Cover
Half Title
General Analytical Chemistry: Separation and Spectral Methods
Copyright
Preface
Acknowledgments
Contents
Glossary
Acronyms
Part I: Separation Methods
Introduction to the Methods of Separation
1. Separation of a Mixture of Distinct Phases
Mixture of Solid Phases
Mixture of Solid and Liquid Phases
Mixture of Liquid Phases
2. Resolution of a Solid Phase in its Constituents
Fractionated Dissolution
Sublimation
3. Separation by Rupture of Phase
Concentration
Precipitation
Isolation by Crystallization
Isolation by Filtering Membranes
4. Partition Coefficient—Thermodynamic Basis
Extraction and Separation
Partial Molal Gibbs Energy
Chemical Potential
Voltage and Electric Current
Equilibrium of One Solute Between Two Liquid Phases
Thermodynamic Partition Coefficient
Partition Coefficient
Partition Coefficient and Solubility
Berthelot-Jungfleich’s Law
Non-Validity of Berthelot-Jungfleich’s Law
Case in Which Both Solvents are Partially Miscible—The Ternary Diagram
5. Dialysis—Osmosis and Reverse Osmosis
Osmosis and Reverse Osmosis
Dialysis
Electrodialysis
6. Generalities Upon the Liquid-Liquid Extractions
General Considerations
More About the Thermodynamic Partitioning Coefficient—Theoretical Considerations
7. One Stage of Liquid-Liquid Extraction: Batch Extraction
Study in the Case of One Stage of Extraction
Example
Practical Methods
Separation and Fractionation
Terms Used in Extraction
Distribution Ratio
Interest in the Liquid-Liquid Extraction
8. Crosscurrent Extraction or Repetitive Batchwise Extraction by an Immiscible Solvent
Principle and Notations
Quantitative Study
Example of Calculation
Practical Points
Extraction with Fractionation
Conclusion
9. Countercurrent Extraction
Principle
Assimilation of an Extraction Column to a Series of N Theoretical Stages
Quantitative Study in the Case of a Regular Distribution
Geometrical Study
Quantitative Study in the Case of an Irregular Distribution
Example of Calculation for a Regular Distribution
Practical Modalities
Applications
10. Countercurrent Separation or Discontinuous Liquid-Liquid Countercurrent Separation
Description of the Apparatus
Preparation of the Experience
Working of the Apparatus-Case of One Solute: A Qualitative and Quantitative Study
Fraction of the Quantity of Substance Present in One Column
The Separation of Several Compounds
Advantages and Drawbacks of the Method
Craig’s Countercurrent Separation Method and Partage Chromatography
11. Solid Phase Extraction and Microextraction
SPE
Non-Exhaustive Methods of Extraction on Solid Phase
12. Distillation
Recalls
Simple Distillation of Miscible Compounds
Rectification or Fractionated Distillation
Other Distillations
Applications of the Distillations
13. Chromatographic Methods: An Overview
General Approach to Chromatographic Methods
From the Countercurrent Separation to the Partition Liquid Chromatography
The Different Steps of a Chromatography
Types of Chromatography
Chromatographic Peaks
Applications
14. Fundamental Theoretical Aspects of Elution Chromatography
Definitions
Brief Overview of the Theories of Chromatography
The Plates Theory
Kinetic Theories
15. Practical Consequences of the Plates Theory: Qualitative and Quantitative Aspects of the Chromatography
Chromatographic Quantities and Factors of Identification of Solutes
Qualitative Aspects
Quantitative Aspects
Separation of Solutes and Resolution
A Brief Study of the Non-Ideal Behavior: Asymmetry Factor
Ratio Signal Noise
16. Basic Principles of Chromatographic Modes
Adsorption
Partition Chromatogra
Ion-Exchange Chromatography
Ion-Pair Chromatography
Size-Exclusion Chromatography
Affinity Chromatography
Applications
17. Instrumental Chromatographic Methods
Gas Chromatography
High-Performance Liquid Chromatography
Planar Chromatography
18. Electro-Migration Techniques
Overview of Theory
Electromigration Techniques
Capillary Electrophoresis
Applications
Part II: Spectral Methods
Introduction to the Spectral Methods
Electromagnetic Radiations
Nomenclature
Spectral Regions
Classification of Spectra
Production of Spectra
A Classification of the Spectral Methods: Studied Methods
Theory of Absorption Spectra
More About the Internal Energy
Origin of the Absorption Bands
Selection Rules
19. Instrumentation in Spectrophotometry
Principal Components of Spectrophotometers
Sources
Wavelengths Selectors and Monochromator
Measurement Cells
Measurement of the Radiant Energy: Radiation Transducers and Photoelectric Detectors
Thermal Transducers (Specifically Infrared)
Signal Treatment
Configurations of Spectrophotometers
20. Ultraviolet-visible Spectroscopy I: Generalities
Generalities
Terminology
Parameters of an UV-Visible Spectrum
Origin of Electronic Transitions and Intensities of Bands
The Dihydrogen Molecule
The Ethylene Molecule
The Formaldehyde
UV-visible Spectra and Molecular Structures
Part Played by the Solvent
21. Ultraviolet-visible Spectroscopy II: Applications Analytiques
UV-visible Spectroscopy and Quantitative Measurements—Beer-Lambert’s Law
Properties and Limits of Beer-Lambert’s Law
Analytical Conditions of the Measurement of Absorbances
Some Kinds of Applications
On the Apparatus
22. Molecular Luminescence Spectrometry: Fluorescence, Phosphorescence and Chemiluminescence
Origin of the Phenomenon of Fluorescence and Phosphorescence
Quantitative Aspects of Fluorescence
Factors Influencing the Intensity of Fluorescence
Apparatus
Fluorescence and Structures of Fluorescent Molecules
Applications of Fluorescence
Phosphorimetry
Chemiluminescence
23. Turbidimetry and Nephelometry
Introduction and Definitions
Theories of Nephelometry and Turbidimetry
Apparatus
Applications
24. Nuclear Magnetic Resonance Spectroscopy with Continuum Waves: General Principles
N.M.R. in Brief
Principle
Behavior of the Active Nuclei in a Magnetic Field
Behavior of Active Nuclei Localized in a Magnetic Field
Energetic Transitions in N.M.R.
The Nuclear Magnetic Resonance
Exchanges of Energy: Saturation
Relaxation Phenomena
Apparatus
Forms of the Peaks, Widths of the Rays and Intensity of an Absorption Signal
Kinetic Processes—Changes in Configurations and Exchanges of Atoms
25. N.M.R. Spectra Fundamentals: Characteristics and Analytical Applications
Definition of N.M.R. Spectrum: Its General Form
The Effect of Electronic Shielding Effect
Chemical Shift
Spin-Spin Coupling
Supplementary Description of a N.M.R. Spectrum
A Comeback into the Domain of Chemical Shifts
A Comeback on the Spin-Spin Couplings
13C N.M.R.
19F N.M.R.
Quantitative Analyses by N.M.R.
Determination of a Quantity of Matter (or of a Concentration)
Determination of the Molar Fractions of the Constituents of a Mixture
Applications of N.M.R.
26. Fourier Transforms and Fourier Transforms N.M.R.
Fourier’s Transform
N.M.R. and Fourier Transforms
The Successive Steps of the Carrying Out of FT N.M.R. Experiment
Principal Steps of the Registering of FT N.M.R. and the Future of Nuclei
A Brief Comparison Between CV N.M.R. and FT. N.M.R.
Advantages and Applications of FT. N.M.R.
27. Electron Spin Resonance (E.S.R.) and Electron Paramagnetic Resonance (E.P.R.)
A Brief Overview of ESR
Some Paramagnetic Centers
Principle of E.S.R.
Paramagnetic Centers in a Magnetic Field
Transitions in E.S.R.
The Parameter g
Hyperfine Structure
Instrumentation
Spin Density
Applications: Spin Label
28. Infrared Spectroscopy I: Fundamentals of Infrared Spectra
Domains of the Infrared Spectroscopy
Origin of the Absorption Spectra IR
Born-Oppenheimer Principle
Motions of Molecules
Characteristics of the Absorption IR Spectra
Obtaining an IR Absorption Spectrum: Example and Tables
Spectra Infrared of Diatomic Molecules
Rotation and Vibration Spectra: Theoretical Studies
29. Infrared Spectroscopy II: Apparatus, Qualitative and Quantitative Analysis MID, Infrared Reflection and Near-Infrared Spectrometries
A Brief Overview
Techniques and Apparatus
Qualitative and Quantitative Analysis
Other Methodologies of IR Spectroscopy
Applications in Physical Chemistry
30. Raman Spectroscopy
Principle: Raman and Rayleigh Effect
Apparatus
Experimental Facts
Selection Rules
Rotational Raman Spectra: Gross Selection Rules and Energy Spacing Successive Levels
A Brief Comparison of Infrared and Raman Spectroscopy
Applications
31. Polarimetry
Definition
Structure of a Luminous Wave
Fundamental Experience: Polarizer and Analyzer
Plane of Polarization
Nature of the Polarized Light
Polarizers and Analyzers
Polarimetry
Variables Affecting the Optical Activity
The Wavelength
Specific Rotatory Power
Molecular Rotation [M] or [ϕ]
Influence of the Solvent
Influence of the Temperature
The True Angular Rotation
Some Applications
32. Rotatory Dispersion: Circular Dichroism
Introduction
Theoretical Aspects
Values of Parameters
Origin of the Phenomena
Apparatus
Applications
Structural Chemistry
Biochemistry
33. Introduction to the Atomic Absorption and Emission Spectroscopies
Generalities
Origin of the Transitions
The Different Steps of an Analysis by Atomic Spectroscopy
Criteria of Choice Between the Atomic Absorption and Emission
Quantitative Aspects
Practical Aspects
Performances of the Analytical Techniques
34. Atomic Absorption Spectrometry
Principle
Apparatus: Some Components
Problems with Correction of the Background Noise
Performances of the Techniques
Applications
Interest of the Atomic Absorption
35. Atomic Emission Spectrometry
General Principle
Emission Spectra
Sources of Energy
Instrumentation for Optical Emission Spectroscopy (OES)
Characteristics of Atomic Emission Spectroscopy
Choice of SAA or ES
Applications
Coupling ICP-MS
36. Analysis by X-Rays
General Characters of X-Rays
Apparatus
X-Ray Spectroscopy by Emission
Absorptiometry of X-Rays
Atomic Fluorescence Spectroscopy
Other Modes of Generation of X-Rays
Some Components of the Apparatus
Diffraction X
37. Radiochemical Methods of Analysis
Radioactivity
Detection and Measurement
Analysis by Radiochemical Methods
Applications
Part III: Various Methods
Introduction: Definitions and Classification of the Thermal Methods of Analysis
38. Thermogravimetry
Principle
Definitions
Apparatus
Examples
Applications of Thermogravimetry
39. Thermal Differential Analysis and Calorimetric Differential Analysis
Definitions
Physical Basic Phenomena
Theoretical Aspects
Apparatus
Applications of ATD and DSC
40. Thermometric Titration
Principle of the Method
Apparatus
Theoretical Possibilities of the Thermometric Titration
True Thermograms
Analytical Possibilities of the Thermometric Titration
Some Examples of Analytical Applications
Applications in the Domain of Physical Chemistry
41. Mass Spectrometry
Definition of Mass Spectrometry and Mass Spectrometer
A Brief Description of Aston’s Apparatus
Different Components of a Mass Spectrometer
The Double Focusing Mass Analyzer
Elementary Description of a Mass Spectrum—Fragmentation
Technical Characteristics of Analyzers
42. Some Kinds of Mass Spectrometry and Some Mass Spectrometers and Components
Inductively Coupled Plasma Mass Spectrometry—ICPMS
Matrix-Assisted Laser Desorption Ionization—Time-of-flight Mass Spectrometry: (MALDI-TOF/MS)
Electrospray Ionization Mass Spectrometry (ESI-MS)
Some Other Components of Mass Spectrometers
Fourier Transform Mass Spectrometers
Mass Spectrometers and Computers
43. Applications of Mass Spectrometry
Identification of Pure Compounds
Biological Applications of Mass Spectrometry
Hyphenated Mass Spectral Methods
Quantitative Applications of Mass Spectrometry
44. Criteria of Purity
Case of Solids
Case of Liquids
Appendices
Bibliography
Index