EFFECT OF ULTRASOUND ON THE KINETICS OF OXIDATION OF OCTAN-2-OL AND OTHER SECONDARY ALCOHOLS WITH SODIUM-BROMATE, MEDIATED BY RUTHENIUM TETRAOXIDE IN A BIPHASIC SYSTEM

The initial rate of oxidation of octan-2-ol and other secondary alcohols to their ketones with NaBrO3, mediated by RuO4 in an aqueous-CCl4 biphasic system, is greater with ultrasonic irradiation than by stirring alone. Under ultrasonic irradiation the initial rate of oxidation of octan-2-ol increases with increasing % duty cycle, [RuO4] and [NaBrO3]. The kinetics of alcohol oxidation appear to be closely linked with the oxidative dissolution of RuO2 to RuO4 by NaBrO3. The observed enhancement in rate with ultrasonic irradiation appear to be association, at least in part, with the increase in interfacial surface area via the formation of an emulsion of aqueous microdroplets containing NaBrO3 in the CCl4 layer containing the non-water-soluble secondary alcohol.

EFFECT OF ULTRASOUND ON THE KINETICS OF REDUCTION OF HEXACYANOFERRATE(III) BY THIOSULFATE IONS MEDIATED BY RUTHENIUM DIOXIDE HYDRATE

Ultrasound promotes the reduction of hexacyanoferrate(III) by thiosulfate ions mediated by RuO2 . xH(2)O under diffusion-controlled conditions. There is a strong correlation between the measured first-order rate constant and the absorbance of the dispersion, which, in turn, is closely related to the specific surface area of the catalyst. The enhancement in rate with ultrasonic irradiation appears to be largely associated with the dispersive action of the ultrasound on the aggregated particles of RuO2 . xH(2)O. The rate of reaction increases with increasing %duty cycle and ultrasonic intensity. The measured overall activation energies for the reaction with and without ultrasound, i.e. 18 +/- 1 and 20 +/- 1 kJ mol(-1), respectively, are very similar to those expected for a diffusion-controlled reaction. The homogeneous reaction is not promoted by ultrasound.

HETEROGENEOUS REDOX CATALYSIS - A NOVEL ROUTE FOR REMOVING BROMATE IONS FROM WATER

The oxidation of water to oxygen by bromate ions is mediated by the heterogeneous redox catalyst ruthenium-Adams, a high surface area and very stable form of ruthenium(IV) oxide. The initial kinetics of catalysis are investigated as a function of [BrO3-], [Ru-Adams], temperature and [anion], where ''anion'' = ClO4- Cl- or Br-. An electrochemical model of heterogeneous redox catalysis, in which the two participating redox couples are both electrochemically irreversible, is used to interpret most of the kinetic data. The observed inhibition of the initial rate of the redox reaction by Cl- and, especially, Br- ions is tentatively attributed to competitive adsorption. In the presence of organic species, such as methanol, ethanol and propan-1-ol, which are more easily oxidised than water by bromate ions, the rate of BrO3- ion reduction is significantly faster, i.e. ca 24-34 times.

ACID ENHANCEMENT EFFECT IN THE CLEAN OXIDATION OF TOLUENES PHOTOCATALYZED BY TIO2

The yield of substituted benzaldehydes and benzoic acids formed by the aerial oxidation of a range of substituted toluenes photocatalysed by titanium dioxide in acetonitrile is dramatically improved by the addition of small amounts of sulfuric acid.

ACTIVATION-ENERGIES IN SEMICONDUCTOR PHOTOCATALYSIS FOR WATER-PURIFICATION - THE 4-CHLOROPHENOL TIO2 O-2 PHOTOSYSTEM

The variation in the activation energy for the initial stage of photomineralization of 4-chlorophenol (4-CP), sensitized by Degussa P25 TiO2 was investigated as a function of P-O2 and [4-CP]. A model was developed based on the incorporation of Arrhenius-type functions in a general rate equation for the initial stage of photomineralization. Values of the essential constants in the model were derived from a few simple experiments. Positive, negative and zero apparent activation energies were predicted using the model, and verified experimentally, under moderate reaction conditions. The general applicability of the model is briefly discussed.

EFFECT OF PH ON THE STABILITY OF TIO2 COATINGS ON GLASS PHOTOCATALYSIS REACTORS FOR WATER-PURIFICATION

TiO2 coated glass shows excellent stability in the range pH 2-9, however, there is rapid and complete stripping of the TiO2 coating between pH 11 and 12.

PHOTOCATALYTIC DEGRADATION OF 4-CHLOROPHENOL MEDIATED BY TIO2 - A COMPARATIVE-STUDY OF THE ACTIVITY OF LABORATORY MADE AND COMMERCIAL TIO2 SAMPLES

The photocatalytic efficiencies of laboratory made and commercial TiO2 samples were compared using a standard test reaction: the photomineralization of 4-chlorophenol (4-CP) to CO2, H2O and HCl mediated by Degussa P25 TiO2 in a batch reactor. The results show that the rate of photodegradation of 4-CP, sensitized by a sample of TiO2, shows no clear simple dependence on physical characteristics such as the degree of crystallinity, the surface area and the percentage of H2O.

PHOTOMINERALIZATION OF SALICYLIC-ACID - A KINETIC-STUDY

The kinetics of the photomineralization of salicylic acid (SA) sensitized by Degussa P25 titanium dioxide (TiO2) dispersions in oxygenated aqueous solution are reported as a function of the following experimental parameters: [TiO2], percentage of O-2, [SA], temperature (T) and light intensity (I). The kinetics of SA photomineralization conform to a Langmuir-Hinshelwood kinetic scheme with SA and O-2 adsorbed at different sites with apparent Langmuir adsorption coefficients of (6.1 +/- 1.2) x 10(4) mol(-1) dm(3) and 0.061 +/- 0.007 kPa(-1) respectively. The overall activation energy for the system was determined as 4.6 +/- 0.2 kJ mol(-1). Two major stable reaction intermediates are identified (dihydroxybenzoic acids (DHBA) and catechol (C)) and the existence of a further pathway involving one or more very unstable and, as yet, unidentified reaction intermediates is proposed. A kinetic model is presented which describes the temporal behaviour of the concentrations of SA, CO2 and the major photogenerated intermediates (DHBA and C). This model is used to predict successfully the temporal behaviour of the major intermediates in the photomineralization of SA under non-standard conditions.

COLORIMETRIC POLYMER FILM SENSORS FOR DISSOLVED CARBON-DIOXIDE

Plasticized and unplasticized polymer colorimetric film sensors for gaseous CO2, containing the dye m-cresol purple, are tested as sensors for dissolved CO2. The plasticized polymer m-cresol purple film sensor develops a measurable degree of opacity when exposed to aqueous solution, especially in neutral, compared with alkaline, solution. However, it is shown that a presoaked, fogged plasticized polymer m-cresol purple film does function as a quantitative sensor for dissolved CO2 over the range 0-4% CO2. An unplasticized polymer m-cresol purple film remains largely dear upon exposure to aqueous solution and also functions as a quantitative sensor for dissolved CO2 over the range 0-4% CO2. However, in both types of films the dye interacts with electrolytes present in solution; invariably the dye appears to be converted from its initial deprotonated form (blue) to its protonated form (yellow) and the rate of this process appears to increase with increasing ionic strength, anionic charge and decreasing pH. The 90% response and recovery times for an unplasticized film are determined as 19 s(CO2:0-->5%) and 21 s (CO2:5-->3.6%), respectively.

KINETICS OF REDUCTIVE DISSOLUTION OF SODIUM BISMUTHATE BY CE-III AND MN-II IONS

The kinetics of reductive dissolution of NaBiO3, by Mn-II and Ce-III ions are studied as a function of [Mn-II] or [Ce-III], [Bi-III], [H+] and temperature. They fit a simple inverse-cubic rate law and can be readily interpreted using a mechanism in which the rate-determining step is the reaction between an adsorbed reducing species (i.e. a Mn-II or Ce-III ion) and its associated surface site; protonation of the surface site promotes the rate of reaction. The rate of dissolution decreases with increasing initial concentration of Bi-III ions owing to competitive inhibition by the latter species. A kinetic model, based on this mechanism, is applied and provides a quantitative description of the observed kinetics.

OXIDATION OF CHLORIDE TO CHLORINE BY CERIC IONS MEDIATED BY THE 3 FORMS OF CRYSTALLINE CARBON

C-60 is more effective than graphite or diamond as a redox catalyst for the oxidation of chloride to chlorine by cerie ions.

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.