Faculty of Applied Sciences
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Item Influence of temperature on molecular interactions of imidazolium-based ionic liquids with acetophenone: thermodynamic properties and quantum chemical studies(Royal Society of Chemistry, 2016) Bahadur, Indra; Masilo, Kgomotso; Ebenso, Eno, E.; Redhi, Gan G.The physicochemical properties namely: densities (ρ), sound velocities (u), viscosities (η), and refractive indices (nD) of a series of alkyl imidazolium-based ionic liquids (ILs) with same cation and different anion and vice versa of ILs: 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM]+[BF4]−, 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM]+[PF6]−, 1-ethyl-3-methylimidazoium ethyl sulphate [EMIM]+[EtSO4]− and 1-ethyl-3-methylimidazolium tetrafluoroborate [EMIM]+[BF4]−, with acetophenone over the wide range of composition and at (293.15, 303.15, 313.15, 323.5 and 333.15) K under atmospheric pressure is reported in this study. The excess molar volumes, (VEm), deviation in isentropic compressibilities (Δκs), deviation in viscosities (Δη) and deviation in refractive indices (ΔnD) were derived from experimental results. The VEm, Δκs and ΔnD values for the mentioned systems are both negative and positive over the entire composition range while the Δη values are negative under the same experimental conditions. The derived properties were fitted to the Redlich–Kister polynomial equation to check the accuracy of experimental results. Furthermore, the inter-ionic interactions between the cations and anions of the ILs both in vacuo and in acetophenone (using continuum solvation) were confirmed using quantum chemical technique such as [Density Functional Theory (DFT)]. The quantum chemical results are in good agreement with the experimental results suggesting that there exist appreciable interactions between the ILs and acetophenone. The theoretical and measured data were interpreted in terms of intermolecular interfaces and structural effects between similar and dissimilar molecules upon mixing in order to obtain more information on the thermophysical and thermodynamic properties of ILs and their binary mixtures. This study will contribute to the data bank of thermodynamic properties of IL mixtures, so as to establish principles for the molecular design for chemical separation processes and to enhance the applications of ILs in certain aspects of research or industrial application.Item Synthesis and characterization of 2′,3′-epoxy propyl-N-methyl-2-oxopyrrolidinium salicylate ionic liquid and study of its interaction with water or methanol(Royal Society of Chemistry, 2016) Vasanthakumar, Arumugam; Bahadur, Indra; Redhi, Gan G.; Gengan, Robert MoonsamyImportant physico-chemical properties of ionic liquids (ILs) can be manipulated by adjusting the nature of the cation or anion. These properties are exploited in applications such as organic synthesis, catalysis and electrochemical processes to mention a few. In this work, the novel pyrrolidone ionic liquid N-(2′,3′-epoxypropyl)-N-methyl-2-oxopyrrolidinium salicylate [EPMpyr]+[SAL]− was synthesized using two steps and characterized. The temperature dependent density and speed of sound for ionic liquid, methanol, water, and their corresponding binary mixtures of {IL (1) + methanol or water (2)} were measured over the entire range of mole fractions at temperatures from T = (293.15 to 313.15) K in steps of 5 K, under atmospheric pressure. The calculated thermodynamic properties such as excess molar volume VEm, isentropic compressibility ks, intermolecular free length Lf, and deviation in isentropic compressibility Δks, were derived from the investigated density and speed of sound data. The resulting experimental data for excess molar volumes VEm, intermolecular free length Lf, and deviation in isentropic compressibility Δks, were well fitted to the Redlich–Kister polynomial equation. The effect of temperature and concentration on thermophysical properties was also provided.Item Volumetric, acoustic and refractive index for the binary system (Butyric acid + Hexanoic acid) at different temperatures(Springer, 2014-04-12) Bahadur, Indra; Deenadayalu, Nirmala; Naidoo, Paramespri; Ramjugernath, DereshIn this paper density, sound velocity, and refractive index for the binary system (butyric acid ? hexanoic acid) were measured over the entire composition range and at 5 K intervals in the temperature range 293.15–313.15 K. The excess molar volumes, isentropic compressibilities, excess isentropic compressibilities, deviation in refractive indices, molar refractions, and deviation in molar refractions were calculated by using the experimental densities, sound velocities, and refractive indices, respectively. The Redlich–Kister equation was used to fit the excess molar volume, excess isentropic compressibility, deviation in refractive index and deviation in molar refraction data. The Lorentz–Lorenz approximation was used to correlate the excess molar volume from the deviation in refractive index and also to predict the density from refractive index or the refractive index from density of the binary mixtures. Four sound velocity mixing rules were tested and the best model for the systems studied in this work was the Berryman mixing rule. The thermodynamic properties are discussed in terms of intermolecular interactions between the components of the mixtures.Item Excess molar volumes of binary mixtures (an ionic liquid + water) : A review(Elsevier, 2015-03) Bahadur, Indra; Singh, Sangeeta; Redhi, Gan G.; Venkatesu, Pannuru; Letcher, Trevor M.This review covers recent developments in the area of excess molar volumes for mixtures of {ILs (1) + H2O (2)} where ILs refers to ionic liquids involving cations: imidazolium, pyridinium, pyrrolidinium, piperidinium, morpholinium and ammonium groups; and anions: tetraborate, triflate, hydrogensulphate, methylsulphate, ethylsulphate, thiocyanate, dicyanamide, octanate, acetate, nitrate, chloride, bromide, and iodine. The excess molar volumes of aqueous ILs were found to cover a wide range of values for the different ILs (ranging from −1.7 cm3 · mol−1 to 1.2 cm3 · mol−1). The excess molar volumes increased with increasing temperature for all systems studied in this review. The magnitude and in some cases the sign of the excess molar volumes for all the aqueous ILs mixtures, apart from the ammonium ILs, were very dependent on temperature. This was particularly important in the dilute IL concentration region. It was found that the sign and magnitude of the excess molar volumes of aqueous ILs (for ILs with hydrophobic cations), was more dependent on the nature of the anion than on the cation.Item Effect of temperature on density, sound velocity, refractive index and their derived properties for the binary systems (heptanoic acid + propanoic or butanoic acids)(Elsevier, 2014-06-14) Bahadur, Indra; Naidoo, Paramespri; Singh, Sangeeta; Ramjugernath, Deresh; Deenadayalu, NirmalaIn this work, the effect of temperature on density (q), sound velocity (u), refractive index (n) and their derived properties for carboxylic acid mixtures was studied. The thermophysical properties: density, sound velocity and refractive index were measured over the entire composition range at T = (293.15, 298.15, 303.15, 308.15 and 313.15) K and at p = 0.1 MPa for the binary systems (heptanoic acid + propa-noic or butanoic acids). The mass fraction of water was found to be unusually large and could not be reduced further. The Lorentz–Lorenz approximation was used to predict the density from refractive index or the refractive index from density of the binary mixtures. Sound velocity mixing rules were applied to the experimental sound velocity data. Excess molar volumes, VEm; isentropic compressibilities, js, excess isentropic compressibilities, jsE, and deviation in refractive indices, Dn, were also calculated from the experimental data. The Redlich–Kister polynomial equation was fitted to the excess properties and the deviation in refractive index data. Thermophysical properties are useful in understanding the intermolecular interactions between the components of mixtures.Item Influence of alkyl group and temperature on thermophysical properties of carboxylic acid and their binary mixtures(Elsevier B.V., 2014-06-30) Bahadur, Indra; Deenadayalu, Nirmala; Naidoo, Paramespri; Ramjugernath, Deresh; Singh, Sangeetan this work, volumetric, acoustic and refractive index methods have been used to study the interactions between carboxylic acids mixtures as a function of temperature and concentration. The density (r), sound velocity (u), refractive index (n) of butanoic acid, pentanoic acid and heptanoic acid and their binary systems (butanoic or heptanoic acid + pentanoic acid) have been measured at 293.15, 298.15, 303.15, 308.15 and 313.15 K and at p = 0.1 MPa. The Lorentz–Lorenz approximation and sound velocity mixing rules were used to test the accuracy of the experimental data. The derived properties such as excess molar volumes, VEm, isentropic compressibilities, ks, excess isentropic compressibilities, ksE, and deviation in refractive indices, Dn, were also calculated. The Redlich–Kister polynomial equation was used to fit the excess/deviation properties. These results are useful for describing the intermolecular interactions that exist between the components in mixtures. This work also tests various sound velocity mixing rules to calculate the sound velocity of the binary mixture from pure component data, as well as examine the use of the Lorentz–Lorenz approximation to predict density from refractive index and vice versa.Item Densities and excess molar volume for the ternary systems (1-Butyl-3-methylimidazolium methyl sulphate + Nitromethane + Methanol or Ethanol or 1-Propanol) at T = (303.15 and 313.15) K(SA Epublications, 2013) Bahadur, Indra; Deenadayalu, NirmalaThe densities of the ternary systems containing the ionic liquid 1-butyl-3-methylimidazolium methyl sulphate ([BMIM]+[MeSO4]–) were determined. The ternary systems studied were ([BMIM]+[MeSO4]– + nitromethane + methanol or ethanol or 1-propanol) at the temperatures (303.15 and 313.15) K. The ternary excess molar volumes were calculated from the experimental densities at each temperature, being negative for all mole fractions of the ionic liquid. The minimum ternary excess molar volumes increase with an increase in temperature for the systems ([BMIM]+[MeSO4]– + nitromethane + methanol or ethanol), and decrease for the system ([BMIM]+ [MeSO4]–+ nitromethane + 1-propanol). The results are interpreted in terms of the alcohol chain length and the intermolecular interactions.Item Excess molar volume and isentropic compressibility for binary or ternary ionic liquid systems(2010) Bahadur, Indra; Deenadayalu, NirmalaThe thermodynamic properties of mixtures involving ionic liquids (ILs) with alcohols or alkyl acetate or nitromethane at different temperatures were determined. The ILs used were methyl trioctylammonium bis(trifluoromethylsulfonyl)imide ([MOA]+[Tf2N]-) and 1-butyl-3- methylimidazolium methyl sulphate [BMIM]+[MeSO4]-. The ternary excess molar volumes (�������� E ) for the mixtures {methyl trioctylammonium bis (trifluoromethylsulfonyl)imide + methanol or ethanol + methyl acetate or ethyl acetate}and (1-butyl-3-methylimidazolium methylsulfate + methanol or ethanol or 1-propanol + nitromethane) were calculated from experimental density values, at T = (298.15, 303.15 and 313.15) K and T = 298.15, respectively. The Cibulka equation was used to correlate the ternary excess molar volume data using binary data from literature. The �������� E values for both IL ternary systems were negative at each temperature. The negative contribution of �������� E values are due to the packing effect and/or strong intermolecular interactions (ion-dipole) between the different molecules. The density and speed of sound of the binary solutions ([MOA]+[Tf2N]- + methyl acetate or ethyl acetate or methanol or ethanol), (methanol + methyl acetate or ethyl acetate) and (ethanol + methyl acetate or ethyl acetate) were also measured at T = ( 298.15, 303.15, 308.15 and 313.15) K and at atmospheric pressure. The apparent molar volume, Vφ , and the apparent molar isentropic compressibility, κφ , were evaluated from the experimental density and speed of sound data. A Redlich-Mayer type equation was fitted to the apparent molar volume and apparent molar isentropic compressibility data. The results are discussed in terms of solute-solute, solute- solvent and solvent-solvent interactions. The apparent molar volume and apparent molar isentropic compressibility at infinite dilution, ��φ �� and κφ ��, respectively of the binary solutions have been calculated at each temperature. The ��φ �� values for the binary v systems ([MOA]+[Tf2N]- + methyl acetate or ethyl acetate or methanol or ethanol) and (methanol + methyl acetate or ethyl acetate) and (ethanol + methyl acetate or ethyl acetate) are positive and increase with an increase in temperature. For the (methanol + methyl acetate or ethyl acetate) systems ��φ �� values indicate that the (ion-solvent) interactions are weaker. The κφ �� is both positive and negative. Positive κφ ��, for ([MOA] + [Tf2N]- + ethyl acetate or ethanol), (methanol + ethyl acetate) and (ethanol + methyl acetate or ethyl acetate) can be attributed to the predominance of solvent intrinsic compressibility effect over the effect of penetration of ions of IL or methanol or ethanol. The positive κφ �� values can be interpreted in terms of increase in the compressibility of the solution compared to the pure solvent methyl acetate or ethyl acetate or ethanol. The κφ �� values increase with an increase in temperature. Negative κφ ��, for ([MOA] + [Tf2N]- + methyl acetate or methanol), and (methanol + methyl acetate) can be attributed to the predominance of penetration effect of solvent molecules into the intra-ionic free space of IL or methanol molecules over the effect of their solvent intrinsic compressibility. Negative κφ �� indicate that the solvent surrounding the IL or methanol would present greater resistance to compression than the bulk solvent. The φ �� values decrease with an increase in the temperature. The infinite dilution apparent molar expansibility, ��φ �� , values for the binary systems (IL + methyl acetate or ethyl acetate or methanol or ethanol) and (methanol + methyl acetate or ethyl acetate) and (ethanol + methyl acetate or ethyl acetate) are positive and decrease with an increase in temperature due to the solution volume increasing less rapidly than the pure solvent. For (IL + methyl acetate or ethyl acetate or methanol or ethanol) systems ��φ �� indicates that the interaction between (IL + methyl acetate) is stronger than that of the (IL + ethanol) or (IL + methanol) or (IL + ethyl acetate) solution. For the (methanol + methyl acetate or ethyl acetate) systems ��φ �� values vi indicate that the interactions are stronger than (ethanol + methyl acetate or ethyl acetate) systems.