The publications presented in this thesis have been divided into 4 main
streams, representing the results of ideas and work in analytical chemistry,
carried out in three centres, Department of Chemistry, Queen's University, Belfast;
Department of Chemistry, The University, Edinburgh; Department of Chemistry, Case
Institute of Technology, Cleveland, Ohio, U.S.A
These four main sections are as follows.
A. Analytical Investigations on Transition Metals
B. Analytical Investigations using Partition Chromatography, Ion-Exchange,
and Solvent Extraction.
C. Analytical Investigations on Inorganic Systems using Newer Instrumental
D. Analytical Investigations on Inorganic Systems by means of Infrared
A. In this section the publications are listed under specific groups of transition metals investigated. These are three in number:
(i) technetium and rhenium, (ii) the Platinum metals, (iii) niobium,
tantalum, molybdenum and associated elements.
Investigations were started on technetium because, at that time, the
analytical chemistry of the element was virtually unknown. Technetium (To⁹⁹)
extracted from the fission products of U²³⁵, of which the element comprises some
6.2 per cent, was used. The element rhenium was involved as a "guide" for
technetium as only small quantities of the latter were available. This proved
satisfactory as the analytical chemistry of rhenium itself was by no means well-known. Publications presented in this section deal with the detection of technetium and rhenium, the separation of each from associated and interfering elements
and the development of new and more precise methods for their determination.
The publications presented on the platinum metals indicate work carried out
Use other side if necessary.
to meet certain deficiencies in the analytical chemistry of these elements. These
were, in the main, a lack of small scale methods of determination, and satisfactory methods for rapid separation,
Studies were also carried out on tantalum, molybdenum, and
associated elements. The results achieved lure indicated in the publications presented which report rapid colorimetric methods for the determination of niobium,
tantalum, molybdenum, titanium and effective means of separation, for analytically
and industrially important groups of metals.
B, The publications in this section represent work which was carried out to
exploit the use of the separatory techniques of partition chromatography, ion-exchange and solvent extraction particularly for the separation of "difficult"
groups of elements.
When the investigations started these techniques were quite novel in their
application to inorganic systems. Success was achieved with the alkali metals;
the alkaline earths; niobium and tantalum; aluminium, gallium, indium, thallium;
chromium, tungsten, molybdenum, vanadium; antimony and tin; and others. Consideration was also given to the method of determination of the separated material
and, in many oases, new reagents or new techniques were developed,
C, The publications in this section report ideas and subsequent research which
was designed to exploit new instrumental methods for the analysis of inorganic
substances. The main fields of interest have been grouped under the headings of
spectroscopic techniques, which include emission spectroscopy, diffuse reflectance
spectroscopy, atomic absorption spectroscopy, and oscillographic polarography
In the emission spectroscopy studies attempts were made to utilise "Tesla-luminescence spectra" analytically by developing the earlier principles of
Stewart who first observed the phenomenon in 1923. In these studies a new
apparatus was designed and developed, and a new technique drawn up and applied
to several inorganic systems. The research was extended to flame excitation
and later, when atomic absorption spectroscopy became available, investigations
were undertaken in this field to exploit the advantages that absorption has
over emission methods.
Recently, a new technique - diffuse reflectance spectroscopy became
available and offered possibilities for the analysis of the inorganic constituents
of precipitates and the study of the structure of substances. Investigations
using this technique were carried out resulting in the development of methods
for the determination of palladium and cobalt, and the study of the structure of chelates of analytical interest,
Polarographic investigations using "fast sweep" or oscillographic polarography were carried out on the platinum and noble metals. These metals were
deliberately chosen because of the inherent difficulties associated with their
usual polarography or electrochemistry. The aim of the research was to study
the polarography of complexes with different ligands of these metals, in a systematic manner. By this approach it was found possible to obtain complexes giving
polarographic half-wave potentials of sufficiently different values to permit the
determination of a number of these metals in the presence of one another,
D. In applying infrared methods to inorganic systems, difficulties arise which
are inherent to that material and lead to broad absorption peaks and complicated
spectra which are of little value analytically. However, by incorporating the
ionically bonded inorganic material into a covalently bonded complex, stronger
and sharper absorption bands were obtained which, used in conjunction with the
alkali halide (KBr) disc technique, were capable of qualitative and quantitative
By this means, methods were developed for the identification and determination of polyatomic inorganic anions, the determination of rhenium and technetium, niobium, tantalum and associated elements, vanadium, molybdenum, tungsten
and the study of chelate compounds of analytical interest.