Kinetics and mechanism of reactions of arenes in the HVO3-sulfuric acid system: Extended compensation effect

Autor:	E. S. Rudakov, L. K. Volkova
Rok vydání:	2006
Předmět:	Reaction mechanism Kinetics General Chemistry Trimethylbenzenes Catalysis Computer Science Applications chemistry.chemical_compound Electron transfer Reaction rate constant chemistry Modeling and Simulation Kinetic isotope effect Physical chemistry Benzene
Zdroj:	Kinetics and Catalysis. 47:858-866
ISSN:	1608-3210 0023-1584
DOI:	10.1134/s0023158406060085
Popis:	Kinetics, activation parameters, and the kinetic isotope effect (KIE) of hydrogen have been determined for the first rate-limiting step of the reactions of benzene, monoalkylbenzenes, dimethylbenzenes, and trimethylbenzenes in HVO3-sulfuric acid (54–70 wt % H2SO4) solutions. The effects of solution acidity on the rate constants (k) and KIE have been studied. The reactions begin with electron transfer from the arene to VO 2 + and end with oxidative coupling: $$PhCH_3 \xrightarrow{{VO_2^ + }}PhCH_3^{ + \cdot } \xrightarrow{{ - H^ \cdot }}PhCH_2^ + \xrightarrow{{PhCH_3 }}PhCH_2 C_6 H_4 CH_3 .$$ logk is a linear function of the ionization potential of the arene (I ArH). A three-parameter correlation is for the first time established between the activation energy (E), the logarithm of the preexponential factor (log A), and I ArH: logA = 0.15E − 0.058I ArH + 49.1 (E and I ArH are expressed in kJ/mol). The reactions of arenes with VO 2 + , NO 2 + , and Co3+ are intercompared.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::5b9b3a2fbec1cd372c6f8edad64c9db9 https://doi.org/10.1134/s0023158406060085 Zobrazit plný text záznamu Plný text ve formátu PDF