Preface Acknowledgements 1. Introduction 2. Atmospheric structure, composition and thermodynamics 3. The continuity and thermodynamic energy equations 4. The momentum equation in Cartesian and spherical coordinates 5. Vertical-coordinate conversions 6. Numerical solutions to partial differential equations 7. Finite-differencing the equations of atmospheric dynamics 8. Boundary-layer and surface processes 9. Radiative energy transfer 10. Gas-phase species, chemical reactions and reaction rates 11. Urban, free-tropospheric and stratospheric chemistry 12. Methods of solving chemical ordinary differential equations 13. Particle components, size distributions and size structures 14. Aerosol emission and nucleation 15. Coagulation 16. Condensation, evaporation, deposition and sublimation 17. Chemical equilibrium and dissolution processes 18. Cloud thermodynamics and dynamics 19. Irreversible aqueous chemistry 20. Sedimentation, dry deposition and air-sea exchange 21. Model design, application and testing Appendix A. Conversions and constants Appendix B. Tables References Index.

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Fundamentals of atmospheric modeling

Unattenuated solar photo rate coefficients and excess energies for dissociation, ionization, and dissociative ionization are presented for atomic and molecular species that have been identified or are suspected to exist in the atmospheres of planets, satellites (moons), comets, or as pollutants in the Earth atmosphere. The branching ratios and cross sections with resonances have been tabulated to the greatest detail possible and the rate coefficients and excess energies have been calculated from them on a grid of small wavelength bins for the quiet and the active Sun at 1 AU heliocentric distance.

Solar photo rates for planetary atmospheres and atmospheric pollutants

A detailed set of reactions treating the gas and aqueous phase chemistry of the most important iodine species in the marine boundary layer (MBL) has been added to a box model which describes Br and Cl chemistry in the MBL. While Br and Cl originate from seasalt, the I compounds are largely derived photochemically from several biogenic alkyl iodides, in particular CH2I2, CH2ClI, C2H5I, C3H7I, or CH3I which are released from the sea. Their photodissociation produces some inorganic iodine gases which can rapidly react in the gas and aqueous phase with other halogen compounds. Scavenging of the iodine species HI, HOI, INO2, and IONO2 by aerosol particles is not a permanent sink as assumed in previous modeling studies. Aqueous-phase chemical reactions can produce the compounds IBr, ICl, and I2, which will be released back into the gas phase due to their low solubility. Our study, although highly theoretical, suggests that almost all particulate iodine is in the chemical form of IO-3. Other aqueous-phase species are only temporary reservoirs and can be re-activated to yield gas phase iodine. Assuming release rates of the organic iodine compounds which yield atmospheric concentrations similar to some measurements, we calculate significant concentrations of reactive halogen gases. The addition of iodine chemistry to our reaction scheme has the effect of accelerating photochemical Br and Cl release from the seasalt. This causes an enhancement in ozone destruction rates in the MBL over that arising from the well established reactions O(1D) + H2O → 2OH, HO2 + O3 → OH + 2O2, and OH + O3 → HO2 + O2. The given reaction scheme accounts for the formation of particulate iodine which is preferably accumulated in the smaller sulfate aerosol particles.

Iodine chemistry and its role in halogen activation and ozone loss in the marine boundary layer: A model study

The coupled vibration—dissociation—recombination process for molecules and atoms has been examined. Techniques for solving the appropriate master equations for both quantum (discrete) and classical (continuous) models are given. It is shown that the process is most easily treated classically and that in this case the master equation can be reduced to an equivalent diffusion equation. It is assumed that, after an initial vibration transient, during which reactions are negligible, the process may be treated using the steady‐state approximation. During the steady‐state phase, the usual phenomenological rate equations are valid and the ratio of the forward and reverse rate constants is the equilibrium constant, though the individual rate constants are depressed below their equilibrium values.Comparison of the results with other theoretical work shows general agreement for similar models; comparison with shock‐tube experiments on molecular dissociation and stellarator experiments on ionic recombination is enco...

Doyle Britton

Papers

The Continuous Absorption Spectra of Chlorine, Bromine, Bromine Chloride, Iodine Chloride, and Iodine Bromide

Shock waves in chemical kinetics: further studies in the rate of dissociation of bromine

Shock waves in chemical kinetics: the hydrogen—bromine reaction

On the Equilibrium Constant for Loosely Bound Molecules