Francis Rouessac - Chemical Analysis

1 Cover

2 Title Page

3 Copyright Page

4 Foreword

5 About the companion website

6 Introduction

7 Chapter 1: General Aspects of ChromatographyINTRODUCTION 1.1 GENERAL CONCEPTS OF ANALYTICAL CHROMATOGRAPHY 1.2 THE CHROMATOGRAM 1.3 GAUSSIAN PEAKS AND REAL PEAKS 1.4 PLATE THEORY 1.5 NERNST PARTITION COEFFICIENT ( K ) 1.6 COLUMN EFFICIENCY 1.7 RETENTION PARAMETERS 1.8 SEPARATION (OR SELECTIVITY) FACTOR 1.9 RESOLUTION FACTOR 1.10 INFLUENCE OF SPEED OF THE MOBILE PHASE 1.11 OPTIMIZATION OF A CHROMATOGRAPHIC ANALYSIS 1.12 CLASSIFICATION OF CHROMATOGRAPHIC TECHNIQUES 1.13 PRINCIPLE AND BASIC RELATIONSHIP 1.14 CHROMATOGRAPHY SOFTWARE 1.15 EXTERNAL STANDARD METHOD 1.16 INTERNAL STANDARD METHOD 1.17 INTERNAL NORMALIZATION METHOD KEY POINTS OF THE CHAPTER PROBLEMS SOLUTIONS

8 Chapter 2: Gas Chromatography 2.1 COMPONENTS OF A GC INSTALLATION 2.2 CARRIER GAS AND FLOW REGULATION 2.3 INJECTION CHAMBER 2.4 TEMPERATURE‐CONTROLLED OVEN 2.5 COLUMNS 2.6 STATIONARY PHASES 2.7 MAIN DETECTORS 2.8 OPTIMIZATION OF A SEPARATION 2.9 FAST CHROMATOGRAPHY AND MICROCHROMATOGRAPHY 2.10 RETENTION INDEXES AND STATIONARY PHASE CONSTANTS KEY POINTS OF THE CHAPTER PROBLEMS SOLUTIONS

9 Chapter 3: High‐Performance Liquid Chromatography 3.1 DESIGN OF AN HPLC APPARATUS 3.2 PUMPS AND ELUTION GRADIENTS 3.3 INJECTORS 3.4 COLUMNS 3.5 STATIONARY PHASES 3.6 MOBILE PHASES 3.7 SPECIFIC COLUMNS 3.8 PRINCIPAL DETECTORS 3.9 HPLC OPTIMIZATION 3.10 NEW DEVELOPMENTS IN HPLC KEY POINTS OF THE CHAPTER PROBLEMS SOLUTIONS

10 Chapter 4: Ion Chromatography 4.1 BASICS OF ION CHROMATOGRAPHY 4.2 STATIONARY PHASES FOR IEC 4.3 MOBILE PHASES 4.4 CONDUCTIVITY DETECTORS 4.5 WATER PEAK AND SYSTEM PEAK 4.6 ION SUPPRESSORS OF THE ELECTROLYTE 4.7 ION‐EXCLUSION CHROMATOGRAPHY 4.8 AMINO ACID ANALYSERS 4.9 PASSAGE FROM IEC TO ULTRA‐IEC KEY POINTS OF THE CHAPTER PROBLEMS SOLUTIONS

11 Chapter 5: Thin‐Layer Chromatography 5.1 PRINCIPLE OF THIN‐LAYER CHROMATOGRAPHY (TLC) 5.2 CHARACTERISTICS OF TLC 5.3 STATIONARY PHASES 5.4 SEPARATION AND RETENTION PARAMETERS 5.5 QUANTITATIVE TLC KEY POINTS OF THE CHAPTER PROBLEMS SOLUTIONS

12 Chapter 6: Supercritical Fluid Chromatography 6.1 SUPERCRITICAL FLUIDS: A REVIEW 6.2 CARBON DIOXIDE AS A MOBILE PHASE 6.3 INSTRUMENTATION IN SFC 6.4 COMPARISON OF SFC WITH HPLC AND GC 6.5 SEPARATION OF ENANTIOMERS BY SFC 6.6 SFC IN CHROMATOGRAPHIC TECHNIQUES KEY POINTS OF THE CHAPTER PROBLEMS SOLUTIONS

13 Chapter 7: Size‐Exclusion Chromatography 7.1 PRINCIPLE OF SEC 7.2 STATIONARY AND MOBILE PHASES 7.3 INSTRUMENTATION 7.4 APPLICATIONS OF SEC 7.5 POLYMER CHARACTERISTICS 7.6 FIELD FLOW FRACTIONATION (FFF) KEY POINTS OF THE CHAPTER PROBLEMS SOLUTIONS

14 Chapter 8: High‐Performance Capillary Electrophoresis 8.1 PRINCIPLE OF CAPILLARY ELECTROPHORESIS 8.2 MIGRATION OF ANALYTES IN THE CAPILLARY 8.3 INSTRUMENTATION 8.4 ELECTROPHORETIC TECHNIQUES 8.5 PERFORMANCE OF CE 8.6 CAPILLARY ELECTROCHROMATOGRAPHY KEY POINTS OF THE CHAPTER PROBLEMS SOLUTIONS

15 Chapter 9: Ultraviolet and Visible Absorption Spectroscopy 9.1 SPECTRAL REGION FROM UV‐VISIBLE TO VERY NEAR IR 9.2 THE ORIGIN OF ABSORPTIONS 9.3 ELECTRONIC TRANSITIONS OF ORGANIC COMPOUNDS 9.4 CHROMOPHORE GROUPS 9.5 SOLVENT EFFECTS 9.6 INSTRUMENTATION IN THE UV‐VISIBLE RANGE 9.7 CONFIGURATIONS OF UV/VIS SPECTROPHOTOMETERS 9.8 MEASUREMENT CELLS AND DEVICES 9.9 QUANTITATIVE ANALYSIS: LAWS OF MOLECULAR ABSORPTION 9.10 METHODS IN QUANTITATIVE ANALYSIS 9.11 METHODS OF BASELINE CORRECTION 9.12 RELATIVE ERROR DISTRIBUTION DUE TO INSTRUMENTS 9.13 DERIVATIVE SPECTROSCOPY 9.14 VISUAL COLORIMETRY BY TRANSMISSION OR REFLECTANCE KEY POINTS OF THE CHAPTER PROBLEMS SOLUTIONS

16 Chapter 10: Infrared and Raman Spectroscopy 10.1 THE ORIGIN OF LIGHT ABSORPTION IN THE INFRARED REGION 10.2 PRESENTATION OF ABSORPTION IN THE INFRARED REGION 10.3 ROTATIONAL–VIBRATIONAL BANDS IN THE MID‐IR REGION 10.4 MECHANICAL MODEL FOR VIBRATIONAL INTERACTIONS BETWEEN ATOMS 10.5 REAL COMPOUNDS 10.6 CHARACTERISTIC BANDS FOR ORGANIC COMPOUNDS 10.7 INFRARED SPECTROMETERS AND ANALYSERS 10.8 SOURCES AND DETECTORS USED IN THE MID‐IR REGION 10.9 SAMPLE ANALYSIS TECHNIQUES 10.10 COUPLED TECHNIQUES 10.11 COMPARISON OF SPECTRA 10.12 QUANTITATIVE ANALYSIS 10.13 ANALYSIS IN THE NEAR INFRARED REGION 10.14 PRINCIPLE OF THE RAMAN EFFECT 10.15 INSTRUMENTATION 10.16 FIELDS OF APPLICATION KEY POINTS OF THE CHAPTER PROBLEMS SOLUTIONS

17 Chapter 11: Fluorescence and Chemiluminescence Spectroscopy 11.1 ORIGIN OF FLUORESCENCE 11.2 FLUORESCENT COMPOUNDS 11.3 RELATIONSHIP BETWEEN FLUORESCENCE AND CONCENTRATION 11.4 RAYLEIGH SCATTERING AND RAMAN SCATTERING 11.5 INSTRUMENTATION 11.6 SPECIFICITIES AND APPLICATIONS 11.7 CHEMILUMINESCENCE KEY POINTS OF THE CHAPTER PROBLEMS SOLUTIONS

18 Chapter 12: X‐Ray Fluorescence Spectroscopy 12.1 BASIC PRINCIPLES 12.2 THE X‐RAY FLUORESCENCE SPECTRUM 12.3 EXCITATION SOURCES IN X‐RAY FLUORESCENCE 12.4 DETECTION OF X‐RAYS 12.5 DIFFERENT TYPES OF INSTRUMENTS 12.6 SAMPLE PREPARATION 12.7 X‐RAY ABSORPTION – X‐RAY DENSITOMETRY 12.8 QUANTITATIVE ANALYSIS BY X‐RAY FLUORESCENCE 12.9 APPLICATIONS OF X‐RAY FLUORESCENCE KEY POINTS OF THE CHAPTER PROBLEMS SOLUTIONS

19 Chapter 13: Atomic Absorption Spectroscopy 13.1 THE EFFECT OF TEMPERATURE ON AN ELEMENT 13.2 APPLICATIONS TO MODERN INSTRUMENTS 13.3 MEASUREMENTS BY AAS 13.4 BASIC INSTRUMENTATION FOR AAS 13.5 PHYSICAL AND CHEMICAL DISTURBANCES 13.6 CORRECTIONS OF NONSPECIFIC ABSORPTIONS 13.7 SENSITIVITY AND DETECTION LIMITS IN AAS KEY POINTS OF THE CHAPTER PROBLEMS SOLUTIONS

20 Chapter 14: Atomic Emission Spectroscopy 14.1 OPTICAL EMISSION SPECTROSCOPY (OES) 14.2 PRINCIPLE OF ATOMIC EMISSION ANALYSIS 14.3 DISSOCIATION OF THE SAMPLE INTO ATOMS OR IONS 14.4 DISPERSIVE SYSTEMS AND SPECTRAL LINES 14.5 SIMULTANEOUS AND SEQUENTIAL INSTRUMENTS 14.6 PERFORMANCE 14.7 APPLICATIONS OF ATOMIC EMISSION SPECTROMETRY 14.8 FLAME PHOTOMETRY KEY POINTS OF THE CHAPTER PROBLEMS SOLUTIONS

21 Chapter 15: Nuclear Magnetic Resonance Spectroscopy 15.1 GENERAL INTRODUCTION 15.2 SPIN/MAGNETIC FIELD INTERACTION FOR A NUCLEUS 15.3 NUCLEI THAT CAN BE STUDIED BY NMR 15.4 BLOCH THEORY FOR I = ½ 15.5 LARMOR FREQUENCY 15.6 SPECTRUM OBTAINED BY PULSED NMR 15.7 THE PROCESSES OF NUCLEAR RELAXATION 15.8 CHEMICAL SHIFT 15.9 MEASURING THE CHEMICAL SHIFT 15.10 SHIELDING AND DESHIELDING OF THE NUCLEI 15.11 FACTORS INFLUENCING CHEMICAL SHIFTS 15.12 HYPERFINE STRUCTURE – SPIN–SPIN COUPLING 15.13 SPIN DECOUPLING AND PARTICULAR PULSE SEQUENCES 15.14 13C NMR 15.15 TWO‐DIMENSIONAL NMR ( 2D‐NMR ) 15.16 FLUORINE AND PHOSPHORUS NMR 15.17 NMR APPLICATIONS KEY POINTS OF THE CHAPTER PROBLEMS SOLUTIONS

22 Chapter 16: Mass Spectrometry 16.1 BASIC PRINCIPLES 16.2 SAMPLE INTRODUCTION 16.3 MAIN VACUUM IONIZATION TECHNIQUES 16.4 ATMOSPHERIC PRESSURE IONIZATION (API) 16.5 ANALYSERS 16.6 ION DETECTION 16.7 IDENTIFICATION BY MEANS OF A SPECTRAL LIBRARY 16.8 ANALYSIS OF THE ELEMENTAL COMPOSITION OF IONS 16.9 FRAGMENTATION OF ORGANIC IONS 16.10 PROTEIN ANALYSIS 16.11 ICP‐MS COUPLING KEY POINTS OF THE CHAPTER PROBLEMS SOLUTIONS

23 Chapter 17: Isotopic Analyses and Labelling Methods 17.1 PRINCIPLE OF ISOTOPIC DILUTION METHODOLOGIES 17.2 MEASUREMENT BY ADDING A RADIOISOTOPE 17.3 MEASURING BY ADDING A STABLE ISOTOPE 17.4 MEASURING ISOTOPE RATIOS FOR AN ELEMENT 17.5 MEASUREMENTS USING ENZYMATIC LABELLING 17.6 NEUTRON ACTIVATION ANALYSIS (NAA) 17.7 REVIEW OF RADIOACTIVE ISOTOPES 17.8 HALF‐LIFE τ, RADIOACTIVITY CONSTANT λ AND ACTIVITY A 17.9 RADIOACTIVE LABELLING OF ORGANIC MOLECULES 17.10 DETECTION AND COUNTING OF RADIOACTIVITY 17.11 SPECIAL PRECAUTIONS KEY POINTS OF THE CHAPTER PROBLEMS SOLUTIONS

24 Chapter 18: Specific Analysers 18.1 SPECIFIC ANALYSES 18.2 ELEMENTAL ORGANIC ANALYSIS 18.3 TOTAL NITROGEN ANALYSERS (TN) 18.4 TOTAL SULFUR ANALYSERS 18.5 TOTAL CARBON ANALYSERS (TC, TIC, AND TOC) 18.6 MERCURY ANALYSERS 18.7 ION MOBILITY SPECTROMETRY (IMS) 18.8 KARL FISCHER VOLUMETRIC METHOD KEY POINTS OF THE CHAPTER PROBLEMS SOLUTIONS