Enlightened sonochemistry

Sonochemistry and photochemistry are initiated by high-energy transient species, which may be prone to mutual interaction. Electronic excitation of solutes by energy transfer from high energy species generated in collapsing bubbles is already supported by experimental evidence. The rates of photochemical reactions can be affected by ultrasound-induced mixing of liquids caused by microstreaming near pulsating cavitation bubbles and shockwaves due to bubble collapse. This may not only improve light absorption but also modify the pathway of reaction by increasing the contact between reagents. Finally, one may speculate about a potentially new chemistry of photoexcited solutes under the extreme conditions inside cavitation microreactors. This work reviews research on the excitation of solutes by sonoluminescence, the combined effects of ultrasound and light on liquid systems and the effect of ultrasound on photocatalytic reactions.     

EQCM Study of the Couple Thallium(I)/Thallium Amalgam at a Thin Film Mercury Electrode

EQCM and voltammetric data show that thallium(I) ions, which are adsorbed in the region of the positive surface charge, most probably, in the form of the ionic pairs, are not reduced. In this potential region, thallium(I) ions are reduced directly from the solution. At more negative potentials, the previously adsorbed stable ionic pairs slowly undergo transition into the less stable form. From this form, thallium(I) ions can be reduced or desorbed into the solution. The process is best described by a model of one electron, i.e., full charge transfer.     

Radioactive Tracer Study of the Displacement of Iodine Adatoms from Platinized Platinum Electrode by Carbon Monoxide

Radioactive tracer studies confirm the earlier electrochemical results that carbon monoxide can virtually completely displace iodine adatoms. For the first time, it is found that iodine adatoms are not displaced by carbon monoxide when iodide anions are adsorbed in the presence of an upd silver monolayer. The possible reasons for the effect observed are discussed.     

Two-Layered Poly-o-phenylenediamine/Polyaniline Composite: Electrosynthesis and Spectroelectrochemical Properties

Spectroelectrochemical properties of poly-o-phenylenediamine (PPD) and the synthesized composite of PPD and polyaniline—two chemically related polymers containing an amino-substituted benzene ring but having different conduction nature—are studied. The polyaniline synthesis on PPD-modified electrodes involves stages of the reaction initiation, the copolymer formation, and the formation of a polyaniline layer at the copolymer/solution interface.     

Adsorption of Kryptate Complexes of Alkali Metals in Electrolytes of Different Compositions and in the Presence of 1-Adamantanol

Data on the adsorption of kryptates of alkali metals on a mercury electrode are obtained for the first time by a method of the measurement of the differential capacitance as a function of potential and are compared to one another. Shown is that there takes place a deep mutual relationship between the structure of a complex and the regularities of its adsorption. An assumption is put forth about the possibility of adsorption of a free ligand in solutions of lithium kryptate, which possesses relatively low strength. The co-adsorption of sodium kryptate with 1-adamantanol, which forms a two-dimensional condensed layer, is investigated. Established is that the C vs. E curves, obtained in 1 M Na₂SO₄ at a constant activity of 1-adamantanol and a varying concentration of Kryptofix^R 222, exhibit two distinctly pronounced portions, each of which corresponds to predominant adsorption of one of the surface-active components. The region of predominant adsorption of Kryptofix^R 222 expands with its concentration.     

Study of the Surface Tension of the Aqueous Solutions of Dodecylamidoethyldimethylbenzylammonium Chloride

The dynamic and equilibrium surface tensions of aqueous dodecylamidoethyldimethylbenzylammonium chloride solutions of various concentrations at 16, 20, 25, 30, and 35°C are studied for the first time. The effects of the concentration and temperature on the surface tension relaxation are discussed. The possibility of two-dimensional phase transition and its effect on the dynamic behavior of surface tension are considered.     

Determination of Hydroxamic Acids by Thermal-Lens Spectrometry

Conditions are determined for the determination of salicylhydroxamic and acetylhydroxamic acids by thermal-lens spectrometry using iron(III) in an aqueous medium. The detection limits are 6 × 10^–8 and 3 × 10^–8 M, respectively. The sensitivity can be enhanced 3–6 times with the use of aqueous–organic media.     

Formation Enthalpies of Water–n-octane–1-propanol–sodium Dodecyl Sulfate Microemulsions at 298.15 K

The solution enthalpies of water–n-octane–1-pentanol (PeⁿOH)–sodium dodecyl sulfate (SDS) microemulsions and their components in 2-propanol at 298.15 K were determined by the thermochemical method at fixed mass fractions of PeⁿOH (0.1450) and SDS (0.0775). The formation enthalpies of microemulsions were calculated using the thermochemical cycle, and it was shown that their values are positive. The results obtained indicate that the intercomponent interactions in the investigated systems are rather weak. The formation of thermodynamically stable microemulsions is determined by entropy changes associated with the disintegration of water and 1-pentanol homoassociates.     

Peculiarities of Adsorption of Some Polar Substances from Vapor Phase on a Microporous Clay Adsorbent

The adsorption of polar organic substances (methanol, pyridine, and acetonitrile) and water was studied from the vapor phase on microporous adsorbent prepared by the substitution of polyhydroxyaluminum ions for the sodium ions of natural montmorillonite clay. The differential isosteric heats of adsorption of these substances were calculated and analyzed in a wide range of fillings.     

Optimization of Mass Transfer Processes in the Zone of the Air Electrode of a Fuel Cell with a Solid Polymer Electrolyte

A two-dimensional mathematical model for the transport of reactants in a fuel cell with a solid polymer electrolyte is developed. The model is used for analyzing spatial distributions of the concentration of reactants and current density over the cell. The effect of the catalytic-layer activity, reactant speed, bipolar-plate geometry, thickness and porosity of current collector and/or gas-diffusion sublayer, and the reaction mixture composition on the fuel cell efficiency is estimated theoretically and experimentally.