No description available.

No description available.

Spectroscopic investigations have been carried out on hollow cathode discharges adapted from laser technology for use as a spectroscopic light source and the argon inductively coupled plasma (ICP) as an excitation source for nonmetal emission. High and low voltage aluminum and copper hollow cathode discharges were studied as a source of ionic and resonant atomic metal emission. The high voltage versions achieve strongly positive current-voltage behavior through utilization of the obstructed discharge phenomenon. The current-pressure-intensity-voltage relationships for low and high voltage copper hollow cathode discharges were studied with the inert gases He, Ne, Ar, Kr, and Xe. The intensity for copper resonant atomic emission with the fill gases Ar, Kr, and Xe improved relative to neon in the high voltage lamp when compared to the low voltage lamp. Absorption measurements through the cathode bore show the ground state atom density to increase with the atomic weight of the fill gas at any given level of intensity, at the fill gas pressure yielding highest resonant atomic copper emission. The estimated ion/atom intensity ratio is increased with fill gases which have metastable or ionization energies greater than the excitation energy of the ion transition. A copper hollow cathode lamp incorporating a short positive column discharge in front of the cathode opening was investigated for its lineshape as measured spectroscopically and by its atomic absorption sensitivity. Incorporation of this positive column allowed higher intensities to be obtained at the same line quality as a commercial hollow cathode lamp. An enlarged cathode volume also improves the lineshape at a given intensity. Inductively coupled plasma spectra for the elements C, O, N, Cl, P, S, and Br were obtained in the vacuum ultraviolet utilizing a vacuum polychromator and SWR film. The detection limit for injected O₂ and N₂ detected electronically by the VUV emissions is 1.3 and 0.9 micrograms respectively with this system. A VUV filter photometer was utilized for oxygen and phosphorus analysis. The detection limit for injected oxygen was 1 microgram with this photometer; the detection limit for phosphorus as inorganic phosphate in aqueous solution is 10⁻³ M. The bandpass of the photometer limits its selectivity.

published_or_final_version / Chemistry / Master / Master of Philosophy

published_or_final_version / abstract / Chemistry / Master / Master of Philosophy

No description available.

The objective of this study was to fully characterise drift phenomena in inductively coupled plasma atomic emission spectroscopy (ICP-AES) in order to develop novel correction procedures to aid routine analysis. Long-term drift of the analytical signal continues to be a potential disadvantage when using ICP-AES and often necessitates regular recalibration. The long-term stability of three commercially available Instruments was studied using In each case a range of analyte and intrinsic plasma emission lines. Long-term fluctuations were observed which generated drift bias of up to 20% on the initial values. The drift pafterns were characterised and found to be qualitatively reproducible. In most cases, similar long-term fluctuations were observed independent of the analyte or nature of the emission line. In addition, high inter-element correlation was observed on the long-term fluctuations even when sequential acquisition was employed. In order to study the fundamental causes of drift, the effect of two key instrumental parameters, i.e. the RF power and the nebutiser gas flow rate were studied with respect to the stability of the signal. Different drift patterns were found depending on the working conditions. Classical statistical methods and a multi-way approach. PARAFAC. were then employed to describe the system. The use of intemal standards to correct for drift has also been investigated, but found to be of benefit only under certain defined conditions (i.e. robust conditions, high RF power and low nebuliserflow rate). At soft conditions, low RF power and medium to high nebuliser flow rate, the system Is very unstable and intemal standardisation is not fully effective as a correction method. For such conditions, a novel correction procedure has been developed, which employs the drift pattem of one intrinsic plasma line (i.e. an argon line) and a correction factor which is specific for each emission line. The drift values were reduced from around 20% before correction to better than ±2% following the described protocol. Finally, the effects of chemical matrices on the long-term stability of the emission signals have been evaluated. Three synthetic matrices were prepared simulating nitric, soil and water matrices. The stability of the instrument when working wrth these matrices at both robust and soft conditions was found to be poor, especially when the solution was matched with the soil matrix. The use of more robust conditions did not improve the long-temi stability of the emission signals. The outcome of this study proved to be a better understanding of drift phenomena and a novel method for drift correction.

Thesis (M.Phil.)--University of Hong Kong, 2000. / Includes bibliographical references. Also available in print.

Thesis (M. Phil.)--University of Hong Kong, 1996. / Includes bibliographical references.

Thesis (M. Phil.)--University of Hong Kong, 2000. / Includes bibliographical references.