Critical evaluation of potentiometric redox titration in enology

Measurements of the zero current potential of a platinum electrode immersed in solutions of tanins or in wines of various origins, were performed during the additions of a solution of Ti(III), or of a solution of dichlorophenolindophenol (DCPIP), in order to obtain a global indication for the resistance to oxidation of some wines. The steady state intensity–potential curves on a platinum electrode highlight the occurrence of mixed potentials between the oxidation of ethanol or catechin and the reduction of oxygen present at very low concentrations, as well as the irreversibility of the redox system Ti(IV)/Ti(III). The adsorption of various species on the platinum and the slowness of the oxidation reactions by DCPIP exclude use of potentiometric titration theory. The shape of the potential–reagent volume curves depends on the nature of the solution and on the rate of reagent introduction. Generally, due to the slowness of the oxidation reactions with DCPIP it is impossible to find a linear relationship between the volume of titrant solution necessary to reach the inflexion point of the curves and the solution composition

Influence of electrical potential on the crystallization and adhesion of potassium hydrogen tartrate crystals

Interfacial interactions between a hydroalcoholic solution of potassium hydrogen tartrate (KHT) and a stainless steel surface are studied, when an electrical potential is applied to the metal substrate. The capacitive domain of the metal–solution interface is determined by cyclic voltammetry. In order to study the influence of the potential on KHT nucleation and crystal adhesion, the solid–liquid interfacial energy is assessed from contact angle and capillary rise measurements. Experimentally, the contact angle between a NaF solution and a stainless steel vs. the potential has a parabolic behaviour. The metal topography has no apparent influence on physicochemical properties of the interface when ethanol is present in a KHT solution. The metal substrate promotes the formation of KHT crystals, which is improved by the application of an anodic potential. The adhesion of crystals becomes more effective when wires of 25 μm diameter are used in comparison with those of 250 μm

Silicate electrochemical measurements in seawater: chemical and analytical aspects towards a reagentless sensor

From the study of molybdenum oxidation in aqueous solutions we developed a semi-autonomous method to detect silicate in aqueous samples. Molybdenum oxidation was used to form molybdate in acidic media. The silicomolybdic complex formed with silicate is detectable by amperometry or cyclic voltammetry. The new electrochemical method is in good agreement with the method conventionally used for environmental water silicate analysis. In the second stage, a completely reagentless method was developed using molybdate and proton produced during molybdenum oxidation. Reproducibility tests show a precision of 2.6% for a concentration of 100 μmol L−1. This new method will be very suitable for the development of new autonomous silicate sensors easy to handle and without reagents. In this paper we present the analytical and chemical aspects necessary for a complete documentation of the method before the development of a new reagentless sensor

Electrochemical microsensors for cutaneous surface analysis: Application to the determination of pH and the antioxidant properties of stratum corneum

Potentiometry and cyclic voltammetry were proposed as simple, reliable and non invasive methods for the simultaneous determination of pH and antioxidant properties of skin. Experiments were performed with microelectrodes just deposited on skin surface without any gel or water added. pH was measured by means of the zero current potential of a tungsten W/WO3 sensor. A nerstian response was recorded in pH range 4 to 6 corresponding to the normal skin pH values. The global antioxidant capacity was deduced from the anodic charge passed during the plotting of cyclic voltammograms on platinum or gold microelectrodes. Comparing the half wave or peak potentials of these curves with those recorded for experiments performed in aqueous solution, the main hydrophilic antioxidants species were detected, i.e. ascorbic acid, uric acid and glutathione. This relatively easy-to-use analytical method made it possible to follow in real time the efficiency of topic treatment as well as to study the influence of oxidative stres

Electrochemical behaviour of N-acetyl-l-cysteine on gold electrode—A tentative reaction mechanism

The electrochemical behaviour of N-acetyl-l-cysteine (NAC) has been investigated by linear and cyclic voltammetry on gold electrode at room temperature. The results showed two oxidation peaks under acid and neutral conditions and only one in basic medium. For each oxidation, as many electron was exchanged as proton. The influence of both the concentration and the potential scan rate on the peak currents highlighted a diffusion-controlled phenomenon for the first peak and an adsorption-limited reaction rate for the second one. The diffusion coefficient of NAC in solution and the surface concentration of the adsorbed species at pH 3 and 7 were close to 2 × 10−4 to 2 × 10−5 cm2 s−1 and 6 × 10−9 to 6 × 10−10 mol cm−2, respectively. Film transfer experiments resulted in an irreversible adsorption of NAC on gold electrode, and the formation of a self-assembled monolayer (SAM)

Exploration of the global antioxidant capacity of the stratum corneum by cyclic voltammetry

Cyclic voltammetry is proposed as a new method for evaluating the antioxidant capacity of skin based on the reducing properties of low molecular weight antioxidants (LMWA). Experiments were performed simply by recording the anodic current at 0.9 V/SCE of a platinum microelectrode placed directly on the epidermis surface without any gel or water. This method ensured a direct, rapid (less than 1 min), reliable (accuracy 12%) and non-invasive measurement of the global antioxidant capacity of the stratum corneum with a high spatiotemporal resolution. At the same time, the pH of the skin surface was determined by recording the cathodic current at 0 V/SCE. Based on an exploratory study involving nine volunteer subjects, the evolution of the amperometric response of the microelectrode with time revealed a periodic modification of the redox properties

Reagentless and calibrationless silicate measurement in oceanic waters

Determination of silicate concentration in seawater without addition of liquid reagents was the key prerequisite for developing an autonomous in situ electrochemical silicate sensor (Lacombe et al., 2007) [11]. The present challenge is to address the issue of calibrationless determination. To achieve such an objective, we chose chronoamperometry performed successively on planar microelectrode (ME) and ultramicroelectrode (UME) among the various possibilities. This analytical method allows estimating simultaneously the diffusion coefficient and the concentration of the studied species. Results obtained with ferrocyanide are in excellent agreement with values of the imposed concentration and diffusion coefficient found in the literature. For the silicate reagentless method, successive chronoamperometric measurements have been performed using a pair of gold disk electrodes for both UME and ME. Our calibrationless method was tested with different concentrations of silicate in artificial seawater from 55 to 140×10−6 mol L−1. The average value obtained for the diffusion coefficient of the silicomolybdic complex is 2.2±0.4×10−6 cm2 s−1, consistent with diffusion coefficient values of molecules in liquid media. Good results were observed when comparing known concentration of silicate with experimentally derived ones. Further work is underway to explore silicate determination within the lower range of oceanic silicate concentration, down to 0.1×10−6 mol L−1

Silicate determination in sea water: toward a reagentless electrochemical method

ilicate has been determined in sea water by four different electrochemical methods based on the detection of the silicomolybdic complex formed in acidic media by the reaction between silicate and molybdenum salts. The first two methods are based on the addition of molybdate and protons in a seawater sample in an electrochemical cell. Cyclic voltammetry presents two reduction and two oxidation peaks giving four values of the concentration and therefore increasing the precision. Then chronoamperometry is performed on an electrode held at a constant potential. A semi-autonomous method has been developed based on the electrochemical anodic oxidation of molybdenum, the complexation of the oxidation product with silicate and the detection of the complex by cyclic voltammetry. This method is tested and compared with the classical colorimetric one during ANT XXIII/3 cruise across Drake Passage (January–February 2006). The detection limit is 1 μM and the deviation between both methods is less than 3% for concentrations higher than 10 μM. Finally a complete reagentless method with a precision of 2.6% is described based on the simultaneous formation of the molybdenum salt and protons in a divided electrochemical cell. This latter method should be very useful for developing a reagentless sensor suitable for long term in situ deployments on oceanic biogeochemical observatories

Application d’un champ électrique de faible amplitude pour l’amélioration de la cristallisation et de la filtration sur supports métalliques en oenologie.

En œnologie, on assiste à l’apparition de matériaux métalliques, utilisés comme support de cristallisation ou média filtrant, qui ont permis la mise en œuvre de méthodes électrochimiques. Des dispositifs expérimentaux ont permis à la fois de moduler le potentiel électrique relatif métal-solution et d’atteindre diverses grandeurs étroitement liées à la physico-chimie de l’interface. Le premier montage permet la mesure de l’angle de contact entre une goutte de solution électrolytique et une plaque métallique polie ou rugueuse. Le deuxième dispositif permet de déduire l’ascension capillaire de la mesure de la masse de solution incorporée dans un matériau métallique poreux. Le dernier est une cellule, où le média filtrant est enchâssé entre deux électrodes métalliques, dans laquelle le débit de filtration peut être aisément mesuré. Les résultats concernent la variation de l’énergie interfaciale avec le potentiel électrique appliqué d’où l’on déduit le point de charge nulle et la capacité différentielle de la double couche électochimique. Pour la cristallisation, on a constaté une dépendance entre la masse de cristaux de bitartrate de potassium déposée sur le support métallique et le potentiel électrique. Pour la filtration, le champ électrique a fait apparaître simultanément une série de phénomènes qui augmente le flux de filtration des vins

Reagentless and silicate interference free electrochemical phosphate determination in seawater

An electrochemical method for phosphate determination in seawater was based on the oxidation of molybdenum in order to form molybdates and protons and subsequently, to create the phosphomolybdic complex electrochemically detectable by means of amperometry at a rotating gold disk electrode [J. Jonca et al., Talanta 87 (2011) 161]. To avoid silicate interferences, the method required an appropriate ratio of protons over molybdates equal to 70. Since the ratio of protons over molybdates created during molybdenum oxidation is only 8, the previous method still needed addition of sulfuric acid and thus was not free from addition of liquid reagents. In the present work, this aspect is solved by modification of the electrochemical cell construction. The method is now totally free from addition of any liquid reagents and gives a possibility to determine phosphate by amperometry in the concentrations range found in the open ocean with a detection limit of 0.11 µM. Having in mind the energy savings for future in situ sensor development, amperometry at rotating gold disk electrode was replaced by differential pulse voltammetry at static one. Phosphate can then be determined with a detection limit of 0.19 µM. Both methods are characterized by good reproducibility with an average measurements precision of 5.7% (amperometry) and 3.8% (differential pulse voltammetry). Results also show a good accuracy with an average deviation from theoretical values of phosphate concentration of 3.1% for amperometry and 3.7% for differential pulse voltammetry