Emissions of gaseous mercury from combustion sources are the major source of Hg in the atmosphere and in environmental waters and soils. Reactions of Hg(o)(g) with halogens are of interest because they relate to mercury and ozone depletion events in the Antarctic and Arctic early spring ozone hole events, and the formation of Hg-halides (HgX2) is a method for removal of mercury from power generation systems. Thermochemistry and kinetics from published theoretical and experimental studies in the literature and from computational chemistry are utilized to compile a mechanism of the reactions considered as contributors to the formation of HgX2 (X = Cl, Br, I) to understand the reaction paths and mechanisms under atmospheric conditions. Elementary reaction mechanisms are assembled and evaluated using thermochemistry for all species and microscopic reversibility for all reactions. Temperature and pressure dependence is determined with quantum Rice Ramsperger Kassel (RRK) analysis for k(E) and master equation analysis for fall-off. We find that reactions of mercury with a small fraction of the reactor surface or initiation by low concentrations of halogen atoms is needed to explain the experimental conversion of Hg to HgX2 in the gas phase. The models do not replicate data from experiments that do not explicitly provide an atom source. The Hg insertion reaction into X2 (Hg + X2 → HgX2) that has been reported is further studied, and we find agreement with studies that report high barriers. The high barriers prevent this insertion path from explaining the experimental data on HgX2 formation and Hg conversion under atmospheric conditions. Mechanism studies with low initial concentrations of halogen radicals show significant conversion of Hg under the experimental conditions.

The formation of cyclic ethers is a major product in the oxidation of hydrocarbons, and the oxidation of biomass derived alcohols. Cyclic ethers are formed in the initial reactions of alkyl radicals with dioxygen in combustion and precombustion processes that occur at moderate temperatures. They represent a significant part of the oxygenated pollutants found in the exhaust gases of engines. Cyclic ethers can also be formed from atmospheric reactions of olefins. Additionally, cyclic ethers have been linked to the formation of the secondary organic aerosol (SOA) in the atmosphere. In combustion and thermal oxidation processes these cyclic ethers will form radicals that react with (3)O2 to form peroxy radicals. Density functional theory and higher level ab initio calculations are used to calculate thermochemical properties and bond dissociation enthalpies of 3 to 5 member ring cyclic ethers (oxirane, yC2O, oxetane, yC3O, and oxolane, yC4O), corresponding hydroperoxides, alcohols, hydroperoxy alkyl, and alkyl radicals which are formed in these oxidation reaction systems. Trends in carbon-hydrogen bond dissociation energies for the ring and hydroperoxide group relative to ring size and to distance from the ether group are determined. Bond dissociation energies are calculated for use in understanding effects of the ether oxygen in the cyclic ethers, their stability, and kinetic properties. Geometries, vibration frequencies, and enthalpies of formation, ΔH°f,298, are calculated at the B3LYP/6-31G(d,p), B3LYP/6-31G(2d,2p), the composite CBS-QB3, and G3MP2B3 methods. Entropy and heat capacities, S°(T) and Cp°(T) (5 K ≤ T ≤ 5000), are determined using geometric parameters and frequencies from the B3LYP/6-31G(d,p) calculations. The strong effects of ring strain on the bond dissociation energies in these peroxy systems are also of fundamental interest. Oxetane and oxolane exhibit a significant stabilization, 10 kcal mol(-1), lower ΔfH°298 when an oxygen group is on the ether carbon relative to the isomer with the oxygen group on a secondary carbon. Relative to alkane systems the ether oxygen decreases bond dissociation energies (BDEs) on carbon sites adjacent to the ether by ∼5 kcal mol(-1), and increases BDEs on nonether carbons ∼1 kcal mol(-1). The cyclic structures have significant effects on the C-H, CO-OH, COO-H, and CO-H bond dissociation enthalpies. These values can be used to help calibrate calculations of larger more complex bicyclic and tricyclic hydrocarbon and ether species.

2,2,4‐Trimethylpentane, also known as isooctane, is used as one of the model fuel species on spark and homogeneous charge compression ignition engines. This study presents thermochemical and kinetic properties in the oxidation of the secondary isooctane radical, which includes the peroxy radical formed from the 3O2 association, the hydroperoxy alkyl radicals formed from the intramolecular hydrogen transfers, and the products formed from reactions of the hydroperoxy alkyl radicals. Geometries, vibration frequencies, internal rotor potentials, and thermochemical properties, ΔfH298∘, S°(T), and C°p(T) (5 K ≤ T ≤ 5000 K) were calculated at the individual B3LYP/6–31G(d,p) and the composite CBS‐QB3 calculation method. The standard enthalpies of formation at 298 K were evaluated using isodesmic reaction schemes with several work reactions for each species. Entropy and heat capacities were determined using geometric parameters and frequencies from the B3LYP/6–31G(d,p) calculations for the lowest energy conformer. Internal rotor barriers were determined. Application of group additivity with comparison to calculated values is also illustrated. Transition states and kinetic parameters for intramolecular hydrogen atom transfer and molecular elimination channels were characterized to evaluate reaction paths and kinetics. Kinetic parameters were determined versus pressure and temperature for the chemical activated formation and unimolecular dissociation of the peroxide adduct. Multifrequency quantum Rice–Ramsperger–Kassel analysis was used for k(E) with master equation analysis for falloff. The kinetic analysis shows that the main reaction channels are the formation of isooctene ((CH3)3CCH=C(CH3)2) + HO2•, and the formation of the cyclic: (CH3)2‐y(CCH2CHO)‐(CH3)2, (CH3)3C‐y(CHCO)‐(CH3)2, and (CH3)3C‐y(CHCHCH2O)‐(CH3).

Cyclic aliphatic hydrocarbons are major components in modern fuels; they can be present in the reactants, and they can be formed during the gas-phase oxidation processes. In combustion and thermal oxidation processes, these cyclics will form radicals that react with (3)O(2) to form peroxy radicals. In this study, density functional theory and higher level ab initio calculations are used to calculate thermochemical properties and bond dissociation energies of 3-5-membered cycloalkanes, corresponding hydroperoxides, hydroperoxycycloalkyl radicals, and cycloalkyl radicals that occur in these reaction systems. Geometries, vibration frequencies, and thermochemical properties, ΔH(f 298)°, are calculated with the B3LYP/6-31 g(d,p), B3LYP/6-31 g(2d,2p), composite CBS-QB3, and G3MP2B3 methods. Standard enthalpies of formation at 298 K are evaluated using isodesmic reaction schemes with several work reactions for each species. Group additivity contributions are developed, and application of group additivity with comparison to calculated values is illustrated. Entropy and heat capacities, S°(T) and C(p)°(T) (5 K ≤ T ≤ 5000), are determined using geometric parameters and frequencies from the B3LYP/6-31 g(d,p) calculations.

Cyclic ethers are an important product from the gas-phase reactions of hydrocarbon radicals with molecular oxygen in the atmospheric chemistry of diolefins and in low to moderate temperature combustion and oxidation reaction systems. They are also important in organic synthesis. Structures, and fundamental thermochemical parameters-enthalpy (ΔH°(f,298)), entropy (S°(298)), and heat capacity (C(p)(T))-have been calculated for a series of cyclic alkyl ethers and their carbon centered radicals. Enthalpies of formation (ΔH°(f,298)) are determined at the B3LYP/6-31G(d,p), B3LYP/6-31G(2d,2p), and CBS-QB3 levels using several work reactions for each species. Entropy (S) and heat capacity (C(p)(T)) values from vibration, translational, and external rotational contributions are calculated using the rigid-rotor-harmonic-oscillator approximation based on the vibration frequencies and structures obtained from the density functional studies. Contributions from the internal methyl rotors are substituted for torsion frequencies. Calculated enthalpies of formation for a series of 12 cyclic ethers and methyl substituted cyclic ethers are in good agreement with available literature values. C-H bond dissociation enthalpies are reported for 28 carbon sites of 3 to 5 member ring cyclic ethers for use in understanding effects of the ring and the ether oxygen on kinetics and stability. Trends in carbon-hydrogen bond energies for the ring and methyl substituents relative to ring size and to distance from the ether group are described.