Supporting Information: From time-resolved experiments we monitor ...
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Supporting Information: From time-resolved experiments we monitor ...
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Reaction Kinetics and mechanisms of neonicotinoid pesticides with sulphate radicals María Laura Dell’Arciprete, Carlos J. Cobos, Daniel O. Mártire, Jorge P. Furlong, and Mónica C. Gonzalez
Supporting Information:
S.I. 1-
Kinetic treatment of time-resolved sulphate radicals absorbance profiles.
From time-resolved experiments we monitor the decay rate of SO4.- radicals, and determine a pseudo first order rate constant obtained from these decays (kapp). In the absence of insecticides, sulphate radicals decay because of their reactions with Na2S2O8 and HO- anions. Since these experimental conditions remain constant throughout the set of experiments we will call the apparent rate constant measured in .
the absence of insecticides k0. SO4 - radicals recombination is of no significance under our experimental conditions of high [Na2S2O8], since otherwise, a mixed first and second order decay would have been observed. In experiments with increasing Insecticide concentrations, kapp values become higher due to the reaction of SO4.radicals and the insecticides. The measured kapp is now due to all these reactions competing for SO4.-. Solution of the mass balance differential equations for SO4.- radicals yields kapp = k0+ k2×[Ins]. Therefore, the slope of the linear plots of kapp vs. [Ins] yield the value of k2.
Table 1. Mulliken atomic charges of C1 and C2 atoms in the radical cation rc for the three insecticides. See Scheme 2 in the main text for the position of the carbon atoms. C1
Figure 1. TD-DFT calculated spectra for the α-aminoalkyl radicals ACTRX (grey line) and ACTRY (black line). The dashed lines stand for the TD-DFT calculated spectra for the same radicals protonated in the pyridine ring.
