Carbon radiolysis

An interesting example of the N(9)-C(8) prototropic tautomerism has been reported for the caffeine radical by pulse radiolysis studies in aqueous solution the transformation of the heteroatom-protonated electron adduct 25 into the carbon-protonated tautomer 26 occurred spontaneously in neutral media [95JCS(F)615]. 

Reactions such as these are of interest in themselves. Beyond that, one can use the pulse radiolysis experiment as a preparative technique for other species. Thus, the reactions of numerous aliphatic, carbon-centered radicals have been evaluated.22 If one employs a reasonably high concentration of solute, say 0.1-1 M CH3OH, the formation of CH2OH is complete within the electron pulse. Following that, reactions such as the following can be studied ... 

There are two additional pulse radiolysis investigations of Pu(VI) reactions that are of importance. These are the rate of reaction of e (aq) with Pu(VI) adsorbed on Si02 colloids and the rate of the reaction between Pu(V) and the carbonate ion radical... 

Thus Pu(VI) in carbonate media will not suffer a net reduction due to radiolysis. 

The conclusions on the occurrence of ion-molecule reaction in the radiolysis of ethylene are not seriously affected by the uncertainties in the neutralization mechanism. It must be assumed that neutralization results in the complex species which constitute the ionic polymer, — i.e., the fraction of the ethylene disappearance which cannot be accounted for by the lower molecular weight products containing up to six carbon atoms. 

Physical properties of carbon black-filled EPR and EPDM elastomers have been found to be comparable with the suUur-cured analogues [372]. Aromatic oils increase the optimum dose requirement for these compounds due to the reaction of the transient intermediates formed during radiolysis of the polymer with the oil as well as energy transfer which is particularly effective when the oil contains aromatic groups. The performance and oxidative stability of unfilled EPDM as well as its blend with PE [373], and the thermal stabdity and radiation-initiated oxidation of EPR compounds are reported by a number of workers [374,375]. 

Carotenoid radicals — Many of the important oxidations are free-radical reactions, so a consideration of the generation and properties of carotenoid radicals and of carbon-centered radicals derived from carotenoids by addition of other species is relevant. The carotenoid radicals are very short-lived species. Some information has been obtained about them by the application of radiation techniques, particularly pulse radiolysis. Carotenoid radicals can be generated in different ways. "... 

Both CO and C02 are reduced by eh. The immediate product of the first reaction is CO-, which reacts with water, giving OH and the formyl radical the latter has been identified by pulse radiolysis. The product of carbon dioxide reduction, C02-, is stable in the condensed phase with an absorption at 260 nm. It reacts with various organic radicals in addition reactions, giving carboxylates with rates that are competitive with ion-ion or radical-radical combination rates. 

In some cases pulse-radiolysis techniques were employed to study the effect of pressure on inorganic reactions. For instance the oxidation of [CuI(phen)2] by dioxygen via the formation of a C -C transient species was studied using this technique (see Section III,A). Other examples include the formation and cleavage of metal-carbon (7-bonds, which formally involve a change in the oxidation state of the metal. A typical example of a volume profile for the formation and cleavage of a Co-CH3 bond is reported in Fig. 21 for the reaction (162)... 

Radiolysis of CO, both in the liquid and gaseous states, also leads to C02 and C302 formation, the latter product appearing mainly as a polymeric solid23-27. A scheme of reactions consisting of the initial production of a carbon and an oxygen atom, followed by (10)-(12) and... 

C20(3E) and C(lS) have been observed spectroscopically during pulse radiolysis of CO29,30. The failure to observe the lower states of carbon atoms may simply be a reflection of their greater reactivity towards CO12,30. 

Liquid carbon dioxide is decomposed efficiently by ionizing radiation79. The decreased radiation stability of the liquid phase compared to the gas phase has been attributed to the much smaller contribution of ion-molecule reactions to radiolysis in the condensed phase, where an efficient geminate charge neutralization process is likely to minimize the occurrence of such processes. Ion-molecule reactions are probably responsible for the rapid reoxidation observed in the gas phase. The yields of CO, 02 and 03 from the y-radiolysis of liquid C02 can be... 

Gamma radiolysis of simple carboxylic acids and N-acetyl amino acids results in loss of the carboxyl group with formation of carbon monoxide and carbon dioxide. In the carboxylic acids, the ratio of C0/C02 produced is approximately 0.1, while in the N-acetyl amino acids the ratio is much smaller. In the poly carboxylic acids and poly amino acids, radiolysis also results in the loss of the carboxyl group, but here the ratio of C0/C02 is greater than 0.1. Incorporation of aromatic groups in the poly amino acids provides some protection for the carboxyl group. The degradation of the poly acids is believed to involve radical and excited state pathways. 

Carbon dioxide is the major product of the radiolysis, and results from the loss of the carboxyl group. Carbon monoxide is found in somewhat smaller yield than carbon dioxide. Vater is also produced, but its yield is often difficult to quantify because of the strong hydrogen bonding which exists between water and carboxylic acid groups. Hydrogen is not normally found in high yield. 

Radiolysis of isobutyric acid at 195 K results in the formation of only one radical intermediate, the hydrogen abstraction radical III. The decarboxylation radical and the anion radical are both unstable at this temperature and react forming the abstraction radical and other products. The hydrogen which is abstracted is generally that which is attached to the carbon atom a to the carboxyl group. 

The range of products formed on gamma radiolysis of N-acetylglycine was similar to that formed on radiolysis of the aliphatic carboxylic acids, but there are some noticeable differences in the yields of products. Carbon dioxide is by far the major volatile product of radiolysis and the corresponding product of the decarboxylation reaction, N-methyl acetamide, is also present in large yield, but the yield of this product was not quantitatively determined. By contrast, carbon monoxide is found in very small yield. The yield of acetamide, the product of N-Ca bond scission, is found in much greater yield. 

A variety of radical products is observed following gamma radiolysis of the N-acetyl amino acids at 77 K (6), depending on the nature of the side chain of the parent amino acid. In the case of N-acetyl alanine, for example, the intermediates are (i) the anion radical IV (ii) the decarboxylation radical V (iii) the deamination radical VI and (iv) the alpha carbon radical VII. 

A similar behaviour has been found to occur with the other N-acetyl amino acids. In each case, the most stable radical observed at 303 K was the alpha carbon radical, as was also observed for the aliphatic carboxylic acids. In Table VI the radical yields observed following gamma radiolysis of a series of N-acetyl amino acids at 303 K are reported, together with the stable radical intermediates observed at this temperature (5). 

Again the close correspondence between the measured radical and carbon dioxide yields for 7-radiolysis of the N-acetyl amino acids in the solid state suggests that the mechanisms for radical production and carbon dioxide formation are closely related, as they were for the aliphatic carboxylic acids. The following mechanism has been proposed (5.) in order to account for the major degradation products and observed radical intermediates. 

POLYCARBOXYLIC ACIDS The gamma radiolysis of the homopolymers of acrylic, methacrylic and itaconic acids have been investigated in the solid state at 303 K, and in each case the yields of carbon monoxide, carbon dioxide and of radical intermediates have been measured. These are reported in Tables VII and VIII respectively. 

Table VII. G-values for carbon monoxide and carbon dioxide formed on radiolysis of poly acids at 303 K...

As with the aliphatic carboxylic acid model compounds, the major volatile product observed on gamma radiolysis of the poly acids is carbon dioxide. However, the carbon dioxide yields are somewhat larger than those observed for the model compounds. 

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