Instrumental Methods of Chemical Analysis, 1st ed. 2023

Langue : Anglais

Auteur : Ahluwalia V. K.

Résumé
Sommaire
Biographie
Commentaire

This textbook describes the theory underlying each instrumental procedure and applications of all instrumental methods. It comprehensively covers the instrumental methods of chemical analysis, chromatography, thermal methods of chemical analysis, electrochemical methods, and instrumental methods of analysis of inorganic compounds. These include thermogravimetric analysis, differential thermal analysis, thermometric titrations, and some miscellaneous thermal methods like derivative thermogravimetric analysis, thermobarography, differential scanning calorimetry, thermomechanical analysis, and electric thermal analysis, flame photometry, fluorimetry and phosphorimetry, nephelometric and turbidimetric techniques, refractory and interferometry, and X-ray methods. Each chapter consists a set of problems to aid self-learning. This textbook is highly useful for graduate and postgraduate students on chemistry and its allied fields. It can also be used as a quick reference material by professionals working in the various fields of chemistry and material science.

Instrumental Methods of Chemical Analysis

V.K. Ahluwalia

Visiting Professor

Dr. B.R. Ambedkar Center for Biomedical Research,

University of Delhi

Ane Books Pvt. Ltd.

New Delhi ♦ Chennai

Contents

Part I: Introduction

Introduction

to Instrumental Methods of Chemical Analysis

1.1

Chemical Analysis

1.2

Instrumental Methods—Their Classification

1.3

Selection of the Instrumental Method

1.4

Application of Instrumental Methods/ Techniques

1.4.1 Chromatographic Methods

1.4.2 Thermal Methods

1.4.3 Electrochemical Methods

1.4.4 Instrumental Methods for the Determination of the

structure of Organic Compounds

1.4.5 Instrumental Methods of Analysis of Inorganic

Compounds

1.4.6 Miscellaneous Instrumental Methods

Part II: Chromatographic Methods

Chromatography

2.1

Introduction

2.2

Principle of Chromatographic Separation

2.3

Types of Chromatography

2.3.1 Partition Chromatography

2.3.2 Adsorption Chromatography

2.3.3 Exclusion Chromatography

2.3.4 Ion-exchange Chromatography

Exercises 16

Paper Chromatography

3.1

Circular (or Radical) Paper Chromatography

3.2

Ascending Paper Chromatography

3.3

Descending Paper Chromatography

3.4

Paper Chromatographic Ceparations

3.4.1 Separation and Identification of Group 1 Cations

(Pb', Ag*,

3.4.2 Separation and Identification of Cations of Group II

(Hg²±, Cd²+ and Bi³±)

viii

Instrumental Methods of Chemical Analysis

3.4.3 Separation and Identification of Cu" and Cd"

Using Paper Chromatography 22

3.4.4 Separation and Identification of Amino Acids by

Descending Paper Chromatography 23

3.4.5 Separation and Identification of Monosaccharides

by Descending Paper Chromatography 24

Exercises 25

Thin Layer Chromatography

4.1

Principle of TLC Separation

4.2

Preparation of TLC Plates

4.3

Procedure for TLC

4.4

Preparative TLC

4.5

Two-dimensional TLC

4.6

High-Performance Thin-Layer Chromatography (HPTLC)

4.7

Reversed Phase Partition Thin Layer Chromatography

4.8

Thin Layer Chromatographic Separations

4.8.1 Separation and Identification of Amino Acids by TLC

4.8.2 Separation and Identification of Carbohydrates by TLC

4.8.3 Separation and Identification of Ketones

Exercises

Column Chromatography

5.1

Principle of Column Chromatography

5.2

Procedure of Column Chromatography

5.3

High Performance Column Chromatography

5.4

Dry Column Chromatography

5.5

Chiral Chromatography

5.6

Columns Chromatographic Separations

5.6.1 Separation and Identification of a Mixture of

o-Nitroaniline and p-Nitroaniline by Column

Chromatography

5.6.2 Separation and Identification of a Mixture of cis- and

trans-Azobenzene by Column Chromatography

5.6.3 Purification of Anthracene by Column Chromatography

Exercises44

Gas Chromatography

6.1

Introduction

6.2

Principle of Gas Chromatography

Contents

6.3

6.4

6.5

6.6

The Chromatographic Instrument

6.3.1 Carrier Gas

6.3.2 Sample Injection System

6.3.3 The Column

6.3.4 The Detector

6.3.5 Temperature Programming

Preparative Gas Chromatography
Applications of Gas Chromatography
Gas Chromatographic Separations

6.6.1 Estimation of Sucrose

6.6.2 Estimation of Aluminium in Water

Exercises 54

High Performance Liquid Chromatography (HPLC)

7.1

Introduction

7.2

Principle of HPLC

7.3

HPLC Instruments

7.3.1 Mobile Phase

7.3.2 Sample Injection Systems

7.3.3 Column

7.3.4 Detector

Exercises 57

Gel Chromatography

8.1

Introduction

8.2

Principle of Gel Chromatography

8.3

Types of Gels

8.4

Applications of Gel Chromatography

Exercises 61

Ion Exchange Chromatography

9.1

Introduction

9.2

Different Types of Resins

9.2.1 Anion Exchange Resins

9.2.2 Cation Exchange Resins

9.3

Principle of Ion Chromatography

9.4

Procedure for Ion Chromatography

9.5

Applications of Ion Chromatography

9.5.1 Determination of Anions

9.5.2 Separation of Lit, Na' and K± Ions

9.5.3 Removal of Phosphate (Interferening Radical)

x Instrumental Methods of Chemical Analysis

9.5.4 Softening of Hard Water 68

9.5.5 Demineralised Water 69

9.5.6 Separation of Amino Acids 70

Exercises 71

10. Electro Chromatography 73

10.1 Introduction 73

10.2 Paper Electrophoresis 73

10.3 Gel Electrophoresis 74

10.4 Capillary Electrophoresis (CE) 75

Exercises 77

Part III: Thermal Methods of Chemical Analysis

11. Thermogravimetric Analysis 81

11.1 Introduction 81

11.2 Thermogravimetric Analysis 82

11.3 Thermogravimetric Analyser 82

11.3.1 Measurement of Weight 82

11.3.2 Heating Arrangement and Temperature Measurement 83

11.3.3 Sample Holders 83

11.3.4 Atmospheric Control 83

11.3.5 Recorders 83

11.4 Thermogravimetric Curve (TG curve) 84

11.4.1 Factors Affecting Thermogravimetric Curves 85

11.5 Applications of TGA 86

11.5.1 Determination of Thermal Stability of Salts 86

11.5.2 Analysis of Mixtures 87

11.5.3 Determination of Curie Temperature 87

11.5.4 Organic Compounds 88

Exercises 89

12. Differential Thermal Analysis 91

12.1 Introduction 91

12.2 Differential Thermal Analyser 92

12.3 Factors Affecting DTA 93

12.4 Applications of DTA 94

12.4.1 Heat of Reaction 94

12.4.2 Specific Heat 94

12.4.3 Identification of Substances 95

12.4.4 Identification of the Products of a Reaction 95

12.4.5 Purity of the Compound 95

12.4.6 Quantitative Analysis 95

12.5 Miscellaneous Applications 95 Exercises 96

Contents

13. Thermometric Titrations

13.1

Introduction

13.2

Thermometric Titration Apparatus

13.3

Titrimetric Procedure

13.4

Applications

13.4.1 Neutralisation Titrations

13.4.2 Precipitation Titrations

100

13.4.3 Complexation Titrations

100

13.4.4 Redox Titrations

101

Exercises 101

14.

Miscellaneous Thermal Methods

103

14.1

Derivative Thermogravimetric Analysis (DTA)

103

14.2

Thermobarography

103

14.3

Differential Scanning Calorimetry (DSC)

103

14.4

Thermomechanical Analysis (TMA)

104

14.5

Electric Thermal Analysis (ETA)

105

Exercises 105

Part-IV: Electrochemical Method

15.

Coulometric

Method Of Analysis

109

15.1

Introduction

109

15.2

Coulometer

110

15.3

Coulometric Analysis

111

15.3.1 Constant Current Coulometric Analysis

111

15.3.2 Controlled Potential Coulometric Analysis

112

15.4

Coulometric Titrations

112

15.4.1 Principles of Coulometric Titrations

112

15.4.2 Advantages of Coulometric Titrations

112

15.4.3 Errors in Coulometric Titrations

112

15.4

Nature of Electrodes Used in Coulometric Titrations

113

15.5

Applications of Coulometric Titrations

113

Exercises 115

16.

Polarography

16.1

Introduction

117

16.2

The Instrument

117

16.3

Factors Affecting Current-voltage Curves

119

16.4

Half Wave Potentials

121

16.5

Applications of Polarography

122

Exercises 123

xii Instrumental Methods of Chemical Analysis

17. Amperometric Titrations 125

17.1 Introduction 125

17.2 Apparatus for Amperometric Titrations 125

17.3 End point in Amperometric Titrations 128

17.4 Advantages of Amperometric Titrations 129

17.5 Disadvantages of Amperometric Titrations 130

17.6 Applications of Amperometric Titrations 130

17.7 Amperometric Titrations with Two Indicator Electrodes 132 Exercises 133

18. Potentiometric Titrations 135

18.1 Introduction 135

18.2 Principle of Potentiometric Titration 136

18.3 Indicator Electrode 137

18.4 Reference Electrodes 138

18.5 Apparatus for Potentiometric Titrations 139

18.6 Applications of Potentiometric Titrations 140

18.6.1 Neutralisation Titrations 140

18.6.2 Oxidation-Reduction Titrations 141

18.6.3 Precipitation Titrations 143

18.6.4 Complexometric Titrations 144

18.7 Differential Titrations 144

18.8 Automatic Titrations 145

18.9 Advantages of Potentiometric Titrations 145 Exercises 146

19. Conductometric Titrations 147

19.1 Introduction 147

19.2 Terms Used in Conductometric Titrations 147

19.3 Applications of Conductometric Titrations 149

19.4 Conductometric Titrations 150

19.4.1 Conductometric Titrations of Acids-alkalies 150

19.4.2 Conductometric Precipitation Reactions 153

19.5 Advantages of Conductometric Titrations 154 Exercises 154

20. Spectrophotometric Titrations 155

20.1 Introduction 155

20.2 Procedure of Titration 156

20.3 Applications 157 Exercises 158

Contents

21. High Frequency Titrations

xiii

159

21.1

Introduction

159

21.2

Instrument

159

21.3

High Frequency Titrations

161

21.4

Applications of High Frequency Methods

162

21.4.1 Acid-base Titrations

162

21.4.2 Measurement of Dielectric Constant

162

21.4.3 Analysis of Binary Mixtures

164

21.4.4 Complexometric Titrations

164

21.5

Advantages of High Frequency Titrations

164

Exercises 164

22.

pH Measurements

167

22.1

Introduction

167

22.2

Determination of pH of a Solution by Potentiometry

169

22.2.1 Determination of pH Using Hydrogen Electrode

169

22.2.2 Determination of pH Using Glass Electrode

171

22.2.3 Determination of pH Using Quinhydrone Electrode

173

22.3

Determination of pH Using a pH Meter

175

22.4

Determination of pH Using pH Indicators

176

Exercises 177

23.

Calorimetry

179

23.1

Introduction

179

23.2

Principle of Calorimeter

181

23.3

Procedure for the Estimation of Cue' in a Unknown Solution

181

Exercises 184

Part V: Instrumental Method for Structure Determination of Organic Compounds

24. Infrared Spectroscopy 187

24.1 Introduction 187

24.2 Basic Theory 189

24.3 Instrumentation 189

24.4 Fourier Transform Infrared (FTIR) Spectrometer 190

24.4.1 Principle of Interferometry 191

24.5 Mode of Vibrations 191

24.5.1 Number of Fundamental Vibrations, Selection Rules 192

24.6 Recording of IR Spectra 193 24.7 Major Bands in the IR Spectra of Different Types of Organic

Compounds 197

xiv Instrumental Methods of Chemical Analysis

24.8 Interpretation of the Infrared Spectra 205

24.9 Applications of Infrared Spectroscopy 219

24.10 IR spectras of Some Typical Compounds 222

24.11 Non-dispersive Infrared Spectroscopy 230

Exercises 230

25. Ultraviolet Spectroscopy 241

25.1 Introduction 241

25.2 Terms used in UV Spectroscopy 243

25.3 Electronic Transitions 244

25.4 Ultraviolet Spectrometer 246

25.5 Characteristic Absorption of Organic Compounds 248

25.6 Interpretation of UV Spectra 269

25.7 Applications of UV Spectroscopy 269

Exercises 273

26. Nuclear Magnetic Resonance (NMR) Spectroscopy 279

26.1 Proton Nuclear Magnetic Resonance ('HNMR or PMR) 279 Spectroscopy

26.1.1 Introduction 279

26.1.2 The NMR Spectrometer 281

26.1.3 Interpretation of the 'HNMR Spectra 284

26.1.4 Chemical Shifts of Different Types of Protons 293

26.1.5 The Splitting of Signals 299

26.1.6 Final Interpreting an 'HNMR Spectra 311
26.1.7 Interpretation of the 'HNMR Spectra of Some

Simple Molecules 314

26.1.8 Predicting the 'HNMR Spectrum of an Organic 316 Compound

26.1.9 Complicated 'HNMR Spectra 317

26.1.10 Applications of Proton Magnetic Resonance 325 Spectroscopy

26.2 Carbon-13 NMR (13C NMR) Spectroscopy 329

26.2.1 Introduction 329

26.2.2 Interpretation of 13C NMR Spectra 330

26.2.3 Chemical Shift 332

26.2.4 Identification of Peaks in 13C NMR Spectra on the

Basis of Hybridization of Each Carbon Atom 335

26.2.5 Two-dimensional (2d) 13C NMR Spectroscopy 338

26.2.6 Applications of 13C Spectra 338
Exercise s 340

Contents

27. Electron Spin Resonance (ESR) Spectroscopy

353

27.1

Introduction

353

27.2

Instrument

355

27.3

Recording an ESR spectra

357

27.4

Hyperfine Splitting

359

27.4.1 ESR Spectra of Hydrogen Atom

359

27.4.2 ESR Spectra of Deuterium

360

27.4.3 ESR Spectra of Methyl Radical

362

27.5

Determination of g—value

362

27.6

Line width

363

27.7

Hyperfine Structure in ESR Spectra

363

27.8

Applications of ESR Spectroscopy

366

27.9

Electron Nuclear Double Resonance (ENDOR)

369

27.10 Electron Double Resonance (ELDOR)

369

Exercise s 369

28.

Mass Spectrometry

373

28.1

Introduction

373

28.2

The Mass Spectrometer

374

28.3

The Mass Spectrum

376

28.4

Determination of Molecular Formula

378

28.4.1 Molecular Formula from Isotopic Peaks

378

28.4.2 Molecular Formula Using High-resolution Mass

Spectrometry

381

28.5

Recognitation of the Molecular Ion Peak

382

28.6

Use of the Molecular Formula

384

28.7

Fragmentation

385

28.7.1 Fragmentation by Cleavage of a C—C Single Bond

385

28.7.2 Fragmentation by Cleavage of More than One Bond

388

28.7.3 Rearrangements

390

28.8

Mass Spectra of Some Typical Classes of Compounds

391

28.8.1 Saturated Hydrocarbons

391

28.8.2 Unsaturated Hydrocarbons

393

28.8.3 Alcohols

395

28.8.4 Phenols

398

28.8.5 Ethers

399

28.8.6 Ketones

400

28.8.7 Aldehydes

403

28.8.8 Carboxylic Acids

404

xvi

Instrumental Methods of Chemical Analysis

28.8.9 Carboxylic Esters

405

28.8.10 Lactones

407

28.8.11 Amines

408

28.8.12 Amides

409

28.8.13 Nitro Compounds

410

28.8.14 Nitrites

411

28.8.15 Nitrates

411

28.8.16 Sulfur Containing Compounds

411

28.8.17 Compounds Containing Halogens

412

28.8.18 Heterocyclic Compounds

414

28.9

Gas Chromatography-Mass Spectrometry

417

28.9.1 Applications of Gas Chromatography-Mass

417

Spectrometry

28.10 Negative Ion Mass Spectrometry

417

28.10.1 Negative Ion Formation

418

28.10.2 Reactions Observed During Negative Ion Chemical

Ionization

418

28.10.3 Fragment Patterns of Negative Ions

419

28.10.4 Applications of Negative Ion Mass Spectrometry

423

28.11 Applications of Mass Spectrometry

425

28.11.1 Determination of Structure of Organic Compounds

425

28.11.2 Determination of Molecular Weight and Molecular

Formula

425

28.11.3 Miscellaneous Applications

426

28.12

Solved Problems

426

Exercises 426

29.

Polarimetry

433

29.1

Introduction

433

29.2

Plane Polarized Light

433

29.3

Optical Activity

434

29.4

Kinds of Molecules Analysed by Polarimetry

435

29.5

Theoretical Considerations

435

29.6

Polarimeter

437

29.7

Applications of Polarimetry

437

Exercises 441

Contents

30. Optical Rotatory Dispersion and Circular Dichroism

xvii

443

30.1

Introduction

443

30.2

Circular Birefringence

445

30.3

Circular Dichroism

445

30.4

Cotton Effect

446

30.5

Optical Rotatory Dispersion (ORD)

446

30.5.1 Types of Optical Rotatory Dispresion Curves

446

30.6

Comparison of ORD and CD Curves

448

30.7

Axial Haloketone Rule

448

30.8

The Octant Rule

449

30.9

Instrumentation for ORD and CD Measurements

451

30.9.1 Instruments for ORD Measurements

451

30.9.2 Instrumentation for CD Measurements

452

30.10 Applications of Optical Rotatory Dispersion and Circular Dichroism

453

Exercises456

Part-VI: Instrumental Methods for Analysis of Inorganic Compounds

31.

Microwave Spectroscopy

459

31.1

Introduction

459

31.2

Differences between Microwave Spectroscopy and IR Spectroscopy

460

31.3

Theory of Microwave Spectroscopy

460

31.4

Diatomic Molecule as a Rigid Rotator

460

31.5

Selection Rules for Rotational Spectra

463

31.6

Instrument for Microwave Spectroscopy

465

31.7

Aplications

467

32.

Exercises470

Nuclear Quadrupole Resonance (NQR) Spectroscopy

473

32.1

Introduction

473

32.2

Theory

473

32.3

NQR Instrument

475

32.4

Applications of NQR

476

33.

Exercises478

Raman Spectroscopy

479

33.1

Introduction

479

35.2

Principle of Raman Spectroscopy

479

33.3

Characteristics of Raman Lines

481

33.4

Differences between Raman Spectra and Infrared Spectra

481

xviii Instrumental Methods of Chemical Analysis

33.5 Polarizability 482

33.6 Explanation of Mechanism of Raman Effect 482

33.7 Raman Spectrometer 485

33.8 Intensity of Raman Peaks 486

33.9 Applications of Raman Spectroscopy 486

Exercises 491

34. Mossbauer Spectroscopy 493

34.1 Introduction 493

34.2 Mossbauer Effect 493

34.3 Mossbauer Spectrometer 494

34.4 Nuclides and their Characteristics 496

34.5 Applications Mossbauer Spectroscopy 496

Exercises 500

35. Emission Spectroscopy 503

35.1 Introduction 503

35.2 Types of Spectra 503

35.3 Comparison of Emission Spectroscopy with Flame Photometry 504

35.4 Instrumentation 505

35.5 Applications of Emission Spectroscopy 510

Exercises 512

Part VII: Miscellaneous Instrumental Methods

36. Atomic Absorption Spectroscopy (AAS) 515

36.1 Introduction 515

36.2 The Instrument and Procedure of Estimation 516

36.3 Determination of the Concentration of Element in ppm 519

36.4 Double Beam Atomic Absorption Spectrometer 520

36.5 Atomic Absorption Spectroscopy Versus Flame Emission

Sprectroscopy 520

36.6 Interference 521

36.6.1 Chemical Interference 521

36.6.2 Solvent Interference 521

36.7 Advantages of Atomic Absorption Spectroscopy 521

36.8 Applications of Atomic Absorption Spectroscopy 522

36.9 Flameless Atomic Absorption Method 526

Exercises 526

37. Flame Photometry 527

37.1 Introduction 527

37.2 Principle of Flame Photometry 527

37.3 Components of a Flame Photometer 529

Contents

37.4

Selection of Appropriate Solvent for Dissolving the Salt in

xix

Flame Photometry

533

37.5

Instrument

533

37.5.1 Simple Flame Photometer

533

37.5.2 Internal Standard Flame Photometer

534

37.6

Techniques of Analysis

535

37.6.1 Analysis Involving Calibration Curves

535

37.6.2 Analysis Involving Internal Standard

535

37.6.3 Analysis Involving Addition of Standard

535

37.7

Preparation of Standard Solutions

535

37.8

Interferences in Flame Photometry

536

37.9

Factors Which Affect Intensity of Emitted Radiation

537

37.10

Limitations of Flame Photometry

538

37.11

Applications of Flame Photometry

538

Exercises 539

38.

Fluorimetry and Phosphorimetry

541

38.1

Introduction

541

38.2

Fluorescence and Absorption Method

542

38.3

Fluoremetry and Phosphorimetry

542

38.4

Theory

542

38.4.1 Relation between Fluorescence Intensity and

Concentration

544

38.5

Types of Transitions in Fluorescence

544

38.6

Instrumentation

545

38.6.1 Instrument for Fluorimetric Analysis

545

38.6.2 Instrument for Phosphorimetric Analysis

547

38.7

Applications of Fluorimetry

548

38.8

Applications of Phosphorimetry

551

38.9

Comparison of Fluorimetry and Phosphorimetry

551

Exercises 552

39.

Nephelometric and Turbidimetric Techniques

553

39.1

Introduction

553

39.2

Turbidimetry and Colorimetry

554

39.3

Nephelometry and Fluorimetry

554

39.4

Choice between Nephelometry and Turbidimetry

554

39.5

Basic Principles of Nephelometry and Turbidimetry

554

xx Instrumental Methods of Chemical Analysis

39.6 Instrumentation 556

39.6.1 Turbidimeters 558

39.6.2 Nephelometers 558

39.7 Applications 559 Exercises 562

40. Refractometry and Interferometry 563

40.1 Introduction 563

40.2 Specific Rotation 564

40.3 Molar Refraction 564

40.4 Determination of Refractive index 566

40.5 Applications of Refractometry 567

40.6 Optical Exaltation 568

40.7 Interferometry 569

40.7.1 Applications of Interferometer 571
Exercises 571

41. X-ray Methods 573

41.1 Introduction 573

41.2 Theoretical Consideration 573

41.3 Instrumentation 576

41.4 Instrument for x-ray Absorption 579

41.5 Instrument for x-ray Diffraction 580

41.5.1 Laue Method 580

41.5.2 Rotating Crystal Method 581

41.6 Application of x-ray Diffraction 581

41.7 X-ray Fluorescence 585

41.7.1 Instrumentation 586

41.7.2 Applications of x-ray Fluorescence Spectroscopy 586
Exercises 587

Index 589-592

V.K. Ahluwalia was Professor of Chemistry at Delhi University for more than three decades teaching graduate, postgraduate, and M.Phil. students. He was also Postdoctoral Fellow between 1960 and 1962 and worked with renowned global names from prestigious international universities. He was Visiting Professor of Biomedical Research at University of Delhi.

V.K. Ahluwalia is widely regarded as Leading Subject Expert in chemistry and allied subjects along with being “Choice Award for an Outstanding Academic Title” Winner. He has published more than 100 titles. Apart from books, he has published more than 250 research papers in national and international journals.

Describes the theory underlying each instrumental procedure and application for all instrumental methods

Deals with a very extensive range of instrumental methods of chemical analysis

Includes a set of problems at the end of each chapter