			Home About us Contact

OH Radicals (oh + radical)

Distribution by Scientific Domains

Chemistry	81%
Life Sciences	9%
3 Other Domains	10%

Distribution within Chemistry

Computational Chemistry & Molecular Modeling	7%

Selected Abstracts

Photoinduced Oxidation Reaction of Benzotrifluoride with OH Radical by the Laser Flash Method

CHINESE JOURNAL OF CHEMISTRY, Issue 1 2008
Ren-Xi ZHANG
Abstract The optical transient and kinetics characterizations of the transients formed in the reaction of OH with benzotrifluoride (BTF) were performed by a laser flash photolysis technique. The results indicated that the formation of ,-type adduct of C6H5(OH)CF3 was the major reaction channel, and the ,-type adduct of C6H5CF3OH formation was an additional minor process in the oxidation reaction of BTF attacked by OH radicals yielded from the photolysis of H2O2. Addition of OH to the CF3 group led to the fluoride ion elimination to yield ,,, -difluorophenylcarbinol (C6H5CF2OH). Trifluoromethylphenol (HOC6H4CF3) of meta -, para - and ortho -substituted isomers resulted from the addition of OH to the BTF aromatic ring. [source]

Use of a bench-top photochemical reactor and solid-phase microextraction to measure semivolatile organic compound-hydroxyl radical rate constants

ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 7 2000
Mary Jo Bernhard
Abstract It is increasingly important to be able to measure semivolatile organic compound-hydroxyl (SOC-OH) radical rate constants and estimate semivolatile organic compounds' (SOCs) atmospheric half-lives because of potential for atmospheric long-range transport. We have used a bench-top photochemical reactor, along with solid-phase microextraction (SPME) and ethyl nitrite, to successfully measure the rate constants of naphthalene, linalool, biphenyl, and phenanthrene with hydroxyl (OH) radical. Biphenyl and phenanthrene underwent wall loss in the reactor. The wall loss rates were determined and were used to correct the measured gas-phase rate constants. The reaction rate constants for naphthalene, linalool, biphenyl, and phenanthrene with OH radical, in our bench-top system at 295 ± 3 K, were determined to be 2.73 ± 0.37 × 10,11, 1.93 ± 0.24 × 10,10, 7.44 ± 1.9 × 10,12, 1.73 ± 0.21 × 10,11 (cm3/molecule/s), respectively, and were in excellent agreement with previous studies and model predictions. Based on the range of experimental and predicted rate constants for these reactants and an estimated average OH concentration in the atmosphere, the atmospheric half-lives of these SOCs are significantly less than 2 d. This indicates that the global presence of these compounds in the atmosphere is primarily due to regional sources and not to atmospheric long-range transport. This study shows that bench-top reactors, combined with corrections for reactant wall loss and simplified analytical tools (such as solid-phase microextraction), can be used to measure SOC-OH rate constants. [source]

Kinetic and product study of the gas-phase reaction of sabinaketone with OH radical

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 7 2007
Nathalie Carrasco
Sabinaketone is one major photooxidation product of sabinene, an important biogenic volatile organic compound. This article provides the first product study and the second rate constant determination of its reaction with OH radicals. Experiments were investigated under controlled conditions for pressure and temperature in the LISA indoor simulation chamber using FTIR spectrometry. Kinetic study was carried out at 295 ± 2 K and atmospheric pressure using the relative rate technique with isoprene as the reference compound. The rate constant was found to be ksabinaketone + OH = (7.1 ± 1.0) × 10,12 molecule,1 cm3 s,1. Acetone and formaldehyde were detected as products of the reaction with the respective yields of Racetone = 0.9 ± 0.2 and RHCHO = 1.2 ± 0.3. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 415,421, 2007 [source]

Ab initio study of the OH + CH2O reaction: The effect of the OH··OCH2 complex on the H-abstraction kinetics

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 5 2006
Shucheng Xu
Kinetics for the reaction of OH radical with CH2O has been studied by single-point calculations at the CCSD(T)/6-311+G(3df, 2p) level based on the geometries optimized at the B3LYP/6-311+G(3df, 2p) and CCSD/6-311++G(d,p) levels. The rate constant for the reaction has been computed in the temperature range 200,3000 K by variational transition state theory including the significant effect of the multiple reflections above the OH··OCH2 complex. The predicted results can be represented by the expressions k1 = 2.45 × 10 -21T2.98 exp (1750/T) cm3 mol,1 s,1 (200,400 K) and 3.22 × 10 -18T2.11 exp(849/T) cm3 mol,1 s,1 (400,3000 K) for the H-abstraction process and k2 = 1.05 × 10 -17T1.63 exp(,2156/T) cm3 mol,1 s,1 in the temperature range of 200,3000 K for the HO-addition process producing the OCH2OH radical. The predicted total rate constants (k1 + k2) can reproduce closely the recommended kinetic data for OH + CH2O over the entire range of temperature studied. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 322,326, 2006 [source]

Rate coefficients for the reaction of OH with OClO between 242 and 392 K,

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 4 2006
Tomasz Gierczak
Rate coefficients are reported for the gas phase reaction of OH with OClO over the temperature range 242,392 K at 25, 50, and 100 Torr (He). Kinetic measurements were made using pulsed laser photolysis with laser induced fluorescence detection of the OH radical. The measured rate coefficients were independent of pressure and are well represented by k1(T) = (1.43,±,0.3),×,10,12 exp(597,±,36/T) cm3 molecule,1 s,1 (k1(298 K) = 1.06,×,10,11 cm3 molecule,1 s,1). The quoted uncertainties are 2, (95% confidence level) and include estimated systematic errors. Discrepancies with the previous OH + OClO rate coefficient measurement by Poulet et al. (Int J Chem Kinet 1986, 18, 847,859) are discussed. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 234,241, 2006 [source]

Measurements of the kinetics of the OH + ,-pinene and OH + ,-pinene reactions at low pressure

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 5 2002
B. Chuong
The rate constants for the OH + ,-pinene and OH + ,-pinene reactions have been measured in 5 Torr of He using discharge-flow systems coupled with resonance fluorescence and laser-induced fluorescence detection of the OH radical. At room temperature, the measured effective bimolecular rate constant for the OH + ,-pinene reaction was (6.08 ± 0.24) × 10,11 cm3 molecule,1 s,1. These results are in excellent agreement with previous absolute measurements of this rate constant, but are approximately 13% greater than the value currently recommended for atmospheric modeling. The measured effective bimolecular rate constant for the OH + ,-pinene reaction at room temperature was (7.72 ± 0.44) × 10,11 cm3 molecule,1 s,1, in excellent agreement with previous measurements and current recommendations. Above 300 K, the effective bimolecular rate constants for these reactions display a negative temperature dependence suggesting that OH addition dominates the reaction mechanisms under these conditions. This negative temperature dependence is larger than that observed at higher pressures. The measured rate constants for the OH + ,-pinene and OH + ,-pinene reactions are in good agreement with established reactivity trends relating the rate constant for OH + alkene reactions with the ionization potential of the alkene when ab initio calculated energies for the highest occupied molecular orbital are used as surrogates for the ionization potentials for ,- and ,-pinene. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 300,308, 2002 [source]

Kinetics and products of the reactions of selected diols with the OH radical

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 5 2001
Heidi L. Bethel
Using a relative rate method, rate constants have been measured at 296 ± 2 K for the gas-phase reactions of OH radicals with 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, and 2-methyl-2,4-pentanediol, with rate constants (in units of 10,12 cm3 molecule,1 s,1) of 27.0 ± 5.6, 23.6 ± 6.3, 33.2 ± 6.8, and 27.7 ± 6.1, respectively, where the error limits include the estimated overall uncertainty of ±20% in the rate constant for the reference compound. Gas chromatographic analyses showed the formation of 1-hydroxy-2-butanone from 1,2-butanediol, 3-hydroxy-2-butanone from 2,3-butanediol, 1-hydroxy-3-butanone from 1,3-butanediol, and 4-hydroxy-4-methyl-2-pentanone from 2-methyl-2,4-pentanediol, with formation yields of 0.66 ± 0.11, 0.89 ± 0.09, 0.50 ± 0.09, and 0.47 ± 0.09, respectively, where the indicated errors are the estimated overall uncertainties. Pathways for the formation of these products are presented, together with a comparison of the measured and estimated rate constants and product yields. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 310,316, 2001 [source]

Ab initio investigation on the reaction path and rate for the gas-phase reaction of HO + H2O , H2O + OH

JOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 13 2003
Tadafumi Uchimaru
Abstract This article describes an ab initio investigation on the potential surfaces for one of the simplest hydrogen atom abstraction reactions, that is, HO + H2O , H2O + OH. In accord with the findings in the previously reported theoretical investigations, two types of the hydrogen-bonding complexes [HOHOH] and [H2OHO] were located on the potential energy surface. The water molecule acts as a hydrogen donor in the [HOHOH] complex, while the OH radical acts as a hydrogen donor in the [H2OHO] complex. The energy evaluations at the MP2(FC) basis set limit, as well as those through the CBS-APNO procedure, have provided estimates for enthalpies of association for these complexes at 298 K as ,2.1 , ,2.3 and ,4.1 , ,4.3 kcal/mol, respectively. The IRC calculations have suggested that the [H2OHO] complex should be located along the reaction coordinate for the hydrogen abstraction. Our best estimate for the classical barrier height for the hydrogen abstraction is 7.8 kcal/mol, which was obtained from the CBS-APNO energy evaluations. After fitting the CBS-APNO potential energy curve to a symmetrical Eckart function, the rate constants were calculated by using the transition state theory including the tunneling correction. Our estimates for the Arrhenius parameters in the temperature region from 300 to 420 K show quite reasonable agreement with the experimentally derived values. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 1538,1548, 2003 [source]

Isotope analysis of hydrocarbons: trapping, recovering and archiving hydrocarbons and halocarbons separated from ambient air

RAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 4 2005
M. Pupek
It is argued that isotope analysis of atmospheric non-methane hydrocarbons (NMHCs) and, in particular, the analysis of the deuterium/hydrogen (D/H) ratio is valuable because the dominant self-cleansing property of the troposphere is based on the OH radical which removes, e.g., CH4 and other alkanes by H-atom abstraction, which induces large kinetic isotope effects. The major obstacle in applying D/H isotope analysis to atmospheric NMHCs is not only the low abundance of D itself but, in particular, the low concentrations of NMHCs in the parts per trillion range. We show how a selection of NMHCs can be quantitatively separated from 300,L air samples together with CO2 as carrier gas matrix, by using high efficiency cryogenic traps. After diluting the extracted NMHC mixtures with hydrocarbon free air, and determining the mixing ratios, good agreement with original whole air sample analysis exists for alkanes and several halocarbons. For unsaturated hydrocarbons and some other halocarbons the extraction and recovery yield under the given conditions fell considerably, as a function of boiling point. Furthermore, the mixture of NMHCs in the CO2 matrix is proven to remain unchanged over several years when conveniently stored in glass ampoules. The ,extracts' or ,concentrates' of condensables extracted from larger air samples will enable the D/H isotope analysis of ultra trace gases in the atmosphere. Copyright © 2005 John Wiley & Sons, Ltd. [source]

High Resolution 1H NMR investigations of the oxidative consumption of salivary biomolecules by ozone: Relevance to the therapeutic applications of this agent in clinical dentistry

BIOFACTORS, Issue 1-4 2006
Martin Grootveld
Abstract High resolution proton (1H ) nuclear magnetic resonance (NMR) spectroscopy was employed to simultaneously evaluate the oxidising actions of ozone (O3) towards a wide range of salivary biomolecules in view of its applications in dental practices, which may serve as a viable and convenient means for the treatment of dental caries. Treatment of supernatants derived from unstimulated human saliva specimens (n=12) with O3 (4.48 mmol) revealed that this reactive oxygen species gave rise to the oxidative consumption of pyruvate (generating acetate and CO2 as products), lactate (to pyruvate and sequentially acetate and CO2), carbohydrates in general (a process generating formate), methionine (giving rise to its corresponding sulphoxide), and urate (to allantoin). Further, minor O3 -induced modifications included the oxidation of trimethylamine and 3-D-hydroxybutyrate, the fragmentation of salivary glycosaminoglycans to NMR-detectable saccharide fragments, and the conversion of polyunsaturated fatty acids to their ozonides. Moreover, evidence for the ability of O3 to induce the release of selected low-molecular-mass salivary biomolecules from macromolecular binding-sites was also obtained. Since many of the oxidation products detectable in O3 -treated samples are identical to those arising from the attack of ,OH radical on biofluid components, it appears that at least some of the modifications observed here are attributable to the latter oxidant (derived from O generated from the single electron reduction of O3). [source]

Atmospheric chemistry of isopropyl formate and tert -butyl formate

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 8 2010
Andre Silva Pimentel
Formates are produced in the atmosphere as a result of the oxidation of a number of species, notably dialkyl ethers and vinyl ethers. This work describes experiments to define the oxidation mechanisms of isopropyl formate, HC(O)OCH(CH3)2, and tert -butyl formate, HC(O)OC(CH3)3. Product distributions are reported from both Cl- and OH-initiated oxidation, and reaction mechanisms are proposed to account for the observed products. The proposed mechanisms include examples of the ,-ester rearrangement reaction, novel isomerization pathways, and chemically activated intermediates. The atmospheric oxidation of isopropyl formate by OH radicals gives the following products (molar yields): acetic formic anhydride (43%), acetone (43%), and HCOOH (15,20%). The OH radical initiated oxidation of tert -butyl formate gives acetone, formaldehyde, and CO2 as major products. IR absorption cross sections were derived for two acylperoxy nitrates derived from the title compounds. Rate coefficients are derived for the kinetics of the reactions of isopropyl formate with OH (2.4 ± 0.6) × 10,12, and with Cl (1.75 ± 0.35) × 10,11, and for tert -butyl formate with Cl (1.45 ± 0.30) × 10,11 cm3 molecule,1 s,1. Simple group additivity rules fail to explain the observed distribution of sites of H-atom abstraction for simple formates. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 479,498, 2010 [source]

Kinetics and mechanisms of OH-initiated oxidation of small unsaturated alcohols

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 3 2010
Kenshi Takahashi
Smog chamber relative rate techniques were used to measure rate coefficients of (5.00 ± 0.54) × 10,11, (5.87 ± 0.63) × 10,11, and (6.49 ± 0.82) × 10,11 cm3 molecule,1 s,1 in 700 Torr air at 296 ± 1 K for reactions of OH radicals with allyl alcohol, 1-buten-3-ol, and 2-methyl-3-buten-2-ol, respectively; the quoted uncertainties encompass the extremes of determinations using two different reference compounds. The OH-initiated oxidation of allyl alcohol in the presence of NOx gives glycolaldehyde in a molar yield of 0.85 ± 0.08; the quoted uncertainty is two standard deviations. Oxidation of 2-methyl-3-buten-2-ol gives acetone and glycolaldehyde in molar yields of 0.66 ± 0.06 and 0.56 ± 0.05, respectively. The reaction of OH radicals with allyl alcohol, 1-buten-3-ol, and 2-methyl-3-buten-2-ol proceeds predominately via addition to the >CCH2 double bond with most of the addition occurring to the terminal carbon. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 151,158, 2010 [source]

Kinetics of the gas-phase reactions of cyclo-CF2CFXCHXCHX , (X = H, F, Cl) with OH radicals at 253,328 K

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 8 2009
L. Chen
Rate constants were determined for the reactions of OH radicals with halogenated cyclobutanes cyclo-CF2CF2CHFCH2(k1), trans -cyclo-CF2CF2CHClCHF(k2), cyclo-CF2CFClCH2CH2(k3), trans -cyclo-CF2CFClCHClCH2(k4), and cis -cyclo-CF2CFClCHClCH2(k5) by using a relative rate method. OH radicals were prepared by photolysis of ozone at a UV wavelength (254 nm) in 200 Torr of a sample reference H2OO3O2He gas mixture in an 11.5-dm3 temperature-controlled reaction chamber. Rate constants of k1 = (5.52 ± 1.32) × 10,13 exp[,(1050 ± 70)/T], k2 = (3.37 ± 0.88) × 10,13 exp[,(850 ± 80)/T], k3 = (9.54 ± 4.34) × 10,13 exp[,(1000 ± 140)/T], k4 = (5.47 ± 0.90) × 10,13 exp[,(720 ± 50)/T], and k5 = (5.21 ± 0.88) × 10,13 exp[,(630 ± 50)/T] cm3 molecule,1 s,1 were obtained at 253,328 K. The errors reported are ± 2 standard deviations, and represent precision only. Potential systematic errors associated with uncertainties in the reference rate constants could add an additional 10%,15% uncertainty to the uncertainty of k1,k5. The reactivity trends of these OH radical reactions were analyzed by using a collision theory,based kinetic equation. The rate constants k1,k5 as well as those of related halogenated cyclobutane analogues were found to be strongly correlated with their CH bond dissociation enthalpies. We consider the dominant tropospheric loss process for the halogenated cyclobutanes studied here to be by reaction with the OH radicals, and atmospheric lifetimes of 3.2, 2.5, 1.5, 0.9, and 0.7 years are calculated for cyclo-CF2CF2CHFCH2, trans -cyclo-CF2CF2CHClCHF, cyclo-CF2CFClCH2CH2, trans -cyclo-CF2CFClCHClCH2, and cis -cyclo-CF2CFClCHClCH2, respectively, by scaling from the lifetime of CH3CCl3. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 41: 532,542, 2009 [source]

Hydroxyl radical reactions with halogenated ethanols in aqueous solution: Kinetics and thermochemistry

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 4 2008
I. Morozov
Laser flash photolysis combined with competition kinetics with SCN, as the reference substance has been used to determine the rate constants of OH radicals with three fluorinated and three chlorinated ethanols in water as a function of temperature. The following Arrhenius expressions have been obtained for the reactions of OH radicals with (1) 2-fluoroethanol, k1(T) = (5.7 ± 0.8) × 1011 exp((,2047 ± 1202)/T) M,1 s,1, (2) 2,2-difluoroethanol, k2(T) = (4.5 ± 0.5) × 109 exp((,855 ± 796)/T) M,1 s,1, (3) 2,2,2-trifluoroethanol, k3(T) = (2.0 ± 0.1) × 1011 exp((,2400 ± 790)/T) M,1 s,1, (4) 2-chloroethanol, k4(T) = (3.0 ± 0.2) × 1010 exp((,1067 ± 440)/T) M,1 s,1, (5) 2, 2-dichloroethanol, k5(T) = (2.1 ± 0.2) × 1010 exp((,1179 ± 517)/T) M,1 s,1, and (6) 2,2,2-trichloroethanol, k6(T) = (1.6 ± 0.1) × 1010 exp((,1237 ± 550)/T) M,1 s,1. All experiments were carried out at temperatures between 288 and 328 K and at pH = 5.5,6.5. This set of compounds has been chosen for a detailed study because of their possible environmental impact as alternatives to chlorofluorocarbon and hydrogen-containing chlorofluorocarbon compounds in the case of the fluorinated alcohols and due to the demonstrated toxicity when chlorinated alcohols are considered. The observed rate constants and derived activation energies of the reactions are correlated with the corresponding bond dissociation energy (BDE) and ionization potential (IP), where the BDEs and IPs of the chlorinated ethanols have been calculated using quantum mechanical calculations. The errors stated in this study are statistical errors for a confidence interval of 95%. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 174,188, 2008 [source]

Kinetic and product study of the gas-phase reaction of sabinaketone with OH radical

Rate coefficients for the gas-phase reactions of OH radicals with methylbutenols at 298 K

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 7 2004
Takashi Imamura
The relative-rate method has been used to determine the rate coefficients for the reactions of OH radicals with three C5 biogenic alcohols, 2-methyl-3-buten-2-ol (k1), 3-methyl-3-buten-1-ol (k2), and 3-methyl-2-buten-1-ol (k3), in the gas phase. OH radicals were produced by the photolysis of CH3ONO in the presence of NO. Di- n -butyl ether and propene were used as the reference compounds. The absolute rate coefficients obtained with the two reference compounds agreed well with each other. The O3 and O-atom reactions with the target alcohols were confirmed to have a negligible contribution to their total losses by using two kinds of light sources with different relative rates of CH3ONO and NO2 photolysis. The absolute rate coefficients were obtained as the weighted mean values for the two reference compound systems and were k1 = (6.6 ± 0.5) × 10,11, k2 = (9.7 ± 0.7) × 10,11, and k3 = (1.5 ± 0.1) × 10,10 cm3 molecule,1 s,1 at 298 ± 2 K and 760 torr of air. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 379,385 2004 [source]

Kinetics of the gas-phase reaction of CF3OC(O)H with OH radicals at 242,328 K

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 6 2004
L. Chen
The rate constants, k1, of the reaction of CF3OC(O)H with OH radicals were measured by using a Fourier transform infrared spectroscopic technique in an 11.5-dm3 reaction chamber at 242,328 K. OH radicals were produced by UV photolysis of an O3,H2O,He mixture at an initial pressure of 200 Torr. Ozone was continuously introduced into the reaction chamber during UV irradiation. With CF3OCH3 as a reference compound, k1 at 298 K was (1.65 ± 0.13) × 10,14 cm3 molecule,1 s,1. The temperature dependence of k1 was determined as (2.33 ± 0.42) × 10,12 exp[,(1480 ± 60)/T] cm3 molecule,1 s,1; possible systematic uncertainty could add an additional 20% to the k1 values. The atmospheric lifetime of CF3OC(O)H with respect to reaction with OH radicals was calculated to be 3.6 years. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 337,344 2004 [source]

Rate constants for the gas-phase reaction of CF3CF2CF2CF2CF2CHF2 with OH radicals at 250,430 K

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 1 2004
L. Chen
The rate constants k1 for the reaction of CF3CF2CF2CF2CF2CHF2 with OH radicals were determined by using both absolute and relative rate methods. The absolute rate constants were measured at 250,430 K using the flash photolysis,laser-induced fluorescence (FP-LIF) technique and the laser photolysis,laser-induced fluorescence (LP-LIF) technique to monitor the OH radical concentration. The relative rate constants were measured at 253,328 K in an 11.5-dm3 reaction chamber with either CHF2Cl or CH2FCF3 as a reference compound. OH radicals were produced by UV photolysis of an O3,H2O,He mixture at an initial pressure of 200 Torr. Ozone was continuously introduced into the reaction chamber during the UV irradiation. The k1 (298 K) values determined by the absolute method were (1.69 ± 0.07) × 10,15 cm3 molecule,1 s,1 (FP-LIF method) and (1.72 ± 0.07) × 10,15 cm3 molecule,1 s,1 (LP-LIF method), whereas the K1 (298 K) values determined by the relative method were (1.87 ± 0.11) × 10,15 cm3 molecule,1 s,1 (CHF2Cl reference) and (2.12 ± 0.11) × 10,15 cm3 molecule,1 s,1 (CH2FCF3 reference). These data are in agreement with each other within the estimated experimental uncertainties. The Arrhenius rate constant determined from the kinetic data was K1 = (4.71 ± 0.94) × 10,13 exp[,(1630 ± 80)/T] cm3 molecule,1 s,1. Using kinetic data for the reaction of tropospheric CH3CCl3 with OH radicals [k1 (272 K) = 6.0 × 10,15 cm3 molecule,1 s,1, tropospheric lifetime of CH3CCl3 = 6.0 years], we estimated the tropospheric lifetime of CF3CF2CF2CF2CF2CHF2 through reaction with OH radicals to be 31 years. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 36: 26,33, 2004 [source]

Importance of O(3P) atoms and OH radicals in hydrocarbon oxidation during the nonthermal plasma treatment of diesel exhaust inferred using relative-rate methods,

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 6 2003
John Hoard
The consumption of acetylene and propene during passage of simulated diesel exhaust through a nonthermal plasma at 453 K and atmospheric pressure was studied using experimental and computational techniques. Experimental observations of the relative decay rates of acetylene and propene and computer modeling of the chemical and physical processes in the plasma suggest that O(3P) atoms and, to a lesser extent, OH radicals are the dominant species responsible for initiating hydrocarbon oxidation in this system. Results are discussed in terms of the gas-phase chemistry occurring during the nonthermal plasma treatment of diesel exhaust. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 231,238, 2003 [source]

Kinetics for the gas-phase reactions of OH radicals with the hydrofluoroethers CH2FCF2OCHF2, CHF2CF2OCH2CF3, CF3CHFCF2OCH2CF3, and CF3CHFCF2OCH2CF2CHF2 at 268,308 K

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 6 2003
L. Chen
Rate constants were determined for the reactions of OH radicals with the hydrofluoroethers (HFEs) CH2FCF2OCHF2(k1), CHF2CF2OCH2CF3 (k2), CF3CHFCF2OCH2CF3(k3), and CF3CHFCF2OCH2CF2CHF2(k4) by using a relative rate method. OH radicals were prepared by photolysis of ozone at UV wavelengths (>260 nm) in 100 Torr of a HFE,reference,H2O,O3,O2,He gas mixture in a 1-m3 temperature-controlled chamber. By using CH4, CH3CCl3, CHF2Cl, and CF3CF2CF2OCH3 as the reference compounds, reaction rate constants of OH radicals of k1 = (1.68) × 10,12 exp[(,1710 ± 140)/T], k2 = (1.36) × 10,12 exp[(,1470 ± 90)/T], k3 = (1.67) × 10,12 exp[(,1560 ± 140)/T], and k4 = (2.39) × 10,12 exp[(,1560 ± 110)/T] cm3 molecule,1 s,1 were obtained at 268,308 K. The errors reported are ± 2 SD, and represent precision only. We estimate that the potential systematic errors associated with uncertainties in the reference rate constants add a further 10% uncertainty to the values of k1,k4. The results are discussed in relation to the predictions of Atkinson's structure,activity relationship model. The dominant tropospheric loss process for the HFEs studied here is considered to be by the reaction with the OH radicals, with atmospheric lifetimes of 11.5, 5.9, 6.7, and 4.7 years calculated for CH2FCF2OCHF2, CHF2CF2OCH2CF3, CF3CHFCF2OCH2CF3, and CF3CHFCF2OCH2CF2CHF2, respectively, by scaling from the lifetime of CH3CCl3. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 239,245, 2003 [source]

Kinetics of the reaction of OH radicals with acetylene in 25,8000 torr of air at 296 K

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 5 2003
M. Sørensen
Relative rate techniques were used to study the kinetics of the reaction of OH radicals with acetylene at 296 K in 25,8000 Torr of air, N2/O2, or O2 diluent. Results obtained at total pressures of 25,750 Torr were in good agreement with the literature data. At pressures >3000 Torr, our results were substantially (,35%) lower than that reported previously. The kinetic data obtained over the pressure range 25,8000 Torr are well described (within 15%) by the Troe expression using ko = (2.92 ± 0.55) × 10,30 cm6 molecule,2 s,1, k, = (9.69 ± 0.30) × 10,13 cm3 molecule,1 s,1, and Fc = 0.60. At 760 Torr total pressure, this expression gives k = 8.49 × 10,13 cm molecule,1 s,1. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 191,197, 2003 [source]

CF3CH(ONO)CF3: Synthesis, IR spectrum, and use as OH radical source for kinetic and mechanistic studies

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 4 2003
M. P. Sulbaek Andersen
The synthesis, IR spectrum, and first-principles characterization of CF3CH(ONO)CF3 as well as its use as an OH radical source in kinetic and mechanistic studies are reported. CF3CH(ONO)CF3 exists in two conformers corresponding to rotation about the RCONO bond. The more prevalent trans conformer accounts for the prominent IR absorption features at frequencies (cm,1) of 1766 (NO stretch), 1302, 1210, and 1119 (CF stretches), and 761 (ONO bend); the cis conformer contributes a number of distinct weaker features. CF3CH(ONO)CF3 was readily photolyzed using fluorescent blacklamps to generate CF3C(O)CF3 and, by implication, OH radicals in 100% yield. CF3CH(ONO)CF3 photolysis is a convenient source of OH radicals in the studies of the yields of CO, CO2, HCHO, and HC(O)OH products which can be difficult to measure using more conventional OH radical sources (e.g., CH3ONO photolysis). CF3CH(ONO)CF3 photolysis was used to measure k(OH + C2H4)/k(OH + C3H6) = 0.29 ± 0.01 and to establish upper limits of 16 and 6% for the molar yields of CO and HC(O)OH from the reaction of OH radicals with benzene in 700 Torr of air at 296 K. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 159,165, 2003 [source]

The fate of the hydroxyalkoxy radical in the OH-initiated oxidation of isoprene

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 4 2002
June E. Reitz
Rate constants for several intermediate steps in the OH-initiated oxidation of isoprene were determined using laser-photolysis/laser-induced fluorescence of OH radicals at total pressures between 3 and 4 Torr at 295 K. The rate constant for decomposition of the hydroxyalkoxy radical was determined to be (3.0 ± 0.5) × 104 s,1 in this pressure range, which is in fair agreement with previous work. The presence of a prompt alkoxy decomposition pathway was also investigated and found to contribute less than 10% to the total hydroxyalkoxy radical decomposition. The rate constant for the reaction of the hydroxyperoxy radical with NO was determined to be (2.5 ± 0.5) × 10,11 cm3 molecule,1 s,1, which is moderately higher than previously reported. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 255,261, 2002 [source]

Kinetics of the reactions of OH with 3-methyl-2-cyclohexen-1-one and 3,5,5-trimethyl-2-cyclohexen-1-one under simulated atmospheric conditions

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 1 2002
James B. McQuaid
Relative rate coefficients for the reactions of OH with 3-methyl-2-cyclohexen-1-one and 3,5,5-trimethyl-2-cyclohexen-1-one have been determined at 298 K and atmospheric pressure by the relative rate technique. OH radicals were generated by the photolysis of methyl nitrite in synthetic air mixtures containing ppm levels of nitric oxide together with the test and reference substrates. The concentrations of the test and reference substrates were followed by gas chromatography. Based on the value k(OH + cyclohexene) = (6.77 ± 1.35) × 10,11 cm3 molecule,1 s,1, rate coefficients for k(OH + 3-methyl-2-cyclohexen-1-one) = (3.1 ± 1.0) × 10,11 and k(OH + 3,5,5-trimethyl-2-cyclohexen-1-one) = (2.4 ± 0.7) × 10,11 cm3 molecule,1 s,1 were determined. To test the system we also measured k(OH + isoprene) = (1.11 ± 0.23) × 10,10 cm3 molecule,1 s,1, relative to the value k(OH + (E)-2-butene) = (6.4 ± 1.28) × 10,11 cm3 molecule,1 s,1. The results are discussed in terms of structure,activity relationships, and the reactivities of cyclic ketones formed in the photo-oxidation of monoterpene are estimated. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 34: 7,11, 2002 [source]

Kinetics and products of the reactions of selected diols with the OH radical

Numerical study on flame structure and NO formation in CH4,O2,N2 counterflow diffusion flame diluted with H2O

INTERNATIONAL JOURNAL OF ENERGY RESEARCH, Issue 14 2004
Dong-Jin Hwang
Abstract Numerical study on flame structure and NO emission behaviour has been conducted to grasp chemical effects of added H2O on either fuel- or oxidizer-side in CH4,O2,N2 counterflow diffusion flames. An artificial species, which has the same thermodynamic, transport, and radiation properties of added H2O, is introduced to feasibly isolate the chemical effects. Special concern is focused on the important role of remarkably produced OH radicals due to chemical effects of added H2O on flame structure and NO emission. The reason why the difference of behaviours between the principal chain branching reaction rate and flame temperature appear is attributed to the drastic change of reaction step (R120) from the production to the consumption of OH. It is also, however, seen that the most important contribution of produced OH due to chemical effects of added H2O is through reaction step (R127). The importantly contributing reaction steps to NO production are also examined. The production rates of thermal NO and prompt NO are suppressed by chemical effects of added H2O. The contribution of the reaction steps related to HNO intermediate species to the production of prompt NO is also stressed. Copyright © 2004 John Wiley & Sons, Ltd. [source]

Synthesis and biological evaluation of new benzo[f]furo[2,3- h]-and benzo[f]pyrano[2,3- h]coumarin derivatives. ,

JOURNAL OF HETEROCYCLIC CHEMISTRY, Issue 3 2007
Maria Tsoukka
Furocoumarins 3,5 and pyranocoumarin 7 were synthesized from the reaction of furonaphthalenediones 2,4 and pyranonaphthalenedione 6 respectively with carbethoxymethylene(triphenyl)phosphorane in refluxing DCM for 3-6 hours or under microwave irradiation in toluene for a few minutes. Compounds 3,5,7 and their precursors were tested as anti-inflammatory/antioxidant agents. They were found to compete significantly high DMSO for OH radicals, to scavenge O2, and to inhibit lipoxygenase to a high extent. [source]

CH3CH2SCH3,+,OH radicals: temperature-dependent rate coefficient and product identification under atmospheric pressure of air,

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 10 2010
Gabriela Oksdath-Mansilla
Abstract Relative rate coefficients have been determined for the gas-phase reaction of hydroxyl (OH) radicals with ethyl methyl sulfide (EMS) using isobutene as a reference compound. The experiments were performed in a 1080,L quartz glass photoreactor in the temperature range of 286,313,K at a total pressure of 760,±,10,Torr synthetic air using in situ FTIR absorption spectroscopy to monitor the concentration-time behaviors of reactants and products. OH radicals were produced by the 254,nm photolysis of hydrogen peroxide (H2O2). The kinetic data obtained were used to derive the following Arrhenius expression valid in the temperature range of 286,313,K (in units of cm3,molecule,1,s,1): The rate coefficient displays a negative temperature dependence and low pre-exponential factor which supports the existence of an addition mechanism for the reaction involving reversible OH-adduct formation. The results are compared with previous data of other sulfides from the literature and are rationalized in terms of structure,reactivity relationships. Additionally, product identification of the title reaction was performed for the first time by the FTIR technique under atmospheric conditions. Sulfur dioxide, formaldehyde, and formic acid were observed as degradation products in agreement with the two possible reaction channels (addition/abstraction). Copyright © 2010 John Wiley & Sons, Ltd. [source]

Enhanced Bactericidal Activity of Modified Titania in Sunlight against Pseudomonas aeruginosa, a Water-Borne Pathogen

PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 5 2010
S. Swetha
Photocatalyst-mediated inactivations generate reactive oxygen species and OH radicals, which induce oxidative destruction of membrane integrity, causing damage to membrane phospholipids of gram negative bacteria like Pseudomonas aeruginosa. Nanosized TiO2 was synthesized by gel to crystalline conversion and Zr-doped TiO2 was synthesized by pulverization using appropriate precursor. The doped nanocrystals retained the anatase phase with a marginal increase in crystallite size, averaging at 25 nm. SEM,EDX analysis of the doped sample depicts the substantial growth of grain size with 1.33 atomic weight % of zirconium. The created electron states in the doped sample act as charge carrier traps suppressing recombination which later detraps the same to the surface of the catalyst causing enhanced interfacial charge transfer. Zr-doped TiO2 at the molecular scale exhibits better photocatalytic activity with lower bandgap energy that can respond to visible light. The redshift caused by the dopants in absorption spectra of TiO2 facilitated the nonintrinsic sample to exhibit nearly 2-fold enhancement of photoinactivation in sunlight. Extent of photoinactivation of P. aeruginosa was observed to be complete (100%) within 150 min of sunlight exposure in the presence of modified TiO2. [source]

Effects of Athamanta turbith fruit essential oils on CCl4 -induced hepatic failure in mice and their antioxidant properties

PHYTOTHERAPY RESEARCH, Issue 5 2010

Abstract The effects of essential oils isolated from mature fruits of Athamanta turbith ssp. hungarica (Borbás) Tutin and A. turbith ssp. haynaldii (Borbás & Uechtr.) Tutin (Umbelliferae) on some liver biochemical parameters in mice intoxicated with carbon tetrachloride were investigated. Pretreatment with both essential oils extenuated the effects caused by carbon tetrachloride. In order to investigate in vitro antioxidant properties of the oils, three methods were applied: scavenging of both 2,2-diphenyl-1-picrylhydrazyl (DPPH) and OH radicals, as well as a test of inhibition of Fe2+/ascorbic-induced lipid peroxidation. Investigated essential oils exhibited modest antioxidant capacity. Therefore, their influence on biochemical parameters in intoxicated animals might be linked to the inhibition of enzymes (cytochrome P450 2E1) involved in metabolic activation of halomethanes. Copyright © 2009 John Wiley & Sons, Ltd. [source]