Thermodynamics
and kinetics of pretilachlor adsorption on organobentonites
modified with hexadecyltrimethyl ammonium chloride were investigated
to reveal the structural effects of organobentonites on the interaction
with pretilachlor and the diffusion of the herbicide and were related
to the controlled release from organobentonites. The adsorption of
pretilachlor was entropically driven by hydrophobic interaction. The
entropy change dropped with increasing surfactant loading from 0.4
to 1.50 times the cation exchange capacity (CEC) of the bentonite
used, corresponding to a decrease in the degree of freedom of pretilachlor
molecules due to the enhanced order of surfactant in the interlayer.
The kinetics of pretilachlor adsorption was well fitted to the pseudo-second-order
model and related to the structural features of organobentonites.
The enhanced packing density of the surfactant in the interlayer generally
resulted in a reduction of the rate constant of the pretilachlor adsorption
onto organobentonites. However, the stepwise increase in the basal
spacing due to the surfactant arrangement transition, from lateral-monolayer
to lateral-bilayer at a loading level of more than 0.8 × CEC,
benefited the diffusion of pretilachlor and diminished the influence
of the increase in surfactant packing density. The release of pretilachlor
from organobentonites was predominated by Fickian diffusion, which
could be understood from the adsorption thermodynamics and kinetics.
The time taken for the release of 50% of active ingredient was 16–23
times that for the control formulation and exhibited a linear increase
with the relative value of the equilibrium constant to the rate constant
of pretilachlor adsorption.
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