Analytical Atomic Spectroscopy

1 Historical Introduction.- 1. Early Developments.- 2. The Newtonian Era.- 3. The Early 1800’s (to Kirchhoff and Bunsen).- 4. The Later 1800’s.- 5. Arc and Spark Excitation.- 6. Flame Emission Spectroscopy.- 7. Atomic Absorption Spectroscopy.- 8. Atomic Fluorescence Spectroscopy.- Selected Reading.- 2 The Origin of Atomic Spectra.- 1. The Nature of Electromagnetic Radiation.- 2. Early Concepts.- 3. The Balmer Equation.- 4. From Balmer to Bohr.- 4.1. Spectral Line Series for Hydrogen.- 4.2. Energy Level Diagrams.- 5. Modifications of the Bohr Theory.- 5.1. Selection Rules for n and k(l).- 5.2. Atoms with Two Valence Electrons.- 5.3. Selection Rules and the Schrödinger Equation.- 6. Alkali Metal Atom Spectra.- 6.1. Doublet Structure of Alkali Metal Spectra.- 6.2. Electron Spin.- 7. Alkaline Earth Atomic Spectra.- 8. Spectral Series and Spectroscopic Term Symbols.- 9. Zeeman and Stark Effects.- 10. Spectral Line Intensities.- 10.1. Statistical Weight.- 10.2. The Boltzmann Distribution Factor.- 11. Transition Probabilities—Oscillator Strengths.- 12. Spectral Linewidths.- 13. Atomic Fluorescence.- 14. Metastable States—Laser Action.- 14.1. Laser Action.- 15. Molecular Spectra (Band Spectra).- Selected Reading.- 3 Filters, Prisms, Gratings, and Lenses.- 1. Filters.- 1.1. Absorption Filters.- 1.2. Interference Filters.- 1.3. Circular Variable Filters.- 2. Prisms.- 2.1. Dispersion of a Prism.- 2.2. Resolving Power of a Prism.- 2.3. Prism Materials.- 2.4. Types of Prisms.- 3. Interferometers.- 4. Diffraction Gratings.- 4.1. Dispersion of a Grating.- 4.2. Resolving Power of a Grating.- 4.3. Production and Characteristics of Gratings.- 4.4. Grating Replicas.- 4.5. Concave Gratings.- 4.6. Holographic Gratings.- 4.7. Echelle Gratings.- 5. Lenses.- 5.1. Uses of Lenses.- 5.2. Lens Defects.- Selected Reading.- 4 Spectrometers.- 1. prism Spectrometers.- 1.1. The Cornu Prism Spectrometer.- 1.2. The Littrow Spectrometer.- 2. Plane Grating Spectrometers.- 2.1. The Ebert Spectrometer.- 2.2. The Czerny—Turner Spectrometer.- 2.3. The Two-Mirror, Crossed-Beam, Plane Grating Spectrometer.- 2.4. The Double-Grating Spectrometer.- 3. Concave Grating Spectrometers.- 3.1. The Rowland Spectrometer.- 3.2. The Paschen-Runge Spectrometer.- 3.3. The Eagle Spectrometer.- 3.4. The Wadsworth Spectrometer.- 3.5. The Grazing Incidence Spectrometer.- 3.6. The Seya-Namioka Spectrometer.- 3.7. Vacuum Spectrometers.- 4. Direct Reading Spectrometers.- 5. Selection of a Spectrometer.- 6. Adjustment and Care of Spectrometers.- 6.1. Vertical Adjustment of the Entrance Slit.- 6.2. Focusing the Entrance Slit.- 6.2.1. Prism Instruments.- 6.2.2. Grating Instruments.- 6.3. Final Adjustments.- 6.4. General Care of Spectrometers.- Selected Reading.- 5 Accessory Equipment for Arc and Spark Spectrochemical Analysis.- 1. The Spectrometer Slit.- 2. The Hartmann Diaphragm.- 3. The Step Filter.- 4. Rotating Sectors.- 5. Excitation Sources.- 5.1. The Direct Current Arc.- 5.2. The Alternating Current Arc.- 5.3. The Electric Spark.- 5.4. The Plasma Arc.- 5.5. The Laser Source.- 5.6. Multiple Source Units.- 6. Arc and Spark Stands.- 6.1. Special Assemblies for the Arc-Spark Stand.- 6.1.1. The Stallwood Jet.- 6.1.2. The Petry Stand.- 6.1.3. Rotating Disk Electrode Device.- 7. Order Sorters.- 8. Densitometers and Comparators.- 9. Miscellaneous Accessory Equipment.- 9.1. Electrodes.- Selected Reading.- 6 Recording and Reading Spectra.- 1. The Photographic Process.- 1.1. Characteristics and Properties of the Photographic Emulsion.- 1.2. The Characteristic Curve.- 1.3. The Reciprocity Law.- 1.4. The Intermittency Effect.- 1.5. The Eberhard Effect.- 1.6. Graininess and Granularity.- 1.7. Resolving Power.- 1.8. Spectral Sensitivity.- 2. Processing of Spectroscopic Films and Plates.- 2.1. The Developing Process.- 3. Hadamard Transform and Fourier Transform Spectroscopy.- 4. Light-Sensitive Phototubes.- 4.1. Spectral Response Designation.- 4.2. General Characteristics of Multiplier Phototubes.- 4.3. Solar Blind Phototubes.- 5. Resonance Detectors.- 6. Vidicon Detectors.- Selected Reading.- 7 Qualitative and Semiquantitative Arc-Spark Emission Spectrochemical Analysis.- 1. Sample Excitation.- 2. Wavelength Measurements.- 2.1. Line Identification by Wavelength Measurement.- 3. Comparison Spectra.- 4. Spectral Charts.- 5. Wavelength Tables.- 6. Some Special Problems and Techniques of Spectrochemical Qualitative Analysis.- 6.1. Spectral Line Interferences.- 6.2. Spectral Band Interferences.- 6.3. Arc Continuum Interference.- 7. Increasing Spectral Line Intensities.- 8. Semiquantitative Spectrochemical Analysis.- 8.1. Determination of a Concentration Level.- 8.2. The Harvey Method of Semiquantitative Spectrochemical Analysis.- 8.3. Matrix Effects.- 8.4. The Wang Method of Semiquantitative Spectrochemical Analysis.- 9. Some Special Spectrochemical Problems.- 9.1. Microsamples.- 9.2. Microarea Sampling.- Selected Reading.- 8 Quantitative Spectrochemical Analysis.- 1. Some General Considerations.- 2. The Internal Standard.- 3. Spectroscopic Buffers.- 4. Excitation of the Sample.- 5. Selection of Spectral Lines.- 6. Comparison Standards.- 7. Sample Preparation.- 8. Emulsion Calibration and Analytical Working Curves.- 8.1. Emulsion Calibration.- 8.2. The Emulsion Calibration Curve.- 9. The Working Curve.- 9.1. Construction of a Typical Analytical Working Curve.- 10. The Calculating Board.- 11. Background Correction.- 12. Multielement Analysis with Direct Read-Out.- 13. Types of Samples.- 13.1. Liquid Samples.- 13.2. Metallic Samples.- 13.3. Powder Samples.- 13.4. Organic Samples.- 13.5. Special Samples.- 14. Some Special Techniques.- 14.1. Fractional Distillation.- 14.2. Carrier Distillation.- 14.3. Transfer Methods.- 14.4 Laser Methods.- 14.5. Controlled Atmospheres.- 14.6. Cathode Layer Excitation.- 14.7. Gases.- 14.8. Radioactive Samples.- 15. Time-Resolved Spectroscopy.- 15.1. Time-Resolving Components.- 15.2. Some Characteristics of Time-Resolved Spectra.- 15.3. Analytical Applications.- 16. Chemical Preparation of Samples.- 17. Applications of Spectrochemical Analysis.- 17.1. Metals and Alloys.- 17.2. Geology.- 17.3. Oils and Water.- 17.4. Plants and Soils.- 17.5. Men and Animals.- 17.6. Environmental Studies.- 17.7. Some Other Applications.- Selected Reading.- 9 Flame Emission Spectroscopy.- 1. Flame Emission Instrumentation Requirements.- 2. The Analytical Flame.- 2.1. Burners and Aspirators.- 2.2. Fuel-Oxidant Control.- 3. The Excitation Process in the Flame.- 3.1. Flame Emission Spectra.- 4. Flame Emission Interferences.- 4.1. Spectral.- 4.2. Ionization.- 4.3. Cation-Anion Interferences.- 4.4. Cation-Cation Interferences.- 4.5. Oxide Formation.- 4.6. Chemiluminescence.- 4.7. Physical Interferences.- 5. Control of Interferences.- 5.1. Spectral.- 5.2. Ionization Interference Control..- 5.3. Cation-Anion Interference Control.- 5.4. Control of Oxide Interference.- 5.5. Control of Physical Interference.- 6. Simultaneous Multielement Analysis.- 7. Analytical Treatment of Data.- 7.1. Establishment of a Working Curve.- 7.2. Background Correction.- 7.3. Sample Bracketing.- 7.4. The Method of Standard Additions.- Selected Reading.- 10 Analytical Atomic Absorption Spectroscopy.- 1. The Atomic Absorption Process.- 2. Instrumentation Requirements.- 3. Radiation Sources.- 3.1. Hollow Cathode Lamps.- 3.1.1. High-Intensity Lamps.- 3.1.2. Multiple-Element Lamps.- 3.1.3. Demountable Lamps.- 3.2. Gaseous Discharge Lamps.- 3.3. Electrodeless Discharge Lamps.- 3.4. Flame Emission Sources.- 3.5. Continuous Sources.- 4. Production of the Atomic Vapor.- 4.1. Nebulization of the Sample.- 4.1.1. Ultrasonic Nebulization.- 4.2. Flame Systems.- 5. Fuels and Oxidants.- 5.1. Atomic Distribution in Flames.- 6. Non-Flame Absorption Cells.- 6.1. Hollow Cathodes.- 6.2. L’vov Furnace.- 6.3. Woodriff Furnace.- 6.4. Delves Cup.- 6.5. Carbon Rod Analyzers.- 6.6. Tantalum Boat Analyzer.- 6.7. Other Non-Flame Cells.- 6.8. Special Systems.- 7. Monochromators.- 8. Detectors.- 8.1. Resonance Detection.- 9. Amplifiers.- 10. Read-Out Devices.- 11. Interferences in Atomic Absorption.- 11.1. Spectral Interferences.- 11.2. Ionization Interferences.- 11.3. Chemical Interferences.- 11.4. Interferences with Flameless Sampling.- 12. Control of Interferences.- 12.1. Spectral Interference Control.- 12.2. Ionization Interference Control.- 12.3. Chemical Interference Control.- 12.3.1. Flame Temperature.- 12.3.2. Fuel-to-Oxidant Ratio.- 12.3.3. Flame Region.- 12.3.4. Releasing and Chelating Agents.- 12.3.5. Chemical Separations.- 12.3.6. Background Correction.- 13. Analytical Treatment of Data.- 13.1. The Working Curve.- 13.2. Analytical Procedures.- 14. Simultaneous Multielement Analysis.- Selected Reading.- 11 Atomic Fluorescence Spectroscopy.- 1. Theoretical Basis of Analytical Atomic Fluorescence Spectroscopy.- 2. Advantages and Limitations of Atomic Fluorescence.- 3. Instrumentation.- 3.1. Excitation Sources.- 3.1.1 Hollow Cathode Lamps.- 3.1.2. Metal Vapor Lamps.- 3.1.3. Electrodeless Discharge Lamps.- 3.1.4. Continuous Sources.- 3.1.5. Laser Sources.- 4. The Sample Cell.- 4.1. Total-Consumption Aspirator Burners.- 4.2. Laminar Flow Burners.- 4.3. Non-Flame Sample Cells.- 5. Monochromators.- 6. Interferences in Atomic Fluorescence.- 6.1. Spectral Interferences.- 6.2. Chemical Interferences.- 6.3. Physical Interferences.- 7. Analytical Procedures.- 7.1. The Analytical Working Curve.- 7.2. Organic Solvents.- 7.3. Detection Limits.- 7.4. Sample Preparation.- 8. Applications and Future Developments.- Selected Reading.- Appendix I. Some Basic Definitions, Physical Constants, Units, and Conversion Factors.- Appendix IV. Spectral Charts.- Appendix V. Absorbance Values Calculated from Percentage Transmittances.- Appendix VI. Numerical Values of the Seidel Function.- Appendix VII. Four-Place Logarithm Table.- Appendix VIII. Detection Limits by Flame Emission and Atomic Absorption.- Appendix IX. Periodic Table of the Elements.- Appendix X. Relative Atomic Weights.- Author Index.