Spectrometry of Fuels

Fuels represent an important aspect of world economy. The study of the chemical properties and compositions of fuels is necessary to provide a better understanding of their reactions, and, possibly, to promote their improved commercial utilization. Spectrometry comprises a valuable group of tools and techniques for the study of fuels and their derivatives. Some of the undesirable by-products from fuels-specifically, pollutants-provide the spectroscopist with an additional vast area for the application of his tools. The fight against pollution of all kinds has spawned one of our most rapidly growing industries. It thus seems pertinent to devote a book to the spectrometric investiga­ tion of fuels and related materials. This book is intended to be of interest to people concerned with fuels, with related chemicals, with applications of the newest spectral methods, or with organic and physical chemistry. The pur­ pose of the book is threefold: (l) To give details of 23 new researches using modern spectral methods on fuels and related materials, (2) to give the reader some feeling for these modern techniques and their applications, and (3) to provide him with indications of material for further reading. The book is not intended to cover details of specific analyses of fuels or of fuel deriva­ tives such as gasoline, lubricating oil, coal gas, etc. ; considerable space in other books and in journals has been devoted to these subjects.

1 High-Resolution Mass-Spectrometric Investigation of Coal Derivatives.- Experimental Procedure.- Results and Discussion.- Mass Spectra of Pitch.- Weathered Road Tar.- Average- and Low-Reactivity Pitch.- Increased Solubility of Reduced Coals.- Deuterated Products from the Reaction of Coal in a D2O Microwave Discharge.- Conclusions.- References.- 2 Field-Ionization Mass Spectra―Structure Correlation for Paraffins.- Discussion of Tables and Figures.- Experimental.- References.- 3 The Analysis of Coal with the Laser Mass Spectrometer.- Coals Used.- Laser Heating.- Obtaining the Spectra.- The Spectra.- Conclusions.- References.- 4 Spectra of Coals and Coal Extracts: Ultraviolet-Visible Spectra of Carbon Disulfide Extracts.- Experimental.- Results.- Discussion.- References.- 5 Spectrometry of Chars―Structure Studies.- Spectrometric Methods.- Infrared Spectrometry.- Other Spectral Methods.- Similar Hydrogenation Reactions of Sucrose and Coal.- Coal-like Chars.- Temperature Effect in the Preparation of Coal-like Chars.- The Effect of Reaction Time.- The Role of Oxygen and Hydrogen in Chars.- Conclusions.- References.- 6 Spectra of Coals and Coal Extracts: Proton Magnetic Resonance Spectra of Pyridine and Carbon Disulfide Extracts.- Experimental.- Results and Discussion.- Elemental Analyses and Extract Yields.- Spectra and Hydrogen Distribution.- Estimation of Carbon Atom Distribution.- Estimation of the Aromaticity of Coal.- References.- 7 13C NMR Chemical Shifts in Selected Hydroaromatic and Aromatic Hydrocarbons.- Experimental.- Spectral Results.- Methylbenzenes.- Ethylbenzenes.- Hydroaromatic Hydrocarbons.- Indan and Dimethylindans.- Other Compounds.- Substituent Effects on Carbon Shieldings.- Spectra-Structure Correlation.- References.- 8 The Potential of 13C NMR in Coal Research.- Experimental.- Results and Discussion.- High-Resolution Studies.- Broadline NMR.- Pulse NMR.- Conclusions.- References.- 9 Spin-Echo Nuclear Magnetic Resonance Studies of Fast Chemical Reactions.- References.- 10 Nuclear Magnetic Resonance Studies of Hydrogen Bonding.- Benzenethiol Complexes.- Amine Complexes.- Water Complexes.- Chloroform Complexes.- Purine and Pyrimidine Complexes.- Self-Association Interactions.- Ternary Complex Involving Metal Binding and Hydrogen Bonding.- ?-Diketone Complexes.- Proton-Exchange Effects.- References.- 11 Nuclear Quadrupole Resonance Spectroscopy and Its Application to Chemistry.- Theory of NQR.- Absorption Frequencies.- Intensities of NQR Transitions.- Detectability of an NQR Signal.- Instrumentation.- Superregenerative Oscillators.- Continuous-Wave Oscillators.- Application of NQR Spectroscopy to Chemistry.- Summary.- References.- 12 Mössbauer Spectroscopy: Principle and Practice.- Theory.- The Isomer Shift.- Quadrupole Splitting.- Hyperfine Splitting.- Experimental.- Applications.- Instrumentation and Methods.- References.- 13 Double-Resonance-Modulated Microwave Spectroscopy.- Qualitative Theoretical Considerations.- Experimental.- Discussion.- Signal Intensity and Linewidth.- Absolute Sensitivity and Comparison with Stark Spectrometer.- Conclusions.- References.- 14 Electron Spin Resonance Studies of Petroleum Asphaltics.- Nature of Free Radical.- Vanadium Unpaired Spin.- Nitrogen Superhyperfine Splittings (shf).- Models for Nonporphyrin Vanadium.- References.- 15 Some Spectral Observations on Coking Lignites.- Results.- Discussion.- References.- 16 Infrared Interferometry―Emission Spectra in the Middle-Infrared Region.- Experimental.- Data Reduction.- Direct Analog Reduction.- Tape-Recorded Reduction.- Digital Reduction.- Results and Discussion.- Emission Spectra of Polymers.- Optical Transformation.- Summary.- References.- 17 Aromatic-Ring-Proton Determination by Infrared-Intensity Measurement in the 1650–2000-Wavenumber Region.- Experimental.- Results.- Discussion.- References.- 18 Characterization of Carbonate Minerals in Oil Shales and Coals by Infrared Spectroscopy.- Carbonates in Oil Shales.- Carbonates in Coals.- Theoretical Aspects of Carbonate Spectra.- Experimental.- Results and Discussion.- Carbonates Identified in Oil Shales.- Carbonates Identified in Coals.- Quantitative Aspects.- References.- 19 The Use of Infrared Spectroscopy to Study Surface Groups and Adsorbed Species on Catalysts.- Surface Groups on Silica-Alumina.- Surface Acid Sites.- Effect of Water on Surface Acidity.- Surface Acidity Model.- Summary.- References.- 20 Self-Association of Phenol in Nonpolar Solvents.- Theoretical.- Experimental.- Equipment and Materials.- Calculations.- Results.- Spectral Data.- Model Fitting.- Thermodynamic Data and End-Group Absorptivity.- Error Study.- Discussion.- Association Models.- End-Group Absorptivity.- Structure of Dimer and Trimer.- Distribution of Species.- References.- 21 Infrared Pseudo Matrix Isolation: A Catalog of Spectra for Chemical Analysis.- Data Handling.- Structure of the Data File.- Applications of the Data File.- Summary.- References.- Appendix―Catalog of Spectra.- 22 ATR-Pyrolysis Spectra of Coal.- Experimental.- Results.- 23 Application of Luminescence Spectrometry to the Analysis of Fuels.- Experimental.- Discussion of Results.- Summary.- References.