Nadezhda Butkovskaya

Water Vapor Effect on the HNO3 Yield in the HO2 + NO Reaction: Experimental and Theoretical Evidence

The influence of water vapor on the production of nitric acid in the gas-phase HO(2) + NO reaction was determined at 298 K and 200 Torr using a high-pressure turbulent flow reactor coupled with a chemical ionization mass spectrometer. The yield of HNO(3) was found to increase linearly with the increase of water concentration reaching an enhancement factor of about 8 at [H(2)O] = 4 x 10(17) molecules cm(-3) ( approximately 50% relative humidity). A rate constant value k(1bw) = 6 x 10(-13) cm(3) molecule(-1) s(-1) was derived for the reaction involving the HO(2)xH(2)O complex: HO(2)xH(2)O + NO --> HNO(3) (1bw), assuming that the water enhancement is due to this reaction. k(1bw) is approximately 40 times higher than the rate constant of the reaction HO(2) + NO --> HNO(3) (1b), at the same temperature and pressure. The experimental findings are corroborated by density functional theory (DFT) calculations performed on the H(2)O/HO(2)/NO system. The significance of this result for atmospheric chemistry and chemical amplifier instruments is briefly discussed. An appendix containing a detailed consideration of the possible contribution from the surface reactions in our previous studies of the title reaction and in the present one is included.

Pressure and temperature dependence of methyl nitrate formation in the CH3O2 + NO reaction.

The branching ratio β = k(1b)/k(1a) for the formation of methyl nitrate, CH(3)ONO(2), in the gas-phase CH(3)O(2) + NO reaction, CH(3)O(2) + NO → CH(3)O + NO(2) (1a), CH(3)O(2) + NO → CH(3)ONO(2) (1b), has been determined over the pressure and temperature ranges 50-500 Torr and 223-300 K, respectively, using a turbulent flow reactor coupled with a chemical ionization mass spectrometer. At 298 K, the CH(3)ONO(2) yield has been found to increase linearly with pressure from 0.33 ± 0.16% at 50 Torr to 0.80 ± 0.54% at 500 Torr (errors are 2σ). Decrease of temperature from 300 to 220 K leads to an increase of β by a factor of about 3 in the 100-200 Torr range. These data correspond to a value of β ≈ 1.0 ± 0.7% over the pressure and temperature ranges of the whole troposphere. Atmospheric concentrations of CH(3)ONO(2) roughly estimated using results of this work are in reasonable agreement with those observed in polluted environments and significantly higher compared with measurements in upper troposphere and lower stratosphere.

Branching Ratios in the Hydroxyl Reaction with Propene

The branching ratios for the reactions of attachment of hydroxyl radical to propene and hydrogen-atom abstraction were measured at 298 K over the buffer gas pressure range 60-400 Torr (N(2)) using a subatmospheric pressure turbulent flow reactor coupled with a chemical ionization quadrupole mass spectrometer. Isotopically enriched water H(2)(18)O was used to produce (18)O-labeled hydroxyl radicals in reaction with fluorine atoms. The β-hydroxypropyl radicals formed in the attachment reactions 1a and 1b , OH + C(3)H(6) → CH(2)(OH)C(•)HCH(3) (eq 1a ) and OH + C(3)H(6) → C(•)H(2)CH(OH)CH(3) (eq 1b ), were converted to formaldehyde and acetaldehyde in a sequence of secondary reactions in O(2)- and NO-containing environment. The (18)O-labeling propagates to the final products, allowing determination of the branching ratio for the attachment channels of reaction 1. The measured branching ratio for attachment is β(1b) = k(1b)/(k(1a) + k(1b)) = 0.51 ± 0.03, independent of pressure over the 60-400 Torr pressure range. An upper limit on the hydrogen-abstraction channel, OH + C(3)H(6) → H(2)O + C(3)H(5) (eq 1c ), was determined by measuring the water yield in reactions of OH and OD radicals (produced via H(D) + NO(2) → OH(OD) + NO reactions) with C(3)H(6) as k(1c)/(k(1a) + k(1b) + k(1c)) < 0.05 (at 298 K, 200 Torr N(2)).

Pressure and temperature dependence of ethyl nitrate formation in the C(2)H(5)O(2) + NO reaction.

The branching ratio beta = k(1b)/k(1a) for the formation of ethyl nitrate, C(2)H(5)ONO(2), in the gas-phase C(2)H(5)O(2) + NO reaction, C(2)H(5)O(2) + NO --> C(2)H(5)O + NO(2) (1a), C(2)H(5)O(2) + NO --> C(2)H(5)ONO(2) (1b), was determined over the pressure and temperature ranges 100-600 Torr and 223-298 K, respectively, using a turbulent flow reactor coupled with a chemical ionization mass spectrometer. At 298 K the C(2)H(5)ONO(2) yield was found to increase linearly with pressure from about 0.7% at 100 Torr to about 3% at 600 Torr. At each pressure, the branching ratio of C(2)H(5)ONO(2) formation increases with the decrease of temperature. The following parametrization equation has been derived in the pressure and temperature ranges of the study: beta(P,T) (%) = (3.88 x 10(-3).P (Torr) + 0.365).(1 + 1500(1/T - 1/298)). The atmospheric implication of the results obtained is briefly discussed, in particular the impact of beta on the evolution of ethyl nitrate in urban plumes.

Pressure Dependence of Iso-Propyl Nitrate Formation in the i-C3H7O2 + NO Reaction

Abstract The branching ratio β = k1b/k1a for the formation of iso-propyl nitrate, i-C3H7ONO2, in the gas-phase reaction of i-C3H7O2 with NO, i-C3H7O2 + NO → i-C3H7O + NO2 (1a), i-C3H7O2 + NO → i-C3H7ONO2 (1b), was determined over the pressure range 55–500 Torr at 298 K using a high-pressure turbulent flow reactor coupled with a chemical ionization quadrupole mass-spectrometer. The β coefficient was found to increase linearly with pressure from about 0.6% at 55 Torr to about 3% at 500 Torr. The atmospheric implication of the results obtained is briefly discussed.

Pressure Dependence of Butyl Nitrate Formation in the Reaction of Butylperoxy Radicals with Nitrogen Oxide

The yield of 1- and 2-butyl nitrates in the gas-phase reactions of NO with n-C4H9O2 and sec-C4H9O2, obtained from the reaction of F atoms with n-butane in the presence of O2, was determined over the pressure range of 100-600 Torr at 298 K using a high-pressure turbulent flow reactor coupled with a chemical ionization quadrupole mass spectrometer. The yield of butyl nitrates was found to increase linearly with pressure from about 3% at 100 Torr to about 8% at 600 Torr. The results obtained are compared with the available data concerning nitrate formation from NO reaction with other small alkylperoxy radicals. These results are also discussed through the topology of the lowest potential energy surface mainly obtained from DFT(B3LYP/aug-cc-pVDZ) calculations of the RO2 + NO reaction paths. The formation of alkyl nitrates, due essentially to collision processes, is analyzed through a model that points out the pertinent physical parameters of this system.

Laboratory Studies of NO3 and OH Reactions of Tropospheric Relevance

Kinetic studies have been performed on the individual steps occurring in the NO3 and OH initiated oxidation of VOCs. The studied reactions include essentially reactions of NO3 with alkenes, di-alkenes and dimethyl sulfide (DMS), reactions of NO3 with intermediate peroxy radicals (HO2, CH3O2, C2H5O2) and reactions of OH with methane and oxygenated VOCs (ethers, alcohols). The rate constants for these reactions have been measured, and mechanistic information has been determined. The experimental methods used were discharge-flow reactors coupled with mass spectrometry, electron paramagnetic resonance (EPR), laser-induced fluorescence (LIF) analysis and the laser photolysis associated with LIF analysis. The discharge-flow LIF and laser photolysis LIF experiments have been especially developed for these studies.