Of The Hydroxyl Radicals Research Articles

Excited-State Decay and Photolysis of O-Nitrophenol before Proton Transfer. I: A Theoretical Investigation in the Microsolvated Atmospheric Environment.

As a potential source of the hydroxyl (OH) radical and nitrous acid (HONO), photolysis of o-nitrophenol (ONP) is of significant interest in both experimental and theoretical studies. In the atmospheric environment, the number of water molecules surrounding ONP changes with the humidity of the air, leading to an anisotropic chemical environment. This may have an impact on the photodynamics of ONP and provide a mechanism that differs from previously reported ones in the gas phase or in solution. Herein, the high-level MS-CASPT2//CASSCF method was performed to elucidate the excited-state decay and the generation of the OH radical for ONP before proton transfer in the microsolvated surrounding. We found that the varying number of water molecules affects the ground-state structures and alters the energy levels of nπ* and ππ* at the Franck-Condon (FC) region. Nevertheless, this is not the case for the excited-state minima, which exhibit very similar adiabatic excitation properties. In addition, the presence of water molecules also significantly influences the intersection structures since hydrogen bonds will hinder or alleviate the rotation or pyramidalization of the nitro (NO2) group. This will, in turn, change the excited-state relaxation mechanism of ONP. Finally, we speculated that the OH radical might be formed in the hot ground state of ONP in the microsolvated surrounding after exploring all possible electronic states.

Excited-State Decay and Photolysis of O-Nitrophenol after Proton Transfer. II: A Theoretical Investigation in the Microsolvated Atmospheric Environment.

Changes in atmospheric humidity affect the number of water molecules surrounding o-nitrophenol (ONP), creating an anisotropic chemical environment. It, in turn, influences the photodynamic behaviors of ONP, differing from those observed in the gas phase and in solution. Recently, we explored the excited-state decay and the generation of the hydroxyl (OH) radical before proton transfer of ONP in the microsolvated environment using the MS-CASPT2//CASSCF approach. As is well known, ONP is capable of converting to its aci-nitro isomer (aciONP) via an excited-state intramolecular proton transfer (ESIPT) process. In the present work, the photoinduced dynamics of aciONP, which can lead to an OH radical and nitrous acid (HONO), was studied using the same computational model. Our calculations demonstrated that increasing the number of water molecules affects the molecular geometries, particularly the key bond lengths and dihedral angles of the HONO group, while also reducing the relative energies of minima and intersections. Moreover, we identified two distinct types of minimum structures: one that retains the intramolecular hydrogen bond and the other that breaks the hydrogen bond with the H atom flipping outward. The latter structure, compared with the former, has a different electronic-state character and facilitates intersystem crossing processes. Subsequently, two major excited-state decay paths were proposed: (PATH I) ESIPT → S1 → S1S0 → S0; (PATH II) ESIPT → S1 → S1-2 → S1T1 → T1 → S0T1 → S0. Furthermore, the T1 state has a relatively long lifetime, allowing for the formation of the OH radical and HONO, and the corresponding energy barriers decrease as the number of water molecules increases. These theoretical findings provide valuable insights into the photodynamics of aciONP in the microsolvated atmospheric environment.

Photodesorption efficiency of OH radical on the ice surface in the wavelength range from ultraviolet to visible

The photodesorption efficiencies of the hydroxyl (OH) radical from the water ice surface were measured in the range of 310–700 nm for the first time. Although isolated H2O molecules and OH radicals do not absorb visible photons, the photodesorption of OH interacting with the ice surface was found to occur by a one-photon process in the entire visible range. The photodesorption efficiency strongly depended on the wavelength, and the analyses of photodesorption cross sections indicated that only strongly bound OH radicals were desorbed at longer wavelengths, whereas both weakly and strongly bound OH radicals were desorbed at shorter wavelengths.

OH and HO<sub>2</sub> radical chemistry in a midlatitude forest: measurements and model comparisons

Abstract. Reactions of the hydroxyl (OH) and peroxy (HO2 and RO2) radicals play a central role in the chemistry of the atmosphere. In addition to controlling the lifetimes of many trace gases important to issues of global climate change, OH radical reactions initiate the oxidation of volatile organic compounds (VOCs) which can lead to the production of ozone and secondary organic aerosols in the atmosphere. Previous measurements of these radicals in forest environments characterized by high mixing ratios of isoprene and low mixing ratios of nitrogen oxides (NOx) (typically less than 1–2 ppb) have shown serious discrepancies with modeled concentrations. These results bring into question our understanding of the atmospheric chemistry of isoprene and other biogenic VOCs under low NOx conditions. During the summer of 2015, OH and HO2 radical concentrations, as well as total OH reactivity, were measured using laser-induced fluorescence–fluorescence assay by gas expansion (LIF-FAGE) techniques as part of the Indiana Radical Reactivity and Ozone productioN InterComparison (IRRONIC). This campaign took place in a forested area near Indiana University's Bloomington campus which is characterized by high mixing ratios of isoprene (average daily maximum of approximately 4 ppb at 28 ∘C) and low mixing ratios of NO (diurnal average of approximately 170 ppt). Supporting measurements of photolysis rates, VOCs, NOx, and other species were used to constrain a zero-dimensional box model based on the Regional Atmospheric Chemistry Mechanism (RACM2) and the Master Chemical Mechanism (MCM 3.2), including versions of the Leuven isoprene mechanism (LIM1) for HOx regeneration (RACM2-LIM1 and MCM 3.3.1). Using an OH chemical scavenger technique, the study revealed the presence of an interference with the LIF-FAGE measurements of OH that increased with both ambient concentrations of ozone and temperature with an average daytime maximum equivalent OH concentration of approximately 5×106 cm−3. Subtraction of the interference resulted in measured OH concentrations of approximately 4×106 cm−3 (average daytime maximum) that were in better agreement with model predictions although the models underestimated the measurements in the evening. The addition of versions of the LIM1 mechanism increased the base RACM2 and MCM 3.2 modeled OH concentrations by approximately 20 % and 13 %, respectively, with the RACM2-LIM1 mechanism providing the best agreement with the measured concentrations, predicting maximum daily OH concentrations to within 30 % of the measured concentrations. Measurements of HO2 concentrations during the campaign (approximately a 1×109 cm−3 average daytime maximum) included a fraction of isoprene-based peroxy radicals (HO2*=HO2+αRO2) and were found to agree with model predictions to within 10 %–30 %. On average, the measured reactivity was consistent with that calculated from measured OH sinks to within 20 %, with modeled oxidation products accounting for the missing reactivity, however significant missing reactivity (approximately 40 % of the total measured reactivity) was observed on some days.

Study of sterilization effects on marine Vibrio sp. using interaction of cavitation with shock wave in a narrow water chamber

Cavitation bubbles could also be called as inertial bubbles because of their oscillation due to the pressure difference between inside and outside. After the passage of an underwater shock wave, the violent collapses of the bubbles are induced and could produce stronger mechanical and biochemical actions so that the marine bacteria around them are inactivated by those productions. In the present study, cavitation inertial bubbles are observed behind multiple waves in a narrow water chamber after an electric discharge is triggered and then interacts with underwater reflected shock waves from the water chamber. The sterilization effects of only these oscillating bubbles and cavitation-shock interaction are investigated by bio-experiments of marine Vibrio sp. The results show that a high sterilization is obtained in the case of the cavitation-shock interaction. Furthermore, the chemical action of free radicals mainly contributes to inactivating the marine bacteria. The generation of the hydroxyl (OH) radicals is clarified by measuring the concentration of H2O2. Subsequently, we focus on a theoretical analysis of the generation condition of the OH radicals by a bubble dynamic model consisting of an oscillation model and an impact model. Finally, the theoretical estimation by the bubble dynamic model is discussed under the conditions of the present experiments. As a result, there is a possibility of effective sterilization by the cavitation-shock interaction without the supply of air microbubbles.

Vacuum ultraviolet photoionization cross section of the hydroxyl radical.

The absolute photoionization spectrum of the hydroxyl (OH) radical from 12.513 to 14.213 eV was measured by multiplexed photoionization mass spectrometry with time-resolved radical kinetics. Tunable vacuum ultraviolet (VUV) synchrotron radiation was generated at the Advanced Light Source. OH radicals were generated from the reaction of O(1D) + H2O in a flow reactor in He at 8 Torr. The initial O(1D) concentration, where the atom was formed by pulsed laser photolysis of ozone, was determined from the measured depletion of a known concentration of ozone. Concentrations of OH and O(3P) were obtained by fitting observed time traces with a kinetics model constructed with literature rate coefficients. The absolute cross section of OH was determined to be σ(13.436 eV) = 3.2 ± 1.0 Mb and σ(14.193 eV) = 4.7 ± 1.6 Mb relative to the known cross section for O(3P) at 14.193 eV. The absolute photoionization spectrum was obtained by recording a spectrum at a resolution of 8 meV (50 meV steps) and scaling to the single-energy cross sections. We computed the absolute VUV photoionization spectrum of OH and O(3P) using equation-of-motion coupled-cluster Dyson orbitals and a Coulomb photoelectron wave function and found good agreement with the observed absolute photoionization spectra.

Application of a novel microwave-assisted plasma ignition system in a direct injection gasoline engine

An experimental study was carried out to investigate the effect of microwave-assisted plasma ignition on the combustion and emission characteristics in a 500cm3 single cylinder direct injection gasoline engine. The microwave-assisted plasma ignition system consisted of a 2.45GHz magnetron (3kW), a waveguide, a mixer and a non-resistor spark plug. The first experiments were performed in a 1400cm3 constant volume combustion chamber (CVCC) to clarify the mechanism of combustion enhancement by microwave ejection. The combustion tests were performed using an acetylene-air mixture at a range of relative air/fuel ratios (λ) under initial ambient pressures of 0.3MPa and 0.5MPa. The microwave-assisted plasma ignition has more advanced combustion phase than the conventional spark ignition showing larger initial flame kernel size and faster flame speed. The imaging results of the hydroxyl (OH) radical in ignition and flame demonstrated the potential of a faster chemical reaction by applying microwave on combustion. The microwave-assisted plasma ignition had a higher spark intensity and larger covering area than the conventional spark plug. The distribution and intensity of OH radicals on the surface of the flame were also higher with microwave ejection. In terms of engine test, lean limit was extended up to lambda 1.55 and the fuel efficiency was improved by 6% by microwave-assisted plasma ignition. The combustion phase was advanced so the peak of in-cylinder pressure and heat release rate increased more than those of conventional spark ignition. Based on the faster combustion, the combustion stability was enhanced so the lean limit was extended to lambda of 1.57. The microwave-assisted plasma ignition system was advantageous in the reduction of carbon monoxide and unburned hydrocarbon emissions, whereas nitrogen oxide emissions increased due to the higher temperatures in the combustion chamber. The engine test results finally demonstrated that the certain level of microwave ejection energy could improve all of engine performance and emission characteristics than conventional spark ignition system.

Laser spark ignition of premixed methane-air mixtures: parameter measurements and determination of key factors for ultimate ignition results.

In this study, we present an experimental investigation of the parameters of the laser spark ignition of premixed methane-air mixtures and the determination of the key factors for the ultimate ignition result. Ignition is achieved in a mesh honeycomb burner using the 1064 nm output of a neodymium-doped yttrium aluminum garnet (Nd : YAG) laser. All pertinent laser ignition parameters, including the minimum ignition energy, the ignition time and blow out time, and the effects that the variation of experimental conditions, such as the spark energy, ignition position, equivalence ratio (ER), and flow rate, have on these parameters have been addressed systematically. To identify the key factors for the ultimate result of laser ignition, several parameters of the ignition processes are measured simultaneously, with an emphasis given to the temporal behavior of the hydroxyl (OH) radicals in relation to the data regarding the spark energy and the local ER. A clear finding of the study is that successful ignition events are always related to higher OH radical photon emissions, considered to be proportional to the concentration level of the OH radicals present, thus indicating a direct link between the OH level at early times (on a microsecond scale) and the ultimate result of laser ignition. Two-dimensional correlation plots of the spark energy, local ER, and OH radical photon count at early times with the ultimate results of laser ignition indicate that the spark energy and local ER do not play a critical role in determining the success or failure of the ignition and that the OH concentration in the early time range is the key factor in determining the final fate of laser ignition. Finally, on the basis of the results obtained here and in the existing literature, some considerations of the mechanism of laser ignition are presented.

Product Study of the OH Radical and Cl Atom Initiated Oxidation of 1,3‐Dioxane

The products of the hydroxyl (OH) radical and chlorine (Cl) atom initiated oxidation of 1,3-dioxane are determined under various reaction conditions in a 50 L teflon reaction chamber using FTIR spectroscopy for analysis. The major products detected in all experiments are (2-oxoethoxy)methyl formate, formic acid and methylene glycol diformate with average molar yields of 0.50±0.05, 0.41±0.02 and 0.03±0.01 respectively for the OH initiated oxidation in the presence of NO(x). The yields of these products do not vary significantly with O(2) partial pressure or oxidising agent (OH or Cl). However, the yield of formic acid decreased by at least a factor of two in the absence of NO(x). The results of these experiments are used to elucidate a simplified gas-phase atmospheric degradation scheme for 1,3-dioxane and also provide valuable information on the atmospheric fate of the cyclic and linear alkoxy radicals produced in these and similar reactions. The available experimental data suggests that the relative importance of the competing pathways (reaction with O(2) and ring opening by C-C or C-O bond fission) is a strong function of the ring strain in the cycloalkoxy radicals.

ChemInform Abstract: Products of the Gas-Phase Reaction of Methyl tert-Butyl Ether with the OH Radical in the Presence of NOx

The products of the reaction of the hydroxyl (OH) radical with methyl tert-butyl ether (MTBE) in NOx-air systems were identified and measured by Fourier transform infrared absorption spectroscopy and gas chromatography. The products observed, and their yields, were as follows: t-butyl formate, 76 ± 7%; formaldehyde, 37%; methyl acetate, 17 ± 2%, and acetone, 2.1 ± 0.9%, where the stated error limits represent both random (two standard deviations) and estimated systematic uncertainties. These products account for ca. 95% of the MTBE carbon reacted. Infrared absorption bands which may be due to small amounts of organic nitrate formation were observed, but organic nitrate yields could not be quantified. These data allow a chemical mechanism for the reaction of MTBE with the OH radical in the presence of NOx to be formulated.

LIF imaging of OH radicals in DC positive streamer coronas

In this study, the LIF detection of the hydroxyl (OH) radicals was performed in a nozzle-to-plane electrode system having an electrode gap of 30 mm during the steady-state positive streamer corona discharge at atmospheric pressure. For monitoring the ground-state OH radicals, OH transition [ A 2 Σ +( v′ = 1) ← X 2Π( v″ = 0)] at 282 nm was used. The time relationship between the regular streamer coronas, laser pulse, OH fluorescence and laser-induced streamer was measured. The time dependence of OH radicals between the successive streamers was measured for the evaluation of OH dynamics when the discharge was in a steady-state condition. The two-dimensional OH distribution in the DC streamer corona discharge was observed. The obtained results showed that the ground-state OH radicals were generated mainly in the filamentary part of the streamers. It was found that LIF detectable amount of ground-state OH radicals stayed in the region where streamers propagate during the steady-state DC positive streamer corona in open air.

LIF Observation of Ground-State OH Radicals in DC Nozzle-to-Plane Positive Streamer Corona

AbstractIn this study, the planar LIF detection of the hydroxyl (OH) radicals was performed in a nozzle-to-plane electrode system having an electrode gap of 30 mm during the steady-state positive streamer corona discharge at atmospheric pressure. For monitoring the ground-state OH radicals, OH transition at 282 nm was used. The two-dimensional OH distribution in the DC corona discharge in air/H

Kinetics of the gas-phase reactions of OH radicals with alkanes and cycloalkanes

Abstract. The available database concerning rate constants for gas-phase reactions of the hydroxyl (OH) radical with alkanes through early 2003 is presented over the entire temperature range for which measurements have been made (~180-2000 K). Measurements made using relative rate methods are re-evaluated using recent rate data for the reference compound (generally recommendations from this review). In general, whenever more than one study has been carried out over an overlapping temperature range, recommended rate constants or temperature-dependent rate expressions are presented. The recommended 298 K rate constants, temperature-dependent parameters, and temperature ranges over which these recommendations are applicable are listed in Table 1.

Photochemical Formation of OH Radicals in Dew Formed on the Pine Needles at Mt. Gokurakuji

Photochemical formation rates and sources of the hydroxyl (OH) radical were determined in dew water formed on the surface of Japanese red pine (Pinus densiflora) needles of declining (NO2 polluted area) and healthy pine stands at Mt. Gokurakuji located west of Hiroshima city in western Japan. The measured OH radical photoformation rates in dew water (n=10), which were normalized to the rate at midday on May 1 at 34°N, ranged from 0.67 to 5.18 µM h−1 (1M=1mol L−1). The mean value (2.69 µM h−1) was higher than that in dew water collected on a Teflon board and higher than the mean value in rain water published previously. Of the total OH radical formation rate observed in dew water on the pine needles, 16.4 % was estimated to originate from N (III) (NO2− and HNO2) and 24.6 % was estimated to originate from NO3−. There were other sources of OH radical photochemical formation in dew water on the pine needles besides photolysis of NO2− and NO3−.

Spin-trapping study on the hydroxyl radical formed from a tea catechin-Cu(II) system.

A spin-trapping method was applied to examine the formation of the hydroxyl (OH) radical from a tea catechin-Cu(II) system to elucidate a previous result that some tea catechin-Cu(II) systems induced DNA scission. Three tea catechins, (-)-epigallocatechin (EGC), (-)-epigallocatechin gallate (EGCg) and (-)-epicatechin (EC), were used. The spin-trapping agent, 5,5'-dimethyl-pyrroline-1-oxide (DMPO), was dissolved in a pH 9 phosphate buffer solution, then a catechin and Cu(II) were added in that order, and the ESR spectral change was monitored for one hour. The order of adding the catechin and Cu(II) was then reversed, and the ESR spectral change was again monitored to examine the coordinating activity of each catechin toward the Cu(II) ion and the effect on OH radical generation. The intensity changes of the spin adducts, DMPO-OH, DMPO-CH3 and DMPO-H, were analyzed, the results suggesting that the OH radical generated in the system decomposed DMPO, resulting in the formation of DMPO-CH3 and DMPO-H. The results show that EGC formed a stable complex with Cu(II) and generated the OH radical. EGCg seemed to have this activity, but the OH radical that was generated was scavenged by the gallate group existing in the complex. EC did not show strong coordinating and OH-generating activities. These characteristics of the three catechins are consistent with the results shown for DNA scission.

Rate coefficients for the gas-phase reaction of OH radicals with selected dihydroxybenzenes and benzoquinones

Rate coefficients have been determined for the gas-phase reaction of the hydroxyl (OH) radical with the aromatic dihydroxy compounds 1,2-dihydroxybenzene, 1,2-dihydroxy-3-methylbenzene and 1,2-dihydroxy-4-methylbenzene as well as the two benzoquinone derivatives 1,4-benzoquinone and methyl-1,4-benzoquinone. The measurements were performed in a large-volume photoreactor at (300 ± 5) K in 760 Torr of synthetic air using the relative kinetic technique. The rate coefficients obtained using isoprene, 1,3-butadiene, and E-2-butene as reference hydrocarbons are kOH(1,2-dihydroxybenzene) = (1.04 ± 0.21) × 10−10 cm3 s−1, kOH(1,2-dihydroxy-3-methylbenzene) = (2.05 ± 0.43) × 10−10 cm3 s−1, kOH(1,2-dihydroxy-4-methylbenzene) = (1.56 ± 0.33) × 10−10 cm3 s−1, kOH(1,4-benzoquinone) = (4.6 ± 0.9) × 10−12 cm3 s−1, kOH(methyl-1,4-benzoquinone) = (2.35 ± 0.47) × 10−11 cm3 s−1. This study represents the first determination of OH radical reaction-rate coefficients for these compounds. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 696–702, 2000

Rate coefficients for the gas‐phase reaction of OH radicals with selected dihydroxybenzenes and benzoquinones

Rate coefficients have been determined for the gas-phase reaction of the hydroxyl (OH) radical with the aromatic dihydroxy compounds 1,2-dihydroxybenzene, 1,2-dihydroxy-3-methylbenzene and 1,2-dihydroxy-4-methylbenzene as well as the two benzoquinone derivatives 1,4-benzoquinone and methyl-1,4-benzoquinone. The measurements were performed in a large-volume photoreactor at (300 ± 5) K in 760 Torr of synthetic air using the relative kinetic technique. The rate coefficients obtained using isoprene, 1,3-butadiene, and E-2-butene as reference hydrocarbons are kOH(1,2-dihydroxybenzene) = (1.04 ± 0.21) × 10−10 cm3 s−1, kOH(1,2-dihydroxy-3-methylbenzene) = (2.05 ± 0.43) × 10−10 cm3 s−1, kOH(1,2-dihydroxy-4-methylbenzene) = (1.56 ± 0.33) × 10−10 cm3 s−1, kOH(1,4-benzoquinone) = (4.6 ± 0.9) × 10−12 cm3 s−1, kOH(methyl-1,4-benzoquinone) = (2.35 ± 0.47) × 10−11 cm3 s−1. This study represents the first determination of OH radical reaction-rate coefficients for these compounds. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 696–702, 2000

Kinetics of reaction between hydroxyl radical formed by beta-rays in tritiated water and tea catechin: Application of the solid state spin trapping method

The aqueous solutions of 5,5-dimethyl-1-pyrroline N-oxide (DMPO) containing various amount of (-)-epigallocatechin gallate (EGCg) were mixed with tritiated water, then frozen and β-ray irradiatedin situ for 90 days at −80°C. ESR spectra were measured as a function of time after melting the sample at room temperature. The intensity of the hydroxyl (OH)_ radical adduct, DMPO-OH, was obtained by the extrapolation to zero time. The ratio of the reaction rate constants of the OH radical with EGCg and DMPO,kEGCg/kDMPO, was obtained kinetically. The result was compared with the case of DNA and EGCg in tritiated water, in order to make clear the mechanism of the protection of DNA from the radiation-induced scission with EGCg.

HO2/OH and RO2/HO2 ratios during the Tropospheric OH Photochemistry Experiment: Measurement and theory

Ambient concentrations of the hydroxyl (OH), hydroperoxyl (HO2), and total peroxy (ΣRO2) radicals were measured as part of the Tropospheric OH Photochemistry Experiment at Idaho Hill, Colorado, during August and September of 1993. OH radicals were measured using ion‐assisted mass spectroscopy and low‐pressure laser‐induced fluorescence (LIF) detection techniques. HO2 was measured using chemical conversion and LIF detection of OH. ΣRO2 radicals were measured using a chemical amplifier technique. The simultaneous measurements of these key species provide an opportunity to test our present understanding of the fast photochemistry of the troposphere. Measured HO2/OH ratios were typically between 15 and 80, and agreed well with predictions under conditions where NO mixing ratios were greater than 100 pptv. However, under clean conditions the measured ratio was a factor of 3–4 lower than predicted. The RO2/HO2 ratio was typically a factor of 4–15 larger than predicted by present theories of tropospheric chemistry. A steady state model was used in an attempt to analyze the discrepancies between the measured HO2/OH and RO2/HO2 ratios with present theories of hydrocarbon oxidation in the troposphere.

Implementation and initial deployment of a field instrument for measurement of OH and HO2 in the troposphere by laser-induced fluorescence

An instrument to detect atmospheric concentrations of the hydroxyl (OH) and hydroperoxyl (HO 2 ) radicals has been developed using the FAGE (fluorescence assay by gas expansion) technique. The instrument is housed in a mobile laboratory and monitors the OH radical via on-resonance laser-induced fluorescence (LIF) spectroscopy of the A 2 Σ + (v′=0)–X 2 Π i (v ″ =0) transition at ca. 308 nm. Ambient air is expanded through a 1 mm nozzle to low pressure where it is irradiated by the laser pulse at a repetition rate of 7 kHz, with the resultant fluorescence being detected by gated photon counting. HO 2 is monitored by chemical conversion to OH by the addition of NO, with subsequent detection using LIF. Following laboratory and field calibrations to characterise the instrument sensitivity, detection limits of 1.8×10 6 and 2.1×10 7 molecule cm -3 were determined for OH and HO 2 respectively, for a signal-to-noise ratio, S/N, of 1 with 150 s signal integration time. The instrument was deployed for the first time during the ACSOE field campaign at Mace Head, Eire, for which illustrative results are given.