《modern methods of chemical analysis second edition》

1 Introduction1

PHASE CHANGES AND SEPARATIONS5

2 Analytical Uses of Phase Changes5

2-1 Introduction5

2-2 Phase Changes for Pure Compounds5

2-3 Phase Changes for Mixtures13

2-4 Fractional Distillation19

2-5 Nonideal Solutions24

3 Extraction28

3-1 Introduction28

3-2 Distribution Law29

3-3 Successive Extractions30

3-4 Separation of Mixtures by Extraction33

3-5 The Craig Method of Multiple Extraction34

3-6 Continuous Countercurrent Extraction38

4 Chromatography41

4-1 Introduction41

4-2 Types of Chromatography42

4-3 Chromatographic Theory44

5 Liquid Column Chromatography54

5-1 Introduction54

5-2 Liquid-Solid Adsorption Chromatography54

5-3 Liquid-Liquid Partition Chromatography59

5-4 High Performance Liquid Chromatography60

5-5 Ion Exchange Methods62

5-6 Gel Chromatography70

6 Plane Chromatography76

6-1 Introduction76

6-2 Paper Chromatography77

6-3 Thin-Layer Chromatography81

6-4 Zone Electrophoresis82

7 Gas Chromatography85

7-1 Introduction85

7-2 Basic GLC Apparatus85

7-3 Carrier Gas86

7-4 Sample Introduction86

7-5 Columns88

7-6 Column Performance88

7-7 Solid Supports89

7-8 Liquid Phases90

7-9 Detectors92

7-10 Qualitative Analysis: Retention Parameters97

7-11 Quantitative Analysis102

7-12 Temperature Effects105

7-13 Gas-Solid Chromatography106

7-14 Applications108

ELECTROMAGNETIC RADIATION115

8 Electromagnetic Radiation and Its Interaction with Matter115

8-1 Introduction115

8-2 Nature of Electromagnetic Radiation115

8-3 Absorption and Emission of Radiation117

8-4 Luminescence Phenomena120

8-5 Refraction and Refractive Index122

8-6 Interference and Diffraction125

8-7 Light Scattering127

8-8 Rotation of Polarized Light128

9 Quantitative Analysis by Absorption of Electromagnetlc Radiation133

9-1 Introduction133

9-2 Quantitative Laws133

9-3 Deviations from Beer's Law138

9-4 Photometric Error142

9-5 Intensity of Luminescence143

10 instrumentation for Spectrometry147

10-1 Introduction147

10-2 Sources of Radiant Energy147

10-3 Monochromators148

10-4 Sample Handling153

10-5 Detection Devices154

10-6 Amplification and Readout of Detector Signals158

10-7 Single-Beam vs.Double-Beam Operation160

10-8 Typical Instruments161

11 Infrared Spectroscopy165

11-1 Introduction165

11-2 Infrared Theory166

11-3 Sample Preparation170

11-4 Infrared Absorption Spectra171

11-5 Infrared Correlation Charts173

11-6 Interpretation of Infrared Absorption Spectra173

11-7 Representative Spectra177

11-8 Elucidation of Structure184

11-9 Tables of Absorption Characteristics201

12 Ultraviolet Spectroscopy226

12-1 Introduction226

12-2 Theory226

12-3 The Chromophores228

12-4 Solvation and Substitution235

12-5 Interpretation and Use of Ultraviolet Spectra237

13 Flame Emission and Atomic Absorption Spectroscopy243

13-1 Introduction243

13-2 Emission and Absorption in Flames243

13-3 Atomization and Ionization245

13-4 Flames246

13-5 Burners and Nebulizers248

13-6 Nonflame Atomization251

13-7 Radiation Sources and Optical Systems253

13-8 Flame Spectra and Interferences256

13-9 Quantitative Analysis259

13-10 Typical Applications262

14 X-ray Methods267

14-1 Introduction267

14-2 Emission, Dispersion and Detection of X rays267

14-3 Absorption of X rays273

14-4 Diffraction of X rays275

14-5 Electron Microprobe Analysis278

15 Nuclear Magnetic Resonance Spectroscopy279

15-1 Introduction279

15-2 Magnetic Properties of the Nucleus279

15-3 Nuclear Resonance281

15-4 Nuclear Relaxation282

15-5 N.M.R. Instrumentation and Technique283

15-6 The Chemical Shift285

15-7 Spin-Spin Splitting292

15-8 Interpretation of N.M.R. Spectra299

15-9 Additional Topics305

MASS SPECTROMETRY316

16 Mass Spectrometry of Organic Compounds316

16-1 Introduction316

16-2 Methods of Ion Production316

16-3 Ion Separators321

16-4 Ion Collection and Recording325

16-5 Sample Handling Techniques325

16-6 Resolution328

16-7 The Mass Spectrum328

16-8 Interpretation of Mass Spectra331

16-9 Behavior of Classes of Compounds334

16-10 Identification of Unknowns343

16-11 Analysis of Mixtures346

16-12 Some Additional Applications347

17 Spark Source Mass Spectrometry353

17-1 Introduction353

17-2 Instrumentation353

17-3 Sample Handling354

17-4 Interpretation of Spectra356

17-5 Qualitative Identification of Elements356

17-6 Quantitative Analysis358

ELECTROANALYTICAL CHEMISTRY361

18 Electrochemical Cells and Potentiometry361

18-1 Introduction361

18-2 Electrochemical Cells362

18-3 Electrode Potentials365

18-4 Types of Electrodes377

18-5 Cell Voltage Measurements383

18-6 Definition of pH and the pH Meter384

18-7 Equilibrium Constants386

18-8 Potentiometric Titrations389

18-9 Coupled Reaction Systems394

19 Some Other Electrochemical Techniques400

19-1 Electrodeposition400

19-2 Controlled Current Electrolysis401

19-3 Controlled Cathode (or Anode) Potential Electrolysis403

19-4 Secondary Coulometric Titrations403

19-5 Polarography406

ACIDS, BASES AND THEIR SALTS AND COMPLEXES413

20 Monoprotic Systems413

20-1 Introduction413

20-2 Acid-Base Concepts413

20-3 Role of the Solvent414

20-4 Relative Strengths of Acids and Bases416

20-5 Equilibria in Monoprotic Systems419

20-6 Acid-Base Titrations in Aqueous Solution427

20-7 Acid-Base Titrations in Nonaqueous Solvents431

21 Polyprotic Systems438

21-1 Introduction438

21-2 Phosphoric Acid System438

21-3 Distribution of Species Diagrams439

21-4 Calculations for Polyprotic Systems442

21-5 Titrations with Polyprotic Systems445

21-6 Polyamine and Amino Acid Systems446

21-7 Amino Acid Titrations451

22 Metal Ion Complexes454

22-1 Introduction454

22-2 Monodentate Ligands454

22-3 Metal Chelates456

22-4 Conditional Formation Constants458

22-5 Titration Equilibria460

22-6 Compleximetric Indicators462

22-7 Scope of EDTA Applications463

RADIOCHEMISTRY466

23 Radiochemical Methods466

23-1 Introduction466

23-2 Radioactive Disintegration466

23-3 Interaction of Radiation with Matter469

23-4 Detection and Measurement of Radioactivity471

23-5 Counting Statistics, Errors and Corrections475

23-6 Some Applications of Radioisotopes480

23-7 Radiation Safety482

EVALUATION AND PROCESSING OF ANALYTICAL DATA485

24 Statistical Treatment of Data485

24-1 Introduction485

24-2 Significant Figures485

24-3 Types of Errors486

24-4 Normal Distribution of Random Errors487

24-5 Statistical Treatment of Small Data Sets490

24-6 Control Charts492

25 Data Processing494

25-1 Introduction494

25-2 Indicating and Recording Devices494

25-3 Integrators497

25-4 Digital Computers501

25-5 Computerized Gas Chromatography503

25-6 Computerized Mass Spectrometry505

25-7 Computerized N.M.R. Spectroscopy509

25-8 Other Analytical Applications of Digital Computers512

25-9 Operational Amplifiers513

25-10 Analog and Hybrid Computers515

AUTOMATIC AND PROCESS ANALYZERS519

26 Automatic Analyzers519

26-1 Introduction519

26-2 Basic Automatic Analyzer520

26-3 Beckman "DSA 560"521

26-4 Ljundberg "Autolab"522

26-5 DuPont "ACA"522

26-6 Technicon "AutoAnalyzer"524

26-7 Electro-Nucleonics "GeMSAEC System"528

27 Process Analyzers531

27-1 Introduction531

27-2 Specific and Nonspecific Analyzers531

27-3 Typical Process Analyzer532

27-4 Sample Handling System533

27-5 Analyzer Calibration534

27-6 Process Gas Chromatograph535

27-7 Oxygen Analyzers538

27-8 Infrared Analyzers540

27-9 Moisture Analyzers542

27-10 Colorimetric Analyzers544

28 Process Control547

28-1 Introduction547

28-2 Feedback Control547

28-3 Dynamic Response of the System549

28-4 Cascade and Feedforward Control551

28-5 Controller Characteristics553

28-6 Applications of Control Systems558

Index564