole guiding. The Stark shift of rotational energy levels of CH₃CN molecule and its population distribution are calculated, and the dynamic processes of electrostatic guiding and energy filtering of CH₃CN molecules from a gas source with room temperature (300 K) are simulated by Monte Carlo Method. The study showed that the longitudinal and transversal temperatures of output cold CH3CN beam could be about ∼2 K and ∼ 420 mK, and the corresponding guiding efficiency was about 10⁻⁵ as the guiding voltage was 3 kV. Furthermore, the temperature of the guided molecules and its guiding efficiency can be controlled by adjusting the guiding voltages applied on electrodes.      

Exploring the chemistry behind low temperature auto-ignition of isopropyl nitrate in an RCM: An experimental and kinetic modeling study

The low-temperature auto-ignition chemistry of isopropyl nitrate (iPN) was experimentally and numerically investigated in the present study. The ignition delay times (IDTs) of iPN were measured stoichiometrically over a temperature range of 560–600 K at effective pressures of 5 and 10 bar in a rapid compression machine. A two-stage ignition phenomenon of iPN was observed. Both the first-stage IDTs and total IDTs vary rapidly within the narrow temperature range investigated (∼40 K). A recent iPN kinetic mechanism proposed by Fuller and Goldsmith for pyrolysis studies was extended. The reaction kinetics of CH₃CHO + NO₂ has been theoretically calculated at 500–1500 K and 0.01–100 atm. The rate information of CH₃ + NO₂ was updated based on previous theoretical results. The O₂-addition channel of acetyl radical (CH₃CO), which accounts for the first-stage IDT, was also considered in the present work. The extended iPN kinetic model predicts the two-stage IDTs well. Simulation results suggest that the IDTs are most sensitive to the following two reactions: (1) CH₃ + NO₂ = CH₃O + NO; (2) CH₃ + NO₂ = CH₃NO₂. The former promotes the overall reactivity by yielding the reactive methoxy radical, while the latter forms a relatively stable product (i.e., CH₃NO₂). The reaction of CH₃CHO + NO₂ = CH₃CO + HONO supplements the formation of CH₃CO. The different consumption channels of CH₃CO radicals (the O₂-addition reaction and the decomposition reaction) lead to different chain reactions yielding OH radicals with increasing temperature in the ignition process. The “NONO₂ loop” is the main route for OH formation in the studied conditions, which is mainly responsible for the iPN ignition.     

Triplet-triplet absorption studies of the intersystem crossing mechanism of 2-aminopurines

The triplet excited states of 2-aminopurine (2-APu) and 2-N, N-dimethylaminopurine (2-DMAPu) in acetonitrile and water have been detected and characterized. Comparison of the initial T-T absorbancies, together with the measured singlet lifetime, in these systems allowed us to determine the relative intersystem crossing rate constants. The ratios k_ISC (2-APu/CH₃CN) : k_ISC (2-APu/H₂O) and k_ISC (2- DMAPu/CH₃CN) were found to be 36.7 and 11.2, respectively. Comparison with the ratios calculated from the luminescence data confirm the previously proposed [1] scheme of electronic levels in these purines.     

Synchrotron photoionization measurements of fundamental autoignition reactions: Product formation in low-temperature isobutane oxidation

Product formation in laser-photolytic Cl-initiated low-temperature (550–700 K) oxidation of isobutane in a slow-flow reactor was investigated by tunable synchrotron photoionization mass spectrometry. These experiments probed the time-resolved formation of products following photolytic initiation of the oxidation, and identify isomeric species by their photoionization spectra. The relative yields of oxygenated product isomers (2,2-dimethyloxirane, methylpropanal, and 3-methyloxetane) are in reasonable concord with measurements from Walker and co-workers (J. Chem. Soc. Faraday Trans. 74 (1) (1978) 2229–2251) at higher temperature. Oxidation of isotopically labeled isobutane, (CH₃)₃CD, suggests that methylpropanal formation can proceed from both (CH₃)₂CCH₂OOH and CH₃CH(CH₂)CH₂OOH isomers. Bimodal time behavior is observed for product formation; the initial prompt formation reflects “formally direct” channels, principally chemical activation, and the longer-timescale “delayed” component arises from dissociation of thermalized ROO and QOOH radicals. The proportion of prompt to delayed signal is smaller for the oxygenated products than for the isobutene product. This channel-specific behavior can be qualitatively understood by considering the different energetic distributions of ROO and QOOH in formally direct vs. thermal channels and the fact that the transition states involved in the formation of oxygenated products are “tighter” than that for isobutene formation.     

Coordination of acetonitrile (CH3CN) to platinum (111): Evidence for an η2(C,N) species

Acetonitrile (CH₃CN) coordination to a Pt(111) surface has been studied with electron energy loss vibrational spectroscopy (EELS), XPS, thermal desorption and work function measurements. We compare data for the surface states with known acetonitrile coordination complexes. For CH₃CN adsorbed on Pt(111) at 100 K, the molecule is rehybridized and adsorbs with the CN bond parallel or slightly inclined to the surface plane in an η²(C, N) configuration. The ν(CN) frequency is 1615 cm^?1 and the C ls and N ls binding energies are 284.6 eV and 397.2 eV respectively. By contrast, weakly adsorbed multilayer acetonitrile exhibits a ν(CN) vibrational frequency of 2270 cm^?1, and C ls and N ls binding energies of 286.9 eV and 400.1 eV respectively. Both the EELS and XPS results are consistent with rehybridization of the CN triple bond to a double bond with both C and N atoms of the CN group attached to the surface. In addition to this majority η²(C, N) monolayer state, evidence is found for a second, more strongly bound minority molecular state in thermal desorption spectra. As a result of the low coverage of this state, EELS was unable to spectroscopically identify it and we tentatively assign it as an η⁴(C, N) species associated with accidental step sites. By contrast to the surface complexes, almost all of the known platinum-nitrile coordination complexes are end-bonded via the N lone-pair orbital. Several cases of side-on bonding are known, however, and we compare the results with the known complex Fe₃(η²-NCCH₃)(CO)₉. The difference in the coordinative properties of a Pt(111) surface versus a single Pt atom must be due to the increased ability of multi-atom arrays to back-donate electrons into the π¹ system of acetonitrile. Previously published EELS and XPS results for monolayer acetonitrile on Ni(111) and polycrystalline films are almost identical to the present results on Pt(111). We believe that the monolayer of $\text{CH}{}_3\text{CN}\text{Ni}\text{(111)}$ is also an η²(C, N) species, not an end-bonded species previously proposed by Friend, Muetterties and Gland.     

Theoretical investigation on the reaction kinetics of NO2 with CH3OH and HCHO under combustion conditions

Methanol (CH₃OH) and formaldehyde (HCHO) reacting with nitrogen dioxide (NO₂) contribute to the largest uncertainty for the CH₃OH/NO_x low temperature combustion mechanism. CH₃OH and NO₂ only undergo H-abstraction reactions, while HCHO + NO₂ involves multiple reaction channels, among which H-abstraction dominates. In the present work, a high level quantum chemical method, CCSD(T)/aug-cc-pVQZ//M06–2X-D3/6-311++G(d,p), was employed to investigate the reaction pathways. The reaction kinetics were explored by RRKM/master equation simulations with multidimensional small-curvature tunneling (SCT) corrections and hindered rotor approximations. The H-abstraction reactions with barriers higher than 20 kcal/mol indicate a nonnegligible quantum tunneling effect even under combustion conditions. Our computations predict the tunneling factors to be 3–4 for the studied reactions at 500 K. A significant tunneling effect is also expected for H-abstraction of large alcohols and aldehydes by NO₂. The computed total rate coefficients show good agreement with previous experimental measurements over narrow ranges of temperature and pressure, ensuring the accuracy of the reported branching ratios covering a wide T, P range for the two reactions. The results of CH₃OH + NO₂ reveal the dominant role of HONO_cis + CH₂OH. It's also uncovered the dominance of HONO_cis + CHO pathway in HCHO + NO₂ under the studied conditions. The detailed reaction kinetics information reported in this work is useful for building rate rules for the mechanisms of other nitrogen-containing alcohol-based fuels.     

Methanol oxidation up to 100 atm in a supercritical pressure jet-stirred reactor

Methanol (CH₃OH) has attracted considerable attention as a renewable fuel or fuel additive with low greenhouse gas emissions. Methanol oxidation was studied using a recently developed supercritical pressure jet-stirred reactor (SP-JSR) at pressures of 10 and 100 atm, at temperatures from 550 to 950 K, and at equivalence ratios of 0.1, 1.0, and 9.0 in experiments and simulations. The experimental results show that the onset temperature of CH₃OH oxidation at 100 atm is around 700 K, which is more than 100 K lower than the onset at 10 atm and this trend cannot be predicted by the existing kinetics models. Furthermore, a negative temperature coefficient (NTC) behavior was clearly observed at 100 atm at fuel rich conditions for methanol for the first time. To understand the observed temperature shift in the reactivity and the NTC effect, we updated some key elementary reaction rates of relevance to high pressure CH₃OH oxidation from the literature and added some new low-temperature reaction pathways such as CH₂O + HO₂ = HOCH₂O₂ (RO₂), RO₂ + RO₂ = HOCH₂O (RO) + HOCH₂O (RO) + O₂, and CH₃OH + RO₂ = CH₂OH + HOCH₂O₂H (ROOH). Although the model with these updates improves the prediction somewhat for the experimental data at 100 atm and reproduces well high-temperature ignition delay times and laminar flame speed data in the literature, discrepancies still exist for some aspects of the 100 atm low-temperature oxidation data. In addition, it was found that the pressure-dependent HO₂ chemistry shifts to lower temperature as the pressure increases such that the NTC effect at fuel-lean conditions is suppressed. Therefore, as shown in the experiments, the NTC phenomenon was only observed at the fuel-rich condition where fuel radicals are abundant and the HO₂ chemistry at high pressure is weakened by the lack of oxygen resulting in comparatively little HO₂ formation.     

Photochemistry of methyl bromide on the α-Cr2O3(0001) surface

The photochemical properties of the Cr-terminated α-Cr₂O₃(0001) surface were explored using methyl bromide (CH₃Br) as a probe molecule. CH₃Br adsorbed and desorbed molecularly from the Cr-terminated α-Cr₂O₃(0001) surface without detectable thermal decomposition. Temperature programmed desorption (TPD) revealed a CH₃Br desorption state at 240 K for coverages up to 0.5 ML, followed by more weakly bound molecules desorbing at 175 K for coverages up to 1 ML. Multilayer exposures led to desorption at ~ 130 K. The CH₃Br sticking coefficient was unity at 105 K for coverages up to monolayer saturation, but decreased as the multilayer formed. In contrast, pre-oxidation of the surface (using an oxygen plasma source) led to capping of surface Cr³⁺ sites and near complete removal of CH₃Br TPD states above 150 K. The photochemistry of chemisorbed CH₃Br was explored on the Cr-terminated surface using post-irradiation TPD and photon stimulated desorption (PSD). Irradiation of adsorbed CH₃Br with broad band light from a Hg arc lamp resulted in both photodesorption and photodecomposition of the parent molecule at a combined cross section of ~ 10^? 22 cm². Photodissociation of the CH₃–Br bond was evidenced by both CH₃ detected in PSD and Br atoms left on the surface. Use of a 385 nm cut-off filter effectively shut down the photodissociation pathway but not the parent molecule photodesorption process. From these observations it is inferred that d-to-d transitions in α-Cr₂O₃, occurring at photon energies < 3 eV, do not significantly promote photodecomposition of adsorbed CH₃Br. It is unclear to what extent band-to-band versus direct CH₃Br photolysis play in CH₃–Br bond dissociation initiated by more energetic photons.     

Kinetics for the reactions of phenyl with methanol and ethanol: Comparison of theory and experiment

The kinetics of the C₆H₅ reactions with CH₃OH and C₂H₅OH has been measured by pulsed-laser photolysis/mass-spectrometry (PLP/MS) employing acetophenone as the radical source. Kinetic modeling of the benzene formed in the reactions over the temperature range 306–771 K allows us to reliably determine the total rate constants for H-abstraction reactions. In order to improve our low temperature measurements down to 304 K we have also applied the cavity ring-down spectrometric technique using nitrosobenzene as the radical source. Both sets of data agree closely. A weighted least-squares analysis of the two complementary sets of data for the two reactions gave the total rate constants k(CH₃OH) = (7.82 ± 0.44) × 10¹¹ exp [?(853 ± 30)/T] and k(C₂H₅OH) = (5.73 ± 0.58) × 10¹¹ exp [?(1103 ± 44)/T] cm³ mol^?1 s^?1 for the temperature range studied. Theoretically, four possible product channels of the C₆H₅ + CH₃OH reaction producing C₆H₆ + CH₃O, C₆H₆ + CH₂OH, C₆H₅OH + CH₃ and C₆H₅OCH₃ + H and five possible product channels of the C₆H₅ + C₂H₅OH reaction producing C₆H₆ + C₂H₅O, C₆H₆ + CH₂CH₂OH, C₆H₆ + CH₃CHOH, C₆H₅OH + CH₃CH₂ and C₆H₅OCH₂CH₃ + H have been computed at the G2M//B3LYP/6?311+G(d, p) level of theory. The hydrogen abstraction channels were predicted to have lower energy barriers than those for the substitution reactions and their rate constants were calculated by the microcanonical variational transition state theory at 200–3000 K. The predicted rate constants are in good agreement with the experimental values. Significantly, the rate constant for the CH₃OH reaction with C₆H₅ was found to be greater than that for the C₂H₅OH reaction and both reactions were found computationally to be dominated by H-abstraction from the hydroxyl group attributable to the affinity of the phenyl toward the OH group and the predicted lower energy barriers for the OH attack.