The extraction of iron (III) by high molecular weight alkylamines

[Typewritten]288 leaves : ill.Thesis (Ph.D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 196

Studies in solvent extraction chemistry and ion-selective electrodes / Robert Walter Cattrall

Consists mainly of offprints of articles by the authorIncludes bibliographies1 v. (various pagings) :Title page, contents and abstract only. The complete thesis in print form is available from the University Library.Thesis (D. Sc.)--University of Adelaide, Faculty of Science, 198

Applications of voltammetric ion selective electrodes to complex matrices

The practical application of two different voltammetric ion selective electrodes (VISE) to measure ion activity in complex solutions has been explored. 7,7,8,8-tetracyanoquinodimethane (TCNQ) and tetrathiafulvalene (TTF) microcrystals adhered to an electrode surface act as a low selectivity voltammetric ion sensor. Resistance drop effects and pH artifacts were minimised by the addition of an innocent supporting electrolyte (buffer) to the analyte solution. In this format, addition of an ionophore to improve selectivity resulted in a reduction in current magnitude, due to competition for the ion. In contrast, voltammetry of a thin film containing a redox active species, electrolyte, ionophore and membrane solvent provides a highly selective ion sensor. Choice of ionophore was shown to affect the upper concentration detection limit. Use of ionic liquids as a combined membrane solvent and electrolyte was demonstrated. Methods to attach both VISE types to low-cost screen-printed electrodes have been explored. Various potential referencing techniques were also investigated. Both the microcrystal and thin film VISEs could be used to determine ion activity in complex solutions, as demonstrated in seawater, beverages, plasma and whole blood. Dissolved oxygen does not need to be removed, as it does not affect the response. However calibration methods are important for sensor accuracy and issues relating to electrode fouling must be addressed. 2013 The Royal Society of Chemistry

Separation of cobalt(II) from nickel(II) by solid-phase extraction into Aliquat 336 chloride immobilized in poly(vinyl chloride)

A solid-phase absorbent obtained by the immobilization of Aliquat 336 chloride in poly(vinyl chloride) is reported to extract preferentially Co(II) from its 7 M hydrochloric acid solutions containing Ni(II). Under the experimental conditions there was no extraction of Ni(II) which allowed the complete separation of these two ions. Co(II) was rapidly and quantitatively back-extracted with deionised water. A mechanism for the extraction of Co(II) is proposed based on the formation of the ion-pair A+[HCoCl4]− where A+ is the Aliquat 336 cation. Fe(III) and Cd(II), usually present in Co(II) and Ni(II) samples, were also extracted into the solid-phase absorbent though at a slower rate than Co(II) and they did not interfere with the separation of Co(II) from Ni(II). It was also demonstrated that this approach allowed the complete separation of Ni(II) from the other metal ions mentioned above

Voltammetric ion-selective electrodes for the selective determination of cations and anions

A general theory has been developed for voltammetric ion sensing of cations and anions based on the use of an electrode coated with a membrane containing an electroactive species, an ionophore, and a supporting electrolyte dissolved in a plasticizer. In experimental studies, a membrane coated electrode is fabricated by the drop coating method. In one configuration, a glassy carbon electrode is coated with a poly(vinyl chloride) based membrane, which contains the electroactive species, ionophore, plasticizer and supporting electrolyte. In the case of a cation sensor, ionophore facilitated transfer of the target cation from the aqueous solution to the membrane phase occurs during the course of the reduction of the electroactive species present in the membrane in order to maintain charge neutrality. The formal potential is calculated from the cyclic voltammogram as the average of the reduction and oxidation peak potentials and depends on the identity and concentration of the ion present in the aqueous solution phase. A plot of the formal potential versus the logarithm of the concentration exhibits a close to Nernstian slope of RT/F millivolts per decade change in concentration when the concentration of K+ and Na+ is varied over the concentration range of 0.1 mM to 1 M when K+ or Na+ ionophores are used in the membrane. The slope is close to RT/2F millivolts for a Ca2+ voltammetric ion-selective electrode fabricated using a Ca2+ ionophore. The sensor measurement time is only a few seconds. Voltammetric sensors for K-, Na +, and Ca2+ constructed in this manner exhibit the sensitivity and selectivity required for determination of these ions in environmentally and biologically important matrixes. Analogous principles apply to the fabrication of anion voltammetric sensors. 2010 American Chemical Society