Rate coefficients for the OH + CFH2CH2OH reaction between 238 and 355 K

The rate coefficient for the reaction OH + CFH2CH2OH --> products (k1) between 238 and 355 K was measured using the pulsed laser photolysis-laser induced fluorescence (PLP-LIF) technique to be (5.15 +/- 0.88)x 10(-12) exp[-(330 +/- 45)/T] cm3 molecule(-1) s(-1); k1(298 K)= 1.70 x 10(-12) cm3 molecule(-1) s(-1). The quoted uncertainties are 2sigma(95% confidence level) and include estimated systematic errors. The present results are discussed in relation to the measured rate coefficients for the reaction of OH with other fluorinated alcohols and those calculated using recently reported structure additivity relationships for fluorinated compounds (K. Tokuhashi, H. Nagai, A. Takahashi, M. Kaise, S. Kondo, A. Sekiya, M. Takahashi, Y. Gotoh and A. Suga, J. Phys. Chem. A, 1999, 103, 2664-2672, ). Infrared absorption cross sections for CFH2CH2OH are reported and they are used to calculate the global warming potentials (GWP) for CFH2CH2OH of approximately 8, approximately 2, and approximately 1, respectively, for the 20, 100 and 500 year horizons. A brief discussion of the atmospheric degradation of CFH2CH2OH is provided. It is concluded that CFH2CH2OH is an acceptable substitute for CFCs in terms of its impact on Earth's climate and the composition of the atmosphere. The room temperature rate coefficient for the reaction OH + CFH2CH2OH --> products (k10) was measured to be 3.26 x 10(-12) cm3 molecule(-1) s(-1), in good agreement with recent measurements from this laboratory.     

Rate coefficients for the reaction of OH with HONO between 298 and 373 K

Rate coefficients, k₁, for the reaction OH + HONO → H₂O + NO₂, have been measured over the temperature range 298 to 373 K. The OH radicals were produced by 266 nm laser photolysis of O₃ in the presence of a large excess of H₂O vapor. The temporal profiles of OH were measured under pseudo-first-order conditions, in an excess of HONO, using time resolved laser induced fluorescence. The measured rate coefficient exhibits a slight negative temperature dependence, with k₁ = (2.8 ± 1.3) × 10^?12 exp((260 ± 140)/T) cm³ molecule^?1 s^?1. The measured values of k₁ are compared with previous determinations and the atmospheric implications of our findings are discussed.     

Rate coefficients for the reaction of the acetyl radical,CH3CO,with Cl2 between 253 and 384 K

Rate coefficients, k, for the gas‐phase reaction CH₃CO + Cl₂ → products (2) were measured between 253 and 384 K at 55–200 Torr (He). Rate coefficients were measured under pseudo‐first‐order conditions in CH₃CO with CH₃CO produced by the 248‐nm pulsed‐laser photolysis of acetone, CH₃C(O)CH₃, or 2,3‐butadione, CH₃C(O)C(O)CH₃. The loss of CH₃CO was monitored by cavity ring‐down spectroscopy (CRDS) at 532 nm. Rate coefficients were determined by first‐order kinetic analysis of the CH₃CO temporal profiles for [Cl₂] < 1 × 10¹⁴ molecule cm^?3 and the analysis of the CRDS profiles by the simultaneous kinetics and ring‐down method for experiments performed with [Cl₂] > 1 × 10¹⁴ molecule cm^?3. k₂(T) was found to be independent of pressure, with k₂(296 K) = (3.0 ± 0.5) × 10^?11 cm³ molecule^?1 s^?1. k₂(T) showed a weak negative temperature dependence that is well reproduced by the Arrhenius expression k₂(T) = (2.2 ± 0.8) × 10^?11 exp[(85 ± 120)/T] cm³ molecule^?1 s^?1. The quoted uncertainties in k₂(T) are at the 2σ level (95% confidence interval) and include estimated systematic errors. A comparison of the present work with previously reported rate coefficients for the CH₃CO + Cl₂ reaction is presented. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 41: 543–553, 2009     

Site-specific rate coefficients for reaction of OH with ethanol from 298 to 900 K

The rate coefficients for reactions of OH with ethanol and partially deuterated ethanols have been measured by laser flash photolysis/laser-induced fluorescence over the temperature range 298-523 K and 5-100 Torr of helium bath gas. The rate coefficient, k(1.1), for reaction of OH with C(2)H(5)OH is given by the expression k(1.1) = 1.06 × 10(-22)T(3.58)?exp(1126/T) cm(3) molecule(-1) s(-1), and the values are in good agreement with previous literature. Site-specific rate coefficients were determined from the measured kinetic isotope effects. Over the temperature region 298-523 K abstraction from the hydroxyl site is a minor channel. The reaction is dominated by abstraction of the α hydrogens (92 ± 8)% at 298 K decreasing to (76 ± 9)% with the balance being abstraction at the β position where the errors are 2σ. At higher temperatures decomposition of the CH(2)CH(2)OH product from β abstraction complicates the kinetics. From 575 to 650 K, biexponential decays were observed, allowing estimates to be made for k(1.1) and the fractional production of CH(2)CH(2)OH. Above 650 K, decomposition of the CH(2)CH(2)OH product was fast on the time scale of the measured kinetics and removal of OH corresponds to reaction at the α and OH sites. The kinetics agree (within ±20%) with previous measurements. Evidence suggests that reaction at the OH site is significant at our higher temperatures: 47-53% at 865 K.     

Rate coefficients for the reaction of OH with a series of unsaturated alcohols between 263 and 371 K

Rate coefficients for the gas-phase reactions of OH radicals with four unsaturated alcohols, 3-methyl-3-buten-1-ol (k1), 2-buten-1-ol (k2), 2-methyl-2-propen-1-ol (k3) and 3-buten-1-ol (k4), were measured using two different techniques, a conventional relative rate method and the pulsed laser photolysis-laser induced fluorescence technique. The Arrhenius rate coefficients (in units of cm(3) molecule(-1) s(-1)) over the temperature range 263-371 K were determined from the kinetic data obtained as k1 = (5.5 +/- 1.0) x 10(-12) exp [(836 +/- 54)/T]; k2 = (6.9 +/- 0.9) x 10(-12) exp [(744 +/- 40)/T]; k3 = (10 +/- 1) x 10(-12) exp [(652 +/- 27)/T]; and k4 = (4.0 +/- 0.4) x 10(-12) exp [(783 +/- 32)/T]. At 298 K, the rate coefficients obtained by the two methods for each of the alcohols studied were in good agreement. The results are presented and compared with those obtained previously for the same and related reactions of OH radicals. Reactivity factors for substituent groups containing the hydroxyl group are determined. The atmospheric implications for the studied alcohols are considered briefly.     

Rate coefficients for the reactions of OH with butanols from 298 K to temperatures relevant for low-temperature combustion

Rate coefficients for the reactions of OH with n, s, and iso-butanol have been measured over the temperature range 298 to ∼650 K. The rate coefficients display significant curvature over this temperature range and bridge the gap between previous low-temperature measurements with a negative temperature dependence and higher temperature shock tube measurements that have a positive temperature dependence. In combination with literature data, the following parameterizations are recommended: k_{1,OH + n-butanol}(T) = (3.8 ± 10.4) × 10⁻¹⁹T^{2.48 ± 0.37}exp ((840 ± 161)/T) cm³ molecule⁻¹ s⁻¹ k_{2,OH + s-butanol}(T) = (3.5 ± 3.0) × 10⁻²⁰T^{2.76 ± 0.12}exp ((1085 ± 55)/T) cm³ molecule⁻¹ s⁻¹ k_{3,OH + i-butanol}(T) = (5.1 ± 5.3) × 10⁻²⁰T^{2.72 ± 0.14}exp ((1059 ± 66)/T) cm³ molecule⁻¹ s⁻¹ k_{4,OH + t-butanol}(T) = (8.8 ± 10.4) × 10⁻²²T^{3.24 ± 0.15}exp ((711 ± 83)/T) cm³ molecule⁻¹ s⁻¹ Comparison of the current data with the higher shock tube measurements suggests that at temperatures of ∼1000 K, the OH yields, primarily from decomposition of β-hydroxyperoxy radicals, are ∼0.3 (n-butanol), ∼0.3 (s-butanol) and ∼0.2 (iso-butanol) with β-hydroxyperoxy decompositions generating OH, and a butene as the main products. The data suggest that decomposition of β-hydroxyperoxy radicals predominantly occurs via OH elimination.     

Rate constant for the reaction of OH with H2 between 200 and 480 K

The rate constant for the reaction of OH radicals with molecular hydrogen was measured using the flash photolysis resonance-fluorescence technique over the temperature range of 200-479 K. The Arrhenius plot was found to exhibit a noticeable curvature. Careful examination of all possible systematic uncertainties indicates that this curvature is not due to experimental artifacts. The rate constant can be represented by the following expressions over the indicated temperature intervals: k(H2)(250-479 K) = 4.27 x 10(-13) x (T/298)2.406 x exp[-1240/T] cm3 molecule(-1) (s-1) above T = 250 K and k(H2)(200-250 K) = 9.01 x 10(-13) x exp[-(1526 +/- 70)/T] cm3 molecule(-1) s(-1) below T = 250 K. No single Arrhenius expression can adequately represent the rate constant over the entire temperature range within the experimental uncertainties of the measurements. The overall uncertainty factor was estimated to be f(H2)(T) = 1.04 x exp[50 x /(1/T) - (1/298)/]. These measurements indicate an underestimation of the rate constant at lower atmospheric temperatures by the present recommendations. The global atmospheric lifetime of H2 due to its reaction with OH was estimated to be 10 years.     

Rate coefficients for the reactions CH3 + Br2 (224–358 K), CH3CO + Br2 (228 and 298 K), and Cl + Br2 (228 and 298 K)

Rate coefficients for the reactions of CH₃ + Br₂ (k₂), CH₃CO + Br₂ (k₃), and Cl + Br₂ (k₅) were measured using the laser‐pulsed photolysis method combined with detection of the product Br atoms using resonance fluorescence. For the reactions involving organic radicals, the rate coefficients were observed to increase with decreasing temperature and within the temperature range explored, were adequately described by Arrhenius‐like expressions: k₂ (224–358 K) = 1.83 × 10^?11 exp(252/T) and k₃ (228–298 K) = 2.92 × 10^?11 exp(361/T) cm³ molecule^?1 s^?1. The total, temperature‐independent uncertainty for each reaction (including possible systematic errors in Br₂ concentration measurement) was estimated as ～7% for k₂ and 10% for k₃. Accurate data on k₅ was obtained at 298 K, with a value of 1.88 × 10^?10 cm³ molecule^?1 s^?1 obtained (with an associated error of 6%). A limited data set at 228 K suggests that k₅ is, within experimental uncertainty, independent of temperature. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 575–585, 2010     

Rate coefficients for the OH + acetaldehyde (CH3CHO) reaction between 204 and 373 K

The rate coefficient, k₁, for the gas‐phase reaction OH + CH₃CHO (acetaldehyde) → products, was measured over the temperature range 204–373 K using pulsed laser photolytic production of OH coupled with its detection via laser‐induced fluorescence. The CH₃CHO concentration was measured using Fourier transform infrared spectroscopy, UV absorption at 184.9 nm and gas flow rates. The room temperature rate coefficient and Arrhenius expression obtained are k₁(296 K) = (1.52 ± 0.15) × 10^?11 cm³ molecule^?1 s^?1 and k₁(T) = (5.32 ± 0.55) × 10^?12 exp[(315 ± 40)/T] cm³ molecule^?1 s^?1. The rate coefficient for the reaction OH (ν = 1) + CH₃CHO, k₇(T) (where k₇ is the rate coefficient for the overall removal of OH (ν = 1)), was determined over the temperature range 204–296 K and is given by k₇(T) = (3.5 ± 1.4) × 10^?12 exp[(500 ± 90)/T], where k₇(296 K) = (1.9 ± 0.6) × 10^?11 cm³ molecule^?1 s^?1. The quoted uncertainties are 2σ (95% confidence level). The preexponential term and the room temperature rate coefficient include estimated systematic errors. k₇ is slightly larger than k₁ over the range of temperatures included in this study. The results from this study were found to be in good agreement with previously reported values of k₁(T) for temperatures <298 K. An expression for k₁(T), suitable for use in atmospheric models, in the NASA/JPL and IUPAC format, was determined by combining the present results with previously reported values and was found to be k₁(298 K) = 1.5 × 10^?11 cm³ molecule^?1 s^?1, f(298 K) = 1.1, E/R = 340 K, and Δ E/R (or g) = 20 K over the temperature range relevant to the atmosphere. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 635–646, 2008     

Rate constants for the reaction of Cl atoms with O3 at temperatures from 298 to 184 K

Using the standard, low pressure, discharge‐flow technique, with resonance fluorescence in the vacuum ultraviolet to observe Cl atoms, rate constants have been determined for the reaction of Cl atoms with O₃ at temperatures down to 184 K. The measured rate constants for 298–184 K fit the Arrhenius expression k(T) = (3.1 ± 1.3₅) × 10^?11 exp((?280 ±100 K)/T) cm³ molecule^?1 s^?1. The results extend the data on this key atmospheric reaction to slightly lower temperatures. The data are in fairly good agreement with those currently in the literature but suggest that the rate constant is approximately 15% lower than that given by currently recommended rate expressions at the lowest temperatures found in the stratosphere.© 2001 John Wiley & Sons, Inc. Int J Chem Kinet 34: 104–109, 2002     

Kinetic study of the gas-phase reaction of OH with Br2

An experimental, temperature-dependent kinetic study of the gas-phase reaction of the hydroxyl radical with molecular bromine (reaction 1) has been performed by using a pulsed laser photolysis/pulsed-laser-induced fluorescence technique over a wide temperature range of 297-766 K, and at pressures between 6.68 and 40.29 kPa of helium. The experimental rate coefficients for reaction 1 demonstrate no correlation with pressure and exhibit a negative temperature dependence with a slight negative curvature in the Arrhenius plot. A nonlinear least-squares fit with two floating parameters of the temperature-dependent k(1)(T) data set using an equation of the form k(1)(T) = AT(n) yields the recommended expression k(1)(T) = (1.85 x 10(-9))T(-0.66) cm(3) molecule(-1) s(-1) for the temperature dependence of the reaction 1 rate coefficient. The potential energy surface (PES) of reaction 1 was investigated with use of quantum chemistry methods. The reaction proceeds through formation of a weakly bound OH...Br(2) complex and a PES saddle point with an energy below that of the reactants. Temperature dependence of the reaction rate coefficient was modeled by using the RRKM method on the basis of the calculated PES.     

Rate coefficients for the O(3P) + Cl2O gas‐phase reaction between 230 and 357 K

Rate coefficients, k, for the gas‐phase reaction of O(³P) atoms with Cl₂O (dichlorine monoxide) over a range of temperatures (230–357 K) at pressures between 12 and 32 Torr (N₂) are reported. Rate coefficients were measured under pseudo‐first‐order conditions in O(³P) using pulsed laser photolysis to produce O(³P) atoms and atomic resonance fluorescence to detect its temporal profile. The rate coefficient temperature dependence is given by the Arrhenius expression k(T) = (1.51 ± 0.20) × 10^?11 exp[?(477 ± 30)/T] cm³ molecule^?1 s^?1, and k(296 K) was measured to be (2.93 ± 0.30) × 10^?12 cm³ molecule^?1 s^?1. The quoted uncertainty limits are at the 2σ (95% confidence) level and include estimated systematic errors. The rate coefficients determined in the present study, under conditions that minimized secondary losses of O(³P), are compared with previous results from other laboratories and the discrepancies are discussed. © 2011 Wiley Peiodicals, Inc.

1 This article is a U.S. Government work and, as such, is in the public domain of the United States of America.

Int J Chem Kinet 43: 312–321, 2011     

Rate coefficients for the gas-phase reaction of OH radicals with dimethyl sulfide: temperature and O2 partial pressure dependence

Rate coefficients for the gas-phase reaction of hydroxyl (OH) radicals with dimethyl sulfide (CH(3)SCH(3), DMS) have been determined using a relative rate technique. The experiments were performed under different conditions of temperature (250-299 K) and O(2) partial pressure (approximately 0 Torr O(2)-380 Torr O(2)), at a total pressure of 760 Torr bath gas (N(2) + O(2)), in a 336 l reaction chamber, using long path in situ Fourier transform (FTIR) absorption spectroscopy to monitor the disappearance rates of DMS and the reference compounds (ethene, propene and 2-methylpropene). OH was produced by the photolysis of H(2)O(2). The following Arrhenius expressions adequately describe the rate coefficients as a function of temperature (units are cm(3) molecule(-1) s(-1)): k = (1.56 +/- 0.20) x 10(-12) exp[(369 +/- 27)/T], for approximately 0 Torr O(2); (1.31 +/- 0.08) x 10(-14) exp[(1910 +/- 69)/T], for 155 Torr O(2); (5.18 +/- 0.71) x 10(-14) exp[(1587 +/- 24)/T], for 380 Torr O(2). The results are compared with previous investigations.     

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 k_OH(1,2‐dihydroxybenzene) = (1.04 ± 0.21) × 10⁻¹⁰ cm³ s⁻¹, k_OH(1,2‐dihydroxy‐3‐methylbenzene) = (2.05 ± 0.43) × 10⁻¹⁰ cm³ s⁻¹, k_OH(1,2‐dihydroxy‐4‐methylbenzene) = (1.56 ± 0.33) × 10⁻¹⁰ cm³ s⁻¹, k_OH(1,4‐benzoquinone) = (4.6 ± 0.9) × 10⁻¹² cm³ s⁻¹, k_OH(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 coefficient for the reaction: Br+Br2O→Br2+BrO

The room temperature rate coefficient for the reaction Br+Br₂O→Br₂+BrO (3) has been measured using the technique of pulse-laser photolysis with long-path transient absorption detection of the BrO reaction product. A value of k₃=(2.0±0.5)×10⁻¹⁰ cm³ molecule⁻¹ s⁻¹ was determined. The photolysis products of Br₂O at 308 nm were also examined. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 571–576, 1998     

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

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     

Observation of adducts in the reaction of Cl atoms with XCH2I (X = H, CH3, Cl, Br, I) using cavity ring-down spectroscopy

The reactions of Cl atoms with XCH2I (X = H, CH3, Cl, Br, I) have been studied using cavity ring-down spectroscopy in 25-125 Torr total pressure of N2 diluent at 250 K. Formation of the XCH2I-Cl adduct is the dominant channel in all reactions. The visible absorption spectrum of the XCH2I-Cl adduct was recorded at 405-632 nm. Absorption cross-sections at 435 nm are as follows (in units of 10(-18) cm2 molecule(-1)): 12 for CH3I, 21 for CH3CH2I, 3.7 for CH2ICl, 7.1 for CH2IBr, and 3.7 for CH2I2. Rate constants for the reaction of Cl with CH3I were determined from rise profiles of the CH3I-Cl adduct. k(Cl + CH3I) increases from (0.4 +/- 0.1) x 10(-11) at 25 Torr to (2.0 +/- 0.3) x 10(-11) cm3 molecule(-1) s(-1) at 125 Torr of N2 diluent. There is no discernible reaction of the CH3I-Cl adduct with 5-10 Torr of O2. Evidence for the formation of an adduct following the reaction of Cl atoms with CF3I and CH3Br was sought but not found. Absorption attributable to the formation of the XCH2I-Cl adduct following the reaction of Cl atoms with XCH2I (X = H, CH3, Br, I) was measured as a function of temperature over the range 250-320 K.