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Research Publications (Applied Sciences)

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    Influence of epoxy group in 2-pyrrolidonium ionic liquid interactions and thermo-physical properties with Ethanoic or Propanoic acid at various temperatures
    (ACS Publications, 2016) Vasanthakumar, Arumugam; Redhi, Gan G.; Gengan, Robert Moonsamy
    In this present study, the interaction between a carboxylic acid and ionic liquids, in terms of their binary mixtures and corresponding thermo-physical properties, was investigated. Here, the novel ionic liquid (IL) [EPMpyr]+[Cl]− was synthesized, and it has been mixed with ethanoic or propanoic acids. The influence of the epoxy group in this ionic liquid was more strongly affected with the acids, and their physicochemical properties at varied temperatures are discussed in term of density (ρ), viscosity (η), speed of sound (u), and refractive index (n) measurements. The density (ρ), speed of sound (u), viscosity (η), and refractive index (n) of the IL, ethanoic acid, propanoic acid, and their corresponding binary mixtures {[([EPMpyr]+[Cl]− (1) + ethanoic or propanoic acid (2)} have been measured at T = (293.15–313.15) K and at P = 0.1 MPa. The theoretical thermodynamic properties of excess molar volumes (VmE), isentropic compressibility (ks), deviation in isentropic compressibility (Δks), and intermolecular free length (Lf) are calculated using experimental density and speed of sound data. The VmE and Δks values for both binary mixtures were found to be negative over the entire mole fraction range of composition at all the investigated temperatures. These results suggest the existence of specific interactions between components in the molecules. The experimental data could be helpful to understand the molecular interactions between the IL and carboxylic acid combinations. The experimental data were fitted to the Redlich–Kister polynomial equation.
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    Synthesis, characterization and thermophysical properties of ionic liquid N-methyl-N-(2′,3′-epoxypropyl)-2-oxopyrrolidinium chloride and its binary mixtures with water or ethanol at different temperatures
    (Elsevier, 2016) Vasanthakumar, Arumugam; Bahadur, Indra; Redhi, Gan G.; Gengan, Robert Moonsamy; Anand, Krishnan
    A novel ionic liquid, namely, N-methyl-N-(2′,3′-epoxypropyl)-2-oxopyrrolidiniumchloride [Epmpyr]+[Cl]− was synthesized and characterized by different techniques such as NMR (1H and 13C), FTIR, and elemental analysis. The water content of the ionic liquid was checked by Karl Fisher titration. Further, the density, ρ, and speed of sound, u, were measured for the above ionic liquid and the corresponding binary systems with water or ethanol at different temperatures ranging from (293.15 to 313.15) K. The derived thermodynamic properties for instance excess molar volumes, VE m isentropic compressibility, κs, and deviation in isentropic compressibility, Δκs, were investigated from the density and speed of sound data, respectively. It is noted that density and speed of sound of the ionic liquid and its binary mixtures were decreased with increase in temperature, whereas excess molar volume, isentropic compressibility, and deviation in isentropic compressibility values increased. Derived properties such as excess molar volumes, and deviation in isentropic compressibility data were fitted to the Redlich-Kister polynomial equation. The measured and calculated data were interpreted in terms of intermolecular interfaces and structural effects between similar and dissimilar molecules upon mixing.
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    Ionic liquid based high performance electrochemical sensor for ascorbic acid in various foods and pharmaceuticals
    (Elsevier, 2016-07-18) Kumar, Bhajanthri Natesh; Arumugam, Vasanthakumar; Chokkareddy, R.; Redhi, Gan G.
    In the present study, 1-butyl-3-methyl imidazolium tetra fluoroborate ionic liquid (IL), boron nitride (BN) and magnetite nanoparticles (Fe3O4NPs) based nanocomposite (IL-BN-Fe3O4NPs) was successfully synthesised and used to fabricate glassy carbon electrode (GCE) for the determination of ascorbic acid (AA). The nanocomposite was characterized by Fourier transformation infrared spectroscopy (FTIR), x-ray diffraction spectroscopy (XRD), scanning electron microscopy (SEM), electron diffraction spectroscopy (EDS) and transmission electron micros-copy (TEM) techniques to observe the surface morphology. Cyclic voltammetry (CV) was performed to assess the electrochemical performance of IL-BN-Fe3O4NPs/GCE towards ascorbic acid (AA) in 0.1 M phosphate buffer solu-tion (PBS) at pH 7. The CV results obtained reveal that the significant enhancement of anodic peak current with increased sensitivity and conductivity. The differential pulse voltammetric results obtained indicates the linear increment of electrochemical signals with an increase in the concentration of AA in the range of 1–12 μM. Based on the calibration plot, limit of detection and limit of quantification were calculated and found to be 0.042 and 0.139 μM respectively. The electrochemical sensor showed outstanding sensitivity, selectivity, repeat-ability and stability. In addition to this IL-BN-Fe3O4NPs/GCE sensor was practically applied for the routine analysis of AA in various food and pharmaceutical samples.
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    Industrial application of ionic liquids for the recoveries of spent paint solvent
    (Elsevier, 2016) Moodley, Kandasamy; Mabaso, Mbongeni Hezekia; Bahadur, Indra; Redhi, Gan G.
    The recovery of industrially valuable organic solvents from liquid waste, generated in chemical processes, is economically crucial to countries which need to import organic solvents. In view of this, the main objective of this study was to determine the ability of selected ionic liquids, namely, 1-ethyl-3-methylimidazolium ethylsulphate, [EMIM][ESO4] and 1-ethyl-3-methylpyridinium ethylsulphate, [EMpy][ESO4] to recover aromatic components from spent paint solvents. Preliminary studies done on the liquid waste, received from a paint manufacturing company, showed that the aromatic components were present in the range of (6–21)% by volume. The separation of the aromatic components was performed with the ionic liquids listed above. The phases, resulting from the separation of the mixtures, were analysed with a gas chromatograph (GC) coupled to a FID detector. Chromatograms illustrate that the chosen ZB-Wax-Plus column gave excellent separation of all components of interest from the mixtures, including the isomers of xylene. The concentrations of aromatics recovered from the spent solvents were found to be in the % ranges of (13 − 33) and (23–49), respectively for imidazolium and pyridinium based ionic liquids. These results also show that there is a significant correlation between π-character of ionic liquids and the level of extraction. It is therefore concluded that ionic liquids have the potential for macro-scale recovery of re-useable solvents present in liquid waste emanating from paint manufacture.
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    Separation of aromatic solvents from oil refinery reformates by a newly designed ionic liquid using gas chromatography with flame ionization detection
    (Wiley Online Library, 2015-02-26) Bahadur, Indra; Singh, Prashanth; Kumar, Sudharsan; Moodley, Kandasamy; Mabaso, Mbongeni Hezekia; Redhi, Gan G.
    The aim of this study was to determine whether the new ionic liquid, N,N-dimethyl-2-oxopyrrolidonium iodide, synthesized in our laboratory is a suitable solvent for the separation of aromatic components benzene, toluene, ethylbenzene, and xylenes from petroleum mixtures (reformates) in liquid–liquid extraction. In pursuance of the above aim, a method to extract all components of a mixture, containing four aromatic components simultaneously, was developed. A new ionic liquid and a previously used liquid were compared for their extraction abilities. These ionic liquids were, respectively, N,N-dimethyl-2-oxopyrrolidinium iodide and 1-ethyl-3-methyl imidazolium ethyl sulfate. The concentrations of each benzene, toluene, ethylbenzene, and xylenes component in the extract and raffinate phases were measured by gas chromatography with flame ionization detection as volume percent to determine the extraction ability of the ionic liquids. The results obtained for both the reformate samples and model mixtures indicated that the new ionic liquid was effective as an extracting solvent for the recovery of aromatic components from reformates. Also the analysis results, using gas chromatography with flame ionization detection, for the reformate samples were as good as the results obtained by a local oil refinery. The extraction results also show that the developed method is very suitable for the separation and analysis of aromatic components in reformates.
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    Phase equilibria measurements of ternary mixtures (sulfolane + a carboxylic acid + pentane) at 303.15 K
    (Elsevier, 2015) Xhakaza, Nokukhanya Mavis; Bahadur, Indra; Redhi, Gan G.; Ebenso, Eno E.
    The Liquid–liquid equilibrium (LLE) data for the mixtures of {sulfolane (1) + a carboxylic acid (2) + pentane (3)} at 303.15 K are reported, where a carboxylic acid refers to acetic acid, propanoic acid, butanoic acid, 2-methylpropanoic acid, pentanoic acid and 3-methylbutanoic acid. The shape of the binodal curves show that the solubility of pentane in (sulfolane + a carboxylic acid) is very much dependent on the carbon number and the type of carboxylic acid. The area of the two phase heterogeneous region for the carboxylic mixtures decreases in the order of acetic acid > propanoic acid > 2-methylpropanoic acid ∼ butanoic acid > pentanoic acid ∼ 3-methylbutanoic acid. Three parameter equations have been fitted to the binodal curve data. The NRTL and UNIQUAC models were used to correlate the experimental data. The NRTL model fitted the experimental data better than the UNIQUAC model with the average mean square deviation of 0.072 mole fraction as compared to 0.359 mole fraction for UNIQUAC model.
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    Influence of the alkyl group on thermophysical properties of carboxylic acids in 1-butyl-3-methylimidazolium thiocyanate ionic liquid at various temperatures
    (Elsevier, 2015) Redhi, Gan G.; Ebenso, Eno E.; Singh, Suren; Bahadur, Indra; Ramjugernath, Deresh
    In the present study, influence of the alkyl group and temperature on the interactions between the carboxylic acid and ionic liquid (IL) mixtures were discussed in term of density and sound velocity measurements. The IL used in this study was 1-butyl-3-methylimidazolium thiocyanate ([BMIM]+[SCN]−). The density (ρ), and sound velocity (u), of the IL, acetic acid, propionic acid, and their corresponding binary systems {[BMIM]+[SCN]− (x1) + acetic or propionic acid (x2)} have been measured at T = (293.15, 298.15, 303.15, 308.15 and 313.15) K and at p = 0.1 MPa. The excess molar volumes, View the MathML sourceVmE, isentropic compressibility, κs, and deviation in isentropic compressibility, Δκs, were calculated using experimental density and sound velocity data, respectively. 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 IL and carboxylic acid mixtures.
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    Liquid–liquid equilibria measurements of ternary systems (acetonitrile + a carboxylic acid + dodecane) at 303.15 K
    (Elsevier, 2015) Redhi, Gan G.; Bahadur, Indra; Xhakaza, Nokukhanya Mavis
    Liquid–liquid equilibrium (LLE) data are reported for the ternary mixtures of (acetonitrile + a carboxylic acid + dodecane) at 303.15 K under atmospheric pressure, where a carboxylic acid refers to acetic acid, propanoic acid, butanoic acid, 2-methylpropanoic acid, pentanoic acid and 3-methylbutanoic acid. The area of the two-phase heterogeneous region for the carboxylic acid mixtures decreases in the order: acetic acid > propanoic acid > butanoic acid > 2-methylbutanoic acid > pentanoic acid > 3-methylbutanoic acid. The relative mutual solubility of each of the carboxylic acids is higher in acetonitrile layer than in dodecane layer. Three 3-parameter equations have been fitted to the binodal curve data. The NRTL and UNIQUAC models were used to correlate the experimental data. The NRTL model fitted the experimental data far better than the UNIQUAC model with the average mean square deviation of 0.0030 mole fraction as compared to 0.2870 mole fraction for UNIQUAC. Selectivity values for solvent separation efficiency were calculated from the tie-line data and show that separation of carboxylic acids from dodecane is feasible by extraction with acetonitrile.
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    Density and speed of sound of 1-ethyl-3-methylimidazolium ethyl sulphate with acetic or propionic acid at different temperatures
    (Elsevier, 2014-11) Singh, Sangeeta; Bahadur, Indra; Redhi, Gan G.; Ramjugernath, Deresh; Ebenso, Eno, E.
    In this work, new density, ρ, and speed of sound, u, were measured for IL, acetic acid, propionic acid, and their binary systems {IL (x1) + acetic or propionic acid (x2)} at 293.15, 298.15, 303.15, 308.15 and 313.15 K under at-mospheric pressure. The IL used in this study was 1-ethyl-3-methylimidazolium ethyl sulphate ([EMIM]+[EtSO4]−). The derived properties such as excess molar volumes, Vm, isentropic compressibility, κs, and deviation in isentropic compressibility, Δκs, were calculated using experimental density and speed of sound data, respectively. Derived properties such as excess molar volumes, Vm, and deviation in isentropic com-pressibility, Δκs, data were fitted to the Redlich–Kister polynomial equation. The measured and calculated data were interpreted on the basis of intermolecular interactions and structural effects between like and unlike mol-ecules upon mixing.