vi, 164 leaves : ill. ; 26 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1977

Thesis (Ph.D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1977.

Thesis (Ph.D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2009. / Committee Chair: Janata, Jiri; Committee Member: Bunz, Uwe; Committee Member: Collard, David; Committee Member: Josowicz, Mira; Committee Member: Kohl, Paul.

Thesis (M.Sc.Eng.)-University of KwaZulu-Natal, Durban, 2009. / Full text also available online. Scroll down for electronic link.

Ionic liquids (ILs), consisting of ions that are liquid at ambient temperatures, can act as solvents for a broad spectrum of chemical processes. These ionic liquids are attracting increasing attention from industry because they promise significant environmental as well as product and process benefits. ILs were used as solvents for two industrially important homogeneous reactions namely metathesis of 1-octene and the hydroformylation of vinyl acetate. In the metathesis of 1-octene, several reaction parameters were investigated, including temperature, catalyst (type and concentration) and influence of ionic solvent and conventional solvents. Temperature and catalyst concentration were found to be rate-determining factors, but played smaller roles in determining the outcomes of the reactions compared to the influence of individual ILs. It was discovered that more polar ILs were favourable in producing high rates and selectivities. Imidazolium-based cations and tetrafluoroborate anions were superior in activity when compared to other combinations of cations and anions. The addition of catalyst promoters such as phenol and tin(II) chloride were also investigated and found to enhance metathesis rates in “neat” reactions. These catalyst promoters inhibited metathesis rates when used in combination with ILs. In the hydroformylation of vinyl acetate, several reaction parameters were investigated, including temperature, catalyst concentration, vinyl acetate concentration, ligand concentration, syngas pressure and influence of ionic solvent and conventional solvents. It was shown that high n : i ratios of aldehyde products were formed with specific IL systems. Also, low ligand concentrations and low vinyl acetate concentrations increased selectivities, although rates of reactions were somewhat compromised. Lower syngas pressure and lower temperatures afforded enhanced selectivities, again at the expense of reaction rates. Depending on whether fast reaction rates or high regioselectivity is required, the IL and general reaction conditions can be tailored to fit the needs of the reaction. It was discovered that aromatic-containing ammonium-based ILs v afforded high rates at low selectivity. Bulkier ammonium cations tended to give lower rates but the selectivity was significantly enhanced. Impurities present in ILs have also been shown to have a marked effect on hydroformylation rates and selectivity. The reader will be accompanied along a path designed to discover an optimised set of reaction conditions, the path of which will take the reader from reactions providing low selectivities, low turnover numbers and low yields to a much brighter picture, namely extremely high selectivities, turnover numbers and yields. / Prof. D.B.G. Williams

Submitted in fulfilment of the academic requirements for the Masters Degree in Technology: Chemistry, Durban University of Technology,2013. / The thermodynamic properties of binary liquid mixtures using an ionic liquid (IL) with alcohols were determined at different temperatures. The ionic liquid used was 1-butyl-3- methylimidazolium methylsulphate [BMIM]+[MeSO4]-. Densities, speed of sound, and refractive indices for the binary mixtures ([BMIM]+[MeSO4]- + methanol, or 1-propanol, or 2-propanol, or 1-butanol) were experimentally measured over the whole range of composition at T = (298.15, E 303.15, 308.15, and 313.15) K. From the experimental data, excess molar volumes, V m , E , deviations in refractive isentropic compressibilities, κ s , excess isentropic compressibilities, κ S indices, ∆n, and molar refractions, R, were calculated. The excess partial molar volumes were also calculated at T = 298.15 K. For the binary systems, ([BMIM]+[MeSO4]- + methanol, or 1-propanol, or 2-propanol, or E E E 1-butanol) V m and κ S are always negative and V m decrease slightly when the temperature increases. The refractive index deviation at T = (298.15, 303.15, 308.15, and 313.15) K is positive over the whole composition range. The measured negative values for excess molar volume of these mixtures ([BMIM]+[MeSO4]- + methanol, or 1-propanol, or 2-propanol, or 1-butanol) indicate strong ion-dipole interactions and packing between alcohols and IL are present. The Redlich-Kister smoothing polynomial equation was satisfactorily applied for the E E fitting of the V m , κ S , and ∆n data to give the fitting parameters and the root-mean-square deviations. The Lorentz-Lorenz (L-L) equation was also used to correlate the volumetric property and predict the density or refractive index of the binary mixtures of ionic liquid and the organic solvents. The Lorentz-Lorenz approximation gives a higher σ when used to correlate the iiiexcess molar volumes for the mixtures ([BMIM]+[MeSO4]- + methanol, or 1-propanol, or 2-propanol, or 1-butanol). The L-L equation gives good results for the prediction of density and refractive index. The results are discussed in terms of solute-solute, solute-solvent and solvent- solvent interactions. / National Research Foundation

The work presented in this thesis involves the application of room temperature ionic liquids (RTILs) as solvents for use in electrochemical experiments. Initially, the fundamentals of electrochemistry is presented, followed by a comprehensive overview of RTILs in terms of their properties, applications and their behaviour as electrochemical solvents compared to conventional aprotic solvents. The results of 8 original studies are then presented as follows: X-Ray photoelectron spectroscopy is used to quantify the concentration of bromide ions in an ionic liquid, and is independently confirmed by potential-step chronoamperometry. The reaction mechanisms and kinetics for the electrochemical reduction of some aromatic nitro compounds (namely nitrobenzene and 4-nitrophenol) are determined. The electrochemistry of phosphorus trichloride and phosphorus oxychloride is studied in detail for the first time, due to the unusual stability of these highly reactive compounds in RTILs. The reductions and oxidations of sodium and potassium nitrate are studied, giving rise to 'melt'-like behaviour. The electrodeposition of sodium oxide on platinum is also demonstrated. The electrochemical oxidation of nitrite and the oxidation and reduction of the toxic gas, nitrogen dioxide, is presented. The oxidation of hydrogen gas is studied in ten RTILs with a range of different cations and anions, and contrasting interactions with the RTIL anions are seen. The electrochemical oxidation of ammonia gas is studied in five RTILs with different anions and a general reaction mechanism is suggested. The reduction of benzoic acid is studied in six RTILs, and the kinetics of the dissociation step are found to be very fast. The first five studies are all carried out in one particular ionic liquid, and the reactions and mechanisms are compared to that observed in conventional aprotic solvents. The last three studies employ several RTILs with different cations and anions to look at the contrasting interaction of protons with the RTIL cation/anion and ultimately help to understand the pH properties of the solvent. The overall findings from the work in this thesis are that some reactions and mechanisms (e.g bromide, nitro derivatives and ammonia) are generally the same in RTILs as in conventional aprotic solvents, but other species (e.g. nitrates, phosphorus derivatives) show remarkably different behaviour. It has also been demonstrated that RTILs are suitable media for the detection of nitrogen dioxide, hydrogen and ammonia gases. This suggests that RTILs could potentially offer many advantages when employed as solvents in electrochemical reactions and in amperometric gas sensors.

Submitted in fulfillment of the academic requirements for the Masters of Applied Science (Chemistry), Durban University of Technology, Durban, South Africa, 2016. / In this work, the thermodynamic properties for the binary mixtures containing the ionic liquid (IL): 1-ethyl-3-methylimidazolium ethyl sulphate ([EMIM] [EtSO4]) were calculated. The binary systems studied were {pyridine (Py) or ethyl acetoacetate (EAA) or thiophene (TS) + [EMIM] [EtSO4]}. The results were interpreted in terms of the intermolecular interactions between the (pyridine + IL), (ethyl acetoacetate + IL), and (thiophene + IL) molecules. The physical properties: density, speed of sound, and refractive index were measured for the binary mixtures over the complete mole fraction range using an Anton Paar DSA 5000 M vibrating U- tube densimeter and an Anton Paar RXA 156 refractometer, respectively. The measurements were done at T = (298.15, 303.15, 308.15, 313.15, and 318.15) K and at p = 0.1 MPa. The experimental data was used to calculate the derived properties for the binary mixtures namely:- excess molar volume (V E ), isentropic compressibility (ks), molar refractions (R) and deviation in refractive index (Δn). For the binary mixtures, (Py or EAA or TS + IL), V E was negative throughout the whole composition range which indicates the existence of attractive intermolecular interaction between (pyridine + IL) and (ethyl acetoacetate + IL) for (thiophene + IL), V E was negative at low mole fraction of thiophene and became positive at high mole fraction of thiophene. For the binary mixtures (pyridine + IL), (ethyl acetoacetate + IL), ks was positive indicating that the binary mixtures were more compressible than the ideal mixture. For the binary mixture (thiophene + IL) ks was negative at low thiophene composition and positive at high composition indicating that the binary mixture was less compressible than the ideal mixture at low thiophene composition and more compressible at high composition of thiophene. The molar refraction, R, is positive for the (Py or EAA or TS + IL) binary systems at T = (298.15 – 318.15) K, molar refraction decreases as the organic solvent composition increases. For the binary mixture (pyridine + [EMIM] [EtSO4]), Δn is negative at mole fractions < 0.75 of pyridine and positive at mole fractions >0.75 at all temperatures and decreases with an increase in temperature. For the binary system (ethyl acetoacetate + [EMIM] [EtSO4]), Δn values are positive over the entire composition range and at all temperatures and increases with an increase in temperature. Δn values for the (thiophene + IL) system are negative for mole fractions of thiophene < 0.62 and becomes positive for mole fractions of thiophene > 0.62 and Δn increases with an increase in temperature. The Redlich-Kister smoothing equation was used successfully for the correlation of V E and Δn data. The Lorentz- Lorenz equation gave a poor prediction of V E , but a good prediction of density or refractive index. / M

A dissertation submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Master of Science in Engineering, 2016 / The use of fuels (from crude oil) in vehicles is responsible for one of the biggest environmental challenges; SO2 emission. As a result most countries regulate their sulfur emissions, with the goal of getting to the use of 10 ppm sulfur fuels. These stringent fuel sulfur content requirements have resulted in intensive research being directed at alternative desulfurization technologies which will ensure the treatment of fuels to acceptable sulfur levels. Extractive desulfurization using ionic liquids (IL) may be considered as one of the most promising of these technologies and is the subject of the study presented in this work. This study served two major purposes: (1) to investigate the capacity as well as key parameters which affect the extraction efficiency of the IL; 1-butyl-3-methylimidazolium octylsulfate as a solvent for deep extractive desulfurization of real Fluid Catalytic Cracking Unit (FCCU) diesel fuel samples collected from a typical South African Refinery, (2) to study/find suitable solvents for the regeneration of sulfur-loaded 1-butyl-3-methylimidazolium octylsulfate and the efficiency and effectiveness of the regenerated IL in the desulfurization of diesel fuel. 1-butyl-3-methylimidazolium octylsulfate was selected due to its properties i.e. good extractive ability for S-compounds and insolubility in fuel oils. A 22.1% sulfur removal was achieved in the desulfurization of FCCU feed stream diesel fuel, while 96% sulfur removal was achieved for FCCU product stream diesel fuel. These results show that the IL is more effective in the selective removal of sulfur (S) from FCCU diesel product than from FCCU feed stream, suggesting that fuel sulfur content and stream composition affects the extraction efficiency and effectiveness of the IL. Based on thermodynamic considerations, hexane was selected as the most suitable solvent for the re-extraction of sulfur from spent IL. Regenerated IL was used for desulfurization of diesel and achieved highest sulfur removal of 95% and the IL was regenerated up to four times without appreciable decrease in efficiency. The results obtained herein show that ILs are effective in the desulfurization of real diesel oil samples when the sulfur concentration is not very high. Further studies on the recoverability of ILs as well as their environmental impact need to be done to support findings in this study. / GR2016

This thesis is concerned with investigating the suitability of room temperature ionic liquids as solvents in which to perform voltammetry, and in characterising electrochemical processes within these media. After providing a general introduction and a background to the ionic liquid field, the results of six original studies are presented, dealing in turn with the following subjects: • The oxidation of N,N,N',N'-tetraalkyl-para-phenylenediamine (TAPD) in five ionic liquids each incorporating the bis(trifluoromethylsulfonyl)imide anion. • The reduction of oxygen in four ionic liquids based on quaternary alkyl -onium cations and heavily fluorinated anions in which the central ion is either nitrogen or phosphorous. The simulation of double potential step chronoamperometry at a disk electrode for the case of unequal diffusion coefficients and its experimental validation using a variety of aqueous, traditional nonaqueous and ionic liquid solutions. • The rate of diffusion of N,N,N',N'-tetramethyl-para-phenylenediamme (TMPD), its radical cation and dication as a function of temperature and ionic liquid viscosity and four such solvents. • The temperature dependence of the viscosity of five ionic liquids along with the translational and rotational diffusion coefficients of dissolved 2,2,6,6- tetramethylpiperidine-N-oxyl (TEMPO). • The kinetics of the reaction between N,N-dimethyl-para-toluidine (DMT) and its electrogenerated radical cation in an ionic liquid solvent. The experimental strategy common to each report involves the application of cyclic voltammetry and chronoamperometry at disk electrodes immersed in uL-samples of ionic liquid solution. The data so measured is then analysed via the appropriate theoretical equations or, as is commonly necessary, by comparison with simulated voltammetry. Combined, these chosen redox systems provide access to information on various aspects of electrochemistry within ionic liquids, specifically (a) mass transport (b) the nature of the electron transfer process and (c) the rate of follow-up homogeneous reactions. It is the overall finding herein that while both diffusion and heterogeneous electron transfer are significantly slowed relative to the same processes in a conventional organic solvent, the rate of subsequent homogeneous chemistry remains largely unchanged.