期刊
CHEMPHYSCHEM
卷 7, 期 2, 页码 488-496出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cphc.200500404
关键词
dimerization; electrochemistry; kinetics; N,N-dimethyl-p-toluidine; room temperature ionic liquid
The reaction between N,N-dimethyl-p-toluidine (DMT) and the radical cation generated through its one-electron oxidation has been studied electrochemically in the room temperature ionic liquid N-methyl-N-butylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [Py-14][NTf2]. Kinetic information obtained as linear sweep and cyclic voltommetry collected at 5 mu m, 10 mu m and 0.3 mm diameter platinum disk electrodes over a range of initial substrate concentrations and scan rates spanning five orders of magnitude was complemented by chronoamperometric measurements designed to probe the rate of diffusion. At the fastest scan rates the homogeneous reactions following the initial electron transfer were effectively out-run, facilitating on assessment of the electrode kinetics using DIGISIM((R)) and a validated Nicholson's method. Through digital simulation the voltommetry was then shown to be consistent with a mechanism established for the some reaction in acetonitrile, involving dimerisation of the DMT radicals following on initial and rate-determining proton transfer step. After careful consideration of oil parameters, a bimolecular rate constant of (3.4 +/- 1.1) x 10(2) dm(3) mol(-1) s(-1) was deduced by fitting the data. This was compared to the equivalent value for acetonitrile and, in light of this, the implications on the viability of ionic liquids for use as alternative mainstream solvents briefly I assessed.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据