OH Concentration Profiles Research Articles

Accurate Kinetic Studies of OH + HO2 Radical-Radical Reaction through Direct Measurement of Precursor and Radical Concentrations with High-Resolution Time-Resolved Dual-Comb Spectroscopy.

The radical-radical reaction between OH and HO2 has been considered for a long time as an important reaction in tropospheric photochemistry and combustion chemistry. However, a significant discrepancy of an order of magnitude for rate coefficients of this reaction is found between two recent experiments. Herein, we investigate the reaction OH + HO2 via direct spectral quantification of both the precursor (H2O2) and free radicals (OH and HO2) upon the 248 nm photolysis of H2O2 using infrared two-color time-resolved dual-comb spectroscopy. With quantitative and kinetic analysis of concentration profiles of both OH and HO2 at varied conditions, the rate coefficient kOH+HO2 is determined to be (1.10 ± 0.12) × 10-10 cm3 molecule-1 s-1 at 296 K. Moreover, we explore the kinetics of this reaction under conditions in the presence of water, but no enhancement in the kOH+HO2 can be observed. This work as an independent experiment plays a crucial role in revisiting this prototypical radical-radical reaction.

New insights into the mechanism of Fered-Fenton treatment of industrial wastewater with high chloride content: Role of multiple reactive species

Hydroxyl radical (OH) is considered the dominant reactive species in the electro-Fenton (EF) and Fered-Fenton (EF-Fere) processes for wastewater treatment. However, in chloride-rich media, this is arguable due to the obscure mechanisms for the oxidant speciation and pollutant degradation. Herein, the role of active chlorine and Fe(IV)-oxo species (FeIVO2+) as primary oxidizing agents in HClO-mediated Fered-Fenton (EF-Fere-HClO) process is discussed, along with the dependence of their contribution on the pollutant structure. HClO generated from anodic oxidation of Cl− can be consumed by added H2O2 to form singlet oxygen (1O2), which is detrimental because this species is quickly deactivated by water. The reaction between HClO and Fe2+ was proved to generate FeIVO2+, rather than OH or Cl suggested in the literature. The yield of FeIVO2+ species was proportional to the Cl− concentration and barely affected by solution pH. The long-lived HClO and FeIVO2+ can selectively react with electron-rich compounds, which occurs simultaneously to the non-selective attack of OH formed from Fenton's reaction. The FeIVO2+ and OH concentration profiles were successfully modelled. Although the accumulation of toxic chlorinated by-products from HClO-mediated oxidation might cause new environmental concerns, the toxicity of pesticide wastewater with 508 mM Cl− was halved upon EF-Fere-HClO treatment.

An Experimental and Numerical Study on Supported Ultra-Lean Methane Combustion

With a much larger global warming potential (GWP) and much shorter lifespan, the reduction of methane emissions offers an additional opportunity and a relatively quick way of mitigating climate change in the near future. However, the emissions from coal mining in the form of ventilation air methane (VAM), usually in ultra-lean concentration, pose the most significant technical challenge to the mitigation of methane emission. Therefore, a better understanding of ultra-lean methane combustion is essential. With three 5 mm × 50 mm rectangle cross-section slot jets, a novel sandwich-type triple-jet burner is proposed to provide stable combustion of an ultra-lean methane–air mixture with equivalence ratios from 0.3 to 0.88, and 0.22 in extreme conditions. The ultra-lean methane flame in the center of the triple-jet burner is supported by the two lean outer flames at an equivalence ratio φ = 0.88. The flow field and combustion chemical reactions are predicted by detailed numerical simulation with GRI-Mech 3.0 reaction mechanisms. Two-dimensional numerical results are validated with those obtained by experimental particle image velocimetry (PIV), as well as visual flame height and temperature measurements. An ultra-lean methane–air mixture has to burn with external support. In addition, the ultra-lean flame is non-propagating with a relatively low temperature. The ultra-lean center flame is seen to start from the outer flame and incline perfectly to the post-flame temperature and OH concentration profiles of the outer lean flame. The adjacent stronger flame provides heat and active radicals, such as OH and HO2, from the post-flame region and in the wall proximity of the gap between the adjacent flame and the central ultra-lean jet to initiate and maintain the combustion of the central ultra-lean flame. The outstanding wall-proximity radical of HO2 is found to be the main contributor to the initiation and stabilization of the central ultra-lean flame by providing a low-temperature oxidation of fuel through the following reaction: HO2 + CH3 ⇔ OH + CH3O. The major chemical reaction paths contributing to fuel decomposition and oxidation of the supported ultra-lean center flame are also identified and delineated.

Behavior of Hydroxyl Groups in Quartz Glass during Heat Treatment in the Range 750–950°C

The concentration of hydroxyl groups in different types of quartz glass tubes, the OH concentration profile across the tube wall, and the kinetics of OH removal during heat treatment in the temperature range 750–950°C have been studied by Fourier transform IR spectroscopy. For TK-I tubes, produced by vacuum electromelting of quartz, followed by annealing in a hydrogen atmosphere, we have calculated the diffusion coefficient of OH groups in this temperature range and the activation energy for diffusion: 215 ± 10 kJ/mol. We have found heat treatment conditions that ensure a considerable decrease in the concentration of OH groups in quartz tubes that are used in the fabrication of reactors for the preparation of extrapure chalcogenide glasses.

Probabilistic inference of reaction rate parameters from summary statistics

This investigation tackles the probabilistic parameter estimation problem involving the Arrhenius parameters for the rate coefficient of the chain branching reaction H + O2 → OH + O. This is achieved in a Bayesian inference framework that uses indirect data from the literature in the form of summary statistics by approximating the maximum entropy solution with the aid of approximate bayesian computation. The summary statistics include nominal values and uncertainty factors of the rate coefficient, obtained from shock-tube experiments performed at various initial temperatures. The Bayesian framework allows for the incorporation of uncertainty in the rate coefficient of a secondary reaction, namely OH + H2 → H2O + H, resulting in a consistent joint probability density on Arrhenius parameters for the two rate coefficients. It also allows for uncertainty quantification in numerical ignition predictions while conforming with the published summary statistics. The method relies on probabilistic reconstruction of the unreported data, OH concentration profiles from shock-tube experiments, along with the unknown Arrhenius parameters. The data inference is performed using a Markov chain Monte Carlo sampling procedure that relies on an efficient adaptive quadrature in estimating relevant integrals needed for data likelihood evaluations. For further efficiency gains, local Padé–Legendre approximants are used as surrogates for the time histories of OH concentration, alleviating the need for 0-D auto-ignition simulations. The reconstructed realisations of the missing data are used to provide a consensus joint posterior probability density on the unknown Arrhenius parameters via probabilistic pooling. Uncertainty quantification analysis is performed for stoichiometric hydrogen–air auto-ignition computations to explore the impact of uncertain parameter correlations on a range of quantities of interest.

Experimental and numerical study of soot formation and evolution in co-flow laminar partially premixed flames

In this work, a set of four partially premixed ethylene–air laminar flames, characterized by different equivalent ratios, was studied. The aim was to investigate the effect of partial premixing on soot formation, which is a relevant parameter for real combustion devices. Quantitative and qualitative information on soot particles were obtained using a modified version of the thermophoretic particle densitometry (TPD) method. Particle thermal emissivity values were measured from the transient thermocouple temperature response. Results show that the emissivity of flame-formed carbon nanoparticles ranges from about 0.5 for soot precursor particles up to 0.95, i.e., the typical emissivity value attributed to mature soot particles. Particle volume fraction was then accurately evaluated by means of the TPD method, using the values of particle emissivity previously measured.The changing of particle features throughout the flame, evidenced by the variation in thermal emissivity, was further investigated using Raman spectroscopy. The analysis of Raman spectra showed that the increase in thermal emissivity follows a reduction in the hydrogen-to-carbon ratio of the investigated soot nanoparticles. Measurements performed with the TPD method also evidence that both particle emissivity and volume fraction are strongly affected by oxidation, which prevents to accurately measure soot concentration in oxidative regions of the flames. An attempt to include soot oxidation in the TPD method for a correct evaluation of volume fraction procedure is also illustrated. OH concentration profiles, obtained from a modeling analysis and validated by radical chemiluminescence measurements, were used in the TPD method to correct particle concentration due to oxidation.

Detection of OH in an atmospheric flame at 1.5 um using optical frequency comb spectroscopy

We report broadband detection of OH in a premixed CH4/air flat flame at atmospheric pressure using cavity-enhanced absorption spectroscopy based on an Er:fiber femtosecond laserand a Fourier transform spectrometer.By taking ratios of spectra measured at different heights above the burner we separate twenty OH transitions from the largely overlapping water background. Weretrieve from fits to the OH lines the relative variation of the OH concentration and flame temperature with height above the burner and compare them with 1-D simulations of the flamestructure. Full Text: PDF ReferencesG. Meijer, M. G. Boogaarts, R. T. Jongma, D. H. Parker and A. M. Wodtke, "Coherent cavity ring down spectroscopy", Chem. Phys. Lett. 217, 1, 112 (1994). CrossRef S. Cheskis, I. Derzy, V. A. Lozovsky, A. Kachanov and D. Romanini, "Cavity ring-down spectroscopy of OH radicals in low pressure flame", Appl. Phys. B 66, 3, 377 (1998). CrossRef X. Mercier, E. Therssen, J. F. Pauwels and P. Desgroux, "Cavity ring-down measurements of OH radical in atmospheric premixed and diffusion flames.: A comparison with laser-induced fluorescence and direct laser absorption", Chem. Phys. Lett. 299, 1, 75 (1999). CrossRef J. Scherer, D. Voelkel and D. Rakestraw, "Infrared cavity ringdown laser absorption spectroscopy (IR-CRLAS) in low pressure flames", Appl. Phys. B 64, 6, 699 (1997). CrossRef R. Peeters, G. Berden and G. Meijer, "Near-infrared cavity enhanced absorption spectroscopy of hot water and OH in an oven and in flames", Appl. Phys. B 73, 1, 65 (2001). CrossRef T. Aizawa, "Diode-laser wavelength-modulation absorption spectroscopy for quantitative in situ measurements of temperature and OH radical concentration in combustion gases", Appl. Opt. 40, 27, 4894 (2001). CrossRef B. Löhden, S. Kuznetsova, K. Sengstock, V. M. Baev, et al., "Fiber laser intracavity absorption spectroscopy for in situ multicomponent gas analysis in the atmosphere and combustion environments", Appl. Phys. B 102, 2, 331 (2011). CrossRef A. Matynia, M. Idir, J. Molet, C. Roche, et al., "Absolute OH concentration profiles measurements in high pressure counterflow flames by coupling LIF, PLIF, and absorption techniques", Appl. Phys. B 108, 2, 393 (2012). CrossRef R. S. Watt, T. Laurila, C. F. Kaminski and J. Hult, "Cavity Enhanced Spectroscopy of High-Temperature H2O in the Near-Infrared Using a Supercontinuum Light Source", Appl. Spectrosc. 63, 12, 1389 (2009). CrossRef C. Abd Alrahman, A. Khodabakhsh, F. M. Schmidt, Z. Qu and A. Foltynowicz, "Cavity-enhanced optical frequency comb spectroscopy of high-temperature H2O in a flame", Opt. Express 22, 11, 13889 (2014). CrossRef A. Foltynowicz, P. Maslowski, A. J. Fleisher, B. J. Bjork and J. Ye, "Cavity-enhanced optical frequency comb spectroscopy in the mid-infrared application to trace detection of hydrogen peroxide", Appl. Phys. B 110, 2, 163 (2013). CrossRef Z. Qu, R. Ghorbani, D. Valiev and F. M. Schmidt, "Calibration-free scanned wavelength modulation spectroscopy ? application to H2O and temperature sensing in flames", Opt. Express 23, 12, 16492 (2015). CrossRef L. Rutkowski, A. Khodabakhsh, A. C. Johansson, D. M. Valiev, et al., "Measurement of H2O and OH in a Flame by Optical Frequency Comb Spectroscopy", CLEO: Science and Innovations SW4H.8 (2016). CrossRef L. S. Rothman, I. E. Gordon, Y. Babikov, A. Barbe, et al., "The HITRAN2012 molecular spectroscopic database", J. Quant. Spectrosc. Radiat. Transf. 130, 4 (2013). CrossRef

A novel linear transformation model for the analysis and optimisation of chemical kinetics

In this study, a novel model for the analysis and optimisation of numerical and experimental chemical kinetics is developed. Concentration–time profiles of non-diffusive chemical kinetic processes and flame speed profiles of fuel–oxidiser mixtures can be described by certain characteristic points, so that relations between the coordinates of these points and the input parameters of chemical kinetic models become almost linear. This linear transformation model simplifies the analysis of chemical kinetic models, hence creating a robust global sensitivity analysis and allowing quick optimisation and reduction of these models. Firstly, in this study the model is extensively validated by the optimisation of a syngas combustion model with a large data set of imitated ignition experiments. The optimisation with the linear transformation model is quick and accurate, revealing the potential for decreasing the numerical costs of the optimisation process by at least one order of magnitude compared to established methods. Additionally, the optimisation on this data set demonstrates the capability of predicting reaction rate coefficients more accurately than by currently known confidence intervals. In a first application, methane combustion models are optimised with a small experimental set consisting of OH(A) and CH(A) concentration profiles from shock tube ignition experiments, species profiles from flow reactor experiments and laminar flame speeds. With the optimised models, especially the predictability for the flame speeds of mixtures of hydrogen, carbon monoxide and methane can be increased compared to established models. With the analysis of the optimised models, new information on the low pressure reaction coefficient of the fall-off reaction H+CH3(+M)⟺CH4(+M) is determined. In addition, the optimised combustion model is quickly and efficiently reduced to validate a new rapid reduction scheme for chemical kinetic models.

Inference of reaction rate parameters based on summary statistics from experiments

We present the results of an application of Bayesian inference and maximum entropy methods for the estimation of the joint probability density for the Arrhenius rate parameters of the rate coefficient of the H2/O2-mechanism chain branching reaction H+O2→OH+O. Available published data is summary statistics in terms of nominal values and error bars of the rate coefficient of this reaction at a number of temperature values obtained from shock-tube experiments. Our approach relies on generating data, in this case OH concentration profiles, consistent with the given summary statistics, using Approximate Bayesian Computation methods and a Markov chain Monte Carlo procedure. The approach permits the forward propagation of parametric uncertainty through the computational model in a manner that is consistent with the published statistics. A consensus joint posterior on the parameters is obtained by pooling the posterior parameter densities given each consistent data set. To expedite this process, we construct efficient surrogates for the OH concentration using a combination of Padé and polynomial approximants. These surrogate models adequately represent forward model observables and their dependence on input parameters and are computationally efficient to allow their use in the Bayesian inference procedure. We also utilize Gauss–Hermite quadrature with Gaussian proposal probability density functions for moment computation resulting in orders of magnitude speedup in data likelihood evaluation. Despite the strong non-linearity in the model, the consistent data sets all result in nearly Gaussian conditional parameter probability density functions. The technique also accounts for nuisance parameters in the form of Arrhenius parameters of other rate coefficients with prescribed uncertainty. The resulting pooled parameter probability density function is propagated through stoichiometric hydrogen–air auto-ignition computations to illustrate the need to account for correlation among the Arrhenius rate parameters of one reaction and across rate parameters of different reactions.

Measurement of OH concentration profiles by laser diagnostics and modeling in high-pressure counterflow premixed methane/air and biogas/air flames

Detailed kinetic mechanisms validated under atmospheric or low-pressure flame conditions cannot generally be directly extrapolated toward high pressure, due to the lack of experimental data or to uncertainties concerning the rate constants of elementary reactions. It is thus necessary to complete the experimental database and to extend the validation domain of combustion mechanisms at high pressure. In this work, OH concentration profiles were measured in high-pressure methane/air and biogas/air laminar premixed counterflow flames by linear laser-induced fluorescence at different equivalence ratios (0.7–1.2) and pressures (0.1–0.7MPa). Each flame was calibrated in absolute OH concentration by a combination of laser absorption and planar laser-induced fluorescence measurements. Experimental results were compared with simulations using the OPPDIF code and three detailed kinetic mechanisms: two versions of the Gas Research Institute Mechanism, GRI-Mech 2.11 and GRI-Mech 3.0, and the recently updated GDFkin®3.0_NCN mechanisms. Results show that the flame front positions are very well predicted by modeling with the three mechanisms for lean and stoichiometric CH4/air flames and stoichiometric CH4/CO2/air flames. However, discrepancies appear at a higher equivalence ratio (Φ=1.2) for the CH4/air flames and at a lower equivalence ratio (Φ=0.7) for the CH4/CO2/air flames. OH mole fractions are quantitatively well predicted at high pressure in all cases, while systematic overestimation by modeling is observed at atmospheric pressure. A kinetic analysis of the results is also presented.

Absolute OH concentration profiles measurements in high pressure counterflow flames by coupling LIF, PLIF, and absorption techniques

A high-pressure combustion chamber enclosing counterflow burners was set-up at ICARE-CNRS laboratory. It allows the stabilization of flat twin premixed flames at atmospheric and high pressure. In this study, lean and stoichiometric methane/air counterflow premixed flames were studied at various pressures (0.1 MPa to 0.7 MPa). Relative OH concentration profiles were measured by Laser Induced Fluorescence. Great care was attached to the determination of the fluorescence signal by taking into account the line broadening and deexcitation by quenching which both arise at high pressure. Subsequently, OH profiles were calibrated in concentration by laser absorption technique associated with planar laser induced fluorescence. Results are successfully compared with literature. The good quality of the results attests of the experimental set-up ability to allow the study of flame structure at high pressure.

Measurements and Automated Mechanism Generation Modeling of OH Production in Photolytically Initiated Oxidation of the Neopentyl Radical

Production of OH in the reaction of the neopentyl radical with O2 has been measured by a laser photolysis/cw absorption method for various pressures and oxygen concentrations at 673, 700, and 725 K. The MIT Reaction Mechanism Generator (RMG) was used to automatically generate a model for this system, and the predicted OH concentration profiles are compared to present and literature experimental results. Several reactions significantly affect the OH profile. The experimental data provide useful constraints on the rate coefficient for the formally direct chemical activation reaction of neopentyl radical with O2 to form OH (CH3)3CCH2 + O2 --> OH + 3,3-dimethyloxetane (Rxn 1) At 673 K and 60 Torr, log k(1) (cm(3) molecule(-1) s(-1)) = -13.7 +/- 0.5. Absolute absorbance measurements on OH and I indicate that the branching ratio for R + O2 to OH is about 0.03 under these conditions. The data suggest that the ab initio neopentyl + O2 potential energy surface of Sun and Bozzelli is accurate to within 2 kcal mol(-1).

Role of atomic hydrogen diffusion in a hydrogen flame

A numerical modeling study of the propagation of a laminar flat homogeneous gas flame has shown that in a hydrogen-air flame, a rapid increase in the concentration of OH radicals begins in the range of low temperatures and the concentration profile has two maxima. The first maximum in the low-temperature region of the front is related to the diffusion of H atoms, formation of HO2 radicals, and the quadratic branching reaction H + HO2 → OH + OH. The second maximum in the OH concentration profile is due to the classical high-temperature branching reactions H + O2 → OH + O and O + H2 → OH + H.

Influence of organophosphorus inhibitors on the structure of atmospheric lean and rich methane-oxygen flames

The inhibition of atmospheric laminar methane-oxygen flames of various compositions by trimethyl phosphate was studied experimentally and by numerical modeling using mechanisms based on detailed kinetics. The H and OH concentration profiles in flames with and without the addition of trimethyl phosphate were measured and calculated. It was shown that the addition of the inhibitor reduced the maximum (in the reaction zone) concentrations of H and OH in lean and rich flames. The concentration reduction was higher in rich flames than in lean flames. The concentration profiles of the phosphorus-containing products PO, PO2, HOPO, HOPO2, and (HO)3PO in lean and rich flames stabilized on a flat burner were measured and calculated. Tests of the previously developed model of flame inhibition by phosphorus compounds showed that the model provides adequate predictions of many experimental results.

Determination of the Rate Constant for the OH(X2Π) + OH(X2Π) → O(3P) + H2O Reaction over the Temperature Range 293−373 K

The rate constant for the reaction OH(X2Pi) + OH(X2Pi) --> O(3P) + H2O has been measured over the temperature range 293-373 K and pressure range 2.6-7.8 Torr in both Ne and Ar bath gases. The OH radical was created by 193 nm laser photolysis of N2O to produce O(1D) atoms that reacted rapidly with H2O to produce the OH radical. The OH radical was detected by quantitative time-resolved near-infrared absorption spectroscopy using Lambda-doublet resolved rotational transitions of the first overtone of OH(2,0) near 1.47 microm. The temporal concentration profiles of OH were simulated using a kinetic model, and rate constants were determined by minimizing the sum of the squares of residuals between the experimental profiles and the model calculations. At 293 K the rate constant for the title reaction was found to be (2.7 +/- 0.9) x 10(-12) cm(3) molecule(-1) s(-1), where the uncertainty includes an estimate of both random and systematic errors at the 95% confidence level. The rate constant was measured at 347 and 373 K and found to decrease with increasing temperature.

Measurements and modeling of SiCl 4 combustion in a low-pressure H 2/O 2 flame

Laser-induced fluorescence (LIF) was used to measure temperature and OH concentration profiles as a function of distance from a McKenna-style burner in premixed one-dimensional low-pressure H 2/O 2/Ar SiCl 4-doped flames. The addition of SiCl 4 was shown to affect the flame temperature and OH concentration profiles. A gas-phase chemical kinetics mechanism for the combustion of SiCl 4 in an H 2/O 2/Ar flame was proposed, and experimental results were compared with predictions for a premixed one-dimensional laminar flame model based on CHEMKIN. The low-pressure flame data are sensitive to the overall kinetics of the mechanism. In order to obtain the best fit to the observed data for all flame configurations, we had to modify six different rates from our original estimates. None of the modified rates are well known for the temperature regime of our flame. Particle formation and surface chemistry were not taken into account.

Measurements of the kinetics of the OH‐initiated oxidation of β‐pinene: Radical propagation in the OH + β‐pinene + O2 + NO reaction system

AbstractThe mechanism of the OH‐initiated oxidation of β‐pinene in the presence of NO has been investigated using a discharge‐flow system at 5 Torr and 300 K. OH radical concentrations were measured as a function of reaction time by laser‐induced fluorescence (LIF). The rate constant for the OH +β‐pinene reaction was measured to be (7.68 ± 0.72) ×10−11 cm3 molecule−1 s−1. OH radical propagation was observed after the addition of O2 and NO, and the measured OH concentration profiles were compared to simulations based on both the Master Chemical Mechanism and the Regional Atmospheric Chemistry Mechanism for β‐pinene oxidation in order to determine the ability of these mechanisms to describe the observed efficiency of radical propagation. Both models are able to reproduce the observed OH concentrations profiles to within 15%. Expanding the MCM to include isomerization of the β‐hydroxy alkoxy radicals improves the agreement with the experimental observations. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 522–531, 2005

Distribution of OH and CH Radicals in the Boundary Layer with Ethanol Combustion

The influence of free-stream turbulence on the distributions of CH and OH radicals is studied with the use of optical methods of measurements in focused beams. The data on CH concentration are obtained for the minimum level of turbulence, and the OH concentration profiles are obtained for three levels of velocity fluctuations: 1, 8, and 18. It is shown that the regions where the OH and CH radicals are observed in the laminar boundary layer are shifted from the temperature maximum toward the oxidizer zone and toward the fuel zone, respectively. The highest level of the OH concentration is close to values typical of hydrogen combustion. The root-mean-square fluctuations of velocity and the mean values of the OH concentration vary nonmonotonically along the flame.

Measurements of the kinetics of the OH-initiated oxidation of -pinene: Radical propagation in the OH+-pinene+O+NO reaction system

The mechanism of the OH-initiated oxidation of α-pinene in the presence of NO has been investigated using a discharge-flow system at 5 Torr and 300 K. The OH concentration was monitored as a function of reaction time by laser-induced fluorescence (LIF). The rate constant for the OH+α-pinene was measured to be (6.09±0.30)×10−11 cm3 molecule−1 s−1. OH radical regeneration was observed after addition of O2 and NO, and the measured OH concentration profiles were compared to simulations based on both the Master Chemical Mechanism and the Regional Atmospheric Chemistry Mechanism for α-pinene oxidation in order to determine the ability of these mechanisms to describe the observed efficiency of radical propagation. Both models are able to reproduce the observed OH concentrations profiles to within 30%. However, expanding the MCM to include isomerization of the β-hydroxy alkoxy radicals improves the agreement with the experimental observations.

Shock tube measurements of toluene ignition times and OH concentration time histories

Ignition delay times and OH radical concentration profiles were measured in toluene/O 2/Ar mixtures behind reflected shock waves. Initial reflected shock conditions spanned 1400–2000 K and 1.5–5.0 atm, with equivalence ratios of 0.5–1.875 and toluene concentrations of 0.025–0.5%. OH time histories were monitored using narrow-linewidth ring dye laser absorption of the well-characterized R 1 (5) line of the OH A–X (0, 0) band at 306.7 nm. Ignition time data were extracted from the OH traces and were found to compare very well with measurements using sidewall pressure. These new data are in agreement with the recent measurements of Burcat et al. [NASA TM-87312, 1986], but not with the measurements of Pitz et al. [Second Joint Meeting, US Sections of the Combustion Institute, Paper 253, 2001] or Burcat et al. [Combust. Flame 36 (1979)]. The results of this study were compared to three detailed kinetic models: Pitz et al. [Second Joint Meeting, US Sections of the Combustion Institute, Paper 253, 2001], Dagaut et al.[Phys. Chem. Chem. Phys. 4 (2002)], and Lindstedt and Maurice [Combust. Sci. Technol. 120 (1996)]. The ability of the mechanisms to predict the measured ignition time data and OH concentration profiles was analyzed. Suggestions to improve model performance have been made, and key reactions that need to be studied further have been identified. This work has yielded the first quantitative measurements of OH time histories during toluene oxidation, and hence provides a critical data set useful for evaluating and refining comprehensive mechanisms on toluene oxidation.