Photochemical chain reactions

H. Yoshida, J.D. Regan (1997). UVB DNA dosimeters analyzed by polymerase chain reactions. Photochem. Photobiol, 66, 82-88. 

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. 

Mixtures of chlorine and hydrogen reaa only slowly in the dark but the reaction proceeds with explosive violence in light. A suggested mechanism for the photochemical chain reaction is ... 

Bromine, like chlorine, also undergoes a photochemical chain reaction with hydrogen. The reaction with bromine, however, evolves less energy and is not explosive. 

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... 

A highly selective photochemical chlorination of esters, amides, and alcohols can be effected in 70%-90% H2SO4 using A-chlorodialkylamines as chlorinating agents. Mechanistic studies indicate that a chain reaction is involved ... 

Sulfoxidation is a photochemical reaction. The radical chain reaction is initiated by triplet sulfur dioxide (3 S02), excited by ultraviolet (UV) light of wavelength longer than 320 nm ... 

Cyclic ethers were also obtained by cyclization of alkoxyl radicals, generated in a radical chain reaction by reacting the thione 42 with (TMSfsSiH under photochemical conditions at 20 °C (Reaction 46). Regioselectivities of cyclization have been investigated and a progressive increase of the 6-endo-trig selectivity along the series R2 = H[Pg.140]

Product quantum yields are much easier to measure. The number of quanta absorbed can be determined by an instrument called an actinometer, which is actually a standard photochemical system whose quantum yield is known. An example of the information that can be learned from quantum yields is the following. If the quantum yield of a product is finite and invariant with changes in experimental conditions, it is likely that the product is formed in a primary rate-determining process. Another example In some reactions, the product quantum yields are found to be well over 1 (perhaps as high as 1000). Such a finding indicates a chain reaction (see p. 895 for a discussion of chain reactions). 

A carbonyl chromophore in a macromolecule can participate in a variety of photochemical processes that can have as end result the degradation of the polymer via processes like the Norrish Type I or Type II reaction, the triggering of a chain reaction leading to peroxidation, the transfer of energy to another chromophore or, it can also behave as an energy sink if a suitable, non-degradative path, is available to the triplet state. 

While yields greater than unity provide evidence for chain reactions, yields less than unity do not indicate the absence of a chain reaction. Quantum yields as high as 106 have been observed in the photochemical reaction between H2 and Cl2. 

It is clear from this discussion that the dose requirement and unit cost will be lower if the material has a higher molar mass M and the reaction has a high G value. Thus, the best candidates will be a polymeric material and a chain reaction. Quite often, a free-radical irradiation is used. The radiation source of choice is usually a 60Co - y facility, although electron beam irradiation is also used. Since most radiation-chemical reactions used in industry can also be brought about by other conventional means such as thermal, or photochemical processes, the processing cost must be below 10irradiation cost one has to include the cost of operation, maintenance, and the like. (Danno, 1960). 

Various authors have studied the ageing of triterpenoid resins to understand and possibly slow their deterioration [3, 4, 12, 13, 17 36]. The main degradation pathway is autoxida-tion, an oxidative radical chain reaction [37, 38] after formation of radicals, oxygen from the air is inserted, leading to peroxides. The peroxides can be homolytically cleaved, resulting in new radicals that continue the chain reaction. The cleavage of peroxide bonds can be induced thermally or photochemically. 

Apart from the traditional organic and combinatorial/high-throughput synthesis protocols covered in this book, more recent applications of microwave chemistry include biochemical processes such as high-speed polymerase chain reaction (PCR) [2], rapid enzyme-mediated protein mapping [3], and general enzyme-mediated organic transformations (biocatalysis) [4], Furthermore, microwaves have been used in conjunction with electrochemical [5] and photochemical processes [6], and are also heavily employed in polymer chemistry [7] and material science applications [8], such as in the fabrication and modification of carbon nanotubes or nanowires [9]. 

Photochemically induced oxidation of benzaldehyde was proved to be the chain reaction (4> >> 1) H. Backstrom [51]... 

The problem of competition of the molecular reaction (direct route) and chain reaction (complicated, multistage route) was firstly considered in the monograph by Semenov [1], The new aspect of this problem appeared recently because the quantum chemistry formulated the rule of conservation of orbital symmetry in chemical and photochemical reactions (Woodward-Hofmann rule [4]). Very often the structure of initial reactants suggests their direct interaction to form the same final products, which are also obtained in the chain reaction, and the thermodynamics does not forbid the reaction with AG < 0. However, the experiment often shows that many reactions of this type occur in a complicated manner through several intermediate stages. For example, the reaction... 

In some reactions involving gases, the rate of reaction estimated by the simple collision theory in terms of the usually infened species is much lower than observed. Examples of these reactions are the oxidation of H2 and of hydrocarbons, and the formation of HC1 and of HBr. These are examples of chain reactions in which very reactive species (chain carriers) are initially produced, either thermally (i.e., by collision) or photochemically (by absorption of incident radiation), and regenerated by subsequent steps, so that reaction can occur in chain-fashion relatively rapidly. In extreme cases these become explosions, but not all chain reactions are so rapid as to be termed explosions. The chain... 

As for any chain reaction, radical-addition polymerization consists of three main types of steps initiation, propagation, and termination. Initiation may be achieved by various methods from the monomer thermally or photochemically, or by use of a free-radical initiator, a relatively unstable compound, such as a peroxide, that decomposes thermally to give free radicals (Example 7-4 below). The rate of initiation (rinit) can be determined experimentally by labeling the initiator radioactively or by use of a scavenger to react with the radicals produced by the initiator the rate is then the rate of consumption of the initiator. Propagation differs from previous consideration of linear chains in that there is no recycling of a chain carrier polymers may grow by addition of monomer units in successive steps. Like initiation, termination may occur in various ways combination of polymer radicals, disproportionation of polymer radicals, or radical transfer from polymer to monomer. 

Conversely, a quantum yield

greater than unity cannot be achieved during a straightforward photochemical reaction, since the second law of photochemistry clearly says that one photon is consumed per species excited. In fact, values of > 1 indicate that a secondary reaction(s) has occurred. A value of > 2 implies that the product of the photochemical reaction is consumed by another molecule of reactant, e.g. during a chain reaction, with one photon generating a simple molecule of, say, excited chlorine, which cleaves in the excited state to generate two radicals. Each radical then reacts in propagation reactions until the reaction mixture is exhausted of reactant. 

Photochemical reactions, like any chemical reaction, can be classified into various groups, depending on the reactants and products, for example, elimination, isomerization, dimerization, reduction, oxidation, or chain reaction. One important practical field of photochemistry is organic photochemistry. In solution photochemical reactions, the nature of the solvent can markedly influence the reaction. The absorbtion of the solvent and of the reaction products is an important parameter for the choice of the reaction conditions. It is useful to have a solvent with a relatively low absorption in the desired wavelength. Sometimes photosensitizers are used these are substances that absorb light to further activate another substance, which decomposes. 

The hydrogen-chlorine chain reaction has proved to be one of the most controversial systems yet studied. After thirty years of investigation Bodenstein43 was able to say in 1931 that every worker on the photochemical synthesis of HC1 had produced his own mechanism even as late as 1940 little positive information had been obtained. However, the accumulated techniques and experience had firmly established the importance of atom chain reactions. The mechanism of photo-initiation and propagation is the same as for the hydrogen bromide photosynthesis, a non-branching chain reaction... 

Understand how photolysis produces radicals by bond cleavage and account for the importance of radical species in photochemical chain reactions, stratospheric ozone chemistry and the photochemistry of the polluted troposphere. 

Photochemically generated radicals in chain reactions are less familiar to synthetic chemists [8,21]. The above mentioned peroxides have been used in the presence of light to initiate radical chain reactions at room or lower temperatures. Azo compounds are also known to decompose photo-lytically to afford alkyl radicals. AIBN has rarely been used under such conditions. 

Furthermore this chapter deals chiefly with polymerizations which are catalyzed by acid-acting catalysts. A comprehensive discussion of not only the thermal but even the photochemical and free radical-initiated polymerizations is outside its scope. The free radical-initiated reactions include those which are induced by metal alkylies, peroxides, oxygen and certain other substances. They depend on free radical initiation of a chain reaction whether or not these free radicals should be considered to be catalysts has been questioned because the radicals enter into the reaction chain and are part of the reaction product. 

The reaction is explosive with fluorine and occurs under all conditions. With chlorine and bromine reaction occurs rapidly when exposed to light, undergoing a photochemical chain reaction. With iodine, the reaction is very slow, even at elevated temperatures. Hydrogen is a strong reducing agent. At high temperatures, the gas reduces many metal oxides to lower oxides or metals ... 

In this section, we use another chain reaction to show the relation between the steady-state treatment and the quasi-equilibrium treatment. The former is more general than the latter, and leads to more complete but also more complicated results. Ozone, O3, is present in the stratosphere as the ozone layer, and in the troposphere as a pollutant. Ozone production and destruction in the atmosphere is primarily controlled by photochemical reactions, which are discussed in a later section. Ozone may also be thermally decomposed into oxygen, O, although... 

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