Fluoroolefins in general represent a valuable class of feedstock materials which have proven integral to a number of industries including (but not limited to) refrigeration, agrochemicals, pharmaceuticals, and propellants. As ligands for transition metals they are privileged in the relative inertness of the C–F bonds and their electrophilicity, which makes them ideal candidates for coordination chemistry with late, electron rich metals. The scope of this thesis encompasses work with TFE and VDF, two readily available fluoroolefins that are used most commonly in the polymer industry. Through the use of low-coordinate nickel systems, value-added derivatives of these two olefins have been prepared. With TFE, a T-shaped perfluoronickelacyclopentane was obtained upon coordination of the bulky SIPr ligand; this complex underwent hydrogenation to give 1H,4H-octafluorobutane at as low as 5 psi of hydrogen, in addition to giving rise to new ring-opened derivatives and a rare perfluorocyclobutyl complex. In the case of VDF, the regioselective hydrodefluorodimerization to a potentially valuable new refrigerant 2,4,4-trifluorobut-1-ene (HFO-1363pyf) catalyzed by nickel is reported, as well as a dimeric 2,4,4-trifluorobut-1-enylnickel derivative which is proposed in this text to originate from the β-fluoride elimination of an unprecedented 5-membered 2H,2H,4H,4H-tetrafluoronickelacycle.

Dynamic simulation programs were created in the Python programming language, to describe a laboratory scale, sub-zero distillation column, that is used to separate mixtures of tetrafluoroethylene (TFE), hexafluoropropylene (HFP) and octafluorocyclobutane (OFCB). Both the equilibrium and rate-based modelling approaches were taken, to generate a comparison between the efficiency and simulation time of both models. A physical properties data bank for the three components had to be created, as the main and many of the sub-models require physical or thermodynamic properties for evaluation. The different physical property models, found in literature, were programmed into functions that could easily return the wanted property, given a set of required inputs. The applicable mixing rules for each property type was also programmed into functions, to allow for easy retrieval. The vapour-liquid equilibrium (VLE) model used, is also one that comes from literature and is based on parameters for the three binary systems. The VLE model consists of the Peng-Robinson equation of state, that utilises the Mathias-Copeman alpha function and the Wong-Sandler mixing rules, to describe the vapour phase. The liquid phase is described by the non-random two liquid (NRTL) activity coefficient model. Furthermore, the γ-Φ VLE formulation was used to put the thermodynamic model together. These models were also written into functions to serve as simulation building blocks. Mass and energy transfer on packed sections in the rate-based model was described by the Maxwell-Stefan diffusion model. The form of this model that was utilised, is the matrix-based, exact solution of the Maxwell-Stefan equations, under the two-film theory. This model was slightly simplified by assuming that the corrective flux matrix reduces to the identity matrix- an assumption that is regularly made in distillation modelling. Emphasis was laid in documenting how the models are put together to build the simulations. Dynamic simulation algorithms rarely accompany distillation models reported in literature, or authors make use of commercial software to order the modelling equations for them. One of the objectives of the research presented here was, therefore, to report on the process developed to solve the problem. Both simulation programs delivered typical responses that can be expected of distillation systems. The actual change in the magnitude of the values, however, proved to be significantly small. The cause of this, being the large liquid molar hold-up values that were produced by the model initialisation. The feed flow rate, in comparison, is too small to bring about a significant effect when suddenly increased. This could mean that the system is not capable of reaching the steady-state produced by the initialisation (as the feed cylinder may be too small to contain the required amount of feed gas) and that the column may have to be run in a continuous dynamic state. To be sure of this, however, the model will first need to be validated against experimental data. Furthermore, the simulation programs proved to progress very slowly, particularly the simulation built around the rate-based model. A time step-size of 0.5 resulted in an integration time around 1 minute and 20 seconds for the equilibrium model, while the rate model ran for over 19 minutes, both for a timespan of 300 s. It is recommended that future research focuses on building start-up simulations for the models, to provide better initial results and to give more insight into the operation of the column. Experimental validation of the models is also important, to establish their accuracies. Finally, work has to be done to improve the simulation speeds, especially if it is required that one of the models are integrated into the column's control system. / Dissertation (MEng)--University of Pretoria, 2019. / Fluorochemical Expansion Initiative / Department of Science and Technology / Department of Trade and Industry / Chemical Engineering / MEng / Unrestricted

Density Functional Theory (DFT) is a powerful tool for treating large organometallic structures efficiently and accurately. DFT calculations on the Hg-catalyzed oxidation of methane to methyl bisulfate in sulfuric acid suggest the lowest energy pathway involves a closed-shell electrophilic C–H activation mechanism coupled with metal alkyl reductive functionalization and oxidation by SO3. Comparison to Tl, Zn, and Cd suggests that Hg is unique in its ability to catalyze this set of reaction steps. Comparison to K2S2O8 highlights the selectivity of this C–H activation reaction as opposed to radical conditions. In contrast, DFT calculations indicate that CoIII(TFA)3 oxidizes methane through a radical TFA ligand decarboxylation pathway. A similar decarboxylation pathway is identified for MnIII(TFA)3, but the low spin ground state of TlIII(TFA)3 favors electrophilic C–H activation over this decarboxylation pathway. DFT calculations indicate that Cp(PPh2Me)Co=CF2 undergoes [2 + 2] cycloaddition with TFE by a unique open-shell singlet diradical mechanism. The significant stability of the perfluorometallacyclobutane reveals why catalytic metathesis with TFE is difficult.

This dissertation details research aimed at designing a small batch distillation column to purify tetrafluoroethylene and hexafluoropropylene from a mixture containing tetrafluoroethylene, hexafluoropropylene and octafluorocyclobutane. As no vapour-liquid equilibrium data are available for these chemicals in this mixture, new vapour-liquid equilibrium data were experimentally generated and modelled for use in the design of the batch distillation column. The data were fitted to the Peng-Robinson equation of state, utilizing the Mathias-Copeman alpha function. The model was used with the Wong- Sandler mixing rules alongside the NRTL alpha function. The model was fitted with mean relative deviations lower than 1.2 %, indicating an acceptably accurate description of the VLE data gathered by the model. The experimental data and the model also passed the thermodynamic consistency test for all the systems and isotherms. The design simulations were completed by means of the Aspen Batch Distillation, a module of the Aspen Technologies package. The results show that the optimum design for recovering high-purity products requires six equilibrium stages in the column. The batch column should consist of a still pot, also functioning as a reboiler, a packed column section and a total condenser. The total condenser and the reboiler both count as equilibrium stages. Using this design, a TFE product purity of 99.999 % is predicted with a recovery of 96 %. An HFP product purity of 99 % is predicted at a recovery of 68 %. The recovery of the HFP product can be increased, but entails a significant loss of product purity. The minimum column diameter required to achieve the flow rates suggested in the simulation is 29 mm. The column diameter was selectedas 1¼ ″ (or 31.75 mm) on the basis of the standard pipe diameters available in the industry. Pall ring packing is suggested for use in the column, with an estimated maximum HETP of 0.5 m. As there are five equilibrium stages in the column itself, the column has to be at least 2.5 m high. Copyright / Dissertation (MEng)--University of Pretoria, 2011. / Chemical Engineering / unrestricted

No description available.