Faculty of Engineering and Built Environment
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Item Infinite dilution activity coefficients and thermodynamic properties of selected organic solutes and water dissolved in 1, 6-hexanediol(Elsevier BV, 2020-12) Nkosi, Nkululeko; Tumba, Kaniki; Ngema, Peterson; Ramsuroop, SureshThe experimental activity coefficients (γ13∞) and gas-to-liquid partition coefficients (KL) at infinite dilution for 34 organic solutes and water were determined in 1.6-hexanediol (HDO) by the gas–liquid chromatography technique (GLC) in the temperature range from (323.15 to 353.15) K. Fundamental thermodynamic functions such as excess partial molar enthalpy (ΔHiE,(∞)), excess partial molar Gibbs energy, (ΔGiE,∞) and entropy, (TrefΔSiE,∞) at infinite dilution were calculated from experimental values of γ13∞. Reported data were discussed in terms of solvent-solute interactions, heat effects and mixing spontaneity. Selectivity (Sij∞) and capacity (kj∞) related to different separation problems were calculated from γ13∞ data and compared to the literature values for selected ionic liquids (ILs), deep eutectic solvents (DESs) and industrial solvents. New data reported in this study suggest that HDO may be proposed as an alternative solvent for the separation of alkanes-pyridine and alkanes-thiophene systems. Furthermore, it was found that adding a hydrogen bond acceptor to HDO enhances its performance as a separation solvent.Item Infinite dilution activity coefficient measurements for 1-Methyl-4-(1-methylethenyl)-cyclohexene as a green solvent for separation(American Chemical Society (ACS), 2022-04-14) Mbatha, Banzi Patrick; Ngema, Peterson Thokozani; Nkosi, Nkululeko; Ramsuroop, SureshInfinite dilution activity coefficients for various solutes, which include alkanes, alkenes, alkynes, cycloalkanes, heterocycles, alcohols, aromatics, ketones, ethers, nitrile, and water, in a 1-methyl-4-(1-methylethenyl)-cyclohexene solvent were measured using gas-liquid chromatography at 303.15, 313.15, and 323.15 K. The focus of this study was to assess 1-methyl-4-(1-methylethenyl)-cyclohexene as a green solvent for separation processes. 1-Methyl-4-(1-methylethenyl)-cyclohexene, a nonpolar monoterpene solvent extracted from essential oils of citrus peels, was investigated as an alternative solvent to currently employed conventional organic solvents in separation processes. Through experimental infinite dilution activity coefficients, γ13∞, the values of partial molar excess enthalpy at infinite (δHiE,∞) were obtained using the Gibbs-Helmholtz equation. The infinite dilution selectivity (Sij∞) and capacity (δkj∞) values were calculated from the experimental limiting activity coefficients and were compared with deep eutectic solvents, ionic liquids, and industrial solvents. From this study, it was observed that 1-methyl-4-(1-methylethenyl)-cyclohexene is not suitable to be used as an alternative for separation processes. In addition, activity coefficients at infinite dilution of different organic solutes in hexadecane were measured at various temperatures to validate the reliability and accuracy of gas-liquid chromatography. Finally, the experimental data were modeled using Aspen Plus, compared with experimental data, and found to be in good agreement.Item Infinite dilution activity coefficient measurements of organic solutes in selected deep eutectic solvents by gas-liquid chromatography(2018) Nkosi, Nkululeko; Ramsuroop, Suresh; Tumba, Kaniki Armel; Osman, KhalidMany separation processes in the chemical and petrochemical industries are energy intensive, and unfortunately, involve a range of solvents that are environmentally harmful and destructive. Alternative, sustainable separation techniques are desired to replace these conventional methods used in the separation of azeotropic as well as close-boiling mixtures, with the intention of reducing energy costs and adverse impact on the environment. In the present study, a new class of solvents called deep eutectic solvents (DESs) of Type III were investigated as alternatives to conventional solvents currently employed in separation processes. DESs are classified as ‘green’ solvents because of a range of favourable properties including lower cost, desirable solubility properties and reduced environmental impact (Abbott et al., 2003b; Smith et al., 2014). The infinite dilution activity coefficients (IDACs) values of 24 solutes – including alk-1-anes, alk-1-enes, alk-1-ynes, cycloalkanes, alkanols, alkylbenzenes, heterocyclics, esters, and ketones – were measured at 313.15, 323.15, 333.15 and 343.15 K by gas-liquid chromatography (GLC) in DESs. The four investigated DESs were as follows: 1) Tetramethylammonium chloride + Glycerol (DES1); 2) Tetramethylammonium chloride + Ethylene Glycerol (DES2); 3) Tetramethylammonium chloride + 1,6 Hexanediol (DES3); and 4) Tetrapropylammonium bromide + 1,6 Hexanediol (DES4). This work focused on the performance of DESs as extractive solvents for selected azeotropic and close-boiling binary mixtures. The two key performance criteria for these extractive solvents – selectivity and capacity – were determined from experimental infinite dilution activity coefficients (IDACs) of various solutes. The effect of solute molecular structure on IDAC values was investigated. Moreover, the effect of varying the hydrogen bond donors (HBDs) in DESs on IDAC values was examined. Partial excess molar enthalpies at infinite dilution were determined from the experimental IDAC data. Moreover, common industrial separation problems were selected to investigate DES potential to separate various mixtures by determining selectivity and capacity at infinite dilution. The results obtained in this study indicate that the use of a long carbon chain HBDs greatly decreases miscibility of DESs with organic solutes. For systems such as n-heptane - toluene, acetone - ethanol, cyclohexane - benzene and n-hexane - benzene systems, DES4 was the best solvent regarding the separation performance index. However, further investigation for DES4 by measurements of vapour-liquid equilibria (VLE) and liquid-liquid equilibria (LLE) data is suggested, as these data would provide additional pertinent information regarding the separation of such mixtures using DES4. The data produced from this study can be used to extend the applicability range of predictive models such as Universal Quasi- Chemical Functional Group Activity Coefficients (UNIFAC) and modified UNIFAC (Do) which are already incorporated in some chemical engineering process simulators.