Chemical kinetics atmospheric reactions

The time required for atmospheric chemical processes to occur is dependent on chemical kinetics. Many of the air quality problems of major metropolitan areas can develop in just a few days. Most gas-phase chemical reactions in the atmosphere involve the collision of two or three molecules, with subsequent rearrangement of their chemical bonds to form molecules by combination of their atoms. Consider the simple case of a bimolecular reaction of the following type-. 

Why Do We Need to Know Ihis Material Chemical kinetics provides us with tools that we can use to study the rates of chemical reactions on both the macroscopic and the atomic levels. At the atomic level, chemical kinetics is a source of insight into the nature and mechanisms of chemical reactions. At the macroscopic level, information from chemical kinetics allows us to model complex systems, such as the processes taking place in the human body and the atmosphere. The development of catalysts, which are substances that speed up chemical reactions, is a branch of chemical kinetics crucial to the chemical industry, to the solution of major problems such as world hunger, and to the development of new fuels. 

The terms rate, speed, and velocity are all synonymous in chemical kinetics, though this is not so in mechanics. It takes different periods of time to complete different reactions. The neutralization reaction between acids and bases, mentioned earlier as an example of homogeneous reactions, takes place almost instantaneously at room temperature and under atmospheric pressure. However, it takes many days for iron to rust under these conditions. Thus, the rates of reactions that may take place under the same conditions of temperature and pressure may differ very significantly. When carbon or sulfur or phosphorus bums in... 

As another example from chemical kinetics, we consider the catalytic reduction of nitric oxide (NO) by hydrogen which was studied using a flow reactor operated differentially at atmospheric pressure (Ayen and Peters, 1962). The following reaction was considered to be important... 

The reaction of ammonia and hydrogen chloride in the gas phase has been the subject of several studies in the last 30 years [56-65], The interest in this system is mainly that it represents a simple model for proton transfer reactions, which are important for many chemical and biological processes. Moreover, in the field of atmospheric sciences, this reaction has been considered as a prototype system for investigation of particle formation from volatile species [66,67], Finally, it is the reaction chosen as a benchmark on the ability, of quantum chemical computer simulations, to realistically simulate a chemical process, its reaction path and, eventually, its kinetics. 

Hampson RF. 1980. Chemical kinetic and photochemical data sheets for atmospheric reactions. Washington, DC U.S. Department of Transportation. 

Slagle, I. R., J. R. Gilbert, R. E. Graham, and D. Gutman. Direct identification of reactive channels in the reactions of hydroxyl radicals with allene, propylene and 2-butene. Int. J. Chem. Kinet. Symp. 1 (Chemical Kinetics Data for the Lower and Upper Atmosphere) 317-328, 1975. 

Cadle, R. D. Experimental studies of Los Angeles air and kinetics of atmospheric reaction, pp. 27-59. In L. H. Rogers, Ed. Proceedings of the Conference on Chemical Reactions in Urban Atmospheres. Technical Report 15. Los Angeles Air Pollution Foundation, 1956. 

Pollutants emitted by various sources entered an air parcel moving with the wind in the model proposed by Eschenroeder and Martinez. Finite-difference solutions to the species-mass-balance equations described the pollutant chemical kinetics and the upward spread through a series of vertical cells. The initial chemical mechanism consisted of 7 species participating in 13 reactions based on sm< -chamber observations. Atmospheric dispersion data from the literature were introduced to provide vertical-diffusion coefficients. Initial validity tests were conducted for a static air mass over central Los Angeles on October 23, 1968, and during an episode late in 1%8 while a special mobile laboratory was set up by Scott Research Laboratories. Curves were plotted to illustrate sensitivity to rate and emission values, and the feasibility of this prediction technique was demonstrated. Some problems of the future were ultimately identified by this work, and the method developed has been applied to several environmental impact studies (see, for example, Wayne et al. ). 

Filby. W. G., The participation of free radicals in atmospheric chemistry, in Chemical Kinetics of Small Organic Molecules IV Reactions in Special Systems (Alfassi, Z. B, ed.). CRC Press, Boca Raton, Florida, 1988. 

The chemistry of the troposphere (the layer of the atmosphere closest to earth s surface) overlaps with low-temperature combustion, as one would expect for an oxidative environment. Consequently, the concerns of atmospheric chemistry overlap with those of combustion chemistry. Monks recently published a tutorial review of radical chemistry in the troposphere. Atkinson and Arey have compiled a thorough database of atmospheric degradation reactions of volatile organic compounds (VOCs), while Atkinson et al. have generated a database of reactions for several reactive species with atmospheric implications. Also, Sandler et al. have contributed to the Jet Propulsion Laboratory s extensive database of chemical kinetic and photochemical data. These reviews address reactions with atmospheric implications in far greater detail than is possible for the scope of this review. For our purposes, we can extend the low-temperature combustion reactions [Equations (4) and (5)], whereby peroxy radicals would have the capacity to react with prevalent atmospheric radicals, such as HO2, NO, NO2, and NO3 (the latter three of which are collectively known as NOy) ... 

In short, while kinetics are very important in determining the importance of reactions in the atmosphere, other aspects such as the formation of reactive intermediates, and the physical and chemical nature of reaction surfaces, should also be taken into account. 

Chemical component of models As we have seen from the examination of kinetics and mechanisms of atmospheric reactions thus far, the chcmistiy of even relatively simple organics can be quite complex. This chemistry has been described in terms of explicit chemical mechanisms, that is, a listing of the individual chemical reactions. The oxidation of even one organic in air includes hundreds of reactions. 

Environmental Fate. Sensitized photolysis studies in water and oxidation/reduction studies in both air and water are lacking, as are biodegradation studies in surface and groundwaters. These kinds of studies are important, since they represent the fundamental removal mechanisms available to isophorone in the environment. In addition, the kinetic studies for the atmospheric reactions are important for understanding the significance of a removal mechanism and predicting the reactions that may control the fate of a chemical in the environment. 

Now we turn to the origin of the rate laws themselves. How do molecules of ozone change into molecules of oxygen What atomic interactions turn a mixture of fuel and air into carbon dioxide and water when it ignites in an engine What is really going on in terms of atoms high in the atmosphere as CFC molecules punch holes in the ozone layer Chemical kinetics and particularly the rate law for a reaction provide the kind of information we need to build a model of the reaction at a molecular level. 

Chemical kinetics is a subject of crucial environmental and economic importance. In the upper atmosphere, for example, maintenance or depletion of the ozone layer, which protects us from the sun s harmful ultraviolet radiation, depends on the relative rates of reactions that produce and destroy O3 molecules. In the chemical industry, the profitability of the process for the synthesis of ammonia, which is used as a fertilizer, depends on the rate at which gaseous N2 and H2 can be converted to NH3. 

The atmospheric chemical kinetics of linear perfluorinated aldehyde hydrates, Cx-F2x+iCH(OH)2, have been measured for x = 1,3, and 4, focusing on formation (from aldehyde, by hydration), dehydration, and chlorine atom- and hydroxyl radical-initiated oxidation.211 The latter reaction is implicated as a significant source of perfluorinated carboxylic acids in the environment. 

Quantum chemistry provides data that improves understanding of chemical kinetics. The data is further used as input for parameterizing transport and deposition models or chemical reaction schemes in models of various other atmospheric processes. As documented in many of the articles in this special edition, theoretical techniques are tested through comparison to laboratory measurements and atmospheric observations, and then further applied towards predicting mechanisms and reaction rates which are currently unknown. 

In atmospheric chemistry the concentrations of trace substances are usually expressed in units of molecules/cm3. Below are data for some gas-phase reactions at 300. K (from the NASA publication Chemical Kinetics and Photochemical Data for Use in Atmospheric Modeling, Evaluation Number 5 ). The term K indicates the use of molecules/cm3 for concentration. Calculate K and Kp for each reaction. 

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