The electrochemical reduction of 1-([(4-halophenyl)imino]methyl)-2-naphthols on graphite electrodes was studied using cyclic voltammetry, chronoamperometry, constant-potential coulometry and preparative constant-potential electrolysis techniques. The data revealed that the reduction on graphite was irreversible and followed an EC mechanism. The diffusion coefficients and the number of electrons transferred were determined using the chronoamperometric Cottrell slope and the ultramicro disc Pt-electrode steady-state current. The number of electrons was also determined by bulk electrolysis. The compounds were subjected to constant-potential preparative electrolysis and the electrolysis products were purified and identified by spectroscopic methods. Based on these findings, a mechanism for the electro-reduction process is proposed. 相似文献
A nucleophilic substitution reaction between 4-tert-butylbenzyl bromide and a series of iodide salts has been performed in oil-in-water microemulsions based on either a fatty alcohol ethoxylate or a sugar surfactant. The reaction kinetics was compared with the kinetics of the same reaction performed in a microhomogeneous reaction medium, d-MeOH. Previous results showing a particularly high reactivity in the microemulsion based on the fatty alcohol ethoxylate was confirmed. It was shown that in both microemulsions the reaction rate was almost independent of the choice of counterion to iodide. This indicates that complexation of the cation with the surfactant headgroup, which, in particular, could have taken place with surfactants containing oligooxyethylene chains (a “crown ether effect”), seems not to be of importance.
127I NMR studies, as well as quadrupole splitting experiments performed by 2H NMR, indicate that there is a certain accumulation of iodide at the oil–water interface of the microemulsions. It is difficult to draw any quantitative conclusions in this respect, however.
The results obtained in this study, combined with results from previous investigations of the same reaction, indicate that the unexpectedly high reactivity obtained in the microemulsion based on a surfactant containing an oligooxyethylene headgroup is most probably due to the nucleophile being poorly solvated when present in the headgroup layer of such a microemulsion. Poorly solvated anions are known to be highly reactive nucleophiles. 相似文献
Selecting, modifying or creating appropriate problems for mathematics class has become an activity of increaing importance in the professional development of German mathematics teachers. But rather than asking in general: “What is a good problem?” there should be a stronger emphasis on considering the specific goal of a problem, e.g.: “What are the ingredients that make a problem appropriate for initiating a learning process” or “What are the characteristics that make a problem appropriate for its use in a central test?” We propose a guiding scheme for teachers that turns out to be especially helpful, since the newly introduced orientation on outcome standards a) leads to a critical predominance of test items and b) expects teachers to design adequate problems for specific learning processes (e.g. problem solving, reasoning and modelling activities). 相似文献
The origin of the widely observed enhancement of rates for electron-ion recombination at very low energies is still unknown.
We investigated the recombination of Au25+ with free electrons in a merged-beams experiment at the UNILAC accelerator of the GSI in Darmstadt. At Erel= 0 eV we found an enormous enhancement factor of 365 compared to the theory of radiative recombination. An increase of the
electron density by a factor of 10 had not much influence on the measured rate coefficient.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
For a Brauer–Severi variety X over a field k of characteristic not two, every symmetric bilinear space over X up to Witt equivalence is defined over k.
Received: 2 February 1998 相似文献
Charge transport in two dimensions provides an ideal laboratory for investigating parameter space geometries. The Onsager relations for anisotropic transport in a parity-violating external field endow these spaces with a highly nontrivial complex (and Kähler) structure, which can be given a simple geometrical interpretation. A large class of Coulomb gases exhibiting this structure have a generalized Kramers-Wannier symmetry (complexfield duality) which is contained in the modular group. Knowledge of this symmetry and the degrees of freedom encoded in the Coulomb gas appear to be sufficient to determine the global phase diagram and the renormalization group fixed-point structure, including the critical exponents. This accounts for all the scaling behavior observed so far in the quantum Hall system. 相似文献