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Krivenko, A. G.; Kotkin, A. S.; Kurmaz, V. A.; Симбирцева, Г. В.

doi:10.1023/a:1020205431405

Cited by 4 publications

(22 citation statements)

References 5 publications

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“…resolved voltammograms for a trifluoromethyl radical. By their appearance these are close to TRV for other organic radicals described in [1,32,111].…”

Section: Combined Methods: Combination Of the Nonelectrochemical (Or supporting

confidence: 76%

“…A group of methods of laser photoemission (LPE), 2 which were designed in the 1960s to 1990s (see, for example, [1,33,85,86,89]) and the references presented there, getting technically ever more perfect [1,32,39,40,83,, continues to be actively used for both the investigation of irreversible and quasi-reversible electrode reactions involving intermediates in aprotic and protogenic media [1,39,40,84,87,88,[98][99][100][101][102][103][104][105][106][107][108][109][110][111] and the investigation of redox properties of intermediates in aprotic media [1,[94][95][96][97].…”

Section: Combined Methods: Combination Of the Nonelectrochemical (Or mentioning

confidence: 99%

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Thermodynamic and kinetic characteristics of intermediates of electrode reactions: Determination by direct and combined electrochemical methods

2005

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The potentialities of electrochemical and combined methods for the determination of thermodynamic characteristics and kinetic parameters of intermediates are analyzed. The electrochemical methods include polarography, versions of voltammetry, and chronopotentiometry. The combined methods combine nonelectrochemical (or indirect) generation of intermediates with electrochemical methods of their subsequent investigation: photomodulation voltammetry, method of polarography of pulsed-radiolysis products, method of indirect electrolysis, electrochemiluminescence, and a group of laser photoemission methods. Theoretical foundations and basic advantages and disadvantages of the laser photoemission methods (the measurement of photocurrents in potentiostatic conditions-method of time resolved voltammograms obtained under chopped illumination and the measurement of the kinetics of variations in the potential of an electrode after illuminating it by a pulsed laser-in coulostatic conditions) are described in detail. The potentialities of the laser photoemission methods for the determination of thermodynamic (standard potentials E 0 of redox pairs / R -, standard adsorption free energies) and kinetic (values of rate constants W 0 at an equilibrium potential, bulk lifetime of radicals and products of their reduction R -) characteristics of intermediates are demonstrated by studying a trifluoromethyl radical.

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“…resolved voltammograms for a trifluoromethyl radical. By their appearance these are close to TRV for other organic radicals described in [1,32,111].…”

Section: Combined Methods: Combination Of the Nonelectrochemical (Or supporting

confidence: 76%

Section: Combined Methods: Combination Of the Nonelectrochemical (Or mentioning

confidence: 99%

Thermodynamic and kinetic characteristics of intermediates of electrode reactions: Determination by direct and combined electrochemical methods

2005

Self Cite

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“…Additional information on the nature of intermediates could be acquired using the methods that combine nonelectrochemical (i.e., indirect) generation of intermediates with their subsequent electrochemical studies. 222 Particularly, this approach can be exemplified by photoemission methods 156, 198, 222 ± 234 where the slow heterogeneous electron transfer step was displaced by the quick homogeneous capture of the solvated (e À s )/hydrated (e À eq ) electron by an acceptor (RH or RHal). If the rate constant (k a ) for the solvated electron capture by the acceptor [step (a) in reaction (32)] was insufficiently high, then in place of e À s , the photoemitted radicals OH .…”

Section: Formation Of Organomercury Derivatives In the Adsorptionmentioning

confidence: 99%

“…However, the results of laser photoemission 223,225 and laser photoinjection 230 methods in non-aqueous solvents (DMSO, DMF, MeCN) have shown that for sufficiently stable benzyl and benzhydryl radicals, not only the redox potentials of R . /R 7 pairs but also their redox constants 222,225,230 virtually coincided at mercury and gold electrodes, i.e., the R . radical does not interact with the mercury electrode.…”

Section: Formation Of Organomercury Derivatives In the Adsorptionmentioning

confidence: 99%

“…2 This was typical of, for example, aliphatic, cycloaliphatic and alkyl aryl ketones, 1, 2 acetaldehyde, 262 benzaldehyde 263 and p-methylbenzaldehyde 133 and also of chalcones. 2 Particularly, this is the reason for severe complications in the photoemission studies in acidic solutions (at pH < 4 ± 4.5) of carbonyl compounds, namely, acetophenone 229 and acetone. 224,233 Protonated but-3-en-2-one at pH < 6.3 was reduced in a single one-electron step to afford a radical, the subsequent reactions of the latter led to Hg[CH 2 CH 2 C(O)Me] 2 .…”

Section: Py2hg2mentioning

confidence: 99%

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Electrode reactions and electroanalysis of organomercury compounds

Kurmaz¹,

Gul’tyai²

2010

Russ. Chem. Rev.

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Thermodynamic and kinetic characteristics of intermediates of electrode reactions: A comparative investigation of a number of alkylaryl and alkyl halide radicals by the laser photoemission methods

2005

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A comparative investigation of thermodynamic and kinetic properties of a number of alkylaryl intermediates (benzyl and benzhydryl radicals) and alkyl halide intermediates (chloromethyl, dichloromethyl, and trifluoromethyl radicals) is performed by methods of laser photoemission. Techniques, aimed at the determination of thermodynamic and kinetic properties of intermediates (standard potentials E 0 of redox pairs / R -, standard adsorption free energies -∆ , values of rate constants W 0 at an equilibrium potential, as well as lifetimes (times of death in the bulk) τ R of radicals and τ X of products of their reduction R -) from a comparison of Tafel plots for quasi-reversible reduction of intermediates with calculated ones and standard potentials E 0 -from Tafel plots for irreversible electroreduction of intermediates, are presented. The transition from irreversible to quasi-reversible reduction in aprotic solvents at E ~ E 0 is observed only in the case of benzyl, benzhydryl, and trifluoromethyl radicals, for which this particular collection of thermodynamic and kinetic properties is obtained, and is not observed for the chloromethyl and dichloromethyl radicals. In this case redox characteristics of intermediates ( E 0 , W 0 ) are estimated from absolute values of rates of their electroreduction. Possible reasons for the differences in the probability of a reversible electron transfer are discussed for the systems studied.

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Cited by 4 publications

References 5 publications

Thermodynamic and kinetic characteristics of intermediates of electrode reactions: Determination by direct and combined electrochemical methods

Thermodynamic and kinetic characteristics of intermediates of electrode reactions: Determination by direct and combined electrochemical methods

Electrode reactions and electroanalysis of organomercury compounds

Thermodynamic and kinetic characteristics of intermediates of electrode reactions: A comparative investigation of a number of alkylaryl and alkyl halide radicals by the laser photoemission methods

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