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Identifying the sources of oxygen in the chlorate process is challenging due to the complex set of chemical and electrochemical reactions involved. Here, two types of electrodes have been investigated-Ti0.7Ru0.3Ox, and electrodes with aimed composition Ti0.34Ru0.3Sn0.3Sb0.06Ox, both compared with platinum anodes. The cell oxygen off-gas was analyzed employing mass spectrometry together with ex situ UV-vis spectroscopy to quantify the kinetic rate constants. Noteworthy is that the respective rates of oxygen formation from anodic and chemical reactions in the presence of hypochlorite are of the same magnitude. The addition of Sn and Sb doubled the surface area of the electrodes and decreased oxygen production when electrodes were used for the first time. However, rate constants for total oxygen production with reused electrodes follow the trend: homogeneous hypochlorite decomposition < TiRu < TiRuSnSb to the highest value obtained by Pt. The same trend is noticed for rate constants concerning the hypochlorite decomposition., QC 20211011

The catalytic and durable electrode coating of ruthenium dioxide (RuO2), applied on nickel (Ni) substrates, is today utilized as electrocatalytic cathodes for hydrogen production, e.g., in the chlor-alkali process and alkaline water electrolysis. The drawback is, however, the sensitivity to reverse currents obtained during power shutdowns, e.g., at maintenance, where the RuO2-based electrodes can be severely damaged unless polarization rectifiers are employed. Through the material characterization techniques X-ray diffraction and X-ray photoelectron spectroscopy, we can now reveal that RuO2 coatings, when exposed to hydrogen evolution at industrially relevant conditions, transforms into ruthenium oxyhydroxide (RuO(OH)(2)). The study further shows that as the hydrogen evolution proceeds the formed RuO(OH)(2) reduces to metallic ruthenium (Ru).

Electrochemical water splitting into H2 and O2 presents a significant and challenging energy loss due to the high overpotential required at the anode. Today, in industrially relevant applications, dimensionally stable anodes (DSA) based on the electrocatalytic active RuO2 are conventionally utilized. To enhance the resistance against corrosion, incorporation of TiO2 in the RuO2-coated electrodes is widely employed. In the present work we have used scanning electrochemical microscopy (SECM) to demonstrate that TiO2-doped RuO2-coated electrodes, in addition to being more durable, also show an electrocatalytic activity that is, on average, 13% higher as compared to the pure RuO2-coated electrodes. We also demonstrate that cracks in the pure RuO2 coating are the most active zones, probably because Ti from the Ti support has diffused into the first applied layer of the RuO2 coating. To reveal the nature of this enhanced activity for water oxidation displayed on TiO2-doped RuO2 electrodes, we have employed X-ray photoelectron spectroscopy (XPS) for material characterization. The results show that the electrocatalytic activity enhancement displayed on the mixed (Ru1−x:Tix)O2 coating is promoted through a charge transfer from the RuO2 to the TiO2, which provides new and more reactive sites designated as activated RuO2δ+., Publication Date (Web): February 11, 2013

A measurement system, based on flow injection analysis (FIA) technique applied to a voltammetric electronic tongue is described. A reference solution was thus continuously pumped through a cell with a voltammetric electronic tongue, and test samples were injected into the flow stream. Responses were obtained by measuring the resulting pulse height. The FIA technique offered several advantages, since relative measurements are performed, the system is less influenced by sensor baseline drift, calibration samples and/or washing solutions can be injected within a measurement series, and the system is well adapted for automatization. The system was used to analyze standard solutions of H2O2, KCl, CuNO3, K4[Fe(CN)6], K3[Fe(CN)6] and NaCl, and results obtained were treated with multivariate data analysis. Principal component analysis performed showed that electrode drift could be considerably decreased, and the set-up was also used for classification of different apple juices. © 2002 Elsevier Science B.V. All rights reserved.

In this work different electrode materials were investigated as sensors in a voltammetric electronic tongue. Basically, the electronic tongue is based on the combination of nonspecific sensors (electrodes) and pattern recognition tools, for example principal component analysis (PCA). Copper. glassy carbon, nickel, palladium, silver, tin, titanium and zirconium together with more traditional electrode materials such as gold, iridium, and platinum were studied. Cyclic voitammetry was applied to study typical model reactions in solutions containing different electroactive compounds, like ascorbic acid, glucose, histidine and potassium hexacyanoferrate(II). Different sensitivity and selectivity were obtained with the electrodes. Large responses were for example found for the amino acid and the carbohydrate using the copper, nickel and silver electrode. Some of the electrodes were employed in multicomponent solutions, i.e., liquid washing detergents from different suppliers together with differential pulse voltammetry. Responses from the electrodes in combination with PCA showed that they separated the detergents to different extents. This was further used when information from the sensors was merged together for successful discrimination of the detergents. It was found that two detergents close to each other in the score plot were from the same supplier. Furthermore. scanning electron microscopy (SEM) was used to monitor surface changes at the nonnoble electrodes (copper, nickel, and silver).

A new sensor technology for liquid sensing is reported, i.e. the electronic tongue based on electrochemical methods. Such a system involves the combination of non-selective sensors (metal electrodes) and a signal processing part. It determines attributes (quality, status of a process etc) rather than single parameters. Transient current responses are obtained as a result of large potential pulses consecutively applied to each electrode. Unique response patterns for liquid samples are interpreted with mathematical and statistical methods, for example principal component analysis (PCA). In this thesis, focus was put on general aspects of development and characterisation of the sensor system, since the long-time objective is to apply it to industrial processes. This was accomplished by studying sensitivity, selectivity, long-term stability and signal processing. The proper choice of sensors and measurement techniques is important for successful discrimination of liquid samples. For example, liquid washing detergents were discriminated with PCA by merging data from several voltammetric electrodes like copper, glassy carbon, gold, iridium, silver and platinum. In another study, fermented milk samples were successfully discriminated as sensors of different measurement technologies were combined, i.e. conductometry, potentiometry and voltammetry. Sensors of each technique alone were not able to separate all samples. Adsorption and/ or porous layer formation lead to drift in electrode responses. The former can inhibit or enhance an electron rate transfer and the latter increases the electrode area and thus, the observed current. Drift counteraction was studied in two different ways. First, mathematical algorithms like component correction (CC) and additive correction (AC) were applied to different data sets. Both methods require the use of reference samples. It was found that CC was better to remove drift in current responses; CC was not as sensitive as AC to dissimilar cha, This project was performed within S-SENCE, the Swedish Sensor Centre, supported by the Swedish Agency for Innovation Systems, VINNOVA , Linköping University and Swedish participating industries.

In this paper, three data compression methods are investigated to determine their ability to reduce large data sets obtained by a voltammetric electronic tongue without loss of information, since compressed data sets will save data storage and computational time. The electronic tongue is based on a combination of non-specific sensors and pattern recognition tools, such as principal component analysis (PCA). A series of potential pulses of decreasing amplitude are applied to one working electrode at a time and resulting current transients are collected at each potential step. Voltammograms containing up to 8000 variables are subsequently obtained. The methods investigated are wavelet transformation (WT) and hierarchical principal component analysis (HPCA). Also, a new chemical/physical model based on voltammetric theory is developed in order to extract interesting features of the current transients, revealing different information about species in solutions. Two model experiments are performed, one containing solutions of different electroactive compounds and the other containing complex samples, such as juices from fruits and tomatoes. It is shown that WT and HPCA compress the data sets without loss of information, and the chemical/physical model improves the separations slightly. HPCA is able to compress the two data sets to the largest extent, from 8000 to 16 variables. When data sets are scaled to unit variance, the separation ability improves even further for HPCA and the chemical/physical model. © 2001 Elsevier Science B.V.

In this article, drift correction algorithms were used in order to remove linear drift in multivariate spaces of two data sets obtained by an electronic tongue based on voltammetry. The electronic tongue consisted of various metal electrodes (Au, Ir, Pt, Rh) combined with pattern recognition tools, such as principal component analysis. The first data set contained different types of liquid, from well defined to more complex solutions. The second data set contained different black and green teas. Component correction (CC) was compared to a simple additive correction. In CC, the drift direction of measured reference solutions in a multivariate space was subtracted from other types of solution. In additive correction, responses from reference samples were subtracted from other samples. CC showed similar or better performance in reducing drift compared to additive correction for the two data sets. The additive correction method was dependent on the fact that the differences in between samples of a reference solution were similar to the changes in between samples of other liquids, which was not the case with CC.

A new sensor technology, an electronic tongue based on voltammetry has been developed at Linköping University. Three different metallic working electrodes are used in combination with a set of voltage "pulses", a waveform, to separate different samples. In this paper, three different waveforms are investigated. This is done through a study with nine different teas. Multivariate data analysis ((MVDA), principal component analysis (PCA)) is used to evaluate the data (the recorded current responses). The waveforms are large amplitude pulse voltammetry (LAPV), small amplitude pulse voltammetry (SAPV), and staircase voltammetry. Each method discriminated between the tea samples to some extent, but differently from each other. Best discrimination is achieved when the combination LAPV and staircase are merged together. When SAPV is included in the combination a worse separation is observed. It is clearly the case that more waveforms do not automatically lead to more information. © 2001 Elsevier Science B.V.

A hybrid electronic tongue is described based on a combination of potentiometry, voltammetry and conductivity. It was used for classification of six different types of fermented milk. Using ion-selective electrodes, pH, carbon dioxide and chloride ion concentrations were measured. The voltammetric electronic tongue consisted of six working electrodes of different metals (gold, iridium, palladium, platinum, rhenium and rhodium) and an Ag/AgCl reference electrode. The measurement principle is based on pulse voltammetry in which current transients are measured due to the onset of voltage pulses at decreasing potentials. The data obtained from the measurements were treated by multivariate data processing based on principal components analysis and an artificial neural net. The hybrid tongue could separate all six samples. Also, the nature of the micro-organisms in the different fermentations was reflected in the principal component analysis. Copyright (C) 2000 Elsevier Science B.V.

Identifying the sources of oxygen in the chlorate process is challenging due to the complex set of chemical and electrochemical reactions involved. Here, two types of electrodes have been investigated -Ti0.7Ru0.3Ox, and electrodes with aimed composition Ti0.34Ru0.3Sn0.3Sb0.06Ox, both compared with platinum anodes. The cell oxygen off-gas was analyzed employing mass spectrometry together with ex-situ UV-Vis spectroscopy to quantify the kinetic rate constants. Noteworthy is that the respective rates of oxygen formation from anodic and chemical reactions in the presence of hypochlorite are of the same magnitude. The addition of Sn and Sb doubled the surface area of the electrodes and decreased oxygen production when electrodes were used for the first time. However, rate constants for total oxygen production with reused electrodes, follow the trend: homogenous hypochlorite decomposition < TiRu < TiRuSnSb to the highest value obtained by Pt. The same trend is noticed for rate constants concerning the hypochlorite decomposition., QC 20210427