A porous-jet flow-through electrode

An electrochemical flow detector, based on a jet of solution directed at a thin porous carbon electrode, is described, along with its electrochemical characteristics and analytical applications. The electrode has a volume of 19 mul and surface area of 1.26 cm(2). The detector exhibits better sensitivity and detectability than a wall-jet detector. Dopamine and ferrocyanide were used as test systems to give detection limits at nanomolar concentration levels. Applications indicated include continuous-flow analysis (utilizing stopped-flow voltammetry) and flow-injection analysis.     

Electrochemical reduction of tricarbonyl compounds: Reduction mechanism of alloxan on a mercury electrode

A study has been carried out on the reduction mechanism of alloxan over a DME corresponding to the first two-electron transfer over the pH range 0–12.Polarographic and voltammetric results show the reduction process to be kinetically controlled. Rate and equilibrium constant data for the prior chemical reaction have been evaluated and several reaction mechanisms for different pH zones have been proposed.     

Electrochemical reduction of some rhodanine derivatives at the DME

The electroreduction of two series of rhodanine derivatives has been investigated at the DME. The first wave was assigned to the saturation of the azomethine linkage and the reduction of the ethylenic double bond in series I and II, respectively. On the other hand, the second wave in both series was assigned to the reduction of the C-S group and partly to the catalytic hydrogen evolution catalyzed by these compounds.     

A faradaic impedance study of the reduction of oxygen from aqueous alkaline solution at the dropping mercury electrode

The reduction of oxygen to hydrogen peroxide at a dropping mercury electrode in an aqueous solution of 1 M KNO₃+0.04 M KOH (pH=12.35) has been studied by means of impedance measurements as a function of frequency and d.c. potential. The reaction appears to be nearly reversible in the dc sense, but quasi-reversible in the ac sense. The impedance data obey the Randles' equivalent circuit with the following apparent values for the kinetic parameters: standard heterogeneous rate constant k_sh^a=0.035 cm s^?1 and cathodic transfer coefficient α^a_c=0.22. The results are interpreted in terms of a two-step charge transfer mechanism with the step O₂+eO₂^? being rate-determining.     

Electrochemical behaviour of some neuroleptics: Haloperidol and its derivatives

The electrochemical characteristics of Haloperidol and related compounds, representative neuroleptics of the butyrophenone family, have been investigated as a function of pH and concentration by direct-current, alternating-current and differential-pulse polarography and cyclic voltammetry at a hanging mercury drop electrode. A single cathodic wave representing an irreversible two-electron reduction is obtained, and its half-wave potential differs from that characteristic of aromatic ketone reduction. Adsorption processes disturb the wave behaviour and an adsorption prewave is observed at high concentrations. Quantitative measurements were successful in the concentration range 1 x 10(-4)-1 x 10(-6)M (0.4 mg/l.), the lower concentration representing the detection limit by differential-pulse polarography.     

Anodic stripping voltammetry in a flow-through cell with a fixed mercury film glassy carbon disc electrode. Part I

Anodic stripping voltammetry at a glassy carbon disc electrode covered by a thin mercury film was adapted for use in a flow-through cell. The resulting system is characterized by extreme simplicity of set-up and operation, high sensitivity and excellent precision and stability. Its performance was tested via the determination of hydrated or labile complex ions of heavy metal ions in sea water, using short (2–10 min) deposition periods. The dependence of the stripping peak charge on metal ion concentration, length of deposition period, solution flow rate and other variables was examined and the reliability of the results obtained were evaluated under conditions resembling continuous monitoring.     

Polarographic reduction of oxygen dissolved in molten acetamide at 85°C

The reduction of oxygen in molten acetamide has been studied polarographically. The two waves observed are irreversible. The first wave has been analysed by the Koutecký procedure and the kinetic parameters calculated. The ECEC mechanism proposed for oxygen reduction from aqueous media holds good in this medium.     

In situ studies of electrode reactions: The mechanism of lithium intercalation in TiS2

The mechanism of lithium intercalation into TiS₂ is poorly understood even though the system Li_xTiS₂ (0 ? x ? 1) has been extensively studied. This mechanism is critical in the functioning of $\text{Li}\text{TiS}{}_2$ nonaqueous batteries. In this report we describe several techniques which are used to study this mechanism. These methods consist of ex situ and in situ optical and X-ray techniques which yield information regarding the mechanism of lithium intercalation and factors which effect this process during the operation of $\text{Li}\text{TiS}{}_2$ batteries.     

Continuous-flow determination of reducing sugars in serum by reaction with periodate ions,with use of a flow-through periodate-sensitive electrode

A continuous-flow method for the determination of reducing sugars in serum is described. The sample reacts with an excess of periodate in a flow system and the decrease in periodate

activity is monitored with a periodate-sensitive flow-through electrode. The recorded potential peak heights are indirectly linearly related to the reducing sugar concentration expressed as glucose, in the range 50–290 mg/100 ml. The analysis is completely automated and requires no sample pretreatment, and samples can be analyzed at the rate of 30 per hour with average errors and relative standard deviation of about 1–2%. Comparison with an enzymatic method for serum gave satisfactory results.     

Stripping voltammetry with collection at a rotating ring-disk electrode

A new electroanalytical technique is described, called "stripping voltammetry with collection." The technique involves the use of a rotating ring-disk electrode and is an improvement over traditional voltammetric stripping at a single electrode in that it is characterized by a lower limit of detection and that the period of deposition before stripping can be shorter. The use of the technique is illustrated by the determination of 10(-10)M Ag(+) in 0.1 M H(2)SO(4) by use of a ring-disk electrode having a disk electrode constructed of glassy carbon and a ring electrode constructed of platinum.     

Electrochemical behaviour of natural and biosynthetic polynucleotides at the mercury electrode: VII. Studies on the adsorption and reduction of DNA and biosynthetic polynucleotides with a new potentiostatic double step-sweep method

By a new potentiostatic double step-sweep method conveniently applicable with common commercial polarographic equipment the adsorption and interfacial behaviour of DNA of different origin and of related biosynthetic polynucleotides has been studied in moderately acid solution (pH 5.6) of different ionic strengths over the whole extended potential range of adsorption up to ?1.6 V (SCE) at the HMDE. Furthermore the new method has proved to be an efficient tool to follow the kinetics of the reduction of strongly adsorbed substances to as well strongly adsorbed reduction products.Three potential ranges corresponding to different interfacial situations can be distinguished for the investigated polynucleotides. In the first range between ?0.4 and ? 1.2 V (SCE) the biopolymer is adsorbed. If the biopolymer has initially a double stranded form progressive irreversible deconformation occurs as well in this potential range furnishing further evidence for the previously developed concept of the sequence of interfacial events. In the second range between ?1.2 and ?1.6 V biopolymers are adsorbed and (in the double stranded case after prior deconformation) the adenine and cytosine moieties undergo a totally irreversible reduction forming according to the nature of the polynucleotide a more or less completely blocking film of strongly adsorbed reduced biopolymer. In the third range beyond ?1.6 V no adsorption and thus reduction occurs.The kinetic parameters k_ct and α_cn_a of the rate determining step of the charge transfer reaction in which the adsorbed biopolymer is reduced have been studied as function of the nature and structure of the polynucleotide, of its base composition and of ionic strengthIn general the measurements improve significantly the understanding of the complicated behaviour of DNA and related biosynthetic polynucleotides at charged interfaces and confirm in various ways our previous resulis and conclusions.     

Tunnel electrode: Part II. Electron-transfer theory at an n-type semiconductor tunnel electrode

The formula for the cathodic tunnel current at an n-type semiconductor tunnel electrode was derived from the double adiabatic perturbation theory considering the vibration in the first coordination sphere. In the low-temperature limiting case, the apparent difference between the normal and the abnormal regions was observed in both the transfer coefficient α and the activation energy E* as a function of potential. It was concluded that the semiconductor tunnel electrode has advantageous characteristics for investigation of the electron-transfer mechanism at high overvoltage.     

Surface enhanced Raman spectra of nucleic acid components adsorbed at a silver electrode

High-resolution vibrational spectra of nucleic acid components adsorbed on a silver electrode were obtained using a spectroelectrochemical method based on the large-intensity enhancement for Raman scattering at electrode surfaces.The laser surface Raman spectra of purine, adenine, adenosine, deoxyadenosine, adenine mononucleotides, adenylyl-3′, 5′-adenosine and polyriboadenylic acid were recorded in the range of 150–3500 cm^?1. The intensities of the vibrational bands were highly dependent upon the electrochemical preparation of the electrode, the applied potential and the nature of the adsorbate species. High-intensity spectra in rather dilute bulk solutions were obtained.The phosphate derivatives of adenosine exhibited strongly enhanced Raman scattering. Spectral band frequencies corresponded closely with normal Raman spectra of these molecules in solution. The adenine ring breathing mode at 740 cm^?1 and the adenine ring skeletal vibration at 1335 cm^?1 produced prominent Raman scattering. A strong band at about 240 cm^?1 for the adenine mononucleotides was attributed to silver/adsorbed phosphate group vibrations.     

Voltammetric oxidation of pharmaceutical organic compounds at a new modified electrode: The aluminum graphite spray-covered electrode

A new graphite spray-modified aluminum electrode has been used to determine clozapine, clothiapine, and loxapine in acetate buffer at pH 4.7 and 20% methanol, down to 5 × 10⁻⁶ M concentrations using differential pulse voltammetry. Reproducibility exceeds that of other solid electrodes, being in the range of 1 to 2%. The electrochemical oxidation products of the latter two compounds are strongly adsorbed, causing diminished electrode response, but response is readily restored by polishing of the sprayed electrode.     

Subtractive differential pulse anodic stripping voltammetry at a stationary mercury-coated glassy carbon electrode

The application of subtractive mode differential pulse anodic stripping voltammetry (SDPASV) at a stationary mercury-coated glassy carbon electrode for the analysis of labile Zn(II), Cd(II), Pb(II) and Cu(II) is described. It is shown that the method has an improved sensitivity to Cu(II) owing to elimination of high background currents normally encountered in normal mode DPASV at the TFME. The sensitivity limits of the present method to Cd(II) and Cu(II) is estimated to be 0.025 and 0.067 ppb respectively, when a 2 min deposition time is used. It is suggested that the high sensitivity of the method coupled to the relative simplicity of the stationary electrodes could make the method useful in environmental and natural water studies.     

Electrochemical behavior of decyl mercuric halides at mercury cathodes in dimethylformamide

Polarograms for decyl mercuric halides in dimethylformamide containing tetraalkylammonium perchlorates exhibit two waves. When large-scale electrolyses of decyl mercuric halides are performed at potentials corresponding to the first polarographic wave, the couldometric n value is unity and didecylmercury is obtained in quantitative yield; electrolyses carried out at potentials on the plateau of the second polarographic wave afford only decane and the n value is essentially 2. Double-potential-step chronocoulometry and staircase voltammetry indicate that, at potentials corresponding to the first polarographic wave, the decyl mercuric halide (which is itself adsorbed onto mercury to the extent of less than a monolayer) undergoes reversible one-electron reduction to adsorbed decyl mercury radicals and to adsorbed decyl mercury radical “polymer”; the adsorbed radicals have a lifetime of approximately 10^?3s and disproportionate into didecylmercury and elemental mercury. In the presence of electrolytically released halide ion, the adsorbed radicals are reoxidized to the decyl mercuric halide; alternately, the adsorbed species are reoxidized to decyl mercury cations at a potential approximately 600 mV more positive than that required for reoxidation to the decyl mercuric halide. At potentials corresponding to the second polarographic wave, reduction of decyl mercuric halides is an irreversible process producing decyl carbanions which are protonated by traces of water in the solvent to give decane.