Radical atmospheric

Two other important kinds of substances in the atmosphere are particles and free radicals. Atmospheric particles are discussed in more detail in Section 6.13. Free radicals are reactive fragments of molecules that are usually very reactive because they possess unpaired electrons (see Section 6.9). 

Proteins and free amino acids contain numerous reactive fimc-tional groups and can become substrates for oxidoreductases or may react with reactive oxygen species, such as hydroxyl radicals (HO"), superoxide radicals (O2 ), singlet oxygen ( 02), fatty acid hydroperoxides (R-O-OH), alkoxyl (RO ) and peroxyl (ROO ) radicals, atmospheric oxygen and other oxidising agents, often under the catalysis of transition metal ions. 

Takahashi, K., Y. Matsumi, T.J. WaUington, and M.D. Hurley (2002), Atmospheric chemistry of CF3CFHOCF3 Reaction with OH radicals, atmospheric lifetime, and global warming potential, J. Geophys. Res., 107, doi 10.1029/2002JD002125. 

The reaction of perfluoroalkyl iodides with alkenes affords the perfluoro-alkylated alkyl iodides 931. Q.a-Difluoro-functionalized phosphonates are prepared by the addition of the iododifluoromethylphosphonate (932) at room temperature[778], A one-electron transfer-initiated radical mechanism has been proposed for the addition reaction. Addition to alkynes affords 1-perfluoro-alkyl-2-iodoalkenes (933)[779-781]. The fluorine-containing oxirane 934 is obtained by the reaction of allyl aicohol[782]. Under a CO atmosphere, the carbocarbonylation of the alkenol 935 and the alkynol 937 takes place with perfluoroalkyl iodides to give the fluorine-containing lactones 936 and 938[783]. 

The reaction follows a free radical mechanism and gives a hydroperoxide a compound of the type ROOH Hydroperoxides tend to be unstable and shock sensitive On stand mg they form related peroxidic derivatives which are also prone to violent decomposi tion Air oxidation leads to peroxides within a few days if ethers are even briefly exposed to atmospheric oxygen For this reason one should never use old bottles of dialkyl ethers and extreme care must be exercised m their disposal... 

During the vapor deposition process, the polymer chain ends remain truly aUve, ceasing to grow only when they are so far from the growth interface that fresh monomer can no longer reach them. No specific termination chemistry is needed, although subsequent to the deposition, reaction with atmospheric oxygen, as well as other chemical conversions that alter the nature of the free-radical chain ends, is clearly supported experimentally. 

Because of the mixture of VOCs in the atmosphere, the composition of smog reaction products and intermediates is extremely complex. formed via reaction 16, is important because when dissolved in cloud droplets it is an important oxidant, responsible for oxidising SO2 to sulfuric acid [7664-93-9] H2SO4, the primary cause of acid precipitation. The oxidation of many VOCs produces acetyl radicals, CH CO, which can react with O2 to produce peroxyacetyl radicals, CH2(C0)02, which react with NO2... 

Most chlorofluorocarbons are hydrolytically stable, CCI2F2 being considerably more stable than either CCl F or CHCI2F. Chlorofluoromethanes and ethanes disproportionate in the presence of aluminum chloride. For example, CCl F and CCI2F2 give CCIF and CCl CHCIF2 disproportionates to CHF and CHCl. The carbon—chlorine bond in most chlorofluorocarbons can be homolyticaHy cleaved under photolytic conditions (185—225 nm) to give chlorine radicals. This photochemical decomposition is the basis of the prediction that chlorofluorocarbons that reach the upper atmosphere deplete the earth s ozone shield. 

Irradiation of ethyleneimine (341,342) with light of short wavelength ia the gas phase has been carried out direcdy and with sensitization (343—349). Photolysis products found were hydrogen, nitrogen, ethylene, ammonium, saturated hydrocarbons (methane, ethane, propane, / -butane), and the dimer of the ethyleneimino radical. The nature and the amount of the reaction products is highly dependent on the conditions used. For example, the photoproducts identified ia a fast flow photoreactor iacluded hydrocyanic acid and acetonitrile (345), ia addition to those found ia a steady state system. The reaction of hydrogen radicals with ethyleneimine results ia the formation of hydrocyanic acid ia addition to methane (350). Important processes ia the photolysis of ethyleneimine are nitrene extmsion and homolysis of the N—H bond, as suggested and simulated by ab initio SCF calculations (351). The occurrence of ethyleneimine as an iatermediate ia the photolytic formation of hydrocyanic acid from acetylene and ammonia ia the atmosphere of the planet Jupiter has been postulated (352), but is disputed (353). 

The characteristic times for waste destmction to an efficiency of 99.99%, for water in a nitrogen atmosphere, where the residue is a typical hydrocarbon breaking into two large fragments, eg, / -butane decomposing into two ethyl radicals would be droplet heatup, 0.073 s droplet evaporation,... 

Shielding and Stabilization. Inclusion compounds may be used as sources and reservoirs of unstable species. The inner phases of inclusion compounds uniquely constrain guest movements, provide a medium for reactions, and shelter molecules that self-destmct in the bulk phase or transform and react under atmospheric conditions. Clathrate hosts have been shown to stabiLhe molecules in unusual conformations that can only be obtained in the host lattice (138) and to stabiLhe free radicals (139) and other reactive species (1) similar to the use of matrix isolation techniques. Inclusion compounds do, however, have the great advantage that they can be used over a relatively wide temperature range. Cyclobutadiene, pursued for over a century has been generated photochemicaHy inside a carcerand container (see (17) Fig. 5) where it is protected from dimerization and from reactants by its surrounding shell (140). 

Both vapor-phase and Hquid-phase processes are employed to nitrate paraffins, using either HNO or NO2. The nitrations occur by means of free-radical steps, and sufftciendy high temperatures are required to produce free radicals to initiate the reaction steps. For Hquid-phase nitrations, temperatures of about 150—200°C are usually required, whereas gas-phase nitrations fall in the 200—440°C range. Sufficient pressures are needed for the Hquid-phase processes to maintain the reactants and products as Hquids. Residence times of several minutes are commonly required to obtain acceptable conversions. Gas-phase nitrations occur at atmospheric pressure, but pressures of 0.8—1.2 MPa (8—12 atm) are frequentiy employed in industrial units. The higher pressures expedite the condensation and recovery of the nitroparaffin products when cooling water is employed to cool the product gas stream leaving the reactor (see Nitroparaffins). 

Microwave spectroscopy is used for studyiag free radicals and ia gas analysis (30). Much laboratory work has been devoted to molecules of astrophysical iaterest (31). The technique is highly sensitive 10 mole may suffice for a spectmm. At microwave resolution, frequencies are so specific that a single line can unambiguously identify a component of a gas mixture. Tabulations of microwave transitions are available (32,33). Remote atmospheric sensing (34) is illustrated by the analysis of trace CIO, O, HO2, HCN, and N2O at the part per trillion level ia the stratosphere, usiag a ground-based millimeter-wave superheterodyne receiver at 260—280 GH2 (35). 

Atmosphere—Water Interaction. Although water is a very minor component of the atmosphere, less than 10 vol % of the atmosphere consisting of water, many important reactions occur ki the water droplets of cloud, fog, and rain. The atmosphere is an oxic environment ki its water phase, gigantic quantities of reductants, such as organic substances, Fe(II), SO2, CH SCH (dimethyl sulfide), and nitrogen oxides, are oxidized by oxidants such as oxygen, OH radicals, H2O2, and Fe(III). 

The most important reactions of trichloroethylene are atmospheric oxidation and degradation by aluminum chloride. Atmospheric oxidation is cataly2ed by free radicals and accelerated with heat and with light, especially ultraviolet. The addition of oxygen leads to intermediates (1) and (2). 

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