Photochemical decompositions

Chain reactions such as those described above, in which atomic species or radicals play a rate-determining part in a series of sequential reactions, are nearly always present in processes for the preparation of thin films by die decomposition of gaseous molecules. This may be achieved by thermal dissociation, by radiation decomposition (photochemical decomposition), or by electron bombardment, either by beams of elecuons or in plasmas. The molecules involved cover a wide range from simple diatomic molecules which dissociate to atoms, to organometallic species with complex dissociation patterns. The... 

CIDNP studies of the decomposition have centred mainly on thermal decompositions photochemical decomposition has generally been less intensively investigated. While most reports of polarization refer to n.m.r. spectra, a number of papers have described polarization of other nuclei, (Kaptein, 1971b Kaptein et al., 1972), (Lippmaa el al., 1970a, b, 1971 Kaptem, 1971b Kaptein et al., 1972 Kessenikh et al., 1971), and F (Kobrina et al., 1972) contained in the peroxide reactant. Additionally, polarization of P has been reported in the products of decomposition of benzoyl peroxide in phosphorus-containing solvents (Levin et al., 1970). 

Timpe, H.-J., Ulrich, S., and Fouassier, J.-P., Photochemistry and use of decahydroacridine-l,8-diones as photosensitizers for onium salt decomposition,/. Photochem. Photobiol., A Chem., 73,139,1993. 

After the primary step in a photochemical reaction, the secondary processes may be quite complicated, e.g. when atoms and free radicals are fcrnied. Consequently the quantum yield, i.e. the number of molecules which are caused to react for a single quantum of light absorbed, is only exceptionally equal to exactly unity. E.g. the quantum yield of the decomposition of methyl iodide by u.v. light is only about 10" because some of the free radicals formed re-combine. The quantum yield of the reaction of H2 -f- CI2 is 10 to 10 (and the mixture may explode) because this is a chain reaction. 

Rabinovitch B S and Setser D W 1964 Unimolecular decomposition and some isotope effects of simple alkanes and alkyl radicals Adv. Photochem. 3 1-82... 

Table B2.5.5. The photochemical decomposition of methyl radicals (UV excitation at 216 nm). ris tire wavenumber linewidth of the methyl radical absorption and /ris the effective first-order decay constant [54].

Relaxation by a photochemical reaction may involve a decomposition reaction in which A splits apart... 

Oxygen Difluoride as a Source of the OF Radical. The existence of the OF radical [12061 -70-0] was first reported in 1934 (27). This work was later refuted (28). The OF radical was produced by photolysis of OF2 in a nitrogen or argon matrix at 4 K. The existence of the OF species was deduced from a study of the kinetics of decomposition of OF2 and the kinetics of the photochemical reaction (25,26) ... 

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. 

The radicals are then involved in oxidations such as formation of ketones (qv) from alcohols. Similar reactions are finding value in treatment of waste streams to reduce total oxidizable carbon and thus its chemical oxygen demand. These reactions normally are conducted in aqueous acid medium at pH 1—4 to minimize the catalytic decomposition of the hydrogen peroxide. More information on metal and metal oxide-catalyzed oxidation reactions (Milas oxidations) is available (4-7) (see also Photochemical technology, photocatalysis). 

Yields of excited states from 1,2-dioxetane decomposition have been determined by two methods. Using a photochemical method (17,18) excited acetone from TMD is trapped with /n j -l,2-dicyanoethylene (DCE). Triplet acetone gives i7j -l,2-dicyanoethylene with DCE, whereas singlet acetone gives 2,2-dimethyl-3,4-dicyanooxetane. By measuring the yields of these two products the yields of the two acetone excited states could be determined. The yields of triplet ketone (6) from dioxetanes are determined with a similar technique. 

Thermal and photochemical decomposition of peroxides (4) and (5) lacking a-hydrogens (those derived from ketones) produces macrocycHc hydrocarbons andlactones (119,152,153). For example, 7,8,15,16,23,24-hexaoxatrispiro [5.2.5.2.5.2] tetracosane (see Table 5) yields cyclopentadecane and oxacycloheptadecan-2-one. 

Vanadium (IV) Chloride. Vanadium(IV) chloride (vanadium tetrachloride, VCy is a red-brown hquid, is readily hydrolyzed, forms addition compounds with donor solvents such as pyridine, and is reduced by such molecules to trivalent vanadium compounds. Vanadium tetrachloride dissociates slowly at room temperature and rapidly at higher temperatures, yielding VCl and CI2. Decomposition also is induced catalyticahy and photochemically. This instabihty reflects the difficulty in storing and transporting it for industrial use. 

Photochemical decomposition of riboflavin in neutral or acid solution gives lumichrome (3), 7,8-dimethyl all oxazine, which was synthesized and characterized by Karrer and his co-workers in 1934 (11). In alkaline solution, the irradiation product is lumiflavin (4), 7,8,10-trimethyhsoalloxazine its uv—vis absorption spectmm resembles that of riboflavin. It was prepared and characterized in 1933 (5). Another photodecomposition product of riboflavin is 7,8-dimethy1-10-foTmylmethy1isoa11oxazine (12). 

Chlorine free radicals used for the substitutioa reactioa are obtaiaed by either thermal, photochemical, or chemical means. The thermal method requites temperatures of at least 250°C to iaitiate decomposition of the diatomic chlorine molecules iato chlorine radicals. The large reaction exotherm demands close temperature control by cooling or dilution, although adiabatic reactors with an appropriate diluent are commonly used ia iadustrial processes. Thermal chlorination is iaexpeasive and less sensitive to inhibition than the photochemical process. Mercury arc lamps are the usual source of ultraviolet light for photochemical processes furnishing wavelengths from 300—500 nm. 

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