Atmospheric isoprene ozonolysis: impacts of stabilised Criegee intermediate reactions with SO₂, H₂O and dimethyl sulfide

Isoprene is the dominant global biogenic volatile organic compound (VOC) emission. Reactions of isoprene with ozone are known to form stabilised Criegee intermediates (SCIs), which have recently been shown to be potentially important oxidants for SO2 and NO2 in the atmosphere; however the significance of this chemistry for SO2 processing (affecting sulfate aerosol) and NO2 processing (affecting NOx levels) depends critically upon the fate of the SCIs with respect to reaction with water and decomposition. Here, we have investigated the removal of SO2 in the presence of isoprene and ozone, as a function of humidity, under atmospheric boundary layer conditions. The SO2 removal displays a clear dependence on relative humidity, confirming a significant reaction for isoprene-derived SCIs with H2O. Under excess SO2 conditions, the total isoprene ozonolysis SCI yield was calculated to be 0.56 (±0.03). The observed SO2 removal kinetics are consistent with a relative rate constant, k(SCI + H2O) / k(SCI + SO2), of 3.1 (±0.5) × 10−5 for isoprene-derived SCIs. The relative rate constant for k(SCI decomposition) / k(SCI+SO2) is 3.0 (±3.2) × 1011 cm−3. Uncertainties are ±2σ and represent combined systematic and precision components. These kinetic parameters are based on the simplification that a single SCI species is formed in isoprene ozonolysis, an approximation which describes the results well across the full range of experimental conditions. Our data indicate that isoprene-derived SCIs are unlikely to make a substantial contribution to gas-phase SO2 oxidation in the troposphere. We also present results from an analogous set of experiments, which show a clear dependence of SO2 removal in the isoprene–ozone system as a function of dimethyl sulfide concentration. We propose that this behaviour arises from a rapid reaction between isoprene-derived SCIs and dimethyl sulfide (DMS); the observed SO2 removal kinetics are consistent with a relative rate constant, k(SCI + DMS) / k(SCI + SO2), of 3.5 (±1.8). This result suggests that SCIs may contribute to the oxidation of DMS in the atmosphere and that this process could therefore influence new particle formation in regions impacted by emissions of unsaturated hydrocarbons and DMS.

Atmospheric isoprene ozonolysis: impacts of stabilized Criegee intermediate reactions with SO₂, H₂O and dimethyl sulfide

Isoprene is the dominant global biogenic volatile organic compound (VOC) emission. Reactions of isoprene with ozone are known to form stabilised Criegee intermediates (SCIs), which have recently been shown to be potentially important oxidants for SO2 and NO2 in the atmosphere; however the significance of this chemistry for SO2 processing (affecting sulfate aerosol) and NO2 processing (affecting NOx levels) depends critically upon the fate of the SCI with respect to reaction with water and decomposition. Here, we have investigated the removal of SO2 in the presence of isoprene and ozone, as a function of humidity, under atmospheric boundary layer conditions. The SO2 removal displays a clear dependence on relative humidity, confirming a significant reaction for isoprene derived SCI with H2O. Under excess SO2 conditions, the total isoprene ozonolysis SCI yield was calculated to be 0.56 (±0.03). The observed SO2 removal kinetics are consistent with a relative rate constant, k(SCI + H2O)/k(SCI + SO2), of 5.4 (±0.8) × 10−5 for isoprene derived SCI. The relative rate constant for k(SCI decomposition)/k(SCI + SO2) is 8.4 (±5.0) × 1010 cm−3. Uncertainties are ±2σ and represent combined systematic and precision components. These kinetic parameters are based on the simplification that a single SCI species is formed in isoprene ozonolysis, an approximation which describes the results well across the full range of experimental conditions. Our data indicate that isoprene-derived SCIs are unlikely to make a substantial contribution to gas-phase SO2 oxidation in the troposphere. We also present results from an analogous set of experiments, which show a clear dependence of SO2 removal in the isoprene-ozone system as a function of dimethyl sulfide concentration. We propose that this behaviour arises from a rapid reaction between isoprene-derived SCI and DMS; the observed SO2 removal kinetics are consistent with a relative rate constant, k(SCI + DMS)/k(SCI + SO2), of 4.1 (±2.2). This result suggests that SCIs may contribute to the oxidation of DMS in the atmosphere and that this process could therefore influence new particle formation in regions impacted by emissions of unsaturated hydrocarbons and DMS.

Notable Substituent Effects on the Rate Constant of Thermal Denitrogenation of Cyclic Azoalkanes: Strong Evidence for a Stepwise Denitrogenation Mechanism

The thermal denitrogenation rates (k) of a series of 7,7-dimethoxy-1,4-diaryl-2,3-diazabicyclo[2.2.1]hept-2-ene derivatives 2 with a variety of aryl groups (p-CNC6H4, C6H5, p-MeC6H4, p-MeOC6H4) were determined to investigate the denitrogenation mechanism. A linear correlation (r = 0.988) between the relative rate-constant (log krel) of the denitrogenation reaction and Arnold’s σα• parameter for benzylic-type radical-stabilization was observed. However, the relative rate-constant was not correlated with the substituent effect on the lifetime of the resulting singlet diradicals DR2. These results indicate that the rate-determining step of denitrogenation of 7,7-dimethoxy-2,3-diazabicyclo[2.2.1]hept-2-ene derivatives involves stepwise C–N bond cleavage.

Solvent isotope effects as a probe of general catalysis and solvation in phosphoryl transfer

Phosphoryl transfer to methanol from tris(p-nitrophenyl) phosphate (PNNN), methyl bis(p-nitrophenyl) phosphate (PMNN), and dimethyl p-nitrophenyl phosphate (PMMN) exhibits general base catalysis by acetate ion but no detectable catalysis by acetic acid. For PNNN, acetate catalysis produces normal solvent isotope effects kROH/kROD of 1.68 ± 0.01 at high ionic strength (0.475) and 1.77 ± 0.04 at low ionic strength (0.048). A linear proton inventory indicates most simply that the isotope effect arises from a one-proton catalytic bridge in the transition state, although this model cannot strongly be distinguished from a generalized solvation effect. Reactions of methoxide ions produce slight inverse isotope effects kROD/kROH of 1.1–1.2, far smaller than the inverseeffect of about 2.5 expected for complete and uncompensated desolvation of the reactant-state methoxide ion. The transition state is thus stabilized by substantial interaction with the solvent. The proton inventory for the least reactive substrate PMMN (relative rate constant 1) is suggestive of transition-state stabilization by a combination of one-proton catalytic bridge(s) and distributed sites, while the proton inventory for the most reactive substrate PNNN (relative rate constant 1388) suggests only generalized transition-state solvation (many distributed sites); the proton inventory for PMNN, a substrate of intermediate reactivity (relative rate constant 60), suggests an intermediate situation. The data are consistent with a model in which transition states with exterior concentrations of charge favor stabilization of the charge by isotope-fractionating one-proton bridges, while transition states with distributed charge favor stabilization of the charge by many distributed sites. Key words: phosphoryl transfer, proton inventories, solvent isotope effects.

Reactions of cumyloxyl radicals with tetrakis(allyloxymethyl)methane

GLC Analysis of decomposition products of dicumyl peroxide has been used for determination of relative rate constant of hydrogen transfer of cumyloxyl radicals with tetrakis(allyloxymethyl)-methane. This constant is 15 times higher than that with 2,2,4-trimethylpentane. In the reaction an only small portion of the oxyl radicals (up to 15% of total amount) is consumed by addition to allyl groups of the monomer even when a great excess of the latter is present in the reaction mixture.