Deep eutectic solvents
(DESs) formed by hydrogen bond donors and
acceptors are a promising new class of solvents. Both hydrophilic
and hydrophobic binary DESs readily absorb water, making them ternary
mixtures, and a small water content is always inevitable under ambient
conditions. We present a thorough study of a typical hydrophobic DES
formed by a 1:2 mole ratio of tetrabutyl ammonium chloride and decanoic
acid, focusing on the effects of a low water content caused by absorbed
water vapor, using multinuclear NMR techniques, molecular modeling,
and several other physicochemical techniques. Already very low water
contents cause dynamic nanoscale phase segregation, reduce solvent
viscosity and fragility, increase self-diffusion coefficients and
conductivity, and enhance local dynamics. Water interferes with the
hydrogen-bonding network between the chloride ions and carboxylic
acid groups by solvating them, which enhances carboxylic acid self-correlation
and ion pair formation between tetrabutyl ammonium and chloride. Simulations
show that the component molar ratio can be varied, with an effect
on the internal structure. The water-induced changes in the physical
properties are beneficial for most prospective applications but water
creates an acidic aqueous nanophase with a high halide ion concentration,
which may have chemically adverse effects.
The control of the noble metal concentration is crucial in order to increase the efficiency of hydrometallurgic processes in mining and in the recovery of precious materials from electronic waste. The present study is devoted to the development of an effective procedure for the quantification of Au(III) species dissolved in aqueous solutions, similar real complex matrices included. In particular, a novel electrode system based on Ti has been studied. This electrode material is still poorly investigated in the framework of electroanalysis, despite its lack of sensitivity to common interfering species, such as oxygen; hence, the determination of metal species can be carried out without performing deaeration of the solution. In addition, the interfering effect due to the presence of other heavy metal ions, such as Ag, Fe and Pb, has been minimised by a proper choice of the conditions adopted for the amperometric measurements. Ti electrodes exhibit reproducible electrochemical responses, even in the presence of high concentration of organic fouling species typical of biosorption processes.
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