KINETICS OF REDUCTION OF HEXACYANOFERRATE(III) BY THIOSULFATE IONS MEDIATED BY RUTHENIUM DIOXIDE HYDRATE

The kinetics of reduction of hexacyanoferrate(III) by excess thiosulfate, mediated by RuO2.xH2O, are investigated. At high concentrations of S2O32- (0.1 mol dm-3) the kinetics of Fe(CN)63- reduction are first order with respect to [Fe(CN)63-] and [RuO2.xH2O] and independent of [Fe(CN)64-], [S2O32-] and [S4O62-]. At relatively low concentrations Of S2O32- (0.01 mol dm-3) and in the presence of appreciable concentrations of Fe(CN)64- and S4O62- (0.01 mol dm-3) the kinetics depend directly upon [Fe(CN)63-] and [RuO2.xH2O] and inversely upon [Fe(CN)64-]. Both sets of kinetics can be rationalised using an electrochemical model of redox catalysts in which a reversible reduction reaction [Fe(CN)63- + e- --> Fe(CN)64-] is coupled to an irreversible oxidation reaction (s2O32- - e- --> 1/2S4O62-), by a dispersion of RuO2.xH2O microelectrodes. At high concentrations Of S2O32- this model predicts that the kinetics of Fe(CN)63- reduction are controlled by the rate of diffusion of the Fe(CN)63- ions to the RuO2.xH2O particles. The kinetics observed at low concentrations of S2O32- are predicted by the electrochemical model, assuming that the Tafel slope for the oxidation Of S2O32- to S4O62- on the RuO2.xH2O particles is 56.4 mV decade-1.

A KINETIC-STUDY OF THE BLEACHING OF RHODAMINE-6G PHOTOSENSITIZED BY TITANIUM-DIOXIDE

The results of a kinetic study of the bleaching of the photostable dye rhodamine 6G by dissolved oxygen, photosensitized by TiO2, are reported. The observed variations in the initial rate of dye photobleaching as a function of the O2 percentage, temperature, incident light intensity and concentrations of rhodamine 6G and sacrificial electron donor are described and the results are rationalized using a proposed photochemical reaction scheme. The photosensitized bleaching of rhodamine 6G dye by TiO2 has a formal quantum yield of 2.65 X 10(-3), but the rate of complete photomineralization is about twofold slower. The overall activation energy for the semiconductor-sensitized dye photobleaching process is 15.0 +/- 1.5 kJ mol-1.

TUNING COLOURIMETRIC AND FLUOROMETRIC GAS SENSORS FOR CARBON-DIOXIDE

The basic theory behind conventional colourimetric and fluorimetric optical sensors for CO2 is examined and special attention is given to the effect on sensor response of the key parameters of initial base concentration and dye acid dissociation constant, K(D). Experimental results obtained in aqueous solution using a variety of different dyes and initial base concentrations are consistent with the predictions made by the theoretical model. A series of model-generated pK(D) versus %CO2 curves for different initial base concentrations allow those interested in constructing an optical CO2 sensor to readily identify the optimum dye/initial base combination for their sensor; the response of the sensor can be subsequently fine-tuned through a minor variation in the initial base concentration. The model and all its predictions appear also to apply to the new generation of plastic film CO2 sensors which have just been developed.

OXIDATION OF RUTHENIUM(II) TRIS(2,2'-BIPYRIDINE) IONS BY THALLIC IONS IN NITRIC-ACID, MEDIATED BY RUTHENIUM DIOXIDE HYDRATE - AN EXAMPLE OF REVERSIBLE HETEROGENEOUS REDOX CATALYSIS

The kinetics of the oxidation of Ru(bpy)32+ to Ru(bpy)33+ by T13+ ions, catalyzed by a dispersion of RuO2-xH2O in 3 mol dm-3 HNO3, are reported as a function of [Ru(bpy)32+], [Tl3+], [Tl+], [RuO2.xH2O], and temperature. The kinetics of Ru(bpy)32+ oxidation fit an electrochemical model of redox catalysis involving electron transfer between the two electrochemically reversible redox couples, i.e. Ru(bpy)33+/Ru(bpy)32+ and Tl3+/Tl+, mediated by the dispersion of microelectrode particles of RuO2.xH2O. In this model, the rate of reaction is assumed to be controlled by the diffusion of Ru(bpy)32+ toward, and Ru(bpy)33+ away from, the catalyst particles. The Arrhenius activation energy for the catalyzed reaction is 25.9 +/- 0.7 kJ mol-1, and the changes in enthalpy and entropy for the reaction are 36 +/- 2 kJ mol-1 and 127 +/- 6 J mol-1 K-1, respectively. This work describes a rare example of reversible heterogeneous redox catalysis.

FLUORESCENCE PLASTIC THIN-FILM SENSOR FOR CARBON-DIOXIDE

The method of preparation of a novel plastic thin-film sensor that incorporates the fluorescent dye 8-hydroxypryrene-1,3,6-trisulfonic acid is described; the shelf-life of the film is over 6 months. The results of a study on the equilibrium response of the sensor towards different levels of gaseous CO2 fit a model there is a 1 + 1 equilibrium reaction between the deprotonated form of the dye (present in the film as an ion pair) and the concentration of gaseous CO2 present. In contrast to the situation in aqueous solution, in the plastic film the pK(a) of the excited form of the dye appears close to that of the ground-state form, although this does not interfere with its use as 8 CO2 sensor. The 0 to 90% response and recovery times of the film when exposed to an alternating atmosphere of air and 5% CO2 are typically 4.3 and 7.1 s, respectively.

PHOTOMINERALISATION OF 4-CHLOROPHENOL SENSITIZED BY TITANIUM-DIOXIDE - A STUDY OF THE EFFECT OF ANNEALING THE PHOTOCATALYST AT DIFFERENT TEMPERATURES

The results of a study of the variation in photocatalytic activity of TiO2, as measured by its ability to photomineralise 4-chlorophenol, as a function of temperature used to anneal the TiO2, are reported. Heat treatment of the TiO2 leads to a marked decrease in its photocatalytic activity at annealing temperatures above 600-degrees-C. This decrease is associated with a concomitant drop in the specific surface area of the TiO2, owing to particle sintering, rather than the anatase to rutile transformation, which occurs largely at temperatures above 700-degrees-C. There is a reasonable correlation between photocatalytic activity and the surface area of the aggregate particles in the dispersions of the different heat-treated TiO2 samples.

PHOTOMINERALIZATION OF 4-CHLOROPHENOL SENSITIZED BY TITANIUM-DIOXIDE - A STUDY OF THE INITIAL KINETICS OF CARBON-DIOXIDE PHOTOGENERATION

The kinetics of photomineralization of 4-chlorophenol (4-CP) sensitized by Degussa P25 TiO2 in O2-saturated solution is studied as a function of the following different experimental parameters: pH, [TiO2], percentage O2 [O2], [4-CP], T, I, lambda and [KNO3]. At pH 2 and T=30-degrees-C the initial relative rate of CO2 photogeneration R(CO2) conforms to a Langmuir-Hinshelwood-type kinetic scheme and the relationship between R(CO2) and the various experimental parameters may be summarized as follows: R(CO2) = gammaK(O2)[O2](I(a))(theta)K(4-CP]0/(1 + K(O2])(1 + K(4-CP)[4-CP]0) where gamma is a proportionality constant, K(O2) = 0.044 +/- 0.005[O2]-1, theta = 0.74 +/- 0.05 and K(4-CP) = (29 +/- 3) x 10(3) dm3 mol-1. The overall activation energy for this photosystem was determined as 16 +/- 2 kJ mol-1. This work forms part of an overall characterization study in which it is proposed that the 4-CP-TiO2-O2 photosystem is adopted as a standard test system for incorporation into all future semiconductor-sensitized photomineralization studies in order to facilitate comparisons between the results of the different studies.

PHOTOMINERALISATION OF 4-CHLOROPHENOL SENSITIZED BY TITANIUM-DIOXIDE - A STUDY OF THE INTERMEDIATES

The photomineralisation of 4-chlorophenol (4-CP) sensitised by Degussa P25 TiO2 in O2-saturated solution represents a possible standard test system in semiconductor-sensitised photomineralisation studies. As part of a detailed examination of this photosystem, the results of the temporal variations in the concentrations of 4-CP, CO2, Cl- and the major organic intermediates, namely, 4-chlorocatechol (4-CC), hydroquinone (HQ), benzoquinone and 4-chlororesorcinol, are reported. The observed variations in [4-CP], [4-CC], [HQ] and [CO2] fit those predicted by a kinetic model which utilises kinetic equations with a Langmuir-Hinshelwood form and assumes that there are three major possible routes in which the photogenerated hydroxyl radicals can react with 4-CP, ie. 4-CP --> 4-CC, 4-CP --> HQ and 4-CP --> (unstable intermediate) --> CO2 and that these routes have the following probabilities of occurring: 48%, 10% and 42%.

OXIDATIVE DISSOLUTION OF RUTHENIUM DIOXIDE HYDRATE BY PERIODATE IONS

The results of a kinetic study of the oxidative dissolution of ruthenium dioxide hydrate to ruthenium tetroxide by periodate ions, IO4-, in acidic solution are described. The kinetics of dissolution give a good fit to a 'soft-centre' model in which the particles of RuO2.xH2O are assumed to be monodispersed, spherical but inhomogeneous in composition, comprising a difficult-to-corrode outer shell and a more easy-to-corrode inner core. In this work metaperiodate appears to act as a two-electron oxidant. The observed kinetics fit a reaction scheme in which the rate-determining step is the reaction between a surface site and an adsorbed IO4 ion and there is competitive adsorption by any IO3- present. In the absence and presence of an excess of IO3- ions, the overall activation energy for the corrosion reaction was determined to be 38 +/- 2 and 54 +/- 4 kJ mol-1, respectively.

EQUILIBRIUM STUDIES ON COLORIMETRIC PLASTIC FILM SENSORS FOR CARBON-DIOXIDE

The equilibrium responses of three new colorimetric plastic film sensors for CO2 as a function of % CO2 and temperature are described. The results fit a model in which there is a 1:1 equilibrium reaction between the deprotonated form of the dye (present in the film as an ion pair) and CO2. The 0-50% and 0-90% response and recovery times of each of these films when exposed to an alternating atmosphere of air and 5% CO2 are determined and in two cases are typically less than 3 s. The shelf life of the films is long (many months); however, prolonged use of the films leads to the permanent generation of the protonated form of the dye over a period of 20-100 h. A possible cause of this latter effect is discussed.

OXIDATION OF WATER BY MNO4- MEDIATED BY THERMALLY ACTIVATED RUTHENIUM DIOXIDE HYDRATE

The kinetics of oxidation of water to oxygen by MnO4-, mediated by thermally activated ruthenium dioxide hydrate, has been studied. The rate of catalysis is 0.8 order with respect to the surface concentration of MnO4- (which in turn appears to fit a Langmuir adsorption isotherm) and proportional to the catalyst concentration, but is independent of the concentration of manganese(II) ions. The catalysed reaction appears to have an activation energy of 50 +/- 1 kJ mol-1. These observed kinetics are readily rationalised using an electrochemical model in which the catalyst particles act as microelectrodes providing a medium for electron transfer between the highly irreversible oxidation of water to O2 and the highly irreversible reduction of MnO4- to Mn2+.

KINETICS OF CORROSION OF RUTHENIUM DIOXIDE HYDRATE BY CEIV IONS

The kinetics of oxidative dissolution of RuO2 .xH2O to RuO4 by Ce(iv) ions are studied. Under conditions of a low [Ce(iv)] : [RuO2 .xH2O] ratio (e.g. 0.35 : 1) and a high background concentration of Ce(III) ions (which impede dissolution) the initial reduction of Ce(iv) ions is due to charging of the RuO2 .xH2O microelectrode particles. The initial rate of charging depends directly upon [RuO2 .xH2O] and has an activation energy of 25 +/- 5 kJ mol-1 Under conditions of a high [Ce(iv] : [RuO2 .xH2O] (e.g. 9 : 1) and a low background [Ce(III] the reduction of Ce(iv) ions is almost totally associated with the dissolution of RuO2 .xH2O to RuO4, i.e. not charging. The kinetics of dissolution obey an electrochemical model in which the reduction of Ce(iv) ions and the oxidation of RuO2 .xH2O to RuO4 are assumed to be highly reversible and irreversible processes, respectively, mediated by dissolving the microelectrode particles of RuO2 .xH2O. Assuming this electrochemical model, from an analysis of the kinetics of dissolution the activation energy for this process was estimated to be 39 +/- 5 kJ mol-1 and the Tafel slope for RuO2 .xH2O corrosion was calculated to be 15 mV per decade. The mechanistic implications of these results are discussed.