Photochemistry of the PtCl62− complex in methanol solution

Grivin, Vjacheslav P.; Khmelinski, I.V.; Plyusnin, Victor F.; Blinov, I.I.; Балашев, К. П.

doi:10.1016/1010-6030(90)87051-c

Cited by 60 publications

(35 citation statements)

References 14 publications

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“…In some experiments the laser-flash photolysis setup described in ref. [16] was used. While measuring the temperature dependence of the reaction rate constants, we have taken into account a change in the concentration of the initial complex due to the heat expansion of a solvent.…”

Section: Methodsmentioning

confidence: 99%

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Photoreduction of IrCl62? complex in alcohol solutions and its reaction with hydroxyalkyl radicals

Glebov

Plyusnin

Grivin

et al. 1998

Int. J. Chem. Kinet.

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The photochemistry of complex in simple alcohols have been studied using 2ϪIrCl 6 laser-flash photolysis. Single electron transfer from the solvent molecule to the light-excited complex has been shown to be the primary photochemical process. Quantum yields of the photoreduction of complex and the rate constants of its reaction with hydroxyalkyl 2ϪIrCl 6 radicals were determined at Deviations of the rate constants from Debye-Smo-200-330 K. luchowski equation for diffusion-controlled reactions are discussed.

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Section: Methodsmentioning

confidence: 99%

“…This mechanism is typical of the photoreduction of halide complexes of transient metals in polar organic solvents [9,10,16]. The present article reports on the quantum yields of photoreduction and shows…”

Section: ϫmentioning

confidence: 96%

Photoreduction of IrCl62? complex in alcohol solutions and its reaction with hydroxyalkyl radicals

Glebov

Plyusnin

Grivin

et al. 1998

Int. J. Chem. Kinet.

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“…Based on the results of the present study, we can propose the following scheme of reactions for the photolysis of FeOH aq 2+ in the presence of phenol: The pairs of reactions (19), (20) and (21), (22) corre spond to processes involving the ortho and para isomers of the Ph(OH) 2 • radical. In terms of the scheme of reactions (17)-(26), we calculated the kinetic curves by the numerical solution of differential equations by the Runge-Kutt method of the fourth order.…”

Section: Resultsmentioning

confidence: 86%

“…22 All measurements were carried out in a cell with an optical path length of 1 cm. A radiation from an XeCl laser or a mercury lamp (DRSh 500) with an array of glass filters to separate particular lines was used for steady state photolysis.…”

Section: Methodsmentioning

confidence: 99%

Optical spectra and kinetic characteristics of radicals formed upon the photolysis of aqueous solutions of a FeOHaq 2+ complex and phenol

et al. 2004

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The nature, optical spectra, and kinetic characteristics were determined for intermediate radicals formed upon the photolysis of aqueous solutions of a FeOH aq 2+ complex with phenol additives. The primary radical • ОН reacts with phenol to form ortho and para isomers of the Ph(OH) 2 • radical. The Ph(OH) 2 • radical eliminates a water molecule to form a phenoxyl radical PhO • . The latter disappears in the reactions with Fe III complexes, recombination, and disproportionation. The final products of photochemical transformations were determined. Among them, o quinone and diphenoquinones were identified.Phenol is a raw materials widely used in the chemical industry for syntheses of plastics, drugs, dyes, pesticides, preservatives, and surfactants. 1 Its world production ex ceeds 6 millions tons per year. 2 The active use of phenol contaminates the environment. The concentration of phenols in sewage can reach 100 µg L -1 ≈ 10 -6 mol L -1 . 3 Phenol is very toxic (maximum allowable concentra tion ≈ 1 µg L -1 ≈ 10 -8 mol L -1 4 ); therefore, the study of mechanisms of its degradation in natural water is of con siderable interest from the ecological point of view. Pho tochemical processes can play an important role in the removal of contaminants from natural aqueous sys tems. 5-7 A special attention is given to photoprocesses involving hydroxo complexes of Fe III , whose photolysis affords an • OH radical, being one of the most active species in chemistry and capable of oxidizing almost all organic admixtures dissolved in water, including such haz ardous substances as derivatives of the phenol series. 8-10 The concentration of iron ions in natural water can ap proach ∼10 -3 mol L -1 . 11,12 In the absence of coordinat ing organic ligands, hydroxo complexes are the main forms of Fe III in water with рН < 5, and the photochemistry of these complexes can exert a substantial effect on the bal ance of organic admixtures. 6,13Among the Fe III hydroxo complexes, the highest pho tochemical activity belongs to a complex FeOH aq 2+ , whose excitation is accompanied by the generation of an • OH radical with a high quantum yield (ϕ = 0.2, λ = 308 nm). 14,15 The activation energy of formation of the • OH radical is only ~10 kJ mol -1 , 15 which explains its formation by the electron phototransfer to the Fe III ion from both the outer sphere hydroxide ion (reaction (1)) and outer sphere water molecule (reaction (2)). 15(1)The formation of the • OH radical by the excitation of the FeOH aq 2+ complex was confirmed in several studies on steady state 6,7,14 and flash photolyses 10,15,16 using ac ceptors of the • OH radical. At least three mechanisms of degradation of phenol and its derivatives photoinduced by the FeOH aq 2+ complex were proposed in the literature. These mechanisms include reactions (3)-(9).

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“…Photoreduction is caused by an electron transfer from a solvent molecule to the light-excited complex [31][32][33] …”

Section: àmentioning

confidence: 99%

Primary photochemical processes for PtCl62− complex in acetonitrile solutions

Matveeva

Pozdnyakov

Grivin

et al. 2016

Journal of Photochemistry and Photobiology A: Chemistry

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Photochemistry of the PtCl62− complex in methanol solution

Cited by 60 publications

References 14 publications

Photoreduction of IrCl62? complex in alcohol solutions and its reaction with hydroxyalkyl radicals

Photoreduction of IrCl62? complex in alcohol solutions and its reaction with hydroxyalkyl radicals

Optical spectra and kinetic characteristics of radicals formed upon the photolysis of aqueous solutions of a FeOHaq 2+ complex and phenol

Primary photochemical processes for PtCl62− complex in acetonitrile solutions

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