Paul W. Seakins

Interception of excited vibrational quantum states by o2 in atmospheric association reactions

Vibrating in a Crowd High-vacuum molecular beam studies can probe the roles of specific vibrations and rotations on molecular reactivity with remarkably fine resolution. Glowacki et al. (p. 1066; see the Perspective by Tyndall) now show, through a combination of spectroscopy and theoretical modeling, that oxidation of acetylene under effectively atmospheric conditions proceeds in part through vibrationally excited intermediates prior to collisional randomization. Vibrationally excited reaction intermediates play a bigger role under atmospheric conditions than previously suspected. Bimolecular reactions in Earth’s atmosphere are generally assumed to proceed between reactants whose internal quantum states are fully thermally relaxed. Here, we highlight a dramatic role for vibrationally excited bimolecular reactants in the oxidation of acetylene. The reaction proceeds by preliminary adduct formation between the alkyne and OH radical, with subsequent O2 addition. Using a detailed theoretical model, we show that the product-branching ratio is determined by the excited vibrational quantum-state distribution of the adduct at the moment it reacts with O2. Experimentally, we found that under the simulated atmospheric conditions O2 intercepts ~25% of the excited adducts before their vibrational quantum states have fully relaxed. Analogous interception of excited-state radicals by O2 is likely common to a range of atmospheric reactions that proceed through peroxy complexes.

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.

In situ , gas chromatographicmeasurements of non-methane hydrocarbons and dimethylsulfide at a remote coastal location (Mace Head, Eire)July–August 1996

Atmospheric non-methane hydrocarbons (NMHC) and dimethyl sulfide (DMS) have been monitored at a remote coastal location (Mace Head, Eire) using adsorption sampling techniques with analysis by in situ gas chromatography as part of the ACSOE OXICOA 1996 campaign. Concentrations varied considerably during the campaign but can be consistently interpreted by consideration of the relevant back-trajectory of the monitored air mass. Isoprene is confirmed as the most important NMHC in determining OH removal, contributing to up to 20%. Isoprene shows strong diurnal variations, although the structure of the diurnal pattern depends on the origin of the air mass. In contrast to previous studies, DMS concentrations during the campaign appeared to show no consistent diurnal variation.

Experimental and Modeling Studies of the Pressure and Temperature Dependences of the Kinetics and the OH Yields in the Acetyl + O2 Reaction

The acetyl + O(2) reaction has been studied by observing the time dependence of OH by laser-induced fluorescence (LIF) and by electronic structure/master equation analysis. The experimental OH time profiles were analyzed to obtain the kinetics of the acetyl + O(2) reaction and the relative OH yields over the temperature range of 213-500 K in helium at pressures in the range of 5-600 Torr. More limited measurements were made in N(2) and for CD(3)CO + O(2). The relative OH yields were converted into absolute yields by assuming that the OH yield at zero pressure is unity. Electronic structure calculations of the stationary points of the potential energy surface were used with a master equation analysis to fit the experimental data in He using the high-pressure limiting rate coefficient for the reaction, k(∞)(T), and the energy transfer parameter, (ΔE(d)), as variable parameters. The best-fit parameters obtained are k(∞) = 6.2 × 10(-12) cm(-3) molecule(-1) s(-1), independent of temperature over the experimental range, and (ΔE(d))(He) = 160(T/298 K) cm(-1). The fits in N(2), using the same k(∞)(T), gave (ΔE(d))(N(2)) = 270(T/298 K) cm(-1). The rate coefficients for formation of OH and CH(3)C(O)O(2) are provided in parametrized form, based on modified Troe expressions, from the best-fit master equation calculations, over the pressure and temperature ranges of 1 ≤ p/Torr ≤ 1.5 × 10(5) and 200 ≤ T/K ≤ 1000 for He and N(2) as the bath gas. The minor channels, leading to HO(2) + CH(2)CO and CH(2)C(O)OOH, generally have yields <1% over this range.

Photolysis of methylethyl, diethyl and methylvinyl ketones and their role in the atmospheric HOx budget.

Quantum yields for acyl (RCO) radical production from ketone photolysis as a function of temperature, pressure and the atmospherically relevant wavelengths (308 and 320 nm) have been determined for methylethyl ketone (MEK), methylvinyl ketone (MVK) and diethyl ketone (DEK) via direct observation of the OH product from the RCO + O2 reaction. The methodology has been applied previously to acetone photolysis. The kinetics and OH yields of the RCO + O2 reactions have been investigated to demonstrate that this technique can be used to monitor the dissociation of higher ketones. These kinetic studies have been used to confirm CH3CO + R as the dominant radical dissociation mechanism in the unsymmetrical ketones MVK and MEK. At 308 nm MEK and DEK photolysis follows conventional Stern Volmer behaviour. MEK and DEK are quenched less efficiently than acetone; quenching efficiency increases with decreasing temperature (213-295 K). At 320 nm Stern Volmer plots of the RCO quantum yields show evidence for the involvement of multiple states in the dissociation. The wavelength dependence of this phenomenon is compared with that for acetone and the atmospheric implications for MEK and DEK lifetimes have been investigated by converting the measured quantum yields to photolysis rates. The calculated rates under typical atmospheric conditions are a factor 2-3 lower than if the quantum yields in the literature are used, influencing both the overall atmospheric lifetime of these ketones and their relative rates of removal by reaction with OH and by photolysis.

Direct studies on the decomposition of the tert-butoxy radical and its reaction with NO

The first laser induced fluorescence (LIF) spectrum for the tert-butoxy radical is reported following radical generation by excimer laser photolysis of tert-butyl nitrite. The laser flash photolysis-LIF technique is used to measure the temperature dependence of the rate coefficient for the reaction with NO (T=200–390 K): which can be represented in either Arrhenius or AT-n format: and the tert-butoxy decomposition. Whilst the former reaction shows no pressure dependence (p=70–500 Torr of helium), the latter reaction is in the fall-off regime over the entire range of experimental conditions (T=303–393 K, p=13–600 Torr helium). The fall-off data were fitted using an inverse Laplace transformation/master equation model to give the following Arrhenius parameters: These Arrhenius parameters are significantly lower than previous indirect measurements or calculations and the atmospheric and mechanistic implications are discussed.Finally, reaction (3) was also studied by monitoring the temporal dependence of the NO LIF signal following the photolysis of tert-butylnitrite with no additional NO. The results are in good agreement with the tert-butoxy monitoring and allow for an estimation of the rate parameters for the tert-butoxy self reaction.

Analysis of the kinetics and yields of OH radical production from the CH3OCH2 + O2 reaction in the temperature range 195-650 K: an experimental and computational study.

The methoxymethyl radical, CH3OCH2, is an important intermediate in the low temperature combustion of dimethyl ether. The kinetics and yields of OH from the reaction of the methoxymethyl radical with O2 have been measured over the temperature and pressure ranges of 195-650 K and 5-500 Torr by detecting the hydroxyl radical using laser-induced fluorescence following the excimer laser photolysis (248 nm) of CH3OCH2Br. The reaction proceeds via the formation of an energized CH3OCH2O2 adduct, which either dissociates to OH + 2 H2CO or is collisionally stabilized by the buffer gas. At temperatures above 550 K, a secondary source of OH was observed consistent with thermal decomposition of stabilized CH3OCH2O2 radicals. In order to quantify OH production from the CH3OCH2 + O2 reaction, extensive relative and absolute OH yield measurements were performed over the same (T, P) conditions as the kinetic experiments. The reaction was studied at sufficiently low radical concentrations (∼10(11) cm(-3)) that secondary (radical + radical) reactions were unimportant and the rate coefficients could be extracted from simple bi- or triexponential analysis. Ab initio (CBS-GB3)/master equation calculations (using the program MESMER) of the CH3OCH2 + O2 system were also performed to better understand this combustion-related reaction as well as be able to extrapolate experimental results to higher temperatures and pressures. To obtain agreement with experimental results (both kinetics and yield data), energies of the key transition states were substantially reduced (by 20-40 kJ mol(-1)) from their ab initio values and the effect of hindered rotations in the CH3OCH2 and CH3OCH2OO intermediates were taken into account. The optimized master equation model was used to generate a set of pressure and temperature dependent rate coefficients for the component nine phenomenological reactions that describe the CH3OCH2 + O2 system, including four well-skipping reactions. The rate coefficients were fitted to Chebyshev polynomials over the temperature and density ranges 200 to 1000 K and 1 × 10(17) to 1 × 10(23) molecules cm(-3) respectively for both N2 and He bath gases. Comparisons with an existing autoignition mechanism show that the well-skipping reactions are important at a pressure of 1 bar but are not significant at 10 bar. The main differences derive from the calculated rate coefficient for the CH3OCH2OO → CH2OCH2OOH reaction, which leads to a faster rate of formation of O2CH2OCH2OOH.

Direct Determination of the Rate Coefficient for the Reaction of OH Radicals with Monoethanol Amine (MEA) from 296 to 510 K

Monoethanol amine (H2NCH2CH2OH, MEA) has been proposed for large-scale use in carbon capture and storage. We present the first absolute, temperature-dependent determination of the rate coefficient for the reaction of OH with MEA using laser flash photolysis for OH generation, monitoring OH removal by laser-induced fluorescence. The room-temperature rate coefficient is determined to be (7.61 ± 0.76) × 10(-11) cm(3) molecule(-1) s(-1), and the rate coefficient decreases by about 40% by 510 K. The temperature dependence of the rate coefficient is given by k1= (7.73 ± 0.24) × 10(-11)(T/295)(-(0.79±0.11)) cm(3) molecule(-1) s(-1). The high rate coefficient shows that gas-phase processing in the atmosphere will be competitive with uptake onto aerosols.

H-atom yields from the photolysis of acetylene and from the reaction of C2H with H2, C2H2, and C2H4.

The photolysis of acetylene at 193 nm has been investigated as a source of the ethynyl radical, C(2)H, for product branching ratio studies, particularly the formation of H atom product as the photolysis, producing a 1:1 ratio of C(2)H and H, provides an internal calibration. Previous literature had suggested that C(2)H and H may only be a minor component of acetylene photolysis at 193 nm. Acetylene was photolyzed at low laser energy densities (<7 mJ cm(-2)), with H atoms being observed as a function of time by VUV laser induced fluorescence. When C(2)H was reacted with C(2)H(2), a reaction that is known to produce H atoms with unit yield, the ratio of photolytic H atom production to chemical production was 0.96 +/- 0.03. The rate coefficient for the reaction of C(2)H with C(2)H(2) could accurately be retrieved from the time evolution of the H atom signal. The results suggest that acetylene photolysis at low laser energies is a good source of C(2)H for product branching studies, and the technique has been applied to the reactions of C(2)H with ethene and propene. For the reaction with ethene between 23 and 81 Torr, the yield of H is 0.94 +/- 0.06, suggesting that an addition elimination mechanism dominates with the formation of vinylacetylene and H atoms. For the reaction of C(2)H with propene, no H atom product was observed, putting a lower limit of <5% for H atom production. Possible explanations for the low H atom yield are discussed. The implications of these results in combustion and planetary atmospheres are briefly considered.

A combined experimental and theoretical study of the reaction between methylglyoxal and OH/OD radical: OH regeneration

Experimental studies have been conducted to determine the rate coefficient and mechanism of the reaction between methylglyoxal (CH(3)COCHO, MGLY) and the OH radical over a wide range of temperatures (233-500 K) and pressures (5-300 Torr). The rate coefficient is pressure independent with the following temperature dependence: k(3)(T) = (1.83 +/- 0.48) x 10(-12) exp((560 +/- 70)/T) cm(3) molecule(-1) s(-1) (95% uncertainties). Addition of O(2) to the system leads to recycling of OH. The mechanism was investigated by varying the experimental conditions ([O(2)], [MGLY], temperature and pressure), and by modelling based on a G3X potential energy surface, rovibrational prior distribution calculations and master equation RRKM calculations. The mechanism can be described as follows: Addition of oxygen to the system shows that process (4) is fast and that CH(3)COCO completely dissociates. The acetyl radical formed from reaction (4) reacts with oxygen to regenerate OH radicals (5a). However, a significant fraction of acetyl radical formed by reaction (R4) is sufficiently energised to dissociate further to CH(3) + CO (R4b). Little or no pressure quenching of reaction (R4b) was observed. The rate coefficient for OD + MGLY was measured as k(9)(T) = (9.4 +/- 2.4) x 10(-13) exp((780 +/- 70)/T) cm(3) molecule(-1) s(-1) over the temperature range 233-500 K. The reaction shows a noticeable inverse (k(H)/k(D) < 1) kinetic isotope effect below room temperature and a slight normal kinetic isotope effect (k(H)/k(D) > 1) at high temperature. The potential atmospheric implications of this work are discussed.