Papers by Keyword: Thermochemical Property

Abstract: The thermochemical properties of varieties of species needed to assess the most prominent pathways of tropospheric ozone transformation have been established. In the troposphere, ozone which is a secondary pollution produced by photochemical induced transformation, acts as an oxidizing agent to numerous atmospheric reactions leading to the formation of particulate matter. Based on the climate related problems resulting from the precursor of particulate matter, it is adequate to establish the feasible routes of ozone formation. In this study, the electronic structure methods which approximate the Schrödinger equation to compute Gibbs free energies and enthalpies of formation of the various chemical species participating in the reactions were used. These thermodynamic properties were determined using four computational model chemistry methods integrated in the Gaussian 03 (G03) chemistry package. Five known reaction pathways for the formation of NO2 (the O3 precursor specie), as well as the dominant ozone formation route from NO2 were examined and their energies determined. Of all the computational methods, the complete basis set (CBS-4M) method produced energies for all species of the five reaction routes. Out of the five routes, only the reactions involving radical species were favoured to completion over a temperature range of -100 and +100oC. The most relevant reaction route for the formation of NO2 and subsequently O3 is that involving the peroxyl acetyl nitrate (PAN) and hydroxyl radicals. Chemical equilibrium analyses of the reaction routes also indicated that reduction in temperature encourages NO2 formation while increase in temperature favours O3 production.

Abstract: The site preference of ternary additions in Ni3X-type GCP compounds was determined from the direction of solubility lobe of the GCP phase on the experimentally reported ternary phase diagrams. In Ni3Nb (D0a), Co and Cu preferred the substitution for Ni-site, Ti, V and W the substitution for Nb-site, and Fe the substitution for both sites. In Ni3V (D022), Co preferred the substitution for Ni-site, Cr the substitution for both sites, and Ti the substitution for V-site. In Ni3Ti (D024), Fe, Co, Cu, and Si preferred the substitution for Ni-site, Nb, Mo and V the substitution for Ti-site. The thermodynamic model, which was based on the change in total bonding energy of the host compound by a small addition of ternary solute, was applied to predict the site preference of ternary additions. The bond energy of each nearest neighbor pair used in the thermodynamic calculation was derived from the heat of compound formation by Miedema’s formula. The agreement between the thermodynamic model and the result of the literature search was excellent. Both transition and B-subgroup elements have two possibilities, i.e., the case of substitution for Ni-site or the case for X-site, depending on the relative value of two interaction energies.

Abstract: The thermochemical properties of varieties of species involved in the formation and consumption or destruction of tropospheric ozone during chemical reactions have been established. Ozone in the troposphere is produced during the day-time; hence it is a photochemically induced transformation process. This compound acts as precursor specie in many atmospheric transformations and constitutes a baseline component worth investigating. This study utilized electronic structure methods of computational model chemistries to evaluate for Gibbs free energies and enthalpies of formation and reactions of the various species. Ten prominent gas-phase and aqueous-phase reactions were analysed using five computational approaches consisting of four ab initio methods and one density functional theory (DFT) method. The computed energy values in comparison to those obtained through experimental approaches yielded an error of mean absolute deviation of 0.81%. The most relevant species that tend to enhance the production of ozone in the troposphere were O* and H2O2 for the gas-phase and aqueous-phase reactions respectively. Chemical equilibrium analysis indicated that the ozone formation and consumption reactions are more favourable in colder regions and at winter.