Thermodynamic Properties: Enthalpy, Entropy, Heat Capacity, and Bond Energies of Fluorinated Carboxylic Acids.

Fluorinated carboxylic acids and their radicals are becoming more prevalent in environmental waters and soils as they have been produced and used for numerous commercial applications. Understanding the thermochemical properties of fluorinated carboxylic acids will provide insights into the stability and reaction paths of these molecules in the environment, in body fluids, and in biological and biochemical processes. Structures and thermodynamic properties for over 50 species related to fluorinated carboxylic acids with two and three carbons are determined with density functional computational calculations B3LYP, M06-2X, and MN15 and higher ab initio levels CBS-QB3, CBS-APNO, and G4 of theory.

Kinetic Analysis of Unimolecular Reactions Following the Addition of the Hydroxyl Radical to 1,1,2-Trifluoroethene.

Fluorinated olefins are valued chemicals in industry, especially as heat transfer fluids in refrigeration applications. As these volatile compounds are widely used, they may be released into the atmosphere, and investigation of their reactions in the atmosphere are therefore of importance. The kinetic analysis of the reaction mechanisms of trifluoroethene (CF═CHF) with hydroxyl radicals is studied using computational chemistry at the M06-2X level with the 6-311++G(2d,d,p) and aug-cc-pVDZ basis sets as well as the composite CBS-QB3 method.

OH-Initiated Reactions of -Coumaryl Alcohol Relevant to the Lignin Pyrolysis. Part II. Kinetic Analysis.

Monolignols are precursor units and primary products of lignin pyrolysis. The currently available global (lumped) and semidetailed kinetic models, however, are lacking the comprehensive decomposition kinetics of these key intermediates in order to advance toward the fundamentally based detailed chemical-kinetic models of biomass pyrolysis. -Coumaryl alcohol (HOPh-CH═CH-CHOH, -CMA) is the simplest of the three basic monolignols containing a typical side-chain double bond and both alkyl and phenolic type OH groups.

OH-Initiated Reactions of -Coumaryl Alcohol Relevant to the Lignin Pyrolysis. Part III. Kinetics of H-Abstraction by H, OH, and CH Radicals.

Lignin is the most complex component of biomass, and development of a detailed chemical kinetic model for biomass pyrolysis mainly relies on the understanding of the lignin decomposition kinetics. -Coumaryl alcohol (-CMA, HOPh-CH═CH-CHOH), the focus of our analysis, is the simplest of the lignin monomers (monolignols) containing a typical side-chain double bond and both alkyl- and phenolic-type OH-groups. In parts I and II of our work (Asatryan, R.

Thermochemistry of Intermediates and Products in the Oxidation Reaction of 1,1,2-Trifluoroethene via OH Radical.

Density functional theory (DFT) and composite ab initio based calculations are performed on trifluoroethane along with intermediate radicals, parent molecules of the radicals, and products related to the reaction of hydroxyl radical with 1,1,2-trifluoroethene, as a reference for hydrofluoroolefins (HFO). Potential energy barriers for internal rotations have been computed. Calculated torsional potentials are incorporated into the determination of entropy, , and heat capacities as a function of temperature, (), for each target molecule.

OH-Initiated Reactions of p-Coumaryl Alcohol Relevant to the Lignin Pyrolysis. Part I. Potential Energy Surface Analysis ⊥.

Cinnamyl alcohols such as p-coumaryl alcohol ( p-CMA) are lignin models and precursors (monolignols) and the most important primary products of lignin pyrolysis. However, the detection of monomers is not straightforward since they either undergo secondary transformations or repolymerize to contribute to the char formation. Both concerted-molecular and free-radical pathways are involved in these processes.

Thermochemical Properties: Enthalpy, Entropy, and Heat Capacity of C2-C3 Fluorinated Aldehydes. Radicals and Fluorocarbon Group Additivity.

Thermochemical properties of fluorinated aldehydes are important for understanding their stability and reactions in the environment and in thermal processes. Structures and thermochemical properties of C1 to C3 fluorinated aldehydes are determined by use of computational chemistry. Standard enthalpies of formation for 30 C- and C-fluorinated aldehydes and 31 radicals were calculated with 11 different ab initio and density functional theory methods: CBS-APNO, CBS-4M, CBS-QB3, M06-2X, ωB97X, B3LYP, G-2, G-3, G-4, and W1U via several series of isodesmic reactions.

Reaction Paths and Chemical Activation Reactions of 2-Methyl-5-Furanyl Radical with O.

Interest in high-energy substituted furans has been increasing due to their occurrence in biofuel production and their versatility in conversion to other useful products. Methylfurans are the simplest substituted furans and understanding their reaction pathways, thermochemical properties, including intermediate species stability, and chemical kinetics would aid in the study of larger furans. Furan ring C-H bonds have been shown to be extremely strong, approximately 120 kcal mol, due in part to the placement of the oxygen atom and aromatic-like resonance, both within the ring.

Thermochemistry of Hydroxyl and Hydroperoxide Substituted Furan, Methylfuran, and Methoxyfuran.

Reaction pathways are influenced by thermochemical properties, species stability, and chemical kinetics. Understanding these factors allows for an understanding of the reaction paths and formation of intermediate species. Enthalpies of formation (ΔH), entropies (S), heat capacities (C(T)), oxygen-hydrogen (O-H), oxygen-oxygen (O-O), and (R-O) bond dissociation energies (BDEs) are reported for hydroxyl and hydroperoxide substituted furan, methylfuran, and methoxyfuran species.

Molecular Products and Fundamentally Based Reaction Pathways in the Gas-Phase Pyrolysis of the Lignin Model Compound p-Coumaryl Alcohol.

The fractional pyrolysis of lignin model compound para-coumaryl alcohol (p-CMA) containing a propanoid side chain and a phenolic OH group was studied using the System for Thermal Diagnostic Studies at temperatures from 200 to 900 °C, in order to gain mechanistic insight into the role of large substituents in high-lignin feedstocks pyrolysis. Phenol and its simple derivatives p-cresol, ethyl-, propenyl-, and propyl-phenols were found to be the major products predominantly formed at low pyrolysis temperatures (<500 °C). A cryogenic trapping technique was employed combined with EPR spectroscopy to identify the open-shell intermediates registered at pyrolysis temperatures above 500 °C.

Thermochemical Properties and Bond Dissociation Energies for Fluorinated Methanol, CH3-xFxOH, and Fluorinated Methyl Hydroperoxides, CH3-xFxOOH: Group Additivity.

Oxygenated fluorocarbons are routinely found in sampling of environmental soils and waters as a result of the widespread use of fluoro and chlorofluoro carbons as heat transfer fluids, inert materials, polymers, fire retardants and solvents; the influence of these chemicals on the environment is a growing concern. The thermochemical properties of these species are needed for understanding their stability and reactions in the environment and in thermal process. Structures and thermochemical properties on the mono- to trifluoromethanol, CH3-xFxOH, and fluoromethyl hydroperoxide, CH3-xFxOOH (1 ≤ x ≤ 3), are determined by CBS-QB3, CBS-APNO, and G4 calculations.

Thermochemistry and Kinetic Analysis of the Unimolecular Oxiranyl Radical Dissociation Reaction: A Theoretical Study.

Oxirane structures are important in organic synthesis, and they are important initial products in the oxidation reactions of alkyl radicals. The thermochemical properties (enthalpy of formation, entropy, and heat capacity) for the reaction steps of the unimolecular oxiranyl radical dissociation reaction are determined and compared with the available literature. The overall ring opening and subsequent steps involve four types of reactions: β-scission ring opening, intramolecular hydrogen transfer, β-scission hydrogen elimination, and β-scission methyl radical elimination.

Cyclopentadienone Oxidation Reaction Kinetics and Thermochemistry for the Alcohols, Hydroperoxides, and Vinylic, Alkoxy, and Alkylperoxy Radicals.

Cyclopentadienone has one carbonyl and two olefin groups resulting in 4n + 2 π-electrons in a cyclic five-membered ring structure. Thermochemical and kinetic parameters for the initial reactions of cyclopentadienone radicals with O2 and the thermochemical properties for cyclopentadienone-hydroperoxides, alcohols, and alkenyl, alkoxy, and peroxy radicals were determined by use of computational chemistry. The CBS-QB3 composite and B3LYP density functional theory methods were used to determine the enthalpies of formation (ΔfH°298) using the isodesmic reaction schemes with several work reactions for each species.

Bond Energies and Thermochemical Properties of Ring-Opened Diradicals and Carbenes of exo-Tricyclo[5.2.1.0(2,6)]decane.

Exo-tricyclo[5.2.1.

Thermochemical Properties Enthalpy, Entropy, and Heat Capacity of C1-C4 Fluorinated Hydrocarbons: Fluorocarbon Group Additivity.

Enthalpies of formation for 14 C2–C4 fluorinated hydrocarbons were calculated with nine popular ab initio and density functional theory methods: B3LYP, CBS-QB3, CBS-APNO, M06, M06-2X, ωB97X, G4, G4(MP2)-6X, and W1U via several series of isodesmic reactions. The recommended ideal gas phase ΔHf298° (kcal mol(–1)) values calculated in this study are the following: −65.4 for CH3CH2F; −70.

Thermochemistry of C7H16 to C10H22 alkane isomers: primary, secondary, and tertiary C-H bond dissociation energies and effects of branching.

Standard enthalpies of formation (ΔH°f 298) of methyl, ethyl, primary and secondary propyl, and n-butyl radicals are evaluated and used in work reactions to determine internal consistency. They are then used to calculate the enthalpy of formation for the tert-butyl radical. Other thermochemical properties including standard entropies (S°(T)), heat capacities (Cp(T)), and carbon-hydrogen bond dissociation energies (C-H BDEs) are reported for n-pentane, n-heptane, 2-methylhexane, 2,3-dimethylpentane, and several branched higher carbon number alkanes and their radicals.

Thermochemistry, reaction paths, and kinetics on the tert-isooctane radical reaction with O2.

Thermochemical properties of tert-isooctane hydroperoxide and its radicals are determined by computational chemistry. Enthalpies are determined using isodesmic reactions with B3LYP density function and CBS QB3 methods. Application of group additivity with comparison to calculated values is illustrated.

Mercury oxidation via chlorine, bromine, and iodine under atmospheric conditions: thermochemistry and kinetics.

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.

Thermochemical properties and bond dissociation enthalpies of 3- to 5-member ring cyclic ether hydroperoxides, alcohols, and peroxy radicals: cyclic ether radical + (3)O(2) reaction thermochemistry.

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.

Thermochemical properties for isooctane and carbon radicals: computational study.

Thermochemical properties for isooctane, its internal rotation conformers, and radicals with corresponding bond energies are determined by use of computational chemistry. Enthalpies of formation are determined using isodesmic reactions with B3LYP density function theory and composite CBS-QB3 methods. Application of group additivity with comparison to calculated values is illustrated.

Thermochemical properties of methyl-substituted cyclic alkyl ethers and radicals for oxiranes, oxetanes, and oxolanes: C-H bond dissociation enthalpy trends with ring size and ether site.

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.

Kinetics of the benzyl + O(3P) reaction: a quantum chemical/statistical reaction rate theory study.

The resonance stabilized benzyl radical is an important intermediate in the combustion of aromatic hydrocarbons and in polycyclic aromatic hydrocarbon (PAH) formation in flames. Despite being a free radical, benzyl is relatively stable in thermal, oxidizing environments, and is predominantly removed through bimolecular reactions with open-shell species other than O(2). In this study the reaction of benzyl with ground-state atomic oxygen, O((3)P), is examined using quantum chemistry and statistical reaction rate theory.

Dihydrogen catalysis: a degradation mechanism for N2-fixation intermediates.

Molecular hydrogen plays multiple roles in activation of nitrogen. Among others, it inhibits the overall process of N(2)-reduction catalyzed by nitrogenase enzyme. The H(2)-assisted dehydrogenation and the H-atom transfer reactions (called dihydrogen catalysis, DHC) are suggested as possible mechanisms for the degradation and removal of potential intermediates formed during the reduction of nitrogen.

Thermochemical properties and bond dissociation energies of C3-C5 cycloalkyl hydroperoxides and peroxy radicals: cycloalkyl radical + (3)O2 reaction thermochemistry.

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.

Thermochemistry and bond dissociation energies of ketones.

Ketones are a major class of organic chemicals and solvents, which contribute to hydrocarbon sources in the atmosphere, and are important intermediates in the oxidation and combustion of hydrocarbons and biofuels. Their stability, thermochemical properties, and chemical kinetics are important to understanding their reaction paths and their role as intermediates in combustion processes and in atmospheric chemistry. In this study, enthalpies (ΔH°(f 298)), entropies (S°(T)), heat capacities (C(p)°(T)), and internal rotor potentials are reported for 2-butanone, 3-pentanone, 2-pentanone, 3-methyl-2-butanone, and 2-methyl-3-pentanone, and their radicals corresponding to loss of hydrogen atoms.