Polarography in hexamethylphosphoramide: Effect of supporting electrolyte cations

Polarographic reductions of various metal ions such as the silver, cupric, zinc, cobaltous, nickel, ferric, ferrous ions and hydrogen ion in hexamethylphosphoramide (HMPA), have been investigated in the supporting electrolytes with various perchlorates. The reduction of most of these ions is strongly influenced by the cation of the supporting electrolyte. In the presence of the tetraethylammonium ion, when the size of the cation of the supporting electrolyte is small and easily adsorbed on the negatively charged electrode surface, the reductions of metal ions are controlled by some preceding processes and are naturally irreversible. The rate of reduction becomes more rapid with the increase of the size of the cation. Thus, in Hex₄NClO₄ or LiClO solutions, the reduction of these various metal ions takes place almost totally under diffusion control, although the waves of most of metal ions show a maximum. These effects of the cation of the supporting electrolytes on reduction can be explained as a phenomenon occurring on the electrode surface. This phenomenon has been reported in previous papers [1] on the reductions of the alkali and alkaline earth metal ions. The difference in the electrocapillary curves in these solutions is rarely shown at the potential around the electrocapillary maximum, but it is very obviously shown at more negative potential. The difference in the effect of the size of the cation of the supporting electrolyte on reduction of metal ion coincides well with the difference in the electrocapillary curves in these solutions: the effect of the size of the supporting electrolyte cation on the polarographic reduction is rarely shown at the potential around the electrocapillary maximum, but it is very obviously shown at more negative potential; therefore this effect is due to the electrode double-layer difference.     

Solvation equilibria in very concentrated electrolyte solutions

A stepwise hydration-equilibrium model for aqueous electrolytes is developed and shown to give a good quantitative account of osmotic coefficients of strong, highly soluble electrolytes up to concentrations of 20–30 m. The main parameters needed are two equilibrium constants describing the stepwise hydration and the number of hydration sites. Choice of ion-size parameter has only a minor effect.This paper was presented at the symposium, The Physical Chemistry of Aqueous Systems, held at the University of Pittsburgh, Pittsburgh, Pennsylvania, June 12–14, 1972, in honor of the 70th birthday of Professor H. S. Frank.Contribution from the Diffusion Research Unit, Research School of Physical Sciences, Australian National University, Canberra, A.C.T., Australia and the University of New England, Armidale, N. S. W., Australia.     

Electrochemical behavior of electrode modified with a cobalt hexacyanoferrate film: Effect of the supporting electrolyte cation

Cobalt hexacyanoferrate films are synthesized on a glassy carbon electrode with sodium, potassium, and ammonium salts in the supporting electrolyte. The electrochemical behavior of the modified electrode is studied in individual solutions of the salts and in their mixtures. The change in electrochemical properties of cobalt hexacyanoferrate agrees with an increase in the interaction of cations with the film in the series Li⁺, Na⁺, K⁺, NH ₄ ⁺ , Cs⁺. The effect of the energy of interaction between the modify ing-substance crystal lattice and counter-ions on the electrochemical processes is discussed     

Microflow electroorganic synthesis without supporting electrolyte

Anodic methoxylation of several organic compounds has been successfully achieved in the absence of intentionally added supporting electrolyte using an electrochemical microflow system.     

Limiting currents in potentiostatic voltammetry without supporting electrolyte

Traditionally, electrochemists study solutions of electroactive salts with excess supporting electrolyte present. The imposition of a large enough potential step on a macroelectrode in such a solution results in a limiting current that obeys Cottrell's equation, declining as t^−1/2. In the present article it is demonstrated that t^−1/2 dependence is preserved even when supporting electrolyte is absent. The limiting current however is shown to depart in magnitude from the Cottrellian prediction by a factor (greater or less than unity) that depends on the charge numbers of the salt's ions and that of the electroproduct.     

The effect of supporting electrolyte on the electrochemical synthesis,morphology, and conductivity of polyaniline

Electrochemical synthesis of polyaniline (PANI) was carried out under cyclovoltammetric conditions using H₂SO₄, HCl, HNO₃, and HClO₄ as supporting electrolytes. The observed different rate of PANI deposit growth depending on the acid in the solution has been explained on the grounds of a different degree of specific adsorption for particular anion. It has been found that morphology of the deposit depends greatly upon the anion present in the solution. Thus, PANI synthesized from the solution of oxyacids results in a dense sponge-like structure while PANI from the hydrochloric acid solution results in a spaghetti-like structure. The structure of the deposit influences the conductivity, being higher for a dense deposit from oxyacid solutions and three orders of magnitude lower in case of a deposit from hydrochloric acid solution. © 1994 John Wiley & Sons, Inc.     

Electroformation of quasi-two-dimensional silver patterns in the absence of supporting electrolyte

Ohne Zusammenfassung     

The role of supporting electrolyte in heterogeneous electron transfer

The effects of supporting electrolyte on the kinetics of the elementary step of electron transfer are considered as unavoidable interplay of interfacial phenomena and ionic equilibria in solution. For the former, the problems to separate contributions of electrostatic electrode-reactant interactions and specific adsorption are addressed, and various aspects of the traditional Frumkin correction (“psi-prime effect”) are discussed. The construction of corrected Tafel plots is shown to be a procedure containing the internal contradiction resulting in an uncertainty. This uncertainty can be eliminated by combining the principles of traditional analysis of the “double layer” effects with physical theory instead of phenomenological approaches. Specific manifestations of parallel electron transfer to an ensemble of reacting species are presented in the context of “mean reactant charge in solution bulk.” The approach to account for non-spherical shape and inhomogeneous charge distribution in reacting species is considered in terms of “molecular psi-prime effect.” Finally, some comments are given on analogy of “double layer” effects at metal/solution interface and interfacial phenomena specific for more complex and highly relevant electrochemical systems.     

Assessment of supporting electrolyte contributions in electrochemically modulated liquid chromatography

This paper reports the results of an investigation on the role of the supporting electrolyte in separations using electrochemically modulated liquid chromatography (EMLC) with a porous graphitic carbon stationary phase. With respect to the identity of the supporting electrolyte, the elution strength of the electrolyte anion increased as F- < OH- < BF4- < ClO4- < PF6- for injections of negatively charged aromatic molecules, whereas a 10-fold increase in electrolyte concentration induced a 60% change in retention for the same solutes. Furthermore, both the concentration and composition of the supporting electrolyte affected retention in a manner that varied with the charge of the analyte and applied potential. This behavior is explained using Gouy-Chapman diffuse double layer theory, coupled with comparisons of this theory with closely related models for ion-pair chromatography. Insights into the retention mechanism reveal that an ion-exchange mechanism controls the retention of negatively charged solutes at applied potentials removed from the potential of zero charge (PZC). At potentials close to the PZC, the electrostatic model is less effective with the predominant retention mechanism likely involving hydrophobic interactions with the carbonaceous stationary phase. The combined effects of these findings are demonstrated by using a temporal gradient in supporting electrolyte concentration to optimize an EMLC separation.     

Effect of supporting electrolyte on obstruction effect and activation energy for the tracer diffusion of cobalt ions in agar gel

The effect of some alkali metal chlorides on obstruction effect // and activation energy /E/ for the tracer-diffusion of cobalt ions is studied in agar gel medium using the zone-diffusion technique. It is observed that both the parameters, and E, decrease with increasing charge density of cation of the supporting electrolyte. This trend is explained on the basis of competitive hydration between ions and agar molecules and the relative distortion in the water structure brought about by these different ions and agar molecules, respectively.     

Formation of solid electrolyte films on porous supporting electrodes

In this work, the method of chemical deposition from the gas phase of organometallic compounds (CVDOM) was used to obtain thin electrolyte films of zirconia stabilized by yttria (YSZ) on a supporting electrode. Tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionato)zirconium and tris(2,2,6,6-tetramethyl-3,5-heptanedionato)yttrium often termed as zirconium (IV) Zr(dpm)₄ and yttrium (III) Y(dpm)₃ dipivaloylmethanates were used as precursors for film deposition. Gas-tight electrolyte films were obtained on a supporting anode with a thickness of 4–10 μm at moderate deposition temperatures of 500–700°C. An electrochemical cell was prepared and tested using the obtained films. The cell allowed obtaining the power density values of 680, 360, and 175 mW/cm² at the temperatures of 800, 700, and 600°C, accordingly.     

Effect of the electrolyte concentration on cation binding in aqueous surfactant solutions.

Electrospray ionisation mass spectrometry (ESI-MS) is used for the qualitative and quantitative study of ion binding to interfaces. The ESI-MS measurements are carried out in aqueous solutions of sodium dodecyl sulphate (SDS) in the presence of NaCl, NH(4)ClO(4) , KCl, or Mg(ClO(4))(2) . The effect of the electrolyte concentration on the fractions, y(cation(+) ), of the DS(-) monomers bound to the cations is shown. Moreover, the binding stability of different cations with DS(-) monomers is determined versus the electrolyte concentration. This stability and the y(Na(+) ) values (the Na(+) ions derived from SDS), estimated in the presence of a given electrolyte, are quantitatively correlated with the electrolyte cation effect on the water structure. We also present calibration curves from which the molar concentrations of the sodium ions (derived from SDS) and of the other cations (derived from the electrolyte), bound to the SDS-micelle surface at a given electrolyte concentration, can be obtained. Besides, specific ion effects (Hofmeister effects) are considered for 1:1 electrolytes.     

Spectrum Correction in Study of Solvation Dynamics by Fluorescence Non-collinear Optical Parametric Ampli cation Spectroscopy

Femtosecond time-resolved fluorescence non-collinear optical parametric amplification spectroscopy can extract the curve of spectral gain from its parametric superfluorescence. This unique spectrum correction method enables fluorescence non-collinear optical parametric amplification spectroscopy acquiring the genuine transient fluorescence spectrum of the studied system. In this work we employ fluorescence non-collinear optical parametric amplification spectroscopy technique to study the solvation dynamics of DCM dye in ethanol solution, and confirm that genuine solvation correlation function and shift of peak frequency can be derived from transient fluorescence spectra after the spectral gain correction. It demonstrates that fluorescence non-collinear optical parametric amplification spectroscopy can benefit the research fields, which focuses on both fluorescence intensity dynamics and fluorescence spectral shape evolution.     

New evidence supporting the formation of a diaziridinium cation in the hydrolytic fission of diaziridines

The isolation and characterization of the bisulfate salt of the 3,3-dimethyldiaziridinium monocation is described. Elemental analysis, infrared, mass spectral, and conductivity data are presented along with results of chemical investigations to support the proposed structure. The only diaziridinium salts isolated previously were formulated as dications, hence the scope of diaziridine salt formation has been greatly expanded and new evidence has been provided which supports the formation of diaziridinium cations in acid hydrolysis and reductive fission.     

Mixed effect of the supporting electrolyte and the zinc anode in the electrochemical homocoupling of 2-bromopyridines catalyzed by nickel complexes in an undivided cell

[reactions: see text] Nickel-catalyzed electroreductive homocoupling of 2-bromomethylpyridines and 2-bromopyridine has been investigated in an undivided cell in the presence of a zinc sacrificial anode. A series of reactions were performed with various types and concentrations of supporting electrolyte. It was observed that a key step in this process is the formation of an arylzinc through a nickel-zinc transmetalation. This intermediate can be transformed back to the reactive arylnickel species to afford the homocoupling as the final product. The back process from the arylzinc intermediate is, however, suppressed in the presence of high concentration (0.2 M) of tetraalkylammonium salts. On the contrary, with NaI, the formation of the dimer is not prevented, whatever the NaI concentration.     

Gas phase hydration and deprotonation of the cyclic C3H3+ cation. Solvation by acetonitrile, and comparison with the benzene radical cation

The binding energies of the first 5 H2O molecules to c-C3H3+ were determined by equilibrium measurements. The measured binding energies of the hydrated clusters of 9-12 kcal/mol are typical of carbon-based CH+...X hydrogen bonds. The ion solvation with the more polar CH3CN molecules results in stronger bonds consistent with the increased ion-dipole interaction. Ab initio calculations show that the lowest energy isomer of the c-C3H3+(H2O)4 cluster consists of a cyclic water tetramer interacting with the c-C3H3+ ion, which suggests the presence of orientational restraint of the water molecules consistent with the observed large entropy loss. The c-C3H3+ ion is deprotonated by 3 or more H2O molecules, driven energetically by the association of the solvent molecules to form strongly hydrogen bonded (H2O)nH+ clusters. The kinetics of the associative proton transfer (APT) reaction C3H3+ + nH2O --> (H2O)nH+ + C3H2* exhibits an unusually steep negative temperature coefficient of k = cT(-63+/-4) (or activation energy of -37 +/- 1 kcal mol(-1)). The behavior of the C3H3+/water system is exactly analogous to the benzene+*/water system, suggesting that the mechanism, kinetics and large negative temperature coefficients may be general to multibody APT reactions. These reactions can become fast at low temperatures, allowing ionized polycyclic aromatics to initiate ice formation in cold astrochemical environments.     

Modulating the redox properties of an osmium-containing metallopolymer through the supporting electrolyte and cross-linking

Thin films of the perchlorate salt of an [Os(N,N'-alkylated-2,2'-biimidazole3)2+/3+-containing polymer have been formed on planar platinum microelectrodes. The electrochemical response associated with the Os2+/3+ couple occurs at -0.19 V. In aqueous perchlorate media at near-neutral pH the voltammetric response is close to that expected for an electrochemically reversible reaction involving a surface-confined reactant. Chronoamperometry conducted on a microsecond time scale indicates that the film and solution resistances are comparable for low concentrations of supporting electrolyte. However, for LiClO4 concentrations greater than 0.4 M, RFilm contributes less than 25% of the overall cell resistance. These results suggest that when the film is dehydrated and the density of redox centers is increased, electron or hole hopping dominates the rate of homogeneous charge transport through the film. The rate of homogeneous charge transport, characterized by D(CT)1/2Ceff, where DCT is the homogeneous charge transport diffusion coefficient and Ceff is the effective concentration of osmium centers within the film, depends weakly on the concentration of LiClO4 as supporting electrolyte decreasing from (8.1 +/- 0.16) x 10(-9) to (4.7 +/- 0.4) x 10(-9) mol cm(-2) s(-1/2) as the perchlorate concentration increases from 0.1 to 1.0 M. These values are about 2 orders of magnitude lower than those of the chemically cross-linked chloride salt of the polymer. The rate of heterogeneous electron transfer is unusually rapid in this system and increases from (5.2 +/- 0.4) x 10(-3) to (7.8 +/- 0.4) x 10(-3) cm s(-1) on going from 0.1 to 0.4 M LiClO4 before becoming independent of the supporting electrolyte concentration at (9.2 +/- 0.6) x 10(-3) cm s(-1) for [LiClO4] > or = 0.6 M.