Atmospheric kinetics

Thermal dehydroxylation of FeOOH has been studied both in vacuum and under various atmospheres. Kinetic studies of these transformations must be carried out under vacuum (Giovanoli Briitsch, 1974) and at a constant temperature. The temperature at which a phase transformation occurs, however, is determined by increasing the temperature of the sample in a controlled manner, i.e. by using a thermobalance (DTA or TGA method, see Ghap. 7). Mechanical and mechanochemical dehydroxylation of FeOOH at room temperature can also be achieved by grinding. 

The fragmentation of a molecule in its ground electronic state is commonly known as unimolecular dissociation [26-28]. [For a recent review see Ref. 29 and the Faraday Discussion of the Chemical Society, vol. 102 (1995).] Because of its importance in several areas of physical chemistry, such as combustion or atmospheric kinetics, there is a high demand of accurate unimolecular dissociation rates. On the other hand, however, the calculation of reliable dissociation rates by dynamical methods (i.e., the solution of the classical or quantum mechanical equations of motion) is, for obvious technical problems, prohibited for all but a few simple molecules. For... 

Atmospheric Kinetics and Photochemistry Group, Atmospheric Chemistry Division, National Center for Atmospheric Research, P.O. Box 3000, Boulder, CO 80307-3000... 

A collaborative effort between the groups of Mabury and Wallington investigated the atmospheric kinetics and reaction dynamics of the FTOHs. 

Mathur, R., Young, J.O., Schere, K.L., and Gipson, G.L., A comparison of numerical techniques for solution of atmospheric kinetic equations, Atmos. Environ., 1998, 32, 1535-1553. 

Procedure 5.5 Inert Atmosphere Kinetics Using Conventional Visible Spectroscopy Methods... 

Atmospheric kinetic samplers, sometimes referred to as diffusion samplers , have a long history of use in roles such as personal monitors or dosimeters to evaluate personal exposure or... 

Ferguson E E 1979 Ion-molecule reactions in the atmosphere Kinetics of Ion-Molecule Reactions ed P Ausloos (New York Plenum)... 

An important part of specifying a chemical reaction mechanism is providing accurate parameterisations of the rate coefficients. In liquid phase and in atmospheric kinetics, the temperature dependence of rate coefficient k is usually described by the Arrhenius equation ... 

The lUPAC collections of atmospheric kinetic data (lUPAC 2014 Atkinson et al. 2004,2006,2007,2008) define the uncertainty of the rate coefficient as follows ... 

The Jet Propulsion Laboratory (JPL) regularly publishes and photochemistry database. Currently the latest version published in 2011 (Sander et al. 2011). an atmospheric kinetics is number 17 that was... 

Cabanas, B., M.T. Baeza, S. Salgado, R Martin, R. Taccone, and E. Martinez (2004), Oxidation of heterocycles in the atmosphere Kinetic study of their reactions with NO3 radical, J. Phys. Chem., 108, 10818-10823. 

As a consequence of these simple deductions, Graham s experiments c effusion through an orifice came to be regarded as one of the earliest direct experimental checks on the kinetic theory of gases. However, a closer examination of his experimental conditions reveals that this view is mistaken. As mentioned earlier, his orifice diameters ranged upwards from 1/500 in., while the upstream pressure was never very much less thai atmospheric. Under these circumstances the molecular mean free path len ... 

Electrons from a spark are accelerated backward and forward rapidly in the oscillating electromagnetic field and collide with neutral atoms. At atmospheric pressure, the high collision frequency of electrons with atoms induces chaotic electron motion. The electrons gain rapidly in kinetic energy until they have sufficient energy to cause ionization of some gas atoms. 

Anhydrous, monomeric formaldehyde is not available commercially. The pure, dry gas is relatively stable at 80—100°C but slowly polymerizes at lower temperatures. Traces of polar impurities such as acids, alkahes, and water greatly accelerate the polymerization. When Hquid formaldehyde is warmed to room temperature in a sealed ampul, it polymerizes rapidly with evolution of heat (63 kj /mol or 15.05 kcal/mol). Uncatalyzed decomposition is very slow below 300°C extrapolation of kinetic data (32) to 400°C indicates that the rate of decomposition is ca 0.44%/min at 101 kPa (1 atm). The main products ate CO and H2. Metals such as platinum (33), copper (34), and chromia and alumina (35) also catalyze the formation of methanol, methyl formate, formic acid, carbon dioxide, and methane. Trace levels of formaldehyde found in urban atmospheres are readily photo-oxidized to carbon dioxide the half-life ranges from 35—50 minutes (36). 

Ma.nufa.cture. Mesityl oxide is produced by the Hquid-phase dehydration of diacetone alcohol ia the presence of acidic catalysts at 100—120°C and atmospheric pressure. As a precursor to MIBK, mesityl oxide is prepared ia this manner ia a distillation column ia which acetone is removed overhead and water-saturated mesityl oxide is produced from a side-draw. Suitable catalysts are phosphoric acid (177,178) and sulfuric acid (179,180). The kinetics of the reaction over phosphoric acid have been reported (181). 

At the high temperatures found in MHD combustors, nitrogen oxides, NO, are formed primarily by gas-phase reactions, rather than from fuel-bound nitrogen. The principal constituent is nitric oxide [10102-43-9] NO, and the amount formed is generally limited by kinetics. Equilibrium values are reached only at very high temperatures. NO decomposes as the gas cools, at a rate which decreases with temperature. If the combustion gas cools too rapidly after the MHD channel the NO has insufficient time to decompose and excessive amounts can be released to the atmosphere. Below about 1800 K there is essentially no thermal decomposition of NO. 

Meteors produce atmospheric plasmas as their kinetic energy is converted to thermal energy (50). Most particles from space are consumed before they reach an altitude of 50 km. Meteors are of Httie practical use, although radio waves can be bounced off the plasmas left in their wakes (see Exthaterresthial materials). ... 

Magnetospheric plasmas are produced and heavily influenced by solar emissions and activity and by magnetic fields of the planets. Interplanetary plasmas result from solar emission processes alone. Protons in the solar wind have low densities (10—100/cm ) and temperatures below 10 to more than 10 K (1—10 eV). Their average outward kinetic energy from the sun is approximately 400 eV (58,59). The various 2ones and phenomena from the sun s visible surface to the upper atmosphere of the earth have been discussed (60—62). 

Representation of Atmospheric Chemistry Through Chemical Mechanisms. A complete description of atmospheric chemistry within an air quaUty model would require tracking the kinetics of many hundreds of compounds through thousands of chemical reactions. Fortunately, in modeling the dynamics of reactive compounds such as peroxyacetyl nitrate [2278-22-0] (PAN), C2H2NO, O, and NO2, it is not necessary to foUow every compound. Instead, a compact representation of the atmospheric chemistry is used. Chemical mechanisms represent a compromise between an exhaustive description of the chemistry and computational tractabiUty. The level of chemical detail is balanced against computational time, which increases as the number of species and reactions increases. Instead of the hundreds of species present in the atmosphere, chemical mechanisms include on the order of 50 species and 100 reactions. 

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