Adsorption of n-Butanol from Aqueous Solutions on a Bi–Ga Electrode

Curves of the differential capacitance at the Bi–Ga/H₂O interface in 0.05 M Na₂SO₄ solutions with different concentrations of n-C₄H₉OH are obtained by a bridge method at 420 Hz and 32°C. Adsorption parameters of n-C₄H₉OH, determined by a regression analysis of these curves, are compared with relevant data for mercury and partially fused polycrystalline bismuth (pBi). That the adsorption behavior of organic molecules at Hg differs from that at pBi and Bi–Ga is due not to their different hydrophilicity but to a different physical interaction water–electrode. The reason for this phenomenon can be an unequal spread of electron density beyond the ionic cores of Hg and Bi. These notions are corroborated by the fact that the Bi–Ga data fit overall correlation dependence between the electronic capacitance of different electrodes in the absence of a chemisorption interaction metal–water and the adsorbability of the n-C₄H₉OH molecules on them.     

Electrical Double Layer on Liquid Sn–Ga Alloy in Aqueous Solutions

Double-layer parameters of a liquid Sn–Ga electrode in aqueous electrolyte solutions are studied. It is shown that Sn in the alloy with Ga is a surface-active component and is forced out onto a surface layer of the electrode. The double-layer parameters of an Sn–Ga electrode (8 at. % Sn), which are measured in the experimentally accessible range of charges, differ radically from the parameters of Ga electrodes and are close to those of Sn electrode. Hence, an Sn–Ga electrode containing 8 at. % Sn simulates electrochemical properties of a liquid Sn electrode. The difference between reciprocal electronic capacitances of Hg and Sn and a corrected electrochemical work function of Sn are determined. It is shown that the chemisorption interaction of an Sn–Ga electrode with water molecules is virtually absent at charges more negative than –7 C/cm². A potential drop on uncharged Sn, which is associated with water chemisorption, is –20 mV. Thus, the hydrophilicity of Sn is slightly higher than that of Hg, Bi–Ga, Pb–Ga, and Tl–Ga and significantly lower than that of In–Ga, Cd–Ga, and Ga.     

Some components of the seed oil ofMalva sylvestris

The lipid composition of the free fatty acids of the seed oil ofMalva sylvestris from the Ukrainian flora has been studied by chromato-mass spectrometry. The fatty acid composition was represented by 20 compounds, among which malvic and sterculic acids were detected. The presence of terpineols and retinol has been shown.Zaporozh'e Medical Institute. Translated from Khimiya Prirodnykh Soedenii, No. 3, pp. 322–325, May–June, 1994.     

Electrical double layer in surface-inactive electrolyte solution and adsorption of halide ions from 0.1 M solutions on liquid Cd–Ga and In–Ga alloys in gamma-butyrolactone

The double-layer characteristics of liquid renewable Cd–Ga (0.3 at % Cd) and In–Ga (14.2 at % In) electrodes in the gamma-butyrolactone (GBL) solutions of various electrolytes are studied by measuring the differential capacitance and using the method of open-circuit jet electrode. For the (Cd–Ga)/GBL and (In–Ga)/GBL interfaces, the zero-charge potentials, which are not distorted by the specific adsorption of ions, and the chemisorption potential drops of solvent are determined. It is shown that, in spite of the fact that the work function decreases as we pass from (In–Ga) to (Cd–Ga), the chemisorption potential drops of solvent on both electrodes are close. This behavior is explained by a closer approach of GBL dipoles to the surface of (Cd-Ga) electrode providing more effective overlapping of donor–acceptor levels of metal and solvent. It is shown that, in GBL, the adsorption parameters of halide ions and their surface activity series depend on the metal nature. On the (Cd–Ga) and (In–Ga) electrodes, the reversed surface activity series of halide ions is observed: on the Hg electrode in various solvents, the surface activity increases in the series Cl^– < Br^– < I^–, whereas on the (Cd–Ga) and (In–Ga) electrodes in GBL, it varies in the reverse series I^– < Br^– < Cl^–.     

Regression analysis of dependences of adsorption potential shifts on the charge in systems (Tl-Ga)/[N-methylformamide + mc KI + (1 − m)c KClO4], (Tl-Ga)/[N-methylformamide + mc KBr + (1 − m)c KClO4] and (Tl-Ga)/[N-methylformamide + mc KCl + (1 − m)c KClO4]

By the regression analysis of dependences of the adsorption potential shift (E _ads) on the electrode charge in systems (Tl-Ga)/[NMF + 0.1m M KI + 0.1(1 ? m) M KClO₄], (Tl-Ga)/[NMF + 0.1m M KBr + 0.1(1 ? m) M KClO₄], and (Tl-Ga)/[NMF + 0.1m M KCl + 0.1(1 ? m) M KClO₄] with the following m fractions of the surface-active anion: 0.05, 0.1, 0.2, 0.5, and 1, the adsorption parameters are calculated in terms of two models based on the Frumkin isotherm both considering the free adsorption energy as a quadratic function of the electrode charge, where one model takes into account the diffuse layer and the other ignores it. It is shown that for the studied electrode charges q ≤ 2 μC/cm², both models provide equal accuracy in calculating E _ads in the systems under study.     

Adsorption of Cl−, Br−, and I− ions from 0.1 M solutions in methanol on Ga, (In-Ga), and (Tl-Ga) electrodes

Adsorption of Cl^?, Br^?, and I^? (Hal^?) ions from 0.1 M solutions in methanol (MeOH) is studied on the liquid renewable Ga, (In-Ga), and (Tl-Ga) electrodes by the methods of differential capacitance and jet electrode. It is shown that the adsorption parameters and the series of surface activity of halide ions in MeOH essentially depend on the metal nature. On the (In-Ga) and (Tl-Ga) electrodes, as well as on the Hg electrode, the surface activity of halide ions increases in the series: Cl^? < Br^? < I^?; on the Ga electrode, it varies in another series: Br^? < Cl^? < I^?. The data for the Ga/MeOH interface support the result, which was first obtained on the Ga/N-methyl formamide (N-MF) interface, that the effect of inversion of surface activity series can be observed not only in the aprotic solvents, but also in the protic solvents. The data, which were obtained in MeOH, are compared with the corresponding data, which were obtained in N-MF, dimethyl formamide (DMF), acetonitrile (AN), and water. For Ga, (In-Ga), and (Tl-Ga) electrodes, the adsorption of Hal^? varies in the series: H₂O < MeOH ≈ N-MF < DMF < AN. The data obtained in MeOH indicate that the energy of metal-Hal^? interaction (ΔG _M-Hal) increases in the series (Tl-Ga) < (In-Ga) < Ga as the electronic work function increases. This is in agreement with the data, which were obtained in other solvents, and is the evidence for the donor-acceptor nature of metal-Hal^? interaction, where the Hal^? ions are the donors of electron pair with respect to the metal.     

Electrical Double Layer at a Liquid Pb–Ga Electrode in Propylene Carbonate Solutions

Differential-capacitance curves and potentials of zero charge are obtained for a liquid Pb–Ga electrode in propylene carbonate (PC) solutions of surface-inactive electrolyte LiBF₄and 0.1 M solutions of LiBr and LiI. In PC and water, double-layer parameters of Pb–Ga differ from those of Ga. The lyophilicity of Pb–Ga in respect to PC is lower than that of Ga and coincides with that of Hg.     

Current distribution of permeable electrodes in the presence of the hall effect in a stream of electrically conducting medium

The two-dimensional problem of the current distribution on the surface of permeable electrodes contiguous with a stream of incompressible medium with Hall effect is considered. An electrically conducting medium with the same physical properties as those of the main stream is pumped in (out) through the electrodes.This problem was solved in [1] for one particular case when the electrodes are impermeable. It was established that due to the Hall effect in magnetohydrodynamic channels the current is distributed non-uniformly on the electrodes; for values of the Hall parameter of the order of several units or greater, the current flows into an isotropically conducting medium mainly from a small portion on the edge of the electrode. It was also noted that this phenomenon creates unfavorable conditions for the operation of electrodes in magnetohydrodynamic devices.It is shown in what follows that the current distribution on the electrodes may be controlled, and in particular made more uniform, by injecting an electrically conducting medium.     

Comparative study of Cl<Superscript>−</Superscript>, Br<Superscript>−</Superscript>, and I<Superscript>−</Superscript> ions adsorption from dimethyl formamide at Hg- and Ga-electrodes

The adsorption of Cl⁻, Br⁻, and I⁻ ions from their 0.1 M solutions in dimethyl formamide at renewable liquid Hg- and Ga-electrodes was studied under similar experimental conditions by the differential-capacitance and jet-electrode methods. The data obtained points out to a strong effect of the metal nature on adsorption parameters and the halogenide-ion surface activity series. The halogenide-ion surface activity at the Hg-electrode increased in the following sequence: Cl⁻ < Br⁻ < I⁻; at the Ga-electrode, in the reverse sequence: I⁻ < Br⁻ < Cl⁻. The results are explained qualitatively in terms of the Andersen-Bockris model. It follows from the obtained data that (1) the free energy of the metal-halogenide-ion interaction increases in the following sequence: I⁻ < Br⁻ < Cl⁻; (2) the free energy of the Ga-halogenide-ion interaction exceeds that of the Hg⁻halogenide-ion interaction; and (3) the difference of the Cl⁻, Br⁻, and I⁻ ions interaction with the metals increased significantly when passing from Hg⁻ to Ga-electrode.     

Nonlinear electric field oscillations in continuous media

Strong nonlinear potential and drift-velocity waves in a nonequilibrium medium, in which the current-carrier collision frequency depends on the electric field, are considered in the hydrodynamic approximation.Translated from Zhurnal Prikladnoi Mekhaniki i Tekhnicheskoi Fiziki, Vol. 10, No. 3, pp. 55–57, May–June, 1969.