53rd Meeting of the International Society of Electrochemistry

Russian Journal of Electrochemistry -     

Correlations in the sand pile model: From the log-normal distribution to self-organized criticality

We have studied the approach of the Abelian sand pile model towards the stationary, self-organized criticality state. The uncorrelated limit is shown both numerically and by a simple analysis to follow the log-normal distribution. We introduce and evaluate several correlation fuctions to study the correlated region.     

Magnetic-Field-Dependent Electronic Relaxation of Gd3+ in Aqueous Solutions of the Complexes [Gd(H2O)8]3+, [Gd(propane-1,3-diamine-N,N,N′,N′-tetraacetate)(H2O)2]−, and [Gd(N,N′-bis[(N-methylcarbamoyl)methyl]-3-azapentane-1,5-diamine-3,N,N′-triacetate)(H2O)] of interest in magnetic-resonance imaging

EPR Spectra have been measured for aqueous solutions of a series of Gd³⁺ complexes at variable temperature and a range of magnetic fields; S-band (0.14 T), X-band (0.34 T), Q-band (1.2 T), and 2-mm-band (5.0 T). The major contribution to the observed line widths is magnetic-field-dependent and is interpreted as being due to the modulation of the zero-field splitting produced by distortion of the complexes from perfect symmetry. The transverse and longitudinal relaxation matrices for an ⁸S ion with such an interaction have been calculated using Redfield theory with vector-coupling methods, and diagonalised numerically to obtain relaxation rates and intensities for the degenerate transitions which contribute to the multiplet. The observed line width, which is inversely proportional to the magnetic field at low temperatures, is best described by the intensity-weighted mean transverse relaxation time for the four transitions with non-zero intensity. A least-squares fit of the data yields the square of the zero-field splitting tensor, Δ², and a correlation time, τ_v, with activation energy, E_v. The physical significance of these parameters and the extent of validity of the theoretical approach are considered. The parameters are used to predict the magnetic-field dependence of the longitudinal and transverse electronic relaxation times, which are discussed in the context of their relevance to ¹H-NMR relaxivity.     

Electrochemical Fluorosulfation of Fluoroalkenes: Factors Determining the Process Selectivity

A comparison of results of indirect and direct electrochemical fluorosulfation of nonsaturated fluorocarbons shows that the main or the only product in potentiostatic conditions is vicinal fluorosulfates. Owing to a high rate of the electrochemical step, which exceeds the rate of desorption of intermediate radicals from the electrode surface into solution, it is possible to improve the process selectivity by increasing the contribution of the ionic reaction route.     

Electrochemical perfluoroalkoxylation of aromatic compounds

New approaches to the electrochemical synthesis of aryl perfluoroalkyl ethers based on a) the electrooxidation of perfluorocarboxylic acid on a consumable PbO₂ anode and b) the simultaneous anodic oxidation of the “aromatic compound-alkaline perfluoroalkoholate” system on a platinum electrode were proposed.     

Behavior of protein-like N-vinylcaprolactam and N-vinylimidazole copolymers in aqueous solutions

The free-radical copolymerization of N-vinylcaprolactam and N-vinylimidazole (at an initial comonomer ratio of 85: 15, mol/mol) initiated by a persulfate-tertiary amine redox system in 10% aqueous DMSO at 25 and 65°C (at temperatures below and above the temperature of phase separation in the reaction system, respectively) yielded macromolecular products that were subsequently separated into thermally precipitating and nonprecipitating fractions. Investigations of these fractions by capillary viscometry, static and dynamic laser light scattering, and high-sensitivity DSC showed that macromolecules of both types of copolymers are strongly associated in aqueous solutions. Upon heating of solutions of thermally nonprecipitating fractions, additional aggregation takes place and this phenomenon is accompanied by a decrease in the size of particles without loss in their solubility until at least 70°C is reached. As for the set of properties exhibited in aqueous solutions, the thermally nonprecipitating fraction of the copolymer synthesized at 65°C may be assigned to protein-like macromolecules.     

Association of poly-N-[tris(hydroxymethyl)methyl] acrylamide with a water soluble β-cyclodextrin polymer

An acrylic polymer with pendent adamantyl groups was synthesized and its properties in an aqueous solution with a β-cyclodextrin (βCD) epichlorhydrin polymer examined. Viscosity properties of precursor and modified polymers show differences at low concentrations, but not at higher concentration probably due to very important hydrogen bonds which prevent the formation of intermolecular hydrophobic bonds. The association of both complementary polymers through the inclusion of adamantyl groups is evidenced by phases separation occurrence. Phase diagrams were established at two different concentrations of polymers. We have shown a maximal association of both polymers at these two concentrations, for the same ratio βCD moles/adamantyl groups: 2.4. Salt addition favors this association and displaces the two phases zone to smaller concentrations of modified polymer. Further, 4-nitrophenol can be extracted by the concentrated phase resulting from mixture of solutions of guest and host polymers, pointing out the availability of the associated phase to trap organic molecules.     

Electrocatalysis at chemically modified electrodes : Detection/determination of redox gaseous species in continuous-flow systems

The electrocatalytic response of chemically modified carbon paste and glassy carbon electrodes with anchored Fe(II)/Fe(III) centers is presented for gaseous species such as NO₂, SO₂, H₂S, and Cl₂. Carbon paste electrodes are modified by direct admixing of tris[4,7-diphenyl-1,10-phenanthroline]iron(II) perchlorate, and glassy carbon electrodes are modified by oxidative electropolymerisation of tris[5-amino-1,10-phenanthroline]iron(II) perchlorate. The electrocatalytic cycle operating in the integrated reaction/pre-electrode layer of chemically modified electrodes results in significant signal enhancement. Chemical modification of the conducting surfaces protects the electrode surface from poisoning. evaluation was done in a continuous-flow system using gravitational flow fo supporting electrolyte carrier propulsion, direct injection of air containing parts per billion or parts per million (v/v) of the gaseous species, and amperometric detection with the chemically modified electrodes as part of a thin-layer cell.