- Title
- Second order globalisation of spectrophotometric data analysis: theory, instrumentation, and application to solution equilibria
- Creator
- Dyson, Raylene M.
- Relation
- University of Newcastle Research Higher Degree Thesis
- Resource Type
- thesis
- Date
- 1997
- Description
- Research Doctorate - Doctor of Philosophy (PhD)
- Description
- This work presents a new development in the analysis of equilibrium investigations using spectrophotometric titrations to now allow the analysis of a number of titrations simultaneously. We describe this as the 'second order globalisation of the analysis'. The background of equilibrium analysis, particularly spectrophotometric analysis, leading up to second order global analysis is traced in Chapter 1. Spectrophotometric analysis was first used for very simple systems measured at one wavelength; this we have termed 'zeroth order analysis'. 'First order global analysis', the analysis of single titrations measured at many wavelengths, is the present standard of spectrophotometric analysis, proving more robust and useful for complex systems. Second order global analysis is shown here to allow the analysis of even more complicated equilibria and to overcome many of the difficulties found in first order global analysis. A computer program, EQUISPEC, was written to perform second order globalisation. The theory behind and characteristics of this program are described in Chapter 2 and its success on real equilibria is demonstrated in Chapter 3. It is shown to overcome the linear dependence of individual titrations (Zn2+-phen), to allow improved definition of minor species (Eu3+-phen, Eu3+-FNAC, and Eu3+-PDA), and to result in reduced uncertainties in the refined equilibrium constants (Cu2+-dien, Cu2+-N₃phenol, and nitr). Further 2nd order global analysis proved invaluable in the investigation of the interaction of DTPA with In3+. This equilibrium was quantified in a series of competition experiments using HBED as an auxiliary coloured ligand. EQUISPEC can also perform first order global analysis in the usual way and this is done in Chapter 4 to examine the equilibria of SM3+ and DTPA versus a bifunctional DTPA analogue of relevance to nuclear medicine. It was also adapted and applied to the investigation of the high spin - low spin equilibrium for an Fe(III) complex. The instrumentation used for acquisition of the spectrophotometric data is described in Chapter 5. This Chapter also contains the description of some synthetic work, as well as the crystal structure of [Eu(FNAC)₂(TOPO)₂(NO₃)]. Fluroescence titrations are described and discussed in the context of seeking a greater understanding of the complexation of Eu3+ by ligands of relevance to fluroimmunoassay procedures.
- Subject
- equilibrium investigations; spectrophotometric titrations; equilibrium analysis
- Identifier
- http://hdl.handle.net/1959.13/1312473
- Identifier
- uon:22402
- Rights
- Copyright 1997 Raylene M. Dyson
- Language
- eng
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