This thesis is concerned with analytical studies on the trace analytes barium, cadmium, cobalt, chromium, copper, iron, manganese, nickel, lead, vanadium and zinc, present in high purity and highly complex matrices. The technique utilises activated alumina microcolumns in a flow injection (FI) system, to perform analyte enrichment and matrix removal. The analytes, after retention on the microcolumn are subsequently eluted and quantified by inductively coupled plasma-emission spectrometry (ICP-ES).Initial studies focus on trace analytes in caesium iodide, however a selection of the alkali metal salts, lithium nitrate, potassium bromide, sodium fluoride and sodium chloride, are investigated. New methodology for the ultratrace determination of high purity alkali metal salts is thus provided. The microcolumn enrichment technique with ICP-ES detection is robust, utilises limited sample handling and simultaneously preconcentrates and separates the analytes from matrix components. Hence possible matrix interferences are eliminated and limits of detection are significantly improved, in comparison to conventional ICP-ES analysis. A technique for the determination of the total content of eleven trace analytes present in natural waters (mineral, reservoir), using microcolumns of activated alumina in a FI-ICP-ES is investigated. The use of the complexing agent tartaric acid is shown to be effective in improving analyte retention. The procedure is successfully applied to determination of these analytes in a certified river water reference material (SLRS-1). Due to low retention and elution efficiencies, the total content of the analytes Fe and V present in Buxton, Redmires and Langsett samples could not be accurately determined by this technique. Activated alumina microcolumns are utilised as a new field sampling tools. Samples are collected in the field and processed through the alumina microcolumns for the effective retention of desired analytes. Hence, an alumina microcolumn sampling stage to effect concentration and isolation prior to analytical measurement is at the core of the investigation. The overall aim is to extend the application of alumina microcolumns, and in particular to provide a new multi-element field sampling device, which gives high sample integrity and preconcentration.

This thesis concerns the thermodynamics of macrocycles and their metal cation complexes in non-aqueous media and these are discussed under two main headings, i) Thermodynamics of Alkali-Metal Cations and Macrocycles in Solution and in the Solid State. Thermodynamic parameters of complexation for alkali-metal cations and macrocycles (18-crown-6 and ethyl p-tert-butylcalix(6)arene hexanoate) in benzo-nitrile at 298.15 K are first reported. These data are compared with those previously reported for cryptand 222 and these cations in this solvent. A 'peak' selectivity for potassium is observed for the complexation of the calix(6)arene ester with alkali metal cations. The process is enthalpy controlled with an exothermic maximum for the potassium cation. Thermodynamic data of complexation are characterised by a lower enthalpic stability and a more favourable entropy (except for K+) than corresponding data involving cryptand 222 or indeed 18-crown-6. Standard enthalpies of solution, DeltasH0, of macrocycles and their sodium and potassium salts in benzonitrile measured calorimetrically are discussed in relation to (i) data for the uncomplexed salts and (ii) previously reported data for sodium and potassium cryptate salts in various solvents. Enthalpies of coordination, DeltacoordH0, for eighteen systems involving sodium and potassium coronates, cryptates and calix(6)arenates are derived and whenever possible these are discussed on the basis of (i) available X-ray crystallographic data and (ii) the anion effect on the coordination process. ii) Thermodynamics of Lower Rim Calix(4)arene Derivatives with the Silver Cation in Different Media at 298.15 K. The DeltasH0 values of p-tert-butyl(bis-diethylamine-bis-methysulphanyl) calix(4)arene (EATCalix4) in various solvents at 298.15 K are reported. Transfer parameters from acetonitrile to other solvents are calculated. The interaction of EATCalix4 and the silver cation was investigated by 1H NMR in deuterated acetonitrile at 298 K showing that the ligand hosts the metal cation through interaction with the different donor atoms (O, N, S). Conductimetric titrations indicate that the stoichiometry of the complex is 1:1. The thermodynamics of complexation of EATCalix4 and silver in six solvents at 298.15 K is reported. The DeltasH0 values of the free and the complex silver perchlorate salts have been also measured in various solvents and these have been combined with DeltacH0 data to derive the DeltacoordH0 of this system. A few representative examples about the use of coordination data are given. The medium effect on the complexation process is assessed in terms of DeltatG0, DeltatH0 and DeltatS0 of the reactants and the product from acetonitrile to the appropriate solvent. The relevance of analysing the solvation changes that these species undergo upon complexation is emphasised.

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Three cage-functionalized polyoxacrown ethers (9, 10 and 12) and four novel cage-functionalized polyoxamonoazacrown ethers (18, 20, 25 and 29) that contain 3,5-disubstituted-4-oxahexacyclo[5.4.0.02,6.03,10.05,9.08,11]dodecane ("oxahexacyclic") moiety have been synthesized and their respective alkali metal picrate extraction profiles along with that of three analogues 13, 14 and 21 have been obtained. The observed avidities and selectivities of the host molecules toward complexation and transport of alkali metal picrates can be related to the size and shape of their respective macrocyclic cavity and the number of donor atoms. The effect of N-alkyl substitution on the complexation properties of azacrown ethers has been studied. The avidity of N-Et azacrown ethers toward complexation with alkali metal cations is generally higher than that of the corresponding non-N-alkylated hosts. However, the presence of an N-Et group appears to have a negligible effect upon their relative selectivities in their regards. The effect of pH on extraction process was studied; it was thereby determined that the alkali metal picrate extraction experiments are best performed at high pH (ca. 11-12).

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Digitized by Kansas Correctional Industries

by J.K. Galt. / "September 17, 1947." / Bibliography: p. 24. / Army Signal Corps Contract No. W-39-039 sc-32037

Thesis (Ph.D.). / Written for the Dept. of Physics. Title from title page of PDF (viewed 2009/06/11). Includes bibliographical references.

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