The stability of the herbicide clopyralid (3,6-dichloro-2-pyridinecarboxylic acid) was studied under different experimental conditions of pH, illumination and initial substrate concentration. It was found that in the pH interval from 1.0 to 9.0 in the presence/absence of daylight, clopyralid solutions were stable for at least a period of two months. The kinetics of the photocatalytic degradation of clopyralid in aqueous suspensions of TiO2 (Degussa P25) under UV and visible light, as well as of direct photolysis using the same radiation sources, were also investigated. It was found that the rate of photocatalytic degradation in the presence of UV light was more than five times higher compared to direct photolysis, whereas in the presence of visible light, the corresponding rates of photocatalytic/photolytic degradation were much lower (more than 15 times). The reaction in the investigation concentration range is zero-order with respect to the degradation of the clopyralid pyridine moiety, with a reaction rate of 3.4?10-6 mol dm-3 min-1 and an adsorption coefficient of the substrate of 2.5?104 dm3 mol-1.
Titanium dioxide sensitized photocatalytic degradation of a pyridine pesticide analogue, 2-amino-5-chloropyridine, was investigated by monitoring the pyridine moiety degradation, as well as by monitoring the chloride generated in the process. Effect of the initial substrate concentration on the rate of its degradation is reported. Here we show that the kinetics of both reactions are of the zero-order in the entire investigated concentration range. The Langmuir-Hinshelwood kinetic model successfully described the influence of the initial substrate concentration on the rate of the pyridine moiety degradation. It was found that dechlorination of the substrate takes place by direct photolysis. The differences in the kinetics of pyridine moiety degradation and dechlorination were explained on the basis of the electrostatic potential for the investigated compound
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