The overall objectives of this thesis were to investigate the potential of the peroxyoxalate
chemiluminescence (POOL) reaction for the quantitative detection of target analytes in non-aqueous
matrices and to compare quantitative performance with fluorescence detection. The
target analytes investigated were polycyclic aromatic hydrocarbons (PAHs) and aliphatic amines.
These were selected as an important class of compounds in engine exhaust emissions and a
detergent additive in diesel fuel respectively.
Chapter one outlines the challenges of analysing petroleum products and engine exhaust emissions
and discusses the potential of luminescence techniques, particularly chemiluminescence (CL), for
the quantification of trace components. The chapter also reviews the technique of flow injection
(FT) as a means of sample delivery for CL detection and as a potential technique for field
deployment. Liquid chromatography techniques are described as a means of separation of
complex matrices, e.g. fuels and engine exhaust particulates, in the laboratory prior to CL
detection.
The luminescence properties of several PAHs were investigated in Chapter Two. Optimum
excitation and emission wavelengths for eleven PAHs in four different solvents were determined
using a batch fluorescence technique. A FI approach was used to determine PAH concentrations
using fluorescence and POCL detection. Two aryl oxalates; bis(2,4-dinitophenyl)oxalate and
bis(2,4,6-trichlorophenyl)oxalate were compared for their suitability for PAH determinations and
an investigation of the key variables (e.g. concentration of aryl oxalate and hydrogen peroxide,
mobile phase composition and pH) affecting POCL was performed. Recommendations for the
optimum conditions for the determination of PAHs by POCL detection were determined, A
comparison between a photodiode based detection device and a low power (12V) photomultiplier
tube was also described.
In Chapter Three the procedure of using POCL detection as a post column liquid chromatography
(LC) detector for PAHs has been considered. The performance of the POCL detection system was
compared with wavelength programmed fluorescence. Both reversed and normal phase LC was
investigated and the suitability of POCL detection with each approach was discussed.
Additionally the procedure for the LC separation and analysis of SRM 1649 (Urban
Dust/Organics) and SRM 1650 (Diesel Particulate Matter) was described. The relative
performance of fluorescence and CL detection are discussed.
Chapter four describes the principles of multivariate calibration of spectrophotometric data, and
three commonly applied techniques (PCR, PLSI and PLS2). Fluorescence data was obtained for
synthetic mixtures of PAHs containing two, three, four and five components. A procedure
whereby individual spectra were 'glued' together before undergoing data analysis has been
developed and the results obtained discussed. POCL emission spectra for five PAHs were
acquired using a two-dimensional charge coupled device (CCD). The sensitivity of the CCD
system toward POCL detection of PAHs and a multivariate investigation using benzo[a]pyrene
and benzo[k]fluoranthene has been described. The potential of the fluorescence and CL
approaches used has been discussed.
Chapter five describes the aryl oxalate sulphorhodamine-101 CL reaction and its application to the
determination of amines. A FI optimisation of the reaction parameters is presented together with
some quantitative data for the detection of a homologous series of amines and dodecylamine (a
commonly added detergent compound in diesel fuels). The application of the technique toward
the detection of dodecylamine in a diesel fuel matrix and the potential as a field deployable
technique was also considered.
Date of Award | 1999 |
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Original language | English |
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Awarding Institution | |
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ANALYTICAL APPLICATIONS OF THE PEROXYOXALATE CHEMILUMINESCENCE REACTION
SANDERS, M. G. (Author). 1999
Student thesis: PhD