An in-house developed method is presented for the purity analysis of nitrogen (N2) built-in purifier (BIPTM)) gas for the trace contaminant gases carbon dioxide (CO2), oxygen (O2)) and carbon monoxide (CO), using gas chromatography with a pulsed discharge helium ionisation detector (GC-PDHID). Nitrogen BIPTM gas is used as a “matrix” gas or diluent gas for the gravimetric preparation of binary reference materials of CO, CO2), sulphur dioxide (SO2)) and nitric oxide (NO) at the CSIR NML gas metrology laboratory. Purity analysis of nitrogen BIPTM is required to decrease the measurement uncertainty of the calculated gravimetric concentrations of the gaseous reference materials produced. The aim of the research was to find a method where amounts <0.25 x 10-6 mol•mol-1 of CO2), O2) and CO could be simultaneously analysed in high purity nitrogen within a short time, with minimum cost and on a routine basis. Gas mixtures of trace amounts of CO2), O2) and CO in N2) were separated and quantified using a parallel dual capillary column configuration with temperature and pressure programming and a pulsed discharge helium ionisation detector (PDHID). The detection limits were 9 x 10-9 mol•mol-1 for CO2), 7 x 10-9 mol•mol-1 for O2) and 37 x 10-9 mol•mol-1 for CO with repeatability precision of 1% for carbon dioxide, 1% for oxygen and 10% for carbon monoxide for a 0.2 x 10-6 mol•mol-1 standard. The detection limits obtained were lower than those reported previously by other investigators for similar methods and the validation for the method as set out in this investigation seems to be the first for trace amounts of CO2), O2) and CO in nitrogen. The method was validated by comparison of the CO2) and CO results with results obtained using a flame ionisation detector and methanisation. The technique of sequence reversal was used to improve the peak shape of CO but there was no improvement on the results obtained with temperature and pressure programming. Although no helium purging was used to reduce atmospheric contamination, it was shown that the main source of contamination from the air was through the sampling system which was reduced to a level of ± 20 x 10-9 mol•mol-1 oxygen simply by using a higher sample flow rate. It was also found that even when large amounts of CO2) were adsorbed onto the molecular sieve column, this made no difference to the column performance at trace levels. The method has also been validated for the analysis of nitrogen in high purity oxygen and may also be used to analyse carbon dioxide and carbon monoxide in oxygen as well. / Dissertation (MSc (Chemistry))--University of Pretoria, 2008. / Chemistry / unrestricted

Flow injection analysis offers distinct advantages in reproducibility, flexibility, sample throughput and cost performance. Since it was introduced in 1975, there are more than 10 000 publications to date. The present study focuses on the development of process analysers for the determination of nitrogen compounds (namely, nitrate, nitrite and protein), nickel, and phosphate in various combination in samples originating from various fields, such as foodstuffs, water, and fertilisers. Nitrite is potentially unstable; it decomposes with time under acidic medium with an increase in decomposition rate as the concentration of acid increases. Raman spectroscopy was employed as a means of determining the rate of decomposition of nitrite in solutions at various pH values. A simple method for the determination of nitrite in foodstuffs by flow injection analysis (FIA) is described. The foodstuffs containing nitrite are digested in a microwave oven and then treated with 1 moℓ/Q NH4CI solution at pH 9. The simultaneous determination of nitrate and nitrite in foodstuffs and water was also studied. Cadmium (coarse powder) was used to reduce nitrate to nitrite. The effect of pH, length of reductor column, and various types of cadmium reductor on the yield of nitrite are investigated. The flow injection method was developed for the spectrophotometric determination of nickel in cured meat. Dimethylglyoxime (DMG) in acetate buffer at pH 6.4 nickel forms a red complex which is measured at 475 nm. The effects of chemical and physical parameters in flow injection analysis were studied. A new bienzymatic amperometric sensor is proposed for the assay of proteins in milk. The sensor is based on two enzymes, namely, carboxypeptidases A and L-amino acid oxidase. The use of flow injection analysis and Raman spectroscopy for the determination of phosphate in foodstuffs and fertilisers, is also compared in this study. / Thesis (PhD (Chemistry))--University of Pretoria, 2007. / Chemistry / unrestricted