Excess molar volumes and excess isentropic compressibilities of ternary mixtures containing ionic liquids and cyclic alkanone
Introduction
In the era of rapidly changing global environment, more and more research attempts have been made to replace fossil fuels (used in devices) for the control of greenhouse gas emissions. Ionic liquids (ILs), a new novel type of green solvents have received widespread attention as an eco-friendly reaction medium for various processes involved in industries [1], [2], [3], [4]. These liquids are composed of an inorganic anion; a bulky organic cation and possess unique properties such as negligible vapor pressure, wide liquid range, non-flammability, excellent solubility, non-volatility, recyclable, reusability, high thermal and electrochemical stability and good selectivity. Due to the unusual and specific properties, ILs can be considered as safer and more sustainable alternative to volatile organic compounds (VOCs) as solvents in various reactions, catalytic activities, extraction systems, adsorption and separation processes [5], [6], [7], [8], [9]. Among the well-known families of ILs, imidazolium based ILs have recently attracted most attention in experimental investigations such as media for bio-electrochemistry, photovoltaic, metal deposition, exploration for absorption/solubility of CO2 and electrolytes in dye sensitized solar cells (DSSCs) to improve the conversion efficiency etc. [10], [11], [12], [13]. 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium tetrafluoroborate and 1-ethyl-3-methylimidazolium tetrafluoroborate are being used in electrochemistry, catalysis, extraction processes, batteries and capacitors [14], [15], [16], [17]. However, pure ILs are highly viscous, and having relatively high cost which impedes their application [18]. Such disadvantages of ILs can be overcome by mixing with some organic solvents [19], [20]. The physico-chemical and thermodynamic properties of IL mixtures such as densities, viscosities, excess molar enthalpies, excess molar volumes, excess heat capacities etc. can be tuned to an extent by slight changes in the cationic and/or anionic groups of IL or mixing with some organic liquid. Thus it is possible to design ILs or their mixtures containing organic liquids possessing desired properties. Experimental data on thermodynamic properties of IL mixtures are also of considerable interest for selecting appropriate mixtures in many industrial applications such as in the oil and gas industries [21] for flow assurance and oil recovery, in chemical industries [22] for the design and separation processes, in pharmaceutical and polymer industries [23] for solvent selection and emission control and in biotechnology for aggregation/separation of proteins [24]. These properties are also required for the proper design and operation of chemical reactions, pumps and heat transfer equipment [25], [26].
Cyclopentanone has the lowest auto-ignition reactivity of a number of biofuels and thus act as blending component to be used in spark-ignition internal-combustion engines [27]. Cyclopentanone and cyclohexanone have important applications in industries like synthesis of aromas and caprolactum intermediates or as final products in reaction medium; solvents in the synthesis of pharmaceuticals, insecticides, pesticides, flavor and fragrance reagents in pharmaceutical, agricultural and cosmetic industries [28], [29], [30]. In recent studies, we have reported excess molar volumes, VE, excess isentropic compressiblities, , excess molar enthalpies, HE and excess heat capacities, CpE data of {1-butyl-2,3-dimethylimidazolium tetrafluoroborate (i) + 1-butyl-3-methylimidazolium tetrafluoroborate (j)}; {1-butyl-2,3-dimethylimidazolium tetrafluoroborate (i) + 1-ethyl-3-methylimidazolium tetrafluoroborate (j)}; {1-butyl-2,3-dimethylimidazolium tetrafluoroborate or 1-butyl-3-methylimidazolium tetrafluoroborate (i) + cyclopentanone or cyclohexanone (j)} mixtures. In continuation of our related studies, we extend our study to ternary mixtures and report densities, and speeds of sound, , values of ternary mixtures containing {1-butyl-2,3-dimethylimidazolium tetrafluoroborate (i) + 1-butyl-3-methylimidazolium tetrafluoroborate or 1-ethyl-3-methylimidazolium tetrafluoroborate (j) + cyclopentanone or cyclohexanone (k)}. The main aim of our work is to provide new experimental data on densities, , and speeds of sound, of IL mixtures. Also it would be of interest to see how Graph and Prigogine-Flory-Patterson (PFP) theory describe the and results for ternary mixtures comprised of two ILs and one organic liquid.
Section snippets
Experimental
1-Butyl-2,3-dimethylimidazolium tetrafluoroborate [Bmmim][BF4]; (mass fraction: 0.990), 1-butyl-3-methylimidazolium tetrafluoroborate [Bmim][BF4]; (mass fraction: 0.985) and 1-ethyl-3-methylimidazolium tetrafluoroborate [Emim][BF4]; (mass fraction: 0.990) were obtained from commercial sources and used after purification by vacuum treatment at residual pressure 5 × 10−2 Pa at 338 K to eliminate the water and other volatile compound traces. Cyclopentanone (CPO) (Fluka, mass fraction: 0.990) and
Results
Table 3 contains experimental values for densities, and speeds of sound, of ternary {[Bmmim][BF4] (i) + [Bmim][BF4] or [Emim][BF4] (j) + CPO or CHO (k)} mixtures at temperatures (293.15, 298.15, 303.15 and 308.15) K. The measured and uijk values were utilized to determine their excess molar volumes, and isentropic compressibilities, using equations:where , Mi, are the mole fraction, molar mass and density
Discussion
The ρ and u values for the purified [Bmmim][BF4], [Bmim][BF4], [Emim][BF4], CPO and CHO were taken from literature [33], [34], [35]. The deviations between measured and literature [44], [45], [46] ρ and u values for [Bmmim][BF4] at various temperatures were discussed in Ref. [33]. The experimental ρ and u values of [Bmim][BF4], [Emim][BF4], CPO and CHO are in agreement with their literature values [47], [48], [49], [50], [51], [52], [53], [54], [55], [56], [57], [58], [59], [60], [61], [62],
Graph theory
The thermodynamic, topological, IR and quantum mechanical studies of excess molar volumes, , excess isentropic compressibilities , excess heat capacities, CpE and excess molar enthalpies, HE values for {[Bmmim][BF4] (i) + [Bmim][BF4] or [Emim][BF4] (j), [Bmmim][BF4] or [Bmim][BF4] or [Emim][BF4] (i) + CPO or CHO (j)} mixtures in the literature [33], [34], [35], [56] have revealed that, (1) [Bmmim][BF4], [Bmim][BF4], [Emim][BF4] are characterized by cohesion forces between (a) hydrogen atom
Excess molar volumes
In the development of Prigogine-Flory-Patterson (PFP) theory of liquid mixtures, strong interactions among the constituent molecules are excluded. However, theory still provides in trusting correlation between the thermodynamic properties of liquid mixtures exhibiting strong molecular interactions. It was, therefore, of interest to predict VijkE and data of the present mixtures possessing strong interactions among the constituent molecules. According to PFP theory [68], excess molar
Conclusions
The excess molar volumes, VijkE and excess isentropic compressibility, (κSE)ijk values of the present mixtures have been determined using measured densities, ρijk and speeds of sound, uijk values. The excess properties, VijkE, (κSE)ijk have been correlated using Redlich-Kister equation to predict ternary adjustable parameters and standard deviations. The VijkE values for {[Bmmim][BF4] (i) + [Bmim][BF4] (j) + CPO (k)} and (κSE)ijk data of {[Bmmim][BF4] (i) + [Bmim][BF4] (j) + CPO or CHO (k)} mixtures
Acknowledgements
The authors are thankful to Mr. K. Chandrasekhar Reddy, SSBN College, Anantapur, for providing Gaussian-09 facility and C-DAC, PUNE, India for providing the computational work. V. K. Sharma is grateful to University Grant Commission (UGC), New Delhi for the award of SAP.
References (72)
- et al.
J. Chem. Thermodyn.
(2016) J. Chromatogr. A
(2004)- et al.
J. Chem. Thermodyn.
(2011) - et al.
J. Chem. Thermodyn.
(2016) - et al.
J. Mol. Liqs.
(2016) - et al.
Electrochim. Acta
(2010) - et al.
J. Chem. Thermodyn.
(2005) - et al.
J. Mol. Liqs.
(2016) - et al.
J. Chem. Thermodyn.
(2014) - et al.
J. Power Sources
(2010)
J. Chem. Thermodyn.
J. Chem. Thermodyn.
J. Mol. Liqs.
J. Chem. Thermodyn.
J. Chem. Thermodyn.
J. Ind. Eng. Chem.
Appl. Catal. A Gen.
J. Chem. Thermodyn.
J. Mol. Liqs.
J. Chem. Thermodyn.
J. Chem. Thermodyn.
Thermochim. Acta.
J. Chem. Thermodyn.
J. Mol. Liqs.
Fluid Phase Equilib.
J. Chem. Thermodyn.
J. Chem. Thermodyn.
J. Chem. Thermodyn.
Polymer
Thermochim. Acta
Thermochim. Acta
J. Mol. Liq.
Thermochim. Acta
Molecules
J. Chem. Eng. Data.
Ind. Eng. Chem. Res.
Cited by (6)
Physical and transport properties of ionic liquids using geometric similitude and a cubic equation of state. Part 2: Thermal conductivity, and speed of sound of water + ionic liquid mixtures
2020, Journal of Molecular LiquidsCitation Excerpt :Mixtures composed by 1-ethyl-3-methylimidazolium trifluoromethanesulfonate and different organic solvents as dimethyl sulfoxide and acetonitrile can be used in pharmaceutical, medical, and microbiology applications [2]. Mixtures of 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium tetrafluoroborate and 1-ethyl-3-methylimidazolium tetrafluoroborate can be used in electrochemistry, catalysis, diesel extractive desulfurization process, batteries and capacitors [3,5]. Ionic liquid mixtures composed of imidazolium salts can be used in reaction systems, lignin degradation, and biomass fractionation [1,4].
Experimental Measurements, Correlation, and Prediction Models to Study 1-Ethyl-3-methylimidazolium Tetrafluoroborate Ionic Liquid Ternary Mixtures
2024, Journal of Chemical and Engineering DataCritical review on graph theory: Estimation of thermodynamic properties of liquid mixtures
2023, Korean Journal of Chemical EngineeringMeasurement and Modeling of Thermodynamic Properties for Ternary Mixtures Containing 1-Butyl-3-methylimidazolium-Based Ionic Liquids with Acetophenone and Acetic or Propionic Acid
2021, Journal of Chemical and Engineering DataExcess molar enthalpies for [Bmmim][BF <inf>4</inf> ] + [Bmim][BF <inf>4</inf> ] or [Emim][BF <inf>4</inf> ] + cyclopentanone or cyclohexanone mixtures
2019, Journal of Thermal Analysis and Calorimetry