Transport Studies of Some 1:1 Copper(I) Perchlorate Complexes in Acetonitrile-Dimethylsulphoxide Mixtures

Abstract

Solvation behaviour of some copper(I) perchlorate complexes has been investigated in binary mixtures of acetonitrile (AN) and dimethylsulphoxide (DMSO) containing 1.0, 0.8, 0.6, 0.4, 0.2 and 0 mol fraction of AN at 298 K by molar conductances and viscosity measurements. The conductance data have been analyzed by using the Shedlovsky method to calculate limiting molar conductance (Λ o ) and the viscosity data by the Jones–Dole equation to evaluate viscosity B-coefficients of various salts. Limiting ion conductances (λ i o ), solvated radii (ri ) and ionic viscosity B ± coefficients in all solvent systems have been evaluated using Gill´s modification based on Bu4NBPh4 as a reference electrolyte. The studies show that all copper(I) complexes are solvated and the extent of solvation is stronger in AN and AN rich regions than in DMSO and DMSO rich regions. The ClO4 - ion is poorly solvated in AN+DMSO mixtures. The viscosity results are in good agreement with the results obtained from the conductance studies.

A conductivity study of preferential solvation of lithium ion in acetonitrile-dimethyl sulfoxide mixtures

“…Fig. 3 shows our viscosity measurements in comparison with reported data by other authors [32,33]. As it can be observed, our measurements agree, within the experimental error (between 2.3 and 3.6%), with viscosity data reported by Grande et al [33] Thus, in order to fit the experimental viscosity data as a function of composition, we chose as input values our experimental data and that reported by these authors.…”

“…Owing to the significant difference between the literature reported viscosity values of the mixtures [32,33] (up to 20% difference for some compositions), we measured the viscosities of ACN-DMSO mixtures in the whole composition range with Cannon-Fenske (Ostwald modification) viscometers size 25 (0.5-2 mPa s) and size 50 (0.8-4 mPa s), calibrated with water.…”

“…The salt molar concentration c was determined from the weights of salt and solvents using the density of the mixture. The thermophysical properties of the ACN-DMSO mixtures (density [32] and dielectric constant [33]) at 298.15 K were fitted with polynomial equations as a function of composition, and the corresponding values for the measured compositions are given in Table 1. Viscosity was fitted in logarithmic scale as a function of composition as will be discussed in Section 4.2. reference electrode vs. the ferroceneferrocenium couple, plotted in Fig.…”

Solvation Behaviour of Some Copper(I) Complexes in Binary Mixtures of Dimethylsulfoxide with Dimethylacetamide and Dimethylformamide at 298 K

“…Limiting ion conductances (λ λ λ λ λ ±°) : The use of an indirect method [16,23] these ionic radii tend to become greater than that for Bu 4 N + as the DMA composition increases, i.e., in the DMA rich region.…”

“…These copper(I) complexes, however, have a marked stability in acetonitrile [13] (AN), benzonitrile [14] (BN) and some other nitriles [15]. Some investigations [16] of the behaviour of these white coloured complexes have been made…”