Influence of chloride anions on the electrodeposition and electroactivity of the polymer matrix in polypyrrole,poly(<Emphasis Type="Italic">N</Emphasis>-methylpyrrole) and polypyrrole derivatives functionalized by titanocene centers,in dry non-aqueous solutions

We report electrochemical studies on the influence of a small concentration of chloride ions on the electroactivity of the polymer matrix of polypyrrole (PPy), poly(N-methylpyrrole) [p(N-MePy)] and a poly(titanocene-propyl-pyrrole) derivative, p(Tc3Py) [Tc(CH₂)₃NC₄H₄; Tc=CpCpTiCl₂; Cp=C₅H₅; Cp=C₅H₄] in acetonitrile (AN), tetrahydrofuran (THF) and N,N-dimethylformamide (DMF). The polymer films were obtained on Pt disc electrodes from AN solutions of the monomers containing 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF₆) as the supporting electrolyte and then transferred to the corresponding monomer-free solution. Studies in Cl^–-containing solutions have shown that the p(Tc3Py) matrix is very sensitive to the presence of Cl^– ions in all the above solvents, namely that it was subjected to electrochemical degradation at potentials above 0.1 V vs. a Ag/0.01 M Ag⁺ in AN reference electrode. Degradation of the p(Tc3Py) matrix was also observed in chloride-free DMF+TBAPF₆ solutions. Addition of chloride ions to the AN solution containing pyrrole, N-methylpyrrole or Tc3Py inhibits the deposition of the polymer films. On the other hand, we have found that PPy and p(N-MePy) matrices after their deposition in chloride-free AN solutions show much more stable redox responses in contact with chloride and/or DMF solutions. Possible mechanisms of these effects are discussed.Abbreviations AN acetonitrile - Cp cyclopentadienyl - DMF N,N-dimethylformamide - N-MePy N-methylpyrrole - p(N-MePy) poly(N-methylpyrrole) - PPy polypyrrole - p(Tc3Py) poly[Tc(CH₂)₃NC₄H₄] - Py pyrrole - Tc titanocene=bis(cyclopentadienyl)titanium dichloride, Cp₂TiCl₂, or its radical CpCpTiCl₂ (Cp=C₅H₄) - Tc3Py titanocene-propyl-pyrrole, Tc(CH₂)₃NC₄H₄ - THF tetrahydrofuran Contribution to the 3rd Baltic Conference on Electrochemistry, Gdansk-Sobieszewo, Poland, 23–26 April 2003Dedicated to the memory of Harry B. Mark, Jr. (28 February 1934–3 March 2003)     

Intensification of the mass transfer performance in packed columns for high-purity liquified gases distillation under elevated pressure

An effect of a simultaneous increase in pressure, temperature, and loading density on the efficiency of mass transfer in a packed distillation column was experimentally and theoretically examined in deep purification of liquefied gases. It was found and experimentally confirmed that the increase in pressure and temperature in the column enables intensifying mass transfer, as well as improving performance and lowering energy consumption of the purifying process.     

Methodology for Determination of the Key Parameters of Conjugated Polymer Electrodeposition,Based on a Combination of Spectroelectrochemistry and Electrochemical Quartz Crystal Microbalance

Russian Journal of Electrochemistry - Methodology based on a combination of experimental data obtained by in situ methods of spectroelectrochemistry and electrochemical quartz crystal microbalance...     

Quantum chemical simulation of silicon tetrachloride hydrogenation

The quantum chemical calculation of the activation parameters of the reduction of a SiCl₄ molecule with molecular hydrogen, atomic hydrogen, and atomic chlorine was performed. The energy parameters were determined within the scope of the density functional theory (DFT) with the complete geometry optimization by the unrestricted UB3LYP/6-311+G(d) method. The calculated activation energies allow one to exclude the participation of molecular hydrogen in processes of dehalogenation of chlorosilanes.     

Electrostatic contribution to the ion solvation energy: cavity effects

Ion solvation process has been analysed for the spherically symmetrical system where an ion is located inside a cavity surrounded by an isotropic nonlocal dielectric medium. It has been proven that for any dielectric properties of the medium, the electric field outside the cavity as well as the ion solvation energy depend only on the total ion charge but not of the particular distribution of the ion charge density inside the cavity. These characteristics remain unchanged if the charge is displaced from the external boundary of the cavity into it. Analytical formulas for them have been derived for a particular model of the nonlocal dielectric function. Comparison of results for the solvation energy on the basis of this new theory and of the conventional approach (disregarding the existence of the cavity) shows a significant difference between their predictions if the ion charge is displaced inside the ion cavity.     

Efficiency of Pyrrole Electropolymerization under Various Conditions

The electrooxidative polymerization of pyrrole on the surface of a glassy carbon electrode was studied, while varying the solvent, the type and concentration of supporting electrolyte, redox mediator addition to the polymerization medium, and hydrodynamic conditions. The efficiency of polymerization was determined as the ratio of the charge of the redox response of the polymer film under the standard conditions to the total charge of film formation in the monomer solution. The above factors were varied to determine the conditions that allow minimization of the ratio in order to obtain the highest yield of the polymer product. This was achieved by using a combination of a redox mediator addition with active stirring of solution.