Pulse radiolysis reactions

Pulse radiolysis reaction of iodide ions with a series of halogenated alkylperoxyl resulted in the oxidation of a total of three iodide ions. The rate constants were determined as a function of pH, polarity of solvent mixtures, and electronegativity of... 

The one-electron reduction of thiazole in aqueous solution has been studied by the technique of pulse radiolysis and kinetic absorption spectrophotometry (514). The acetone ketyl radical (CH ljCOH and the solvated electron e were used as one-electron reducing agents. The reaction rate constant of with thiazole determined at pH 8.0 is fe = 2.1 X 10 mole sec in agreement with 2.5 x 10 mole sec" , the value given by the National Bureau of Standards (513). It is considerably higher than that for thiophene (6.5 x 10" mole" sec" ) (513) and pyrrole (6.0 X10 mole sec ) (513). The reaction rate constant of acetone ketyl radical with thiazolium ion determined at pH 0.8 is lc = 6.2=10 mole sec" . Relatively strong transient absorption spectra are observed from these one-electron reactions they show (nm) and e... 

Pulse radiolysis results (74) have led other workers to conclude that adsorbed OH radicals (surface trapped holes) are the principal oxidants, whereas free hydroxyl radicals probably play a minor role, if any. Because the OH radical reacts with HO2 at a diffusion controlled rate, the reverse reaction, that is desorption of OH to the solution, seems highly unlikely. The surface trapped hole, as defined by equation 18, accounts for most of the observations which had previously led to the suggestion of OH radical oxidation. The formation of H2O2 and the observations of hydroxylated intermediate products could all occur via... 

Some of the most important questions one can ask in the study of kinetics concern the rates of reactions of the intermediates. In some cases, values can be obtained by direct experiments. For example, one might generate the intermediate by an independent method capable of producing it much more rapidly than it reacts. Then it can be examined in its own right. Chapter 11 presents methods for doing so, such as flash photolysis and pulse radiolysis. 

Some of the most conclusive studies of the mechanisms of chain reactions come from experiments in which some of the propagating steps have been independently measured directly. This measurement can sometimes be done by the use of flash photolysis and pulse radiolysis (Chapter 11). Such determinations can verify the occurrence of a certain reaction in the sequence and provide its rate constant. 

The absorption of radiation produces unstable species. Flash photolysis does so by interaction of light with a solute. The transient may be a photoexcited state or a molecular fragment. Pulse radiolysis starts with highly reactive entities formed by dissociation of the solvent (e.g., H, eaq, and HO from H20) and consists of a study of their reactions or of reactive transients derived from them. In either case one monitors the ensuing reactions by luminescence (for excited states), light absorption, or conductivity changes. 

Photolytic methods are used to generate atoms, radicals, or other highly reactive molecules and ions for the purpose of studying their chemical reactivity. Along with pulse radiolysis, described in the next section, laser flash photolysis is capable of generating electronically excited molecules in an instant, although there are of course a few chemical reactions that do so at ordinary rates. To illustrate but a fraction of the capabilities, consider the following photochemical processes ... 

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 ... 

Pulse radiolysis. Consider the reaction shown in Eq. (11-58). Show that H and e q are related as conjugate acid and base. Calculate the pKa of H. ... 

Pulse radiolysis. If one wishes to determine the rate constant for the reaction of e q with a substrate A, the approximate value of which is 107 LmoP1 s l, what is the lowest pH that can be used ... 

Veltwisch and colleagues45 studied the reaction of OH with several sulfoxides by pulse radiolysis using electrical conductivity for the detection of formation or disappearance of ions. Pulse radio lysis of N20-saturated aqueous solution of DMSO (10-3m) leads to a decrease in conductivity at basic pH (pH = 9.0) and an increase in conductivity at acidic pH (pH = 4.4). This is explained by the reactions... 

This review is concerned with the formation of cation radicals and anion radicals from sulfoxides and sulfones. First the clear-cut evidence for this formation is summarized (ESR spectroscopy, pulse radiolysis in particular) followed by a discussion of the mechanisms of reactions with chemical oxidants and reductants in which such intermediates are proposed. In this section, the reactions of a-sulfonyl and oc-sulfinyl carbanions in which the electron transfer process has been proposed are also dealt with. The last section describes photochemical reactions involving anion and cation radicals of sulfoxides and sulfones. The electrochemistry of this class of compounds is covered in the chapter written by Simonet1 and is not discussed here some electrochemical data will however be used during the discussion of mechanisms (some reduction potential values are given in Table 1). 

The development of pulse radiolysis techniques have led to the determination of a number of the important kinetic processes of the species produced by the irradiation of H2O. The results that have been obtained for a number of the most important reactions are presented in Table II. These results demonstrate that the net effect of radiation is H2O decomposition in the absence of any reactive substrate. 

The application of techniques of pulse radiolysis offers the potential to determine rates of primary radiolysis induced reaction processes. This knowledge can be of great value in the determination of redox processes of Pu ions occurring in a wide variety of aqueous solutions. As a matter of fact, such information is essential to a prediction of the Pu oxidation states to be expected in breached repository scenarios. For an... 

In pulse radiolysis studies it is feasible to eliminate undesired radical reactions by the use of "scavengers". For example, to produce a totally reducing system simple aliphatic alcohols are added and the ensuing reaction... 

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... 

The product CO3 radical can react with a variety of inorganic ions including the carbonato complex of Pu(V). Thus, in a pulse radiolysis experiment, Pu(VI) in 0.05 M Na2C03, He saturated, there are the parallel reactions (17) and (18)... 

In marked contrast there exists a volumnous literature on pulse radiolysis studies of nitric acid solutions (9). The NO3 radical has been identified as a major product although the mechanism of formation is still a matter of debate. While a number of reactions of this radical have been reported (10) there has evidently not been any pulse radiolysis studies of reactions with Pu ions. 

Tl(III) < Pb(IV), and this conclusion has been confirmed recently with reference to the oxythallation of olefins 124) and the cleavage of cyclopropanes 127). It is also predictable that oxidations of unsaturated systems by Tl(III) will exhibit characteristics commonly associated with analogous oxidations by Hg(II) and Pb(IV). There is, however, one important difference between Pb(IV) and Tl(III) redox reactions, namely that in the latter case reduction of the metal ion is believed to proceed only by a direct two-electron transfer mechanism (70). Thallium(II) has been detected by y-irradiation 10), pulse radiolysis 17, 107), and flash photolysis 144a) studies, butis completely unstable with respect to Tl(III) and T1(I) the rate constant for the process 2T1(II) Tl(III) + T1(I), 2.3 x 10 liter mole sec , is in fact close to diffusion control of the reaction 17). 

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. "... 

Sumiyoshi and coworkers studied the radiolysis of aqueous solution of methyl methylthiomethyl sulfoxide [ H3S(0) H2S H3 MTMSO] at various pH by pulse radiolysis. They found that the reaction of e with MTMSO (in the presence of 1M t-butyl alcohol to scavenge OH" radicals) leads to formation of a transient with a broad absorption band of = 375 nm. The absorbance at 375 nm as a function of pH are of S shape, indicating an equilibrium due to reaction with H. Similar to the finding in dimethyl sulfoxide they suggested the scheme. 

In studies of this kind, methods developed in radiation chemistry and photochemistry are often applied The methods of pulse radiolysis and flash photolysis allow one to investigate the mechanism of reactions in which free radicals, electrons and positive holes are the intermediates. In order to understand the mechanisms of processes that occur on colloidal particles it is important to know how free radicals... 

A precursor of the studies on electron transfer reactions between short-lived radicals and colloidal particles was the development of a fast pulse radiolysis method to measure. the polarograms of radicals in the 10 s range . After considerable information had been acquired about the electron transfer reactions of a few dozen radicals at the mercury electrode, this compact electrode was replaced by metal colloids somewhat later, by semiconductor colloids These studies led to the detection of the electron-storing properties of certain colloids and of reactions of the stored electrons. 

In a pulse radiolysis study of solutions of CdS of different particle size, the rate of reaction of the OH radical with the colloidal particles was studied as well as the absorption spectrum of the products The hydroxyl radical reacts on its first encounter... 

In the pulse radiolysis studies on the reaction of MV with TiOj, the sol contained propanol-2 or formate and methyl viologen, MV Ionizing radiation produces reducing organic radicals, i.e. (CH3)2COH or C02 , respectively, and these radicals react rapidly with MV to form MV. The reaction of MV with the colloidal particles was then followed by recording the 600 nm absorption of MV . The rate of reaction was found to be slower than predicted for a diffusion controlled reaction. 

Pulse radiolysis studies showed that the rate of the reaction of MV with a-Fc203, in which an electron is transferred to the colloidal particles, is slower than predicted for a diffusion controlled reaction. For pH > 8, the reaction is incomplete as the reverse reaction Fe203 - - - Fe203 - - MV takes place more efficiently... 

Adams, G.E. and Redpath, J.L. (1974). Selective free-radical reactions with proteins and enzymes pulse radiolysis and inactivation studies on papain. Int. J. Badiat. Biol. 25, 129-136. 

Forni, L.G., Packer, J.E., Slater, T.F. and Willson, KL. (1983). Reactions of the trichloromethyl and halothane derived peroxyl radicals with unsaturated fatty acids a pulse radiolysis study. Chem. Biol. Interact. 45, 171-177. 

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