Data pulse radiolysis

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 optical absorption spectra of sulfonyl radicals have been measured by using modulation spectroscopy s, flash photolysis and pulse radiolysis s techniques. These spectra show broad absorption bands in the 280-600 nm region, with well-defined maxima at ca. 340 nm. All the available data are summarized in Table 3. Multiple Scattering X, calculations s successfully reproduce the experimental UV-visible spectra of MeSO 2 and PhSO 2 radicals, indicating that the most important transition observed in this region is due to transfer of electrons from the lone pair orbitals of the oxygen atoms to... 

In general, reduction potentials of nucleobases have been studied much less than their oxidation potentials, and in particular water-based data are rather lacking [2, 35]. We therefore listed the available polarographic potentials measured in dimethylformamide and data obtained from pulse radiolysis studies or fluorescence quenching measurements. From the data in Table 1, it is evident that the pyrimidine bases are most easily reduced. The reduction potential of the T=T CPD lesion is close to the estimated value of the undamaged thymine base [34, 36]. 

Figure 14.10 shows the spectral changes over time on the pulse radiolysis of ASTA in the presence of LYC. Similar data were observed for 11 pairs of carotenoids and have allowed the electron... 

However, much work has to be done before these intermediates are known well enough for us to understand, and control if possible, the stereo, regio- and chemo-selectivity of the bromination of any olefin. So far, most of the available data concern the two first ionization steps, but the final, product-forming, step is still inaccessible to the usual kinetic techniques. It would therefore be highly interesting to apply to bromination either the method of fast generation of reactive carbocations by pulse radiolysis (McClelland and Steenken, 1988) or the indirect method of competitive trapping (Jencks, 1980) to obtain data on the reactivity and on the life time of bromocation-bromide ion pairs that control this last step and, finally, the selectivities of the bromination products. 

One striking prediction of the energy gap law and eq. 11 and 14 is that in the inverted region, the electron transfer rate constant (kjjj. = ket) should decrease as the reaction becomes more favorable (lnknr -AE). Some evidence has been obtained for a fall-off in rate constants with increasing -AE (or -AG) for intermolecular reactions (21). Perhaps most notable is the pulse radiolysis data of Beitz and Miller (22). Nonetheless, the applicability of the energy gap law to intermolecular electron transfer in a detailed way has yet to be proven. 

The systems that we investigated in collaboration with others involved intermolecular and intramolecular electron-transfer reactions between ruthenium complexes and cytochrome c. We also studied a series of intermolecular reactions between chelated cobalt complexes and cytochrome c. A variety of high-pressure experimental techniques, including stopped-flow, flash-photolysis, pulse-radiolysis, and voltammetry, were employed in these investigations. As the following presentation shows, a remarkably good agreement was found between the volume data obtained with the aid of these different techniques, which clearly demonstrates the complementarity of these methods for the study of electron-transfer processes. 

The most abundant rate data concern the reductive cleavage of aryl chlorides and bromides, obtained by either direct or indirect electrochemistry (Section 2.2) or by pulse radiolysis. They show (Figures 3.19 and 3.20), a rough linear... 

In a first type of systems, redox centers are randomly distributed in a rigid matrix, glass or polymer [73, 74, 75], Donor or acceptor centers are initially created photochemically or by pulse radiolysis, and the study of the return to equilibrium of the system allows the determination of the law k(R) giving the rate variation as a function of the intercenter distance R. The experimental data are well described by an exponential law, which is considered as reflecting an exponential variation of the electronic factor ... 

To make clear what type of oxidation potential data are being cited, when thermodynamics-based pulse radiolysis data are cited, such data will be labeled E°, while Eh2 will be used for reversible CV data. IPs are obtained under adiabatic conditions, with no gain or loss of heat. 

The experimental kinetic data obtained with the butyl halides in DMF are shown in Fig. 13 in the form of a plot of the activation free energy, AG, against the standard potential of the aromatic anion radicals, Ep/Q. The electrochemical data are displayed in the same diagrams in the form of values of the free energies of activation at the cyclic voltammetry peak potential, E, for a 0.1 V s scan rate. Additional data have been recently obtained by pulse radiolysis for n-butyl iodide in the same solvent (Grim-shaw et al., 1988) that complete nicely the data obtained by indirect electrochemistry. In the latter case, indeed, the upper limit of obtainable rate constants was 10 m s", beyond which the overlap between the mediator wave and the direct reduction wave of n-BuI is too strong for a meaningful measurement to be carried out. This is about the lower limit of measurable... 

Hydrogen abstraction from propan-2-ol and propan-2-ol- /7 by hydrogen and deuterium atoms has been studied by pulsed radiolysis FT-ESR. A secondary kinetic isotope effect was observed for H (D ) abstraction from the C—H (C—D) bonds. The results were compared with ab initio data. In similar work, the kinetic isotope effects in H and D abstraction from a variety of other alcohols in aqueous solvents have been measured. It was found that, compared with the gas phase, the reactions exhibit higher activation energies in agreement with the ability of solvation to decrease the dipole moment from the reactant alcohol to the transition state. 

Pulsed radiolysis in NO-saturated aqueous solution at a variety of wavelengths has been used to generate hydroxyl radicals and measure the rate of addition to 1,4-benzoquinones. Mechanistically, the kinetic data indicated that the first-formed adduct undergoes a rapid keto-enol tautomerism to give (56). ... 

The kinetics data on the reactions of silyl radicals with carbon-centred radicals are also available. The rate constant for the cross-combination of CHs with MesSi was measured to be 6.6 x 10 M s in the gas phase [19]. Studies on the steady-state and the pulse radiolysis of EtsSiH in methanol showed that the cross-combination of Et3Si with CH30 andHOCH2 occurs with rate constants of 1.1 x 10 and 0.7 x 10 M s , respectively [20]. 

Figure 4.2. Dissociative electron transfer rates from aromatic anion-radicals to alkyl halides detetmined by cyclic votommeiry or by pulse-radiolysis (a) iodobutane (b) 1 -iodo-I -methylpropanc. Solvent N-methylpyrroHdone or dimethylformamidc. Data from refs, [3,5].

Pulse-radiolysis experiments allow an examination of the first steps in the decay of radical-cations. Solutions of the radical-cation in the region of 10 M are generated. Bimolecular reactions between species at this level of concentration proceed relatively slowly and this simplifies interpretation of the experimental data. Particularly, electron transfer between radical-cations and radical species derived from them is not observed during the experiment. 

Advances in pulse radiolysis studies in the gas phase have been summarized in several review papers. In a comprehensive review by Sauer [4], a review presented by Firestone and Dorfman [5] in 1971 was referred to as the first review on gas-phase pulse radiolysis. Experimental techniques and results obtained were summarized by one of the present authors [6], with emphasis on an important contribution of pulse radiolysis to gas-phase reaction dynamics studies. Examples were chosen by Sauer [7] from the literature prior to 1981 to show the types of species that were investigated in the gas phase using pulse radiolysis technique. Armstrong [8] reviewed experimental data obtained from gas-phase pulse radiolysis together with those from ordinary steady-state radiolysis. Advances in gas-phase pulse radiolysis studies since 1981 were also briefly reviewed by Jonah et al. [9], with emphasis on an important contribution of this technique to free radical reaction studies. One of the present authors reviewed comprehensively the gas-phase collision dynamics studies of low-energy electrons, ions, excited atoms and molecules, and free radicals by means of pulse radiolysis method [1-3]. An important contribution of pulse radiolysis to electron attachment, recombination, and Penning collision studies was also reviewed in Refs. 10-15. 

The shift of the spectrum has been well discussed previously. The early pulse radiolysis data suggested that the kinetics at 1300 nm [28] matched the kinetics in the blue [16], which led to the description of the kinetics as a two-state problem. However, the results measured by Chase and Hunt, where the kinetics at 1050 nm were considerably slower than the kinetics at 500 and 1300 nm, suggested that the kinetics were more... 

Electron attachment to solutes in nonpolar liquids has been studied by such techniques as pulse radiolysis, pulse conductivity, microwave absorption, and flash (laser) photolysis. A considerable amount of data is now available on how rates depend on temperature, pressure, and other factors. Although further work is needed, some recent experimental and theoretical studies have provided new insight into the mechanism of these reactions. To begin, we consider those reactions that show reversible attachment-detachment equilibria and therefore provide both free energy and volume change information. 

With the development of the picosecond pulse radiolysis, the kinetics data of the geminate ion recombination have been directly obtained. The history of picosecond and subpicosecond pulse radiolysis is shown in Fig. 7. Very recently, the first construction of the femtosecond pulse radiolysis and the improvement of the subpicosecond pulse radiolysis started in Osaka University. 

The kinetics data of the geminate ion recombination in irradiated liquid hydrocarbons obtained by the subpicosecond pulse radiolysis was analyzed by Monte Carlo simulation based on the diffusion in an electric field [77,81,82], The simulation data were convoluted by the response function and fitted to the experimental data. By transforming the time-dependent behavior of cation radicals to the distribution function of cation radical-electron distance, the time-dependent distribution was obtained. Subsequently, the relationship between the space resolution and the space distribution of ionic species was discussed. The space distribution of reactive intermediates produced by radiation is very important for advanced science and technology using ionizing radiation such as nanolithography and nanotechnology [77,82]. 

Shortly after the discovery of the hydrated electron. Hart and Boag [7] developed the method of pulse radiolysis, which enabled them to make the first direct observation of this species by optical spectroscopy. In the 1960s, pulse radiolysis facilities became quite widely available and attention was focussed on the measurement of the rate constants of reactions that were expected to take place in the spurs. Armed with this information, Schwarz [8] reported in 1969 the first detailed spur-diffusion model for water to make the link between the yields of the products in reaction (7) at ca. 10 sec and those present initially in the spurs at ca. 10 sec. This time scale was then only partially accessible experimentally, down to ca. 10 ° sec, by using high concentrations of scavengers (up to ca. 1 mol dm ) to capture the radicals in the spurs. From then on, advancements were made in the time resolution of pulse radiolysis equipment from microseconds (10 sec) to picoseconds (10 sec), which permitted spur processes to be measured by direct observation. Simultaneously, the increase in computational power has enabled more sophisticated models of the radiation chemistry of water to be developed and tested against the experimental data. 

Reactions of e. It is convenient to consider these reactions here. That the electron can react with solutes before it becomes solvated is clearly demonstrated by the data in Fig. 3, which were obtained by picosecond pulse radiolysis [31]. The data show that there is no good correlation between the C37 value of a solute and its rate constant k for reaction with measured at the same high concentrations of solute used to determine C37. The parameter C37 is the concentration of solute that lowers the earliest measurable value of G(gaq) to 37% of the value obtained in the absence of solute. A linear correlation between C37 and k would be expected if the solute merely reacted with e before this earliest time of... 

By comparison with G e, relatively few independent measurements of G( OH) have been made. In contrast to, only the relative change in G( OH) with time has been reliably measured by pulse radiolysis [51]. In practice, absolute values of G( OH) have been obtained from scavenger studies or by material balance (reaction (7)). Fig. 7 shows data for aerated solutions of formate ion [52] and hexacyanoferrate(II) [53] taken from Fig. 1 of Ref. 54. The data for formic acid, which were included by LaVerne and Pimblott [54], have been omitted here because they were obtained at low pH where the primary yields are different (see Section 3.4). The solid line shows the best fit obtained using Eqs. (16) and (17) and the broken line is the best fit when the term u[5]/2 is omitted from Eq. (17). The respective sets of parameters are a = 1.64 and 1.69 nsec, g( OH) = 2.53 and 2.50 molecules (100 eV) and G°( OH) = 4.48 and 4.86 molecules (100 eV) These values differ significantly from those obtained by LaVerne and Pimblott [54], which were a = 0.258 nsec, g(" OH) = 2.66 molecules (100 eV) and G°( OH) = 5.50 molecules (100 eV) The reason for the difference is that LaVerne and Pimblott [54] chose G°( OH) = 5.50 molecules (100 eV) ... 

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