Partial molar volumes and viscosity B-coefficients for N,N/-ethylene-bis(salicylideneiminato)-diaquochromium(III) chloride in methanolic solutions of 1-butyl-2,3-dimethylimidazolium tetrafluoroborate at T = (298.15, 308.15, and 318.15) K

doi:10.1016/j.jct.2013.09.018

The Journal of Chemical Thermodynamics

Volume 68, January 2014, Pages 260-269

https://doi.org/10.1016/j.jct.2013.09.018 Get rights and content

Highlights

•
Methanolic solutions of 1-butyl-2,3-dimethylimidazolium tetrafluoroborate used as solvent.
•
N,N^/-ethylene-bis(salicylideneiminato)-diaquochromium(III) chloride, used as solute.
•
Parameters discussed on the basis of ion–ion and ion–solvent interactions.
•
Presence of strong solute–solvent interactions.
•
Thermodynamics of viscous flow were discussed.

Abstract

Ion–ion and ion–solvent interactions for N,N^/-ethylene-bis(salicylideneiminato)-diaquochromium(III) chloride, [Cr(salen)(H₂O)₂]Cl, dissolved in solutions of 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, [bdmim]BF₄ (0.005 to 0.020 mol · dm⁻³) in methanol (MeOH) were investigated by a combination of physicochemical properties at 298.15, 308.15 and 318.15 K under ambient pressure. From measured solution densities and viscosities apparent molar volume (φ_V), the slope ( $S_{V}^{*}$ ), standard partial molar volume ( $φ_{V}^{0}$ ), transfer volume ( $Δ_{t} φ_{V}^{0}$ ), the viscosity B-coefficient, its temperature derivative (∂B/∂T), solvation number (S_n), etc. were calculated and discussed on the basis of ion–ion and ion–solvent interactions. In the investigated temperature range, the relation: $φ_{V}^{0} = a_{0} + a_{1} T$ , was used to determine the temperature dependence of the partial molar volumes $φ_{V}^{0}$ , i.e., partial molar expansibilities ( $φ_{E}^{0}$ ). Temperature dependence of the viscosity B-coefficient (∂B/∂T) values revealed the complex to be a long-range structure breaker. Thermodynamics of viscous flow were discussed on the basis of the transition state theory.

Graphical abstract

Introduction

Chemical reactions and equilibria in solutions, very often, involve ionic species. In all such systems ions interact with one another and with the solvent molecules surrounding them. Chemical reactions and thermodynamic parameters in such systems largely depend on the extent of ion–ion and ion–solvent interactions. Depending on the extent of the inter-ionic interactions and ion–solvent interactions, solutions of ionic species may contain ion pairs like contact, solvent separated and solvent shared ion pairs [1]. Among the many potential materials, Schiff bases are considered as “privileged ligands” and they are easily obtained from the condensation of aldehydes and amines [2], [3]. Transition metal complexes of Schiff bases can catalyze various reactions such as oxidation, hydroxylation, and epoxidation [4], [5], etc. The chemistry of transition metal complexes containing salen-type Schiff base ligands is of enduring significance, since such complexes have common features with metalloporphyrins regarding their electronic structure and catalytic activities [6], etc. Schiff base complexes of Cr(III) such as N,N^/-ethylene-bis(salicylideneiminato)-diaquochromium(III) chloride, [Cr(salen)(H₂O)₂]Cl is a new kind of GTF model [7] and can reduce the symptoms of diabetes like hyperglycemia and cholesterol [8], [9]. On the other hand, Ionic liquids (ILs) are organic electrolytes generally with asymmetric organic cations and non-coordinating counter inorganic anions [10], [11]. Because of their unique properties and variety, ionic liquids are regarded as high-performance fluids and find a wide range of engineering and material science applications [12], [13], [14], [15]. Sometimes the catalytic activities of transition metal salen complexes improve by the addition of ionic liquids to the reaction mixture [16] and exploration the potentiality of ionic liquids as reaction media is very demanding in relation to green chemistry. Also the addition of co-solvents like water, methanol, etc. has been found to strongly affect various physico-chemical properties of ionic liquids [17]. Hence various thermophysical properties of systems comprising of transition metal complex, ionic liquid and molecular solvents can provide valuable information about ion–ion and ion–solvent interactions that probably characterize their solution thermodynamics and structure in solution phase and such information would permit developing a convenient experimental procedure for a suitable biphasic reusable catalytic system. Anyway, to the best of our knowledge there is no report of the physico-chemical properties of the system: [Cr(salen)(H₂O)₂]Cl + [bdmim]BF₄ + MeOH in the literature. Hence in the present work we reported some physico-chemical properties of the ternary mixtures of [Cr(salen)(H₂O)₂]Cl + [bdmimBF₄] + MeOH at 298.15, 308.15 and 318.15 K under ambient pressure and discussed the results in terms of ion–ion and ion–solvent interactions.

Section snippets

Materials

A. R. grade CrCl₃.6H₂O; 1,2-ethylenediamine and salicylaldehyde, each of purity >99%, were procured from SD Fine chemicals, India. The ionic liquid 1-butyl-2,3-dimethyl immidazolium tetrafluoroborate of purity >98% was procured from Sigma–Aldrich, Germany. Spectroscopic grade methanol (minimum assay, GC > 99.8% with 0.05% of water) was procured Merck, India. All the chemicals were used as received from the vendor. Table 1 contains provenance and purity of the chemicals used in this work. The

Results and discussion

The experimental values of molalities (m), densities (ρ), viscosities (η) and derived parameters for the experimental solutions of [Cr(salen)(H₂O)₂]Cl in different mixed solvents at various temperatures are reported in table 3.

Conclusion

In summary, partial molar volumes $φ_{V}^{0}$ and viscosity B-coefficients for [Cr(salen)(H₂O)₂]Cl in the ternary solutions indicate the presence of strong solute–solvent interactions; these interactions strengthen at higher temperatures but decrease at higher content of [bdmim]BF₄ in the studied solutions. Also [Cr(salen)(H₂O)₂]Cl acts as a net structure breaker for the studied solutions.

Acknowledgements

The authors are grateful to the Departmental Special Assistance Scheme under the University Grants Commission, New Delhi (No. F540/27/DRS/2007, SAP-1) for financial support. One of the authors (D. B) is also thankful to UGC, India for granting him UGC BSR Research Fellowship in Science (Ref. No: 4-1/2008 (BSR)).

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Partial molar volumes and viscosity B-coefficients for N,N/-ethylene-bis(salicylideneiminato)-diaquochromium(III) chloride in methanolic solutions of 1-butyl-2,3-dimethylimidazolium tetrafluoroborate at T = (298.15, 308.15, and 318.15) K

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Materials

Results and discussion

Conclusion

Acknowledgements

J. Mol. Struct.

Thermochim. Acta

J. Inorg. Biochem.

J. Inorg. Biochem.

Inorg. Chim. Acta

J. Chromatogr. A

Electrochim. Acta

Catal. Commun.

J. Chem. Thermodyn.

Chem. Soc. Rev.

Trans. Met. Chem.

Trans. Met. Chem.

Green Chem.

J. Chem. Technol. Biotechnol.

Electrochemistry

Chem. Commun.

Partial molar volumes and viscosity B-coefficients for N,N^/-ethylene-bis(salicylideneiminato)-diaquochromium(III) chloride in methanolic solutions of 1-butyl-2,3-dimethylimidazolium tetrafluoroborate at T = (298.15, 308.15, and 318.15) K