Comparison Between a Charge Transfer Process and an Electrocatalytic Process in Cyclic Voltammetry and Cyclic Voltcoulommetry. Application to the Oxidation of Ferrocyanide at a Ferrocene‐Monolayer Modified Gold Electrode

Ferrocyanide oxidation catalyzed by a ferrocene‐alkylthiolate monolayer at gold electrodes has been investigated by using cyclic voltammetry (CV) and cyclic voltcoulommetry (CVC). The voltammetric current‐potential curves obtained present a stationary sigmoidal feature which points out to a very high rate constant for the chemical step, whereas the charge‐potential curves do not reach an stationary behavior in any case. Simple expressions are presented for the characterization of the CV and CVC curves under Nernstian conditions for the charge transfer step. From these expressions, a value for the chemical rate constant 2.5×10⁴ M^?1 s^?1 has been easily obtained from an anodic plateau of the CV curves or from the linear anodic region of the CVC curves.     

Adsorption of ions onto polymer surfaces and its influence on zeta potential and adhesion phenomena

 The adhesion behavior that governs many technologically and biologically relevant polymer properties can be investigated by zeta potential measurements with varied electrolyte concentration or pH. In a previous work [1] it was found that the difference of the adsorption free energies of Cl^- and K⁺ ions correlates with the adhesion force caused by van der Waals interactions, and that the decrease of adhesion strength by adsorption layers can be elucidated by zeta potential measurements. In order to confirm these interrelations, zeta potential measurements were combined with atomic force microscopy (AFM) measurements. Force–distance curves between poly(ether ether ketone) and fluorpolymers, respectively, and the Si₃N₄ tip of the AFM device in different electrolyte solutions were measured and analysed. The adsorption free energy of anions calculated from the Stern model correlates with their ability to prevent the adhesion between the polymer surface and the Si₃N₄ tip of the AFM device. These results demonstrate the influence of adsorption phenomena on the adhesion behavior of solids. The results obtained by AFM confirm the thesis that the electrical double layer of solid polymers in electrolyte solutions is governed by ion adsorption probably due to van der Waals interactions and that therefore van der Waals forces can be detected by zeta potential measurements. Received: 18 November 1997 Accepted: 19 January 1998     

Enhanced graphite passivation in Li-ion battery electrolytes containing disiloxane-type additive/co-solvent

This article reports the synthesis details and film-forming properties of 1,1,3,3-tetramethyl-1,3-bis(3-(ω-hexadecyloxy-deca(ethylenoxy)propyl)disiloxane, a new potential electrolyte additive/functional co-solvent for propylene carbonate (PC)-based Li-ion cells with graphitic anodes. Galvanostatic charge/discharge characteristics and scanning electron microscopy images provide direct evidence for the suppression of solvent intercalation and graphite exfoliation in the presence of the additive. In terms of irreversible capacity, the additive’s efficiency is the highest for 15% weight ratio in the solvent mixture. Potentiodynamic measurements have revealed that disiloxane component undergoes irreversible reduction at potential significantly higher then PC decomposition. Energy dispersive spectroscopy analysis of graphite flake surfaces confirm that silicon species from the disiloxane decomposition are built in the passive layer. The reported compound may be considered as a basis for alternative cost-effective electrolyte compositions for low-temperature applications.     

Corrosion inhibition of mild steel in hydrochloric acid by betanin as a green inhibitor

The effect of betanin (2,6-pyridinedicarboxylic acid, 4-(2-(2-carboxy-5-(beta-D-glucopyr-anosyloxy)-2,3-dihydro-6-hydroxy-1H-indol-1-yl)ethenyl)-2,3-dihydro-(S-(R*,R*))) on the corrosion inhibition of mild steel has been investigated in 1 M HCl solution. Weight loss method, potentiodynamic polarization, and electrochemical impedance spectroscopy techniques were applied to study the mild steel corrosion behavior in the absence and presence of different concentrations of betanin under the influence of various experimental conditions. The results obtained showed that betanin is a good “green” inhibitor for mild steel in 1 M HCl solution. Scanning electron microscopy observations of the steel surface confirmed the protective role of the inhibitor. The polarization curves showed that betanin behaves mainly as a mixed-type inhibitor. Maximum inhibition efficiency (98%) is obtained at betanin concentrations of 0.01 M. The results obtained from weight loss, polarization, and impedance measurements are in good agreement.     

Photoinduced electron transfer at liquid|liquid interfaces. Part VII. Correlation between self-organisation and structure of water-soluble photoactive species

The self-organisation of a variety of dyes at the water|1,2-dichloroethane interface was studied by admittance measurements, photocurrent–potential curves and light polarisation anisotropy of the photocurrent. The heterogeneous photo-oxidation of ferrocene was studied at interfaces sensitised by Sn(IV) meso-tetra-(4-carboxyphenyl) porphyrin dichloride (SnTPPC), chlorin e-6, protoporphyrin IX (protoIX) and Fe(III) protoporphyrin IX chloride (Fe-protoIX). Cyclic voltammograms and capacitance voltage curves exhibit different features associated with the self-assembly of the dye species at the liquid|liquid boundary. In the case of SnTPPC, the capacitance curves displayed the characteristic responses commonly associated with the specific adsorption of ionic species. On the other hand, chlorin e-6, protoIX and Fe-protoIX show rather complex behaviour suggesting not only changes in the excess charge but also in the dielectric permittivity of the interface. Differences in the photocurrent efficiency were also observed under the same experimental conditions. The relative magnitude of the photocurrent responses were rationalised in terms of the phenomenological electron transfer rate constant, the photon capture cross-sections and the lifetime of the triplet state as obtained from nanosecond flash photolysis. Finally, the average molecular orientation of the adsorbed photoactive species was estimated from the photocurrent dependence on the angle of light polarisation in total internal reflection. The results show a clear correlation between the orientation of the transition dipole and the distribution of the peripheral carboxyl groups responsible for the hydrophilic nature of the dyes.     

Micellar-stabilized room-temperature phosphorimetric determination of the fungicide thiabendazole in canned pineapple samples

A method for the determination of the fungicide thiabendazole (TBZ) by micellar-stabilized room-temperature phosphorescence is described. It does not require any separation step and allows the direct determination of the fungicide in canned pineapple samples. The effect of various experimental conditions is discussed in detail. The analytical curve of thiabendazole gives a linear dynamic range of 23.8–500.0 ng mL^–1 and a detection limit of 23.8 ng mL^–1. Recoveries of 103.9 and 89.2% for syrup and canned pineapple pulp, respectively, were obtained for 250 ng mL^–1 thiabendazole. Received: 30 April 1997 / Revised: 18 July 1997 / Accepted: 23 July 1997     

Dynamic reference electrode for investigation of fluoride melts containing beryllium difluoride

Existing designs of reference electrodes for potentiometric measurements in fluoride melts do not meet basic requirements of the long exposure corrosion tests to be performed. A new diaphragm-free three-electrode meter with a nonstationary (dynamic) beryllium reference electrode for the redox potential measurements was developed. Optimum conditions of forming dynamic beryllium reference electrode were determined in the laboratory tests in isothermal cell. The device for redox potential measurement was designed and it was shown that it is highly sensitive to changes redox potential within ±5 mV. Reliability and efficiency of diaphragm-free device with dynamic reference electrode was confirmed in the thermal convection corrosion loop operating more than 1200 h with molten 15LiF-58NaF-27BeF₂ mixture (mol%) at a maximum temperature of about 700 °C.     

A theory of single-electron non-adiabatic tunneling through a small metal nanoparticle with due account of the strong interaction of valence electrons with phonons of the condensed matter environment

A theory of electrochemical behavior of small metal nanoparticles (NPs) which is governed both by the charging effect and the effect of the solvent reorganization on the dynamic of the electron transfer (ET) is considered under ambient conditions. The exact expression for the rate constant of ET from an electrode to NP which is valid for all values of the reorganization free energy E(r), bias voltage, and overpotential is obtained in the non-adiabatic limit. The tunnel current/overpotential relations are studied and calculated for different values of the bias voltage and E(r). The effect of E(r) on the full width at half maximum of the charging peaks is investigated at different values of the bias voltage. The differential conductance/bias voltage and the tunnel current/bias voltage dependencies are also studied and calculated. It is shown that, at room temperature, the pronounced Coulomb blockade oscillations in the differential conductance/bias voltage curves and the noticeable Coulomb staircase in the tunnel current/bias voltage relations are observed only at rather small values of E(r) in the case of the strongly asymmetric tunneling contacts.     

Examination of the atypical electrophoretic mobility behavior of charged colloids in the low salt region using the O’Brian-White theory

 Polystyrene microspheres having roughly the same size but different negative surface charge densities were prepared by emulsion polymerization. The amount of sulfate groups on the surface of the particles was controlled by variation of the amount and the decomposition rate of the initiator used, potassium, persulfate. After the cleaning process involving dialysis and extensive ultrafiltration the surface-charge density of the samples was determined and their electrokinetic behavior was studied. A simple model based on the Gouy–Chapman theory and the O’Brian–White approach allows the calculation of the dependence of the electrophoretic mobility on salt concentration. Comparison of the theoretical and experimental curves showed that they were in good agreement in a number of qualitative features. Moreover, the model revealed that a monotonously increasing zeta potential with falling electrolyte concentration results in a mobility maximum, and that this so-called atypical behavior is in accordance with the standard electrokinetic theory. No ion adsorption mechanism or the existence of a charged hairy layer, current standard explanations for this anomality, had to be invoked. Received: 13 February 1997 Accepted: 2 June 1997     

Infrared and X-ray studies of hydrogen intercalation in different tungsten trioxides and tungsten trioxide hydrates

Hydrogen intercalation via spillover reaction in various tungsten trioxides leads to the formation of blue hydrogen bronzes. These reversible reactions induce changes in the W-O bond system while maintaining the W-O skeleton. The effect of the intercalation process on the host crystalline structure has been studied with respect to the ν(O-W-O) stretching vibration changes and lattice parameter variations by means of infrared and X-ray diffraction measurements. Among the main results, the intercalation process is shown to be strongly influenced by the structural type of the host compound as well as its amorphous versus crystalline nature. For instance, for the ReO₃ type oxides (monoclinic and cubic WO₃) and hexagonal WO₃, ν(O-W-O) shifts to higher frequency are assigned to a shortening effect of W-O bonds. A W-O bond system arrangement is also measured for the crystallized and amorphous hydrates WO₃ · H₂O, but no detectable changes could be found in the pyrochlore WO₃ and in the hydrate WO₃·1/3 H₂O. Received: 5 March 1997 / Accepted: 21 May 1997     

Thermal Decomposition of Ternary Sodium Graphite Intercalation Compounds

Graphite intercalation compounds (GICs) are often used to produce exfoliated or functionalised graphene related materials (GRMs) in a specific solvent. This study explores the formation of the Na-tetrahydrofuran (THF)-GIC and a new ternary system based on dimethylacetamide (DMAc). Detailed comparisons of in situ temperature dependent XRD with TGA-MS and Raman measurements reveal a series of dynamic transformations during heating. Surprisingly, the bulk of the intercalation compound is stable under ambient conditions, trapped between the graphene sheets. The heating process drives a reorganisation of the solvent and Na molecules, then an evaporation of the solvent; however, the solvent loss is arrested by restacking of the graphene layers, leading to trapped solvent bubbles. Eventually, the bubbles rupture, releasing the remaining solvent and creating expanded graphite. These trapped dopants may provide useful property enhancements, but also potentially confound measurements of grafting efficiency in liquid-phase covalent functionalization experiments on 2D materials.     

Application of a magnetic suspension balance to the oxidation study of the zirconium based alloys under high pressure water vapour

The fuel claddings in the Pressurised Water Reactor are corroded in water at high temperature and high pressure. The technical device ableto follow continuously the corrosion rate in conditions close to this medium does not yet exist. That is the reason why a high pressure thermogravimetric installation based on magnetic suspension has been designed to study in situ the oxidation kinetics of the zirconium based alloys under water vapour until 50 bars of pressure at 415°C. The accuracy of measurements is about 5·10⁻⁵ g under 2 bars, and 10⁻⁴ g under 50 bars. The reproducibility of measurements was verified and the deviation regarding post test weighing at room temperature is around 5·10⁻⁵ g what is clearly satisfying. Finally, the results presented in this work allow validating the high pressure thermogravimetric measurements obtained with this magnetic suspension device.     

Phenomenological model for the interpretation of impedance/admittance spectroscopy results in polymer light-emitting electrochemical cells

A phenomenological model has been developed to account for the results of impedance/admittance spectroscopy measurements from light-emitting electrochemical cells (LECs) comprising a polymer electrolyte and two different conjugated polymers used as organic semiconductor. The application of a d.c. offset bias superimposed to the a.c. modulation voltage was used to observe the transition from the behavior prior to device operation and after the formation of the electrochemical p-i-n junction. The analysis of the whole device “conductivity” as a function of the applied bias and of the frequency was used to support the assumptions considered to develop the model. The results show that the device, after the p-i-n junction formation, can be considered as composed by two highly conductive electrochemically doped (n and p) regions and a thin (few tens nanometers), insulating layer, where the electrical current is dominated by electronic charge carrier injection via tunneling through a rectangular energy barrier. Before the p-i-n junction formation, there is no doping of semiconductor material, and the device electrical properties are dominated by the intrinsic electronic charge carriers in the organic semiconductor. Results from devices made of organic semiconductors with different band gap energy and different layer thicknesses are used to corroborate the proposed model.     

The use of digital simulation to improve the cyclic voltammetric determination of rate constants for homogeneous chemical reactions following charge transfers

Cyclic voltammetry (CV) is a very useful electrochemical tool used to study reaction systems that include chemical steps that are coupled to electron transfers. This type of system generally involves the chemical reaction of an electrochemically generated free radical. Published methods exist that are used to determine the kinetics of electrochemically initiated chemical reactions from the measurements of the peak current ratio (i_pa/i_pc) of a cyclic voltammogram. The published method requires working curves to relate a kinetic parameter to the peak current ratio.In the presented work, a digital simulation package was used to obtain improved working curves for specific working conditions. The curves were compared with the published results for the first- and second-order chemical reactions following the charge transfer step mechanisms.According to the presented results, the previously published working curve is reliable for a mechanism with a first-order chemical reaction; however, a change in the switching potential requires a recalculation of the curve. In the case of mechanisms with a second-order step (dimerisation and disproportionation), several different views exist on how the second-order chemical term should be expressed so that different values of the constant are obtained. Parameters such as electrode type, electrode area, electroactive species concentration, switching potential, scan rate and method for peak current ratio calculation modify the working curves and must always be specified.We propose a standardised method to obtain the most reliable kinetic constant values.The results of this work will permit researchers who handle simulation software to construct their own working curves. Additionally, those who do not have the simulation software could use the working curves described here.The revelations of the presented experiments may be useful to a broad chemistry audience because this study presents a simple and low-cost procedure for the study of free radicals that otherwise should be studied with more sophisticated and expensive techniques, such as ESR or pulse radiolysis.     

Preparation of Fe2O3-exfoliated graphite composite and its electrochemical properties investigated in alkaline solution

In the present work, a simple method of preparation of FeCl₄⁻- graphite intercalation compounds from HCl/FeCl₃ solution with the aid of chemical oxidant is presented. Based on X-ray diffraction measurements it was concluded, that stages 8, 6, and 5 FeCl₄⁻-graphite intercalation compounds were obtained. The compounds thus obtained were thermally treated to obtain Fe₂O₃-exfoliated graphite composites. The dispersion of Fe₂O₃ in the exfoliated graphite flakes was examined with the aid of the energy dispersive X-ray analysis combined with a scanning electron microscopy. Electrochemical behavior of electrodes was investigated in 6 M KOH solution. Electrochemical investigations proved the formation of FeOOH on the surface of exfoliated graphite during the anodic process. Besides, electrochemical investigations showed that the lower limit potential strongly affects the redox behavior of the Fe₂O₃-EG electrode.     

Shrinking-core modeling of binary chromatographic breakthrough

Most chromatographic processes involve separation of two or more species, so development of a simple, accurate multicomponent chromatographic model can be valuable for improving process efficiency and yield. We consider the case of breakthrough chromatography, which has been considered in great depth for single-component modeling but to a much more limited degree for multicomponent breakthrough. We use the shrinking core model, which provides a reasonable approximation of particle uptake for proteins under strong binding conditions. Analytical column solutions for single-component systems are extended here to predict binary breakthrough chromatographic behavior for conditions under which the external transport resistance is negligible. Analytical results for the location and profile of displacement effects and expected breakthrough curves are derived for limiting cases. More generally, straightforward numerical results have also been obtained through simultaneous solution of a set of simple ordinary differential equations. Exploration of the model parameter space yields results consistent with theoretical expectations. Additionally, both analytical and numerical predictions compare favorably with experimental column breakthrough data for lysozyme-cytochrome c mixtures on the strong cation exchanger SP Sepharose FF. Especially significant is the ability of the model to predict experimentally observed displacement profiles of the more weakly adsorbed species (in this case cytochrome c). The ability to model displacement behavior using simple analytical and numerical techniques is a significant improvement over current methods.     

Primary methods of measurement in chemical analysis

 Primary methods of measurement have a central function in metrology. They are an essential component in the realisation of the SI units and therefore are indispensable for establishing traceability of measurements of all kinds of physical quantities to the corresponding SI units. This is also true for chemical analysis. Gravimetry, titrimetry, coulometry, and isotope dilution mass spectrometry (IDMS) are evaluated with regard to their potential to be primary methods according to a general definition of primary methods recently given by the Comité Consultatif pour la Quantité de Matière (CCQM). Optical absorption spectrometry and methods based on colligative properties are also considered. A general scheme for establishing traceability of chemical measurements to the SI units using primary methods is discussed. Received: 17 April 1997 · Accepted: 9 August 1997     

Electroanalytical and spectroscopic procedures for examination of interactions between double stranded DNA and intercalating drugs

A method is presented for the electroanalytical characterization of interactions of dsDNA with a drug, under conditions that both agents are dissolved in the phosphate buffer solution and both are electroactive. Normal pulse, square wave, differential pulse, and cyclic voltammetries were employed in the measurements of the drug and dsDNA oxidation signals at carbon electrodes. UV–Vis spectroscopy was used as a non-electrochemical method to support the electroanalytical data. An anticancer drug, C-1311 (5-diethylaminoethyl-amino-8-hydroxyimidazoacridinone), has been selected for the examination. Normal pulse voltammetry was particularly useful in showing that under the conditions employed neither dsDNA nor the drug were adsorbed at the electrode surface. Necessary conditions for the appearance of the well-defined dsDNA voltammetric signal (guanine peak) are: rigorous chemical and biological purity in the cell and appropriate purity of DNA. An analysis of the obtained results confirmed that there were two modes of interaction between C-1311 and dsDNA: by intercalation and electrostatically. In the presence of excess NaCl the electrostatic interactions deteriorate. The binding constants (K ₁ and K ₂, respectively) and the number (n) of nucleic base pairs (bp) and the number (m) of phosphate groups (pg) interacting with one molecule of drug have been determined. For strong interactions (intercalation) the values of the binding constant, K ₁, and the binding-site size, n, equal 3.7 × 10⁴ M⁻¹ and 2.1, respectively. For the weak electrostatic interactions the K ₂ and m parameters equal 0.28 × 10⁴ M⁻¹ and 4.7. The intercalation process is rather slow and its rate (the conditions of pseudo-first-order reaction) was estimated to equal 7 × 10⁻⁴ s⁻¹. The possibility of independent determination of both interacting agents was very useful in the study. Figure Intercalation of C-1311 into a dsDNA fragment