Measured OH Concentrations Research Articles

Measurements of Hydroxyl Radical Concentrations during Indoor Cooking Events: Evidence of an Unmeasured Photolytic Source of Radicals.

The hydroxyl radical (OH) is the dominant oxidant in the outdoor environment, controlling the lifetimes of volatile organic compounds (VOCs) and contributing to the growth of secondary organic aerosols. Despite its importance outdoors, there have been relatively few measurements of the OH radical in indoor environments. During the House Observations of Microbial and Environmental Chemistry (HOMEChem) campaign, elevated concentrations of OH were observed near a window during cooking events, in addition to elevated mixing ratios of nitrous acid (HONO), VOCs, and nitrogen oxides (NOX). Particularly high concentrations were measured during the preparation of a traditional American Thanksgiving dinner, which required the use of a gas stove and oven almost continually for 6 h. A zero-dimensional chemical model underpredicted the measured OH concentrations even during periods when direct sunlight illuminated the area near the window, which increases the rate of OH production by photolysis of HONO. Interferences with measurements of nitrogen dioxide (NO2) and ozone (O3) suggest that unmeasured photolytic VOCs were emitted during cooking events. The addition of a VOC that photolyzes to produce peroxy radicals (RO2), similar to pyruvic acid, into the model results in better agreement with the OH measurements. These results highlight our incomplete understanding of the nature of oxidation in indoor environments.

Intercomparison of OH radical measurement in a complex atmosphere in Chengdu, China.

Atmospheric oxidation is a driving force of complex air pollution, and accurate hydroxyl radical (OH) measurement is helpful in investigating the radical-cored photooxidation mechanism in the troposphere. A self-developed laser-induced fluorescence instrument by the Anhui Institute of Optics Fine Mechanics, Chinese Academy of Sciences (AIOFM-LIF), was able to measure OH concentration with high sensitivity and good time resolution, and a detection limit of 1.7 × 105 cm-3 (1σ, 30 s). A long-period, multi-level intercomparison of hydroxyl radical (OH) measurements between AIOFM-LIF and PKU-LIF (the Peking University laser-induced fluorescence system) was conducted in Chengdu, China. The measurement between two instruments was in excellent agreement in the 5-min time resolution. Linear regression analysis reported a linear slope of 0.96 with a 0.68 × 106 cm-3 offset, and the correlation coefficient R2 was 0.85. The overall linearity with only a slight offset indicated a negligible influence on OH measurement. No noticeable artifacts from ozonolysis were observed under the condition of high ozone and ozonolysis-related compound concentrations. In addition to the subtraction of background signal through wavelength modulation, the dynamic correction on ozone photolysis interference ensured high intercomparison quality in both relatively constant and rapidly varying periods. Based on the reliability of OHAIOFM and OHPKU, comparisons under different oxidation-related species (NOx, VOCs, O3, PM2.5) levels and typical scenarios (rich-BVOC and high-reactivity) were carried out to evaluate the performance under complex atmospheres. A slightly higher drift was observed in a certain scenario, but the general data variability due to environmental changes did not affect the measurement accuracy. The intercomparison demonstrated that both systems are able to achieve reliable OH data under typical conditions of complex atmospheric pollution in China. Additional improvements are necessary for future intercomparisons in order to enhance the confidence in OH detection accuracy.

Direct Measurements of Isoprene Autoxidation: Pinpointing Atmospheric Oxidation in Tropical Forests.

2-Methyl-1,3-butadiene (isoprene), released from biogenic sources, accounts for approximately a third of hydrocarbon emissions and is mainly removed by hydroxyl radicals, OH, the primary initiator of atmospheric oxidation. In situ measurements in clean tropical forests (high isoprene and low NOx) have measured OH concentrations up to an order of magnitude higher than model predictions, which impacts our understanding of global oxidation. In this study, direct, laser flash photolysis, laser-induced fluorescence measurements at elevated temperatures have observed OH recycling in the presence of isoprene and oxygen under conditions where interference from secondary or heterogeneous chemistry is minimal. Our results provide the first direct, time-resolved, experimental validation of the theory-based Leuven Isoprene Mechanism (LIM1), based on isomerization of isoprene-RO2 radicals and OH regeneration, that partially accounts for model:measurement divergence in OH. While our data can be fit with only minor alterations in important LIM1 parameters, and the overall rate of product formation is similar to LIM1, there are differences with the recent experimental study by Teng et al. J. Am. Chem. Soc.2017, 139, 5367–5377. In addition, our study indicates that the dihydroperoxide products are significantly enhanced over previous estimates. Dihydroperoxides are chemical and photochemical sources of OH, and the implications of enhanced hydroperoxide formation on the agreement between models and observations in tropical forests are examined.

Photooxidation of pinonaldehyde at ambient conditions investigated in the atmospheric simulation chamber SAPHIR

Abstract. The photooxidation of pinonaldehyde, one product of the α-pinene degradation, was investigated in the atmospheric simulation chamber SAPHIR under natural sunlight at low NO concentrations (<0.2 ppbv) with and without an added hydroxyl radical (OH) scavenger. With a scavenger, pinonaldehyde was exclusively removed by photolysis, whereas without a scavenger, the degradation was dominated by reaction with OH. In both cases, the observed rate of pinonaldehyde consumption was faster than predicted by an explicit chemical model, the Master Chemical Mechanism (MCM, version 3.3.1). In the case with an OH scavenger, the observed photolytic decay can be reproduced by the model if an experimentally determined photolysis frequency is used instead of the parameterization in the MCM. A good fit is obtained when the photolysis frequency is calculated from the measured solar actinic flux spectrum, absorption cross sections published by Hallquist et al. (1997), and an effective quantum yield of 0.9. The resulting photolysis frequency is 3.5 times faster than the parameterization in the MCM. When pinonaldehyde is mainly removed by reaction with OH, the observed OH and hydroperoxy radical (HO2) concentrations are underestimated in the model by a factor of 2. Using measured HO2 as a model constraint brings modeled and measured OH concentrations into agreement. This suggests that the chemical mechanism includes all relevant OH-producing reactions but is missing a source for HO2. The missing HO2 source strength of (0.8 to 1.5) ppbv h−1 is similar to the rate of the pinonaldehyde consumption of up to 2.5 ppbv h−1. When the model is constrained by HO2 concentrations and the experimentally derived photolysis frequency, the pinonaldehyde decay is well represented. The photolysis of pinonaldehyde yields 0.18 ± 0.20 formaldehyde molecules at NO concentrations of less than 200 pptv, but no significant acetone formation is observed. When pinonaldehyde is also oxidized by OH under low NO conditions (maximum 80 pptv), yields of acetone and formaldehyde increase over the course of the experiment from 0.2 to 0.3 and from 0.15 to 0.45, respectively. Fantechi et al. (2002) proposed a degradation mechanism based on quantum-chemical calculations, which is considerably more complex than the MCM scheme and contains additional reaction pathways and products. Implementing these modifications results in a closure of the model–measurement discrepancy for the products acetone and formaldehyde, when pinonaldehyde is degraded only by photolysis. In contrast, the underprediction of formed acetone and formaldehyde is worsened compared to model results by the MCM, when pinonaldehyde is mainly degraded in the reaction with OH. This shows that the current mechanisms lack acetone and formaldehyde sources for low NO conditions like in these experiments. Implementing the modifications suggested by Fantechi et al. (2002) does not improve the model–measurement agreement of OH and HO2.

E-peroxone process for the treatment of laundry wastewater: A case study

The treatment of laundry wastewater by ozonation, electro-oxidation (EOX), electro-oxidation with oxygen sparging (EOX with O2 sparging) and the combined electro-peroxone (E-peroxone) process was investigated. E-peroxone process is based on the production of H2O2 electrochemically from O2 in sparged ozone generator effluent (O2 and O3 gas mixture) using carbon-polytetrafluorethylene (carbon-PTFE) cathodes. The electro-generated H2O2 then reacts with sparged O3 to produce OH. The concentration of H2O2 and OH was determined as ∼10gL1− and 0.1567μM in the E-peroxone process, respectively. While no OH was produced in EOX, the measured OH concentration was 0.1872μM in the ozonation process, which is greater than E-peroxone. All advanced processes adopted in this study effectively removed turbidity. Although, E-peroxone was not highly effective in eliminating chemical oxygen demand (COD) from laundry wastewater, it removed almost 77% methylene blue active substance (MBAS), whereas EOX and ozonation processes removed 86% MBAS. Besides, anion concentration increased dramatically during E-peroxone treatment. This suggests that E-peroxone is insufficient to remove inorganics. Regarding the toxicity analysis, the lowest toxicity was observed in E-peroxone process as the inhibition rate was reduced to 22.45% from 80.64%. Moreover, specific energy consumption (SEC) values were calculated as 0.003, 0.079 and 0.067kWhkg−1 for EOX, ozonation and E-peroxone, respectively. Hence, E-peroxone was found to be more cost-effective than ozonation in this case. However, EOX was found to be the most cost-effective process for laundry wastewater treatment.

Numerical and Experimental Studies on a Syngas-Fired Ultra Low NOx Combustor

Simulations and exhaust measurements of temperature and pollutants in a syngas-fired model trapped vortex combustor for stationary power generation applications are reported. Numerical simulations employing Reynolds-averaged Navier–Stokes (RANS) and large eddy simulations (LES) with presumed probability distribution function (PPDF) model were also carried out. Mixture fraction profiles in the trapped vortex combustor (TVC) cavity for nonreacting conditions show that LES simulations are able to capture the mean mixing field better than the RANS-based approach. This is attributed to the prediction of the jet decay rate and is reflected on the mean velocity magnitude fields, which reinforce this observation at different sections in the cavity. Both RANS and LES simulations show close agreement with the experimentally measured OH concentration; however, the RANS approach does not perform satisfactorily in capturing the trend of velocity magnitude. LES simulations satisfactorily capture the trend observed in exhaust measurements which is primarily attributed to the flame stabilization mechanism. In the exhaust measurements, mixing enhancement struts were employed, and their effect was evaluated. The exhaust temperature pattern factor was found to be poor for baseline cases, but improved with the introduction of struts. NO emissions were steadily below 3 ppm across various flow conditions, whereas CO emissions tended to increase with increasing momentum flux ratios (MFRs) and mainstream fuel addition. Combustion efficiencies ∼96% were observed for all conditions. The performance characteristics were found to be favorable at higher MFRs with low pattern factors and high combustion efficiencies.

OH reactivity at a rural site (Wangdu) in the North China Plain: contributions from OH reactants and experimental OH budget

Abstract. In 2014, a large, comprehensive field campaign was conducted in the densely populated North China Plain. The measurement site was located in a botanic garden close to the small town Wangdu, without major industry but influenced by regional transportation of air pollution. The loss rate coefficient of atmospheric hydroxyl radicals (OH) was quantified by direct measurements of the OH reactivity. Values ranged between 10 and 20 s−1 for most of the daytime. Highest values were reached in the late night with maximum values of around 40 s−1. OH reactants mainly originated from anthropogenic activities as indicated (1) by a good correlation between measured OH reactivity and carbon monoxide (linear correlation coefficient R2 = 0.33) and (2) by a high contribution of nitrogen oxide species to the OH reactivity (up to 30 % in the morning). Total OH reactivity was measured by a laser flash photolysis–laser-induced fluorescence instrument (LP-LIF). Measured values can be explained well by measured trace gas concentrations including organic compounds, oxygenated organic compounds, CO and nitrogen oxides. Significant, unexplained OH reactivity was only observed during nights, when biomass burning of agricultural waste occurred on surrounding fields. OH reactivity measurements also allow investigating the chemical OH budget. During this campaign, the OH destruction rate calculated from measured OH reactivity and measured OH concentration was balanced by the sum of OH production from ozone and nitrous acid photolysis and OH regeneration from hydroperoxy radicals within the uncertainty of measurements. However, a tendency for higher OH destruction compared to OH production at lower concentrations of nitric oxide is also observed, consistent with previous findings in field campaigns in China.

Radical chemistry at a rural site (Wangdu) in the North China Plain: observation and model calculations of OH, HO<sub>2</sub> and RO<sub>2</sub> radicals

Abstract. A comprehensive field campaign was carried out in summer 2014 in Wangdu, located in the North China Plain. A month of continuous OH, HO2 and RO2 measurements was achieved. Observations of radicals by the laser-induced fluorescence (LIF) technique revealed daily maximum concentrations between (5–15) × 106 cm−3, (3–14) × 108 cm−3 and (3–15) × 108 cm−3 for OH, HO2 and RO2, respectively. Measured OH reactivities (inverse OH lifetime) were 10 to 20 s−1 during daytime. The chemical box model RACM 2, including the Leuven isoprene mechanism (LIM), was used to interpret the observed radical concentrations. As in previous field campaigns in China, modeled and measured OH concentrations agree for NO mixing ratios higher than 1 ppbv, but systematic discrepancies are observed in the afternoon for NO mixing ratios of less than 300 pptv (the model–measurement ratio is between 1.4 and 2 in this case). If additional OH recycling equivalent to 100 pptv NO is assumed, the model is capable of reproducing the observed OH, HO2 and RO2 concentrations for conditions of high volatile organic compound (VOC) and low NOx concentrations. For HO2, good agreement is found between modeled and observed concentrations during day and night. In the case of RO2, the agreement between model calculations and measurements is good in the late afternoon when NO concentrations are below 0.3 ppbv. A significant model underprediction of RO2 by a factor of 3 to 5 is found in the morning at NO concentrations higher than 1 ppbv, which can be explained by a missing RO2 source of 2 ppbv h−1. As a consequence, the model underpredicts the photochemical net ozone production by 20 ppbv per day, which is a significant portion of the daily integrated ozone production (110 ppbv) derived from the measured HO2 and RO2. The additional RO2 production from the photolysis of ClNO2 and missing reactivity can explain about 10 % and 20 % of the discrepancy, respectively. The underprediction of the photochemical ozone production at high NOx found in this study is consistent with the results from other field campaigns in urban environments, which underlines the need for better understanding of the peroxy radical chemistry for high NOx conditions.

Investigation of potential interferences in the detection of atmospheric RO<sub><i>x</i></sub> radicals by laser-induced fluorescence under dark conditions

Abstract. Direct detection of highly reactive, atmospheric hydroxyl radicals (OH) is widely accomplished by laser-induced fluorescence (LIF) instruments. The technique is also suitable for the indirect measurement of HO2 and RO2 peroxy radicals by chemical conversion to OH. It requires sampling of ambient air into a low-pressure cell, where OH fluorescence is detected after excitation by 308 nm laser radiation. Although the residence time of air inside the fluorescence cell is typically only on the order of milliseconds, there is potential that additional OH is internally produced, which would artificially increase the measured OH concentration. Here, we present experimental studies investigating potential interferences in the detection of OH and peroxy radicals for the LIF instruments of Forschungszentrum Jülich for nighttime conditions. For laboratory experiments, the inlet of the instrument was over flowed by excess synthetic air containing one or more reactants. In order to distinguish between OH produced by reactions upstream of the inlet and artificial signals produced inside the instrument, a chemical titration for OH was applied. Additional experiments were performed in the simulation chamber SAPHIR where simultaneous measurements by an open-path differential optical absorption spectrometer (DOAS) served as reference for OH to quantify potential artifacts in the LIF instrument. Experiments included the investigation of potential interferences related to the nitrate radical (NO3, N2O5), related to the ozonolysis of alkenes (ethene, propene, 1-butene, 2,3-dimethyl-2-butene, α-pinene, limonene, isoprene), and the laser photolysis of acetone. Experiments studying the laser photolysis of acetone yield OH signals in the fluorescence cell, which are equivalent to 0.05 × 106 cm−3 OH for a mixing ratio of 5 ppbv acetone. Under most atmospheric conditions, this interference is negligible. No significant interferences were found for atmospheric concentrations of reactants during ozonolysis experiments. Only for propene, α-pinene, limonene, and isoprene at reactant concentrations, which are orders of magnitude higher than in the atmosphere, could artificial OH be detected. The value of the interference depends on the turnover rate of the ozonolysis reaction. For example, an apparent OH concentration of approximately 1 × 106 cm−3 is observed when 5.8 ppbv limonene reacts with 600 ppbv ozone. Experiments with the nitrate radical NO3 reveal a small interference signal in the OH, HO2, and RO2 detection. Dependencies on experimental parameters point to artificial OH formation by surface reactions at the chamber walls or in molecular clusters in the gas expansion. The signal scales with the presence of NO3 giving equivalent radical concentrations of 1.1 × 105 cm−3 OH, 1 × 107 cm−3 HO2, and 1.7 × 107 cm−3 RO2 per 10 pptv NO3.

OH regeneration from methacrolein oxidation investigated in the atmosphere simulation chamber SAPHIR

Abstract. Hydroxyl radicals (OH) are the most important reagent for the oxidation of trace gases in the atmosphere. OH concentrations measured during recent field campaigns in isoprene-rich environments were unexpectedly large. A number of studies showed that unimolecular reactions of organic peroxy radicals (RO2) formed in the initial reaction step of isoprene with OH play an important role for the OH budget in the atmosphere at low mixing ratios of nitrogen monoxide (NO) of less than 100 pptv. It has also been suggested that similar reactions potentially play an important role for RO2 from other compounds. Here, we investigate the oxidation of methacrolein (MACR), one major oxidation product of isoprene, by OH in experiments in the simulation chamber SAPHIR under controlled atmospheric conditions. The experiments show that measured OH concentrations are approximately 50% larger than calculated by the Master Chemical Mechanism (MCM) for conditions of the experiments (NO mixing ratio of 90 pptv). The analysis of the OH budget reveals an OH source that is not accounted for in MCM, which is correlated with the production rate of RO2 radicals from MACR. In order to balance the measured OH destruction rate, 0.77 OH radicals (1σ error: ± 0.31) need to be additionally reformed from each reaction of OH with MACR. The strong correlation of the missing OH source with the production of RO2 radicals is consistent with the concept of OH formation from unimolecular isomerization and decomposition reactions of RO2. The comparison of observations with model calculations gives a lower limit of 0.03 s−1 for the reaction rate constant if the OH source is attributed to an isomerization reaction of MACR-1-OH-2-OO and MACR-2-OH-2-OO formed in the MACR + OH reaction as suggested in the literature (Crounse et al., 2012). This fast isomerization reaction would be a competitor to the reaction of this RO2 species with a minimum of 150 pptv NO. The isomerization reaction would be the dominant reaction pathway for this specific RO2 radical in forested regions, where NO mixing ratios are typically much smaller.

OH and HO<sub>2</sub> radical chemistry during PROPHET 2008 and CABINEX 2009 – Part 1: Measurements and model comparison

Abstract. Hydroxyl (OH) and hydroperoxyl (HO2) radicals are key species driving the oxidation of volatile organic compounds that can lead to the production of ozone and secondary organic aerosols. Previous measurements of these radicals in forest environments with high isoprene, low NOx conditions have shown serious discrepancies with modeled concentrations, bringing into question the current understanding of isoprene oxidation chemistry in these environments. During the summers of 2008 and 2009, OH and peroxy radical concentrations were measured using a laser-induced fluorescence instrument as part of the PROPHET (Program for Research on Oxidants: PHotochemistry, Emissions, and Transport) and CABINEX (Community Atmosphere-Biosphere INteractions EXperiment) campaigns at a forested site in northern Michigan. Supporting measurements of photolysis rates, volatile organic compounds, NOx (NO + NO2 and other inorganic species were used to constrain a zero-dimensional box model based on the Regional Atmospheric Chemistry Mechanism, modified to include the Mainz Isoprene Mechanism (RACM-MIM). The CABINEX model OH predictions were in good agreement with the measured OH concentrations, with an observed-to-modeled ratio near one (0.70 ± 0.31) for isoprene mixing ratios between 1–2 ppb on average. The measured peroxy radical concentrations, reflecting the sum of HO2 and isoprene-based peroxy radicals, were generally lower than predicted by the box model in both years.

Hydroxyl in the stratosphere and mesosphere – Part 1: Diurnal variability

Abstract. Diurnal variations in hydroxyl (OH) in the stratosphere and mesosphere are analyzed using measurements from the Aura Microwave Limb Sounder (MLS). The primary driver for OH diurnal variations is the ultraviolet actinic flux that initiates the photochemical production of reactive hydrogen species. The magnitude of this flux is governed largely by changes in solar zenith angle (SZA) throughout the day, and OH diurnal variations are well approximated by an exponential function of the secant of SZA. Measured OH concentrations are fit to a function of the form exp[−βsec(SZA)], where the parameter β is a function of altitude. We examine the magnitude of β and show that it is related to the optical depths of ultraviolet absorption by ozone and molecular oxygen. Values of β from SLIMCAT model simulations show the same vertical structure as those from MLS and the average level of agreement between model and measurements is 6%. The vertical profile of β from MLS can be represented by a simple analytic formulation involving the ozone and water vapor photodissociation rates. This formulation is used to infer the altitude dependence of the primary production mechanisms for OH: the reaction of excited-state atomic oxygen with water vapor versus the direct photodissociation of water vapor.

Modelling trends in OH radical concentrations using generalized additive models

Abstract. During the TORCH campaign a zero dimensional box model based on the Master Chemical Mechanism was used to model concentrations of OH radicals. The model provided a close overall fit to measured concentrations but with some significant deviations. In this research, an approach was established for applying Generalized Additive Models (GAM) to atmospheric concentration data. Two GAM models were fitted to OH radical concentrations using TORCH data, the first using measured OH data and the second using MCM model results. GAM models with five smooth functions provided a close fit to the data with 78% of the deviance explained for measured OH and 83% for modelled OH. The GAM model for measured OH produced substantially better predictions of OH concentrations than the original MCM model results. The diurnal profile of OH concentration was reproduced and the predicted mean diurnal OH concentration was only 0.2% less than the measured concentration compared to 16.3% over-estimation by the MCM model. Photolysis reactions were identified as most important in explaining concentrations of OH. The GAM models combined both primary and secondary pollutants and also anthropogenic and biogenic species to explain changes in OH concentrations. Differences identified in the dependencies of modelled and measured OH concentrations, particularly for aromatic and biogenic species, may help to understand why the MCM model predictions sometimes disagree with measurements of atmospheric species.

ATMOSPHERIC FIELD MEASUREMENTS OF THE HYDROXYL RADICAL USING LASER-INDUCED FLUORESCENCE SPECTROSCOPY

The hydroxyl radical, OH, is the most important cleansing agent in the Earth's atmosphere, removing the majority of trace gases by oxidation, including greenhouse gases and CFC replacements. It is intimately involved in the chemistry that generates photochemical smog, which includes many substances harmful to health, such as ozone and particulate matter. In this review, the technique of laser-induced fluorescence for the detection of OH in the atmosphere is described, using as an example the fluorescence assay by gas expansion (FAGE) instrument developed at the University of Leeds. The comparison of measured OH concentrations at a given field site with those calculated by an atmospheric model, which is a mathematical representation of the underlying chemistry, provides one of the best methods to test whether the key chemical and physical processes are understood. Examples are given for field measurements made in clean and polluted environments.

Urban Atmospheric Chemistry During the PUMA Campaign 1: Comparison of Modelled OH and HO2 Concentrations with Measurements

Photochemical box modelling was undertaken to investigate OH and HO2 radical chemistry during summer and winter field campaigns in the urban city-centre of Birmingham in the UK. The model employed the most recent version of the Master Chemical Mechanism (v3.1) and was constrained to 15-minute average measurements of long-lived species determined in situ at the site. The model was used to predict OH and HO2 concentrations for comparison with measurements made by the fluorescence assay by gas expansion technique. Whilst there was generally good agreement between the modelled and measured OH concentrations, particularly during summer, there was sometimes a significant model under-prediction during daylight hours, which significantly skews the overall model: measured agreement. There were less measured data available for HO2, but the agreement between model and measurement for the days where measurements existed were less good than for OH, with one or two exceptions. The modelled:measured ratios between the hours of 11:00–15:00 h for OH were 0.58 and 0.50 for summer and winter respectively. For HO2, the same ratios were 0.56 in the summer and 0.49 in the winter. Sensitivity studies were conducted to attempt to understand the model-measurement discrepancy. The predicted radical concentrations were particularly sensitive to changes in NOX concentrations. Constraining the model to the observed HO2 concentrations made the OH predictions worse. These results highlight the fact that there are many complexities in urban areas and that more highly-instrumented campaigns are required in the future to further our understanding.

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

High-Temperature Measurements of the Reactions of OH with Toluene and Acetone

The reaction of hydroxyl [OH] radicals with toluene [C6H5CH3] was studied at temperatures between 911 and 1389 K behind reflected shock waves at pressures of approximately 2.25 atm. OH radicals were generated by rapid thermal decomposition of shock-heated tert-butyl hydroperoxide [(CH3)3-CO-OH], and monitored by narrow-line width ring dye laser absorption of the well-characterized R1(5) line of the OH A-X (0,0) band near 306.7 nm. OH time histories were modeled by using a comprehensive toluene oxidation mechanism. Rate constants for the reaction of C6H5CH3 with OH were extracted by matching modeled and measured OH concentration time histories in the reflected shock region. Detailed error analyses yielded an uncertainty estimate of +/-30% at 1115 K for the rate coefficient of this reaction. The current high-temperature data were fit with the lower temperature measurements of Tully et al. [J. Phys. Chem. 1981, 85, 2262-2269] to the following two-parameter form, applicable over 570-1389 K: k3 = (1.62 x 10(13)) exp(-1394/T [K]) [cm3 mol(-1) s(-1)]. The reaction between OH radicals and acetone [CH3COCH3] was one of the secondary reactions encountered in the toluene + OH experiments. Direct high-temperature measurements of this reaction were carried out at temperatures ranging from 982 to 1300 K in reflected shock wave experiments at an average total pressure of 1.65 atm. Uncertainty limits were estimated to be +/-25% at 1159 K. A two-parameter fit of the current data yields the following rate expression: k6 = (2.95 x 10(13)) exp(-2297/T [K]) [cm3 mol(-1) s(-1)].

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.

Evaluation of pulse detonation engine modeling using laser-based temperature and OH concentration measurements

Two novel, laser-based sensors employing ultraviolet (UV) wavelengths are developed and applied to measure time-resolved temperature and OH concentration in a pulse detonation tube. These results, along with pressure data, are employed to evaluate two computational simulations utilizing different chemistry and heat transfer models to predict pulse detonation engine (PDE) flowfields. The first sensor applies 266 and 306 nm UV laser absorption to infer temperature from 2000 to 4000 K because of broadband CO 2 absorption. These results represent the first thermometry based on line-of-sight, cw UV laser absorption by CO 2. The second sensor utilizes a single 306 nm UV laser to probe an individual OH absorption feature. Time-resolved OH concentration is inferred from the measured absorption, temperature, and pressure. These two sensors provide microsecond time-resolved measurements, over a dynamic range of temperatures and pressures (2000–4000 K and 0.5–30 atm), of two important parameters needed for evaluation of PDE computational models. The first computational model evaluated utilizes a frozen gas composition assumption; the second model incorporates finite-rate chemistry and includes losses due to heat transfer and friction. The results show that the frozen gas composition simulation can successfully predict temperature and pressure profiles, although the agreement is artificial in that inclusion of heat transfer effects would negate this agreement. The simulation including finite-rate chemistry and no heat transfer overpredicts the measured temperature and OH concentration. However, with the proper inclusion of losses due to heat transfer, the finite-rate chemistry code accurately predicts all three measured parameters. We conclude that both finite-rate chemistry and heat transfer are important for correct modeling of PDE flowfields.

Hydroxyl radical concentration measurements near the deposition substrate in low-pressure diamond-forming flames

OH radical profiles were measured in the near-deposition-surface region in low-pressure, stagnation-flow diamond-forming flames using laser-induced fluorescence (LIF). The objective of these measurements was to explore the chemistry of the diamond chemical-vapor deposition (CVD) process by resolving the OH profile near the deposition substrate. Detailed OH LIF measurements were performed in stagnation-flow diamond-forming C 2H 2/O 2 flames with equivalence ratios of 1.80, 2.10, and 2.32. The flame with an equivalence ratio of 1.80 exhibited no diamond film growth, while the flame with an equivalence ratio of 2.32 exhibited significant diamond film growth. The LIF measurements were performed in the linear LIF regime and the laser frequency was scanned across the spectral profile of the P 1(3) line in the (1,0) band of the A 2 Σ +– X 2 Π electronic transition at each spatial location. In earlier H 2 CARS measurements, the temperature gradients near the deposition substrate were resolved and good agreement between the measured temperature profiles and the numerical modeling results was demonstrated. The measured LIF profiles were corrected for electronic quenching and the variation of the Boltzmann fraction with temperature. Major species profiles were calculated using the results of the numerical flame code. The laser beam spatial profile was accounted for by convolving the theoretical OH profiles from the numerical model with the measured laser beam profile. The experimental OH profiles for all three cases are compared with theoretical results calculated using a stagnation-flame model that includes the diamond-formation surface chemistry. The measured OH concentrations near the deposition surface are substantially lower than theoretical results from a flame model that does not include the surface chemistry, but somewhat higher than for the model that does include the diamond-formation surface chemistry, especially for the flames with equivalence ratios of 1.80 and 2.10. The measured OH profile for the flame with an equivalence ratio of 2.32 is in good agreement with the profile calculated using a theoretical model with diamond-formation surface chemistry.