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Abstract Characterisation of crude oil properties in real-time by spectroscopic methods has been a major challenge to the oil industry. While current methods can show the presence of oil, a quantitative determination of oil physical and chemical properties has yet to be found. Also the mechanisms of oil photophysics are far from being fully understood. This thesis seeks to address these issues by two principle objectives. First, the determination of fluorescence lifetimes for crude oils by the Frequency Domain method and second, the analysis of the effects of dilution and temperature on the photophysical properties of crude oils. As a primary objective, a Frequency Domain (FD) method was developed to measure the fluorescence lifetimes of a series of crude oils. Analysis of the average lifetimes was made based on how many decay terms and the type of fitting model used. Correlations were made between the bulk chemical data for the oils and average lifetimes from distribution and discrete models. The FD method was then applied to the analysis of Hydrocarbon Fluid Inclusions (HCFI) where individual inclusions could be isolated and the average lifetime determined for the included oils. Comparisons were made between the lifetimes for the bulk oils and HCFI. The second objective of the thesis was to examine the effects of dilution and temperature on the photophysical behaviour of crude petroleum oils. Comparisons were made between lifetimes over the range of temperatures sampled and differences between dilute and neat average lifetime values gave estimations of quenching effects. Lifetimes were monitored over a range of temperatures and were found to follow a simple Arrhenius-like behaviour. A modified Stern-Volmer quenching model could be applied to the crude oil lifetime data showing the presence of both static and dynamic quenching and the calculated quenching rate constants have been found to vary linearly with oil type. Neat and dilute oils also followed a reverse Eyring i
Abstract behaviour allowing calculation of activation enthalpy and entropy values. Although the theory for the Arrhenius, Eyring and Stern-Volmer models is based on single fluorophore systems, they were found to apply for a complex system of multiple emitting and interacting fluorophores. In the context of these simple models, the average lifetime calculated for crude oils represented an summation of the excited state processes. ii
Page 1: Time-Resolved Fluorescence Spectros
Page 5 and 6: Contents List of Publications and P
Page 7 and 8: Contents 2.3 Temperature based Life
Page 9 and 10: List of Publications and Presentati
Page 11 and 12: Abbreviations Abbrev Definition API
Page 13 and 14: Chapter 1 Introduction For many yea
Page 15 and 16: Introduction temperature increases
Page 17 and 18: A seal or cap-rock that prevents th
Page 19 and 20: Introduction Figure 1.2: Crude oil
Page 21 and 22: Introduction eroatoms (O, S, N) and
Page 23 and 24: Introduction toluene, dichlorometha
Page 25 and 26: 1.2 Fluorescence Spectroscopy 1.2.1
Page 27 and 28: Introduction S1 state for a certain
Page 29 and 30: Introduction The peaks in the absor
Page 31 and 32: Introduction Figure 1.9: Jablonski
Page 33 and 34: Introduction Figure 1.10: Static qu
Page 35 and 36: Introduction the ratio of τ 0/τ i
Page 37 and 38: 1.2.5 Measuring fluorescence lifeti
Page 39 and 40: Introduction Figure 1.14: Time-reso
Page 41 and 42: Introduction The autocorrelation fu
Page 43 and 44: Introduction case, the molecules ex
Page 45 and 46: From Equation 1.26, Introduction ω
Page 47 and 48: m = 1 P 2 + Q 2 Introduction (1.36
Page 49 and 50: Introduction based average lifetime
Page 51 and 52: Introduction Figure 1.21: General p
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Introduction TAC output pulse is gi
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Introduction at each frequency acco
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Introduction diagram showing the op
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Introduction Figure 1.26: Schematic
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Introduction provides enhanced cont
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Introduction PAH’s. It has been s
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to heavy oils (low API gravity). In
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Introduction The balance between en
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Introduction Figure 1.34: Fluoresce
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Introduction used [126, 129, 132] a
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Introduction Figure 1.36: Plot of a
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fractional contributions over time
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Introduction concentration and Ksv
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1.5 Crude oil photophysics Introduc
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Introduction stages of thermal matu
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Introduction yellow to red fluoresc
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1.7 Thesis goal Introduction This i
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Materials and Methods concentration
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Table 2.2: Fractionation Data for B
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Materials and Methods 2.2 Frequency
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Materials and Methods was within ±
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Materials and Methods The dichroic
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Figure 2.5: Transmission characteri
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Materials and Methods Figure 2.7: S
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Materials and Methods The variation
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Materials and Methods Figure 2.9: L
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Materials and Methods Figure 2.10:
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Materials and Methods Comparison ca
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Materials and Methods with ρ param
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Materials and Methods 2.3 Temperatu
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Materials and Methods IRF of the sy
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Materials and Methods 2.4 Temperatu
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Materials and Methods a series of w
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Materials and Methods 2. Using the
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Lifetime study on crude oils by the
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Table 3.3: Average lifetime and sin
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Table 3.5: Average lifetime and sin
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3.5 Single Lifetime distributions L
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Energy Transfer and Quenching proce
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Influence of low temperature on flu
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Conclusions and Future Work model (
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Appendix A Reference Lifetime Stand
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Appendix Figure A.2: FD response fo
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A.3 SPA N-(3-sulfopropyl) acridiniu
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A.4 Rhodamine B Appendix Rhodamine
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A.5 Acridone Appendix The highly ph
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Appendix Figure A.11: FD response f
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Table B.1: Frequency Domain average
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Appendix Table B.3: Emission λmax
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Table B.5: Frequency Domain lifetim
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Appendix for the determination of t
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Appendix Figure C.3: Multifrequency
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Appendix Figure C.5: FLIM intensity
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Appendix Table C.1: Fluorescence li
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Appendix D Published Work 281
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998 J Fluoresc (2008) 18:997-1006 s
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1000 J Fluoresc (2008) 18:997-1006
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1002 J Fluoresc (2008) 18:997-1006
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1004 J Fluoresc (2008) 18:997-1006
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1006 J Fluoresc (2008) 18:997-1006
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Bibliography [10] W. G. Dow (1977),
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Bibliography [31] M. A. Ali and W.
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Bibliography [53] R. D. Spencer and
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Bibliography [75] K. Konig (2000),
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Bibliography [93] C. Pasquini and A
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Bibliography [113] C. Ralston, X. W
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Bibliography [132] A. Ryder (2004),
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Bibliography variable-angle synchro
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Bibliography [171] R. K. McLimans (
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Bibliography using fluorescence spe
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Bibliography [210] H. Mishra, S. Pa
Page 327 and 328:
Bibliography [229] N. Boens, W. W.
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