Submitted in fulfilment of the academic requirements of Masters in Applied Sciences (Chemistry), Durban University of Technology, 2017. / This thesis forms part of the Durban University of Technology Thermodynamics Research Unit’s project which is aimed at developing a method for determination of the liquid-liquid equilibria (LLE) data for the azeotrope {methanol + water} with an ionic-liquid (IL) using DSA5000M to assess the efficiency of the ionic liquid to be used in liquid-liquid extractions for the recovery and recycling of methanol from petroleum refinery. The objective of this study was to determine the liquid-liquid equilibria data of the azeotrope {methanol + water} using 1-ethyl-3-methylimidazolium ethyl sulfate ionic liquid with the intention to recycle methanol from the Fischer-Tropsch (FT) process by- products in petroleum industries and to utilize it in gasoline additives in a new methanol to gasoline (MTG) petroleum process. LLE studies of systems containing alcohols and water are important due to the increasing demands of oxygenated compounds to produce lead free gasoline. Light alkanols such as methanol and ethanol are reported to be suitable compounds in order to produce lead free gasoline, but the use of methanol in gasoline blends can cause phase separation problems in: 1. dry conditions, these are due to its partial solubility in saturated hydrocarbons. 2. the presence of water from ambient humidity or in storage tanks, this depend on unfavourable distribution factor between aqueous and the hydrocarbon phase. To determine the possibility of separating methanol from water using ionic liquid, the liquid-liquid equilibria data was determined at room temperature, T = 298.15 K and atmospheric pressure to investigate whether it separate from water and/or a non-phase separation if it is used as an additive. The experimental data generated was compared to that of the literature for the system {methanol (1) +toluene (2) + dodecane (3)} and showed good agreement with the literature data with only maximum deviation of ± 0.0015 in the mole fraction using density calculations and ± 0.0092 in the mole fraction when using refractive index calculations The selectivities and distribution coefficients for this system were also calculated and the maximum deviation between the two methods (nD and ρ) was ± 1.33 in selectivities and found to be ±0.001 for distribution coefficients. The maximum deviation in distribution coefficients from literature when using nD calculations for system 1 was ±0.04 and ±0.01 for ρ. For the selectivity values the deviation from that of literature of nD when compared was found to be ± 1.28 and 0.29 for ρ respectively. The selectivity values from the density calculations were found to be in the range 2.82 – 7.66 for this system with the distribution coefficient values reported in the range 0.17 – 0.23. In the second system (system 2) the generated experimental data was also compared to that of the literature for the system {water (1) + methanol (2) + cyclohexane (3)} and in good agreement with literature values with only maximum deviation of ± 0.0091 in the weight fraction based on density calculations. The selectivities and distribution coefficients were also calculated and the maximum deviation between the literature and the experimental data was computed to be at ± 0.0003 for selectivity and ±0.09 in distribution coefficient. The selectivity values were found to be in a range 0.00 - 0.04 for this system and were constant throughout the phases but significantly less than one; with the distribution coefficient values in the range 0.00 – 0.008. For 1-ethyl-3-methylimidazolium ethyl sulfate system (Ionic liquid system) the selectivity values were not constant throughout the two-phase region and the values were found to be in the range 0.63 -0.99 still below one which indicates that the ionic liquid used in this study could not be considered as a potential solvent for the separation of the investigated azeotrope. The distribution coefficients for this system were determined and found to be in the range 0.23 – 0.74. The certainty and reliability of experimentally measured tie-line data was ascertained by applying Othmer-Tobias (OT) correlations and the Non-Random, Two Liquid (NRTL) parameters. The OT correlations for system 1 was linear and indicated the certainty of the five tie-lines prepared for this system. In system 2 the OT correlation was not linear and indicated extensively high errors as well as high systematic multiplicative and additive errors in calculations of mole fractions. For the IL system the OT correlation was linear throughout the whole tie-line range and indicated the adequate precision, which denotes that the investigation was carried out with minimal random and systematic errors and indicated the efficiency of the DSA 5000 M to generate the liquid-liquid equilibria data. All the ternary systems were well correlated and in good agreement with the estimated NRTL data. It was only system 1{methanol (1) + toluene (2) + dodecane (3)} that gave a high maximum deviation ( %RSMD) of 1.288 when using the RI measurements with the minimum error margin of 0.6320, this account as to why RI measurements were not applied in other systems (system 2 and ionic liquid system). Similarly for the same system; system 1{methanol (1) + toluene (2) + dodecane (3)} when using the density measurements; the NRTL model gave a maximum deviation of 0.5620 and minimum error margin of 0.2590. The NRTL obtained for system 2 {water (1) + methanol (2) + cyclohexane (3)} gave the maximum deviation of 0.5752 and minimum error margin of 0.0127. The NRTL for the ionic liquid ternary system {[EMIM][EtSO4](1) + methanol (2) + water (3)}showed a good agreement between the experimental data and the NRTL model tie- line data with the %RSMD of 1.0201 on the upper limit and 0.1620 as a lower deviation. / M

Submitted in the fulfilment of the requirement for the Degree of Doctor of Philosophy: Chemistry, Durban University of Technology, 2016. / The work conducted in this study comprised three aspects: syntheses, characterizations, and multi-component liquid-liquid extractions. The main objectives of the project were: (1) to evaluate the efficacy and efficiency of ionic liquids to extract aromatic components from catalytic reformates and paint solvent wastes, and (2) to validate the method(s) used in this project to qualitatively and quantitatively analyze the aromatic molecules (BTEX) in multi-component mixtures. Therefore, this research critically investigated the major effects of the chosen ionic liquids as extractive solvents for the recovery of BTEX components from model and industrial organic mixtures. The project was concerned with the nature of solvents currently used in most industries for the separation by extraction of aromatic hydrocarbons from non-aqueous or organic mixtures. Most solvents currently employed for this purpose are highly volatile; hence they contribute significantly towards environment pollution. In addition, the extraction efficiency of these conventional solvents is limited only to mixtures containing aromatic hydrocarbons of 20% or more. Furthermore, conventional solvents are organic compounds which are generally toxic, flammable, and expensive to recover or regenerate from extract phases due to methods which involve several steps. In addition, they demand high energy input for the distillation steps. used in the analysis of aromatic components were evaluated for validity. According to the literature no such work was carried out by previous researchers. The study targeted four ionic liquids, namely, 1-ethyl-3-methylimidazolium ethyl sulphate [EMIM][ESO4], 1-ethyl-3-methylpyridinium ethyl sulphate [EMpy][ESO4], 1- Butyl-1-methyl-2-pyrrolidonium bromide [BNMP][Br], and 1,1-Dimethyl-2- pyrrolidonium iodide [MNMP][I] in an attempt to address this concern. These ionic liquids were synthesized and characterized in our laboratories using previously accepted methods. After synthesis and purification, they were characterized by techniques including FTIR, 1H-NMR, and 13C-NMR. The densities and moisture content of both the synthesized and standard ionic liquids were also determined using density meters and Karl-Fischer apparatus, respectively. The extractions were carried out on both the model and industrial mixtures using ionic liquids. Each ionic liquid was mixed with a target mixture in a water-jacketed vessel and then stirred vigorously at constant temperature achieved by a thermostatically controlled water-bath. After a selected period of time the operation was stopped and the resulting mixture was left to stand overnight to allow phase equilibration to be reached. The two phases were then separated and analyzed for the content of individual aromatic components in each phase using GC-FID calibrated with external standards of the components present in the mixtures being investigated. According to the results obtained from the synthesis and characterization methods the percentages yield of ionic liquids were reasonably high (> 95%). In addition, spectral studies showed high purity with fewer traces of impurities based on the observed relative intensities. Results from GC-FID indicated a relatively lower concentration of aliphatic hydrocarbons in the extract phase. On the other hand, the concentrations of aromatic II components in the extract phase were relatively higher than those of aliphatic hydrocarbons. The results obtained from the three extraction stages showed the total recovery of greater than 50% for the aromatic components. This suggests that at least six extraction stages would be required in order to achieve a total recovery of 100% aromatic components which is an indication of good efficiency. Also noticeable was that the first extraction stages for all ionic liquids recovery values were much higher than those values obtained from successive stages which showed approximately the same extraction results. In most experiments, 1-ethyl-3-methylpyridinium ethyl sulphate gave higher recovery values than the other three ionic liquids. It was also noted that the recovery values obtained from the extractions performed on model mixtures of the entire concentration range (0.5 – 25%) of individual aromatic components did not show any significant difference. Proportional difference in recoveries occurred across the entire concentration range of model mixtures. The results also indicated that the solubility of aromatic hydrocarbons in the ionic liquids decreases in the order: benzene > toluene > ethyl benzene >xylenes. This phenomenon is attributed to a decrease in π-π, cation- π, cation- anion interactions occurring between the ionic liquid and each of the aromatic molecules in this order. The recovery values for BTEX ranged from 80 to 120 % by volume for the three extraction stages. This is in line with results previous research studies carried out on liquid-liquid extractions involving ternary systems containing only one aromatic component in each mixture. Therefore this study shows that ionic liquids are capable extraction solvents for simultaneous recovery of the aromatic components from any organic mixtures containing low to high BTEX concentrations. In addition, the outcomes of this project have proved that ionic liquids are economically viable as potential extraction solvents since they can be easily recycled and reusable many times without any noticeable degradation. The results of this study are envisaged to make significant contributions to the current research efforts aimed at achieving greener environments and minimization of global warming. The findings of this project are also geared to boost the economy of our country through job creation using economically viable methods. / D

Submitted in fulfillment of the requirements for the degree of Doctor of Technology: Chemistry, Durban University of Technology, Durban, South Africa, 2017. / The thermodynamic properties of mixtures involving ionic liquids (ILs) with organic acid (acetic acid or propanoic acid) or acetonitrile at different temperatures were determined. The ILs used were imidazolium-based: 1-ethyl-3-methylimidazolium ethyl sulphate [EMIM]+[EtSO4]-, 1-butyl- 3-methylimidazolium thiocyanate [BMIM]+[SCN]- and 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide ([BMIM]+[Tf2N]-. The ternary excess molar volume (V E ), isentropic compressibility (ks) and deviation in isentropic compressibility ( ks123 ) were determined for four ternary liquid mixtures of {[EMIM]+[EtSO4]- or [BMIM]+[SCN]− + acetic or propionic acid + acetonitrile} at different temperatures (293.15, 298.15, 303.15, 308.15 and 313.15) K and at a pressure of 0.1 MPa with aid of the experimental density (ρ), speed of sound (u) data. The calculated data were correlated by using the Cibulka equation with the help of Redlich–Kister parameters obtained from fitting the Redlich–Kister equation for the corresponding binary systems. Furthermore, the density and speed of sound were also measured for eight corresponding binary systems at the same experimental conditions. The binary excess molar volume, isentropic compressibility and deviation in isentropic compressibility were also calculated for measured systems and fitted to the Redlich–Kister equation to obtain the Redlich–Kister parameters as well as to check the accuracy of measured data which were used to correlated experimental data using Cibulka equation. These results were discussed, in terms of how the sign and magnitude of thermodynamic functions were influenced by the addition of a third component to liquid systems. Also, the possible molecular and pair-wise interactions between component molecules and the effect of temperature on the thermophysical and thermodynamic properties were predicted. In addition, the work focussed on application of ([BMIM]+[Tf2N]-) ionic liquid for the separations of (alkane/aromatic), (alkane/alk-1-ene), (cycloalkane/aromatic) and (water/alkan-1-ol) using gas- liquid chromatography (GLC) technique. The activity coefficients at infinite dilution, , for 31 organic solutes (alkanes, cycloalkanes, alkenes, alkynes, aromatics, alkanol and ketones) and water in ionic liquid were measured at temperatures of (323.15, 333.15, 343.15, 353.15 and 363.15) K. Stationary phase loadings of (42.83 and 68.66) % by mass were used to ensure repeatability of E , measurements. Partial molar excess enthalpies at infinite dilution, H1 , were also determined. The selectivities, S , and capacities, k , were determined for the above separations. The separating ij j ability of the investigated ionic liquid was compared with previously investigated ionic liquids and industrial solvents such as sulfolane, n-methyl-2-pyrrolidine (NMP) and n-formylmorpholine (NFM). The results obtained suggested that in general, the [BMIM]+[Tf2N]− had outperformed the conventional solvents such as sulfolane, NMP and NFM in terms of selectivity, while the [BMIM][Tf2N] had in general, performed better overall when the performance index was used for comparison. / D

The complexation properties of the two isomers of the cyclic polyether dicyclohexyl-18-crown-6 are examined in aqueous solution for a series of metal ions at various reaction temperatures. The results are discussed in terms of size relationships and salvation characteristics of both polyether and metal ions. ΔCp° values are determined from the temperature dependence of the ΔH° values. A discussion of the errors involved in the determination of ΔH° from the temperature dependence of log K values is also included. Comparisons are made between the results of this study and those of a similar study by H. K. Frensdorff, E. I. duPont de Nemours and Co., Wilmington, Delaware, in press. The complexation reactions of dicyclohexyl- and dibenzo-18-crown-6 and benzo-15-crown-5 with Na^+ and K^+ ions are reported in non-aqueous solvents and methanol-water mixtures. The results are discussed with reference to their application in model systems of ion transport. In general the stabilities of the polyether-cation complexes were found to increase with decreasing dielectric constant of the solvent medium. In the methanol-water mixtures large compensating ΔH° and ΔS° changes were observed above 70 weight percent methanol, while the log K values showed a nearly linear increase with increasing methanol concentration. Salvation of the polyethers and metal ions and complexation of ion pairs in non-aqueous solvents are discussed.

Abstract not available

This work showcases the utility of switchable materials. Included are a switchable room-temperature ionic liquid, a switchable solvent, a switchable heterogeneous catalyst system, and a switchable gel. First, the switchable ionic liquid 2-butyl-1,1,3,3-tetramethylguanidium methylcarbonate is fully investigated. Its use in a complete chemical process (including reaction, separation, reformation, and recycle) is demonstrated with several reactions. Furthermore, its potential use for bitumen separation and purification and SO2 capture/isolation are discussed, and preliminary data is presented. Next, piperylene sulfone (PS), a switchable solvent, is synthesized and fully characterized. Anionic nucleophilic substitution reactions were performed in PS, the products were isolated in high yields, and then the PS was reformed for reuse. Then, we designed an immobilized fluorous microphase system that uses F-MonoPhos to induce high enantioselectivities as a switchable heterogeneous catalyst system. Finally, stable reversible polyethyleimine-CO2 gels have been synthesized with 1-octanol. Our findings indicate that PEI-1200/octanol/CO2 gels have potential as a possible drug carrier matrix for transdermal delivery applications.

Novel solvents utilizing a reversible CO₂ induced property switch are presented. The synthetic procedure for designing the solvents is discussed, along with detailed characterizations on both solvent forms to serve as a tool for optimal solvent identification as well as future solvent design. A reflectance infrared spectroscopic technique is introduced to allow for the examination of CO₂ and solvent composition under high pressures and temperatures. The magnitude of solvent property changes afforded by this "switch" creates opportunities for sustainable processing; discussed are the application to coupling reactions and separations, and CO₂ capture. The switchable solvents are shown to serve as effective media for running reactions, with the switch providing facile recovery of products and catalysts for solvent recycling. Lastly, the switch itself is exploited to provide for the separation of CO₂ from low partial pressure feed streams, and structure-property relationships were successfully used to develop next generation materials with enhanced absorption capacities. The viscosity of the solvents, as a function of temperature and composition, is also presented.

Ionic liquids (ILs) are liquid organic salts at room temperature which are composed of only ions (cations and anions). Ionic liquids are regarded as “novel solvents” and have been gaining attention as alternatives to volatile molecular organic solvents. Ionic liquids have outstanding properties, such as negligible vapor pressure (no or limited evaporation or volatilization), low melting point, thermal stability, and ionic conductivity. They can be used in efficient and clean energy production and storage. The synthesis of the low-cost and performance-effective ionic liquids using inexpensive raw materials is presented and characterized. Characterization was done using Thermogravimetric Analysis (TGA), Fourier Transform Infrared Spectroscopy (FTIR), and Scanning Differential Thermometry (DSC-TGA). Cost effective ionic liquids were synthesized and characterized and then compared to commercially available ionic liquids. Results for newly synthesized ionic liquids suggest that these cost effective ionic liquids were electroconductive and thermally stable when compared to the raw materials used for synthesis of ionic liquids. The thermal stability of these ionic liquids was less, however, when compared to the regular higher cost ionic liquids. FTIR characterization also provided secondary evidence on expected functional groups of newly synthesized ionic liquids. Viscosity of the syntehsized ionic liquids was higher when comapred to the commercially avaialable ionic liquids.

Efficient heat management in energy intensive applications such as server and data centers has become a national concern due to the magnitude of the energy consumed. In that matter, the absorption refrigeration system is an attractive solution because the abundant waste heat available in the data centers can be recycled to run the heat pump, which will bring about significant cooling cost savings. The use of absorption refrigeration has been limited due to the drawbacks related to the working fluids in commercially available equipment. Recently, ionic liquids (ILs) have been suggested as the absorbent in absorption heat pumps due to their tunable properties, negligible volatility and high thermal stability. The non-random-two-liquid-model was initially used to analyze the feasibility of the new IL based working fluid. Hydrofluorocarbons (HFCs) were paired with IL absorbents due to their good properties as refrigerants. The cooling-to-total-energy (CE) efficiency had a local maximum with respect to desorber temperature due to the solubility limit at lower temperatures and large heating requirements at higher temperatures. The waste heat recycling coefficient of performance (COP) continually increased with respect to desorber temperature and among the HFCs studied in this work, R134 gave the highest COP value, which is up to 40 times higher than that of typical vapor compression systems and 60 times higher than NH3/H2O and H2O/LiBr absorption refrigeration systems. A Redlich-Kwong equation of state (RK-EOS) was employed for accurate computation of mixture properties over a wide range of operating conditions. Analysis using the RK-EOS model showed that the CE trend in refrigerants followed the trend of solubility in the [bmim][PF6] IL. However, the trend in COP was different from that of CE as the operating pressure ranges became an important factor. Required pumping work of the working fluids has also been analyzed using a two phase pressure drop equation and the results show that the impact of viscous IL flow is insignificant compared to the total pumping work. The HFCs studied in this work have very similar structures. However, the extent of solubility and system efficiency in the same IL, [bmim][PF6], made a large difference. Most surprisingly, even when the refrigerant had the same chemical formula, the change in fluorine position in tetrafluoroethane showed significantly different system performance. The symmetrical tetrafluoroethane had superior CE and COP over the asymmetrical tetrafluoroethane most likely due to the higher probability to form hydrogen bonding with the absorbent. The computational results for various HFC/IL pairs show that in selecting the working fluid pairs, the refrigerant should have high overall solubility in the IL and a large gradient of solubility with respect to temperature. Also, refrigerants with small pressure ranges are preferred. In addition to the simulation study, a bench-top absorption refrigeration system was built and operated using IL based working fluids for the first time. The effect of cooling was observed by operating the test system. The experimental results were congruent with the predictions from the modeling work. In conclusion, an absorption refrigeration system based on the IL chemical compressor has been shown to be a promising solution in applications which need efficient cooling and generate abundant waste heat.

In this work, ionic liquids (ILs) were investigated for use as battery electrolytes. The ILs were synthesized from quaternary ammonium and phosphonium salts and TFSI-. A dendrite free lithium metal anode was demonstrated by deposition of a lithium-potassium alloy. Several phosphonium ILs were synthesized using the TFSI- and PF6- anions until a room temperature IL was obtained. The smaller size, highly symmetric PF6- anion yielded high melting point salts, while TFSI- yielded much lower melting point ILs. When a room temperature IL, Bu3HexP+TFSI-, was obtained the analogous ammonium IL, Bu3HexP+TFSI-, was synthesized and compared. The phosphonium-based ionic liquid showed improved stability and physical properties compared to the analogous ammonium-based IL. The phosphonium-based IL had higher conductivity, 0.43 mS/cm, than the ammonium-based IL, 0.28 mS/cm. The addition of LiTFSI to both ILs led to a decrease in conductivity and increase in viscosity. The lower viscosity and higher stability of the phosphonium-based IL led to higher current density and stability for electrodeposited lithium metal. IL reduction interfered with lithium deposition reflecting lower coulombic efficiencies and giving the appearance of an unstable lithium couple. An optimum deposition potential was found which was bounded by the electrochemical stability of each IL. The stability of lithium in the ILs increased at lower temperature due to slower reactivity with the IL. Addition of higher quantities of lithium ions caused a higher fraction of the cathodic current going to lithium deposition that was reoxidized. The stability of lithium in the ILs increased at lower temperature due to slower reactivity with the IL. The electrodeposition and reoxidation of potassium was also demonstrated. Deposition of a lithium-potassium alloy caused slight increases in the cathodic and anodic currents along with higher coulombic efficiencies. Also, it was found that a lithium-potassium alloy could be deposited at high current for long times without the occurrence of dendrites.