Das Analytical Chemistry Second Edition Sample Chatper PDF

Second Edition
ANALYTICAL
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CHEMISTRY yr
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Dhruba Charan Dash

Analytical Chemistry
Second Edition
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Dhruba Charan Dash
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Formerly, Professor and Head
Postgraduate Department of Chemistry
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Sambalpur University
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Odisha
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Delhi-110092
2016
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ANALYTICAL CHEMISTRY, Second Edition

Dhruba Charan Dash
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© 2011 by PHI Learning Private Limited, New Delhi. All rights reserved. No part of this book
may be reproduced in any form, by mimeograph or any other means, without permission
in writing from the publisher.
ISBN-978-81-203-0000-0
The export rights of this book are vested solely with the publisher.
Published by Asoke K. Ghosh, PHI Learning Private Limited, M-97, Connaught Circus,
New Delhi-110001 and Printed by ----------------------------------------------------------------------
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Contents
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Preface xix
Preface to the First Edition xxi
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UNIT 1
1. Qualitative Analysis
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1.1 Introduction 3
1.1.1 Solubility Product Principle 3
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1.1.2 Common Ion Effect 4
1.2 Separation of Cations into Groups 4
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1.3 Detection and Separation of Cations of Each Group 10

1.3.1 Separation and Detection of Group I (Silver Group) Cations 10
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1.3.2 Separation of Group IIA from Group IIB Cations

(by Yellow Ammonium Sulphide) 11
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1.3.3 Separation and Detection of Group IIA Cations (Copper Group) 11

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1.3.4 Separation and Detection of Group IIB Cations (Arsenic Group) 14

1.3.5 Separation and Detection of Group IIIA Cations (Iron Group) 16
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1.3.6 Separation and Detection of Group IIIB Cations (Zinc Group) 18

1.3.7 Separation and Detection of Group IV Cations 20
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1.3.8 Separation and Detection of Group V Cations 21

1.4 Separation and Detection of Acid Radicals (Anions) 23
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1.4.1 Detection of Group I Anions 23

1.4.2 Detection of Group II Anions 27
1.4.3 Group III Anions (Precipitation Group) 38
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Group A Questions on Qualitative Analysis of Basic Radicals (Cations) 44

A. Objective Type Questions 44
B. Short Answer Type Questions 46
C. Long Answer Type Questions 48
Group B Questions on Qualitative Analysis of Acid Radicals (Anions) 49
D. Multiple Choice Questions 49
E. Short Answer Type Questions 50
F. Long Answer Type Questions 53
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vi Contents
UNIT 2
2. Quantitative Analysis—Volumetric (Titrimetric) Analysis 57–100
2.1 Introduction 57
2.2 Volumetric (Titrimetric) Calculation 59
2.2.1 Calculation Based on Normality (N) of the Solution 60
2.2.2 Calculation Based on Molarity (M) of the Solution 60
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2.3 Conditions for Volumetric (Titrimetric) Analysis 61
2.4 Types of Titrimetric Analysis 62
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2.5 Acid-base Titration and Ways of Locating End Point 62
2.5.1 Theory of Acid-base Titration 62
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2.5.2 Ways of Locating the End Point of an Acid-base Titration 63
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2.5.3 Titration of Strong Acid with Strong Base 65
2.5.4 Titration of Weak Acid with Strong Base 66
2.5.5 Titration of Weak Base with Strong Acid 68
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2.5.6 Titration of Weak Acid with Weak Base 69
2.5.7 Factors Determining the Exact Form of a pH Curve 70
2.6
2.6.1 Theory of Redox Titration ht
Oxidation Reduction (Redox) Titration and Ways of Locating End Point
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2.6.2 Study of Redox Titration by Electrochemical Potential Method 72
2.6.3 Ways of Locating the End Point for Redox Titration 73
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2.7 Complexometric Titration and Ways of Locating End Point 79

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2.7.1 Theory of Complexometric Titration Involving EDTA 79

2.7.2 Study of EDTA Complex Formation Taking Disodium Salt of EDTA and
Effect of pH 83
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2.7.3 Ways of Locating the End Point 84

2.7.4 Estimation of Calcium and Magnesium by Complexometric
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Titration by EDTA 85
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2.8 Problems Involved in Titrimetric Methods 86

2.8.1 Problems on Acid-base Titration 86
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2.8.2 Problems on Redox Titration 93

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B. Very Short Answer Type Questions 98
C. Short Answer Type Questions 99
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D. Long Answer Type Questions 100

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3. Quantitative Analysis—Precipitation Gravimetry 101–135

3.1 Introduction 101
3.1.1 Precipitation Gravimetry 101
3.1.2 Gravimetric Calculation and Gravimetric Factor 101
3.1.3 Requirements for Successful Gravimetry 102
3.1.4 Steps Involved in Gravimetric Analysis 102
3.2 Precipitation 103
3.2.1 Definition of Precipitation 103
3.2.2 Conditions of Precipitation 103
Contents vii
3.2.3 Theories of Precipitation 103
3.2.4 Homogeneous Precipitation 105
3.2.5 Contamination of the Precipitate 107
3.2.6 Errors in Precipitation 111
3.3 Digestion (Aging) 111
3.3.1 Reasons for Digestion 111
3.4 Filtration 112
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3.5 Washing of the Precipitate 113
3.5.1 Ideal Qualities of a Washing Liquid 113
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3.5.2 Types of Wash Solution 113
3.5.3 Mode of Washing 114
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3.6 Drying and/or Incineration of the Precipitate 114
3.6.1 Conditions of Drying 114
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3.6.2 Purpose of Ignition 115
3.6.3 Ignition Temperature 115
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3.7 Weighing 115
3.8 Specific and Selective Precipitation 116
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3.9 Organic Precipitants 116
3.9.1 Types of Organic Precipitants 116
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3.9.2 Advantages of Using Organic Precipitants 119
3.9.3 Disadvantages of Using Organic Precipitants 120
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3.10 Sequestering (or Masking) Agent 120
3.11 Problems Involved in Precipitation Gravimetry 121
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3.11.1 Problems on Gravimetric Factor (GF) 121

3.11.2 Problems on Determination of Elements and Percentage of Purity 123
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3.11.3 Determination of Sample Size 126

3.11.4 Analysis of Alloy 130
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UNIT 3
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4. Statistical Methods of Analysis 139–175

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4.2 Significant Figures 139

4.2.1 Definition of Significant Figure 139
4.2.2 Rules for Determining Significant Figures 140
4.3 Errors and Their Causes 142
4.3.1 Definition of Errors 142
4.3.2 Classification of Errors 142
4.3.3 Determinate Errors 142
4.3.4 Causes of Determinate Errors 143
4.3.5 Indeterminate Errors 145
viii Contents
4.4 Propagation of Errors 146

4.4.1 Uncertainty Involving Addition and Subtraction 146
4.4.2 Uncertainty Involved in Multiplication and Division 146
4.5 Accuracy and Precision 147
4.5.1 Accuracy 147
4.5.2 Methods of Expressing Accuracy 148
4.5.3 Precision 149
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4.5.4 Comparison between Accuracy and Precision 149
4.5.5 Methods of Expressing Precision 150
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4.6 Test of Significance 155
4.6.1 Comparing a Mean Value with a True Value (The Student’s t Test) 156
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4.6.2 Comparing Two Experimental Means 157
4.6.3 Comparison of Two Standard Deviations (F Test) 158
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4.6.4 Chi-square Test (l2 Test) 159
4.7 Rejection of a Result 159
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4.7.1 Rule Based on Average Deviation 159
4.7.2 Rule Based on the Range (Q Test) 160
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4.8 Problems Involved in Data Analysis 161
4.8.1 Problems on Significant Figures 161
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4.8.2 Problems on Rounding off Number 162
4.8.3 Problems on Uncertainties 163
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4.8.4 Problems on Errors and Uncertainty 164
4.8.5 Problem on Relative Error 165
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4.8.6 Problems on Expressing Precision 166

4.8.7 Problems on Propagation of Errors 169
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4.8.8 Problem on Confidence Level 171

4.8.9 Problem on Rejection of Data 171
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4.8.10 Problem on Student t Test 171

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UNIT 4
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5. Estimation of Organic Compounds 179–210

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5.2 Detection of Elements (Principles Only) 179

5.2.1 Detection of Carbon and Hydrogen 179
5.2.2 The Preparation of Sodium Extract (Lassaigne’s Test) 180
5.3 Estimation of Elements 181
5.3.1 Estimation of Carbon and Hydrogen (Liebig’s Combustion Method)
Principle 181
5.3.2 Estimation of Nitrogen 185
5.3.3 Estimation of Sulphur (By Carius Method) 190
5.3.4 Estimation of Halogens (By Carius Method) 190
5.3.5 Estimation of Phosphorus (By Carius Method) 191
Contents ix
5.4 Estimation of Glucose 192
5.5 Estimation of Phenol 193
5.6 Estimation of Aniline 195
5.7 Estimation of Keto Group 196
5.8 Analysis of Oils and Fats 197
5.8.1 Determination of Iodine Value 197
5.8.2 Determination of Saponification Values 199
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5.8.3 Determination of Reichert–Meissel Value (RM Value) 200
5.9 Problems Involved in Estimation of Organic Compounds 201
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5.9.1 Problems on Estimation of Carbon and Hydrogen 201
5.9.2 Problems on Estimation of Nitrogen 202
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5.9.3 Problems on Estimation of Halogens and Sulphur 203
5.9.4 Problems on Estimation of Sugar 204
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5.9.5 Problems on Saponification Value and RM Value 204
5.9.6 Problems on Estimation of Phenol and Aniline 205
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C. Short Answer Type Questions
D. Long Answer Type Questions
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UNIT 5
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6. Separation Techniques 213–262

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6.2 Solvent Extraction Method 213

6.2.1 Introduction 213
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6.2.2 Principle of Solvent Extraction 214

6.2.3 Comparison between Single and Multiple Extraction 217
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6.2.4 Separation Factor 220

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6.2.5 Methods of Solvent Extraction 221

6.3 Application of Solvent Extraction 223
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6.3.1 Solvent Extraction of Metal Ions by Chelation 223

6.3.2 Conclusions on Extraction of Metal Chelates 224
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6.4 Chromatographic Methods and Their Classification 225

6.4.2 Definition of Chromatography 225
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6.4.3 Classification of Chromatographic Methods 226

6.5 General Theory and Principle of Column or Adsorption Chromatography 228
6.6 Ion-Exchange Chromatography 234
6.6.1 Principle 234
6.6.2 Cation Exchange Resin 235
6.6.3 Anion Exchange Resin 236
6.6.4 Mechanism of Ion Exchange 236
6.6.5 Ion Exchange Capacity 237
6.6.6 Factors Affecting Ion Exchange Equilibria 237
x Contents
6.6.7 Experimental Set-up 238

6.6.8 Packing of Column 239
6.6.9 Applications of Ion Exchange Chromatography 239
6.7 Paper Chromatography 240
6.7.1 Principle 240
6.7.2 Theory of Paper Chromatography 240
6.7.3 Technique of Paper Chromatography 242
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6.7.4 Applications of Paper Chromatography 246
6.8 Thin Layer Chromatography (TLC) 247
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6.8.1 Principles 247
6.8.2 Choice of Adsorbent for TLC 247
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6.8.3 Choice of Solvent 247
6.8.4 Experimental Techniques 248
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6.8.5 Sample Application 248
6.9 Development of the Chromatogram 248
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6.10 Gas Chromatography 251
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6.10.2 Principle of Gas Chromatography 251
6.10.3 Applications of Gas Chromatography 255
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7. Purification Techniques 263–284

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7.2 Purification Techniques for Solid Organic Compounds 263

7.2.1 Crystallization 264
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7.2.2 Fractional Crystallization 267

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7.2.3 Sublimation 267

7.2.4 Sublimation under Reduced Pressure 268
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7.2.5 Solvent Extraction 269

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7.3 Purification Techniques for Liquids 270

7.3.1 Simple Distillation 270
7.3.2 Fractional Distillation 271
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7.3.3 Distillation under Reduced Pressure 273

7.3.4 Steam Distillation 275
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7.4 Chemical Method of Separation and Purification 278

7.5 Criteria of Purity 281
Contents xi
UNIT 6
8. Electroanalytical Techniques—Electrogravimetry 287–315
8.2 Classification of Electroanalytical Techniques 287
8.3 Electrical Components 288
8.3.1 Electrodes and Electrode Potential 288
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8.3.2 Electrochemical Cell 290
8.3.3 Electrical Circuit 291
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8.3.4 Galvanostat and Potentiostat 292
8.4 Electrogravimetry 292
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8.4.2 Theory and Principle of Electrogravimetry 292
8.4.3 Types of Electrogravimetry 293
8.5 Electrolysis in a Simple Cell 294
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8.6 Electrolysis in a Non-galvanic Cell 294
8.6.1 Concept of Decomposition Potential 295
8.6.2
8.6.3
Ohmic Potential or IR Drop
Overpotential (Overvoltage) ht
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8.6.4 Causes of Overvoltage 297
8.6.5 Expression for Total Potential Applied to Cause Electrolysis 298
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8.7 Electrolysis in a Galvanic Cell 298

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8.8 Electrolysis at Constant Current 299

8.9 Electrolysis at Constant Voltage 302
8.10 Electrolysis at Controlled Potential 302
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8.11 Spontaneous or Internal Electrolysis 304

8.11.1 Electrolysis at the Anode 304
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8.12 Problems Involved in Electrogravimetry 305

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9. Electroanalytical Techniques—Coulometry 316–338

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9.2 Coulometric Calculation 316
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9.3 Determination of Charge, Q 317

9.4 Coulometers 318
9.4.1 Silver Coulometer 318
9.4.2 Iodine Coulometer 319
9.4.3 Gas Coulometer (Hydrogen-Oxygen Coulometer) 319
9.5 Constant Current Coulometry 320
9.6 Comparison of Constant Current Coulometry with Conventional Volumetric
Titration 322
xii Contents
9.7 Coulometric Titration 322

9.7.1 Primary Coulometric Titration 322
9.7.2 Secondary Coulometric Titration 323
9.7.3 End Points in Coulometric Titration 324
9.8 Applications of Coulometric Titration 324
9.8.1 Neutralization (Acid-Base) Titration 324
9.8.2 Precipitation Titration 325
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9.8.3 Redox Titration 326
9.8.4 Complexometric Titration 326
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9.9 Controlled Potential Coulometry 327
9.10 Applications of Controlled Potential Coulometry 329
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9.11 Problems Involved in Coulometry 330
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10. Electroanalytical Techniques—Polarography

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10.2 Principle of Polarography 339
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10.2.1 Factors Affecting Current Flow in a Polarographic Cell 339
10.2.2 Explanation for Residual Current 340
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10.2.3 Elimination of Convection Current 340

10.2.4 Elimination or Suppression of Migration Current 340
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10.2.5 Measurement of Diffusion Current 341

10.2.6 Ilkovic Equation 342
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10.2.7 Derivation of Ilkovic Equation 343

10.2.8 The Concept of Half-wave Potential (E1/2) 344
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10.3 Difficulties Encountered in Polarography 346

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10.4 Experimental Set-up 348

10.5 Advantages and Disadvantages of DME 349
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10.6 Applications of Polarography 350

10.6.1 Qualitative Evaluation of Polarographic Data 350
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10.6.2 Quantitative Evaluation of Polarographic Data 350

10.6.3 Determination of Formation Constants of Complexes 353
10.6.4 Analysis of Mixture of Ions 354
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10.6.5 Determination of Dissolved Oxygen 355

10.7 Problems Involved in Polarography 355
Contents xiii
UNIT 7
11. Spectroanalytical Techniques—Ultraviolet and Visible
Spectral Method 365–414
11.2 Principle of UV-visible Spectroscopy 366
11.2.1 Origin of UV-visible Spectroscopy 366
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11.2.2 Absorption Law 367
11.2.3 Nature of Electronic Spectrum 370
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11.2.4 Selection Rules for Absorption 371
11.3 Techniques Involved in UV-visible Spectroscopy 373
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11.3.1 Description of UV-visible Spectrophotometer 373
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11.3.2 Types of UV-visible Spectrophotometer 374
11.3.3 Working Principle 375
11.3.4 Choice of Solvent 375
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11.4 Types of Eletronic Transition 376
11.4.1 Transitions Involving s, p and n (Non-bonding Electrons) 376
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11.4.2 Absorbing Species Involving d or f Electrons
11.4.3 Charge Transfer (CT) Spectral Absorption 380
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11.5 Type of Absorptions Bands 381
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11.5.1 K-Bands 381
11.5.2 R-Bands 381
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11.5.3 B-Bands (Benzeneoid Bands) 381

11.5.4 E-Bands (Ethylenic Bands) 382
11.6 The Concept of Chromophore and Auxochrome 383
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11.6.1 Chromophore 383

11.6.2 Auxochrome 384
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11.7 Shifting of Absorption Band and Change in Intensity 385

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11.7.1 Terminology Used in UV-visible Spectroscopy 385

11.7.2 Effect of Conjugation of Chromophore 386
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11.7.3 Additive Characteristics 386

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11.7.4 Effect of Aromatic Rings 387

11.7.5 Effect of Substitution of Auxochrome 387
11.7.6 Effect of Solvent Polarity 388
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11.7.7 Stereo Chemical Factors 389

11.8 Application of UV-visible Spectral Method 390
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11.8.1 Structural Analysis 390

11.8.2 Empirical Rules for Calculation of Absorption Maxima (lMax) 391
11.8.3 Additivity of Absorbance 397
11.8.4 Multiple Analysis 397
11.8.5 Determination of the pK Value of Indicator 398
11.8.6 Composition of the Coloured Complex 400
11.8.7 Quantitative Analysis 404
11.8.8 Detection of Impurities 404
11.8.9 In Tautomeric Equilibria 405
xiv Contents
11.9 Some More Problems Involved in UV-visible Spectral Method 405

12. Spectroanalytical Techniques—Infrared (IR) Spectral Method 415–456
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12.2 Molecular Vibrations and Vibrational Frequency 415
12.2.1 Vibration of Diatomic Molecules 415
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12.2.2 The Vibration of Polyatomic Molecules 418
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12.2.3 Types of Molecular Vibrations 418
12.3 Selection Rule for IR Absorption 422
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12.4 Breakdown of Selection Rule and Occurrence of Overtones, Combination
Bands and Difference Bands 423
12.5 Symmetries of Vibration and Their IR Activity 424
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12.6 Instrumentation 428
12.7 Concept of Group Vibrational Frequencies 429
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12.7.1 Factors Influencing Group Vibrational Frequencies 430
12.8 Important Spectral Regions in the Infrared and Presentation IR Spectra 433
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12.9 IR Characteristics of Some Organic Compounds 435
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2.10 IR Characteristics of Some Inorganic Compounds
(Especially Metal Complexes) 448
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13. Spectroanalytical Techniques—Nuclear Magnetic Resonance

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13.2 Principle of NMR 457
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13.2.1 Magnetic Properties of Nuclei and Their Angular Momentum 457

13.2.2 Magnetic Moments of the Nuclei 458
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13.2.3 Effect of External Magnetic Field 459

13.2.4 Potential Energy of a Nucleus in a Magnetic Field 459
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13.2.5 Potential Energy of a Proton in a Magnetic Field 460

13.2.6 Classical Description of NMR 462
13.2.7 Intensity of NMR Signals 463
13.3 Technique Involved in NMR Spectroscopy 464
13.4 Prediction of Number of NMR Signals 466
13.5 Position of the Signals and Chemical Shift 468
13.6 Factors Influencing Chemical Shifts 471
13.6.1 Effect of p Electrons Circulation (Magnetic Anisotropy) 471
13.6.2 Inductive Effect 473
13.6.3 Effect of Electron Withdrawing and Electron Donating Groups 474
13.6.4 Hydrogen Bonding 475
Contents xv
13.7 Spin-Spin Coupling (or Splitting) 477
13.7.1 Explanation for Spin-Spin Interactions 477
13.8 Multiplicity of NMR Peaks 481
13.9 Problems Involving Chemical Shift and Spin-Spin Splitting 482
13.10 Coupling Constant (J) 489
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14. Spectroanalytical Techniques—Electron Spin Resonance
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14.2 Basic Principle 497
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14.2.1 Interaction between Electron Spin and Magnetic Field 497
14.2.2 Potential Energy of Electron When Placed in a Magnetic Field 498
14.2.3 Resonance Condition 499
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14.3 Relaxation Process and Line Width in ESR Transition 500
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14.4 Techniques of ESR Spectroscopy 502
14.4.1 Instrumentation 502
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14.4.2 Sample Concentration and Choice of Solvent 503
14.4.3 Presentation of ESR Spectra 503
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14.4.4 Interpretation of Derivative Curve 504

14.4.5 Use of Standards 504
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14.5 Hyperfine Splitting 504

14.6 Zero Field Splitting and Kramer’s Degeneracy 511
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14.7 Application of ESR 514

14.7.1 Determination of g Value 514
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14.7.2 Shape and Type of Hybridization 515

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14.7.3 Study of Free Radicals 515

14.7.4 Study of Internal Motion (Rotation) 516
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14.7.5 ESR and Steric Hinderance 516

14.7.6 Analysis of Electron Transfer Reactions through ESR 516
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14.7.7 ESR in Polymer Chemistry 517

14.7.8 Spin Labelling of Biomolecules 517
14.7.9 ESR Studies of Inorganic Compounds, Mainly Complexes 517
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15. Spectroanalytical Techniques—Mass Spectral Method 525–574

15.2 Theory (Basic Principle) 525
xvi Contents
15.3 Instrumentation 527

15.3.1 Sample Introducing System 528
15.3.2 Ion Source and Accelerating Chamber 528
15.3.3 Mass Analyzer and Magnet 528
15.3.4 Ion Collector/Detector and Amplifier 530
15.3.5 Recorder 530
15.4 Interpretation of Mass Spectra 531
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15.5 Type of Ions Produced in a Mass Spectrometer 532
15.5.1 Molecular Ion or Parent Ion 532
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15.5.2 Isotope Ions 534
15.5.3 Metastable Ions or Peaks 534
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15.5.4 Fragmented Ion and Fragmentation Modes 537
15.6 Mass Spectra of Some Organic Compounds 543
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15.6.1 Straight Chain Alkanes 543
15.6.2 Branched Chain Alkanes 544
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15.6.3 Alkens (Olefins) 545
15.6.4 Cycloalkanes 547
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15.6.5 Cyclo Olefins 548
15.6.6 Alkynes (Acetylenes) 548
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15.6.7 Aromatic Compounds 548
15.6.8 Alkyl Halides 551
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15.6.9 Alcohols, Ethers and Amines 551
15.6.10 Fragmentation Mode of Aromatic Alcohols, Phenols, Aromatic
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Amines, Aryl Ethers 557

15.6.11 Aliphatic Aldehydes and Ketones 560
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15.6.12 Aromatic Aldehydes and Ketones 563

15.6.13 Carboxylic Acids, Esters and Amides 563
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15.6.14 Aromatic Acids 568

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15.6.15 Fragmentation Modes of Nitro Compounds 568

15.6.16 Fragmentation Modes of Aliphatic Nitriles R — CH2 — C ºº N 569
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15.6.17 Fragmentation Modes of Aliphatic Nitrites 570

15.6.18 Fragmentation Modes of Aliphatic Nitrates 570
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16. Thermoanalytical Techniques 575–597

16.2 Thermogravimetric Analysis (TGA) 575
16.2.2 Principle of TGA 576
16.2.3 Instrumentation for TGA 577
16.2.4 Factors Affecting TGA 579
16.2.5 Applications of TGA 581
Contents xvii
16.3 Derivative Thermogravimetric Analysis (DTGA) 585
16.4 Differential Thermal Analysis (DTA) 586
16.4.2 Occurrence of Endothermic and Exothermic Peaks 587
16.4.3 Principles and Methods 587
16.4.4 Instrumentation for DTA 589
16.4.5 Factors Affecting DTA 589
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16.4.6 Applications of DTA 590
16.5 Simultaneous TGA-DTA Study 592
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16.6 Problems Involved in TGA and DTA 594
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Index 599–605
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Preface
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This edition has been thoroughly revised and is an enlarged version of first edition including a
new chapter on “Thermo Analytical Technique”. This has been supplemented to cater the needs
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of the students including most of the topics as prescribed in the presently restructured syllabus
on analytical chemistry by University Grants Commission meant for +3 students of Indian
Universities.
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As in first edition, this addition continues to lucidly present the broad understanding of principles,
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applications and the instrumentation involved. Besides the theoretical topics in analytical chemistry,
some more topics dealing with practical subjects like qualitative analysis, quantitative analysis
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(volumetric and precipitation gravimetry) estimation of organic compounds, separation techniques
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etc are included in this book so that it will be beneficial to the students in learning both theory and
practical subjects. Hearty thanks are due to Dr. Raj Kishora Dash, Mrs. Reeta Kumari Dash,
Dr. Ranjan Kumar Dash and Dr. Ranjan Kumar Mohapatra for their constant inspiration and
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encouragement towards publication of this edition.

Last but not the least the overwhelming appreciations received from the students and teaching
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community and contribution by the authors referred to are gratefully acknowledged.

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Dhruba Charan Dash

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xix
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Preface to the First Edition
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This book is written exclusively for +3 B.Sc. (Pass and Hons) students of chemistry according to
the recently restructured syllabus prescribed by various Indian universities.
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The general objective of this book is to provide a broad understanding of the principles,
applications and limitations of the various techniques involved in analytical chemistry in a systematic
and lucid manner, so that even an average student can grasp the intricacies of the subject. It
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includes qualitative and quantitative analysis, data analysis, elemental analysis for organic
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compounds, separation and purification techniques, electroanalytical techniques such as
electrogravimetry, coulometry, polarography, spectroanalytical techniques such as ultraviolet and
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visible spectral method, infrared spectral method, nuclear magnetic resonance spectral method,
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electron spin resonance spectral method and mass spectral method. Each chapter provides a brief
but sufficient overview of the definitions, theoretical principles and instrumentation involved.
These are further elucidated by suitable examples and numerical problems. Different types of
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objective type questions (multiple type, true and false type, and fill in the blanks type), short
questions, hints and sets of problems with answers are provided in each chapter, so that a student
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can easily judge his/her understanding of the subject.

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The book will stimulate the students to face the academic and research challenges in analytical
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chemistry for the new millennium. Contributions by several authors referred to in the present
book is gratefully acknowledged.
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Dhruba Charan Dash

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xxi
CHAPTER 4
Statistical Methods of Analysis
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4.1 INTRODUCTION
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It is impossible to perform a chemical analysis in such a way that the results are totally free from
errors or uncertainties. For example, while measuring weights, volume or pH, etc. the measured
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values will differ from the actual values. All one can hope is to minimize these errors and to
estimate their size with acceptable accuracy. In this chapter typical types of errors encountered and
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their statistical analysis are discussed which involve the followings:
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(a) Significant figures to represent the data
(b) Errors and their causes
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(c) Accuracy and precision

(d) Methods of expressing accuracy and precision.
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4.2 SIGNIFICANT FIGURES

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To represent the analytical data obtained from the measurement, certain figures which involve the
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number of digits are necessary. The figures used to estimate the uncertainty involved in the
measurement are called significant figures.
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4.2.1 Definition of Significant Figure

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Significant figure in a number may be defined as all the certain digits plus one doubtful
(or uncertain) digit. For instance, if the volume of the liquid is measured by a burette, which is
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graduated, to 0.1 ml any volume reported should reflect this. For example, volumes of 12.6 ml and
12.60 ml are numerically the same. But from the analytic point of view 12.6 ml containing three
figures (1, 2, 6) is significant when the burette is graduated to 0.1 ml whereas actual volume is
12.6 ± 0.1, 12.60 ml containing four figures (1, 2, 6, 0) is significant only if the burette is graduated
to 0.01 ml In the above example, the numbers 1 and 2 are known with certainty while there is some
uncertainty in the last digit so that the actual volume could be anything between 12.5 and 12.7 ml.
On the other hand, a reading of 12.60 ml implies that the actual volume could be anything between
12.59 and 12.61 when the burette is graduated to 0.01ml, i.e. actual volume is 12.60 ± 0.01.
139
140 Analytical Chemistry
Suppose the weight of an object weighed in an ordinary triple beam balance is 3.45 g. If the
reproducibility of the balance is ± 0.02 g, the second figure past the decimal is uncertain.
The weight of the object should lie in the range of 3.43 to 3.47 g and any effort to report the weight
in the third decimal place such as 3.450 g by weighing on the above balance is wasted effort. Thus
the significant figures in this example are three (3, 4 and 5).
If the same object is weighed in an analytical balance that has a reproducibility of ± 0.002, then
the weight of the object should lie in the range of 3.448 to 3.452 g and the figures (3, 4, 5, 0) in
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3.450 are said to be significant. The following rules are helpful in determining the number of
significant figures in a given number.
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4.2.2 Rules for Determining Significant Figures
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Non-zero integers
All the non-zero integers are significant. For example, 5.231 has four significant figures. 2.45 has
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three significant figures and 6.251 have four significant figures.
Recognition of zero as significant figures
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The digit zero may or may not be significant figure. In the burette graduated to 0.01 ml, let the
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burette reading be 20.05 ml. This contains four significant figures. Here both zeros are treated as
significant figures. If the above burette reading is expressed in litre, it could be 0.02005 litre. Since
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the number of significant figures cannot change just by changing the unit, this number should
have only four significant figures. The function of zero preceding 2 (or initial zero) is only to
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locate the decimal point. Hence initial zeros are not significant. Similarly, a volume of 2 litres
expressed in ml. (2000 ml) must contain only one significant figure which is 2. To avoid ambiguity,
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it is safe to express the number in powers of ten. Thus 2 litres should be written as 2 ´ 103 ml
(one significant figure). If, however, the volume expressed in litre is 2.1, the volume in millilitre
g
will be 2.1 ´ 103 (two significant figures in both cases).

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The following examples illustrate the points mentioned

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Number Expression Significant figures Remarks

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0.612 612 ´ 10–3 3 0 is not significant here

70.9 709 ´ 10–1 3 0 is significant figure here
0.007 7 ´ 10–3 1 Zeros are not significant figures here
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6.023 ´ 1023 4 Zero is significant figure here

1.03 ´ 10–13 3 Zero is significant figure here
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From the above discussion it is clear that there are three classes of zeros.
Leading zeros: Zeros that precede all the non-zero digits are called leading zeros. These are not
counted as significant figures. They merely indicate the position of decimal point. For example, in
0.007, the zeros are leading zeros so that 0.007 has one significant figure.
Captive zeros: Zeros between two non-zero digits are called captive zeros. These are always
counted as significant figures. For example, in 70.9, 0 is captive zero and thus it is taken as significant
figure. Therefore 70.9 has three significant figures. Similarly, 5.02 has three significant figures.
Statistical Methods of Analysis 141
Trailing zeros: Zeros at the right end of the number are called trailing zeros. They are significant
if the number contains a decimal point. Thus in 900.00, the zeros are example of trailing zero and
are significant as these are present after the decimal point. When the number ends in zeros that are
not to the right of the decimal point, the zeros are not necessarily significant. For example, the
number 240 can have two or three significant figures. Similarly, 20500 can have three, four or five
significant figures.
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Exponential notation
In exponential notation, the numerical portion represents the number of significant figures.
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For example, 3 ´ 106 has one significant figure 3.2 ´ 10–4 has two significant figures.
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Rounding off the non-significant figures
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The non-significant figures in the measurement are rounded off as per the following rules. If the
digit following the last significant figure is greater than 5, the number is rounded off to the next
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higher digit. For example, 9.48 can be rounded off to 9.5. If it is less than 5, the number is rounded
off to the present value of the last significant figure. For example, 9.42 is rounded off to 9.4. If the
last digit is 5, the number is rounded off to the nearest even digit. For example,
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8.65 is rounded off to 8.6, 8.75 is rounded off to 8.8, 8.55 can be rounded off to 8.6.
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The following rules are to be followed while doing calculations involving significant figures.
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Rules for calculations involving significant figures
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Rule for addition and subtraction: The rule here is to retain as many decimals in the final
result as the number with the fewest decimal. Let us take the following operation.
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14.22 + 8.145 – 3.6750 + 120.4 = 139.09

The number, in the above, containing the fewest decimals is 120.4. So the result should contain
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one decimal. Hence the result 139.09 to be rounded off to 139.1 so that it contains one decimal.
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Rule for multiplication and division: The rule followed is to retain only as many significant
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figures as those in the number with the fewest significant figures. For example,
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25 0.524
0.131
100.0
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In this example, the number 25 has two minimum number of significant figures. Hence, the result
should contain only two significant figures. Hence the result 0.131 is rounded off to 0.13.
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Rule for logarithm and antilogarithm: A logarithm is composed of two parts such as a whole
number called the characteristic and a decimal fraction called the mantissa. The characteristic is a
function of position of the decimal in the number whose logarithm is being determined and therefore,
is not a significant figure. The mantissa is the same regardless of the position of
the decimal and all the digits are considered significant. For example, consider the logarithm of
2.3 ´ 103. The characteristic is 3. Using a log table, the mantissa is found to be 0.3617. Since the
number 2.3 has two significant figures, its mantissa should contain only the same number of
significant figures. Hence mantissa can be expressed as 0.36. While taking antilogarithm,
the result should contain the same number of significant figures as that is mantissa. Thus antilog
of 1.946 is 99.3. As its mantissa, i.e. 0.946 contains three significant figures, its antilog should
also contain the same number of significant figure, that is, three.
4.3 ERRORS AND THEIR CAUSES
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The measured value of a property will never be the accurate value of the property. The difference
between the two is called error.
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4.3.1 Definition of Errors
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An error may be defined as the difference between a measured value and the true value of a
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property.
Mathematically, E = (O – T) where E is the error in the experiment, O is the observed value,
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T is the true value. Errors are generally expressed relatively as
E
percentage error (E%) =
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T
100
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E
and per thousand error, E0 00 = 1000
T
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4.3.2 Classification of Errors

Several factors introduce error into the measured value of a property. The errors, which creep in
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analytical measurements, are broadly classified as:

(i) Determinate errors or constant errors or systematic errors
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(ii) Indeterminate errors or unsystematic or random errors.

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4.3.3 Determinate Errors

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Those errors, which can have definite values and assignable causes, are termed determinate errors.
These errors can be either determined, avoided or corrected. These errors are therefore called
systematic errors.
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Classification of determinate errors

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Determinate errors can be classified into constant error and proportionate error as follows.
Constant errors: Constant error are those in which the absolute error is independent of sample
size (weight). Consider, for instance, a sample of 10 mg weighs 10.5 mg due to constant misuse of
uncalibrated weight. A constant error of 0.5 mg will be introduced every time when a measurement
is made in this faulty weight. It is to be noted that constant errors introduce the same absolute error
in a measurement but the relative errors increases as the sample size is decreased as seen from the
following example.
Suppose a precipitate is shown to have a weight of 500.5 mg when its measurement is made
with a faulty weight. Let the actual weight of the precipitate be 500 mg.
CHAPTER 5
Estimation of Organic Compounds
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5.1 INTRODUCTION
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For the investigation and characterization of an organic compound after it has been obtained in a
pure state, a complete molecular diagnosis is necessary. This involves the following steps:
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(a) Detection of elements, i.e. the determination of the qualitative elementary composition of
the substance.
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(b) Estimation of elements, i.e. the determination of quantitative elementary composition or
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percentage composition of the substance.
(c) Calculation of empirical formula, i.e. the percentage composition found above leads to the
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calculation of the empirical formula of the substance.

(d) The determination of molecular weight leading to the calculation of molecular formula.
C
For the above stoichiometric calculations involved in a chemical reactions in which the reactants
combine in a simple whole number ratio are equally important. The principle of detection of elements
g
present in an organic compounds and their estimation, the principle and the methods of determination
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of some organic compounds especially of glucose, phenol, aniline, keto compounds and analysis
of fats or oils are discussed in this chapter.
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5.2 DETECTION OF ELEMENTS (PRINCIPLES ONLY)

5.2.1 Detection of Carbon and Hydrogen
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Detection of carbon and hydrogen in an organic compound is carried out by oxidizing the substance
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with copper oxide at high temperature. Carbon and hydrogen of the substance are oxidized to
carbon dioxide and water respectively. Carbon dioxide turns lime water milky while water turns
anhydrous copper sulphate (white substance) blue. The reactions involved are:
2CuO + C ¾® 2Cu + CO2
CuO + 2H ¾® Cu + H2O
Precaution: Cupric oxide is a hygroscopic substance. It should, therefore, be carefully ignited
before use. The apparatus used for the purpose cited above should also be absolutely dry and free
from moisture.
179
5.2.2 The Preparation of Sodium Extract (Lassaigne’s Test)

The detection of nitrogen, halogen and sulphur present in an organic compound is carried out
from the sodium extract of organic compound as follows:
A small piece of freshly cut sodium metal (pea size) is melted in a small fusion tube and then
fused with the organic compound. The red hot tube is broken by immersion in cold distilled water
in a dish. The glass pieces are boiled in water to extract the fused mass and then filtered.
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The filtrate is called sodium extract. It is alkaline in nature due to formation of NaOH.
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Detection of nitrogen from Na-extract
Nitrogen, if present, in combination with sodium and carbon of the compound forms sodium
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cyanide. To about 1 ml of the solution, freshly prepared ferrous sulphate solution is added, boiled
and then cooled. The cooled solution is acidified with dilute sulphuric acid. Appearance of a green
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or Prussian blue colour confirms the presence of nitrogen in an organic compound.
Reactions involved:
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Na + C + N ¾® NaCN
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Sodium cyanide
FeSO4 + 2NaCN ¾® Fe(CN)2 + Na2SO4
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Fe(CN)2 + 4NaCN ¾® Na4[Fe(CN)6]
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Sodium ferrocyanide
Sodium ferrocyanide reacts with ferric ion produced by oxidation of Fe2+ by air in the presence of
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OH– to give a precipitate of Prussian blue NaFe[Fe(CN)6]. Sulphuric acid is added to dissolve the
bluish green ferrous hydroxide, which might otherwise mask the Prussian blue precipitate.
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Na4[Fe(CN)6] + Fe3+ ¾® NaFe[Fe(CN)6] + 3Na+

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(Sodium ferric ferrocyanide) (Prussian blue)

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It is to be noted that when the nitrogen present in a sample is small, the Prussian blue may be
present is colloidal form so that the solution is green.
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Detection of sulphur from Na-extract

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Sulphur, if present, forms sodium sulphide. The presence of sodium sulphide in Na-extract can be
confirmed as follows:
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(a) Sodium nitroprusside test: To about 1 ml of Na-extract, sodium nitroprusside solution

is added. The formation of a purple colour indicates the presence of sulphide.
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2Na + S ¾® Na2S
Na2S + Na2[Fe(CN)5NO] ¾® Na4[Fe(CN)5NOS]
Sodium nitroprusside Purple-coloured complex
(b) Lead acetate test: To about 1 ml of Na-extract when lead acetate solution is added, a
black precipitate of lead sulphide is produced.
Na2S + (CH3COO)2Pb ¾® PbS + 2CH3COONa
Lead acetate Black ppt.
CHAPTER 11
Spectroanalytical Techniques
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Ultraviolet and Visible
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Spectral Method
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11.1 INTRODUCTION
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Spectroscopy involves interaction of electromagnetic radiation with matter. Electromagnetic
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radiation is considered as waves of energy propagated from a source in space and consists of
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oscillating electric and magnetic field at right angles to each other. Each electromagnetic radiation
È 1Ø
has characteristic wavelength (l), frequency (n ) or wave number, v É Ù. The absorption or
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Ê MÚ
emission of electromagnetic radiation is quantized and each quantum or radiation is called photon.
The energy (E) of a photon is given by Planck’s law, i.e. E = hn, where h is Planck’s constant and
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n is the frequency of radiation. Some important electromagnetic radiations are radio wave,
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microwave, infrared, visible, ultraviolet, x-rays and gamma rays with decreasing order of
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wavelength or increasing order of frequency or energy. Molecule or ion may absorb energy from
electromagnetic radiation of suitable wavelength (or frequency) resulting in:
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(i) Electronic excitation caused by absorption of UV-visible radiation leading to UV-visible

spectroscopy.
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(ii) Molecular rotation by absorption of microwave radiation leading to microwave

spectroscopy.
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(iii) Vibrational excitation caused by absorbing infrared radiation leading to infrared

spectroscopy.
The instrument used for investigation of such absorption phenomena is called spectrophotometer
which consists of the following components:
(a) Radiation source: Tungsten filament lamp (for visible), hydrogen discharge lamp (visible
and UV), xenon discharge lamp (UV), mercury arc (UV), IR source being global, nernst
glower, heated nichrome wires, heated alumina tube or walshbach mentle.
365
CHAPTER 12
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Infrared (IR) Spectral Method
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12.1 INTRODUCTION
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The atoms in a molecule do not remain in fixed relative positions but vibrate about some mean
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positions. In fact, even in solid state near the absolute zero temperature, the atoms are in constant
vibration. The atoms of the molecule also rotate. Thus a molecule has electronic, vibrational and
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rotational energy. When a molecule absorbs infrared radiation, only its vibrational and rotational
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energy will change which causes vibrational and rotational transitions. There will be no electronic
transition in this case as it requires higher energy corresponding to UV-visible region. Thus infrared
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absorption spectra of a molecule result from transitions between vibrational and rotational energy
levels. These are displayed in the form of bands called vibrational rotational band, i.e. IR spectral
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band. However in condensed gases, liquids and solids, generally only vibrational bands are observed
in the IR region. An infrared spectrum shows downward peaks corresponding to absorption plotted
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against wave number (O ).

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IR region of electromagnetic radiation lies in between visible and microwave regions covering
a wide range of wave number ranging from 12,500 cm–1 to 100 cm–1. From instrumentation
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and application point of view, it is generally divided into approximately three sub-regions,
namely near IR region (from 12,500 cm–1 to 4000 cm–1), the mid IR region (from 4000 cm–1 to 667
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cm–1) and far IR region extending from 667 cm–1 to 100 cm–1. This feature of characteristic
absorption of radiation by many molecules in the IR region has provided an extremely elegant and
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powerful tool for the elucidation of molecular structure.

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12.2 MOLECULAR VIBRATIONS AND VIBRATIONAL FREQUENCY
The point of interest here is to discuss the various modes of vibration of atoms in molecules.
Let us consider vibration of a diatomic molecule for simplicity.
12.2.1 Vibration of Diatomic Molecules

In a covalently bonded diatomic molecule, vibratory motion of the atoms causes compression and
extension of the bond like a mechanical spring obeying Hook’s law. The potential energy curve
415
(iii) The force constants of bending vibrations are generally less than those of stretching
vibrations. Due to smaller force constant, the bending (or deformation) vibrations are
more sensitive to environment influence.
PROBLEM 12.3 Calculate the number of stretching vibration and bending vibration mode in
case of
(i) Benzene and
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(ii) Ethane.
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Solution
(i) In case of benzene (C6H 6), N = 12. It is a non–linear molecule, so the number of
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fundamental mode of vibrations is given by 3N – 6 rule = 30. The number of stretching
vibration for non-linear molecule is given by N – 1 rule, i.e. 11. The number of bending
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modes as given by 2N – 5 rule is (2 ´ 12 – 5) = 19.
(i) In case of ethane (C2H6), N = 8. It is a linear molecule, so the number of fundamental
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mode of vibrations is given by 3N – 5 rule = 19. The number of stretching vibration for
linear molecule is given by N –1 rule, i.e. 7. The number of bending modes is given by
2N – 4 rule = 12.
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12.3 SELECTION RULE FOR IR ABSORPTION
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It can be seen from quantum mechanics and group theory that absorption takes place in the IR
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region in accordance with the following selection rules:

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(i) There should be change in the magnitude or direction of the dipole of a molecule as it
vibrates. This creates an oscillating dipole moment which interacts with electrical
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component of IR radiation and hence, absorption takes place. If q be the coordinate of

in
dm
vibrational motion and m is the dipole moment then should be nonzero for infrared
dq
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2
dm
activity. The intensity of IR absorption is proportional to ÔZ i Z j dU where yi and
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dq
yj are wave functions for two vibrational energy levels corresponding to vibrational
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quantum number i and j respectively between which the transition takes place. It may be
concluded that more polar a bond, the more intense will be IR spectral band. Thus, the
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intensity order is : > C == O > C == N >> C == C, as the polarity of the bond decreases in
the above order.
(ii) The second selection rule followed from the harmonic oscillator approximation states
that in the absorption of radiation only transitions for which Dn = ± 1 can occur, where
Dnÿindicates the change in vibrational quantum number between two vibrational energy
levels. Since most molecules are in the vibrational level at room temperature, v = 0, most
transitions will occur from the state v = 0 to v = 1 as shown in Figure 12.8 by an arrow.
The frequency corresponding to such transition is called the fundamental frequency.
Spectroanalytical Techniques—Infrared (IR) Spectral Method 423
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Figure 12.8 Vibrational states corresponding to normal vibrational mode in a harmonic oscillator.
ht
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The energy difference (DEvib) between the lowest energy possible vibrational energy level of a
bond and the next higher energy level is given by
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È 1Ø È 1Ø
DEvib = É1 Ù hX osc É0 Ù hX osc hX osc
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(12.4)
Ê 2Ú Ê 2Ú
The IR frequency corresponding to the above transition,
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Evib hX osc
v = = = X osc .
g
hc hc
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12.4 BREAKDOWN OF SELECTION RULE AND OCCURRENCE OF

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OVERTONES, COMBINATION BANDS AND DIFFERENCE BANDS

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The vibrational energy levels as given in Eq. (12.3) are expected to be equally spaced. However,
these levels converge by virtue of the molecule undergoing anharmonic rather than harmonic
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oscillation so that Eq. (12.3) is not obeyed. This deviation from harmonic oscillation occurs in all
the molecules and become greater as the vibrational quantum number increases.
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Since most molecules are not perfect harmonic oscillators, the selection rule breaks down and
the transitions corresponding to v = 2 to 3 (0 ® 2 and 0 ® 3) occur which are indicated by arrows
(0 ® 2) and (0 ® 3) respectively in the same Figure 12.8.
The transition designated as (0 ® 2) is found to have poor intensity and in known as first
overtone. It occurs at a frequency twice that of fundamental (0 ® 1) transition and hence designated
as 2v1. The transition (0 ® 3) is found to have negligible intensity and is known as second overtone.
It occurs at a frequency thrice that of fundamental (0 ® 1) and is designed as 3v1. The higher
overtones are too weak to be realised experimentally.
It is to be noted that the transitions from v = 1 to higher energy levels are not observed unless the
temperature of the sample is high. This is due to the fact that population in v = 1 level is negligible
CHAPTER 13
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Nuclear Magnetic Resonance
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Spectral Method
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13.1 INTRODUCTION
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The study of absorption of radio frequency radiation by a magnetic nucleus in the presence of an
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applied magnetic field is called nuclear magnetic resonance, often abbreviated as NMR. This is
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one of the powerful techniques especially for

(i) Structural elucidation for organic compounds.
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(ii) Determination of the nature of environment of practically all commonly occurring

functional groups, as well as of fragments that are not otherwise accessible to other
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spectroscopic or analytical techniques.

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(iii) Quantitative determination of compounds in mixtures and hence for studying the progress
of chemical reactions.
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(iv) Determination of kinetic and thermodynamic parameters for certain types of chemical
processes.
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(v) Determination of magnetic nuclei within molecules.

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13.2 PRINCIPLE OF NMR

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It is based on the following.
13.2.1 Magnetic Properties of Nuclei and Their Angular Momentum

All nuclei, the main constituent of which are proton and neutron, carry positive charges and they
spin about their own axes. The magnitude of angular momentum vector L associated with the
spinning of the nucleus having total spin quantum number I is given by
L= I (I 1) h / 2Q (13.1)
457
According to quantum mechanics, the angular momentum vector cannot have any arbitrary
direction but can point only along certain directions (space quantization of the angular momentum
vector). These directions are such that the component of angular momentum vector along a certain
reference known as Z-axis have only quantized value. The reference axis is usually taken to the
direction of an external magnetic field. The permitted values of components of angular momentum
along the Z-axis are given by the expression MI (h/2p), where MI is known as nuclear magnetic
spin quantum number and can have the following values:
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(i) For integral spins,
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MI = I, (I – 1), …, 0, …, –(I – 1) · –I
(ii) For half-integral spins,
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MI = I, (I – 1), …, +1/2, –1/2, …, –(I – 1) · –I
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There are a total of (2I + 1) components in each case. Some empirical rules based on experimental
facts regarding the total spin number, I are available. These are:
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1. Nuclei with both protons (p) and neutrons (n) even (hence charge and mass even) have
zero spin (e.g. He4, C12, O16, S32 etc.), I = 0.
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2. Nuclei with both p and n odd (hence charge odd, but mass = p + n, even) have integral
spin (e.g. H2, N14(I = 1), B10(I = 3), etc.
ig
3. Nuclei with odd mass have half integral spins (e.g. H1, N15(I = 1/2), O17(I = 5/2),
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F19 (I = 1/2) and Cl35 (3/2) etc.)
The nuclei for which the spin number I = 0 are known as non-magnetic nuclei, those with
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I ¹ 0 are known as magnetic nuclei which will give NMR.

The nucleus of an Isotope whose total spin quantum number I is greater than zero shows
C
absorption in the NMR spectroscopy. The NMR spectroscopy studied for the absorption of most
abundant natural Isotope of Hydrogen H1 is called proton magnetic resonance (PMR) spectroscopy.
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The numerical value of I is related to the mass number and the atomic number of the concerned
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isotope.
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13.2.2 Magnetic Moments of the Nuclei

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The spinning of nucleus is equivalent to the circulation of a positive charge around the axis of
spinning. This, in turn, produces a tiny magnet placed along the spin axis. The magnetic moment
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(mm) of the generated magnet can be calculated with the help of Ampere’s law and is given by
mm = g (e / 2m p c) ( I (I 1) h / 2S
PH
Gaussian system:
= g (eh / 4Q m p c) ( I (I 1) = g I (I 1) C / (13.2)
where, bN = (eh/4pmpc), mp = mass of proton in gm, c = velocity of light in cm/s, h = Plank’s

constant in the unit of erg sec, I = spin quantum number of the nucleus and g is nuclear splitting
factor which is the ratio of magnetic moment vector to the angular momentum vector. bN is called
nuclear magnetron and it is the basic unit of nuclear magnetic moment. The value of bN in Gaussian
system is 5.047 ´ 10–24 erg/gauss and in SI unit, it is 5.047 ´ 10–27 J/T.
Spectroanalytical Techniques—Nuclear Magnetic Resonance Spectral Method 459
PROBLEM 13.1 Calculate the angular momentum and magnetic moment values for a proton,
given g = 5.585.
Solution Angular momentum L = I ( I 1) h / 2Q
For proton I = 1/2 , h = 6.626 ´ 10–34 Js
Thus we have
L = 1/2(1/2 1) h / 2Q
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= 0.866 h/2p = 0.914 ´ 10–34 Js
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and magnetic moment
mm = g I (I 1) C / ,
at
bN = 5.047 ´ 10–27 J/T
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Hence, mm = g I (I 1) C /
= 5.585 1/2(1/2 1) 5.047 10 27 J/T
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= 2.44 ´ 10–26 J/T
13.2.3 Effect of External Magnetic Field ht

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For a particular value of total spin quantum number (I) of the nucleus, there are 2I + 1 possible
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components corresponding to nuclear spin magnetic quantum number M1 = –I to I. These
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components are normally degenerate, (i.e. all of them have the same energy). This degeneracy is
lifted up in the presence of a magnetic field. The NMR is basically due to this lifting up degeneracy
of energy levels.
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For example, for a proton I = 1/2, the nuclear magnetic spin momentum quantum number MI
g
will have values +1/2 (a) and –1/2 (b) corresponding to two orientations of spin motion of proton.
in
This will give rise to two nuclear spin states. In the absence of magnetic field, two MI states remain
rn
degenerate. An imposition of an external magnetic field, H removes the degeneracy and establishes
2I + 1 = 2 ´ 1/2 + 1 = 2, non-degenerate levels.
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13.2.4 Potential Energy of a Nucleus in a Magnetic Field

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The potential energy, E of a nucleus placed in a magnetic field H is given by the relation
E = – Hmz (13.3)
PH
where mz is the Z-component of the magnetic moment vector. Let Q be the angle between the
magnetic moment vector and the Z-axis, then
mz = mm cos Q (13.4)
Substituting Eq. (13.2) in Eq. (13.4), we get
mz = ( g C / I ( I 1) ) cos (13.5)
The angle Q cannot have any arbitrary value, but only a few allowed discrete values which satisfy
CHAPTER 14
l
ia
Electron Spin Resonance
er
at
Spectral Method
M
ed
14.1 INTRODUCTION
ht
ig
Electron spin resonance (ESR) is a branch of absorption spectroscopy in which radiation having
yr
frequency in the microwave region is absorbed by paramagnetic substance to induce transition
between magnetic energy levels of electron with unpaired spins. It is also called by other names
op
such as electron paramagnetic resonance (EPR) or electron magnetic resonance (EMR).

The main interest of ESR lies in the study of:
C
(i) Free radicals having unpaired electrons;

(ii) Determination of trace amounts of paramagnetic ions in biological samples;
g
(iii) Paramagnetic molecules like O2, NO and NO2;

in
(iv) Metal complexes with unpaired electrons, for example, copper(II) acetate monohydrate
rn
and bis (acetyl acetanato) oxovanadium(IV), in order to understand their structures; and
(v) Lanthanide ions, etc.
ea
14.2 BASIC PRINCIPLE

IL
14.2.1 Interaction between Electron Spin and Magnetic Field

PH
For an electron with spin quantum number S = 1/2, the magnetic spin momentum quantum number
Ms will have values +1/2 and –1/2 corresponding to two orientations of spin motion of the electron.
This will give rise to two spin energy states or two Ms states. In the absence of magnetic field, the
two Ms states remain degenerate, i.e. the free electron may exist in either of the two states (+1/2 or
–1/2) of equal energy. The spinning of electron around its own axis generates a magnetic dipole,
the magnetic moment mm of which is given by the relation:
È e Ø h
mm = g ÉÊ Ù S (S 1) (14.1)
2 mc Ú 2Q
497
CHAPTER 15
l
ia
Mass Spectral Method
er
at
M
15.1 INTRODUCTION
ed
In this technique, the compound under investigation is bombarded with a beam of energetic
ht
electrons. The molecules are ionized and dissociate into several fragments, some of which are
positive ions. Each kind of ion has a particular ratio of mass to charge, i.e. m/e ratio. Since multiple
ig
charged ions are produced only rarely relative to singly charged ions, the charge can normally
yr
be taken as one. Thus for most ions, m/e ratio is simply the molecular mass of the ion.
A mass spectrum is a presentation of the masses of positively charged fragments versus
op
their relative intensity abundance. The m/e ratio is taken along the abscissa while the
relative abundances are taken along the ordinate. The important advantages of mass spectral
C
method are:
(i) High sensitivity, reproducibility and accuracy,
g
(ii) Materials present in concentrations less than 1 ppm can be easily detected by this technique,
in
(iii) In addition to elucidation of molecular structure, mass spectra are useful for determining
rn
molecular weight, investigating reaction mechanisms, identifying a functional group and

in tracer technique etc.
ea
The instrument used for investigation is known as mass spectrometer which is designed to
perform the following functions:
IL
1. To vapourize compounds of varying volatility.

2. To produce ions from the neutral compounds in the gas phase.
PH
3. To separate ions according to their mass to charge ratio.

4. To detect the ions and producing a corresponding signal.
15.2 THEORY (BASIC PRINCIPLE)
A mass spectrum consists of an array of peaks of different height. The nature of the spectrum is
dependent on properties of the molecule, ionization potential, sample pressure and the instrument
design. The mass spectrometer bombards a molecule M with high energy electrons which is
525
C H A P T E R 16
l
ia
Thermoanalytical Techniques
er
at
M
ed
16.1 INTRODUCTION
ht
Thermoanalytical techniques include measurement of changes in physical and/or chemical
ig
properties of a substance as a function of temperature. A brief summary of some of the important
thermoanalytical techniques according to the properties of the substance measured is given below
yr
in Table 16.1
op
Table 16.1 Thermoanalytical techniques

Name of the technique Properties measured Instrument used
C
Thermogravimetric analysis (TGA) Change in weight Thermobalance

g
Derivative thermogravimetric analysis (DTGA) Rate of change of weight Thermobalance

in
Differential thermal analysis (DTA) Difference in temperature DTA apparatus

Thermometric titration (TT) Change of temperature Titration calorimeter
rn
Differential scanning calorimetry (DSC) Rate of change of enthalpy Calorimeter

ea
Only the thermoanalytical techniques such as TGA, DTGA and DTA are discussed in this chapter.
IL
16.2 THERMOGRAVIMETRIC ANALYSIS (TGA)

PH
16.2.1 Introduction
The technique of thermogravimetric analysis is concerned with the measurement of weight
change of a substance due to dehydration or decomposition as a function of temperature increased
at a predetermined and preferably at a linear rate. The results are expressed in the form of
thermogravimetric curve (TG curve) in which weight changes of the substance taken as ordinate
are plotted against the temperature taken as abscissa. The TG curve is also known as thermogram.
There are in fact three types of thermogravimetry, which are as follows:
575
Steps Temperature range (°C)
(i) CuSO4 5H2O(s)  CuSO4(s)  3H2O + 2H2O(g) 90–150

(ii) CuSO4  3H2O(s)  CuSO4 H2O(s) + 2H2O(g) 90–150
(iii) CuSO4  H2O(s)  CuSO4(s) + H2Og 200–275
(iv) 2CuSO4(s)  2(CuO)2  SO3(s)+ SO2(g) + 1/2O2(g) 700–900
(v) (CuO)2 SO3(s)  2CuO(s) + SO2(g) + ½ O2(g)
l
700–900
ia
(vi) 2CuO(s)  Cu2O(s) + ½ O2(g) 1000–1100
er
The TG curve does not reveal all these changes clearly, for example, the TGA curve gives
at
impression that CuSO4  5H2O gives rise to CuSO4  H2O in a single step. However, the inflection
M
point B (showing the change in the slope of weight loss curve) implies formation of intermediate
compound CuSO4  3H2O from CuSO4  5H2O. Similarly, the TG curve makes it appears as if 2CuSO4
gives rise to 2CuO, 2SO2 and O2 in a single step. However, the inflection point C indicates the
ed
formation of golden yellow intermediate compound of composition 2CuO  SO3.
The DTG curve, however, shows six peaks corresponding to six steps, as mentioned above. It
ht
can be noted that the inflection points B and C on the TGA curve are revealed as shallow troughs
ig
between peaks 1 and 2 and between peaks 4 and 5, respectively. The peaks on the derivative curve
correspond to the maximum slope on the TG curve.
yr
dW dW
In DTG curve, where there is no weight loss, = 0 . When is minimum, but not zero, than
dT dT
op
there is an inflection, i.e., change of slope in the TG curve implying the formation of intermediate
compound. Commercial thermobalances have been provided with electronic circuits to take the
C
derivative curve automatically.

However, the points of inflection B and C obtained on the TG curve of copper sulphate
g
pentahydrate may be resolved into a plateau if a slower heating rate is used. Hence, detection of
in
intermediate compounds by thermogravimetry is dependent the heating rate employed.

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16.4 DIFFERENTIAL THERMAL ANALYSIS (DTA)

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16.4.1 Introduction
IL
The technique of differential thermal analysis is concerned with the measurement of temperature
difference (DT) between the sample and thermally inert reference compound (usually alumina,
PH
silicon carbide, or glass bead), as the temperature of both are increased at a constant rate. The
results are expressed in the form of a differential thermoanalytical curve (DTA curve) in which
the temperature differences taken as ordinate are plotted against the temperature differences taken
as abscissa. A typical DTA curve is shown in Figure 16.8. If the sample does not undergo any
physical or chemical change, then there is no temperature difference between the sample (S) and
reference (R) as shown by the horizontal portion of the curve. If physical or chemical changes
take place, then the temperature of the sample will be different from that of reference, resulting in
temperature difference (DT) defined as (TS – TR), where as TS and TR are the temperature of sample
and reference, respectively.

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Second Edition

Dhruba Charan Dash

ANALYTICAL CHEMISTRY, Second Edition

1.3 Detection and Separation of Cations of Each Group 10

1.3.2 Separation of Group IIA from Group IIB Cations

1.3.3 Separation and Detection of Group IIA Cations (Copper Group) 11

1.3.4 Separation and Detection of Group IIB Cations (Arsenic Group) 14

1.3.6 Separation and Detection of Group IIIB Cations (Zinc Group) 18

1.3.8 Separation and Detection of Group V Cations 21

1.4.1 Detection of Group I Anions 23

Group A Questions on Qualitative Analysis of Basic Radicals (Cations) 44

2.7 Complexometric Titration and Ways of Locating End Point 79

2.7.1 Theory of Complexometric Titration Involving EDTA 79

2.7.3 Ways of Locating the End Point 84

2.8 Problems Involved in Titrimetric Methods 86

2.8.2 Problems on Redox Titration 93

A. Objective Type Questions 97

D. Long Answer Type Questions 100

3. Quantitative Analysis—Precipitation Gravimetry 101–135

3.11.1 Problems on Gravimetric Factor (GF) 121

3.11.3 Determination of Sample Size 126

A. Objective Type Questions 131

B. Very Short Answer Type Questions 133

D. Long Answer Type Questions 135

4. Statistical Methods of Analysis 139–175

4.2 Significant Figures 139

4.4 Propagation of Errors 146

4.8.6 Problems on Expressing Precision 166

4.8.8 Problem on Confidence Level 171

4.8.10 Problem on Student t Test 171

A. Objective Type Questions 172

C. Long Answer Type Questions 175

5. Estimation of Organic Compounds 179–210

5.2 Detection of Elements (Principles Only) 179

6. Separation Techniques 213–262

6.2 Solvent Extraction Method 213

6.2.2 Principle of Solvent Extraction 214

6.2.4 Separation Factor 220

6.2.5 Methods of Solvent Extraction 221

6.3.1 Solvent Extraction of Metal Ions by Chelation 223

6.4 Chromatographic Methods and Their Classification 225

6.4.3 Classification of Chromatographic Methods 226

6.6.7 Experimental Set-up 238

7. Purification Techniques 263–284

7.2 Purification Techniques for Solid Organic Compounds 263

7.2.2 Fractional Crystallization 267

7.2.3 Sublimation 267

7.2.5 Solvent Extraction 269

7.3 Purification Techniques for Liquids 270

7.3.3 Distillation under Reduced Pressure 273

7.4 Chemical Method of Separation and Purification 278

8.7 Electrolysis in a Galvanic Cell 298

8.8 Electrolysis at Constant Current 299

8.11 Spontaneous or Internal Electrolysis 304

8.12 Problems Involved in Electrogravimetry 305

A. Objective Type Questions 312

B. Very Short Answer Type Questions 313

D. Long Answer Type Questions 315

9. Electroanalytical Techniques—Coulometry 316–338

9.1 Introduction 316

9.3 Determination of Charge, Q 317

9.7 Coulometric Titration 322

10. Electroanalytical Techniques—Polarography