Analytical Chemistry Dhruba Charan Dash PDF

Analytical Chemistry
Dhruba Charan Dash

Formerly, Professor and Head
Postgraduate Department of Chemistry
Sambalpur University
Orissa
New Delhi-110001
2011
ANALYTICAL CHEMISTRY
Dhruba Charan Dash
© 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-978-81-203-4077-0
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 Mohan Makhijani at Rekha Printers Private Limited,
New Delhi-110020.
To My Parents
Contents
Preface xvii
UNIT 1
1. Qualitative Analysis 353
1.1 Introduction 3
1.1.1 Solubility Product Principle 3
1.1.2 Common Ion Effect 4
1.2 Separation of Cations into Groups 4
1.3 Detection and Separation of Cations of Each Group 10
1.3.1 Separation and Detection of Group I (Silver Group) Cations 10
1.3.2 Separation of Group IIA from Group IIB Cations
(by Yellow Ammonium Sulphide) 11
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
1.3.5 Separation and Detection of Group IIIA Cations (Iron Group) 16
1.3.6 Separation and Detection of Group IIIB Cations (Zinc Group) 18
1.3.7 Separation and Detection of Group IV Cations 20
1.3.8 Separation and Detection of Group V Cations 21
1.4 Separation and Detection of Acid Radicals (Anions) 23
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
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
v
vi Contents
UNIT 2
2. Quantitative AnalysisVolumetric (Titrimetric) Analysis 57100
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
2.3 Conditions for Volumetric (Titrimetric) Analysis 61
2.4 Types of Titrimetric Analysis 62
2.5 Acid-base Titration and Ways of Locating End Point 62
2.5.1 Theory of Acid-base Titration 62
2.5.2 Ways of Locating the End Point of an Acid-base Titration 63
2.5.3 Titration of Strong Acid with Strong Base 65
2.5.4 Titration of Weak Acid with Strong Base 65
2.5.5 Titration of Weak Base with Strong Acid 67
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 Oxidation Reduction (Redox) Titration and Ways of Locating End Point 71
2.6.1 Theory of Redox Titration 71
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
2.7 Complexometric Titration and Ways of Locating End Point 79
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
2.7.3 Ways of Locating the End Point 84
2.7.4 Estimation of Calcium and Magnesium by Complexometric
Titration by EDTA 85
2.8 Problems Involved in Titrimetric Methods 86
2.8.1 Problems on Acid-base Titration 86
2.8.2 Problems on Redox Titration 93
B. Very Short Answer Type Questions 98
C. Short Answer Type Questions 99
D. Long Answer Type Questions 100
3. Quantitative AnalysisPrecipitation Gravimetry 101135

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 111
3.5 Washing of the Precipitate 113
3.5.1 Ideal Qualities of a Washing Liquid 113
3.5.2 Types of Wash Solution 113
3.5.3 Mode of Washing 114
3.6 Drying And/Or Incineration of the Precipitate 114
3.6.1 Conditions of Drying 114
3.6.2 Purpose of Ignition 115
3.6.3 Ignition Temperature 115
3.7 Weighing 115
3.8 Specific and Selective Precipitation 116
3.9 Organic Precipitants 116
3.9.1 Types of Organic Precipitants 116
3.9.2 Advantages of Using Organic Precipitants 119
3.9.3 Disadvantages of Using Organic Precipitants 120
3.10 Sequestering (or Masking) Agent 120
3.11 Problems Involved in Precipitation Gravimetry 121
3.11.1 Problems on Gravimetric Factor (GF) 121
3.11.2 Problems on Determination of Elements and Percentage of Purity 123
3.11.3 Determination of Sample Size 126
3.11.4 Analysis of Alloy 130
UNIT 3
4. Statistical Methods of Analysis 139175
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
4.5.4 Comparison between Accuracy and Precision 149
4.5.5 Methods of Expressing Precision 150
4.6 Test of Significance 155
4.6.1 Comparing a Mean Value with a True Value (The Students t Test) 156
4.6.2 Comparing Two Experimental Means 157
4.6.3 Comparison of Two Standard Deviations (F Test) 158
4.6.4 Chi-square Test (l2 Test) 159
4.7 Rejection of a Result 159
4.7.1 Rule Based on Average Deviation 159
4.7.2 Rule Based on the Range (Q Test) 160
4.8 Problems Involved in Data Analysis 161
4.8.1 Problems on Significant Figures 161
4.8.2 Problems on Rounding off Number 162
4.8.3 Problems on Uncertainties 163
4.8.4 Problems on Errors and Uncertainty 164
4.8.5 Problem on Relative Error 165
4.8.6 Problems on Expressing Precision 166
4.8.7 Problems on Propagation of Errors 169
4.8.8 Problem on Confidence Level 171
4.8.9 Problem on Rejection of Data 171
4.8.10 Problem on Student t Test 171
UNIT 4
5. Estimation of Organic Compounds 179210
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 (Lassaignes Test) 180
5.3 Estimation of Elements 181
5.3.1 Estimation of Carbon and Hydrogen (Liebigs 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
5.8.3 Determination of ReichertMeissel Value (RM Value) 200
5.9 Problems Involved in Estimation of Organic Compounds 201
5.9.1 Problems on Estimation of Carbon and Hydrogen 201
5.9.2 Problems on Estimation of Nitrogen 202
5.9.3 Problems on Estimation of Halogens and Sulphur 203
5.9.4 Problems on Estimation of Sugar 204
5.9.5 Problems on Saponification Value and RM Value 204
5.9.6 Problems on Estimation of Phenol and Aniline 205
UNIT 5
6. Separation Techniques 213262
6.2 Solvent Extraction Method 213
6.2.1 Introduction 213
6.2.2 Principle of Solvent Extraction 214
6.2.3 Comparison between Single and Multiple Extraction 217
6.2.4 Separation Factor 220
6.2.5 Methods of Solvent Extraction 221
6.3 Application of Solvent Extraction 223
6.3.1 Solvent Extraction of Metal Ions by Chelation 223
6.3.2 Conclusions on Extraction of Metal Chelates 224
6.4 Chromatographic Methods And Their Classification 225
6.4.2 Definition of Chromatography 225
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
6.7.4 Applications of Paper Chromatography 246
6.8 Thin Layer Chromatography (TLC) 247
6.8.1 Principles 247
6.8.2 Choice of Adsorbent for TLC 247
6.8.3 Choice of Solvent 247
6.8.4 Experimental Techniques 248
6.8.5 Sample Application 248
6.9 Development of the Chromatogram 248
6.10 Gas Chromatography 251
6.10.2 Principle of Gas Chromatography 251
6.10.3 Applications of Gas Chromatography 255
7. Purification Techniques 263284

7.2 Purification Techniques for Solid Organic Compounds 263
7.2.1 Crystallization 264
7.2.2 Fractional Crystallization 267
7.2.3 Sublimation 267
7.2.4 Sublimation under Reduced Pressure 268
7.2.5 Solvent Extraction 269
7.3 Purification Techniques for Liquids 270
7.3.1 Simple Distillation 270
7.3.2 Fractional Distillation 271
7.3.3 Distillation under Reduced Pressure 273
7.3.4 Steam Distillation 275
7.4 Chemical Method of Separation and Purification 278
7.5 Criteria of Purity 281
Contents xi
UNIT 6
8. Electroanalytical TechniquesElectrogravimetry 287315
8.2 Classification of Electroanalytical Techniques 287
8.3 Electrical Components 288
8.3.1 Electrodes and Electrode Potential 288
8.3.2 Electrochemical Cell 290
8.3.3 Electrical Circuit 291
8.3.4 Galvanostat and Potentiostat 292
8.4 Electrogravimetry 292
8.4.2 Theory and Principle of Electrogravimetry 292
8.4.3 Types of Electrogravimetry 293
8.5 Electrolysis in a Simple Cell 294
8.6 Electrolysis in a Non-galvanic Cell 294
8.6.1 Concept of Decomposition Potential 295
8.6.2 Ohmic Potential or IR Drop 296
8.6.3 Overpotential (Overvoltage) 297
8.6.4 Causes of Overvoltage 297
8.6.5 Expression for Total Potential Applied to Cause Electrolysis 298
8.7 Electrolysis in a Galvanic Cell 298
8.8 Electrolysis at Constant Current 299
8.9 Electrolysis at Constant Voltage 302
8.10 Electrolysis at Controlled Potential 302
8.11 Spontaneous or Internal Electrolysis 304
8.11.1 Electrolysis at the Anode 304
8.12 Problems Involved in Electrogravimetry 305
9. Electroanalytical TechniquesCoulometry 316338

9.2 Coulometric Calculation 316
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
9.8.3 Redox Titration 326
9.8.4 Complexometric Titration 326
9.9 Controlled Potential Coulometry 327
9.10 Applications of Controlled Potential Coulometry 329
9.11 Problems Involved in Coulometry 330
10. Electroanalytical TechniquesPolarography 339362

10.2 Principle of Polarography 339
10.2.1 Factors Affecting Current Flow in a Polarographic Cell 339
10.2.2 Explanation for Residual Current 340
10.2.3 Elimination of Convection Current 340
10.2.4 Elimination or Suppression of Migration Current 340
10.2.5 Measurement of Diffusion Current 341
10.2.6 Ilkovic Equation 342
10.2.7 Derivation of Ilkovic Equation 343
10.2.8 The Concept of Half-wave Potential (E1/2) 344
10.3 Difficulties Encountered in Polarography 346
10.4 Experimental Set-up 348
10.5 Advantages and Disadvantages of DME 349
10.6 Applications of Polarography 350
10.6.1 Qualitative Evaluation of Polarographic Data 350
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
10.6.5 Determination of Dissolved Oxygen 355
10.7 Problems Involved in Polarography 355
Contents xiii
UNIT 7
11. Spectroanalytical TechniquesUltraviolet and Visible
Spectral Method 365414
11.2 Principle of UV-visible Spectroscopy 366
11.2.1 Origin of UV-visible Spectroscopy 366
11.2.2 Absorption Law 367
11.2.3 Nature of Electronic Spectrum 370
11.2.4 Selection Rules for Absorption 371
11.3 Techniques Involved in UV-visible Spectroscopy 373
11.3.1 Description of UV-visible Spectrophotometer 373
11.3.2 Types of UV-visible Spectrophotometer 374
11.3.3 Working Principle 375
11.3.4 Choice of Solvent 375
11.4 Types of Eletronic Transition 376
11.4.1 Transitions Involving s, p and n (Non-bonding Electrons) 376
11.4.2 Absorbing Species Involving d or f Electrons 380
11.4.3 Charge Transfer Spectral Absorption 380
11.5 Type of Absorptions Bands 381
11.5.1 K-Bands 381
11.5.2 R-Bands 381
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
11.6.1 Chromophore 383
11.6.2 Auxochrome 384
11.7 Shifting of Absorption Band and Change in Intensity 385
11.7.1 Terminology Used in UV-visible Spectroscopy 385
11.7.2 Effect of Conjugation of Chromophore 386
11.7.3 Additive Characteristics 386
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
11.7.7 Stereo Chemical Factors 389
11.8 Application of UV-visible Spectral Method 390
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 TechniquesInfrared (IR) Spectral Method 415456

12.2 Molecular Vibrations and Vibrational Frequency 415
12.2.1 Vibration of Diatomic Molecules 415
12.2.2 The Vibration of Polyatomic Molecules 418
12.2.3 Types of Molecular Vibrations 418
12.3 Selection Rule for IR Absorption 422
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
12.6 Instrumentation 428
12.7 Concept of Group Vibrational Frequencies 429
12.7.1 Factors Influencing Group Vibrational Frequencies 430
12.8 Important Spectral Regions in the Infrared and Presentation IR Spectra 433
12.9 IR Characteristics of Some Organic Compounds 435
2.10 IR Characteristics of Some Inorganic Compounds
(Especially Metal Complexes) 448
13. Spectroanalytical TechniquesNuclear Magnetic Resonance

13.2 Principle of NMR 457
13.2.1 Magnetic Properties of Nuclei and Their Angular Momentum 457
13.2.2 Magnetic Moments of the Nuclei 458
13.2.3 Effect of External Magnetic Field 459
13.2.4 Potential Energy of a Nucleus in a Magnetic Field 459
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
14. Spectroanalytical TechniquesElectron Spin Resonance

14.2 Basic Principle 497
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
14.3 Relaxation Process and Line Width in ESR Transition 500
14.4 Techniques of ESR Spectroscopy 502
14.4.1 Instrumentation 502
14.4.2 Sample Concentration and Choice of Solvent 503
14.4.3 Presentation of ESR Spectra 503
14.4.4 Interpretation of Derivative Curve 504
14.4.5 Use of Standards 504
14.5 Hyperfine Splitting 504
14.6 Zero Field Splitting and Kramers Degeneracy 511
14.7 Application of ESR 514
14.7.1 Determination of g Value 514
14.7.2 Shape and Type of Hybridization 515
14.7.3 Study of Free Radicals 515
14.7.4 Study of Internal Motion (Rotation) 516
14.7.5 ESR and Steric Hinderance 516
14.7.6 Analysis of Electron Transfer Reactions through ESR 516
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
15. Spectroanalytical TechniquesMass Spectral Method 525574

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
15.5 Type of Ions Produced in a Mass Spectrometer 532
15.5.1 Molecular Ion or Parent Ion 532
15.5.2 Isotope Ions 534
15.5.3 Metastable Ions or Peaks 534
15.5.4 Fragmented Ion and Fragmentation Modes 537
15.6 Mass Spectra of Some Organic Compounds 543
15.6.1 Straight Chain Alkanes 543
15.6.2 Branched Chain Alkanes 544
15.6.3 Alkens (Olefins) 545
15.6.4 Cycloalkanes 547
15.6.5 Cyclo Olefins 548
15.6.6 Alkynes (Acetylenes) 548
15.6.7 Aromatic Compounds 548
15.6.8 Alkyl Halides 551
15.6.9 Alcohols, Ethers and Amines 551
15.6.10 Fragmentation Mode of Aromatic Alcohols, Phenols, Aromatic
Amines, Aryl Ethers 557
15.6.11 Aliphatic Aldehydes and Ketones 560
15.6.12 Aromatic Aldehydes and Ketones 563
15.6.13 Carboxylic Acids, Esters and Amides 563
15.6.14 Aromatic Acids 568
15.6.15 Fragmentation Modes of Nitro Compounds 568
15.6.16 Fragmentation Modes of Aliphatic Nitriles R CH2 C ºº N 569
15.6.17 Fragmentation Modes of Aliphatic Nitrites 570
15.6.18 Fragmentation Modes of Aliphatic Nitrates 570
Index 575581
Preface
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.
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 includes qualitative and quantitative analysis, data analysis, elemental analysis for
organic compounds, separation and purification techniques, electroanalytical techniques such as
electrogravimetry, coulometry, polarography, spectroanalytical techniques such as ultraviolet and
visible spectral method, infrared spectral method, nuclear magnetic resonance spectral method,
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
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
can easily judge his/her understanding of the subject.
The book will stimulate the students to face the academic and research challenges in analytical
chemistry for the new millennium. Contributions by several authors referred to in the present
book is gratefully acknowledged.
Dhruba Charan Dash
xvii
UNIT 1
1. Qualitative Analysis
CHAPTER 1
Qualitative Analysis
1.1 INTRODUCTION
The word analysis means those chemical reactions by which substances can be identified in the
presence of one another. It is of two typesqualitative analysis and quantitative analysis. Qualitative
analysis deals with the detection of constituents of a substance or a mixture of substances or their
solutions whereas quantitative analysis deals with the estimation of constituents of a substance.
Depending upon the quantity of the sample used to start the analysis, the following methods are
used.
Method of analysis Quantity of the sample

Macro analysis 100 mg1 gm
Semimicro analysis 10 mg100 mg
Micro analysis 1 mg10 mg
Ultramicro analysis Less than 1 mg
Generally qualitative analysis involves analysis of metallic parts in the form of cations
(or basic radicals) and non-metallic parts in the form of anions (acid radicals). The common metallic
cations are divided into five groupsgroup I, group II, group III, group IV and group V based on
solubility product and common ion effect as discussed below.
1.1.1 Solubility Product Principle

If a sparingly soluble salt (like AgCl, BaSO4 etc.) is put in water, a very little amount of it dissolves
in water and thus the solution becomes saturated. But whatever might be the amount dissolved in
water, it gets completely ionized. Then equilibrium is established between the undissolved salt and
the ions in solution.
AB ZZX
YZZ A + + B
Undissolved salt Ions in solution
Applying the law of mass action, we get
[A ][B ]
k=
[AB]
or k[AB] = [A ] [B] where k is equilibrium constant
+
3
4 Analytical Chemistry
But since only a little of the salt AB goes into solution, the concentration of undissolved salt nearly
remains constant. Hence,
K ´ constant = [A+] [B]
or Ksp = [A+] [B]
where Ksp is another constant and is known as solubility product of the salt AB. For general study,
let us discuss the sparingly soluble compound AxBy
ZZX xAy+ + yBx
AxBy YZZ
Hence the solubility product of such salt, AxBy is given by
Ksp = [Ay+]x ´ [Bx]y
where x and y represent the number of ions in the formula of the compound.
From the above expression of the solubility product, it is obvious that
(i) When the ionic product is equal to the solubility product, the solution is saturated.
(ii) When the ionic product is less than the solubility product, the solution is unsaturated and
more of salt can be dissolved in it.
(iii) When the ionic product exceeds the solubility product, the solution is supersaturated. To
keep the ionic product equal to the solubility product, the excess of the ions will recombine
to form solid and thus precipitation takes place. In other words, precipitation occurs
when the product of the ionic concentration of the salt exceeds its solubility product.
1.1.2 Common Ion Effect

It states that if, to a solution of a weak electrolyte (AB), a solution of a strong electrolyte (AC) is
added, this furnishes an ion common to that furnished by the weak electrolyte (here A +), then the
ionization of the weak electrolyte is suppressed.
ZZX A+ + B
AB YZZ
[A ] ¹ [B ]
K= K is dissociation constant of AB
[AB]
AC being a strong electrolyte gives a large amount of A+ ions; as a result the concentration of A+
ions increases. In order to keep K constant, either the concentration of B ion should decrease or
the concentration of AB should increase. In other words, this ionization of AB is suppressed due to
a common ion effect.
The separation of cation into various groups and their corresponding group reagents based on
the above principles are discussed below.
1.2 SEPARATION OF CATIONS INTO GROUPS
The common metallic cations are divided into five groupsgroup I, group II, group III, group IV
and group V. The metallic cations of any group are precipitated by a particular group reagent.
Qualitative Analysis 5
The identification of cations within each group is based on specific characteristics of each group
as discussed below.
Group I cations
Pb2+, Ag+, Hg22+ ions are included in this group. By addition of dil HCl to the solution containing
these ions, they are precipitated as PbCl2, AgCl, Hg2Cl2 as the solubility products of their salts are
exceeded. Here dil HCl is group reagent for group I cations. The chlorides of the cations other than
Ag+, Pb+2 and Hg22+ ions are not precipitated because their solubility products are very large
compared to their ionic products.
Group II cations
Hg2+, Pb2+, Cu2+, Cd2+, Bi3+, As3+ or 5+, Sb3+ or 5+ and Sn2+ or 4+ ions are included in this group.
These are precipitated as sulphides by passing H2S to the solution containing these ions in the
presence of 0.3 M HCl. This is explained as follows:
H2S is a weak dibasic acid for which
ZZZX
H 2S YZZZ H HS
K1
[H ] [HS ]
= K1 = 9.1 ´ 108 (1.1)
[H 2S]
HS ZZZ
K
X H S2
YZZZ 2
[H ] [S2 ]
= K2 = 1.2 ´ 1015 (1.2)
[HS ]
where K1 and K2 are respectively the primary and secondary dissociation constants of H2S at
18°C. On multiplying Eqs. (1.1) and (1.2), we get
[H ]2 [S2 ]
= K1 ´ K2 » 1022
[H 2S]
1022 [H 2S]
[S2] »
[H ]2
If H2S gas at 1 atm is bubbled through water forming a saturated solution, the concentration of
H2S » 0.1 mol L1
10 22 0.1
[S2] »
[H ]2
1023
» (1.3)
[H ]2
Equation (1.3) shows if [H+] increases, [S2] decreases. In other words, dissociation of H2S is
suppressed. Thus to a solution of a weak electrolyte (here H2S), when a solution of a strong
electrolyte like HCl (HCl ® H+ + Cl) is added, this furnishes an ion identical to that furnished by
the weak electrolyte (here H+), the dissociation of the weak electrolyte is suppressed due to a
common ion effect. Here [S2] is inversely proportional to the square of hydrogen ion concentration.
It can be varied by changing [H+] as exemplified below.
If pH = 0, [H+] = 1 mol L1
[S2] » 1022
But if pH = 12, [H+] = 1012 mol L1
1023
[S2] » 10 mol L1
(1012 ) 2
In practice, if [H+] of the solution is adjusted to 0.3 M (yellow-green colour to methyl violet
indicator) by adding HCl prior to passing H2S, the group II sulphides are precipitated selectively
because this decreased concentration of S2 ions is sufficient to precipitate the cations of group II
having low Ksp values (~1022 M) which are given below.
Substances Solubility product

PbS 5 ´ 1029
HgS 4 ´ 1054
CuS 1 ´ 1044
CdS 1.4 ´ 1028
Bi2S3 1 ´ 1048
If the concentration of the acid is much higher than 0.3 M, [S2] is reduced still further so that
CdS is either not precipitated at all or incompletely precipitated. If the concentration of the acid is
much lower (than 0.3 M), the solubility products of MnS, NiS, CoS, ZnS are exceeded, as a result
Mn2+, Ni2+, Co2+, Zn2+ (ions which are not included in group II) are precipitated as sulphides.
The solubility products of these ions are given below.
Substances Solubility product

ZnS 1 ´ 1023
NiS 1.4 ´ 1024
CoS 5 ´ 1022
MnS 1.4 ´ 1015
Explanation for inclusion of Pb2+ in group I as well as group II

Pb2+ is precipitated in group I as PbCl2. However, it is partially soluble in dil HCl, as a result a part
of it goes to the filtrate, which is tested for group II cations. Thus on passing H2S gas, it gives a
black precipitate of PbS.
Pb2+ + H2S ¾® PbS + 2H+
Classification of group II cations into group IIA and IIB
Group II cations are further classified into group IIA and group IIB based on the solubility of their
sulphide with yellow ammonium sulphide. It is a form of ammonium sulphide containing more
sulphur in it and is represented as (NH4)2 Sx where x varies from 2 to 5. The sulphides of Hg2+,
Bi3+, Pb2+, Cu2+ and Cd2+ ions are not soluble in yellow ammonium sulphide and these ions are
included in group IIA whereas the sulphides of As3+ or 5+, Sb3+ or 5+ and Sn2+ or 4+ are soluble in
(NH4)2Sx forming thiosalts as follows. These ions are included in group IIB.
Sb2S3 + 3(NH4)2S2 ¾® 2(NH4)3SbS4 + S
Ammonium thioantimonate
SnS2 + (NH4)2S2 ¾® (NH4)2SnS3 + S

Ammonium thiostannate
As2S3 + (NH4)2S2 ¾® 2(NH4)3AsS4 + S

Ammonium thioarsenate
In case of As2S3, Sb2S3 and SnS2 even ordinary ammonium sulphide may be used as in that case
soluble ammonium thioarsenites are formed.
As2S3 + 3(NH4)2S ¾® 2[NH4]3AsS3
But for SnS, yellow ammonium sulphide is essential as SnS (stannous sulphide) is oxidized first
by the excess of sulphur present in yellow ammonium sulphide into stannic sulphide, which form
soluble thiostannate as given above.
SnS + S ¾® SnS2
Group III cations
This group includes Al3+, Fe3+, Cr3+, Ni2+, Co2+, Mn2+ and Zn2+ cations. The solubility product of
hydroxides of Al3+, Fe3+, Cr3+ are 8.5 ´ 1023, 3.8 ´ 1038 and 2.9 ´ 1029 respectively while
the solubility products of hydroxides of Ni2+, Co2+, Mn2+ and Zn2+ are 8.7 ´ 1019, 1.6 ´ 1018,
4.0 ´ 1014 and 1 ´ 1017 respectively. All these ions can be precipitated as hydroxides if ammonium
hydroxide is added to the solution containing these ions. NH4OH is a weak base for which the
following equilibrium exists.
NH4OH YZZ ZZX NH 4+ + OH
[NH 4 ] [OH ]
for which = Kb = 1.8 ´ 105
[NH 4 OH]
Kb is called the base dissociation constant of NH4OH
[NH 4 ] [OH ] = 1.8 ´ 105 ´ [NH4OH]

But [NH 4 ] = [OH]
[OH]2 = 1.8 ´ 105 ´ [NH4OH]
For 1 M NH4OH
[OH]2 = 1.8 ´ 105
[OH] = 4.24 ´ 103 mol L1
For 0.1 M NH4OH
[OH]2 = 1.8 ´ 105 ´ 101 = 1.8 ´ 106
[OH] = 1.34 ´ 103 mol L1
Hence if a solution of NH4OH alone is added, [OH] is enough to exceed the requirement to the
solubility product for the hydroxides of all these above ions and hence get precipitated as their
hydroxides. However, Al3+, Fe3+ and Cr3+ cations can be selectively precipitated by addition of
NH4OH in the presence of excess of NH4Cl due to a common ion effect as explained below.
Classification of group III cations into IIIA and IIIB

NH4Cl is a strong electrolyte, which gives a large amount of NH4+ ions as it is strongly dissociated.
NH4Cl ¾® NH 4+ + Cl
NH 4+ ions furnished by NH4Cl are common to that furnished by weak electrolyte NH4OH. As a
result, the dissociation of NH4OH is suppressed due to common ion effect, so that concentration of
OH ions falls considerably low. Under such condition, the solubility products of the hydroxides
of Al3+, Fe3+, Cr3+ are exceeded so that they are precipitated as hydroxides by adding NH4OH in
the presence of NH4Cl while those of other ions (like Co2+, Ni2+, Mn2+, Zn2+) which have high
value of solubility products are prevented precipitation. Thus the ions like Al3+, Fe3+, Cr3+ which
get precipitated as hydroxides Al(OH)3 Fe(OH)3, Cr(OH)3 respectively are included in a separate
group IIIA; the NH4OH solution with excess of NH4Cl being its group reagent. The other cations
of the group III (such as Co2+, Ni2+, Mn2+, Zn2+) are precipitated as sulphides by passing H2S
through their ammonical solutions. They form separate group called Group IIIB. At ammonical
medium, dissociation of H2S is favoured
ZZX 2H+ + S2
H2S YZZ
H+ + OH ¾® H2O
As the concentration of H+ decreases due to combination of OH furnished by NH4OH, the
[S2] increases in order to maintain its dissociation constant. It is found that the concentration of
S2 in the presence of NH4OH and NH4Cl is large enough to exceed the requirements of the
solubility products for sulphides of Co2+, Ni2+, Zn2+ and Mn2+ ions and thus get precipitated as
their sulphides. Thus H2S gas in the presence of NH4OH and NH4Cl is the group reagent for
group IIIB cations.
Explanation of precipitation of iron in the form Fe3+ instead of Fe2+
Iron forms two important series of salt such as ferrous salt in which the metal is divalent and
ferric salt in which the metal is trivalent. For satisfactory precipitation with the group reagent
(NH4OH + NH4Cl) all of the three cations (Al3+, Fe3+ and Cr3+) must be present as trivalent
cations. It is, therefore, necessary to test the solution for ferrous ion with potassium ferricyanide
which form a dark blue precipitate due to formation of potassium ferro-ferricyanide
Fe2+ + K3[Fe(CN)6] ¾® KFe[Fe(CN)6] + 2K+

Potassium ferricyanide Potassium ferro-ferricyanide
If Fe2+ ions are present in the mixture under analysis, they must be oxidized to Fe3+ ions (with
concentrated HNO3) prior to the precipitation of group IIIA hydroxides. This is because of the
following reasons:
(i) Ksp for Fe(OH)2 is 4.8 ´ 1016 and Ksp for Fe(OH)3 is 6 ´ 1038. The [OH] produced on
addition of NH4OH and NH4Cl is therefore insufficient to reach that required by the
solubility product for Fe(OH)2. Fe2+ ions are not therefore precipitated in group IIIA
but appear in group IIIB as FeS for which Ksp is 4 ´ 1019 comparable with solubility
products of the group IIIB sulphide. FeS will then interfere with the further analysis of
these sulphides. However, Fe3+ is completely precipitated as Fe(OH)3 under the same
condition.
(ii) Further Fe(OH)2 is oxidized slowly to ferric hydroxide. Instead of getting a precipitate of
definite colour, the precipitate is differently coloured.
(iii) Moreover, Fe(OH)2 is green in colour like Cr(OH)3 whereas Fe(OH)3 is brown in colour.
Thus the colour of the precipitate of Fe(OH)3 helps to distinguish it from Cr(OH)3.
Explanation for presence of Mn2+ in group IIIA as well as group IIIB
Manganese when present in manganous state is not precipitated in group IIIA by excess of
ammonium hydroxide solution in the presence of excess NH4Cl. In practice, however, the
manganous ion is slightly oxidized by the exposure of the solution to air and accordingly some
manganese may be precipitated as brown coloured hydrated manganese dioxide MnO2 · xH2O by
the group IIIA reagent. For this reason provision is usually made for the detection of Mn2+ in
group IIIA as well as group IIIB.
Group IV cations
Ca2+, Ba2+ and Sr2+ ions are included in this group. These ions are precipitated as insoluble
carbonates in ammonical medium when ammonium carbonate is added to the solution containing
these ions in the presence of NH4OH and NH4Cl.
NH4Cl ¾® NH 4+ + Cl
ZZX 2NH 4+ + CO32
(NH4)2CO3 YZZ
Due to a common ion effect, ammonium chloride suppresses the ionization of ammonium carbonate.
However, the low concentration of CO32 ions is sufficient to exceed the solubility products of the
carbonates of calcium, strontium and barium, while magnesium ion remains in solution because
the solubility product of magnesium carbonate is comparatively high.
Explanation of addition of NH4OH in group IV
The group reagent (NH4)2CO3 usually contains a large amount of ammonium bicarbonate.
Bicarbonates of Ba2+, Ca2+ and Sr2+ are soluble in water. NH4OH converts ammonium bicarbonate
to ammonium carbonate so that the above IV group cations do not escape precipitation.
NH4HCO3 + NH4OH ¾® (NH4)2CO3 + H2O
Hence NH4OH is added along with (NH4)2CO3 and NH4Cl to completely precipitated IV group
cations as their carbonate. Ba(OH)2, Ca(OH)2, Sr(OH)2 and Mg(OH)2 are not precipitated under
the above condition as their solubility products are not exceeded.
Group V cations
Mg2+, Na+, K+ and even NH 4+ ions are included in this group. There is no specific group reagent
for these ions. Na+ and K+ belong to the alkali metal group. NH 4+ ion is included in this group
since its compounds resemble those of alkali metals particularly of potassium. The detection and
separation of cations of each group are discussed below.
1.3 DETECTION AND SEPARATION OF CATIONS OF EACH GROUP
The cations of each group can be separated and detected on the basis of solubility product, common
ion effect and other chemical reactions such as precipitation, complexation and redox reactions as
described below.
1.3.1 Separation and Detection of Group I (Silver Group) Cations

(Ag + , Hg 22+ , Pb 2+ )
All the cations (Ag+, Hg22+ and Pb2+) of group I are characterized by their precipitation as chlorides
by dil hydrochloric acid. PbCl2 is slightly soluble in water and hence is not completely precipitated
as chloride in this group. It is, therefore, also found in group II where it is precipitated as highly
insoluble sulphides.
Separation of PbCl2 from Hg2Cl2 and AgCl (by boiling with water)
The precipitate containing PbCl2, AgCl and Hg2Cl2 is boiled with water and filtered hot. PbCl 2
goes into solution in hot water but separates out again as needles when the solution is cooled.
The presence of Pb2+ is conformed by the formation of yellow precipitate of PbCrO4 by addition of
K2CrO4 to its hot solution. It is insoluble in acetic acid and in ammonia solution but soluble in
alkali hydroxides, due to formation of sodium plumbite.
PbCl2 + K2CrO4 ¾® PbCrO4 + 2KCl
Yellow precipitate
PbCrO4 + 4NaOH ¾® Na2[PbO2] + Na2CrO4 + 2H2O

Sodium plumbite
Separation of AgCl from Hg2Cl2 (by reaction with ammonium hydroxide solution)
The residue (HgCl2 + AgCl) when treated with dil NH4OH solution, AgCl goes into solution due
to formation of complex ion, diammine silver(I), [Ag(NH3)2]+ whereas Hg2Cl2 turns into black
due to formation of (Hg + Hg(NH2)Cl). Thus AgCl is separated from Hg2Cl2 by reaction with NH3
solution.
AgCl + 2NH4OH ¾® [Ag(NH3)2]Cl + 2H2O
Detection of Ag+
[Ag(NH3)2Cl] + dil HNO3 ¾® AgCl + 2NH4NO3
White precipitate
Detection of Hg22+
When Hg2Cl2 is treated with ammonium hydroxide NH4OH, a black precipitate consisting of a
mercuric amino chloride and finely divided mercury is formed.
Hg2Cl2 + 2NH4OH ¾® HgNH2Cl + Hg + NH4Cl + 2H2O
The detection and separation of group I cations (Ag+, Pb2+, Hg 22 ) can be written in a tabular form
as shown in Table 1.1.
Table 1.1 Separation and detection of group I cations (Ag+, Hg22+, Pb2+)
Solution containing Ag+, Pb2+ and Hg 22 ions

Dil HCl
(AgCl + PbCl2 + Hg2Cl2)
Boil with water and filter hot
¯ ¯
Residue Filtrate
May contain Hg2Cl2 and AgCl. Wash the precipitate May contain PbCl2, which may crystallize out on
several times with hot water until the washings give cooling. To the hot solution, add ammonium acetate
no precipitate with K2CrO4 solution. This ensures solution followed by K2CrO4 solution. A yellow
complete removal of Pb2+. precipitate of PbCrO, soluble in dilute NaOH,
Pour 34 ml of warm dil NH3 solution over the indicates that Pb2+ ion is present.
precipitate.
Black: Hg(NH2)Cl + Hg. Hg22+ is present. May contain Ag(NH3)2Cl. When acidified with
HNO3 a white precipitate of AgCl indicates the
presence of Ag+ ion.
1.3.2 Separation of Group IIA from Group IIB Cations (by Yellow Ammonium
Sulphide)
On passing H2S gas into acidified solution (0.3 M HCl), group II cations are precipitated as sulphides
of different colour. Sulphides of group IIA are separated from those of group IIB cations by yellow
ammonium sulphides due to the formation of water soluble thiosalts. On filtration, the residue
contains the sulphides of group IIA cations while the filtrate contains the thiosalts.
1.3.3 Separation and Detection of Group IIA Cations (Pb2+, Bi3+, Hg2+, Cd2+, Cu2+)
(Copper Group)
Separation of HgS (from PbS, Bi2S3, CdS, CuS by 50% nitric acid)
To the sulphides of the above ions when 50% HNO3 is added, all the sulphides except HgS go into
solution due to the formation of water soluble nitrates. Thus HgS gets separated from other sulphides
of this group by HNO3.
2HNO3 ¾® 2NO + H2O + 3O
3(PbS + O ¾® PbO + S)
3(PbO + 2HNO3 ¾® Pb(NO3)2 + H2O)
3PbS + 8HNO3 ¾® 3Pb(NO3)2 + 2NO + 4H2O + 3S
Similar reaction occurs with Bi2S3, CuS, CdS leading to the formation of water soluble Bi(NO3)2,
Cu(NO3)2 and Cd(NO3)2 respectively.
Detection of Hg2+ from HgS
HgS goes into solution with aqua regia (which is a mixture of 3 parts of conc HCl and 1 part of
conc HNO3). From aqua regia, nascent chlorine is formed by the oxidation of HCl which react
with HgS forming water soluble HgCl2.
2(HNO3 + 3HCl ¾® NO + 2H2O + 3Cl)
3(HgS + 2Cl ¾® HgCl2 + S)
3HgS + 2HNO3 + 6HCl ¾® 3HgCl2 + 3S + 2NO + 4H2O
Redox reaction of HgCl2 with SnCl2

HgCl2 solution when treated with SnCl2 solution, a white precipitate of Hg2Cl2 is first obtained
which is further reduced by the excess of the reagent to grey black metallic mercury due to redox
reaction as shown below.
2HgCl2 + SnCl2 ¾® SnCl4 + Hg2Cl2 (White ppt.)

Hg2Cl2 + SnCl2 ¾® SnCl4 + 2Hg (Grey black ppt.)
Separation and detection of Pb2+

Pb2+ is separated from other cations (Cu2+, Cd2+, Bi3+) by precipitating it as PbSO4 by addition of
dil H2SO4. This precipitate is soluble in ammonium acetate solution and when K2CrO4 solution is
added, a yellow precipitate due to formation of PbCrO4 indicates the presence of Pb2+.
PbSO4 + 2CH3COONH4 ¾® Pb(CH3COO)2 + (NH4)2SO4

Ammonium acetate
Pb(CH3COO)2 + K2CrO4 ¾® PbCrO4 + 2CH3COOK
Yellow precipitate
Separation and detection of Bi3+

Bi3+ forms white precipitate of Bi(OH)3. When NH3 solution is added to the solution containing
Bi3+, Cd2+ and Cu2+ the following reaction occurs.
Bi3+ + 3NH4OH ¾® Bi(OH)3 + 3NH 4+
White precipitate
Water soluble complex cations are present in case of Cd2+ and Cu2+.
Cd2+ + 4NH3 ¾® [Cd(NH3)4]2+ tetraammine cadmium(II) ion

Cu2+ + 4NH3 ¾® [Cu(NH3)4]2+ tetraammine copper(II) ion
A deep blue solution is obtained when Cu2+ is present due to the formation of [Cu(NH3)4]2+ ion.
This white precipitate of Bi(OH)3 is turned black when reacted with sodium stannite solution
due to the formation of finely divided bismuth due to the following redox reaction.
3 ´ (SnO 2 2
2 + 2OH ¾® SnO 3 + 2e)
Stannite Stannate
2 ´ (Bi(OH)3 + 3e ¾® Bi + 3OH)
2Bi(OH)3 + 3SnO 2 2
2 ¾® 2Bi + 3SnO3 + 3H2O
Separation and detection of Cd2+

If Cu2+ is absent, Cd2+ gets precipitated as yellow CdS when H2S gas is passed into its solution.
[Cd(NH3)4]2+ + H2S ¾® CdS + 2NH4+ + 2NH3
If Cu2+ is present, the solution will be blue and a chocolate coloured precipitate of cupric ferrocyanide
will be obtained by the reaction with K4Fe(CN)6 which is insoluble in acetic acid.
2Cu2+ + K4[Fe(CN)6] ¾® Cu2 [Fe(CN)6] + 4K+
Cupric ferrocyanide
Detection of Cd2+ in presence of Cu2+

When potassium cyanide solution is added, Cu2+ ion is reduced to cuprous ion forming a more
stable cuprocyanide and blue solution gets discharged while Cd2+ forms less stable tetracyano
cadmimate(II) ion or cadmicyanide ion which gives yellow precipitate of CdS when H2S is passed
through the solution containing the above ions. The following reactions occur.
2[Cu(NH3)4]2+ + 4CN ¾® Cu2(CN)2 + (CN)2 + 8NH3
Cu2(CN)2 + 6CN ¾® 2[Cu(CN)4]3 no ppt.
H2S
[Cd(NH3)4]2+ + 2CN ¾® Cd(CN)2 + 4NH3

Cd(CN)2 + 2CN ¾® [Cd(CN)4]2 CdS
H 2S
Yellow ppt.
Here KCN is used as masking agent. Marked difference in the value of instability constants of the
complex ions [Cd(CN)4]2 and [Cu(CN)4]3 serve as the basis of the separation of Cu2+ and Cd2+
ion. The detection and separation of group IIA cations can be written in a tabular form as shown in
Table 1.2.
Table 1.2 Detection and separation of group IIA cations (Cu2+, Cd2+, Bi3+, Hg2+, Pb2+) (Copper group)
Solution containing group II cations

0.3 M HCl + H2S
HgS + PbS + Bi2S3 + CuS + CdS + sulphide of group IIB cations
Yellow ammonium sulphide
Residue: May contain HgS, PbS, Bi2S3,CdS, CuS Filtrate: Thiosalt of group IIB cations
dil HNO3(50%) boiled
(Contd...)
Table 1.2 Detection and separation of group IIA cations (Cu2+, Cd2+, Bi3+, Hg2+, Pb2+) (Copper group)
(Contd...)
Residue Filtrate
Black HgS. Dissolve it in aqua regia. Boil off the May contain nitrates of Pb, Bi, Cu and Cd. Test a
aqua regia solution to a small volume. Dilute with small portion of Pb2+ by adding dilute H2SO4 and
water. Add SnCl 2 solution. A white precipitate alcohol. A white precipitate of PbSO4 indicates Pb2+
changing to grey or black with excess SnCl2 solution is present. If Pb2+ is present, add dil H2SO4 to the
indicates the presence of Hg2+ ions. remainder of the solution, concentrate it in the fume
cupboard until white fumes, due to SO3, appear. Cool,
dilute with water and filter it.
White PbSO4. Add ammonium acetate solution to May contain nitrate and sulphates of Bi3+, Cu2+ and
dissolve it. Add a few drops of dilute acetic acid and Cd2+. Add conc NH 3 solution until solution is
then K2CrO4 solution. A yellow precipitate of PbCrO4 distinctly alkaline. Filter it.
indicates Pb2+ is present.
White. May be Bi(OH)3. Dissolves it in a minimum May contain [Cu(NH 3 ) 4 ] 2+ and [Cd(NH 3 ) 4 ] 2+ .
volume of HCl. Add sodium stannite solution. Black If deep blue colour, Cu2+ may be present. Cu2+ may
precipitate indicates the presence of Bi3+. be confirmed by acidifying a portion of the filtrate
with dilute acitic acid and adding K4[Fe(CN)6]
solution. Raddish brown precipitate indicates Cu2+
is present. To the remainder filtrate, add KCN
solution dropwise until blue colour is discharged.
Pass H2S. A yellow precipitate of CdS implies Cd2+
is present.
1.3.4 Separation and Detection of Group IIB Cations

(As3+ or 5+, Sb3+ or 5+, Sn2+ or 4+)(Arsenic Group)
The sulphides of group IIB cations go into solution when treated with yellow ammonium
sulphides due to the formation of water soluble thiosalts such as (NH 4)3AsS4, (NH4)3SbS4
and (NH4)2SnS3 which are again precipitated as their corresponding sulphides on addition of
dil HCl.
2(NH4)3AsS4 + 6HCl ¾® As2S5 + 3H2S + 6NH4Cl
2(NH4)3SbS4 + 6HCl ¾® Sb2S5 + 3H2S + 6NH4Cl
(NH4)2SnS3 + 2HCl ¾® SnS2 + 2NH4Cl + H2S
Separation of As2S5 from Sb2S5 and SnS2

When As2S5, Sb2S5 and SnS2 are boiled with conc HCl, Sb2S5 and SnS2 go into solution forming
H[SbCl4] and H2[SnCl6] while As2S5 is insoluble. On filtration the residue contains As2S5 (yellow
precipitate) while the filtrate contains H[SbCl4] and H2[SnCl6].
As2S5 + conc HCl ¾® no reaction
Sb2S5 + 8HCl ¾® 2H[SbCl4] + 2S + 3H2S
SnS2 + 6HCl ¾® H2[SnCl6] + 2H2S
Detection of arsenic (As3+ or 5+) from the residue containing As2S5 or As2S3
The As2S3 or As2S5 goes into solution with dilute NH3 due to the formation of water-soluble
ammonium arsenite and ammonium thioarsenite as follows:
As2S3 + 6NH3 + 3H2O ¾® (NH4)3AsO3 + (NH4)3AsS3

As2S5 + 6NH4OH ¾® (NH4)3AsS3 + (NH4)3AsO3 + 2S + 2H2O
The arsenite is oxidized to arsenate when treated with H2O2
H2O2 ¾® H2O + O
AsO33 O ¾® AsO34
H 2 O 2 AsO33 ¾® AsO34 H 2 O
On adding magnetia mixture (a solution containing MgSO4, NH4Cl and NH4OH) to the above
solution, a white crystalline precipitate of hydrated magnesium ammonium arsenate
MgNH4AsO4 · 6H2O is obtained which confirms the presence of As3+ or As5+.
(NH4)3AsO4 + MgSO4 ¾® Mg(NH4)AsO4 + (NH4)2SO4
The presence of arsenic is further confirmed as follows:

As2S5 is heated with conc HNO3 and ammonium molybdate (NH4)2 MoO4 solution is added to it,
a yellow precipitate of ammonium arsenomolybdate is formed indicating the presence of arsenic.
5(2HNO3 ¾® 2NO + H2O + 3O)

3(As2S5 + 5O + 3H2O ¾® 2H3AsO4 + 5S)
3As2S5 + 10HNO3 + 4H2O ¾® 10NO + 6H3AsO4 + 15S
H3AsO4 + 12(NH4)2MoO4 + 21HNO3 ¾® (NH4)3Mo12AsO40 + 21NH4NO3 + 12H2O
Ammonium arsenomolybdate
Separations and detection of antimony (Sb3+ or Sb5+)

The filtrate containing H2(SnCl6) and H[SbCl4] is made just alkaline with NH3 solution and is
divided into two parts. To the first one, oxalic acid is added and H2S gas is passed on boiling
condition. Only orange precipitate of Sb2S3 is obtained. No precipitation of stannic sulphide in the
presence of oxalic acid is obtained due to the formation of stable complex ion of the type
[Sn(C2O4)4(H2O2)]4 which forms the basis of method of separation of antimony from tin.
H2C2O4 + 2NH4OH ¾® (NH4)2C2O4 + 2H2O
Oxalic acid Ammonium oxalate
H[SbCl4] + 3C2O42 ¾® [Sb(C2O4)3]3 + 4Cl

[SnCl6]2 + 4C2O42 ¾® [Sn(C2O4)4]4 + 6Cl1
On passing H2S gas through the above solution antimony sulphide gets precipitated because oxalato
complex of tin being more stable, it does not dissociate sufficiently to exceed the solubility product
of tin sulphide.
Detection of tin (Sn2+ or 4+)

To the second part, iron wire is added followed by hydrochloric acid. On heating the above solution,
iron reduces stannic state in [SnCl6]2 to stannous state which gives a white or grey precipitated of
Hg2Cl2 and Hg when reacted with HgCl2.
H2[SnCl6] + Fe ¾® SnCl2 + FeCl3 + 2HCl
SnCl2 + 2HgCl2 ¾® SnCl4 + Hg2Cl2
Hg2Cl2 + SnCl2 ¾® SnCl4 + 2Hg
The separation and detection of all the group IIB cations are summarized in Table 1.3.
Table 1.3 Separation and detection of group IIB cations

Solution containing As3+ or 5+, Sb3+ or 5+ and Sn2+ or 4+
H2S + HCl (0.3 M)
Sulphide of group IIB cations
Yellow ammonium sulphide
No residue Filtrate
(Absence of group IIA cations) The filtrate may contain the thiosalt (NH4)3AsS4,
(NH4)3SbS4 and (NH4)3SnS3
Dil HCl
Sulphide of group IIB cation
Boiled with conc HCl
Residue Filtrate
May contain sulphide of As. Dissolve the residue H[SbCl4] and H2[SnCl6].
with NH3 solution till alkaline (litmus test). Add 3% Divide into two parts.
H2O2 solution followed by addition of a few ml of Part-I: Make just alkaline with conc NH3 solution,
magnesia mixture reagent. Allow to stand for 5 add 0.3 g of oxalic acid, and pass H2S. An orange
minutes with frequent stirring and shaking. A white precipitate of Sb2S3.
precipitate of Mg(NH4)AsO4 · 6H2O indicates the Sb3+ or 5+ present.
presence of As3+ or 5+. Part-II: Introduce a piece of clean iron wire or a
pinch of iron filings, and heat on a water bath for 3
5 minutes. If the solution is not clear, filter. To the
clear solution, add HgCl2 solution dropwise. White
or grey, precipitate.
Sn2+ or 4+ present.
1.3.5 Separation and Detection of Group IIIA Cations (Fe3+, Al3+, Cr3+) Iron
Group
All these ions are precipitated as Al(OH)3, Fe(OH)3 and Cr(OH)3 by adding NH4OH along with
NH4Cl to their solution.
Separation of Fe(OH)3 from Al(OH)3 and Cr(OH3)
When the above hydroxides are treated with NaOH in the presence of H2O2, Al(OH)3 and Cr(OH)3,
go into solution forming aluminate, AlO2 and chromate ion CrO 24 respectively, while Fe(OH)3
remain as such. On filtration, the residue contains Fe(OH)3 and the filtrate contains AlO 2 and
CrO 24 ions.
Al(OH)3 + NaOH ¾® NaAlO2 + 2H2O
2Cr(OH)3 + 5OH ¾® CrO 24 + 3e + 4H2O
3(H2O2 + 2e ¾® 2OH)
2Cr(OH)3 + 3H2O2 + 4OH ¾® 2CrO 24 + 3H2O
Detection of Fe3+ by analysis of the residue Fe(OH)3

The residue is dissolved in dil HCl and the resulting solution containing Fe3+ is divided into two
parts:
Part I + KSCN solution ¾® Blood red colouration
Part II + K4[Fe(CN)6] solution ¾® Blue colouration or precipitate
Fe3+ + SCN ¾® [Fe(SCN)]2+, Blood red colouration
Fe3+ + K4[Fe(CN)6] ¾® K[Fe(Fe(CN)6], Potassium ferric ferrocyanide
(Blue precipitate or colouration)
Detection of Al3+ and Cr3+ ions by analysis of filtrate containing AlO2 and CrO42 ions
The presence of CrO 24 ion is indicated of the filtrate is yellow. The solution is divided into two
parts:
Part I + acetic acid + lead acetate solution ¾® yellow precipitate of PbCrO4 (Cr3+ is indicated).
Part II is acidified with dil HCl (red litmus paper turns blue).
Then NH4OH solution is added till ammonical. On heating, the resulting solution to boiling a
gelatinous precipitate of Al(OH)3 indicates the presence of Al3+.
AlO2 + 4H+ ¾® Al3+ + 2H2O
Al3+ + 3NH4OH ¾® Al(OH)3 + 3NH 4+
The separation and detection of all the cations of group IIIA is summarized in Table 1.4.
Table 1.4 Separation and detection of group IIIA cations (Al3+, Fe3+, Cr3+)
A solution containing (Al3+, Fe3+ and Cr3+)
NH4Cl + NH4OH
Al(OH)3, Cr(OH)3, Fe(OH)3
Transfer the hydroxides of group IIIA cations to a small beaker with the aid of about 510 ml water.
Add 5 ml of NaOH solution and 5 ml of 3% H2O2 solution. Boil gently until the evolution of O2 stops
(23 minutes). Filter.
(Contd...)
Table 1.4 Separation and detection of group IIIA cations (Al3+, Fe3+, Cr3+) (Contd...)
Residue A Filtrate A
May contain Fe(OH)3. May contain NaAlO 2 (colourless), Na 2 CrO 4
Dissolve it in dil HCl. Divide the solution into two (Yellow).
parts: If colourless, CrO 42 is absent and need not be
considered further. If yellow, CrO42 is indicated.
Divide the filtrate into two parts:
Part I + KSCN solution. Part I: Acidify with acetic acid and add lead acetate
Deep red colour. solution.
Yellow precipitate of PbCrO4.
Cr3+ present.
Part II + potassium ferrocyanide solution. Blue Part II: Acidify with dil HCl (litmus test), then add
colour or precipitate, Fe3+ present. dil NH3 solution until just alkaline. Heat to boiling
White gelatinous precipitate of Al(OH)3.
Al3+ present.
1.3.6 Separation and Detection of Group IIIB Cations Co2+, Ni2+, Mn2+ and Zn2+
(Zinc Group)
All these ions are precipitated as CoS, NiS, MnS and ZnS by passing H2S through their ammonical
solutions containing NH4Cl.
Separation of CoS and NiS
ZnS and MnS go into solutions forming ZnCl2 and MnCl2 on heating with dil HCl while CoS and
NiS are insoluble. On filtration the black residue contains NiS and CoS, while the filtrate contains
MnCl2 and ZnCl2.
Analysis of the black residue (CoS + NiS)
The residue is dissolved in aqua regia on heating
2(HNO3 + 3HCl ¾® NO + 2H2O + 3Cl)

3(CoS + 2Cl ¾® CoCl2 + S)
3CoS + 2HNO3 + 6HCl ¾® 3CoCl2 + 3S + 2NO + 4H2O
Similarly, 3NiS + 2HNO3 + 6HCl ¾® 3NiCl2 + 3S + 2NO + 4H2O
The dry mass is dissolved in water, which contains NiCl2 and CoCl2.
Detection of Co2+ (CoCl2 + NiCl2)
To the solution containing NiCl2 and CoCl2 when solid ammonium thiocyanate (NH4SCN) is
added, a blue solution due to tetrathiocyanato cobaltate (II) or cobalt thiocyanate ion [Co(SCN)4]2
is produced. If amyl alcohol is added to the above blue solution and shaken, the blue colour passes
into the alcohol layer.
Co2+ + 4SCN ¾® [Co(SCN)4]2

blue in colour
Detection of Ni2+
The solution containing NiCl2 and CoCl2 is made ammonical by adding NH4OH and to ammonical
solution, dimethyl glyoxime is added when a red precipitate due to formation of nickel bis(dimethyl
glyoximato) nickel(II) complex or nickel dimethyl glyoxime is obtained indicating the presence of
Ni2+.
Analysis of the filtrate containing (ZnCl2 + MnCl2)

Separation of Mn2+ as MnO2xH2O: When to the solution containing Zn2+ and Mn2+, NaOH is
added in excess followed by H2O2, a brown precipitate due to formation of hydrated manganese
dioxide, MnO2xH2O is obtained while Zn2+ forms water-soluble zincate ion. The following reactions
take place.
Mn2+ + 2NaOH ¾® Mn(OH)2 + 2Na+
The precipitate readily becomes brown on addition of H2O2 facilitating the oxidation of Mn(OH)2.
H2O2 ¾® H2O + O
Mn(OH)2 + O ¾® MnO2 + H2O
Mn(OH)2 + H2O2 ¾® MnO2 + 2H2O
Zn2+ + 2NaOH ¾® Zn(OH)2 + 2Na+
A white gelatinous precipitate of Zn(OH)2 being amphoteric goes into solution is excess of NaOH
forming Zincate ion (ZnO22)
Zn(OH)2 + 2OH ¾® ZnO22 + 2H2O
So on filtration, the residue contains MnO2xH2O and the filtrate contains ZnO22 ion.
Detection of Mn2+ from the residue containing MnO2xH2O
The residue is dissolved in dil HNO3. On addition of solid sodium bismuthate NaBiO3, the solution
becomes purple due to the formation of per manganic acid (HMnO4) as follows:
3(B1O 3 + 2e + 6H+ ¾® Bi3+ + 3H2O)
2(MnO2 + 2H2O ¾® HMnO4 + 3e + 3H+)
2MnO2 + 3BiO 3 + 12H+ ¾® 3Bi3+ + 2HMnO4 + 5H2O
Detection of Zn2+ from its zincate solution

Zn2+ is detected as ZnS (white precipitate), by passing H2S through its zincate solution.
ZnO22 + H2S ¾® ZnS + 2OH
The detection and separation of all the cations group IIIB are summarized in Table 1.5.
Table 1.5 Separation and detection of group IIIB cations (Co2+, Ni+, Mn2+, Zn2+)
A solution containing (Co2+, Ni2+, Mn2+ and Zn2+ ions)
NH4OH + NH4Cl + H2S
CoS, NiS, and ZnS, MnS
HCl
Residue Filtrate
If black may contain CoS and NiS. May contain MnCl2, ZnCl2. Add excess of NaOH
Dissolve the residue carefully with minimum amount solution, followed by 1 ml of 3% H2O2 solution. Boil
of aqua regia, boil-off the excess aqua regia. Dilute for 3 minutes. Filter.
with water and divide into 2 parts.
Part I: Add 1 ml amyl alcohol and 2 gm solid
NH4SCN and shake well. Amyl alcohol layer becomes
blue.
Co2+ present.
Part II: Add 2 ml of NH 4Cl solution and then
NH 3 solution till alkaline. Add excess of
dimethylglyoxime reagent. Red precipitate.
Ni2+ present.
Largely MnO2xH2O. Dissolve the precipitate in 5 ml May contain Na2[ZnO2]. Acidify with acetic acid and
of dil HNO3. Add few drops of 3% H2O2 solution. pass H2S. White precipitate of ZnS.
Boil and then add 0.05 g of sodium bismuthate, stir Zn2+ present.
and allow to settle. Purple solution of HMnO4.
Mn2+ present.
1.3.7 Separation and Detection of Group IV Cations (Ca2+, Ba2+, Sr2+)

These ions are precipitated as BaCO3, CaCO3 and SrCO3 by adding ammonium carbonate to their
solution in ammonical medium in the presence of NH4Cl. The precipitates get dissolved in hot 2N
acetic acid.
BaCO3 + 2CH3COOH ¾® Ba(CH3COO)2 + CO2 + H2O

SrCO3 + CH3COOH ¾® Sr(CH3OO)2 + CO2 + H2O
CaCO3 + CH3COOH ¾® Ca(CH3COO)2 + CO2 + H2O
Separation and detection of Ba2+

To the above hot solution when K2CrO4 solution is added, a yellow precipitate due to formation of
BaCrO4 is obtained indicating the presence of Ba2+.
Ba(CH3COO)2 + K2CrO4 ¾® BaCrO4 + 2CH3COOK

Yellow ppt.
On filtration, the filtrate contains Ca2+ and Sr2+.

Separation and detection of Sr2+
To the filtrate containing Ca2+ and Sr2+, saturated (NH4)2SO4 solution is added followed by sodium
thiosulphate. The resulting solution when heated in a beaker of boiling water and allowed to stand,
a white precipitate of SrSO4 is obtained while Ca2+ forms soluble thiosulphato complex ion and its
precipitation as CaSO4 is prevented.
Ca2+ + 2S2O32 ¾® [Ca(S2O3)2]2
Sr2+ + (NH4)2(SO4) ¾® SrSO4 + 2NH 4+
White ppt.
Detection of Ca2+
The filtrate containing [Ca(S2O3)]2 is heated with sodium oxalate solution when a white precipitate
of calcium oxalate, CaC2O4 is obtained indicating the presence of Ca2+.
[Ca(S2O3)2]2 + C2O42 ¾® CaC2O4 + 2S2O32
White ppt.
The separation and detection of all cations of group IV are summarized in Table 1.6.
Table 1.6 Separation and detection of group IV cations (Ca2+, Ba2+, Sr2+)
Solution containing group IV cations (Ca2+, Ba2+, Sr2+)
NH4Cl + (NH4)2CO3 + NH4OH
Residue Filtrate
¯ dil acetic acid (Rejected)
Goes into the solution
¯ K2CrO4 solution and filter
Residue Filtrate
Yellow BaCrO4. Wash well with hot water. Dissolve To 2 ml of the cold solution add 2 ml of saturated
the precipitate in a little concentrated HCl, evaporate (NH4)2SO4 solution, followed by 0.2 g of sodium
almost to dryness and apply the flame test. Green thiosulphate. Heat in a beaker of boiling water for
flame indicates the presence of Ba2+. 5 minutes and allow to stand for 12 minutes. Filter.
Largly SrSO4. Wash with a little water. Transfer May contain Ca complex. Add a little of (NH4)2C2O4
precipitate with filter paper to a small crucible, and solution and warm on a water bath. A white
heat until paper has charred. Moisten the ash with a precipitate of CaC2O4 indicates Ca2+ is present.
few drop of conc HCl and apply the flame test.
Crimson flame indicates the presence of Sr2+. Confirm by flame test on the precipitate. Brick red
flames indicates the presence of Ca2+.
1.3.8 Separation and Detection of Group V Cations (Na+, K+, Mg2+, NH 4+)
As there is no specific group reagent for these cations of this group, these ions are tested individually
as described below. The solution containing above ions is divided into four parts.
Detection of Mg2+ from first part
The solution containing Na+, K+, Mg2+, NH 4+ ions is made ammonical on addition of NH4OH
solution followed by the addition of disodium hydrogen phosphate Na2HPO4 in presence of NH4Cl
when a white crystalline precipitate of MgNH4PO4 is obtained on scratching with a glass rod
indicating the presence of Mg2+ ion. The addition of NH4Cl is necessary to prevent the precipitation
of Mg(OH)2.
Mg2+ + Na2HPO4 + NH4OH ¾® MgNH4PO4 + H2O + 2Na+
The precipitate gets dissolved by dil HCl. On addition of Magneson reagent and excess of NaOH
solution, a blue precipitate is formed confirming the presence of Mg2+ ion. Magneson reagent is
a dyestuffs of para-Nitrobenzene-azo-resorcinols.
Detection of Na+ from second part
When potassium pyroantimonate solution is added to the second part, a white precipitate due to
the formation of sodium pyroantimonate is obtained indicating the presence of Na+ ion.
Na+ + K2H2Sb2O7 ¾® Na2H2Sb2O7 + 2K+
Potassium pyroantimonate
Detection of K+ from third part

When the third part is treated with sodium cobaltic nitrite Na3[Co(NO2)6] solution a yellow
precipitate due to the formation of potassium cobaltic nitrite, K3[Co(NO2)6] is obtained indicating
the presence of K+ ion.
3K+ + Na3[Co(NO2)6] ¾® K3[Co(NO2)6] + 3Na+
Sodium cobaltic nitrite is prepared by mixing well-cooled solution of Co(NO 3)2 and NaNO2 and
acidifying the mixture in the glacial acetic acid.
Co2+ + 7NO2 + 2H+ ¾® Co(NO2)63 + H2O + NO
Detection of NH4+ from fourth part
NH 4+ ion is detected by Nesslers reagent test as follows:
When excess of KI is added to HgCl2 solution, a solution of potassium tetraiodo mercurate(II)
K2[HgI4] is obtained. This solution when made strongly alkaline with KOH or NaOH is called
Nesslers reagent. When added to the fourth part of the solution containing NH 4+ ion, a brown
precipitate due to the formation of iodide of Millons base, NH2Hg2I3 is obtained on heating
indicating the presence of NH 4+ ion.
2(NH 4 OH
'
NH H 2 O)
3
2 (K 2 HgI 4 ¾® 2KI HgI 2 )
HgI 2 2NH 3 ¾® HgINH 2 NH 4 I
Mercuri amidoiodide
HgINH 2 HgI 2 ¾® Hg 2 I3 NH 2
2K 2 HgI 4 2NH 4 2OH ¾® NH 2 Hg 2 I3 4KI NH 4 I 2H 2 O

Iodide of Millons base
1.4 SEPARATION AND DETECTION OF ACID RADICALS (ANIONS)
Scheme of classification
No satisfactory scheme has yet been proposed for the separation of common anions into major
groups as done in case of cations. For the sake of convenience, they may be classified into group I
(dil HCl/H2SO4 group), group II (conc H2SO4 group), group III (precipitation group) and group IV
(oxidation and reduction group) as discussed below. It is advisable to prepare sodium carbonate
extract (SCE) before the analysis of the anion for the reason given below.
Reason for preparation of Sodium Carbonate Extract (SCE)
Most of the anions can be detected by a preliminary acid test with dil HCl or dil H2SO4 and conc
H2SO4 on their solid salts (or mixture). However, for detailed information the anions are to be
analyzed in their aqueous solutions. But the anions do not go into solution by simply addition of
water to their salts as they have the tendency to form water insoluble salts with metal ions.
In order to convert the anions into soluble forms, the salts (or mixture) are to be boiled with conc
Na2CO3 solution so that double decomposition occurs with production of insoluble carbonates of
the metal ions. On filtration, the filtrate called sodium carbonate extract contains water-soluble
sodium salts of the anions. Suppose univalent anions, A forms insoluble salt of the type MA2 with
a bivalent metal ion, M2+. When this salt is boiled with conc Na2CO3 solution, the following
double decomposition reaction takes place.
MA2 + Na2CO3 ¾® MCO3 + 2NaA
Insoluble Insoluble Soluble
So the sodium carbonate extract will contain water soluble NaA salt.

1.4.1 Detection of Group I Anions (CO2 2 2 2
3 , SO3 , S2O3 , S , NO2 )
When dil HCl or dil H2SO4 is added to the anions of this group, effervescence takes place with
evolution of gases. Such group includes carbonates (CO 32), bicarbonate (HCO 3), sulphite
(SO 32), thiosulphate (S2O 32), sulphide (S2), nitrite (NO2), cyanide (CN) and cyanate (CNO), etc.
The detection of the following anions of this group is given below. However, it is advisable to
use dil HCl instead of dil H2SO4 as it forms insoluble sulphate layer if Pb2+, Ba2+, Sr2+ and Ca2+
ions are present. This layer prevents further reaction. The identity of the gas gives the nature of
acid radicals.
Detection of CO32
When CO32 ion reacts with dil HCl, a colourless and odourless gas of CO2 is evolved which
produces white turbidity when passed through lime water, Ca(OH)2, due to formation of CaCO3.
CO32 + 2HCl ¾® CO2 + H2O + 2Cl
Ca(OH)2 + CO2 ¾® CaCO3 + H2O
The turbidity disappears on passing excess of CO2 due to the formation of water-soluble calcium
bicarbonate Ca(HCO3)2.
CaCO3 + H2O + CO2 ¾® Ca(HCO3)2
Detection of SO32
When SO32 reacts with dil HCl, a colourless gas of SO2 having smell of burnt sulphur is evolved
which turns filter paper moistened with acidified K2Cr2O7 solution green.
SO 32 + 2HCl ¾® SO2 + H2O + 2Cl
C2O72 + 14H+ + 6e ¾® 2Cr3+ + 7H2O
3(SO2 + 2H2O ¾® SO 24 + 4H+ + 2e)
2
3SO2 + Cr2O 2 + 3+
7 + 2H ¾® 2Cr + 3 SO 4 + 2H 2O
Reason for detection of CO32 and SO32 in presence of each other

SO2 like CO2, produces white turbidity with lime water due to formation of CaSO3 which disappears
on passing excess of SO2 because of formation of water-soluble calcium bisulphite, Ca(HSO3)2.
Ca(OH)2 + SO2 ¾® CaSO3 + H2O
CaSO3 + H2O + SO2 ¾® Ca(HSO3)2
It is, therefore, necessary to carry out the test for carbonate in the presence of sulphite while
carrying out the analysis of mixture of acid radicals.
Detection of CO32 and SO32 in presence of each other
The solid mixture (containing CO32 and SO 32 ) is heated with dil H2SO4 and the evolved gas
(SO2 + CO2) is passed through in a tube containing K2Cr2O7 and dil H2SO4. The solution will be
turned green due to reaction of SO2 from SO32 and the residual gas when passed through lime
water produces white turbidity due to formation of CaCO 3 as SO2 will be completely reacted with
K2Cr2O7. Refer to the reactions given for CO32 and SO 32 .
Detection of S2 ion
When S2 ion reacts with dil HCl, H2S gas is evolved which may be identified by its characteristic
smell of rotten egg and by blackening of filter paper moistened with lead acetate solution due to
the formation of PbS.
S2 + 2HCl ¾® H2S + 2Cl
H2S + Pb(CH3COO)2 ¾® PbS + CH3COOH
Lead acetate (Black ppt.) Acetic acid
The presence of S2 is confirmed by sodium nitroprusside test given below.

Sodium nitroprusside test for S2 ion
Solution containing S2 ion gives a purple colour with sodium nitroprusside solution in ammonical
medium.
S2 + Na2[Fe(CN)5NO] ¾® [Fe(CN)5NOS]4 + 2Na+
Sodium nitro prusside Purple
Detection of thiosulphate (S2O32 ) anion
To the thiosulphate solution when dil HCl is added, turbidity soon appears due to separation of
sulphur. On warming the solution SO2 is evolved which is recognized by its odour and its action
upon filter paper moistened with acidified dichromate solution (it turns green). The unstable
thiosulphuric acid is first formed which soon decomposes into sulphurous acid and sulphur
S2 O32 + 2HCl ¾® H2S2O3 + 2Cl

H2S2O3 ¾® H2SO3 + S
S2 O32 2HCl ¾® H 2SO3 S 2Cl
H2SO3 ¾® SO2 + H2O
Reason for special test for mixture of anions of S2, SO32 and S2O32
Upon addition of dil HCl (or dil H2SO4) to the solid mixture containing S 2, SO 32 and S2 O32 ,
H2S is liberated from S2 while SO2 is liberated from SO 32 and S2 O32 . Further, H2S and SO2
react so that sulphur is precipitated.
2H2S + SO2 ¾® 3S + 2H2O
The same sulphur may be obtained from thiosulphate alone. This complication necessitates to
adopt special procedure to detect the above anions in the presence of each other from its sodium
carbonate extract as shown below.
Separation and detection of S2, SO32 and S2O32 in presence of each other
The Na2CO3 extract is shaken with CdCO3 solid, as a result, precipitate due to formation of CdS is
obtained. On filtration, the residue contains CdS and excess of Cd(CO3) while the filtrate contains
SO 32 and S2 O32 ions.
Detection of S2 by analysis of the residue (CdS, + CdCO3 )
The residue when digested with acetic acid excess of CdCO3 decomposes leaving a yellow residue
of CdS. The yellow residue when heated with dil HCl, produces H2S gas which is marked by its
rotten egg smell and turning lead acetate paper black.
S2 + CdCO3 ¾® CdS + CO 2

3
CdS + 2HCl ¾® H2S + CdCl2
H2S + Pb(CH3COO)2 ¾® PbS + 2CH3COOH
(Black ppt.)
Separation and detection of SO32 from the filtrate containing SO32 and S2O32
When Sr(NO3)2 solution is added to the filtrate containing SO32 and S2O 2
3 , a white precipitate
due to formation of SrSO3 is obtained indicating the presence of SO 2
3 . On filtration the residue
contains SrSO3, while the filtrate contains S2 O32 ion.
Detection of SO32 by the analysis of residue (SrSO3 )

The residue (SrSO3) is dissolved in dil HCl and a few drops of dilute solution of iodine is added
to the resulting solution. The iodine solution is decolourized indicating the presence of SO32 .
The following reactions occur:
SO 32 + Sr(NO3)2 ¾® SrSO3 + 2NO 3
SrSO3 + 2HCl ¾® SrCl2 + H2SO3
I2 + H2O ¾® 2HI + O
H2SO3 + O ¾® H2SO4
I 2 H 2SO3 H 2 O ¾® 2HI H 2SO 4
Detection of S2O32 from the filtrate containing S2O32

On boiling the filtrate with dil HCl, SO2 gas is evolved and S is precipitated indicating the presence
of S2 O32 . (Reaction already given in the test for S2 O32 ).
The separation and detection of S2, SO 32 and S2 O32 are summarized in Table 1.7.
Table 1.7 Separation and detection of (S2, SO 32 , S2O 32 )
Detection of NO2 ion

When NO 2 ion reacts with dil HCl, it decomposes to NO which in contact with air forms NO2
recognized by its reddish brown vapour.
NO 2 + HCl ¾® HNO2 + Cl
3HNO2 ¾® HNO3 + 2NO + H2O
2NO + O2 ¾® 2NO2
Reddish brown vapour
The presence of NO2 is further confirmed by its brown ring test as given below.
Brown ring test for nitrite
When a solution containing NO2 ion is added to a concentrated solution of FeSO4 acidified with
acetic acid or dil H2SO4 a brown ring due to the compound [Fe(H2O)5 NO] SO4 is formed at the
junction of the two liquids.
NO2 + CH3COOH ¾® HNO2 + CH3COO
3HNO2 ¾® H2O + HNO3 + 2NO
FeSO4 + NO + 5H2O ¾® [Fe(H2O)5NO]SO4
Brown ring
However, I, Br, NO 3, coloured ions and anions that give coloured compounds with ferrous salt
must be absent.
1.4.2 Detection of Group II Anions [F, Cl, Br, I, NO3, borates, SCN, Fe(CN)64,
and Fe(CN)63]
Flouride, chloride, bromide, iodide, nitrate, chlorate, perchlorate, permangenate, bromate, borate,
ferrocyanide, ferricyanide, thiocyanate, and some organic anions like formate, acetate, oxalate,
tartrate and citrate anions are included in this group. When conc H2SO4 is added to solid mixture
containing these anions, effervescence takes place with evolution of gasses or acid vapours. The
detection of the following anions of these groups is given below.
Detection of Fluoride (F)

To a pinch of fluoride salt (mixture containing fluoride) when a few drops of conc H2SO4 is added
and warmed, a colourless, corrosive gas, HF is evolved. It fumes in moist air and the test tube
acquires a greasy appearance as a result of corrosive action of the vapour on the silica in the glass,
which liberates the gas, silicon tetra fluoride, SiF4. By holding a moistened glass rod in the vapour,
a waxy mass is deposited on the rod.
F + H2SO4 ¾® HF + HSO4
SiO2 + 4HF ¾® SiF4 + 2H2O
Silica
Silicon tetraflouride is hydrolyzed by water to give a waxy deposit of silicic acid (H4SiO4) and
hydrofluosilicicacid [H2SiF6]
3SiF4 + 4H2O ¾® 2H2[SiF6] + H4SiO4
Detection of Cl
When a few drops of conc H2SO4 is added to a chloride salt (mixture containing Cl), effervescence
takes place with evolution of HCl gas, which is marked by its pungent odour, and production of
white fumes of NH4Cl when a glass rod moistened with ammonia solution is shown near the
mouth of the tube. The following reaction take place
Cl + H2SO4 ¾® HCl + HSO4
NH4OH + HCl ¾® NH4Cl + H2O
The detection of Cl is confirmed by chromyl chloride test as given below.
Chromylchloride test for Cl
The solid chloride salt/mixture is intimately mixed with powered potassium dichromate in a small
distilling flask and conc H2SO4 is added to it. On warming the above mixture, deep red vapours of
chromylchloride, CrO2Cl2, are evolved which produce a yellow solution when passed into NaOH
solution taken in a test tube due to formation of sodium chromate. A yellow precipitate of lead
chromate, PbCrO4 is obtained when lead acetate solution is added it. The following reaction takes
place
Detection of Br
To a pinch of bromide salt (mixture containing Br) when a few drops of conc H2SO4 is added, a
reddish brown gas due to Br2 is evolved. The intensity of the gas increases by addition of a pinch
of MnO2 to the reaction mixture on warming. The gas is recognized by its staining of starch paper
to orange red.
H2SO4 is mild oxidizing agent. It oxides HBr to Br2.
2(Br + H2SO4 ¾® HBr + HSO4)
H2SO4 + 2H+ + 2e ¾® SO2 + 2H2O
2HBr ¾® 2H+ + Br2 + 2e
2Br + conc H2SO4 ¾® Br2 + 2HSO4
So the evolved gas is a mixture of Br2 and HBr. The intensity of reddish brown gas is increased in
the presence of MnO2 as it being a strong oxidizing agent oxidizes Br to Br2 quantitatively in acid
medium.
MnO2 + 4H+ + 2e ¾® Mn2+ + 2H2O
2Br ¾® 2Br2 + 2e
The detection of Br is confirmed by chlorine water test as described below.
Chlorine water test for Br
The addition of chlorine water dropwise to a solution of a bromide salt or sodium carbonate extract
containing Br liberates free bromine which colours the solution orange red on addition of carbon
disulphide, chloroform or carbon tetrachloride solvent.
2Br + Cl2 ¾® Br2 + 2Cl
Test for I
To a pinch of iodide salt/mixture containing I when a few drops of conc H2SO4 is added and
warmed, violet vapours of I2 are evolved which turn starch paper blue. The detection of I is
further confirmed by chlorine water test.
2I + 3H2SO4 ¾® I2 + SO2 + 2HSO4 + 2H2O
Chlorine water test for I
When chlorine water is added dropwise to a solution of iodide (sodium carbonate extract containing
iodide), iodine is liberated which colours the solution violet on shaking it with carbon tetrachloride,
or carbon disulphide or chloroform as solvent.
2I + Cl2 ¾® I2 + 2Cl
Test for nitrate NO3
To a pinch of nitrate salt (or mixture containing NO3) when a few drops of conc H2SO4 is added
and warmed, a reddish brown vapours of NO2 is evolved. The intensity of the gas increases by
addition of a pinch of copper turnings to the reaction mixture and the solution acquires a green
colour on heating owing to the production of cupric nitrate as given below.
NO3 + conc H2SO4 ¾® HSO 4 + HNO3
4HNO3 ¾® 4NO2 + O2 + 2H2O
Reddish brown vapour
Reaction of copper with HNO3
2HNO3 + 2H+ + 2e ¾® 2NO2 + 2H2O

Cu ¾® Cu2+ + 2e
Cu + 2HNO3 + 2H+ ¾® Cu2+ + 2NO2 + 2H2O
Cu2+ + 2HNO3 ¾® Cu(NO3)2 + 2H+
The presence of nitrate can be detected by brown ring test with freshly prepared FeSO4 solution
and concentrated H2SO4 as given below.
Brown ring test for nitrate (NO3) ion
This test involves addition of freshly prepared FeSO4 solution to nitrate solution (or sodium carbonate
extract containing NO 3) along with addition of conc H2SO4 slowly down the side of the test tube
so that a brown ring due to [Fe(H2O)5NO]SO4 is formed at the junction of two layers (H2SO4 and
aqueous layers).
NO3 + conc H2SO4 ¾® HSO4 + HNO3
2HNO3 ¾® 2NO + H2O + 3O
3{2FeSO4 + O + H2SO4 ¾® Fe(SO4)3 + H2O}
6FeSO4 + 2HNO3 + 3H2SO4 ¾® 3Fe2(SO4)3 + 2NO + 4H2O
FeSO4 + NO + 5H2O ¾® [Fe(H2O)5NO]SO4
Brown ring
However, this test is unreliable in the presence of Br, I and NO2 ions due to the following
reasons:
Reason for detection of nitrate in presence of nitrite: When the mixture is heated with conc
H2SO4 to detect NO3 ions, nitrite (if present) also decomposes to give NO2 gas which interferes
with the NO3 ions. In order to test for the presence of NO 3 ions, nitrite ions are to be destroyed first
(with urea or NH4Cl) and the remaining solution is tested for NO3. Therefore, a special procedure
is adopted for detection of nitrate in the presence of nitrite as follows.
Detection of nitrate (NO3) in presence of nitrite (NO2) ions
(a) Urea method: When sodium carbonate extract containing NO2 is heated with urea
(NH2CONH2) and dil H2SO4, nitrite changes to N2 gas and thus gets removed.
2NO2 + H2SO4 ¾® 2HNO2 + SO2
4
NH2CONH2 + 2HNO2 ¾® 2N2 + CO2 + 3H2O
(b) Ammonium chloride method: When sodium carbonate extract containing NO2 is
heated with (NH4Cl), nitrite changes to N2 gas and thus gets removed.
NO2 + 4NH4Cl
'
NH NO 4 2+ Cl
NH4NO2 ¾® N2 + H2O
The nitrate can then be detected by the brown ring test (write the same reaction as done in case of
(NO3) after decomposition of nitrite by the above methods):
Reason for detection of nitrate in presence of bromide and/or iodide
When a mixture containing NO3, Br and/or I is heated with conc H2SO4, deep brown vapours
of Br 2 and deep violet vapours of I 2 interfere with brown gas (NO 2) available from
nitrate. Also nitrate ion cannot be tested by brown ring test because Br2(from Br ) and I2
(from I) available from the reaction of the mixture on treatment with conc H2SO4 will obscure the
brown ring.
Thus, all these complications necessitate to adopt a special procedure to detect the nitrate ions
in the presence of bromide and iodide.
Detection of nitrate in presence of bromide and iodide (Devardas alloy test)
In this case, nitrate is converted to NH3 by aluminium powder or zinc dust or Devardas alloy by
boiling with NaOH solution. If ammonium radical present in the mixture, it must be removed by
boiling the mixture with NaOH before proceeding to test for nitrate otherwise NH3 will be obtained
from NH 4+ radical present in the mixture. The following reaction occurs with zinc dust or Al
powder.
4(Zn + 4OH ¾® ZnO22 + 2H2O + 2e)
Zincate ion
NO3 + 6H2O + 8e ¾® NH3 + 9OH
NO3 4Zn 7OH ¾® NH 3 4ZnO 22 2H 2 O

8(Al + 4OH ¾® AlO2 + 2H2O + 3e)
Aluminats ion
3(NO3 + 6H2O + 8e ¾® NH3 + 9OH)
8Al 3NO3 5OH 2H 2 O ¾® 3NH 3 + 8AlO 2
The evolution of NH3 can be detected by its characteristic small and its action upon red litmus
paper which will turn blue or phenolphthalein paper turning pink.
Reason for detection of chloride in presence of bromide and/or iodide
When to a mixture containing Cl , Br or I, conc H2SO4 is added, the colourless gas of HCl
evolved gets mixed with either reddish brown vapour of Br2 from Br or violet vapour of I2 from
I. If the mixture contains Cl, Br and I, only violet vapours or reddish brown vapours depending
upon the amount are possibly observed. HCl from Cl and Br2 from Br get mixed with violet
vapours of I2 from I.
This complicacy necessitates to adopt special procedure to detect the presence of Cl in a
mixture with the following:
1. Detection of chloride in the presence of bromide
2. Detection of chloride in the presence of iodide
3. Detection of chloride in the presence of bromide and iodide
4. Detection of bromide and iodide in the presence of each other
5. Detection of chloride, bromide and iodide in the presence of each other.
(i) Detection of chloride in the presence of bromide: The detection of Cl in the
presence of Br as described below is based on the following facts.
Cl can form only chromyl chloride when reacts with conc H2SO 4 + K2Cr2O7
(write the reaction for the chlromyl chloride test) whereas Br is oxidized to Br2 under
the above condition which yield colourless solution on passing the gas through NaOH
solution.
Mixture (Cl, Br)
conc H2SO4 + K2Cr2O7 (Chromyl Chloride test)
CrO2Cl2 Na CrO

NaOH
2 4 (Yellow solution) PbCrO (Yellow ppt.)
Pb(CH3COO)2
4
(ii) Detection of chloride in the presence of iodide: Cl
can be detected in the presence
of I by AgNO3 test as summarized below. It is based on the solubility of AgCl in dil
NH4OH solution and the practical insolubility of AgI in this reagent
AgCl + 2NH3 ¾® [Ag(NH3)2]Cl

Diammine silver(I)
chloride soluble in water
AgI + NH3 ¾® Practically no reaction
(iii) Detection of chloride in the presence of bromide and iodide: The detection of Cl in
presence of Br and I is based an the following facts.
(a) The hydrolysis of ammonium carbonate in aqueous solution gives rise to free dilute
ammonia solution in which only AgCl is dissolved but not AgBr or AgI.
(b) The addition of Br ion to the solution of AgCl in ammonia results in the solubility
product of AgBr being exceeded and precipitation occurs.
(NH4)2 CO3 + H2O 2(NH

Hydrolysis
3 + H2O) + H2CO3
AgCl + 2NH3 ¾® [Ag(NH3)2]Cl
Diammine silver(I) chloride
[Ag(NH3)2]+ + Br ¾® AgBr + 2NH3

Pale yellow ppt.
The procedure for detection of Cl in the presence of Br and I is summarized
below.
The Na2CO3 prepared solution is acidified with dil HNO3 followed by addition
of AgNO3 solution with constant stirring till the formation of AgCl, AgBr and AgI is
complete. On filtering, the residue contains a mixture of AgCl, AgBr and AgI from
which chloride is analysed as follows:
(iv) Detection of bromide and iodide in the presence of each other (chlorine water test):
The detection of Br and I in the presence of each other as described below is based on
the following facts on the basis of distribution law. To the solution (or neutralised Na2CO3
extract containing I and Br) when chlorine water is added along with chloroform or
carbon tetrachlorise, both iodine and bromine will be formed.
2I + Cl2 (Chlorine water) ¾® I2 + 2Cl
2Br + Cl2 (Chlorine water) ¾® Br2 + 2Cl
Out of I2 and Br2, I2 will go first into organic layer as I2 gets dissolved in organic layer
chloroform or carbon tetrachloride giving violet colouration.
This is because distribution coefficient of iodine is greater than that of bromine.
On further addition of chlorine water, iodine is oxidized to iodate which produces
colourless solution so that violet colour is discharged. On continuing this process of
addition of chlorine water, a reddish brown colouration of organic layer will appear due
to dissolved bromine.
5(Cl2 + 2e ¾® 2Cl)
I2 + 6H2O ¾® 2IO3 + 12H+ + 10e
5Cl2 + I2 + 6H2O ¾® 10Cl + 2IO3 + 12H+
At first Na2CO3 prepared solution is acidified with dil HCl. Then a few drops of chlorine
water is added to it. The resulting solution is shaken with 23 ml of chloroform or carbon
tetrachloride. A violet colour of the organic layer is observed indicating the presence
of I. The addition of chlorine water drop by drop is continued and the resulting solution
is shaken after each addition. A violet colour gets discharged and reddish brown colour
develops indicating the presence of Br.
(v) Detection of Cl, Br and I, in the presence of each other: In order to detect Cl,
Br and I in the presence of each other, the solution containing these ions (or sodium
carbonate extract containing these ions) is heated with dil H2SO4 to remove CO2. The
resulting solution is successively heated with solid NaNO2 (to remove I2 as violet vapour)
and conc HNO3 (to remove Br2 as brown fumes). The colourless solution left behind
contains Cl ions which is confirmed by chromyl chloride test discussed earlier.
2NaNO2 + H2SO4 ¾® Na2SO4 + 2HNO2

Removal of I ions:
2I + H2SO4 ¾® SO42 + 2HI
2HNO2 + 2HI ¾® 2NO + 2H2O + I2
Removal of Br ions:
2(HNO3 + H+ + e ¾® NO2 + H2O)
2Br ¾® Br2 + 2e
2HNO3 + 2Br + 2H+ ¾® Br2 + NO2 + H2O
Reasons for detection of iodate and iodide in the presence of each other
The addition of dilute acid to the mixture of iodate and iodide results in the production of free
iodine due to redox reaction between I and IO3 in the presence of acid as given below:
2IO 3 + 12H+ + 10e ¾® I2 + 6H2O
5(2I ¾® I2+2e)
2IO3 + 10I + 12H+ ¾® 6I2 + 6H2O
Thus a violet vapour of iodine is evolved when dil acid, HCl, H 2SO4 or acetic acid, is added to
the mixture of iodides and iodates. Neither iodides nor iodates alone do this with dilute acid.
Hence to detect iodate and iodide in the presence of each other, the following procedure is adopted.
Procedure for detection of iodate and iodide in the presence of each other
The iodide is completely removed from the solution containing I and IO 3 (or their neutralised
sodium carbonate prepared solution) by addition of Ag2SO4 solution, so that it gets precipitated as
AgI while IO3 remains in solution. On filtration, the residue contains yellow precipitate of AgI
whereas the filtrate contains IO3. On passing SO2, IO3 gets reduced to I, which is identified in
obtaining a yellow precipitate of AgI insoluble in NH4OH on addition of silver nitrate solutions.
IO3 + 6H+ + 6e ¾® I + 3H2O
3(SO2 + 2H2O ¾® SO42 + 4H+ + 2e)
IO3 + 3SO2 + 3H2O ¾® I + 3SO42 + 6H+
The detection of I and IO3 can be expressed in tabular form as follows:
Detection of borate (BO33 B4O72, BO2)
The borates are of three types such as orthoborate, BO3 2
3 , pyroborate B 4O 7 and metaborate

BO2. When any borate is heated with conc H2SO4 and ethyl alcohol, volatile ethyl borate (C2H5O)3B
is formed which burns at the mouth of the test tube with a green edged flame.
2BO33 + 3H2SO4 ¾® 2H3BO3 + 3SO42
2BO2 + H2SO4 + 2H2O ¾® 2H3BO3 + SO42
B4O72 + H2SO4 + 5H2O ¾® 4H3BO3 + SO42
H3BO3 + 3C2H5OH ¾® (C2H5O)3B + 3H2O
(C2H5O)3 B + burn ¾® green-edged flame at the mouth of test tube
Reason for detection of borate in presence of copper or barium salts

If copper or barium salts are present, they may give similar green flame as in case of borate by the
flame test. Therefore, a special procedure as mentioned below is adopted for detection of borate if
copper or barium salts are present. A paste is made by thoroughly mixing the mixture (containing
borate, copper or barium salts) with powdered calcium fluoride and conc H2SO4. The paste is then
brought very close to the non-luminous flame by means of glass rod without actually touching it.
Volatile born trifluoride BF3 is formed which colours the flame green. Copper and barium salts do
not form non-volatile compounds under the above experimental conditions and hence do not
interfere.
CaF2 + H2SO4 ¾® CaSO4 + 2HF
H3BO3 + 3HF ¾® BF3 + 3H2O
Detection of thiocyanate (SCN)

Thiocyanate salt solution with conc H2SO4 produces a yellow colouration. Upon warming, a violent
reaction occurs with evolution of carbonyl sulphide (COS) which burns with a blue flame.
SCN + 2H2SO4 + H2O ¾® COS + 2HSO4 + NH 4+
The detection of SCN is further confirmed by the following test.
CuSO4 test
To a mixture of solution of copper sulphate and sulphurous acid (produced from the reaction of
Na2SO3 with dil HCl), thiocyanate solution is added when a white precipitate due to formation
of cuprous thiocyanate is obtained. It is insoluble in dil HCl or dil H2SO4. The following reactions
occurs.
H2SO3 + H2O ¾® SO42 + 4H+ + 2e
2(Cu2+ + e ¾® Cu+)
2(Cu+ + SCN ¾® Cu(SCN))
2SCN + H2SO3 + 2Cu2+ + H2O ¾® SO42 + 2CuSCN + 4H+
FeCl3 test
When ferric chloride solution is added dropwise to the solution of SCN, a blood red colouration
due to the formation of complex ferric thiocyanate [Fe(SCN)]2+ is obtained. The colour can be
extacted by shaking with ether.
SCN + Fe3+ ZZX

YZZ [Fe(SCN)]2+
Blood red colouration
Detection of ferrocyanide [Fe(CN)6]4 ion

The salt containing [Fe(CN)6]4 on prolonged heating with conc H2SO4 produces carbon monoxide
gas which burns with a blue flame.
[Fe(CN)6]4 + 6H2SO4 + 6H2O ¾® Fe2+ + 6CO + 6NH 4+ + 6SO42
The detection of [Fe(CN)6]4 ion is further confirmed by the following test.
CuSO4 test
When CuSO4 solution is added to a solution of [Fe(CN)6]4 a brown precipitate due to formation
of copper ferrocyanide Cu2[Fe(CN)6] obtained. It is insoluble in dil acetic acid but decomposed by
caustic alkali.
FeCl3 test
When FeCl3 solution is added to a solution of Fe(CN)64, an intense blue precipitate of ferric
ferrocyanide (Prussian blue) is obtained which is decomposed by solution of caustic alkali forming
a brown precipitate of ferric hydroxide
3[Fe(CN)6]4 + 4Fe3+ ¾® Fe4[(FeCN)6]3
Detection of ferricyanide [Fe(CN)6]3 ion

The salt containing [Fe(CN)6]3 on warming with conc H2SO4 produces carbon monoxide gas
which burns with a blue flame.
[Fe(CN)6]3 + 6H2SO4 + 6H2O ¾® 6CO + 6NH 4+ + Fe3+ + 6SO42
The detection of ferricyanide ion is further confirmed by the following test.
CuSO4 test
When CuSO4 solution is added to a solution of [Fe(CN)6]3, a green precipitate due to formation
of cupric ferricyanide is obtained. It is insoluble in hydrochloric acid.
FeCl3 test
When FeCl3 solution is added dropwise to a solution of [Fe(CN)6]3, a brown colouration due to
formation of ferric ferricyanide [Fe(CN)6]4 is obtained. It turns prussian blue on addition of a little
stannous chloride solution or (H2O2) because of reduction of ferricyanide to ferrocyanide ion
which then react with ferric ion to produce Prussian blue (colouration or precipitate) due to formation
of ferric ferrocyanide.
Fe3+ + [Fe(CN)6]3 ¾® Fe[Fe(CN)6]
3(Sn2+ ¾® Sn4+ + 2e)
6[Fe(CN)6]3 + e ¾® [Fe(CN)6]4]
8Fe3+ + 6[Fe(CN)6]4 ¾® 2Fe4[Fe(CN)6]3
6Fe(CN)63 + 8Fe3+ + 3Sn2+ ¾® 2Fe4[Fe(CN)6]3 + 3Sn4+
Reasons for detection of SCN, Fe(CN)64 and Fe(CN)63 in the presence of each other
From the individual test of the above ions, it is noted that when the above ions react with conc
H2SO4 a blue flame is obtained due to COS from SCN and CO from Fe(CN64 and Fe(CN)63.
Further all these ions respond to FeCl3 and CuSO4 test which complicate the detection in the
presence of each other. Therefore, a special procedure as discussed below is adopted to detect the
above ions in the presence of each other.
Detection of thiocyanate (SCN) ferrocyanide [Fe(CN)6 ]4 ferricyanide [Fe(CN)63 in the
presence of each other
The detection of SCN, [Fe(CN)6]4 and [Fe(CN)6]3 is based on the following facts:
The neutralized sodium carbonate extract (containing SCN, [Fe(CN)6]4 and [Fe(CN)6]3 is
acidified with acetic acid and thorium nitrate solution is added to it when a gelatinous precipitate
of thorium ferrocyanide, Th[Fe(CN)6] is obtained. A little Gooch asbestos is added to it to facilitate
the filtration of gelatinous precipitate. On filtration, the residue contains Th[Fe(CN)6] and asbestos
whereas the filtrate contains [Fe(CN)6]3 and SCN.
Detection of [Fe(CN)6 ]4 from residue containing Th[Fe(CN)6] and asheless floc
The residue is digested with 2MNaOH so that Th[Fe(CN)6] goes into solution. It is acidified with
dil HCl and FeCl3 solution is added dropwise to it, as a result, a prussian blue precipitate due to
ferric ferrocyanide Fe4[Fe(CN)6]3 is obtained indicating the presence of [Fe(CN)6]4.
Th(NO3)4 + [Fe(CN)]4 ¾® Th[Fe(CN)6] + 4NO3
Th[Fe(CN)6] [Fe(CN) ]
NaOH
6
4 + Th4+
3[Fe(CN)6]4 + 4Fe3+ ¾® Fe4[Fe(CN)6]3
Detection of [Fe(CN)6 ]3 from filtrate containing [Fe(CN)6 ]3 and SCN
The filtrate containing [Fe(CN)6]3 and SCN is thoroughly shaken with CdSO4 solution so
that an orange precipitate due to formation of cadmium ferricyanide, Cd3[Fe(CN)6]2 is obtained.
On filtration, the residue contains Cd3[Fe(CN)6]2 and filtrate contains SCN ion.
Analysis of the residue containing Cd3[Fe(CN)6 ]2
It goes into solution with dil NaOH. The solution is acidified with dil HCl and a freshly prepared
FeSO4 solution added to it. Formation of a prussian blue precipitate due to ferro-ferricyanide
Fe3[Fe(CN)6]2 indicates the presence of [Fe(CN)6]3.
2[Fe(CN)6]3 + 3CdSO4 ¾® Cd3[Fe(CN)6]2 + 3SO42

Orange precipitate
Cd3[Fe(CN)6]2
3

NaOH
2+
2Fe(CN)63 + 3Cd2+
2Fe(CN)6 + 3Fe ¾® Fe3[Fe(CN)6]2
The blue precipitate due to Fe3[Fe(CN)6]2 was formerly known as Turnbulls blue.
Detection of SCN from filtrate (containing SCN ion)
On addition of FeCl3 solution a red colour due to the formation of ferric thiocyanate extractable by
ether indicates the presence of SCN (See the reaction for SCN).
The above procedure is summarized in Table 1.8.
Table 1.8 Separation and detection of thiocyanate (SCN ) ferrocyanide [Fe(CN)6]4 ferricyanide
[Fe(CN)6]3 in presence of each other
1.4.3 Group III Anions (Precipitation Group) (SO 42, AsO33, AsO43 and PO43)
Sulphate, persulphate, phosphate, phosphite, hypophosphite, arsenate, arsenite, silicate,
silicofluoride oxalate, etc. are included in this group. The detections of some anions of this group
are given below.
Detection of sulphate ion (SO42)
The salt solution containing SO42 (or sodium carbonate extract containing SO42) is acidified with
dil HCl and BaCl2 solution is added to it, as a result, white precipitate due to the formation of
BaSO4 is obtained. It is insoluble in dil HCl or dil HNO3.
BaCl2 + SO42 ¾® BaSO4 + 2Cl
The detection of sulphate is further confirmed by sodium carbonate fusion method.
The precipitate (BaSO4) is fused on charcoal with sodium carbonate, as a result, sodium sulphide
is formed. The latter is extracted with water and is treated with freshly prepared sodium nitroprusside
solution so that a purple colouration is obtained.

BaSO4 + Na2CO3 + 4C ' Na2S + BaCO3 + 4CO
Na2S + Na2[Fe(CN)5NO] ¾® Na4[Fe(CN)3NOS]
Sodium nitroprusside Purple colouration
Detection of silicate ion (SiO32)

The salt solution containing SiO32 is treated with NH4Cl or (NH4)2 CO3 solution. A white gelatinous
precipitate of silicic acid (H2SiO3) is obtained
SiO32 + 2NH4Cl ¾® H2SiO3 + 2NH3 + 2Cl
SiO32 + (NH4)2CO3 ¾® H2SiO3 + CO32 + 2NH3
The detection of silicate is further confirmed by microcosmic salt bead test as described below:
Microcosmic salt bead test: The microcosmic salt (NaNH4HPO44H2O) first fuses to a transparent
bead (mainly sodium meta phosphate Na3PO4) when heated in a loop of platinum wire. When
minute quantity of solid silicate (even in solution) is introduced into the bead and heated, a white
opaque mass or skeletons due to formation of silica (SiO2) will swim about the fused mass as it
will not dissolve in the bead.
Detection of silicofluoride ion (Fluosilicate) [SiF6 ]2
The salt solution (or sodium carbonate extract) containing SiF62 is acidified with dil HCl
and BaCl2 solution is added to it. A white crystalline precipitate due to formation of barium
silicofloride Ba[SiF6] is obtained. On heating the precipitate with conc H2SO4, in a lead crucible
hydrogen fluoride and silicon fluoride (SiF4) are evolved, which etch glass indicating the presence
of [SiF6]2.
BaCl2 + SiF62 ¾® BaSiF6 + 2Cl
Ba[SiF6] + H2SO4 ¾® BaSO4 + 2HF + SiF4
Reasons for detection of fluoride (F), silicofluoride SiF62 and sulphate (SO42) in the
presence of each other
From the individual tests of each ion, it is noted that both SiF62 and SO42 get precipitated respectively,
as BaSiF6 and BaSO4 by addition of BaCl2 solution. F ion, if present, also responds to etching test
as done in case of SiF62. It is, therefore, felt necessary to adopt a special procedure for detection of
the above ions in presence of each other.
Detection of F, SiF62 and SO42 in presence of each other
It is based on the difference in their solubilities of their lead salt as follows:
The salt solution (or practically neutralized sodium carbonate extract) containing F, SiF62 and
SO42 when heated with lead acetate solution, F and SO42 ions are precipitated as PbF2 and PbSO4
while SiF62 remains in solution as PbSiF6 because it is soluble in water. So on filtration the residue
contains PbF2 and PbSO4 while the filtrate contains SiF62 ion.
2F + Pb(CH3COO)2 ¾® PbF2 + 2CH3COO
White precipitate
SO42 + Pb(CH3COO)2 ¾® PbSO4 + 2CH3COO

White precipitate
SiF62 + Pb(CH3COO)2 ¾® PbSiF6 + 2CH3COO
Detection of F and SO42 by analysis of the residue

The residue is divided into two parts. To first part excess of 2M acetic acid is added so that PbF2
gets dissolved. On filtration, the white residue obtained is PbSO4 soluble in 6M ammonium acetate
solution.
The second part is tested for F (see the test for F) as usual by heating with conc H2SO4.
Detection of silico fluoride (SiF62) from the filtrate containing SiF62
When BaCl2 solution is added to the filtrate containing SiF62, and warmed a white crystalline
precipitate is obtained due to the formation of BaSiF6 indicating the presence of SiF62. The detection
of SO42, F, and SiF62 in presence of each other is summarized in Table 1.9.
Table 1.9 Detection of fluoride (F), silico fluoride [SiF 62] and sulphate SO 42 in presence of each other
Detection of phosphate (PO43)

The salt solution (sodium carbonate extract) containing PO43 when treated with ammonium
molybdate solution in presence of conc HNO3, a canary yellow precipitate due to the formation of
ammonium phospho molybdate, (NH3)3[PO4Mo12O36] is obtained. It dissolves in ammonium acetate
solution on boiling.
PO43 + 3HNO3 ¾® H3PO4 + 3NO3

H3PO4 + 12(NH4)2 MoO4 + 21HNO3 ¾® (NH4)3[PO4Mo12O36] + 12H2O + 21(NH4)NO3
The detection of PO43 is further confirmed by AgNO3 test as follows.

To the salt solution (neutral solution of Na2CO3 extract) containing PO43 when AgNO3 solution is
added, a yellow precipitate due to the formation of Ag3PO4 soluble in both dil NH4OH and dil
HNO3 indicates the presence of PO43.
Detection of arsenate [AsO4]3
The salt solution (or neutral Na2CO3 extract) containing arsenate when boiled with ammonium
molybdate solution in the presence of conc HNO3, a yellow crystalline precipitate of ammonium
arsenomolybdate (NH4)3[AsO4Mo12O36] is obtained.
AsO43 + 3HNO3 ¾® H3AsO4 + 3NO3
H3AsO4 + 12(NH4)2 + 21HNO3 ¾® (NH4)(AsO4Mo12O36) + 12H2O + 21HNO3
The detection of AsO43 is further confirmed by AgNO3 test.
To the salt solution (or neutral solution of Na2CO3 extract) containing AsO42, when AgNO3
solution is added, a brownish red precipitate due to the formation of silver arsenate, Ag3AsO4 is
obtained. It is insoluble in acetic acid but goes into solution in NH4OH.
AsO43 + 3AgNO3 ¾® Ag3AsO4 + 3NO 3
Detection of arsenite (AsO33)
To the salt solution (or neutral solution of Na2CO3 extract) when silver nitrate solution is added, a
yellow precipitate due to formation of silver arsenite Ag3AsO3 is obtained. It is soluble in ammonia
and in nitric acid.
Reasons for detection of phosphate, arsenate and arsenite in presence of each other
From the individual tests for the above ions, it is noted that all these ions respond to AgNO3 test
and both phosphate and arsenate give a yellow precipitate on warming with ammonium molybdate
solution and nitric acid. It is, therefore, felt necessary to adopt a special procedure for detection of
the above ions in the following manner.
Detection of phosphate in presence of arsenate
It is based on the fact that arsenate can be reduced to arsenite by sulphur dioxide whereas
phosphate remains intact. On passing H2S through the resulting sultion containing arsenite and
phosphate, a yellow precipitate due to arsenious sulphide is obtained. On filtration, the filtrate
containing phosphate is treated with ammonium molybdate solution in presence of nitric acid so
that a canary yellow precipitate of ammonium phosphomolybdate is obtained (see the reaction for
phosphate).
AsO43 + 2H+ + 2e ¾® AsO33 + H2O

SO2 + 2H2O ¾® SO42 + 4H+ + 2e
AsO43 + SO2 + H2O ¾® AsO33 + SO42 + 2H+
2AsO33 + 3H2S + 6H+ ¾® As2S3 + 6H2O
PO43 + SO2 ¾® No reaction
Detection of phosphate, arsenate and arsenite in presence of each other
The detection of phosphate in the presence of arsenate is not suitable in presence of arsenite for the
reason given above AsO43 is to be reduced to AsO33 while testing for PO43. Hence a special
method as discussed below is adopted here.
Detection of arsenite in presence of PO43 and AsO43 by magnesia mixture
At first, the phosphate and arsenate are precipitated as magnesium ammonium phosphate and
magnesium ammonium arsenate by adding magnesia mixture (MgSO4 + NH4Cl + NH4OH) to
their solution whereas arsenite remains unreacted. On filtration, the filtrate containing arsenite is
acidified with dil HCl. On passing H2S to the acidified solution of arsenite, a yellow precipitate of
arsenous sulphide is immediately produced.
AsO33 + 3HCl ¾® H3AsO3 + 3Cl
2H3AsO3 + 3H2S ¾® As2S3 + 6H2O
Yellow ppt.
Mg2+ + NH 4+ + PO43 ¾® MgNH4PO4 (White ppt.)
Mg2+ + NH 4+ + AsO43 ¾® MgNH4AsO4 (White ppt.)
Detection of AsO43 from analysis of the residue containing

(MgNH4PO4 + MgNH4AsO4 )
The residue is heated with conc HCl and NH4I to reduce AsO43 to AsO33. On passing H2S gas to
the resulting solution, a yellow precipitate of As2S3 is obtained. On filtration, the filtrate contains
PO43 ions only.
2MgNH4AsO4 + 6HCl ¾® 2MgCl2 + 2NH4Cl + 2H3ASO4
NH4I ¾® NH3 + HI
H3AsO4 + 2HI ¾® H3AsO3 + I2 + H2O
2H3AsO3 + 3H2S ¾® As2S3 + 6H2O
Detection of PO43 from the filtrate

H2S gas is boiled from the filtrate. On adding (NH4)2MO4 solution with conc HNO3 to the filtrate,
a canary yellow precipitate due to formation of ammonium phosphomolybdate indicates the presence
of PO43 (see the reaction for PO43).
The above detections are summarized in Table 1.10.
Table 1.10 Detection of phosphate, arsenate and arsenite in presence of each other
Reason for detection for F and oxalate C2O42 in presence of each other
Both F and C2O42 get precipitated as CaF2 and CaC2O4 respectively with CaCl2 solution in presence
of dilute acetic acid. In order to avoid this difficulty, a special procedure for detection is adopted as
discussed below.
Detection of oxalate in presence of fluoride
Test for fluoride: The nutralised sodium carbonate extract (SCE) is treated with CaCl2 solution
followed by 2M acetic acid. On filtration, the residue contains CaC2O4 and CaF2. It is analyzed for
detection of fluoride ion following the procedure as indicated earlier, i.e. by the reaction with conc
H2SO4.
Test for oxalate: The residue is treated with H2SO4 so that some of its portions get dissolved.
On filtration, the residue contains CaF2. The filtrate contains oxalate ion. When a few drops of
KMnO4 soluton is added, the pink colour of KMnO4 solution is discharged.
CaC2O4 + H2SO4 ¾® H2C2O4 + CaSO4
5(H2C2O4 ¾® 2CO2 + 2H+ + 2e)

2(MnO4 + 8H+ + 5e ¾® Mn2+ + 4H2O)
2MnO4 + 5H2C2O4 + 6H+ ¾® 2Mn2+ + 10CO2 + 8H2O
Reasons for calling silicate, fluorides, borate and phosphates as interfering radicals and
their removal: Borates and fluorides of metals of group IIIB, IV and magnesiums are insoluble
in ammonia solution and therefore liable to be precipitated at the stage. They may be removed by
repeated evaporation with conc HCl before proceeding for group III analysis.
Silicate forms white gelatinous precipitate of silicic acid when reacted with ammonium chloride
or ammonium carbonate. It is likely to be confused with Al(OH)3. Hence, it must be removed
before proceeding to group III analysis. Repeated evaporation with conc HCl converts silicates
into a granular form of hydrated silica which is filtered off.
The phosphates of the metals of group IIIA, IIIB, IV and magnesium are insoluble in water and
in ammonia solution and may be precipitated at this stage. Hence phosphate if present must be
removed after group II as the medium becomes ammonical after group II analysis. An excellent
method for removal of phosphate by zirconyl nitrate method as described below.
Phosphate separation by zirconyl nitrate method: When zirconyl nitrate reagent is added to a
solution of a phosphate in acidic medium a white gelatinous precipitate of zirconyl phosphate
ZrO(H2PO4)2 or ZrO(HPO4) is obtained. This is filtered off prior to the analysis of group III
ZrO(NO3)2 + 2PO43 + 4H+ ¾® ZrO(H2PO4)2 + 2NO3
or ZrO(NO3)2 + PO43 + H+ ¾® ZrO(HPO4) + 2NO3
GROUP A
QUESTIONS ON QUALITATIVE ANALYSIS OF BASIC RADICALS

(CATIONS)
A. Objective Type Questions
1. Multiple choice questions
(i) When H2S gas is passed through an acidic solution containing Cu2+ and Zn2+ ions
(a) Cu2+ is precipitated as sulphide (b) Zn2+ is precipitated as sulphide
(c) Both Zn2+ and Cu2+ will be precipitated (d) None of the above
(ii) When NaOH solution is added to a solution containing Fe3+ and Al3+ in excess and the
resulting precipitate is filtered off, the residue contains
(a) Reddish brown precipitate of Fe(OH)3
(b) Gelatinous precipitate of Al(OH)3
(c) A mixture of both the above hydroxide
(d) None
(iii) When (NH4OH + NH4Cl) is added to the solution containing Fe2+ and Fe3+ ions
(a) Fe2+ will be qualitatively precipitated as Fe(OH)2
(b) Fe3+ will be quantitatively precipitated as Fe(OH)3
(c) Both Fe2+ and Fe3+ will be completely precipitated as their hydroxide
(d) No precipitate will be obtained
(iv) Addition of NH4OH and (NH4)2CO3 the solution containing Ca2+, Ba2+, Sr2+ and Mg2+
yields
(a) Precipitates of CaCO3, BaCO3 and SrCO3
(b) Precipitates of CaCO3, BaCO3, SrCO3 and MgCO3
(c) Precipitates of hydroxides of the above ions
(d) None of the above
(v) PbCrO4 is soluble in
(a) acetic acid (b) NH4OH
(c) NaOH (d) None of the above
(vi) Hg2Cl2 is soluble in
(a) Aqua regia (b) NH4OH
(c) Hot water (d) Dil HNO3
(vii) The white precipitate of Bi(OH)3 when reacted with sodium stannite solution is turned
(a) Black (b) Red
(c) Purple (d) Nothing happens
(viii) As2S5 is soluble in
(a) acetic acid (b) dil NH3 solution
(c) conc HNO3 (d) conc HCl
(ix) To the solution containing Ni2+ and Co2+, when solid ammonium thiocyanate is added
followed by amyl alcohol, the alcohol lager become
(a) Red (b) Blue
(c) Violet (d) Colourless
(x) Addition of saturated solution of (NH4)2SO4 to the solution containing Ca2+ and Sr2+ in
presence of sodium thiosulphate yields
(a) Precipitate of SrSO4 (b) Precipitate of CaSO4
(c) Precipitate of SrSO4 + CaSO4 (d) Ca(S2O3)2 complex
2. State whether the following statements are true or false. If false, write the correct statements
(i) H2S must be boiled off from the filtrate of group II before proceeding to group III.
(ii) Na2CO3 can be used as group reagent in group IV analysis.
(iii) H2SO4 can be used for dissolving carbonates of group IV cations.
(iv) Dil HNO3 may be used instead of dil HCl in group II analysis.
(v) Zn2+ ion can be precipitated as ZnS in acidic medium.
(vi) NiS is insoluble in dil HCl.
(vii) Sr2+ can be precipitated as SrSO4 by addition of dil H2SO4.
(viii) Al(OH)3 is amphoteric.
(ix) Zn(OH)2 is soluble in dil NaOH.
(x) BaSO4 is soluble in dil HNO3.
3. Fill in the blanks
(i) HgS is dissolved in ................... only.
(ii) Bi3+ ion is converted to Bi when reacted with ................... .
(iii) ................... is used to detect Cd2+ in presence of Cu2+.
(iv) AgCl is dissolvd in ................... to produce ................... .
(v) ................... is used to convert Fe2+ to Fe3+ in qualitative analysis.
(vi) ................... is used to detect Ni2+ in presence of Co2+ in ammonical medium.
(vii) ................... reagent is used to detect NH 4+ ion.
(viii) ................... reagent is used to detect K+.

(ix) Magnesia mixture contains ..................., ................... and ................... .
(x) Mg2+ can be detected by addition of (NH4)2HPO4 in presence of ................... and
................... .
(xi) Precipitate of PbSO4 is soluble in ................... .
(xii) The chemical formula of Nesslers reagent is ................... .
B. Short Answer Type Questions

4. Answer the followings
(i) How would you convert stannous salt to stannic salt and vice versa?
(ii) How would you convert a trivalent salt of arsenic to pentavalent and vice versa?
(iii) How would you account the following:
(a) Solubility of calcium oxalate in dil HCl
(b) Precipitation of ZnS from an acidic solution of zinc salt in the presence of sodium
acetate.
(c) Mixture of NH4OH, NH4Cl and (NH4)3PO4 solution is used to precipitate Mg2+ in the
group V (sodium group).
(iv) A precipitate obtained on passing H2S gas in an acidic solution of a salt dissolves in yellow
ammonium sulphide. Addition of dil HCl to the resulting solution yields an orange
precipitate. What should be the precipitate?
(v) When H2S gas is passed into an acidic solution containing a cation of group II, a black
precipitate (A) is obtained. A is dissolved dil HNO3 to yield a colourless solution.
On addition of dil H2SO4 and ethyl alcohol, a white precipitate (B) appears which dissolves
a ammonium acetate solution. Addition of K2CrO4 solution produces a yellow precipitate
(C). Identify A, B and C and the cation of the original salt solution.
(vi) A solution of Cu2+, Zn2+, Bi3+, Mn2+ and Co2+ ions at pH = 1 is treated with H2S which
cations will be precipitated?
(vii) A solution may contain Pb2+, Ag+, Hg2+ and Hg22+ cations. The addition of dil HCl to it
produces a white precipitate soluble in boiling water. However, the precipitate turns black
on addition of NH4OH. What cations are actually present in the solution?
(viii) A salt solution containing cations of group IIA and cations of group IIIA yields a black
precipitate on passing H2S gas. It is soluble in dil HNO 3 and the solution turns deep blue
on addition of NH4OH. After separation of the precipitate by filtration, the filtrate is boiled
to remove H2S and addition of dil NH4OH to it. Produces a white gelatinous precipitate
soluble in NaOH. What are the probable cations present in the salt solution?
(ix) A salt solution may contain Bi3+, Sn2+, Cr3+, Zn2+ and Ca2+. When H2S gas pass through
its acidic solution, a dirty yellow precipitate soluble in yellow ammonium sulphide
is obtained. It is filtered off and the filtrate is boiled to remove H2S. The addition of NH4OH
and NH4Cl produces no precipitate even on passing H2S but a white precipitate is obtained
on addition of (NH4)2CO3 solution. What are the probable cations present in the solution?
(x) A salt solution may contain Fe3+, Al3+, Ba2+ and Ca2+. The addition of NH4OH in the
presence of NH4Cl produces white gelatinous precipitate soluble in dil NaOH. On filtration,
the filtrate when treated with K2CrO4 solution produces a yellow precipitate. What are the
cations present in the salt solution?
(xi) A salt solution may contain Ag+, Pb2 and Hg2+. When it is treated with dil HCl, a white
precipitate partially soluble in boiling water is obtained. The substance that left as insoluble
in boiling water dissolves completely in dil NH4OH solution. What are the probable cations
present in the salt solution?
(xii) A mixture of two salts is found to be soluble in water. When K4[Fe(CN)6] solution is added
to its aqueous solution, a prussion blue precipitate is obtained. The solution also produces
red colour on addition of NH 4SCN solution to it. When heated with NaOH,
a gas of pungent smell is obtained which turns Nesslers reagent brown. What are the
probable cations present in the mixture?
(xiii) A salt solution containing a cation of group IV when treated with NH4OH and (NH4)2CO3
in the presence of NH4Cl, a white precipitate is obtained. It dissolves in dil H2SO4 and
decolourizes KMnO4 solution. Identify the cation in the solution.
(xiv) A green-coloured solution of a metallic chloride when heated with NaOH and H2O2 produces
a yellow solution. The yellow solution gives yellow precipitate when reacted with lead
acetate solution. Identify the metallic part of the chloride salt.
(xv) A certain inorganic compound (MX) shows the following reaction:
(a) On passing H2S through its acidic solution, a brown precipitate is formed, which is in
soluble in yellow ammonium sulphide.
(b) The above precipitate dissolves in dil HNO3 and turns black when sodium stannite
solution is added in it. Identify the cationic part of the compound.
5. What happens when (state with balanced equations)
(i)NH4OH solution is added to Hg2Cl2?
(ii)KCN solution is added to CuSO4 solution?
(iii)K4Fe(CN)6 solution is added to FeSO4 solution?
(iv) Dimethyl glyoxime reagent is added to a NI(II) salt solution in ammonical medium?
(v) Sodium bismathate solid is added to a Mn(II) salt solution in the presence of conc HNO3?
(vi) HgS is treated with aqua regia followed by addition of SnCl2 solution, initially dropwise
and then in excess?
(vii) Bi(OH)3 is treated with sodium stannite solution?
6. How would you detect the followings?
(i) Pb2+ in presence of Cu2+
(ii) Ag+ in presence of Al3+
(iii) Zn2+ in presence of Ca2+
(iv) Cd2+ in presence of Co2+
(v) Ba2+ in presence of Ca2+
(vi) Cd2+ in presence of Cu2+
(vii) Ag+ in presence of Hg22+
(viii) Ni2+ and Co2+ in presence of each other
(ix) Fe3+ and Cr3+ in presence of each other
(x) Ca2+ and Sr2+ in presence of each other
(xi) Antimony in the form of H[SbCl4] in presence of tin in the form of H2SnCl6
(xii) K+ and Na+ in presence of each other
(xiii) Mg2+ in presence of Sr2+
7. Complete and balance the following reactions
(i) Hg2Cl2 + dil NH4OH ¾®
(ii) As2S5 + NH4OH ¾®
(iii) [SnCl6]2 + Fe ¾®
(iv) [BiO3]3 + Mn2+ + H+ ¾®
(v) Bi(OH)3 + SnO32 ¾®
(vi) Al(OH)3 + NaOH ¾®
8. Explain why
(i) Concentration of HCl is to be maintained ~0.3 M for group II analysis.
(ii) Pb2+ is included both in group I and group II cations.
(iii) Fe2+ if present must be converted to Fe3+ in qualitative analysis.
(iv) NaOH and NaCl are not used as group reagent for analysis of cations of group IIIA.
(v) Mn2+ is to be detected both in group IIIA and group IIIB analysis.
(vi) Conc HCl should not be used in group I and group II analysis.
(vii) H2S must be boiled off from the filtrate before proceeding to group III.
(viii) Na2CO3 cannot be used as group reagent in group IV analysis in place of (NH4)2CO3.
(ix) Sometime yellow or white precipitate is obtained in the second group even in the absence
of cations of that group.
(x) Only acetic acid not dil H2SO4 is used for dissolving carbonates of group IV cations.
C. Long Answer Type Questions

9. Discuss the applications of solubility product and common ion effect especially for the
analysis of sulphides of group II and hydroxides of group IIIA cations.
10. Write the basic principle involved in detection and separation of cations of group I (silver
group).
11. Discuss the detection and separation of cation of group IIA (copper group) writing the
reaction involved.
12. Explain the principles of detection and separation of group IIB cations (arsenic group)
indicating the reaction involved.
13. Write the principles of detection and separation of group IIIA cations (iron group) indicating
the reactions involved.
14. Write how would you qualitatively analyze cations of group IIIB (zinc group).
15. Describe how would you detect the cations of group IV (calcium group). Write the reaction
involved.
16. Is there any specific group reagent for cations of group V? If not, how would you detected
the individual cation of this group?
GROUP B
QUESTIONS ON QUALITATIVE ANALYSIS OF ACID RADICALS (ANIONS)
D. Multiple Choice Questions
17. Choose the correct answer among the followings
(i) Which one of the following combines with Fe (II) ions form a brown ring.
(a) N2O (b) NO
(c) N2O3 (d) N2O5
(ii) Which of the following oxides of nitrogen is a reddish brown gas?
(a) NO2 (b) NO
(c) N2O (d) N2O5
(iii) Which of the following is formed when cold barium nitrite is mixed with dil H2SO4.
(a) HNO2 + BaSO4 (b) HNO3 + BaSO4
(c) HNO2 (d) HNO3
(iv) An acidified solution of KI iodine is liberated by the action of
(a) Nitrite (b) Nitrate
(c) Both nitrite and nitrate (d) None of the above
(v) The browning in the detection of NO2 is due to formation of
(a) NO (b) NO2
(c) N2O (d) FeSO4NO
(vi) Br2 can be liberated from KBr solution by the action of
(a) Iodine (b) Chlorine
(c) Sodium chloride (d) Potassium iodate
(vii) When I2 dissolves in CCl4, the colour that results is
(a) Violet (b) Brown
(c) Colourless (d) Bluish green
(viii) Sodium chloride when heated with conc H2SO4 and K2Cr2O7 produces
(a) Chromic chloride (b) Chromyl chloride
(c) Chromous chloride (d) None
18. State whether the following statements are true or false. If false, write the correct
statements
(i) Sodium carbonate extract contains water-soluble sodium salts of anions.
(ii) On boiling of thiosulphate solution with dil HCl, H2S gas is evolved producing a clear
solution.
(iii) By holding of moistened glass rod in the vapour of SiF4, a waxy mass is deposited on the
rod.
(iv) Deep red vapours of chromyl chloride produces a red solution when passed into NaOH
solution.
(v) When a pinch of bromide salt is heated with conc H2SO4, a reddish brown gas is produced
due to HBr.
(vi) The oxidation state of ion in [Fe(H2O)5NO]SO4 is two.
(vii) The nitrate in presence of bromide and/or iodide can be detected by the ring test.
(i) When H2S is passed through ammonical solution of sodiumnitroprusside, complex
compound formed is ................... .
(ii) A solution of SO2 in water reacts with H2S precipitating ................... .
(iii) The chemical formula of the browning due to nitrate or nitrite is ................... .
(iv) AgCl precipitate gets dissolved in dil NH2OH due to formation of ................... .
(v) Detection of bromide and iodide in presence of each other can be done by ...................
test.
(vi) The salt containing I when reacts with chlorine water in presence of chloroform, the
colour of organic layer becomes ................... .
(vii) The addition of dil HCl to the mixture of iodate, an iodide results in the production of
................... vapour of ................... .
(viii) When borate salt heated with core H2SO4 and ethyl alcohol, ................... is formed which
burns the ................... flame.
(ix) ................... is used to detect borate in presence of copper or barium salts.
(x) When a thiocyanate salt is heated with conc H2SO4, ................... is evolved which burns
with ................... coloured flame.
(xi) The blood red colouration produced by the addition of FeCl3 solution to a salt solution
containing SCN is due to formation of ................... .
(xii) The chemical formula of ammonium phosphomolybdate is ................... .
E. Short Answer Type Questions

(i) How would you convert arsenite to arsenate acid and vice versa?
(ii) How would you get
(a) Cl2 gas from a chloride salt?
(b) Br2 gas from bromide salt?
(c) I2 gas from bromide salt?
(iii) How would you convert I to IO 3 and vice versa?
(iv) A gas obtained on addition of dil HCl to a salt produces white turbidity when passed
through lime water but does not turn lead acetate paper black or paper dipped in acidified
K2Cr2O7 solution green. Name the gas and the anion present in the salt.
(v) When conc H2SO4 is added to a mixture containing an anion of group II in presence of
k2Cr2O7, deep red vapours (A) are produced which yield yellow solution (B) when passed
through NaOH. A yellow precipitate (C) is obtained on addition of lead acetate solution to
(B). Identify A, B, C, and the anion of the salt.
(vi) A salt solution which may contain S2, Cl and I produces a precipitate on addition of
AgNO3 solution which dissolves in dil HNO3 and gives violet colour when Na2[Fe(CN)5NO]
solution is added to it. What is the anion present in the salt solution?
(vii) A salt solution which may contain Br, I, IO 3, produced violet vapour on treatment with
dil HCl. What are the anions present in the salt.
(viii) A salt solution which may contain SCN, Fe(CN6)4 and Fe(CN) ions produces white
precipitation on addition of thorium nitrate solution. What is the anion present in the salt?
(ix) Explain why phosphate separation is necessary before proceeding to group III analysis.
21. Complete and balance the followings
(i) SO32 + H+ + Cr2O72 ¾® (ii) Cl + MnO2 + H+ ¾®
(iii) Zn + NO3 + OH ¾® (iv) I2 + SO32 + H2O ¾®
(v) F + H2SO4 + SiO2 ¾® (vi) Al + NO3 + OH ¾®
(vii) NO2 + NH4Cl
'
(viii) IO 3 +I + H+ ¾®
(ix) IO3 + SO2 + H2O ¾® (x) SCN + H2SO3 + Cu2+ + H2O ¾®
(xi) [Fe(CN)6]3 + 8Fe3 + Sn2+ ¾® (xii) MnO4 + H2C2O4 + H+ ¾®
(xiii) AsO43 + SO2 + H2O ¾®
22. Give reasons
(i) Preparation of sodium carbonate extract is necessary for the analysis of anions.
(ii) CO32 and SO32 ions are to be detected in presence of each other.
(iii) A special test for the mixture of anions of S2 and SO32 is to be done.
(iv) Nitrite ion is to be decomposed first before performing the ring test for nitrate.
(v) Ring test for nitrate is not done in presence of bromide and/or iodide.
(vi) Detection of iodide and iodate in presence of each other is to be done.
(vii) Detection of SCN and Fe(CN)63 is to be done in presence of each other.
(viii) Phosphate, arsenite and arsenate anions are to detected in presence of each other.
23. What happens when (write the reactions involved)
(i) CO2 passed through the lime water?
(ii) Sodium nitro prusside solution is added to a salt containing sulphide ion?
(iii) Freshly prepared FeSO4 solution is added to a solution containing nitrite ion in presence of
dil HCl?
(iv) A solid chloride salt mixed with power K2Cr2O7 is heated with conc H2SO4?
(v) Chlorine water is added dropwise and then in excess to a salt solution containing Br and
I ions?
(vi) Dil HCl is added to a solution containing S2O32 ion?
(vii) Dil HCl is added to a nitrite salt?
(viii) NO2 salt is heated with (a) urea (b) NH4Cl in the presence of dil H2SO4?
(ix) Ammonium thiocynate solution is added to
(a) acidified CuSO4 solution in the presence of Na2SO3?
(b) FeCl3 solution?
(x) K4[Fe(CN)6] is heated with conc H2SO4?
(xi) K4[Fe(CN)6] is added to FeSO4 solution?

(xii) Sodium thiosulphate solution reacts with
(a) AgNO3 solution?
(b) Iodine solution?
(i) A mixture containing two salts when treated with dil H2SO4 and the gas evolved is passed
through a tube containing K2Cr2O7 and dil H2SO4, the solution turned green and the residual
gas when passed through lime water produces a white turbidity. What are the probable
anions present in the mixture?
(ii) A mixture containing two salts when reacted with conc H2SO4 in presence of pinch of
copper turnings, again reddish brown vapour is evolved and the solution turn a green
colour. The same vapour is also formed when dil H2SO4 is added to the mixture. What are
the probable anion present in the mixture.
(iii) When a mixture is heated with NaOH solution, in the presence of Devardaa alloy,
a gas of pungents small of NH 3 comes out which turns red litmus paper blue.
When Na2CO3 extract of the mixture is acidified with dil HCl and a few drops of chlorine
water is added to it and when the resulting solution is shaken wih chloroform a reddish
brown colour is produced in the organic layer. What are the probable anions present in the
mixture?
(iv) A mixture containing two anions out of I , Br, NO2, NO3 and Cl when heated with conc
H2SO4, a violet vapour is evolved. When the mixture is heated with conc H2SO4 in process
of K2Cr2O7 and the resulting vapour is passed through NaOH solution, a yellow colour is
developed which yields yellow precipitate on addition of lead acurate solution. What are
the probable anions present in the mixture?
(v) The sodium carbonate extract (containing two anions) is acidified with dil HCl and a few
drops of chlorine water is added to it. The resulting solution when shaken with chloroform,
at first a violet colour of the orgainc layer is produced. On further addition of chlorine
water, the violet colour is discharged and a reddish brown colour is deveoped. What are
the probable anions present?
(vi) A mixture containing two salts when heated with conc H2SO4, a reddish brown vapour is
evolved. But ammonia gas does not come when the mixture is heated with NaOH in the
presence of zinc dust. However, the tube acquires a greasy appearance. What are the probable
anions present in the mixture?
(vii) When a salt solution is treated with ammonium molybdate, (NH4)2[MoO4] solution in the
presence of conc HNO3, a canary yellow precipitated is formed. But when the same salt
solution is heated with NH4I and conc HCl and H2S is passed through it, yellow precipitate
is obtained. What is the most probable anion present in the solution?
25. Explain why
(i) Diluted nitric acid can not be used in place of dil HCl or dil H2SO4 in dry test for anions.
(ii) AgNO3 solution is stored in black-coloured bottle.
(iii) Bromide and iodides do not respond to chromyl chloride test.
(iv) Na2CO3 extract is to be boiled with dil HNO3 before proceding the test for anions.
(v) Ba(NO3)2 solution cannot be used in place of BaCl2 solution for detect on of SO42 ion.
(vi) Freshly prepared FeSO4 solution is to be used for the ring test of nitrates.
26. Write the chemistry involved in deletion of the following anions
(i) NO 2 (ii) NO 3
(iii) F (iv) IO3
(v) AsO4 3 (vi) PO43
(vii) SCN (viii) [Fe(CN)6]3
27. How would you detect the followings?
(i) CO32 in presence of SO32.
(ii) NO 3 in presence of NO2.
(iii) Borate in presence of a barium or copper salt.
(iv) Phosphate in presence of arsenate.
(v) Cl in presence of Br.
(vi) Iodate and iodide in presence of each other.
(vii) Br and I in presence of each other.
F. Long Answer Type Questions

28. Name the anions detected by dil H2SO4 or dil HCl. How are these anions detected ? Write
the reactions involved.
29. Write the chemistry involved in direction of (a) Cl, Br and I in presence of each other,
(b) NO3 in presence of Br and I
30. Write the chemistry involved in the detection of S2, S2O32, SO32 and SO42 in the presence
of each other.
31. Describe how would you detect arsenate, arsenite and phosphate in the presence of each
other. Write the reactions involved.
32. Give the chemistry for the detection of anions which are neither affected by H2SO4 (diute
or conc).
33. Give the chemistry involved for detecting ferrocyanide, ferricynide and thiocyanate in
presence of each other.
34. Give the chemistry for the detection of (a) oxalate in presence of fluoride, (b) phosphate in
presence of arsenite.
35. Explain why a special procedure for detection of F, SiF62 and SO42 in the presence of
each other to be adopted. Write the chemistry behind the detection of such radical in the
presence of each other.
UNIT 2
2. Quantitative AnalysisVolumetric (Titrimetric) Analysis
3. Quantitative AnalysisPrecipitation Gravimetry
CHAPTER 2
Quantitative Analysis
Volumetric (Titrimetric) Analysis
2.1 INTRODUCTION
Volumetric or titrimetric analysis is one of the powerful methods of quantitative chemical analysis.
Quantitative analysis means the determination of amount of a particular substance (called analyte)
present in a sample. The laboratory technique employed has led the classification of quantitative
analysis into:
1. volumetric (titrimetric),
2. gravimetry and
3. instrumental method of analysis.
Only volumetric (titrimetric) and gravimetric methods of analysis are discussed in Chapters 2 and
3 respectively.
Volumetric analysis involves the exact measurement of the volume. This term has now been
replaced by titrimetric analysis since the former may be confused with measurement of volume
involving gases. The term titrimetric analysis involves exact measurement of the volume of a
solution of known concentration (called standard solution) which is required to react completely
with the analyte. Some important terms used in this technique are as follows.
Titration
The process of addition of standard solution from a burette (called titrant) to a conical flask which
contains known volume of the solution of the analyte (called titrand) till the completion of the
reaction is called titration. The volume of the titrant needed to complete the titration is determined
from the difference between initial and final burette reading.
End point and equivalence point
The end point is the stage during titration at which the titrant and titrand just completely react.
Thus the end point in a titration is the experimental observation indicating the completion of the
reaction while the equivalent point indicates the actual theoretical completion of the reaction.
In an ideal titration, the end point observed should coincide with the actual theoretical point, i.e.
equivalence point. However, in practice, a very small difference usually does occur between the
57
end point and the equivalence point. This difference is known as titration error. It should be as
minimum as possible to get the accurate result.
Indicator
The end point can be detected by some change produced by the standard solution as in case of
potassium permanganate or by addition of another reagent called indicator. Indicator provides a
clear visual change (either colour change or formation of turbidity) when added to the titrand in
titration. Some cases it is added in the beginning while some cases it is added towards the end of
the titration depending on the experimental conditions. Typical indicator changes include the
appearance or disappearance of a colour, change in colour or the appearance or disappearance of
turbidity.
Standard solution
A standard solution (or standard titrant) is a reagent of known concentration (usually in normality)
that is used to carry out a titrimetric analysis.
The substance used in preparing standard solutions for titrimetric analysis may be primary or
secondary standard as follows.
Primary standard
It is a substance of high purity and stability whose standard solution can be prepared by direct
weighing followed by dilution to give solution of definite volume. As the accuracy of the titrimetric
method of analysis is critically dependent on the properties of primary standard, some requirements
for it are given below.
Requirements for primary standard
(i) High purity: It must be easily available into pure form or in a state of known purity at
a reasonable cost. The total amount of impurities, if any, should not exceed 0.01 to 0.02
percent.
(ii) High stability: It should not be hygroscopic. It should neither be affected by carbon
dioxide gas nor be oxidized by air, i.e. its composition must not change during the storage.
(iii) Easy drying: It should be easy to dry preferably in between 110º to 120ºC. Hydrated
salts are not used as primary standard because of difficulty of efficient drying.
(iv) High solubility: It should have high equivalent mass and molecular mass so that
weighing errors may be minimized and it must go into solution in titration medium.
(v) Stoichiometric: Its solution should react instantaneously and stoichiometrically.
The titration error should be negligible as far as possible.
Examples of primary standards: Substances like sodium carbonate, potassium hydrogen
phthalate, benzoic acid, sodium oxalate, potassium bromate, potassium dichromate, etc. which
are obtained in a high purity and stability are taken as primary standards. The solution of primary
standard is used directly in titrimetric analysis as the titrant.
Secondary standard
A secondary standard substance is that whose standard solution cannot be prepared by direct
weighing. Examples of such substances include alkali hydroxides such as NaOH and KOH,
Quantitative Analysis—Volumetric (Titrimetric) Analysis 59
some inorganic acids such as HCl and H2SO4 and various deliquescent substance. When these
substances are required for a titration, their solutions of the approximate normality required are
first prepared. These are then standardized by titration against a primary standard solution of
known concentration. This process is called standardization.
Requirements for secondary standard
(i)The concentration of the solution should remain unaltered for months and even years.
(ii)It should react rapidly with the titrand.
(iii)Its reaction with the titrand should be complete so that a sharp end point can be detected.
(iv) Its reaction with the titrand should be represented by a simple chemical equation so that
the necessary calculations can be carried out properly and easily.
(v) The end point must be easily detectable.
KMnO4, I2, sodium thiosulphate(hypo), etc. are used as secondary standard because of the
following reasons.
Reasons for KMnO4 as secondary standard
It is difficult to obtain KMnO4 perfectly pure and completely free from MnO2. Also ordinary
distilled water is likely to contain reducing substances (traces of organic matters, etc.) which will
react with KMnO4 to form MnO2 which catalyses the auto decomposition of permanganate solution
on standing
4MnO4 + 2H2O ¾® 4MnO2 + 3O2 + 4OH
Reason for sodium thiosulphate pentahydrate (Na2S2O3·5H2O) as secondary standard

There is always some uncertainty as to the exact water content because of the efflorescent nature
of the salt.
Reason for I2 as secondary standard
Aqueous solution of iodine has an appreciable vapour of iodine and therefore concentration of
iodine solution decreases on account of volatilization.
However, it is to be noted that though hydrated salts are not good standards yet those salts
like copper(II) sulphate pentahydrate CuSO 45H 2O and sodium tetraborate decahydrate
(Na2B4O7 · 10H2O), which do not efflorescence, may be taken as secondary standard.
2.2 VOLUMETRIC (TITRIMETRIC) CALCULATION
A titrimetric method of analysis is based on a chemical reaction such as

aA + bT ¾® Products (2.1)
where a mole of an analyte A, reacts completely with b mole of a titrant T. The volume of
titrant needed for completion of the reaction is determined by controlled addition of the titrant
from a burette to a known volume of the solution of the analyte taken in a conical flask. The point
at which this occurs is called equivalence point (theoretical end point). In order to know when to
stop the addition of titrant, an indicator is used which responds to the appearance of excess titrant
by changing colour.
2.2.1 Calculation Based on Normality (N) of the Solution

Suppose V1 ml of a solution of an analyte (A) is taken in a conical flask, V2 ml of titrant (T) of
normality N2 is added to reach the equivalence point. Then at the equivalent point
Number of milliequivalent of analyte A = Number of milliequivalent of titrant T
Let the normality of the analyte be N1, then number of milliequivalent of A = N1V1
Similarly number of milliequivalent of T = N2V2
At the equivalent point
N1V1 = N2V2 (2.2)
Equation (2.2) is known as the law of titrimetry.
If w is the wt of analyte in gram and E be its gram equivalent weight, then
w
N1V1 1000 meq
E
w
1000 N 2V2
E
E
or w N 2V2 g (2.3)
1000
Thus, the amount w (in gram) of the analyte can be determined provided the gram equivalent
weight, E of the analyte is known.
2.2.2 Calculation Based on Molarity (M) of the Solution

Let the molarity of analyte to be determined by titration be M1.
The number of millimole of analyte present in V1 ml of analyte = M1V1.
Let V2 be the volume of titrant of molarity, M2 required to reach the end point. The number of
millimole of titrant which reacts completely with analyte = M2V2.
From the chemical Eq. 2.1, it is clear that a mole of an analyte reacts with b mole of a titrant.
M1V1 millimole of analyte reacts with b/a ´ M1V1 millimole of titrant.
b
´ M1V1 = M2V2
a
M 1V1 a
or =
M 2V2 b
Thus, if the stoichiometry of the reaction between the standard (titrant) and the analyte is known
and the equivalence point (or stoichiometric point) is located precisely, then the amount of analyte
can be known as follows:
a M 2V2
M 1V1
b V1
Let w be the weight of analyte

w
M1V1 = ´ 1000 millimole
M
where M = molecular wt of analyte
a M 2V2
w M (2.4)
b 1000
2.3 CONDITIONS FOR VOLUMETRIC (TITRIMETRIC) ANALYSIS
The estimation by volumetric or titrimetric analysis is only feasible if the reaction involved fulfils
the following conditions.
(i) The reaction must be simple and expressible by a chemical equation. The substance to
be quantitatively determined should react completely with the substance in the standard
solution in stoichiometric or equivalent proportion.
(ii) The reaction should be practically instantaneous under the experimental conditions
maintained. There should not be side reaction. The reaction between metaboric acid and
sodium hydroxide given by the equation
HBO2 + OH ¾® BO2 + H2O
is not sufficiently complete to satisfy the requirement.
(iii) The reaction should be complete, i.e. irreversible under the condition by which titration
is carried out. This may be achieved by heating the solution, using a catalyst or adding
an excess reagent. In the last case, a back titration of the excess reagent will be used to
locate the stoichiometric point for the primary reaction. The equilibrium constant for the
reaction should be very large.
(iv) An indicator or some instrumental methods must be available to know when to stop the
addition of titrant, i.e. to detect the end point. For example, there is no suitable indicator
available to detect the end point for the precipitation of certain metal ion by sulphide
ion.
(v) There must be a marked change in free energy leading to alternation in some physical or
chemical properties of the solution at the equivalence point.
(vi) The reaction should proceed with great speed so that the titration can be completed
within a few minutes. For example, the reaction between ethyl alcohol and acetic acid is
unsuitable for titration as it is too slow.
(vii) There should not be any side reaction during titration. For example, the reaction between
tin(II) and KMnO4 is not suitable in the presence of air. This is because of side reaction
occurring as tin(II) is readily oxidized by atmospheric oxygen.
2.4 TYPES OF TITRIMETRIC ANALYSIS
The chemical reactions, which may serve as the basis for titrimetric determinations, are conveniently
grouped into four types:
(i) Neutralization (acid-base) reaction.
(ii) Oxidation reduction (Redox) reaction.
(iii) Complex formation reaction.
(iv) Precipitation reactions.
The titration are named according to the reactions involved such as:
(a) Acid-base titration
(b) Oxidation reduction (Redox) titration.
(c) Complexation titration or complexometric titration
(d) Precipitation titration.
Only (a), (b), and (c) are discussed below.
2.5 ACID-BASE TITRATION AND WAYS OF LOCATING END POINT
Acid-base titration includes acidimetry and alkalimetry defined as follows:

The process of addition of a standard acid from a burette to a conical flask, which contains a
known volume of the solution of a base, is called acidimetry. While the reverse process, i.e.
addition of a standard solution of a base from a burette to a conical flask which contains a known
volume of the solution of an acid is called alkalimetry. The primary standards used in such titration
are as follows.
Primary standard acids: Potassium hydrogen phthalate C6H4(COOK)(COOH), benzoic acid
C6H5COOH, constant boiling HCl, potassium hydrogen iodate, KH(IO3)2.
Primary standard bases: Sodium carbonate Na2CO3, magnesium oxide MgO and sodium
tetraborate Na2B4O7.
2.5.1 Theory of Acid-base Titration

Let us consider an acid HA and base BOH. They ionize as follows when dissolved in water
HA ZZX
YZZ H+ + A
BOH ZZX
YZZ OH + B+
On addition of one to the other, the only reaction occurring is the neutralization of hydrogen ion
with hydroxide ion to form unionized water as shown by the following equations:
H+ + A + B+ + OH ZZX
YZZ B+ + A + H2O
There are four types of acid-base titration such as
(i) Strong acid with strong base titration, e.g. HCl vs NaOH or KOH, H2SO4 vs NaOH or
KOH, HNO3 vs NaOH or KOH.
(ii) Strong acid with weak base titration, e.g. HCl or H2SO4 vs NH4OH.
(iii) Weak acid with strong base titration, e.g. acetic acid, CH 3COOH vs NaOH.
(iv) Weak acid with weak base titration, e.g. CH3COOH vs NH4OH.
2.5.2 Ways of Locating the End Point of an Acid-base Titration

As the majority of solutions of acids and bases used in volumetric analysis are colourless, it is
necessary to have external visible means of detecting the end point. There are four principal ways
of doing this:
(i) Visual method (by the use of an acid-base indicator)
(ii) pH method (by measuring the pH of the solution obtained by addition of acid to a base
or via versa and then plotting a graph between the pH taken as Y-axis and the volume of
acid or base added taken as X-axis).
(iii) Conductimetric method
(iv) Potentiometric method
Only the visual method and pH method of locating the end point are discussed here.
Detection of end point by visual method
The visual method involves use of acid-based indicators. These are weak organic acids represented
as (HIn) or weak organic bases represented as (InOH). Both are derivatives of organic dyes.
They have different colours in ionized and non-ionized states as shown below
HIn ZZX
YZZ H+ + In
InOH ZZX
YZZ OH + In+
Non-ionized colour Ionized colour
The colour of the indicator depends on the relative proportions of its unionized states and ionized
states. The action of acid indicator such as phenolphthalein and base indicator such as methyl
orange are discussed as follows:
(a) Action of phenolphthalein: It is a weak acid (HPh) which is colourless in its unionized
form. On ionization, it gives colourless H+ ions and pink coloured Ph ions
HPh ZZX H+ Ph
YZZ
Colourless Colourless Pink
In the presence of acid due to increase in the concentration of common H + ions,

the dissociation of HPh is suppressed due to common ion effect and then the solution
becomes colourless. On the other hand, on addition of strong bases (like NaOH, KOH),
the OH ions produced from them combine with H+ ions from the phenolphthalein to form
the unionized water. The equilibrium is thus disturbed and more of the phenolphthalein is
ionized to produce Ph ions producing pink colour to the solution.
(b) Action of methyl orange: It is a weak base and can be expressed as MeOH.
Its undissociated molecule is yellow which gives red colour Me+ ion on dissociation.
ZZX Me+ OH
MeOH YZZ
Yellow Red Colourless
If a base (i.e. OH ions) is added to the indicator, the OH ions will suppress the ionization
of the indicator due to the common ion effect. Hence the indicator remains yellow in
alkali. However, if a small excess of acid (say, HCl) is added, the later will force the
equilibrium to the right by removing OH to form H2O. This will result in the formation of
red coloured Me+ ions in the solution.
(c) Colour change interval of indicator: From the examples of phenolphthalein and methyl
orange indicators, we know that phenolphthalein changes its predominantly acid colour
(unionized colour) to alkaline colour (ionized coloured) on addition of base while methyl
orange changes its predominantly alkaline colour (unionized state) to acidic colour (ionized
colour) on addition of acid. However, this change of colour is not sudden and abrupt but
takes place within a small interval of pH (usually about two pH units). This small interval
of pH is called the colour change interval of the indicator. Thus for acid-base titration we
should select an indicator which exhibits distinct colour change at pH close to that at the
equivalence point. Table 2.1 summarizes the details of some most commonly used acid-
base indicators.
Table 2.1 Some commonly used acid-base indicators

Common name Colour change interval Colour change
Thymol blue 1.2 2.8 Red to yellow
Methyl yellow 2.9 4.0 Red to yellow
Methyl orange 3.1 4.4 Red to orange
Bromocrsol green 3.8 5.4 Yellow to blue
Methyl red 4.2 6.3 Red to yellow
Bromothymol blue 6.2 7.6 Yellow to blue
Phenol red 6.8 8.4 Yellow to red
Cresol purple 7.6 9.2 Yellow to purple
Phenol Phthalein 8.3 10.0 Colourless to red
Thymol phthalein 9.3 10.5 Colourless to blue
Alizarin yellow 10.0 12.0 Colourless to yellow
pH method
Let us consider the titration of an acid with alkali. Initially pH of the solution will be low (due to
acid only). On titration with a base, pH of the solution will go on increasing slowly. At a certain
point, there will be a large change in pH by the addition of even small amount of a base. If a graph
is plotted between pH taken on Y-axis and volume (in ml.) of a base added taken on X-axis, it is
found that, toward the vicinity of the end point, the curve becomes almost parallel to pH axis and
then bends away. Such a curve is called pH titration curve. The region of abrupt change of pH in
the titration curve includes the equivalence point (end point or stoichiometric point). The nature
of pH curves and the indicators to be used for titration of strong acid against strong base and vice
versa, weak acid against strong base and vice versa, weak base against strong acid and vice versa,
weak acid against weak base are discussed as follows.
2.5.3 Titration of Strong Acid with Strong Base

Let us consider the titration of V ml. of HCl (strong acid) of strength NA with NaOH strong
base of strength NB. Let the volume of NaOH needed to reach the equivalence point be X ml.
Then
V · NA = X · NB
V NA
X ml
NB
Before the equivalence point, HCl is present in excess and the pH is determined by the concentration
of excess HCl. Since HCl is a strong acid, [H+] = [HCl]
pH = log[H+] = log [excess HCl]
After the equivalence point, NaOH will be present in excess and the p(OH) will be determined by
the concentration of excess NaOH. Since NaOH is a strong base, [OH] = [NaOH]
p(OH) = log [OH] = log [excess NaOH]
pH = 14 p(OH)
At equivalence point
[HCl] = [NaOH]
or [H+] = [OH]
We know ionic product of water = KW = [H+][OH]
[H+]2 = KW
[H+] = (KW)1/2
pH = log[H+] = log(KW )1/2 = 1/2pKW = 1/2 ´ 14 = 7
(KW = 1014, pKW = logKW = log1014 = 14)
pH titration curve
The pH titration results show that as the titration proceeds initially the pH rises very slowly, but in
the vicinity of the equivalence point, the pH of the solution rises rapidly from pH ~3 to pH ~11.
Hence all the indicators which have pH range between 3 and 11 are suitable for the titration of
strong acid with strong base. A typical pH titration curve for strong acid with strong base depending
on the various concentrations of NaOH as shown in Figure 2.1.
It is to be noted that the titration of a strong base against a strong acid is handled with the
same manner except that strong base is in excess before the equivalence point and strong
acid is in excess after the equivalence point. The pH titration curve in this case in shown in
Figure 2.2.
Figure 2.1 pH titration curve for strong acid against strong base.
Curve 1:100 ml of 0.1 M Hcl versus 0.1 M NaOH.
Curve 2:100 ml of 0.01 M HCl versus 0.01 M NaOH.
Curve 3:100 ml of 0.001 M HCl versus 0.001 M NaOH.
Figure 2.2 pH titraton curve for 100 ml of 0.1 M NaOH versus 0.1 M HCl.
2.5.4 Titration of Weak Acid with Strong Base

Let us consider the titration of V ml of acetic acid (weak acid) of strength NA with NaOH (strong
base) of strength NB. Let the volume of NaOH needed to reach the equivalence point be X ml, then
V · N A = X · NB
V NA
or X= ml
NB
Acetic acid being a weak acid, it is not 100% dissociated. Hence [H+] ¹ [acetic acid]. In this case,
the concentration of H+ ion is given by the relation, [H+] = K a [acetic acid] where Ka is the
acid dissociation constant of acetic acid.
Initial pH of the solution (i.e. before addition of any NaOH)
pH = log[H+] = log K a [acetic acid]

1 1
= log Ka log [acetic acid]
2 2
1 1
= pKa log[NA]
2 2
Addition of NaOH converts a portion of acetic acid to its conjugate base (acetate ion).
CH3COOH + OH ZZX H 2O(1) + CH3COO

YZZ
Acetic acid Acetate ion
Any solution containing a weak acid and its conjugate base is acid buffer for which the pH of the
solution is calculated by Henderson equation, i.e.
[Conjugate base]
pH = pKa + log
[Weak acid]
[CH 3COO ]
Here, pH = pKa + log (2.5)
[CH 3COOH]
At the equivalence point, the millimole of acetic acid initially present and the millimole of NaOH
added are identical. Since the reaction proceeds to completion, the predominant ion in solution is
CH3COO which is hydrolyzed to give a basic solution CH3COO + H2O ® CH3COOH + OH.
The pH of the solution under this condition (i.e. at equivalence point) = ½ pKW + ½ pKa ½ Pc,
where c is the concentration of acetic acid, at the equivalence point. The pH of the solution will be
more than 7.
After the equivalence point, NaOH is present in excess. Then p(OH) will be determined from
the concentration of excess NaOH.
p(OH) = log[OH] = log[excess NaOH]
Since at the equivalence point, pH is more than 7, any indicator, which has pH range above 7,
may be used. For example, phenolphthalein thymolblue may be used for this purpose. Methyl
orange can not be used as its pH range lies between 3.1 and 4.4, i.e. below 7. A typical pH titration
curve for the titration of weak acid against strong base is shown in Figure 2.3.
Figure 2.3 pH titration curve for 100 ml of 0.1 M CH3COOH versus 0.1 M NaOH.
2.5.5 Titration of Weak Base with Strong Acid

The calculation for the titration of weak base with strong acid is handled in a similar manner
except the excess weak base determines the initial pH. The pH at the equivalence point by its
conjugate acid due to hydrolysis and the pH after the equivalence point by the concentration of
excess strong acid is determined as follows.
Let us consider the titration for V ml of NH4OH (weak base) of strength NB with HCl (a strong
acid) of strength NA.
Let the volume of HCl required to reach the equivalent point is X ml, then
N B · V = X · NA
NB V
or X=
NA
NH4OH is a weak base and hence it is not 100% dissociated. Hence [OH] ¹ [NH4OH]. In this
case [OH] is given by the relation [OH] = Kb [NH 4 OH] , where Kb is the base dissociation
constant of NH4OH.
Initial p(OH) of the solution before addition of HCl is given by
p(OH) = ½ pKb ½ log [NH4OH]
Initial pH = 14 p(OH)
Addition of HCl converts a portion of NH4OH to its conjugate acid (NH 4+ ion)
NH4OH + H+ ¾® NH 4+ + H2O
Any solution containing a weak base and its conjugate acid is basic buffer for which the p(OH) of
the solution is given by Henderson equation:
[Conjugate acid]
p(OH) = pKb + log
[Weak base]
[NH 4 ]
= pKb + log (2.6)
[NH 4 OH]
At the equivalence point, the reaction of NH4OH with HCl is complete, the predominant ion in
solution is NH 4+ ion which is hydrolyzed to give an acidic solution
NH 4+ + H2O ¾® NH4OH + H+
The pH of the solution under this
condition = 7 ½ pKb + ½ pC, where c
is the concentration of NH4OH at the
equivalence point. The pH of the
solution at the equivalence point will be
less than 7.
The results show that at the equiva-
lence point, pH is less than 7 (~5 to 3).
It is necessary to use an indicator with
a pH range on the slightly acid side
(3 to 6.5) such as methyl orange, methyl
red, bromophenol blue or bromo
thyamol green, etc. Neither thymol-
phthalein nor phenolphthalein can be
Figure 2.4 pH titration curve for 100 ml of 0.1 M NH4OH
employed as an indicator in this case.
versus 0.1 M HCl.
The pH titration curve for the titration
of weak base against strong acid is shown in Figure 2.4.
2.5.6 Titration of Weak Acid with Weak Base

Let us consider the titration of V ml of acetic acid (weak acid) of strength NA with NH4OH (weak
base) of strength NB. The pH at the equivalence point is given by
1 1 1
pH = pKW + pKa pKb
2 2 2
where Ka and Kb are dissociation constants of acetic acid and NH4OH respectively. A typical
pH titration curve of weak acid against weak base is shown in Figure 2.5 in which 25 ml N/10
acetic acid titrated against N/10 NH4OH solution. The chief feature of the curve is that the change
of pH near the equivalence point and also during the whole of the titration curve is very gradual.
There is no sudden change in pH and hence no sharpened point can be found with any
simple indicator. The pH at the equivalence point will be almost 7 if Ka » Kb. However, an
approximate end point can be detected by using phenol red indicator having pH range between
6.8 and 8.4.
From the results of the above pH titration curves we may conclude the following factors affecting
the pH titration curves.
2.5.7 Factors Determining the Exact Form of a pH Curve

The exact form of a pH curve depends on
(a) Whether acid or base is strong or weak electrolyte.

(b) The molarities of the solution used in the titration.
Figure 2.5 pH titration curve for CH3COOH versus NH4OH.
The above factors may give rise to the following pH curves.

(i) pH curve obtained by titration of a strong acid with a strong base.
(ii) pH curve obtained by titration of a strong acid with a weak base.
(iii) pH curve obtained by titration of a weak base with a strong acid.
(iv) pH curve obtained by titration of a weak acid with a weak base.
(c) If either acid or alkali is weak, the parallel part of the curve become shorter as compared to
strong acidstrong base curve. On the other hand, if both the acid and base are weak,
the range is usually non-discernible, i.e. not easily judged.
(d) For acid base titration, the primary reaction involved is the neutralization reaction. At the
point of equivalence, the pH of the solution will be =, > or < 7 depending on the hydrolysis
of the salt formed, i.e.
(i) In the titration of a strong acid with a strong base, the resulting salt is not hydrolyzed
by water and pH of the solution at the end point would be equal to 7.
(ii) In the titration of a strong acid with a weak base, the resulting salt is hydrolyzed by
water and pH at the end point will be less than 7.
(iii) In the titration of weak acid with a strong base the resulting salt is hydrolyzed by
water to give a basic solution and pH at the end point will be greater than 7.
2.6 OXIDATION REDUCTION (REDOX) TITRATION AND WAYS OF

LOCATING END POINT
Oxidationreduction titration (or Redox titration) includes oxidimetry and reducimetry, which
can be defined as follows.
The process of addition of a standard solution of an oxidizing agent (oxidant) from a burette to
a conical flask, which contains a known volume of the solution of a reducing agent (reductant) is
called oxidimetry, while the reverse process, i.e. addition of a standard solution of a reducing
agent from a burette to a conical flask which contains a known volume of the solution of an
oxidizing agent is called reducimetry. Both the processes involve transfer of electron/electrons
from reducing agent to oxidizing agent. The primary standard used in such titration is as follows.
Oxidant primary standard
K2Cr2O7, Potassium bromate (KBrO3), Potassium iodate, (KIO3), etc.
Reductant primary standard
Sodium oxalate, Na2C2O4, arsenic(III) oxide, As2O3 and pure iron, etc. The properties and behaviour
of some important redox reagents are given in Table 2.2.
Table 2.2 Some important redox reagents

Half reactions Eºvolt Conditions
Oxidising agents
Potassium permanganate MnO4 + 8H+ + 5e ® Mn2+ + 4H2O 1.5 Strong acid
(KMnO4) MnO4 + 4H+ + 3e ® MnO2 + 2H2O 1.69 Weak acid/neutral
MnO4 + e ® MnO4 0.56 Strong base
Ceric sulphate Ce(SO4)2 Ce4+ + e ® Ce3+ 1.44 Strong acid
2
Potassium dichromate Cr2O7 + 14H+ + 6e ® 2Cr3+ + 7H2O 1.33 Strong acid
(K2Cr2O7)
Bromate bromide mixture BrO3 + 5Br + 6H+ ® 3Br2 + 3H2O 1.05 Dilute acid
Reducing agents
Ferrous sulphate (FeSO4) Fe2+ ® Fe3+ + e 0.771 Dil H2SO4
Arsenous acid (H3AsO3) H3AsO3 + H2O ® H3AsO4 + 2H+ + 2e 0.559 Acidic medium
Sodium thiosulphate (Na2S2O3) 2S2O32 ® S4O62 + 2e 0.08 Neutral/dil acid
Oxalic acid (H2C2O4) H2C2O4 ® 2CO2 + 2H+ + 2e 0.49 Dil H2SO4
2.6.1 Theory of Redox Titration

Let us consider a redox reaction in which the analyte is a reductant (Ared) and the titrant is an
oxidant, (Tox). The titration reaction is
A(red) + T(ox) ZZX
YZZ A(ox) + T(red)
where A(ox) is the oxidized form of analyte and T(red) is the reduced form of titrant. The equilibrium
constant, K(redox), for the above redox reaction is given by the law of mass action.
[ A(ox) ] · [T(red) ]
K (redox)
[ A(red) ] · [T(ox) ]
Determination of minimum value for K(redox)

The above redox reaction to be quantitative, there should be 99.9% conversion of reactants to
A(ox) T
products at the end point. Thus at the end point 103 and (red) 103.
A(red) T(ox)
Minimum value of K(redox) @ 103 ´ 103 @ 106
Hence, for the redox reaction, the value of K(redox) > 106.
2.6.2 Study of Redox Titration by Electrochemical Potential Method

The reaction between reductant (Ared) and the oxidant (Tox) is considered to involve two half cells
such as A(red)/A(ox) and T(ox)/T(red). If n be the number of electrons transferred during the process
the half cell reactions are:
A(red) ¾® A(ox) + ne and T(ox) + ne ¾® T(red)
Potential for such a reaction E(redox) = ET(ox) /T(red) E A(ox) /A(red) , where ET(ox) /T(red) and E A(ox) /A(red) are
reduction potential for T(ox)/T(red) and A(ox)/A(red) half cells respectively. After each addition of
titrant, the reaction between the analyte and titrant reaches a state of equilibrium so that
ET(ox) /T(red) = E A(ox) /A(red)
From the above relation we may conclude that potential for either of the half cells may be used to
monitor the titration process.
At the end point of the titration, the following relation holds good.
A(ox) T(red)
(i) and the potential E at the end point is given by
A(red) T(ox)
E Aº (ox) / A(red) ETº (ox ) / T(red)

(ii) E
2
ETº / T and E Aº / A are standard reduction potential for A(ox)/A(red) and T(ox)/T(red) half
(ox ) (red) (ox) (red)
cells respectively at the end point.
For example, in the titration of iron(II) with Ce(IV) in the presence of dil H2SO4, the reaction
involved Fe2+ + Ce4+ YZZ ZZX Ce3+ + Fe3+ and the potential E, at the end point
Eº 3
Fe2
E ºCe4 Ce3
Fe 0.75 1.45
1.1 V
2 2
For a general reaction
aA(red) + bT(ox) ZZX
YZZ aA(ox)+ bT(red)
The potential, E, at the end point is given by
b · E Aº (ox) A(red) a · ETº(ox) T(red)

E
a b
For example, in the titration of Fe2+ with MnO4 in the presence of dil H2SO4, the reaction involved
is 5Fe2+ + MnO4 + 8H+ ZZX
YZZ 5Fe3+ + Mn2+ + 4H2O, here a = 5, b = 1 so that the electrochemical
potential at the end point is given by
1 EFe
º
3
Fe 2
5 EMn
º
2 1 0.75 5 1.5
4 Mn
E=
6 6
8.25
= 1.375 V
6
The difference in standard reduction potential (DEº) is given as the difference between standard
reduction potentials of two half cells T(ox)/T(red) and A(ox)/A(red) at 25o C
0.0593
Eº ETº(ox) T(red) E Aº (ox) A(red) log K (redox)
n
As we know the minimum value of Kredox is 106, then the minimum value of
0.0593 0.355
Eº log106 V
n n
For n = 1, the minimum value E º = 0.355 V.
The conclusions drawn from the above relation of the Redox Titration are
(a) If value of n increases, DE º decreases, thus if n > 1, the minimum value of DEº < 0.355
volt.
(b) If the value of ETº / T for T(ox)/ T(red) half cell is greater than that of A(ox)/A(red) half cell,
(ox ) (red)
then the value of Kredox will be more so that redox reaction is possible.
2.6.3 Ways of Locating the End Point for Redox Titration

There are mainly two ways to locate the end points (i) visual method (using indicator)
(ii) Electropotential method as discussed below.
By visual methods (using indicators)
There are three types of visual indicators used to signal the end point in a Redox titration.
Self indicator: Some of the titrants themselves act as indicators if these are highly coloured.
These are called self-indicators. For example, KMnO4 solution has dark purple colour. During
Redox titration of KMnO4 with FeSO4 in acidic medium, KMnO4 (the oxidant) is taken in a
burette and FeSO4 solution taken in a conical flask. During the titration by dropwise addition of
KMnO4 solution to FeSO4 solution, the pink colour gets discharged because of the formation of
colourless Mn2+ ion as MnO4 is reduced to Mn2+ by the reductant Fe2+ ion. The reaction being
MnO4 + 8H+ + 5Fe2+ ¾® Mn2+ + 5Fe3+ + 4H2O
As soon as the reaction is complete, i.e. the entire Fe2+ ion is converted to Fe3+ ions, a single drop
of KMnO4 imparts faint pink colour which is the end point. So KMnO4 acts as a self-indicator as
its oxidized form MnO4 and reduced forms (Mn2+) have different colours i.e pink and colourless
respectively.
Specific visual indicator: There are certain substances, which react with specific oxidized or
reduced species to produce colour. Such substances are used as specific visual indicator.
For example, a freshly prepared starch solution can be used as specific visual indicator for iodimetry
and iodometry titrations as discussed below.
Iodimetry: It refers to titration with a standard solution of iodine with sodium thiosulphate,
Na2S2O3 solution. As iodine is insoluble in water, its solution is prepared in KI solution because
of the formation of water soluble potassium triodide KI3.
KI + I2 ¾® KI3
Its reaction with sodium thiosulphate is as follows
I2 + 2e ¾® 2I
2S2O32 ¾® S4O62 + 2e
I2 + 2S2O32 ¾® 2I + S4O62
Tetrathionate ion
A list of substances determined by iodimetry is given in Table 2.3.
Table 2.3 List of substances determined by iodimetry

Substance Reaction with iodine
H 2S ® S + 2I + 2H+
H 2S + I 2
SO32 ® SO42 + 2I + 2H+
SO32 + I2 + H2O
Sn2+ ® Sn4+ + 2I
Sn2+ + I2
As (III) H3AsO3 + I2 + H2O ® H3AsO4 + 2HI
N2H4 N2H4 + 2I2 ® N2 + 4H+ + 4I
These titrations are usually performed in neutral or mildly alkaline (pH 8) to weakly acid solution.
If the solution is too alkaline, I2 will be disproportionate to hypoiodide and iodide.
I2 + 2OH ¾® IO + I + H2O
If the solution is strongly acidic
(i) The starch used for the end product leads to hydrolysis or decomposition in strong acid.
(ii) I ions produced in the reaction tends to be oxidized by dissolved oxygen in acid solution
4I + O2 + 4H+ ¾® 2I2 + 2H2O
The pH of the solution can be maintained neutral by adding NaHCO3. The CO2 formed
removes the dissolved oxygen and maintains a blanket of CO2 over the solution to prevent
air oxidation of the iodide ions.
Iodometry: It refers to titration of iodine liberated in a chemical reaction (redox reaction).
In this method a known volume of oxidant (K 2Cr2O7, CuSO4, 5H2O, etc.) is treated with KI
solution (reductant) in acidic medium and the I2 produced is titrated with standard sodium
thiosulphate solution taken in a burette.
I2 acts as oxidant and thiosulphate (S2O2
3 ) acts as reductant and the Redox reaction is:
2S2O32 ¾® S4O62 + 2e

Tetrathionate
I2 + 2e ¾® 2I
I2 + 2S2O32 ¾® S4O62 + 2I
Some examples of iodometry are given below.

(a) Standardization of sodium thiosulphate by K2Cr 2O7: Sodium thiosulphate is
standardized iodometrically by potassium dichromate and by adding potassium iodide
solution in acidic medium. The following reaction occurs
K2Cr2O7 ¾® 2K+ + Cr2O72

Cr2O72 + 14H+ + 6e ¾® 2Cr3+ + 7H2O
3 ´ (2I ¾® I2 + 2e)
Cr2O72 + 14H+ + 6I ¾® 3I2 + 2Cr3+ + 7H2O
The liberated iodine produced in the above reaction or its solution in KI is always titrated
with standard solution of sodium thiosulphate taken in a burette because the reaction
between I2 and sodium thiosulphate is quantitative. The completion of the above reaction
(the end point) can be detected by using starch solution as an indicator which imparts blue
colour because of formation of starch iodine complex. However, the starch solution should
be added near the end point when the iodine solution becomes stint yellow. This is because
under this condition, the concentration of iodine is very small and the complex will not be
so strong. Therefore, a few drops of reducing agent (thiosulphate solution) will be needed
to break the complex and get the end point which is detected by the change of blue colour
due to the starch Iodine complex to colourless.
I2 + starch ¾® I2 starch (Blue complex)

I2 starch + 2S2O32 ¾® 2I + S4O62 + starch (Colourless)
A standard solution of K2Cr2O7 is prepared by accurately weighing K2Cr2O7. Here 6

electrons are involved per dichromate ion and hence equivalent weight (E) of
Molecular weight of K 2 Cr2 O7 294

K 2 Cr2 O7 49
6 6
N
So in order to prepare 250 ml of K Cr O solution, the amount of solid K2Cr2O7 to be
10 2 2 7
Normality E V (in ml) 0.1 49 250 1225
taken = 1.225 g
1000 1000 1000
Then the normality of sodium thiosulphate solution is determined by the law of titrimetry,
i.e. N1V1 = N2V2

It is to be noted that the thiosulphate though reductant is not titrated directly with oxidant
like potassium dichromate due to the following reasons.
Reasons for not titrating sodium thiosulphate directly with potassium dichromate:
(i) Strong oxidizing agent like K2Cr2O7 oxidizes thiosulphate to sulphate where the oxidation
State of sulphur is higher than that in tetrathionate.
(ii) The reaction between dichromate and thiosulphate is not stoichiometric.
(iii) The thiosulphate ions has tendency to form complex with strong oxidizing agent.
(iv) The oxidizing power of strong oxidizing agent is destroyed on reaction with iodide, and
equivalent amount of I2 is produced, which will react stoichiometrically with thiosulphate,
for which a satisfactory indicator exists.
(b) Estimation of copper by iodometry: Copper can be estimated iodometrically by the

reaction of copper sulphate with potassium iodide.
The following redox reactions occur with CuSO4 5H2O:
CuSO45H2O ¾® Cu2+ + SO42 + H2O
2(Cu2+ + e ¾® Cu+) (Cuprous ion)
2I ¾® I2 + 2e
2Cu + 2I ¾® Cu2I2 (Cuprous iodide)
+
2Cu2+ + 4I ¾® Cu2 I2 + I2

When copper(II) is titrated iodometrically, the end point is diffuse unless the thiocyanate
ion is added. Iodine is adsorbed on the surface of the cuprous iodide precipitate and only
slowly reacts with the thiosulphate titrant. The thiocyanate covers the precipitate with
SCN and displaces the iodine from the surface. However, the potassium thiocyanate should
be added near the end point, as it is slowly oxidized by iodine to sulphate. The pH must be
buffered to around 3. If it is too high, copper(II) ion is hydrolyzed and cupric hydroxide
will precipitate. If it is too low, air oxidation of iodide become appreciable, as it is catalyzed
in the presence of copper(II) ion . Some examples of iodometric determination are listed in
Table 2.4.
Redox indicator: Just as acid-base indicators are employed to mark the sudden change in pH
during acid-base titrations, oxidation-reduction (redox) indicators are also used to mark the sudden
change in electrochemical potential in the vicinity of equivalence point in redox reaction.
These are also highly coloured dyes that are weak reducing or oxidizing agents. They exhibit
Table 2.4 List of substances determined by iodometry
Substance determined Reaction with iodide
MnO4 2MnO4 + 10I + 16H+ ® 2Mn2+ + 5I2 + 8H2O
Cr2O72 Cr2O72 + 6I + 14H+ ® 2Cr3+ + 3I2 + 7H2O
IO3 IO3 + 5I + 6H+ ® 3I2 + 3H2O
BrO3 BrO3 + 6I + 6H+ ® Br + 3I2 + 3H2O
Ce4+ 2Ce4+ + 2I ® 2Ce3+ + I2
Fe3+ 2Fe3+ + 2I ® 2Fe2+ + I2
H2O2 H2O2 + 2I + 2H+ ® 2H2O + I2
As (v) H3AsO4 + 2I + 2H+ ® H3AsO3 + I2 + H2O
SeO32 SeO32 + 4I + 6H+ ® Se + 2I2 + 3H2O
O3 O3 + 2I + 2H+ ® O2 + I2 + H2O
Cl2 Cl2 + 2I ® 2Cl + I2
Br2 Br2 + 2I ® 2Br + I2
HClO HClO + 2I + H+ ® Cl + I2 + H2O
different colours (colour A in oxidized form and colour B in reduced form). Let the oxidized form
and reduced form of the indicator be designed as In(ox) and In(red) respectively.
In( ox ) ne ½ In( red )

Colour A Colour B
The potential E of the system is given by the Nernst equation at 25ºC as

0.059 [ In(red) ]
E EInº log
n [ In(ox) ]
where EInº is the standard reduction potential of the indicator. If we assume that indicators colour
In(red)
in solution changes from that of In(ox) to In(red), when the ratio changes from 0.1 to 10.
In(ox)
In(red)
Let us assume that if the ratio is 10, or greater, only the colour due to In(red) (say,
In(ox)
colour B) can be seen in the eye and if the ratio is 0.1, only the colour due to In(ox) (say, colour A)
is observed. If n = 1, then
for colour B
10
E EInº 0.059 log EInº 0.059 V
1
for colour A
1
E EInº 0.059 log EInº 0.059 V
10
So DE ~ ± 0.12 V
Thus a change in potential of about 0.12 V is required to bring about a change in colour of the
indicator. This is called transition potential of the indicator. Some of the most commonly used
redox indicators are listed in Table 2.5.
Table 2.5 Some most commonly used redox indicators
Name of the indicator Transition Colour
potential in volt Oxidized form Reduced form
Nitroferroin +1.25 Pale Blue Red
O-Dianisidine +0.85 Red Colourless
Diphenylamine +0.76 Violet Colourless
Methylene blue +0.53 Colourless Blue
Neutral Red +0.24 Red Colourless
Ferroin +1.14 Pale blue Red
P-Nitrodiphenylamine +1.06 Violet Colourless
Diphenylamine sulphonic acid +0.85 Purple Colourless
4-Ethoxy-2,4-diamino azobenzene +0.76 Pale yellow Red
1-N-Naphthol-2-sulphnoic acid indophenol +0.54 Red Colourless
Indigo tetra sulphonate +0.36 Blue Colourless
Selection of the redox indicator: The transition potential of the redox indicator should match
with the potential at the equivalence point of redox reaction. For example, in the titration of
Iron(II) with Cerium(IV) sulphate the potential at the equivalence point is found to be 1.06 V.
Referring to Table 2.5, it is the ferroin with a transition potential of 1.14 V is a suitable indicator.
When ceric sulphate solution is added from the burette and ferroin indicator is added to reducing
agent in the titration flask, the end point is marked by change of red colour to blue.
Electropotential method
In this method the electrode potential E of the solution is measured by addition of an oxidant to a
reductant or vice versa. A graph is plotted between E (on the Y-axis) and the volume of titrant
added (on the X-axis). There will be an abrupt change (large change in potential) in the vicinity of
the equivalence point. A typical redox titration curve for titration of 100 ml of 0.1 M iron(II) with
0.1 M cerium sulphate is shown in Figure 2.6.
Figure 2.6 Redox titration curve for 100 ml of 0.1 M Fe2+ versus 0.1 M Ce4+.
The shape of the curve depends upon the following:
(i) The value of n, i.e. the number of electrons involved in redox reaction. Thus the
iron(II), iron(III) curve (n = 1) is steeper than the tin(II)tin(IV) curve (n = 2). Flatness
of the curve increases with an increase in the value of n.
(ii) The standard potentials of the two oxidition-reduction systems that are involved and
upon the equilibrium constants of the reaction.
2.7 COMPLEXOMETRIC TITRATION AND WAYS OF LOCATING END

POINT
Complexometric titration
This is a process of addition of a standard solution of a ligand from a burette to a conical flask,
which contains a known volume of the solution of an analyte (especially metal ions). Ligand is a
substance that has at least one pair of unshared electrons (i.e. N, O, S atom in its molecule) and it
acts as a Lewis base (electron pair donor). Metal ions act as a Lewis acids (electron pair acceptors)
and the reaction involved between them is called complexation reaction. Ligand donating one
pair of electron is called monodentate ligand while those donating two or more than two electron
pairs are called multidentate ligands (if two donor atoms bidentate, three donor atoms tridentate
and so on). These ligands are called chelating ligands as they form ring/rings called chelate rings
when complexed with metal ion leading to extra stability due to chelate effect. Thus the complexes
involving multidentate ligand/ligands are called metal chelates. Monodentate ligands like ammonia
are rarely used as titrating agent because a sharp end point corresponding to a stiochiometric
complex is generally difficult to achieve. However, multidentate ligand capable of complexing
with metal ion forming five or six member chelate ring can be used in complexometric titration
because stoiochmetric complexes corresponding to sharp end point are formed.
If the analyte be a metal ion M and the titrant be a ligand L, (charges are omitted for simplicity),
the reaction involved during titration is complexation reaction
ZZX ML
M + L YZZ
Complex
The complex formed should be soluble, undissociated (stable) and stoichiometric for which the
following conditions are required.
(i) A suitable ligand.
(ii) Experimental conditions (such as pH, temperature, use of buffer, etc.) are to be maintained
suitable for optimum titration.
(iii) Selecting a suitable method for detecting the end point of the titration.
The most widely used chelating agent for complexometric titration which satisfies the above
conditions is ethylenediaminetetra acetic acid EDTA which forms a strong 1:1 complex with the
metal ions of any charge.
2.7.1 Theory of Complexometric Titration Involving EDTA

The structure of EDTA is shown in Figure 2.7. The structure I is preferred to structure II since it
has been shown from the measurement of dissociation constant that two hydrogen atoms are
probably held in the form of zwitterions and can be represented as H4Y as it has four ionisable
protons
Figure 2.7 Structure of EDTA.
It has six bonding sites (the four carboxylate groups and two amino groups) providing six pairs
of electrons and hence acts as a hexadentate ligand forming strainless five-membered rings.
The resulting metal EDTA complex in which EDTA forms a cage-like structure around the divalent
metal ions is shown in Figure 2.8
Figure 2.8 EDTA complex (MY2) with divalent metal ion, M2+.
The cage structure prevents the formation of complexes other than 1:1 stoichiometry.
The actual number of bonding sites depend on the size and charge of the metal ion. However,
most of the metal EDTA complexes have 1:1 stoichiometry.
EDTA is a tetraprotic acid having four ionizable hydrogen atoms. For simplicity it is written as
H4Y, which ionizes to give H3Y, H2Y2, HY3 and Y4 as follows:
H4Y ZZZ
YZZ
K1
X
Z H3Y1 + H+; K1 = 102
ZZZX
H3Y1 YZZZ
K2
H2Y2+H+; K2 = 2.2 ´ 103
H2Y2 ZZZ
YZZZ
K3
X HY3 + H+; K3 = 6.9 ´ 107
ZZZX
HY3 YZZZ
K4
Y4 + H+; K4 = 5.5 ´ 1011
The relative amount of these five species varies as a function of pH as shown in Figure 2.9. If we
consider the unprotanated ligand, Y4 to be used in complexation with the metal ions the following
equilibrium exists from which equilibrium constant/stability constant can be determined.
Figure 2.9 Fraction of EDTA species as a function of pH.
Stability constants of EDTA complexes

The stability of an EDTA complex is characterized by the stability constant K given by the following
expression.
ZZX [MY(n 4)+]
Mn+ + Y4 YZZ
[MY ( n 4)+ ]
K=
[M n ] [Y 4 ]
At a particular pH, [Y4] = a ´ CT, where CT is the total molar concentration of uncomplexed
EDTA, i.e. CT = Y4 + HY3 + H2Y2 + H3Y + H4Y and a is a number. Thus metal EDTA
complex formation is pH dependent. Hence EDTA titrations are always performed in buffered
condition of known pH. a is the fraction of total EDTA that exists as Y4 depending on pH.
Conditional stability constant
At a particular pH, [Y4] = a ´ CT. Substituting this value in the above equation, we get
[MY (n 4)+ ]
K=
[M n ] D CT
[MY ( n 4)+ ]
a·K=
[M n ] CT
a · K = K¢
K¢ is known as conditional stability constant as it describes the condition of the pH to be maintained
and is also related to stability constant K. Taking logarithm on both sides, we get
log K¢ = log K + log a
Figure 2.10 shows how K¢ changes with pH for three metal EDTA chelates with moderate (Ca)
to strong (Hg) formation constant. However, at pH 13, all K¢ values are virtually equal to K
values because a is essentially unity, i.e. the EDTA is completely dissociated to Y4. The curves
are parallel to one another because at each pH, each K is multiplied by the same a value to
obtain K¢.
Figure 2.10 Effect of pH and K¢ value for EDTA chelates.
The conditional stability constant for Mg EDTA complex at pH = 5 and pH = 10 can be calculated
as follows.
For Mg EDTA complex, K = 4.9 ´ 108 and a = 3.5 ´ 107 at pH = 5 so that conditional stability
constant,
K¢ = K ´ a
= (4.9 ´ 108)(3.5 ´ 107)
= 1.73 ´ 102
and at a pH = 10, K¢ = K ´ a = (4.9 ´ 108)(3.5 ´ 101) = 1.73 ´ 108. Hence pH = 10 is maintained
for the titration of Mg2+ but not pH = 5 as stoichiometric reaction requires K¢ > 106.
Figure 2.11 shows the minimum pH at which different metal ions can be titrated with EDTA.
These points on the curve represent the pH at which conditional stability constant K¢ for each
metal ion ~106, which is the minimum value needed for a sharp end point. It is to be noted that the
smaller the value of K¢, the more alkaline be the solution to obtain a K¢ of »106. Thus Ca2+ with K¢
of only about 1010 requires a pH about 8 or above. The dashed line in the figure divides the metal
ions into separate groups according to their stability constant. One group is titrated in quite acidic
(pH < 4) solution, a second group at pH 4 to 7 and a third group at pH > 7.
Figure 2.11 Minimum pH for effective titration of various metal ion with EDTA.
2.7.2 Study of EDTA Complex Formation Taking Disodium Salt of EDTA and
Effect of pH
For practical purpose, the disodium salt of Na2H2Y is preferred as standard solution. This is
because this salt has a distinctly higher solubility than EDTA and avoids extensive hydrolysis as
compared to tetrasodium salt, Na4Y. In Na2H2Y, the complex forming H2Y2 ion reacts with
metal ion in 1:1 ratio. Its reaction with metal ions may be written as follows:
ZZX MY2 + 2H+
M2+ + H2Y2 YZZ
For other metal ions, the reaction may be expressed as
M3+ + H2Y2 ZZX
YZZ MY + 2H+
M4+ + H2Y2 ZZX
YZZ MY + 2H+
In general,
Mn+ + H2Y2 ZZX
YZZ M(n 4)+ + 2H+
From the above reaction is it clear that one mole complex forming ion H 2Y2 reacts with one mole
of metal ions in all cases and in each case, two moles of H+ ions are formed. The stability of the
complex depends on the H+ ion concentration. At low pH (i.e. at high H+ concentration) according
to Le Chateliers principle, the equilibrium shifts towards left and as a result the complex becomes
less stable. It is thus concluded that the stability of the complex decreases if pH decreases i.e.
[H+] increases. Table 2.6 shows the minimum pH range at which EDTA complexes of some metal
ions exist which indicate the conditions for titration to be carried out.
Table 2.6 Minimum pH range at which metal EDTA complexes exist

pH range Metal ions
13 Zr4+, Hf4+, Th4+, Bi3+, Fe3+
46 Pb2+, Cu2+, Zn2+, Co2+, Ni2+, Mn2+, Fe2+, Al3+, Cd2+, Sn2+
810 Ca2+, Sr2+, Ba2+, Mg2+
It seems that the EDTA complexes with divalent metal ions are stable in slightly acidic or alkaline
medium, whereas complexes with higher valent metal ions are stable in distinctly acidic solution.
2.7.3 Ways of Locating the End Point

Only the visual method using indicators to mark the end point for complexometric titration is
discussed here.
The indicators used for complexometric titrations are themselves chelating agents and hence
are known as metal ions indicators discussed below.
Theory of metal ion indicators
Metal ion indicators, also known as metallochromic indicators are used in EDTA titration.
These are dyes, which are capable of acting as a chelating agents to give dye-metal complexes.
These complexes are different in colour from the dyes themselves. However, they have a lower
stability constant than the metal EDTA complexes. The colour of the solution is due to the dye
complex until the end point is reached. As soon as there is slightest excess of EDTA, the metal
dye complexes decompose to produce free dye; this is accomplished by change in colour.
The reactions involving metal ion indicators in a EDTA titration can be written as:
(a) When the indicator (In) is added to the metal ion solution
M + In ¾® M-In
[M-In]
KIn =
[M] [In]
where KIn is the indicator constant.
(b) When titrated with EDTA
M-In + EDTA ¾® M-EDTA + In
This reaction can take place only if the stability constant of M-In complex is less than that of
M-EDTA complex. The M-In complex ionizes to a very small extent. During the titration (EDTA
in burette) free metal ions (in titration flask) are progressively complexed with EDTA until all
the metal ions are displaced from M-In complex to form the free indicator as the end point is
reached.
Effect of pH
In the above discussion the effect of pH on colour change has not been taken into account.
This can now be considered by taking Solochrome Black (Eriochrome Black T) as an example.
Eriochrome Black T: It is a typical indicator as shown in Figure 2.12.
Figure 2.12 Structure of Eriochrome Black T.
It contains two ionisable protons from two phenolic groups and can be represented as H2In.
The colour change at various pH ranges can be shown as:
H2In pH HIn2 pH In3
Û Û
Red 5.37.3 Blue 10.512.5 Yellowish-orange
The colour of this indicator in the pH range of 810 is blue due to HIn2 and it forms red complexes
with many metal ions. These colours are extremely sensitive. Thus, the colours of the dyes and
their metal complexes vary with pH. These facts, together with complex stability, must be
considered when deciding at which pH to carry out a titration. It is also essential to use a buffer
solution to maintain the required pH during the titration.
This can be used for the titration of Mg2+ with EDTA. A small amount of indicator is added to
the analyte solution and as a result a red complex due to MgIn is formed, while the colour of
uncomplexed indicator is blue. During titration of EDTA, the following reaction occurs at the end
point.
Mg2+ + H2In2 ® MgIn + H+
MgIn – + H 2 Y 2 MgY HIn H
2 2
Blue
+
Red Colourless
It is therefore recommed to carry out EDTA titration at pH range 810 while using Eriochrome
Black T as indicator.
2.7.4 Estimation of Calcium and Magnesium by Complexometric Titration by

EDTA
A known volume of solution containing Ca2+ and Mg2+ is taken in a conical flask. Ammonium
chloride and ammonum hydrooxide buffer solution is added to it to maintain its pH range 7 to 11.
A little amount of Eriochrome Black T is added to it and as a result a red solution due to
Ca-indicator and Mg-indicator is obtained. During titration with EDTA, the Ca2+ and Mg2+ get
displaced from their respective indicator complex to form Ca-EDTA and Mg-EDTA complex
leaving free indicator. The end point is marked by the sudden change of red colour of the solution
to blue colour.
In order to estimate only calcium ion, the magnesium ion is converted to stable Mg(OH)2 at
pH 13 by addition of stronger base like NaOH or diethyl amine. However, Eriochrome Black T in
this pH range connot be used as it imparts yellow to orange colour in this pH range so that the
sharp end point cannot be detected for this purpose. Another indicator specially calcon indicator
is used instead of Eriochrome Black T as it imparts blue colour at the pH range 13. During
titration with EDTA, Ca2+ from Ca-Calcon complex which gets displaced to form Ca-EDTA
complex and the end point is marked by sudden change of red colour due to Ca-Calcon complex
to blue colour due to free calcon.
Calculation
Let the volume of EDTA of strength 0.1 M be required to react completely (using Eriochrome
Black T indicator) with V ml of solution containing Ca 2+ and Mg2+ = V1 ml.
Let the volume of EDTA of the same strength be required to react completely with same volume
of solution (i.e. V ml) containing Ca2+ and Mg2+ at pH 13 = V2 ml Ca2+ (using calcon indicator) =
V2 ml.
The volume of EDTA required to react completely with Mg2+ ion = (V1 V2) ml.
We know that 1 mole of EDTA reacts with 1 mole of Ca2+ ion and 1 mole of Mg2+ ion.
\ 1000 ml of 1 M EDTA solution @ 1 mole of Ca2+ ion, i.e. = 40 g
40
\ V2 ml of 0.1 M EDTA solution @ 0.1 V2 g of Ca 2
1000
@ 0.004 ´ V2 g of Ca2+
Similarly,
1 mole of EDTA reacts with 1 mole of Mg2+ ion
\ 1000 ml of 1 M EDTA solution » 1 mole of Mg2+ ion, i.e. = 24 g
24
\ (V1 V2) ml of 0.1 M EDTA solution @ 0.1 (V1 V2 ) g of Mg 2 ions
1000
@ 0.0024 ´ (V1 V2) g of Mg2+ ion
2.8 PROBLEMS INVOLVED IN TITRIMETRIC METHODS
2.8.1 Problems on Acid-base Titration

PROBLEM 2.1 7.35 g of a dibasic acid was dissolved in water and diluted to 250 ml. 25 ml of
the solution neutralizes 15 ml of 1 N NaOH. Calculated the equivalent weight and hence molecular
weights of the acid.
Solution 25 ml of acid solution º 15 ml of 1 N NaOH
250 ml of acid solution º 150 ml of 1 N NaOH
Here w = 7.35 g, N2 = 1, V2 = 150

We know
w
1000 = N2V2
E
w 1000 7.35 1000
E= 49
N 2V2 1 150
Equivalent weight of the acid = 49

\ Molecular weight of the acid = Equivalent weight ´ basicity = 49 ´ 2 = 98
Determination of basicity of acid
PROBLEM 2.2 0.45 g of an acid of molecular weight 90 was neutralized by 20 ml of 0.5 N
caustic soda. What is the basicity of the acid?
Solution Here w = 0.45 g, N2 = 0.5, V2 = 20 ml
Let the equivalent of acid be E.
We know
w
1000 = N2V2
E
w 1000 0.45 1000
E= 45
N 2V2 0.5 20
Molecular weight 90
\ Basicity of the acid = 2
Equivalent weight 45
PROBLEM 2.3 A solution of HCl was standardized by titrating against sodium carbonate
solution 0.159 of anhydrous Na2CO3 requires 30 ml of the acid. Determine the normality of the
acid.
Solution Here, w = 0.159
E = Equivalent weight of NaCO3 = 53
V2 = 30 ml, N2 = ?
We know
w
1000 = N2V2
E
0.159 1000
= N2 ´ 30
53
0.159 1000
\ N2 = 0.1 N
53 30
\ Normality of the acid = 0.1 N
PROBLEM 2.4 What is the weight of oxalic acid required to neutralize 100 ml of normal
solution of NaOH?
Solution Let the weight of oxalic acid required be w g
Oxalic acid is a dibasic acid.
Hence
Molecular weight
Equivalent weight =
Basicity
90
= 45
2
We know
w
1000 = N2V2
E
N 2V2 E
\ w=
1000
Here, N2 = 1, V2 = 100
1 100 45
w= 4.5 g
1000
PROBLEM 2.5 Find the equivalent weight of a metal carbonate of 0.84 g which reacts exactly
with 40 ml of N/2 H 2SO4.
Solution We know
w
1000 = N2V2
E
0.84 1000
E= 42
0.5 40
Equivalent weight of metal carbonate = 42.
PROBLEM 2.6 Calculate the weight of NaOH required to neutralize 25 ml of 1 M H2SO4.
Solution 2NaOH + H2SO4 ¾® Na2SO4 + 2H2O
Let the weight of NaOH required be w g
Here, a = 2, b = 1, M = Molecular weight of NaOH = 40, M2 = 1, V2 = 25 ml
We know
a M 2V2 2 1 25 2 25
w M M 40 2g
b 1000 1 1000 1 1000
N
PROBLEM 2.7 1 g of an impure sample of CaCO3 is treated with 230 ml of HCl.
10
The residual acid requires 8 ml of 0.45 N NaOH for neutralization. Calculate the % of purity of
CaCO3 in the sample.
1
Solution Milliequivalent of HCl = 230 23
10
Milliequivalent of HCl remains unreacted = Milliequivalent of NaOH = 8 ´ 0.45 = 3.6
\ Milliequivalent of HCl reacted with CaCO3 = 23 3.6 = 19.4
Equivalent weight of pure CaCO3
E = 50
Let the amount of pure CaCO3 present in the sample = x gm
We know
x 1000
= N2V2
E
Here N2V2 = milliequivalent of HCl reacted with CaCO3
x 1000
\ = 19.4
E
19.4 50
\ x= 0.97
1000
1 g of impure CaCO3 contains 0.97 g of pure CaCO3
100 g of impure CaCO3 contains 97 g of pure CaCO3
% of purity of CaCO3 = 97
PROBLEM 2.8 0.21 g of a metal was treated with 100 ml of 0.5 N H2SO4 till the metal dissolves.
The residual acid requires 32.5 ml of normal caustic soda for complete neutralization. Calculate
the equivalent weight of the metal.
1
Solution Milliequivalent of H2SO4 initially added = 100 50
2
Milliequivalent of H2SO4 remains unreacted = Milliequivalent of caustic soda = 32.5 ´ 1 = 32.5
Milliequivalent of H2SO4 reacted with metal = 50 32.5 = 17.5
We know that
w 1000
= N2V2
E
Here, N2V2 = Milliequivalent of H2SO4 reacted with metal
0.21 1000
\ = 17.5
E
0.21 1000
\ E= 12
17.5
\ Equivalent weight of the metal = 12
N
PROBLEM 2.9 0.5 g of a limestone dissolved in 30 ml of HCl and the solution was made
10
N
up to 100 ml. 25 ml of this solution requires 2.5 ml of NaOH. Calculate the % of calcium
25
carbonate in the limestone.
1
Solution Milliequivalent of HCl added = 30 3
10
N
25 ml of the solution º 2.5 ml of of NaOH
25
N
\ 100 ml of the solution º 10 ml of of NaOH
25
Milliequivalent of HCl which,

N 1
Remains unreacted = Milliequivalent of of NaOH = 10 0.4
25 25
Milliequivalent of HCl reacted with calcium carbonate = 3 0.4 = 2.6
w
\ 1000 = 2.6
E
2.6 E
\ w=
1000
E = Equivalent weight of CaCO3 = 50
2.6 50
\ w= 0.13 g
1000
0.6 g of limestone contains 0.13 g of pure CaCO3
0.13
100 g of limestone contains 100 21.67 g of CaCO3
0.6
\ % of CaCO3 in the sample = 21.67%
PROBLEM 2.10 50 ml of 0.1 HCl is titrated against 0.1 N NaOH. Calculate the pH after
addition of
(i) 40 ml of NaOH
(ii) 60 ml of NaOH
Solution Given that
V = 50 ml, NA = 0.1, NB = 0.1
Let volume of NaOH required at the equivalence = x ml
\ x ´ NA = V ´ NB
x ´ NA = 50 ´ 0.1
50 0.1
x= 50 ml
0.1
(i) Volume of NaOH, y = 40, y < x
Milliequivalent of HCl = 50 ´ 0.1 = 5
Milliequivalent of NaOH added to 50 ml of 0.1 HCl = 40 ´ 0.1 = 4
\ Milli equivalent of HCl remain unreacted = 5 4 = 1
And the volume of the solution = 50 + 40 = 90 ml
1
\ Concentration of excess HCl = 0.011
90
Alternatively we may conclude that when the volume of NaOH (y) is less than that
required for equivalent point, then
V N A y NB
[Excess acid] =
Vy
50 0.1 40 0.1
=
50 40
54 1
= 0.011
90 90
pH = log [excess HCl]
= log 1.1 ´ 102
= 2 log 1.1
= 2 0.04 = 1.16
(ii) Volume of NaOH added = 60 ml
Milliequivalent of NaOH added = 60 ´ 0.1 = 6
Milliequivalent of NaOH remained in excess = 6 5 = 1
And volume of solution = 50 + 60 = 110 ml
1
Concentration of excess NaOH = 9.1 103
110
p(OH) = log [excess NaOH]
= log 9.1 ´ 103
= 2.04
\ pH = 14 2.04 = 11.96
Alternatively, if the volume of NaOH added with excess (Z) that required for equivalence
point (X ) i.e. when Z > X
Z N B VN A
[Excess NaOH] =
V Z
60 0.1 50 0.1 1
= 9.1 103
50 60 110
PROBLEM 2.11 50 ml of 0.1 M acetic acid (Ka = 1.75 ´ 105) is titrated against 0.1 M NaOH.
Calculate the pH at the start of titration and after the addition of 10 ml 50 ml of NaOH.
Solution It is a case of titration of weak acid (acetic acid) against strong base. Given V = 50 ml,
NA = 0.1 ml. The volume of NaOH required to reach the equivalence point
V NA 50 0.1
X 50 ml
NB 0.1
Calculation of pH at the start of the reaction
[H+] = K a Concentration of acetic acid

= 1.76 105 0.1 1.32 103
pH = log [H+] = log 1.32 ´ 103 = 2.88
pH after addition of 10 ml of NaOH = 10, y < x
V N A y NB
[Excess acetic acid] =
Vy
50 0.1 10 0.1 4 1
= M 0.067
50 10 60 15
CH3COOH + NaOH ¾® CH3COONa + H2O
y ´ NB milliequivalent of NaOH when react with acetic acid y ´ NB milliequivalent sodium acetate
will be formed
YN B 10 0.1 1
[CH3COO] = 0.017
V Y 50 10 60
[CH 3COO ]
pH = pK a log
[CH 3COOH]
5 0.017
= log 1.75 10 log
0.067
= 4.757 0.59
= 4.167
pH at equivalent value point, i.e. after addition of 50 ml of NaOH.
c = concentration of acetic acid at the equivalence point
pH = ½ pKw + ½ pKa ½ pc
VN A 50 0.1 5
c= 0.05 5 102
x V 50 50 100
pH = ½ ´ 14 + ½ ´ 4.76 ½ log 5 ´ 102 ( Pkw = 14)
= 7 + 2.38 + 0.7 = 9.45
PROBLEM 2.12 100 ml of 0.1 M aqueous ammonia (Kb = 1.8 ´ 105) is titrated with 0.1 M
HCl. Calculate the pH of the solution at the equivalence point and also indicate the indicator to be
used for such titration.
Solution It is a case of weak base titrated against string acid.
Volume of 0.1 M HCl required to reach the equivalence points
V NB 100 0.1
X 100 ml
VA 0.1
Volume of the solution at the equivalent point = 100 + 100 = 200 ml
So the pH at the equivalence point is given by the relation 7 ½ pKb + ½ pc, where c is the
concentration of ammonium hydroxide at the equivalence point c is given by the relation
V N B 100 0.1
c= 0.05
V x 100 100
pc = log (c) = log (0.05) = 1.3
pH = 7 ½ ´ 4.76 + ½ (1.3)
= 7 2.37 + 0.65 = 5.28
It is necessary to use an indicator with a pH range on the slightly, acid side (36.5) such as methyl
orange, methyl red, bromophenol blue or bromocreasol.
PROBLEM 2.13 100 ml of 0.1 M acetic acid (Ka = 1.8 ´ 105) is titrated with 0.1 M aqueous
ammonia (Ka = 1.8 ´ 105). Calculate the pH at the equivalence point. Give your comments on the
result.
Solution It is a case of titration of weak acid against weak base, so the pH of the solution at the
equivalence point = ½ pKw + ½ pKa ½ pKb = 7 + 2.37 2.37 = 7.
The pH of the solution at the equivalence point for the titration of weak base with weak acid is
the same as in the case of strong acid with strong bases.
2.8.2 Problems on Redox Titration

PROBLEM 2.14 5.5 g of a mixture of FeSO47H2O and Fe2(SO4)33H2O requires 5.4 ml of
0.1 N KMnO4 for complete oxidation. Calculate the amount of ferric salt in the mixture.
Solution KMnO4 oxidizes Ferrous salt to Ferric salt. Let the amount of Ferrous salt = w g
E = Equivalent wt of FeSO47H2O = Molecular weight of FeSO47H2O (since for the conversion
of ferrous to ferric, one electron is involved)
We know
w 1000
N 2V2
E
Given N2 = 0.1 and V2 = 5.4
0.1 5.4 Equivalent weight of FeSO 47H 2 O
\ w=
1000
0.1 5.4 275
= 0.15 g
1000
Amount of Fe2(SO4)33H2O = 5.5 0.15 = 5.35 g
PROBLEM 2.15 0.42 g of an iron ore is converted to ferrous form. It requires 42.0 ml of 0.1 N
solution of KMnO4 for complete oxidation. Find the % of iron in the ore.
Solution W = 0.42 g, N2 = 0.1, V2 = 42.0 ml
We know
w 1000
N 2V2
E
0.1 42 E
\ w
1000
Equivalent weight of ferrous iron = 56
0.1 42 56
\ w= 0.235 g
1000
4.2 g of iron ore contains 0.235 g of iron.

0.235
100 g of iron ore contains 100 56 of iron
4.2
% of iron in ore = 56%
PROBLEM 2.16 How many ml of 0.05 M KMnO4 is required to oxidize 20 ml of 0.1 M FeSO4
solution?
Solution MnO4 + 5Fe2+ + 8H+ ¾® Mn2+ + 5Fe3+ + 4H2O
Hence, a = 1, b = 5
M1 = 0.05, M2 = 0.1
V1 = ? and V2 = 20 ml
a
We know M1V1 = M 2V2
b
a M V
V1 = 2 2
b M1
1 0.1 20
= 8 ml
5 0.05
PROBLEM 2.17 A sample of K2Cr2O7 weighing 0.245 g is dissolved in water. The solution is
acidified and excess KI is added. The liberated iodine requires 50 ml of sodium thiosulphate
solultion for titration. Calculate the normality of sodium thiosulphate.
Solution Given w = 0.245, N2 = ? and V2 = 50
We know
w 1000
= N2V2
E
0.245 1000
= N2 ´ 50
49
0.245 1000
\ N2 = 0.1
49 50
PROBLEM 2.18 A sample of iron ore weighing 0.74 gm and containing 24% Fe2O3 is dissolved.
The ferric iron is reduced to Fe2+ by addition of 25 ml of 0.05 M SnCl2 solution. The excess of
SnCl2 is oxidized to Sn4+ using 0.05 M HgCl2. How many ml of HgCl2 solution is required?
0.74 24
Solution Amount of Fe2O3 = 0.1776 g
100
1 mole of Fe2O3 contains 2 mole of ferric iron
\ 160 g of Fe2O3 contains 2 ´ 56 = 112 g of ferric iron
112
0.1776 g Fe2O3 contains 0.1776 0.124 g = 0.124 g of ferric ion
160
2Fe3+ + Sn2+ ¾® Sn4+ + 2 Fe2+
Millimole of SnCl2 initially added = 25 ´ 0.05 = 1.25
Here a = 2, b = 1, w = 0.124
We have to find the millimole of SnCl2 required = M2V2
We know
w a
1000 M 2V2
M b
b w 1 0.124
\ M 2V2 1000 1000 1.11
a M 2 56
Hence, milliequivalent of excess SnCl2 = 1.25 1.11 = 0.14
Let the volume of 0.05 M HgCl2 required to oxidize the excess of SnCl2 be x ml
\ Millimole of HgCl2 required = x ´ 0.05
Sn2+ + 2Hg2+ ¾® 2Hg+ + Sn4+
\ 1 millimole of Sn2+ º 2 millimole of Hg
2
\ 0.14 millimole of Sn2+ = 0.14 0.28
1
x ´ 0.05 = 0.28
0.28
x= 5.6 ml
0.05
The volume of 0.05 M HgCl2 required = 5.6 ml
Analysis of calcium in limestone
PROBLEM 2.19 Calcium is determined in a limestone by precipitaing calcium as calcium
oxalate, CaC2O4. The precipitate is dissolved in H2SO4 and the resulting solution is titrated with
standard KMnO4. The calcium oxalate precipitate from a limestone sample weighing 0.448 g
requires 32 ml of 0.02 M KMnO4 for titration. Calculate the % of CaO in the sample.
Solution Millimole of KMnO4 required = 32.0 ´ 0.02 = 0.64
CaO + H2C2O4 ¾® CaC2O4 + H2O
CaC2O4 + H2SO4 ¾® CaSO4 + H2C2O4
2KMnO4 + 5H2CrO4 + H2SO4 ¾® K2SO4 + 2MnSO4 + 10CO2 + 8H2O
1 mole of CaO º 1 mole of H2C2O4
5 mole of H2C2O4 º 2 mole of KMnO4
or 5 millimole of CaO º 2 millimole of KMnO4
5
\ 0.64 millimole of KMnO4 º 0.64 = 1.60 millimole of CaO
2
Let the weight of CaO present in limestone be w
w
Millimole of CaO required for the above reaction = 1000
M
w
= 1000
Mole weight of CaO
w
= 1000
56
w
\ 1000 1.6
56
1.6 56 89.6
w 0.0896
1000 1000
0.448 g of limestone sample contains 0.0896 g of CaO
0.0896
\ 100 g of limestone sample contains 100 20
0.448
% of CaO in the sample = 20%
PROBLEM 2.20 The ion Xn+ is oxidized toXO3 by KMnO4 in acidic medium. 2.68 ´ 103
mole of Xn+ required 1.61 ´ 103 mole of MnO4. Find the value of n.
Solution 5(Xn+ + 3H2O + (5 n) e) ¾® XO3 + 6H+
(5 n)(MnO4 + 8H+ + 5e ¾® Mn2+ + 4H2O)
\ 5 mole of Xn+ º (5 n) mole of MnO4
5n
1 mole of Xn+ = mole of MnO 4
5
È 5 nØ 3
2.68 ´ 103 mole of Xn+ = É Ù 2.68 10 mole of MnO4
Ê 5 Ú
È 5 nØ 3
É Ù 2.68 10 = 1.61 ´ 103
Ê 5 Ú
1.61 5 8.05
5n= 3
2.68 2.68
n=2
PROBLEM 2.21 A solution of KMnO4 is 0.025 M. It is used for titration in a solution of
pH = 10, where MnO4 is reduced to MnO2.
(a) Write the half reaction that occurs. What is the normality of the solution?
(b) If the solution is used in 1 M NaOH the MnO4 is reduced to MnO42. Write the half reaction.
What is the normality of the solution?
Solution At pH = 10
MnO4 + 3e + 2H2O ¾® MnO2 + 4OH
In MnO4 oxidation state Mn is +7
In MnO2 oxidation state of Mn is +4
Number of electrons involved per MnO4 is 3
Normality of KMnO4 = Number of electrons involved per KMnO4 ´ molarity of KMnO4
= 3 ´ 0.025 = 0.075 N
At 1 M NaOH, the half reaction is
MnO4 + e ¾® MnO42
Number of electron involved per MnO42 = 1
Normality of KMnO4 = Number of electron involved per KMnO4 ´ Molarity
= 1 ´ 0.025 = 0.025 N

(i) Methyl Orange gives red colour in the case of
(a) Sodium carbonate solution (b) Sodium chloride solution
(c) Hydrochloric acid solution (d) Potassium hydroxide solution
(ii) Phenolphthalein does not act as an indicator for the titration between
(a) KOH and H2SO4 (b) Ba(OH)2 and HCl
(c) NaOH and acetic acid (d) Oxalic acid and KmnO4
(iii) When KMnO4 solution is titrated with a solution containing Fe 2+, the indicator used in the
titration is
(a) Phenolphthalein (b) Methyl orange
(c) Methyl red (d) None of these
(iv) Starch can be used as an indicator for the defection of trace of
(a) Glucose in aqueous solution (b) Protein in blood
(c) Iodine in aqueous solution (d) Urea in blood
(v) In the titration of oxalic acid using KMnO4 in acidic medium, the best indicator is.
(a) Phenolphthalein (b) Starch
(c) Methyl orange (d) KMnO4
(vi) The indictor used in the titration of iodine against sodium thiosulphate is
(a) KI (b) K2CrOH
(c) K3[Fe(CN)6] (d) Starch
(vii) 10 ml of 1 M NaOH solution will neutralize
(a) 2.5 ml (b) 5 ml
(c) 10 ml (d) 20 ml of 1 M H2SO4
(viii) The indicator methyl orange works in the pH range
(a) 3.55 (b) 12
(c) 810 (d) 46
(ix) In the presence of dil H2SO4, the equivalent of dichromate is
(a) ½ of its molecular weight (b) 1/6 of its molecular weight
(c) 1/10 of its molecular weight (d) ¼ of its molecular weight.
(i) In the titration of strong acid with strong base, both the titrant and analyte are strongly
ionised.
(ii) A titration curve is plotted by plotting pH of the solution as a function of volume of the
titrand added.
(iii) An indicator for acid-base titration is a weak acid or weak base whose colour of ionised
form is different from that of unionized form.
(iv) pH titration range required to go from one colour to the other is 2 pH units.
(v) If we use phenopthalein as an indicator in a titration of Na2CO3 with HCl, the usual result
is no visible change occurs.
(vi) No indicator can be used for the titration of a weak acid against a weak base.
3. Fill in blanks
(i) The colour of the indicator methyl orange in acid medium is .............. .
(ii) A solution containing a known weight of the substance in a definite volume of it is called
.............. .
(iii) Murexide, a metal indicator is used in .............. titration.
(iv) At equilibrium, the potential of each half reaction is .............. .
(v) In redox reaction, the value of Kredox should exceed .............. value.
(vi) A potential change of .............. volt is needed for a redox titration.
(vii) KMnO4 is an example of .............. indicator.
(viii) Starch is .............. indicator.
(ix) 10 ml of 1 M NaOH solution will be neutralized by .............. ml of 1 M H 2SO4.
(x) When 100 ml of N NaOH solution and 100 ml of 5 M sulfuric acid solutions are mixed
together, the resulting solution will be .............. .
(xi) When 10 ml of 10 M solution of H2SO4 and 100 ml of 1 M solution of NaOH are mixed,
the resulting solution will be .............. acidic.
(xii) The pink colour of the phenolphthalein in alkaline indicator is due to its .............. form.
(xiii) If 10 ml of a monoacid base exactly neutralizes 50 ml of an acid, the normality of an acid
is .............. .
(xiv) Titration with a chelating agent is .............. .
B. Very Short Answer Type Questions

(i) Define titration.
(ii) Distinguish between titrant and titrand.
(iii) Distinguish between end point and equivalence point.
(iv) What is meant by titration error?
(v) What do you mean by an indicator?
(vi) Define standard solution.
(vii) Define primary standard.
(viii) Give at least two examples of primary standard.
(ix) What is meant by standardization?
(x) Give at least two examples of secondary standard.
(xi) What are various types of titrimetric analysis?
(xii) Define acidimetry and alkalimetry.
(xiii) Name at least two indicators used in acid-base titration.
(xiv) Name the indicator used for the titration of weak acid against weak base.
(xv) Define oxidimetry and reducimetry.
(xvi) What is the minimum value of DE° for redox titration.
(xvii) Under what condition the redox titration curve is asymmetric about the equivalence point.
(xviii) Name the various ways of locating the redox titration end point.
(xix) Names the various types of indicators used in redox titration to detect the end point.
(xx) Define redox indicator.
(xxi) What is a metal indicator?
(xxii) What is meant by a chelate?
(xxiii) What is the pH range of methyl orange as indicator?
(xxiv) Which indicator can be used in the titration of strong acid with strong base?
(xxv) Which indicator is used in the titration of Na2CO3 and HCl?
(xxvi) Which indicator can be used in the titration of oxailic acid with a carbolic soda?
C. Short Answer Type Questions

(i) What are the requirements for a primary standard?
(ii) What are the requirements for a secondary standard?
(iii) Show that at equivalence point N1V1 = N2V2, where V1 ml of analyte of strength N1 reacts
with V2 ml of a titrant of strength N2.
(iv) What are the conditions for titrimetric analysis?
(v) What do you know by colour change interval of an indicator?
(vi) How would you detect the end point of an acid-base titration by pH method?
(vii) What are the factors affecting the pH curve for acid-base titration?
0.355
(viii) Show that the minimum value of DE º for redox titration is V.
n
(ix) What are the factors affecting redox titration curve?
(x) What do you mean by specific visual indicator? Explain the action of starch as specific
indicator.
(xi) Explain iodimetry.
(xii) Explain iodometry.
(xiii) Explain the basis of selection for redox indicator for a redox titration.
(xiv) Mention various conditions for complexometric titration.
6. Give reasons
(i) KMnO4 can not be used as primary standard.
(ii) I2 is used as secondary standard.
(iii) The reaction between ethyl alcohol and acetic acid is unsuitable for titration.
(iv) Thiosulphate ion(II) can not be titrated against KMnO4 solution.
(v) Phenolphthalein solution, which is colourless, becomes pink on addition of a strong base.
(vi) Methyl orange solution turns red on addition of hydrochloric acid.
(vii) Boric acid cannot be titrated against NaOH.
(viii) Methyl orange cannot be used as an indicator for the titration of acetic acid against NaOH.
(ix) Phenolphthalein cannot be used as an indicator for the titration of NH4OH against HCl.
(x) Redox titration curve can be generated through electrochemical potential for either titrant
or the reactant.
(xi) KMnO4 solution can be used as self indicator.
(xii) Why does the typical acid-base indicator exhibit its colour change over a range of 2pH
units?
D. Long Answer Type Questions

7. What are acid-base indicators? Explain the action of phenolphthalein and methyl orange
as acid-base indicators.
8. Discuss the theory of titration of strong acid with a strong base. Give your comments on
the nature of pH curve and the indicators to be used for such a titration.
9. Discuss the theory of titration of weak acid with a strong base. Give your comments on the
nature of pH curve and the indicators to be used for such a titration.
10. Discuss the theory of titration of weak base with a strong acid. Give your comments on the
nature of pH curve and the indicator to be used for such a titration.
11. Discuss the theory of oxidation-reduction (or redox) titration. How would you detect the
end point of such a titration?
12. Discuss the theory of complexometric titration. How would you detect the end point of
such a titration involving complexation of EDTA with a metal ion indicator.
CHAPTER 3
Quantitative Analysis
Precipitation Gravimetry
3.1 INTRODUCTION
Gravimetry encompasses all techniques in which we measure weight or change in weight.

It includes:
(a) Precipitation gravimetry
(b) Electrogravimetry
(c) Volatilization gravimetry
(d) Particulate gravimetry
Only precipitation gravimetry is discussed in this chapter.
3.1.1 Precipitation Gravimetry

This is an analytical technique in which the amount of an analyte of a sample can be determined by
selectively converting into an insoluble form (called precipitate) by addition of a precipitating
agent (or precipitant) to the solution of the analyte. The precipitate is then filtrated, washed free of
impurities and either weighed as such after drying or is weighed after ignition to another substance
of known composition. From the weight and knowledge of its chemical composition, the weight of
the analyte can be calculated based on gravimetric calculation and gravimetric factor as follows.
3.1.2 Gravimetric Calculation and Gravimetric Factor

A gravimetric method of analysis is based on a chemical reaction such as
aA + rR ¾® AaRr
where a moles of analyte, A, are converted to a new substance AaRr by reacting with r moles of a
reagent, R. The substance, AaRr, is usually slightly soluble in water and is known as precipitate.
This can be weighed as such after drying or can be ignited to another substance of known
composition and then weighed. Suppose the substance is weighed as such after drying and let its
weight be w p.
Let the weight of the sample be w s gm and let it contains w A gm of the analyte, then
101
wt of analyte
% of analyte = 100
wt of sample
wA
= 100
ws
To calculate the weight of analyte, wA, from the weight of precipitate, w p, a parameter called
gravimetric factor is often employed.
Gravimetric factor (GF)
It is defined as the number of grams of an analyte in one gram of a precipitate weight of analyte in
gram, i.e.
w A = wt of precipitate in gram ´ gravimetric factor
= wp ´ (GF)
If wA gram of analyte be present in w s gram of the sample, then
wA
% of analyte = 100
ws
wp (GF) 100
=
ws
Gravimetric methods though time consuming yet provide precise and accurate results and have
found a wide utility in chemical analysis for many years. The analysis of rocks, ores, soils,
metallurgical and other inorganic sample for their major components is usually carried out by
gravimetric method.
3.1.3 Requirements for Successful Gravimetry

The following requirements should be met in order that the gravimetric method be successful.
(i) The precipitation process should be sufficiently complete so that the quantity of analyte
left unprecipitated is 0.1 mg or less in determining major constituent of a macro sample.
(ii) The substance weighed should have a definite composition and should be pure or very
nearly so. Otherwise erroneous result may be obtained.
(iii) The precipitate should be sufficiently insoluble so that the amount lost due to solubility
will be negligible.
3.1.4 Steps Involved in Gravimetric Analysis

The various steps involved in precipitation gravimetry, after the sample has been dissolved an the
solution is prepared in proper form for precipitation, are:
(a) Precipitation (b) Digestion
(c) Filtration (d) Washing
(e) Drying and/or Incineration (f) Weighing
Quantitative Analysis—Precipitation Gravimetry 103
3.2 PRECIPITATION
3.2.1 Definition of Precipitation

The process of conversion of an analyte into its insoluble precipitate by adding suitable precipitating
agent (precipitant) is called precipitation. In order to be of gravimetric value, the precipitation
process must fulfil the following conditions.
3.2.2 Conditions of Precipitation

(i) The precipitate must be formed quantitatively and within reasonable time. It must have a
low solubility otherwise complete precipitation does not take place.
(ii) The solubility of the precipitate should be low enough for a quantitative separation to be
made.
(iii) The precipitate should consist of crystals of large particle size so that it can be filtered
easily as it will not clog the filter pores.
(iv) It must have a stable stoichometric composition when dried so that its weight can
be related to the amount of analyte. For example, silver is precipitated as silver
chloride dried at 130150° C and weighed as silver chloride. If not so, it must be possible
to convert the precipitate to a stoichiometric weighable form usually by ignition.
For example, magnesium is precipitated as ammonium magnesium phosphate
Mg(NH4)PO4 · 6H2O which is ignited to get stable magnesium pyrophosphate (Mg2P2O7).
However, in both the cases the weighed form must be non-hygroscopic.
(v) Ideally the precipitate should have larger molecular weight so that errors in weighing
may be reduced.
(vi) As far as possible conditions are to be made (by adjusting the pH, or temperature) so that
a precipitant specifically precipitates only one cation or anion in a mixture of ions present
in a solution. For example, 8-hydroxyquinoline (oxine) can be used to precipitate a large
number of metallic cations. But by the control of pH, the cations can be precipitated
selectively. Thus, Al3+ can be precipitated at pH 4. At this pH the concentration of anion
form of oxine is too low but only suitable for precipitate Al3+ ion.
3.2.3 Theories of Precipitation

The following theories for precipitation have been put forth for the formation of pure and filterable
precipitate as its formation is of major importance in gravimetry.
(a) Solubility product principle: When the ionic product of a compound exceeds its solubility
product, precipitation occurs.
(b) Particles size and filterability of the precipitate: The size of the particles of the
precipitate plays a prominent role in deciding the filterability of the precipitate. It mainly
depends on two important events such as nucleation and particle growth, which occur
during precipitation. Nucleation means the initial formation of the smallest particle of the
precipitate capable of spontaneous growth. The smallest particle of the precipitate is known
as nucleus. Particle growth means the growth of initial nucleus by deposition of other
precipitate particles to form a crystal of certain geometrical shape. If the rate of nucleation
is small compared to the rate of growth of nuclei, a fewer particles are finally produced and
these particles are relatively large in size so that they can be easily filtered off. Hence the
analyst has to adjust the conditions during precipitation so that the rate of nucleation is
small compared to the rate of particle growth. The conditions are derived from
von Weimarns theory of relative supersaturation as given below.
von Weimarns theory of relative supersaturation
Supersaturation means a stage at which the solution phase contains more of the dissolved solute
than that in its saturated solution as shown in Figure 3.1 (region AB). It is a temporary condition
and supersaturation stage is lost when precipitation starts. This is brought by addition of crystal of
solute usually termed as seeding (region BC). According to the von Weimarns theory, the particle
size of the precipitate is inversely proportional to relative supersaturation (RSS) defined as
AB
RSS =
B
where A is the actual concentration of the solute when precipitation begins due to addition of
precipitant and B is the equilibrium concentration of the solute in saturated solution. The term
AB
A B represents the degree of supersaturation. The ratio is also called von Weimarns ratio.
B
Since the particle size of the precipitate is inversely proportional to RSS, it is evident that the size
of the particle will be large if RSS is small. Hence in order to get the particle of a larger size the
AB
conditions are to be adjusted to make the von Weimarns ratio as small as possible.
B
Figure 3.1 Solubility behaviour.
Selection of conditions of precipitation from von Weimarns theory

von Weimarns ratio should be made as small as possible. This is achieved by making A low or
B high.
Conditions for making A low
(i) Diluted solutions are to be used to reduce supersaturation.
(ii) The precipitating agent should be added dropwise with stirring.
Conditions for making B high
(i) Heating the solution to an elevated temperature and thus carrying out precipitation in hot
solution.
(ii) By adjusting pH of the solution and precipitating at low pH as possible.
(iii) By using complex forming agent.
For example, salts of weak acids such as calcium oxalate, CaC2O4 and zinc sulphide, ZnS are
better precipitated in weakly acidic rather than alkaline solution, BaSO4 is better precipitated in
0.01 M to 0.05 M HCl solution, since B is increased by the formation of bisulphate ion. There are
certain compounds such as hydroxides of Fe(III), Al(III), and Cr(III) which are insoluble even in
AB
acid solution so that the value of is still large resulting gelatinous precipitate formation.
B
However, a dense precipitate of above ions can be obtained by the process of homogenous
precipitation as discussed below.
3.2.4 Homogeneous Precipitation

This is a technique in which the precipitating reagent is not added but slowly generated within the
solution by a homogeneous chemical reaction. As the solvent remains homogeneous with respect
to both the ions of the reactant and the reagent (precipitant) at all times during the process of
precipitation, hence the name of the technique is called homogeneous precipitation. This process
leads to both large and pure particles of a precipitate minimizing supersaturation. This technique
involves two methods such as (i) anion-releasing method and (ii) cation-releasing method as
discussed below.
Anion-releasing method
In this method anions are slowly generated which then combine with cations to form precipitates.
Some of the examples of slow generation of anions acting as precipitant are given below.
(a) Generation of hydroxide anions: Hydroxide anions are generated by the hydrolysis of urea.
Urea is a weak base (Kb = 1.5 ´ 1014) and hydrolyses rapidly at 90100ºC.
Generation reaction:
The OH ions generated combine with Al3+, Fe3+ and Th4+ to form the precipitates of their hydroxides
or basic salts.
Advantage: Hydroxides of Fe3+ and Al3+ are bulky gelatinous masses which are heavily
contaminated and difficult to filter when they are formed by direct addition of base. In contrast, the
same products are dense, easily filterable in pure form when they are produced by homogeneous
generation of hydroxide ions.
(b) Generation of oxalate (C2O42) anions: An acid solution containing hydrogen oxalate ion,
HC2O4 can be made to ionize slowly with the addition of urea forming oxalate ion, C2O42 and
raising the pH of the solution. Under the condition calcium ions can be precipitated as a dense
precipitate of calcium oxalate.
Generation reaction:
Dimethyl oxalate and diethyl oxalate can be hydrolyzed to form oxalate ions which can be used to
precipitate Ca2+, Mg2+, Zn2+ and Th4+ as oxalates.
(c) Generation of sulphate ion, SO42: Sulphate ions are generated by hydrolysis of sulphamic
acid or dimethyl sulphate as follows:
Homogeneous precipitation of BaSO4, PbSO4, SrSO4, PbSO4 are produced by the use of the above
reactions.
(d) Generation of phosphate ion, PO43: Phosphate ions, formed by the stepwise hydrolysis of
dimethyl or trimethyl phosphate, can be used to precipitate insoluble metal phosphates.
+ 3H2O ¾® PO43 + 3H+ + 3CH3OH
The above reaction finds application in the homogeneous precipitation of zirconium or Hafnium
as phosphates. Thus 18 M sulphuric acid solution containing Zirconyl ions, ZrO2+ on heating
with trimethyl phosphate solution form a dense precipitate, which is filtered, ignited and weighed
as zirconium pyrophosphate, ZrP2O7. Meta phosphoric acid can also be used as it reacts in warm
acid solution to form phosphate ion.
Cation-release method
In this method, cations are slowly generated when they combine with anions to form precipitates.
An interesting example of this is the precipitation of SO42 by the soluble Ba-EDTA 1:1 complex in
the presence of hydrogen peroxide, H2O2. The peroxide at 80ºC liberates Ba2+ ions by oxidizing
the organic ligand (here EDTA). The generated Ba2+ ions then react with SO42 ions to form
precipitates of BaSO4. As the reaction proceeds slowly, precipitates of large particle size are produced
which can be easily filtered. Thus local supersaturation is avoided.
Advantages
(i) Precipitation from homogeneous solution avoids high local supersaturation, which is the
case when a precipitating reagent is directly added to the solution.
(ii) By changing the rate of chemical reaction and producing the precipitate in the
homogeneous solution, the required particle size of the precipitate can be obtained.
(iii) Contamination of the precipitate can be avoided.
3.2.5 Contamination of the Precipitate

The precipitate obtained from gravimetry process is always contaminated with other ions present
in the solution. The main causes of contamination are:
(a) Coprecipitation and
(b) Postprecipitation
Coprecipitation
The process by which a precipitate gets contaminated by substances, which are normally soluble
in the mother liquor, is called coprecipitation. For example, the addition of BaCl2 solution to a
solution of Na2SO4 precipitates BaSO4 contaminated with a significant amount of Na2SO4 and
NaHSO4 even their sodium salts are soluble in water. Thus coprecipitation is a precipitation of
soluble substance along with an insoluble precipitate.
Mechanism of coprecipitation
Coprecipitation may occur in one or more of the following ways:
(i) Inclusion
(ii) Occlusion
(iii) Surface adsorption
Inclusion
It involves the random distribution of contaminated ions or molecules throughout the lattice sites
of the precipitate. It may be isomorphic or non-isomorphic as discussed below.
Isomorphic inclusion
It involves the replacement of one of the ions in the crystal lattice of the precipitate by a contaminating
ion. For this type of exchange to occur, both the ions should have the same charge and nearly the
same size. For example, in the precipitation of Mg2+as magnesium ammonium phosphate.
MgNH4PO4, K+ ion has nearly the same size as that of NH4+ so that it can replace it to form
magnesium potassium phosphate, MgKPO4. BaSO4 formed by adding BaCl2 to a solution containing
sulphate, lead and acetate ions is found to be severely contaminated by PbSO4 even in the presence
of acetate ion, which normally prevents precipitation of PbSO4 by complexing the Pb2+ ions. This
is because the Pb2+ ions replace Ba2+ ions in the BaSO4 crystal. This process is known as mixed
crystal formation. Other examples of coprecipitation by mixed crystal formation include SrSO4 in
BaSO4 and MnS in CdS.
Non-isomorphic inclusion: Inclusion is non-isomorphic when the lattice dimension of the ions
forming the precipitate and that of contaminant ions are different. Under such conditions inclusion
appears to from a solid solution. The contamination of BaSO4 with alkali nitrate is an example of
non-isomorphic inclusion. Inclusion in general is a troublesome problem and only way to minimize
it is through reprecipitation.
Occlusion
In this process the ionic impurities get entrapped within crystal. It involves the non-homogeneous
distribution of contaminant ions or molecules within imperfection of crystal lattice of the precipitate.
For example, crystalline precipitates such as BaSO4 sometimes adsorb impurities when the particles
are small. As the particles grow in size, the impurity may become enclosed in the crystal. Occluded
impurities cannot be removed by washing the precipitate.
Less soluble ions are occluded most. For example, nitrate ions are occluded on barium sulphates
more strongly than chloride ion, because barium nitrate is less soluble than barium chloride.
This is prevented by (a) decreasing the rate of precipitation and (b) digestion after precipitation.
Surface adsorption
It is a mode of coprecipitation involving adsorption of the contaminants to the surface of the
precipitate.
Causes: The surface of the precipitate has either positive or negative charges. These may attract
the contaminant ions from the mother liquor so that these ions get adsorbed on the surface of the
precipitate and thereby the precipitate is contaminated. This process of adsorption is governed by
a law called Paneth-Fajan-Hahn law stated as follows:
Paneth-Fajans-Hahn law: This law states that a precipitate preferentially adsorbs that ion which
forms least soluble compound with its lattice ion. For example, calcium oxalate preferentially
adsorbs magnesium ions more than sodium ions because magnesium oxalate is less soluble than
sodium oxalate. Thus ion adsorption is selective and it depends on the (a) nature of electrostatic
attraction, (b) concentration of ions in solution, (c) size of the ion and (d) solubility as indicated by
the Paneth-Fajans-Hahn law.
Illustration of surface adsorption
Surface adsorption in case of AgCl precipitate: When AgNO3 solution is added to a solution
containing Cl ions, the initial precipitate of AgCl adsorbs Ag+ ions to form positively charged
[(AgCl)Ag]+ ions. In this case Ag+ ions form layer around AgCl called primary adsorption layer.
NO3 ions from the solution get adsorbed to [(AgCl)Ag]+ ion as counter ions forming a secondary
layer shown in Figure 3.2. Thus AgCl gets contaminated forming [(AgCl)AgNO 3].
In other words AgNO3 which is soluble in water gets coprecipitated with AgCl due to surface
adsorption phenomenon.
Figure 3.2 Surface adsorption in case of AgCl precipitate.
Surface adsorption in case of arsenic sulphide, As2 S3

When As2S3 is precipitated by passing H2S through an acidic solution of AsCl3, the adsorbed ions
are S2 ions and the counter ions are hydronium ion, H3O+. However, in the above process if AsCl3
solution contains ZnCl2, the primary layer is of S2 ion whereas the secondary layer will be of Zn2+
ions so that As2S3 gets contaminated with ZnS. In the former case, the contaminants can be removed
on ignition as they get volatilized as H2O and H2S while in the latter case it is difficult to remove
ZnS even on ignition as it is non-volatile. Thus one may conclude that adsorption coprecipitation
depends on the nature of adsorbed ion and counter ions.
Procedure for minimizing surface adsorption
(i) By washing the precipitate: Since the adsorbed impurities are on the surface of the
precipitate particles, they can be removed by washing.
(ii) By Digestion: Digestion leads to increase in the particle size and decreases in the overall
surface area to volume ratio so that surface adsorption can be minimized.
Postprecipitation
Sometimes when the precipitate is allowed to stand in contact with mother liquor, a second substance
(impurities) will slowly form a precipitate with precipitating agent.
The process by which an impurity is precipitated after the precipitation of the desired substance
(primary precipitate) is called postprecipitation.
Causes
The solution becomes supersaturated with respect to precipitate of the impurities. The primary
precipitate actually becomes a nucleus for the postprecipitation of impurities from these
supersaturated solution.
Examples of postprecipitation
(i) When an acid solution of ammonium oxalate is added to an acidified solution containing
Ca2+ and Mg2+ ions, calcium oxalate separates out as the primary precipitate. Magnesium
oxalate does not immediately precipitate since it tends to form supersaturated solution.
Magnesium oxalate will slowly precipitate on the primary precipitate of calcium oxalate
if the solution is allowed to stand for longer period.
(ii) Similarly, if H2S is passed into acid solution of a mixture of Cu2+ and Zn2+ ions, only
CuS will be precipitated initially but if it is left in contact with the solution for a longer
time, ZnS will also be precipitated.
Factors affecting postprecipitation
(i) Temperature: It increases at high temperature.
(ii) Time: It increases with time.
Procedure for avoiding postpecipitation
(i) The primary precipitate may be filtered off as quickly as possible.
(ii) The acidity of the solution should be regulated and the ions likely to be postprecipitated
should be protected by complex formation.
(iii) It may be redissolved and reprecipitated as before.
(iv) The addition of finely divided solids like silica gel BaSO4 and broken glass reduces
postprecipitation. For example, postprecipitation of ZnS on CuS can be slowed down by
the addition of Al3+ ion or sulphur compound such as cystein.
Comparison between postprecipitation and coprecipitation
Postprecipitation Coprecipitation
(i) Contamination due to this increases (i) Contamination due to this decreases with
with time time
(ii) Contamination is enhanced on ignition (ii) It is not enhanced on ignition
(iii) Extent of contamination is large (iii) Extent of contamination is less compared
to postprecipitation
3.2.6 Errors in Precipitation

Coprecipitation is often a serious source of errors. Coprecipitated impurities cause either positive
or negative errors in analysis. If the contaminant is not a compound of the ion being estimated,
positive errors will always result. Thus a positive error is observed when colloidal AgCl adsorbs
AgNO3 during the chloride analysis. On the one hand, when the contaminant contains the ion
being estimated, either positive or negative errors may be observed. For example, in the estimation
of Ba2+ ions by precipitation as BaSO4, occlusion of other barium salts occurs. If the occluded
contaminant is Ba(NO3)2, a positive error will be observed because the compound has a formula
weight larger than BaSO4 that would have formed if there is no coprecipitation. If, on the
other hand, if BaCl2 is the occluded contaminant, a negative error would arise because the formula
weight is less than that of BaSO4.
Errors arising from the coprecipitation may be minimized in the following ways:
(i) The relative supersaturation (RSS) is kept as low as possible to ensure the formation of
large crystals so that coprecipitation due to surface adsorption is minimized. This is
achieved by adding precipitant slowly while stirring constantly to a hot dilute solution of
the ion to be estimated.
(ii) Coprecipitated contaminants due to surface adsorption are removed by washing with a
liquid containing a small amount of volatile electrolyte.
(iii) Contamination by occluded impurities in the case of crystalline precipitate is minimized
by digestion. Digestion also helps in the formation of large coagulated particles instead
of colloidal precipitates.
(iv) Dissolving the precipitate and re-precipitating is helpful in minimizing contamination.
(v) Precipitation for homogeneous solution is resorted to keep the relative supersaturation
low.
3.3 DIGESTION (AGEING)
The process of allowing the precipitate to stand either at room temperature, at low flame or on a
water bath (depending upon the nature of precipitate) for a few hours 1224 (sometimes overnight)
along with mother liquor is called digestion (or aging).
3.3.1 Reasons for Digestion

(i) Complete precipitation takes place.
(ii) Granular dense precipitate in a readily filterable form is obtained.
(iii) Any contaminant which may be trapped along with the precipitate escapes and a purer
crystal results.
(iv) Promotes the formation of regular crystals shape with lesser surface area so that
coprecipitation by adsorption would be less.
(v) If the precipitate is colloidal in nature, the Brownian motion prevents settling down the
precipitate particles under the influence of gravity. Digestion causes the individual colloidal
particles to coagulate or agglomerate to give a filterable non-crystalline mass that rapidly
settles down.
3.4 FILTRATION
It is the process of separation of the precipitate from its mother liquor. It is carried out by means of
filtering devices, which include funnels, filter paper and filtering crucibles. In this process the
precipitate remains on the filtering device while the mother liquor passes through it.
The most commonly used filters are
(i) Sintered-glass crucibles,
(ii) Gooch crucibles and
(iii) quantitative filter papers which are ashless known as Whatman filter paper.
These papers are manufactured in various grades of porosity for different types of precipitates as
shown in Table 3.1.
Table 3.1 Characteristics of Whatman filter papers

Grade Types of precipitate Filter speed
NO 42 Very fine crystalline precipitate (e.g. BaSO4) Slow
NO 41 Gelatinous or large crystals (e.g. Fe2O3·H2O) Fast
NO 40 Small- or medium-sized particles (e.g. AgCl) Medium
The ashless papers are used for quantitative works in which the paper is ignited away and leaving
a precipitated suitable for weighing.
The filter paper is folded in the shape of a cone
with the overlap edges of the two quarters not quit
meeting (1/8 inches apart). It is fitted to a glass
funnel of proper size, which is mounted, on a filter
stand. By fitting the filter paper properly, the
formation of air bubbles can be avoided and the
rate of filtration can be increased.
The sintered-glass crucibles are normally
available in three porosity that are labeled as F, M
and C for fine, medium and coarse. The crucible is
usually fitted with an adapter and mounted on a
filtering flask which is connected to a vacuum pump
through a trap. Figure 3.3 illustrates the
experimental set up for filtration using the sintered
crucible.
Figure 3.3 Filtration using sintered crucible.
Depending upon the nature of precipitate, various
filters are used in filtration. For example,
if the precipitate is to be simply dried and weighed, sintered-glass crucibles are to be used. On the
other hand, if the precipitates require, ignition ashless filter papers are generally used.
The precipitates collected in a filter paper are transferred to a silica or porcelain crucible for
ignition.
3.5 WASHING OF THE PRECIPITATE
The precipitates usually carry impurities on their surface. Further these are wet with mother liquor.
These surface impurities and mother liquor can be removed by washing the precipitate after filtering.
The washing liquid should have the following qualities.
3.5.1 Ideal Qualities of a Washing Liquid

(a) It should not have the tendency to dissolve the precipitate but have the tendency to dissolve
the impurities adhered to the precipitate.
For example, organic solvents like ethanol and ether may be used for washing.
(b) It should have no peptizing action upon the precipitate. Peptization means the reverse of
coagulation, i.e. the precipitate reverses to colloidal state. As the pure water may cause
peptization of a precipitate, washing the precipitate by pure water is not preferred.
(c) It should not undergo any chemical reaction with the precipitate.
(d) It should be dilute solution of an electrolyte. The electrolyte used for washing the precipitate
must be volatile at the temperature at which drying or ignition is done. For example, dilute
nitric acid is used as the wash solution for AgCl obtained by addition of AgNO3 solution to
a solution of KCl. The nitric acid replaces the adsorbed layer of the precipitating agent and
is volatilized at the drying temperature of AgCl. Further as far as possible, the electrolyte
should have a common ion with the precipitate so that solubility error is reduced.
For example, dilute ammonium oxalate solution is used for washing calcium oxalate. KNO3
solution cannot be used as it is a non-volatile. However, NH4NO3 can be used as a washed
electrolyte for ferric oxide as it is decomposed to NH3 · HNO3 · N2 and oxide of nitrogen
when the precipitated is dried by ignition at high temperature.
(e) It should not contain any such substance which may interfere with subsequent determination
in the filtrate.
Dilute solution of ammonium salts, ammonia and dilute acids are usually used as wash solution
in order to fulfil the above conditions. Wash solutions fulfilling the above conditions are mainly of
three types as given below.
3.5.2 Types of Wash Solution

1. Solutions, which do not allow the precipitate to become colloidal and pass through
the filter. This tendency is observed in case of gelatinous or flocculated precipitates.
A solution of electrolyte like an ammonium salt is used for washing such precipitate.
For example, dilute ammonium nitrate is employed for washing ferric hydroxide, which is
gelatinous.
2. Solutions, which have the tendency to reduce the solubility of the precipitate. If the wash
solution has anion common to an ion of the precipitate, the solubility of the precipitate
would be less in wash solution. For example, dilute ammonium oxalate is used for washing
calcium oxalate.
3. Solution which do not allow the hydrolysis of precipitate which is a salt of weak acid and
bases. If the precipitate is a salt of weak acid, it has the tendency to undergo hydrolysis to
produce base. The wash liquid must therefore be a basic so that hydrolysis is prevented. For
example, MgNH4PO4 hydrolysis to yield HPO42 and OH ion and therefore it should be
washed with dilute aqueous ammonia which produces OH ion to prevent hydrolysis of
MgNH4PO4.
3.5.3 Mode of Washing

In addition to the choice of suitable wash liquid, the mode of washing is also equally important.
The following procedures are adopted.
1. Using a set of wash liquid, the precipitate on the filter paper should be thoroughly stirred.
This should be followed by washing the edges of the filter paper with the set of wash liquid
since the precipitate might spread out during washing.
2. A large number of washes with a small volume of wash liquid is more efficient to remove
the impurities than a small number of washes with a large volume of wash liquid.
3. If the precipitate is almost insoluble under hot condition, hot wash solutions are preferred
due to greater solubility of impurities and increased speed of filtration.
4. Filtration and washing must be simultaneous otherwise, the precipitate would become dry
and washing would become difficult.
The substance to be weighed must be pure, stable and of definite composition for the result of
analysis to be accurate. These requirements are achieved if precipitates which are collected by
filtration and washing are either dried or incinerated.
3.6 DRYING AND/OR INCINERATION OF THE PRECIPITATE
The precipitate of the substance usually contains the following:

(i) Superficially adherent water.
(ii) Occluded water, present in the cavities within the crystal or in solid solution.
(iii) Adsorbed water, present on the solid surfaces. These depends upon the humidity of the
atmosphere.
(iv) Essential water, present as water of crystallization as in case of CaC 2O4·H2O
·Mg(NH4)PO4·H2O etc.
The main purpose of drying is either to remove water (present in different forms with the precipitate)
or convert the precipitate to a weighable form.
3.6.1 Conditions of Drying

Drying should be done at a temperature at which electrolyte associated with the precipitate is
completely volatilized. Two cases may arise.
In the first case, the precipitate obtained after drying may have known and definite composition
so that it can be in weighable form. In most of the cases such precipitates are formed by organic
precipitant. For example, the red precipitate of nickel dimethyl glyoxime formed by the reaction of
Ni2+ with dimethyl glyoxime can be weighed as such after drying. In such case sinter glass crucibles
are used for filtration. Drying is usually done by keeping the sintered-glass crucible containing the
precipitate in an air oven at 110o120oC for nearly 12 hours.
In the second case, precipitates obtained after drying may not be in weighable forms.
This happens in case of most of the precipitates obtained by inorganic precipitants barring few
precipitates like AgCl. In such cases the precipitates are collected using filter paper. Then the filter
paper along with the precipitates is inserted into either a porcelain crucible or silica crucible and
ignited at elevated temperature. Ignition is done for the following purposes.
3.6.2 Purpose of Ignition

(i) To convert the precipitate into some other stable form of known and definite composition.
(ii) To volatilize the electrolyte which needs elevated temperature.
(iii) To remove strongly adsorbed or occluded water which is found mainly among gelatinous
precipitates such as hydrated oxides of aluminium, iron and silicon. The temperature at
which the precipitate should be ignited depends on the following facts.
3.6.3 Ignition Temperature

(a) The precipitate should be ignited at such a temperature range at which it is converted into
new compound of known and definite composition. For example, calcium oxalate
monohydrate CaC2O4H2O after ignition at a temperature in the range of 400600°C
undergoes decomposition and is weighed as calcium carbonate
CaC 2 O 4 H 2 O CaC O

100 250ºC
CaCO + CO
2 4
400 600ºC
CaC 2 O 4 3
(b) The ignition may not alter the chemical composition of the precipitate. Thus, for example,
BaSO4 and PbSO4 are usually weighed as such after ignition. However, in such cases,
the precipitates are to be filtered through sintered-glass crucible and not through filter paper.
This is because during ignition the precipitate may be reduced by the carbon resulting from
the burning of the filter paper.
(c) Ignition at higher than optimum temperature should be avoided as it may cause loss of the
precipitate due to volatilization, sublimation or decomposition. For example, CaCO3 on
heating in the range of 700850°C is decomposed to more stable CaO.
CaCO3 CaO CO

700 850ºC
2
(d) Ingnited residue must be cooled inside a descicator containing dehydrating agent to remove
moisture that might have been adsorbed in the residue when exposed to the atmosphere
during cooling.
3.7 WEIGHING
After drying or incineration the precipitate in the sintered crucible/porcelain crucible is weighed in
an analytical balance to constant weight by repeating the heating and weighing cycle. Constant
weight is considered to be achieved when successive weighing agrees within about 0.30.4 mg.
The crucible should be allowed to cool in a dessicator for at least half an hour before weighing.
Red hot crucibles should be allowed to cool before placing them in the dessicator. Nickel-plated or
stainless steel tongs are used to handle the crucibles. These are expensive. They should be handled
carefully to get reliable gravimetric data. They should never be touched but must always be handled
with a pair of tongs.
3.8 SPECIFIC AND SELECTIVE PRECIPITATION
A specific precipitant may be defined as that precipitant which causes quantitative precipitation of
only one ion from a mixture of ions. In practice no precipitant is found to be specific. This is an
ideal case and rarely possible. However, there are some precipitants which are close to ideal
specificity.
For example, dimethyl glyoxime (DMG) is regarded as a specific precipitant for palladium or
nickel depending on the pH of the solution. A selectivity of precipitant can be achieved by carrying
out the precipitation under carefully controlled condition such as pH, temp., etc. For example,
oxine forms precipitate with many metal ions. It can be made selective by controlling pH to
precipitate Al3+ or Mg2+ from a mixture of other metal ions.
A selective precipitant is defined as that precipitant which precipitates a small group of ions.
Each ion within any group will then interfeare with the analysis of other ions in that group unless
they are either removed by a preliminary separation or made to remain in solution by a suitable
technique.
3.9 ORGANIC PRECIPITANTS
A number of organic reagents called organic precipitants have been developed for the gravimetric
analysis of inorganic species. Many of them are selective precipitants.
3.9.1 Types of Organic Precipitants

There are two types of organic precipitants such as organic precipitant forming chelate compounds
and organic precipitant forming salt-like precipitates as discussed below.
(i) Organic precipitants forming chelate compounds
Most of the organic precipitants form sparingly soluble compounds with the metallic ions through
co-ordination. These precipitant generally contain at least two functional groups capable of donating
electrons to the metal ions. The metal ion interacting with both of these groups becomes part of a
heterocyclic ring. The functional groups are located in the reagent molecules in such a way that a
five- or six-membered ring results from the reaction. Co-ordination compounds which form
complexes of this type are called chelates and the organic reagent leading to the formation of
chelates are called chelating agents. A typical example of a chelating agent is 8-hydroxy quinoline
(often called oxine or 8-quinolinol) which form neutral chelates with a number of metallic ions
like Zn2+ and Al3+. The chelate formation with Al3+ is shown in Figure 3.4.
Figure 3.4 Chelate formation of aluminium with oxinate.
Generally the metal chelate are neutral and sparingly soluble in water but soluble in less polar
solvent such as chloroform and carbon tetrachloride, etc. A list of a few organic chelating agents
which are useful in gravimetric analysis is given in Table 3.2.
Table 3.2 Some important organic chelataing agents
Name of the reagent Structural formula Metal ions precipitant
Salicylaldehyde oxime Cu(II) in CH3COOH(specific)
1-Nitroso-2-naphthol Principally used for precipitation of

(a-Nitroso-b-napthol) Co(II) in presence of Ni(II) in slightly
acidic medium
Anthranilic acid (HR) Mn+ + nHR ¾® MRn + nH+
Quinaldic acid Used for determination of Cd(II),

Cu(II) and Zn(II)
2-methyl-8-hydroxy Bi(III), Cd(II), Fe(II), Fe(III)

quinoline
(Contd...)
Table 3.2 Some important organic chelataing agents (Contd...)

Diphenylcarbazide Cr(III)
Dimethylglyoxime (HR) Ni(II) in NH3, Pd(II) in HCl

(nearly specific)
M2+ + 2HR ¾® MR2 + 2H+
Furil-a-dioxime Ni(II) in NH3 (specific)
Cyclohexane-1,2- Pd(II) (specific)

dionedioxime
Nioxime
Ammonium salt of Mn+ + nNH4R ¾® MRn + nNH4+

N-nitroso-N-phenyl mainly used for separation of Fe3+
Hydroxylamine and Ti4+ from Al3+
(cupferron) (NH4R)
Ammonium salt of Fe(II) and Cu(II)

N-nitroso-N-2-napthyl
hydroxylamine
(Neo-cupferron)
N-Benzoyl-N-Phenyl
Hydroxylamine
8-Hydroxy quinoline Many metal ions such as Al3+, Mg2+,

(oxine) (HR) etc. for selective precipitation
Mn+ + nHR ¾® MRn + nH+
(Contd...)
Table 3.2 Some important organic chelataing agents (Contd...)
a-benzoin Oxime M2+ + H2R ¾® MR + 2H+
(Cupron) (H2R) M2+ = Cu2+, MO22+, WO22+
Sodium diethyl dithio Many metal ions from acid solultion

Carbamate (NaR) Mn+ + nNaR ¾® MRn + nNa+
(ii) Organic precipitants forming salt-like precipitates

Some organic precipitants form salts rather than chelate complexes with inorganic ions.
For example, oxalic acid, is well known in analytical process for its use in precipitation of calcium
as calcium oxalate is an insoluble salt. There are a number of organic precipitants which form
precipitates with both the cations and anions. A few of them are listed in Table 3.3.
Table 3.3 Organic precipitants forming salt-like precipitates

Name of the reagent Structural formula Comments
Sodium tetraphenylboron Na+B(C
6H 5)4 (NaR) Used principally for K+; in
0.1 M HCl only NH4+, Hg2+, Rb+ and
Cs+ interfere
Mn+ + nNar ¾® MRn + nNa+
Tetraphenylarsonium (C6H5)4As+Cl Thallium(III), Cr2O72, MnO,
chloride ReO4, MOO42, WO42, ClO4I3; in
acidic solution
An + nRCl ¾® RnA + nCl
Benzidine Used principally for SO42
Arsonic acid Mainly precipitates quadrivalent

metal ions such as Sn, Th and Zr
R = Phenyl, n propyl in acid media
3.9.2 Advantages of Using Organic Precipitants

Organic reagents as precipitants offer several advantages:
(a) Most of the precipitates are very insoluble in water so that metal ions may be quantitatively
precipitated.
(b) The precipitating agent has a high molecular weight. As a result a small amount of metals
yields a large amount of precipitate. This gives more accurate results, as the % of weighing
error is less.
(c) Some of them are very selective yielding precipitates with only a limited number of metal
ions under control experimental conditions like pH and presence of masking reagents, etc.
(d) The precipitates formed are often coarse and bulky and hence can be suitable for filtration
and washing the precipitate.
(e) Most of the precipitates can be dried at suitable temperature and weighed without ignition
so that the process becomes quicker.
3.9.3 Disadvantages of Using Organic Precipitants

There are also certain disadvantages in the use of organic reagents as precipitants.
(a) They have a very limited solubility in water because of their covalent nature.
There is a danger of contaminating the precipitate with excess reagent, which may be settled
down as solid (due to insolubility in water) along with the precipitate. In some cases the
reagent can be washed out of the precipitate with a solvent such as hot water or alcohol.
(b) In some cases drying of precipitate yields a dried product of uncertain composition.
(c) Some of the metal chelates tend to volatilize at the temperatures required to remove water.
In some cases, decomposition of chelates sets in before drying to constant weight.
(d) Precipitates are not easily wetted by water and hence tend to float on the surface of the
solution and to creep up the sides of the glass vessel. This causes difficulties in filtering.
3.10 SEQUESTERING (OR MASKING) AGENT
A sequestering agent or masking agent is one which selectively complexes with a metal ion which
would interfere with gravimetric (or titrimetric) estimation of another ion. The complex formed by
the metal ion and masking agent is highly stable and is retained in solution so that it fails to react
with reagents added for the estimation of desired metal ion. For example, consider the estimation
of calcium as calcium oxalate in the presence of iron(III). The precipitation of calcium oxalate
requires an ammonical medium in which iron(III) would also be precipitated as the hydroxide of
iron. If the precipitation of calcium oxalate is carried out in presence of added ammonium fluoride,
the fluoride ions complex Fe(III) selectively as [FeF6]3 which remains in solution as stable species;
only calcium oxalate will be precipitated which can be filtered and estimated by the usual gravimetric
procedure. Here, the fluoride ions from ammonium fluoride serves as masking agent. Other masking
agents employed to form stable complexes with iron (III) are tartrate and citrate ion.
Another example to illustrate the use of masking agent is the gravimetric estimation of Mg(II)
as magnesium oxinate. Copper(II), if present, is an interfering ion and should be masked.
The cyanide ion is used for this purpose. It forms a soluble complex with copper [Cu(CN)4]2
which is inert toward oxine. Therefore, magnesium in the presence of copper can be estimated as
magnesium oxinate if the cyanide ion is used as masking agent.
3.11 PROBLEMS INVOLVED IN PRECIPITATION GRAVIMETRY
3.11.1 Problems on Gravimetric Factor (GF)

PROBLEM 3.1 Find the gravimetric factor to the following:
(i) Ag in AgCl
(ii) Ba in BaSO4
(iii) Fe in Fe2O3
Solution
(i) Molecular of AgCl = 108 + 35.5 = 143.5
Atomic weight of Ag = 108
In AgCl 1 mole of Ag is present in 1 mole of AgCl
1 mole of Ag Atomic wt of Ag 108
\ GF for Ag = 0.753
1 mole of AgCl Molecular wt of AgCl 143.5
(ii) In BaSO4 1 mole of Ba is present in 1 mole of BaSO4
1 mole of Ba Atomic wt of Ba 127
\ GF for Ba in BaSO4 = 0.588
1 mole of BaSO 4 Molecular wt of BaSO 4 233
(iii) In Fe2O3, 2 mole of Fe is present in 1 mole of Fe2O3
2 mole of Fe 2 Atomic wt of Fe
\ GF for Fe in Fe2O3 =
1 mole of Fe 2 O3 Molecular wt of Fe2 O3
2 56 112
= 0.7
160 160
PROBLEM 3.2 Find the gravimetric factor (GF) for the followings (the substance is):
(i) K in K2 [PtCl6]
(ii) CaO in CaCO3
(iii) Cr2O3 in Ag2CrO4
(iv) NH3 in (NH4)2 [PtCl6]
Solution
(i) In K2[PtCl6], 2 mole of K is present in per mole of K2 [PtCl6]
2 mole of K
GF =
1 mole of K 2 [PtCl6 ]
2 × Atomic wt of K 2 39
= 0.16
Molecular wt of K 2 [PtCl6 ] 486
(ii) In CaCO3, CaCO3 ¾® CaO + CO2, 1 mole of CaCO3 = 1 mole of CaO

1 mole of CaO Molecular wt of CaO 56

GF = 0.56
1 mole of CaCO3 Molecular wt of CaCO3 100
(iii) In Ag2CrO4, 2Ag2CrO4 º Cr2O3
2 mole of Ag2CrO4 º 1 mole of Cr2O3
1 mole of Cr2 O3 Molecular wt of Cr2 O3

GF = =
2 mole of Ag 2 CrO 4 2 × Molecular wt of Ag 2 CrO 4
152
= 0.229
2 332
(iv) In (NH4)2 [PtCl6]
1 mole of (NH4)2 [PtCl6] » 2 mole of NH3
2 mole of NH3
GF =
1 mole of (NH 4 ) 2 [PtCl6 ]
2 molecular wt of NH 3
=
Molecular wt of (NH 4 ) 2 [PtCl6 ]
2 17
= 0.076
444
PROBLEM 3.3 Calculate the gravimetric factor (GF) for the followings (the substance weighted
is given first, then the substance sought):
(i) Zn2P2O7, ZnO
(ii) BaSO4, FeS2
(iii) U3O8, UO2
(iv) KClO4, K2O
Solution
(i) In Zn2P2O7, 1 mole of Zn2P2O7 º 2 mole of ZnO
2 mole of ZnO 2 molecular wt of ZnO
\ GF = =
1 mole of Zn 2 P2 O7 1 molecular wt of Zn 2 P2 O7
2 81
= 0.533
304
(ii) In the conversion of BaSO4 to FeS2
2 mole of BaSO4 º 1 mole of FeS2
1 mole of FeS2 Molecular wt of FeS2 120
\ GF = = = = 0.257
2 mole of BaSO 4 2 Molecular wt of BaSO 4 2 × 233
(iii) In the conversion of U3O8 to UO2
1 mole of U3O8 º 3 mole of UO2
3 × Molecular wt of UO 2 3 × Molecular wt of UO 2
\ GF = =
1 Molecular wt of U 3O8 Molecular wt of U3 O8
3 270.7
= 0.962
844.1
(iv) In the conversion of KClO4 to K2O
2 mole of KClO4 = 1 mole of K2O
1 mole of K 2 O 1 Molecular wt of K 2 O
\ GF = =
2 mole of KClO 4 2 Molecular wt of KClO 4
94
= 0.339
2 138.5
3.11.2 Problems on Determination of Elements and Percentage of Purity

PROBLEM 3.4 The calcium in a 200 ml sample of natural water was determined by precipitating
the cation as calcium oxalate. The precipitate was filtered, washed and ignited to calcium oxide,
which weighs 0.1132 g. Calculate the amount of Ca per 100 ml of water.
Solution In CaO, 1 mole of Ca is present per mole of CaO
1 mole of Ca Atomic wt of Ca
\ GF for Ca = =
1 mole of CaO Molecular wt of CaO
40
= 0.714
56
Amount of Ca, WA = wt of CaO ´ GF = 0.1131 ´ 0.714 = 0.0808 g
200 ml of natural water contains 0.0808 g of calcium
0.0808
100 ml of natural water contains 100 0.0404 g calcium
200
PROBLEM 3.5 0.485 g sample of an iron ore is dissolved in acid and the iron is oxidized to +3
state and then precipitated as the hydrous oxide, Fe2O3 ´ H2O by the addition of NH4OH.
The precipitate is filtered, washed and ignited to Fe2O3, which is found to be 0.248 g. Calculate
the percentage of iron in the sample.
Solution Here the analyte is Fe and let its wt be WA
Given Ws = 0.485 g
Wp = 0.248 g
2 mole of Fe is present in per mole of Fe2O3
2 mole of Fe
\ GF for Fe =
1 mole of Fe 2 O 3
2 Atomic wt of Fe 2 × 56
= = = 0.7
1 Molecular wt of Fe 2 O3 160
\ WA = Wp ´ GF = 0.248 ´ 0.7 = 0.1736 g

WA 0.1736
% of analytic = 100 100 35.79%
Ws 0.485
PROBLEM 3.6 1 g of sample of potash alum is dissolved in water and its sulphate content is
precipitated as BaSO4, which weighs 0.3486 g after it is washed and ignited. Calculate the % of
aluminium present in the sample.
Solution Here Ws = 1.00 g
We are to find first the amount of sulphate present in BaSO4
1 mole of sulphate is present in 1 mole of BaSO4
1 mole sulphate = 96 g º 233 g of BaSO4
\ 233 g of BaSO4 contains 96 g of sulphate
96
\ 0.3486 g contains 0.3486 0.1436
233
Again per mole of potash alum contains 4 moles of sulphate which is present in 2 moles of
aluminium.
\ 4 moles of sulphate º 2 moles of aluminium
\ 4 ´ 96 g of sulphate º 2 ´ 27 g of aluminium
2 27
\ 0.1436 g of sulphate º 0.1406
4 96
\ 1.00 g of sample of potash alum contains 0.1406 g of aluminium
100 g of sample contains 0.1406 ´ 100 = 14.06 g of aluminium
% of Al present in the sample = 14.06%
PROBLEM 3.7 The aluminium in a 1.2 g of impure aluminium sulphate was precipitated with
an aqueous ammonia as the hydrous Al2O3 ´ H2O. The precipitate was filtered ignited to 1000ºC
to give anhydrous Al2O3, which weighed 0.1798 g. Find out the % of Al in the sample.
Solution Here the analyte is Al and let wt be WA, Ws = 1.2 g
Given Wp = 0.1798 g, Ws = 1.2 g
In Al2O3, 1 mole of Al2O3 contains 2 mole of Al
2 mole of Al 2 27
GF for Al in Al2O3 = 0.53
1 mole of Al 2 O3 102
\ WA = Wp ´ GF = 0.1798 ´ 0.53 = 0.0953 g

WA
\ % of Al = 100 7.94%
Ws
PROBLEM 3.8 The addition of dimethyl glyoxime (DMG) (H2C4H6O2N2) to 100 ml solution
containing nickel(II) gives rise to a precipitate, which weighs 158 mg.
Calculate the amount of nickel(II) present in per litre of the solution
Ni2+ + 2H2C4H6O2N2 ¾® Ni(HC4H6O2N2)2 + 2H+
Solution Here, the analyte is nickel

1 mole of nickel
GF for Ni in Ni(HC4H6O2N2)2 =
1 mole of Ni(HC 4 H 6 O 2 N 2 ) 2
Atomic wt of nickel
=
Molecular wt of Ni(HC4 H 6 O 2 N 2 )2
59.97
= 0.206
289.7
WA = Ws ´ GF = 0.158 ´ 0.206 = 0.0325 g
\ 100 ml of the nickel(II) solution contains 0.0325 g of nickel(II)
\ 1000 ml of the nickel(II) solution contains 0.0325 ´ 10 = 0.325 g of nickel(II).
PROBLEM 3.9 26.23 mg of hydrous magnesium oxalate MgC2O4 · H2O and an inert material is
heated to constant wt at 1200ºC leaving a residue weighing 20.98 mg. A sample of pure
MgC2O4 · H2O when treated in the same fashion undergoes 69.08% change in its mass. Determine
È wØ
the % of É Ù MgC2 O 4 ¹ H 2 O in the sample
Ê wÚ
Solution Change in mass when analysing the mixture (MgC2O4 · H2O + inert material) =
26.23 20.98 = 5.25 mg
Changing in mass when analysing the pure MgC2O4 · H2O in the same fashion = 69.08%
Loss of 69.08 mg º 100 mg pure MgC2O4 · H2O
100
Loss of 5.25 mg º 5.25 7.60 mg of pure MgC2O4 · H2O
69.08
26.23 mg of impure sample contains 7.60 mg of pure MgC2O4 · H2O
7.60
\ 100 mg of impure sample contains 100 28.9 mg of pure MgC2O4 · H2O
26.23
\ % of MgC2O4 · H2O = 28.9%
PROBLEM 3.10 The lead in 0.552 g sample of an ore is precipitated as PbSO4. The precipitated
is washed, dried and found to weigh 0.442 g. Calculate the percentage of lead in the sample.
Solution Here, the analyte is lead and let its wt be WA
Given Wp = 0.442 g, Ws = 0.552 g
1 mole of PbSO4 contains 1 mole of Pb
1 mole of Pb 207
\ GF for Pb = 0.683
1 mole of PbSO 4 303
wt of Pb = WA = Wp ´ GF = 0.442 ´ 0.68 = 0.3019

WA 0.3019
% of Pb = 100 100 54.69
Ws 0.2552
3.11.3 Determination of Sample Size

PROBLEM 3.11 What is the amount of the sample containing 18% of Fe3O4 to be taken for
analysis in order to get a precipitate of Fe3O4 weighing 0.4 g?
Solution 2Fe3O4 º 3Fe2O3
3 mole of Fe2O3 is produced from 2 mole of Fe3O4
\ 3 ´ 160 g of Fe2O3 is produced from 2 ´ 232 g of Fe3O4
2 232 0.4
\ 0.4 g of Fe3O4 is produced from 0.388 g of Fe3O4
3 160
18 g of pure Fe3O4 is present in 100 g of impure sample Fe3O4
100
\ 0.388 g of pure Fe3O4 is present in 0.388 2.155 g of impure sample of Fe3O4
18
The amount of sample to be taken = 2.155 g
PROBLEM 3.12 What is the amount of the sample containing 12% (w/w) of chloride to be
taken to obtain AgCl which weighs 0.5 g.
Solution Here, the analyte is chlorine. Let its wt be WA.
Given, Wp = 0.5 g
1 mole of Cl 35.5
GF for Cl in AgCl = 0.247
1 mole of AgCl 143.5
WA = Wp ´ GF = 0.5 ´ 0.247 = 0.1235 g
WA 100
12
Ws
WA 100 0.1235 100
\ WS = 1.03 g
12 12
The amount of sample to be taken = 1.03 g
PROBLEM 3.13 Calculate the volume of BaCl2 solution (16 g of BaCl2 per litre) required to
precipitate the sulphur as BaSO4 in a 0.6 g of sample containing 12% of S.
Solution 100 g of sample contains 12 g of S
12
\ 0.6 g of sample contains 0.6 0.072 g of S
100
S ¾® SO42
SO42 + BaCl2 ¾® BaSO4 + 2Cl
\ 1 mole of S º 1 mole of BaCl2
32 g of S º 208 g of BaCl2
208
\ 0.072 g of S º 0.072 0.468 g of BaCl2
32
16 g of BaCl2 is present in 1000 ml of BaCl2 solution.
1000
\ 0.468 of BaCl2 is present 0.468 29.25 ml of BaCl2 solution
16
\ The volume of BaCl2 solution required = 29.25 ml
PROBLEM 3.14 What mass of AgCl can be produced from a 0.4 g sample that assays 41.3% of
KCl?
Solution In 100 g of sample, 41.3 g of pure KCl is present
41.3
\ 0.4 g of sample contains 0.4 0.1652 g of pure KCl
100
KCl + AgNO3 ¾® AgCl
\ 1 mole of KCl º 1 mole of AgCl
1 mole of KCl = 74.5 g
1 mole of AgCl = 143.5 g
\ 74.5 g of KCl produces 143.5 g of AgCl
143.5
0.1652 g of KCl produces 0.1652 0.318 g of AgCl
74.5
PROBLEM 3.15 A sample of impure pyrite is known to contain 90% (w/w) of FeS2. It is to be
analysed by oxidising sulphur to SO42 and precipitating as BaSO4. How many grams of the sample
must be taken to get 1 g of BaSO4 from the sample?
Solution FeS2 ¾® 2BaSO4
2 mole of BaSO4 º 1 mole of FeS2
2 ´ 233 g of BaSO4 º 120 g of FeS2
120
\ 1 g of BaSO4 = 0.257 g of FeSO4
2 233
90 g of pure FeS2 is present in 100 g of impure FeS2.
100
0.257 g of pure FeS2 is present in 0.257 0.285 g of impure FeS2
90
\ Amount of sample to be taken = 0.285 g
PROBLEM 3.16 340 mg of a sample containing KCl and NaCl gave 706.2 mg of silver chloride.
Find the % of KCl and NaCl in the sample.
Solution Let x mg of KCl and y mg of NaCl be present in the mixture
74.5 mg of KCl º 143.5 mg of AgCl
143.5
\ x mg of KCl º x mg of AgCl
74.5
= 1.93 x mg of AgCl
58.5 mg of NaCl º 143.5 mg of AgCl
143.5
\ y mg of NaCl = y mg of AgCl
58.5
= 2.45 y mg of AgCl
1 mole of KCl ¾® 1 mole of AgCl
1 mole of NaCl ¾® 1 mole of AgCl
\ 1.93x + 2.45y = 706.2 (i)
x + y = 340
or 1.93 (x + y) = 340 ´ 1.93
or 1.93x + 1.93y = 340 ´ 1.93 (ii)
Subtracting (ii) from (i), we get
(2.45 1.93)y = 706.2 656.2 = 50
0.52y = 50
50
y= 96.15
0.52
x = 340 96.15 = 243.85
243.85
% of KCl = 100 71.73
340
% of NaCl = 100 71.73 = 28.27
PROBLEM 3.17 516.7 mg of a sample containing K2SO4 and (NH4)2SO4 was dissolved in
water and treated with BaCl2 thereby precipitating SO42 as BaSO4. The resulting precipitate is
made free from impurities and dried to a constant weight yielding 863.5 mg of BaSO4. What is the
% of (w/w) K2SO4 in the sample?
Solution Let x mg of K2SO4 and y mg of (NH4)2SO4 be present in the sample.
K2SO4 + BaCl2 ¾® BaSO4 + 2KCl
(NH4)2SO4 + BaCl2 ¾® BaSO4 + 2NH4Cl
1 mole, i.e. 174 g of K2SO4 yields 1 mole, i.e. 233 g of BaSO4 or, 174 mg of K2SO4 yields 233 mg
of BaSO4
233
x mg of K2SO4 yields x mg of BaSO4 = 1.34 ´ x mg of BaSO4
174
1 mole (NH4)2SO4, i.e. 132 g yields 1 mole, i.e. 233 mg of BaSO4 or, 132 mg of (NH4)2SO4 yields
223 mg of BaSO4
233
\ y mg of (NH4)2SO4 yields y 1.765 y mg of BaSO4
132
1.34x + 1.765y = 863.5 (i)
x + y = 516.7
1.34 (x + y) = 516.7 ´ 1.34 (ii)
Subtracting (ii) from (i), we get
(1.765 1.34)y = 863.5 692.38 = 171.12
0.425y = 171.12
171.12
y= 402.63 mg
0.425
x = 516.7 402.63 = 114.07 mg
114.07
\ % of K2SO4 = 100 22.07
516.7
PROBLEM 3.18 1.0 g of a sample containing 75% of K2SO4 and 25% of another metal sulphate
MSO4 dissolved in water and the sulphate is precipitated as BaSO4. The weight of dry BaSO4
precipitated is found to be 1.49 g , What is the molecular mass of MSO4?
Solution K2SO4 + BaCl2 ¾® BaSO4 + 2KCl
MSO4 + BaCl2 ¾® BaSO4 + MCl2
1 mole of K2SO4 º 1 mole of BaSO4
1 mole of 174 g of K2SO4 º 233 g of BaSO4
MSO4 + BaCl2 ¾® BaSO4 + 2M+
1 mole of MSO4 = 1 mole of BaSO4
75 75
Amount of K2SO4 = × wt of sample = 1.0 0.75 g
100 100
\ Amount of MSO4 = 1 0.75 = 0.25 g
233
\ 0.75 g of K2SO4 º 0.75 1.004 g of BaSO 4
174
Similarly, 1 mole of MSO4 º 1 mole of BaSO4
Let the atomic wt of M be x
Molecular wt of MSO4 = (x + 96)
\ (x + 96) g of MSO4 º 233 g of BaSO4
È 233 Ø È 58.25 Ø
0.25 g of MSO4 º É Ù 0.25 É g of BaSO4
Ê x 96 Ú Ê x 96 ÙÚ
È 58.25 Ø
\ É x 96 Ù 1.004 = 1.49
Ê Ú
È 58.25 Ø
É x 96 Ù = 1.49 1.004 = 0.486
Ê Ú
58
x + 96 = 119.85
0.486
\ x = 119.85 96 = 23.85 » 24
Molecular wt of MSO4 = 24 + 96 = 120
PROBLEM 3.19 0.4 g of a hydrated sodium sulphate Na2SO4 · H2O yields 0.289 g of BaSO4.
Find the value of x.
Solution Na2SO4 · H2O + BaCl2 ¾® BaSO4 + 2NaCl + x H2O
\ 1 mole of Na2SO4 · xH2O º 1 mole of BaSO4
Molecular wt of Na2SO4 · xH2O = (2 ´ 23 + 32 + 64 + 18x)
= (142 + 18x)
\ (142 + 18x) g of Na2SO4 · xH2O º 233 g of BaSO4
È 233 Ø 93.2
0.4 g of Na2SO4 · xH2O º É Ù 0.4 g of BaSO4
Ê 142 18 Ú 142 18x
93.2
= 0.289
142 18x
93.2
= 142 + 18x
0.289
321.8 = 142 + 18x
18x = 321.8 142 = 180
x = 10
3.11.4 Analysis of Alloy
PROBLEM 3.20 Brass contains 8.6% of Sn, 5.8% of Pb and 4.7% of Zn and 80.9% of Cu.
The elements are determined gravimetrically by weighing the following: precipitated SnO2,
PbSO4, ZnP2O7 and CuSCN from 0.5 g sample of brass. Find the weight in gram of each of the
precipitate obtained.
WA
Solution % of analyte = 100
Ws
WA = GF ´ Wp
GF W p 100
% of analyte =
Ws
% of analyte Ws
Wp =
GF 100
8.6 0.5
\ For SnO2 Wp =
GF for Sn in SnO 2 100
8.6 0.5 4.3

Wp = 0.05
118.7 78.8
100
150.7
Wt of PbSO4 precipitate
5.8 0.5 2.9
0.0424
207
100 68.3
303
4.7 0.5 4.7 0.5
Wt of Zn2P2O7 = 0.0549 g
GF for zinc in Zn 2 P2 O7 100 2 65
100
308
80.9 0.5 80.9 0.5 40.45
Wt of CuSCN = 0.774 g
GF for Cu in CuSCN 100 63.5
100 52.26
121.5

(i) A precipitate of Fe(OH) 3 is contaminated with Mg(OH)2. The best way to get rid of the
impurity is
(a) Washing (b) Digestion
(c) Ignition (d) Re-precipitation
(ii) Colloids which carry down only a small quantity of water when coagulated are said to be
(a) Lyophobic (b) Suspensoids
(c) Emulsoid (d) None of the above
(iii) The process of dispersing an insoluble material into a liquid as a colloid is called
(a) Occlusion (b) Nucleation
(c) Peptization (d) Coagulation
(iv) Which of the following does not promote the formation of large crystal of CaC2O4?
(a) Slow mixing of dilute solution
AB
(b) Decreasing
B
(c) Digestion
(d) Precipitation at high pH rather than low pH
(v) The most suitable precipitant for estimation of Ni2+ is
(a) Cupferron (b) Oxime
(c) DMG (d) EDTA
(vi) The size of the particle of precipitate will be large if
(a) RSS is small (b) RSS is large
(c) The degree of supersaturation is large (d) None of the above
(vii) The contamination of BaSO4 with alkali nitrite is an example of

(a) Non-isomorphic inclusion (b) Isomorphic inclusion
(c) Occlusion (d) Postprecipitation
(viii) Al can be precipitated by oxine in the presence of Cu and Zn if the later is masked with
(a) KCN (b) Sodium tatrate
(c) NH4OH (d) NaF
(ix) Cupferron is selective for
(a) Cu(II) (b) Ni(II)
(c) Zn(II) (d) None of the above
(x) Compounds AB and AC2 each have solubility product equal to 4 ´ 1018. Then
(a) AB is more soluble than AC2
(b) AC2 is more soluble than AB
(c) AB and AC2 are of equal solubility
(d) None of the above
(i) The selective precipitant for Ni(II) and Pd(II) is .............. .
(ii) .............. precipitates quantitatively a particular ion or a substance from a solution containing
several ions.
(iii) BaSO4 is digested at the temperature range .............. .
(iv) Benzidine is .............. type precipitant.
(v) According to von Weimarns theory, the particle size of the precipitate is inversely
proportional to .............. .
(vi) The electrolyte used for washing the precipitate must be .............. at the temperature at
which drying or ignition is done.
(vii) The mass of Ag2CrO4 that can be produced from 1.2 g of K2CrO4 is .............. .
(viii) The ammonium salt of N-nitroso-N-phenyl hydroxylamine is called .............. .
(ix) Heating of an aqueous solution of sulphamic acid results in slow release of .............. ion.
(x) The gravimetric factor for Ca in CaCO3 is .............. .
statements
(i) The precipitation of magnesium oxalate in the presence of calcium oxalate is an example of
postprecipitation.
(ii) The hydroxides of iron(III) obtained from homogeneous precipitation is easily filterable.
(iii) The higher the degree of supersaturation, the greater the rate of particle growth.
(iv) For Fe(OH)3, the RSS is large.
(v) Occluded impurities are easily removed.
(vi) Ammonium fluoride is a sequestering agent for ion(II) in a basic medium.
(vii) Contamination due to postprecipitation increases with time for which the desired precipitate
is left in contact with mother liquor.
(viii) In gravimetry, the precipitate is digested with mother liquor to decrease the particle size of
the precipitate.
(ix) The wash liquid for silver chloride should contain a small amount of non-electrolyte.
(x) In gravimetric analysis, the condition of minimum solubility for the precipitate is
maintained.

(i) Mention how coprecipitation can be decreased.
(ii) Mention the remedy for postprecipitation.
(iii) How would you prevent peptization?
(iv) What are possible errors in weighing?
(v) What is meant by gravimetric factor?
(vi) What procedure is adopted to remove occluded impurities?
(vii) What are the possible errors in the final steps of ignition?
(viii) Name the elements for which estimation the filter paper is burnt separately from the
precipitate.
(ix) What is meant by filter-pulp?
(x) Write the name of the elements in which estimation filter-pulp is used.
(xi) Name the various anions, which are precipitated along with BaSO4.
(xii) What precautions can be taken in the estimation of nickel in the presence of iron?
(xiii) Name the precipitates, which can be ignited without drying, and incineration.
(xiv) What are the conditions to be used to obtain precipitate of large particle size?
(xv) Why sintered-glass crucible is not used for the filtration of BaSO4 precipitate?
(xvi) Why dil HCl is added before precipitation of BaSO4?
(xvii) In the estimation of Ba2+ as BaSO4, why the ash of the filter paper is treated with conc HCl
and conc H2SO4?

5. Explain the followings
(i) Gravimetric factor
(ii) Gelatinous precipitate
(iii) von Weimarns ratio
(iv) Peptization
(v) Nucleation
6. Explain the differences between

(a) A colloidal and a crystalline precipitate.
(b) Specific and selective precipitating reagent.
(c) Precipitation and coprecipitation.
(d) Peptization and coagulation.
(e) Occlusion and mixed crystal formation.

(f) Nucleation and particle growth.
7. Propose a method for the selective precipitation of the followings
(a) Al3+1 from a solution that also contains Mg2+.
(b) Ni2+1 from a solution that also contains Cu2+.
(c) Ba2+ from a solution that also contains Pb2+.
(d) Ca2+ from a solution that also contains Cu2+.
8. Explain why
(i) Silver iodide coprecipitates silver acetate much more than silver chloride.
(ii) Gelatinous precipitates are not digested.
(iii) Curdy precipitates are not digested.
(iv) Occluded impurities are not removed by washing.
(v) Fe(OH)3 is usually precipitated in acidic medium.
(vi) Chelating agents are generally insoluble in water but soluble in organic solvent.
(vii) BaCl2 solution is not added in excess during the estimation of SO42 as BaSO4.
(viii) Sintered-glass crucible is not used for the filtration of BaSO 4.
(ix) HNO3 is added to the solution before the precipitation of AgCl.
(x) AgCl precipitate is washed with water containing a few drops of dil HNO3.
(xi) AgCl becomes violet when exposed to sunlight.
(xii) Large excess of HCl must be avoided during precipitation of AgCl.
(xiii) Excess of DMG is not added during the precipitation of nickel(II).
(xiv) The solution is made alkaline by adding NH4OH during the precipitation of nickel dimethyl
glyoxime.
(xv) Oxidant like HNO3 must be absent during precipitation of CuSCN.
(xvi) NH4Cl cannot be used as a substitute of NH4NO3 as wash solution.
(xvii) Excess of NH4OH should not be added during the precipitation of Fe(OH)3.
(xviii) Fe(OH)3 is ignited in excess of air at 1000ºC.
(xix) Methyl red indicator is used in the estimation of elements.
(xx) AgCl precipitate is never filtered in filter paper.
(xxi) Dilute HCl is added before precipitation of BaSO4.
(xxii) In the estimation of Ba2+ as BaSO4, the ash of the filter paper is treated with conc
H2SO4.
(i) Name the specific and selective precipitants used for the gravimetric estimation of Cl,
SO42, Mg2+, Ni2+, Zn2+ and Sn2+.
(ii) What are the advantages of using organic precipitants over inorganic precipitants?
(iii) What is the major source of error in the estimation of magnesium as magnesium oxinate?
(iv) Derive an expression for % of analyte from gravimetric calculation.
(v) What do you mean by gravimetric factor? How is it related to % of analyte?
(vi) Mention the conditions for precipitation.
(vii) What is von Weimarn ratio? Define the terms associated with this ratio.
(viii) What information concerning optimum conditions of precipitation does von Weimarn ratio
give us?
(ix) How are the errors in the estimation of Mg as magnesium oxinate avoided?
(x) How is copper estimated gravimetrically?
(xi) Explain the function of the following precipitants
(a) Nitron
(b) Cupferron
(c) Oxine
(d) Salicylalaldehyde oxine
(xii) Explain the functions of the following precipitants
(a) Pyrogallol
(b) 1nitroso2naphthol
(c) Quinaldic acid
(d) Anthralic acid
(xiii) Write the characteristics of whatmann filter paper.
(xiv) Explain sequestering agent giving a suitable example.

10. Briefly describe the various steps involved by gravimetric analysis.
11. Describe briefly the mechanism of precipitate formation.
12. Explain precipitation from the homogeneous solution giving suitable examples. What are
the advantages of this process?
13. What is meant by coprecipitation? Mention its causes and remedy giving suitable examples.
14. Explain postprecipitation with examples. What is the remedy to this problem?
15. Why is a filtered precipitate washed? Why does a wash liquid generally contain an
electrolyte? What is the requirement for such electrolyte?
16. Discuss the method of separation of the precipitate from its mother liquior.
17. What do you mean by a digestion of a precipitate? Mention various reasons for it.
18. Why is drying or incineration of the precipitate necessary? Discuss the various methods of
drying giving suitable example.
19. What are the advantages and disadvantages of using organic precipitate? Give some examples
of important organic precipitant used in gravimetry.
20. What are the various errors involved in precipitation? How are they overcome?
UNIT 3
4. Statistical Methods of Analysis
CHAPTER 4
Statistical Methods of Analysis
4.1 INTRODUCTION
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
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
their statistical analysis their are discussed which involve the followings:
(a) Significant figures to represent the data
(b) Errors and their causes
(c) Accuracy and precision
(d) Methods of expressing accuracy and precision.
4.2 SIGNIFICANT FIGURES
To represent the analytical data obtained from the measurement, certain figures which involve the
number of digits are necessary. The figures used to estimate the uncertainty involved in the
measurement are called significant figures.
4.2.1 Definition of Significant Figure

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
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
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
3.450 are said to be significant. The following rules are helpful in determining the number of
significant figures in a given number.
4.2.2 Rules for Determining Significant Figures

Non-zero integers
All the non-zero integers are significant. For example, 5.231 has four significant figures. 2.45 has
three significant figures and 6.251 have four significant figures.
Recognition of zero as significant figures
The digit zero may or may not be significant figure. In the burette graduated to 0.01 ml, let the
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
the number of significant figures can not 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
locate the decimal point. Hence initial zeros are not significant similarly a volume of 2 liters
expressed in ml. (2000 ml must contain only one significant figure as which is 2. To avoid ambiguity,
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
will be 2.1 ´ 103 (two significant figures in both cases).
The following examples illustrate the points mentioned
Number Expression Significant figures Remarks

0.612 612 ´ 103 3 0 is not significant here
70.9 709 ´ 101 3 0 is significant figure here
0.007 7 ´ 103 1 Zeros are not significant figures here
6.023 ´ 1023 4 Zero is significant figure here
1.03 ´ 1013 3 Zero is significant figure here
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.
Exponential notation
In exponential notation, the numerical portion represents the number of significant figures.
For example, 3 ´ 106 has one significant figure 3.2 ´ 104 has two significant figures.
Rounding off the non-significant figures
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
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,
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.
The following rules are to be followed while doing calculations involving significant figures.
Rules for calculations involving significant figures
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.
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
one decimal. Hence the result 139.09 to be rounded off to 139.1 so that it contains one decimal.
Rule for multiplication and division: The rule followed is to retain only as many significant
figures as those in the number with the fewest significant figures. For example,
25 0.524
0.131
100.0
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.
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
The measured value of a property will never be the accurate value of the property. The difference
between the two is called error.
4.3.1 Definition of Errors

An error may be defined as the difference between a measured value and the true value of a
property.
Mathematically, E = (O T) where E is the error in the experiment, O is the observed value,
T is the true value. Errors are generally expressed relatively as
E
percentage error (E%) = 100
T
E
and per thousand error, E0 00 = 1000
T
4.3.2 Classification of Errors

Several factors introduce error into the measured value of a property. The errors, which creep in
analytical measurements, are broadly classified as:
(i) Determinate errors or constant errors or systematic errors
(ii) Indeterminate errors or unsystematic or random errors.
4.3.3 Determinate Errors

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.
Classification of determinante errors
Determinante 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.
Absolute error = 500.5 mg 500 mg = 0.5 mg
0.5
Relative error Er% = 100 0.1%
500
If we take a smaller quantity of precipitate which is shown to have a weight of 50.5 mg when
measurement is made with a faulty weight. Let its actual weight be 50 mg. In this case also the
absolute error = 50.5 50 = 0.5 mg as the same faulty weight is used.
However, the relative error
0.5
E r% 100 1%
50
Thus we may conclude that the error become more serious as the quantity of the sample to be
measured decreases.
Proportionate errors: Proportionate errors are those errors in which the absolute error increases
in direct proportion to the sample quantity (weight). One cause of such error is the presence of
impurities in chemicals used in analysis or impurities present in the sample to be analyzed as
explained below.
For example, in the analysis of copper, Cu2+ oxidizes I, so that the iodine liberated is titrated
against sodium thiosulphate. If ferric ion is present as contaminant in cupric salt, it also oxidizes I
to iodine so that analysis of copper will yield a high percentage of copper. If the quantity of the
sample is doubled the amount of iodine liberated by Cu2+ and Fe3+ will also be doubled. Hence,
the absolute will also be doubled. However, the relative error will be the same, since the absolute
is proportional to the quantity of the sample reported percentage of copper will depend on the
quantity of the contaminated sample.
From the above, we may conclude that when error in the experiment are such that absolute error
is the same but relative error varies, the errors introduced are constant error. On the other hand, when
absolute error varies and relative error remains constant, the error introduced is proportionate error.
Besides the above, the following characteristics of determinant error to be noted.
(i) They may also be variable but of such a nature that can be accounted for correction.
(ii) These are generally unidirectional with respect to the true value (either high or low).
(iii) Determinate errors are reproducible and can be predicted by a person who thoroughly
understands all the aspects of the measurement.
4.3.4 Causes of Determinate Errors

The determinate errors may arise due to various factors and in general can be classified into the
following four types depending upon the system measured, observer and the instrument used.
(i) Instrumental errors
(ii) Methodic errors
(iii) Operational errors
(iv) Personal errors or Human errors
Instrumental errors
These errors arise due to faults in the tools used by the analyst. Glasswares such as pipettes,
burettes, measuring flasks, etc. used in volumetric analysis, instruments using electronic circuits,
such as pH meter are all calibrated at a certain temperature. If these are used in some other
temperature, the calibration is disturbed and the measurements become unreliable. So instrumental
errors are due to the use of uncalibrated weights, ungraduated glassware and other instruments
such as pH meter. Errors may also be introduced due to voltage fluctuation in the source of current
supply.
Methodic errors
Adoption of defective experimental methods causes these errors. These may arise due to
incompleteness of a reaction and incorrect sampling. For example, Kjeldahls method (refer to
Chapter 5) used for the determination of nitrogen may not give consistent results in certain cases
as in case of some organic compounds, containing ring nitrogen. The digestion with concentrated
H2SO4 may not completely convert the ring nitrogen to ammonium sulphate. This is particularly
true for pyridine compounds in which the results of nitrogen determination are low. Some sources
of methodic errors include coprecipitation, postprecipitation, of impurities, side reaction, slight
solubility of precipitate, impurities in reagent, etc. These are most serious errors. These are inherent
in the method and can not be minimized or corrected unless the conditions of the determination are
changed.
Operational errors
These errors arise due to lack of knowledge or total ignorance of handling equipment and not
taking the necessary precautions in measurements as exemplified below.
(a) Lack of experience of the analyst resulting error in weighing and volume readings.
(b) Introduction of foreign materials in the experimental sample due to carelessness such as
not covering the sample container.
(c) Errors may be due to defective operations such as during transfer of solution, incomplete
drying of samples and bumping during sample dissolution, etc.
(d) Weighing a crucible when it is hot and cooling in a desiccator with a poor desiccant.
(e) The use of indicators in quantities is more than necessary. This leads to erroneous results,
since the indicator may also get titrated.
(f) Ignition of precipitate in incorrect temperature.
(g) Allowing hygroscopic materials to absorb moisture before or during weighing.
(h) Failure to apply buoyancy correction when required.
Frequently the sources of an error may lie in more than one of these categories. For example,
some error may always be expected in weighing a hygroscopic substance, but it may be increased
further if the analyst has a poor balance technique.
Personal error or human errors
These errors are due to factors for which the individual analyst is responsible and are not connected
with the method or procedure.
These errors may arise as a consequence of faulty ideas, improper technique, carelessness,
ignorance and physical limitations of the experiments. Such error may be due to physical disability
like colour blindness, which may make incorrect judgement of colour. Some examples of personal
errors are
(a) Mechanical loss of material in various steps of analysis.
(b) Errors in reading in burette.
(c) Improper washing of a precipitate.
(d) Insufficient cooling of crucible.
(e) Using impure reagent.
(f) Mathematical error in calculation.
By an appropriate choice of equipment, calibration of apparatus used, and the method of analysis,
systematic error can be minimized to an acceptable level.
4.3.5 Indeterminate Errors

These are random or accidental errors which arise from uncertainties in a measurement that are
unknown and not controlled by the analysts. These are revealed by small differences in values of
successive measurements made under identical condition by the same analyst. These errors follow
a random distribution. Thus the mathematical law of probability can be applied to get most probable
result from a series of experiments made. A normal distribution curve (Gaussian curve) is shown
in Figure 4.1 for such errors which shows that:
Figure 4.1 Gaussian curve for indeterminate errors.
(a) Small errors occur more frequently than large one.

(b) Positive and negative errors of the same magnitude are likely to occur equally.
(c) Narrow peaked curves with steep slopes indicate a relatively high precision.
(d) Broad curve indicates a relatively low degree of precision.
These errors can not be attributed to any known cause. They are random in nature and lead to
both high and low results with equal probability. They cannot be eliminated or corrected and are
the ultimate limitation on the measurement.
4.4 PROPAGATION OF ERRORS
The uncertainty in each measured value such as weight, volume, length etc. (measured twice or
more) must be estimated. This can be done according to the following rules of propagation of
errors.
4.4.1 Uncertainty Involving Addition and Subtraction

If the measured values are added or subtracted to get the result, the uncertainty in the results is
equal to the sum of the uncertainties of the individual measured value. If the measured values are
a and b and their uncertainties are ±Da and ±Db respectively, then
a + b = c; Dc = ±(Da + Db)
Similarly
a b = c; Dc = ±(Da + Db)
For example, in measuring volume with a burette, the uncertainty involved is calculated as follows.
Let the volume delivered = V ml
V = Final burette reading Initial burette reading
If the uncertainty in both the reading is ±0.02, then the uncertainty involved in the volume
delivered in the burette, DV = ±(uncertainty in final burette reading + uncertainty in initial burette
reading)
i.e. ±(0.02 + 0.02) = ±0.04
The uncertainty involved in measuring the temperature from the following data is calculated as
follows:
51.2 ± 0.2ºC 23.4 ± 0.2ºC
Here a = 51.2, b = 23.4
c = ab
= 51.2 23.4
= 27.8°C
Da = ± 0.2ºC and Db = 0.2ºC
Hence, Dc = ±(Da + Db)
= ±(0.2 + 0.2)
= ±0.4ºC
Hence, the net result of the above data is 27.8 ± 0.4.
4.4.2 Uncertainty Involved in Multiplication and Division

If the measured values are multiplied or divided to get the final result, then relative uncertainties
are added to get the relative uncertainty in the final result.
Consider the following relationship of a multiplication
c=a´b
where a and b are values of two measurable quantity. If Da and Db are the uncertainty associated
with the measurable quantity a and b respectively, then the actual value are a ± Da and b ± Db
respectively. Therefore, the resulting value will be c ± Dc. These are related as follows:
Dc/c = ± (Da/a + Db/b)
The same relationship holds good for division also.
c = a/b then Dc/c = ± (Da/a + Db/b)
For example, when 250 gm of water is heated through 10ºC and if the uncertainty in weight is
±1 gm and that in temperature is ±0.2ºC, then the uncertainty involved in the heat absorbed is as
follows:
Here a = 250 gm and b = 10°C
Da = ±1 gm and Db = ±0.2°C
Heat absorbed = mass of water in gram ´ specific heat of water ´ temperature to which heated
Specific heat of water = 1
so heat absorbed c = a ´ b = 250 ´ 10 = 2500
(Dc/c) = ±(Da/a) + (Db/b)
= ±(1/250 + 0.2/10)
= ±(0.004 + 0.02)
= ±0.024
Dc = ±0.024 ´ c
= 0.024 ´ 2500 = 60
Hence the heat absorbed should be 2500 ± 60 calorie.
4.5 ACCURACY AND PRECISION
The correctness and reproducibility of a measurement can be expressed in terms of accuracy and
precision respectively as follows.
4.5.1 Accuracy
Accuracy is a measure of how closely the result of an experiment agrees with the true or accepted
value. In other words, it expresses the correctness of a measurement. However, accuracy is never
known. It is known within certain limits only. It can be approached but never be attained. It is
because, the results cannot be expressed by any finite number of digits due to mistake made by
experimenter and by the use of measuring device. However, the only kind of physical quantities
that can be measured with perfect accuracy are a tally of discrete objects like rupee and coin; etc.
There are two possible ways of determining the accuracy
(i) Absolute method
(ii) Comparative method
Absolute method
In this method to determine the accuracy the experiments are repeated several times. This is know
as replicate analysis. The consistency of the result in replicate analysis is very often taken as a test
of accuracy. However, this is not always so since for some unidentifiable reasons the magnitude of
error in every measurement might have been the same and the result consequently might have
been consistent although necessarily accurate. The difference between the mean of an adequate
number of results and the actual result may be taken as the measure of the accuracy of the method.
Comparative method
In this method the accuracy is judged by using two or more independent techniques such as
gravimetric, titrimetric, spectrophotometric, etc. to solve the same problem. Independent techniques
are methods based on different physical and chemical principles. If two independent techniques
give the same result the result is thought to be free from error, hence accurate.
In strict sense accuracy can never be determined unless the true value of the measured property
is known but the limit of the accuracy can be estimated. It is the task of the analyst to judge the best
value from replicate measurements for a property of the given sample. Mathematical and statistical
methods are employed determine or to judge the best value and reliability of result in expressing
the accuracy as follows:
4.5.2 Methods of Expressing Accuracy

The accuracy of a measurement can be expressed in terms of
(i) absolute error,
(ii) relative error and
(iii) relative accuracy.
Absolute errors
The difference between the measured value xm and the true value xt with regard to sign is called
absolute error (E). It is reported in the same unit.
Absolute error, E = (xm xt)
Thus, if 2.68 g of a sample of material is analyzed to be 2.59 g, the absolute error = (2.59 2.68) g
= 0.09 g.
Relative error
It is the value obtained by dividing the absolute error by the accepted or true value.
( xm xt )
Relative error, Er =
xt
The relative error gives the error relative to the size of the measured value. It can be expressed as
the percentage or parts per thousand (ppt) of the true value as given below.
Absolute error 100
Percent relative error, Er% =
Accepted value or true value
( xm xt )
= 100
xt
( xm xt )
Parts per thousand error Er (0 00) = 1000
xt
In the above analysis, the percent relative error
0.09 100
= = 3.3%
2.68
The relative error in parts per thousand, Er (0 00) = 33

Relative error can be minimized by precise measurement and eliminating the error of procedure.
Relative accuracy
It is the measured value expressed as the percentage of the true value.
Thus
Measured value
Relative accuracy = 100
True value
xm
= 100
xt
In the above analysis the percent relative accuracy
2.59
100 96%
2.68
4.5.3 Precision
When a sample is analyzed several times, the individual results are rarely the same. Instead, the
results are randomly scattered. Precision is a measure of how closely the result of an experiment
agrees with those of other measurements made in the same ways. In other words, it expresses the
reproducibility of the results. This can be achieved unlike accuracy.
4.5.4 Comparison between Accuracy and Precision

It is to be noted that precision always accompanies accuracy but a good precision does not mean
good accuracy due to the following reasons.
(a) The same mistake may be made over and over again.
(b) An experimental procedure may be precise but due to some constant and unknown errors
the results may be inaccurate.
This can be best illustrated by the following example.
A substance know to contains 42.10 ± 0.02% of a constituent X. The result obtained by two
analysts using the same substance and the same analytical method were as follows:
Analyst 1% X: 42.01, 42.25, 42.08, 42.14, the arithmetic mean is 42.12% and the result ranges
from 42.01% to 42.25%
Analyst 2% X: 42.40, 42.44, 42.42, 42.42, the arithmetic mean is 42.42% and the result ranges
from 42.40% to 42.44%. The result of the analysis can be summarized as follows:
(i) The values obtained by analyst 1 are accurate (very close to
the correct result), but precision is inferior to the results
given by analyst 2. The values obtained by analyst
2 are very precise but not accurate.
(ii) The results of analyst 1 are both sides of the mean values
and this may be attributed to random error. However, there is
a constant systematic error present in the result of analyst 2.
(iii) The various cases of accuracy and precision are shown in
Figure 4.2.
The goal in any measurement should be to obtain both
precision and accuracy.
4.5.5 Methods of Expressing Precision

While analyzing a sample, each set of analytical results should be
accompanied by an indication of the precision of the analysis. The
precision can be expressed in terms of mean and median, range or
spread, average deviation, relative average deviation, standard
deviation, relative standard deviation, variance, standard deviation
of the mean, relative standard deviation of the mean and confidence
limit as described below.
The mean and medians
Quite obviously single measurement cannot give an indication of the
reliability of results. It is the general practice therefore to carry out
replicate analysis using the same method and equipment and obtained
a number of values for the same property of a given substance. For Figure 4.2 Accuracy and
precision.
example, in titrimetry, an experiment is repeated three or four times
with the same solution and the same apparatus in the selection of the best values from the various
values. Two methods are commonly adopted to determine average and the median.
The Mean: The term mean, arithmetic mean and average x are synonymous for the numerical
value obtained by diving the sum of the values of a set of replicate measurement by the number of
measurements made.
If x1, x2, x3, , xn are the values of n replicate measurements, then
x1 x2 x3 "x Ç
i
n
xi
n 1
x
n n
where xi represents the value of ith measurement and n is the number of independent measurements.
The Median: The median (xmed) is the value for a set of ordered data for which one half being
numerically smaller and the other half being numerically greater. At first the values of the
measurement are to be arranged in increasing order. If the set consists of an odd number of
measurements (suppose n), the selection of the median may be done directly taking the value of
È n 1Ø
ÉÊ Ù th measurement. For a set containing an even number of measurements (n), the average of
2 Ú
È nØ n 1Ø
the central pair such as the value corresponding to É Ù th and ÈÉ th measurement is taken as
Ê 2Ú Ê 2 ÙÚ
the median.
Illustration 1 Calculate the mean and median for the following set of results 10.06, 10.20, 10.08
and 10.10.
10.06 10.20 10.08 10.10

Mean, x 10.11
4
In order to find the median, the above data are to be arranged in the increasing order 10.06, 10.08,
10.10, 10.20. The set contains an even number of entries for which the central pair is 10.08 and
10.10. Hence,
10.08 10.10
median = = 10.09
2
Illustration 2 Calculate the mean and median for the following set of results 0.124, 0.130, 0.128,
0.126 and 0.122
0.124 0.130 0.128 0.126 0.122
Mean, x =
5
= 0.126
Median: On arranging the number in increasing order 0.122, 0.124, 0.126, 0.128, 0.130, the
median is 0.126.
Expression of precision in terms of Mean and Median
A commonly used method to express precision of a measurement is deviation of a value (xi) from
the mean or the median of a set of values without regard to signs denoted by the symbol mod.
Thus, precision = xi x or xi xmed
The deviation from the mean xi x is generally denoted by the letter d.

Besides the above, the precision can be expressed in the following ways.
Expression of precision by range
The Range: The range (w) of a set of data is simply the difference between the maximum and
minimum value in the data set. The range is also called spread.
Range = w = xlargest xsmallest
Expression of precision by mean deviation or average deviation, d and relative average

deviation
It may be defined as the mean of the difference of individual measured value and the mean of the
measurement without regard to sign.
If x1, x2, , xn are the values for 1st, 2nd, , nth measurement respectively and x is the mean
value, then average deviation
d =
[( x1 x )] [( x2 x )] " [(x
n x )]
n
i n
Ç [( x x )]
i 1
i
=
n
where xi = individual measured values
x = mean of the measurement
S represents summation.
Illustration 3 Average deviation d , from the following data 61.45, 61.51, 61.12 and 61.40 can
be calculated as follows
61.45 61.51 61.12 61.40
x 61.37
4
Here n = 4
i 4
Ç[(x x )] = (61.45 61.37) (61.51 61.37) (61.12 61.37) (61.40 61.37)

i
i 1
= 0.08 0.14 0.25 0.03 0.50

0.50
\ d = 0.125
4
Relative average deviation: Often the average deviation is expressed relative to mean as a per
hundred (%) or per thousand ().
d
Relative average deviation (%) = 100
x
d
Relative average deviation () = 1000
x
In the above example,
0.125
Relative average deviation (%) = 100 0.204
61.37
0.125
Relative average deviation () = 1000 2.04
61.37
Expression of precision by standard deviation, relative standard deviation and variance
Standard deviation (s or s): The standard deviation s of an infinite set of experimental data is
theoretically the square root of the mean of square of the difference between the individual measured
value (xi) and the mean (m) of the infinite number of measurement.
Thus
V
Ç(x i P )2
where n ® ¥
n
In practice, it is only possible to calculate the individual deviation from the mean x of a limited
number of measurements, i.e. xi x . Hence it is desirable to define a quantity which is an
experimentally reliable estimate of the standard deviation. Such a quantity is called the estimated
standard(s), which is applicable to a finite set of data and is given by
s
Ç(x x )i
2
n 1
where n is the number of measurement and the number (n 1) is called the number of degrees of
freedom or independent measurements.
The term degrees of freedom may be defined as the number of individual observations that may
be allowed to vary, provided that x and s once determined are held constant. For example, once
the mean is obtained and we decide to keep it constant then all but one observation can be varied;
the last one is fixed by x and all its x values, so there can be (n 1) number of independent
measurement possible, i.e. the degree of freedom = n 1 for n measurements. When n is greater
than 30, it is safe to assume s ® s.
Significance of standard deviation: Standard deviation of a set of experimental measurements
is a predication that 68 percent of an infinite number of replicate measurements will lie in the
interval about the mean. Thus, if in a given case the standard deviation for a set of result with a
mean of 12.86 is 0.02, then it means that if an infinite number of measurement are made 68 percent
of the measurement will lie in the interval 12.86 ± 0.02 about the mean.
Relative standard deviation: The standard deviation may be expressed relative to mean as per
hundred % or per thousand ()
s
Relative standard deviation (%) = 100
x
s
Relative standard deviation () = 1000
x
The relative standard deviation in part per hundred is called the coefficient of variation (CV).
s
\ CV 100
x
Variance, s2: The square of the standard deviation is called the variance.
Variance, s2 =
Ç (x
i x )2
n 1
Expression of precision by standard deviation of the mean and relative standard deviation
of the mean
Standard deviation of the mean: The standard deviation of the mean is an estimate of the
probable error in the mean of a series of observation and is referred to as standard error defined as
follows:
s
Standard error = s (mean) =
n
where n is the number of measurement and s is the standard deviation of standard deviation.
Relative standard deviation of the mean: Like the standard deviation of the mean, it is possible
to define relative standard deviation of the mean (relative s mean)
s(mean)
Relative s mean =
x
The confidence limit: In quantitative analytical work, one deals with relatively small number of
measurements. When the number of measurement is a small finite number, one deals with s instead
of s and x instead of m. s and x are the only estimate of s and m. Thus we may conclude that
though standard deviation of a set of data provides an indication of precision inherent in a particular
procedure of analysis, it does not give any information about how close the experimentally
determined mean might be with the true mean value m.
Statistical theory allows us to estimate the range within which the true value might fall within a
given probability defined by the experimental mean and standard deviation. This range is called
the confidence interval and the limits of the range are called the confidence limit. The likelihood
that the true value falls within this range is called probability or confidence level usually expressed
in terms of percent. The confidence limit is given by
ts
Confidence limit = x
n
where t is a statistical factor that depends on the number of degrees of freedom n, (n = n 1) and
the confidence of desired level. The values of t at different confidence levels and degrees of freedom
are given in Table 4.1.
From Table 4.1 it is seen that on increasing the number of replicate measurements both the
s
values t and decrease so that the confidence interval is smaller.
n
Table 4.1 t Values for various confidence levels
Number of Number of Probability levels
observation degree of freedom
(n) n1 90% 95% 99%
2 1 6.314 12.706 63.660
3 2 2.920 4.303 9.925
4 3 2.353 3.182 5.841
5 4 2.132 2.776 4.604
6 5 2.015 2.571 4.032
7 6 1.943 2.447 3.707
8 7 1.895 2.365 3.500
9 8 1.860 2.306 3.355
10 9 1.833 2.262 3.250
11 10 1.812 2.228 3.169
12 11 1.800 2.200 3.110
Illustration 4 For example, a soda ash sample is analyzed by titration with standard hydrochloric
acid. The analysis is performed in triplicate with the following results93.50, 93.58 and 93.43%
Na2CO3. The range within which the true value lies with 95% confidence can be calculated as
follows:
Here n = 3, so the degrees of freedom n = 3 1 = 2. The mean
93.50 93.58 93.43
x 93.50%
3
The standard deviation,
( x1 x ) 2 ( x2 x )2 ( x3 x ) 2
s=
n 1
(93.5 93.5) 2 (93.58 9.5) 2 93.41 93.5) 2

s=
3 1
= 0.075%
At the 95% confidence level and two degrees of freedom t = 4.303
ts
n
4.303 0.075
= 93.5 93.50 0.196
3
4.6 TEST OF SIGNIFICANCE
In developing a new analytical method it is often desirable to compare the result of that method
with those of an accepted (standard) method. This can be done by the following tests known as test
of significance.
4.6.1 Comparing a Mean Value with a True Value (The Students t Test)
W. S. Gosset, an English chemist writing under the pen name of student proposed a test to know
whether there is a significant difference between a new method and a standard method or not. This
test is called students t test as described below.
(i) Two sets of replicate measurement are made by two different methods, one is the new
method and the other is the standard method, the two ways in which t test can be used are:
(a) A series of replicate analysis are done in a single sample (having the same concentration
by two methods).
(b) A series of analysis are done on a set of different samples (with different concentrations
by two methods).
(ii) The students t value is calculated by applying the following equation
For the first method (a)
n
t xP
s
where m is the true mean value, s is the standard deviation, x is the average value for n
number of observations.
For the second method (b), the difference (Di) between each of the paired measurement on
each sample is computed with regard to sign, i.e. actual sign (±) of the difference is considered
and the average difference ( D) is calculated and the individual difference each from D ,
i.e. Di D is used to compute a standard deviation, sd. The t value is calculated from
D
t= n
sd
sd =
Ç ( D D)
i
2
n 1
(iii) The calculated t value is compared with the tabulated t value for a given number of
measurements at the desired confidence level (Table 4.1). If the calculated t value exceeds
the tabulated value then there is a significant difference between the results of the two
methods at that confidence level. If it does not exceed the tabulated value, then we can
predict that there is no significant difference between the two methods.
Illustration 5 For example, if mean of 12 determination, x = 8.37 and the true value, m = 7.91
and standard deviation, s = 0.17, then whether the result is significant or not at 90% confidence
level can be decided as follows:
12
t 8.37 7.91 9.4
0.17
For n = 12, the number of degrees of freedom = 12 1 = 11.
From t table, for eleven degrees of freedom, the value of t at 90% confidence level is 1.80.
Therefore, the calculated value exceeds the tabulated t value. Hence there is a significant difference
between the results of the two methods at 90% confidence level.
Illustration 6 Following are the two sets of results for a number of individual samples by a new
analytical method and a known standard method to determine whether there is significant difference
between the two methods at 95% confidence level.
Sample New analytical method Standard method Di Di D ( Di D )2
A 10.2 10.5 0.3 0.6 0.36

B 12.7 11.9 0.8 0.5 0.25
C 8.6 8.7 0.1 0.4 0.16
D 17.5 16.9 0.6 0.3 0.09
E 11.2 10.9 0.3 0.0 0.00
F 11.5 11.1 0.4 0.1 0.01
Ç 1.7 Ç 0.87
Here, there are six samples for analysis, hence n = 6 and number of degrees of freedom =
61=5
1.7
\ D = 0.28
6
0.87
sd = 0.42
6 1
0.28
t= 6 1.63
0.42
The tabulated t value at 95% confidence level for 5 degrees of freedom of is 2.57. Therefore,
tcalc < ttable and there is no significant difference between the two methods at 95% confidence
level.
4.6.2 Comparing Two Experimental Means

Suppose that a sample has been analyzed by two different methods, yielding means x1 and x2 and
standard deviation s1 and s2. Let n1 and n2 are the number of individual results obtained by the two
methods. The first step is to calculate a t value using the formula.
x1 x2 n1n2
t
s n1 n2
This procedure assumes that s1 and s2 are the same (nearly same). The second step involve entering
t table at a degree of freedom given by (n1 + n2 2) and at the desired probability (or confidence)
level. If the value in the table is greater than the t calculated from the data, the difference between
the mean is not significant.
Illustration 7
Suppose for 1st method x1 = 42.34, s1 = 0.10 and n1 = 5
2nd method x2 = 42.44, s2 = 0.12 and n2 = 4
In order to find whether the two methods are significantly different or not at the 95% probability
level, we are to use the modified equation of t test, i.e.
x1 x2 n1n2
t
s n1 n2
We can take either value of s
42.34 42.44 54

t 1.491
0.10 54
From Table 4.2, at degrees of freedom (n1 + n2) 2 = 7, t for the 95% probability level, t = 2.36 and
since 1.491 < 2.365, the difference is not significant.
4.6.3 Comparison of Two Standard Deviations (F Test)

This is a test designed to indicate whether there is a significant difference between the two methods
based on their standard deviations. F is defined in terms of the variance of the two methods, where
variance is the square of the standard deviation.
s12
F where s12 ! s22
s22
If the calculated value of F exceeds a tabulated value at selected confidence level, then there is
a significant difference between the values of the two methods, i.e. new and the accepted
methods. Some sample F values are given in Table 4.2 for a probability level of 95%. F values
corresponding to (n1 1)th column and (n2 1)th row of the table are to be taken for s1 > s2.
Table 4.2 F Values at the 95% probability level

n 1 for n 1 for larger s2
smaller s2 3 4 5 6 10 20
3 9.28 9.12 9.01 8.94 8.79 8.66
4 6.59 6.39 6.26 6.16 5.96 5.80
5 5.41 5.19 5.05 4.95 4.74 4.56
6 4.76 4.53 4.39 4.28 4.06 3.87
10 3.71 3.48 3.33 3.22 2.98 2.77
20 3.10 2.87 2.71 2.60 2.35 2.12
Illustration 8 The standard deviation for one set of 4 determinations is s1 = 0.12 by 1st method
and standard deviation for 5 determinations by 2nd method is s2 = 0.10. We are to determine
whether there is any significant difference between the precision of these two sets of result or not
in the following way by using F test.
Here s1 = 0.12 and s2 = 0.10 as (s1 > s2), n1 = 4 and n2 = 5
Therefore
s12 (0.12) 2
F= 2 1.44
s2 (0.1) 2
Column will be taken corresponding to n1 1, if s1 > s2 and the row will be taken coresponding to
n2 1. Consulting Table 4.2, the F value corresponding to column 4 1 = 3 and row 5 1 = 4 is 6.59.
Since 6.59 >1.44, the standard deviation for these two methods are not significantly different.
4.6.4 Chi-square Test (l2 Test)

This test is used to determine whether or not a set of data differ significantly from a theoretical or
defined distribution, i.e. whether the observed frequency of an occurrence corresponds to the
predicted frequencies.
Chi-square is calculated from the equation
(O E ) 2
O2 Ç E
where O is the observed frequency and E is the expected frequency. Suppose a coin is tossed
100 times and the tails come up 25 times. In order to ascertain whether any real indication of bias
or not, we are to perform l2 test. Here O = 25. Normally we would expect an equal chance of
obtaining heads or tails. Then in this case 50 heads or 50 tails are expected, hence E = 50.
(25 50) 2 (75 50)2 2 625

O2 25
50 50 50
For one degree of freedom the l2 table given the following value 1% level 6.63, 0.1% level 10.83.
The value of 25 obtained in the above calculation is well beyond 10.83 and we can say that there
is a significant bias in the spinning of the coin.
4.7 REJECTION OF A RESULT
It is found that when a series of replicate analysis is performed, one of the results may be abnormal, i.e.
differs markedly from the others. The following rules decide whether to reject the result or to retain it.
4.7.1 Rule Based on Average Deviation

To apply this rule, first calculate the mean x and average deviation d of the good result.
Determine the deviation of the suspected result from the mean of good one, i.e. let the suspected
value be x and if x ³ 4d , i.e. if the deviation of the suspected value from the mean is at least four
times the average deviation, then the rejection is justified.
Illustration 9 Analysis of a given quantity gave the following values 46.62, 46.67, 46.64, 46.76,
46.53, 46.60, 46.71, 46.60, 46.71, 46.34. We are to predict whether the tenth value, i.e. 46.34 is to
be rejected or to be retained.
Mean average deviation of the retained value
46.62 46.47 46.64 46.76 46.53 46.60 46.71 46.60 46.71
x = = 46.627
9
i 9
d =
Çx
i 1
1 x
n
0.007 0.137 0.013 0.133 0.97 0.127 0.083 0.027 0.083
= 0.070
9
x = (suspected value) = 46.627 46.34 = 0.287
4 d = 0.070 ´ 4 = 0.28
Hence 0.287 is more than 4 times the average deviation and hence the rejection is justified.
4.7.2 Rule Based on the Range (Q Test)

Q test is applied as follows:
(i) The data are arranged in a decreasing order
(ii) The range (w) of the results is calculated.
(iii) The difference (a) between the suspected result and its nearest neighbour is found.
(iv) The difference (a) obtained in step (iii) is divided by range (w) in step (ii) to obtain the
rejection quotient Q.
a Suspected value – Nearest value
Q
w Largest value – Lowest value
(v) The computed values of Q is compared with the values presented in the already prescribed
Q table. If the value of Q is greater than or equal to the value in the Q table, then the
suspected result can be discarded. The tabulated values of Q at 90% confidence levels are
given in Table 4.3.
Table 4.3 Value of rejection quotient, Q

Number of observations Q0.90
3 0.94
4 0.76
5 0.64
6 0.56
7 0.51
8 0.47
9 0.44
10 0.41
Illustration 10 Determination of the vitamin C content of citrus fruit drink gave the following
results: 0.218, 0.219, 0.230 and 0.220. Apply the Q test to see whether 0.230 value can be discarded
or not.
Arrange in decreasing order 0.230, 0.220, 0.219, 0.218, 0.215.
a = 0.230 0.220 = 0.01
w = 0.230 0.215 = 0.015
a 0.01
Q= 0.67
w 0.015
The value of Q at n = 5 is 0.64, since 0.67 > 0.64, the rule says that the result can be discarded.
4.8 PROBLEMS INVOLVED IN DATA ANALYSIS
4.8.1 Problems on Significant Figures

PROBLEM 4.1 Express the number of significant figure for the followings:
(a) 0.00200 (b) 9.023 ´ 1023
(c) 99.9 (d) 100.0
(e) 3.05 ´ 108 (f) 40.500
(g) 0.317 (h) 9.202
(i) 0.00149
Solution
(a) In 0.00200, three zeros precede a non-zero digit (here) and hence these are leading
zeros which are not significant. There are two zeros at the right end of the non-zero digit
(here two) and the number contains a decimal point and hence significant. There are three
significant figures.
(b) 9.023 ´ 1023: The number has been written in the exponential form. Hence, the number
of significant figures is equal to the numerical portion, i.e. 4, 0 is included as a significant
figure as it is a captive zero.
(c) 99.9 contains only non-zero digits and hence all the digits are significant. The number of
significant figure in 99.9 is 3.
(d) In 100.0, there are three zeros at the right end of the number, which contains a decimal
point. Hence all those zeros are trailing zeros and therefore significant. The number of
significant figures in 100.0 is 4.
(e) 3.05 ´ 108 has been written in the exponential form. Hence the number of significant
figures is equal to the numerical protion, i.e. 3 (Zero being captive and has been taken as
significant figure).
(f) 40.500 has one captive zero and two trailing zeros and hence the number of significant
figures in 40.500 is 5.
(g) 0.317 has one leading zero and hence not a significant figure and three non-zero digits,
hence the number of significant figures in 0.317 is 3.
(h) In 9.202, there is one captive zero and three non-zero digits. Hence the number of significant
figures is 4.
(i) 0.00149 has three leading zeros, hence not significant. It has three non-zero digits.
PROBLEM 4.2 Express the result of the following arithmetical operations using the correct
number of significant figure.
7.34 103 (4.080)

(a) 236.30 + 12.2 1.6342 (b)
0.0280 (6.18 104 )
(c) log 12.6 ´ 104 (d) log 9.642 ´ 103
(e) Antilog 23.78 (f) Antilog 0.0252
Solution
(a) The result of operation is 246.8658. As the minimum number of significant figures is three,
the result should contain three digits, i.e. 247.
(b) As per the rule, its result should contain three significant figures. The correct result is
1.73 ´ 105.
(c) In the logarithm of 12.6 ´ 104 = 1.26 ´ 105, the characteristic is 5. Using a log table the
mantissa is found to be 0.10037. Since the number 1.26 has three significant figures,
the mantissa should also have three significant figures and can be expressed as 0.100.
The result is, therefore, 5.100.
(d) In the logarithm of log 9.642 ´ 103, the characteristic is 3. Using a log table, the mantissa is
found to be 0.98416. Since the number 9.642 has four significant figures, the mantissa
should have also four significant figures and can be expressed as 0.9842. The result is
therefore 3.9842.
(e) While taking antilogarithm the result should contain the same number of significant figures
as that in the mantissa. The antilog of 23.78 is 6.0256 ´ 1023. The mantissa (0.78) has two
significant figures, so the antilogarithm of 23.78 should be 6.0 ´ 1023.
(f) The antilog of 0.0252 is 1.0597. Since the mantissa 0.0252 has three significant figures
(there are two leading zeros and hence are not significant), the result should contain three
significant figures and the correct result is 1.06.
4.8.2 Problems on Rounding off Number

PROBLEM 4.3 Round off the following terms to two significant figures
(i) 2.65
(ii) 2.75
(iii) 2.69
(iv) 7.266
Solution
(i) In 2.65, the digit coming after the desired number of significant figure is 5 and its preceding
digit is 6 which is even, 5 is dropped, hence the correct result is 2.6.
(ii) In 2.75, the preceding digit of 5 is 7 which is odd and hence one is added to it, so the correct
result in terms of the significant figure is 2.8.
(iii) In 2.69, the first digit comes following the point of round off is 9 which is greater than 5.
Hence one is added to the preceding digit (6) so the correct result in term of two significant
figure is 2.7.
(iv) In 7.266, the first digit following the point of round off is 6 which is greater than 5. Hence
one is added to the preceding digit (2), so the correct result is 7.3.
PROBLEM 4.4 Express the following numbers to four significant figures
(i) 5.607892
(ii) 32.392800
(iii) 1.78986 ´ 103
(iv) 0.0070837
Solution
(i) 5.607892 has 7 significant figures. In order to express it into four significant figures,
the first digit following point of round off is 8 which is greater than 5. Hence one is added
to its preceding digit so that the correct number is 5.608.
(ii) 32.392800 has 8 significant figures. In order to express it into four significant figures, the
first digit following the point of round is 2 which is 2 less than five, hence dropped. So the
correct result 32.39.
(iii) 1.78986 ´ 103 has 6 significant figures. In order to express it into four significant figures, 9
is to be round off. Since the first digit following 9 is 8 which is greater than 5, one is added
to it so that the correct result is 1.790 ´ 103.
(iv) 0.0070837 has three leading zeros (hence are not significant), one captive zero which is
significant. So 0.0070837 has 5 significant figures. In order to express it into four significant
figures, 3 is to be round off, since first digit following 3 is 7 which is greater than 5, one is
added to its preceding digit so that correct result is 0.007084.
PROBLEM 4.5 Which is the correct reading that has been recorded from a device calibrated to
one hundredth of a unit?
(i) 5.452 or 5.45 or 5.4
(ii) 10.25 or 10.256 or 10.2
Solution
(i) 5.45
(ii) 10.25
4.8.3 Problems on Uncertainties

PROBLEM 4.6 Find the maximum uncertainties in the following measurement of temperature.
51.2 ± 0.2ºC 23.4 ± 0.2ºC.
Solution Here a = 51.2ºC, b = 23.4ºC
Da = ±0.2ºC, Db = ±0.2ºC
c = a b = (51.2 23.4)°C = 27.8°C
Dc = ±(Da + Db) = ±(0.2 + 0.2) = ±0.4°C
Hence c + Dc = 23.8 ± 0.4°C.
PROBLEM 4.7 The melting point of a substance was quoted as 52.5°C, 52.57°C, 52.571°C and
52.3713°C. Which of the values would be most acceptable and which will have maximum
uncertainty and why?
Solution The above quantities may be represented with their uncertainties in their last digit and
can be represented as:
for 1st reading 52.5 ± 0.1
2nd reading 52.57 ± 0.01
3rd reading 52.571 ± 0.001
4th reading 52.3713 ± 0.0001
As in the 4th reading, the uncertainty is 1 in 523713, it is found to be least and hence most acceptable.
4.8.4 Problems on Errors and Uncertainty
PROBLEM 4.8 If an analyst finds a value of 22.44% iron in a sample, which actually contains
20.34%, calculate (i) absolute error (ii) relative error in % (iii) relative error in 0/00.
Solution Absolute error, E = Measured value True value
= 20.44 20.34 = 0.10
Absolute error
Relative error in % = 100
True value
0.10
= 100 0.49
20.34
0.10
Relative error in 0/00 = 1000 4.9
20.34
PROBLEM 4.9 The uncertainty in each reading on a trip balance is ± 0.01 g. How large a
sample should be taken using this balance so that the relative uncertainty in weight will be 2.0
parts per thousand.
uncertainty
Solution Relative uncertainty in 0/00 = 1000
wt of sample
0.01×1000
2=
wt of the sample
0.01 1000
\ wt of the sample = 5g
2
PROBLEM 4.10 A beaker is weighed to the fourth decimal place. If the beaker weighs 100 g,
what is the relative uncertainty in the weight in parts per thousand (ppt)?
Solution Here the uncertainty = 0.0001
uncertainty
Relative uncertainty in ppt = 1000
wt of sample
0.0001
= 1000
100
= 0.001
PROBLEM 4.11 If the relative uncertainty in the weight of the above beaker is 0.1%, to what
decimal place should it be weighed?
uncertainty
Solution Relative uncertainty in % = 100
wt of sample
uncertainty
0.1 = 100
100
\ Uncertainty = 0.1
\ The beaker should be weighed to the first decimal.
4.8.5 Problem on Relative Error
PROBLEM 4.12
(a) Determine ppt for a relative error of 0.5%.
Error
Solution Relative error in % = 100
True value
Error
0.5 = 100
True value
Error 0.5
=
True value 100
Error 0.5
Relative error in ppt = 1000 1000 5
True value 100
(b) Determine percent error for a relative error of 2.0 parts per 500.
Error
Solution Relative error parts per 500 = 500
True value
Error
2= 500
True value
Error 2
=
True value 500
Error
Relative error in percentage = 100
True value
2
= 100 0.4
500
(c) Determine parts per 100 for a relative error of 5 parts per 2000.
Solution Per 2000, the error is 5
Per 100, the error is
5
100 0.25
2000
(d) Assuming an uncertainty of ±1 in the last digit, what is the relative uncertainty in ppt in the
following numbers (i) 40 and (ii) 500?
Solution
1
(i) Relative uncertainty in ppt = 1000 25
40
1
(ii) Relative uncertainty in ppt = 1000 2
500
4.8.6 Problems on Expressing Precision
PROBLEM 4.13 Find the mean and median for the following set of date:
Set I: 10.06, 10.20, 10.08, and 10.10
Solution Here n = 4, x1 = 10.06, x2 = 10.20, x3 = 10.08 and x4 = 10.10
x1 x2 x3 x4
Mean =
n
10.06 10.20 10.08 10.10
=
4
40.44
= 10.11
4
Median: Firstly, the numbers are arranged in increasing order, i.e. 10.06, 10.08, 10.10, 10.20.
This set contains the even number of date, of which the centre pair is 10.08 and 10.10, hence the
10.08 10.10
median = 10.09.
2
PROBLEM 4.14 An analyst reported the following percentage of FeO in a sample: 16.65,
16.70, 16.68, 16.60, 16.58 and 16.63.
For this set of results, calculate mean, median, range, average deviation, relative average deviation
(ppt), standard deviation, and co-efficient of variation.
Solution Here n = number of observations = 6
16.65 16.70 16.68 16.60 16.58 16.63
Mean, x =
6
99.84
= 16.64
6
To calculate the median, we are to arrange the data in increasing order
16.58, 16.60, 16.63, 16.65, 16.68, 16.70
3rd value + 4th value
As n is even, the median value =
2
16.63 16.65
=
2
33.28
= 16.64
2
R = Range = Highest value Lowest value
= 16.70 16.58 = 0.12
Average deviation
i 6
Ç (x
i 1
i x)
d =
6
= 16.58 16.64 16.60 16.64 16.63 16.64 16.65 16.64
16.68 16.64 16.70 16.64
0.06 0.04 0.01 0.01 0.04 0.06
=
6
0.22
= 0.036 0.04
6
Relative average deviation (ppt)
d 0.04
1000 = 1000 = 2.4038 = 2.4
x 16.64
1
Ç
Ë 2 Û2
xi x
Standard deviation = s = Ì Ü
Ì n 1 Ü
Í Ý
1
ÎÑ (0.06) 2 (0.04) 2 (0.01) 2 (0.01) 2 (0.04)2 (0.06) 2 Þ
Ñ2
= Ï ß
ÐÑ 5 Ñ
à
1
È 0.0036 0.0016 0.0001 0.0001 0.0016 0.0036 Ø 2
= É Ù
Ê 5 Ú
= 0.046
s 0.046
Co-efficient of variation = 100 100 0.276 0.28
x 16.64
PROBLEM 4.15 Calculate the standard deviation and variance of the following set of analytical
results 12.67 g, 12.69 g and 13.03 g.
Solution Here n = 3, x1 = 12.67, x2 = 12.69, x3 = 13.03
12.67 12.69 13.03
x=
3
38.39
= 12.796 12.80
3
Ç (x x )2 = ( x1 x ) ( x2 x ) ( x3 x )
2 2 2
i
= (12.67 12.80)2 + (12.69 12.80)2 + (13.03 12.80)2
= (0.13)2 + (0.11)2 + (0.23)2
= 0.0169 + 0.0121 + 0.0529
= 0.0819
Standard deviation, s =
Ç (x x ) 2
n 1
0.0819
= 0.20
2
Variance, s2 = (0.2)2 = 0.04
PROBLEM 4.16 Find the
(i) Mean deviation, d ,
(ii) Relative mean deviation (%) and
(iii) Relative mean deviation (0/00) form the following data:
61.45, 61.51, 61.12 and 61.40
Solution Here x1 = 61.45, x2 = 61.51, x3 = 61.12 and x4 = 61.40
61.45 61.51 61.12 61.40
Mean, x = 61.37
4
Mean deviation,
( x1 x ) ( x2 x ) ( x3 x ) ( x4 x )
d =
4
61.45 61.37 61.51 61.37 61.12 61.37 61.40 61.37
=
4
0.08 0.14 0.25 0.03
=
4
0.50
= 0.125 0.12
4
d
Relative mean deviation (%) = 100
x
0.12
= 100 0.195 0.2
61.37
0.12
Relative mean deviation (0/00) = 1000 1.95 2.0
61.37
4.8.7 Problems on Propagation of Errors

PROBLEM 4.17 The experimentally measured values of A, B and C are 235.4 ± 0.5,
AB
216.3 ± 0.25 and 107.95 ± 0.55 respectively. Calculate the value of .
C
Solution A B = (235.4 216.3) ± (0.5 + 0.25)
= 19.1 ± 0.75
AB 19.1 0.75
=
C 107.95 0.55
a = 19.1 Da = ±0.75
b = 107.95 Db = 0.55
19.1
Here d= 0.18
107.95
'd È 'a 'b Ø
= É
d Ê a b ÙÚ
È 0.75 0.55 Ø
= É Ù
Ê 19.1 107.95 Ú
= ±(0.392 ± 0.0051)
= ±0.0443
Dd = ±0.0443 ´ 0.18 = 0.008
AB
= 0.18 ± 0.01
C
50.5 2.0
PROBLEM 4.18 Calculate the uncertainty in A where, A = .
18.5 0.3
Solution Here a = 50.5 Da = ± 2.0
b = 18.5 Db = ± 0.3
a 50.5
c= 2.73
b 18.5
'c È 'a 'b Ø
= É
c Ê a b ÙÚ
È 2.0 0.3 Ø
= É Ù
Ê 50.5 18.5 Ú
= ±(0.0396 + 0.0162)
= ±(0.0558)
Dc = ±(0.0558) ´ 2.73 = ±0.15

A = c + Dc = 2.73 ± 0.15
PROBLEM 4.19 Calculate the maximum uncertainty involve in the following (30.2 ± 0.2) ´
(15.1 ± 0.3).
Solution Here a = 30.2 Da = 0.2
b = 15.1 Db = ± 0.3
c = a ´ b = 30.2 ´ 15.1 = 456.02
'c È 'a 'b Ø
= É
c Ê a b ÙÚ
È 2.0 0.3 Ø
= É Ù
Ê 30.2 15.1Ú
= ±(0.0066 + 0.0199)
= ±(0.0265)
Dc = ±(0.0265) ´ 456.02 = ±12.08
Maximum uncertainty = ±12.08
PROBLEM 4.20 In the titration of 10.00 ± 0.04 ml of 0.104 ± 0.002 N HCl, 23.02 ± 0.04 ml of
NaOH is required for neutralization. Calculate the normality of NaOH and indicate the uncertainty
of this value.
Normality of HCl Volume of HCl
Solution Normality of NaOH =
Volume of NaOH
(0.104 0.002) (10.00 0.040)
=
23.02 0.04
Here a = 0.104 Da = 0.002
b = 10.00 Db = 0.04
c = 23.02 Dc = ±0.04
Let the normality of NaOH be d and its uncertainty is Dd
ab 0.104 10.00

\ d= 0.045
c 23.02
'd È 'a 'b 'c Ø
= É Ù
d Ê a b c Ú
È 0.002
0.04 0.04 Ø
= É Ù
Ê 0.104
10 23.02 Ú
= 0.0192 + 0.004 + 0.0017
= 0.0249
Dd = 0.0249 ´ 0.045 = 0.001
Normality of NaOH = 0.045 ± 0.001
4.8.8 Problem on Confidence Level

PROBLEM 4.21 From the following results in percentage 93.50, 93.58, 93.43, find the confidence
limit at 95% confidence level t = 4.303.
Solution Here n = 3, so the degrees of freedom = 3 1 = 2
Here, the mean
93.50 93.58 93.43
x = 93.50%
3
The standard deviation
( x1 x ) ( x2 x ) ( x3 x )
s=
n 1
(93.5 93.5) 2 (93.58 93.5) 2 (93.43 93.5) 2
=
2
= 0.075%
At the 95% confidence level and two degrees of freedom t = 4.303.
ts
n
4.303 0.075
= 93.5
3
= 93.50 ± 0.19%
This result implies that the true value falls in the range of 93.31 to 93.69% with 95% confidence.
4.8.9 Problem on Rejection of Data
PROBLEM 4.22 The following sets of data are found for chloride analysis: 103, 106, 107 and
114 m eq/liter. One value 114 appears suspect. Determine if it can be rejected or retained at the
95% confidence level.
Solution The data in decreasing order 114, 107, 106, 103
Here a = 114 107 = 7
w = 114 103 = 11
a 7
\ Q= 0.64
w 11
The tabulated value for four observations is 0.829. Since the calculated Q is less than the tabulated
Q, the suspected number may not be rejected.
4.8.10 Problem on Student t Test

PROBLEM 4.23 A chemist analyzes a sample of iron ore furnished by the National Institute of
Standard and Technology (NIST) and obtained the following result: x = 10.52, s = 0.05, n = 10.
The NIST value for the sample is 10.6% Fe. Are the result significantly different at 95% probability
level? Given at 95% probability level corresponding to 9 degrees of freedom, t = 2.262.
n
Solution t= x P
s
10
t = (10.52 10.60)
0.05
0.08 10
= 5.06
0.05
Since 5.06 > 2.262, the results are significantly different from the NIST value.
PROBLEM 4.24 A sample of soda ash (Na2CO3) is analyzed by two different methods giving
the following results:
Method I Method II
x1 42.34 x2 42.44
s1 = 0.10 s2 = 0.12
n1 = 5 n2 = 4
Are the two means significantly different at the 95% probability level?
Solution Given t = 2.365 corresponding to 95% probability level for 7 degrees of freedom.
x1 x2 n1n2
t=
s n1 n2
(42.34 42.44) 54
=
0.10 54
t = 1.491
t = 2.365 at degree of freedoms n1 + n2 2 = 7 for 95% probability level. Since 1.491 < 2.365, the
difference is not significant.

(i) The number of significant figures in 12.3460 is
(a) 2 (b) 4
(c) 6 (d) 3
(ii) The number of significant figures in the value 6.023 ´ 1023 is
(a) 3 (b) 4
(c) 7 (d) 3
(iii) The result of the arithmetical operation 21.1 ´ 0.023 ´ 83.2 expressed to the correct number
of significant figure is
(a) 50.91008 (b) 50.91
(c) 50.910 (d) 51
(iv) The result of the arithmetical operation 60.3 + 1.03 0.162 expressed to the correct number
of significant figure is
(a) 61.2 (b) 61.188
(c) 61.19 (d) 61.20
(v) The square of the standard derivation is known as
(a) The co-efficient of variance (b) The absolute deviation
(c) The variance (d) The relative standard deviation
(vi) The average of 64 results is more reliable than the average of 4 results by
(a) 2 (b) 4
(c) 8 (d) 16
(vii) Which of the following statements is true
(a) The variance is the sequence root of standard deviation.
(b) Precise values are always accurate.
(c) The number 0.02040 contains only four significant figures.
(d) Two to the above are true.
(viii) Titration A obtains a mean value of 12.96% and a standard deviation of 0.05 for the purity
of a sample. Titration B obtains the corresponding values as 13.12% and 0.08. Compared
to titration B, titration A is
(a) Less accurate but more precise (b) More accurate and more precise
(c) Less accurate and less precise (d) More accurate but less precise
statements
(i) All precise values are accurate.
(ii) The accuracy can not be approach but actually obtained.
(iii) The numbers 0.0306 has four significant figures.
(iv) Variance is the square of the standard deviation.
(v) From the analytical point of view, out of 19.5 ml and 19.50, 19.5 containing of three figures
(1, 9, 5) is significant when the burette is graduated to 0.1 ml.
(vi) All the non-zero integers are significant.
(vii) The digit zero is always significant.
(viii) The number of significant figures does not change by changing the unit.
(ix) The volume expressed in litre and the same volume expressed in ml has the same number
of significant figures.
(i) The number of significant figures in 12.3460 g is .............. .
(ii) The result of arithmetical operation 60.3 + 1.05 0.162 expressed to the correct number of
significant figure is .............. .
(iii) The number of significant figure in the value 6.023 ´ 1023 is .............. .
(iv) The result of multiplication operation 21.1 ´ 0.029 ´ 83.2 expressed to the correct number
of significant figures .............. .
(v) The square of standard deviation is called .............. .
(vi) The magnitude of random errors determines the .............. of analytical results.
(vii) The errors that can be presumably avoided or corrected are called .............. .
(viii) The difference between the true value and measured value with regard to sign is the ..............
error.
(ix) The absolute error expressed as a percentage of the true value is known as .............. error.
(x) Burette reading of 15.60 ml implies that the actual volume could be anything between
.............. and .............. when the burette is graduated to 0.01 ml.
(xi) The number 0.0005 has .............. significant figure.
(xii) 8.75 is rounded off to .............. .
(xiii) In the addition, 14.15 + 11.230 + 9.2, the result should contain .............. significant figures.
28 0.526
(xiv) In , the result should contain .............. significant figures.
100.0
(xv) In the logarithm of 2.5 ´ 103+, the mantissa should contain .............. significant figures.
(xvi) The antilog of 1.946 should contain .............. significant figures.

4. Explain the followings
(a) Significant figure.
(b) Leading zero, captive zero and trailing zero giving suitable example.
(c) Average deviation.
(d) Co-efficient of variation and variance.
(e) Confidence interval.
(f) Constant error.
5. What do you mean by
(a) Degrees of freedom?
(b) Determinate error?
(c) Gaussian (normal) distribution?
(d) Proportional error?
(e) Standard deviation?
(f) Relative average deviation?
(g) Indeterminate error?
(a) Explain clearly the meaning of confidence interval of the mean at
(i) 95% and (ii) 99%.
(b) Explain clearly how to test two sets of results to determine whether they differ significantly
or not.
7. Explain the difference between the followings
(a) Accuracy and precision.
(b) Random and systematic error.
(c) Mean and median.
(d) Absolute and relative error.
(e) Variance and standard deviation.

8. Explain significant figures giving suitable examples. What rules are to be followed for
determining the significant figures?
9. Define errors. Mention their causes. Differentiate between determinate and indeterminate
error.
10. Write propagation of errors in addition, subtraction, multiplication and division by giving
suitable examples.
11. Define the term accuracy. Why no measurement can be done with absolute certainty?
How is accuracy expressed?
12. Define precision. How will you justify the statement that good precision does not assure
good accuracy? What are the different ways of expressing precision?
13. Name and explain different tests of significance.
14. Explain different tests for rejection of data.
UNIT 4
5. Estimation of Organic Compounds
CHAPTER 5
Estimation of Organic Compounds
5.1 INTRODUCTION
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:
(a) Detection of elements, i.e. the determination of the qualitative elementary composition of
the substance.
(b) Estimation of elements, i.e. the determination of quantitative elementary composition or
percentage composition of the substance.
(c) Calculation of empirical formula, i.e. the percentage composition found above leads to the
calculation of the empirical formula of the substance.
(d) The determination of molecular weight leading to the calculation of molecular formula.
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
present in an organic compounds and their estimation, the principle and the methods of determination
of some organic compounds especially of glucose, phenol, aniline, keto compounds and analysis
of fats or oils are discussed in this chapter.
5.2 DETECTION OF ELEMENTS (PRINCIPLES ONLY)

5.2.1 Detection of Carbon and Hydrogen
Detection of carbon and hydrogen in an organic compound is carried out by oxidizing the substance
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 (Lassaignes 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.
The filtrate is called sodium extract. It is alkaline in nature due to formation of NaOH.
Detection of nitrogen from Na-extract
Nitrogen, if present, in combination with sodium and carbon of the compound forms sodium
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
or Prussian blue colour confirms the presence of nitrogen in an organic compound.
Reactions involved:
Na + C + N ¾® NaCN
Sodium cyanide
FeSO4 + 2NaCN ¾® Fe(CN)2 + Na2SO4
Fe(CN)2 + 4NaCN ¾® Na4[Fe(CN)6]
Sodium ferrocyanide
Sodium ferrocyanide reacts with ferric ion produced by oxidation of Fe2+ by air in the presence of
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.
Na4[Fe(CN)6] + Fe3+ ¾® NaFe[Fe(CN)6] + 3Na+
(Sodium ferric ferrocyanide) (Prussian blue)
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.
Detection of sulphur from Na-extract
Sulphur, if present, forms sodium sulphide. The presence of sodium sulphide in Na-extract can be
confirmed as follows:
(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.
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.
Estimation of Organic Compounds 181
Detection of halogens
If the original organic compound contains a halogen, its sodium extract contains sodium halide.
Sodium cyanide or sodium sulphide may also be present if nitrogen or sulphur were present in the
organic compound. The sodium extract is boiled with concentrated nitric acid so that cyanide is
removed as HCN or sulphide is removed as H2S which would otherwise gave a white precipitate
of silver cyanide or a black ppt of silver sulphide with silver nitrate which is required
for identification of halogen. The solution is then cooled and treated with silver nitrate solution.
The formation of a precipitate indicates the presence of halogen as follows:
Colour of the precipitate Solubility Halogen

White Soluble in dil NH4OH Chlorine
Straw-Yellow Soluble in conc NH4OH Bromine
Pale-Yellow Insoluble in conc NH4OH Iodine
Reactions involved:
Na + X ¾® NaX
Na + C + N ¾® NaCN
NaCN + HNO3 ¾® NaNO3 + HCN
Na2S + 2HNO3 ¾® 2NaNO3 + H2S
NaX + AgNO3 ¾® AgX + NaNO3
Silver halide precipitate
Detection of S and N in presence of each other

If sulphur is present along with nitrogen, metallic sodium in combination with C, N and S of the
organic compound forms sodium sulphocyanide which gives a blood red colour due to formation
of ferric sulphocyanide in addition to ferric chloride.
Na + C + N + S ¾® NaSCN
SCN + Fe3+ ¾® [Fe(CNS)]2+
Blood red colour
Detection of phosphorus
The organic compound containing the phosphorus is fused with fusion mixture so that phosphorus
is oxidized to phosphate. The fused mass is extracted with water and heated with concentrated
nitric acid and ammonium molybdate. The formation of canary yellow precipitate due to ammonium
phosphomolybdate indicates the presence of phosphate and hence phosphorus in the organic
compound.
5.3 ESTIMATION OF ELEMENTS
5.3.1 Estimation of Carbon and Hydrogen (Liebigs Combustion Method)

Principle
Both carbon and hydrogen are estimated together by the same method. If organic compound
containing carbon and hydrogen is strongly heated with dry cupric oxide, carbon is oxidized to
carbon dioxide while hydrogen is oxidized to water vapour. The apparatus is so designed that the
carbon dioxide and water vapour formed can be collected and weighed separately. Knowing the
weights of these products, the percentage of carbon and hydrogen can be calculated as follows:
CuO ¾® Cu + O
CxHy + (x + y/4)O2 ¾® xCO2 + y/2 H2O
Experimental set-up
The apparatus used for estimation of C and H consists of three units, i.e. oxygen supply unit,
combustion tube and absorption unit as discussed below.
(i) Oxygen supply unit: Oxygen is passed through tubes containing pumic stone soaked
in concentrated sulphuric acid and KOH to remove moisture and CO2 (see Figure 5.3).
Dry oxygen free from CO2 thus obtained is supplied to the combustion tube.
(ii) Combustion tube: It is a hard glass tube AB open at both ends. It is packed as shown
in Figure 5.1.
Figure 5.1 Combustion tube.
A layer of wire form copper oxide held between two asbestos pads is placed in position
and roll of oxidized copper spirel is placed on its right. The end B is closed by a rubber
stopper through which a delivery tube passes. On the left side of the wire form copper
oxide, a porcelain boat and oxidized copper spiral both attached each other are placed.
These are further attached to the cork on the left. Thus by pulling out the cork on the left,
both oxidized copper spiral and porcelain boat are taken out. The hard glass tube is
heated in a combustion furnace.
(iii) Absorption apparatus: The products of combustion are carbon dioxide and water
vapour. The apparatus used for absorption is shown in Figure 5.2.
It consists of
(a) Weighed calcium chloride tube containing granulated (not fused) and sieved calcium
chloride to absorb water vapour.
(b) Potash bulb containing 50% caustic potash solution to absorb carbon dioxide.
(c) A small calcium chloride tube is weighed along with the potash bulb to absorb any
moisture that the bubbling gases are likely to take away with them from the potash
bulbs.
(d) A guard tube to ward off the atmospheric mixture.
Procedure
The whole apparatus used in estimation of carbon and hydrogen is shown in Figure 5.3.
Figure 5.2 Absorption apparatus.
Figure 5.3 Estimation of carbon and hydrogen.
(i) The combustion tube is placed in the furnace and connected at one of its end to Dreschel
bottle (as shown in oxygen supply unit) containing concentrated sulphuric acid and the
other end is connected to an unweighed calcium chloride tube (guard tube) to prevent
moisture from air diffusing back into the tube.
(ii) It is then heated in a current of dry oxygen for about half an hour. This drives off any
moisture or carbon dioxide from the tube and ensures complete oxidation of the copper
spiral and copper oxide.
(iii) The combustion tube is cooled and connected to the absorption unit. Its other end is
opened for a while and the boat containing the weighed organic compound is introduced.
(iv) The tube is again heated strongly to burn the compound completely.
(v) Finally, a strong current of oxygen is passed through the combustion tube to remove any
traces of carbon dioxide or moisture which may have been left in it.
(vi) The U-tube and the potash bulbs are then detached. The increase in weight of each of them
is determined. The increase in the weight of U-tube gives the weight of water formed. The
increase in the weight of potash bulb gives the weight of carbon dioxide formed.
Calculation
Let the weight of organic compound taken = W g
Let the increase in the weight of calcium chloride tube = wt of water produced = x g
Similarly, let the increase in the weight of potash bulb = wt of CO2 produced = y g
1 mole of CO2 contains 1 mole of carbon
44 g of CO2 contains 12 g of carbon
12
y g of CO2 contains y g of carbon.
44
Similarly, 1 mole of H2O contains 2 mole of hydrogen
Or, 18 g of H2O contains 2 g of hydrogen
2
x g of H2O contains x g of hydrogen
18
12 2
\ W g of organic compound contains y g of carbon and x g of hydrogen
44 18
12 y
% of carbon = 100
44 W
2 x
% of hydrogen = 100
18 W
Precautions
(i) Combustion tube and its contents should be free from moisture and carbon dioxide.
(ii) Flow of air through the combustion tube should be properly regulated.
Necessary modifications
If the substance contains nitrogen, sulphur and halogen, their oxide will also get formed which on
being absorbed in KOH will increase the weight of the potash bulb. Hence in such cases the
following modifications should be made.
(a) If the substance contains nitrogen: If nitrogen is present in the compound, it will be oxidized
to oxides of nitrogen, which are absorbed in the potash bulbs. In order to prevent this, a bright
copper gauze spiral is placed near the exit of the combustion tube. This reduces the oxides of
nitrogen to nitrogen gas which escapes unabsorbed.
NO2 + NO + 3Cu ¾® N2 + 3CuO
(b) If the substance contains halogens: Volatile copper halides are produced which may be
absorbed in the absorption apparatus. A roll of silver is placed near the exit of the combustion tube.
This helps to decompose these copper halides and form non-volatile silver halides.
CuX2 + 2Ag ¾® Cu + 2AgX
(c) If the substance contains sulphur: If S is present, a layer of lead chromate is placed near
the exit of the combustion tube. Lead chromate being an oxidizing agent, oxidizes oxides of sulphur
(SO2) to PbSO4 (a non-volatile)
2PbCrO4 ¾® 2PbO + Cr2O3 + 3O
PbO + SO2 + O ¾® PbSO4
5.3.2 Estimation of Nitrogen

The two important methods used for the estimation of nitrogen are:
(a) The Dumas method and (b) The Kjeldahls method as described below.
Dumas method
Principle: This method is based on the fact that when a nitrogeneous organic compound is
heated strongly with copper oxide and the products of combustion are passed over a bright copper
spiral, carbon, hydrogen and sulphur (if present) are oxidized to CO2, H2O and SO2 respectively.
These can be absorbed in caustic potash solution. Nitrogen, if present, forms oxides of nitrogen,
which are again reduced to nitrogen gas by copper spiral. From the volume of nitrogen collected
over caustic potash, percentage of nitrogen can be calculated as follows:
Reactions involved
C + 2CuO ¾® CO2 + 2Cu
2H + CuO ¾® H2O + 2Cu
2N + CuO ¾® Oxidize of nitrogen (NO2 + NO)
NO2 + NO + Cu ¾® 3CuO + N2
The volume of nitrogen gas is collected after careful levelling, i.e. when the level of potash solution
in the reservoir and the graduate tube is the same. Levelling is done so that the pressure of the gas
is equal to the atmospheric pressure. The atmospheric pressure, room temperature and aqueous
tension at that room temperature are also recorded.
Experimental setup: The apparatus used in Dumas methods consists of three units, namely
carbon dioxide generator units, combustion tube and Schiffs nitrometer shown in Figure 5.4.
Figure 5.4 Dumas method for estimation of nitrogen.

(i) Carbon dioxide generator: The carbon dioxide generator often consists of a hard glass
tube containing magnesite (MgCO3) · NaHCO3 or a Kipps apparatus containing marble
and dilute hydrochloric acid.
MgCO3 Heat
MgO + CO2
CaCO3 + 2HCl ¾® CaCl2 + CO2 + H2O
2NaHCO3 ¾® Na2CO3 + CO2 + H2O
The gas, carbon dioxide, produced is bubbled through conc H2SO4 to free it from moisture
(ii) Combustion tube: It is a hard glass tube open at both end, about 1215 mm in internal
diameter and about 90 cm in length. It can be placed in an iron tube and heated in a
combustion furnace. The combustion tube is packed as shown in Figure 5.4.
Near the entrance on the left an oxidized copper roll (CuO gauze) is placed. Next is the
layer of fine copper oxide mixed with a known weight of the organic compound held in a
position between two wire-guaze plugs. This is followed by a layer of wire forms copper
oxide (coarse copper oxide) placed similarly between two wire-gauze plugs. Near the exit
on the right a reduced copper spiral is placed.
(iii) Schiffs nitrometer: It is a graduated tube filled with caustic potash solution and provided
with a funnel and a tap at its upper end and two side tubes near the lower end. One of the
side tubes is connected with a caustic potash solution reservoir and the other with the
combustion tube. A little of mercury at the bottom acts as a seal.
Procedure
(i) The apparatus is fitted as shown in Figure 5.4, and a known weight of organic substance
mixed with fine copper oxide is placed in combustion tube.
(ii) The combustion tube is put in an iron tube and placed in the combustion furnace.
(iii) The tap of nitrometer is opened and a current of carbon dioxide is now passed through
the combustion tube.
(iv) When no air bubbles collected in the nitrometer, it shows that whole of the air has been
displaced. Upper tap of the nitrometer is now opened and the reservoir is raised till the
caustic potash solution level reaches the tap, which is then closed.
(v) The combustion tube is now heated in the furnace. Fine and coarse copper oxides oxidize
the organic compound and oxidized copper spiral oxidizes any substance which tends to
diffuse that side. Bright copper spiral reduces any oxide of nitrogen to gaseous nitrogen.
All products of combustion, i.e. carbon dioxide, water vapour and sulphur dioxide are
absorbed by caustic potash except nitrogen gas which collects in the nitrometer.
(vi) When the combustion is complete a rapid stream of carbon dioxide is passed through the
combustion tube to sweep away the last traces of nitrogen. The volume of nitrogen is
now noted after careful levelling (making level of caustic potash solution in the two
limbs equal). Room temperature and the pressure are also noted.
Calculation
Wt of organic compound = W g
Volume of moist nitrogen gas collected = x ml
Room temperature = t ºC = (t + 273) K
Atmospheric pressure = P mm of Hg
Aqueous tension at room temperature (tºC) = f mm of Hg
Volume of nitrogen collected is changed to volume at NTP with the help of equation
PV
1 1 P2V2
T1 T2
Here P1 = (P f ) mm P2 = 760 mm
V1 = x ml V2 = ?
T1 = (t + 273) K T2 = 273 K
Volume of nitrogen at NTP
PV T
V2 =
1 1
2
T1 P2
( P f ) x 273
= = y ml (say)
(t 273) 760
We know 22400 ml of a gas at NTP = 1 mole of gas
= 1 g molecular wt of gas
\ 22400 ml of nitrogen gas at NTP = 28 g of nitrogen gas
28
y ml of nitrogen gas at NTP = y g of nitrogen gas
22400
This amount of nitrogen must be present in organic compound.
28
\ W g of organic compound contains y g of nitrogen
22400
28 y
100 g of organic compound contains 100 g of nitrogen
22400 W
28 y
% of Nitrogen = 100
22400 W
Kjeldahls method
This is a very convenient method generally used for the estimation of the nitrogen in agricultural
(analysis of fertilizer) and biological laboratories (analysis of foodstuffs).
Principle: This method depends on the fact that most of the organic compounds containing
nitrogen are quantitatively decomposed to give ammonium sulphate when heated strongly with
concentrated sulphuric acid. The resultant liquid is heated with concentrated alkali. The ammonia
gas evolved is passed through a known excess of standard acid solution. The volume of the unreacted
acid is determined by titrating with a standard alkali solution. From the amount of ammonia evolved,
the nitrogen in the given organic compound is estimated.
Reactions involved: Organic compounds containing
(C + H + N) + H2SO4
'

(NH4)2SO4
(NH4)2SO4 + 2NaOH ¾® Na2SO4 + 2H2O + 2NH3
NH3 + HCl ¾® NH4Cl
Experimental setup: The apparatus used in Kjeldahls method is shown in Figure 5.5.
Figure 5.5 Kjeldahls flask.
Procedure: The experiment is carried out in three steps as follows:

(i) Formation of ammonium sulphate: A weighed quantity of the organic compound (0.3
to 0.5 g) is placed in a long-necked flask known as Kjeldahls flask (Figure 5.5).
About 25 ml of concentrated sulphuric acid together with a little potassium sulphate and
copper sulphate (known as Kjeldahls liquid) is added to it. Potassium sulphate raises the
boiling point and thus ensures complete reaction while copper sulphate acts as the catalyst.
The flask is loosely stoppered by a glass bulb. It is heated gently till the brown colour of the
liquid first produced, disappears. At this point, all the nitrogen present in the organic
compound gets quantitatively converted into ammonium sulphate.
[C + H + N] + H2SO4 CO + H O + (NH ) SO

Heat
2 2 4 2 4
(ii) Distillation with alkali: The Kjeldahls flask is cooled and its contents are diluted with
distilled water. Kjeldahlised liquid is transferred into a large round bottom flask.
A few porcelain pieces are added to avoid bumping. A few pieces of zinc are also added
which react with sodium hydroxide solution to produce hydrogen gas which acts as a carrier
for ammonia gas. Round bottom flask is fitted with Kjeldahls trap and a water condenser
as shown in Figure 5.6.
The lower end of the condenser is dipped into a major volume (excess) of standard H2SO4
acid solution. The flask is also fitted with a dropping funnel and sodium hydroxide solution
is added through it. The round bottom flask is heated and ammonia evolved is passed
through sulphuric acid. The Kjeldahls trap does not allow any alkali solution to pass into
the condensers due to the bumping on vigorous boiling.
(NH4)2SO4 + 2NaOH ¾® Na2SO4 + 2H2O + 2NH3
The distillation is stopped when a drop of the distillate does not turn red litmus blue.
Figure 5.6 Kjeldahls method for estimation of nitrogen.
(iii) Titration of excess acid: The excess acid left behind is then determined by titration with
standard alkali. Phenolphthalein is used as an indicator.
Calculation
Let the weight of the compound taken = W g
Let the volume of alkali of normality N1 required for neutralization with excess acid = x ml
Since x ml of N1 alkali = x ml of N1 acid solution
Hence acid left unused = x ml of N1 acid solution
If V ml of H2SO4 of strength N1 is added initially, then volume of H2SO4 consumed due to
neutralization of NH3 = (V x) ml of acid of normality N1.
The amount of NH3 evolved = (V x) ml of H2SO4 of normality N1 = (V x) ml of NH3 solution
of normality N1
We know 1000 ml of 1 N NH3 solution = 1 g equivalent of NH3 = 17 g of NH3 = 14 g of nitrogen
14
(V x) ml of N1 NH3 solution = N1 (V x ) g of nitrogen
1000
This amount of nitrogen must be present in W g of the compound
14 N (V x) 100
% of Nitrogen = 1
1000 W
N1 (V x)
= 1.4
W
5.3.3 Estimation of Sulphur (By Carius Method)

Principle
This method is based on the fact that when an organic compound containing S is heated with
fuming nitric acid, it is oxidized to sulphuric acid. It is precipitated as barium sulphate by addition
of excess of barium chloride solution. From the weight of the barium sulphate formed, percentage
of the sulphur can be calculated.
Reactions involved
3(2HNO3 ¾® 2NO2 + H2O + O)

Organic compound containing S
S + 3O + H2O ¾® H2SO4
Organic comp (S) + 6HNO3 ¾® 6NO2 + 2H2O + H2SO4
H2SO4 + BaCl2 ¾® BaSO4 + 2HCl
White ppt
Calculation
Let the wt of organic compound taken = W g
Wt of BaSO4 = x g
One mole of BaSO4 contains one mole of S.
1g molecular wt of BaSO4 = Gram atomic wt of S
Gram atomic wt of S
1g of BaSO4 = of Sulphur
Molecular wt of BaSO 4
32 x
x g of BaSO4 = g of S
Molecular wt of BaSO 4
This amount of S must be present in W g of organic compound
32 x 100
\ % of S =
Molecular wt of BaSO 4 W
Molecular wt of BaSO4 = Atomic wt of Ba + Atomic wt of S + 4 ´ Atomic wt of O
= 137 + 32 + 64 = 233
32 x
% of S = 100
233 W
5.3.4 Estimation of Halogens (By Carius Method)

Principle
The Carius method for estimation of halogens is based on the fact that when an organic substance
containing halogen is heated in a sealed tube with fuming nitric acid in the presence of silver
nitrate, silver halide is formed. From the amount of silver halide produced, the percentage of
halogen is calculated.
Reactions involved
Organic compound containing halide X + AgNO3

'
AgX.
Calculation
Let the wt of organic compound taken = W g
Wt of AgX formed = a g
Since one mole of AgX contains one mole of X,
\ 1 g molecular wt of AgX = Gram ionic wt of X

Gram ionic wt of X
1 g of AgX =
Molecular wt of AgX
Gram ionic wt of X –
a g of AgX = a
Molecular wt of AgX
This amount of halide must be present in W g of organic compound
Gram ionic wt of X – a
% of halogen = 100
Molecular wt of AgX W
5.3.5 Estimation of Phosphorus (By Carius Method)

Principle
This method is based on the fact that when an organic compound containing P is heated with
fuming nitric acid, it is oxidized to phosphoric acid, H3PO4. It is precipitated as magnesium
ammonium phosphate MgNH4PO4 by addition of magnesia mixture (MgCl2 + NH4Cl + NH4OH).
The precipitate of magnesium ammonium phosphate is ignited and weighed accurately as magnesium
pyrophosphate. From the amount of magnesium pyrophosphate, the percentage of phosphorus can
be calculated.
Reactions involved
5(2HNO3 ¾® 2NO2 + H2O + O)

2P + 5O + 2H2O ¾® 2H3PO4
2P + 10HNO3 ¾® 10NO2 + 2H3PO4 + 2H2O
NH4Cl + H3PO4 + MgNH PO

MgCl2 + NH4 Cl + NH 4OH
Magnesia mixture 4 4
Magnesium ammonium phosphate
MgNH4PO4
'
Mg P O
2 2 7 + 2NH3 + H2O
Magnesium pyrophosphate
Calculation
The same calculation is adopted as the one for estimation of halide or sulphur.
2 × Atomic wt of P wt of Mg 2 P2 O7
% of P = 100
Molecular wt of Mg 2 P2 O 7 wt of organic compound
2 31 wt of Mg 2 P2 O 7
= 100
222 wt of organic compound
Molecular wt of Mg2P2O7 = 2 ´ atomic wt of Mg + 2 ´ atomic wt of P + 7 ´ atomic wt of O
= 2 ´ 24 + 2 ´ 31 + 7 ´ 16 = 222
Principle and method of estimation of some organic compounds, based on stoichiometric calculation,
are given as follows.
5.4 ESTIMATION OF GLUCOSE

Principle
Glucose is a reducing monosaccharide having the following structural formula.
The estimation of glucose is based on the fact that in alkaline medium glucose reduces Cu2+ ion
present in Fehling solution to Cu2O. Fehling solution is a mixture of two solutions such as
Fehling A and Fehling B. Fehling solution A is CuSO4 solution in water whereas Fehling solution
B is a solution of Rochele salt, i.e. sodium potassium tartrate in NaOH solution.
Reactions involved
Cu(OH)2 ¾® CuO + H2O
2CuO ¾® Cu2O + O
The above reaction can be studied by titrimetric method as follows.

Titrimetric method
A known volume (say, V ml) of mixture of Fehlings solution A and Fehlings solution B is
titrated in hot condition with a standard solution of glucose. At the end point, the precipitation of
Cu2O is complete and the blue colour of CuSO4 disappears. The end point is detected by
carrying out the titration in the presence of methylene blue indicator which shows a sharp
disappearance of blue colour at the end point. The experiment is repeated with unknown solution
of glucose after making up the given solution to 100 ml and the end point is determined by the
same procedure.
Calculation
Weight of glucose in 100 ml of standard glucose solution = W g
V ml of a mixture of Fehling A + Fehling B solution requires V1 ml of standard glucose solution
V ml of a mixture of Fehling A + Fehling B solution requires V2 ml of unknown glucose solution
\ V1 ml of standard glucose solution = V2 ml of unknown glucose solution
W
The amount of glucose present in V1 ml of standard glucose solution = V1 g
100
W
Þ V2 ml of unknown solution should contain V1 g of glucose
100
W V W V1
\ 100 ml unknown glucose solution should contain 1 100 g of glucose
100 V2 V2
5.5 ESTIMATION OF PHENOL
Principle
Phenol is an aromatic compound with OH group directly attached to benzene ring as shown
below
The estimation of phenol is based on the fact that phenol reacts with bromine to give (2, 4, 6)-
tribromophenol. For the purpose of estimation it is not convenient to use standard bromine solution
as its concentration may vary because of volatile nature of bromine. Hence, instead of standard
bromine solution, a bromidebromate mixture known as Winklers solution is used in the estimation
of phenol, which readilty liberated bromine in acidic medium. Further, the bromidebromate mixture
is fairly stable and its concentration does not vary with time.
Reactions involved
2BrO3 + 12H+ + 10e ¾® Br2 + 6H2O
5(2Br ¾® Br2 + 2e)
2BrO3 + 10Br + 12H+ ¾® 6Br2 + 6H2O
or BrO3 + 5Br + 6H+ ¾® 3Br2 + 3H2O
The above reaction can be studied by titrimetric method as follows.

Titrimetric method
A given volume of phenol is made up to 100 ml. A known volume (V ml) out of it is treated with an
excess of potassium bromide and potassium bromate mixture (V1 ml) in an acidic medium (conc
HCl). A white precipitate of (2, 4, 6)-tribromophenol is formed due to reaction of phenol with
bromine. The unreacted bromine remaining after the completion of the reaction as determined by
adding excess of KI solution so that an equivalent amount of iodine is liberated.
Br2 + 2KI ¾® I2 + 2KBr
The liberated I2 is titrated with a standard sodium thiosulphate solution using starch as indicator
towards the vicinity of the end point.
I2 + Na2S2O3 ¾® Na2S4O6 + 2NaI
Sodium thiosulphate Sodium tetrathionate
The end point is marked by a sudden change of a blue colour, due to starch-iodine complex,
to colourless.
I2 + Starch ¾® Starch-iodine complex Starch + Na S O + 2NaI

Na 2S2O3
2 2 6
blue colourless
The thiosulphate, equivalent to Winkler solution, is determined separately by titrating V1 ml of the

Winkler solution with standard sodium thiosulphate solution by the same method without phenol.
Calculation
Let the normality of sodium thiosulphate solution be N1.
The volume of sodium thiosulphate solution required for V1 ml of Winkler solution (without phenol)
= V2 ml
The volume of sodium thiosulphate solution required for reaction with excess Winkler solution in
the presence of phenol = V3 ml
The volume of sodium thiosulphate equivalent to V ml of phenol @ (V2 V3) ml
Let the normality of phenol be N.
Then according to the law of titrimetry, we have
V ´ N = (V2 V3)N1
(V2 V3 ) N1
N=
V
Since 1 mole of phenol reacts with 3 moles of bromine, i.e. 6 equivalent of bromine,
Molecular of phenol
\ Equivalent weight of phenol =
6
94
i.e. Equivalent weight of phenol =
6
94
1000 ml of 1 N solution of phenol should contain gram equivalent weight of phenol, i.e. g of
6
phenol.
(V2 V3 ) N1 94 (V2 V3 ) N1
1000 ml of normal solution of phenol should contain g of phenol.
V 6 V
94 (V2 V3 ) N1 100 94 (V2 V3 ) N1 1
100 ml of phenol should contain g of phenol.
6 V 1000 6 V 10
5.6 ESTIMATION OF ANILINE
Principle
Aniline reacts with bromine to (2, 4, 6)-tribromoaniline
Thus, the principle and method employed for the estimation of aniline are exactly the same
as those employed for phenol. Only the equivalent weight of aniline, i.e. 93/6 is taken instead of
94/6.
(V V3 ) N1 93 1
100 ml of aniline should contain 2 g of aniline, where V is the volume of
V 6 10
aniline solution taken out of 100 ml of solution,
N1 is the normality of sodium thiosulphate solution,
V2 is the volume of sodium thiosulphate solution of normality N1 required for titration of known
volume (V1 ml) of Winkler solution without aniline,
V3 is the volume of sodium thiosulphate solution of normality N1 required for titration of the same
volume (V1 ml) of Winkler solution with aniline.
(V2 V3) is the volume of sodium thiosulphate solution of normality N1 = V ml of aniline
solution.
5.7 ESTIMATION OF KETO GROUP
Principle
A dimethyl ketone like acetone reacts with iodine in the presence of sodium hydroxide solution to
yield iodoform.
Reaction involved
One mole of consumes 6 equivalent of iodine.
Molecular wt 58
\ Equivalent weight of acetone =
6 6
A known volume of acetone is treated with excess of iodine solution in alkaline medium.
After completion of the reaction the unreacted iodine is determined by titrating against standard
sodium thiosulphate solution. Knowing the iodine equivalent to thiosulphate the amount of acetone
present can be calculated.
Procedure
A given volume of acetone solution is made up to 100 ml. V ml of made up solution is pipetted into
an iodine bottle. A known excess of iodine solution (V1 ml) is added to it. The resulting mixture
solution is made alkaline by addition of approximately 1 N KOH and is allowed to stand for about
half an hour with occassional shaking.
The mixture is acidified with 1N H2SO4 and the excess of iodine is titrated against sodium
thiosulphate using starch as indicator. The thiosulphate equivalent of iodine solution is determined
by titrating the same volume of iodine solution (V1 ml) by the same method without acetone.
Calcualtion
Let the normality of the sodium sulphate be N1.
The volume of thiosulphate solution required for titration of V1 ml iodine solution without
acetone = V2 ml.
The volume of thiosulphate solution required by the mixture of V ml of made up solution + V1 ml
solution = V3 ml.
Thus the volume of thiosulphate equivalent to V ml of acetone solution = (V2 V3) ml
Let the normality of acetone solution be N.
Then according to the law of titrimetry
NV = (V2 V3)N1
(V2 V3 ) N1
i.e. N=
V
58
1000 ml of 1 N acetone solution contains one gm equivalent weight of acetone, i.e. g of
6
acetone
(V2 V3 ) N1 58 (V2 V3 ) N1
\ 1000 ml of normal acetone solution contains g of acetone
V 6 V
(V V3 ) N1 58 (V2 V3 ) N1 100 58 (V2 V3 ) N1
100 ml of 2 normal solution contains =
V 6 V 1000 6 V
1
´ g of acetone.
10
5.8 ANALYSIS OF OILS AND FATS
Oils and fats are glyceryl esters or glycerides of higher fatty acids represented by the formula
RCOOR. Those, which are liquids at ordinary temperature, are called oils. These contain a
larger proportion of unsaturated acids than fats, which are solids at room temperature.
The composition and purity of a given fat/oil are determined by means of a number of physical and
chemical tests. The various chemical parameters which give an inidcation of the type of fatty acids
present in the fat or oil are Iodine value, Saponification value, and ReichertMeissel value.
5.8.1 Determination of Iodine Value

Definition
Iodine value of oil is defined as the number of grams of iodine that combine with 100 g of oil.
It is a measure of the degree of unsaturation of an oil.
Principle
Since the reaction between an olefinic double bond present in oil and iodine is extremely slow and
stable addition product is non-formed, the amount of iodine consumed is determined indirectly by
using a reactive reagent derived form iodine. There are the solution of iodine monochloride (ICl)
in glacial acetic acid, called Wijs reagent or iodine monobromide (IBr) in acetic acid called
Hanus reagent. ICl or IBr solution is taken in excess and allowed to react with bonds in
the oil. The amount of reagent remaining after completion of the reaction is estimated as iodine by
converting ICl or IBr to I2 by the reaction with KI.
ICl + KI ¾® I2 + KCl
IBr + KI ¾® I2 + KBr
From the iodine equivalent to ICl or IBr used, the amount of iodine consumed can be calculated.
Thus Wijs method or Hanus method can be employed for the determination of iodine value.
(a) The Wijs Method

Principle
Oil contains unsaturation, i.e. olefinic double bond ( ), which undergoes addition reaction
with iodine.
A known weight (W g) of the oil in carbon tetrachloride is treated with (say, V ml) excess of ICl
in acetic acid. After about an hour, when the reaction is complete, KI solution is added and the
liberated iodine is titrated with standard sodium thiosulphate solution of strength N1. The end
point is indicated by adding starch solution near the end point (when the solution is light yellow)
due to change of blue colour to colourless. Let the titre volume be V1. This gives the amount of
unreacted ICl or IBr to I2.
A blank titration is carried out with the same volume of ICl or the ICl solution as that used in the
oil. Let the titre value be V2. The difference between V2 and V1 gives the thiosulphate equivalent of
ICl, which is also the thiosulphate equivalent of iodine.
Calculation
Let the weight of oil = W g
Normality of thiosulphate solution = N1
Volume of ICl solution used = V ml
Volume of thiosulphate solution required to react with V ml of ICl + W g of oil = V1
Volume of thiosulphate required to react with V ml of ICl without oil = V2 ml
Volume of thiosulphate solution equivalent of I2, which reacted with the oil = (V2 V1) ml
1000 ml of 1 N thiosulphate solution º gram equivalent wt of iodine = 126.9 g of iodine
126.9 (V2 V1 ) N1
\ (V2 V1) ml of N1 thiosulphate solution º g of iodine
1000
This amount of iodine must have reacted with W g of the oil. Hence according to the definition, the
iodine value of the oil
N1 126.9(V2 V1 ) 12.69(V2 V1 ) N1
100
1000 W W
Iodine values of some common oils are given as follows:
Name of the oil Iodine value
Coconut oil 10
Olive oil 8.8
(b) Hanus Method

The same method as done in case of Wijs method is followed by taking Hanus agent (IBr solution
in acetic acid) in place of Wijs reagent.
5.8.2 Determination of Saponification Values

Oil are esters of fatty acids and can be represented by the general formula R COOR¢. When oil
is refluxed with alcoholic KOH, the following reaction called saponification takes place:
R COOR¢ + KOH ¾® R COOK + R¢OH
Definition of saponification value
It may be defined as the number of milligram of KOH required to react (saponify) 1 g of fat or oil.
Principle
The oil is refluxed with a known excess of KOH and the KOH remaining after the saponification
is back titrated against standard acid, HCl.
KOH + HCl ¾® KCl + H2O
Determination of saponification value
A known weight of the oil (W g) is refluxed with an excess of alcoholic KOH for about an hour.
The solution is then cooled and the amount of KOH remaining after hydrolysis is titrated with
standard solution of HCl of normality N1. Let the titre value be V1 ml. A blank titration is carried
out with the same quantity of KOH as used in the oil. Let the titre value for the blank be V2 ml.
Calculation
Weight of the oil taken = W g
Normality of HCl solution = N1
Volume of HCl solution required to react with oil and KOH = V1 ml
Volume of HCl solution required to react with KOH but without oil = V2 ml
\ Volume of HCl equivalent to KOH which reacted with the oil = (V2 V1) ml
We know that 1000 ml of 1 N HCl solution º gram equivalent wt of KOH = 56 g of KOH
56 (V2 V1 ) N1
\ (V2 V1) ml of N1HCl solution = g of KOH
1000
This amount must have reacted with the oil
56 (V2 V1 ) N1
\ W g of the oil º g of KOH
1000
56 (V2 V1 ) N1
\ 1 g of the oil º g of KOH
1000 W
56 (V2 V1 ) N1 1000
= mg of KOH
1000 W
56 (V2 V1 ) N1
= mg of KOH
W
56 (V2 V1 ) N1
\ According to definition, saponification value of oil =
W
Significance of saponification value

The quantity of an alkali needed to convert a oil into soap can be known. It helps to assess quality
or to detect adulteration in oil.
5.8.3 Determination of ReichertMeissel Value (RM Value)

Definition
RM value is defined as the number of ml of 0.1 N KOH solution required to neutralize the steam
volatile water soluble acid obtained by saponification of 5 g of oil or fat.
Principle
A known weight of the fat is refluxed with KOH so that saponification of the fat occurs.
After saponification, the potassium salt of the fatty acid produced is acidified with standard H 2SO4
and then subjected to steam distillation. The distillate is then titrated with standard KOH solution.
From the titre value, the RM value can be calculated as follows.
Determination of RM value
A known amount (suppose W g) of the oil/fat is refluxed with excess of KOH solution in glycerol
until it is completely saponified. The mixture is then acidified with H2SO4 and then steam distilled.
The distillate is filtered and the volume of KOH of known strength (N1) required to neutralize the
water soluble acid in the filtrate is determined by using phenolphthalein as indicator.
Calculation
Let the weight of the oil or fat = W g
Normality of KOH solution = N1
Volume of KOH solution required to neutralize the volatile acids = V1 ml
Let the volume of KOH of normality (0.1 N) required to neutralize the above acid = V2 ml
Then from the law of titrimetry
V2 ´ 0.1 = V1 ´ N1
V1 N1
V2 = 10 V1 N1
0.1
Thus the numbers of milllitre of 0.1 N KOH required to neutralize the volatile acid obtained from
W g of the fat/oil = 10 V1N1
W g of oil or fat º 10 V1N1 ml of 0.1 N KOH
10 V1 N1 50 V1 N1
\ 5 g of oil or fat º 5 ml of 0.1 N KOH
W W
50 V1 N1
According to definition, RM value of fat or oil =
W
5.9 PROBLEMS INVOLVED IN ESTIMATION OF ORGANIC COMPOUNDS
5.9.1 Problems on Estimation of Carbon and Hydrogen

PROBLEM 5.1 0.25 g of an organic compound gave on combustion 0.5 g of carbon dioxide and
0.2 g of water. Calculate the % of carbon and hydrogen in it.
Solution In CO2, 44 g of CO2 contains 12 g of C
12
\ 0.5 g of CO2 contains 0.5 = 1.136 g of C
44
\ 0.136 g of Carbon is present in 0.25 g of organic compound
0.136
\ % of Carbon = 100 54.4%
0.25
In H2O, 18 g of H2O contains 2 g of H
\ 0.022 g of H is present in 0.25 g of organic compound
0.022
% of hydrogen = 100 8.8
0.25
PROBLEM 5.2 0.25 g of an organic compound containing carbon, hydrogen and oxygen was
analyzed by the combustion method. The increase in weight of calcium chloride tubes and potash
bulbs was found to be 1.5 and 0.18 g respectively. Calculate the % composition of the compound.
Solution Weight of organic compound = 0.25 g
Increase in weight of CaCl2 tube due to absorption of water = 0.15 g
Increase in weight of potash bulb due to absorption of CO2 = 0.18 g
We known 44 g of CO2 contains 12 g of C
12
\ 0.18 g of CO2 contains 0.18 0.049 g of C
44
\ 0.25 g of organic compound contains 0.049 g of C
0.049 100
\ 100 g of organic compound contains 19.6%
0.25
We also known that 18 g of H2O contains 2 g of hydrogen
\ 18 g of H2O contains 2 g of hydrogen

2
\ 0.15 g of H2O contains 0.15 0.017 g of hydrogen
18
\ 0.25 g of organic compound contains 0.017 g of hydrogen
0.017 100
\ 100 g of organic compound contains = 6.8% of hydrogen
0.25
\ % of oxygen = 100 (19.6 + 6.8) = 73.6%
5.9.2 Problems on Estimation of Nitrogen

Problem on Dumas method
PROBLEM 5.3 0.2 g of an organic substance gave on combustion with copper oxide 30 ml of
moist nitrogen measured at 27ºC and 732.7 mm pressure. What is the % of nitrogen in the compound?
(If aq. tension at 27ºC = 12.7 mm).
Solution Weight of nitrogen compound = 0.2 g
Volume of nitrogen collected = 30 ml
Pressure of dry gas = 732.7 12.7 = 720 mm
We are to calculate the volume of nitrogen gas at NTP
Let its volume be V1
PV
1 1 P2V2
Then, =
T1 T2
760 V1 720 30
or =
273 300
720 30 273
or V1 = 25.86 ml
760 300
22400 cc of N2 gas at NTP weigh gram molecular weight of N2 gas, i.e. 28 g
28
\ 25.86 cc of N2 gas 25.86 = 0.032 g of nitrogen
22400
\ 0.2 g of organic compound contains 0.032 g of nitrogen
0.032
\ 100 g of organic compound contains 100 16 of nitrogen
0.2
\ % of N = 16
Problem on Kjeldahls method
PROBLEM 5.4 0.35 g of an organic compound on analysis by Kjeldahls method gave ammonia,
which was absorbed in 70 ml N/5 H2SO4. The excess of the acid required 40 ml of N/5 NaOH for
complete neutralization. Calculate the % of nitrogen in the compound.
Solution Volume of N/5 H2SO4 taken = 70 ml
Volume of excess acid (H2SO4) = 40 ml of N/5 NaOH = 40 ml of N/5 H2SO4
\ Ammonia liberated reacts with (70 40) ml of N/5 H2SO4 = 30 ml of N/5 H2SO4
We know 1000 ml of 1 N H2SO4 º 1 g of equivalent of NH3 = 17 g
17 30
\ 30 ml of N/5 H2SO4 = 0.102 g of NH3
1000 5
14
0.102 g of NH3 contains 0.102 = 0.084 g nitrogen
17
0.35 g of organic compound contains 0.084 g of nitrogen
0.084 100
100 g of organic compound contains 24 of nitrogen
0.35
% of N = 24%
5.9.3 Problems on Estimation of Halogens and Sulphur

PROBLEM 5.5 0.2 g of an organic compound gave 0.35 g of silver iodide (by Carius method).
Find the % of iodine in the compound.
Solution 1 mole of AgI contains 1 mole of iodide
\ 1 g of molecular wt of AgI contains 1 g of ionic wt of iodide
235 g of AgI contains 127 g of iodine
127
0.35 g of AgI contains 0.35 0.189 g of iodine
235
\ 0.25 g of organic compound contains 0.189 g of iodine
0.189
100 g of organic compound contains 100 94.5 of iodine
0.2
% of iodine = 94.5
PROBLEM 5.6 0.25 g of organic compound gave 0.45 g of barium sulphate in Carius
determination. Calculate the % of sulphur in the compound.
Solution 1 mole of BaSO4 contains 1 mole of sulphur
1 g of molecular wt of BaSO4 contains 1 g of atomic wt of sulphur
233 g of BaSO4 contains 32 g of sulphur
32
\ 0.45 g of BaSO4 contains 0.45 0.062 g of sulphur
233
\ 0.25 g of organic compound contains 0.062 g of sulphur
0.062 100
100 g of organic compound contains 24.8 g of sulphur
0.25
% of S = 24.8
5.9.4 Problems on Estimation of Sugar

PROBLEM 5.7 20 ml of mixture of Fehling A and Fehling B solution required 25 ml of standard
glucose (6% w/v) for completion of reaction whereas the same volume of Fehling solution requires
30 ml of unknown sugar solution for completion of reaction. Calculate % of sugar (w/v) in unknown
solution.
È wØ
Solution 30 ml of unknown glucose solution º 25 ml of 6% É Ù glucose solution.
Ê Ú v
È wØ 6
The amount of glucose present in 25 ml of 6% É Ù glucose solution = 25 1.5 g
Ê vÚ 100
This amount (1.5 g) of glucose must be present in 30 ml of unknown glucose solution
È wØ 1.5 100
% of glucose É Ù in the unknown = 5 gm 100 ml
Ê vÚ 30
Alternatively % of sugar (w/v) in standard glucose W = 6 g/100 ml
Volume of standard glucose, 6%(w/v) = V1 = 25 ml
Volume of unknown solution of glucose, V2 = 30 ml
W V1 6 25
\ % of sugar (w/v) in unknown solution = 5 gm 100 ml
V2 30
5.9.5 Problems on Saponification Value and RM Value

PROBLEM 5.8 10 g of linseed oil is refluxed with 50 ml of N/2 KOH.
The excess of alkali required 45 ml of N/10 HCl. Find the saponification value of the oil.
Solution Given wt of the linseed oil W = 10 g
Normality of HCl, N1 = 1/10
50 ml of N/2 KOH º 50 ml of N/2 HCl = V1
Titre value for the sample = V2 = 45 ml of N/10 HCl
Titre value for the blank = V1 = 250 ml of N/10 HCl
(V1 V2 ) N1 56
Saponification value =
W
1
(250 45) 56
10
= 114.8
10
PROBLEM 5.9 10 g of castor oil was treated with wijs reagent and 1 < 9 solution. The liberated
iodine was titrated with 0.2 N Na2S2O3 solution. A blank titration was similarly done. If the difference
of volume of N2S2O2 used for blank and sample titration is 31.5 ml, calculate the iodine value of
castor oil.
Solution Atomic wt of iodine = 127
Given wt of the oil = W = 10 gm
Normality of thiosulphate solution = N1 = 0.2
V2 V1 = 31.5 ml
(V2 V1 ) N1 127
\ Iodine value for the oil = 100 31.5
1000 W
PROBLEM 5.10 6 g of coconut oil is refluxed with excess of KOH until it is completely
saponified. The mixture is acidified with H2SO4 and then steams distilled. The distillate is filtered.
The water-soluble acid in the filtrate requires 2.5 ml of N/20 KOH for neutralization. Calculate the
RM value of the oil.
Solution Weight of the oil W = 6 g
Strength of the KOH = N1 = 1/20
Volume of KOH required to neutralize volatile acid = V1 = 25
1
N1V1
25
20
Let the value of 0.1 N KOH required percolates neutralization = 12.5 ml
0.1 0.1
N1V1 5 5
RM value 12.5 10.4
0.1 W 6
5.9.6 Problems on Estimation of Phenol and Aniline

PROBLEM 5.11 The given solution of phenol is made up to 100 ml. A 20 ml of phenol is treated
with 30 ml of Winklers solution. The unreacted bromine remaining after the completion of reaction
is determined by adding excess of KI solution so that the equivalent of iodine liberated is titrated
with N/10 sodium thiosulphure solution; the titre value being 5 ml. It required 20 ml of N/10
thiosulphate solution for titration of 15 ml of Winklers solution without phenol. Find the amount
of phenol present in the solution.
Solution 15 ml of Winklers solution (without phenol) = 20 ml of N/10 Na2S2O3 solution.
\ 30 ml of Winklers solution without phenol = 40 ml N/10 Na2S2O3 solution.
The volume of sodium thiosulphate required for reaction with excess of Winklers solution = 5 ml
of N/10 Na2S2O3.
\ Volume of N/10 sodium thiosulphate solution equivalent to 20 ml of phenol = (40 5)
= 35 ml of N/10 Na2S2O3
Let the normality of phenol = N
1
\ 20 ´ N = 35
10
35 7
N=
20 10 40
94
Equivalent weight of phenol =
6
94
1000 ml of 1 N solution of phenol should contain g of phenol
6
7 94 7
\ 1000 ml of N solution should contain g of phenol
40 6 40
7 94 7 100
\ 100 ml of N solution should contain = 0.274 g phenol
40 6 40 1000
PROBLEM 5.12 A given solution of aniline is made up to 100 ml. 25 ml of aniline is treated
with 40 ml of excess Winklers solution. The unreacted bromine remaining after completion of the
reaction is determine by adding excess of KI solution so that the equivalent of iodine liberated is
titrated with N/10 sodium thiosulphate solution; the titre value being 7.5 ml. It required 15 ml of N/
10 sodium thiosulphate solution for titration of 20 ml of Winklers solution without aniline. Calculate
the amount of aniline present in the solution.
Solution
20 ml of Winklers solution (without aniline) º 15 ml of N/10 Na2S2O3 solution
40 ml of Winklers solution (without aniline) = 30 ml of N/10 Na2S2O3 solution
The volume of sodium thiosulphate required for reaction with excess of Winklers solution =
7.5 ml of N/10 Na2S2O3 solution.
\ Volume of N/10 Na2S2O3 solution equivalent to 25 ml of aniline
= (30 7.5) ml of N/10 Na2S2O3 solution
= 22.5 ml of N/10 Na2S2O3 solution
Let the normality of aniline = N
1
\ 25 ´ N = 22.5
10
22.5
N=
25 10
93
Equivalent of aniline =
6
93
1000 ml of N solution of aniline contains g of aniline
6
22.5 93 22.5
\ 1000 ml of N solution of aniline contains g of aniline
250 6 250
22.5 93 22.5 1
\ 100 ml N solution of aniline = 0.1395 g of aniline
250 6 250 10

(i) In detection of carbon, Ca(OH2) turns milky due to formation of
(a) CaO (b) CaCO3
(c) Ca(HCO3)2 (d) None
(ii) Lassaignes test is used in the qualitative analysis to detect
(a) Nitrogen (b) Sulphur
(c) Chlorine (d) All of these
(iii) Organic compound is fused with sodium piece in Lassaignes test in order to
(a) Increase the ionization of compound
(b) Increase the volume of the compound
(c) Increase the reactivity of the compound
(d) Convert the covalent compound to a mixture of a electrovalent compounds
(iv) A compound, which does not give positive test for N, is
(a) Urea (b) Azobenzene
(c) Glycine (d) Phenyl hydrazine
(v) Sodium extract of an organic compound gives blood red colour with FeCl3. It contains
(a) N (b) S
(c) N and S (d) S and Cl
(vi) The presence of moisture can be detected by
(a) An hydrous ZnCl2 (b) An hydrous AlCl3
(c) An hydrous Na2SO4 (d) An hydrous CuSO4
(vii) A compound containing 80% of C and 20% of H is likely to be
(a) C6H6 (b) C2H6
(c) C2H4 (d) C2H2
(viii) The equivalent weight of acetone by the iodoform method is
(a) Half of its molecular weight (b) One-sixth of its molecular weight
(c) One-third of its molecular weight (d) Its molecular weight
(ix) Iodine value is a measure of
(a) Unsaturation in oils and fats (b) Adulteration
(c) Fatty acids (d) Reducible groups
(x) Glucose is estimated by titrating it with standard
(a) Borscheas regent (b) Fehling solution
(c) Dichromate solution (d) Permanganate solution
(xi) A mixture of KBrO3 and KBr is known as
(a) Fehlings solution (b) Hanus solutions
(c) Winklers solution (d) Wijs solution
(xii) A solution of iodine monochloride is known as

(a) Wijs solution (b) Hanus solution
(c) Winklers solution (d) Fehlings solution
statements
(i) Hydrazine gives a positive test easily in the Lassaignes test for nitrogen.
(ii) Iodobromide is known as Hanus solution.
(iii) Oils and fats are esters of higher fatty acids and glycerol.
(iv) Fehlings solution A and B is a mixture of copper sulphate and alkaline potassium tatrate
solution respectively.
(v) Hanus solution is more reactive than iodine solution.
(vi) The equivalent weight of phenol is one-eighth of its molecular weight.
(vii) In Kjeldahls method, nitrogen present in an organic compound is estimated as nitrogen
gas.
(viii) In Lassaignes test for N, S and halogens, the organic compound is fused with copper.
(i) The nitrogen content in an organic compound is converted to .............. in sodium fusion
test.
(ii) In Lassaignes test for nitrogen, the blue colour is due to the formation of .............. .
(iii) In Lassaignes test when both N and S are present, the blood red colour is due to the
formation of .............. .
(iv) Sodium extract of an organic compound gives violet colouration with sodium nitroprusside
indicating the presence of .............. and the violet colour is due to the formation of
.............. .
(v) The copper wire test is called .............. and this test is used to detect .............. .
(vi) Kjeldahls method is used in the estimation of .............. .
(vii) In Dumas method, nitrogen present in an organic compound is estimated as .............. .
(viii) Winklers solution is mixture of .............. and ............... .
(ix) .............. mg of KOH required to hydrolyze 1 g of the oil.
(x) Iodine solution is standardized using a standard solution of ............ .
(xi) The purity of vegetable oil may be checked by determining its .............. value.
(xii) The Beilstein test for organic compound is used to detect .............. .

(i) In organic chemistry which element is always estimated by difference in weight?
(ii) Name the methods for estimation of N in organic compound.
(iii) Name the gas finally collected in Dumas methods.
(iv) Name the method by which halogens can be estimated.
(v) What are Fehlings solution A and B?
(vi) What are the oils and fats?
(vii) Name the various parameters for analysis of oils and fats.
(viii) Name the reactive reagents derived form iodine.
(ix) Define Saponification value.
(x) Write the structure of glucose.
(xi) Name two important methods for estimation of nitrogen.
(xii) What is the equivalent weight of dimethyl ketone (acetone)?
(xiii) How will you get NaCN from an organic compound containing N?

(i) What are the various steps involved in complete molecular diagnosis of an organic
compound?
(ii) Write the principle involved in the detection of carbon and hydrogen.
(iii) How is sodium extract of an organic compound prepared?
(iv) Write the principle involved in the detection of phosphorus.
(v) Describe the apparatus used for absorption of combustion products of a hydrocarbon, CxHy.
(vi) How will you get steam volatile water soluble acid from oil and fat?
(vii) What is the role of CuSO4 in the Kjeldahls method of estimation of nitrogen?
(viii) How will you proceed to show the various elements present in chloroform?
(ix) 65 g of an organic compound contains 24 g of C 8 g of H and the rest is oxygen. What is
the empirical formula of the compound?
(x) A student used moist cupric oxide in the detection of C and H in the organic compound.
What mistake has he committed?
(xi) Calculate the equivalent of aniline in its estimation using Winklers solution.
6. Explain why
(i) Sodium extract is heated with HNO 3 before testing of halogens.
(ii) The equivalent weight of phenol is one-sixth of its molecular weight.
(iii) Hanus solution or Wijs solution is used instead of iodine in determining iodine value.
(iv) Dry copper oxide is used in the estimation of hydrogen.
(v) Standard bromine solution is not used in the estimation of aniline or phenol.
(vi) Sometimes green solution is obtained in place of blue solution while detecting N in an
organic compound.
7. What happens when (write the reactions involved)
(i) An organic compound containing S is heated with fuming nitric acid and the resulting
solution is treated with BaCl2 solution?
(ii) An organic compound containing halogen is heated with fuming nitric acid and the resulting
solution is treated with AgNO3 solution?
(iii) An organic compound containing P is heated with fuming nitric acid and the resulting
solution is treated with magnesia mixture?
(iv) Glucose solution is heated with Fehling solution?

(v) Phenol is treated with Winklers solution?
(vi) Aniline is treated with Winklers solution?
(vii) Dimethyl ketone is treated with iodine in the presence of sodium hydroxide?
(viii) An organic compound containing N is heated strongly with concentrated H2SO4 and the
resulting mixture is heated with concentrated alkali?
(ix) An organic compound containing C and H is heated strongly with copper oxide and the
products of combustion are passed through a tube containing anhydrous calcium chloride?

8. Describe the chemistry involved in the detection of N in an organic compound. If N is
detected in the presence of S, give a suitable procedure and reaction to detect them.
9. Describe the chemistry involved in the detection of halogens in the organic compounds.
Is it possible to detect halogen in the presence of N? If so, write the reactions involved.
10. Discuss the chemistry involved in the estimation of C and H in an organic compound.
11. Describe Dumas method of estimating N in an organic compound.
12. Describe how would you estimate nitrogen content of an organic compound by Kjeldahls
method.
13. Describe Carius methods of estimation of phosphorus and sulphur.
14. Describe how would you estimate halogen present in an organic compound by Carius method.
15. Describe the method of estimating glucose. Write the relevant chemical equations.
16. Describe the estimation of carbonyl compound containing CH3-CO-group.
17. Describe the method of estimation of phenol in detail.
18. Explain the principle of estimation of aniline. Describe the procedure for its estimation.
19. Define saponification value. Describe the procedure of its determination. Mention its
significance.
20. Define iodine value and outline the method of determination of iodine value of oil.
21. Define ReichertMeissel value and describe the method of its determination.
UNIT 5
6. Separation Techniques
7. Purification Techniques
CHAPTER 6
Separation Techniques
6.1 INTRODUCTION
In order to analyze a sample present in a mixture, separation of sample and purification are required.
Various methods available for the separation of inorganic and organic compounds based on their
physical and chemical properties are shown in Table 6.1.
Table 6.1 Methods of separation based on physical and chemical properties

Basis of separation Separation technique
(i) Size (i) (a) Filtration
(b) Dialysis
(c) Size-exclusion
(d) Chromatography
(ii) Mass and density (ii) Centrifugation
(iii) Complex formation (iii) Masking
(iv) Change in physical state (iv) (a) Distillation
(b) Sublimation
(c) Recrystallization
(v) Change in chemical state (v) (a) Precipitation
(b) Ion-exchange
(c) Electrode deposition
(vi) Partitioning between phases (vi) (a) Extraction
(b) Chromatography
Only the separation methods based on partitioning between two phases such as extraction, preferably
solvent extraction and chromatography are discussed in this chapter.
6.2 SOLVENT EXTRACTION METHOD

6.2.1 Introduction
It is one of the separation techniques in which a solution (usually aqueous) is brought in contact
with a second solvent (usually organic) immiscible with the first in order to bring about a transfer
213
of the solute into the second solvent. This occurs through a partitioning process, which involves
the distribution of a solute between two immiscible liquid phases. This technique is also called
liquidliquid extraction which is considered to be the most versatile and popular method of separation
of various components of a mixture sample. For example, the mixture of carboxylic acid and
phenol can be separated into individual component by dissolving the mixture in ether and extracting
the ether solution with dilute sodium carbonate solution so that the carboxylic acid is almost
completely transferred to aqueous phase. This method can be used for the purpose of preparation,
purification, enrichment, separation and analysis of compounds. It has come to the forefront in
recent year as it is elegant, simple, and rapid and is applicable at tracer and microgram concentration
level.
6.2.2 Principle of Solvent Extraction

When a solute (liquid or solid) is added to a heterogeneous system of two immiscible liquids
(in both of which the solute is soluble), the solute distributes between the two liquids.
The distribution is governed by Nernst distribution law, as discussed below.
Nernst distribution law
(a) The distribution of solute, A, between two immiscible solvents (suppose aqueous and organic
solvents) is an equilibrium process
Aaq ZZX
YZZ Aorg
where the subscripts aq and org refer to aqueous and organic phases.
(b) The ratio of concentration of solute, A, in solvent, a to the concentration of the solute, A,
in another solvent, b is constant at a particular temperature provided the molecular state of
the solute in both the solvent is the same. This constant is called distribution (or partition)
coefficient, represented by the term, KD.
Mathematically, if the concentration of solute, A in the solvent, a is [A]a, and that of
solute, A in solvent, b is [A]b, then
[ A]a
KD = (6.1)
[ A]b
[ A]org
or KD = (6.2)
[ A]aq
where, a = organic solvent and b = aqueous solvent

Gibbs phase rule
Solvent extraction follows Gibbs phase rule
P+V=C+2
where P is called the number of phases and C is the number of components, V is the degree of
freedom. In solvent extraction we have two phases, namely the aqueous and the organic phase,
only one component, i.e. solute distributed between the two phases. As the extraction is carried out
Separation Techniques 215
at constant temperature and pressure, only one degree of freedom is involved in solvent extraction.
Thus in solvent extraction process P = 2, V = 1 and C = 1, so that 2 + 1 = 1 + 2,
i.e. P + V = C + 2.
Concept of distribution ratio
Very often the solute that is distributed between two phases undergoes disassociation or association
in one or both the phases.
Consider, for example, the extraction of benzoic acid from an aqueous solution by addition of
organic solvent like ether benzoic acid (HBZ)C6H5COOH which is slightly ionized in aqueous
solution as follows:
C6H5COOH ZZX
YZZ C6H5COO + H+
Benzoic acid Benzoate ion
The ionization constant, Ka is given as
[H + ]aq [C6 H 5 COO ]aq

Ka = (6.3)
[C 6 H 5 COOH]aq
When the aqueous solution of the acid is shaken with immiscible solvent like ether, the distribution
coefficient, KD is given by the relation.
[C6 H 5 COOH]ether
KD = (6.4)
(C6 H5 COOH) aq
However, part of benzoic acid in aqueous layer will exist as C6H5COO depending on the magnitude
of Ka and pH of the aqueous layer. Hence, quantitative separation may not be achieved. However,
in solvent extraction, the primary interest is the fraction of the total solute that is transferred into
either of the two phases and association or dissociation is immaterial. A different term called the
distribution ratio D has been introduced which takes account of the solute in all its forms (ionized
or dimeric or both) in the two phases. It is defined as the ratio of the concentration of the species of
the solute in each phase. In the above example, it is given by
[C6 H5 COOH]ether
D= (6.5)
[C6 H5 COOH]aq + [C6 H5 COO ]aq
Relation between D and KD

We can readily derive the relation between D and KD from the equilibria involved, taking example
of benzoic acid from Eq. (6.4).
K a [C6 H5 COOH]aq
[C6H5COOH]aq = (6.6)
[H + ]aq
[C6H5COOH]ether = KD[C6H5COOH]aq (6.7)

Substitution of Eqs. (6.6) and (6.7) into Eq. (6.5) gives

K D [C6 H 5COOH]aq
D=
K a [C6 H5 COOH]aq
[C6 H5 COOH]aq
[H + ]aq
KD
D= (6.8)
K
1 +a
[H ]aq
Conclusion
From the relation given by Eq. (6.8), it is clear that
(a) When [H+]aq >> Ka, D is nearly equal to KD
(b) If KD is large, benzoic acid will be extracted into ether layer and D is maximum under these
conditions.
K D [H + ]aq
(c) When [H+] << Ka, then D reduces to , which will be very small, and benzoic
Ka
acid will remain in aqueous layer. This implies that in alkaline solution, the benzoic acid is
ionized and cannot be extracted. On the other hand, in acidic solution, benzoic acid remains
undissociated and hence gets extracted in ether solvent.
(d) Equation (6.8) predicts that the extraction efficiency (D) will be independent of original
concentration of the solute. This is one of the attractive features of solvent extraction.
The method is applicable to tracer levels, e.g. radioactive level and to macro levels provided
the solubility of the solute in one of the phases is not exceeded and there are no side reaction
such as dimerisation of the extracted solute.
(e) If the concentration of H+ ions changes, the extraction efficiency (D) will change. In this
example (benzoic acid) the [H+] will increases with an increase in benzoic acid concentration
unless an acid-base buffer is added to keep [H+] constant.
If we confine our attention to the distribution of the solute, A, between water and organic solvent,
we may use the term percentage of extraction, E%, defined below.
Percentage of extraction, E%
If Vaq and Vorg represent the volume of aqueous and organic phases respectively in litre, and E
moles of solute, A, out of 100 moles of A, is present in organic phase and (100 E) moles of A is
in aqueous phase then
E
[C A ]org V org
D= =
[C A ]aq 100 E
Vaq
E Vaq
=
Vorg (100 E )
or 100DVorg DVorg E = E ´ Vaq
or 100DVorg = E(DVorg + Vaq )
È Vaq Ø
or 100D = E É D Ù
Ê Vorg Ú
100D
or E= (6.9)
Vaq
D
Vorg
From Eq. (6.9), it is clear that the fraction extracted (E) can be increased by decreasing the ratio
Vaq
, i.e. by increasing the volume of organic phase.
Vorg
If Vaq = Vorg, then
100D
E= (6.10)
D 1
From the above relation it is clear that more efficient way of increasing the extracted amount is to
use the same volume of organic liquid to perform successive extraction with smaller individual
Vaq
volume of organic solvent. For example, with D = 10, = 1, the percentage of solute extracted
Vorg
Vaq
is » 90.91%. Decreasing the ratio to 0.5 (i.e. doubling Vorg) would result in the increase of the
Vorg
Vaq
extraction amount to 95%. But performing two successive extraction with = 1, would result
Vorg
in overall extraction of 99%.
From the above results, we may conclude the following:
(i) When a solute is extracted from an aqueous solution with extracting organic solvent in a
single step (i.e. using the whole solvent in one lot), the complete separation of the solute
does not take place.
(ii) When a solute is extracted from an aqueous solution by performing successive extraction
with smaller portions of the same volume of solvent, the complete separation of the
solute takes place. This process is called multiple extraction.
6.2.3 Comparison between Single and Multiple Extraction

If Vaq ml of an aqueous solution containing x0 mole of a solute is extracted n times, taking equal
volume of organic solvent Vorg ml in each extraction, then the mole of the solute xn remaining in the
water layer is given by
n
È Vaq Ø
xn = x0 É Ù (6.11)
Ê DVorg Vaq Ú
where D is the distribution ratio of the solute between water and a given solvent.
Derivation of Eq. (6.11)

x0 mole of solute A, in Vaq ml of an aqueous solution is extracted with Vorg ml of an immiscible
organic solvent. At equilibrium x1 mole of A will remain in aqueous layer and (x0 x1) mole will be
transferred to the organic layer. The concentration of A in the two layers will be
x1
[Aaq] =
Vaq
( x0 x1 )
and [Aorg] =
Vorg
Now we have
Èx x Ø
0 1
É Ù
Ê Vorg Ú
D=
È x Ø
1
É Ù
Ê Vaq Ú
x1 x0 x1
D =
Vaq Vorg
D x x
x1 1 = 0
Vaq Vorg Vorg
Ë D 1 Û x0
x1 Ì Ü =
V
ÍÌ aq
Vorg ÝÜ Vorg
Ë DVorg Vaq Û x0
x1 Ì Ü =
ÌÍ Vaq ¹ Vorg Ü
Ý
Vorg
[ DVorg Vaq ]
x1 = x0
Vaq
Ë Vaq Û
\ x1 = Ì Ü x0
Ì
Í
DVorg Vaq Ü
Ý
Similarly, the number of moles x2 remaining after a second extraction with the same volume of
solvent will be
Ë Vaq Û
x2 = Ì Ü x1
Ì DVorg Vaq Ý
Í Ü
Substituting the expression of x1 into the expression of x2, we get

2
Ë Vaq Û
x2 = Ì Ü x0
ÌÍ DVorg Vaq ÜÝ
By the similar argument, the number of moles xn, that remains after n times of successive extraction
taking Vorg ml of organic solvent in each case. We can show that
n
È Vaq Ø
xn = x0 É Ù
Ê DVorg Vaq Ú
Finally, Eq. (6.11) can be written in terms of the initial [Aaq] and final concentration [Aaq] in
aqueous layer by substituting the relationship
x0 xn
[Aaq]0 = and [ Aaq ]n
Vaq Vaq
n
Ë Vaq Û
Thus [Aaq]n ´ Vaq = Ì Ü [ Aaq ]0 Vaq
ÌÍ DVorg Vaq ÜÝ
n
Ë Vaq Û
or [Aaq]n = Ì Ü [ Aaq ]0 (6.12)
ÌÍ DVorg Vaq ÜÝ
If single extraction is carried out using n ´ Vorg solvent at a time and if x mole is the amount of
solute left then
x0 x
nVorg
D=
x
Vaq
x x0 x
D =
Vaq nVorg
Ë D 1 Û x0
xÌ Ü =
Ì Vaq
Í
nVorg ÝÜ nVorg
È DnVorg Vaq Ø x0
xÉ Ù =
Ê Vaq nVorg Ú nVorg
( DnVorg Vaq )
x = x0
Vaq
Ë Vaq Û
x = x0 Ì Ü (6.13)
Ì
Í
DnVorg Vaq Ü
Ý
1 1
Since
( DVorg Vaq ) ( DnVorg Vaq )
n
\ xn < x
It follows that multiple small-scale extractions are more efficient than single extraction using all
the extractant.
Illustration 1 In the extraction of Ce(IV) with 2-thenoyl trifluoro acetone in benzene, the
distribution ratio was 999. If the volume of organic phase was 20 ml and that of aqueous phase
50 ml, what is the percentage of extraction?
Solution Here Vaq = 50 ml, Vorg = 20 ml and D = 999
100D
E=
Vaq
D
Vorg
100 999 99900 99900

\ E= 99.75%
50 999 2.5 1001.5
999
20
Illustration 2 Calculate the weight of Fe(III) left unextracted from 100 ml of a solution having
400 mg of Fe3+ ion in 6M HCl after two extractions with 25 ml of diethyl ether (D = 150).
Solution Here Vaq = 100 ml, Vorg = 25 ml and n = 2
x0 = 400 mg
We have to find xn , given by the relation
n 2
È Vaq Ø È 100 Ø
xn = x0 É Ù 400 É Ù
Ê DVorg Vaq Ú Ê 150 25 100 Ú
2
100 Ø
È
= 400 É Ù 400 0.000675
Ê 3850 Ú
= 0.2698 mg
6.2.4 Separation Factor

If a solution contains two (or more) solute say, A and B, it is often observed that when conditions
are such that A is extracted, some amount of B is also extracted. The extent of separation can be
found by a quantity called the separation factor b that is related to the distribution ratio of A and B
by the equation
[ Aorg ] / [ Aaq ] D A
b= (6.14)
[ Borg ] / [ Baq ] DB
From this equation it is clear that in order to make b large, we need to made an appropriate choice
of extractant and adjust the volume ratio. When DA = 10 and DB = 0.1, the separation factor b will
be 100. A single extraction in such case removed about 91% of A and 9% of B. Hence we conclude
that when DA is large and DB is very small, almost complete extraction of A takes place. When DA
and DB are close to each other, both A and B are extracted at the same time. In this case b can be
increased by adjusting the volume ratio given by Bush Densen equation
Vorg 1
= (6.15)
Vaq ( DA DB )1 2
6.2.5 Methods of Solvent Extraction

There are three methods used for solvent extraction. These are (i) batch extraction, (ii) continuous
extraction and (iii) countercurrent extraction as given below.
Batch extraction
The apparatus used for solvent extraction is the separating funnel
as shown in Figure 6.1. Usually a solute is extracted from an
aqueous solution into an immiscible organic solvent. The
aqueous solution containing the solute is shaken with the
immiscible organic solvent for a few minutes and the phases
are allowed to separate. The denser solvent occupies the bottom
layer and is withdrawn by opening the stopcork.
For example, ethyl alcohol contaminated with benzene can
be extracted by this technique. When water is added to the
solution containing ethyl alcohol and benzene, benzene being
insoluble in water forms a separate layer in the funnel while
alcohol being soluble in water goes to aqueous layer and the
layer is removed. When the extracted liquid is lighter than water,
Figure 6.1 Separating funnel.
a modified separating funnel (Figure 6.2) is used. In this type
of funnel, mercury is introduced into the bulb of the funnel
through the stopcock at the bottom of the funnel after the
equilibrium is reached. The lighter organic layer rises upward
and is withdrawn through the stopcock at the top of the funnel.
This method is used for larger KD values.
Continuous extraction
When an organic compound to be extracted has nearly the same
solubility in water as well as in the organic solvent (i.e. the
distribution coefficient between the organic solvent and water
is small), a large quantity of organic solvent is employed to
obtain even a moderately efficient extraction. This can be
avoided by continuous extraction using an apparatus known as
continuous extractor as described below where only relatively
small volume of solvent is required.
The experimental units that can be used to extract an organic Figure 6.2 Modified separating
substance from an aqueous solution with a solvent which is funnel.
more or less dense than water are shown in Figures 6.3(a) and (b) respectively. The organic substance
in aqueous phase is placed in an extraction vessel (A) fitted with cold finger or reflux condenser.
The extracting solvent or extractant (immiscible with water) is adjusted at the level of overflow
tube or solvent return tube. Extractant heavier than water lies below aqueous phase is shown in
Figure 6.3(a) and that (such as ether) which is lighter than water lies above the aqueous phase is
shown in Figure 6.3(b). A portion of the extractant is placed in the heated solvent reservoir (B) and
vaporised. The vapour is passed into the extraction vessel which goes up to the condenser and
condensed into liquid state. The liquid drops are passed downwords containing the organic solute
and doing so they carry certain amount of solute. This causes the organic solvent to flow over into
the reservoir through the overflow tube or return tube to maintain the level of the solvent in reservoir
(B). As the process continues, the organic solute concentration in aqueous phase is gradually
depleted as it concentrates in reservoir (B). The organic solute is thus continuously extracted by
the organic solvent and accumulates in the reservoir.
It is to be noted that in the isolation of organic compound from aqueous solution, use is made of
the fact that the solubility of many organic compounds in water is considerably decreased by the
presence of dissolved inorganic salts such as sodium chloride, calcium chloride and ammonium
sulphate, etc. This is called the salting out effect. Due to this effect, the solubility of partially
miscible organic solvents such as ether is considerably less in salt solutions, thus reducing the loss
of solvent in extraction.
Figure 6.3 Continuous extraction.
Countercurrent extraction
This method was developed by Craig and accordingly an
extractor used for this purpose is called Craig countercurrent
extractor. This method is used when two or more substances
which are simultaneously extracted to different extent to be
separated. It consists of as many as 300 to 4000 separating
chambers as connected in the form of a train. A single chamber
is shown in Figure 6.4. The extractant and the solution
containing the solute are introduced through A and B and
equilibrated there. When the two phases are separated, the
apparatus is tilted so that the upper layer or phase gets decanted
through C and is collected in D. When the apparatus is again Figure 6.4 A single separation
made vertical, the liquid in D passes through E into the next chamber in the Craig
equilibrium chamber (similar to B). The lighter phase thus countercurrent extractor.
gradually travels through the train of separating chambers. Components of a given sample travel at
different rates depending upon their distribution ratios and then collect each in a separate group of
chambers. The distribution follows binomial pattern.
6.3 APPLICATION OF SOLVENT EXTRACTION
6.3.1 Solvent Extraction of Metal Ions by Chelation

The most widely used method of extracting metal ions is through formation of a chelate molecule
with an organic chelating agent. Many of these reagents are weak acids that ionize in water. The
ionizable proton is displaced by the metal ion when the chelate is formed and the charge in the
organic compound neutralizes the charge in the metal ion. An example is diphenyl thio carbazone
(dithizone) which forms a chelate with lead ion.
The usual practice is to add the chelating agent to the organic phase. The extraction process
involves four equilibrium steps as given below:
First, the chelating agent HR distributes between the aqueous and the organic phases:
(HR)aq ZZX
YZZ (HR)org
[HR]org
and DHR =
[HR]aq
Second, the reagent in aqueous phase ionizes:

[H + ]aq [R – ]aq
(HR)aq ZZX
YZZ H+ + R and Ka =
[HR]aq
Third, the metal ion chelates with the reagent anion to form uncharged molecules in aqueous
phase
Mn+ + nR YZZZZX MRn
[MR n ]aq
Kf =
[M n ]aq [R – ]aq
n
Finally, the chelate distributes between the organic and aqueous phases:
[MRn]aq Û [MRn]org
[MR n ]org
and DMR =
[MR n ]aq
DRH and DMRn are the distribution coefficient of the reagent and the chelate respectively, Ka is the
ionization constant of the reagent, and the Kf is the formation constant of the chelate. The following
assumptions are made:
(i) The chelated portion of the metal distributes largely into the organic phase.
(ii) The metal ion does not hydrolyze in the aqueous phase.
(iii) The chelate is essentially undissociated in the non-polar organic solvent.
(iv) The distribution ratio D is evaluated considering the chelate MRn in the organic phase
and the metal ions, Mn+ in the aqueous phase so that
[MR n ]org
D=
[M n ]aq
Combining the above equations, we get
DMR n K f K an [HR]norg n
[HR]org
D= K (6.16)
( DHR ) n [H ]aq
n
[H ]aq
n
DMR n K f K an
K=
( DHR ) n
On examining the terms in Eq. (6.16) the following conclusion for extraction of metal chelate can
be made.
6.3.2 Conclusions on Extraction of Metal Chelates

(a) The extraction efficiency can be affected only by changing the reagent concentration and
by changing the pH. A ten-fold increase in the reagent concentration will increase the
extraction efficiency by the same amount as increase in the pH of one unit (ten-fold decrease
in hydrogen ion concentration). By using a high reagent concentration, extraction can be
performed in more acid solution.
(b) The more stable the chelate (the larger the Kf value) and more solubility of chelate in
organic phase (larger DMRn ) value, the greater is the extraction efficiency and this principle
serves as the basis for the separation of many metals.
(c) An acidic reagent (larger Ka), and small DHR value favour good extraction. But chelate
stability generally decreases as the reagent acidity increases and hence the effects of Ka and
Kf must be considered together for a series of different chelating agents.
(d) Taking logarithm of Eq. (6.16), we get
log D = log K + n log [HR]org + log [H+]n
aq
= log K + n log [HR]org + n pH
Thus on plotting a graph of log D against log [HR]org at the particular pH, we get a straight
line showing linear relationship from slope of which n can be calculated.
(e) If the reagent concentration, HR is kept constant then D = K* · [H+]naq so
log D = log K* + n pH
Again D is related to % of extraction (E) as shown in Eq. (6.10). When Vorg = Vaq, we have
E
D=
100 E
Taking logarithm on both sides, we get
E
log D = log
100 E
= log K* + n pH
When E = 50%
the pH for 50% extraction is denoted as pH(½)
50
log = log K* + n pH(½)
100 50
or log K* = n pH(½), i.e. pK* = n pH(½)
1
or pH(½) = pK * , when E = 50% and Vorg = Vaq
n
\ The magnitude of pH(½) is dependent only on the valence (n) of the ion and the value of
constant K*.
Synergistic extraction: Exaction is enhanced on account of the use of two extractants, e.g.
extraction of uranium with tributyl phosphate (TBP) as well as 2-thenoyl trifluoroacetone (TTA).
Although either TBP or TTA are individually capable of extracting uranium if mixture of these two
extractants are used, enhanced extraction is achieved. Hence the phenomenon in which two reagents,
when used together, extract a metal ion with enhanced efficiency compared to their individual
action is known as synergism.
6.4 CHROMATOGRAPHIC METHODS AND THEIR CLASSIFICATION
6.4.1 Introduction
Chromatography is an analytical technique that is widely used for the separation, isolation and
identification of closely related chemical components of a complex mixture such as organic
substances like amino acids, sugars, vitamins, hormones and plant pigments, etc. This technique
was invented by M. Tswett, a Russian botanist in 1906. He employed chromatographic technique
to separate various plant pigments such as chlorophylls and xanthophylls and several other coloured
substances by passing solution of these compounds (vegetable extracts) through a glass column
packed with finely divided calcium carbonate. The calcium carbonate column acted as an adsorbent
and different components were adsorbed to different extents and this gave rise to coloured bands
at different positions of the column. Tswett called this system of coloured bands as the
chromatogram and the method chromatography. (chroma and graphy in Greek means colour
and writing respectively).
The column of calcium carbonate used in Tswetts method remains stationary and is therefore
referred to as the stationary phase. The solution of the vegetable extract moves or flows down the
column and is therefore referred to as the mobile phase. Thus chromatography may be consider as
a method of separation in which separation of solute occurs between a stationary phase and a
mobile phase.
6.4.2 Definition of Chromatography

According to Keuleman, chromatography may be defined as a physical method of separation of a
mixture of solutes brought about by the dynamic partitions or distribution of dissolved materials
between two immiscible phases, one of which (called the mobile phase) moves past the other
(called the stationary phase).
The chromatographic methods of separation, in general, involve the following steps:
(i) Adsorption or retention of a substance or substances on the stationary phase.
(ii) Separation of the adsorbed substances by the mobile phase.
(iii) Recovery of the separated substances by continuous flow of mobile phase; the method
being called elution.
(iv) Qualitative and quantitative analysis of the eluted substances.
6.4.3 Classification of Chromatographic Methods

Chromatographic methods can be classified in three ways:
(i) On the basis of the physical state of the mobile phase and stationary phase.
(ii) By the method of contact between the mobile phase and stationary phase.
(iii) By the chemical or physical mechanism responsible for separating the samples
constituents.
Classification based on physical state

The first method of classification is based on physical state of the mobile phase and stationary
phase. The stationary phase may be either a solid or a liquid film coated on a solid surface while
the mobile phase may be either a liquid or a gas. They fall into four categories such as gasliquid,
gassolid, liquidsolid and liquidliquid. The summary of chromatography based on physical state
of mobile phase and stationary phase is given in Table 6.2.
Table 6.2 Summary of types of chromatography based on physical sate of mobile phase and stationary
phase
Type Mobile phase Stationary phase Name of the method
I Liquid Solid Liquidsolid chromatography (LSC)
II Liquid Liquid Liquidliquid chromatography (LLC)
III Gas Solid Gassolid chromatography (GSC)
IV Gas Liquid Gasliquid chromatography (GLC)
Classification based on contact between mobile phase and stationary phase

The second method of classification based on contact between mobile phase and stationary phase
is given in Table 6.3.
Table 6.3 Summary of types of chromatography based on contact between mobile phase and stationary
phase
Type Method of fixing the Name of the method
stationary phase
I Liquidsolid (i) Solid stationary phase held in a tubular (i) Column chromatography
chromatography column through which the mobile (ii) Ion-exchange chromatography
(LSC) phase moves under the influence of
gravity or pressure
(ii) Stationary phase being finely divided
ion-exchange resin held in a tubular
column
II Liquidliquid Liquid stationary phase held in the pores Paper chromatography
chromatography of a thick paper. Mobile phase moves
(LLC) through the stationary phase by capillary
action or under the influence of gravity
III Gassolid Solid stationary phase held in a tubular GSC (Gassolid chromatography)
chromatography column
(GSC)
IV Gasliquid Liquid stationary phase adsorbed on a GLC (Gasliquid chromatography)
chromatography porous solid held in a tube or adsorbed
(GLC) on the inner surface of a capillary tube
Besides the above, there is another method which includes liquidsolid or liquidliquid called
thin layer chromatography (TLC). In the former case, the stationary phase is finely divided solid
held on a glass plate through which the mobile phase (liquid) passes while in the latter case, the
stationary phase is liquid being adsorbed in an adsorbent coated on a glass plate.
Classification based on chemical or physical mechanism
The third method of classification is based on chemical or physical mechanism is given in Table 6.4.
Table 6.4 Separation based on mechanism involved

Type Mechanism involved Name
I (LSC) (i) Column chromatography Adsorption Adsorption chromatography
(ii) Ion-exchange Ion-exchange Ion-exchange chromatography
II (LLC) Paper chromatography Partition of solute between Partition chromatography
two immiscible liquids
III (GSC) Gassolid chromatography Adsorption chromatography Adsorption chromatography
IV (GLC) Gasliquid chromatography Partition of solutes between Partition chromatography
gaseous mobile phase and a
liquid stationary coated
on the solid packing material
or on the columns wall
The basis of separation in TLC can be either adsorption for solid stationary phase or partition
for liquid stationary phase. The most powerful methods of chromatography have been developed
nowadays, which include high-performance liquid chromatography (HPLC), size-exclusion

chromatography and super critical fluid chromatography, which are beyond the scope of the present
book.
Only the general theory and principles of chromotography techniques for type-I (coulmn and
ion-exchange chromatography), type-II (paper chromatography), TLC and gas chromatography
are discussed below.
6.5 GENERAL THEORY AND PRINCIPLE OF COLUMN OR ADSORPTION

CHROMATOGRAPHY
In column chromatography the stationary phase is a solid (the adsorbent) and the mobile phase is
a liquid (the solvent). In this method solution of the sample (dissolve in suitable solvent) is poured
down a column filled with adsorbent. The component which has maximum adsorption affinity is
adsorbed in the upper part of the column. The next component is adsorbed in the lower portion of
the column which has less adsorption affinity than the first component. This method is continued.
As a result the components are partially separated and adsorbed on the various parts of the column.
These are marked by different bands or zones. If at the stage the pure solvent is allowed to flow
through the column, the bands become well defined. The banded column of the adsorbent is termed
chromatogram, and the operation is called development of chromatogram.
In this method the mass (m) of the solute adsorbed per unit weight of adsorbent depends on the
concentration (C) of solute and the process is governed by an equation called Langmuir adsorption
isotherm equation.
K1 K 2 C
m
1 K2C
where K1 is a measure of number of active site per unit weight of the adsorbed and depends on the
nature of the adsorbent. K2 is a measure of affinity of solute for the adsorbent.
If, after the development of chromatogram the flow of solvent is continued, the adsorbed
components are desorbed or eluted. The least of easily adsorbed components is carried off first.
As more and more of the solvent is allowed to flow, the various components get eluted one after
another such that the most strongly adsorbed components are carried down last. The solvent
containing the eluted components is called elute. The pure compound is separated from the elute
by removing the solvent from it. Nowadays the separated components are quantitatively analyzed
by means of a suitable instruments called detectors. A plot of the detector signal as a function of
time or volume of the eluted mobile phase known as chromatogram and it consists of peak for each
of the separated solute bands as shown in Figure 6.5.
Figure 6.5 Typical chromatogram showing the separation of mixture of components A and B.
Characterization of the chromatography peak
Chromatography peak may be characterized by retention time, tR and baseline width W, as shown
in Figure 6.6. The baseline width is determined by the intersection of tangent lines drawn through
the inflection point on either side of the chromatography peak with the baseline. The retention
time tR is the time elapsed from the introduction of solute to the peak maximum (A). Besides the
solute peak, Figure 6.6 also shows a small peak (B) eluted soon after the sample is injected into the
mobile phase. This peak result from solutes that move through the column at the same rate as
mobile phase. Since these solutes do not interact much with the stationary phase, they are non
retained. The time required to elute the non-retained components is called the columns void time,
tM. Thus if L is the length of the column, then the average rate of solute migration
L
v
tR
and the average linear velocity of the molecule in the mobile phase is
L
u
tM
Figure 6.6 A typical chromatogram showing retention time (tR) and baseline width W.
Chromatographic resolution
The goal of chromatography is to separate a sample into a series of chromatography peaks.
Resolution is a quqantative measure of the degree of separation between two chromatographic
peaks A and B (shown in Figure 6.5) defined as
(t R ) B (tR ) A 2'tR
R= (6.17)
0.5(WB WA ) WB WA
where (tR)A and (tR)B are the retention time for the component A and B respectively. WA and WB are
the base line width for A and B respectively. As shown in Figure 6.5, the degree of separation
between two chromatographic peaks increases with an increase in DtR. From Eq. (6.17), it is clear
that resolution may be improved either by
(i) Increasing DtR
(ii) By decreasing WA or WB. We may increase DtR by enhancing interaction of the solute with
the column or by increasing columns selectivity for one of the solute. Resolution is
governed by several factors as discussed below.
Factors governing column chromatography
Migration rate, partition ratio and capacity factor: The distribution of a solute, A between
mobile phase and stationary phase can be represented by an equilibrium reaction.
Am ZZX
YZZ As
This equilibrium constant K for this reaction is called partition ratio or partition coefficient
defined as
Cs
K
Cm
where Cs is the molar analytical concentration of the solute in the stationary phase and Cm is the
analytical concentration of the solute in the mobile phase.
To determine the migration rate of the solute on column, an experiment parameter called capacity
factor, K¢ is widely used. K¢ is defined as
Vs
K K
Vm
where Vs and Vm is the volume of stationary and mobile phase respectively. Then the migration rate
of the solute is given by the expression
L L 1
v
tR tM (1 K )
Rearranging the above equation, we get
tR tM
K
tM
Significance of capacity factor, K¢
(i) If K¢ < 1, elution occurs so rapidly that determination of retention time becomes difficult.
(ii) If K¢ lies above 5, elution times become inordinately long. Ideally separation is performed
in which K¢ lies in the range of 1 and 5.
Selectivity factor
The selectivity factor a of a column for the two species A and B is defined as
K B
D
K A
where, K B and K A are the capacity factor to B and A respectively

(tR ) B tM
tM (tR ) B tM
D
(tR ) A tM (tR ) A tM (6.18)
tM
Thus a = 1, when (tR)B = (tR)A and a > 1, when (tR)B > (tR)A.
Column efficiency
Chromatography column is assumed to consist of discrete section at which partition of the solute
between the stationary phase and mobile phase occurs. Each section is known as theoretical plate.
Column efficiency can be defined in terms of the number of theoretical plates N or the height of a
theoretical plate, H by the relationship
L
N
H
The number of theoretical plates can be calculated by the simple relationship
2
È tR Ø
N 16 É Ù
ÊW Ú
where tR is the retention time and W is the baseline width of a chromatographic peak.
The successful separation of components of the sample using column chromatography depends
upon the following:
(i) The nature of the adsorbent
(ii) The nature of the solvent used to elute the sample
(iii) The rate of flow of solvent through the column
(iv) The temperature and
(v) The geometry of the column containing adsorbent.
The tendency of different substances to get adsorbed follows the order
Acid, base > alcohol > aldehyde > unsaturated hydrocarbon > saturated hydrocarbon
Illustration 3 Substances A and B were found to have retention time of 17.30 and 19.92 minutes
respectively on a 25.0 cm column. The width (at the base) for A and B were 1.10 and 1.22 minutes
respectively. Calculate resolution, the average number of plates in the column.
Solution Column resolution
2't R
R=
WB WA
where WA and WB are the width at the base for A and B respectively.
DtR is the difference in time of their arrival at the detector.
DtR = (19.92 17.30) min = 2.62 min
WA = 1.10 min and WB = 1.22 min
2 2.62 5.24
R= 2.2586
1.10 1.22 2.32
Number of plates
2
È tR Ø
N = 16 É Ù
ÊW Ú
2
È 17.30 Ø
Thus NA = 16 É Ù 16 (15.727)2 3957.5
Ê 1.10 Ú
2
È 19.92 Ø
and NB = 16 É 16 (16.3279) 2
Ù 4265.6
Ê
1.22 Ú
3957.5 4265.6
Average N= 4111.55
2
Experimental set-up for column chromatography
The apparatus used for the purpose is shown in Figure 6.7. It consists of the following:
(i) Aglass tube (C) drawn at the lower end with a plug of glass wool (G) placed at the top of
the constricted portion to retain the adsorbent (A) in the tube.
(ii) A filter flask (F). A tube is connected to the filter flask by means of a one-holed rubber
stopper.
(iii) A reservoir (R) containing the solvent is fitted on the top of the tube.
Procedure: It involves the following steps:
(i) Packing of glass column with adsorbent: A long glass tube (called glass column)
having (about 230 cm) stop cock near the bottom is taken. A plug of glass wool or
cotton is placed at the bottom to support the adsorbent as shown in Figure 6.8.
Figure 6.7 Apparatus for column chromatography. Figure 6.8 Packing of the column.
The adsorbent is to be packed uniformly in the column excluding air bubble and channels.
Two methods are adopted, namely wet packing and dry packing which discussed below.
(a) Wet packing: A slurry of solvent and adsorbent is poured into column through
open end and allowed to settle. The solvent and slurry will flow out slowly through
the column thereby increasing the uniformity of the packing process.
(b) Dry packing: This method involves the addition of sufficient adsorbent to fill
12 cm of the column and then tapping this down gently before adding another portion
of the adsorbent. The solid adsorbent can be pushed down with a ram rod which is a
long glass rod attached to a cork having diameter slightly less than the inner diameter
of the column.
(ii) Development of chromatogram: The mixture to be separated is dissolved in a suitable
solvent. The column is wetted by pouring the same solvent and allowed it to drain so that
the liquid level concide with the top of the bed. A small portion of the sample solution
(0.12 ml) is carefully pipetted onto the top of the bed. The liquid reservoir is positioned
such that the flow of the mobile phase is started. The desired flow rate is obtained by
gravity alone or by applying a gentle suction through the filtering flask. After the sample
solution has traversed through the entire length of the column, the developing solvent is
introduced and is allowed to flow steadily through the column. As the developer percolates
through the column, then various constituent of the mixture get separated. If the
components are coloured, different coloured zones are observed in the column. As the
process of development continues, the separation become more and more pronounced.
The well-developed column is called chromatogram. If the substances separated are
colourless, identification of the separated bands is made possible by the use of the
ultraviolet lamp.
(iii) Elution of different components and their recovery: After obtaining the well-
developed chromatogram, a suitable solvent (or developer liquid) which consists of a
mobile phase kept in reservoir is passed through the column gradually and the components
of the mixture are removed from the adsorbent surface. This process of removal of various
components from the adsorbent is called elution and the solvent used is called eluent.
The various eluted portions are collected one after the other and on evaporation of the
solvent from each of the fractions, the pure components are recovered.
Application of column chromatography: The main application of adsorption chromatography
is the separation of mixture into pure individual components. However, there are other valuble
application of column chromotography. These include:
(i) The purification of compounds by the removal of small amount of contaminants.
(ii) The determination of the homogeneity of chemical substances.
(iii) The comparision of compounds thought to be identical.
(iv) The concentration of substance from dilute solutions such as those obtained when natural
products are extracted from plants by extraction with a large volume of organic solvent.
A successful separation of components from a mixture using the column chromatography
technique will depend upon the right choice of the adsorbent and the solvent.
Adsorbents: There are several considerations which govern the choice of adsorbent for a given
chromatography separation.
It should be insoluble in the solvent to be used for separation and it must neither react with the
substance to be separated nor act as a catalyst for their decomposition, rearrangement or isomeration.
It should be colourless if zones containing coloured compound are to be located usuallly.
The adsorbent particle should nither be too coarse nor too fine; the average particle size should be
about 812 mm in diameter.
The most widely used adsorbent is alumina (Al2O3). The most powerful adsotrbing variety is
prepared by heating commercial activated alumina at red heat for a period of about 4 hours
and then cooling it in an evacuted desiccator. Alumina activated in this manner is too strong
adsorbent and it is difficult to remove the adsorbed material from it. Material more suitable for
general use can be obtained by heating commercial alumina for a shorter period of time at a lower
temperature.
Solvent: It is a common practice to use a relative non-polar solvent to replace the mixture of
component to be separated on the column, then to use a somewhat polar solvent to develop the
chromatograph and an even more polar solvent to elute the adsorbed material. The choice of the
solvent is subject to a wide variation, depending on the nature of the mixture to be seperated.
An approximate order of increasing polarity of the common solvent is as follows: Petroleum
ether, carbon tetrachloride, cyclohexane carbon disulphide, ether, acetone, benzene, ester of
carboxylic acid chloroform, alcohol, water pyridine. In a representative chromatography
process, a mixture may be placed on the column as solution in pertroleunm ether, the chromatogram
developed with benzene and the different bands eluted with ethnol. It is also possible to use mixed
solvent such as petroleum ether-benzene, benzene-ethanol and ethonol-water for development and
elution to separate compounds which resemble each other closely.
6.6 ION-EXCHANGE CHROMATOGRAPHY

6.6.1 Principle
It is that form of solidliquid chromatography in which the stationary phase is an ion-exchange
resin. Most of the ion-exchange resins consist of an insoluble polystyrene organic polymer cross
linked with divinyl benzene (Figure 6.9) with a large number of ionic functional groups (acidic or
basic groups) covalently attached to free phenyl group present in it.
These ionic functional groups are called active groups. The ionic active groups are hydrophilic
and can exchange reversibly with other ions of similar charge present in the solution, which acts as
mobile phase. In this process the ions held on a porous and insoluble solids are exchanged with the
ions present in the solution when brought in contact with the solid. The exchange may be cationic
or anionic as given below
Cation exchange: X+ + RY+ YZZ ZZX Y+ + RX+
Anion exchange: X + R Y YZZ
+ ZZX Y + R+X
where X = sample ion
Y = mobile-phase ion (counter ion)
R = ionic site of the exchanger
Figure 6.9 Polystryne polymer cross linked with divinyl benzene.
For cation exchange the resins used are called cation exchange resins whereas for anion exchange
the resins used are called anion exchange resins as discussed below.
6.6.2 Cation Exchange Resin

It is a high molecular weight cross linked polymer having sulphonic carboxylic and phenolic
group as an integral part of the resin and equivalent number of cations as (ResA)B+, where Res is
the basic polymer of resin to which is attached the anion A and the mobile cation B +.
Then (ResSO3)H+ or Na+ is the sulphonated styrene in the hydrogen or sodium form. When a
cation exchange resin is placed in a solution, the mobile or active cations of the resin are exchanged
with cations of the solution. The strong acid cation exchange resin has sulphonic, SO3H group
attached to polymeric matrix, whereas weak acid cation exchange resin has carboxylic(COOH)
group attached to the polymeric matrix. Thus cations exchange can be represented as
2R¢SO3H+ + M2+ ZZX
YZZ (R¢SO3)2 M + 2H+
and 2R¢COOH+ + M2+ ZZX
YZZ (R¢COO)2M + 2H+
where R¢ represents the resin.
The equilibrium can be shifted to left or right by increasing [H+] and [M2+] respectively.
The strong acid cation exchange resins are usually supplied in the sodium form. They are treated
with concentrated hydrochloric acid solution to convert them into hydrogen form. Thus
[ResA]Na+ + H+ ZZX
YZZ [ResA]H+ + Na+
6.6.3 Anion Exchange Resin

It is a high molecular weight cross linked polymer having N+(R)3, N+H(R)2, N+H2(R), N+H3
groups as an integral part of the resins, and equivalent amount of anion such as Cl, SO42, OH,
etc. Thus an anion exchange resins contain a polymeric cation to which active anons are attached.
Thus an anion exchange resin can be represented as (ResB+)A, where Res is the basic polymer
resin to which the cation B+ and a mobile anion A are attached. Where an anion exchange resin is
placed in the solution, the mobile or active anions of the resin are exchanged for anions of the
solution. Thus
(ResB+)A + C ZZX
YZZ [ResB+]C + A
The strong base type anion exchanger resin contains (N+(R)3OH) group whereas weak base type
anion exchanger resin contains N+H(R)2OH, N+H2(R)OH, N+H3OH. The exchange reaction
can be represented as
R¢NR3+OH + A ZZX
YZZ R¢NR3+A + OH
R¢NH3+OH + A ZZX
YZZ R¢NH3A + OH
R represents the resin and R is alkyl group usually methyl group. The strong base anion exchanger
resins are usually supplied in the chloride form, which can be converted into hydroxide form with
concentrated sodium hydroxide solution.
Some common examples of commercially available ion exchange resins are:
(i) Strong acid cation exchanger resins: Zerolit ZCS, Amberlite 120, Dowex 50 etc.
(ii) Weak acid cation exchanger resins: Zerolit 226, Amberlite 50 and Duolite C63
(iii) Strong base anion exchanger resins: Zerolit FF, Amberlite 400, Dowex A1
(iv) Weak base anion exchanger resins: Zerolit H, Amberlite45 and Duolite A1 to 7.
6.6.4 Mechanism of Ion Exchange

The actual ion exchange mechanism is thought to be composed of five distinct steps:
(i) Diffusion of the ion to the exchanger surface. This occurs very quickly in homogeneous
solution;
(ii) Diffusion of the ion through the matrix structure of the exchanger to the exchange site.
This is dependent upon the degree of cross linkage of the exchanger and the concentration
of the solution. This process is thought to be the feature which controls the rate of the
whole ion exchange process;
(iii) Exchange of ions at the exchange site is an instantaneous equilibrium process.
The more highly charged the species to be exchanged, the tighter it binds to the exchanger
and the less readily it is displaced by other ions;
(iv) Diffusion of the exchanged ions through the exchanger to the surface;
(v) Selective desorption by the eluent and diffusion of the species into the external solution.
The selective desorption of the bound species is achieved by changes in pH and/or ionic
concentration or by affinity elution.
6.6.5 Ion Exchange Capacity

An ion exchange resin may be characterized by the number of ion active groups. This is called the
total ion exchange capacity. It is expressed in terms of milliequivalents per gram of ion exchange
resin. The exchange capacity of a cation exchange resin is usually found in the laboratory by
determining the number of milliequivalents of sodium ion, which are adsorbed by 1 g of the dry
resin in the hydrogen form. A solution of sodium chloride of known concentration is passed through
a column containing a known weight of the resin and the acid eluting from the column is collected
and titrated with a standard solution of an alkali. If V ml of an alkali solution of strength N is
required to titrate all the acid eluted from the resin weighting W g, then ion exchange capacity is
given by
V N
Ion exchange capacity =
W
Similarly, the exchange capacity of an anion exchanger is determined by passing a solution of
sodium nitrate of known concentration through a column. The concentration of chloride ions or
the hydroxide ions in the solution eluting from the column is found by titration with a standard
solution of silver nitrate or acid respectively.
6.6.6 Factors Affecting Ion Exchange Equilibria

The factors determining the distribution of ions between ions exchange resin and a solution include
the following:
Nature of exchanging ions
(a) If we compare the hydrated ions of the same size, it is observed that the ionic charge plays
an important role to determine their capacity to undergo exchange reaction. According to
this view, the extent of exchange with H+ ions among cations has been found to decrease in
the following order:
Th4+ > Al3+ > Ca2+ > Na+
This indicates the resin prefers the ions of the highest charge in a series of ions.
(b) The capacity among anions of the same size has been found to decrease in the following
order:
PO43 > SO42 > I
(c) If we compare the ions carrying the same charge, the size of the hydrated ion plays an
important role to determine their capacity to undergo exchange reactions. For example,
with alkali metals, the following order is generally found with cation exchange resin for H+
ions exchange
Cs+ > Rb+ > K+ > Na+ > Li+
This result indicates the ions with the smallest hydrated radius is most strongly held by the
resin. Thus in the above series, Cs+ whose hydrated radius is the smallest is most strongly
held in the resin while Li+ whose hydrated radius is the largest is least strongly held.
(d) Among the doubly charged cations, the capacity has been found to decrease in the following
order:
Ba2+ > Pb2+ > Sr2+ > Ca2+ > Co2+ > Ni2+ = Cu2+ > Zn2+ = Mg2+ > Mn2+ > Be2+Cd2+
(e) Among the univalent anions, the capacity has been found to decrease in the following order:
I > NO3 > Br > CN > CI > OH > F
If the active polyvalent ion in a resin is to be exchanged with an ion of lower valency,
the exchange has been found to be favourable by using much higher concentration of the
solution.
Nature of ion exchange resin
The quality of an ion exchange resin is determined by its ion exchange capacity which in turn
depends upon the total number of ion-active groups per unit weight of the resin. The greater the
number of active ions, the greater is the capacity of the resin for the exchange process.
The efficiency of the resin has been found to depend upon the degree of cross-linking, i.e. the
greater the cross-linking, the higher the efficiency of the resin.
6.6.7 Experimental Set-up

Generally the column method is employed in ion exchange chromatography. The apparatus used
in this method consists of a glass column fitted with a glass wool plug or a sintered glass disc at the
lower end. An ordinary burette can also be used. The column is shown in Figure 6.10.
Figure 6.10 Apparatus for ion exchange chromatography.
The resin to be used should have a small particle size. This provides a large surface area for
contact between the solution and the resin. Slurry of the resin is made with distilled water and any
fine particles are removed by decantation. The tube is filled with distilled water and is drain via the
stopcock until the plug is virtually free of the any air bubble. The stopcock is then closed and the
tube is filled to about three-quarter full distil water. The slurry of fully swollen resin is poured
along the wall of the tube so that the resin bed of about 15 ml in volume is obtained. The settling
of the resin may be promoted by gentle tapping of the tube. Care being taken so that no air bubbles
are formed in the packed column.
6.6.8 Packing of Column

However, the level of water must never be allowed to fall below that of the surface of the resin,
otherwise the resin may dry up and channels may be formed in the resin bed. In such case, there
will be incomplete contact between the solution and the resin when the column is subsequently
used. The sample is applied on the top of the column using water as solvent or buffer aqueous
solution of suitable pH. Elution is brought about by passing more solvent through the column.
It is to be noted that in preparing ion exchange column, the resin must be fully hydrated with
deionized water because if it is put on the column in the dry forms, the swelling pressure when
water is added may burst the column.
6.6.9 Applications of Ion Exchange Chromatography

(i) Separation of similar ions from one another: Ion exchange chromatography is being
used to separate similar ions from one another because the different ions undergo exchange
reactions to different extents. For instance, a mixture of Li+, Na+ and K+ ion can be
separated by passing their solution through a cation exchanger. Subsequently, 0.1 N HCl
has been used as an eluent.
Similarly, ion exchange chromatography has been used to separate a mixture containing
Cl, Br and I. The mixture solution is passed through a basic anion exchanger. Sodium
nitrate solution has been used as an eluent. When 0.5 N sodium nitrate is used, Cl ion
will come first in the eluate.
(ii) Removal of interfering radicals: In the estimation of Ca2+ or Ba2+ ions by the
oxalate or sulphate method, phosphate ion is found to interfere. Therefore, its removal
becomes necessary which is achieved by passing a solution of Ca2+ or Ba2+ ions having
phosphate ions through a sulphonic acid cation exchanger. The Ca2+ or Ba2+ ions get
exchanged with H + ions while the phosphate ions will pass as such through the
column. The process has to be repeated so that the phosphte ions are completely
removed. Now, the Ca2+ or Ba2+ ions held by resin will be removed by using suitable
eluent. Finally, these ions are estimated by the usual methods.
(iii) Softening of hard water: We are aware of the fact that the hardness of water is due to
the presence of Ca2+, Mg2+ and other divalent ions. These ions may be removed by passing
hard water through cation exchangers charged with Na+ when the following exchange
reaction takes place.
2NanR + nCa2+ ¾® CanR2 + 2nNa+

Resin Hard water Resin Solution
The Ca2+ and Mg2+ ions are retained in the column whereas the Na+ ions pass into the
solution. These Na+ ions are harmless for washing purposes. After using the ion exchanger
for a long time, it becomes inactive. Its activity can be revived by percolating a concentrated
solution of NaCl through when the following reverse reaction takes place.
CanR2 + 2nNa+ ¾® nCa2+ + 2NanR

Resin Solution Resin Regenerated
(iv) Complete demineralization of water: This requires the removal of cations as well as
anions. For their removal, the water is first passed through an acidic cation exchanger
when the metallic cations (Na+, Ca2+, Mg2+, etc.) are exchanged by H+ ions. The water
obtained from cation exchanger is then passed through a basic anion exchanger when the
anions commonly present in water (Cl, NO2, SO42, etc.) are exchanged by OH ions of
the exchanger. The H+ and OH ions, which pass into solution in exchange for cations,
and anions respectively combine to form unionized water. Generally sulphonic acid resin
is employed as the cation exchanger while a strong basic resin is employed as the anion
exchanger.
Separation of lanthanides and actinides
Lanthanides and Actinides can be separated by the process of ion-exchange chromatography.
6.7 PAPER CHROMATOGRAPHY

6.7.1 Principle
This technique is a type of partition chromatography developed by Consden, Gorden, Martain and
Sirnge in England in the 1944. In this technique the substances are distributed between two liquids,
i.e. one is the stationary liquid (usually water) which is held in the pores of the filter paper (whatmann
paper) and called the stationary phase, while the other is mobile phase (organic solvent) which is
either immiscible or partially miscible with the stationary phase.
The paper is thus considered to be the analog of a column containing a stationary aqueous
phase. Solutes are then partitioned between this water held in the pores of the paper and the mobile
phase (usually organic solvent).
The mobile phase rises by the capillary action and by adsorption on the filter paper.
The components of the mixture to be separated migrate at different rates due to the difference in
their partition coefficients and appear as spots at different point on the filter paper forming
chromatogram. Although partition plays a dominant role, preferential, adsorption and capillary
action are also involved in this technique.
6.7.2 Theory of Paper Chromatography

Two types of forces are involved when a drop of solution is applied to the filter paper and treated
with the solvent (mobile phase). The forces are as follows.
Propelling forces
It tries to drag the substance in the direction of the flow of solvent. This depends upon:
(a) The rate of the solvent flow and
(b) The solubility of the substances in the solvents. Substances have different solubility in
different solvents and the solubility is affected by temperature. Thus at a certain temperature,
different components of mixture will dissolve differently in a selected solvent.
The components having higher solubility will move rapidly along the strip of the filter
paper than the less soluble component. Thus the difference in solubility of two substances
in the same solvent should be as wide as possible.
Retarding Force (RF)
Retarding force tries to drag the substance behind towards its point of application of the solution
on the filter paper. This depends upon the adsorption and partition. When a drop of solution of the
sample is treated with the solvent on the strip of a paper, the more strongly adsorbed components
remain toward the point of application while the less strongly adsorbed components will move
along the paper with the solvent. The process of partition also occurs an the paper.
Thus the different components of the sample migrate with different rates from their original
position depending upon the above forces. The positions of the migrated spots are indicated by
different parameters called migration parameters such as Rf , Rx are discussed below.
Migration parameters
Rf : Rf refers to retention factor or ratio of fronts. It is defined as the ratio of the distance travelled
by the solute from the original line and the distance travelled by the solvent from the original line.
It is pictorially represented in Figure 6.11.
Figure 6.11 Diagrammatic representation of Rf .
If we consider the point of application of the solution of a substance on the original line drawn
on the filter paper, and the distance travelled by the centre of the spot of the solute is A and the
distance travelled by the solvent front is B then
Distance travelled by the solute from the original line
Rf =
Distance travelled by the solvent front from the original line
A
=
B
Rf is a function of the partition coefficient. It is a constant for a given substance, provided the
conditions of chromatographic system are kept constant. It defines the movement of the substance
relative to the solvent front in a given chromatographic system. Each compound has a different Rf
value. Thus an unknown compound can be identified by comparing its Rf value with the literature
value. Since its value differs with the solvent used, it is better to quote the Rf value of a particular
compound with reference to the solvent used.
Thus Rf value of a substance depends upon a number of factors, which are:
(i) The nature of the solvent employed for preparing the solution.
(ii) The medium used for separation, i.e. the quality of paper in case of paper chromatography.
(iii) The nature of the substance.
(iv) The temperature.
(v) The solvent or solvent mixture employed for developing the chromatogram.
Rx: In some cases, the solvent front runs off the end of filter paper. The movement of substance in
such cases is expressed as Rx but not Rf . Rx value is the ratio of the distance travelled by the
substance from the original line to the distance travelled by a chemically similar standard
substance, x.
Pictorial representations of Rx have been made in Figure 6.12.
Figure 6.12 Diagrammatic representation of Rx.
Distance travelled by the substance from the original line A

Rx =
Distance travelled by the standard substance, x from the original line B
6.7.3 Technique of Paper Chromatography

The various operations involved in paper chromatography are:
1. Choice of the filter paper.
2. Preparation of the solution of the sample.
3. Application of the sample solution to the paper.
4. Development of the chromatogram.
5. Drying the paper.
6. Location of the substance and paper chromatogram and quantitative estimation.
1. Choice of the filter paper: Generally whatmann filter papers are extensively used in
paper chromatography. The paper should satisfy the following conditions:
(i) Excellent rate of movement of the solvent.
(ii) Negligible diffusion of the spots developed on the paper due to application of the sample.
(iii) Clarity of separation.
2. Preparation of the solution: If the sample is solid, it should be dissolved in a small
quantity of suitable solvent. Concentrated solutions are usually applied on the filter paper
to avoid diffusion through the paper. If the sample is liquid it can be applied directly to the
filter paper.
3. Application of the sample to the paper: The most common shape of filter paper is
either rectangular or square planar. Normal dimension are 15 to 30 cm in length and 1 to
5 cm in width depending upon the type of the work involved. Once the size and grade of
paper are selected, a pencil line (called the baseline) is drawn about 5 cm from one end as
shown in Figure 6.13.
Figure 6.13 Ascending paper chromatography.
If the mixture to be separated contains four compounds (A, B, C and D), then mark five
points crosses on the baseline on the filter paper. A minute drop (about 1 to 2 ml) of the
solution of the sample (test solution) is spotted by means of micropipette or a capillary tube
on to the one marked spot. Similar drops of solutions of each of known compounds (A, B,
C and D) are spotted on the remaining four marked spots. The solvent is allowed to evaporate.
The spots are dried more rapidly by blowing hot air with a hair drier. This entire process is
called spotting.
4. Development of the chromatogram: Depending upon the separation of the components
being carried out in one direction or two directions, there are one-dimensional, or two-
dimensional paper chromatogram possible giving rise to one-dimensional and two-
dimensional chromatography as discussed below:
One-dimensional paper chromatography: Depending upon the direction of flow of
the mobile phase, three different experimental procedures for one-dimensional paper
chromatography are known. These are ascending, descending and radial paper
chromatography as discussed below.
(a) Ascending paper chromatography: In this method the solvent (developing solvent
or eluting solvent) is placed in a trough at the bottom of a glass tank saturated with the
vapour of the solvent. The spotted paper strip is then suspended vertically by means of
a glass rod from a hook with paper clip in such a way that the pencil line end dips in
the solvent. However, the pencil line containing the spots should be well above the
surface of the solvent as shown in Figure 6.13. The tanke is closed with a lid or glass
plate cover.
Because of the capillary action, so as to saturate the atmosphere with the solvent
on the pores of the paper the solvent rises up. The solvent dissolves the compound
and flows up until the force due to capillary is counterbalanced by the downward
force due to gravity. When the solvent reaches a suitable height or the top, the paper is
taken out of the tank. The solvent front is marked with a pencil and the paper is allowed
to dry.
Different ingredients of the mixture travel through different heights on the filter
paper depending on their solubility and their degree of adsorption by the paper and
correspond to the heights travelled by known compounds (A, B, C, D) as shown in
Figure 6.13. Thus, different constituents of the mixture are separated as well as
identified. In this case as solvent is moving upward it is termed ascending paper
chromatography.
(b) Descending paper chromatography: In the preceding discussion we described the
ascending method in which the mobile phase ascends upward during the process.
Although this method is the most suitable and convenient, it is of little use for the
separation of the slow moving compounds, i.e. with low Rf values, because the distance
travelled by the solvent front is limited. For this purpose, the descending method is of
particular use in which the mobile phase (solvent) moves downward as shown in
Figure 6.14.
Figure 6.14 Descending paper chromatography.
In descending technique the mobile solvent is placed in a trough at the top of the tall
glass jar. The paper strip after spotting is anchored in the solvent trough placed at the top
of the glass jar so that, it is hung in the jar in the manner as shown in Figure 6.14.
The glass jar is saturated with the vapour of the solvent. A thick glass rod is used as a
weight and this prevents the paper from slipping out of the trough. A small amount of
the solvent is also poured in the jar and the jar is sealed to prevent the solvent from
evaporation.
In this technique, the solvent moves down the paper by pull of gravitational force as
well as by the capillary action. The solutes migrate from their original position under
the force of flow of solvent and thus get separated on the basis of their Rf values
producing chromatogram. The rate of flow of the solvent is greater in this technique.
So the chromatogram is developed in a comparatively shorter time. In this case, of
course, the Rf values cannot be measured, because the solvent can run off the paper
under the influence of the gravity. In such case the Rx can be measured by comparing
the compound with a standard reference compound, such as glucose.
Distance travelled by a coumpound
Rx
Distance travelled by glucose
(c) Radial or circular paper chromatography: This is a convenient method for rapid
separation of mixtures as shown in Figure 6.15.
A circular filter paper is taken and a thin strip is cut parallel to radius from the edge
to the centre. This thin strip is called as wick or tongue. The sample solution is applied
Figure 6.15 Radial paper chromatography.
at the upper end of the wick in the centre. After drying the paper wick is bent downward
at 90° to the plane of the paper descending through the aperture in the glass plate into
the solvent present in a petri dish. The petri dish is covered with a circular glass plate
to prevent evaporation of solvent and to saturate the dish with the vapour of the solvent.
The solvent constantly rises up through the strip due to capillary action and
spreads throughout the filter paper. This dissolves the solutes and the solution
spreads throughout the filter paper. Due to differential adsorption partition different
ingredients of the sample travel at different radial distances and thus get separated
producing chromatogram in the form of concentric circular zones as shown in

Figure 6.15.
(d) Two dimensional paper chromatography: This technique is convenient for the
separation of the compounds, which have similar Rf values. The two-dimensional paper
chromatography consists of rechromatographing of the separated mixture at right angles
to the first direction of development using a different solvent for the second direction
of development.
The mixture is separated by ascending chromatography in one direction with a
solvent, which should be volatile. Then after drying, the paper is turned through a
right angle and separation is carried out in the second solvent. After locating the spots,
a map is obtained and compounds can be identified by comparing their position with a
map of known compounds developed under the same condition. This technique is
particularly useful when the number of components is large. It has been used for the
separation of a natural mixture of twenty or more amino acids.
5. Drying the chromatogram: The chromatogram is taken out from the glass jar and the
position of the solvent front is marked with the pencil. The chromatogram is then dried by
blowing hot air.
6. Location of the compound: The compounds on the chromatogram can be located by
either
(a) Physical method, or
(b) Chemical methods.
Coloured compounds (marked as coloured spots) are easily located on the paper but the
compounds of biological origin are usually colourless and hence cannot be located in the
chromatogram sample by visual inspection. They have to be located by either of the following
ways:
(i) By using ultra violet lamp. Some compounds absorb light of shorter wave length (UV
light ) and emit light of longer wave length, i.e. they fluorescence. This property imparts
colour to them, which helps in their identification.
(ii) By converting the colourless compound into coloured compound by reaction with
some reagent such as H2S in the detection of metal ions forming coloured sulphides.
(iii) By spraying method. The chromatogram is sprayed with the solution of the locating
reagent by means of atomizer or chromatographic spray bottles, and then hanged on
suitable racks. For example, the position of amino acids are located by spraying the
chromatogram with ninhydrin reagent and developing the colour (purple) by pressing
it in an oven at 100ºC for 5 to 10 minutes.
(iv) By dipping method. The locating reagent is taken in a glass tray and the chromatogram
is dipped into the solution without touching the sides, so that coloured products are
formed, which help in their identification of the components.
6.7.4 Applications of Paper Chromatography

(i) Separation of amino acids: Paper chromatography is mainly employed for the
separation of amino acids, carbohydrates, etc. In such cases of amino acids, the spots are
made visible by spraying a dilute solution of Ninhydrin. In case of the separation of
carbohydrate, the spots are sprayed with aniline hydrogen phthalate.
(ii) Paper chromatography has been very successfully applied to problems in organic and
inorganic chemistry and also in biochemistry. Metals with similar chemical properties
are easily resolved. For example, nickel, manganese, cobalt and zinc can be easily separated
by paper chromatography. Their Rf values are approximately 0.1, 1.215, 0.55 and 0.9
respectively. Almost any mixture of organic compounds can be separated.
(iii) This method is often used for quick check of purity in the manufacture of pharmaceutical
and food products.
(iv) The method is successfully used in the detection of drugs in human and animals; detection
of adulterants and contaminants in food articles and syrups, squashes and various other
drinks.
6.8 THIN LAYER CHROMATOGRAPHY (TLC)

6.8.1 Principles
Stahl and Demolein developed the technique of thin layer chromatography in the year 1956 and it
resembles paper chromatography to a great extent. In TLC, an adsorbent coated with a glass plate
serves as the stationary phase. Depending upon the preparation of the plate with the coating of the
adsorbent, the fixed phase can either be solid adsorbent or water supported by the adsorbent.
Commonly the adsorbent is applied as a thin film on the plate in the form of an aqueous slurry and
dried in an air oven at 110°C for several hours.
This process known as activation, removes all the residual water and the stationary phase in this
case is a solid phase. If the adsorbents are not activated by heating; under these conditions the
residual water acts as the stationary phase.
6.8.2 Choice of Adsorbent for TLC

The most commonly used adsorbents, which are available in grades specially prepared for TLC
include silica gel, alumina, kieselguhr and cellulose powder. Alumina is preferred in the separation
of weak polar compounds while silica gel is preferred for polar compounds such as amino acids
and sugars. Magnesium silicate, calcium silicates and activated charcoal can also be used as
adsorbents.
6.8.3 Choice of Solvent

A little amount of sample is dissolved in a small volume of a volatile solvent such as benzene,
ether or ethanol. The choice of solvent depends on two factors:
(i) The nature of the substance to be separated, and
(ii) The nature of the adsorbent.
The common procedure is to match the polarity of the solvent to that of the substance being
separated. For polar substance such as alcohols, carboxylic acids and amines, the solution should
be made in polar solvent and cellulose or silica gel layers are selected. Polar solvent produces
greatest migration and thus gives a better separation. Less polar substances should be dissolved in
a suitable non-aqueous solvent. Combination of two solvents gives better separation than obtained
with a single solvent.
6.8.4 Experimental Techniques

The essential requirement for TLC are suitable adsorbent, suitable solvent, glass plate, a suitable
device to apply a thin adsorbent layer, a means of holding the plate and tank or glass jar to run the
plates. The experimental technique consists of the following steps.
Preparation of thin layer of adsorbent on the plate (chromatoplates)
Glass plates usually 20 cm ´ 5 cm of uniform thickness are selected. These are thoroughly cleaned
and all greasy matters from its surface are removed. Aqueous slurry of adsorbent powder is prepared
with the binder such as plaster of Paris, gypsum, or polyvinyl alcohol to help it to adhere to the
plate. The slurry is spread on the plate in a thin film typically from 0.1 to 0.3 mm thickness, by
means of spreader. Sometimes spraying the slurry on the glass plate or dipping the plate in the
slurry is also used to prepare the plate. The thin layer thus spread is then dried in an oven at 100ºC
to activate the adsorbent plate. It is then allowed to cool and kept in desiccator just before use. The
stationary phase in the plate prepared by activating fashion is solid and the plate prepared in this
manner are called chromatoplates.
6.8.5 Sample Application

Test sample is dissolved in a suitable solvent to get its clear solution. Before sample application a
starting line at the height of 1.5 to 2.0 cm from the edge of the plate is marked. It is called baseline.
Also another line called the finish line about 10 cm from the baseline is also marked. The sample
solution is applied on the baseline with a micro syringe or micro pipette. The solution thus
spotted is then allowed to evaporate to get dry plate by applying a stream of warm air from a hair
drier.
6.9 DEVELOPMENT OF THE CHROMATOGRAM
The chromatogram is usually developed by ascending method (in which the solvent moves from
bottom to the top direction) in a specially design developing jar or tank containing the developing
solvent as shown in Figure 6.16.
Since Rf values are affected by the degree of saturation of the atmosphere, it is thus necessary
that a paper impregnated with the solvent should be placed round the sides of the tank to
ensure that the atmosphere of the tank is saturated with the solvent vapour. The chromatoplate is
immersed in the tank and its lower end containing the baseline is made to stand in the developing
solvent to a depth of 0.5 cm leaning against the side of the tank nearly at an angle of 45º as shown
in Figure 6.16. The baseline should above the surface of the solvent. The tank is then closed firmly
with the lid.
The solvent (mobile phase and developing phase) kept in the tank moves up the thin layer of
the solid adsorbent on the plate due to capillary action and dissolves the solute in the spot of the
baseline. As it moves, sample solutes are carried along at rates which depend upon their solubilities
Figure 6.16 Apparatus for thin layer chromatography.
in the moving phase and their interactions with the solid adsorbed coated on the plate. This leads
to separation of the components of the mixture sample. This process is continued till the solvent
reaches the finishing line at the top end of the chromatoplate. The plate is then removed from the
tank and dried without heating. Usually currents of dry air are passed over the plate surface. In this
way a chromatogram is developed on the chromatoplate. After removal, the position of various
components are located.
Recording the distance moved from the baseline by the compound and the distance moved by
the solvent front the baseline, retention factor Rf can be calculated as
Distance moved by the compound from the baseline

Rf
Distance moved by the solvent from the baseline
Under identical experimental conditions only the factors on which Rf value of substance depends
are:
(i) The particle size of different batches of the adsorbent.
(ii) The solvent composition and quality.
(iii) The degree of saturation of the tank atmosphere with solvent vapour.
(iv) Thickness of the adsorbent layer.
(v) Prior activation and storage condition of the plate.
Location of the compound on the chromatogram

Coloured substance can be located without any difficulty. But when the compounds are
colourless, physical or chemical means must be used for the purpose. This can be done in the
following ways:
(i) By spraying the plate with appropriate reagents (chromogenic spray reagent), many of
them are selective for particular functional groups and may be extensively sensitive, i.e.
Ninhydrine reagent for detection of amino acid which produces coloured areas in the
region which they occupied.
(ii) Frequently colourless or non-fluorescent spots can be visualized by exposing the

chromatogram to iodine vapour. The dried plate is allowed to stand as a closed tank
containing iodine crystals placed at the bottom of the tank. The iodine vapour interacts
with the sample components to produce a colour especially dark brown colour. Iodine is
very useful nondestructive locating reagent in identifying a large number of organic
compounds.
(iii) Thin layer plate and sheet are commercially available which incorporate a fluorescent
dye in the powdered adsorbent. When held under ultraviolet light, dark spots appear
where sample spot occurs due to quenching of the plate fluorescence.
(iv) A common technique for organic compounds is spraying to the plate with a sulphuric
acid solution and then heating it to char the compounds and develop black spots.
Application of TLC
TLC technique is very sensitive and gives sharp zones and better resolution. Some applications of
TLC is given below.
(i) TLC has been widely used for isolation, purification and identification of the individual
components in the mixture.
(ii) TLC technique is very common technique for checking the purity of the product obtained
in the organic synthesis. The observation of the single spot on developing the plates is
conclusive for the formation of a single product. Formation of by-product can be usually
detected by the observation of more than one spot. In addition to identification, a product
can be confirmed by comparing the Rf values of the product with that of the authentic
sample.
(iii) It is applied as purification process.
(iv) The method is used in the laboratory for quick check on whether the reaction is complete
or not.
(v) TLC often serves in the identification of plant extract, drugs and adulterants in food
products.
(vi) TLC can easily carry out separation of metal with similar chemical properties. For example,
Ni, Co, Mn and Zn can be separated by this technique.
Superiority of TLC over paper chromatography

Though TLC and paper chromatography can be considered to be two form of planar chromatography,
TLC has certain advantages over paper chromatography because of the followings:
(i) The time taken for the development of the chromatogram is much shorter for TLC as
compared to paper chromatography.
(ii) Since TLC employs glass plates as support for adsorbent, TLC plates can be dried at
higher temperatures without any risk of destruction of the plates, while in paper
chromatography extreme care must be taken while drying the paper.
(iii) TLC is more sensitive than paper chromatography. The spots obtained in TLC are sharp
and compact while those obtained in paper chromatography are usually diffused.
(iv) The capacity of thin layers of the adsorbent is higher than that of paper.
6.10 GAS CHROMATOGRAPHY

6.10.1 Introduction
Gas chromatography is undoubtedly the most important and extensively applied technique for
analytical and industrial purpose. Gas chromatography was developed in 1941 by A.J.P. Martin
and R.L.M. Synge (both were award Nobel prize in 1952 for the discovery of gas chromatography).
In the year 1952 A.J.P. Martin and A.T. James first separated fatty acid by this technique for the
first time. It is rapidly becoming an important process in chemical plant and refineries.
Gas chromatography refers to a physical process by which a mixture is separated into its
constituent by moving gas phase over a stationary adsorbent. Based upon the nature of stationary
phase, the gas chromatography can be classified into gas-solid chromatography (GSC) and gas-
liquid chromatography (GLC). In GSC the stationary phase consists of an active solid adsorbent
such as granular silica, alumina or carbon. The process involves adsorption of gases on the solid
surface and is chiefly applied to the separation of permanent gases and low boiling hydrocarbons.
The technique has certain limitations such as non-linear adsorption, difficulty in reproduction,
surface condition and excessive retention of reactive gas causing the reproduction of available
area for adsorption. In GLC separation occurs by partitioning a sample between a mobile gas
phase and a thin layer of non-volatile liquid coated on an inert support.
6.10.2 Principle of Gas Chromatography

When a gas or vapour comes in contact with an adsorbent, certain amount of it gets adsorbed on
x
the solid surface. The phenomenon occurs according to the Freundlichs law KC1/ n or
m
Langmuirs law x K1C K 2C where x is the mass of the gas or vapour adsorbed in mass m of
m
the sorbent, C is the vapour concentration in the gas phase, K, K1 and K2 are constants. If the
gas or vapour comes in contact with a liquid, a definite amount of it gets dissolved in the liquid
x
according to Henrys law of partition KC. Both the phenomena are selective and we get
m
different K-values for different vapour-sorbent pairs. The forces involved in the chromatography,
in general, are van der Waals, London, dispersion forces, inductive forces, hydrogen bonding,
charge transfer or covalent bonding. The first three forces are involved in GLC.
Experimental technique
The apparatus used is called gas chromatograph. Its schematic diagram is shown in Figure 6.17.
It consists of the following parts:
1. A high-pressure cylinder containing a mobile gas phase (known as carrier gas) with pressure
regulator and flow regulator.
2. Sample injection system.
3. Chromatographic column.
4. Thermostated column.
5. Detector.
6. Strip chart recorders.
7. Separate thermostat compartment for housing the column and the detector so as to regulate
its temperature.
Figure 6.17 Schematic diagram of a gas chromatography.
1. Carrier gas supplier: The gaseous mobile phase, which is known as carrier gas must be
chemically inert. Helium is the most common carrier gas, althoug hydrogen, nitrogen, carbon
dioxide and argon are also used. These gases are available in pressurize cylinder. Pressure regulator,
flow controller, and flow meter are required to control the flow rate of the gas. The choice of a
carrier gas depends upon.
(i) Nature of the sample.
(ii) The type of the detector being employed.
(iii) Column efficiency.
(iv) Availability.
(v) Purity required.
(vi) Consumption. Hydrogen and helium are most suited for use with a thermal conductivity
type of detector as they have high thermal conductivity and low density.
2. Sample injection system: The amount of sample required for gas chromatography depends
upon
(i) The nature and concentration of the solute.
(ii) The size of the column.
(iii) Sensitivity of the detector.
The usual range is from 0.1 to 50 micro litre for gases and liquids and fraction of miligram for
solids. The device by which measured sample can be introduced into the carrier gases are:
(i) Micro syring for liquid and gas sample.
(ii) Glass and ampoule for the solid sample.
(iii) Valve for gaseous sample.
Sample injection system for introducing liquid sample by micro syringe technique is shown in
Figure 6.18.
Figure 6.18 Introducing sample by hypodermic syringe.
The liquid samples are injected by a micro syringe through a self-sealing silicon rubber septum
into a heated metal block located at the head of the column. Here the sample is vaporized and
carried into the column by the carrier gas. The metal block should be heated, by a controlled-
resistance heater about 50ºC above the boiling point of the least volatile compound of the sample.
The condition is such that the liquid is rapidly vaporized without either decomposing or fractionating.
3. Chromatographic columns: The columns used in gas chromatography are made of variety
of materials such as stainless steel, copper, glass or plastic depending upon the nature of substances
to be separated. It may be coiled in a U- or W-shaped to permit convenient thermosetting in an
oven. For most of the analysis, columns are from 120 cm to 5 cm in length and have a inside
diameter of 2 mm to 10 mm. The column is packed with an inert support material of large surface
area such as diatomaceous earth and Kieselguhr. The liquid that is immobilized or held in the
column is used as hydrocarbon of high molecular mass, i.e. squalene. Polar liquid such as poly
ethylene glycol and polar carbowaxes can also be used. The liquid thus immobilized in the column
acts as the stationary phase.
4. Column thermosetting: To obtain a good separation and reproducible chromatography peak
shapes, the column temperature is to be controlled within a few tenth of a degree. For this reason
the coiled column is housed in a thermostatic oven. The optimum temperature depends on the
boiling point of sample components.
5. Detector: Detector is a device that senses the arrival of the separated components of the
sample present in the carrier gas as they leave the column by providing corresponding electrical
signal. The temperature of the detector compartment must be sufficiently high to prevent
condensation of sample vapour but not to cause sample decomposition. The most widely used
detectors are thermal conductivity detector and flame ionization detector.
6. Recorder: Almost all the detectors give rise to small and weak electrical signal. It is therefore
necessary to pass the signal through an amplifier before being fed to the recorder. The recorder
consists of two parts:
(i) A mobile recording pen activated by the signal.
(ii) A recording chart strip which is moving with pre-selected speed. The amplified signals
drive the pen on the moving strip of paper and trace out a series of peak forming
chromatogram on the paper.
Working
The carrier gas, obtained from a steel gas cylinder, passes through a flow regulator for the adjustment
of flow rate, and enters into the sample injector. A little amount of the sample
is introduced into the sample injector with the help of a hypodermic syringe. The sample injector
is maintained at a temperature higher than the boiling point of the highest boiling components of a
sample in order to ensure rapid vaporization of the liquid samples. The carrier gas entering the
sample injector sweeps off the vaporized sample and passes down the thermostated or
temperature programmed column. The components of the samples are distributed between the
stationary and the mobile phases and pass down the column at the different rates. This results in
the separation of the components of the sample. The carrier gas with the separated components
now enters the detector, which measures the change in composition of the carrier gas as it passes
through it. This change is amplified before it is fed into a recorder, which drives the recording pen
on a moving strip of paper, and a chromatogram is obtained.
Characteristics of gas chromatography peak and resolution
The most widely used means of identification of chromatograms by the use of peak position known
as retention value VR which is the volume of the carrier gas that passes out of the column to the
time the peak maximum is obtained. It is given by
VR = tRFC
where tR is the retention time, i.e. the time from the point of injection of the sample to the time of
emergence of the separated component from the column. The retention time depends upon.
(i) the flow rate, FC of the carrier gas,
(ii) column temperature, TC,
(iii) the weight of the liquid phase,
(iv) the affinity between sample component and liquid phases comparing the stationary phase.
If we consider the retention times of air (tair) and retention volume of air (Vair) which is known
from the appearance of air peak, then the adjusted retention volume V¢R is given by
V¢R = VR Vair
= tR FC tair FC
A typical gas chromatographic peaks for two components of a sample is shown in Figure 6.19.
Figure 6.19 Gas chromatography peaks for two components of a sample.
If we consider the separation of two components of the sample, the separation efficiency of gas
chromatography generally expressed in terms of separation factor called resolution (R) is given by
VR,2 VR,1
R=
0.5(W1 W2 )
2(t R,2 tR ,1 )
=
W2 W1
where W1 and W2 are the baseline width for the component 1 and 2 respectively. VR,1 and VR,2 are
adjusted retention volume for component 1 and 2 respectively. Whereas tR1 and tR2 are their retention
times.
The main conditions affecting the resolution are:
(i) Nature of the stationary phase.
(ii) Cross sectional areas of the column.
(iii) Length of the column, (L).
(iv) Nature of the linear velocity of the carrier gas.
(v) The phase ratio.
(vi) Temperature.
6.10.3 Applications of Gas Chromatography

The applications given below will show the versatile nature of gas chromatography.
1. Separation of benzene (b.p.353.1K) and cyclohexane (b.p.353.8K). This separation is
virtually impossible by fractional distillation. By GLC, the separation of the two can be
accomplished in a few minutes.
2. Separation of hundred of hydrocarbons petroleum by GLC. This separation, which is now
routine analysis in petroleum industries, would have been perhaps impossible without GLC.
3. By using molecular sieves, gas-solid chromatography has been used to separate a mixture
of H2, CO2.CO, O2, CH4, C2H2, C2H4 and C2H6.
4. Automobile exhaust gases which cause main pollutant hazards have been analyzed by GLC.
5. Volatile substances such as human breath, environmental air and urine have been analyzed
by GLC.
6. Flavour and aromas of flowers and foods are the result of a combination of hundreds of
organic compounds in trace amounts. These have been separated by GLC.
7. The high degree of resolution of GLC allows purity of sample to be checked.
8. GLC has also been used in the separation of radioactive products.
9. Gas chromatography has also been used to study reaction mechanism.
1. Multiple choice questions (on solvent extraction)

(i) The distribution coefficient of solute between two immiscible solvents is governed by
(a) Nernst distribution law (b) Henrys law
(c) Oswalds law (d) Raoults law
(ii) The distribution coefficient (KD) is equal to distribution ratio D when the solute
(a) Ionize (b) Dime rise
(c) Neither ionize nor dime rise (d) Both (a) and (b)
(iii) If benzoic acid is extracted with ether layer D is maximum when
(a) [H+] >> Ka (b) [H+] << Ka
(c) [H+] = Ka (d) None of these
(iv) Benzoic acid remains mostly in the aqueous layer
(a) [H+] >> Ka (b) [H+] << Ka
(c) [H+] = Ka (d) None of these
(v) In solvent extraction the extraction efficiency D
(a) Depends on the original concentration of solute
(b) Independent of the original concentration of the solute
(c) Inversely proportional to the original concentration of the solute
(d) None of these
(vi) The percentage of extraction increases by
Vaq Vaq
(a) Decreasing the ratio (b) Increasing the ratio
Vorg Vorg
(c) Making Vaq = Vorg (d) None of these
Vaq
(vii) When D = 10, and = 1, the percentage of solute extracted is
Vorg
(a) 90.91% (b) 95%
(c) 99% (d) None of these
(viii) Complete separation of solute is possible in
(a) Single extraction (b) Multiple extractions
(c) Double extraction (d) None of these
(ix) For the single extraction of two solute A and B for which DA = 10 and DB = 0.1, the
separation factor B will be 100 if
(a) A is removed by 91% and B is removed by 9%
(b) A is removed by 9% and B is removed 91%
(c) When % of extraction of both A and B are equal
(d) None of these
(x) Batch extraction method is used for
(a) Larger value of KD (b) Smaller value of KD
(c) Both larger and smaller value of KD (d) None of these
(xi) When organic compound to be extracted has nearly the same solubility in water as well as
in organic solvent, then
(a) Batch extraction is preferred
(b) Continuous extraction is preferred
(c) Countercurrent extraction is preferred
(d) All of the above are preferred
(xii) The most efficient solvent extraction method for the extraction of the two or more
substances is
(a) Batch method (b) Continuous extraction method
(c) Craig method (d) All of the above
2. Multiple choice questions (on chromatographic methods)
(i) A mixture of chloride and bromide ion can be separated by making use of a
(a) Strong-acid cation exchanger (b) Weak-acid cation exchanger
(c) Strong-base anion exchanger (d) Weak-base anion exchanger
(ii) The common locating agent used to identify amino acids is
(a) Iodine vapour (b) Ninhydrin
(c) Permanganate (d) Hydrogen sulphide
(iii) M. Tswett, a Russian Botanist invented chromatography in the year
(a) 1906 (b) 1910
(c) 1900 (d) 1899
(iv) The basis of separation of ion-exchange chromatography is
(a) Chemical change (b) Adsorption
(c) Absorption (d) None of these
(v) The purpose of solid support in a GLC column is to
(a) Immobilize the stationary liquid phase
(b) Adsorbed the sample component that are insufficiently soluble in the stationary liquid
phase
(c) Provide a back up stationary phase in the event the liquid is lost by evaporation
(d) Remove impurities from the carrier gas
(vi) Helium, rather than nitrogen, is sometimes used as the carrier gas in GLC because
(a) Being lighter than nitrogen, helium elutes the sample components more rapidly
(b) Helium is less expensive than nitrogen
(c) Nitrogen has stable isotopes which separate and caused anomalies column behaviour
of the much higher thermal conductivity
(d) None of these
(vii) Raising the column temperature in GLC decrease solute retention time primarily because
(a) Solute diffusion coefficient in liquid phase decreases with an increase in temperature.
(b) Vander Waals interactions between solute and stationary phase are stronger at higher
temperature.
(c) Gases are generally less soluble in liquid at high temperature.
(d) Detector sensitivity is a function of temperature, specially with a thermal conductivity
cell.
(viii) Which of the following would have practically no effect upon the retention volume of a
solute in the GLC?
(a) Changing the carrier gas flow rate
(b) Increase the stationary liquid loading of the column packing to 10% by weight
(c) Increase the column temperature
(d) Changing the chemical nature of the stationary liquid
(ix) The separation factor in chromatography depends upon the
(a) Length of the column
(b) Square root of the length of the column
(c) The nature of the stationary liquid phase
(d) The number of theoretical plate in the column
(x) In GLC interaction of the solute with the solid support will often cause
(a) Increase narrow elution bands (b) Symmetric elution band with tailing
(c) Exclusive eddy diffusion (d) Decreasing detector sensitivity
(xi) Increase in the quantity of the stationary liquid phase applied to the column packing will
(a) Increase tR of the solute (b) Decrease tR of the solute
(c) Not influence tR of the solute (d) None of these
3. Fill in the blanks (solvent extraction)
(i) The basis of separation technique involving partitioning between two immiscible phases
are .............. and .............. .
(ii) The mixture of carboxylic acid and phenol can be separated by extracting ether solution
with .............. .
(iii) Solvent extraction involves .............. system of two phases.
(iv) The principle of solvent extraction is governed by .............. law.
(v) When Vaq = Vorg, the % of extraction is given by the expression .............. .
(vi) The various methods of solvent extraction are .............., .............. and .............. .
(vii) The extraction efficiency can be affected by changing the reagent concentration and by
changing .............. .
4. Fill in the blanks (chromatographic method)
(i) Hard water can be softened by applying .............. chromatography.
(ii) The reagent which can be used for the separation of benzoic acid and naphthalene
is .............. .
(iii) Paper chromatography is a form of partition chromatography in which the stationary phase
is .............. .
(iv) For identification purpose in chromatography the spots are characterized by their ..............
factors.
(v) Chromatography is the technique which is employed for the .............., .............., ..............
and .............. of the components of the mixture.
(vi) In chromatography, the essential process involves .............. between two phases.
(vii) The eluent or the solvent may be .............. or a mixture of .............. .
(viii) The success of the column chromatography depends upon ............., ............. and ............ .
(ix) Separation efficiency in column chromatography .............. with decrease in particle size.
(x) The acidic adsorbent is .............. while .............. is a basic adsorbent.
(xi) The adsorbent should be finely divided to provide .............. .
(xii) Fine cellulose paper is hydrophilic in nature and is .............. .
(xiii) Retention factor (Rf) is the ratio of the distance travelled by the solute from the original line
to .............. .
statements (on solvent extraction)
(i) Solvent extraction is based on partitioning of solute between homogeneous system of two
phases.
(ii) Solvent extraction obeys Gibbs phase rule.
(iii) For benzoic acid extraction the distribution coefficient KD and distribution ratio are of the
same value.
(iv) If the concentration of H+ ion is changed then the distribution ratio D will change.
(v) The % of extraction can be increased by increasing the volume of organic phase.
Vaq
(vi) Performing two successive extractions with 1, would result in overall performance
Vorg
of 99%.
(vii) Separation factor can be increased by adjusting the volume ratio given by Bush Densen
equation.
(viii) Craigs countercurrent extraction follows binomial distribution.
(ix) The more stable is the metal chelate the less is the extraction efficiency.
(x) Efficient extraction is achieved with several small volumes of solvent rather than a single
larger one.
statements (on chromatography)
(i) The stationary phase in paper chromatography is a liquid.
(ii) Sulphonated polystyrene is an example of a strong-base anion exchange resin.
(iii) The principle involved in column chromatography is adsorption.
(iv) In the preparation of the polystyrene from styrene divinely benzene can be added to introduce
cross linkage.
(v) In chromatography, the components to be separated get distributed between two phases.
(vi) The solvent used for separation of the component in the mixture is called elutes.
(vii) A solution which is more soluble component the bottom run rapidly.
(viii) The process of removing each component from the column and collecting them are called
elution.
(ix) The retention factor or retardation factor of a solute is independent of the concentration of
the solute.
(x) An adsorption works better if it has a larger surface area.
(xi) The adsorption should react with one component of the mixture.
(xii) Diluent is a mixture of two solvents.
(xiii) In radial paper chromatography each component of mixture appears a colour band.

7. Answer the followings (on solvent extraction)
(i) Define distribution on coefficient. Is its temperature dependent?
(ii) Explain distribution ratio giving the example of benzoic acid.
(iii) Establish a relationship between distribution coefficient and distribution ratio.
(iv) What is the effect of pH on the extraction of benzoic acid from an aqueous solution by
addition of ether.
(v) Explain percentage of extraction.
(vi) What do you mean by multiple extraction?
(vii) Explain separation factor.
(viii) State Bush Densen equation.
(ix) Enumerate the factors for enhancing the rate and selectivity of extraction on metal chelates.
(x) What is meant by synergistic extraction?
8. Answer the followings (on chromatography)
(i) Give at least two applications of column chromatography.
(ii) Write the principle involved in ion-exchange chromatography.
(iii) What do you mean by cationic and anionic exchanger? Explain with suitable examples.
(iv) Write the mechanism of ion exchange
(v) Explain the ion-exchange capacity.
(vi) Give at least two examples of ion-exchange chromatography.
(vii) What is paper chromatography? Write the theory involved in it.
(viii) What is migration parameter involved in paper chromatography?
(ix) Write how the sample is applied in the paper chromatography?
(x) Distinguish between ascending paper chromatography and descending paper
chromatography.
(xi) Write the principle involved in radial or circular paper chromatography.
(xii) Explains two-dimensional paper chromatography.
(xiii) How the various spots in the paper chromatography are located?
(xiv) Give at least two applications of paper chromatography.
(xv) What do you mean by TLC?
(xvi) What are the adsorbent and solvent used in TLC?
(xvii) Write how a thin layer of adsorbent is prepared in TLC.
(xviii) Write the method of development of chromatogram in TLC.
(xix) Write how the various components are located on the chromatogram in TLC?
(xx) Give at least two applications of TLC.
(xxi) Explain GLC and GSC.
(xxii) Write the principle of gas chromatography.
(xxiii) What do you mean by carrier gas?
(xxiv) What factors are involved in selecting a carrier gas in GLC?
(xxv) Discuss sample injection system.
(xxvi) Give the schematic diagram of a sample injection system in GLC.
(xxvii) How a gas chromatography peak is characterized?
(xxviii) Give at least two applications of gas chromatography.

(i) On solvent Extraction
9. Differentiate between distribution coefficient KD and distribution ratio D and establish a
relation between them in solvent extraction involving benzoic acid partitioning between
organic solvent and aqueous phase.
10. Derive the expression for the amount of substance (Xn) unextracted in solvent extraction
using V ml of an organic solvent in each extraction for n times. If the single extraction is
carried out using (n ´ V) ml organic solvent in a single extraction, what is the amount of
solute left? Give your comment on the above result.
11. Describe the various equilibrium process involved in the solvent extraction of metal chelate.
Write an expression for the distribution ratio D for the above system. Mention the condition
for better extraction of metal chelates.
12. Discuss the following methods of solvent extraction
(i) Batch extraction,
(ii) Continuous extraction:
(a) when the extractant is heavier than water,
(b) when the extractant is lighter than water.
(iii) of Craig countercurrent extraction of chromatography.
(ii) On chromatography
13. Define chromatography. Write how the chromatography methods are classified on the basis
of
(i) physical state,
(ii) mobile and stationary phase and
(iii) mechanism involved between mobile and stationary phase.
14. Describe the principle and technique of column chromatography. How does the technique
serve as a useful analytical technique?
15. Describe with a suitable sketch how the chromatography separation can be made by
(i) ascending paper chromatography,
(ii) descending paper chromatography and
(iii) radial paper chromatography.
16. What is ion-exchange chromatography? Write the principle and technique involved in it.
How this technique is used for purification of water?
17. Describe the principle and technique involved in TLC (Thin layer chromatography). TLC
is considered as a better technique than the paper chromatography. Justify.
18. Describe the principle and technique involved in GLC. Mention some of its important
applications.
CHAPTER 7
Purification Techniques
7.1 INTRODUCTION
Most of the organic compounds when isolated from organic reactions from the laboratories are
usually contaminated with small amounts of other compounds (impurities) due to side reactions.
Even compounds obtained from the natural sources are never found free of impurities. Therefore,
before subjecting the compound for qualitative and quantitative analysis, it must be purified.
Similarly all the organic chemicals, medicines and utility compounds require purification thoroughly
before they are sent to the market. Thus, purification of compounds, though tedious, is an
indispensable operation. The methods of purifying compounds depend upon
(i) the nature of the compound and
(ii) the nature of impurities present in them.
Purification of some of the organic compounds has been discussed here under the following
headings.
(a) Purification techniques for solid organic compounds.
(b) Purification techniques for liquids.
(c) Chemical methods of separation and purification.
7.2 PURIFICATION TECHNIQUES FOR SOLID ORGANIC

COMPOUNDS
There are five important purification techniques for solid organic compounds mentioned below.
(i) Crystallization
(ii) Fractional crystallization
(iii) Sublimation
(iv) Sublimation under reduced pressure
(v) Solvent extraction
263
7.2.1 Crystallization
Solid organic compounds when isolated from organic reactions are usually contaminated with
small amount of other compounds (impurities) due to side reaction. The purification of impure
crystalline compounds is usually done by crystallization from suitable solvent or mixture of solvents.
It is based on the two facts, namely
(i) most solids are more soluble in hot solvents than cold solvents and
(ii) the solubility of different compounds in a given solvent is different. For this purpose
(a) The impure sample is dissolved in minimum volume of the suitable organic solvent
at or near the boiling point.
(b) The hot solution is filtered to remove particles of insoluble materials and dust.
(c) The hot filtrate is allowed to cool to room temperature or below so that the dissolved
substance crystallises out.
(d) The crystals are separated from the supernatant solution (or mother-liquor) by
filtration (usually under suction).
(e) The resulting solid after drying is tested for purity by melting point determination.
Choice of the solvent
The solvent chosen for crystallization has the following characteristics:
(i)It has a high power for dissolving the substance to be purified at a higher temperature.
(ii)It does not dissolve the substance completely at a room temperature or below.
(iii)It dissolves the impurities either to a small extent or not at all.
(iv) It possesses a relatively low boiling point so that it can be easily removed from the crystal
of pure substance after it is separated from the mother liquor.
(v) It should yield well-formed crystal of the purified compound.
(vi) The solvent does not react chemically with the substance.
The following rough generalization can be used to choose a suitable solvent for crystallization:
(i) A substance is likely to be most soluble in a solvent to which it is closely related in
physical and chemical characteristics.
(ii) A polar substance is more soluble in polar solvent and less soluble in non-polar solvent.
The organic compound with hydrogen atom attached to electronegative atoms like nitrogen
and oxygen are capable of forming hydrogen bonds and such compounds (alcohol,
carboxylic acid and amide) can be crystallized from hydroxylic solvent such as water and
alcohol.
(iii) Most organic compounds, which lack hydrogen, bonded hydrogen atom dissolve only in
ether, benzene or petroleum ether.
(iv) Chlorinated hydrocarbons, chloroform and carbon tetrachlorides are excellent solvents
for compounds, which lack a hydrogen-bonded hydrogen atom.
Some commonly used solvents are listed in Table 7.1 in order of decreasing polarity.
Purification Techniques 265
Table 7.1 Common solvent for recrystallization
Solvent Boiling point in ºC Dielectric constant at 25ºC
Water 100 79
Acetonitrile 80 38
Methnol 65 33
Ethanol 78 24
Acetone 56 21
Methylene chloride 41 9
Acetic acid 118 6
Chloroform 61 5
Diethyl ether 35 4
Benzene 80 2.3
Dioxane 101 2.2
Carbon tetra chloride 77 2.2
Petroleum ether 3060 2
6090 2
90120 2
Cyclohexane 81 2
Pentane 36 1.8
Technique of Crystallization
(i) Dissolving the impure (or crude) sample in some suitable solvents at or near the
boiling point
The impure organic solid is heated with a suitable solvent in a
flask fitted with a long tube as a reflux condenser on a sand bath
as shown in Figure 7.1. The reflux brings back the solvent by
condensing its vapour and thus checks its loss by vaporization.
After some time, the solute dissolves completely in the solvent. In
order to clarify the solution, a pinch of animal charcoal may be
added to the solution during boiling.
(ii) Filtering the hot solution from particles of insoluble
materials and dust
The saturated solution obtained above is filtered hot by means of
hot water funnel (Figure 7.2) which consists of copper jacket
containing hot water which supports the glass funnel containing a
filter paper. This prevents cooling and consequent crystallization
of the solid over filter paper. For small quantity of solution, a fluted
filter paper (Figure 7.3) can be used.
(iii) Cooling and separation of crystals
The hot solution is then cooled in a container surrounded by
ice cold water. The pure solid separates out as crystalline
precipitate from the supernatant solution (or mother liquor) Figure 7.1 Apparatus for
which is separated by filtration. For filtering large quantities, use making solution.
Figure 7.2 Hot water funnel. Figure 7.3 Fluted filter paper.
of filter pump (Figure 7.4) can be made. The suction applied makes the filtration quick and more
efficient.
(iv) Drying
The resulting solid is dried in a steam oven or hot air oven at a suitable temperature. Sometimes
drying is done by means of vacuum desiccator (Figure 7.5).
Figure 7.4 Apparatus for separation of crystal. Figure 7.5 Vacuum desiccator.
(v) Recrystallization
It is often seen that a solid is not completely purified by subjecting it to crystallization once.
Therefore, it is recrystallized by repeating all the steps described above.
The following points are to be noted in order to carry out successful crystallization.
(i) The slower the rate of cooling of the solution, the larger the size of the crystal.
(ii) Seeding with the crystal of desired substance usually initiates recrystallization, which
may otherwise not occur at all.
(iii) Sometimes mixed solvents or solvent pairs are used, if the substance is highly soluble in
one solvent and highly insoluble in another. Some common solvent pairs are alcohol-
water, alcohol-benzene, acetic acid-water, etc.
(iv) The crystals may be contaminated with coloured impurities. These are removed by boiling
the solution containing the compound with small quantity of activated charcoals so that
the coloured impurities are absorbed preferentially.
(v) If the solvent used is non-volatile, its complete removal from the crystal is difficult.
In such case the crystal is washed several times with low boiling solvent in which the
crystal is insoluble but the crystallizing solvent is miscible.
7.2.2 Fractional Crystallization

If the impure substance is a mixture of two substances A and B which are soluble in the same
solvent but their solubility differs, then the less soluble (suppose A) will crystallize out first from a
saturated solution. It may be contaminated with a little of B. The mother liquor on further
concentration will deposit crystal of B contaminated with A. The process is repeated several times
to get pure sample of A and B. This is called fractional crystallization. It involves separation of two
or more than two substances present in an impure sample by fractions at various stages of
crystallization. Thus fractional crystallization may be defined as the process of separating a less
soluble substance from a more soluble one from the same solution.
Examples of fractional crystallization
(i) The separation of mixture of potassium chloride and potassium chlorate can be done by
fractional crystallization as follows. The solubility of KCl and KClO3 are about 35 and
7 at 293 K while at 323 K, the respective solubility are 40 and 20. A mixture containing
(say, 20 g) each of KCl and KClO3 is dissolved in 100 ml of water. The solution is heated
to 323 K and then cooled. KClO3 will separate at once while KCl and a little of KClO 3
remain in the solution.
The crystal of KClO3 obtained above also contains a little KCl. To get pure potassium
chlorate, it is again crystallized when KCl remains in solution. The solution containing
KCl and a little KClO3 is now heated to the crystallization point when the former gets
separated. It is obtained in the pure form by crystallization.
(ii) The separation of benzoic acid and cinnamic acid using hot water as solvent can be done
by the process of fractional crystallization based on the difference in their solubility.
7.2.3 Sublimation
Certain organic compounds pass directly from solid to vapour state on heating and vice-versa on
cooling. The examples of such compounds are napthalene, anthracene, camphor and indigo, iodine,
ammonium chloride, etc. The following equilibrium exists for such compounds.
Solid ZZX
YZZ Vapour
The sublimation is very useful in separating substance, which sublimes on heating (called volatile
solid) from nonvolatile impurities.
Technique of sublimation
A simple apparatus for the process of sublimation is shown in Figure 7.6. The substance (to be
sublimed) is placed in an evaporating dish (china dish). It is covered with a perforated filter paper
(or perforated asbestos sheet) and inverted funnel is placed on the sheet. The stem of the funnel is
closed with cotton plug to avoid vapours of the sublimate to go out. The asbestos sheet serves two
purposes:
Figure 7.6 Apparatus for sublimation.
(i) It keeps the side of the funnel cool and thus the volatile substance gets easily deposited.
(ii) It does not allow the deposited sublimate to funnel back in the dish.
The dish is gently heated, as a result the solid substance changes to vapour from crude sample.
The vapours rise up and pass through the holes in the perforated sheet and get deposited on the
cooler walls of the funnel. The funnel is kept cool by wrapping it with a wet filter paper or wet
cloth. Heating is stopped when most of the material in the dish has vapourized. The rate of heating
must be such that the funnel should not become hot. The rate of sublimation may be increased by
applying suction at the stem of the funnel. Camphor contaminated with small amount of
non-volatile impurities such as succinic acid can be purified by this method. However, this method
is not applicable for the substances which decompose at their sublimation temperature. For this
type of substances, a technique called sublimation under reduced pressure is employed as follows.
7.2.4 Sublimation under Reduced Pressure

The simple apparatus for sublimation under reduced pressure is shown in Figure 7.7. It consists of
two tubes of which one is fitting into the other. The sample is placed at the bottom of the outer tube
connected to a vacuum pump through the outlet and is warmed gently by immersion into an oil-
bath. Inner tube is fitted with two-glass tube, one brings in cold water and the other acts as an
overflow. On heating the outer tube, the substance vaporizes and then condenses on the cooler
surface of the inner tube.
Figure 7.7 Apparatus for sublimation under reduced pressure.
7.2.5 Solvent Extraction

Continuous extraction process for organic solid has been discussed (refer to 6.2.5). For continuous
extraction of a solid from a solid mixture a Soxhlet extraction method is employed as follows:
The Soxhlet apparatus is shown in Figure 7.8.
Figure 7.8 Soxhlet apparatus for purification of organic solid.
It consists of wide tube provided with a side tube on the left, a siphon tube on the right and a water
condenser at the top. The organic solid mixture is placed in the wide tube and the apparatus is
fitted in the neck of a flask F containing a suitable solvent.
The solvent in the flask F is boiled so that the vapour of the solvent find their way through the
side tube into the water condenser where they got condensed. The droplet of the condensed hot
solvent fall on the mass placed in the wide tube and dissolve out the soluble constituent from it.
The level of the solution goes on rising till the siphon begins to work and the solution passes
through the siphon tube back into the flask F. The process continues and more and more of the
soluble constituent passes in solution collected in F. The solid is then separated as usual by
crystallization from the solution obtained above.
Alkaloids, essential oil of flower and leaves, vegetable colouring matter of leaves and soluble
constituents of certain roots can also be extracted very easily with a suitable solvent in the solvent
apparatus.
7.3 PURIFICATION TECHNIQUES FOR LIQUIDS
Various techniques are employed for the purification of liquids depending on the nature of the
liquids and the nature of impurities present as follows:
1. Simple distillation
2. Fractional distillation
3. Distillation under reduced pressure
4. Steam distillation
7.3.1 Simple Distillation

Liquids, which boil under ordinary pressure without decomposition and are associated with
non-volatile impurities are generally purified by simple distillation. It involves boiling of an impure
liquid at atmospheric pressure and condensing the vapours to obtain pure liquid.
Thus distillation is a process of converting a liquid into its vapour state which is then condensed
to liquid. The experimental assembly for carrying out simple distillation is shown in Figure 7.9.
Figure 7.9 Apparatus for distillation.

The distillation assembly consists of a distilling flask, a water condenser, a thermometer and a
receiver. The distillation flask is charged to about two-third capacities with the liquid to be purified
and it is heated on asbestos centred wire gauze or on oil-bath. Heating is done rapidly in the
beginning, but the rate of heating is reduced once the boiling starts. As the liquid boils, it changes
into vapours, which are led into water condenser where they cool and condense into pure liquid.
It is finally collected in the receiver flask. The water contaminated with common salts can be
purified by distillation. The source of heat is adjusted so that the condensed liquid is collected at
the rate of one or two drops per second.
The following facts are to be taken into consideration:
(a) Almost all liquids tend to superheat (rise to temperature somewhat above the boiling point)
to some extent. This is a metastable condition and causes bumping, i.e. this can be avoided
by the addition of a few bits of porous porcelain. The small pores in the porcelain provide
a site for the formation of bubble nuclei and thereby provide smooth boiling.
(b) The bulb of the thermometer should be located slightly below the level of the side tube of
still head so that its is bathed in a flow of vapor.
(c) If the boiling point of liquid is greater than 374 K, the water-cooled condenser should be
replaced by an air condenser. It is just a long glass tube without any air jacket. It is cooled
by the air inside and hence its name.
(d) The head and tail portions of the distillate should be rejected and only the middle portion is
to be collected.
(e) In case of a very volatile liquid and inflammable liquid such as ether, acetone, etc. the
distillation flask is heated on a water bath and not in a wire gauze. If the boiling point of the
liquid is very high, the flask is heated directly with a naked flame.
This technique of simple distillation can be applied to two liquids whose boiling points differ
widely. As a general rule, a mixture of any two components whose boiling points differ by at least
80ºC can be separated by simple distillation. For liquids whose boiling points differ by 30ºC to 80ºC,
separation is possible by repeated simple distillation or fractional distillation as discussed below.
7.3.2 Fractional Distillation

When the mixture of two liquids A and B is heated in a distilling flask, the low boiling constituent
(suppose A), contaminated with a little high boiling constituent (suppose B) distils over first and is
collected separately. The two fractions are further purified by repeating the above separation number
of times. To decrease the number of distillations or to separate A from B when their boiling points
are closer to each other, a fractionating column is used. It consists of a long vertical tube provided
with obstructions to the passage of the vapours upwards and that of the liquids downwards.
A typical assembly for carrying out fractional distillation is given in Figure 7.10.
The liquid mixture to be fractionated is placed in a distillation flask fitted with a fractionating
column, a thermometer and a condenser as shown in Figure 7.10. The flask is heated from below.
The liquid vaporizes and the vapours rise into the fractionating column where some of them condense
and start flowing down. At each obstruction in the fractionating column there occurs an exchange
of constituents between the up-going vapours and the down coming liquid. The vapours lose more
and more of high boiling constituent (B) by condensation as they rise up and the liquid loses more
and more of low boiling constituent (A) by evaporation. Thus pure A passes at the top and pure B
remain in the flask below.
Figure 7.10 Apparatus for fractional distillation.
The fractionating column used for the purpose is known as Vigreux column. The two other
commonly used fractionating columns are Dufton column and Hempel columns.
The selection of a column for a particular distillation is governed by the boiling point of the
liquid being separated the volume of the material being distilled and the degree of separation.
Table 7.2 lists the boiling point difference to the corresponding number of theoretical plates that
are required to effect a good separation (about 99% purity of the distillate).
Table 7.2 Theoretical plates necessary for separation

Boiling point difference, ºC Plates required
30 8
20 13
10 22
7 35
5 50
4 65
3 80
2.5 100
The efficiency of the column is commonly expressed in terms HETP (height equivalent
to theoretical plate) units. The commonly used Vigreux column has a typical HETP value of
10 cm. This means that in order to have 8 theoretical plates the length of the columns will be
10 ´ 8 = 80 cm. Thus a 80 cm Vigreux columns with 8 theoretical plates is used for the separation
of two liquids having boiling point difference 30ºC. For example, benzene (b.p. 80ºC) and tolune
(b.p. 110ºC) can be separated by using the above columns. On the other hand, to separate
O-toluidine (b.p. 200ºC) and m-toludine (b.p. 203ºC) which differ in their boiling point only by
3ºC, the number of theoretical plates is about 80 and the Vigrex column used will have to be
80 ´ 10 = 800 cm (8 metre).
The separation of the mixtures of xylenes (ortho xylene, b.p. 142ºC, mxylene, b.p. 139ºC and
pxylene, b.p. 138ºC) is carried out by this procedure. It also finds wide applications in modern
industry such as fractional distillation of petroleum and coaltar (which consists of mixture of
several aromatic hydrocarbons).
However, simple distillation or fractional distillation is not applicable for organic substances
that decompose below their boiling point. For example, glycerol decomposes at its boiling point
(553 K). It can be safely distilled at 453 K under reduced pressure of 12 mm by the technique of
distillation under reduced pressure as discussed below.
7.3.3 Distillation under Reduced Pressure

Principle of the method
A liquid begins to boil at the temperature at which its vapour pressure becomes equal to the
atmospheric pressure. It can be made to boil at lower temperature by lowering the pressure and
vice versa. Thus a liquid can be made to boil at any temperature by changing pressure to which it
is subjected. Thus if we have an organic compound which decomposes at its boiling point, we can
make it to boil at a temperature before it can decompose. This can be done by distillation at
pressures below atmospheric pressure. Such type of distillation is known as distillation under
reduced pressure or vacuum distillation based on Troutans rule and ClapeyronClausius equation
described below.
Troutans rule: For normal unassociated liquids, the ratio of molar heat of vaporization in calories
to the normal boiling point at the absolute scale is approximately constant and has a value of 21 cal
degree1 mole1.
Clapeyron-Clausius equation: If P1 and P2 are two pressures at which the boiling points are T1
and T2, respectively, then
È P2 Ø H È1 1Ø
ln É Ù
Ê P1 Ú R ÉÊ T1 T2 ÙÚ
where H is the molar heat of vaporization and R is the universal gas constant. This is the integrated
form of Clapeyron-Clausius equation.
It is possible to show that the normal boiling point TN is related to the boiling point TR at the
reduced pressure P (in mm) by the following equation.
10.5TN
TR
17.133 ln P
Illustration 7.1 The normal boiling point of chloro benzene is 132ºC (132 + 273 = 405 K).
The boiling point at a pressure of 25 mm will be
10.5 405 4252.5
TR 306 K or 33º C
17.133 ln 25 13.95
Thus when the pressure is reduced from 760 mm to 25 mm, the boiling point of high boiling liquid
is reduced by about 100ºC.
Experimental set-up
The apparatus used for vacuum distillation is shown in Figure 7.11.
Figure 7.11 Apparatus for vacuum distillation.
The liquid to be distilled is taken in the distilling flask (A), the right-hand side arm of which can
be attached to the condenser (C) and thermometer (T). The flask (A) also carries a screw-cap
adapter through which a glass tube (B) is inserted and drawn out to a capillary, at its lower end.
The tube (B) carries at its upper end a short piece of pressure tubing and a screw clip (S).
The condenser (C) is attached to the receiver flask (E) and the receiver adapter (D) is connected to
a trap (T), a water or oil pump (P) and a manometer (M) as shown in Figure 7.12.
Figure 7.12 Accessory for vacuum distillation.
A water pump using water at 20ºC is capable of reducing the pressure to about 25 mm which is
adequate for many distillations. Oil pumps are generally capable of reducing the pressure to
1 mm or less. When it is necessary to use an oil vacuum pump to attain low pressures, it is essential
to prevent large volumes of solvent vapour from passing into the pumping system.
The oil pump should therefore be guarded with a suitable trap.
To carry out a distillation under reduced pressure, the liquid is poured into the flask (A) so that
it is about half full. The apparatus is completely assembled as shown in Figure 7.11. The pump is
then turned on to reach its maximum capacity with the screw clip (S) almost fully closed. It is then
adjusted so that a fine steam of air bubbles passes through the liquid in order to minimize bumping.
When a satisfactory vacuum has been achieved, the flask is heated with a water or oil bath.
The temperature of bath should be 2025ºC above the boiling point of the liquid at the recorded
pressure. When the liquid commences to boil, the boiling point and the corresponding pressure
shown by the manometer are noted.
The process of distillation under reduced pressure is also employed for the concentration of
sugar cane juice in sugar industry. Besides the vacuum distillation, another procedure called steam
distillation is adopted for many high-boiling liquids, which may decompose at or below their
normal boiling points as discussed below.
7.3.4 Steam Distillation

This process is applicable for organic liquids, which have the following characteristics.
(i) Immiscible with water.

(ii) Contain non-volatile impurities.
(iii) Possess high vapour pressure.
(iv) Volatile in steam (i.e. volatile at 100ºC).
In this method steam is bubbled through the impure liquid kept in a flask heated on a sand bath.
Vigorous boiling sets in and vapours of the organic substance mixed with steam rise up and condense
as they pass through water condenser. Thus the condensate is a mixture of organic substance and
water. The two being immiscible are separated in a separating funnel. In case the organic compound
is partially miscible with water, it is extracted with a suitable solvent. Pure organic compound is
then recovered in the extract by fractional distillation.
The example of such liquid is aniline. Aniline boils at 184ºC at 760 mm pressure. It forms
hydrogen bonded complex with water molecule whose boiling point is 97ºC. Therefore, aniline
can be separated as steam volatile compound from its non-volatile impurities. Similarly many
natural occurring substances such as alkaloids and terpenes can be separated in the pure form as
steam-volatile substances. A mixture of ortho and p-hydroxy aceto phenone, ortho and para nitro
phenols can be separated by this procedure. The ortho derivatives are steam volatile due to intra
molecular hydrogen bonding whereas para isomers are not.
Theory of steam distillation
A liquid boils at a temperature at which its vapour pressure becomes equal to the atmospheric
pressure. In steam distillation, a mixture of water (suppose A) and organic liquid (suppose B)
heated. The mixture boils when the combined vapour pressures of water ( p1) and that of organic
liquids ( p2) is equal to the atmospheric pressure ( p), i.e.
when p = p1 + p2
or p2 = p p1
Let W1 = wt of water which distils over
W2 = wt of the substance carried off with steam
W1 W1
n1 = no. of mole of water vapour =
Molecular wt of water 18
W2 W2
n2 = no. of mole of substance =
Molecular wt of substance M
n1
f1 = Mole fraction of water in vapour =
n1 n2
n2
f2 = Mole fraction of substance in vapour =
n1 n2
p1 p2
f1 and f2
P P
f1 p
\ = 1
f2 p2
n1
n1 n2 p
or = 1
n2 p2
n1 n2
n1 p
\ = 1
n2 p2
W1
or 18 = p1
W2 p2
M
W1 p1 W2
or =
18 p2 M
W1 18 p1
or =
W2 p2 M
W1
If the vapour is condensed, the ratio would express the mass of water and organic liquid in the
W2
condensed.
Illustration 7.2 Consider the distillation of a mixture of water and bromobenzene, which is
almost completely immiscible with water. At 95.3ºC the vapour pressure of water is 641 mm and
that of bromobenzene is 119 mm. The vapour pressure of the mixture is therefore (641 + 119),
i.e. 760 mm. Hence a mixture of water and bromobenzene will distil at 95.3ºC and the molar ratio
119
of bromobenzene to water in the distillate will be only . But the molecular wt of bromobenzene
641
is 157 compared to 18 for water.
wt of bromobenzene 119 157

1.6
wt of water 641 18
Despite the much lower vapour pressure of bromobenzene, on a weight basis it will distill 1.6
times as fast as water.
Experimental set-up
A simple apparatus for steam distillation is shown in Figure 7.13.
Figure 7.13 Apparatus for steam distillation.
Procedure
The impure compound and some water are placed in a round bottom flask connected to a steam
generator on one side and a water condenser on the other.
Steam from steam generator (G) is admitted into the steam distillation flask (F) and the vapours
from flask (F) are passed through a condenser (C) and then the distillate is collected in the receiver
(R). The distillation flask (F) should be less than half filled with the mixture to be steam distilled,
since additional water will be condensed in it during steam distillation. The vapours of steam
volatile compounds (crude liquid) with steam pass over the flask through U tube and through a
condenser where they are condensed and collected in the receiver. The distillate is obtained as on
immiscible mixture (or emulsion) of water and the pure organic substance (liquid) from which the
organic substance can be separated by using a separating funnel or by extraction with suitable
solvent.
By the process of steam distillation the molecular weight of the substance can be determined as
illustrated below.
Illustration 7.3 The hydrocarbon terpinene was found to distil freely in steam at a temperature
of 95ºC when the atmosphere pressure was 744 mm. The vapour pressure of pure water at this
temperature is 634 mm and the distillate contained 55% by the weight of terpinene. Calculate the
molecular weight of the terpinene.
Let terpinene be A and water be B.
P = pA + pB
744 = pA + 634
pA = 744 634
= 110 mm
WA M A pA M A 110
=
WB M B pB 18 634
If WA is 55 g then WA + WB = 100 g
WB = 100 55 = 45 g
55 M A 110
=
45 18 634
MA = 127
(the actual molecular weight of terpinene is 136)
Advantages of steam distillation
(i) It allows high boiling point liquids to be distilled at a temperature much less than their
normal boiling point. Hence it is a convenient substitute for vacuum distillation.
(ii) It is useful for the separation of small amount of material from a large bulk of solid or
tarry material which makes ordinary distillation filtration and extraction difficult
or impractical. Thus this technique is used in the isolation of natural product and of
reaction product which are contaminated with large amount of tarry material.
(iii) It is useful in the separation of slightly volatile organic compound in the following cases:
(a) Aqueous mixture containing inorganic salt.
(b) From other organic compounds which are not appreciable volatile with steam.
(iv) It can be applied to determine the approximate molecular weight of a substance that is
almost immiscible with water. This can be done provided the composition of the steam
distillate and the vapour pressures of the two components are known.
7.4 CHEMICAL METHOD OF SEPARATION AND PURIFICATION
This method is adopted if there is a substantial difference in acidity and/or basicity between the
substances to be isolated and the contaminant with which it is associated. Let us apply this chemical
method of separation to a binary mixture (containing two components). Following are the various
possible types of binary mixture. The procedure involved for separating components from some
types of a binary mixture is discussed below.
Chemical method of separation and purification for binary mixture
(a) Binary mixture containing two neutral organic compounds.
Type 1: One component is ether soluble and the other is insoluble in it.
Binary mixture

Shake
with ether
Insoluble component
Ether solution
Ether soluble component
Evaporate
ether
The ether from the ethereal extract is either evaporated or distilled off in order to recover the ether
soluble component.
Some binary mixture of this type are:
(i) Naphthalene + Glucose
(ii) Phthalimide + p-toluidine
(iii) thiourea + p-hydroxy benzaldehyde.
Type 2: One component is water-soluble and the other is insoluble in it.
Mixture
Shake with
H 2 O and filter
Soluble component (aqeuous solution) (a)
Insoluble component (b)
(i) Evaporate the aqueous solution a slowly on water bath to recover the soluble component.
Direct heating may be avoided, otherwise the organic compound may decompose or
char.
(ii) Wash the insoluble components with water and dry between the filter papers before it is
put to analysis.
Some binary mixtures of this type are:
(i) Urea + Naphthalene
(ii) Glycine + Diphenylamine
Type 3: Binary mixture containing one acid component and one neutral component.
Neutralize the mixture with 10% sodium hydroxide solution as shown below.
Mixture
Shake with
10% NaOH
Insoluble component (a)
Soluble component in aqous solution (b)
The acid may separate either in the form of a solid or liquid. If the acid is separated in the form of
solid, filter, wash and dry it before analyzing. If the acid is separated in the form of liquid, separate
it by solvent extraction using suitable solvent.
Type 4: Both the components are acidic.
Dissolve the mixture under analysis in sodium hydroxide solution and saturated the solution by
passing carbon dioxide gas through it. Extract the solution so formed with ether. All the phenolic
compounds which do not contain any carboxyl or nitro groups pass into the ethereal layer.
Mixture (two acidic components)
Dissolve in
Aqueous solution
NaOH solution
Ethereal layer (a)

Pass CO2 gas
extract with ether Aqueous layer (b)
Neutralise with ppt. (aromatic acid)
dil. HCl Filtrate (Test for aliphatic acids)
Evaporate or distill off ether from the ethereal layer (a) to recover the phenolic component from
it. The aqueous layer (b) is acidify with dilute hydrochloric acid. A precipitate indicates the presence
of some aromatic acid. Cool it and filter the precipitate. Wash the precipitate with water and then
analyze. Test the filtrate for some other aliphatic acids.
(i) a-Naphthol + p-nitrobenzoic acid
(ii) Oxalic acid + Resorcinol

(iii) Sulphanic acid + Catechol
Type 5: One component of the binary mixture is basic.
Shake the mixture with dilute hydrochloric acid. The basic component dissolves and forms an
aqueous layer.
(i) If the other component is an insoluble solid, filter and wash it with a little dilute
hydrochloric acid. Finally wash it with water, dry and then analyze.
(ii) If the other component is insoluble liquid, then separate it from the aqueous solution by
means of a separating funnel. Wash the liquid component with water and dry before
analysis.
Mixture (one components is basic)

Shake with
dil. HCl
Soluble component (salt of amine)
Insoluble component (solid or liquid)
The soluble component is a salt of an amine. Add 10% aqueous sodium hydroxide till it is
alkaline to litmus. Cool and scratch the sides.
(a) The formation of precipitate indicates the presence of an aromatic amine. Filter it and wash
with water. Finally dry between the filter papers before analysis.
(b) If instead, an oil or oily suspension is formed then cool it and extract with ether. Separate
the etheral layer. Dry over anhydrous sodium sulphate and filter. Finally distil off ether to
recover amine.
(i) p-toludine + 1,3 Dinitrobenzene
(ii) 1,2 phenylene diamine + Benzophenone
(iii) 2-Naphthylamine + Diphenyl
Type 6: The components of the mixture are soluble in ether.
The components present in the mixture may be neutral (N), acidic (HA) or basic (B). Let us
assume that the organic salt are distributed almost entirely in the aqueous layer and all other organic
substances (HA, B and N) distributed almost entirely in the ether layer. Table 7.3 outline the
general scheme of separating a mixture of acidic, basic and neutral components by extraction
procedure.
The acidic, basic and neutral components separated in this way can be purified by adopting the
usual techniques.
Apart from the above a substance may be frequently converted into a crystalline derivative by
means of a reagent which does not react with impurities as follows:
Separation and purification of a substance by converting into crystalline derivative
This can be best illustrated by taking an example of crude acetone prepared from pyroligneous
acid. The crude acetone is shaken with a strong solution of sodium bisulphite. The acetone forms
a crystalline bisulphite compound, which is separated from the impurities. The crystalline compound
decomposes when warmed with a solution of sodium carbonate or sodium hydroxide. Acetone, so
liberated is distilled, dried over anhydrous calcium chloride and redistil.
Methyl alcohol and acetaldehyde are purified in a similar manner by forming their crystalline
derivative.
Table 7.3 Separation of acidic (HA), basic (B) and neutral (N) components by extraction method
7.5 CRITERIA OF PURITY
A pure organic compound has characteristics of physical properties such as refractive index,
specific gravity, melting point and boiling point etc. A substance is said to be pure if it shows the
properties, which a pure compound is known to possess. In recent years, more sophisticated methods
like spectroscopy are also used to check the purity of a compound. However, in most laboratory
work the melting point of solid substance and boiling point of a liquid substance is used to check
its purity.
Checking of purity of a solid by melting point method

A pure solid melts sharply at its melting point temperature to give a clear liquid while an impure
solid melts over a range of temperature to give a semi solid mass. The purity of the solid is further
confirmed by determining the mixed melting point as discussed below.
Mixed melting point: The melting point of an intimate mixture of two substances is called
mixed melting point. The substance whose purity is to be tested is mixed with the pure sample of
the same compound in about equal quantities. The melting point of the mixture is determined. If it
is sharp and comes out to be the same as that of pure compound, it is confirmed that the compound
under the test is pure. On the other hand, if the melting point of the mixture is less than that of the
pure compound, the compound under the test is said to be impure.
Checking of purity of a liquid by its boiling point method
For liquid the most commonly used criterion of purity is its boiling point. A pure liquid boil at a
constant temperature and the entire liquid is converted into vapour at this temperature which is the
boiling point of the liquid. For impure liquid there may be more than one boiling point corresponding
to more than one compound. For the liquid to be converted completely into vapour the temperature
have to be raised over a range whose magnitude will depend on the type and relative amount of the
impurities.

(i) A bottle containing two immiscible liquids can be separated by
(a) Fractional distribution (b) Separating funnel
(c) Vacuum distillation (d) Steam distillation
(ii) A mixture of oil and water can be separated by
(a) Filtration (b) Separating funnel
(c) Fractional distillation (d) Sublimation
(iii) Fractional crystallization is carried out two separate mixture
(a) Organic solids mixed with organic solid
(b) Organic solid slightly soluble in water
(c) Organic solids having small differences in their solubility in a suitable solvent
(d) Organic solids having greater differences in their solubility in a suitable solvent
(iv) Which of the following is not a sublimate
(a) Napthalene (b) Camphor
(c) Chorine (d) Benzoic acid
(v) The process of distillation includes all the following processes except
(a) Change of state (b) Boiling
(c) Condensation (d) Evaporation
(vi) Fractional distillation is useful in distillation of
(a) Petroleum (b) Coal tar
(c) Crude alcohol (d) None
(vii) Impure glycerine can be purified by
(a) Steam distillation (b) Simple distillation
(c) Vacuum distillation (d) Extraction with a solvent
(viii) Vacuum distillation is used to purify liquids, which are
(a) Highly volatile (b) Explosive in nature
(c) Decompose below their boiling point (d) None of the above
(ix) Steam distillation is used for the purification of substance, which are
(a) Insoluble in water (b) Volatile in steam
(c) Associated with non steam volatile (d) All of the above
2. Choose the correct statement out of the followings
(a) Ammonium chloride can be easily purified by sublimation.
(b) A mixture of benzene and toluene can be separated by fractional distillation.
(c) Simple distillation separates over those liquid which differ in their boiling points by 5ºC.
(d) Glycerene and glycol can be separated by fractional distillation.
(e) Presence of impurities in an organic liquid raises its boiling points.
(f) Anthracene is purified by crystallization, whereas turpentine oil can be purified by the
process of steam distillation.
(g) The boiling point of liquid decreases with an increase in pressure.
(i) Volatile substances, which on heating directly form vapours, are purified by .............. .
(ii) Simple distillation is a technique, which is employed for separating liquids having ......... .
(iii) Glycerol is generally purified by .............. .
(iv) Impure naphthalene is purified by .............. .
(v) Distillation under reduced pressure is known as .............. .
(vi) Compounds, which are decomposed at their boiling point, can be purified by .............. .
(vii) Raw juice is concentrated in factory by .............. .
(viii) Aniline is purified by .............. .
(ix) Essential oils are extracted by .............. .

4. How will you separate?
(i) A mixture of the volatile liquid which differs in the boiling points by 10ºC.
(ii) An organic compound from its aqueous solution.
(iii) An organic compound, which decomposes before its boiling point.
(iv) An organic compound which is insoluble in water but steam volatile.
(i) What is an index of purity of solid?
(ii) Which is the most common method of purifying a liquid?
(iii) When a solid has a high vapour pressure, by which methods its purification can be achieved?

(i) How will you purify an impure sample of
(a) Anthracene
(b) Aniline
(ii) How will you purify a liquid, which decomposes before its boiling point is reached?
(iii) How will you separate a mixture of o-nitro phenol and p-nitro phenol?
(iv) How liquid contaminated with non-volatile impurities can be purified?
(v) How could you separate a mixture of comphor and benzoic acid?
(vi) How would you separate the following?
(a) A mixture of acetone and methanol
(b) Water and alcohol
(vii) How would you separate the mixture whose distillate is unchanged in composition?
(viii) How would you separate benzene and chlorobenzene?
(ix) How would you separate a mixture of two soluble substances with different solubility?
7. Explain why
(a) Absolute alcohol cannot be obtained by simple fractional distillation.
(b) Bromobenzene can be purified by steam distillation.
(c) During crystallization of solid, the hot solution is not treated with animal charcoal.

8. What is crystallization? Describe various steps involved in the process of crystallization.
9. Name a mixture of two substances, which can be separated by fractional crystallization.
Describe the process in detail.
10. Name at least two mixtures, which can be separated by sublimation. Describe the process
in detail with a labeled diagram.
11. What do you mean by distillation? Describe how substances can be purified by this process
with a labeled diagram.
12. In organic reactions two volatile organic liquids A and B with boiling points 333 K and 340
K were found. What method would you adopt to get them in pure state? Describe the
method with a labeled diagram.
13. Name the process of purifying an organic liquid, which decomposes on heating to its boiling
point. Illustrate it with a diagram.
UNIT 6
8. Electroanalytical TechniquesElectrogravimetry
9. Electroanalytical TechniquesCoulometry
10. Electroanalytical TechniquesPolarography
CHAPTER 8
Electroanalytical Techniques
Electrogravimetry
8.1 INTRODUCTION
Electroanalytical techniques include measurement of electrical properties such as current, resistance

and potential voltage, reciprocal of resistance (conductance) and evaluation of materials generated
at the electrode. All the measurements are directly related to concentration of analyte.
A brief summary of various electroanalytical techniques classified according to the quantity
measured is given below.
8.2 CLASSIFICATION OF ELECTROANALYTICAL TECHNIQUES
Potentiometry
It is the direct application of Nernst equation. It involves measurement of potentials of non-
polarized electrodes under conditions of zero current.
Chronopotentiometry and chronoamperometry
In chronopotentiometry, a known constant current is passed through the solution and the potential
appearing across the electrodes is observed as a function of time. The related measurement of
current changes following application of constant potential is known as chronoamperometry.
Voltametry and polarography
The method of studying the composition of dilute electrolytic solutions by plotting current-voltage
curve is known as Voltametry. When a dropping mercury electrode is used as cathode and mercury
pool is used as anode, the technique is called polarography.
Conductometry
In this analytical method, two identical inert electrodes are employed and the conductance (reciprocal
of resistance) between them is measured. Technique involving titration is called conductometric
titration.
287
Oscillometry
This method permits one to observe change in conductance, dielectric constant or both by the use
of high frequency alternating current. Electrodes are not kept in contact with the solution directly.
Amperometry
It refers to the measurement of current under a constant applied voltage. Under these conditions, it
is the concentration of analyte, which determines the magnitude of the current.
Electrogravimetry
In this analysis, the element to be determined is deposited electroanalytically upon a suitable
electrode by the process of electrolysis.
Coulometry
This method of analysis involves the application of Faradays laws of electrolysis relating the
equivalence between the quantity of electricity passed and the amount of substance generated at
the corresponding electrodes.
Controlled potential separation
It is possible to quantitatively separate species by means of electrolytic oxidation or reduction at
an electrode, the potential of which is carefully controlled. The quantity of separated species may
be measured coulometrically or electrogravimetrically.
Only three electroanalytical techniques such as electrogravimetry, coulometry and polarography
based on exhaustive electrolysis of analyte are discussed in Chapters 8, 9 and 10 respectively.
Exhaustive electrolysis means the analyte is quantitatively oxidized or reduced at the electrodes in
an electrochemical cell.
Before going to discuss the topics it is thought worthwhile to give a brief idea about the various
electrical components involved in electroanalytical techniques as follows.
8.3 ELECTRICAL COMPONENTS
8.3.1 Electrodes and Electrode Potential

Electrode is a system through which current enters or leaves the electrolytic solution. It may be
metallic or membrane. Only metallic electrode relevant to the topic is discussed here. These are
conveniently classified into three categories such as (I) electrodes of the first kind, (II) electrodes
of second kind, and (III) inert redox electrodes.
Electrodes of the first kind
It consists of a pure metal, M dipped in a solution of its own ion, Mn+. Potential difference (electrode
n
potential) is set up at the interface. A single reaction such as M (aq) ne ½ M (s) is involved and
the electrode potential, E is given by Nernst equation:
2.303 RT
E E0 log a ( M n )
( M n /M ) nF
Electroanalytical Techniques—Electrogravimetry 289
Where aM n denotes the activity of the ion Mn+ in solution. Approximated activity is replaced
by its molar concentration [Mn+]. F is the Faraday and n is the number of electrons transferred
in the electrode reaction. E 0 n is a constant which is a characteristic of the metal when
( M /M )
aM n = 1. This constant is also termed standard electrode potential. By IUPAC convention, the
standard electrode potential corresponds to reduction. The standard oxidation potentials of the
metals would, of course, have the same numerical value but opposite sign. For example, the oxidation
expression Ze ® Zn2+ + 2e with a standard oxidation potential of 0.763 V is equivalent to the
reduction Zn2+ + 2e ® Zn with a standard reduction value 0.763 V. The examples of such electrodes
include Ag/Ag+ and Hg/Hg 22+ in neutral solution and Cu/Cu2+, Zn/Zn2+, Cd/Cd2+, Bi/Bi3+, Tl/Tl+
and Pb/Pb2+ in deaerated solution.
Electrodes of the second kind
It consists of a pure metal M coated with one of its sparingly soluble salt of the type MXn. In this
electrode, the potential is a function of the concentration of X in an MXn/M redox reaction.
MXn(s) + ne ® M(s) + nX (aq)

The Nernst expression for this process is

2.303RT
E 0
EMX · log[ X ]n
n
nF
0
where EMX n
is the standard potential of this type of electrode. The examples of such electrodes
are saturated calomel electrode (SCE). This electrode consists of mercury, mercurous chloride
(calomel) and a saturated solution of KCl for which half reaction is
Hg 2 Cl2 + 2e ½ 2Hg + Cl ; 0
ECalomel 0.268 V
The shorthand notation of this electrode is Hg/Hg2Cl2(Satd), KCl. Another example is
silver/silver chloride electrode; Ag/AgCl (Satd), KCl.
AgCl + e ½ Ag Cl ; 0
EAgCl 0.2223 V
Inert redox electrode

Such type of electrode includes inert conductor like gold, platinum or palladium immersed in a
solution containing redox system. It is an inert electrode, which serves as a source or sink
for electrons for a redox reaction. For example, platinum electrode immersed in a solution
containing Ce3+ and Ce4+ ions is an example of such electrodes. The reaction being involved is
Ce4+ + e Û Ce3+ and the Nernst equation for this electrode
0 2.303RT [Ce3+ ]
E ECe 4 · log
F [Ce4+ ]
Pt/Fe2+, Fe3+ is another examples of such electrode.
8.3.2 Electrochemical Cell

Electrochemical measurements are done in electrochemical cell. It consists of two electrodes,
namely the cathode and anode, each of which is immersed in an electrolytic solution. However, in
most of the cells, the solutions surrounding the two electrodes are different and must be separated
to avoid direct reaction between the reactants. This is done buy inserting a salt bridge between the
solutions. Conduction of current from one electrolyte solution to the others occurs by migration of
K+ ions in the bridge in one direction and Cl ions in other direction. An electrochemical cell may
be either galvanic or electrolytic as follows.
Galvanic cell
A galvanic cell stores electrical energy. In this cell electrochemical reaction, i.e. oxidation at one
electrode (anode) and reduction at the other electrode (cathod) occurs spontaneously. When the
circuit is completed by placing an external connection between the two electrodes, the electrons
involved in the oxidation step are transferred at the electrode surface, pass through external circuit
and then return to the other electrode, where reduction takes place. The cell shown in Figure 8.1 is
a galvanic cell.
Figure 8.1 A typical galvanic cell.
It develops a potential of 0.412 V when electrons flow through the external circuit from copper
anode to the silver cathode. In this cell (ve) polarity is assigned to anode and (+ve) polarity is
assigned to cathode.
Chemists frequently use a shorthand notation to describe electrochemical cell. The cell in
Figure 8.1 is described by
Cu Cu 2+ || Ag | Ag
(0.02M) (0.2M)
By convention anode and cathode are displayed on the left and right ends of this representation.
A single vertical line in this scheme indicates that a potential develops at the phase boundary
whereas double vertical line represents salt bridge. The overall cell potential in the cell,
Ecell = Ec Ea, where Ec and Ea are reduction potential of cathode and anode respectively.
Electrolytic cell
It is an electrochemical cell through which the current is forced to flow by supplying electrical
energy from an external source. This results in electrolysis. In this cell, the cathode and anode are
attached to negative and positive terminal of the external source (battery). Generally in an
electrochemical cell, the potential of one of the electrodes is sensitive to analytes concentration.
It is called working or indicator electrode. The second electrode is called counterelectrode, which
serves to complete the electric circuit and provides a reference potential against which the working
electrodes potential is measured. Ideally the counterelectrode potential remains constant so that
any change in the overall cell potential is attributed to the working electrode.
However, if the passage of current changes the concentration of the species in the electrochemical
cell, the potential of the counterelectrode may change over time. This problem is eliminated by
replacing the counterelectrode with two electrodes: a reference electrode through which no current
flows and whose potential remains constant; and an auxiliary electrode that completes the electric
circuit and through which current is allowed to flow. The most common reference electrodes are:
standard hydrogen electrode (SHE).
Pt(s), H2g, (1atom)/H+(aq), 1M: E 0 + 0; saturated calomel electrode (SCE) and silver/silver
H 2 /H
chloride electrode Ag(s)/AgCl solid, KCl solution.
8.3.3 Electrical Circuit

The electrical circuit that is generally used in electroanalytical technique is shown in Figure 8.2.
Figure 8.2 The electrical circuit used in electrolysis.
In this circuit a storage battery C is connected across a uniform resistance wire, AB along
which a contact maker, D can be moved. The fall of potential between A and D can be varied
gradually. A voltmeter, V is placed between the two electrodes of cell to indicate the emf applied
(Eapp) to the cell for electrolysis. A millimeter, M is placed in the circuit to indicate the magnitude
and direction of any current in the cell and S is the switch.
8.3.4 Galvanostat and Potentiostat

Modern electrochemical instruments provide automated, electronic means of controlling and
measuring current and potential. These include galvanostat and potentiostat. A galvonostat is a
device used to control the current in an electrochemical cell while potentiostat is a device used to
control the potential in an electrochemical cell.
8.4 ELECTROGRAVIMETRY
8.4.1 Introduction
Electrogravimetry is an electroanalytical technique in which the amount of an analyte present in a
sample in solution is found by determining the weight of the product of analyte deposited at the
electrode during exhaustive electrolysis. In this method, generally the metal to be determined is
quantitatively plated on to platinum cathode and from the weight gained by the cathode,
the amount of the metal present in a sample is calculated.
8.4.2 Theory and Principle of Electrogravimetry

Electrogravimetry is governed by Ohms law, Faradays two laws of electrolysis as discussed
below.
Ohms law
This law expresses the relation between three fundamental quantities such as current, electromotive
force and resistance. According to this law the current, I, is directly proportional to the electromotive
force, E and inversely proportional to the resistance, R, i.e. I = E/R.
Faradays first law
The amount of different substances deposited or liberated at the electrode of a cell is directly
proportional to the quantity of electricity passed through the solution. Mathematically,
Wµ Q
W = ZQ
where, W = Weight of the substance deposited at the electrode of a cell, Z is a constant of
proportionality called the electrochemical equivalent of the substance and Q is the quantity of
electricity passed.
Faradays second law
The amounts of different substances, which are deposited or liberated by the passage of the same
quantity of electricity, are proportional to their chemical equivalents.
Chemical equivalent is calculated by dividing atomic (or molecular) weight by the number of
electrons involved in the respective electrode process.
Thus, it follows from the second law that when a given current is passed in series through a
solution containing copper(II) sulphate and silver nitrate solutions respectively, then the weights
of copper and silver deposited at their respective cathodes will be in the ratio of their chemical
equivalents, i.e.
wt of copper deposited Chemical equivalent of copper 31.75
= =
wt of silver deposited Chemical equivalent of silver 108
Electrogravimetric calculation
Let the weight of the sample containing the analyte be Ws g. Suppose the analyte be a metal ion,
Mn+. It will be plated on to a cathode (generally, platinum gauze) as metal, M due to reduction
during electrolysis of its aqueous solution.
Mn+ + ne ® M(s) (Reduction at cathode)
Let the weight of the properly cleaned and dried cathode be W1 g before electrolysis.
After the electrolysis, the cathode is removed from the solutions, properly washed and dried.
Let the weight of this plated cathode be W2 g.
Wt of the metal deposited at the cathode during exhaustive electrolysis = W2 W1 g
Ws g of the sample contains (W2 W1) g of analyte.
W2 W1
% of analyte present in the sample = 100
Ws
Advantages of electrogravimetry
(i) No filtration is required.
(ii) Co-deposition of the metals, i.e. deposition of other metal ions along with analyte can be
avoided by controlling the experimental conditions.
(iii) It is rapid, selective and equally sensitive.
Some important requirements for electrogravimetry
1. The deposit must adhere firmly to the electrode.
2. The deposit must be quantitative.
3. The deposit must be inert and of known composition.
8.4.3 Types of Electrogravimetry

Electrolysis of an electrolytic solution is dependent on a number of factors such as
(i) Applied voltage, electrode potential of the working electrode, the current flowing in the
cell and the amount of electricity consumed during electrolysis.
(ii) Smooth deposition is also affected if evolution of a gas takes place simultaneously and if
the current is too large.
Therefore, by adjusting either the current or the voltage applied to the cell, the current and gas
evolution are controlled.
Based on these factors, the electrogravimetric methods give rise to the following types of
electrogravimetry.
(a) Electrolysis in a simple cell.

(b) Electrolysis at constant current.
(c) Electrolysis at constant voltage.
(d) Electrolysis at controlled potential.
(e) Spontaneous or internal electrolysis.
(f) Electrolysis at the anode.
These methods are discussed as follows.
8.5 ELECTROLYSIS IN A SIMPLE CELL
Electrogravimetry involving simple cells such as non-galvanic and galvanic cells is discussed
below.
8.6 ELECTROLYSIS IN A NON-GALVANIC CELL
Electrolysis may be carried out in a simple cell, which is non-galvanic. This type of cell consists of
a pair of inert electrodes (often platinum) dipped into a electrolytic solution. For example, the two
platinum electrodes inserted into an aqueous solution of copper(II) sulphate and electrical connection
are made as shown in Figure 8.3.
Figure 8.3 Apparatus for electrolysis in a non-galvanic cell.
As the two identical electrodes are placed in the same solution, they have the same potential and
there is no potential difference between them. So the cell is non-galvanic.
8.6.1 Concept of Decomposition Potential

At first, as the applied voltage is gradually increased by moving the contact maker D towards B
(Figure 8.2), virtually no current (except a small residual current) flows through the cell. However,
when the applied voltage reaches a certain value, a noticeable reaction will be observed. For example,
in the case of copper(II) sulphate solution, the cathode becomes reddish-brown due to deposition
of copper and bubbles of oxygen gas around the anode are evolved indicating electrolysis to take
place. The electrolytic reaction being:
Cu2+ + 2e ¾® Cu(s) (Reduction at cathode)
2H2O ¾® O2 + 4H+ + 4e (Oxidation at anode)
On plotting the current (taken along Y-axis) and applied voltage (taken along X-axis), a curve
similar to that shown in Figure 8.4 is obtained.
Figure 8.4 Current-voltage curve for electrogravimetry.
At a particular point (A) on the current-voltage curve (A), the current suddenly increases. The
voltage corresponding to point at voltage axis is termed decomposition potential. Evolution of
gases, namely hydrogen and oxygen in the forms of bubbles commences at this point. Thus
decomposition potential, ED of an electrolyte may be defined as the minimum external voltage that
must be applied in order to bring about continuous electrolysis. As soon as the decomposition
potential is exceeded, with further increase in the applied voltage, the current increases linearly in
accordance with Ohms law.
Explanation for decomposition potential (the concept of counterpotential or back potential)
During an electrogravimetric operation, a galvanic cell is built up from the products of, electrolysis
on the electrodes. If the current is switched off, the products tend to produce a current in the
direction opposite to that passed during electrolysis. The voltage applied to the electrolysis cell
(Eappl) must exceed that of the galvanic cell, which is created during electrolysis. This is always in
opposition to applied voltage and can be written as Eback. Thus if there is no other factors affecting
electrolysis, the potential Eback will be equal to the galvanic cell potential set-up during electrolysis
and this also accounts the decomposition potential.
Hence,
Eback = ED = Ecathode Eanode
where Ecathode and Eanode are the reduction potential of cathode and anode respectively of a galvanic
cell created during electrolysis.
Thus during electrolysis of copper(II) sulphate solution, deposition of copper in the cathode
produces copper electrode Cu2+/Cu and evolution of oxygen at the anode produces oxygen electrode
H2O, H+/O2 producing a galvanic cell Cu/Cu2+, H2O, H+/O2.
Suppose for simplicity, the ions are at unit activity, and the partial pressure of oxygen above the
solution is 1 atm, we can calculate the standard emf or voltage of the cell from the values of
standard reduction potential.
E0cell = E 0cathode Eanode
0
where, E 0cathode and Eanode

0 are the reduction as potential of cathode and anode respectively. In the
above example:
E0 = EO0 2 E 0 2+
Cu
where
Cu2+ + 2e Cu
0 = 0.34 V
E Cu
O2 + 4H+ + 4e 2H O 2
EO0 2 = 1.23 V
Ecell = 1.23 0.34 = 0.89 V
Thus to initiate electrolysis we must apply larger voltage than the galvanic cell potential, 0.89 V. In
the above example, 0.89 V is said to be decomposition potential or back potential for copper(II)
sulphate electrolyte if no other phenomena are taking place. However, the requirement of the
applied voltage is more than that of theoretical back potential because of the following phenomena.
8.6.2 Ohmic Potential or IR Drop

Electrochemical cells like the metallic conductor resist the flow of current in accordance with
Ohms law. If E is the potential difference in volts across the cell, then according to Ohms law,
E = IR, where R is the cell resistance in ohms and I is the current passing through the cell in
ampere.
The product (IR) on the right-hand side of the equation is called Ohmic potential or IR drop of
the cell. Thus, in order to develop a current of I ampere in an electrolytic cell, it is necessary to
apply an external potential (EAppl), that is, IR volt larger than the thermodynamic cell potential,
Ecell or the theoretical back potential, Eback
EAppl = Ecell + IR (8.1)
For example to pass a current of 0.1 A through an electrolytic cell containing copper(II) sulphate
solution whose resistance is 5 W, the external potential or voltage to be applied is (0.89 + IR) V
= (0.89 + 0.1 ´ 5) V
= 1.39 V
8.6.3 Overpotential (Overvoltage)

Equation (8.1) can be rearranged as
1 1
I EAppl Ecell (8.2)
R R
For a small current or a brief period of time, Ecell remains relatively constant during electrolysis.
Hence, according to Eq. (8.2), a plot of current passing in an electrochemical cell as a function of
the applied potential, Eappl should be a straight line with the slope equal to reciprocal of resistance.
However, as the applied potential increases and electrolysis proceeds, the current deviates
significantly from linearity. When the cell exhibits this type of non-linear current voltage behaviour,
they are said to be polarized and the degree of polarization is described by a term called overvoltage or
overpotential symbolized by p. Overvoltage may occur at anode as well as cathode. Due to this,
the experimentally determined decomposition potential of an electrolyte varies with the nature of the
electrode employed for the electrolysis and in many instances higher than the calculated (theoretical)
back potential. This excess potential over the calculated potential is termed overvoltage and
overpotential.
8.6.4 Causes of Overvoltage

The overvoltage arises due to concentration polarization and activation factor as discussed below.
Concentration polarization
If there is a change in concentration or concentration gradient exists in the immediate vicinity of
the electrode, a new phenomenon called concentration polarization arises. For example, in the
electrolysis of acidic solution of copper(II) sulphate between two platinum electrodes, concentration
change occurs near the vicinity of anode and cathode. At the cathode, depletion of copper ions
occurs near the surface, as a result, the reversible potential of the copper electrode shifts in the negative
direction. At the anode, accumulation of hydrogen ions (due to 2H 2O ¾® O2 + 4H+ + 4e) and
evolution of oxygen gas cause the reversible potential of oxygen electrode to shift in the positive
direction. Both these effects tend to increase the back potential (or back EMF). Thus the excess voltage
developed due to concentration polarization is called concentration overvoltage. This can be
diminished by stirring solution but can be increased by increasing current density.
Activation over potential
This arises due to slow kinetic step in the overall electrodes process and is particularly pronounced
when a gas is liberated at the electrode. For example, in the reduction of H+ at a cathode,
the initial electron-transfer step yield hydrogen atoms:
H+ + e ¾® H
To form the final product, hydrogen gas, the atoms must combine:
2H ¾® H2
But the rate of combination may be slow and to form the product H2 at an appreciable rate, the cathode
may have to be more negative than the Nernstian value. This effect, which is called activation
overpotential, will be included in p term in writing an expression for the required applied voltage.
Another instance of activation overpotential is encountered during oxidation of water to form

O2 occurring at anode. The magnitude of this overpotential depends on the chemical nature of
electrode material and its physical state (e.g. surface area), the temperature, the rate at which the
electrolysis is performed and current density, etc.
8.6.5 Expression for Total Potential Applied to Cause Electrolysis

When the overvoltage is taken into account, Eq. 8.2 becomes
Eappl = Ecathode + Eoc Eanode Eoa + IR
= (Ecathode Eanode) + (Eoc Eoa) + IR
= Ecell+ + p + IR (8.3)
where, Eoc and Eoa are overpotential at cathode and anode respectively and
p = Eoc Eoa
In the above example (e.g. electrolysis of Cu(II) sulphate solution), the overvoltage due to evolution
of oxygen at anode is 0.4 V, thus the applied potential required to carry out the electrolysis for
deposition of copper from copper(II) solution = 1.39 + 0.4 = 1.79 V.
8.7 ELECTROLYSIS IN A GALVANIC CELL
The galvanic cell as shown in Figure 8.1 can be made electrolytic cell by connecting the positive
terminal of the battery having a potential somewhat greater than 0.412 V to the silver electrode and
negative terminal to the copper electrode as shown in Figure 8.5.
Figure 8.5 Conversion of a galvanic cell to an electrolytic cell.

An external voltage source (battery) is required for the conversion of galvanic to electrolytic
cell. The arrow through the source means we can vary the external voltage applied to galvanic cell.
If we apply a voltage greater than 0.412 V, a current will flow but it will be in opposite direction.
Electrons will flow from the negative side of the external source into the copper electrode and they
will flow away from the silver electrode to the external circuit. Cu 2+ will be reduced to Cu and Ag
will be oxidized to Ag+ so that the cell reaction has been reversed. The overall cell reaction is
2Ag(s) + Cu2+ ¾® 2Ag+ + Cu
This process is called electrolysis and the cell, which was galvanic cell earlier, is now an electrolytic
cell.
8.8 ELECTROLYSIS AT CONSTANT CURRENT
Principle
In this method, electrolysis is carried out at constant current. As the electrolysis occurs,
the concentration of the analyte steadily decreases, as a result, the current due to its oxidation or
reduction steadily decreases. Hence to maintain a constant current, the applied voltage is to be
continually increased. However, the potential of the working electrode of the electrolytic cell
cannot be controlled and this technique is therefore known as electrogravimetry without potential
control of the working electrode.
Experimental set-up
The apparatus used for the electrolysis at constant current is shown in Figure 8.6. It consists of an
electrolytic cell and a direct current (DC) power supply as given below.
Figure 8.6 Apparatus for electrolysis at constant current.

Electrolytic cell
It consists of cell in which the working electrode (cathode) is a platinum gauze cylinder and the
anode is a solid platinum-stirring paddle that is located inside and connected to the cathode through
the external circuit.
External circuit
It consists of
(i) A dc power supply (usually a storage battery) as a source of current.
(ii) An ammeter (A) and voltmeter (V) to indicate the current and voltage respectively applied
to the cell.
(iii) A rheostat (R) to adjust the applied voltage so that the initial voltage reading in voltmeter
is maintained till the end of the electrolysis.
A galvanostat may also be used to control the current and this process is called amperostatic
electrogravimetry.
Working: During electrolysis, the Eappl is adjusted with the rheostat so that the constant current
is maintained. Stirring is done to avoid concentration polarization.
By the method, the system gets enough current to complete the electrolysis in a reasonable
length of time.
Problems encountered in electrolysis at constant currents
In this technique, cathode potential is not controlled. During electrolysis, as the concentration of
analyte being deposited at cathode decreases, cathode potential also decreases. As a result, a new
electrode process can occur. If this new process is a deposition of a second metal, the selectivity of
the analysis is lost because the weight of the deposit does not represent a pure metal. If no other
metal ion that can be deposited is present, then hydrogen gas is evolved by the reduction of water.
2H2O + 2e ¾® H2 + 2OH
Sometimes this may be helpful since the gas evolution may improve mass transfer of the metal
being deposited, thereby shortening analysis time. However, if appreciable evolution of hydrogen
occurs, the deposit will usually broken up so that irregular spongy poor adherent deposits are
obtained under such condition.
Technique to avoid gas evolution (by the use of depolarizer or potential buffer)
A useful technique that avoids gas evolution and imparts selectivity to the constant-current
electrogravimetry is the use of cathodic or anodic depolarizers or potential buffers. These buffers
are used to maintain or limit electrode potential, thereby preventing unwanted oxidation or reduction
processes. In the electrodeposition of Cu from a mixture of Cu2+ and Pb2+, nitrate ions can be
added to the solution to prevent deposition of Pb along with Cu. The reduction of NO3 to NH 4+
occurs by the electrode process is given by
NO3 + 10H+ + 8e ¾® NH4+ + 3H2O
The above reaction occurs at a potential intermediate between those for reduction of Cu2+ and
Pb2+. As Cu2+ is exhausted from the solution, deposition of Pb is prevented because reduction of
NO3 depolarizes or fixes the potential of the cathode electrode at a value more positive than the
potential required for the deposition of Pb.
Further as the nitrate ion is reduced to ammonium ion at a less negative cathode potential than
that required for the reduction of H2O to H2 gas, the possibility of evolution of H2 gas by the
reduction of water is thus prevented. Here the behaviour of nitrate ion is similar to that of a buffer
stabilizing pH and hence it is known as cathodic potential buffer or cathodic depolarizer.
Anodic depolarizer
Hydrazine is an example of an anodic depolarizer, which can be used when Cl is present in the
sample. Chloride causes difficulty because chlorine formed at the anode can dissolve some platinum
from the electrode that can be deposited on to the cathode or it may reoxidise the deposited material.
In either case, this leads to an error in the weight of the deposit. Hydrazine, which is more easily
oxidized at the platinum anode, reacts by the process
N2H4 ¾® N2 + 4H+ + 4e
Hydrazine can prevent the oxidation 2Cl ¾® Cl2 + 2e, because its oxidation potential is more
than the oxidation potential required for oxidation of Cl ion to Cl2 gas. Thus hydrazine can act as
anodic potential buffer or anodic depolarizer.
For example, in the absence of hydrazine, there is possibility of oxidation of CuCl 32 at the
anode thereby preventing the deposition of Cu at cathode.
CuCl 32 ¾® Cu2+ + 3Cl + e
However, in the presence of hydrazine, the oxidation of hydrazine is preferred to that of CuCl 32
ion.
Application of electrolysis at constant current
This process is limited to the separation of metals lying below in the electrochemical series from
those above it. For example, standard electrode potential for copper and cadmium are 0.34 V and
0.433 V respectively. Thus cadmium lies above hydrogen and Cu lies below hydrogen in
electrochemical series. Hence it is possible to deposit copper in the presence of Cd2+, i.e. in the
presence of a cathodic depolarizer like nitrate ion as discussed below.
(i) Electrodeposition of copper from a solution containing Cu2+ and Cd2+ ions If a
current is passed through a solution containing Cu2+ and Cd2+ ions, copper gets deposited,
as its reduction potential is more than that of cadmium. However, as copper gets deposited
the electrode potential of working electrode decreases thereby causing deposition of
cadmium at the cathode. This can be avoided, if nitrate ions are added to the solution.
Reduction of NO3 to NH 4+ occurs at a potential intermediate between those for reduction
of Cu2+ and Cd2+. As Cu2+ is exhausted from the solution deposition of Cd is prevented
because reduction of NO3 depolarizes or fixes the potential of the electrode at a value
more positive than that at which deposition of Cd2+ occurs. During the final stage
simultaneous reduction of NO3 exerts no effect on purity of the deposit.
(ii) Electrodeposition of copper from a solution containing Cu2+ and Pb2+ Standard
reduction potential of Cu is 0.34 V and for Lead is 0.126 V.
Thus Cu2+ can be deposited from a solution containing Cu2+ and Pb2+ in the presence of
depolarizer like NO3 by constant current electrolysis as in case of deposition of Cu in the
presence of Cd2+ ions. Deposition of Pb2+ ion in cathode is prevented due to the presence
of NO3. However, Pb2+ can be deposited simultaneously at the anode by the process
Pb2+ + 2H2O ¾® PbO2(S) + 4H+ + 2e
Thus simultaneous determination of both the metals can be done by weighing the amount
deposited at each electrode (anode and cathode).
If, however, the metal lies only slightly (closely) above the other metals in the
electrochemical series separation is possible through the formation of appropriate complex
as exemplified below.
Electrodeposition bismuth from a solution containing Cu2+ and Bi3+
The difference in potential between Bi3+/Bi and Cu2+/Cu electrodes is only 0.024 V. Separation by
constant current electrolysis is not possible under this condition. However, such a separation is
possible if the solution of two ions is treated with cyanide ions. The Cu2+ ions is reduced to
cuprous (+1 state) forming a cyanocomplex as shown below.
Cu2+ + 4CN ¾® [Cu(CN)4]3
The potential of the complex ion, [Cu(CN) 4]3 is much lower (move negative) than that of
uncomplexed Cu2+ ion where as the concentration of Bi3+ ion and its electrode potential Bi3+/Bi
are not affected as a result Bi will deposit first under this condition making to its separation possible
from copper.
8.9 ELECTROLYSIS AT CONSTANT VOLTAGE
It has been calculated that for deposition of copper and evolution of hydrogen, voltage of at least
1.43 V and 2.2 V are required. Hence if the voltage is maintained at a constant value between
1.43 V and 2.2 V, copper is deposited without evolution of hydrogen gas. Unfortunately, this method
is usually accompanied by small current, and requires long separation time, hence rarely used.
8.10 ELECTROLYSIS AT CONTROLLED POTENTIAL

Principle
During electrolysis, the concentration polarization if not checked, causes the potential of the working
electrode so negative that co-deposition of other species present in the electrolytic solution begins
before the analyte is completely deposited. A large negative drift in the working electrode (usually
a cathode) can be avoided if electrolysis at controlled potential is performed and for which the
experimental set-up is discussed below.
Experimental set-up
The controlled potential apparatus is shown in Figure 8.7. It consists of a cell in which three
electrodes are used in order to avoid concentration polarization. The electrodes used are the working
electrode (cathode), reference electrode (usually saturated calomel electrode, SCE) and a
counterelectrode. A counterelectrode has no effect on the reaction at the working electrode. It
feeds electron to the working electrode.
Figure 8.7 Apparatus for electrolysis at controlled potential.
Two independent electrical circuits namely, the electrolysis circuit and the reference circuit
share the working electrode. The electrolysis circuit consists of a source (dc power supply),
a potential divider (ACB) that permits continuous variation in the external applied potential,
Eappl across the working electrode, a counterelectrode and a current meter. The reference circuit
includes SCE, high resistance digital voltmeter and the working electrode. This circuit has a large
resistance so that the entire current is supplied by the electrolysis circuit for deposition of the metal
causing electrolysis. The reference circuit only monitors the potential between working electrode
and reference electrode continuously.
When the potential in the reference circuit reaches a level at which co-deposition of an interfering
species begins, the potential across the working electrode and counterelectrode is decreased by
moving contact, C to the left. Throughout electrolysis, the applied cell potential has to be
continuously decreased and monitored. To speed up this process, controlled-cathode potential
electrolysis is performed with automated instrument called potentiostant, which electronically
maintains a constant cathode potential. Hence this method is known as potentiostatic gravimetry.
Application
This method is a potent tool for the separation of metals whose electrode potentials differ slightly.
An example illustrating the power of the method involves determining Cu, Bi, Pb, Cd, Zn and
Sn in mixture as follows.
The first three metals are deposited from a nearly neutral solution containing tartrate ion
to complex the tin(IV) and prevents its deposition, copper is first reduced quantitatively by
maintaining the cathode potential at 0.2 V with respect to SCE. After being weighed, the copper-
plated electrode is returned to the solution and then bismuth and lead are removed at a potentials of
0.4 V and 0.6 V respectively. When lead deposition is complete, the solution is made strongly
ammonical and Cd and Zinc are deposited successively at 1.2 V and 1.5 V. Finally, the solution
is acidified in order to decompose the tin/tartrate complex by the formation of undissociated tartaric
acid. Tin is then deposited at a cathode potential of 0.65 V. A fresh cathode must be used here
because zinc redissolves under these conditions.
8.11 SPONTANEOUS OR INTERNAL ELECTROLYSIS
Principle
In this method, current is not obtained form an external source but is obtained through the conversion
of chemical energy of a secondary reaction taking place within the cell itself. In such a system,
anode in the cell reacts with the electrolyte of the cell. When connected to cathode,
the whole system becomes a galvanic cell (or short-circuited battery).
The experimental set-up for spontaneous electrolysis for analysis of Cu is shown in Figure 8.8.
It is explained as follows.
Figure 8.8 Apparatus for internal electrolysis.
Zn anode is immersed in ZnSO4 solution. It is isolated form the Cu2+ ion solution being analyzed.
Thus direct deposition of copper on zinc is prevented. Isolation can be done by using a paper or a
porous ceramic cap. ZnSO4 solution is placed in the cap. Platinum cathode is connected to zinc
anode with the help of connecting wire. Thus the electrolysis starts. The Cu2+ ions get deposited
quantitatively on the platinum electrode (cathode). The following reactions occur in the cell.
Zn ¾® Zn2+ + 2e
Cu2+ + 2e ¾® Cu
Zn + Cu2+ ¾® Zn2+ + Cu
Internal electrolysis depends mainly upon the internal resistance of the cell because the rate at
which the deposition takes place is dependent upon this variable. For spontaneous electrolysis,
large currents are required which can be obtained if resistance R is kept small. R can be kept small
by using reasonably high concentration of electrolyte, with efficient stirring and large electrode.
Determination of element by internal electrolysis is given in Table 8.1.
8.11.1 Electrolysis at the Anode

Oxide of certain metals can be made to deposit on anode. Electrodes used for cathode and anode
are made up of platinum gauze but anode has a large surface area. An example of electrolysis at the
anode is given below.
Table 8.1 Determination of element by internal electrolysis
Elements Anodes
Cu Zn, ZnCl2
Ni Mg, MgSO4
Cd Zn, ZnCl2
Bi Mg, MgCl2
Pb Zn, ZnCl2
Zn Mg, NH4Cl, HCl
Ag Cu, CuSO4
Cu NH4Cl, HCl
Deposition of PbO2 at anode

The electrolyte used for the purpose is a mixture of lead nitrate and nitric acid. Electrolysis is done
at a temperature close to boiling because under this condition, the tendency of deposit oxide to
change into hydrate is prevented.
Pb2+ + 2H2O + ¾® PbO2 + 4H+ + 2e
8.12 PROBLEMS INVOLVED IN ELECTROGRAVIMETRY
Problem on determination of % of constituent present in alloy
PROBLEM 8.1 A sample of brass is analyzed for copper electrogravimetrically. A portion of the
alloy weighing 2.1 g is dissolved in nitric acid and the copper is plated on to a platinum gauze
weighing 13.5 g. After the electrolysis is complete, the cathode is removed from the solution,
washed and dried. It weighed 14.7 g. Calculate the % of copper in the brass sample.
Solution
Wt of the cathode = 13.5 g
Wt of the copper plated cathode = 14.7 g
Wt of copper = (14.7 13.5) g = 1.2 g
Thus 2.1 g of the alloy contains 1.2 g of copper
1.2
100 g of the alloy contains 100 = 57.14 of copper
2.1
\ % of copper in the brass sample = 57.14%
Problems on back EMF
PROBLEM 8.2 Calculate the value of back emf produced during the electrolysis of 1 molar
solution of zinc bromide between smooth platinum electrodes.
0
Given EZn 2 = 0.76 V
0
and EBr2
= 1.07 V
Solution During electrolysis, the electrode reactions are:

Zn2+ + 2e ¾® Zn (Reduction at cathode)
2Br ¾® Br2 + 2e (Oxidation at anode)
Zn2+ + 2Br ¾® Zn + Br2
Thus, during electrolysis deposition of Zn at the cathode produces zinc electrode, Zn/Zn2+ and
bromine at the anode produces bromine electrode Br2/Br. The produced galvanic cell can be
represented as
Zn/Zn 2+
(aq), Br (aq)/Br 2(g)
The cell reaction being reserved to that of electrolysis.

Zn + Br2 ¾® Zn2+ + 2 Br
1 molar Zn and Br2 produces 1 molar Zn2+ ions and 2 molar Br ions and hence
[Zn2+] = 1 M and [Br] = 2M
Substituting these values in Nernst equation at 25ºC
0 0.06 [Zn 2 ] [Br ]2

Ecell = Ecell log
2 [Zn][Br2 ]
0 0 0.06 1 22
= EBr EZn 2+ log
2
2 1
= 1.07 (0.76) 0.03 log (1) (2) 2
= 1.83 0.03 ´ 2 log 2
= 1.83 0.018
= 1.812 V
\ The theoretical back emf produced = 1.812 V
PROBLEM 8.3 Calculate the theoretical potential needed to initiate the deposition of copper
from a solution that is 0.15 M in Cu2+ and buffered to a pH of 0.3. Oxygen is evolved at the anode
at 1.0 atm.
0
Given ECu 2+ 0.34 V and EO0 2 1.23 V .
Solution The electrode reaction during electrolysis
2 ´ Cu2+ + 2e ¾® Cu (at cathode)
2H2O ¾® 4H+ + O2 + 4e (at anode)
The net reaction: 2Cu2+ + 2H2O ¾® 2Cu + 4H+ + O2

During electrolysis, deposition of Cu2+ at cathode produces copper electrode and liberation of
oxygen gas at anode produces oxygen electrode so that galvanic cell is created during electrolysis
is Cu/Cu2+, H +aq/O2(g). The cell reaction being reversed to that of electrolysis.
2Cu + 4H+ + O2 ¾® 2Cu2+ + 2H2O
0 0.06 [Cu 2+ ]2
Ecell = Ecell log
4 [H + ]4
0 0.06 0.15 0.15
= Ecell log ( pH = 3, [H+] = 103]
4 (10 3 ) 4
0 0.06 0.06
= Ecell 2 log 0.15 ( 12) log 10
4 4
= 0.89 0.03 log 0.15 0.18
= 0.735
PROBLEM 8.4 Calculate the initial potential needed for a current of 0.078 A in the cell
Co|Co2+ (6.4 ´ 102 M| |Zn2+ (3.75 ´ 103 M| Zn
Given that this cell has a resistance of 5 W.
Solution The cell reaction
Co(s) ¾® Co2+ + 2e
Zn2+ + 2e ¾® Zn(s)
Co(s) + Zn2+ ¾® Co2+ + Zn(s)
0 0.06 [Co2+ ]
Ecell = Ecell log
2 [Zn 2+ ]
È 6.4 102 Ø
= 0.76 (0.28) 0.03 log É 3 Ù
Ê 3.75 10 Ú
= 0.048 0.03 ´ 1.23
= 0.48 0.037
= 0.517 V
The applied electrode potential needed = 0.517 V
IR drop = E ´ R = 0.078 ´ 5 = 0.390
Actual potential needed = (0.517 + 0.39) V = 0.907 V
Problem on over voltage
PROBLEM 8.5 Calculate the magnitude of overvoltage if during electrolysis at cathodes, copper
was deposited which was 104 M but copper in bulk solution was 102 M. Given E0Cu2+ = 0.34 V
Let E1 = The electrode potential at 25ºC when [Cu2+] = 102
Cu2+ + 2e Cu(s)
Applying Nernst equation at 25ºC
0 0.06 1
E1 = ECu 2 log
2 Cu 2+
= E 0 2 0.03 log [Cu 2+ ]

Cu
= 0.34 + 0.03 log 102

= 0.34 + 0.03 ´ (2) log 10
= 0.34 0.06 = 0.28 V
Let E2 = The electrode potential at 25ºC when [Cu2+] = 104
0.06
0
E2 = ECu 2 log 10 4
2
= 0.34 + 0.03(4) log 10
= 0.34 0.12 = 0.22 V
This is the case of overvoltage due to concentration polarization.
\ The magnitude of overvoltage due to concentration polarization
= 0.28 0.22 = 0.06 V
Problem on total voltage applied
PROBLEM 8.6 What voltage must be applied to a pair of smooth platinum electrodes immersed
in 0.01 M solution of Cu2+ ion in order to pass current of 0.8 A. The cell resistance is 1.5 W and the
overpotential at the anode and cathode are 0.58 V and 0.21 V respectively.
Given E 0 2 0.34 V and EO0 2 1.24 V, [H + ] 1.
Cu
Solution The electrode reaction during electrolysis
2(Cu2+ + 2e ¾® Cu) (at cathode)
2H2O ¾® 4H+ + O2 + 4e (at anode)
The net reaction: 2Cu2+ + 2H2O ¾® 2Cu + 4H+ + O2
During electrolysis, deposition of Cu2+ at cathode produces copper electrode and liberation of
oxygen gas at anode produces oxygen electrode. So the galvanic cell created during electrolysis is
Cu/Cu 2+ +
(aq), H (aq) /O 2(g), the cell reaction being reversed to that of electrolysis.
2Cu + 4H+ + O2 ¾® 2Cu2+ + 2H2O
0 0.06 [Cu 2+ ]2
Ecell = Ecell log
4 [H + ]4
0 0 0.06 (102 ) 2
= ( EO2 ECu 2+ ) log
4 (1)4
0.06
= (1.23 0.34) ( 4) log 10
4
= 0.89 + 0.06 = 0.95 V
The voltage required to overcome IR drop
IR drop = 0.8 ´ 1.5 = 1.2 V
Overpotential = Eoc Eoa = 0.21 0.58 = 0.37
The applied voltage required to overcome the overpotential = 0.37 V
\ The total applied voltage required to carry out electrolysis in passing 0.8 A current =
0.95 + 1.2 + 0.37 = 2.52 V
Problem on determination of concentration of a solution
PROBLEM 8.7 A solution, which is 0.2 M in Cu2+ and 0.2 M in H+ is electrolyzed between
platinum electrodes. Assuming overvoltage for hydrogen evolution is negligible, what is the
concentration of Cu2+ when H2 gas is to be liberated at the cathode.
Solution The reactions involved
Cu2+ + 2e ¾® Cu
2H+ + 2e ¾® H2
For the liberation of H2 gas at the cathode, the reduction potential of copper electrode =
The reduction potential of hydrogen electrode
0.06
ECu 2 = E 0 2+ log [Cu 2+ ]
Cu 2
0.06
EH = E 0 + log [H + ]2
H 2
0.06
= 0 log (0.2) 2
2
= 0.03 ´ 2 log (0.2)
= 0.06 ( 0.7) = 0.042
\ 0.34 + 0.03 log [Cu2+] = 0.042
0.03 log [Cu2+] = 0.042 0.34 = 0.38
0.38
log [Cu2+] = 12.66
0.03
[Cu2+] = 1012.66 = 2.18 ´ 1013
Problem on determination of pH
PROBLEM 8.8 What must be the pH of a solution so that the concentration of Cd2+ can be
reduced by electrolysis at a platinum cathode to 1 ´ 106 M before the evolution of H2 commences.
Assume that the overpotential for H2 formation is zero. Given E 0 2+ 0.403 V
Cd
Solution Cd2+ + 2e ¾® Cd
0.06
ECd 2 = E 0 2+ log [Cd 2+ ]
Cd 2
0.06
0
= ECd2+ log [1 106 ]
2
= 0.403 0.03 ´ 6
= 0.583 V
For the evolution of H2 to commence its potential will be equal to 0.583 V. Let the concentration
of H+ be x mole lit1
0.06
EH0 + = E 0 + log [H + ]
H 1
= 0 + 0.06 log [H+]
= 0.06 log [H+] = 0.583
0.583
log [H+] =
0.06
0.583
log [H+] = = 9.7
0.06
\ pH = 9.7
Problems based on formation of product
PROBLEM 8.9 Asolution contains the following ions, each at a concentration of 1.0 M : Zn2+,
H+, Cu2+ and Ag+. Platinium electrodes are inserted and applied voltage is increased until electrolysis
begins. What product is formed at the cathode first?
Solution The standard potentials are
Ag+ + e ¾® Ag, E 0 = + 0.80 V
Cu2+ + 2e ¾® Cu, E 0 = + 0.34 V
1
H+ + e ¾® H2, E 0 = 0 V
2
Zn2+ + 2e ¾® Zn, E 0 = 0.76 V
As the reduction potential of Ag is the highest, Ag is the first product deposited at the cathode.
PROBLEM 8.10 A solution containing 0.1 M Zn2+ and 0.1 M H+ ions is electrolyzed using
platinum electrode
(a) Assume that the overpotential term for H2 evolution is zero. What is the first product at the
cathode?
(b) If the overpotential term for H2 is 1.0 V, what is the first product at the cathode?
Given E 0 2 0.76 V
Zn
Solution
(a) We are to calculate reduction potential for Zn/Zn2+
Zn2+ + 2e ¾® Zn
0.06
EZn 2 = E 0 2 log [Zn 2 ]
Zn 2
= 0.76 + 0.03 log [0.1]
= 0.76 0.03 ´ 1 = 0.79 V
Reduction potential for hydrogen electrode
1
H+ + e ¾® H 2( g )
2
EH+ = EH0 2 0.06 log [H ]
= 0 + 0.06 log [0.1] = 0.06
As the reduction potential for deposition of H+ from H2 is more than that of Zinc, hydrogen
is the first product at the cathode.
(b) If we consider overpotential term for H2 which is 1 V in this case, the potential required for
deposition of hydrogen is 1.06 which is less than Zn. Hence Zinc will be first product at
the cathode.
Problem on separation of two metal ions
PROBLEM 8.11 Is a quantitative separation of Cu2+ and Pb2+ by electrolytic deposition feasible
in principle? If so what range of cathode potential vs SHE can be used? Assume that the sample
solution is initially 0.1 M in each ion and that quantitative removal of ions is realised when only
one part in 10,000 remain undeposited (Given E 0 2 = 0.337 V and E 0 2 = 0.126 V).
Cu Pb
Solution Cu2+ + 2e ¾® Cu(s); E 0 = 0.337 V
Pb2+ + 2e ¾® Pb(s); E 0 = 0.126 V
If the reduction potential for deposition of copper is more than that of lead, copper will deposit
before lead. The cathode potential, Ecathode when [Cu2+] = 104 of original concentration, i.e.
0.1 ´ 104 = 105
0 0.059 1
E = ECu 2 log
2 [Cu 2 ]
0.0592 1
= 0.337 log = 0.189 V
2 10 5
Similarly, we can derive the cathod potential at which lead begins to deposit
0 0.0592 1
E = EPb 2 log
2 [Pb 2 ]
0.059 1
= 0.126 log 0.156 V
2 0.1
Therefore, if the cathode potential is maintained between 0.189 and 0.156 V (vs SHE), then
quantitative separation of copper should occur.

(i) The technique involving measurement of potential of non-polarise electrode under condition
of zero current is known as
(a) voltametry (b) potentiometry
(c) conductometry (d) amperometry
(ii) Calomel electrode is an example of electrode of
(a) first kind (b) second kind
(c) inert redox (d) none of these
(iii) The cells Cu/Cu2+ (0.02 M)/Ag+(0.02 M)/Ag develop a potential of
(a) 0.412 V (b) 1.402 V
(c) 0.214 V (d) 0.142 V
(iv) Potentiostat is a device used to control
(a) potential (b) current
(c) both potential and current (d) none of these
(v) The amount of substance deposited in gram during the process of 1 coulomb of electricity
will be equal to
(a) its electrochemical equivalent (b) its gram equivalent
(c) its atomic weight (d) none of these
(vi) Concentration over potential is associated with
(a) slow electron transfer process (b) concentration gradient in the solution
(c) usually low activity coefficient (d) large IR drops through the solution
(vii) Active overpotential is associated with
(a) slow step in the overall electrode process
(b) very fast step in the overall electrode process
(c) development of concentration gradient in the solution
(d) none of these
(viii) Concentration polarization can be prevented by
(a) frequent stirring the solution
(b) allowing the solution to stand for a few hours
(c) heating the solution
(d) cooling the solution
(ix) The reaction 2AgS + Cu2+ ¾® 2Ag+ + Cu takes place in
(a) galvanic cell (b) non-galvanic cell
(c) electrolytic cell (d) none of these
(x) Electrolysis at control potential method is a potent tool for the separation of metals
(a) copper and bismuth (b) copper and cadmium
(c) copper and lead (d) copper and zinc
(i) The metallic ions are transported to electrode surface by .............., .............. and .............. .
(ii) A three-electrode system is used to avoid .............. .
(iii) Pt/Fe2+, Fe3+ is a .............. type electrode.
(iv) Electrolysis at controlled potential is limited to the seperation of metal whose electrode
potential is .............. .
(v) Hydrazine acts as a .............. .
(vi) Lead storage battery is .............. type of cell.
(vii) A Galvanic cell stores .............. .
(viii) A Galvanostate controls .............. in an electrochemical cell.
(ix) The minimum external voltage that must be applied to bring out continuous electrolysis is
called .............. .
(x) Bi and Pb can be easily separated by .............. process.
(xi) Pb can be deposited as .............. at anode.
(i) An electrode is said to be polarized if its potential deviates from its equillibrium value.
(ii) The reversible potential required for electrolysis is determined by the concentration of the
electro active species at the bulk of the solution.
(iii) The combined overpotential of each electrode in a cell is called overpotential.
(iv) Electrogravimetry without cathode potential control is limited to seperation of metals lying
below hydrogen in electrochemical series from those above it.
(v) It is not absolutely necessary that the material to be deposited require 100% current efficiency.
(vi) Copper can be determined by internal electrolysis using Zn/ZnCl2 solution.
(vii) NO3 can act as anodic polarizer.
(viii) Hydrogen gas is evolved at anode by oxidation of water.
(ix) 0.1 g equivalent weight of the substance can be deposited by the passage of 9650 coulombs
of electricity.
(x) Ag/AgCl(satd KCl) is an example of electrode of first kind.
(xi) The standard reduction potential of hydrogen electrode is zero.

(i) What is meant by working electrode?
(ii) What is potentiostatic electrogravimetry?
(iii) What is meant by a depolarizer?
(iv) Name the various types of electrogravimetry.
(v) What is meant by IR drop?
(vi) Define deposition potential.
(vii) State Faradays law of electrolysis.
(viii) State Ohms law.
(ix) What is the function of an amperostat?

(x) What are the factors affecting metal deposition?

5. Distinguish the followings
(i) Concentration polarization and kinetic polarization.
(ii) Galvanostat and Amperostat.
(iii) Reference electrode and counter electrode.
(iv) Electrolysis circuit and reference circuit in controlled potential method.
(v) Anodic and cathodic depolarizer.
6. Explain why
(i) During the determination of copper by constant current procedure, nitric acid used should
be free from nitrous acid.
(ii) Some metal ions (i.e., Cu2+, Zn2+, and Pb2+) are more easily reduced at a mercury cathode
than at a platinum cathode.
(iii) Controlled cathode potential electrolysis is required to separate silver from copper but
electrolysis at constant current is adequate for separating silver from zinc in aqueous dilute
acid solution.
(iv) In electrogravimetry it is not essential to maintain 100% current efficiency.
(v) External voltage must be applied to carry out the electrolysis.
(vi) Nitrate ion acts as cathodic depolarizer.
(vii) A three-electrode system is used in electrolysis at controlled potential.
(i) Define electrograviametry. What is the principloe of this technique?
(ii) What is back emf? How does it arise?
(iii) Decsribe the process used to deposit cobalt oxide by the method of internal (or spontaneous)
electrolysis.
(iv) Describe a galvanic cell. How would you convert it into electrolytic cell?
(v) Describe electrolysis circuit and reference circuit.
(vi) What are the functions of potentiostat and galvanostat?
(vii) What are potential buffers? Explain by giving suitable examples.
(viii) Write an expression for total voltage required for electrolysis.
8. How would you determine electrolytically the following in the presence of other one?
(i) Nickel in presence of zinc
(ii) Silver in presence of copper
(iii) Copper in presence of cadmium
(iv) Iron in presence of nickel
(v) Zinc in presence of cobalt
(vi) Copper in presence of nickel
(vii) Copper in presence of lead
9. How would you determine electrolytically the following in presence of each other?
(i) Ag in presence of Pb and Bi
(ii) Zn in presence of Cd and Cu
(iii) Zn in presence of Ni and Cu
(iv) Cu2+, Bi3+, Pb2+, Cd2+, Zn2+ and Sn2+ ions present in a mixture?

10. Define electrogravity. Write the principle involved during electrolysis in a non-galvanic
cell.
11. Write the principle of electrogravimetry without potential control of the working electrode
Draw the schematic diagram of the instrumentation involved in the above method.
12. What are possible electrode reactions in solution containing CuSO4 and H2SO4? Write the
overall electrolysis cell reactions.
13. What is overvoltage? What are its causes? What are the factors affecting overvoltage?
Write its important applications.
14. Discuss the principle involved in electrolysis at controlled potential. Draw the schematic
diagram of the instrumentation involved in the above technique.
15. Describe the principle involved and apparatus used in spontaneous electrolysis.Write its
important applications.
CHAPTER 9
Coulometry
9.1 INTRODUCTION
Coulometry is an analytical technique in which the amount of an analyte of a sample present in the
solution is determined by measuring the quantity of electricity passed through the solution during
electrolysis. There are two types of coulometry depending on whether the substance to be estimated
directly undergoes reaction at one of the electrodes or reacts with another substance generated by
an electrode reaction. The former is called primary coulometry while the later process is called
secondary coulometry. The electrode reaction should proceed with 100% current efficiency (i.e.
no side reaction) such that the quantity of substance reacted can be expressed by means of Faradays
law.
Thus, in coulometry, the quantity of electricity passed through the electrolytic solution of an
analyte is measured and from that the amount of analyte present in a sample can be determined
from Faradays first law of electrolysis. So, it involves
(i) Coulometric calculation
(ii) Determination of quantity of electricity (or charge)
9.2 COULOMETRIC CALCULATION
Let W be the weight of the substance produced or consumed in an electrolysis involving Q coulombs
of electricity. Then according to Faradays first law of electrolysis
W = ZQ (9.1)
where Z is the electrochemical equivalent of the substance.
We know that by the passage of 1 Faraday or 96500 coulombs of electricity, 1 gram-equivalent
weight of the substance is either deposited or consumed. If E be the equivalent weight of the
substance, then
96500 coulombs of electricity º E g of the substance
E
\ 1 coulomb of electricity º g of the substance
96500
316
Electroanalytical Techniques—Coulometry 317
Electrochemical equivalent, Z of a substance is defined as the amount of substance (in gram)
produced or consumed at the electrode by the passage of 1 coulomb of electricity. So according to
E
the definition Z = gm coulomb1. Substituting this value of Z in Eq. (9.1), we get,
96500
E
W= Q (9.2)
96500
M
If n be the number of electrons involved in an electrode reaction of the substance, then E ,
n
where M is the atomic weight or molecular weight of the substance. Substituting the value of
E in Eq. (9.2), we get
M
W= Q (9.3)
n 96500
W Q
or = (9.4)
M n 96500
If N be the number of mole of the substance produced or consumed at the electrode, then
W
N=
M
Therefore, Eq. (9.4) can be written in terms of mole as
Q
N=
n 96500
or Q = N ´ n ´ 96500 coulombs (9.5)
9.3 DETERMINATION OF CHARGE, Q
For a constant current, the charge Q is given by

Q = I te
where te is the electrolysis time in second and I is the amount of current passed in ampere. If the
current varies with time, Q is given by
te
Q Ô 0
I dt (9.6)
The integration may also be performed graphically by measuring, the area of the curve obtained
from current versus time plot between t = te and t = 0, which gives the total charge, Q. It can also
be automatically obtained by means of electronic or electromechanical current-time integrators.
Thus in coulometry, current and time are measured accurately and then Eqs. (9.1), (9.2), (9.3),
(9.4) and (9.5) are used to determine the amount of an analyte.
Therefore, to obtain accurate value of W or N of an analyte, the current must result in analytes
oxidation or reduction only at the electrodes. In other words, coulometry requires 100% current
efficiency. A chemical device called coulometer as described below can also determine the value
of Q.
9.4 COULOMETERS
The tedious and often inaccurate process of obtaining and interpreting current time data may be
avoided by the insertion of another electrolytic cell in series with the cell, which contains the
analyte. This second electrolytic cell which operates at 100% current efficiency with well-defined
electrode reaction is called coulometer.
Thus a coulometer is a device that is used to measure the quantity of electricity by determining
the amount of chemical change brought about by the current. The most common coulometers are:
(i) the silver coulometer,
(ii) the iodine coulometer and
(iii) gas coulometer as described below.
9.4.1 Silver Coulometer

This is the most accurate coulometer as shown in Figure 9.1. It consists of pure silver anode
(in the form of rod) suspended inside of a platinum crucible which acts as the cathode for the
electrolysis of 10% pure silver nitrate solution kept in it. The silver anode is enclosed in a porous
cup to catch any particle of metallic silver, which may drop off. The silver is plated at the cathode
according to the reaction.
Ag+ + e ¾® Ag
Figure 9.1 Silver coulometer.
The cathode (here the platinum crucible) is weighed before electrolysis. After electrolysis,
the crucible is washed, dried and again weighed. The increase in weighed (W g) gives the amount
of silver deposited. Knowing that 1 gramequivalent of silver, i.e. 108 g is deposited by the passage
of 1 Faraday or 96500 coulombs of electricity, the quantity of electricity passed (Q) to deposit W g
of silver can be calculated by using the relation (Eq. (9.2)).
Wt of silver (in gm) × 96500 coulombs

Q=
108 (in gm)
W 96500
= coulombs (9.7)
108
where W is the weight of silver deposited at the cathode on passing Q coulombs of electricity and
F being the Faraday, i.e. 96500 coulombs.
9.4.2 Iodine Coulometer

It contains a pair of platinum electrode immersed in potassium iodide solution. At the end of the
determination, the liberated iodine produced at the anode by the reaction
2I ¾® I2 + 2e is titrated with sodium thiosulphate solution from which the number of
coulombs passed can be calculated.
Let the volume of sodium thiosulphate solution of normality N1 required for titration with iodine
be V1.
\ N1 ´ V1 milliequivalent of sodium thiosulphate is required for the titration of iodine obtained by
the passage of Q coulombs of electricity @ N1V1 milliequivalent of electricity.
\ We know 1 equivalent of electricity = 1 Faraday or 96500 coulombs
N1V1 milliequivalent of electricity = 96500 ´ N1V1 ´ 103 coulombs
Q = 96.5 ´ N1V1 coulombs (9.8)
9.4.3 Gas Coulometer (Hydrogen-Oxygen Coulometer)

This type of coulometer as shown in Figure 9.2 consists of a graduated tube (about 40 cm long and
having 2 cm internal diameter) which terminates in a tap at its upper end and has its lower end
joined by a flexible tube to a levelling tube. The latter is connected to the movable calibrated tube
Figure 9.2 Hydrogen-oxygen coulometer.

with the help of a pressure rubber tube. Thus it is possible to adjust the pressure of the collected
gas to the atmosphere (by using the movable tube) before measuring the volume of the gas.
The electrolyte solution generally taken is potassium sulphate. Two platinum electrodes are sealed
into the lower end of the tube, and the upper end, is surrounded by a water jacket so that the gas
within the tube can be maintained at constant temperature.
This type of coulometer depends on the volume of gas produced by passing the current through
a cell where electrolysis of water takes place. Hence, it is also called water coulometer. Hydrogen
and oxygen are evolved at the two electrodes during electrolysis.
Cathode 4H+ + 4e ¾® 2H2
Anode 2H2O ¾® 4H+ + O2 + 4e
2H2O ¾® 2H2 + O2
The overall reactions yield 3 moles of gas for every four moles of electrons. Since a mole of any
gas occupies the same volume under identical conditions, it is necessary to determine only the
total volume to the evolved gas at NTP then the number of moles of gas
Volume at NTP (litre)
=
22.4
Q
If Q is the amount of electricity used, then number of moles of electron involved in electrolysis =
F
From the above reaction it is clear that
4 moles of electron º 3 moles of gas
3
\ 1 mole of electron º moles of gas
4
Q 3 Q
\ moles of electron º moles of gas
F 4 F
3 Q Volume at NTP (in litre)
=
4 F 22.4 (in litre)
Q 4 Volume at NTP (in litre)
= (9.9)
F 3 22.4 (in litre)
There are two distinct and different techniques involved in coulometry such as constant current
coulometry and controlled potential coulometry.
9.5 CONSTANT CURRENT COULOMETRY
Principle
In this technique, constant current is passed through electrolytic cell until an indicator indicates
completion of reaction (end point). The magnitude of current and the time for which it has been
passed help calculating the quantity of electricity (charge) required to attain the end points by the
relation: current (ampere) ´ time (in second). Both the current and time can be measured with high
accuracy with relatively simple equipment and technique. Hence the method of coulometry is both
simple and accurate.
Experimental set-up
The experimental set-up as shown in Figure 9.3 includes the following components:
Figure 9.3 Apparatus for constant current coulometry.
(i) Constant current source: An amperostat is used as a constant current source.

(ii) Electrolysis cell: It contains the working (or generator) electrode at which the reagent
is electrogenerated and the auxiliary (counter) electrode. The generator electrode is made
up of platinum, silver or mercury whereas the counterelectrode is made up of platinum.
This electrode is generally placed in a separate glass tube closed at its lower end by a
porous glass disc to prevent products from the electrode from reacting with component
of the sample.
(iii) Current measuring device: A current meter is used to measure the current. It is a
carefully calibrated milliammeter.
(iv) Time measurement: A digital timer is used for measuring the electrolysis time whose
capacity is up to 1000 second or more. The readings are precise up to 0.01 second per
operation.
(v) Switch: The switch, S stops the electrolysis current. The same switch also controls
the digital timer.
Working: Movement of the switch to position 1 simultaneously starts the timer and initiates
a current in the electrolytic cell. When the switch is moved to position2, the electrolysis and
the timing are discontinued. With the switch in the position, electricity continues to flow to
the source through a dummy resistor RD that has about the same electrical resistance as the cell.
This arrangement ensures or maintains the current at constant level.
Constant current coulometric method is also called coulometric titration ,because of their
similarity to conventional titration.
9.6 COMPARISON OF CONSTANT CURRENT COULOMETRY WITH

CONVENTIONAL VOLUMETRIC TITRATION
For constant current coulometry, I = constant. Let te = electrolysis time in second and Q = I · te.
Substituting this value of Q in Eq. (9.5), we get
I · te = N ´ n ´ 96500
I
or N= te (9.10)
n 96500
The above equation can be compared with the relationship between the moles of a strong acid (like
HCl) and the moles of a strong base (like NaOH) of known concentrations, when the strong acid is
titrated with the strong base, so that
N=M´V
where M is the molarity of base/acid and V is the volume of base/acid required for completion of
the reaction, i.e. to reach the end point.
Thus
(i) The titrant (standard solution in volumetric method) in a conventional titration is
comparable to a constant current sources of known magnitude whose current is analogous
to the titrants molarity and the electron being its reagent.
(ii) The time needed for an exhaustive electrolysis (i.e. to reach the end point) takes the place
of the volume of the titrant needed to reach the end point.
(iii) The switch for starting and stopping the electrolysis serves the same function as a burettes
stopcock and the electronic timer corresponds to the burette.
In view of the facts cited above, coulometric titrations are carried out with a constant-current
source known as amperostat. Depending on the reaction involved, it may be classified as primary
coulometric titration and secondary coulometric titration as discussed below.
9.7 COULOMETRIC TITRATION
9.7.1 Primary Coulometric Titration

In this method, the substance to be estimated undergoes direct reaction at one of the electrodes
with 100% efficiency. The titrant is generated directly from the electrode either by an oxidation or
reduction process at the working electrode. The use of silver anode for generation of silver ion for
titration of halides, sulphides, mercaptans, etc. is an important example of primary coulometric
titration.
For example, in the titration of a halide, X, AgX initially gets deposited directly onto the
electrode or Ag+ is generated according to
Ag ¾® Ag+ + e
Ag+ + X ¾® AgX
Ag + X ¾® AgX + e
As X is consumed, a stage may come when the rate at which it can be supplied to the electrode
becomes smaller than the rate at which Ag+ is formed. Under the condition, the Ag+ generated
anodically diffuses into the bulk of the solution, so that precipitation of AgX proceed in the bulk
but not on the electrode.
The Hg2+ ions generated from Hg anode is another example of primary coulometric titrant,
which is useful for complexometric titration. However, primary coulometric titrations are seldom
attempted because of the following reasons:
(i) As the titration proceeds, the concentration of analyte decreases, as a result, the current
decreases.
(ii) To maintain constant current, the applied cell potential is to be increased.
The above facts will result in shifting of the potential of working electrode favourable for an
undesirable electrode reaction which may contribute an unknown quantity to the total number of
coulombs to give erroneous results. The above difficulties may be avoided by adopting secondary
coulometry as discussed below.
9.7.2 Secondary Coulometric Titration

In this method the substance being determined may react in solution with another substance
generated by an electrode reaction. For example, consider the coulometric titration of iron(II) at a
platinum anode. At the beginning of the titration, the primary anodic reaction is:
Fe2+ ¾® Fe3+ + e
The current in the cell decreases as the concentration of iron(II) decreases. However, to maintain
a constant current, the applied cell potential is to be increased. This increase in potential causes the
anode potential to increase to the point where the decomposition of water become a competing
process
2H2O ¾® O2(g) + 4H+ + 4e
Because of this competing process, the quantity of electricity required to complete the oxidation of
iron(II) exceeds the quantity required as per theory and so the current efficiency is less than 100%.
This lowered current efficiency is avoided by introducing a secondary titrating agents like
cerium(III) which is oxidized at a lower potential than that of water, i.e. at a potential intermediate
between Fe2+ and H2O
Ce3+ ¾® Ce4+ + e
The electrolytically generated Ce4+ ions in turn oxidizes any remaining Fe2+ ions present in the
solution
Ce4+ + Fe2+ ¾® Ce3+ + Fe3+
Thus the net effect is an electrochemical oxidation of iron (II) with 100% current efficiency,
even though only a fraction of that is directly oxidized at the electrode surface. The species such
as Ce3+, which is used to maintain 100% current efficiency, is called mediator. The overall
process is equivalent to volumetric titration of Fe2+ with Ce4+ for which an indicator is required to
detect the end point.
If direct oxidation of F2+ were attempted, oxygen would be liberated before the oxidation of
Fe2+ is complete and the analysis could not have been valid.
It is not necessary, of course, that the substance being titrated be itself electroactive as it was in
the example of above. For instance, bromine generated by anodic oxidation of bromide ion may be
used to titrate phenol.
Since phenol does not react at either electrode, the process in totally indirect. In this case, a dye
such as indigo carmine which is destroyed by excess of Br2 may be added for a visual end point.
9.7.3 End Points in Coulometric Titration

Coulometric titrations like their volumetric counterparts require indicator for determining completion
of a reaction. The same types of indicators as required for volumetric analysis are used. For example,
the titration of iron(II) is an oxidation-reduction or redox reaction for which a redox indicator such
as 1, 10, phenanthroline may be used. Similarly an adsorption indicator can be employed in
coulometric titration of chloride ions by the Ag+ ion generated at the silver anode.
9.8 APPLICATIONS OF COULOMETRIC TITRATION
The coulometric generation of titrant is widely applicable to acid-base, redox, precipitation and
complexometric titrations as discussed below.
9.8.1 Neutralization (Acid-Base) Titration

The basis of such titration is reduction and oxidation of water at platinum electrode:
2H2O + 2e ¾® H2(g) + 2OH (at cathode)
2H2O ¾® O2(g) + 4H+ + 4e (at anode)
Consequently anodic electrogeneration of hydrogen ions at the platinum anode for the titration of
bases (both strong and weak) is possible. It is essential to isolate the auxiliary cathode in order to
check the reduction of anodically generated H+ ions at the cathode (i.e. 2H+ + 2e ® H2(g))
otherwise, it will hinder the determination process. Similarly, both weak and strong acid can be
titrated using electrogenerated hydroxide ions at the cathode. Here also the auxiliary platinum
anode must be isolated by a diaphragm from the main solution (containing acid analyte) otherwise,
hydrogen ions produced by anodic oxidation of water mar the determination process. In order to
avoid the generation of H+ ions, a silver wire can be substituted for platinum anode provided
chloride or bromide ions are added to the analyte solution.
Ag(s) + Br ¾® AgBr + e
so that AgBr does not interfere with neutralization reaction. For titration of bases, the cathode
must be isolated from the analyte solution to prevent interference from the hydroxide ions.
The end point for such titration is determined by potentiometric method. Some examples of
coulometric neutralization are given in Table 9.1.
Table 9.1 Coulometric neutralization

Reagent Electrode Electrode Analytical Substance
generated composition reaction reaction titrated
H+ Na2SO4(0.2 M) 2H2O ¾® 4H+ + O2 + 4e H+ + OH ¾® H2O Bases (both weak

and strong)
OH Na2SO4(0.2 M) 2H2O + 2e ¾® H2 + 2OH OH + H+ ¾® H2O Acid (both weak
and strong)
9.8.2 Precipitation Titration

Silver(I) generated from silver anode is used for the precipitation of chloride, bromide, iodide or
mercaptans in precipitation titration.
Ag ¾® Ag+ + e (at anode)
Ag + Cl ¾® AgCl(s)
+
The end point of such reaction is detected by potentiometric method. The other precipitating reagents
that can be generated coulometrically are given below in Table 9.2.
Table 9.2 Coulometric precipitation
Reagent Generator Substance to Secondary analytical
generated reaction be determined reaction
Ag+ Ag ¾® Ag+ + e Cl, Br, I Mercaptan Ag+ + Cl ¾® AgCl(s)

(at silver anode) (RSH) Ag+ + Br ¾® AgBr(s)
Ag+ + I ¾® AgI(s)
Ag + RSH ¾® AgSR + H+
+
Hg22+ 2Hg ¾® Hg22+ + 2e Cl, Br, I Hg22+ + 2Cl ¾® Hg2Cl2(s)

(at mercury anode) Hg22+ + 2Br ¾® Hg2Br2(s)
Hg22+ + 2I ¾® Hg2I2(s)
[Fe(CN)6]4 [Fe(CN)6]3 + e Zn2+ 3Zn2+ + 2K+ + 2[Fe(CN)6]4
¾® [Fe(CN)6]4 ¾® K2Zn3[Fe(CN)6]2(s)
(at cathode)
9.8.3 Redox Titration

A variety of redox reagents can be generated coulometrically. A brief summary of coulometric
titrations involving oxidation and reduction are given in Table 9.3.
Table 9.3 Coulometric redox titration
Reagent generated Generator electrode reaction Substance determined by titration
Br2 2Br ¾® Br2 + 2e (at anode) Sb(III), U(IV), Tl(I)
Cl2 2Cl ¾® Cl2 + 2e (at anode)
I2 2I ¾® I2 + 2e (at anode) I, SCN, NH2OH, varieties of organic
compounds like phenol, aniline,
mustard gas, 8-hydroxy quinoline
Ce4+ Ce3+ ¾® Ce4++ e (at anode) Fe(II), [Fe(CN)6]4, Ti(III), U(IV), As(III)
Mn3+ Mn2+ ¾® Mn3+ + e (anode) Oxalic acid, Fe(II), As(III)
Ag2+ Ag+ ¾® Ag2+ + e (at anode) As(III), V(IV), Ce(III), Oxalic acid
Fe2+ Fe3+ + e ¾® Fe2+(at cathode) Cr(VI), V(V), MnO4, Ce(IV)
Ti3+ TiO2+ + 2H+ + e ¾® Ti3+ + H2O Fe(II), U(VI), Ce(IV), V(V)
(at cathode)
CuCl 2
3 Cu2+ + 3Cl + e ¾® CuCl 2
3 Cr(VI), V(V), IO3, Br2
(at cathode)
U4+ UO2+ + 4H+ + 2e ¾® U4+ + 2H2O Ce(IV), Cr(VI)
The advantage of the method is that some reagents which are unstable and not used in volumetric
work can be used here, Examples are Mn3+, Ag2+, Ti3+, Cl2, Br2 and chloro complex of copper(I)
such as CuCl 2
3 . Since these ions are generated and consumed as soon as they are formed, there is
no need for the storage of the species.
9.8.4 Complexometric Titration

The complexing agent like ethylenediaminetetraacetate ion (HY3) is generated coulometrically
by the reduction of ammine mercury pool cathode in an ammonia-nitrate buffer.
[Hg(NH3)Y]2 + NH 4+ + 2e ¾® Hg(l) + 2NH3 + HY3
The electrogenerated HY3 can form complexes with Cd2+, Cu2+, Zn2+, and Pb2+ ions, etc.
HY3 + Cu2+ ¾® CuY2 + H+
Advantages of coulometric titration
(i) There is no need for time consuming preparation of standard solution.
(ii) No need to store unstable titrants.
(iii) It is not necessary that the substance being titrated be itself electroactive. For instance,
bromine generated by anodic oxidation of Br ion may be used to titrate phenol which is
not electroactive.
(iv) A very small amount of titrate may be generated when required. This solves the
difficulty involved in the standardization and storage of dilute solution. Hence this type
of titration may be adopted in micro and semimicro scale.
(v) As extremely minute quantity of titrant can be accurately generated, a small quantity of
electricity required for this which can be measured with a high degree of precision and
accuracy and this method is therefore highly sensitive and accurate.
9.9 CONTROLLED POTENTIAL COULOMETRY

Principle
In this technique the potential of the working electrode is maintained at constant level to the
prevent undesirable electrode reaction. Only the analyte conducts the charge across the electrode.
Solution interfaces so that 100% current efficiency is achieved. The current flowing through an
electrochemical cell under a constant potential is proportional to the concentration
of the analyte. As electrolysis progresses, the concentration of the analyte decreases, as a result,
the current decreases. The resulting current versus time profile for controlled potential coulometry,
which is also known as potentiostatic coulometry, is shown in Figure 9.4.
Figure 9.4 Current time curve for control potential coulometry.
The current decreases exponentially from a relatively larger value to practically zero
(or background current). Integrating the area under the curve (Eq. (9.6)), from t = 0 to t = te,
(electrolysis time) gives the total charge, Q from which the amount of analyte can be determined
by the equation Q = NnF. This can also be determined by a chemical coulometer connected in
series with the electrolytic cell.
Determination of electrolysis time, te in controlled potential coulometry

As the current is approximated to undergo exponential decay, the current at a time t is given by
I = I0eKt (9.11)
where I0 is the initial current and K is a constant that is directly proportional to the area of the
working electrode and the rate of stirring and inversely proportional to the volume of the solution.
For an exhaustive electrolysis in which 99.99% of the analyte is oxidized or reduced, the current at
the end of the analysis time (i.e. at time te) may be approximated as
I £ 104I0
Substituting this value into Eq. (9.11) and solving for te, gives the minimum time for an exhaustive
electrolysis as
1 9.21
te ln (104 ) (9.12)
K K
From Eq. (9.12), we see that increasing K leads to a shorter analysis time. For this reason
controlled potential coulometry is carried out in small volume of electrochemical cells using
electrode with large surface area and with high stirring rate as K increases under the above condition.
A quantitative electrolysis typically requires approximately 3060 minutes.
Experimental set-up controlled coulometry
The apparatus used in controlled potential coulometry or potentiostatic coulometry is shown in
Figure 9.5 involving the following components.
(i) Coulometric cell: It uses three electrodesa working electrode, a reference electrode
(usually a saturated calomel electrode) and an auxiliary electrode (separated from the
working electrode by means of sintered glass frit).
(ii) Potentiostat: It is used to control the potential of working electrode. It consists of
potential measuring device, variable voltage source and electronic control link as shown
in Figure 9.5.
(iii) A device such as coulometer or electronic integrator is connected in series with the
coulometric cell to measure the number of coulombs consumed by the analyte.
(iv) Current measuring devices
Figure 9.5 Apparatus for controlled potential coulometry.
Working: The electrical connection is done as shown in Figure 9.5. The current flows between
auxiliary electrode and working electrode so that the electrolysis start. In this way the electrolysis
is allowed to go completion by adjusting the potential of the working electrode by potentiostat to
a value at which the substance is either oxidised or reduced. A coulometer placed in series with the
electrolysis circuit measures the total quantity of electricity, Q in coulombs for which the amount
of analyte can be determined by using the Eqs. 9.1 to 9.5. The potentiostat adjusts the applied
voltage of the two electrodes to maintain the desired working electrode potential relative to the
reference electrode. The sintered glass frit prevents the electrolysis products from undergoing side
reactions at the working electrode. Efficient stirring is done by a magnetic stirrer for rapid
electrolysis.
9.10 APPLICATIONS OF CONTROLLED POTENTIAL COULOMETRY
(i) This process does not need weighable product. It can be applied to the system that yield
deposits of poor physical properties and even does not produce solid product.
(ii) Pb in the presence of Cd, Cu in the presence of Bi and Ni in the presence of Co can be
determined by this technique.
(iii) Analysis of alloys: Composition of an alloy containing Ag, Bi, Cd and Sb can
be determined by dissolving the sample and placing it in a matrix of 0.2 M H2SO4.
A platinum-working electrode is immersed in the solution and held at a constant potential
of + 0.40 V versus SCE. At this potential Ag(I) deposits on the platinum electrode as Ag
and the other metal ions remain in the solution. When electrolysis is complete, the total
charge is used to determine the amount of silver in the alloy. The potential of the platinum
electrode is then shifted to 0.08 V versus SCE depositing Bi on the working electrode.
When the coulometric analysis for bismuth is complete, antimony is determined by shifting
the working electrode potential to ~0.33 V versus SCE depositing Sb. Finally, Cd is
determined following its electrodeposition on the platinum electrode at a potential of
0.80 V versus SCE.
(iv) In nuclear chemistry: Elements such as uranium and polonium can be determined at trace
levels. For example, microgram quantities of uranium in medium of H2SO4 can be
determined by reducing U(VI) to U(IV) at a mercury working electrode.
(v) In quantitative analysis of organic compound
(a) Picric acid can be analyzed by reducing it to triaminophenol on a mercury cathode
whose potential has been suitably controlled.
(b) Successive reduction of trichloroacetate (Cl3CCOO) to dichloroacetate (Cl2CCOO)
and dichloroacetate to monochloroacetate on a mercury cathode which potential is
controlled.
Mixture of trichloroactate and dichloroacetate are analyzed by selecting a critical potential at

which only one more easily reducible such as trichloroacetate is reduced first. When its electrolysis
is complete, the potential is shifted to a more negative potential at which dichloroacetate is reduced.
The total charge for the first electrolysis is used to determine the amount of trichloroacetate and
the difference in total charge between the first and the second electrolysis gives the amount of
dichloroacetate.
9.11 PROBLEMS INVOLVED IN COULOMETRY
PROBLEM 9.1 How many gram of cadmium will be deposited in four hours by a current of 2A?
Solution Time t = 60 ´ 60 ´ 4 = 14400 s
Q = It = 14400 ´ 2 = 28800 coulombs
We know 1 Faraday, i.e. 96500 coulombs will deposit gram equivalent, i.e.
112
56 g of cadmium
2
56
Thus 28800 coulombs will deposit = 28800
96500
= 16.712 g of cadmium
PROBLEM 9.2 Calculate time needed for a constant current of 0.96 A to deposit 0.5 g of Co(II) as
(a) elemental cobalt on the surface of cathode.
(b) Co3O4 on an anode.
Solution
(a) Co2+ + 2e ¾® Co (at cathode)
Here n = 2, W = 0.5 g and I = 0.96 A
Let the time required be t s
\ Q = 0.96 ´ t coulombs
We know that
M Q At. mass of Cobalt
W= = 0.96 t
n 96500 2 96500
58.93 0.96 t
0.5 =
2 96500
0.5 96500 2
\ t= 1705.76 s 28.4 minutes
58.93 0.96
(b) 3Co2+ + 4H2O ¾® Co3O4 + 8H+ + 2e at anode
Here n = 2
3 mole of Co2+ @ 1 mole Co3O4
3 ´ 58.93 g of Co2+ @ (3 ´ 58.93 + 4) g of Co3O4 = 240.79 g of Co3O4
240.79
\ 0.5 g of Co2+ = 0.5 g of Co3O4
3 58.93
= 0.68 g of Co3O4
By applying the formula
M Q
W=
n 96500
where M = molecular mass of Co3O4
240.79 0.96 t
0.68 =
2 96500
0.68 2 96500
\ t= 567.749 s 9.46 minutes
240.79 0.96
PROBLEM 9.3 In coulometric determination of Zn, 35.4 ml of a mixture of H 2 and O2 was
evolved at NTP after reduction of Zn2+ to Zn. Find out the amount of zinc deposited.
Solution We know that 22.4 litre of H2 and 11.2 litre of O2 at NTP are evolved for deposition of
one gram-equivalent of metal.
\ (22.4 + 11.2) = 33.6 litre of (H2 + O2) at NTP
º gram-equivalent of Zinc
65.4
= = 32.7 g of Zn
2
32.7
1 litre of (H2 + O2) at NTP º g of Zn
33.6
32.7
35.4 ´ 103 litre of (H2 + O2) at NTP º ´ 35.4 ´ 103 g of Zn
33.6
= 0.0342 g of Zn
PROBLEM 9.4 Show that every ten-fold decrease in metal ion concentration makes the cathode
0.0591
potential V more negative at 25ºC, where n is the valency of the metal ion. Give your
n
comments on the results.
Solution Let the ionic concentration solution at the commencement of estimation be Ci.
0.0591
The cathode potential at 25ºC will be EM 0
log Ci.
n
If the ionic concentration is reduced by deposition to one-tenth of its original value, the new
0.0591
cathode potential will be EM0
log Ci 10 1.
n
È 0 0.0591 Ø È 0 0.0591 Ø
\ Change in cathode potential = É EM log Ci Ù É EM log Ci 10 1 Ù
Ê n Ú Ê n Ú
0.0591 Ci 0.0591
= log
n Ci 101 n
\ Change in electrode potential is inversely proportional to n, i.e. number of electrons involved
in electrode reaction.
Problems on acid-base titration

PROBLEM 9.5 0.1516 g of sample of a purified organic acid was neutralized by the hydroxide
ion produced in 5 minutes and 24 seconds by a constant current of 0.401 A. Calculate the equivalent
weight of the acid.
Solution Here titration time = 5 minutes 24 seconds = 324 s
Q = I · te = 0.401 A ´ 324 s
= 0.401 ´ 324 A s
= 129.924 coulomb
Let the equivalent wt of the acid be E, we know
E
W Q1
96500
Here W = 0.1516 g
E
\ 0.1516 = 129.924
96500
0.1516 96500
\ E= 112.6
129.924
Thus the equivalent weight of the acid =112.6
PROBLEM 9.6 A constant current of 0.8 A is used to deposit copper at the cathode and oxygen
at the anode of an electrolytic cell. Calculate the number of grams of each product formed in
15 minutes assuming no other redox reaction. (Given 1 F = 96485 coulombs)
Solution The two half reactions are:
Cu2+ + 2e ¾® Cu(s) (at cathode)
2H2O ¾® O2(g) + 4H+ + 4e (at anode)
Thus 1 mole of copper is equivalent to 2 mole of electron and 1 mole of oxygen is equivalent to 4
mole of electrons, given t = 15 ´ 60 = 900 s
Q = It = 0.8 ´ 900 coulombs = 720 coulombs
720
Number of Faraday = 7.46 103 F 7.46 103 mole of electrons
96485
2 mole of electrons = 1 mole of copper = 63.5 g of copper
'
( 1F corresponds to charge 1 mole electrons)
63.5
\ 7.46 ´ 103 mole of electrons = 7.46 10 3 g of copper
2
= 63.5 ´ 3.73 ´ 103 g of copper
= 236 ´ 103 g
= 0.236 g of copper
Similarly, 4 mole of electrons º 1 mole of oxygen = 32 g of oxygen
32 7.46 103
\ 7.46 ´ 103 mole of electrons = g of oxygen
4
3
= 8 ´ 7.46 ´ 10 g of oxygen
= 59.6 ´ 103 g of oxygen
= 0.0596 g of oxygen
PROBLEM 9.7 The nitrobenzene in 210 mg of an organic mixture was reduced to phenyl
hydroxyl amine at a constant potential of 0.96 V (vs SCE) applied to a mercury cathode.
The sample is dissolved in 100 ml of methanol. After electrolysis for 30 minutes the
reaction was judged complete. An electronic coulometer in series with the cell indicated that the
reduction requires 26.74 coulombs. Calculate the % of nitrobenzene in the sample.
(Given 1 F = 96485 coulombs).
Solution We know
Q M
W=
F n
Here
Q = 26.74 coulombs
M = Molecular mass of nitrobenzene = 123 g
n = Number of electrons involved in reduction = 4
F = Faraday, i.e. 96485 coulombs
W = wt of nitrobenzene
26.74 123
\ W=
96485 4
= 0.0085 g
210 mg, i.e. 210 ´ 103 gm of the sample contains 0.0085 g of nitrobenzene
0.0085
100 gm of sample contains 100g of nitrobenzene = 4.05 g
210 103
% of nitrobenzene = 4.05
PROBLEM 9.8 A sample of sodium thiosulphate weighing 0.1342 g is transferred to a 100 ml
volumetric flask and diluted to the mark with distilled water. A 10 ml solution is transferred to an
electrochemical cell using I ions as mediator. It is subjected to electrolysis at constant current of
36 mA. It required 220 second for completion of the reaction. Calculate the purity of the sample.
Solution Here I is mediator and I3 is the titrant which is electrochemically generated as follows:
2I ¾® I2 + 2e
I2 + I ¾® I 3
3I ¾® I 3 + 2e
2S2O32 ¾® S4O62 + 2e
I 3 + 2e ¾® 3I
I3 + 2S2O32 ¾® S4O62 + 3I
Here
te = 220 s
I = 36 m A = 36 ´ 103 A
M = Molecular wt of Na2S2O3 = 158 g
Q = I · te = 36 ´ 103 ´ 220 coulombs
Oxidation of S2 O32– to S4 O62– requires one electron per S2 O 32– ion, hence n = 1
QM Ite M 36 103 220 158

We know W = 12.97 103 g
nF nF 1 96500
This amount represents the amount of Na2S2O3 in a 10 ml portion of solution.
100 ml solution of the sample contains 12.97 ´ 103 ´ 10 = 12.97 ´ 102 g
\ 0.1342 g of impure Na2S2O3 contains 0.1297 g of pure Na2S2O3
0.1297
% of purity = 100 96.65%
0.1342
PROBLEM 9.9 The iron in a 0.1 g sample was converted to Fe3+ and titrated coulometrically
with electrogenerated (Ti3+) ions. A current of 15 mA was used and the time to reach the end point
was found to be 123 s. Calculate the % of iron in the sample.
Solution Fe3+ + e ¾® Fe2+
Ti3+ ¾® Ti4+ + e
Fe3+ + Ti3+ ¾® Fe2+ + Ti4+
Here n = 1, te = 123 s and I = 15 mA
= 15 ´ 103 A
M
We know W = wt of iron = Q
nF
Q = I ´ te = 15 ´ 103 ´ 123 coulombs
= 1845 ´ 103 coulombs
F = 96500 coulombs
M = atomic wt of iron = 56 g
56
W= 1845 103 g
1 96500
= 1.07 ´ 103 g
1.07 10 3
Thus % of iron = 100
0.1
= 1.0
PROBLEM 9.10 In Coulometric titration of 20 ml of K2Cr2O7 with Fe(III) which is generated in
solution, took 25 minutes to reduce when 200 mA current was used. What is the normality of
K2Cr2O7 solution?
Solution Here I = 200 mA = 200 ´ 103 ampere, te = 25 minutes = 25 ´ 60 s
Q = I ´ te = 200 ´ 103 ´ 25 ´ 60 coulombs = 300 coulombs
If 96500 coulombs @ 1 gram-equivalent
1 300
300 coulombs @ gram-equivalent
96500
1 300
20 ml solution contains = gram-equivalent of K2Cr2O7
96500
1 300 1000
1000 ml solution contains gram-equivalent
96500 20
= 0.1554 gram-equivalent
Normality of K2Cr2O7 solution = 0.1554

(i) If a current-time curve is recorded during a controlled potential coulometry, the number
coulombs is found from
(a) The slope of the curve when t = 0
(b) The slope of a tangent to the curve
(c) The area under the curve
(d) The slope of the curve where t = 0
(ii) The number of divalent cations reduced at the surface of a cathode during each second
when an electrochemical cell operated at 0.02 A.
(a) 6.2 ´ 1016 (b) 6.2 ´ 1023
(c) 6.2 ´ 1020 (d) 6.2 ´ 1019
(iii) The number of coulombs of electricity required to convert an analyte to its product is
determined by
(a) Chemical coulometer (b) Calorimeter
(c) Potentiometer (d) Spectro photometer
(iv) The technique in which quantity of electricity is measured to determine the amount of
analyte is known as
(a) Thermogravimetry (b) Electrogravimetry
(c) Polarography (d) Coulometry
(v) The analysis in which the substance being determined directly undergoes reaction at one of
the electrodes is known as
(a) Primary coulometric analysis (b) Thermal analysis
(c) Secondary coulometric analysis (d) Polarography
(vi) The weight of the substance produced or consumed in coulometry involving Q coulomb of
electricity is
M Mn
(a) W (b) W
QnF QF
FN Q
(c) W (d) W
MQ MnF
(vii) In controlled-current coulometry
(a) Current continues to flow even where the analyte has been completely oxidized or
reduced
(b) Flow of current stops as the analyte is completely oxidized or reduced
(c) Flow of current stops before the completion of reaction
(d) None of these
(viii) Microquantity of uranium can be determined using controlled potential coulometry by
(a) Reducing U(VI) to U(IV) at mercury working electrode
(b) Reducing U(IV) to U(III) at mercury working electrode
(c) Reducing U(VI) to U(II) at mercury working electrode
(d) None of these
(ix) For the reduction of picric acid to triamino phenol in controlled potential coulometry
(a) 6 electrons are involved (b) 18 electrons are involved
(c) 2 electrons are involved (d) 3 electrons are involved
(x) In controlled potential coulometry, the end point is detected by
(a) Using an indicator
(b) When the current decreases to a constant background
(c) When the current increases to maximum
(d) None of these
(i) Electronically generated species during precipitation of Cl is Hg2+ 2 ion.
(ii) In the coulometric redox titration of Cr2 O72– , Fe3+ ion acts as a mediator.
(iii) Controlled potential coulometry is called amperostatic coulometry.
(iv) Electrons act as the reagent in coulometric titration.
(v) The change in current as a function of time in controlled-potential coulometry is approximated
by an exponential decay.
(vi) The potential in controlled potential coulometry is set using three-electrode potentiostat.
(vii) Controlled-current coulometry is also known as coulometric titrimetry.
(viii) The typical electrolysis time for controlled current coulometry is less than 10 minutes.
(ix) Integrating current-time curve is necessary in controlled current coulometry.
(x) To maintain a constant current, the cell potential is to be maintained constant.
(i) Constant-current coulometry is known as .............. .
(ii) The use of silver anode for generation of Ag+ ions for the titration of halides is an example
of .............. titration.
(iii) For the coulometric titration of acid .............. is electrogenerated.
(iv) The minimum time interval for exhaustive analysis by control potential coulometry is
.............. .
(v) In controlled potential coulometry, the electrode whose potential is controlled is known as
.............. .
(vi) Addition of .............. solves the problem of maintaining 100% current efficiency.
(vii) .............. is used to provide visual end point for the Ce3+ mediated coulometric analysis of
Fe2+.
(viii) The working electrode used in coulometric titration is called .............. .
(ix) In controlled potential coulometry, silver deposits at potential of .............. volt versus
SCE.

(i) How would you detect the completion of reaction in controlled potential coulometry?
(ii) What is measured in coulometric method of analysis?
(iii) For a variable current, I, write an expression for the charge, Q.
(iv) Name the types of coulometric method.
(v) In coulometric titration, what are considered as the reagent, molarity of a standard solution,
and the volume measurement in conventional titrimetry?
(vi) What is the most fundamental requirement in coulometry.
(vii) Name the important components involved in controlled-potential coulometry.
(viii) Draw the current-time profile of a controlled potential coulometry.
(ix) Name the constant-current source involved in coulometric titration.
(x) Write the generator electrode reaction as for generation of Mn3+, Ag2+.
(xi) What are the functions of an amperostat and potentiostat?

(i) What are the advantages of constant-current coulometry over controlled potential coulometry?
(ii) How constant current is maintained in constant current coulometry?
(iii) What are the suitable means of determining the end point of the reaction in coulometric
titration?
(iv) Giving suitable example, explain how current efficiency of 100% is maintained in
coulometric titration.
(v) What is mediator? Explain its role in coulometric titration.
(vi) Explain why constant-current coulometric method is called coulometric titration.
(vii) What do you mean by coulometric titration?
(viii) Distinguish between primary coulometry and secondary coulometry.
(ix) What are the advantages of coulometric methods of analysis?
(x) Explain why auxiliary reagents are essential in coulometric titration.
(xi) Why is it necessary to isolate the working electrode from the counterelectrode in a controlled-
potential coulometric analysis?
(xii) How would you analyze the components of alloy containing Ag, Bi, Cd?
(xiii) How would you determine the amount of trichloroacetic acid by controlled potential
coulometry?
(xiv) How would you determine dichromate by a coulometric redox titration?
(xv) Explain why pure N2 is bubbled through the solution containing dissolved oxygen.
(xvi) Draw the diagram of typical coulometric titration cell.
(xvii) Describe control circuit involved in controlled potential coulometry.
(xviii) How would you determine the minimum time required in controlled potential coulometry?
(xix) What are advantages of coulometric titrations over conventional volumetric analysis?

6. What is meant by coulometry? Write the principle involved in it.
7. What is coulometer? Describe various types of coulometers.
8. Describe the principle and detailed description of coulometry at constant current.
9. Justify the statement that the coulometry at constant current is called coulometric titration.
Describe the coulometric titration instrument.
10. Describe primary and secondary coulometric titration giving suitable examples.
11. Write the application of coulometric titration with reference to neutralization, redox titration,
complexometric titration and precipitation titration.
12. Describe the principle and detailed description of coulometry at controlled potential.
13. Distinguish between amperostatic coulometry and potentiostatic coulometry. Write their
important applications.
CHAPTER 10
Polarography
10.1 INTRODUCTION
Polarography is an electroanalytical technique, which involves electrolysis of a solution containing

electroactive species (usually a metal ion) so that reduction of it takes place at the polarized electrode
acting as cathode. Polarizable electrode is also known as microelectrode because a small surface
of an electrode usually enhances the polarizable character. Of the various microelectrodes available,
the most commonly employed electrode is the Dropping Mercury Electrode (DME). The curves
obtained by plotting the current flowing through the electrolytic cell against applied voltage are
known as current voltage curves. As the curves are graphical representation of the polarization of
the dropping mercury electrode, these are known as polarograms. The technique is called
polarography and the apparatus used for this purpose is known as polarograph. The electrolyte cell
used is known as polarographic cell.
Polarography is one of the most powerful and versatile technique for qualitative and quantitative
analysis developed by Janoslav Heyrovsky at the Charles University, Prague in 1922. It is one
aspect of a general technique known as voltametry in which information about analyte can be
obtained by studying the current-voltage curve.
10.2 PRINCIPLE OF POLAROGRAPHY
In this technique electrolysis of a solution of an electroactive substance is carried out in a

polarographic cell. This type of cell consists of dropping mercury electrode (DME) acting as
cathode and a reference electrode (a pool of mercury or saturated calomel electrode, SCE)
functioning as anode. The range of DME is 02 V against a SCE. The following factors affect the
current flow in a polarographic cell.
10.2.1 Factors Affecting Current Flow in a Polarographic Cell

The factors which affect the current flow in a polarographic cell are
1. Migration current 2. Residual current
3. Convection current and 4. Diffusion current
339
Electroactive material (i.e. any species that can be reduced or oxidized at an electrode) can
reach the surface of an electrode by three process: convection, migration and diffusion. Convection
refers to the movement of material due to difference in density and temperature in solution. Migration
refers to the movement of charged particles in the electric field due to the potential gradient between
the anode and the cathode. Diffusion of particles arises due to the concentration gradient of the
analyte between the surface of the electrode and bulk of the solution. Each of these three processes
are associated with appropriate current, namely convection current, migration current and diffusion
current.
10.2.2 Explanation for Residual Current

Whenever an electrode comes into contact with an electrolyte solution, there is an electrode-
electrolyte interface. The interface is usually considered to be a double layerone layer which is
the electrode and the other layer is the electrolyte solution. If the two layers are taken to be fixed,
then the electrical double layer simulates the behaviour of a parallel plate capacitor or condenser.
When a voltage is applied to an electrode-electrolyte interphase which behaves like a parallel plate
capacitor, a small amount of current will flow to charge the two plates of the capacitor.
This current is known as the charging current or the capacitor current or condenser current and is
directly proportional to the applied voltage. Further, a small amount of current will also result due
to the reduction of small amounts of heavy metal impurities that are invariably present in the distilled
water employed in the preparation of the electrolyte solution. This current is known as Faradaic
current. The current resulting due to condenser current and Faradaic current is collectively known
as residual current.
Residual current = Condenser current + Faradaic current
Since Polarographic technique involves measurement of diffusion current only, the other currents
(migration and convection currents) are to be eliminated as far as possible. However, the residual
current cannot be eliminated. A correction must be made for the residual current in order to obtain
the true-diffusion current of an electroactive material.
10.2.3 Elimination of Convection Current

By keeping the polarographic cell on a solid support, free from vibration, conducting the analysis
without stirring and maintaining a uniform temperature, convection current can be eliminated.
10.2.4 Elimination or Suppression of Migration Current

Heyrovsky (1934) had proved that suppression of migration current can be achieved by having an
excess of supporting or indifferent electrolyte (together with an electroactive species) in
concentration so large that its ions carry essentially all the current. The supporting electrolyte,
whose concentration is 50 to 100 fold of the electroactive component, should be such that it conducts
the current, but does not react with the substance under examination nor with the electrodes.
It should discharge at the higher potential than the electroactive material. Usually KCl and KNO3
are used as supporting electrolytes.
Electroanalytical Techniques—Polarography 341
Under the conditions mentioned above, the current carried by the electroactive species is almost
entirely due to diffusion and any current measured will be only diffusion current. For example, a
cation like Cd2+ might feel. The electrostatic pull of a negatively charged electrode (cathode).
However, this is virtually prevented by large excess of supporting electrolyte (like KCl). The
tendency of Cl ions to cluster about Cd2+ ions in the solution and the tendency of K+ ions to form
a positively charged cloud around the negatively charged electrode (cathode) wihtout being
discharged on it prevents electrostatic attraction of Cd2+ ions from the bulk of the solution by the
cathode.
10.2.5 Measurement of Diffusion Current

Consider the application of a potential in a typical polarographic cell without stirring which contains
a supporting electrolyte and a small concentration of a reducible ion such as M2+. Assume also the
M2+ ion undergoes a reduction process to the metal, M at the cathode (the dropping mercury
electrode) to form the metal amalgam, M(Hg). The polarogram for the reduction of M2+ in the
presence of supporting electrolyte after electrolysis is shown in Figure 10.1.
Figure 10.1 A typical polarogram for the reduction of M2+ ion in presence of supporting electrolytes.
The initial application of the voltage will result in the slight rise in the residual current as shown
in the region AB. After the applied potential reaches a certain value, (deposition potential), M2+
will be reduced to M(Hg) at the surface of the electrode according to the reaction
M2+ + 2e ¾® M(Hg)
The sharp rise in the current from B to C corresponds to the reduction of M2+. Due to lack of
stirring, a concentration gradient occurs between the [M2+] at the surface of the electrode and that
in the bulk of the solution so that concentration polarization takes place. This condition exists
along the sharply rising position of the curve. At the point C, reduction is complete and the region
CD corresponds to limiting value of current. The rate of diffusion of ion and the current which is
due to this diffusion are directly proportional to the concentration gradient as stated by the equation
i
k [M 2 ]b [M 2 ]0 (10.1)
where
i = the current at any applied potential known as diffusion current
k = a proportionality constant
[M2+]b = the concentration of M2+ in the bulk of the solution and
[M2]0 = the concentration of the metal ion at the surface of the dropping mercury electrode
Continuous application of increasing larger potential will result in decreasing of [M2+]0, increasing
of the concentration gradient and increasing of the current, i. Eventually, a change in applied
potential can cause only a slight change in [M2+]0. The concentration gradient and therefore the
current reach a constant value and Eq. (10.1) is simplified to yield
i k [M 2 ]b
At this point, the current i, becomes the limiting diffusion current denoted as id.
\ id = k[M2+]b (10.2)
Hence, the limiting diffusion current, id is directly proportional to the concentration of the reducible
ion, [M2+]b in the bulk of the solution. It may be regarded as the diffusion current corresponding to
limiting concentration value (i.e. the lowest value, [M2+]0 = 0) of the electroactive material at the
surface of DME. The height of the curve (wave height) is the limiting diffusion current id.
The residual current part of the polarogram immediately preceding the rising part of the polarogarm
can be extrapolated. The diffusion current will then be the difference between this extrapolated
and current-voltage plateau. In addition to the concentration of the electroactive material, id depends
on the other factors also as given by the following equation known as the Ilkovic equation.
10.2.6 Ilkovic Equation

According to this equation, Id is given by
Id 607 n D1 2 m 2 3 t1 6 C (10.3)
where
Id = the average limiting diffusion current in micro amperes
n = the number of Faradays of electricity required per mole of the electrode reaction (or the
number of electrons involved in the reduction of 1 mole of the electro active species)
D = diffusion coefficient of the electroactive species expressed in cm2 s1
m = flow rate of mercury expressed in mg s1
t = drop time in seconds
C = concentration of the electroactive species in millimoles per dm3
The constant 607, is a combination of natural constants including the Faraday constant; the value
is slightly temperature dependent. The value given here is for 25ºC. The principle importance of
the Ilkovic equation is that it shows in a quantitative manner the influence of many factors on the
diffusion current.
It is convenient to divide the factors in the Ilkovic equation into two parts:
(a) nD1 2C , which is determined by the properties of the solution and
23 16
(b) m t , which is dependent upon the characteristics of the capillary of DME. It is called
capillary constant.
The various steps involved in deriving the above equation are summarized as follows.
10.2.7 Derivation of Ilkovic Equation

The current flow using on a polarizable electrode is given by
nFAD[C C0 ]
i k (C C0 ) (10.4)
G
where, n is the number of electrons transferred, F is the Faraday, (96,500 C). A is the surface area
of the polarizable electrode, D is the diffusion coefficient of the analyte, C and C0 are the
concentrations of the analyte in bulk of the solution and at the surface of the electrode respectively.
The distance across which the concentration changes from C to C0 is given by the symbol d and is
called the thickness of the diffusion layer. The lowest possible value of C0 is zero and under this
condition, the value of the diffusion current is the maximum. This maximum value is called the
limiting diffusion current id and is given by
nFADC
id (10.5)
G
It can be shown that
G (S Dt )1/ 2 (10.6)
where D is the diffusion coefficient and t is the time taken for the analyte to reach the surface of the
electrode from the bulk of the solution. On substituting Eq. (10.6) in Eq. (10.5), the expression for
the limiting diffusion current becomes
nFADC nFAD1 2C
id (10.7)
(S Dt )1 2 (S t )1 2
The surface area A of the DME can be determined in an indirect fashion as follows. The volume, V,
of a single drop of mercury can be related to the flow rate, m, and the drop time, t, as given by
mt
V
U
where, r is the density of mercury which has a value of 13.6 g cm3 at 25ºC. Since, m is usually
expressed in mgs1, density is also expressed in mg cm3, i.e. 13600 mgs1. Thus,
mt
V
13, 600
If the mercury drop is assumed to be spherical, the volume is given by
4
S r3
V
3
where r is the radius of the drop. Combining these two expressions for the volume, it is possible to
evaluate r as
13
È 3 Ø
r ( mt )1 3 É Ù
Ê 13, 600 4S Ú
1/3
or r = 0.026 (mt )
The surface area of a sphere can, therefore, be calculated as
23
A = 4p r2 = 4p (0.026)2 ( mt )
23
A = 8.49 ´ 103 ( mt )
According to Ilkovic, this value of A should be corrected to take into account the fact that the area
of the drop changes during the course of its formation from a minimum value of zero to a maximum
7
value. The correction factor suggested by Ilkovic is 1.528. Hence,
3
23
A = 1.528 ´ 8.49 ´ 103 ( mt )
23
or A = 0.013 ( mt )
Substituting the value of A into Eq. (10.7), we get
0.013nFD1 2 ( mt ) 2 3 C
id (10.8)
(S t )1 2
This, on simplification becomes
0.013nFD1 2 m2 3t1 6C
id (10.9)
S1 2
\ id 706 n D1 2 m 2 3 t1 6 C (10.10)
This is the expression for the instantaneous limiting diffusion current at time, t. The average limiting
6
diffusion current can be shown to be th of instantaneous current. Hence, the average limiting
7
diffusion current, Id becomes
6 È 6Ø
Id = id = É Ù 706 n D m t C
12 2 3 16
7 Ê 7Ú
Thus, Id = 607 n D1 2 m 2 3 t1 6 C
which is the Ilkovic equation.
10.2.8 The Concept of Half-wave Potential (E1/2)

Another characteristic feature of the polarogram is the half-wave potential, E1/2 which is the potential
at which the current is equal to one-half of the id as shown in Figure 10.2. The potential at the point
of inflation of current voltage curve (polarogram), i.e. one-half the distance between the residual
current and the final limiting current plateau also denotes half-wave potential, E1/2. It can be shown
that E1/2 for a particular metal ion is approximately equal to E0 ESCE, where E 0 is the standard
reduction potential for the metal ion and ESCE is the reduction potential of the saturated calomel
electrode. It is the characteristic of the nature of reacting material and constitutes the essential
basis of qualitative and quantitative polarographic analysis.
Figure 10.2 The concept of half-wave potential.
The significance of half-wave potential can be best understood by considering the redox process
at the dropping mercury electrode represented as follows.
Oxidant + n Electrons ZZX
YZZ Reductant
or OX + ne ZZX
YZZ Red
In polarography the reversible reduction of oxidant to a reductant at a dropping mercury cathode is
considered. The electrode potential, for this process is given by Nernst equation
RT [OX]s
E ET ln (10.11)
nF [Red]s
where Eq is the standard potential of the reaction against a reference electrode used to measure the
potential of the dropping electrode and the potential E refers to the average value during the life of
a mercury drop. [OX]s and [Red]s are the concentrations of the oxidant and reductant that exist at
electrodesolution interface and denoted by the subscript s. R is the gas constant, T is the absolute
temperature, n is the number of the electron involved in the reaction, and F is the Faraday constant.
The current i at any point on the polarographic wave is given by the rate of diffusion of oxidant
from the bulk of the solution to the electrode surface under a concentration gradient [OX] to
[OX]s , where [OX] is the concentration of the oxidant at the bulk of the solution.
i = K[[OX] [OX]s] (10.12)
where, K is a constant.
When [OX]s is reduced to almost zero, then the current becomes the diffusion current id and
Eq. (10.12) becomes
i = K[OX] = id (10.13)
From Eqs. (10.12) and (10.13), we get

(id i )
[OX]s (10.14)
K
The current i is also proportional to the concentration of the reductant that exists at electrode-
solution interface denoted by [Red]s so that
i = k[Red]s (10.15)
i
or [Red]s =
k
Substituting the values of [OX]s and [Red]s into Eq. (10.11), we get
RT K RT id i
E = ET ln ln
nF k nF i
RT id i
= ET

ln (10.16)
nF i
RT K
where ET
ET k and k ln
nF k
id
When i is equal to , Eq. (10.16), reduces to
2
id
RT
E E1 2 ET
ln 2 ET
(10.17)
nF id
2
The potential at the point on the polarographic wave where the current is equal to one-half of the
diffusion current is termed half-wave potential and is designated by E1/2. It is quite clear from
Eq. (10.17), that E1/2 is a characteristic constant for a reversible redox system and its value is
independent of the concentration of the oxidant [OX] in the bulk of the solution. It follows from
Eqs. (10.16) and (10.17) that at 25ºC.
0.059 i i (10.18)
E E1 2 log d
n i
The above equation represents the potential as a function of the current at any point on the
polarographic wave. Therefore, it is termed the equation of the polarographic wave.
10.3 DIFFICULTIES ENCOUNTERED IN POLAROGRAPHY
Occurrence of polarographic maxima

The current-voltage curves obtained with dropping mercury electrodes are distorted by the
occurrence of maxima or peaks. These maxima vary in shape from sharp peaks to round humps
and are reproducible. The removal or suppression of maxima is very important as they interfere in
the measurement of true diffusion current. Such maxima can be eliminated by the addition of
organic surfactants (or surface active agents) such as gelatin, fuschine, agar-agar, methyl red,
synthetic detergents and triton X-100 etc. These surfactants are known as maximum suppressor.
A typical example is shown in Figure 10.3. In this figure, curve A and B respectively represent the
polarogram obtained in the absence and presence of the surface active agents.
Gelatin is widely used as maximum suppressor but its concentration should not exceed 0.1% as
higher concentration can lead to distortion, lowering and shifting the positions of polarographic
waves. More recently, the commercial surfactant, Triton-X has become more widely used because
it works as well as gelatin and its stock solution are more stable. Typically, only very small
concentrations of suppressors are required. As the suppressors have some effect on the diffusion
current, it is desirable to study the effect of suppressor concentration on the polarogram and then
to employ the minimal concentration which is effective. The suppressor concentration should be
constant in all unknown and standard solution which are to be compared.
Figure 10.3 Occurrence of polarographic maxima.
The function of any such maximum suppressor is probably to form an adsorbed layer on the
aqueous side of the mercury-solution interface which resists compression. This prevents the
streaming movement of the diffusion layer at the interface which is believed to be responsible for
the current maxima.
Formation of polarographic waves due to dissolved oxygen
If the dissolved oxygen is not removed from the electrolytic solution, then oxygen itself gives rise
to two polarographic waves corresponding to the following reactions:
O2(g) + 2H+ + 2e ¾® H2O2
H2O2 + 2H+ + 2e ¾® 2H2O
Therefore, the solution to be analyzed should be flushed with a stream of a pure inert gas like
N2 or H2 for about 23 minutes. Unless oxygen is removed, the two waves corresponding to these
two reactions will interfere with the polarographic wave obtained for the analysis.
10.4 EXPERIMENTAL SET-UP
The apparatus required for polarographic analysis consists of the following components as shown
in Figure 10.4.
The basic components of the experiment set-up are
1. a dc source of constant voltage (D)
2. a precision voltage divider or potentiometer (P)
3. voltmeter (V)
4. a microammeter or galvanometer (G)
5. a polarographic cell
Figure 10.4 A typical polarograph with its basic components.
Description of polarographic cell

The polarographic cell is an H-shaped vessel, the two limbs of which are connected through an
agar-agar salt bridge (B) and a sintered glass disc (d). One-half of the cell acts as the anode (A)
which is usually a reference electrode such as a saturated calomel electrode (SCE). The other half
of the cell contains the solutions of the sample, analyte (a) and the DME serves as the cathode (C).
In the actual polarographic determination, the solution in the polarographic cell contains:
(a) the sample with the species to be determined in the optimum concentration range of 102M
to 105M;
(b) the supporting electrolyte in a concentration at least 50 to 100 times that of the species to be
determined;
(c) any reagents, such as a buffer or complexing agent, necessary to establish appropriate
conditions for the determination; and
(d) a maximum suppressor.
Description of dropping mercury electrode (DME)
The DME consists of a 830 cm long capillary tube, with an inner diameter of 0.050.1 mm, fixed
vertically through which mercury is forced under pressure exerted by approximately a 50 cm
column of mercury connector to a mercury reservoir (R). Under this condition, a continuous series
of highly reproducible spherical drops of mercury are formed having a diameter 0.1 to 1 mm.
Electrical connection is made by a wire dipping into the mercury in the reservoir. As mercury
flows through the capillary, drops grow at the tip until they become heavy enough to get detached
from the tube. The typical drop time (namely the time taken for the drop to form completely and
get detached from the tube) is in the range of 2 to 6 seconds. The drop-time is inversely proportional
to the height of the mercury column, and directly proportional to the length of the capillary. It has
also provision for flushing the analyte with a stream of an inert gas like hydrogen or nitrogen (g).
Procedure
At first nitrogen/hydrogen is passed through the electrolytic solution to remove the dissolved oxygen.
The DME is connected to the negative terminal of the dc source while the SCE is connected to the
positive terminal of the dc source. By suitably controlling the potentiometer any emf up to 3 V may
be gradually applied to the cell. Since the DME is connected to the negative terminal of dc source,
the applied voltage (read on the voltmeter (V)) is given a negative sign by convention. Also, by
convention, the current read on the ammeter (G) flowing across the cell is taken to be positive. The
plot of current on the Y-axis or ordinate against applied potential on the abscissa or X-axis is
known as a polarogram from which the diffusion current id and half-wave potential for the
electroactive species (mostly metal ions) can be determined.
10.5 ADVANTAGES AND DISADVANTAGES OF DME
Advantages of DME
(a) Mercury forms amalgams (solid solution with many metals). Amalgam formation lowers
the activity of the metal, thereby facilitating the reduction of the metal ion.
(b) The surface of mercury is reproducible, smooth and continuously renewed with fresh
mercury. This is conducive to good reproducibility of the current potential curve and
eliminates passivity or poisoning effects.
(c) Mercury forms highly reproducible spherical drops, whose surface area can be calculated
from their flow rate, m and drop time t. Hence, it is possible to relate the limiting diffusion
current with m and t as done in the Ilkovic equation.
(d) The diffusion current assumes a steady value immediately after each change of applied
potential and is reproducible. Thus polarographic analysis is rapid.
(e) The hydrogen overvoltage on mercury is very high and hence, there is no risk of evolution
of hydrogen while polarographic analysis is carried out in acidic solutions especially with
metal ions like Zn2+, which require large negative potentials.
Although DME is the most versatile electrode used in polarography yet it suffers from the
following disadvantages.
Disadvantages of DME
(a) The most important disadvantage of mercury as an electrode, compared with more
noble metals such as platinum is the oxidation of mercury itself to mercurous ion at
potentials more positive than + 0.4 V. This means that the use of DME as an anode is very
limited. Thus DME is seldom useful at potentials more positive than about + 0.4 V vs. SCE,
while a platinum anode can be used up to the potential where water begins to oxidize
(+1.4 V vs. SCE).
(b) At a potential more negative than about 1.8 V vs. SCE, visible hydrogen evolution occurs
in acid solutions and the usual supporting electrolytes commence to discharge. The range
may be extended to about 2.6 V vs. SCE by using supporting electrolytes having higher
reduction potentials than the alkali metals: Tetra-alkyl ammonium hydroxides or their salts
are satisfactory for this purpose. In view of the above facts DME is used over the range
+0.4 to 1.8 V with reference to SCE.
(c) The residual current for DME is quite large in comparison to that on noble metals like
platinum. This limits the sensitivity of the polarographic methods of analysis. Thus, the
concentration of the analyte should be at least 105 M. If the concentration is lower than
this, the residual current is likely to be greater than the diffusion current.
(d) The area of mercury drop is constantly changing as the size of drop changes. This leads to
an oscillation in the galvanometer readings.
(e) The capillary may be easily plugged. So care must be taken to avoid touching the tip of
capillary with any foreign material, especially the fingers.
(f) The mercury is volatile and toxic, therefore, safety precaution must be observed.
10.6 APPLICATIONS OF POLAROGRAPHY
10.6.1 Qualitative Evaluation of Polarographic Data

The half-wave potential, E1/2, is a constant for any specific oxidation-reduction process in a specific
supporting electrolyte and may be used for the qualitative identification of the unknown ion. Because
a number of ions may possess E1/2s very close to each other, unequivocal identification requires
the matching of E1/2s for a particular reduction process in three or four different supporting
electrolytes.
10.6.2 Quantitative Evaluation of Polarographic Data
Diffusion current-concentration plot
In this method the standard solutions of different concentrations of the metal-ions whose amount
is to be determined (test ion) are prepared under the same condition having the same composition
of the supporting electrolyte and the suppressor. A family of polarographic curves in a metal-ion
system is shown in Figure 10.5.
Figure 10.5 A family of polarographic curves for the same metal ion.
Curves A, B and C represent various concentration of the ion. The vertical dashed line represents
the chosen potential for the determination of the amount of metal ions and the vertical solid line
shows the E1/2. As the diffusion current is directly proportional to concentration, its value increases
as the concentration increases. The respective diffusion currents are given by id(A), id(B) and id(C)
for curves A, B and C respectively. A plot of diffusion currents against concentration yields a
straight line (Figure 10.6) which goes through the origin.
Figure 10.6 A plot of diffusion current against concentration for the same metal ion.
This is known as calibration curve. The current-voltage curve of the unknown solution of the
same metal ion is recorded. The diffusion current (id)x is now measured exactly in the same manner
as the standard solution. If the unknown concentration of the metal ion be Cx, then the following
relationship holds good
(I d ) s Cs
(10.19)
(Id )x Cx
where (Id)s and (Id)x are the diffusion currents of the standard and unknown respectively and Cs
and Cx are the respective concentration of the standard and unknown. Again from a knowledge of
diffusion current (Id)x for the unknown solution, the concentration can be determined from the
calibration curve by the method of interpolation.
Absolute method
The magnitude of diffusion current is related to the concentration of reducible species by Ilkovic
equation.
Id 607 n D1 2 m 2 3 t1 6 C
If all the factors in the equation are known, then the concentration of a species can be
calculated.
Pilot ion method (internal standard method)
In this method the wave heights (or diffusion currents) of the standard solution of the test ion
(suppose M1) and pilot or reference ion (M2) (whose half-wave potentials should differ by 0.2 V
from the test ion) are measured separately. Then the relative wave-height (diffusion currents) of
the solution containing test ion (M1) of unknown concentration (Cx) and the reference ion (M2) of
known concentration Cs are measured.
The schematic diagram of polarogram for the pilot ion technique is shown in Figure 10.7.
Figure 10.7 A schematic diagram for the polarogram for the pilot ion method.
If ( I d ) M1 and ( I d ) M 2 are the diffusion currents of the test ion M1 and pilot ion M2 respectively
for concentration of [M1] and [M2], then
( I d )M1 [M1 ]
K (10.20)
( I d )M 2 [M 2 ]
In a mixture, let the diffusion current be (Id)x for the test ion and (Id)s for the reference ion respectively.
As the diffusion currents are proportional to the concentration of the respective ion, we have
(Id )x C
K x (10.21)
(I d ) s Cs
Substituting the value of K from Eq. (10.20), we get
( I d ) x Cs ( I d ) x ( I d ) M 2 M1
Cx Cs (10.22)
( I d )s K ( I d ) s ( I d )M1 M 2
However, this method has limited applications because a very few ions act as pilot or reference
ion.
Standard addition method
The polarogram of the unknown solution is first recorded, after which a known volume of a standard
solution of the same ion is added to the cell and a second polarogram is taken. From the magnitude
of the heights of the two waves, the known concentration of ion added, and after the addition of the
volume of the solution, the concentration of the unknown may be readily calculated as follows. If
I1 is the observed diffusion current (º wave height) of the unknown solution of volume V cm3 and
of concentration Cx, and I2 is the observed diffusion current after v cm3 of a standard solution of
concentration Cs have been added. The concentration (C) of the resulting solution is given by
(VC x vCs )
C (10.23)
(V v)
As the diffusion currents are proportional to concentration of the solution, we have
I1 µ Cx and I2 µ C
I1 Cx
so that (10.24)
I2 C
Substituting the value of C from Eq. (10.23) to Eq. (10.24), we have
I1 I1 (VC x vCs )
Cx C (10.25)
I2 I2 (V v)
The above Eq. (10.25) on simplification gives
I1vCs
Cx (10.26)
( I 2 I1 ) (V v) I1v
10.6.3 Determination of Formation Constants of Complexes

Let us consider the general case of the dissociation of a complex ion,
MX (pn pb )

ZZX M n pXb
YZZ (10.27)
The instability constant may be written as
[M n ] [Xb ] p
Kinstab (10.28)
[MX (pn pb) ]
We may imagine the electrode reaction to be (assuming amalgam formation)

Mn+ + ne + Hg ZZX M(Hg)
YZZ (10.29)
Combining Eqs. (10.27) and (10.29), we have
MX(n
p
pb)+ + ne + Hg Û M
(Hg) + pX
b
Lingane derived the following relationship between the molar concentration of the ligand Xb and
the shift of the half-wave potential brought about by its presence.
0.0591 0.0591
E1 2 E1 2 log K instab log [X b ] p (10.30)
c n n
Here p is the coordination number of complex ion formed, Xb is the ligand and n is the number of
electrons involved in the electrode reaction. E1 2 and E1 2 are the half-wave potentials for the
c
complexed and the uncomplexed cation respectively at 25ºC.
From Eq. (10.30), it is clear that the half-wave potential will also shift with a change in the
concentration of the ligand and if the former is determined at two different concentrations of the
same ligand Xb, we have
0.0591
'E1 2 p ' log [Xb ] (10.31)
n
where DE1/2 is the change in half-wave potential.
The above relationship enables one to determine the coordination number p of the complex ion
provided n is known. It can be further shown that
0.0591 0.0591
E1 2 E1 2 log Kinstab p log [X b ] (10.32)
c n n
Thus a plot of E1 2 E1 2 taken in Y-axis against log [Xb] taken in X-axis gives a straight
c
0.0591 0.0591
line with the negative slope p and intercept log Kinstab . We know that. Hence once
n n
the instability constant is determined, the stability constant of the complex can be calculated taking
1
its reciprocal, i.e. log Kinstab = log log Kstab .
K stab
The shift of the half-wave potential of metal ions is of value in polarographic analysis to eliminate
the interfering effect of one metal ion upon another and to promote sufficient separation of the
waves of metal ions in mixture to make their simultaneous determination possible. Thus in the
analysis of copper-base alloys for nickel, lead, etc., the reduction wave of copper(II) ions in most
supporting electrolytes precedes that of the other metal ions and swamps those of the other metal
ions present by using a cyanide supporting electrolyte, the copper is converted into the difficult
reducible cyanocuprate(I) ion and in such a medium, nickel, lead, etc., can be determined.
10.6.4 Analysis of Mixture of Ions

The identification and estimation of metallic ions can also be carried out on mixtures of metallic
ions. The resulting polarograms will have as many waves as the number of ions in the mixture.
For each of the waves, the wave height is a measure of the concentration and E1/2 is the characteristic
for the identification of the ion. For example, Figure 10.8 shows the polarogram of a mixture of
silver(I), thallium(I), cadmium(II), nickel(II) and zinc(II), each of which is 0.1 mM. The supporting
electrolyte is 1 M NH3/1 M NH4Cl.
Figure 10.8 Polarogram of mixture of metal ions.
10.6.5 Determination of Dissolved Oxygen

The determination of dissolved oxygen in aqueous solution or in organic solvents can be carried
out successfully with the help of polarography. In this method, the dissolved oxygen is not swept
out with nitrogen gas, as with other samples. Instead the oxygen waves are measured and the
dissolved oxygen produces two polarographic waves corresponding to
O2 + 2H+ + 2e ZZX
YZZ H2O2
and H2O2 + 2H+ + 2e ZZX
YZZ 2H2O
10.7 PROBLEMS INVOLVED IN POLAROGRAPHY
PROBLEM 10.1 For a solution of lead ion of concentration 1.0 mM, the limiting diffusion
current is 8.76 mA and the capillary constant value is found to be 1.9987. Calculate the diffusion
coefficient of Pb2+.
Solution While deriving Ilkovic equation, C, concentration, is expressed in millimole per litre
(mm), different currents in microampere and diffusion coefficient in cm2 s1.The reaction involved
is Pb2+ + 2e ¾® Pb, so that n = 2 Substitution of the value of Id, capillary constant m 2 3t1 6 and
concentration in appropriate unit in Ilkovic equation gives
Id = 607 n D1 2 m 2 3 t1 6 C
Id 8.76
D1 2 =
607 n m 23
t 16
C 607 2 1.9987 1
D1 2 = 3.6103 ´ 103
D = 1.303 ´ 105 cm2 s1
PROBLEM 10.2 The half-wave potential for Ni(II) in 0.1 M NaClO4 was found to be 1.02 V
versus SCE. In a solution that contains 0.1 M NaClO4 and 0.1 M ethylene diamine the half-wave
potential was 1.60 V. Calculate the stability constant (Kstab) of the complex between the two
species assuming its formula to be [Ni(en)3]2+.
Solution The Lingane equation is
0.0591 log Kstab 0.0591

E1 2 E1 2 p log [Xb ]
c s n n
For Ni(II), n = 2 and for the complex [Ni(en)3], p = 3
0.0591 0.591 3
\ 1.6 (1.02) = log Kstab log[0.1]
n 2
0.0591
log K stab = 1.6 1.02 + 0.0886
2
0.0591
log K stab = 0.6686
2
log Kstab = 22.626
Kstab = 4.23 ´ 1022
PROBLEM 10.3 Mercury from a DME was collected for 100 s and was found to weigh
0.196 g. The time required for 10 drops of mercury to form was found to be 43.2 s. When this
electrode was employed with a 0.001 M solution of Pb2+, a limiting current of 8.75 mA was observed.
Subsequently a solution of Pb2+ of unknown concentration produced a limiting current of 16.31
mA with a new electrode which had a found rate of 3.85 mg s 1 and drop time of 6.13 s. Calculate
the concentration of unknown solution of Pb2+.
Solution For the first electrode
0.196 103
m 1.96 mg s 1
100
43.2 g
t 4.32 s and n = 2 for Pb2+, m2/3t1/6 = (1.96)2/3 (4.32)1/6 = 2.01,
10 drops
C = 0.001 M = 1 mM
ID 8.75 607 n D1 2 m 2 3t1 6C 607 2 D1 2 2.01 1
D1/2 = 3.56 ´ 103
or D = 1.29 ´ 105 cm2 s1
For the second electrode,
m = 3.85 mg s1, t = 6.13 s,
m 2 3t1 6 (3.85) 2 3 (6.13)1 6 3.32
ID = 16.31 = 607 ´ 2 ´ 3.59 ´ 103 ´ 3.32 ´ C
Therefore C = 1.13 mM
PROBLEM 10.4 For a particular DME, the capillary constant m2/3 ´ t1/6 is 1.79 with m in
mg s1 and t is in second. Using 0.5 mM of an electroactive species, ID is found to be 7.3 mA.
Given that diffusion coefficient of the species to be 7.3 ´ 106 cm2 s1, calculate the no. of electrons
involved in this process.
Solution ID = 607 n D1 2 (m 2 3t1 6 ) C 607 n (7.3 106 )1 2 1.79 0.5

7.3 = 1.47n
7.3
n= 5
1.47
\ Number of electrons involved in the reduction of the organic compound is 5.
PROBLEM 10.5 A 25.00 ml sample of an unknown Cd2+ solution gave a diffusion current of
1.94 mA. When 10.00 ml of 1.68 ´ 103 M solution was added to the 25.00 ml sample, the resulting
solution gave a diffusion current of 4.92 mA. Calculate the concentration of cd2+ ion solution.
I1vCs
Solution Unknown concentration C x
( I 2 I1 ) (V v) I1v
Here I1 = 1.94 mA, Cs = 1.68 ´ 103 M

V = 25ml, v = 10 ml, I2 = 4.92 mA
1.94 10 1.68 10–3
\ Cx 2.63 10 –4 M
(4.92 1.94) (25 10) 1.94 10
PROBLEM 10.6 Bismuth and cadmium gave well-separated polarographic waves in 1 N HCl.
A 4.0 ´ 104 M solution of Bi3+ had a diffusion current of 4.82 mA and a 3.7 ´ 104 M solution of
Cd2+ had a diffusion current of 2.29 mA. In a mixture containing 5.8 ´ 104 M Cd2+, the cadmium
diffusion current was 4.59 m and that of bismuth was 5.67 mA. Calculate the bismuth concentration
in the mixture.
Solution This is the internal standard method or pilot ion method for estimation. Here Cd2+ is
used as pilot ion. For the method, we know that
( I d ) x ( I d ) M 2 [M1 ]
Cx Cs
( I d ) s ( I d ) M1 [M 2 ]
Here [B13+] = M1 = 4.0 ´ 104 M

[Cd2+] = [M2] = 3.7 ´ 104 M
( I d ) M1 4.82 PA and ( I d ) M2 2.29

(Id )x 5.67 PA and ( I d ) s 4.59 PA, Cs 5.8 104
5.67 2.29 4.0 10–4
Cx
5.8 104 4.7 10 4 M
4.59 4.82 3.7 10 4
PROBLEM 10.7 What is the diffusion current value of cadmium if C = 3 ´ 103 mole/litre =
3 mM, D = 0.72 ´ 105 cm2 s1, m = 3 mg s1 and t = 4s (n = 2 for Cd).
Diffusion current can be found from Ilkovic equation.
Solution Id = 607 n C D1 2 ( m 2 3t1 6 )
= 607 2 3 (0.72 10 ) 3 4
–5 1 2 23 16
= 3642 3 4 (0.72 10 )
23 16 –5 1 2
= 25.4 mA
PROBLEM 10.8 In a particular polarographic analysis of copper, C = 1 ´ 104 M, I d1 = 17.5 mA

and for unknown solution of copper, I d2 = 27.9 mA. What would be its concentration (C2) with
other factor constant?
Solution We know
I d1 C1
=
I d2 C2
17.5 1 104
=
27.9 C2
(1 10 –4 27.9)
C2 = = 1.59 ´ 104 M
17.5
PROBLEM 10.9 In a polarographic analysis of mercury with equal volume of 5.50 ´ 104 M
solution and unknown solution gave a diffusion current of 58.5 mA, while unknown solution gave
a diffusion current of 47.4 mA. Calculate the concentration of mercury in unknown sample.
Solution We know
I1vCs
Cx
( I 2 I1 ) (V v) I1v
I1 = 47.4 mA, I2 = 58.5 mA, Cs = 5.5 ´ 104
Here V = v,
I1VCs
So Cx =
( I 2 I1 ) (V V ) I1V
I1Cs I1Cs
=
2( I 2 I1 ) I1 2 I 2 I1
47.40 5.5 10 4 47.4
= 5.5 104
(2 58.5 ) 47.40 69.6
= 3.75 ´ 104 M

(i) Limiting diffusion current is directly proportional to concentration of reducible ion
(a) At the bulk of the solution (b) At the surface of DME
(c) Concentration gradient (d) None of these
(ii) The typical drop time of mercury drop in DME is
(a) Between 2 and 6 seconds (b) Between 0.3 and 6 seconds
(c) Between 10 and 20 seconds (d) More than 20 seconds
(iii) If m and t are respectively the flow rate and drop time of mercury of the DME, the limiting
diffusion current Id is proportional to
23 16 16 23
(a) m t (b) m t
32 16
(c) m t (d) m1 6t1 6
(iv) Polarography maxima can be suppressed by addition of
(a) Picric acid (b) b -naphthol
(c) Phenol (d) Gelatin
(v) Before carrying out polarographic analysis the solution to be analyzed is flushed with a
stream of
(a) Oxygen (b) Nitrogen
(c) Carbon dioxide (d) Chlorine
(vi) The potential corresponding to the point of inflation of the polarographic curve is known as
the
(a) Decomposition potential (b) Half-wave potential
(c) Overpotential (d) Electrode potential
(vii) The polarographic analysis is carried out under unstirred condition so as to minimize
(a) Migration current (b) Residual current
(c) Diffusion current (d) Residual current
(viii) In pilot ion method, the half wave potential of test ion and pilot ion, must differ by
(a) 0.2 V (b) 2 V
(c) 1 V (d) none of these
(ix) In polarographic analysis for the mixture of analytes the polarogram will have
(a) As many waves as the number of ions present in the mixture
(b) Always less number of waves compared to the number of ions present in the
mixture
(c) Always greater number of waves than the number of ions presents in the mixture
(d) Will have unpredictable waves
(x) Polarography analysis involves
(a) Reversible reduction of oxidant to reductant at DME
(b) Reversible oxidation of reductant to oxidant at DME

(c) No redox process
(d) None of these
statements
(i) The DME is a polarizable electrode.
(ii) A concentrated solution of cadmium sulphate is commonly employed as a supporting
electrolyte.
(iii) The half-wave potential for the reduction of Zn2+ is less negative than that of Ag+.
(iv) The residual current in polarography is also known as capacitor current.
(v) Due to ion diffusion, the concentration becomes maximum at the surface of the electrode.
(vi) There is no other means by which the ions reach the electrode surface except diffusion.
(vii) The half-wave potential is independent of the concentration of the solution.
(viii) In limiting current density, the rapid increase of potential is observed.
(ix) Limiting current density is independent of concentration of the solution.
(x) A diffusion layer in a solution cannot be fully eliminated.
(i) Diffusion current is proportional to .............. of electroactive species.
(ii) Polarographic maxima or the distortion polarographic wave is minimized by adding ...............
.
(iii) The term .............. is used where the polarizable electrode is a dropping mercury electrode.
(iv) Standard calomel electrode or mercury pool acts as .............. electrode in polarography.
(v) The instrument in determining the entire current voltage curve is called .............. .
(vi) A plot of .............. versus.............. is called polarogram.
(vii) The wave heights of the polarogram represent .............. current.
(viii) The purpose of using supporting electrolyte is to minimize .............. current.
(ix) The DME cannot be used at potentials more positive than .............. because Hg gets oxidized
at such potential.
(x) The unit for the diffusion coefficient of an ion is .............. .
(xi) The half-wave potential is the characteristic of .............. .
(xii) The DME potential at which the current is one-half of its limiting value is called
.............. .
(xiii) Polarographic technique can be employed to determine the .............. involved in reduction
process.

(i) Define polarography.
(ii) Why polarizable electrode is called microelectrode?
(iii) Name the cathode and anode used in a polarography.
(iv) What is electroactive material?
(v) What are the processes involved for an electroactive material to reach the surface of an
electrode?
(vi) Under what condition electrical double layer behaves as a parallel capacitor?
(vii) What is convection current? How is it eliminated?
(viii) Name the two supporting electrolytes used in polarography.
(ix) What is diffusion current?
(x) What do you mean by limiting diffusion current?
(xi) What is capillary constant?
(xii) What do you mean by thickness of diffusion layer?
(xiii) Write the equation for the polarographic wave.
(xiv) What is the role of maximum suppressor?
(xv) Which is responsible for polarographic maxima?
(xvi) Name the basic components of a polarograph.
(xvii) What happens when a potential more negative than 1.8V vs SCE is applied to a polarographic
cell?
(xviii) What is the cause of oscillation in the galvanometric readings?
(xix) Write the various methods adopted for quantitative evaluation of polarographic data.
(xx) How is the E1/2 value shifted? Giving an example mention the advantages of such shifting.

(i) What are the factors affecting the current flow in the polarographic cell?
(ii) Explain the cause of residual current.
(iii) Explain the nature of polarogram obtained by the reduction of M+2 ion in the presence of
supporting electrolytes without stirring.
(iv) What are the factors affecting diffusion current?
(v) Write Ilkovic equation. Explain the terms involved in it.
(vi) How do you determine
(a) The surface area of DME and
(b) The thickness of diffusion layer.
(vii) Define half-wave potential. What is its significance?
(viii) Give examples of at least two maximum suppressor. Mention their role in polarography.
(ix) What are the advantages and disadvantages of DME?
(x) What precautionary measures are adopted while using DME?
(xi) Describe how the calibaration curve is produced in polarography.
(xii) Describe how will you determine the concentration of analyte by Id-C plot.
(xiii) State the equation relating to the molar concentration of ligand and the shift of half-wave
potential.
(xiv) How would you determine the coordination number of a metal ion by polarographic method?
(xv) Describe the construction of DME.
6. Give reasons
(i) Supporting electrolytes of high concentration of 100 fold than that of analyte is used in
polarography.
(ii) Oxygen must be removed from the electrolytic solution by flushing with a stream of N2 or
H2 during polarographic analysis.
(iii) DME is used as cathode in polarography.
(iv) DME is used over the range of +0.4 to 1.8 V with reference to SCE.
(v) Polarographic analysis is useful in qualitative and quantitative analysis of unknown
ions.

7. Discuss briefly the principle on which polarography is based.
8. Explain clearly the terms
(i) Concentration polarization
(ii) Polarizable electrode
(iii) Migration current
9. What is meant by limiting current density and diffusion current? Derive Ilkovic equation.
Mention its importance.
10. Write a detailed note on half-wave potential.
11. Polarography is an important analytical toolcomment on the statement.
12. Explain the following terms: polarogram, half-wave potential and limiting diffusion current.
13. Discuss the basis of the polarographic method of analysis. What is the significance of
limiting diffusion current and half-wave potential?
14. Give in detail the experimental set-up for polarography.
15. Write notes on polarography. How would you estimate cadmium present in an alloy by the
polarographic method?
16. How would you determine the concentration of analyte by
(a) Pilot ion method?
(b) Standard addition method?
17. How would you determine the formation constant and cordination number of the complex
by polarographic method?
UNIT 7
11. Spectroanalytical TechniquesUltraviolet and Visible Spectral
Method
12. Spectroanalytical TechniquesInfrared (IR) Spectral Method
13. Spectroanalytical TechniquesNuclear Magnetic Resonance
Spectral Method
14. Spectroanalytical TechniquesElectron Spin Resonance Spectral
Method
15. Spectroanalytical TechniquesMass Spectral Method
CHAPTER 11
Spectroanalytical Techniques
Ultraviolet and Visible
Spectral Method
11.1 INTRODUCTION
Spectroscopy involves interaction of electromagnetic radiation with matter. Electromagnetic

radiation is considered as waves of energy propagated from a source in space and consists of
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
Ê OÚ
emission of electromagnetic radiation is quantized and each quantum or radiation is called photon.
The energy (E) of a photon is given by Plancks law, i.e. E = hn, where h is Plancks constant and
n is the frequency of radiation. Some important electromagnetic radiations are radio wave,
microwave, infrared, visible, ultraviolet, x-rays and gamma rays with decreasing order of
wavelength or increasing order of frequency or energy. Molecule or ion may absorb energy from
electromagnetic radiation of suitable wavelength (or frequency) resulting in:
(i) Electronic excitation caused by absorption of UV-visible radiation leading to UV-visible
spectroscopy.
(ii) Molecular rotation by absorption of microwave radiation leading to microwave
spectroscopy.
(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
(b) Monochromator: Glass prism (visible), fused silica or quartz (visible and UV) or reflection
gratings.
(c) Sample cell to contain the sample.
(d) Radiation detector to measure the intensity of transmitted radiation.
(e) Signal processor and recorder to display the spectra.
Magnetic nuclei as well as unpaired electron present in the molecular system/ion may give rise
to resonant absorption of electromagnetic radiation when the sample is placed in a magnetic field.
The electromagnetic radiation used for such phenomena are microwave and radio frequency leading
to electron spin resonance (ESR) and nuclear magnate resonance (NMR) respectively. The
experimental set-up consists of
(a) A source of monochromatic radiation (the source of radio frequency is usually a crystal
controller oscillator while for microwave the source being klystron tube).
(b) A sample holder (resonant cavity) so that the sample can be placed in a uniform magnetic
field and simultaneously irradiated with radio frequency in case of NMR and microwave
in case of ESR.
(c) A detector to measure the resonant power absorption by the sample. This chapter deals
with UV-visible spectral method and other spectral methods such as IR, NMR, ESR and
mass spectral methods are discussed in Chapters 12, 13, 14 and 15 respectively.
11.2 PRINCIPLE OF UV-VISIBLE SPECTROSCOPY
11.2.1 Origin of UV-visible Spectroscopy

The UV-visible spectral method involves UV-visible spectroscopy. This arises due to absorption
of ultraviolet (UV) or visible radiation with sample resulting in electronic transition within the
molecule or ion. The relationship between the energy absorbed in an electronic transition, the
frequency (n ), wavelength (l) and wave number (v ) of radiation producing the transition is
c
'E hQ h hv c (11.1)
O
where h is Plancks constant, c is the velocity of light.
DE is the energy absorbed during electronic transition in a molecule or ion from a lower-
energy state (E1) (ground state) to a high-energy state (E2) (excited state)
The energy absorbed is given by
\ DE = E2 E1 = hn (11.2)
The wavelength corresponding to such transition is given by,
hc
O , which usually falls in the range of 200 nm 800 nm of the electromagnetic spectrum,
'E
which covers the UV and visible region of electromagnetic radiation as shown in Figure 11.1.
Spectroanalytical Techniques—Ultraviolet and Visible Spectral Method 367
Figure 11.1 Electromagnetic spectrum covering UV and visible region.
PROBLEM 11.1 Find the wavelength of electromagnetic radiation required for electronic
transition between two electronic states of energy difference 5 eV. Give comment on the result.
Solution Given
DE = hn = 5 eV
12
= 5 1.6 10 ergs
= 8.0 1012 ergs
hc 6.62 1027 ergs 3 1010 cm s 1
\ O =
'E 8 10 12 erg
5
= 2.5 10 cm
5
= 2.5 10 10 A
8
= 2500 A
= 250 nm
The wavelength corresponds to ultraviolet region of electromagnetic spectrum.
11.2.2 Absorption Law

There are two laws which govern the absorption of light by the molecule. These are:
(i) Lamberts law and (ii) Beers law.
Lamberts law
It states that When a beam of monochromatic radiation passes through homogeneous absorbing
medium, the rate of decrease of intensity of radiation with thickness of absorbing medium is
proportional to the intensity of the incident radiation. Mathematically, the law can be expressed as
dI
I (11.3)
dx
where I = intensity of radiation after passing through a thickness x of the medium.

dI = Infinitesimally small decrease in the intensity of radiation on passing through infinitesimally
dI
small thickness dx of the medium. rate of decrease of intensity of radiation with thickness
dx
of the absorbing medium.
Beers law
The law states that when a beam of monochromatic radiation is passed through a solution of an
absorbing substance, the rate of decrease of intensity of radiation with thickness of the absorbing
solution is proportional to the concentration of the solution.
Mathematically, this law is stated as
dI
C (11.4)
dx
where C = Concentration of the solution in moles/litre.
Combining Eq. (11.4) with Eq. (11.3), we get
dI
C I (11.5)
dx
Equation (11.5) is known as LambertBeers law which is stated as follows.
LambertBeers law
The law states that when a beam of monochromatic radiation is passed through a solution of an
absorbing substance, the rate of decrease of intensity of radiation with thickness of the absorbing
solution is proportional to the intensity of incident radiation as well as to the concentration of the
solution.
Mathematically, this law is stated as:
dI
kCI (11.6)
dx
where k = proportionality constant or absorption coefficient. Its value depends upon the nature of
the absorbing medium.
Let I0 be the intensity of the radiation before entering the absorbing medium (x = 0), then I, the
intensity of radiation, after passing through any thickness, say x of the medium so that
I x x
dI
Ô I
=
x
Ô k C dx
I0 0
I
ln =kCx (11.7)
I0
I
or = ekcx
I0
Equation (11.7) can also be written as
È I Ø k
log É Ù =
Cx H Cx
Ê I0 Ú 2.303
È I0 Ø
log É Ù = H Cx (11.8)
Ê I Ú
or A = H Cx
k I
where H and A = log 0 , is called absorbance or optical density of the solution.
2.303 I
The absorption spectrum is generally studied by monitoring the intensities of the incident (I0)
and transmitted radiation (I). If C is the molar concentration of absorbing species in mole dm3
(mole litre1), then absorption of UV or visible light is governed by LambertBeers law,
I0
A log HCx (11.9)
I
where A is absorbance or optical density, e is molar absorptivity or molar extinction coefficient of
the absorbing medium and x is the thickness of the absorbing medium (or path length) respectively.
I
The path length may also be expressed as l so that A = e C l. The ratio is called transmittance,
I0
I
T and 100 is called percentage transmission, %T. There exists a relationship between
I0
absorbance, A, the transmittance, T and molar absorption coefficient (e) which is given by
1
A HCx log log T (11.10)
T
I
Again %T = 100
I0
I
\ log %T = log log 100
I0
I0
= log 2
I
= A + 2
\ A = 2 log (%T ) (11.11)
A
Unit of e: In the relation H it is clear that if the conc C is expressed as mole lit1 and l
C ¹l
is cm then unit of H will be mole1 lit cm1 as A is a dimentionless quantity.
PROBLEM 11.2 The molar absorptivity of a particular solute is 2.0 ´ 104 mole1 lit cm1.
Calculate the % of transmittance through a cuvette with a 5.00 cm light path for a 106 M
solution.
Solution Given
e = 2.0 ´ 104
C = 106 M
l = 5 cm
\ Absorbance, A = e C l = 2.0 ´ 106 ´ 5
= 10 ´ 102 = 101 = 0.1
log (%T ) = 2 A = 2 0.1 = 1.9
%T = Anti log of 1.9 = 79.43
PROBLEM 11.3 0.55 g sample of an alloy steel was dissolved and its manganese content
was oxidized to permanganate. The volume of the solution was diluted to 100 ml in a volumetric
flask. The solution shows an absorbance of 0.42 at 530 nm due to permanganate ion. Calculate
the % of manganese in the alloy steel if path length is 1 cm and e for permanganate ion is
4.2 ´ 103 mole1 lit cm1.
A 0.42
Solution C [MnO 4 ] 10 3 mole lit –1
Hl 4.2 103 1
Thus, 1 litre or 1000 ml solution contains 103 mole of MnO 4– or 103 mole of Mn.
10 3 100
\ 100 ml of solution contains = 104 mole of Mn
1000
= 55 ´ 104 g of Mn
\ 4
0.55 g of alloy steel contains 55 ´ 10 g of Mn
55 10 4 100
\ 100 g of alloy steel contains 1%
0.55
PROBLEM 11.4 Calculate the energy associated with radiation having wavelength of 200 nm
absorbed per mole of absorbing species.
hc
Solution From the relation 'E the energy absorbed per mole by the absorbing species
O
Nhc
will be given by (where N is the Avogadros number). Substituting the values of N, h, c
O
and l, the energy absorbed in kJ/mole is equal to 11.9809 ´ 104/l, where l is expressed in nm.
Here l = 200 nm.
11.9809 104
\ The energy absorbed in kJ/mole =
200
= 5.99045 102 kJ/mole
= 1.4263 102 k cal/mole
11.2.3 Nature of Electronic Spectrum

Since the absorption (or emission) of visible or UV energy is quantized (i.e. DE = hn),
the absorption spectrum resulting from a single electronic transition is expected to contain
single discrete line (sharp line). Again electronic transition is very rapid compared to nuclear
motion. The former occurs generally without changes in internuclear distance. This is known as
Franck Condon principle. However, in a molecular species the spectra appear as band spectra.
This is because electronic excitation arising from absorption of UV or visible energy is
accompanied by vibration and rotational energy changes in the molecule resulting the overall
shape of absorption band to be broad. This is displayed by plotting molar absorptivity
(or absorbance) or even transmittance taken as ordinate against the corresponding values of
wavelength (nm or Å) or wave number (in cm1) taken as abscissa. In some cases logarithm of
molar extinction coefficient is plotted against the wavelength or frequency. These plots are shown
in Figures 11.2(a), (b) and (c).
Figure 11.2 Representation of electronic spectra.
11.2.4 Selection Rules for Absorption

The position of absorption band and its intensity is governed by the following selection rules:
1. Energy requirement: The position of absorption band corresponds to the wavelength
hc
of radiation whose energy is equal to that required for an electronic transition, i.e. O
.
'E
2. The probability of interaction: The molar absorptivity is governed largely by the
probability of interaction between the radiant energy and absorbing system leading to
electronic transition given by the relation
e = (0.87 ´ 1020) P ´ A (11.12)
where
P = Transition probability with values of 0 to 1.
A = Target area of the absorbing system where photon hits.
For many organic molecules the target area is about 100 square Å so that for a transition of
unit probability, e = 105. The transitions with value of emax more than 104 are usually
called allowed transition giving rise to more intense band while those with emax values less
than 103 are called forbidden transition giving rise to less intense band.
3. Electric dipole mechanism: Electronic transition occurs through electric dipole
mechanism in which electrical component of electromagnetic radiation interacts with dipole
of the absorbing system. Thus an electric dipole transition will be intense if it is accompanied
by large change in dipole moment (i.e. there is considerable charge distribution during the
transition) which is related to square of transition moment integral Q given by the expression
<ya|M|yb>, where ya and yb are the total wave functions of the states between which
transition is occurring and M is dipole moment operator. The probability of transition can
be expressed in terms of another measure of intensity called oscillator strength, f given by
the relation
f Ô
4,315 109 H dv (11.13)
Ô
Here the integral H dv is the measure of integrated absolute intensity. It is evaluated from
the area of the curve obtained by plotting e taken as ordinate and v as abscissa. It may be
also obtained on approximation by multiplying emax by Dv, where Dv is the called the half
1
bandwidth, where H H max as shown in Figure 11.3.
2
Figure 11.3 Half bandwidth of electronic spectra.
v1 and v2 correspond to the points on the curve, where the line parallel to v axis and
1
passing through the point (e = emax) meets.
2
The following relation exists between the oscillator strength (f ) and transition moment
integral Q
f = 1.096 ´ 1011 vmax Q2 (11.14)
Thus, in order to electronic transition take place, due to absorption of radiation, the transition
moment integral must be non-zero.
4. Symmetry of ground and excited state: For electronic transition to take place, both
the ground and excited state wave function cannot be u (ungerade or antisymmetric) or
g (gerade or symmetric) whereas g « 4 or u ® g transition is allowed.
Thus u ® u or g ® g transition is forbidden. This is called Laporte Rule.
5. Spin selection rule: Electronic transition takes place between states of the same spin
multiplicity (i.e. singletsinglet or triplettriplet) whereas singlettriplet or vice versa is
forbidden.
6. Only one electron transition is allowed: The transition of only one electron from lower
energy state to higher energy state by absorption of UV or visible radiation gives rise to
more intense band whereas transition involving two or more than two electrons is forbidden
giving rise to less intense band (even not detected).
11.3 TECHNIQUES INVOLVED IN UV-VISIBLE SPECTROSCOPY
11.3.1 Description of UV-visible Spectrophotometer

The commercially available instrument for the measurement of absorption in UV-visible region is
called UV-visible spectrophotometer. The essential components of a UV-visible spectrophotometer
are:
Radiation source
(i) For visible region (~ 350 nm to 800 nm): Tungsten incandescent filament lamp.
(ii) For UV-region (~ 175 nm to 400 nm): Hydrogen or deuterium discharge lamp, Xenon
discharge lamp and mercury arc are used. A radiation source must satisfy the following
conditions:
(a) Providing sufficient radiant energy so that the transmitted energy can be detected at
the end of the optical path.
(b) Sufficiently stable so that fluctuations are reduced.
(c) Supplying continuous radiation over the entire wavelength of required region.
Monochromatic system (for wavelength control)
For an effective absorption by the sample, a narrow beam of required wavelength from a continuous
source is provided by the monochromatic system. It consists of an entrance slit, a collimating lens
or a concave mirror to produce a parallel beam of radiation, a dispersing element to disperse the
polychromatic radiation into its component wavelength, a focusing lens and an exit slit on the
focal plane. The dispersing element includes a prism or diffraction gratings. The prisms are made
of glass for visible region and of quartz or fused silica for UV-region.
Sample cells
The cells that contain samples for analysis should fulfil the following three main conditions:
(a) They must be uniform in construction. The thickness must be constant and the surface
facing the incident light must be optically flat.
(b) They must transmit light of the wavelength used.
(c) The materials used for the construction of the cell should be inert to solvent.
The most commonly used cells are made of quartz or fused silica. These are readily available
in matched pairs where sample cell is almost identical to the reference cell where the solvent is
taken. Rectangular cells with path length of 1 cm are commonly used.
Radiation detector
A detector is a device which converts radiant energy into an electrical signal for measurement.
These include:
(i) Photo voltaic cell (or barrier-layer cell)
(ii) Photo emissive cell (photo cell or phototube)
The sensitivity of a photo emissive cell can be increased considerably by employing photo
multiplier tube.
Signal processors and read out system (recoding system)

The signal from the detector is amplified by an external electronic amplifier and the amplified
signal is fed as voltage to a voltmeter which has a read-out system. This may include galvanometer,
potentiometer, pen recorder or oscilloscope. For recording system (shown in Figure 11.4), signal
is converted to ac which drives a servomotor resulting the movement of attenuator wedge (optical
wedge). As the recorder pen is linked to the attenuator wedge, the movement of the later moves
the former up and down on a chart paper fixed on a rotating drum. If the motor which drives the
monochromator is also made to drive the drum on which chart paper is fixed, than it is possible to
obtain a slot of wavelength versus optical wedge position which becomes wavelength versus
transmittance or absorbance.
Power supply
The power supply serves the following:
(i) Decrease line voltage to the instruments operating level with a transformer.
(ii) Converts ac to dc with a rectifier if direct current is required by the instrument.
(iii) Smooth out any ripple which may occur in the line voltage in order to deliver a constant
voltage to the source lamp and instrument.
11.3.2 Types of UV-visible Spectrophotometer

The spectrophotometer may be classified as single beam and double beam. In single beam
spectrophotometer, radiation is first passed through the solution under analysis. In double beam,
the radiation is split into two equal halves, one-half passes through the cell containing the sample
while the other half passes through the second cell (reference cell) containing the solvent (blank
solution). The signal for the absorption due to the reference is automatically subtracted from that
due to sample cell giving rise to net signal corresponding to the absorption of component of the
sample solution. The double beam type may have two matched detectors or the radiation may be
flashed alternatively over two paths to a simple detector. Some important types of single beam
and double beam UV-visible spectrophotometer are given below.
Manual (non-recording) spectrophotometer

Example
(a) Single beam direct reading spectrophotometer Spectronic-20
(b) Single beam null balance spectrophotometer Beckmann model DU-2
(c) Double beam null balance spectrophotometer Cary model-16
Other examples are Unicom SP600 and Unicom SP500
Automatic or recording spectrophotometer

Almost all recording spectrophotometers are of double beam type. However, commercially available
recording double beam spectrophotometers are direct reading, optical null and potentiometric
null types as exemplified below.
Example
(a) Direct reading double beam recording spectrophotometer Beckmann model DB-G
(b) Optical null double beam recording spectrophotometer Perkins Elmer model-202
(c) Potentiometric null double beam spectrophotometer Cary model-14
The block diagram of a typical double beam optical null type recording UV-visible
spectrophotometer is shown in Figure 11.4.
Figure 11.4 Block diagram of a double beam optical null type UV-visible spectrophotometer.
11.3.3 Working Principle

Radiation from a source is allowed to pass through the monochromatic system. The resulting
narrow beam of radiation through monochromator encounters a chopper. The chopper driven by
synchronous motor is rotating mirror, which permits the beam to pass straight during the half of
its period of rotation. During the other half, the beam encounters the reflecting surface which
turns it at right angle directing it upwards as shown in Figure 11.4. The direction as desired may
be changed again by other stationary mirror. Thus two beams are obtained by the single beam
emerging from the monochromator. One beam passes through the sample cell while the other
passes through a reference cell (containing solvent). The alternating beams reach the detector
where they recombine to give a resultant ac signal. The outputs (ac signals) are amplified and
then transmitted to the recorder where the absorbance or transmittance is recorded on a chart
paper as a function of wavelength.
11.3.4 Choice of Solvent

Many solvents are available for use in the UV region. Three common solvents are cyclohexane,
95% ethanol and 1, 4-dioxane. Cyclohexane may be freed of aromatic and olefinic impurities by
percolating through activated silica gel and is transparent down to about 210 nm. Aromatic
compounds, particularly poly-nuclear aromatics, are usually soluble and their spectra generally
retain their fine structure when determined in cyclohexane. The fine structure is often lost in more
polar solvent. 95% ethanol is good choice when a more polar solvent is required. It is transparent
down to 210 nm. Commercial ethanol should not be used as it contains benzene, which absorbs
strongly in UV region. 1, 4-dioxane can be purified by distillation from sodium. Benzene
contamination can be removed by the addition of ethanol followed by distillation to remove
benzene-methanol a zeotrope. 1, 4-dioxane is transparent down to 220 nm.
Different types of spectral grade solvents for UV analysis is now commercially available.
Care should be taken to choose a solvent that will be inert to the solute (i.e. spectra of aldehydes
should not be determined in alcohol).
11.4 TYPES OF ELETRONIC TRANSITION
Depending on the nature of absorbing species, electronic transitions may be of the following types:
(i) Transitions involving s, p and non-bonding (n) electrons.
(ii) Transitions involving d or f electrons.
(iii) Change transfer transitions.
11.4.1 Transitions Involving s, p and n (Non-bonding Electrons)

The electron in molecules can be classified as sigma (s), pi (p) and non-bonding (n) electrons.
The s electrons are associated with single covalent bonds. Since they are tightly bound, radiation
of high energy is required for their excitation. The excitation is from a bonding MO (s-MO) to an
anti-bonding (s* -MO) and the resulting transition is known as s ® s* transition. The electrons
associated with multiple bonds (double or triple bonds) are known as p -electrons. The p -electrons
are rather easily excited to the higher level. Here, the transition of an electron is from a bonding
pi MO (p MO) to anti-bonding pi MO (p*MO) resulting p ® p* transition.
If a molecule contains a hetero atom like nitrogen and oxygen etc., the hetero atom has unshared
electron pairs which are non-bonding in nature. These non-bonding electrons can be excited to
either s* MO or p* MO resulting n ® s* or n ® p* transitions. It is to be noted that s ® p* and
p ® s* transitions do not take place because these are Laporte forbidden. The absorbing species
involving s, p and n electrons mainly include organic molecules and inorganic anions such as
nitrate, nitrite and carbonate anions, etc. The various energy levels and electronic transitions are
shown in Figure 11.5. The energy required for various transitions obey the following order
s ® s* > n ® s* > p ® p* > n ® p*
Figure 11.5 Various energy levels and types of electronic transition.

s s* transition
This transition can occur in compounds in which all the electrons are involved in the formation of
single bonds (s -bond only) and there is no lone pair of electron. Example of such transitions are
saturated hydrocarbon like methane, ethane, etc. Such transition requires radiation of very short
wavelength (less than 150 nm or high energy). The usual spectroscopic measurement cannot be
done below 200 nm, since oxygen (present in air) begins to absorb strongly. To study such high
energy transition (below 200 nm), the entire path length must be evacuated. Thus the region of
transition below 200 nm is called vacuum ultraviolet region. The region is less informative. Methane
which contains only C H, s -bond can undergo s ® s* transition exhibiting absorption peak at
125 nm. Ethane has an absorption peak at 135 nm which also must arise from the same type of
transition but here electrons of C C bond appear to be involved. Since the strength of the
C C bond is less than that of C H bond, less energy is required for excitation, as a result,
absorption occurs at lower wavelength. Thus organic molecules in which all the valence shell
electrons are involved in the formation of s -bonds do not show absorption in the normal ultraviolet
region, i.e. 180400 nm.
n s* transition
This types of transitions takes place in saturated compound containing one hetero atom with
unshared pair of electrons. Examples of such transitions are saturated alkyl halides, alcohols,
ethers, amines, etc. Such transition is brought about by radiation in the region of 150 to 250 nm.
The absorption data for some typical compounds involving n s * transition are given below.
Compounds lmax(nm) emax

Water 167 1480
CH3OH 184 150
CH3OCH3 184 2520
(CH3)3N 227 900
The molar absorptivities (e) for this type of absorption are intermediate in magnitude and
usually in the range 1003000 molel lit cm1.
In saturated alkyl halides, the energy required for such a transition decreases with the increase
in the size of halogen atom (or decrease in the electronegativity of the atom). For example, the n
electrons on chlorine atoms are comparatively difficult to excite. The absorption maximum (lmax)
for methyl chloride is 172175 nm whereas that for methyl iodide is 258 nm as n electrons on
iodine atom are loosely bound because of its increase in size and less electronegativity value.
emax is also higher compared to methyl chloride. Similarly amines absorb at higher wavelength as
compared to alcohol and hence the extinction coefficient for amines will be larger.
Thus, when absorption measurements are made in UV-region, compounds such as aliphatic
alcohol and alkyl halide are commonly used as solvent, because they start to absorb at 260 nm.
However, these solvent cannot be used when measurement are to be made in 200260 nm.
In such cases saturated hydrocarbons which only give rise to s - s* transition must be used.
However, the drawback is that these are poor solvating agent.
p p* transition
This type of transition occurs in the unsaturated centres of the molecules, i.e. in compound
containing double or triple bond and also in aromatics. Examples of such transitions are alkenes,
alkynes, carbonyl compounds, cyanide, azo compounds, etc. The excitation of p electrons requires
smaller energy and hence, transition of this type occurs at a longer wavelength within the
region of UV-spectrophotometer. In unconjugated alkenes, absorption bands appear around
170190 nm. In carbonyl compounds, the band due to p p* transitions appears at around 180 nm
and is more intense, i.e. the value of molar extinction coefficient is high. The introduction of alkyl
group to the olefinic linkage shifts the position of the band to longer wavelength by 35 nm per
alkyl group. The shift depends on the type of the alkyl group and the stereochemistry about the
double bond.
n p* transition
This type of transition can occur in unsaturated bond containing at least one hetero atom like O,
N, S and halogen with n electrons. Examples of such transition are aldehydes and ketones, etc.
This type of transition requires least amount of energy out of all the transitions discussed above
and hence occurs at longer wavelength. Saturated aldehydes (C == O) show both types of transitions,
i.e. low energy n ® p * and high energy p ® p * occurring around 290 nm and 180 nm respectively.
In aldehydes and ketones n ® p * transition arises from excitation of a lone pair of electrons in a
2p orbital of oxygen atom with the anti-bonding p orbital of carbonyl group. When hydrogen is
replaced by alkyl group as in ketone, this results in shift of band to shorter wavelength. Besides
the above transition, a high energy but quite intense p ® p * transition also occurs in carbonyl
compounds. However, the molar extinction coefficient (e) values associated with n ® p * transition
are generally low and range from 10 to 100 while values for p ® p * transitions, on the other hand,
normally fall in the range between 1000 and 10000. The various types of transitions taking place
in carbonyl compounds are summarized below.
High energy transition
(i) n ® s* (intense)
(ii) p ® p* (intense)
Low energy transition
n ® p* transition (weak or less intense)
In order to characterize n ® p * transition, two methods are used. These are
1. Acid addition method: The electronic spectral band due to n ® p * transition generally
disappears due to addition of acid to the solution. This is because of the formation of bond
between acidic proton and lone pair of the electron on the hetero atom. Interesting example
is the disappearance of the band due to n ® p * transition in pyridine on addition of acid
due to formation of pyridinium ion.
2. Comparison method: By comparing the spectrum of a compound containing hetero
atom with unshared pair of electron with a similar compound not containing hetero atom,
np * transition can be detected. An interesting example is when a spectrum of pyridine is
recorded it exhibits a band with lmax at about 300 nm. On the other hand, the spectrum of
benzene does not exhibits this band. This may arise due to promotion of a lone pair of
electron on the nitrogen atom into anti bonding p * orbital of aromatic system.
Summary of various electronic transitions
The probable transitions and the regions where the various electronic transitions take place are
stated below for easy understanding.
Nature of transitions Absorption range emax
lmax (in nm)
s ® s* transition 125150 nm
n ® s* transition 150200 nm 1004000
p ® p* transition 170200 nm 10001000000 (very high)
n ® p* transition 200700 nm 10100 (very low)
A number of inorganic anions exhibit lmax in the UV region due to n ® p* transitions, e.g.
NO3– (313 nm), CO32– (217 nm) and NO 2– (360 nm).
PROBLEM 11.5 The lmax (in nm) and emax values of the following organic compounds are
given below. Identify the electronic transition for each.
Compounds lmax e max
(a) 1-hexanethiol 224 126
(b) n-butyl iodide 257 486
(c) Ethylene 165 10,000
(d) Acetylene 173 6,000
(e) Acetone 190 1,860
280 15
(f) 1, 3-butadiene 217 21,000
(g) 1, 3, 5-hexatriene 258 35,000
(h) Ethane 135
Solution For
(a) n ® p*, (b) n ® s*, (c) p ® p*,
(d) p ® p*, (e) n ® s*, n ® p*, (f) p ® p*,
(g) p ® p*, (h) s ® s*
PROBLEM 11.6 The UV spectrum of nitrite ion shows three absorption bands at
lmax = 354.6 nm emax = 23
lmax = 210 nm emax = 5380
lmax = 287 nm emax = 9
Identify the electronic transition for each.
Solution The band at lmax = 354.6 nm, emax = 23 is due to n ® p* transition involving oxygen
lone pair. The band at lmax = 210 nm, emax = 5380 is assigned due to p ® p* transition and another
weak band at lmax = 287, emax = 9 is assigned as another n ® p* transition involving oxygen lone
pair.
11.4.2 Absorbing Species Involving d or f Electrons

In transition metals (d-block elements) there are incomplete d orbitals. The ligand fields created
by the ligands cause splitting of d orbitals. For example, in octahedral field, the penta degenerate
d orbitals get split up to three-fold degenerate, t2g and two-fold degenerate, eg set by D(10 Dq)
called crystal field splitting energy as shown in Figure 11.6. On being excited, the electron in t2g
orbitals absorbs energy equal to the crystal field splitting energy and moves to eg orbitals in
octahedral field. Since the values D is low, absorption takes place in the visible region, as a result,
transition metal complexes are coloured. Such type of transitions is called d-d transition as t2g and
eg set belong to the same d orbitals. For the f -block elements, transitions are also possible due to
f orbital electrons. However, the band obtained due to f-f transition is narrow due to screening of
inner orbitals from external influence. However, such transition is Laporte forbidden as reflected
from the low values of emax.
Figure 11.6 Octahedral crystal field splitting of five-fold degenerate d-orbital.
Depending upon the capacity of splitting, i.e. D, ligands are arranged in a series called
spectrochemical series as shown below.
I < Br < Cl < F < OH < Oxalate 2 < H 2 O < SCN < NH 3 < CO < NO 2 < CN
In this series, the ligands are arranged in order of their field strength, i.e. in order of Dq values. As
Dq increases, lmax decreases as exemplified below since Dq is inversely proportional to lmax.
[(Ni Cl6 ) 4 ] (1370 nm), [(Ni(NH 3 ) 6 ]2+ (925 nm)

[Ni(H 2 O)6 )]2+ (1279 nm), [Ni(en)3 ]2+ (863 nm)
11.4.3 Charge Transfer Spectral Absorption

In such case absorbing species should contain both electron donor and electron acceptor. A change
transfer is always followed by a change in the dipole moment, hence such transitions are allowed
and occur with high intensity (1000 to 10,000). If the separation between the states is more,
the transition may occur in the UV region. But in many cases the change transfer transition involves
low energy and occurs in the visible region making the compounds coloured. For example, in
MnO –4 and Cr2 O7 , the central metal ions are Mn+7 and Cr+6 with no unpaired electrons.
2–
They, however, show purple and orange colours. This is because of charge transfer form
O2 to Mn+. As the charge on a metal ion goes on increasing, its electronegativity increases, hence
transfer of electrons form O2 takes place at lower energy leading to absorption in visible region
resulting in the colour of the above ions. Such phenomena may also take place in metal halides.
For example, charge transfer from less acidic I is easier and this is the reason as to why some
metal iodides are coloured, e.g. AgI. The colours in cadmium, arsenic and antimony sulphides are
also due to charge transfer from sulphide ion to the metal ion. In organic molecules like N-methyl
pyridium iodide, there is also a charge transfer from I to N-methyl pyridium ion.
C-T band is more intense than d-d band as the former band is the allowed band as per selection
rule.
11.5 TYPE OF ABSORPTIONS BANDS
The following types of bands originate as a result of the possible transitions in a compound.
11.5.1 K-Bands
K-bands originate due to p ® p* transitions and appear in the spectra of molecules containing
conjugated p systems such as butadiene or mesityl oxide. Such bands may also appear in aromatic
molecules possessing chromophoric substitution-styrene, benzaldehyde, or acetophenone.
The values of e max of K-bands are usually more than 104 and hence are allowed bands.
The K-bands absorption due to diene or polyene systems are unresponsive to change in solvent
polarity as the hydrocarbon double bonds are non-polar whereas due to enones, the K-bands
undergo a bathochromic shift (red shift) accompanied by increasing intensity as the polarity of
the solvent is increased. The red shift presumably results from a reduction in the energy level of
the excited state accompanying dipole-dipole interaction and hydrogen bonding. Shifting of band
position to higher wavelength is known as bathochromic shift (or red shift).
11.5.2 R-Bands
Such types of bands originate due to n ® p* transition of a single chromophoric group such
as carbonyl or nitro group and having at least one lone pair of electrons on the hetero atom.
These are less intense with e max values less than 100. Hence R-bands are called forbidden bands.
Compounds exhibiting R-bands include acetaldehyde, acrolein, acetophenone, methyl vinyl ketone,
crotonaldehyde, etc. These are further characterized by the hypsochromic or blue shift observed
with an increase in solvent polarity. Shifting of band position to shorter wavelength is known as
hypsochromic shift or blue shift.
11.5.3 B-Bands (Benzeneoid Bands)

Such type of bands arise due to p ® p* transition in aromatic or hetero aromatic compound.
For example, benzene shows a broad absorption band containing multiplate peaks or fine structure
in the near UV region between 230 and 270 nm (e of most intense peak at 255 nm). The fine
structure arises from vibrational sublevels affecting the electronic transition. When a chromophoric
group is attached to an aromatic ring, the B-bands are observed at longer wavelength than the
more intense K-bands. For example, styrene has p ® p* transition at l max 244 nm (emax 12,000),
and a B-band at l max 282 (e max 450). When an n ® p* transition appears in the spectrum of an
aromatic compound that contains p ® p* transition (including B-bands), the R-bands due to
n ® p* transition is shifted to longer wavelengths. For example, in acetophenone the R-bands
appears at 319 nm e max 50, while K and B bands appear at 240 and 278 nm respectively. The fine
structure of B-bands may be absent in the spectra of substituted aromatic compounds. It is also
destroyed by the use of polar solvent.
11.5.4 E-Bands (Ethylenic Bands)

Such bands originate due to electronic transitions in the benzenoid systems with three ethylenic
bonds which are in closed cyclic conjugation. These are further characterized by E1 and E2 bands,
which are observed near 180 nm and 200 nm, respectively in case of benzene. Auxochromic
substitution (discussed in Section 11.6.2) brings the E2 band near the ultraviolet region, although
in many cases it may not appear at wavelengths over 210 nm. In auxochromic substitution, the
heteroatom with the lone pair of electrons shares these electrons with the p -electron system of the
ring, facilitating the p ® p* transition and thus causing a red shift of the E-bands. The molar
absorptivity of E-bands generally varies between 2000 and 14,000.
PROBLEM 11.7 Assign the types of absorption bands possible in the following compounds.
(a) 1, 3-butadiene 217 21.000
(b) 1, 3, 5-hexatriene 258 35,000
(c) Acrolein 210 11,5000
315 14
(d) Benzene About 180 60,000
About 200 8,000
255 215
(e) Styrene 244 12,000
282 450
(f) Toluene 208 2,460
262 174
(g) Acetophenone 240 13,000
278 1,110
319 50
(h) Phenol 210 6,200
270 1,450
Solution
(a) K-bands due to p ® p* transition
(b) K-bands due to p ® p* transition
(c) K-bands due to p ® p* transition
R-bands due to n ® p* transition
(d) E1-bands due to aromatic p ® p* transition
E2-bands due to aromatic p ® p* transition
B-bands due to aromatic p ® p*transition
(e) K-bands due to aromatic p ® p* transition
B-bands due to aromatic p ® p* transition
(f) E2-bands due to aromatic p ® p* transition
(g) K-bands due to aromatic p ® p* transition
R-bands due to n ® p* transition
(h) E2-bands due to aromatic p ® p* transition
11.6 THE CONCEPT OF CHROMOPHORE AND AUXOCHROME
The absorption of radiation in the visible and UV regions depends primarily on the number and
arrangement of electrons in the absorbing molecules or ions. This led to the concept of chromophore
and auxochrome discussed below.
11.6.1 Chromophore
It may be defined as covalently bonded unsaturated group of atoms responsible for the absorption
of radiation in the visible and UV region. Two types of chromophores are known in organic
molecules.
(i) Chromophores which contain the p-electrons only and undergo p ® p* transitions.
Such chromophores contain unsaturated (double or triple) bonds such as ethylenic group,
(C == C) and acetylenic group (C ºº C).
(ii) Chromophores which contain both p-electrons and n(non-bonding) electrons. Such
chromophores undergo two type of transitions, i.e. p ® p* and n ® p*.
Examples of this type include carbonyl group, (azo group (N == N), nitrile
(C ºº N), nitro groups (NO 2), carboxyl, amido, azo methane, nitrate and nitrite group
(ONO), etc.
PROBLEM 11.8 Assign the possible chromophoric group and probable transition present in
the following compounds for which the values of lmax and emax are given.
(a) Acetaldehyde 290 16
(b) Acetone 188 900
279 15
(c) Acetic acid 204 60
(d) Acetamide 208
(e) Acetoxime 190 5,000
(f) Acetonitril 160

(g) Azomethane 347 4.5
(h) Ethyl nitrite 270 12
(i) Nitromethane 171 18.6
(j) Amyl nitrite 218.5 1,120
346
(k) Ethylene 165 15,000
(l) Acetylene 173 6,000
Solution
(a) Carbonyl chromophore n ® p* transition
(b) Carbonyl chromophore p ® p* and n ® p* transition
(c) Carboxyl chromophore n ® p* transition
(d) Amido chromophore n ® p* transition
(e) Azomethine chromophore p ® p* transition
(f) Nitrite chromophore p ® p* transition
(g) Azo chromophore n ® p* transition
(h) Nitrite chromophore n ® p* transition
(i) Nitro chromophore n ® p* transition
(j) Nitrite chromophore p ® p* and n ® p* transition
(k) Ethylene chromophore p ® p* transition
(l) Acetylene chromophore p ® p* transition
11.6.2 Auxochrome
The term auxochrome applies to an atom or group of atoms which does not give rise to absorption
band of its own, but changes the absorption characteristics of chromophore (both intensity and
wavelength) when conjugated to it. Some of the important characteristics of auxochrome are:
(i) An auxochrome does not give rise to absorption band of its own but when conjugated to
a chromophore, both the intensity and wavelength of absorption band are changed.
(ii) It may be an atom or group of atoms.
(iii) It is colour enhancing group.
For example, absorption maxima of benzene is 255 nm (e max = 203). When an auxochrome
like amino group is substituted in benzene as in aniline, its absorption maximum shifts to longer
wavelength at 280 nm and e max becomes higher (e max = 1430). The effect of the auxochrome is
due to its ability to extend the conjugation of a chromophore by sharing of its non-bonding electrons.
Thus an auxochrome must have at least one atom with unshared pair/pairs of electrons.
Such atoms are generally present in the molecule in the form of a polar group like O H,
NH2, OCH3 or halogen atom (X), etc.
Another example is chloroethylene CH2 ==CHCl in which the C==C group is chromophore
and halogen (chlorine) atom is an auxochrome. Substitution of hydrogen atom in ethylene by a
halogen atom causes shift of position of band toward longer wavelength and also increases the
intensity of absorption band.
11.7 SHIFTING OF ABSORPTION BAND AND CHANGE IN INTENSITY
The wavelength and intensities of the absorption bands due to chromophore are sensitive to nature
of the solvent, inductive effect and pH, etc. It is useful to define the following terminology with
regard to change in wavelength and intensity.
11.7.1 Terminology Used in UV-visible Spectroscopy

Bathochromic shift
A shift of l max to longer wavelength (also called red shift) due to the presence of an auxochrome
or change of solvent. The n ® p* transition for carbonyl compounds experience bathochromic
shift when the polarity of solvent is decreased.
Hypsochromic shift
A shift of l max to shorter wavelength (also called blue shift). It may arise due to removal of
conjugation or change in polarity of the solvent.
Hyperchromic shift
Increase in the intensity of an absorption band usually with reference to emax. The introduction of
an auxochrome increases the intensity of absorption band.
Hypochromic shift
Decrease in the intensity of an absorption band with reference to the value of e max.
The absorption and intensity shifts are shown in Figure 11.7. The introduction of group which
disturbs the geometry of a group causes such type of shift.
Figure 11.7 Absorption and intensity shift.
The following factors influence the values of lmax and e max.

11.7.2 Effect of Conjugation of Chromophore

According to MO theory, p electrons can further be delocalized by the conjugation process.
The effect of this delocalization is to lower the energy level of p* orbital and hence to shift the
absorption maximum to longer wavelength. Some typical examples are
Examples Chromophore nm max
Ethylene 171 15530 p ® p*
Butadiene 217 20900 p ® p*
Acetaldehyde 180 10000 p ® p*

290 17 n ® p*
Crotonaldehyde 218 18000 p ® p*
320 30 n ® p*
Acetic acid 208 32 n ® p*
Crotonic acid 206 13500 p ® p*
242 250 p ® p*
Here p ® p* transition is one that corresponds to C == C system of the molecules.
Thus, when the chromophores are separated in a molecule by only single bond, conjugation
occurs. In other words, in conjugated systems there are alternate multiple bonds such as,
C == C C == C C == C or C == C C == O system. The effect of conjugation can
also be illustrated by observing that the wavelength of absorption maximum (l max) is 265 for
divinyl ethylene CH2 == CH CH == CH CH == CH2, where as for non-conjugated counterpart
such as diallyl (CH2 == CH CH2 CH2 CH == CH2), is 180 nm. In case of extensive
conjugation, i.e. when the molecule contains a number of conjugated double bonds, the wavelengths
of absorption maxima become sufficiently high and hence the absorption occurs in the visible
region and the compounds appear coloured. For example, a-carotene, with ten conjugated double
bonds absorbs the violet portion of visible radiation (l max = 445 nm) and hence red in colour,
similarly b-carotene with eleven conjugated double bonds is yellowish green in appearance and
absorb in the region of 420 480 nm.
A system containing two double bonds in conjugation may be cis isomer or trans isomer.
The cis isomer absorbs at a lower wavelength as compared to trans isomer due to slight decrease
in conjugation because of crowding.
11.7.3 Additive Characteristics

When a molecule contains two or more chromophores separated by more than one single
bond, the absorption of radiation by the molecules become additive. In other words, the total
absorption is the sum of absorption characteristic of each chromophore. For example, diallyl
CH2 == CH CH2 CH2 CH == CH2 contains two ethylinic linkages separated by three single
bonds. It absorbs radiation about the same wavelength as ethylene but the amount of radiation
absorbed for similar concentration is approximately double that of ethylene.
11.7.4 Effect of Aromatic Rings

In aromatic system, the benzene ring is the simplest chromophore. Two or more benzene rings in
conjugation giving rise to polycyclic compounds result in the absorption of radiation corresponding
to higher wavelengths in the visible region. For example, the corresponding values of l max for
benzene, naphthalene and anthracene are 268, 311 and 476 nm respectively. But when the
chromphores are substituted into the benzene nucleus, the resulting compounds have different
absorption spectrum from that of benzene itself and the substituent chromophores. This arises
because of mutual electrostatic interaction between the chromophores. Compounds with the same
number of carbon atoms as that in benzene, but with double bond arranged as in benzoquinone
are much more effective chromophores than the benzene itself. For example, phenolphthalein
possesses different structures in acidic and basic solution, as shown below.
Phenol phthalein in acidic and basic medium
It is because in basic solution (because of extended conjugation) the entire anion forms a
chromophore whereas in acidic solution, the molecule contains three separate benzene rings (here
conjugation is not extended) and hence less chromophoric.
11.7.5 Effect of Substitution of Auxochrome

As discussed earlier, auxochrome causes a bathochromic (red) shift of lmax and hyperchromic
shift in the intensity of absorption band.
For example, the benzene ring is much less effective as a chromophore. But substitution of
some polar groups into the benzene nucleus increases the wavelength of absorption maxima in
the visible region and hence also the absorption value. The effect of some auxochromes on the
absorption characteristic of benzene in solvent hexane are as follows.
Effect of auxochromes on benzene chromophore in solvent haxene

Auxochrome Compound l max emax
Benzene 256 250
NH2 Aniline 280 200
OH Phenol 275 200
Cl Chloro benzene 265 360
Br Bromo benzene 245 295
11.7.6 Effect of Solvent Polarity

The polarity of the solvent has pronounced effect on the position and intensity of bands arising
due to n ® p* and p ® p* transitions. In fact, the shifts exhibited by the bands on increasing the
polarity of the solvent can be used to identify the type of transition.
Effect of solvent polarity on n ® p* transition
The effect of solvent on the absorption characteristics has been illustrated below by taking mesityl
oxide (4-methyl-3-pentene-2-one) as an example.
Solvent l max e max Transition
Hexane 230 12,600 p ® p*
329 47 n ® p*
Water 243 10,000 p ® p*
303 60 n ® p*
These data indicate that the wavelength due to n ® p* absorption is shifted by 26 nm to shorter
wavelength (higher energy) in the more polar solvent. Thus increase in polarity of solvent causes
a hypsochromic shift (blue shift) for n ® p* band.
Causes of hypsochromic shift of n ® p* transition in polar solvent
The solvation is most effective with polar hydrolytic solvent like water or alcohol in which hydrogen
bond formation between the solvent proton and non-boned electron pair is extensive. As a result
the energy of the n-orbital is lowered by an amount approximately equal to the energy of hydrogen
bond as diagrammatically represented in Figure 11.8(a). A blue shift, also roughly corresponding
to the energy of hydrogen bond, is therefore, observed. The effect of solvent polarity on p ® p*
transition is just opposite to that of n ® p* transition. Thus the band at 230 nm in hexane is shifted
to 243 nm in water. The increase in polarity in this case has caused a bathochromic shift
(red shift).
Effect of solvent polarity on p ® p* transition
The effect of solvent on the absorption characteristics has also been illustrated by taking mesityl
oxide (4-methyl-3-pentene-2-one) as an example.
These data as mentioned above indicate that the wavelength due to p ® p* bsorption is shifted
by 13 nm to higher wavelength (lower energy) in the more polar solvent. Thus increase of polarity
of solvent causes a bathochromic shift. (red shift) for p ® p* band.
Causes of bathochromic shift of p ® p* in polar solvent
This is due to fact that p* orbital is more polar than the p orbital and then p* orbital is stabilized to
a greater extent in the presence of a polar solvent as shown diagrammatically in Figure 11.8(b)
resulting red shift.
Figure 11.8
11.7.7 Stereo Chemical Factors

Since co-planarity is essential for efficient overlap of p-orbitals, factors which affect the co-
planarity will influence the position and intensity of absorption maxima. Two common factors
are:
(a) Restricted rotation around single bonds and
(b) Absence of rotation around double bonds.
Restricted rotation around single bonds
The effect of hindered rotation around a single bond is best illustrated by the UV spectra of
diphenyls. The parent molecule diphenyl can readily achieve co-planarity since there is no restriction
for rotation about C C single bond between the two benzene rings. If larger groups are present
in ortho position, rotation at around the single bond is restricted and hence co-planarity cannot be
achieved, resulting in loss of conjugation. For example, in dimesityl, restricted rotation around
C C single bond causes loss of co-planarity.
It is seen that the loss of co-planarity results in a marked decrease in the value of molar
absorptivity.
Absence of rotation about double bonds
This is best illustrated by considering the data presented below for two compounds such as cinnamic
acid and stilbene which can exhibit geometrical isomerition.
Cis-isomer Trans-isomer
Compound l max emax l max emax
Cinnamic acid 168 10,700 272 15,900
Stilbene 278 9550 294 24,000
On each pair of geometrical isomers, the cis form would be expected to be more sterically
hindered and the trans form would be expected to achieve co-planarity of the p electron system
more readily.
11.8 APPLICATION OF UV-VISIBLE SPECTRAL METHOD
11.8.1 Structural Analysis

UV-visible spectra provide a valuable tool in the identification of unsaturated organic compounds
and in the elucidation of their structure. Information concerning a compound of unknown structure
can sometimes be obtained by a direct comparison of its absorption spectrum with those of model
compound of known structure. For example, investigation of the compound cannabidiol
(a substance isolated from Minnesota wild hemp), chemical evidence showed its structure to be
either A or B as shown in Figure 11.9. UV absorption spectra were determined for cannabidiol
and for the model compounds, 5-amylresorcinol and 4-amylcatechol (C and D respectively) in
Figure 11.9. It is seen that the spectrum of the unknown resembles C very closely whereas D is
Figure 11.9 Absorption spectrum of cannabidiol compared to those of certain phenol.

quite different. This observation provides strong evidence in favour of A rather than B for the
structure of cannabidiol.
11.8.2 Empirical Rules for Calculation of Absorption Maxima (lmax)

Woodward and Fieser formulated certain empirical rules for calculation of l max for different
dienes, trienes (polyenes), Ketones and aldehydes as discussed below.
Wood wardFieser rules for l max for dienes, trienes (polyenes)
There are three types of systems under this category
Alicyclic dienes or diene These are contained in an open chain, where 1, 3 butadiene system
(C == C C == C) is present, the basic value is 217 nm.
Heteroannular diene A heteroannular diene means that the two double bonds in conjugation
are present in different rings.
Basic unit for such system is 214 nm.

Homoannular diene A homoannular diene means that the two double bonds in conjugation are
present in the same ring.
Basic unit for such system is 253 nm.

Exocyclic and endocyclic diene are shown in the following examples.
Double bond exocyclic to ring B
Double bond exocyclic to ring A
Double bond (A) as exocyclic to ring B and double bond (B) as exocyclic to ring A.
The creation of exocyclic double bond causes an additional bathochromic shift of 5 nm.
Increments for each substituent

1. Alkyl substituents or ring residue on the double bond causes bathochromic shift of 5 nm.
2. Each double bond with extended conjugation causes bathochromic shift of 30 nm.
3. The presence of polar groups auxochrome such as Cl, Br, OR, SR, etc. causes
bathochromic shift of l max as shown below.
Auxochromes Bathochromic shift

OR + 6 nm
SR + 30 nm
Cl, Br + 5 nm
NR2 + 60 nm
OCCH3 0
PROBLEM 11.9 Predict the l max values for the following compounds.
(a) (b) (c)
Solution
(a) Basic values = 217 nm
(2 × 5) = 10
2-alkyl substituent
227 nm
(b) Basic value = 217 nm
(2 × 5) = 10
2-alkyl substituent
227 nm
(c) Basic value = 217 nm
(1 5) 5
1-alkyl substituent
222 nm
PROBLEM 11.10 Predict the l max values for the following system.
(a) (b)
(c)
Solution
(a) Basic value 217 nm
2-alkyl substituent (2 ´ 5) = 10
(1 5) 5
1-exocyclic bond
232 nm
(b) Basic value 217 nm
3-alkyl substituents 3 ´ 5 = 15
(1 5) 5
1 exocyclic bond =
237 nm
(c) Basic value of 217 nm
4-ring residue (4 ´ 5) = 20
(2 5) 10
2-exocyclic bond
247 nm
PROBLEM 11.11 Predict the l max for the following system.
(a) (b)
(c) (d)
Solution
(a) Basic value (heteroannular) 215 nm
2-ring residue (3 ´ 5) = 15 nm
(1× 5) = 5
1-exocyclic double bond
235 nm
(b) Basic value = 215 nm (hetero annular)
(1× 5) = 5
235 nm
(c) Basic value (homoannular diene) 253 nm
(1 5) 5
278 nm
(d) Basic value 253 nm
2-extended double bond (2 ´ 30) = 60 nm
3-exocyclic double bond (3 ´ 5) = 15 nm
(5 5) 25
5-ring residue
353 nm
Enones (a, b unsaturated ketone)
Woodward and Fieser framed certain empirical rules for estimating absorption maximum for a, b
unsaturated carbonyl compound. The l max is calculated for p ® p* transition. The rules are
summarized below.
Base value for a, b unsaturated Ketone (cyclic/six-membered) = 215 nm. For a compound
containing == CH COX; basic value is 215 if X is alkyl group.
(i) If X == H, the base value = 207 nm
(ii) If X == OH, the base value = 193 nm.
(iii) If double bond and carbonyl group in conjugation are present in five-membered ring,
then for a, b unsaturated Ketone, basic value = 202 nm.
Structural increment
(i) For each exocyclic double bond + 5 nm
(ii) Double bond extending conjugation + 30 nm
(iii) For a homoannular conjugated diene + 39 nm
(iv) For each double bond endocyclic in five or + 5 nm
seven-membered ring except cyclo-Pent-2-enone
For each alkyl substituent or ring residue at
a-position +10 nm
b-position +12 nm
g-position +18 nm
or d-position
or higher position
Increments (nm) for various auxochrome in the various a, b, g position are given below:
Auxochrome a b g d or higher
OH +35 +30 50
OAC +6 +6 +6 +6
Cl +15 +12
Br +25 +35
OR +35 +30 17 31
SR +85
NR2 +95
PROBLEM 11.12 Predict l max for the following system.
(a) (b)
(c) (d)
Solution
(a) Base value 215 nm
(2 12) 24
2-b-alkyl (substituent)
Omax 239 nm
(b) Base value 215 nm
2-b-alkyl (2 ´ 12) = 24 nm
(1 5) 5 nm
1-oxocyclic double bond
Omax 244 nm
(c) Base value 215 nm
Homoannular diene 39 nm
1-a ring residue (1 ´ 10) = 10 nm
1-d ring residue (1 ´ 18) = 18 nm
1-exocyclic double bond (1 ´ 5) = 5 nm
1-double bond extending (1 ´ 30) = 30 nm
lmax = 317 nm
(d) Base value 215 nm
1-b ring residue (1 ´ 12) = 12 nm
1-d ring residue (3 ´ 18) = 54 nm
2-for higher d
2-double bond extending conjugation (2 ´ 30) = 60 nm
(2 5) 10
O max 351 nm
Correction for change in the polarity of solvent
It may be noted that the value of l max is changed due to change in the polarity of the solvent i.e.
l max is solvent dependent. More polar solvent will experience hydrogen bonding with the carbonyl
group and p ® p* transition will experience blue shift. Solvent corrections may be noted as
follows.
Solvent Correction (n)

Ethanol 0
Methanol 0
Dioxane +5
Chloroform +1
Rule for calculating l max for devivaltius of acyl benzene

Like WoodwardFieser rules, Scott devised a set of rules for calculating l max for the derivatives
of acyl benzene. These rules help in estimating the position of absorption maximum in ethanol in
a number of monosubstituted aromatic ketones aldehydes, acids and esters.
For a compound of , the rules are summarized below:
(i) The basic value is 246 nm, if X is an alkyl group or alicyclic residue.
(ii) If X is halogen atom, the basic value becomes 250 nm.
(iii) The basic value is 230 nm, if X = OH or OR. The structural increment in nm for
further substitution on the aromatic ring in the Ortho, Meta and Para positions are given
below.
Auxochrome Increment in nm position of the substituent
Ortho Meta Para
Alkyl +3 +3 +10
OH, OR +7 +7 +.25
Cl 0 0 +10
Br +2 +2 +15
NH2 +13 +13 +58
NHCOCH3 +20 +20 +45
NR2 +20 +20 +85
O +11 +20 +75
PROBLEM 11.13 Predict l max for the following systems.
(a) (b)
(c)
Solution
(a) Basic value = 246 nm
1-PCl (1 ´ 10) = 10 nm
l max = 256 nm
(b) Basic value = 246 nm
1-mOH (1 ´ 7) = 7 nm
1-POH (1 ´ 25) = 25 nm
l max = 278 nm
(c) Basic value = 230 nm
1-PBromo (1 ´ 15) = 15 nm
l max = 245 nm
11.8.3 Additivity of Absorbance

In our discussion of Beers law, it was pointed out that the absorbance is proportional to the
number of particles which are effective in absorbing radiation at a specified wavelength. This can
be extended to cover the presence of more than one absorbing species in the same solution.
We can write A 6 Ai , where Ai represents the absorbance of a component, i which means
i
absorbance is an additive property. This relation presumes, of course, that there is no chemical
interaction between the solutes. The additivity of absorbance can be useful in a number of ways:
(a) It permits subtraction from an observed absorbance of the contribution due to solvent or
reagent, i.e. the familiar use of a blank.
(b) It also enables one to subtract from the spectrum of an unknown absorbance due to a
chromophore known to be contained there in order to identify a second chromophore.
For example, in Figure 11.10 curve a is the observed absorption spectrum of the
4-nitrobenzoate of the steroid 7-dehydrocholesteryl. To identify this ester from what it is,
the known spectrum b of another ester of the same acid (cyclohexyl-4-nitrobenzoate) is
subtracted from curve a. The resulting curve c is found to be essentially identical with
the spectrum determined on the free sterol itself.
Figure 11.10 UV absorption spectra of (a) 7-dehydrocholesteryl 4-nitrobenzoate, (b) cyclohexyl

4-nitrobenzoate, and (c) 7-dehydrocholestrol, determined by subtraction; solvent, n-hexane.
11.8.4 Multiple Analysis

The additive absorbance is also important in multiple analysis, e.g. for the simultaneous
determination of two or more absorbing substances as illustrated in Figure (11.11) in which curves
1 and 2 are the absorption spectra of pure components 1 and 2 respectively, whereas curve 3 is the
spectrum of a mixture.
Figure 11.11 Two-component analysis with a spectrophotometer.
In principle, n absorbance measurements at n different wavelengths are needed to determine

the concentrations of n components in a mixture. This procedure gives n independent simultaneous
equations in n unknowns. The molar absorptivities must be known. For example, in case of
two-component mixture, two simultaneous equations are required for two unknown concentrations
as given by the following equations.
The absorbance of curve 3 at lv will be given by
A3v = A2v + A1v = e2v lc2 + e1v lc1 (11.15)
And the absorbance of curve 3 at lu is given by
A3u = A2u + A1u = e2u lc2 + e1u lc1 (11.16)
where c1 and c2 represent the concentrations of two components in the mixture, A3v and A3u
represent the absorbance of the mixture at wavelength l v and lu respectively. A2v and A1v represent
the absorbance of the individual substances 2 and 1 respectively at wavelength lv corresponding
to their molar extinction coefficient e2v and e1v respectively. A2u and A1u also represent the
absorbance of the individual substances 2 and 1 respectively at wavelength lu corresponding to
their molar extinction coefficient e2u and e1u.
Thus, the two unknown concentrations are calculated by solving these two simultaneous
equations, which are obtained by measuring the absorbance of the mixture at two different
wavelengths.
The values of molar absorption coefficients can be deduced from the measurement of the
absorbances of pure solution of substances 1 and 2 by applying Lambert-Beers law, i.e.
A = e c l, and then by measuring the absorbance of the mixture at wavelength lu and lv,
the concentrations of the components can be calculated.
11.8.5 Determination of the pK Value of Indicator

Spectrophotometric study is well suited for the determination of the dissociation constant of
an acid-base indicator. Let us illustrate the method by the determination of acid dissociation
constant of methyl red (MR). The acidic (HMR) and basic (MR) forms of methyl red are depicted
below:
On applying the law of mass action, the dissociation constant K is defined by the equation
[H ] [MR ]
K=
[HMR]
[MR – ]
pK = pH log (11.17)
[HMR]
Form the above relation, the determination of pK involves the following steps:
(i) Both HMR and MR exhibit strong absorption peaks in the visible portion of the spectrum.
From these spectra, the wavelengths at which HMR(lA) and MR(lB) show maximum
absorption are determined.
(ii) Verification of Beers law for both HMR and MR at wavelengths lA and lB.
(iii) The relative amounts of HMR and MR present in a solution as a function of pH are
determined by using two equations.
AA = H A(HMR) [HMR] H A(MR – ) [MR – ] (11.18)
AB = H B(HMR) >HMR @ H B(MR ) [MR ] (11.19)
where H AHMR, H A(MR ) , H BHMR and H B(MR are molar absorptivity of HMR and MR at
wavelengths lA and lB respectively in a cell of 1cm path length. AA and AB correspond to
absorbance at wavelength lA and lB respectively. Solving the simultaneous Eqs. (11.18)
and (11.19), the ratio [MR] [HMR] can be obtained and then the pK value can be
calculated on substituting this value in Eq. (11.17), provided pH value is known.
11.8.6 Composition of the Coloured Complex

Consider the formation of a complex MnLp, where M is a metal ion and L is a ligand:
ZZX MnLp
nM + pL YZZ
The molar ratio of the two components of a complex is determined by spectrophotometric methods.
The important methods used are
(a) Yoes mole ratio,
(b) Jobs method of continuous variation, and
(c) Slope ratio method.
Yoes mole ratio method

In the mole ratio method as shown in Figure (11.12), the absorbance is measured for series of
solutions which contain varying amount of one constituent, i.e. either metal ion (M) or ligand (L)
with constant amount of the other. A plot of absorbance as a function of ratio of moles of ligand to
moles of metal ion at a particular wavelength gives a straight line passing through origin with
inflation at point of equivalence and then it becomes horizontal as all the metal cations are consumed
and addition of excess of ligand produces no more colour. The intersection of the extra plotted
linear segments determines the ratio of mole of ligand/mole of metal from which the composition
can be determined. Figure 11.12 shows the formation of 1 : 1 complex (ML).
Figure 11.12 Yoes mole ratio method.
Jobs method of continuous variation

One of the most generally applicable and widely used technique for elucidating the composition
of a complex is Jobs method of continuous variation. Suppose that a complex of composition
MnLp is formed from a metal ion (M) and a ligand (L) by the following equation.
ZZX MnLp
nM + pL YZZ
In order to determine p/n, a series of solutions are prepared in which the sum of the moles of
metal ion, M and the ligand L is the same for each solution. Thus total concentration of M and L is
kept constant while their ratios are continuously varying. Representing these concentrations by
TM and TL for metal ion and ligand respectively, we get
TM + TL = C (Total concentration)
A quantity x is defined in such a way that in any one of the series of solution TL = xC and
TM = (1 x) C
In any mixture of M and L,
Free metal ion concentration
[M] = (1 x) C n [MnLp]
Free ligand concentration
[L] = xC p [MnLp]
Obviously, the concentration of the complex will reach a maximum at a certain value of x.
This value of xmax can be obtained by setting d[MnLp]/dx = 0, which leads to p/n = xmax/(1 xmax)
(derivation given below). If the absorbance is measured at a wavelength, where the complex
absorbs but M and L do not absorb, the value of x at the point of maximum absorbance will
correspond to the maximum concentration of MnLp.
Accordingly, when the absorbance of the solution is plotted against x, at a particular
wavelength the ratio of stoichiometry coefficient (p/n) can be calculated. For 1:1 complex (ML),
the absorbance will pass through maximum at x = 0.5 i.e. p = n. If this complex has formula ML2,
the maximum will occur at x = 0.67. If the formula is M2L, the maximum will be found at x = 0.33.
In Figure 11.13, the continuous variation plot for the 1:1 complex (ML) is given.
Figure 11.13 Jobs method of continuous variation for 1:1 complex.
Derivation for p/n = xmax/1 xmax

ZZX MnLp
nM + pL YZZ
[ M n Lp ]
K=
[ M ]n [ L] p
K[M]n[L]p = [MnLp]
Taking derivative of [M], [L] and [MnLp] with respect to x, we get
Ë d [L] d [M ] Û d[M n Lp ]
K Ì[ M ]n p[ L ] p 1 n[ M ]
n 1
[ L] p Ü =
Í dx dx Ý dx
d[M n Lp ]
For xmax, =0
dx
d [ L] d [M ]
\ [ M ]n p[ L] p 1 n[ M ]n 1[ L ] p =0
dx dx
Dividing the above equation by [M]n 1[L]p 1, we get
d [ L] d [M ]
p[ M ] n[ L] =0
dx dx
We know, [M] = (1 x) c n[MnLp]
d[M ] d [M n Lp ]
= c n c
dx dx
d [ L] d [M n Lp ]
Again, [L] = xc p[MnLp], = c p c
dx dx
d [M ] d [ L]
Substituting the value of and in the above equation, we get
dx dx
p[M]c + n[L] (c) = 0
p[(1 xmax) c n[MnLp]] = n[xmax c p [MnLp]]
p(1 xmax) = n xmax
p x
or =
n 1 x
PROBLEM 11.14 To determine the formula for the complex between Fe2+ and o-penanthroline,
a series of solutions was prepared in which the total concentration of metal and ligand was held
constant at 3.15 104 M. The absorbance of each solution was measured at a wavelength of
510 nm. Using the following data, determine the formula for the complex.
XL Absorbance XL Absorbance
0.0 0.000 0.6 0.693
0.1 0.116 0.7 0.809
0.2 0.231 0.8 0.693
0.3 0.347 0.9 0.347
0.4 0.462 1.0 0.000
0.5 0.578
Solution To determine the formula of the complex, we plot absorbance versus the mole fraction
of ligand, obtained the result shown in the graph.
The maximum absorbance is determined by extrapolating the two linear portions of the plot.
The intersecting of the extrapolated lines corresponds to a mole fraction of ligand of 0.75. Solving
for the value of y gives
XL 0.75
y 3
1 XL 1 0.75
And the formula for the metal-ligand complex is Fe(o-phenanthroline)32+.
Slope ratio method
If the complex formation proceeds according to the reaction
ZZX MnLp
nM + pL YZZ
In this method two sets of solutions are prepared. The first set consists of fixed concentration of L
but much greater than the variable concentration of the metal ion. The concentration of the complex
formed will be proportional to CM, as given below.
[MnLp ] = CM/n
If the absorbance due to other species besides MnLp is ignored, the absorbance of the solution
CM
will equal to A H· (e being the molar absorption coefficient of the complex and 1 cm is the
n
H
cell length). The plot of absorbance against CM will be a straight line with slope equal to .
n
A second set of solution is prepared with a fixed concentration of metal ion but in large excess
than the variable concentration of the ligand. Under this condition we may assume that all the
ligand is complexed and the concentration of the complex formed will be proportional to CL,
as given below
[MnLp ] = CL/p
CL
The absorbance of the solution will equal to A H · (e being the molar absorption coefficient
p
of the complex and 1 cm is the cell length). The plot of absorbance against CL will be a straight
H
line with slope equal to .
p
1 1
Since the ratio of the slopes in these two cases is : , i.e. p : n, then the ratio M : L of the
n p
complex can be evaluated. However, if more than one complex is formed at the same time,
the method becomes inapplicable, since the concentration of the complex in this case is not directly
proportional to the analytical concentration of the components in either cases.
11.8.7 Quantitative Analysis

For determination of the concentration of a substance, wavelength of its maximum absorption is
selected. The absorbance of the solution of the compound is measured for different concentrations
of the solution known as standard solution. Then absorbance is plotted against the concentration
of the solution which produces a straight line. This plot may be used as a calibration curve for
unknown sample. The solution of the unknown sample is put on the spectrophotometer and its
absorbance is measured. Corresponding to this absorbance the concentration of unknown sample
can be measured from calibration plot as shown in Figure 11.14.
Figure 11.14 Calibration plot.
11.8.8 Detection of Impurities

UV absorption spectroscopy is one of the best methods for detecting impurities especially in
organic compounds. For example, in nylon manufacture, the starting materials like adipic acid
and hexa methylene diamine should be very pure. If the starting materials are not pure, the nylon
obtained will be of very poor quality. The purity of these materials can be tested by UV absorption
spectroscopy. Traces of unsaturated and aromatic impurities can be detected because the starting
materials are transparent at the near UV-region.
11.8.9 In Tautomeric Equilibria

UV spectroscopy can be used to determine the various keto and enol forms present in tautomeric
equilibrium. The best example is that in ethyl aceto acetate where the equilibrium is
The keto form has l max = 275 nm and C = 16 and there is only the weak n ® p* band of the
isolated carbonyl group. On the other hand, enol form has l max = 244 nm and C = 1600. Thus
from the strength of the 244 nm band, one can measure the proportion of tautomerst present in the
ethyl aceto acetate.
Besides the above, UV-visible spectral method can also be applied to chemical kinetics,
molecular weight determination, spectrophotometric titration, octahedral-square planner equilibria,
square-planar-tetrahedral equilibria, geometrical isomerisation etc.
11.9 SOME MORE PROBLEMS INVOLVED IN UV-VISIBLE SPECTRAL

METHOD
PROBLEM 11.15 Explain how the ultraviolet spectrum can be used to decide between the
following isomeric system.
(a) (b)
(c) (d)
Solution
l max for (a) Base 214 nm
Extent 30 nm
No. of alkyl group 2 ´ 5 = 10 nm
254 nm
l max for (b) Base 214 nm
Substituent 5 nm
219 nm
l max for (c) Base 253 nm
Substituent 5 ´ 3 = 15 nm
268 nm
l max for (d) Base 253 nm

1-extended conjugation 30 nm
Substituent 3 ´ 5 = 15 nm
298 nm
PROBLEM 11.16 Develop equation for the spectrophotometirc determination of the
concentration of three substances present in a solution if the substance have the following specific
absorptivity at the following wavelengths. Express concentration in milligrams per millilitre.
Let the cell thickness be 1 cm.
Substance Wavelength
400 nm 500 nm 600 nm
A 0 0 1.00
B 2.00 0.05 0
C 0.60 1.80 0
Solution For substance A, specific absorptivity at 600 nm = 1 only. Hence absorbance Al = 600
= CA · CA · l
When l = 1 cm
AO 600 AO 600
CA AO 600
a 1
\ CA = Al = 600
For substance B and C.
Molar absorptivity at l = 400 are 2 and 0.6 respectively whereas the respective values at
l = 500 nm are 0.05 and 1.8. The concentration of B and C can be determined by using simultaneous
equation for l = 400 nm.
Al = 400 = al = 400 For B ´ [B] + al = 400 for C ´ [C] = 2 ´ [B] + 0.6 [C] (1)
Al = 500 = al = 500 For B ´ [B] + al = 500 for C ´ [C] = 0.05[B] + 1.8 [C] (2)
Solving both the equations,
[B] = (3 Al = 400 Al = 500)/5.95
[C] = (40 Al = 500 Al = 400)/71.4
PROBLEM 11.17 At a wavelength of 356 nm, the molar absorptivity of a phenolic compound
in 0.1 M HCl is 400, in 0.2 M NaOH is 17,100. In pH 9.50 buffer, the molar absorptivity is 9800.
Calculate the pK of the phenolic compound.
Solution Let the phenolic organic compound in 0.1 M HCl (in acidic medium) be represented
at RH whereas the same compound in alkaline medium be represented as R. The following
equilibrium exist
ZZX R + H+
RH YZZ
[R – ]
pK = pH log
[RH]
According to the problem molar absorptivity of RH, RH = 400, molar absorptivity of R,
R = 17100.
In pH 9.5 buffer, let the RH concentration be X, so that R concentration is 1 x, where the
molar absorptivity of the solution under this condition is 9800
Using simultaneous equation
9800 = 400[RH] + 17100[R]
9800 = 400 x + 17100 (1 x)
Solving the equation
9800 = 400 x + 17100 17100 x
or 16700 x = 17100 9800 = 7300
7300
or x=
16700
7300 16700 7300 9400
Hence, 1 x = 1
16700 16700 16700
[R – ]
pK = pH log
[RH]
1 x
= 9.5 log
x
9400
= 9.5 log
7300
= 9.5 0.11 = 9.39
PROBLEM 11.18 An aromatic organic amine (R) have the following molar absorptivity.
Wavelength
280 nm 340 nm
Amine (R) 6607 2089
Amine in (RH+) 3020 0
Acidic form
The above amine buffered at pH 3.91 showed an absorbance of 0.44 and 0.080 respectively at
280 and 340 nm. What is the pKa of the RH+.
RH ZZZX
K
YZZZ
a
R + H+
[R] [H]+
Ka =
[RH + ]
According to the problem, using simultaneous equation
AA = eAR[R] + eARH [RH+]
AB = eBR[R] + eBRH [RH]
Here eAR = 6670 and eARH = 3020 and AA = 0.44, when lA = 280 nm
0.44 = 6607 [R] + 3020 [RH+] (1)
Similarly eBR = 2089 and eBRH = 0 and AB = 0.08, when lB = 340 nm
0.080 = 2089 [R] + 0[RH+] (2)
Hence
[R] = 0.080/2089
We know [R] + [RH] = 104 so [RH+] = .0001 0.080/2089 = 0.000062
[R]
Hence pKa = pH log
[RH + ]
0.000038
= 3.91 log
0.000062
= 4.12

(i) In polyne each double bond with extended conjugation causes bathochromic shift of
(a) 5 nm (b) 30 nm
(c) 15 nm (d) 10 nm
(ii) Basic value for a, b-unsaturated ketone(cyclic/six membered) is
(a) 215 nm (b) 207 nm
(c) 193 nm (d) none of these
(iii) Increase of polarity of solvent causes
(a) Hypsochromic shift for n p* band (b) Bathochromic shift for p p* band
(c) Hypsochromic shift for n p* band (d) Bathochromic shift for p p* band
(iv) Hypochromic shift indicates
(a) A shift of l max to longer wavelength
(b) A shift of l max to shorter wavelength
(c) Increase in the intensity of an absorption band
(d) Decrease in the intensity of an absorption band
(v) K-bands originates due to
(a) Conjugated p-system
(b) n p* transition of a single chromophore such as C == O or NO2 group
(c) p p* transition in aromatic or heteroaromatic compound
(d) None of these
(vi) Radiation source for visible spectrophotometer is
(a) Tungsten filament lamp (b) Nernst glower
(c) Xenon discharge lamp (d) Heated nichrome wire
(vii) Absorbance A is related to % of transmittance by the equation
(a) A = 2 + log %T (b) A = 2 log %T
(c) A = 2 + %T (d) A = 2 %T
(viii) The energy required for various electronic transition obey the following order
(a) s ® s * n ® s * p ® p* n ® p*
(b) s ® s * p ® p* n ® s* n ® p*
(c) n ® s * s ® s* p ® p* n ® p*
(d) s ® s * n ® s* n ® p* p ® p*
(ix) A typical example of a chromophore is
(a) (b) OH
(c) NH2 (d) Cl
(x) In the electromagnetic spectrum, the frequency range 7.5 ´ 1015 to 3.75 ´ 1014 Hz
corresponds to
(a) Visible radiation (b) Infrared radiation
(c) X-radiation (d) Microwave radiation
2. State whether the following statements are true or false, if false write the correct statements
(i) s ® s * transition does not occur in normal ultraviolet region, i.e., 180400 nm.
(ii) B-band is more intense than R-band.
(iii) Butadiene absorbs at 217 nm, corresponding to max 1000.
(iv) The wavelength of UV light is shorter than IR radiation.
(v) Auxochromic groups do not show characteristics absorption above 200 nm.
(vi) The n ® p* transition for carbonyl compounds experiences bathochromic shift when polarity
of the solvent is increased.
(vii) The n ® s * transitions are very sensitive to H-bonding.
(viii) In molecular species, the electronic spectra appears as band spectra.
(ix) u-u or g-g transition is Laporte allowed.
(x) Photovoltaic cell is a radiation detector.
(xi) Perkins-Elmer model-202 is a optical null double beam recording spectrophotometer.
(xii) 95% ethanol is used as polar solvent on UV-spectroscopic measurement.
(xiii) The band obtained due to f-f transition is broader than that obtained due to d-d transition.
(xiv) Auxochromes is a colour enhancing group.
(xv) Restricted rotation around a single bond causes marked decrease in the value of molar
absorptivity.
(xvi) A heteroannular diene means two double bond with extended conjugation are present in
different rings.
(i) Azo group chromophore shows .............. and .............. transitions.
(ii) The unit of molar extinction co-efficient is .............. .
(iii) .............. is used as the monochromator in single beam electronic spectrophotometer.
(iv) The l max due to .............. transition in mesityl oxide is more intense than due to ..............
transition.
(v) Among geometrical isomer, the l max of the .............. isomer is greater than of the ..............
isomer.
(vi) The detector used in the UV-spectrophotometer is .............. .
(vii) n ® p* transition takes place in compounds like.............., .............. and.............. .
(viii) An auxochrome group is called .............. .
(ix) A compound suffers blue shift due to .............. or .............. .
(x) Toluene absorbs at .............. compared to benzene due to the presence of .............. .
(xi) Butadiene absorbs at .............. nm corresponding to max value .............. .
(xii) The wavelength range for s - s* transition is .............. and the margin below 200 nm is
called .............. .
(xiii) n - s* transition occurs in the region .............. and max value for such transition less in
the range of .............. .
(xiv) The electronic transition involved in metal complexes gives rise to .............. .
(xv) The colour of cadmium sulphide is due to charge transfer from .............. to .............. .
(xvi) The value of max for K-bands are usually more than .............. and hence are ..............
bands.
(xvii) R-bands originate due to .............. transition whereas K-bands originate due to ..............
transition.
(xviii) B-bands originate due to .............. transition in .............. compounds.
(xix) The trans isomer absorbs at .............. wavelength with .............. intensity than the cis
isomer.
(xx) Normally the charge transfer transition occurs in which the metal is .............. and ligand is
.............. .
(xxi) The spectra of condensed ring systems are useful as .............. .
(xxii) Woodward rules give reliable results only for those compounds in which there is ..............
around the chromophore.
(xxiii) Trans cinnamic acid absorbs at .............. nm.
(xxiv) In case there is cross conjugation in a compound, then the value of absorption maximum is
estimated by considering .............. system.
(xxv) If the steric hinderance to coplanarity about a single bond is more than there is marked
.............. in intensity.

(i) Mention the range of near UV or quartz region in nm.
(ii) What is the limit of molar extinction coefficient?
(iii) Name the radiation source used in UV-visible spectrometry.
(iv) Give the example of a compound showing n ® p*, n ® s* transition.
(v) Why does conjugation shifts l max to longer wavelength?
(vi) Name some of the solvents used in UV-spectroscopy.
(vii) K-bands arise due to which type of electronic transition?
(viii) Mention the relation between probability of a transition and molar extinction coefficient.
(ix) What is the effect of H-bonding to UV absorption?
(x) What is the range of max for allowed transition? Is p ® p* transition is allowed or
forbidden?
(xi) What type of transition are observed in benzophenone?
(xii) Which of the following compound have higher l max?
(a) H2N C6H5
(b) Cl H3N+ C6H5
(xiii) Why is ethanol a good solvent in ultraviolet?

(i) Explain the origin and nature of E-bands.
(ii) Explain the concept of chromophore giving suitable examples.
(iii) Explain the concept of auxochrome. Mention some of its characteristics.
(iv) Write the terminology used in UV-visible spectroscopy in respect to shifting of absorption
band and change in band intensity.
(v) How would you distinguish between hyperchromic and hypochromic shift.
(vi) Explain additive characteristics of absorption of addition giving suitable examples.
(vii) Explain mutual electrostatic interaction between the chromophores giving suitable
examples.
(viii) Write a note on choice of solvent for UV-visible spectral measurement.
(ix) Write the mechanism involved in electronic transition.
(x) Write how electronic spectral band are displayed.
(xi) How would you study the following by spectrophotometric method
(a) Detection of impurities
(b) Tautomeric equilibria
(xii) Discuss the origin of UV-visible spectroscopy.
(xiii) What do you mean by absorbance, molar extinction co-efficient, transmittance, percentage
transmission. Establish a relation between them.
(xiv) Diagramatically show the various energy levels and electronic transitions. Arrange the
energy of the electronic transitions in decreasing order.
(xv) Give your comments on the UV spectrum of nitrite ion.
(xvi) Explain spectrochemical series. What is the advantages of this series?
(xvii) What is charge transfer absorption? Give your comment on the nature of such absorption.
(xviii) What are various types of possible electronic spectral band?
(xix) What is the effect of solvent polarity on K-bands in case of polyne system and enones.
(xx) Explain the nature of absorption bands exhibited by benzene.
(xxi) Explain the nature of absorption bands exhibited by aceto-phenone.
(xxii) How would you quantitatively analyze a sample by spectrophotometric method?
(xxiii) Mesityl oxide consists of two isomers (i) and (ii) as shown below. One isomer absorbs
maximum at 235 nm with = 12000 while the other shows no high-intensity absorption
above 220 nm. Which of the two isomers absorbs at 235 nm?
(i) (ii)
(xxiv) a-cyperone exists as (i) and (ii)
(i) (ii)
Using Woodwards rule, decide whether structure (i) and (ii) is consistent with observed
value of 252 nm.
(xxv) Predict the transition involved in
(a) Methyl chloride, (b) Methyl iodide,
(c) Methanol and (d) Trimethyl amine.
(xxvi) Amine absorbs at higher wavelength than alcohols. Why?
(xxvii) The position of absorption of acetone shifts in different solvents are: 279 nm in hexane,
272 nm in ethanol and 264.5 nm in water. Why?
(xxviii) Name the electronic transitions possible when UV light is absorbed by
(a) HCHO, (b) CH4 and
(c) CH3Cl
(xxix) What determines the wavelength of UV absorption by organic compound?
(xxx) The C == C generally produces an absorption band at about 18001900 Å while
group in aldehydes and ketones show absorption maximum near
27002900 Å. Why?
(xxxi) Predict the transition involved in the following compounds
(a) Alkenes, (b) Alkynes,
(c) Carbonyls, (d) Cyanides and
(e) Azo-compounds
(xxxii) Which type of transitions are considered to be the origin of charge transfer bands?
(xxxiii) Why the solvent like hexane produces fine structure?
(xxxiv) The complex [Ti(H2O)6]+ absorbs green and yellow light from the white light and appears
purple. Why?
(xxxv) Octahedral Co(III) complex, [Co(NH3)6]3+ appears pink in solution but Co(III) complex
[Co(CN6)]3 appears yellow. Why?
(xxxvi) Following the Woodward-Fieser rules, calculate the absorption maximum for each of the
following compounds:
(a) (b)
(c) (d)
(e) (f)
(xxxvii) Biphenyl shows the following ultraviolet absorption data. In its 2, 2¢-dimethyl derivative,
the absorption pattern becomes almost similar to o-xylene. Why?
19000 270
6. Give reasons
(i) When amino group is substituted in benzene as in aniline, its absorption maximum shifts
to longer wavelength and max becomes higher.
(ii) Band electronic spectrum is obtained for a molecular species.
(iii) The band due to f-f transition is narrower than that of d-d transition.
(iv) CH4 has absorption peak at 125 nm where ethane has an absorption peak at 135 nm though
both are saturated hydrocarbon.
(v) The absorption maximum for CH3Cl is 172 nm while that for CH3I is 258 nm though in
both cases the transitions are n - s*.
(vi) Compounds such as aliphatic alcohol and alkyl halides are commonly used as solvent in
UV-visible spectroscopy.
(vii) The bands occurring due to n - p*transition disappears on adding acid.
(viii) Pyrazine exhibits an electronic band at l max = 300 nm while benzene does not do so.
(ix) Transition metal complexes are coloured.
(x) MnO4 and Cr2O72 ions are coloured even though they do not contain unpaired electron.
(xi) R-bands are forbidden bands.
7. Discuss the various absorption laws involved in UV-visible spectral method. Derive
Lambert-Beers law.
8. Discuss the various electronic transitions involved in organic molecules. Write a note on
various electronic spectral bands. Give your comments on their origin and characteristics.
9. Discuss the effect of solvent polarity in
(i) n - p* transition,
(ii) p - p* transition
10. Draw the schematic diagram for a double beam spectrophotometer and write its working
principles.
11. (a) Explain the following
(i) half bandwidth
(ii) oscillator strength and transition moment integral
(b) Write the various selection rules involved in UV-visible spectroscopy
12. Discuss the following
(a) The effect of some of auxochrome absorption characteristics of benzene.
(b) The effect of stereochemical factors on the electronic absorption band.
13. What are the empirical rules for calculation of absorption maxima in case of polynes?
Explain by giving suitable examples.
14. What are the empirical rules for calculation of absorption maxima for a-b unsaturated
ketone? Explain by giving suitable examples.
15. Discuss the various rules for calculation of absorption maxima in case of acyl benzene.
16. Giving suitable examples write how would you carry out multiple analysis by UV-visible
spectral method.
17. Discuss the various method used for determining the composition of complex by
spectrophotometric method.
18. Write the basic principle involved in UV-visible spectroscopy. How would you use this
technique for determination of indicator constant for a acid-base indicator.
CHAPTER 12
Infrared (IR) Spectral Method
12.1 INTRODUCTION
The atoms in a molecule do not remain in fixed relative positions but vibrate about some mean
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
rotational energy. When a molecule absorbs infrared radiation, only its vibrational and rotational
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
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
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
against wave number (Q ).
IR region of electromagnetic radiation lies in between visible and microwave regions covering
a wide range of wave number ranging from 12,500 cm1 to 100 cm1. From instrumentation
and application point of view, it is generally divided into approximately three sub-regions,
namely near IR region (from 12,500 cm1 to 4000 cm1), the mid IR region (from 4000 cm1 to 667
cm1) and far IR region extending from 667 cm1 to 100 cm1. This feature of characteristic
absorption of radiation by many molecules in the IR region has provided an extremely elegant and
powerful tool for the elucidation of molecular structure.
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 Hooks law. The potential energy curve
415
obtained by the plot of potential energy of the system as a function of distance between two masses
will be regular parabola which is symmetrical about the potential energy axis and the value of
potential energy will be minimum at equilibrium internuclear distance, re as shown in Figure 12.1.
Figure 12.1 Potential energy versus distance, r for a harmonic oscillator.
This model of a vibrating diatomic molecule (XY) may be assumed to be like a simple harmonic
oscillator which forms an excellent starting point for the discussion of vibrational spectra (IR
spectra). The oscillation frequency (wosc) of such a system is given by:
1 K
wosc = Hz (12.1)
2S P
m X mY
where m is the reduced mass of the system (in grams) given by P . mX and mY = mass
m X mY
(g) of atom X and atom Y respectively. K is the force constant of bond. The unit most usually
employed in IR spectroscopy is wave number (Z osc ). Therefore to convert the frequency to wave
number we must divide wosc by the velocity of light, c expressed in cm s1 obtaining
1 K
Z osc = 2S c P
cm 1 (12.2)
Under the above-mentioned units, the unit for force constant is dyne cm1. Vibrational energies
(Ev) like all other molecular energies are quantized and the allowed vibrational energies for any
particular system may be calculated from the Schrodinger equation. For the simple harmonic
oscillator this turns out to be
1Ø
Ù hZ osc (v
È
Ev = É v 0, 1, 2,...) (12.3)
Ê 2Ú
where v is called the vibrational quantum number.
For an absorption to take place the difference between energy level expressed in cm1 must
correspond to the wave number of spectral lines absorbed which lies in IR region of electromagnetic
radiation.
Spectroanalytical Techniques—Infrared (IR) Spectral Method 417
Factor influencing vibrational frequencies
Again as seen from Eq. (12.1), the vibrational frequency depends on bond strength (as force constant
depends on it) and reduced mass m. Thus if the bond strength increases or reduced mass decreases,
the value of vibrational frequency increases. For covalent single bond of type A H, (where
A == C, N and O or atom of low atomic weight), the reduced mass is very small
and hence, the stretching frequencies is very high, i.e. in order of 3000 cm1 .This is the
reason why stretching frequency of the bonds such as C H, O H, and N H is in the region
of 3600 cm1 to 2700 cm1. If the hydrogen atom, in the group A H, is replaced by deuterium
atom, the stretching frequency decreases by a factor of 2 assuming that the force constant for
A H and A D are the same.
On the other hand, the stretching frequency of the group M Y (where M is a metal atom)
is very low, because the reduced mass of the group M Y is very high. Thus for example,
the stretching frequency of Fe C in iron carbonyls, is about 550 cm1.
The force constant of a double bond is about twice of a single bond, while the force constant of
a triple bond is about thrice of that single bond. Thus we expect the stretching frequencies of the
C C, C ºº C, C == C to be in the ratio 1: 2 : 3 , i.e. 1:1.414:1.732. The approximate value of
the stretching frequencies of C C, C == C, C == C are found to be 1200, 1600, and 2100 cm1
respectively which are in the expected ratio. To assign an approximately the same value
(i.e. 5 ´ 105 dyne cm1) of the force constant of a single bond is not strictly correct. For example,
a superficial comparison of the C H group with the F H group, on the basis of atomic masses,
might lead to the conclusion that the stretching frequency of the F H bond is higher than that for
the C H bond. However, the increase in the force constant from left to right
across the first two rows of the periodic table has a greater effect than the mass increase. Thus, the
F H group absorbs at a higher frequency (4138 cm1) than the C H group (3040 cm1).
PROBLEM 12.1 Calculate the stretching frequency of C H bond. Given force constant of
C H bond = 5 ´ 105 dyne cm1.
m X mY
Solution We are to find the reduced mass P . If we consider X = C and Y = H,
m X mY
then mx = mass of carbon atom = 12/6.023 ´ 1023 = 19.9 ´ 1024 g. Similarly, mY = mass of
hydrogen atom = 1/6.023 ´ 1023 = 1.66 ´ 1024 gm. Thus, m = 1.532 ´ 1024. The stretching
K
frequency is given by Zosc 1
cm 1 . Substituting the value of K, m and the value of c
2S c P
which is equal to 3 ´ 1010 cms1, Z osc = 3030 cm1.
PROBLEM 12.2 The vibrational frequency of C H bond is 3060 cm1 . Predict the
vibrational frequency of C D bond, assuming that the force constant is the same for C H
bond and C D bond.
KC — H
Solution Zosc C — H = 1 cm 1
2S c PC — H
1 KC — D
similarly Zosc C — D = cm 1
2S c PC — D
Zosc C — H PC — D
=
Zosc C — D PC — H
since KC H = KC D
mC H = 1.532 ´ 1024 g
whereas mC D = 2.847 ´ 1024 g
Zosc C — H
So = 1.363
Zosc C — D
since Zosc C — H = 3060 cm1
the value of Zosc C — D = 2245 cm1.
12.2.2 The Vibration of Polyatomic Molecules

As discussed earlier a molecule can have three types of motions such as
(i) Translational,
(ii) Rotational and
(iii) Vibrational motions.
In a molecule with N number of atoms, each atom has three degrees of freedom along X-, Y-
and Z-axes. Hence, there should be 3N number of degrees of freedom for a polyatomic molecule
consisting of N atoms corresponding to the sum of translational, rotational and vibrational motions.
For a nonlinear molecule, there are three combinations which correspond to rotation and three
combinations which correspond to translation motion along the three principal axes of the molecule.
Therefore, for non-linear molecule there are 3N 6 numbers of vibrations possible. However, in
case of a linear molecule, rotation around the molecular axis is not possible; hence there are
3N 5 vibrations expected for a linear molecule. These vibrational degrees of freedom are called
normal or fundamental mode of vibrations. In general, a normal vibration is defined as a molecular
motion in which all the atoms move in phase and with the same frequency.
12.2.3 Types of Molecular Vibrations

The vibration of polyatomic molecules can be classified into two types such as
1. Stretching and
2. Bending vibrations according to their mode of vibrations as discussed below.
Stretching vibration
In this type of vibrations, two bonded atoms continuously oscillate in such a way that no changes
in bond axis or bond angle occur. There are two types of stretching vibrations such as symmetric
stretching and asymmetric stretching.
Symmetric stretching: In this type, the vibrations of the bonded atoms with respect to a particular
atoms (central atom) in a molecule take place in the direction as shown in Figure 12.2 in which
both sides stretch or compress together.
Figure 12.2 Symmetric stretching.
Asymmetric stretching: In this type of vibration, one atom approaches the central atom while
the other departs from it as shown in Figure 12.3 where one bond is stretching and the other is
compressing.
Figure 12.3 Asymmetric stretching.
Bending vibration (Deformation)

In this type of vibration, the angle between the axes changes, i.e. the position of the atoms changes
with respect to the original bond axis. The bending vibrations are also called deformation vibrations.
It may be
(i) Bending in plane vibration and
(ii) Bending out of plane vibration.
Bending in plane vibration: In this type, the molecule undergoes bending vibrations but all the
atoms of the molecule are maintained in the same plane. This may be of two types such as
(a) scissoring and (b) rocking vibration.
(a) Scissoring vibrations: In this type, two atoms (nonbonded) connected to a central
atom move towards each other with a change in bond angle as shown in Figure 12.4.
Figure 12.4 Scissoring vibration.
(b) Rocking vibrations: In this type, the atoms (non-bonded) connected to a central atom
move in the same direction as shown in Figure 12.5.
Figure 12.5 Rocking vibration.
Bending out of plane vibration: In this mode of bending, the atoms do not remain in the same
plane. This may be of two types such as (a) wagging and (b) twisting vibrations.
(a) Wagging vibration: In this type, two atoms (non-bonded) connected to a central atom
move up (represented by (+) sign) or move down below the plane (represented by
() sign) as shown in Figure 12.6.
(b) Twisting vibration: In this type of vibration, out of two atoms (non-bonded) one atom
moves up (+ sign) the plane while the other atom moves down the plane ( sign) with
respect to a central atom as shown in Figure 12.7.
Figure 12.6 Wagging vibration.
Figure 12.7 Twisting vibration.
Symbolic representation of vibration

The symbol nn is used to label the various frequencies of fundamental vibrations. By convention,
the highest totally symmetric vibration is represented by v1, the second highest totally symmetric
vibration is by v2, etc. When the symmetric vibration is counted, next followed by the remaining
asymmetric vibrations in order of decreasing frequencies. Another common convention of labelling
stretching vibrations (v), bending vibrations (d ), out of plane of bending vibrations p. Subscripts
(as) for asymmetric, (s) for symmetric and (d) for degenerate are used with symbols. Band intensities
have been indicated by the symbols: s for strong, m for medium, w for weak and v for
variables.
Comparison between stretching and bending vibrations
(i) As more energy is required to stretch the bond than that required to bend it, therefore,
stretching vibrations occur at higher frequencies as compared to the bending vibrations
of the same bond. Again, as the symmetric stretching is easier than asymmetric stretching,
hence the frequencies (wave number) lie in the order:
Asymmetric stretching > symmetric stretching > bending vibrations.
(ii) Stretching vibrations correspond to one-dimensional motion and for non-cyclic system
containing N atoms, there will be (N 1) stretching vibrations. In contrast, bending
vibrations correspond to two-dimensional motions and there will be (3N 6) (N 1)
= (2N 5) bending vibrations for non-linear molecules. For linear molecule the number
of bending vibration will be (3N 5) (N 1) = (2N 4).
(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
(ii) Ethane.
Solution
(i) In case of benzene (C6H6), N = 12. It is a nonlinear molecule, so the number of
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
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
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.
12.3 SELECTION RULE FOR IR ABSORPTION
It can be seen from quantum mechanics and group theory that absorption takes place in the IR
region in accordance with the following selection rules:
(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
component of IR radiation and hence, absorption takes place. If q be the coordinate of
dm
vibrational motion and m is the dipole moment then should be nonzero for infrared
dq
2
dm
activity. The intensity of IR absorption is proportional to Ô\ i
dq
\ j dW where yi and
yj are wave functions for two vibrational energy levels corresponding to vibrational
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
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
Dn indicates 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.
Figure 12.8 Vibrational states corresponding to normal vibrational mode in a harmonic oscillator.
The energy difference (DEvib) between the lowest energy possible vibrational energy level of a
bond and the next higher energy level is given by
1Ø 1Ø
Ù hZ osc Ù hZ osc hZ osc
È È
DEvib = É1 É0 (12.4)
Ê 2Ú Ê 2Ú
The IR frequency corresponding to the above transition,
Evib hZ osc
v = = = Z osc .
hc hc
12.4 BREAKDOWN OF SELECTION RULE AND OCCURRENCE OF

OVERTONES, COMBINATION BANDS AND DIFFERENCE BANDS
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 an harmonic rather than harmonic
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.
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
at room temperature and it becomes appreciable at higher temperature. The transitions are known
as hot bands as they appear only at high temperature.
The number of fundamental mode observed in IR spectra of polyatomic molecules may not be
equal to the theoretical 3N 6 or 3N 5 rule. When the observed value is less than the theoretical
value, the two or more modes of vibrations may be equivalent and these are called degenerate
modes which give rise to one IR spectral band. In some cases the observed value might be more
than the number of fundamental modes expected. This may be due to:
(a) The possibility of overtones occurring at frequencies 2n1, 3n1, 2n2, 3n2, 2n3, etc.,
where each ni represents fundamental mode.
(b) Formation of combination and difference band. The former arises simply from the addition
of two or more fundamental frequencies or overtones, such as n1 + n2, 2n1 + n2, n1 + n2
+ n3 , etc. whereas the difference band arises due to the difference in frequencies
between two or more fundamental frequencies or overtones such as n1 n2, 2n1 n2, n1
+ n2 n3 , etc. However, such bands have weak intensities.
(c) It may happen that two different vibrational modes in a particular molecule have
frequencies very close to each other and have nearly the same symmetry. They are described
as accidentally degenerate. It is generally found most often between a fundamental and
some overtone or combination mode. The two vibrations interact by a typical quantum
mechanical resonance to give rise to a pair of bands (a doublet) of nearly equal intensity
and the frequency of one is raised and the other is lowered. This phenomenon is called
Fermiresonace. Examples of overtones degeneracy, combinations and difference bands
are given below (Section 12.5).
12.5 SYMMETRIES OF VIBRATION AND THEIR IR ACTIVITY

Though it is possible to visualize the possible vibrations in case of small molecule, it becomes
difficult in cases of bigger molecule (or complex molecules). Further it is difficult to imagine
whether a vibration will cause change in the dipole moment and IR will be active or not.
A qualitative aspect of how the vibrations depend on the symmetry of molecules and their IR
activity will be discussed by giving examples of the following molecules.
(i) H2O: It is a bent triatomic molecule having 3N 6, or, 3 ´ 3 6 = 3, fundamental
modes of vibration. These are: a symmetric stretching mode (n1), a symmetric
bending (scissoring) mode (n2) and an asymmetric stretching mode (n3). In order to decide
whether all three are infrared active and whether any degeneracy exists, it is helpful to
depict the vibrational modes as shown in Figure 12.9.
Figure 12.9 Normal mode of vibration of H2O molecule.

All these three modes of vibration are infrared active (undergo a change in dipole moment)
and are non-degenerate. The observed absorptions occur at 3652, 3756 and 1595 cm1
corresponding to n1,n3 and n2 vibrations respectively.
(ii) CO2: It is a linear triatomic molecule having 3N 5, or, 3 ´ 3 5 = 4, fundamental
modes of vibrations. These are: a symmetric stretching mode, an asymmetric stretching
mode, bending (in plane) and bending (out of plane) which may be represented as shown
in Figure 12.10.
Figure 12.10 Normal mode of vibration of CO2 molecule.
Out of the above four vibrational modes, the symmetrical stretch (v1) will be infrared-
inactive since no change in dipole moment occurs during the vibration. The two bending
modes (3 and 4) are degenerate (v2) and will absorb at the same frequency. Thus we
conclude that CO2 should exhibit two fundamental IR active bands, one due to
asymmetrical stretch (v3) and another due to doubly degenerate bending modes (3 and 4)
known as v2 band. In practice, these two absorption bands, i.e. v3, v2 are observed at
2349 cm1 and 667 cm1 respectively. Besides the above, a band at 1340 cm1 in CO2 is
also observed. Actually, it is an intense doublet with band maxima at 1286 cm1 and
1388 cm1. This splitting is due to Fermi resonance between the fundamental v1 and the
overtone 2v2, i.e. 2 ´ 667 = 1334 cm1 as v1 and 2v2 (overtone) have the same symmetry.
As a result, frequency of one is raised and that of other lowered.
(iii) SO2 molecule: It is also a bend triatomic molecule and is predicted to have three normal
modes from 3N 6 rule as depicted in Figure 12.11.
Figure 12.11 Three fundamental vibrations for SO2 molecules.

These are: a symmetric stretching mode (n1), a symmetric bending mode (n2) and an
unsymmetric stretching mode (n3). All the modes are IR active and hence high intensity
fundamental bands are observed at 1361 cm1, 1151 cm1, and 519 cm1 corresponding
to v3, v1 and v2 vibrations respectively. However, bands are also observed at 606 cm1,
1871 cm1, 2305 cm 1 and 2499 cm1 corresponding to difference bands v1 v2,
combination bend v2 + v3, the overtone of v1, i.e. 2v1 and another combination band
v1 + v3 respectively.
(iv) Pyramidal molecule of the type XY3: NH3 molecule (X = N, Y = 3) is a trigonal
pyramidal-shaped molecule having (3 ´ 4 6) = 6 fundamental modes of vibrations as
depicted in Figure 12.12.
Figure 12.12 Normal vibrational mode of pyramidal molecule XY3.
Out of the six vibrations, there are two non-degenerate vibrations (v1 and v2) while the
rest correspond to two doubly degenerate types (v3 and v4 ) and all of them are IR active.
Thus four IR bands should be observed.
(v) Trigonal planar molecule of the type XY3: BF3 molecule (X = B, Y = 3) is a trigonal
planar molecule. Here also the total number of vibrations obtained is (3 ´ 4 6) = 6 as
Figure 12.13 Normal vibrational mode of planar molecule XY3.

Two vibrations (v1 and v2) are non-degenerate while four vibrations are two doubly
degenerate (v3 and v4). Out of them v1 is IR inactive while the rest are IR active.
Thus, three IR bands should be observed.
(vi) Tetrahedral molecule of the type XY4: CH4 molecule (X = C, Y = 4) is a tetrahedral
molecule which corresponds to (5 ´ 3 6) = 9, the fundamental modes of vibrations are
Figure 12.14 Normal vibrational mode of tetrahedral molecule XY4.
Vibration represented by (v1) is non-degenerate and IR inactive. Vibrations represented

by (v2) are doubly degenerate and also infrared inactive whereas other six vibrations
correspond to two triply degenerate modes (v3 and v4) are IR active. Thus two IR bands
should be observed.
(vii) Square planar molecule XY4: Here also the number of fundamental mode of vibrations
is (5 ´ 3 6) = 9 as depicted in Figure 12.15.
Figure 12.15 Normal vibrational mode of square planar molecule XY4.

Out of them vibrational modes represented by (v1), (v2), (v3), (v4) and (v5) are non-
degenerate whereas (v6) and (v7) are each doubly degenerate. However, vibrational modes
(v3), (v6) and (v7) are IR active. Hence three IR bands corresponding to (v3), (v6) and (v7)
modes are obtained for a square planar molecule.
(viii) Octahedral molecules XY6: In this case, there are fifteen vibrations (7 ´ 3 6) = 15
possible as depicted in Figure 12.16.
Figure 12.16 Normal vibrational mode of octahedral molecule XY6.
Out of them mode (v1) is non-degenerate, mode (v2) is doubly degenerate while modes
(v3), (v4), (v5) and (v6) are each triply degenerate. Only v3 and v4 are IR active.
12.6 INSTRUMENTATION
The IR spectra are recorded in IR spectrophotometer, the components of which are as follows:
(i) Radiation source
(ii) Monochromator and optical materials
(iii) Sampling area
(iv) Detector
(v) Amplifying system
(vi) Recorder.
The schematic diagram of a IR spectrometer is shown in Figure 12.17.
Figure 12.17 The schematic diagram of a IR spectrometer.
Radiation source
The Nernst glower, globar and incandescent wire source are commonly employed in IR radiation.
Monochromators and optical systems
Prism or a reflection grating is used as a monochromator. For prism material glass or quartz cant
be used since they absorb strongly IR radiation. Most IR spectrophotometer use prism of alkali
halides. Lithium fluoride is used for near IR region, crystalline sodium chloride (Rock salt) for
mid-IR region and crystalline potassium bromide or ceasium chloride for far-IR region.
Sample
IR spectra can be obtained for gases, liquids and solids. The spectra of solid samples are frequently
determined as an alkali halide pallet or mull. The most commonly used mulling agent is nujol
which is a mixture of high molecular weight liquid paraffine oils.
Detectors and amplifying system
Usually thermal detectors are used. These are thermocouple, bolometre and golay detectors. Detector
converts IR energy into electrical energy. It is then amplified with the help of amplifier. It is
coupled to a motor which drives an optical wedge. The movement of the wedge is in turn coupled
to a pen recorder which draws absorption bends on the calibrated chart.
12.7 CONCEPT OF GROUP VIBRATIONAL FREQUENCIES
One of the most important applications of infrared spectroscopy is structural analysis of organic
compounds. The most common analysis involves the group vibration concept of various functional
groups in the molecule.
Group vibrations involve the vibration of small group of atoms of a molecule, the other atoms
being nearly stationary. For example, certain functional groups such as ,
etc. have more or less the same frequencies irrespective of the molecular environment. This means
that any of these groups must vibrate at frequencies independent of the rest of the molecules. Such
frequencies are called group frequencies. Hence group frequencies are means of identifying their
presence on the molecule. The acetone molecule (CH3 CO CH3), for example has the following
modes of group frequencies.
1. C == O stretching (with negligible motion of other atoms) absorbs at 1700 cm1.
2. CH3 group frequency (independent of the motion of carbonyl group).
The followings are the characteristic absorption bands of methyl group vibrations.
Type of vibrations Range of absorption (cm1)
Symmetric C H stretch ~2870 cm1
Asymmetric C H stretch ~2960 cm1
Asymmetric bending (out of plane bending of C H bond) ~1450 cm1
Symmetric bending (in plane bending of C H bond) ~1375 cm1
Methylene group CH2 has the following six characteristics vibrations.
Type of vibrations Range of absorption (cm1)
(i) Asymmetric stretching (vas CH2) ~2930 cm1
(ii) Symmetric stretching (vs CH2) ~2850 cm1
(iii) In plane bending (scissoring) ~1465 cm1
(iv) Out of plane bending (wagging) ~1150 cm1
(v) In plane bending (rocking) ~720 cm1
(vi) Out of plane bending (twisting) ~1350 cm1
Thus division of the molecule into groups is a valuable approximation referred to as a concept
of group vibrations. Many functional groups in unknown compounds have been identified by
using this assumption. While the complete analysis of the vibrational spectrum of a polyatomic
molecule containing several atoms is often very lengthy and tedious, most IR spectroscopic
investigations rely on the concept of group frequencies. Unfortunately, in many complicated
molecules there are many group vibrations that overlap and assignment of the bands in a spectrum
becomes difficult. It has also been observed that calculated values of frequency differ from the
experimental values. The factors which cause the difference are as follows.
12.7.1 Factors Influencing Group Vibrational Frequencies

Electronic effect
The frequency shifts from the normal position of absorption for a particular group take place when
the substituent in the neighbourhood of that particular group are changed due to electronic effects
which include (i) inductive effects, (ii) mesomeric effect, (iii) field effects, etc. Under the influence
of these effects, the force constant or the bond strength changes and its absorption frequency shift
from the normal value.
(i) Inductive effect: The introduction of alkyl groups causes +I effect which results in the
lengthening or the weakening of the bond. Due to this, absorption occurs at lower wave
number. This is illustrated comparing the wave number of vC == O absorption for the
following compounds.
1. Formaldehyde, HCHO 1750 cm1
2. Acetaldehyde, CH3CHO 1745 cm1
3. Acetone (CH3COCH3) 1715 cm1
In the above the methyl group attached to the carbonyl group causes +I effect.
Similarly, the introduction of electronegative atoms (like Cl) or groups causes. I effect
and raises the wave number of absorption because of increase in bond order as exemplified
below:
1. Acetone (CH3COCH3) 1715 cm1

2. Chloroacetone (ClCH2COCH3) 1725 cm1
3. Dichloroacetone (Cl2CHCOCH3) 1740 cm1
(ii) Mesomeric effect: This causes lengthening or the weakening of a bond leading to
lowering of absorption frequency due to conjugation as shown in case of methyl vinyl
ketone and acetophenone as a result vC == O band is shifted to lower frequency region.
(iii) Mesomeric effect vs inductive effect: In many cases, mesomeric effect works along
the inductive effect and cannot be ignored. In some cases, inductive effect dominates
over mesomeric effect while reverse holds for other cases as discussed below giving the
example of benzamide and methylbenzoate.
In both the compounds, lone pair of electrons are present on the atom (N atom in case of
benzamide and O atom in case of methylbenzoate) in conjugation with the double bond
of a group (say, carbonyl), so that the mobility of the lone pair of electrons plays an
important role, as a result, I effect due to more electronegative N or O is dominated by
mesomeric effect and thus the absorption frequency falls. If we compare the carbonyl
frequency of methylbenzoate with that of phenylacetate, in the former, the carbonyl group
is in conjugation with phenyl ring, so its frequency is lowered (1720 cm1), while in the
later the carbonyl frequency is 1770 cm1 which is the normal value of ester because of
the absence of conjugation of phenyl group with carbonyl group.
In some cases mesomeric effect predominates over the inductive effect and in some
cases inductive effect predominates over mesomeric effect. The above facts are further
exemplified as follows.
Consider the absorption frequencies of the following compounds: I, II, III and IV
In p-amino acetophenone (I) due to low electronegativity of Natom the lone pair of
electrons participates in conjugation. Thus, here mesomeric effect predominates, whereas
in p-methoxy acetophenone (III) due to high electronegativity of oxygen atom I inductive
effect predominates over mesomeric effect. As a result, the absorption takes place at a
higher wave number region as in compounds (III) (1685 cm1) compared to that in
compound (I) (1670 cm1). In compounds (II) and (IV), inductive effects (I) dominate
over mesomeric effects. Thus, absorption occurs at a higher frequency region at
1700 cm1 and 1770 cm1 for the compounds II and IV respectively. Conjugation is
diminished and absorption occurs at high wave number due to electrostatic interaction of
non-bonding electrons present especially on o-substituted compounds. This is called field
effect.
(iv) Field effect: In o-substituted compounds, the lone pair of electrons on two atoms
influences each other through space interactions and change the vibrational frequencies
of both the groups. This effect is known as field effect as exemplified in case of o-halo
acetophenone.
The non-bonding electrons present on oxygen atom and halogen atom cause electrostatic
repulsions. This results in a change in the state of hybridization of C == O group and also
makes it to go out of the plane of double bond. Conjugation is diminished and absorption
occurs at higher wave number. Thus, for such substituted compounds, cis isomer absorbs
at a higher frequency (due to field effect) than the trans isomer.
Hydrogen bonding
Hydrogen bonding brings about dramatic downward frequency shifts. The stronger the hydrogen
bonding, the greater is the absorption shift towards lower wave number from the normal value.
Two types of hydrogen bonds can be readily distinguished in the infrared technique. Generally,
intermolecular hydrogen bonds give rise to broadbands whereas bands arising from intramolecular
hydrogen bonds are sharp and well defined. Bands due to intermolecular hydrogen bond are
concentration dependent. On dilution, the intensities of such bands decrease and finally disappear.
Intramolecular hydrogen bonding is internal effect and persists at a very low concentration.
Frequency differences between free and associated molecules (H-bonded) is small in case of
intramolecular hydrogen bonding than that in intermolecular association.
Hydrogen bonding in O H and N H compounds deserve special attention. Mostly non-
associating solvents like CS2, CHCl3, CCl4, etc. are used because some solvents like benzene,
acetone, etc. influence O H and N H compounds to a considerable extent. As nitrogen atom
is less electronegative than an oxygen atom, hydrogen bonding in amines is weaker than that in
alcohols and thus, the frequency shifts in amines are less dramatics.
For example, amines show N H stretching at 3500 cm1 in dilute solution (not H bonded)
while in condensed phase spectra (H bonded) absorption due to vN H occurs at 3300 cm1. While
alcohols exhibiting intermolecular hydrogen bonding absorbs between 3400 and 3200 cm1
which is much less than that observed (3600 cm1) in case of free alcohol.
b-diketones usually exist as mixtures of tautomeric keto and enol forms. The enolic form does
not show the normal absorption of conjugated ketones. Instead, a broadband appears in the range
of 16401580 cm1 (6.106.33 mm) region, which in more intense than normal carbonyl absorption.
The intense and displaced absorption results from intramolecular hydrogen bonding, the bonded
structure being stabilized by resonance as shown in case of acetyl acetone.
12.8 IMPORTANT SPECTRAL REGIONS IN THE INFRARED AND

PRESENTATION IR SPECTRA
The identification of a compound by the IR technique involves a systematic examination of certain

regions in the IR spectrum in a systematic way to obtain clues as to ascertain the presence or
absence of certain group frequencies. Some of the important regions are considered below.
(i) Hydrogen stretching region in the range of 3700 to 2700 cm1: Absorption peaks in
the region of 3700 to 3100 cm1 are ordinarily due to various O H and N H stretching
vibrations, with the former tending to appear at higher wave numbers.
Aliphatic C H vibrations fall in the region between 3000 and 2850 cm1. Most aliphatic
compounds have a sufficient number of C H bonds to make this a prominent peak.
The acetylenic C H bond is strong and occurs at about 3300 cm1. The hydrogen on
the carbonyl group of an aldehyde usually produces a distinct peak in the region of 2745
to 2710 cm1. Substitution of deuterium for hydrogen causes a shift to lower wave number
by a factor of approximately 1 2 as would be predicted from Eq. (12.2). This effect has
been employed to identify C H stretching peaks.
(ii) The triple-bond region between 2700 and 1850 cm1: A limited number of groups is
absorbed in this spectral region; their presence is thus readily seen. Triple-bond stretching

results in a peak at 2250 to 2225 cm1 for C ºº N, at 2180 to 2120 cm1 for — N C
and at 2260 to 2190 cm1 for C ºº C .
(iii) The double-bond region between 1950 and 1550 cm1: The carbonyl stretching
vibration is characterized by absorption throughout this region. Ketones, aldehydes,
acids, amides and carbonates all have absorption peaks around 1700 cm1. Esters, acid
chlorides and acid anhydrides tend to absorb at slightly higher wave numbers, i.e.
1770 to 1725 cm1. Conjugation tends to lower the absorption peak by about 20 cm1.
It is frequently impossible to determine the type of carbonyl that is present solely on the
basis of absorption in this region. However, examination of additional spectral regions
may provide the supporting evidence needed for clear cut identification. For example,
ester have a strong C O R stretching peak at about 1200 cm1, while aldehydes
have a distinctive hydrogen stretching peak just above 2700 cm1.
Absorption peaks arising from C == C and C == N stretching vibrations are located in
the range of 1690 to 1600 cm1. Valuable information concerning the structure of olefins
can be obtained from the exact position of such a peak. The region between 1650 and
1450 cm1 provides important information about aromatic rings. Aromatic compounds
with a low degree of substitution exhibit four peaks near 1600, 1580, 1500 and
1460 cm1. Variations of the spectra in this region with the number and arrangement of
substituent groups are usually consistent but independent of the type of substituent;
considerable structural information can thus be obtained from a careful study of aromatic
absorption in the IR region.
(iv) The fingerprint region between 1500 and 700 cm1: Besides characteristic group
vibrations, other vibration involving nearly all the atoms of a molecular skeleton called
skeletal vibration also plays an important role for identification of organic molecules.
The region (1500700 cm1) corresponding to skeletal vibration is called fingerprint
region. The IR bands occurring in the region are referred to fingerprint bands. A molecule
or structural moiety can only be recognized by appearance of the bands in the region.
Small differences in the structure and constitution of a molecule results in significant
changes in the IR peaks in this region of the spectrum.
As a result, a close match between two spectra in the fingerprint region (as well as
others) constitutes strong evidence for the identity of the compounds yielding the spectra.
Most single bonds give rise to absorption bands at these frequencies because their energies
are about the same. Strong interaction occurs between neighbouring bonds. The absorption
bands are thus composites of these various interactions and depend upon the overall
skeletal structure of the molecule. Exact interpretation of spectra in this region is seldom
possible because of their complexity. On the other hand, it is this complexity that leads to
uniqueness and the consequent usefulness of the region for identification purposes.
A few important group frequencies are to be found in the fingerprint region.
These include the C O C stretching vibration in ethers and esters at about
1200 cm1 and the C Cl stretching vibration at 700 to 800 cm1.
(v) Presentation of IR spectra: IR spectra are usually represented as plot of % of
transmittance (T) vs. wave number ( Q in cm1) or wavelength (l in mm). The common
practice is to indicate both Q and l scale. A typical IR spectrum of di-n-butyl ether is
shown in Figure 12.18. The two bands at 2950 and 2820 cm1 are due to C H stretching.
The two bands 1460 and 1380 cm1 are respectively due to in plane and out of plane
bending vibration of CH2 group while the IR band at 1100 cm1 is due to C O
stretching vibration.
Figure 12.18 IR spectrum of di-n-butyl ether.
12.9 IR CHARACTERISTICS OF SOME ORGANIC COMPOUNDS

In this technique, almost all groups absorb characteristically within a definite range.
Hydrocarbons
Hydrocarbons (CxHy) may be alkanes, alkenes, alkynes, cyclics or aromatics.
(a) Alkanes: Alkanes contain CH3 and CH2 which cause C H stretching and C H
deformation absorptions. Commonly two C H stretching absorption bands appear just bellow
3000 cm1; one for symmetrical and other for asymmetrical vibrational frequencies. The various
C H bending vibrations in alkanes appear in the region 14851340 cm1, C C linkage are
less characteristic and appear as weak bands in the region 1300800 cm1. Alkanes are non-polar
and do not exhibit hydrogen bonding. Thus, the positions of absorption are little effected by the
change in polarity of the solvent. The bands resulting from C H bending vibration of CH3
group and that of CH2 occur at 13751450 cm1 and 1465 cm1 respectively. The band resulting
from CH2 rocking vibration (in phase) occurs at ~720 cm1.
PROBLEM 12.4 IR spectrum of n-dodecane is given below (Figure 12.19). Indicate the position
of some characteristics absorption in this compound.
Figure 12.19 IR spectrum of n-dodecane.
Solution Positions of some characteristic absorption n-dodecane

A = 2960 cm1; C Hstr
B = 2870 cm1; C Hstr in methyl/methylene
C = 1465 cm1; C Hdef in CH2
D = 1372 cm1; C Hdef in CH3
E = 770 cm1; CH2 (rocking)
(b) Alkenes: In alkenes, C Hstr absorption band appears in the region 31003000 cm1.
The C == C stretching shows weak band at 16801620 cm1. The important modes of alkenes are
out of C H banding vibration (C Hdef) between 1000650 cm1. Besides, C H in plane
banding appears as a strong band in the region 14501420 cm1. For trans alkenes, C Hdef
appears near 970 cm1 and for corresponding cis isomer; it appears near 700 cm1. This helps in
distinguishing cis and trans alkene.
PROBLEM 12.5 IR spectrum of 1-decene is given below (Figure 12.20). Indicate the position
Figure 12. 20 IR spectrum of 1-decene.

Solution Positions of some characteristic absorption 1-decene
A = 3050 cm1; C Hstr in olefin
B = 29602850 cm1; C Hstr in methyl/methylene
C = 1645 cm1; C == Cstr in CH2
D = 985 cm1; C Hdef.out of plane
E = 720 cm1; CH2 (rocking)
PROBLEM 12.6 Describe the various characteristic absorption bands in case of 1-Hexene in
infrared spectroscopy.
Solution The structure of 1-Hexene is H3C H2C H2C H2C HC == CH2
Some of its important characteristic absorption bands are:
(i) C Hstr in alkene = ~ 3050 cm1
(ii) C Hstr in CH2, CH3 == ~ 28602950 cm1
(iii) C == Cstr ~ 1680 cm1
(iv) C H (in plane) bending ~ 1460 cm1
(v) C Hdef 980 cm1
(vi) CH2 rocking 720 cm1
PROBLEM 12.7 The infrared spectrum of a hydrocarbon containing 14.3 per cent hydrogen
gave the following absorptions bands.
(i) 3040 cm1,
(ii) 960 cm1,
(iii) 1670 cm1.
What is the probable geometry of the compound?
Solution Percentage of hydrogen = 14.3, Percentage of carbon = 100 14.3 = 85.7
From this data , the formula of the compound is (CH2)n where n = 1, 2
(i) The absorption at 3040 cm1 shows == C Hstr. It may be alkene.
(ii) The band at 960 cm1 suggests that the geometry of the alkene may be trans.
(iii) The band at 1670 cm1 which is medium may be due to C = Cstr.
When n = 2 or 3, we get C2H4 or C3H6 · C2H4 is ethene and C3H6 is propene (CH3 CH == CH2).
For these compounds, there is no question of geometrical isomerism.
When n = 4, we get C4H8. If C4H8 is the formula, then it can be written in the transform.
So the probable geometry is trans-butene.
(c) Alkynes: In alkynes, a strong band for C Hstr appears near 3300 cm1 and a weak
C ºº C stretch occurs at about 22602100 cm1. The band near 3300 cm1 is strong
and narrow and can be distinguished from the hydrogen bonded O H and N H stretching
occurring in the same region. The band due to C H deformation mode occurs in the range of
700610 cm1 as strong band. In some cases the first overtone of C H bending appears as a
weak broadbrand in the regions 13701220 cm1.
PROBLEM 12.8 Describe the various infrared bands in case of 1-hexyne.

Solution The structure of 1-hexyne H3C H2C H2C H2C C == CH
Some of its important absorption bands in infrared spectroscopy are
(i) == C Hstr ~3300 cm1
(ii) C Hstr in CH2 and CH3 == ~ 28602950 cm1
(iii) C ºº Cstr ~2100 cm1
(iv) C Hdef (overtone) 1370 cm1
(v) C Hdef (fundamental) ~ 700 cm1.
(d) Cycloalkanes: In cycloalkanes, the value of C Hstr increases with increasing angle of
strain in the ring. C Hstr vibration for cyclopropane is between 31003000 cm1 and that for
cyclohexane is 2990 cm1, while cyclisation decreases the frequency of CH2 scissoring vibration,
for example, cyclopropane absorbs at 1440 cm1, cyclopentane absorbs at 1450 cm1 and
cyclohexane at 1455 cm1, while n-hexane absorbs at 1470 cm1.
(e) Cycloolefins: Absorption of the ring double bond in the unstrained cyclohexene system similar
to that of cis isomer in an acyclic system. The C == C vibration is coupled with the C C stretching
of the adjacent bonds.
The substitution of alkyl groups for an a-hydrogen atom in strained ring system serves to increase
the frequency of C == C absorption. For example, cyclobutene absorbs at 1566 cm1, whereas
1-methylcyclobutene absorbs at 1641 cm1.
(f) Aromatic hydrocarbons: In aromatic hydrocarbons, C Hstr absorption occurs in the region
of 30503000 cm1; C == Cstr at 1650 to 1450 cm1. For aromatic compounds, the most characteristic
C Cstr bands are at ~1600 cm1, 1580 cm1, 1500 cm1 and 1450 cm1(m). If there is no absorption
in this region, it may be concluded that the compound is not aromatic.
C Hdef mode for mono-substituted benzene occurs at 900700 cm1 (m, s). For meta-di-substituted
benzene derivatives two medium bands at 850750 cm1 and 710690 cm1 occur due to C Hdef
mode. For ortho-di-substituted and para-di-substituted benzene derivatives C Hdef mode occur
at 770735 cm1 (m) and 840800 cm1(m) respectively.
PROBLEM 12.9 The IR spectrum (Figure 12.21) of a hydrocarbon with molecular formula,
C8H10 is given below:
(i) 3016 cm1, (ii) ~ 1602 cm1, 1578 cm1,
(iii) 1460 cm1, (iv) 705 cm1 (m), 790 cm1 (m).
Indicate the structural formula hydrocarbon from its IR spectrum.
Solution Positions of some characteristic absorptions
A = 3030 cm1 C Hstr in olefins/aromatics
B = 2940 cm1 C Hstr for CH3
C, D, E, F = 1610, 1582, 1492, 1462 cm1 C == Cstr in aromatic nucleus
G = 1370 cm1 C Hdef in methyl
H and I = 770 and 695 cm1 meta-di-substituted benzene.
Figure 12.21 IR spectra of hydrocarbon of formula C8H10.
The appearance of bands at 1610, 1582, 1492 and 1462 cm1 indicates that the compound is
aromatic. These bands are due to C == Cstr. The aromatic structure is also supported by a C Hstr
absorption at 3030 cm1. Two bands, one at 770 cm1 (m) and the other at 695 cm1(m), show that
the ring is the meta-di-substituted. Hence, the compound under investigation is meta-xylene.
Its structural formula is
Alcohols and phenols: Alcohols and phenols show prominent absorption bends due to
O H stretching, C O stretching and O H bending.
O H stretching vibration: Alcohol and phenol exhibit an excellent property of hydrogen
bonding. Due to this, the spectra of alcoholic compounds are generally recorded in dilute
solutions in non-associating solvents. Spectra for alcohols are the best taken in the vapour state. In
polar solvents, O Hstr appears at the lowest wave number, i.e. near 3200 cm1. It is due to
interaction of alcohol molecules with the solvent molecules. In concentrated solutions or in the
solid state, O Hstr absorption band becomes broad and occurs at lower wave number in the
range (32003400 cm 1) due to H bonding. Hydrogen bonding tends to broaden the peaks and
moves them towards lower wave number. Thus the solution of an alcohol at fairly high concentration
exhibits its two peaks, a sharp one at 3630 cm1 (due to free hydroxyl group) and another broader
one at 35003200 cm1 due to hydrogen bonded hydroxyl group. On dilution it is observed that the
peak at 3630 cm1 becomes more intense as the concentration of the free hydroxyl group increases.
At the same time, the broader peak becomes less intense and disappears at sufficiently large
dilution. The above description applies to OH groups involved in intermolecular hydrogen
bonding. If the OH group is involved in intramolecular hydrogen bonding as in case of
O-nitrophenol, dilution will not have any effect on intensity or position of the broadband.
The absorption maximum for O H stretching depends upon concentration, nature of the solvent
and temperature. Absorption frequencies of alcoholic and phenolic O H are given below.
Group Type of vibration Region

(in cm1 and intensity)
Free* O H group O Hstr 37003500 (n, sh)
Intermolecular hydrogen bonding OH@ O Hstr 34003200 (s, b)
Polymeric association
Intramolecular hydrogen bonded OH @@ O Hstr 35703450 (n, sh)
Chelate compounds O Hstr 30002500 (m, b)
* Free O H means that the compound does not undergo intramolecular or intermolecular association.
@ absorption shifts to higher wave-number on dilution.
@@No absorption shift on dilution
C O stretching vibration: The C O stretching vibration in alcohol and phenol result in a

strong band near 12601000 cm1. The C O stretching is coupled with the adjacent C C
stretching vibration giving rise to bands at 14601260 cm1 and 11501050 cm1 as shown below
in case of primary, secondary and tertiary alcohols.
Nature of alcohol Type of vibration Range of absorption (cm1)
Primary alcohol (i) 13501260(s)
(R CH2 OH) C O stretching (ii) 10001050(s)
Secondary alcohol (i) 13501260(s)
R CH(R) OH C O stretching (ii) ~1100(s)
Tertiary alcohol (i) 14601310(s)
R C(R)2 OH C O stretching (ii) ~ 1150(s)
In phenol, interaction between O H bending and C O stretching occurs. As a result, two
bands in the region 13901330 cm1 and 11801160 cm1 are obtained.
O H bending vibration: The O H in plane bending vibration interacts with C H wagging
vibrations in case of primary and secondary alcohols. As a result, two bends near 1420 cm1 and
1330 cm1 are obtained in such alcohols. However, tertiary alcohol shows a single bend in the
region 14101310 cm1 because of the absence of C H wagging mode. In some cases, especially
in liquid state, a broad band near 770650 cm1 is obtained because of out of plane bending mode
of bonded O H group.
PROBLEM 12.10 The IR spectra of ethyl alcohol is given below (Figure 12.22). Indicate the
position of some characteristics absorption band.
Solution Positions of some characteristic absorptions
A = 3330 cm1 O Hstr (hydrogen bonded)
B = 2960 cm1 C Hstr (asymmetric)
C = 2924 cm1 C Hstr (symmetric)
D = 1050 cm1 C Ostr (for primary alcohols)
Figure 12.22 IR spectra of ethyl alcohol.
PROBLEM 12.11 An organic compound (molecular mass =108) gave the following peaks in its
infrared spectrum: (i) 3400 cm1 (s, b), (ii) 3030 cm1 (w), 1600 cm1 (w, sh), 1580 cm1 (w),
1500 cm1 and 1450 cm1 (w). With alkaline potassium permanganate, it is oxidized to a solid.
It gives a negative test with ferric chloride solution. Assign the structural formula to the compound
from the above data.
Solution
(i) A peak at 3400 cm1 shows that the compound contains an OH group. The OH
group cannot be phenolic as it does not responed to ferric chloride test.
(ii) The bands at 3030 cm1 (w), 1600 cm1 (w, sh), 1580 cm 1 (w), 1500 cm1and
1450 cm1 (w) show that it is aromatic as indicated by stretch at 3030 cm1. Thus, the
structural units of compound are: (i) C6H5 and (ii) OH group. These two units
amount to 77 + 17 = 94 mass units.
The remaining 14 mass units (10894 units) correspond to CH2 group. Clearly, OH group
is attached to the ring through CH2 group. Hence, the compound under examination is benzyl
alcohol. Benzyl alcohol on oxidation with alkaline potassium permanganate gives benzoic acid.
Amines
Primary amines show two bands due to N Hstr (symmetrical and asymetrical) in the region 3500
3300 cm1. Secondary amines give only one band in this region while tertiary amines do not absorb
in the N H absorption region. Both N H and O H show the property of hydrogen bonding
and their absorptions get superimposed making the identification difficult. As N-atom is less electro-
negative, we say that hydrogen bonding is less pronounced in amine as compared to that in alcohols.
Alipatic amines are more sensitive to hydrogen bonding than aromatic amines since they are
stronger bases. The N H absorption is usually broad unless spectrum is scanned in dilute
solution. The N H bending (scissoring) vibrations for primary amines occur at higher wave
number (16501590 cm1) as compared to secondary amines (16001550 cm1). Besides the
above, the amines exhibit bands at 12201020 cm1 due to v C N vibrations.
IR characteristics of compounds containing carbonyl ( ) group

Ketones, aldehydes, carboxylic acids, carboxylic esters, acid amide, acid anhydride, acid halides,
etc., show a strong carbonyl stretching absorption band in region 18701540 cm1.
Within its range the position of the vC == O band is determined by the following factors:
(i) The physical state (ii) Electronic and mass effect of neighbouring substituent
(iii) Conjugation (iv) Hydrogen bond
(v) Ring strain as discussed below in each category of compounds
Aldehydes and ketones

Aldehydes can be readily distinguished from other carbonyl compounds due to the appearance of
two C Hstr absorption bands; near 2820 cm1 and 2720 cm1 due to H attached to carbonyl
group. Usually, a band near 2720 cm1 is seen and is most characteristic for aldehyde. Saturated
aldehydes absorb in the range of 17401720 cm1. The presence of electron donating group (+ I
group) lower the absorption value while the presence of electron attracting groups (I group) raise
the wave number of absorption. The wave number of absorption is also lowered if carbonyl group
is directly attached to the aromatic ring or carries a, b-unsaturation.
Ketones absorb at low wave number (~1700 cm1) due to large +I effect caused due to the
presence of more alkyl groups. As H attached to carbonyl group which is substituted by alkyl
group, no characteristic IR band due to vC H is possible in ketones.
PROBLEM 12.12 The IR spectrum of benzaldehyde is given in Figure 12.23. Indicate the position
of characteristics bands.
Figure 12.23 IR spectrum of benzaldehyde.

Solution The position of absorption are:
A = 3050 cm1 C Hstr olefines/aromatics
B, C = 2960 cm1, 2850 cm1 C Hstr
D = 2710 cm1 C Hstr (characteristic of aldehydes)
E = 1690 cm1(s) C == Ostr aromatic or a, b-unsaturated aldehydes
F, G, H = 1600, 1580, ~ 1500 cm1 C == Cstr aromatic nucleus
PROBLEM 12.13 The IR spectra of carbonyl compound of formula C4H8O is given in
Figure 12.24. Examine the spectra and indicate whether the compound is aldehyde or ketone.
Write its structure.
Figure 12.24 IR spectra of carbonyl compound.
Solution Positions of absorptions are

A = 3002 cm1 C Hstr olefines/aromatics
B = 2940 cm1 C Hstr
C = 1715 cm1 C == Ostr
D = 1450 cm1 C Hdef in methyl/methylene
E = 1466 cm1 C Hdef in CH2
F = 1360 cm1 CH Hdef in CH3
The absence of band at 2720 cm 1 indicate the absence of aldehydic group. Hence,
the probable structure of the compound is a ketone with structure
Carboxylic acids
(a) Carboxylic group which consists of carbonyl and hydroxyl group is the easiest
functional group to detect by this technique. The absorption of O H group in an acid
appears as a broad band near 3000 cm1. The C == Ostr absorption in aliphatic acids occur
at 17251700 cm1. a, b-unsaturation acids or aryl acids show C == O absorption at a
lower wave number. Some acids like acetic acids, benzoic acids, etc., exist as dimmers
(Figure 12.25) due to hydrogen bonding.
Figure 12.25 Dimer of a carboxylic compound.
Formation of bridge lowers the force constant and hence C == O absorption occurs at
lower wave number. As the hydrogen bonded structure is stabilized by resonance, the
O H stretching occurs as a broad band in the region 30002500 cm1. If the acid is
converted into soluble salts. The carboxylate anion is formed. The carboxylate anion has
two strongly coupled carbon to oxygen bonds with bond strength intermediate between
C == O and C O due to resonace given below
Resonating structure of carboxylate anion
The carboxylate anion gives rise to a strong asymmetric stretching bond near 1650
1550 and a weaker, symmetrical stretching band near 1400 cm1. In cis and trans isomer of
an acids, small differences in vC == O absorption are observed. But in case of cis and trans
cinnamic acid, maleic acids and fumeric acids, etc., vC == O absorption differences are
larger. It is explained due to steric effect caused by the bulky groups on the same side of the
double bond. Due to repulsive interaction, the C == O part of COOH group goes out of the
plane of double bond. Thus, conjugation is diminished and absorption occurs at higher
wave number as shown below.
Similar explanation can be given to cis and trans cinnamic acid. Intramolecular
hydrogen bonding reduces the frequency of carbonyl stretching vibration to a greater
extent compared to intermolecular hydrogen bonding. That is why salicylic acid absorbs at
1665 cm1 while p-hydroxyl benzoic acid absorbs at 1680 cm1. Substitution in the µ position
with electron withdrawing group, such as halogens causes minor increase in the C == O
absorption frequency due to I effect. It is expected as due to I effect of OH group,
absorption for acid should occur at higher wave number as compared to aldehydes. But it is
not so as vC == O absorption for acid is lowered due to internal conjugation (lone pair in
oxygen in conjugate with C == O) acting in opposite direction.
(i) vC == O 1702 cm1(s) (i) v C == O 1680 cm1(s)
The absorption at higher wave number
is due to diminshed conjugation
(ii) vC Hstr = ~3000 cm1 (ii) v C Hstr = ~ 3000 cm1
(iii) vC Cstr = 1650 cm1 (iii) v C == Cstr = 1650 cm1
Esters Esters have two characteristically strong absorption bands arising from
C == O and C O stretchings. The intense C == O stretching band occurs at higher frequency
(18201760 cm1). This is because the force constant of carbonyl bond is increased by the electron
attracting nature of adjacent oxygen atom (I effect). The C O stretching vibrations of ester
usually consists of two asymmetric coupled vibrations: C C(== O) O and O C C, the
former being more important. These bands occur in the region of 13001000 cm1.
Acid halides The presence of electronegative atom bonded to carbonyl carbon causes
I effect which increases the force constant of carbonyl group. Hence, the wave number of carbonyl
absorption increases. It occurs in the range of 18151785 cm1.
Acid anhydride It can be easily detected by the appearance of a doublet usually
separated by 60 cm1 in the region 18501750 cm1. The doublet appears because of coupled
vibration of two C == O groups. Besides, it exhibits a strong band in the region 13001050 cm1
because of stretching vibration.
Acid amide In amides, the presence of nitrogen atom may cause I effect and
+M effect as well. As +M effect dominates over I effect, the vC == 0 absorption band occurs at
lower wave number in the region 16301690 cm1. This band due to primary amide group
( ) is known as amideI band. The presence of NH2 group in primary amide is indicated
by the appearance of two bands in the range of 34003500 cm1 due to symmetrical and asymmetrical
vibrations of NH2 group. All the primary amides show a sharp absorption band known as amide
II band in the region 16501620 cm1 because of NH2 bending. The C N stretching band of
primary amide occurs near 1400 cm1. Besides, a broadband of medium intensity appears in the IR
spectra of primary and secondary amide as a result of out of plane NH wagging.
PROBLEM 12.14 The IR spectrum (Figure 12.26) of aniline is given below. Indicate the position
Figure 12.26 IR spectrum of aniline.
Solution Positions of some characteristic absorption

A and B = 3450 cm1 and 3390 cm1, N Hstr in primary amines
C= 3226 cm1; N Hstr hydrogen bonded.
D= 3030 cm1; == C Hstr in olefines/aromatics.
E, F, G = 1600, 1580, 1460 cm 1; C Cstr in aromatics nuclei.
H and I = 1306, 1275 cm1, C Nstr in primary aromatic system.
J and K = 754 and 696 cm1; characteristic of monosubstitution benzene.
PROBLEM 12.15 An organic compound (A) with molecular formula C3H9N shows the following
peaks in its infrared spectrum.
(i) 3012 cm1 (m), (ii) 3423 cm1 (s),
(iii) 3236 cm1 (m), (iv) 1615 cm1 (m).
When the compound A is treated with nitrous acids, we get a compound B which shows a
strong peaks at 3450 cm1. What are A and B and explain the reactions involved?
Solution The two bands at 3423 cm1 and 3236 cm1 are due to asymmetrical N Hstr and
symmetrical.
Clearly, the compound contains NH2 group.
The bands at 3012 cm1 is due to C Hstr.
The bands at 1615 cm1 is due to N H bending. The probable structure consistent with the given
molecular formula and data is: CH3 CH2 CH2 NH2 which on reaction with alcohols gives
CH3 CH2 CH3 CH2 OH as indicated by the appearance of vO H band at 3450 cm1.
PROBLEM 12.16 How would the IR spectrum of the following pair of compounds differ:
(i) Acetone and ethanol
(ii) Acetic acid and methanol?
Solution
(i) Acetone shows an absorption bands at 1710 cm1. It is a strong band due to C == Ostr.
Ethanol shows an absorption bands between 32003600 cm1 due to hydrogen bonded
O Hstr. In case of acetone, the bond in the region 32003500 cm1 will be missing.
(ii) Acetic acids shows v C == Ostr at 17001725 cm1. Also a very broad band in the region
25003000 cm1 results due to O Hstr. Methanol shows a broad band only due to
hydrogen bonded O H group in the region 32003500 cm1.
PROBLEM 12.17 Give appropriate position of the characteristic infrared bands in
(i) CH3 CH2 OH (ii) CH2 == CH CHO
Solution
(i) In CH3 CH2 OH
(a) C Hstr 32003600 cm1
(b) C Hstr 29003000 cm1
(ii) Characteristic IR band
(a) C Hstr 27002800 cm1 (characteristic of aldehyde)
(b) C == Cstr 16201680 cm1
PROBLEM 12.18 How are the structures of the following compounds indicated in the infrared
spectral data:
(a) Acetophenone (b) But-1-ene (c) Phenol
Solution
(a) For acetophenone, the Infrared bands are
(i) n C == Ostr 17051725 cm1
(ii) n C H aromatic ~ 3010 cm1
(iii) n C Cstr ~ 1600 cm1, ~1500 cm1, ~1460 cm1
(iv) For mono substitution C H bending ~ 730770 cm1
(b) But-1-ene: This compound shows the following characteristic absorption bands:
n C Hstr in alkene ~ 30103040 cm1
n C Hstr in CH2, CH3 28602950 cm1
n C == Cstr ~1410 cm1
(c) Phenol: Phenol gives the following characteristic bands in infrared technique.
n C Hstr in aromatic ~ 30103040 cm1
n O Hstr ~ 35803650 cm1
n C Ostr ~ 1410 cm1
PROBLEM 12.19 How would you interprete the infrared spectrum of C5H5 CH2NH2 and
Solution Benzyl amine shows the following characteristic absorptions.

(i) n C Hstr ~ 31003040 cm1
(ii) n C Cstr ~ 1600 cm1, ~1500 cm1, ~1460 cm1 (aromatic)
(iii) n N Hstr ~32503500 cm1
NN-Dimethyl acetamide shows bands at
n C == Ostr ~ 1675 cm1 (s), n C Hstr ~ 3000 cm1
12.10 IR CHARACTERISTICS OF SOME INORGANIC COMPOUNDS

(ESPECIALLY METAL COMPLEXES)
When a fixed number of ligand ions or molecules (L) get coordinated with the central metal ion
(M), resulting in the formation of the complex, there are certain changes in the properties of the
ligand due to the formation of the new M L bond and these can be usefully studied for the
elucidation of the complex by spectral data. The following changes may take place.
1. The coordination of the ligand atom with the metal ion results in the movement of electron
density from the ligand atom and thus there is a negative inductive effect causing the
polarization of the bonds of the ligand atom with other atoms of the molecules. For example
coordination of nitrogen in NH3 or amines with the metal ion (M) causes polarization of the
N H bond and hence n N H band of free ammonia at ~3100 cm1 occurs at lower
frequency. The lowering has been correlated with the strength of the metal ligand bond.
The greater the metal ligand bond strength, the greater is the lowering of
n N H band position. The condition of N atom of the ligand to the metal ion is further
confirmed by the appearance of n M N band in IR spectra of the complex ion in the
region ~500 cm1 which is absent in the IR spectra of the ligands.
2. The coordination of the ligand molecule with the metal ion can change the symmetry of
the molecule. It is normally reduced and hence a band which is IR inactive in the free ion
or molecule may become IR active on its coordination with a metal or a single band
corresponding to degenerate vibrations may split up in the complex due to the lowering of
symmetry. For example water in inorganic salts may be classified as lattice or co-ordinated
water. In general lattice water absorbs at 35503200 cm1 (antisymmetric and symmetric
OH stretching) and at 16301600 due to HOH bending (scissoring). When it is coordinated
to the metal ion by donation of lone pair electrons of O atom of H2O to the metal ion
forming aquo (H2O) complexes, in addition to the fundamental modes of free water as
cited above in case of lattice water, coordinated water exhibits other modes such as rocking
rr(H2O) and wagging rw (H2O) in the regions 900800 cm1 and 600500 cm1 respectively.
An extra band at far R region ~500400 cm1 also occurs due to n M O stretching. This
has been further illustrated as follows giving examples of nitro and nitrito complexes,
carbonato and nitrates complexes, sulphato and perchlorato complexes and oxalato complexes.
(a) Nitro and nitrito complexes: Nitrite ion can be present in the complex in the
following forms:
(i) Anionic nitrite (free nitrite) as in complex of the type (MXn) (NO2)m where M is
a metal ion of charge m, X is a neutral unidentate ligand and n is the coordination
number of the metal ion. NO2 ion is outside the coordination sphere.
(ii) NO2 can coordinate either through N or O atoms. If it coordinates through N
atom with the metal ion, the resulting complex is called nitro complex.
(iii) On the other hand, if NO2 is coordinated through one O atom with the metal ion,
resulting complex is called nitrito complex.
(iv) If NO2 ion coordinates with metal ion through both of O atoms, a chelating nitro
complex is formed.
(v) NO2 can also act as bridging ligand simultaneously coordinating with two metal
ions through its two oxygen atoms resulting the formation of a bridging nitro
complex as depicted below.
This can be decided with the help of IR spectra. An anionic NO2 group has C2v symmetry
and hence shows three IR bands at 1335, 1250 and 850 cm1 due to nas(NO ), ns(NO ) and
2 2
bending d (ONO) respectively. On coordination of NO2 through the nitrogen atom as in
[Co(NO2)6]3 complex ion, the symmetry of the NO2 group remain C2v. Hence all the
above bands occur in the complex with some change in the positions. However, there is
a new band at ~625 cm1 corresponding to the out of plane bending of NO2 (wagging)
with the metal ion.
If the coordination of NO2 is through the oxygen atom the symmetry is reduced to
Cs. The two nN = O and nN O bands occur at ~1468 cm1 and ~1065 cm1 respectively
which are well separated. Whereas in nitro complexes both NO are equivalent and
hence nas and nS have a separation of ~100 cm1. Further the band due to the wagging
mode in nitro complexes disappears in the nitrito complexes. In chelated and bridge
forms NO2 has also, symmetry C2v. In the chelating form, both the symmetric and
asymmetric NO2 stretching frequencies are lower and ONO bending frequency is higher
than those of unidentate N-bonded nitrogroup. When the nitro group form a bridge
between two metal atoms, all the three (n as (NO2) nS (NO2) and d (ONO) appear at
higher frequency regions 1520, 1290 and 860 cm1 respectively.
(b) Carbonato (CO3) and Nitrato (NO3) complexes: CO32– or NO –3 can be present
in three different form in complexes as shown below.
(i) In free ionic form with D3h symmetry
(ii) As monodentate ligand with coordination from one oxygen atom with Cs symmetry.
(iii) As bidentate ligand coordinating with the metal ion through two oxygen
atoms, symmetry being reduce to C2v. Nitrate can also be in the bridged form
coordinated to two metal ions. Symmetry is C2v in this case also. The ionic
carbonate with D3h symmetry has three IR active vibrations v2, v3 and v4. On
coordination as monodentate ligand, symmetry is reduced to Cs. The symmetrical
stretching vibration (v1) which is IR inactive in free carbonate becomes IR active,
v3 and v4 vibration which are doubly degenerate in free carbonate lose their
degeneracy in the complex and hence splitting of v3 and v4 bands occurs. Three
stretching bands at 1453, 1373, 1070 cm1 and three bending vibration at 850,
750, and 678 cm1 are observed in the IR spectrum of [CO(NH3)5 CO3]Br with
unidentate carbonate. However, in bidentate ligand CO32– the splitting of the
degenerate vibration is more. For example in [CO(NH3)3CO3Cl] with bidentate
carbonate, three stretching vibration of CO are observed at 1593 and 1265 and
1030 cm1 with a difference of 328 cm1 between the first two. Whereas for
monodentate carbonate in [CO(NH3)5CO3]Br the separation between first two
bands is only 80 cm1.
In case of nitrato complexes also the monodentate and bindentate forms have
the same number of fundamental vibrations. But the bindentate forms show a
greater separation, for example in [Ni(en)2 (NO3)2] with unidentate nitrate, three
bands are observed at 1420 cm 1, 1305 cm 1 and 1008 cm1 but in
[Ni(en)2NO3]ClO4 with bidentate chelating nitrates the bands are at 1476, 1290
and 1025 cm1. The first two bands have a greater difference in case of bidentate
nitrates. It is, however, difficult to distinguish between chelated and bridge nitrate
by the help of IR spectra.
(c) Sulphato (SO4) and Perchlorato (ClO4) complexes: SO 2– 4 or ClO 4 ions are present
–
in the complexes in the following forms.

(i) Ionic forms with Td symmetry.
(ii) Coordinated through one of the oxygen atoms as a monodentate ligand with C3v
symmetry.
(iii) Coordinated through two oxygen atoms to the metal ion as a bidentate chelating
ligand with C2v symmetry.
(iv) Sulphate can also bridge two metal ions by coordinating through one oxygen
atom to both. Symmetry is C2v in this case also as shown below.
Two bands are observed at ~1100 cm1 and 600 cm1 in [CO(NH3)6]2(SO4)3, where
sulphate is ionic due to IR active n3 and n4 vibrations. However, on coordination as a
monodentate ligand as in [CO(NH3)5SO4]Br, the symmetry of SO4 is reduced to C3v.
v1 and v2 bands become IR active and occurs with medium intensity at 970 cm1 and
438 cm1, respectively. There is also splitting of v3(~1040 cm1 and 1125 cm1) and
v4 bands into two (645 cm1 and 604 cm1).
The chelating and bridging sulphate have C2v symmetry. Due to further lowering
of symmetry v1 and v2 appears with medium intensity and v3 and v4 split up into three
bands each. For example in the IR spectrum of bridged sulphate.
Three v3 bands appears at 1050 cm1, 1170 cm1 and 1005 cm1 and in [CO(en)2 SO4]
Br with bidentate chelated sulphate, three v3 bands occurs at 1211 cm1, 1176 and
1075 cm1. Thus bridge and chelated sulphate cannot be distinguished by the number
of IR spectral band. Only distinction is that in case of chelated sulphate the v3 bands
occurs at higher frequency than in case of bridged sulphate.
The perchlorate ion is weakly coordinated and hence is present in the complexes as
anion or as an unidentate or rarely as bidentate ligand. Just as in case of sulphate, the
complexes with anionic perchlorate exhibit only stretching frequency at 1170 cm1
due to vas v3. A less intense band due to v4 is observed at 935 cm1. In complexes with
unidentate perchlorate [Ni(CH3CN)4(ClO4)2], v1 vibration becomes IR active and is
observed as an intense band at 972 cm1.
In the complexes [Ni(CH3CN)2(ClO4)2] with bidentate perchlorate, v1 is observed
at 920 cm1 and v3 is split up into three bands at 1195 cm1, 1106 cm1 and 1100 cm
1 due to C symmetry of bidentate perchlorate.
2v
(d) Oxalato complexes: Free oxalate ion has D2h symmetry. Its symmetry is reduced to
C2v when coordinated as a bidentate ligand in the complexes. Hence the IR inactive
vibration in the free oxalate become IR active in the coordinated ion and hence the
number of IR bands in the oxalate complexes is more. In other word in the oxalate ion
all the four C O are equivalent, whereas on coordination two COs are coordinated
to metal ion are C O and two free are C == O. Thus there will be two different
stretching vibrations corresponding to vC O and vC — O.

(i) The midIR region of the electromagnetic spectrum is about:
(a) 4000660 cm1 (b) 12,5004000 cm1
(c) 66050 cm 1 (d) 5010 cm1
(ii) The absorption of IR radiation is accompanied by transitions involving:

(a) Electronic levels (b) Vibrational levels
(c) Nuclear spin levels (d) Electron spin levels
(iii) A typical wavelength in the IR region of the electromagnetic radiation is 6 mm. The energy
expressed in joules of one photon of this radiation is:
(a) 3.313 ´ 1020 (b) 1.325 ´ 1047
(c) 3.976 ´ 1039 (d) 6.626 ´ 1040
(iv) A common source of IR radiation is the
(a) Tungsten lamp (b) Deuterium discharge lamp
(c) Hg-vapour lamp (d) Nernst glower
(v) A common detector employed to detect IR radiation is the
(a) Photomultiplier (b) Photovoltaic cell
(c) Thermocouple (d) Crystal detector
(vi) The number of fundamental modes of vibration of the acetylene molecule is
(a) 2 (b) 4
(c) 6 (d) 8
(vii) The cells for IR spectrophotometry are usually made of
(a) Calcium chloride (b) Sodium chloride
(c) Aluminium chloride (d) Magnesium chloride
(viii) Aldehydes can be distinguished from ketones by an absorption near
(a) 1000 cm1 (b) 2720 cm1
(c) 980 cm1 (d) 1720 cm1
(ix) The force constant for the C H bond in ethane is
(a) 5.1 ´ 104 dyne cm1 (b) 3.1 ´ 105 dyne cm1
5
(c) 5.1 ´ 10 dyne cm 1 (d) 5.1 ´ 107 dyne cm1
(x) The fingerprint region in IR spectra ranges from
(a) 1500700 cm1 (b) 19501550 cm1
(c) 22602190 cm 1 (d) None of these
2. State whether the following statements are true or false. Write the correct statements.
(i) Absorption in Infrared region is due to the changes in the vibrational and rotational levels.
(ii) Enantiomers of a compound have exactly similar Infrared spectrum.
(iii) Less energy is required for stretching as compared to bending vibrations.
(iv) In infrared, electron donating groups lower the wave number of absorption while the electron
attracting groups raise the wave number.
(v) For meta substituted compounds, the absorption is estimated by considering only the
inductive effect.
(vi) Hydrogen bonding lowers the wave number of absorption and also make the bands broad.
(vii) The absence of absorption bands between 1650 and 1900 cm1 shows that carbonyl group
is absent.
(viii) Intermolecular hydrogen bonding is concentration independent.
(ix) The lowering in wave number of absorption also depends upon the extent of conjugation.
(x) The frequency of the symmetric stretching vibration of the water molecule is greater than
that of asymmetric stretching vibration.
(xi) The stretching frequency of the C == O group in amides is less than that in anhydries.
(xii) The IR absorption peaks due to the OH stretch in alcohols are sharp and intense.
(i) Ordinary IR region extends from 2.515 m and the one from 15200 m, is called
.............. .
(ii) Some factors which shift the wave number of absorption are .............., ..............,
.............., and .............. etc.
(iii) The various type of bending vibrations are .............., .............., .............. and ............... .
(iv) Glass cannot be used as cell container because it .............. .
(v) Some mulling reagents for making a paste in IR spectroscopy are .............., .............., etc.
(vi) Intramolecular hydrogen bonding is concentration while intermolecular hydrogen
bonding is .............. .
(vii) In unsaturated dicarboxylic acid, cis isomer absorbs at higher wave number because of
........... .
(viii) Prism monochromators used in IR spectroscopy are made of .............. .
(ix) If a vibrational mode should be active in the IR, it should involve a change in .............. .
(x) The paraffin oil usually employed for the preparation of mulls is .............. .
(xi) The most useful vibrations occur in the narrower range of .............. mm.
(xii) .............. is the most widely used infrared detector.
(xiii) FTIR is especially useful for examining .............. samples.
(xiv) Infrared is most informative because most functional groups are not .............. .
(xv) The localized vibrations are either stretching, bending rocking, ..............or .............. .
(xvi) Bending vibrations usually appear in the .............. region below 1500 cm1.
(xvii) Write Fermi resonance is operative in .............. molecules.
(xviii) Coupling is found in .............. group and the .............. ion.
(xix) Conjugation with olefinic or acetylic groups .............. the frequency and .............. the
intensity.
(xx) The more electronegative the group X in the system R CO X , the .............. is the
frequency.

(i) Predict the number and give the names of the fundamental modes of vibration of hydrogen
chloride.
(ii) How many fundamental modes of vibration would you expect to observe in the infrared
absorption spectrum of water? Give their names.
(iii) How will you distinguish an aliphatic aldehydes from an aliphatic ketones.
(iv) How will you distinguish between an aliphatic and aromatics compound?
(v) Explain why does maleic acid absorb at a higher frequency as compared to fumeric acid?
(vi) Why is methanol a good solvent for UV and not for IR determination?
(vii) What do you mean by the fundamental vibration?
(viii) Mention characteristic absorption bands of the carbonyl group in the IR spectra of
(a) CH3COCH3 (b) CH3CHO
(c) C6H5CHO (d) CH3COOH
(ix) Give characteristic absorption bands of C N group in the IR spectra of following
compounds:
(a) CH3NH2 (b) C6H5NH2
(c) (C6H5)2NH (d) (C6H5)3N
(x) In case of the following molecules, mention whether the vibration will be active or inactive
in IR region?
Molecule Motion
(a) SO2 Symmetric stretching
(b) CH3 CH3 C C stretching
(c) CH3 CCl3 C C stretching
(d) CH2 == CH2 C H stretching
(xi) Which of the following molecules will show IR spectrum HCl, CH4, CO2, H2O, H2, and
N2O?
(xii) Give absorption frequency of the following groups in the IR region:
(a) OH in phenol,
(b) CO in aliphatic aldehydes,
(c) C ºº N in aromatics nitriles,
(d) O H stretch in carboxylic acid dimmers,
(e) N H bending vibration in primary amines.
(xiii) Why water cannot be used as a solvent in IR spectroscopy?
(xiv) Why carbon tetrachloride does not yield prominent bands in the main region of IR while
chloroform gives?
(xv) What is the necessary condition for a molecule to absorb infrared radiation?
(xvi) Why IR absorption due to C == O stretch occurs at higher frequency than C == C stretch?
(xvii) Why C == O stretching for salicylic acid occurs at 1665 cm1 while for p-Hydroxybenzoic
acid it occurs at 1680 cm1?
(xviii) Why transitional motion is not involved in molecular spectra?
(xix) Why absorptions of ultraviolet and visible radiation can be studied together, but IR absorption
studied are made separately?
(xx) The frequency of O H stretching is observed at higher range than the C H stretching.
Explain.
(xxi) How would you distinguish lattice water and co-ordinated water from IR spectra?
(xxii) How many normal vibrational modes are possible in the linear molecule ethane and non-
linear molecule benzene?
(xxiii) How many fundamental vibrational frequencies can be observed in the infrared absorption
spectrum of water?
(xxiv) Predict the number of fundamental modes of vibration of HCl.
(xxv) How many fundamental vibrational frequencies would you expect to observe in the
IR spectrum of CO2?
(i) Briefly describe the scanning of an infrared spectrum of an organic compound.
(ii) How will you detect the type of hydrogen bonding involved in a particular compound by
Infrared spectrum?
(iii) A compound in the vapour state absorbs for a particular bond (stretching frequency) at a
higher wave number as compared to that when it is the solid state, why?
(iv) An organic compound shows absorption at 3452 cm1, 3264 cm1 and 1665 cm1. Write the
probable functional groups present in the compound.
(v) An organic compound A with molecular formula, C3H6O absorbs at 1715 cm1 strongly.
When it is reduced with hydrogen, another compound B, (C3H8O) appears. In B,
absorption at 1715 cm1 was missing and a band at about 3600 cm1 appeared. What are A
and B?
(vi) An organic compound (A) with molecular formula (C3H7NO) gives absorption peaks in
the region 3413 cm1 (m), 3236 (m), 30302899 (m), 1667 (s), 1634 (s) and 1460 cm1.
Give its probable structure.
(vii) IR spectrum of acetone gives two maxima due to C H vibration at 1360 cm1 and 3000
cm1. Identify the stretching and bending mode.
(viii) Two isomers A and B of the molecular formula C3H6O give IR absorption band near
1650 cm1 and 1710 cm1. Assign structural formulae to A and B consistent with their IR
absorption bands.
(ix) A compound of formula C8H8O has a strong Infra-red band near 1690 cm1, which of the
following structures is likely to be one of the compounds.
(a) C6H5 CH2CHO (b) C6H5 O CH == CH2
O
||
(c) C6H5 C CH3
(x) Give the approximate position of the important IR absorption frequencies for the following
compounds
(a) Toluene (b) Acetic acids
(c) Ethyl alcohol (d) Dimethyl ether
(xi) Give approximate positions of characteristic infrared bands in the following compounds?
(a) CH3CH2OH (b) CH3COCH3
(c) CH2 == CHCOCH3
(xii) How will you distinguish a ketone and a carboxylic acid by the Infrared spectroscopy?
(xiii) What information can you obtain from the following compounds by the application of IR
spectroscopy?
(a) Acetophenone (b) Cinnamic acid
(c) Phenol (d) Benzylamine
(xiv) Using IR spectroscopy show how you could distinguish between
(a) Orthohydroxy benzaldehyde and metahydroxy benzaldehyde
(b) C6H5COC2H5 and CH3 C6H4 COCH3
(xv) Draw the IR spectra of the following compounds:

(a) Butene-2(cis) (b) Diphenyl ketone
(c) Butanol (d) Aniline
(xvi) Mention approximate position of the various absorption bands.

6. What are the factors which influence the positions of IR absorption bands from their normal
values?
7. Describe the effect of intermolecular and intramolecular hydrogen bonding on the positions
of IR absorption frequency of a compound. Give examples.
8. How will you distinguish the following pairs of compounds with the help of
infrared technique?
(i) Ethanol and dimethyl ether
(ii) Propanol and propanone
(iii) Ethanol and Ethylamine
9. Discuss in detail the various factors which influence the vibration frequency of a particular
group. Give examples.
10. How will you distinguish the following pairs using IR spectra?
(a) Acetone from acetylene (b) Ethanal from ethanol
(c) Acetonitrile from acetamide (d) Aniline from N-methyl aniline
(e) o-Hydroxybenzoic acid from m-Hydroxybenzoic acid.
11. Write the basic principle of Infrared spectroscopy. Describe the various molecular vibrations
in this technique?
12. Briefly describe the various modes of vibrations for the following molecules
(a) H2O (b) SO2
(c) CO2 (d) NH3
Out of them, which are infrared active?
13. Describe various vibrational modes of
(a) Square planar molecule (b) Tetrahedral molecule
(c) Octrahedral molecule
Give comments on their IR activities.
14. Write notes on
(a) Selection rules of IR absorption (b) Stretching and bending vibrations
(c) Overtones (d) Fermi resonance
(e) Fingerprint region.
15. How will you distinguish the followings from study of IR spectra?
(i) Lattice water and co-ordinated water.
(ii) Nitrito and nitro complexes
(iii) Chelating nitro complex and bridging nitro complex.
16. Discuss the study of the following complexes by means of IR spectra
(i) Carbonato complexes (ii) Nitrato complexes
(iii) Perchlorato complex (iv) Sulphato complexes
(v) Oxalato complexes.
CHAPTER 13
Nuclear Magnetic Resonance
Spectral Method
13.1 INTRODUCTION
The study of absorption of radio frequency radiation by a magnetic nucleus in the presence of an
applied magnetic field is called nuclear magnetic resonance, often abbreviated as NMR. This is
one of the powerful techniques especially for
(i) Structural elucidation for organic compounds.
(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
spectroscopic or analytical techniques.
(iii) Quantitative determination of compounds in mixtures and hence for studying the progress
of chemical reactions.
(iv) Determination of kinetic and thermodynamic parameters for certain types of chemical
processes.
(v) Determination of magnetic nuclei within molecules.
13.2 PRINCIPLE OF NMR
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 / 2S (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:
(i) For integral spins,
MI = I, (I 1), , 0, , (I 1) · I
(ii) For half-integral spins,
MI = I, (I 1), , +1/2, 1/2, , (I 1) · I
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:
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.
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.
3. Nuclei with odd mass have half integral spins (e.g. H1, N15(I = 1/2), O17(I = 5/2),
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
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
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.
The numerical value of I is related to the mass number and the atomic number of the concerned
isotope.
13.2.2 Magnetic Moments of the Nuclei

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
(mm) of the generated magnet can be calculated with the help of Amperes law and is given by
Gaussian system: mm = g (e / 2m p c) ( I (I 1) h / 2S
= g (eh / 4S m p c) ( I (I 1) = g I (I 1) E 1 (13.2)
where, bN = (eh/4pmpc), mp = mass of proton in gm, c = velocity of light in cm/s, h = Planks

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 ´ 1024 erg/gauss and in SI unit, it is 5.047 ´ 1027 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 / 2S
For proton I = 1/2 , h = 6.626 ´ 1034 Js
Thus we have
L = 1/2(1/2 1) h / 2S
= 0.866 h/2p = 0.914 ´ 1034 Js
and magnetic moment
mm = g I (I 1) E 1 ,
bN = 5.047 ´ 1027 J/T
Hence, mm = g I (I 1) E 1
= 5.585 1/2(1/2 1) 5.047 10 27 J/T
= 2.44 ´ 1026 J/T
13.2.3 Effect of External Magnetic Field

For a particular value of total spin quantum number (I) of the nucleus, there are 2I + 1 possible
components corresponding to nuclear spin magnetic quantum number M1 = I to I. These
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.
For example, for a proton I = 1/2, the nuclear magnetic spin momentum quantum number MI
will have values +1/2 (a) and 1/2 (b) corresponding to two orientations of spin motion of proton.
This will give rise to two nuclear spin states. In the absence of magnetic field, two MI states remain
degenerate. An imposition of an external magnetic field, H removes the degeneracy and establishes
2I + 1 = 2 ´ 1/2 + 1 = 2, non-degenerate levels.
13.2.4 Potential Energy of a Nucleus in a Magnetic field

The potential energy, E of a nucleus placed in a magnetic field H is given by the relation
E = Hmz (13.3)
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 E 1 I ( I 1) ) cos (13.5)
The angle Q cannot have any arbitrary value, but only a few allowed discrete values which satisfy
the condition of quantization of the component of angular momentum vector along the axis of the
magnetic field, i.e.
( I (I 1) h / 2S ) cos = MI h/2p
I (I 1) cos 4 = MI (13.6)
Substituting Eq. (13.6) in Eq. (13.5), we get

mz = gbN MI
Substituting the above relation in Eq. (13.3), we have
E = H(bN gMI) (13.7)
Thus, the potential energy of interaction of a nucleus with external magnetic field depends on the
value of MI.
Let us calculate the potential energy of a proton in a magnetic field.
13.2.5 Potential Energy of a Proton in a Magnetic field

The value of spin quantum number, I for proton is +1/2. Thus, MI can have two values, namely
+1/2 (a) and 1/2 (b). The schematic variations of potential energies of a and b protons are shown
in Figure 13.1.
Figure 13.1 Variation of potential energy a and b protons in the presence of a magnetic field.
The value of g for protons is found to be 5.5854. Substituting the values of MI, g and bN in
Eq. (13.7), we get
E = H(bN gMI)
E+1/2 = (5.047 ´ 1024 erg gauss1) (5.5854) (1/2)H
or E+1/2/erg = 1.410 ´ 1023(H gauss1)
E1/2 = (5.047 ´ 1024erg gauss1) (5.5854) (1/2)H
or E1/2/erg = +1.410 ´ 1023(H gauss1)
From the above relation, we may conclude that the proton with spin +1/2(a) will have a lower
potential energy as indicated in Figure 13.1. The energy difference, DE between MI = +1/2 level
and MI = 1/2 level, is
DE = E1/2 E1/2 = 1.410 ´ 1023 erg H gauss1 (1.410 ´ 103 erg H gauss1)
= 2.82 ´ 1023 erg H gauss1
The energy difference (DE) between the two consecutive energy levels is given by
DE = gbN DMIH = gbNH, since DMI = 1
Substituting the value of g = mz/I, we get
Pz E N H
DE = (13.8)
I
whereas mz = magnetic momentum of the spinning nucleus along the direction of H, i.e. applied
magnetic field which is taken as the Z-axis which is also taken as m.
When the nucleus absorbs energy in the form of electromagnetic radiation of frequency f, then
Eq. (13.9) is obtained.
PE N H
DE = hf (13.9)
I
Thus the resonance condition is attended. As a result, the transition between the lower spin state to
higher spin state takes place producing a signal which is recorded as a band called NMR spectral
band.
PROBLEM 13.2 For a proton find out the resonance frequency required for transition at field
strength 14092 gauss. Give your comments on the result.
Solution For a proton DE = hf = gbN H, Given H = 14092 gauss
gE N H
So f=
h
5.585 × 5.047 ×10 –24 erg/gauss ×14092 gauss
=
6.626 1027 erg. s
= 60 MHz
Hence, in a magnetic field of 14092 gauss, the proton will process 60 million times per second or
60 MHz which corresponds to radio frequency (rf) region of electromagnetic radiation.
Thus resonant absorption of rf (radio frequency) energy in the presence of an external magnetic
field is referred to as nuclear magnetic resonance (NMR).
PROBLEM 13.3 Calculate the magnetic field strength required for PMR at 220 MHz.
Solution Since, DE = hf = gbN H
hf
H=
gEN
Given f = 220 MHz = 220 ´ 106 Hz
6.626 10 27 erg s × 220 ×106 /s
=
5.585 × 5.047 ×10 –24 erg/gauss
= 5.171 ´ 104 gauss = 5.171 T
13.2.6 Classical Description of NMR

If protons are involved, it may be called proton magnetic resonance (PMR). Any spinning charge
has a magnetic moment. If a magnetic nucleus is placed in an external magnetic field of strength
H, the magnetic moment experiences a couple forces which rotate the magnetic moment vector
around the field direction keeping its orientation angle Q constant, i.e. the magnetic moment starts
processing around the magnetic field as shown in Figure 13.2.
Figure 13.2 Larmor precession.
This precession is known as Larmor precession. Eq. (3.2) can be written in the form of w, the
angular frequency of precession under resonance condition as:
PE N H
w = 2S f 2S (13.10)
hI
or
Z =
2S f 2SPE N
(13.11)
H H hI
The ratio
Z is a fundamental constant characteristic of any nuclear species. This is called the
H
gyromagnatic ratio (or the magnetogyric ratio) given the symbol g = 2p mbN /hI.
Thus gyromagnetic ratio g, is expressd as a ratio between the magnetic moment in nuclear
magneton with angular momentum of rotating particle in the unit of h/2p. It has a characteristic
value for each type of nucleus
Z
\ =g
H
or w =gH (13.12)
2pf = H i.e. f = g H/2p (13.13)
PROBLEM 13.4 Calculate the value of gyromagnetic ratio.
Solution Gyromagnetic ratio is given by
g = 2pmbN /hI, g = µ/I
= 2pgbN /h
Substituting the value of g, bN and h
2 × 3.14 × 5.047 ×10 –27 J/T × 5.585
g =
6.626 10 –34 J s
= 2.671 ´ 108 T1s1
The study of NMR spectra gives the following information:
(i) The position and magnitude of NMR peak provide information about the molecular
environment of the nuclei.
(ii) The number of resonating nuclei present in the similar environment.
(iii) The nature of environment.
Thus from NMR spectra we can elucidate the structure of simple and complex molecule.
13.2.7 Intensity of NMR Signals

The excitation of a nucleus from the lower energy levels to higher one can occur only if the lower
level is more populated than the higher one. The relative populations of nuclei over the available
energy levels can be calculated from the Boltzmann equation
n2/n1 = exp(DE/kT) (13.14)
where n1 and n2 are the number of nuclei in the lower and higher energy levels, respectively.
DE is the energy difference between these two levels, k is the Boltzmann constant (k = R/NA) and
T is the absolute temperature. The value of k = 1.38 ´ 1016 erg K1.
PROBLEM 13.5 Calculate the relative population of protons in the two available energy levels
at room temperature (300 K) under the influence of 10000 gauss (i.e. 1 T). Give comment on the
result.
Solution For a proton = E1/2 E+1/2 = 2.82 ´ 1023 erg H/gauss
Given T = 300 °K and H = 10000 gauss, kT = 1.38 ´ 1016 erg K1 ´ 300°K = 4.14 ´ 1014 erg
DE = 2.82 ´ 1023 erg. 10000 gauss/gauss
= 2.82 ´ 1019 erg
n2/n1 = exp (DE/kT);
Considering DE/kT to be very small
» 1 DE/kT
= 1 2.82 ´ 1019 erg/4.14 ´ 1014 erg = 0.999993
Thus if ground level, for example, contains 106 molecules, then the upper level will contain
0.999993 ´ 106 molecules. Hence, there exists a population difference of about 7 molecules out of
a total of 106 + 0.999993 ´ 106 molecules (i.e. 2 million molecules).
However, the intensity of absorption can be enhanced either by carrying NMR at low temperatures
and/or by employing high magnetic field. Both these factors help in increasing the population
difference between the two levels in accordance with the Boltzmann distribution law.
Saturation and relaxation process

The two levels will have the same population only when the term DE/kT in Eq. (13.14) has a zero
value. This is possible only when the temperature of the system is infinite which is an impossible
proposition. This leads to the point of saturation so that the absorption ceases. But, in practice the
population in the two states do not become equal, because the nucleaus in the high energy level is
constantly returning to the lower energy level. The difference in population between the two spin
levels is always maintained even during the absorption process. The various ways by which a
nucleus returns to the lower energy level from the higher energy level without emitting radiation
are known as relaxation process. Two types of relaxation process involved in NMR are spin-spin
relaxation and spin-lattice relaxation. Thus, it may be concluded that the lowest level is always
more populated than the upper level. The intensity of NMR signal depends on the relative population
of magnetic nuclei between magnetic quantum states.
13.3 TECHNIQUE INVOLVED IN NMR SPECTROSCOPY
An experimental set up for NMR spectrometer is shown in Figure 13.3. The main components in
an NMR instrument are:
(i) The magnet,
(ii) The field sweep generator,
(iii) The radio frequency source,
(iv) The signal detector and recorder system,
(v) The sample holder and probe.
Figure 13.3 Experimental set-up for NMR.
(i) The magnet

The accuracy and quality of an NMR instrument depends upon the strength of the magnet.
Spectrometric magnets are of three types.
(a) Permanent magnet: Commercial magnet generates field of 7046 or 14092 G,
corresponding to proton absorption frequencies of 30 and 60 MHz. Good thermostats are
needed as the magnets are temperature sensitive.
(b) Electromagnet: Commercial magnet generates fields of 14,092, 21,140 and 23,490 G,
corresponding to proton absorption frequencies of 60, 90 and 100 MHz. Such magnets
need a cooling system.
(c) Superconducting solenoid (supercon): Fields as great as 110,390 G are attained,
corresponding to a proton frequency of 470 MHz. This is used in the highest resolution
instrument.
(ii) The field sweep generator
A pair of coils located parallel to the magnet faces as shown in Figure 13.3 permits alteration of the
applied field over a small range. By varying a direct current through these coils, the effective field
can be changed by a few hundred milligauss without loss of field homogeneity.
(iii) The radio frequency source
The signal from a rf oscillator (transmitter) is fed into a pair of coils mounted at 90 degree to the
path of the field. A fixed oscillator of exactly 60, 90 or 100 MHz is ordinarily employed.
(iv) The signal detector and recorder system
(v) Sample handling and sample holder

For a routine analysis, samples of about 550 mg used. For high resolution work, samples must be
in a non-viscous liquid state. Generally, solutions of the sample (2 to 15%) are employed.
The best solvent of proton NMR spectroscopy contains no protons. From this point, CCl4 is
ideal. The low solubility of many compounds in CCl4 limits its value. However, a variety of duterated
solvents are used instead. The most commonly used solvents are duterated chloroform, CDCl3,
duterated benzene C6D6, DMSO and D2O.
The solution is introduced into the cell (often constructed of borosilicate glass which does not
absorb rf radiation within the range in which the sample is expected to absorb). The usual NMR
sample cell consists of a 5 mm outer diameter glass tube containing about 0.4 ml of solvent.
The solution should be free of paramagnetic and insoluble impurities. An internal reference
compound (TMS) is added to the solution, and the tube is lowered into a probe placed between the
poles of the magnet.
(vi) Probe
Probe is a device for holding the sample tube in a fixed spot in the field. It contains a sample
holder, sweep source and detector coils. The detector and receiver coils are oriented at 90° to each
other. The sample probe rotates the sample tube at a hundred r.p.m. on the longitudinal axis.
Working principle
The sample is placed between the poles of a huge electromagnet of adjusted field (10,000 to
15,000 gauss). Sweeper coils are used to adjust the field. The strong homogeneous magnetic field
causes the nuclei to precess. Radiant energy corresponding to radio frequency is then imposed
with a radio frequency transmitter. When the applied frequency from the radio transmitter is equal
to the Larmor frequency, the two are said to be in resonance. The net result of this resonance is that
some nuclei are excited from the low energy (MI = +1/2) state to the high energy state (MI = 1/2)
by absorption of energy from the source at a frequency equal to Larmor frequency. The frequency
(resonance frequency) at which the loss in energy from the transmitter occurs can be measured by
using signal detector and device.
Presentation of NMR spectra
Resonance phenomenon can be achieved by either of the two ways: 1. By varying the frequency of
oscillator keeping the external magnetic field constant, 2. by varying the external magnetic field
keeping the frequency of the oscillator constant. In actual practice in most of the instruments a
fixed frequency (usually 60 MHz) is supplied by a crystal controlled oscillator and the magnetic
field applied to the sample is varied by an electromagnet. Thus the NMR spectrum of a compound
is a plot of absorption of compound as a function of the external magnetic field. In a low resolution
NMR spectrum (lower magnetic field strength), each kind of nucleus is characterized by a single
absorption peak, the location of which appears to be independent of the chemical state of the atom.
If, however the spectral region around one of the nuclear absorption peaks is examined in detail
with a high resolution instruments (using higher magnetic field strength), the single peak is usually
found to be composed of several peaks (known as multiplet). The position and the intensity of the
component peaks depend critically upon the chemical environment of the nucleus responsible for
the absorption. This dependence can be explained on the basis of
(i) Prediction of number of NMR signal
(ii) Chemical shift and
(iii) Spin-spin coupling (splitting).
These points are discussed below with reference to protons. NMR in the case of protons is referred
to as PMR (or 1HMR), i.e. Proton Magnetic Resonance and it is discussed in the subsequent sections.
13.4 PREDICTION OF NUMBER OF NMR SIGNALS
In a given molecule the set of protons with the same chemical environment are said to be equivalent.
The number of signals in the NMR spectrum tells the number of different sets of equivalent protons
in a molecule, i.e. how many kinds of protons the molecule has. It may be noted that magnetically
equivalent protons are chemically equivalent protons. Let us find various sets of equivalent protons
(signals) in the following compounds:
1.
Since all the protons are in the exactly similar environment, so only one signal is observed.
2. Compounds showing more than one signal are as follows:
3. Strictly speaking, chemically equivalent protons must be stereo chemically equivalent. From
stereo chemical equivalence, following examples furnish the explanation.
Consider 1, 2-dichloropropane CH3 CHCl CH2Cl. In this case four NMR signals are
observed which can be explained on the basis of stereo chemical formula.
The environment of the two protons on the front carbon atom in the Newman projection
formula is not the same as the protons are non-equivalent and so absorbs at different field
strengths. Rotation around C C single bond in this molecule cannot bring similar
environment for the said hydrogen atoms.
However, NMR does not distinguish between mirror images or enantiomers. The number
of NMR signals expected for the following compounds are given below:
13.5 POSITION OF THE SIGNALS AND CHEMICAL SHIFT
The same nucleus gives absorption signals at different positions, if it is in different chemical
environments. This can be determined by a phenomenon called chemical shift. Every nucleus
is surrounded by cloud of electrons. The density of this cloud varies with the number and nature
of neighbouring atoms. When nucleus is placed in a magnetic field, the electrons surrounding
the nucleus tend to circulate in such direction as to produce secondary magnetic field, or induced
magnetic field. If the induced magnetic field opposes the applied field, the nucleus is said to
be shielded while in the reverse case the nucleus is said to be de-shielded. It follows, therefore,
that either the frequency or the magnetic field will have to be changed slightly to bring the
shielded nucleus into resonance. Shielding shifts NMR peak up field while deshielding shifts
the NMR peak down field to get effective field strength necessary for resonant absorption. Such
shifts on the position of NMR signals with a shielding or deshielding effect are called chemical
shift.
Let us consider the chemical shift due to shielding. In this case the effective field (HN) observed
by nucleus is not equal to the external magnetic field (H0), but a little less by a factor equal to the
induced magnetic field (Hinduced), i.e. HN = H0 Hinduced. Again Hinduced is directly propotional to
the applied field, H0, i.e. Hinduced = sH0, where s is a constant called shielding constant.
HN is given by
HN = H0 (1 s) (13.15)
The value of s depends on several factors such as
(i) Hybridization,
(ii) Electronegativity of the groups attached to the atom containing the nucleus being studied
and
(iii) Chemical environment of the nucleus but independent of applied field.
However, an accurate measurement of HN and H0 is difficult. Instead, a reference material is
employed and the difference between the field strength at which sample nucleus and reference
nucleus absorb is measured. From Eq. (13.15), we have
\ HS = H0 (1 sS) and HR = H0 (1 sR)
where sS and sR are shielding constants for the sample and reference respectively, and HS and HR
are the effective fields observed by the sample nucleus and reference nucleus respectively.
Hence,
HS HR = H0(sR sS).
For a given probe, the field experinced by the nucleus that is necessary for any proton to undergo
resonance, H is a constant. So that
H = HS(1 sS) and H = HR (1 sR)
Consequently
\ HS(1 sS) = HR (1 sR)
1VR HS
or = (13.16)
1VS H R
Subtracting one from both sides and rearranging, we get
VS VR HS HR
= (13.17)
1 VS HR
Since, sS <<< 1, Eq. (13.17) becomes
HS HR
d = sS sR =
HR
where, d is the chemical shift, defined as the difference between the shielding constants of the
sample and reference. Since the separation between reference and sample signals is often measured
in units of frequency (cps), Eq. (13.17) for d is more conveniently written as
Q S Q R
d = sS s R = (13.18)
QR
JH
by using the relation v .
2S
The quantities nS and nR are very large numbers which are slightly different than n0, the fixed
frequency of the probe (commonly 40 or 60 MHz for a proton), as a result Eq. (13.18) can be
rewritten as
Q S Q R
d = sS s R = (13.19)
Q0
The quantity nS nR can be written by the symbol D which is very small and is expressed in Hz,
whereas n0 (probe frequency or spectrometer frequency) is expressed in MHz. It is seen from
Eq. (13.19) that d is dimensionless and its value is very small. Hence it is multiplied by a factor
106 to express it in a convenient number, so that the dimensionless unit turns to be units of parts
per million (ppm).
Thus we have
d= 106 ppm (13.20)

Q0
The reference compound which is universally selected for hydrogen resonances in non-aqueous
solvent is tetrametyl silane (TMS), that is, (CH3)4Si. It is used as an internal standard. The use of
TMS has the following advantages:
(a) It is chemically inert.
(b) Its resonance signal is very sharp due to twelve equivalent protons in it.
(c) Its boiling point is very low so that it can be easily removed under study.
(d) Its resonance position is to the high field side of various types of protons due to large
diamagnetic shielding.
(e) Most of the organic compounds for structural investigation are soluble in TMS.
With this standard substance, two scales are used for measuring chemical shift.
(a) d scale This sets the resonance of TMS arbitrarily at zero and counts lower field as positive.
PROBLEM 13.6 Calculate the chemical shift for proton signal appearing at 120 Hz relative to
TMS at given oscillator frequency of 60 MHz.
Solution We know,
'
d= 106 ppm
Q0
Given D = 120 Hz and n0 = 60 MHz = 60 ´ 106 Hz
Therefore,
120 Hz 120 Hz 120 106
d= ppm 2ppm
60 MHz 60 106 Hz 60 106
In this d scale a positive value of d means down field absorption by the sample. Absorption at
lower field corresponds to a higher d value.
(b) t scale (tau scale) This scale sets the TMS resonance at 10. Thus the resonance are
measured at lower than 10. Absorption at lower field corresponds to lower t value. The d
scale and t scale are shown below (Figure 13.4).
Figure 13.4 d scale and t scale for chemical shift.
Thus the relation between t and d is

d = 10 t (13.21)
It is to be noted that the substance having higher t or lower d values are said to be at up field
indicating greater shielding effect while in the reverse case the substance is said to be at down field
indicating de-shielding effect. Upfield and downfield cases are discussed below under the heading,
the factors influencing chemical shifts.
13.6 FACTORS INFLUENCING CHEMICAL SHIFTS
Some of the factors affecting the chemical shifts to predict the position of signals due to different
sets of equivalent protons are discussed below.
13.6.1 Effect of p Electrons Circulation (Magnetic Anisotropy)

Alkyne
In alkyne like acetylene, H C ºº C H, the electronic circulation around triple bond takes
place in such a way that proton experiences diamagnetic shielding effect. The proton feels smaller
field strength, hence resonance occurs at higher applied field. The molecular axis of acetyelene
lies parallal to the direction of applied field and p electrons are induced to circulate around the axis
in such a way that induced field opposes the applied field (Figure 13.5). This results in an increase
t value.
Figure 13.5 Shielding of acetylene.
Alkene
In case of alkene like ethylene CH2 == CH2, the plane of the double bond is perpendicular to the
applied field. The p electrons are induced to circulate in such a way that it causes diamagnetism
around the carbon atom and paramagnetism around proton (Figure 13.6). Thus the proton feels
greater field strength and resonance occurs at lower field. This results in decreased t values.
For both acetylene and ethylene, the magnitude of the induced magnetic field depends
upon orientation of the molecular axis with respect to the applied field. Hence multiple bonds
(double and triple) are called magnetically anisotropic. The anisotropy is further discussed in case
of benzene.
Figure 13.6 Deshielding of ethylene.
Thus for CH2 == CH2 (d = 5.8 ppm) and CH ºº CH (d = 2.9 ppm)

Benzene
In case of benzene the p-electrons are delocalized cylindrically over aromatic ring. When a molecule
of benzene is oriented with respect to the magnetic field H0 as shown in Figure 13.7, the loops of
electrons are induced to circulate in the presence of applied field producing ring current.
This current generates induced magnetic field whose direction is such that it reinforces H0 at the
periphery of benzene ring (causing paramagnetism, deshielding), while opposing H0 above and
below the plane of the benzene ring, (causing diamagnetism, shielding). Thus the aromatic protons,
which are at the periphery of the benzene ring, experience a magnetic field greater in magnitude
than the applied field. Such protons are said to be deshielded, and hence smaller applied field
(higher value of d) will be required to bring them to resonance. Ring protons resonates at
d = 7.26 ppm. In a molecule like toluene, the methyl protons resonate at d = 2.34 ppm whereas the
ring protons resonate at d = 7.26 ppm.
Figure 13.7 Deshielding of aromatic compound.
Further examples of magnetic anisotropy is given below.

(a) Aldehydic proton gives NMR peak at unexpected low field position (d ~10 ppm). In this
case the effect of applied magnetic field is greatest along the transverse axis of C == O
bond. The geometry is such that aldehydic proton is in the deshilding portion of the induced
magnetic field. This type of deshielded protons resonate at d ~10 ppm.
(b) A spectacular example of shielding and deshielding by ring current is furnished by aromatic
[18]-annulene (Figure 13.8).
Figure 13.8 Annulene.
The protons outside the ring (twelve) are strongly deshielded at d = 9.28 ppm. Whereas those
protons inside the ring are strongly shielded giving 1H NMR peak at d = 2.29 ppm.
In contrast with the striking anisotropic effects of circulating p electrons, the s electrons of a
C C bond produce a small effect. The axis of the C C bond is the axis of the deshielding cone
(Figure 13.9). Shielding is marked by (+) and deshielding is marked by ().
Figure 13.9 Shielding (+) and deshielding () zone for C C bond involving s electron.
This figure accounts for the deshielding effect of successive alkyl substituents on a proton
attached to a carbon atom. Further hydrogen is more electropositive than carbon, with the result
that every replacement of hydrogen by an alkyl group causes a downfield shift. Thus the protons
are found progressively downfield in the sequence of
CH4 CH3 CH3 (CH3)2CH2 (CH3)3CH (CH3)4C
d ~0.2 ~0.86 ~1.33 ~1.68 ~1.77 ppm
13.6.2 Inductive Effect

A proton is said to be deshielded if it is attached with an electronegative atom or group. This is
because the electrons are dragged towards more electronegative atom. Greater the electronegativity
of the atom, greater is deshielding caused to the proton. If the deshielding is more for a proton,
then its d value will also be more. Consider the following compounds:
b a b a
(i) CH3 CH2F (ii) CH3 CH2 Cl
d = 4.3 ppm d = 3.6 ppm
Two signals are expected for each of the compounds. Deshielding for proton a in compound
(i) is more than that for similar protons in compound (ii) as F is more electronegative than Cl.
Thus, the electronegative elements shift the signals downfield. As the distance from the
electronegative atom increases, the effect diminishes. Electropositive elements (Like Li, Si) shift
the signals upfield. Thus TMS (tetramethyl silane), having four electron releasing methyl group
bonded to silicon cause powerful shielding effect and TMS protons (all equivalent) resonate at
highest field corresponding to d = 0.
TMS (Tetramethyl silane)
13.6.3 Effect of Electron Withdrawing and Electron Donating Groups

Polar groups attached directly to a benzene ring cause upfield and downfield shifts more or less in
the same way that they do on a simple double bond.
The effect of a p-donor and p-acceptor group are seen in the structures above. The signals of the
ortho- and para-hydrogens are shifted upfield by electron releasing group like methoxy
(CH3 O ) group relative to the signals of benzene. The situation becomes different when an
electron withdrawing groups like (NO2 group, carbonyl ) group are attached to benzene
ring. In case of acetophenone, all the ring protons are found downfield because of ring current
effect. Moreover, the ortho protons are shifted slightly further downfield (meta, para d ~7.40,
ortho d ~7.85) because of the additional deshielding effect of the carbonyl group as the carbonyl
bond and benzene ring are coplanar. If the molecule is oriented so that the applied magnetic field
H0 is perpendicular to the plane of the molecule, the circulating p electrons of the C == O bond
shield the conical zones above and below them and deshield the lateral zones in which the ortho
proton is located as shown in Figure 13.10. As a result ortho protons are shifted slightly further
downfield. Nitrobenzane shows similar effect as that in case of acetophenane.
Figure 13.10 Shielding and deshielding zones for acetophenone.
13.6.4 Hydrogen Bonding

Hydrogen atom exhibiting property of hydrogen bonding in a compound absorbs at a low field in
comparison to one which does not. This is because a hydrogen atom involves in a hydrogen bonding
is sharing its electron with two electronegative elements. As a result it is deshielded by itself and
comes into resonance at low field. The downfield shift depends upon the strength of hydrogen
bonding. Intermolecular and intramolecular hydrogen bonding can be easily distinguished as the
latter does not show any shift in absorption due to change in concentration.
The resonance position of most signals is little affected by temperature, although OH, NH and
SH protons resonate at higher fields at higher temperature because the degree of hydrogen bonding
is reduced. The much stronger intermolecular hydrogen bonding in carboxylic acid dimmers
(i) Leads to very low-field absorption at d in ppm and the corresponding intramolecular
hydrogen bonding of enolised b-diketones
PROBLEM 13.7 Find the number of protons 1H NMR signals and their respective positions in
1H NMR spectra ethyl alcohol in low resolution.
Solution In ethyl alcohol, CHc3 CH2b OHa, we have three different types of protons:
1. The hydroxyl protons (a),
2. The methylene protons (b) and
3. The methyl protons (c)
Out of these, the hydroxyl protons is expected to be the least shielded as it is attached to the more
electronegative oxygen atom. Consequently, this proton will come into resonance at a field lower
than those of methylene and methyl protons. Out of methylene and methyl group, the hydrogen
atoms attached to the former are expected to be less shielded as CH2 groups is directly attached to
the oxygen atom. Thus, the methylene protons will come into resonance earlier than those of
methyl protons. The expected spectrum of ethyl alcohol is shown in Figure 13.11. It has three
absorption signals. The signal at the low-end field is due to the hydroxyl proton (a), at the high-end
field is due to the methyl protons (c) and at the centre is due to methylene protons (b). The area
under these peaks will follow the ratio 1 : 2 : 3 as they represent one proton of OH group, two
protons of CH2 group and three protons of CH3 group, respectively.
The spectrum as shown in Figure 13.11 which shows only the effects of chemical shift,
is known as low-resolution spectrum.
Figure 13.11 Lower resolution spectrum of ethyl alcohol.
The range of proton chemical shift for a series of organic compounds are illustrated in Table 3.1.
In general this serves to give a fairly reliable means of distinguishing protons on quite similar
functional groups.
Table 13.1 Chemical shifts of some organic compounds
Types of protons Chemical shift in ppm
d t
(i) Cyclo-propane 0.2 9.8
(ii) Primary R CH3 0.9 9.1

(iii) Vinyl C == C H 4.65.8 5.44.2
(iv) Acetylinic C ºº C H 23.5 86.5
(v) Aromatic Ar H 69.0 41.0
(vi) Fluorides HCF 44.5 66.5
(vii) Chlorides H C Cl 34 76
(viii) Alcohols H C OH 3.44 6.66
(ix) Ethers H C OR 3.34 6.76
(x) Esters H C COOR 22.2 87.8
(xi) Acids H C COOH 22.5 87
(xii) Aldehydes RCHO 910 10
(xiii) Hydroxyl R OH 15.5 94.5
(xiv) Phenolic Ar OH 412 6 to 2
(xv) Enolic C == C OH 1517 5 to 7
(xvi) Carboxylic RCOOH 10.512 0.5 to 2
13.7 SPIN-SPIN COUPLING (OR SPLITTING)
NMR spectra of many molecules when examined under high resolution are found to be contained
multiplet structure (fine structure). The occurrence of fine structure in NMR peak may be attributed
due to the phenomenon known as spin-spin splitting which arises because of interaction of spin of
neighbouring nuclei with that proton. The separation J between the peaks comprising the fine
structure is referred to as the spin-spin coupling constant. This parameter is usually expressed in
cycle s1 or Hz which lies between 1 and 20 Hz and is field independent.
13.7.1 Explanation for Spin-Spin Interactions

The actual field observed by a proton, besides depending on the surrounding electron density, is
also influenced by the neighbouring magnetic active nuclei. This is due to the spin-spin interactions.
A proton can have either a-spin (MI = +1/2) or b-spin (MI = 1/2). These spins are represented
by arrows, a-spin is represented by an arrow pointing upwards () and b-spin is shown by an
arrow pointing downwards (¯). Consider a situation in which the proton A is present in the
neighbourhood of the other proton B. The field observed by the proton A will be dependent upon
the spin of the proton B, and vice versa. We can consider the following two alternatives:
(i) Proton B has a a-spin When the proton B has a-spin, then it creates a magnetic field
on A which acts in the opposite direction of the external magnetic field (Figure 13.12).
Thus the actual field observed by the proton A is
Hobserved = Happlied Hinteraction
where Hinteraction is the field generated by the proton B on the proton A.
Figure 13.12 Spin-spin coupling between two protons.
(ii) Proton B has b-spin When the proton B has b-spin, it creates a magnetic field on the
proton A which acts in the same direction as that of the external magnetic field
(Figure 13.12). Thus the actual field seen by the proton A is
Hobserved = Happlied + Hinteraction
where Binteraction is the field generated by the proton B on the proton A.
The potential energy of proton A will now be given by the relations

Ea = bN g (Happlied Hinteraction) MI
and Eb = bN g(Bapplied + Binteraction) MI
where the subscripts a and b represent, the spins a and b respectively of the neighbouring
proton B. The variation in potential energy with the external magnetic field is shown in Figure 13.13.
Figure 13.13 Variation of potential energy of proton in the presence and absence of neighbouring proton,
the levels aa and bb are destabilized and the levels ab and ba are stabilized.
If the system is irradiated with radiation of 60 MHz (or of any other frequency), then it can be
concluded from Figure 13.13 that the single absorption which is expected to occur in the absence
of spin-spin interaction (shown by broken line), splits into two symmetrically placed absorption,
one with a-spin of the neighbouring proton and the other b-spin of the neighbouring proton (shown
by solid line). The absorption corresponding to the a-spin of the neighbouring proton lies towards
the high-end field whereas that of the b-spin towards the low-end field. The area under these two
peaks will be identical to that the one peak observed in the absence of spin-spin coupling.
The spin-spin splitting separation between the component lines usually has a small value as compared
to the chemical shift of the involved protons and can be observed only if the spectrometers of high
resolution are employed. It is for this reason the recorded spectrum is known as the high resolution
spectrum.
The spin-spin interaction decreases very rapidly as the distance between the protons is
increased. In molecules, it operates only between the next nearest neighbours. Moreover,
the interaction is always mutual, i.e. if the splitting of A occurs due to the interaction of the
neighbouring proton B, then there will also occur the splitting of the signal of B. It is an
intramolecular behaviour, i.e. the PMR signal of one molecule will not be affected by the protons
of the other molecule. The spin-spin splitting separation between the component lines is also
found to be independent of the external magnetic field.
In organic molecules, the spin-spin interaction may involve more than one neighbouring proton.
For example, the methyl alcohol in which the hydroxyl proton interacts with the three identical
protons of methyl groups. Now we consider the scheme for this type of interactions. We restrict
ourselves to the simple type of molecules in which the chemical shift between the involved protons
is much larger than the coupling constant (the separation between the two splitted lines of the same
signal). Such types of molecules are abbreviated as AnXm, where, A and X represent the two
different neighbouring protons in a molecule. Below we discuss the scheme of spin-spin interactions
with the typical examples of methyl alcohol and ethyl alcohol.
High resolution spectrum of methyl alcohol
The three hydrogen atoms of methyl group have the same chemical environment and thus have the
same shielding constant. Consequently, the chemical shifts of all the three hydrogen atoms are
identical. The rotation of methyl group around the C O bond makes all the three protons of
methyl group magnetically equivalent to the hydroxyl proton and the interactions of methyl protons
with hydroxyl proton are all equal.
(i) Coupling of methyl protons with the hydroxyl proton The methyl protons will
observes two possible arrangements of the hydroxyl proton, viz. a and b, and hence the
field observed by methyl protons is modified in two different ways. Remembering that
the field generated by a-spin acts in the opposite direction and that generated by b-spin
in the same direction of the external magnetic field, we may conclude that the actual field
observed by methyl protons will be slightly greater than the external field when the
hydroxyl proton has b-spin and it will be slightly less when the hydroxyl proton has
a-spin.
(ii) Coupling of hydroxyl proton with methyl protons The hydroxyl proton couples with
the three neighbouring methyl protons. Each proton can have either a-spin or
b-spin. The total number of possible arrangements which the hydroxyl proton observes
when each proton of methyl group has either a-spin or b-spin is shown below.
There are eight arrangements in all. These fall into the following categories.
1. All the three protons have a-spin (only one).
2. Two of them have a-spin and the third has b-spin (three).
3. Two of them have b-spin and the third has a-spin (three).
4. All the three protons have b-spin (only one).
Now if the system is irradiated with a radiation of 60 MHz, we find that the two absorption lines
are observed for methyl protons and four absorption lines for hydroxyl proton. The two absorption
lines of methyl protons will have identical intensities whereas those of hydroxyl protons will have
the intensity ratio of 1 : 3 : 3 : 1. The number of such combinations in each of the above four
categories are 1, 3, 3 and 1 respectively.
The expected high resolution of methyl alcohol is shown in Figure 13.14.
High resolution spectrum of ethyl alcohol
Figure 13.14 High resolution spectrum of methylalcohol.
We get three peaks corresponding to one hydroxyl proton at the low-end field, three methyl protons
at the high-end field and two methylene protons in between these two fields. In high-resolution
spectrum, the absorption peaks of methyl proton will split into three peaks with relative intensities
as 1, 2, 1 since it is attached to the methylene group. The absorption peaks of methelyne protons
will primarily split into four peaks with intensities 1, 3, 3, 1 due to the interaction with the methyl
protons. Each of these four peaks will further split into two peaks of equal intensity due to the
coupling with the hydroxyl proton. Thus in a very high resolution spectrum, the methylene protons
will exhibit an octet with relative intensities 1, 1, 3, 3, 3, 3, 1, 1. If the resolution is not very large,
one often finds quintet with intensities 1, 4, 6, 4, 1, as if it has coupled with four protons (three
from methyl and one from hydroxyl). The hydroxyl proton will split into three peaks of intensities
1, 2, 1 due to coupling with methylene protons.
The expected high-resolution spectrum of ethyl alcohol is shown in Figure 13.15(a).
Ethyl alcohol spectrum in the presence of trace of acid or alkali
The hydroxyl proton of ethyl alcohol is not immutably locked in any particular ethyl alcohol
molecule. It is, in fact, being continuously exchanged from one molecule to the other molecule.
The rate of the exchange is relatively slow in pure ethyl alcohol. The time spent by the proton on
any ethyl alcohol molecule is quite sufficient to allow the interaction with the neighbouring
methylene protons and thus causing spin-spin splitting. In the presence of acid or alkali, the rate of
transfer of hydroxyl proton from one molecule to other is very much enhanced and thus the time
spent by the hydroxyl proton with any particular molecule is too small to allow the interactiom
with the methylene protons. Thus the splitting of hydroxyl and methylene protons due to each
other is completly prevented and thus one observes a single peak of the hydroxyl protons. Likewise,
the methylene protons show only splitting due to the neighbouring methyl protons and hence the
quintet is replaced by the quartet. The resultant spectrum is shown in Figure 13.15(b).
Ethyl alcohol spectrum in the presence of D2O
On adding D2O in ethyl alcohol, the hydroxyl proton of the latter is replaced by deuterium
nucleus. It is thus expected that under such conditions, the absorption peak of hydroxyl proton
will disappear (Figure 13.15(c)). Through deuterium nucleus is also magnetic active (I = 1), no
absorption peak corresponding to this is observed in the magnetic field range over which the
spectrum is scanned.
Figure 13.15 High resolution 1H NMR of ethyl alcohol.
13.8 MULTIPLICITY OF NMR PEAKS
If a proton is coupled with n number of equivalent protons (magnetically and chemically),

then the number of absorption peaks (NMR) observed are (n + 1) or (2nI + 1), where I is the
nuclear spin quantum number of protons which is equal to ½. The relative intensities of the
peaks of a multiplet correspond to the numerical coefficient of the term in the binomial expansion
of (1 + X)n as shown below.
n = number of Number of Binomial expansion Relative intensity

neighbouring peaks of of the peak
proton multiplet
1 1+1=2 (1 + x)1 = 1 + x 1:1
2 2+1=3 (1 + x)2 = 1 + 2x + x2 1:2:1
3 3+1=4 (1 + x)3 = 1 + 3x + 3x2 + x2 1:3:3:1
4 4+1=5 (1 + x)4 = 1 + 4x + 6x2 + 4x3 + x4 1:4:6:4:1
5 5+1=6 (1 + x)5 = 1 + 5x + 10x2 + 10x3 + 5x4 + x5 1 : 5 : 10 : 10 : 5 : 1
5 6+1=7 (1 + x)6 = 1 + 6x + 10x2 + 20x3 + 15x4 + 6x5 + x6 1 : 6 : 15 : 20 : 15 : 6 : 1
Their relative intensities are given by

nC
n!
=
m m ! ( n m) !
where m goes from 0 to n.
A simple way to remember the terms in a binomial expansion is with the aid of Pascals triangle.
The triangle is constructed by placing 1 at the top and at the two outer edges of each horizontal row
of numbers. The intermediate numbers in the triangle are obtained by adding the two adjacent
numbers in the series immediately above the desired number in the triangle as shown below.
n Relative peak area/binomial coefficient
0 1
1 1 1
2 1 2 1
3 1 3 3 1
4 1 4 6 4 1
5 1 5 10 10 5 1
The above general rule will be applicable only in case of AnXm molecules where the chemical shift
between the involved protons are much larger than the spin-spin coupling constant.
However if n and n¢ are the number of protons in different environment, the multiplicity of a
particular multiplet = (n + 1) (n¢+1). Similarly, if n, n¢ and n¢¢ are the number of protons in different
environments, the multiplicity of a particular multiplet = (n + 1) (n¢ + 1) (n¢¢ + 1).
13.9 PROBLEMS INVOLVING CHEMICAL SHIFT AND SPIN-SPIN

SPLITTING
PROBLEM 13.8 Give your comments on 1H NMR signals and their multiplicity in the following
compounds in case of methylene protons.
(a) 1 : 1 dibromo 3 : 3 dichloropropane
(b) 1-bromo, 3-chloropropane.
Solution
(a) In 1 : 1 dibromo 3 : 3 dichloropropane Br2CaH CbH2 CcHCl2, we see three sets of
protons. Protons a and c are non-equivalent (with different chemical shifts) and thus
influence the methylene ( CH2, i.e. protons b) protons differently. Thus, the signal
for CH2 protons appears as multiplet and consists of (n + 1) (n¢ + 1) = (1 + 1) (1 + 1)
= 4 lines where n and n¢ are the numbers of protons of the kind a and c, respectively.
(b) In 1-bromo, 3-chloropropane BrCaH2 CbH2 Cc H2Cl, the signal for the central
methylene ( CH2) protons will clearly be a multiplet consisting of (n + 1) (n¢ + 1)
= (2 + 1) (2 + 1) = 9 peaks where n and n¢ are the number of protons a and c, respectively.
The central CH2 protons being influenced by two kinds of protons (two in each set)
with different chemical shift.
PROBLEM 13.9 Calculate the multiplicity of the signal corresponding to proton a in methyl
cyclohexadine shown below:
Solution In this compound, proton a is under the influence of three sets of protons with different
chemical environments. These protons are b, c and d. Thus, the signal for proton a is expected
to be a complicated pattern consisting of (n + 1) (n¢ + 1) (n¢¢ + 1) lines, i.e. (1 + 1) (1 + 1) (3 + 1)
= 16 lines.
PROBLEM 13.10 The 1H NMR spectrum at 60 MHz of a solution containing the following
components (IVII) in dueteriochloroform, display the present peaks at d = 0,1.43, 2.10, 2.75,
3.61, 5.3 and 7.33 ppm in d scale
(I) CH3COCH3 (II) CHCl3
(III) (IV) CH2Cl2
(V) (VI) (CH3)4Si
(VII) Cl3CCH3
(a) Match each of the components with the corresponding peak at Hz, d- and t-scales.
(b) What would be the position (in Hz) of the chloroform peak at 60 MHz with reference
to the cyclohexane peaks?
(c) What would be the separation of these peaks at 100 MHz? Give the answer in each
of the three scales.
Solution
(a) The position of absorption of a proton depends on its electronic environments. A less shielded
proton shows the signal at the low end field and more shielded at the high-end field.
All protons in the above list of molecules are identical and hence will exhibit only one
absorption. The shielding constants of proton in given molecules are expected to follow the
following order. Thus the assignment of peaks is described below.
Molecules d -scale t-scale Hz*
VI 0 10 0
III 1.43 8.57 85.8
I 2.1 7.9 126
V 2.75 7.25 165
VII 3.61 6.39 216.6
IV 5.3 4.7 318
II 7.33 2.67 439.8
(* Hz = d-scale ´ Applied Frequency in MHz.)
In this problem, Applied Frequency = 60 MHz.
(b) Chloroform peak is at 439.8 Hz and that of cyclohexane at 85.8 Hz. Thus, chloroform
peak lies 354 Hz (= 439.8 Hz85.8 Hz) away from the cyclohexane peak towards the
low-end field.
(c) The separation of line in Hz will be increased by employing high frequency of radiation.
Since the separation is directly proportional to the frequency of radiation, the separation
of each line will be increased by a factor of (100/60). The d- and t-values, however, will
remain unaltered.
PROBLEM 13.11 The PMR spectrum of dimethyl formamide at 40 MHz and at room temperature
is shown in Figure 13.16.
Figure 13.16 PMR spectrum of dimethyl formamide.
The doublet B and C might arise either from chemically different groups or from spin-spin
coupling.
(i) What feature of the spectrum immediately rules out one of these explanations in this
case?
(ii) What experimental operations offer a general method for distinguishing between the
chemical shift and spin-spin splitting?
(iii) Explain the origin of the lines A, B, C.
(iv) What will be the effect of temperature on the above spectrum?
Solution
(i) The doublet B and C arise due to the chemically different methyl groups. This results
because of the restricted rotation around C N axis. The possibility of spin-spin splitting
may be excluded since it is on the mutual basis, i.e. if methyl protons are split into two,
the C H peak would have been split into seven peaks.
(ii) The chemical shift and the spin-spin splitting can be distinguished on the basis of their
behaviour when the molecule is placed in a changing magnetic field. The chemical shift
changes in proportion to the change in the magnetic field where spin-spin splitting remains
unchanged.
(iii) Peak A is due to the proton of C H group as it is least shielded.
Peak B is due to the protons of methyl group near the C O group (i.e. in the cis position)
and the peak C is due to the trans methyl group.
(iv) On increasing the temperature, the restricted rotation around C N axis is decreased.
At very high temperatures, the rotation speed is very large and both the methyl groups
become identical. This will result in the collapse of the two given signals into a single peak.
PROBLEM 13.12 Write down all possible structural formulae having molecular formula C3H6Cl2.
Is it possible to identify them on the basis of low or/and high PMR spectra? Ignore the interactions
of Cl-atoms with H.
Solution The structural formulae of C3H6Cl2 along with their low and high resolution spectra
are given below.
Formula Low resolution High resolution

1. CH3CH2CHCl2 3 peaks 3-proton triplet, 2 proton quintet, 1-proton triplet
2. CH3CHClCH2Cl 3 peaks 2-proton doublet, 1-proton sixtet, 3-proton doublet
3. CH3CCl2CH3 1 peak No splitting
4. ClCH2CH2CH2Cl 2 peaks 4-proton triplet, 2-proton quintet
It may be concluded that the structural formulae are identifiable on the basis of low and high
resolution spectra. The only exception is the identical low resolution spectra of compounds
(I) and (II). However, they may be distinguished from the following points.
(i) The t-value of the first peak of compound(I) is expected to be much lower than that of
the first peak of the compound(II), since the former represents a proton attached to the
two chlorine atoms while the latter represents a proton attached to the one chlorine atom.
(ii) The chemical shift between the first and second peaks of compound(I) is expected to be
larger than the corresponding chemical shift of compound(II).
PROBLEM 13.13 How will you distinguish the following two compounds on the basis of their
low or/and high resolution PMR spectra?
Solution Low-Resolution PMR spectra. The expected order of shielding constants of protons
in the given compounds are
s1, s2, s3 are shielding constants for proton 1, 2 and 3 respectively.

The low-resolution PMR spectra is shown below.
Since the two spectra are not identical, the two compounds are distinguishable from their low-
resolution spectra.
High-Resolution PMR spectra. Peak 2 in both the low-resolution spectra will split into four
as the methylene group is attached to the methyl group. Similarly, peak 3 in both the spectra will
split into three. Peak 1 will remain unaffected. The high-resolution PMR spectra is shown below.
PROBLEM 13.14 The low-resolution PMR spectrum of C6H10O2 is given in Figure 13.17.
Suggest its structure.
Figure 13.17 Low resolution PMR spectra of C6H10O2.

Solution Analysis of the spectrum
(i) The relative areas of different peaks suggest the presence of two methylene groups (peaks
1and 2) and two methyl groups (peaks 3 and 4).
(ii) If we subtract two methylene and two methyl groups from C6H10O2, we get C2O2.
The latter may represent two CO groups.
The probable structure consistent with the above facts is
3 1 2 4
CH3COCH2COCH2CH3
PROBLEM 13.15 The low-resolution spectrum of C5H10O2 is given in Figure 13.18. Suggest its
structure.
Figure 13.18 Low resolution spectrum of C6H10O2.
Solution Analysis of the spectrum

The relative areas of different groups suggest that
(i) Peak 1 must be due to a CH group. The latter must be attached with a stronger electron
withdrawal group.
(ii) Peak 2 must represent a methyl group.
(iii) Peak 3 must represent two identical methyl groups. Protons of these methyl groups are
more shielded than the protons of the other methyl group (peak 2).
If we subtract CH, CH3 and two CH3 groups from C5H10O2, we get CO2 as the remaining
fragment. We may conclude that the molecule is a derivative of a carboxylic acid. The two identical
methyl groups and one CH group may arise from the isopropyl group. Since CH group shows peak
at the high d-value, we may conclude that it is attached directly to the carboxylate group. The
probable structure consistent with the above facts is
PROBLEM 13.16 PMR spectrum of C8H14O4 is given below. Suggest its structure.
Solution Analysis of the spectrum:

(i) The hydrogen atoms represented by the peak 1 must be attached to a methyl group.
(ii) The hydrogen atoms represented by the peak 3 must be attached to a methylene group.
The above two points taken together suggest the presence of ethyl group. The relative
intensities of peak 1 and 3 suggest the presence of two such ethyl groups placed in a
symmetrical manner with respect to each other.
(iii) The peak 2 has a relative intensity of 4 which is identical with that of peak 1. We may
conclude the presence of two other identical methylene groups. Since the peak 2 shows
no splitting, the two identical methylene groups are not attached to the neighbouring
groups containing hydrogen atoms.
(iv) If we subtract two CH3CH2 groups and two CH2 groups from C8H14O4, we get C2O4 as
the remaining fragment. These may represent two groups.
(v) The two methylene groups of ethyl fragments must be attached to the electron withdrawal
groups as the peak 1 has the highest d-value.
(vi) The two bare methylene groups must be attached to the carbons of two carboxylate groups.
The probable structure consistent with the above facts is
PROBLEM 13.17 PMR spectrum of the compound C3H5ON in an acidic medium is shown
below. Suggest its structure. Given that the peak 1 disappears in the presence of D2O.
Solution Analysis of the spectrum:
(i) Since the peak 1 disappears in the presence of D2O, it may represent a group containing
active hydrogen. This group may be a hydroxyl group.
(ii) The peaks 2 and 3 must represent the hydrogen atoms attached to the methylene group.
(iii) The analysis of integral trace indicates the presence of 1, 2 and 2 protons within the
peaks 1, 2 and 3 respectively.
The point (iii) suggests the presence of two methylene groups. These must be attached each
other (point (ii)).
The only structure consistent with the above facts is
HOCH2CH2CN
13.10 COUPLING CONSTANT (J)
The distance between the centres of the two adjacent peaks in a multiplet usually constant and
is called the coupling constant. The value of the constant is independent of the external field. It is
measured in Hertz or cycles per second. It is denoted by the letter J. Let us consider a compound
in which two signals are expected in its NMR spectrum. Under the influence of three
equivalent proton a, the signal for proton b will appear as quartet due to spin-spin coupling as
shown in Figure 13.19. The distance between any two adjacent peaks in this multiplet (here quartet)
will be exactly the same what ever be the magnetic field applied. Hence we may conclude that the
value of J is independent of applied magnetic field.
If we consider 1HNMR spectrum of propyl iodide, , the signal for b kind of
protons are under the influence of a type protons and c type protons. It is found that Jab (coupling
constant between a and b protons is 6.8 cps whereas coupling between b and c type protons
is 7.3 cps. Since the value of J are close enough, at three protons c type group and
2 protons of a type are said to be equivalent and the signal for CH2 (b) proton shows a sextet
under the influence of 5 equivalent protons as per (n + 1) rule.
Figure 13.19 Representation of J.
On the other hand, in 1HNMR spectrum of pure ethanol , Jab = 5.0 cps and
Jbc = 7.2 cps and a type proton and c by protons are not equivalent as the Jab and Jbc value are
quite different. Hence, we do not expect a quintet corresponding to 3 + 1 = 4 protons. Rather a
group of eight lines are observed in the multiplet corresponding to b type protons according to
(n + 1) (n¢ + 1) rule i.e. (3 + 1) (1 + 1) = 8.
Thus we may conclude that the values of J depends upon the number of covalent bonds through
which protons may interact and also upon the structural relationship between the coupled protons.
Some important coupling between protons are given below.
1. Germinal coupling: Protons attached on the same carbon atoms having different chemical
environment are called germinal protons and coupling between them is called germinal
coupling, Jgem. Thus germinal protons are separated by two bonds and can have any sign
( or +).
The value of Jgem increases with increase in bond angles (or increase in s-character) and
increase in electronegativity of the atoms or group which withdraws s electrons. The value
of Jgem decreases if an electronegative substituent withdraws electron from p-bonds. For
mono substituted olefins, Jtrans > Jcis > Jgem. This is illustrated in case of styrene.
In styrene, H(1) and H(2) protons are germinal H(1) and H(3) are cis protons H(2) and H(3)
protons are trans protons. It is found Jtrans > Jcis > Jgem.
i.e. Jtrans [H(2), H(3)] = 17.4 cps
Jcis [H(1), H(3)] = 10.6 cps
Jgem [H(1), H(2)] = 1.4 cps
2. Vicinal coupling: Vicinal protons are the protons which are separated by three bonds
and the coupling between them is known as vicinal coupling. The vicinal coupling constant
is designated by Jvicinal. For vicinal protons, the value of Jvicinal varies with dihedral angle.
The values of Jvicinal are largest when the dihedral angle is 0º or 180º. It is slightly negative
when dihedral angle is 90º. This is best illustrated by considering the confirmation of malic
acid.
The values of J as a result of various types of interacting nuclei are given as

J(Hb, Hc)gem = 17.0 cps
J(Ha, Hc)vicinal-anti = 7.1 cps
J(Ha, Hb)vicinal gauche = 4.4 cps
We may conclude that in the gauche and anti-conformation of a compound, Jvicinal-anti >
Jvicinal-gauche.
3. Long-range coupling: Proton-proton coupling beyond 3 bonds may occur in olefins,
acetylenes, aromatics, hetero aromatics and in strained ring systems. Such type of coupling
is known as long-range coupling.
In the p-bond system, appreciable couplings are frequently observed between protons
separated by even four or five bonds. Coupling through conjugated polyacetylenic chains
may occur through as many as nine bonds. Metacoupling in benzene ring is 1 to 3 Hz and
paracoupling 0 to 1 Hz. In 2, 4-dicholorbenzaldehyde, long range coupling takes place
between the aldehydic proton and ring proton. The effects of the nuclear spin are transmitted
from (C H bond, s bond) by coupling the resulting electron spin on carbon atom with p
electron as cited in the above examples.
From the value of coupling constant J, one can distinguish between the two singlets and
one doublet and also a quartet from two doublets. It can be done simply by recording the
spectrum at different radio frequencies. If the separation (in Hz) between the lines (value
of J) does not change, then the signal is a doublet. On the other hand, if the separation
between the lines increases with increasing frequency, then the signal in fact will be two
singlets. In this way, we can distinguish a quartet from two doublet. The value of J usually
lies between 0 and 20 Hz.

(i) In NMR spectroscopy, the radiation used for nuclear excitation is
(a) Microwave (b) Radio wave
(c) IR (d) UV
(ii) In an applied magnetic field, the number of orientations of a nucleus with a spin number I,
is given by the formula
(a) I + 1 (b) I + 2
(c) 2I + 1 (d) 2(I + 1)
(iii) Nuclei with an even number of protons and neutrons have
(a) Zero spin (b) Integral spin
(c) Half-integral spin (d) Fractional values other than half for spin
(iv) The value of TMS protons (in NMR) in d-scale is
(a) 10 (b) 0
(c) Not predictable (d) 10
(v) When a halogen atom is attached to a methyl group, the value of d
(a) Decreases with eletronegativity of X (b) Is not affected by electronegativity
(c) Increases with electronegativity (d) Becomes negligible
(vi) When there are n-protons adjacent to a given proton, the multiplicity of its NMR peak is
given by
(a) 2n + 1 (b) n + 1
(c) 2n 1 (d) n + 2
(vii) In NMR, 2-bromopropane will produce
(a) 3H (singlet), 4H (quartet) (b) 3H (triplet), 2H (sextet), 2H (triplet)
(c) 1H (quartet), 6H (doublet) (d) None of these
(viii) The PMR spectrum 1, 1 difluoro, 1, 2 dichloro ethane shows
(a) A triplet (b) A doublet
(c) A singlet (d) A quartet
(ix) The NMR spectrum of ethane shows
(a) Six signals (b) Two signals
(c) One signals (d) None of these
(x) A quartet has an intensity ratio of
(a) 1 : 3 : 2 : 1 (b) 1 : 2 : 3 : 1
(c) 1 : 3 : 3 : 1 (d) 1 : 1 : 2 : 3
(i) In the absence of external magnetic field, the energies of the spin states of protons are
degenerate.
(ii) The effect of extra nuclear electrons on the strength of the applied magnetic field is known
as magnetic shielding.
(iii) NMR absorption lines from the more shielding protons, appear on the left or low field area.
(iv) When the resonances of two or more protons give rise to only one absorption peak in
NMR, they are chemically equivalent.
(v) For nuclear magnetic resonance spectrum, radiation of radio frequency range is used.
(vi) Only those nuclei which have a finite value of spin quantum number (I > 0) will precess
along the axis of rotation.
(vii) A proton precessing in aligned orientation can pass into opposed orientation by losing
energy.
(viii) Keeping the external field same, the effective field strength is different for different sets of
protons.
(ix) Propane as well as 2-butene (cis) will show equal number of signals in their NMR spectra.
(x) Chemical shift is the difference in the absorption position of the proton with respect to
TMS signal.
(xi) For NMR spectrum, water can be successfully used as solvent.
(xii) In alkynes, the protons ( C H) experience diamagnetic shielding effect and signal occurs
upfield.
(xiii) In n-propyl bromide the signal due to protons on methylene carbon appears as a sextet.
(xiv) TMS is insoluble in water.
(i) Like any other charged body, the nucleus of hydrogen atom also generates .............. .
(ii) A signal in the NMR spectrum is obtained when the quantum energy (hn) of electromagnetic
matches the energy difference .............. .
(iii) The number of signals in 1-propanal are .............. while those in 2-propanal are .............. .
(iv) Shielding shifts the signal .............. while the deshielding shifts the signal .............. .
(v) TMS is most suitable reference as it is .............. , .............. and .............. .
(vi) The important solvents used in the NMR spectroscopy are .............. , .............. , ..............,
etc.
(vii) Hydrogen bonding shifts the NMR signal .............. .
(viii) The exact position of resonance signal in NMR spectrum for the different types of protons
as compared to the TMS signal is referred to as their .............. .
(ix) The distance between the two adjacent peaks in a multiplet is usually constant and is called
.............. .
(x) The magnetically equivalent protons are .............. equivalent protons.

(i) How many peaks are expected in the low resolution NMR spectrum of
(a) vinyl chloride (b) ethyl cyclopropane?
(ii) Predict the number of signals with relative intensities in the low resolution NMR spectrum
of the following isomers:
(a) CH3CH2OH and (CH3)2O (b) CH3CH2CH2OH and (CH3)2CHOH
(iii) The low resolution H1 NMR spectrum of the formula C4H4O2 shows two peaks of equal
intensity. Assign the structure consistent with this information.
(iv) Why C12, O16, O18 and S32 do not exhibit NMR spectra?
(v) Why H1, N15, F19, P31, etc. show NMR spectra?
(vi) Calculate the value of spin numbers of the following nuclei

H1, F19, C13, B11, Cl35, Br79, Br81, P31
(vii) Mention the splitting pattern in the NMR spectrum of ethane.
(viii) State the splitting pattern in case of ethyl bromide
(ix) Calculate the multiplicity of methyl and methylene protons in ethyl chloride CH3CH2Cl.
(x) How many signals would you expect in the NMR spectrum of neopentane, (CH 3)4C?
(xi) Why a singlet for hydroxyl proton is observed in the NMR spectrum of acidified alcohol?
(xii) Write the value of the SI unit for the nuclear magneton.
(xiii) Sketch the NMR spectrum of ethanol.
(xiv) Explain why the 1H NMR spectrum of N-methylacetamide shows signals for two different
N-methyl groups.
(xv) What is the scale used for NMR measurements?

(i) Analyse the following compounds on the basis of NMR spectroscopy.
(a) CH3 CH2 Br (b) CH3 CHCl CH3
(c) CH3 O CH2 CH3 (d) CH3 CHO
(ii) Predict the appearance of high resolution NMR spectrum of
(a) Propanoic acid (b) Acetaldehyde
(c) Acetic acid
(iii) Identify signals in NMR spectrum of
(a) Methyl ethyl ketone (b) Ethyl bromide
(c) Methyl isopropyl ketone (d) 1-chloropropane
(e) 2-chloropropane
(iv) Predict the appearance of high resolution NMR spectrum of
(a) Toluene (b) Ethyl benzene
(c) Isobutene (d) a-chloro propanoic acid
(v) The methyl protons of n-propyl alcohol show an absorption peak 528.4 Hz upfield from a
benzene external-reference peak, using the Rf field of 90 MHz.
(a) If the benzene peak occurs at d = 6.73 ppm (downfield) from the TMS peak, what is the
chemical shift of the sample peak relative to TMS?
(b) If the applied frequency had been 200 MHz, at what equivalent frequency from the
benzene peak would the absorption peak have occurred?
(vi) Predict the relative shape of the NMR spectrum for methyl ethyl ketone (2-butanone).
Compare it with that for acetone. Include the number of peaks and their relative areas.
(vii) Using the Larmor equation and the fact that hydrogen resonates at 90 MHz in a field of
21,138 gauss.
(a) Calculate the gyromagnetic ratio for hydrogen;
(b) Calculate the resonance frequency for hydrogen in a spectrometer with a magnetic
field strength of 23,487 gauss.
(viii) Define, illustrate, or explain each of the following terms:
(a) Frequency-sweep spectrometer; (b) Spin-lattice relaxation;
(c) Chemical shift; (d) TMS;
(e) Ring current.
(ix) (a) What is the chemical shift of a proton whose NMR signal is observed at 320 Hz
downfield from TMS in a spectrometer whose basic resonance frequency for hydrogen
is 90 MHz?
(b) What is the chemical shift difference between two different hydrogens whose NMR
signals are observed at 180 and 400 Hz from TMS in a spectrometer operating at
60 MHz?
(c) An NMR signal is observed at 7.3 ppm downfield from TMS in a spectrometer operating
at 200 MHz. Calculate the position in Hertz of the same signal in a spectrometer
operating at 400 MHz.
(x) Sketch the 1H NMR spectrum for each of the following compounds:
(a) Ethylalcohol (b) t-butylamine
(c) 1, 3, 5-trimethylbenzene (d) 1, 1, 1-trifluoroethane

6. Describe briefly the theory of NMR spectrometry. What information can be obtained from
the NMR absorption peaks.
7. What do you understand by the positions of the signals in an NMR spectrum? How many
signals are expected in each of the following compounds?
(a) Propane (b) Isobutane
(c) Ethanol (d) Cyclobutane
(e) Ethyl methyl ether (f) Butanol
(g) Glycol
8. What is meant by the term chemical shift?
Write with examples, the shielding and deshielding effects involved in NMR spectroscopy.
9. Describe the instrumentation involved in NMR spectroscopy. Write how NMR spectrum is
scanned?
10. What do you understand by the term splitting of signal? Explain with an example. What
are the factors affecting J value?
11. Explain why NMR spectrum of benzene is observed at a lower field whereas that of acetelyne
is observed at a higher field strength. What are the factors affecting chemical shift?
12. Define coupling constant. Draw and explain the NMR spectrum of isopropyl alcohol and
n-propyl alcohol.
13. How will you interpret the NMR spectra of the following:
(a) C6H5CH3 (b)
(c) (d)
14. Derive an expression of potential energy of a proton in a magnetic field. What do you mean
by nuclear magneton? Mention its value in various units. Calculate the magnetic field strength
required for PMR at 100 MHz.
15. Write classical description of NMR and calculate the value of gyromagnetic ratio. Give
your comments on the intensity of NMR signals.
16. Sketch the 1H NMR spectra of the following compounds mentioning the absorption position
of the signals.
(i) Phenyl acetylene (ii) m-cresol
(iii) p-anisidine (iv) Propionamide
(v) 2-propyne-1-ol (vi) Crotonaldehyde
(vii) 1-ethynyl-1-cyclohexanol (viii) 1-bromo-3-chloropropane
(ix) 2,3-di bromo propane and (x) a-bromo butanoic acid
17. What do you mean by coupling constant? Explain various types of couplings giving suitable
examples.
CHAPTER 14
Electron Spin Resonance
Spectral Method
14.1 INTRODUCTION
Electron spin resonance (ESR) is a branch of absorption spectroscopy in which radiation having
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
such as electron paramagnetic resonance (EPR) or electron magnetic resonance (EMR).
The main interest of ESR lies in the study of:
(i) Free radicals having unpaired electrons;
(ii) Determination of trace amounts of paramagnetic ions in biological samples;
(iii) Paramagnetic molecules like O2, NO and NO2;
(iv) Metal complexes with unpaired electrons, for example, copper(II) acetate monohydrate
and bis (acetyl acetanato) oxovanadium(IV), in order to understand their structures; and
(v) Lanthanide ions, etc.
14.2 BASIC PRINCIPLE
14.2.1 Interaction between Electron Spin and Magnetic Field

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 É Ù S (S 1) (14.1)
Ê 2 mc Ú 2S
497
È eh Ø
= g É Ù S (S 1)
Ê 4S mc Ú
= g S ( S 1) E
where g is known as Lande splitting factor, b is the basic unit of magnetic moment of electron
known as Bohr magneton (BM).
1 BM = eh/4pmc, where e is the charge of electron, h is Plancks constant, m is mass of electron
and c is the velocity of light.
The value of b in Gaussian system = 9.2741 ´ 1021 erg/gauss; in SI unit = 9.2741 ´ 1024 J/T.
For free electron g = 2.003. It is given by the relation:
J ( J 1) S ( S 1) – L( L 1)
g = 1 (14.2)
2 J ( J 1)
where S is the total number of spin, S = n/2, n = total number of unpaired electrons, L is total
orbital quantum number (L = Sml where ml is the magnetic quantum number corresponding to
azimuthal quantum number l for a particular electron). J is either L + S or L S according to
whether a particular sub-shell is more or less than half filled. The values of S, L, J in case of
Ti+3(3d1) are 1/2, 2, 3/2 while for Fe+2(3d6), the values of S, L, J are 2, 2, 4 respectively in their
ground state.
The negative sign in Eq. (14.1) indicates that the direction of magnetic moment vector is opposite
h
to that of spin angular momentum S ( S 1) due to spinning motion of electron as shown in
2S
Figure 14.1.
Figure 14.1 The orientation of magnetic moment vector relative to that of spin angular momentum vector.
14.2.2 Potential Energy of Electron When Placed in a Magnetic Field

The potential energy, E of the electron in a magnetic field H as applied in the Z direction is given
by the relation
E = mzH = Hmmcosq
where q is the angle between Z-axis and magnetic moment vector, mz is the Z component of
magnetic moment vector, i.e. mz = mm cos q
Spectroanalytical Techniques—Electron Spin Resonance Spectral Method 499
Substituting the expression of mm from Eq. (14.1), we get
E = H ( g E S ( S 1) ) cos T
= gHb MS (14.3)
where MS is the Z components of spin angular momentum vector, i.e. M S S ( S 1) ) cos T .
When S = 1/2, then MS = +1/2 or 1/2. The energy level E+1/2 corresponding to MS = +1/2 is
1/2 gHb and the energy level E1/2 corresponding to MS = 1/2 is 1/2 gHb. The variation of
E+1/2 and E1/2 with magnetic field is shown in Figure 14.2.
Figure 14.2 The variation of potential energy of an electron in the presence of an external magnetic field.
Thus imposition of an external magnetic field removes the degeneracy of MS state and establishes
two non-degenerate levels as shown in Figure 14.2. The state corresponding to MS = 1/2 is the
lowest. The separation between these energy levels (DE) at a particular value of magnetic field
H is given by
1 È 1 Ø
DE = E1 2 E1 2 gH E É ghE Ù gH E (14.4)
2 Ê 2 Ú
14.2.3 Resonance Condition

Transition from one state to the other can be induced by irradiation of the electron with
electromagnetic radiation of frequency, n. The interaction between the magnetic dipole of the
electron and the oscillating magnetic field component of the electromagnetic radiation causes the
transition.
When the energy, hn of electromagnetic radiation coincides the energy level separation between
the two MS states, the resonance absorption takes place causing the excitation of electron.
Thus under resonance conditions
DE = hn = gHb (14.5)
Generally the frequency is held constant and the magnetic field is varied. At a particular value of
magnetic field resonance, absorption of energy occurs resulting in a peak in the spectrum, known
as ESR peak.
PROBLEM 14.1 Calculate the frequency of radiation absorbed by a free electron under the
magnetic field of 10,000 gauss on resonance condition. Give your comments on the above
result.
Solution For free electron, the frequency of absorption is given by
H
v= g E
h
= 1.3995 ´ 106 gH cycle s1
= 1.3995 ´ gH M cycle s1 (' 1M6 cycle s11
= 10 cycle s )
where b = 9.274 ´ 1021 erg/gauss and h = 6.625 ´ 1027 erg s.
For a free electron, g = 2.0023
hence, v = 1.3995 ´ 2.0023 ´ H M cycle s1
= 2.8022 H M cycle s1 (Provided H is in Gauss )
When a magnetic field of 10,000 gauss is applied
v = 2.8022 ´ 10,000 M cycle s1
= 2.8 ´ 1010 cycle s1 = 2.8 ´ 1010 Hz
Thus a free electron under the influence of a strong magnetic field can be brought into resonance
in the microwave region of electromagnetic radiation.
14.3 RELAXATION PROCESS AND LINE WIDTH IN ESR TRANSITION
If we are to observe any absorption of energy in ESR spectrometer under the resonance condition
hv = gbH, the population in the ground state should be higher than that in the excited state.
The relative population ratio of the two energy levels is governed by Boltzmann distribution law
nupper 'E

e kT (14.6)
nlower
where k is Boltzmann constant (1.38 ´ 1016 erg K1). Expansion of the exponential term in Eq. (14.6)
leads to
nupper 'E 1 È 'E Ø + L
2
1 ÉÊ kT ÙÚ (14.7)
nlower kT 2f
'E
In view of magnitude of being small, all terms after first two terms in RHS may be neglected.
kT
Hence,
nupper 'E
1 (14.8)
nlower kT
PROBLEM 14.2 Calculate the relative population ratio between the ground state and the higher
energy state at 300ºK for an electron for which g = 2 and with a magnetic field of 3300 gauss. Give
your comments on the result.
Solution Here T = 300ºK, H = 3300 gauss and g = 2
k = 1.38 ´ 1016 erg K1 and b = 9.274 ´ 1021 erg/gauss
Since, DE = gHb = 2 ´ 3300 gauss ´ 9.274 ´ 1021 erg/gauss = 6.12 ´ 1017 erg
nupper 'E 6.12 1017

\ 1 1 0.998
nlower kT 1.38 1016 300
It follows, therefore, that for every 1000 electrons in the low energy level, 998 are in the high
energy level. Hence, there is a small but definite excess of population in the ground state,otherwise
the spectrometer would not have shows any absorption at all. However, there will be net absorption
of energy observed experimentaly in ESR. Apparently, there is some process that makes the excited
state species return to ground state without emission of energy besides Boltzmann population
distribution. The process is called relaxation process which converts the energy of the excited
electron into the translational or rotational energy and electron therefore goes to the ground state.
Relaxation process involves
(i) spin-lattice relaxation and
(ii) spin-spin relaxation.
Spin-lattice relaxation is a mechanism by which the excess energy of a paramagnetic species is
transferred to the vibrational degree of freedom of the lattice. At low temperature, the spin-lattice
relaxation becomes less efficient there by increasing the relaxation time. So that reasonably good
and sharp ESR spectrum is obtained. The temperature should be lowered to that of liquid nitrogen
or liquid helium.
Spin-spin relaxation is a mechanism by which paramagnetic species shares its excess energy
with the neighbouring electron spins. This process reduces the lifetime of the excited state (relaxation
time) so that a broad ESR line results. This broadening of ESR line is known as concentration
broadening. This can be avoided by magnetically diluting the paramagnetic species in a diamagnetic
isomorphous host lattice.
Line width of ESR transition
The line width of an ESR transition is related to the lifetime of the excited state by Heisenbergs
Uncertainty Principle,
h
'v ('t )
2S
where Dv is the width of ESR transition and Dt is the lifetime of the excited state or relaxation time.
È h Ø
If Dt is small, Dv is large to make their product constant É Ù , then a broad line may be obtained.
Ê 2S Ú
If the excited electron spin has a long time, in revers slowly to the low energy state resulting in
long relaxation time, a narrow line will be observed. Thus line width depends on the relaxation
time of the spin state. It has been found that for most of the sample, the relaxation time is 101s. By
substituting the value in Heisenberg Uncertainty relation, a frequency of uncertainty (line width)
can be found to be »1 gauss, whereas in NMR it is much less than 0.1 gauss. Because of wider
lines, ESR signal are measured as derivative signals to improve the accuracy.
14.4 TECHNIQUES OF ESR SPECTROSCOPY
14.4.1 Instrumentation
The instrument used to study ESR spectra is called ESR spectrometer. It consists of the following
components
1. A large electromagnet.
2. Source of microwave radiation
(Klystron).
3. Sample cavity.
4. Solvent.
5. Crystal detector.
6. Autoamplifier.
7. Recorder or an oscilloscope.
A schematic diagram of a typical ESR
spectrometer is shown in Figure 14.3.
In an ESR spectrometer, the source
of the microwave is a Klystron oscillator
which is operated to produce
monochromatic radiation of frequency
of about 9500 MHz. An electromagnet Figure 14.3 Schematic diagram of a typical ESR
connected to sweep generator and spectrometer.
subsidiary coil (Helmholtz coil) provides
a variable field strength. An electromagnet with field strength (H) ranging from 5000 gauss to
15000 gauss can be used. The microwave radiation is transmitted into sample cavity by means of
wave guide (made of brass or copper tubing) is to the sample placed in a small quartz tube (known
as sample cavity cell or resonant cavity cell) positioned between the poles of permanent magnet.
To measure the ESR spectrum of a sample, the sample is placed in a magnetic filed of resonant
cavity cell in which the macro wave radiation is transmit by means of wave guide (made of brass
or copper tubing). The interaction of magnetic spin with oscillating magnetic field of the
electromagnetic radiation leads to ESR transition. The ESR spectrum can be recorded varying
either magnetic field strength or the microwave frequency. Usually magnetic field strength is varied
over a wide range and the frequency is kept constant. The microwave energy is modulated and the
microwave power absorbed by the sample at resonance is measured by photosensitive detector
circuit, amplified and finally recorded on a chart in the x-y recorder. A semiconducting silicon-
tungsten crystal is also used as a detector which acts as rectifier and converts the microwave power
to direct current.
14.4.2 Sample Concentration and Choice of Solvent

The sample can be in the form of a powder, solution, single crystal or gas. If frozen solution sample
is obtained from a solvent (methyl cyclohexane) which freezes to form a glass, a reasonably good
ESR spectrum is observed. Due to the presence of strong hydrogen bonding, water is a poor glass
forming solvent. On the other hand, most organic solvents form glasses at 77 K (liquid
nitrogen temperatures). Methyl cyclohexane, glycerol, toluene, isooctane, nujol (paraffin oil) are
examples of some of the important solvents which form good glasses. Mixtures like propane +
propene, ethyl alcohol + methyl alcohol, toluene + acetone, toluene + chloroform, etc., form good
glasses and are used in ESR studies. Solvents having high dielectric constant such as water, alcohol,
etc. are not used in ESR studies because they strongly absorb microwave radiation. However, for
structure determination and quantitative analysis the concentration should be about 106 M.
14.4.3 Presentation of ESR Spectra

An ESR spectrum is obtained by plotting the intensity of absorption against the strength of a
magnetic field. However in quantitative studies, ESR spectrum is obtained as a derivative curve in
which the first derivative (i.e. the slope) of the absorption curve is plotted against the strength of
magnetic field. The two modes of representation are easily interconverted and the relationship
between two kinds of spectra is illustrated in Figure 14.4. In Figure 14.4(a), a single absorption
peak with no fine structure is represented; Figure 14.4(b) shows the derivative curve that corresponds
to Figure 14.4(a). The derivative curve crosses the abscissa at a maximum in the absorption curve,
as the slope changes sign at a maximum. The curve shown in Figure 14.4(c) is the absorption
Figure 14.4 ESR spectrum as absorption and derivative curves.

counterpart of the derivative curve in Figure 14.4(d). It is to be noted that shoulders in (c) never
pass through a maximum and as a result the absorption peak in (d) corresponding to the shoulders
do not cross the abscissa.
14.4.4 Interpretation of Derivative Curve

(i) The derivative curve crosses the abscissa at a maximum in the absorption curve, as the
slope changes sign at a maximum.
(ii) The shoulders in (c) never pass through a maximum, as a result the absorption peak in (d)
corresponds to these shoulders does not cross the abscissa.
(iii) The number of shoulders in the absorption curve can be determined from the number of
minima (marked with an asterisk in (d)) in the derivative curve.
(iv) The total area covered by either absorption curve or derivative curve is proportional to
the number of unpaired electrons in the sample. The number of such electrons in the
unknown sample can be determined by comparing the same line shape of a standard
sample whose number of unpaired electrons is known. The widely used standard is
discussed below.
14.4.5 Use of Standards

In order to calculate the number of electrons in an unknown sample or to measure g factor, a
standard sample is used as a reference. In general the standards should be stable, should have line
width close to that of sample and should have the number of unpaired spins close to that of the
sample. The most widely used standard is 1, 1 diphenyl-2-picrylhydrazyl (DPPH) free radical
(Figure 14.5). It is a chemically stable substance having the splitting factor, g = 2.0036. It contains
1.53 ´ 1021 unpaired electrons per gram. However, DPPH cannot be used as an internal standard
for other free radicals, because only a slight variation in the g values takes place for which the
unknown sample cannot be distinguished. Therefore, in case of free radical, a trace of Cr(III) in a
tiny chip of ruby crystal fixed permanently in the sample cell is used as standard. This standard
shows a strong resonance and its g value is 1.4.
Figure 14.5 Structure of DPPH radical.
14.5 HYPERFINE SPLITTING
Since the electron is usually delocalized over the whole molecule of species or at least a larger part
of it, the unpaired electron comes into contact with many nuclei. Nuclei possessing a magnetic
moment may interact and cause a further splitting of the ESR signal, i.e. a single absorption signals
split into more than one signals known as hyperfine structure. This phenomenon is called hyperfine
splitting. Thus the splitting of ESR signals due to interaction of magnetic moment of electron with
those of surrounding magnetic active nuclei resulting hyperfine structure is known as hyperfine
splitting.
The interaction depends on the relative direction of magnetic moment of the electron relative to
that of proton. This interaction energy is expressed as AMSMI, where A is called the hyperfine
splitting or coupling constant and MI is the spin quantum number of the coupling nucleus. Generally
the hyperfine coupling constant is a small fraction of electron splitting. On a spectrum it is the
distance between associated peaks of a submultiples measured in gauss.
The energies of a coupled level is given by
E = gbHMS + AMSMI (14.9)
Illustration
(a) For hydrogen atom (1H1)
Let us illustrate the hyperfine splitting by considering an example of a hydrogen atom having one
1Ø È 1Ø
proton ÈÉ I Ù and one electron É S Ù . While the electron spin can have two orientations;
Ê 2Ú Ê 2Ú
1 1
one corresponding MS = and the other to ms = , the nuclear spin quantum numbers for
2 2
1 1
each of these two MS states may be MI = and MI = . Thus in total, the four energy levels are
2 2
possible.
The four possible energy levels for the hydrogen atom are shown in Figure 14.6.
Figure 14.6 Energy levels for hydrogen atom (a) splitting due to magnetic field; (b) hyperfine splitting.
Although three ESR transitions appear to be possible, only two are permitted by the ESR selection
rules, i.e. DmS = ± 1 and Dml = 0. The two transitions shown in Figure 14.6 obey these selection
rules. The energies of the two transitions obtained from Eq. (14.9) are:
1 1 È 1 1 Ø 1
gE H A É gE H AÙ = g E H A
2 4 Ê 2 4 Ú 2
1 1 È 1 1 Ø 1
gE H A É gE H AÙ = g E H A
2 4 Ê 2 4 Ú 2
Thus the separation between two ESR signals will give us a measure of A. It may be noted that
A is independent of the magnetic field strength (H).
Hence a splitting of an ESR line due to an interaction between the nuclear spin and the electron
spin of the same atom is known as hyperfine splitting. From the number and intensity distribution
of the spectral lines one can tell how many nuclei interact with unpaired electron.
(b) For Deuterium (1H2)
The deuterium (1H2) is another simple example of a system with I = 1. Energy levels are computed
in a similar manner as done in case of hydrogen atom. Corresponding to MS = +1/2, there are three
values of MI, i.e. MI = 1, 0 and 1. Similarly, corresponding to MS = 1/2, there are three values of
MI, i.e. MI = 1, 0, 1. The energy of all the six energy levels are as follows:
1 1
E1/2, 1 = gEH A
2 2
1
E1/2, 0 = gE H
2
1 1
E1/2, 1 = gEH A
2 2
1 1
E1/2, 1 = gEH A
2 2
1
E1/2, 0 = g E H
2
1 1
E1/2, 1 = g E H A
2 2
By virtue of the selection rules DMS = ± 1 and DMI = 0, there are three allowed transitions and thus
three lines corresponding to these transitions in the ESR spectrum of 1H2 are expected.
The allowed transitions are E(1/2, 1) to E(+1/2, 1), E(1/2, 0) to E(+1/2, 0) and E(1/2, 1) to
E(+1/2, 1). These lines will be of equal intensity, since there is no coincidence of states, i.e. the
state are all non-degenerate.
(c) For Methyl radical (CH3)
An examination of ESR spectrum of methyl radical (CH3) is helpful in studying the intensities of
peaks. In this radical, the unpaired electron is moving in the neighbourhood of three equivalent
hydrogen nuclei or protons. The total nuclear spin quantum number of the three hydrogen nuclei,
I = 3 ´ 1/2 = 3/2, so that there are four possible ml values, namely +3/2, +1/2, 1/2 and 3/2.
The ESR selection rules, DMI = 0 and DMS = ± 1 will permit four transitions. The energies of the
transitions are as follows:
MS = 1/2, MI = 3/2 ® MS = +1/2, MI = +3/2
1 3 Ë 1 3 Û
DE = gE H A Ì gE H A
2 4 Í 2 4 ÜÝ
6
= gE H
A
4
MS = 1/2, MI = 1/2 ® MS = +1/2, MI = +1/2
1 1 Ë 1 3 Û
2 4 Í 2 4 ÜÝ
2
= gE H
A
4
MS = 1/2, MI = 1/2 ® MS = +1/2, MI = 1/2
1 1 Ë 1 1 Û
2 4 Í 2 4 ÜÝ
2
= gE H
A
4
MS = 1/2, MI = 3/2 ® MS = +1/2, MI = 3/2
1 3 Ë 1 3 Û
2 4 Í 2 4 ÜÝ
6
= gE H A
4
The intensities of the transition corresponding to m1 = +1/2 and m1 = 1/2 are the same but nearly
three times as great as those corresponding m1 = +3/2 and m1 = 3/2 states. This is so because
m1 = +1/2 and m1 = 1/2 may exist in as many as three ways, whereas m1 = +3/2 and
m1 = 3/2 admit only one arrangement, as shown in Figure 14.7.
Figure 14.7 Interpretation of ESR for methyl radical.
The ESR spectrum of methyl radical as illustrated in Figure 14.8 contains the four peaks expected
from these considerations.
The hyperfine splitting of a signal by three equivalent protons into four signals can also be
represented by the stick-diagram Figure 14.9 where a is the hyperfine splitting constant.
Figure 14.8 ESR spectrum of methyl radical. Figure 14.9 Stick-diagram for hyperfine splitting.
The signal given by the electron is split into two by proton 1. Each of the two is further split into
two by proton 2 and so on. On the whole, there are eight splitting of which three coincide to give
an intense signal and similarly another three coincide. Thus there are four signals of which the
middle two are intense.
Calculation of ESR splitting
Thus we see that when a single electron interacts with a nucleus, the number of ESR splitting will
be equal to 2I + 1, where I is the spin quantum number of the nucleus. The oxovanadium(IV) ion
belongs to 3d1 system and vanadium nucleus has I = 7/2. This means that the unpaired electron is
in the vicinity of I = 7/2 of its own mother nucleus. Then the isotropic ESR spectrum of a magnetically
dilute oxovanadium(IV) complex gives (2 ´ 7/2 + 1) = 8 lines as shown in Figure 14.10 and its
ESR spectrum is shown in Figure 14.11.
Figure 14.10 Energy level diagram for VO(IV) ion.

Figure 14.11 ESR spectrum of magnetically dilute VO(IV) complex.
If a single electron interacts magnetically with n equivalent nuclei, the ESR signal is split up
into (2nI + 1) multiplet; the relative intensities of these lines follow the co-efficient of binomial
expansion (1 + x)n. If the unpaired electron couples with non-equivalent protons, each proton will
have its own coupling constant. In general, n non-equivalent protons will produce a spectrum with
2 n-hyperfine lines. On the other hand, if there is a set of n equivalent nuclei having
nuclear spin Ii and another of m equivalent nuclei having nuclear spin Ij and the splitting is caused
by both the sets, then the number of lines in ESR is given by (2nIi + 1) (2mIj + 1). For example, the
ESR spectrum of the distorted tetrahedral dichloro (orthophenanthroline) copper(II) exhibits 2 ´
3/2 + 1 = 4 major peaks due to hyperfine interaction of 63Cu (I = 3/2) as in the case with ESR
spectra of CuCl2 . 2H2O and CuSO4 . 5H2O. Each of the four peaks splits into 2 ´ 2 + 1 = 5 peaks
due to hyperfine interaction of the nitrogen (I = 1) atoms of the coordinated orthophenanthroline.
The hyperfine interaction resulting from the ligand donor atoms is called super hyperfine interaction.
Although 35Cl has a nuclear spin quantum number I = 3/2, the chloride superfine interaction is not
observed as the chloride super hyperfine splitting constant is small in a copper(II) complex.
The ESR spectrum of bis (salicylaldiminato) copper(II) (Figure 14.12) is also an interesting
example of super hyperfine splitting.
Figure 14.12 Bis (salicylaldiminato) copper(II).
The spectrum has four main groups of lines resulting from the coupling of the 63Cu nucleus
having I = 3/2 with unpaired electron copper(II). The super hyperfine structure in each of the
groups consists of eleven peaks. These peaks originate from the splitting by two equivalent nitrogens
and two equivalent hydrogens C H of the ligands on the spectrum. The number of expected
peaks is (2 ´ 2 ´ 1 + 1) ´ (2 ´ 2 ´ 1/2 + 1) = 15. Some of the expected 15 lines overlap, so that only
11 lines are visible, as shown in Figure 14.13.
Figure 14.13 Interpretation of ESR spectrum of bis (salicylaldiminato) copper(II).
The splitting by the two equivalent nitrogens are indicated in (b) and the subsequent splitting by
two equivalent protons is indicated in (c). The two nitrogens split the resonance into five peaks of
relative intensity 1 : 2 : 3 : 2 : 1. These values are denoted in (b) by 4d, 4e and 4f where the
intensities correspond to d = 1, e = 2 and f = 3. The splitting by two equivalent protons will give
rise to three lines for each line in (b), with an intensity ratio of 1:2:1. The intensities indicated by
letters underneath the lines in (c) result from the summation of the expected intensities. Since the
relative intensities are d = 1, e = 2 and f = 3, the ratio of the intensities of the band in (c) is
1 : 2 : 3 : 4 : 5 : 6 : 5 : 4 : 3 : 2 : 1. The experimental spectra agree with this interpretation is further
substantiated by the following results:
1. Deuteration of N H groups produced a compound which gave an identical spectrum.
2. When the H hydrogen were replaced by methyl group, the EPR spectrum for this compound
consisted of four main groups, each of which consisted of five lines resulting from nitrogen
splitting only. The hyperfine splitting by the N H proton and that by the protons on the
methyl group are either too small to be detected or non-existent.
This spectrum (as shown in Figure 14.14) furnishes conclusive proof of the delocalization of
the odd electron in this complex onto the ligand. This can be interpreted only as covalence in the
metalligand interaction.
Figure 14.14 ESR derivatives spectrum of bis (salicylaldiminato) copper(II) complex.

So far we have confined our discussion to single, unpaired electron. The situation becomes
interesting and complicated when we have two unpaired electrons located on the same atom or one
electron each on the two atom of a dimmer. In such cases, specially for transition metal complexes,
phenomena like zero field splitting and Kramers degeneracy need to be discussed. This is done in
the following section.
14.6 ZERO FIELD SPLITTING AND KRAMERS DEGENERACY
Consider the case of a molecular ion with two unpaired electrons i.e. S = 1. This S = 1 admits as
many as three MS values, +1, 0 and 1. In a field free situation, the three MS values remain degenerate
but split on the application of a magnetic field. From the relation E = g MS H, we note that while
the energy of the MS = 0 state will remain unaltered, the energy of the MS = +1 state will go up and
that of MS = 1 state will go down. The splitting will be symmetrical. Under the ESR selection
rules, two transitions (namely MS = 0 ® MS = +1 and MS = 1 ® MS = 0) are possible, but these
two transitions are of equal energy and hence we should observe only a single transition in ESR
spectrum [Figure 14.15(a)]. But in fact, the ESR spectrum of S = 1 system shows two allowed
transitions (namely DMS = ± 1) evidently of two different energies and sometimes also a third
transition (DMS = 2) which is forbidden. Such a spectrum is possible only if the degeneracy of the
three MS state is lifted even when no magnetic field is applied. This is possible for transition metal
complexes where a metal ion is placed in a crystal field, so that the spin level may be split in the
absence of magnetic field. This phenomenon is called zero field splitting. The zero field splitting
remove the degeneracy in MS as indicated in Figure 14.15(b). When subsequent splitting by the
applied field occurs, the resulting transitions are not degenerate. As a result, in this example cited
above, two peaks are observed in the spectrum when zero field exists but only one peak is observed
when zero field is absent. Figure 14.15(b) is the energy level diagram for the splitting of the
ground state of Ni(II) ions in an octahedral field where zero field splitting occurs.
Figure 14.15 Energy level diagram showing the transitions of a molecule or ion with S = 1.
Another possibility is that in ions or atoms with more than one unpaired electrons there are
interactions between the individual electromagnetic moment and magnetic field generated by the
other electrons (electron). This cause the degeneracy of MS states to be lifted even in the absence
of magnetic field. The well-known examples include dimeric Cu(II) and Oxovanadium(IV)
complexes for which zero field splitting have been observed.
Dinuclear copper(II) and vanadium(IV) complexes consist of isolated pair of copper(II) ions or
vanadium(IV) ions each containing one unpaired electron which strongly interacts through exchange
forces, so that each pair forms a lower singlet (S = 0) states and an upper triplet (S = 1) states. In
the presence of zero state splitting, the degeneracy in MS level is removed and we are expected to
get three peaksout of which, 2 due to DMS = ±1 transitions and 1 due to DMS = ±2 transition
(though forbidden). The copper nucleus has I = 3/2 so in dinuclear copper(II) complex, each ESR
component is expected to split into 2 ´ 2 ´ 3/2 + 1 = 7 lines with intensity ratio 1 : 2 : 3 : 4 : 3 : 2 : 1.
The nucleus 51V has I = 7/2 so in dinuclear oxovanadium(IV) complex, each ESR component is
expected to split 2 ´ 2 ´ 7/2 + 1 = 15 lines as shown in Figure 14.16 involving DMS = ±2 transition
as in case of [VO(2-hydroxy napthaldehyde-ortho amino phenol]2.
Figure 14.16 ESR spectrum of dimeric [VO(2-hydroxy napthaldehyde-ortho amino phenol]2 involving
DMS = ±2 transition.
Kramers degeneracy
Whenever the number of unpaired electrons (n) is even, the resultant spin quantum number is such
that it will admit an MS = 0 state, e.g. S = 1 (n = 2) has MS = ±1, 0 and S = 2 (n = 4) has
MS = ±2, ±1 and 0. But when n is odd and more than 1 (i.e. 3, 5 ), MS = 0 state is no longer
admissible. For example, for n = 3, S = 3/2 has MS = ±3/2 and ±1/2 and S = 5/2 has MS = ±5/2,
±3/2 and ±1/2. This means that when the number of unpaired electrons is odd and more than
1, we have only doubly degenerate spin states and no MS = 0 state. For example, d3 chromium III
(S = 3/2 ) has MS = ±3/2, ±1/2 and hence two doubly degenerate state are expected as shown in
Figure 14.17. d5 Mn(II) has MS = ±5/2, ±3/2, ±1/2 and hence three doubly degenerate states are
expected as shown in Figure 14.18. Thus, when the species contain odd number of unpaired electron
the spin degeneracy of every level remain double degenerate. Such a degeneracy is known as
Kramers degeneracy. In the above example, we expect two Kramers degenerate levels for
d3 system, S = 3/2 (and three Kramers degenerate levels for d5 system S = 5/2). The zero field
splitting produces such level. Each of these levels is split into two singlet by the applied magnetic
field producing four-level system and six-level in case of d3 and d5 system respectively. As a result
of these splitting, three transitions (3/2 ® 1/2, 1/2 ® 1/2, 1/2 ® 3/2) for octahedral Cr(III)
complex and five transitions (5/2 ® 3/2, 3/2 ® 1/2, 1/2 ® 1/2, 1/2 ® 3/2,
3/2 ® 5/2) for octahedral Mn(II) complex are expected. The spectrum is further complicated by
the hyperfine splitting. For example, Mn nucleus (I = 5/2). Thus each of the five peaks due to the
above transition splits into six hyperfine components as per (2nI + 1) rule.
Figure 14.17 Splitting of the levels in octahedral Cr(III) complex.
Figure 14.18 Splitting of the levels in octahedral Mn(II) complex.

Thus, we should note that for a two (i.e. even) unpaired electron system, the permitted ESR
lines due to zero field splitting are two (i.e. even) whereas for a three or five (odd) unpaired
electron system, the permitted ESR lines due to zero field splitting (Kramers Degeneracy) always
odd, i.e. three or five respectively.
Some important applications of ESR are given below.
14.7 APPLICATION OF ESR
14.7.1 Determination of g Value

We know that hv = gbH or g = hv/bH). Thus, g can be conveniently determined if the
microwave frequency (n) at which the ESR spectrometer is operating and the resonance
magnetic field (H) of the sample are known. The calculation of g from the experimental data
(H = 3250 gauss, n = 9.114 ´ 109 cycle/s) can be done as
hv 6.62517 10 27 erg s 9.114 109 cycle /s

g= 2.00
EH 0.92731 10 20 erg/gauss 3250 gauss
If the microwave frequency is not known appropriately, the spectrum may be calibrated with certain
reference substance such as DPPH which has g value of 2.0036. For measuring the value of g, the
best method is to measure the field separation between the centres of the unknown spectrum and
that of reference substance. When sample is placed with DPPH (standard) in the same chamber of
a dual cavity cell, the ESR spectrum shows two peaks separated by DH · g value for the sample is
given by
È '+ Ø
g = g S É1
Ê + ÙÚ
È HØ
If DPPH is used g = 2.0036 É1 Ù where DH is the difference between the resonance magenetic
Ê H Ú
field (H) of the sample and that of DPPD. DH is positive if the sample has its centre at a resonance
magnetic field higher than that of DPPH. DH is negative if the sample has its centre at a resonance
magnetic field lower than that of DPPH. The resonance magnetic field H is obtained from the
field set (in the ESR spectrometer) and the scan range used in the measurement or from the
resonance frequency. In a powdered sample, magnetic susceptibility measurements lead only to an
average g-value, whereas ESR measurements can give the individual components of the
g-tensor.
The value of g depends upon the orientation of the molecule having the unpaired electron with
respect to applied magnetic field. In case of a gas or solution, the molecules have free motion and
the value of g is averaged overall orientations. In case of paramagnetic ion or radical situated in a
perfectly cubic crystal site, the value of g is the same in all directions, i.e. the value of g does not
depend upon the orientation of the crystal and it is called isotropic. On the other hand, the value of
g in paramagnetic ion or radical situated in a crystal of low symmetry depends upon the orientation
of the crystal and is known as anisotropic g value. An unsymmetrical shape of ESR line is
characteristic of an anisotropic g value. Anisotropy means the g value and hence the resonance
frequency vary according to the orientation of the external magnetic field.
In any particular direction, g value is the resultant of three components gx, gy and gz in mutually
perpendicular directions. The gz value is equivalent to g11, i.e. the g value obtained when the Z-
axis is parallel with the external magnetic field. The gx and gy are equal in a tetragonal site and
referred to as gI,, i.e. the g value obtained when the external magnetic field is perpendicular to the
Z-axis. Hence
g|| = gz and g^ = gx = gy
The g value averaged overall directions can be given by
1 2
g2 = (g + gy2 + gz2)
3 x
1
= (2 g^2 + g||2)
3
If the angle between magnetic field and Z-axis, q, is measured, the experimental g value for a
system with axial symmetry can be obtained by
g2 = g^2 sin2 q + g||2 cos2 q
14.7.2 Shape and Type of Hybridization

This can be illustrated with the methyl radical. The ESR spectrum of 13CH3 has been studied and
the hyperfine splitting constant has been measured. The methyl radical may have planar structure
corresponding to sp2 hybridization or tetrahedral due to sp3 hybridization. In the former case the
hyperfine splitting constant is expected to be 25 gauss, whereas in the latter case its value is
expected to be ~300 gauss. The observed splitting for methyl radical is about 41 gauss suggesting
planar structure for methyl radical.
14.7.3 Study of Free Radicals

Free radicals can be studied readily by ESR, even in very low concentrations. For instance,
a signal for DPPH radical can be detected even if there is 1012 g of the substance in the spectrometer.
ESR has been used to study the detection of a free radical intermediate in chemical process such as
conversion of hydroquinone to quinone. Hydroquinone and quinone are not ESR active because
none of them contains an odd electron. But in this redox system, semiquinone free radical anion
exists as an intermediate. The first derivative spectrum of this system contains five peaks, hyperfine
pattern which arises due to magnetic spin interaction between the odd electron and the 4H atoms
on the ring. The intensities of five lines are in the ratio of 1 : 4 : 6 : 4 : 1.
Several free radicals have been produced by photolysis and ESR studies were made on them.
For example, if photolysis is carried out by mixing acidified solution of titanium chloride with
CH3OH and C2H5OH as well as H2O2, the free radicals like CH
2 — OH and CH3 — CH — OH

are produced which can be studied by ESR.

14.7.4 Study of Internal Motion (Rotation)

Studies of aromatic radical ions containing unsaturated substituents have provided interesting
information about internal motion and isomerization in radicals. Thus p-nitrobenzaldehyde anion,
in DMF shows coupling to five magnetically different protons. This observation is interpreted as
resulting from constraint of the CHO group to the plane of the aromatic ring. Such constraints
lower the symmetry of radical and result in magnetic inequivalence of all four ring protons.
14.7.5 ESR and Steric Hinderance

For example, consider substituted nitrobenzene radical anion.
In the unsubstituted nitrobenzene anion radical, the nitrogen splitting constant is 10.3 gauss.
For the 2, 6-dimethylnitrobenzene radical, it is 17.8 gauss. The enhanced value of the hyperfine
splitting constant (HSC) in the latter case indicates that the odd electron is more or less localized in
the nitro group and delocalization in the benzene ring is prevented, as the system is no more
planar.
Several sterically hindered free radicals have longer life (i.e. the greater stability) than the
unhindered ones as indicated by ESR spectral evidence. For example, chichibabins hydrocarbon
contains small percentage of a diradical.
When the four ortho positions are occupied by four chlorine atoms, the amount of the free
radical formed is more due to its lower reactivity on account of steric hinderance.
14.7.6 Analysis of Electron Transfer Reactions through ESR

Let us consider the transfer of electron between a neutral molecule (N) and a radical ion (N).
When naphthalene is added to a solution of naphthalene radical anion, an electron exchange will
occur. This causes the broadening of the hyperfine component of ESR resonance line. This
broadening can be employed to calculate the rate of constant for the exchange between naphthalene
and naphthalene radical anion.
The rate of electron transfer has been studied, for example, electron transfer between neutral
tetracyanoethylene molecule (TCNE) and its radical anion.
Tetracyanoethylene (TCNE) anion radical is formed by the reduction of TCNE with alkali metals
in etheral solution. When no TCNE is present, TCNE anion radical gives 9 lines ESR spectrum
due to 4 equivalent nitrogen nuclei by (2nI + 1) rule, where n = 4 nitrogen atoms; I = 1 for 14N.
On adding TCNE to the anion radical the line first broaden, then coalesce into broad spectrum and
finally at a very high concentration of TCNE, a single line is obtained. In this situation the electron
jumps from one molecule to another so rapidly that the hyperfine structure is lost and only one line
representing this average effect is observed. This is called exchange narrowing phenomenon.
14.7.7 ESR in Polymer Chemistry

The course of polymerization with intermediate formation of free radicals can be followed with
ESR technique. For example, polyethylene yields a seven-fold resonance pattern which may be
due to the formation of
14.7.8 Spin labelling of Biomolecules

Some synthetic free radicals are chemically attached to the biomolecules under study. From the
ESR spectrum of the free radical attached to the biomolecule and the changes in the spectrum
observed, information about the electronic environment in the biomolecule, close to the binding
site (and sometimes about the biomolecule as a whole) can be obtained. The free radical used is
called spin label radical and the technique is called spin labelling. The spin label compound
contains a nitroxide ring or a transition metal complex providing unpaired electron. The label must
have active group of atom to form bridges between the free radical and the macromolecule. The
five- or six-member heterocyclic molecules containing a nitroxyl group whose nitrogen atom is
bonded to a tertiary carbon atom are the best spin labelling compounds for macromolecules. Proteins
and cell membranes have been studied by this method.
14.7.9 ESR Studies of Inorganic Compounds, Mainly Complexes

Several inorganic molecules like O2, NO and NO2 contain unpaired electrons. Similarly, many
metal ions, particularly transition metal ions (with incompletely filled orbitals) also contain odd
electrons. Such molecules and ions have been subjected to ESR studies.
An interesting example is provided by crystalline XeF4 exposed to g radiation at temperature of
77 K, when the crystal turns blue. The spectrum shows three ESR signals, namely a doublet, a
quartet and an octet. These indicate the presence of the radical, [XeF4]. The doublet is due to the
interaction of the odd electron with 19F (spin = 1/2) and the even mass numbered Xe (spin = 0).
Here the multiplicity (2nI1 + 1) (2nI2 + 1) = (2 ´ 1 ´ 1/2 + 1) (2 ´ 1 ´ 0 + 1) = 2. The quartet

is due to the presence of 129Xe with a spin of 1/2: here (2 ´ 1 ´ 1/2 + 1) (2 ´ 1 ´ 1/2 + 1) = 4.
The octet is due to the presence of 131Xe with a spin of 3/2; it is explained by the expression,
(2 ´ 1 ´ 1/2 + 1) (2 ´ 1 ´ 3/2 + 1) = 8.
In detecting the presence of unpaired electrons, ESR is more sensitive than paramagnetic
suspectibility measurements. Consider liquid sulphur equilibrium
S8 rings ZZX S8 chains

YZZ
The S8 rings are completely spin paired, (diamagnetic), but in S8 chains, there is unpaired
electron at each end of a chain, as evidenced by ESR studies. These chains are so long that the
concentration of the corresponding radicals is very low and the paramagnetism cannot be detected
with a Goy balance.
An unpaired electron in an isolated metal ion would show only one sharp line in ESR spectrum,
but if the metal ion is connected to a ligand, multisignal absorption results showing that the electron
has been partly transferred to the ligand orbital. Thus trimesityl borate ion radical [B(C6H2Me3)3]
in THF solvent gives ESR signal with four peaks indicating that the odd electrons couple with the
spin of 11B nucleus (I = 3/2).
ESR spectrum of the radical anion [NO(SO3)2]2 in chlorofom gives a triplet due to the interaction
of the odd electron with 14N nucleus (I = 1) conforming that the electron is localized on N atom.
Similarly ESR spectrum of nitroprusside ion radical [Fe(CN)5NO]2 shows three lines with the
same intensity, because of the interaction of the electron with the nitrosyl 14N (I = 1). The ESR
spectrum of [IrCl]2 indicates that the unpaired electron is not 100% localized on the metal ion; it
is spread over each Cl also to the extent of about 5%. In other words, there is overlap of metal
orbitals and ligand orbitals (i.e. covalent character).
ESR provides detailed information about the symmetry and magnitudes of the ligand field present
in complex ion and on the interaction of unpaired electron with various ligand atoms and gives the
accurate g values. Both g and A variables can be used to determine the bonding characteristics of
the coordination compounds. The g value cannot be isotropic if the ligand field to which the
central ion in a complex is not of cubic symmetry. The deviation of g value from spin value of 2.00
is due to the interaction between the ground and the higher ligand field terms in a spin-orbit
coupling. Mn2+ and Fe3+ having an orbitally non-degenerate ground state (6S) give g values almost
equal to the free electron value. This shows there is practically no orbital angular momentum. In
case of octahedral Ni(II) complexes, g value can be obtained from the following equation:
g = 2 8l/10 Dq
where l is the spin-orbit coupling constant. The experimental g value for [Ni(H2O)6]2+ is 2.25
8O
which means 0.25 . The electronic spectrum of the ion yields 10 Dq = 8500 cm1 giving
10 Dq
l = 270 cm1. For free Ni(II) ion, the value of l = 324 cm1. This change in the value of l after
complex formation is a measure of the extent of mixing of metal orbitals with ligand orbitals. From
the above it is clear that g value depends on the magnitude of l and 10 Dq.
PROBLEM 14.3 ESR spectrum of the complex ion [Mo(CN)8]3 in solution consists of one
line. If the sample is enriched with C13, the spectrum consists of nine lines. Explain this fact.
Solution This can be explained on the basis of Mo(V) in [Mo(CN)8]3 has d1 configuration and
only a single line is expected. But for C13 enriched sample (for C13, I = 1/2), there will be 2nI + 1
or nine lines because 8 C atoms in the CN groups surround the Mo atom.
PROBLEM 14.4 Derive structural information from the complex ion
[(NH3)5Co O O Co(NH3)5]5+ from ESR.
Solution
(a) The two Co(III) atoms may be connected by an O2 bridge or
(b) The Co(III) and Co(IV) may be linked by a peroxy, O22 bridge or
(c) There may be two equivalent cobalt atoms, the unpaired electron is undergoing equal
interaction with both cobalt atoms.
If structure (a) is correct, one should expect a single line in the ESR spectrum. For structure (b),
eight lines are expected (I = 7/2 for 59Co). For structure (c), fifteen lines may be observed.
The actual ESR spectrum shows fifteen lines. This supports the structure (c). But this does not rule
out the possibility of contribution of structure (a). Thus the actual structure of cobalt complex may
be a combination of structures (a) and (c). However, the final confirmation of correct structure can
be obtained from O17 hyperfine splitting.
PROBLEM 14.5 The benzene radical anion C6H6 has a g-value of 2.0025. At what field would
you search for resonance in a spectrometer operating at 9.302 GHz?
Solution We have
n = 9.302 GHz = 9.302 ´ 109 s1
DE = hn = (6.626 ´ 1034 Js) (9.302 ´ 109 s1)
= 6.164 ´ 1024 J
Now since, DE = gb H, we have
H = DE/gb = 6.164 ´ 1024 J/2.0025 ´ 9.274 ´ 1024 JT1
= 0.332 T
PROBLEM 14.6 A radical containing two non-equivalent protons with splitting constant
2.0 mT and 2.6 mT gives a spectrum centred on 332.5 mT. At what field do the hyperfine lines lie,
and what are their relative intensities?
Solution The fields of hyperfine lines can be computed from the expression
H = H0 + a1mI1 + a2mI2
where we can identify a1 = 2.0 mT, a2 = 2.6 mT at each quantum number, mI1 and mI2 can have
values of +1/2 and 1/2. Thus, we expect to observe lines at the following fields.
H1 = 332.5 mT + (2.0 mT) (1/2) + (2.6 mT) (1/2) = 334.8 mT
H2 = 332.5 mT + (2.0 mT) (1/2) + (2.6 mT) (1/2) = 332.2 mT
H3 = 332.5 mT + (2.0 mT) (1/2) + (2.6 mT) (1/2) = 332.8 mT
H1 = 332.5 mT + (2.0 mT) (1/2) + (2.6 mT) (1/2) = 334.8 mT
All the four lines are equally intense.
PROBLEM 14.7 Predict the intensity distribution in the hyperfine lines of the ESR spectrum of
the radical .CD3 (I = 1 for D).
Solution The number of ESR signals will be given by the relation 2nI + 1. Here, n = 3 and
I = 1. Hence the number of ESR signals = 2 ´ 3 ´ 1 + 1 = 7.
Thus, the ESR signals will include seven lines with relative intensities of 1 : 2 : 3 : 4 : 3 : 2 : 1.
PROBLEM 14.8 Predict the form of ESR spectrum of a radical containing one 14N nucleus
(I = 1, a = 1.03 mT) and two equivalent protons (I = 1/2, a = 0.35 mT).
Solution Due to 14N, the ESR line will split into three lines (2I + 1 = 3) of equal intensities with
the separation of 1.03 mT. Each line will further split into three lines due to the presence of two
equivalent protons by the relation n + 1. The separation between them will be 0.35 mT and have
relative intensities of 1 : 2 : 1 as given by the Binomial coefficient (1 + x)2. Thus the overall
protons will have three equivalent triplets (1 : 2 : 1) each with internal splitting 0.35 mT and
separated from its neighbour by 1.03 mT.
PROBLEM 14.9 Predict the nature of ESR signal of CH3 CH2. radical.
Solution Ethyl radical contains two types of protons such as methylene and methyl protons.
Due to methylene protons, the ESR line will split into three lines of relative intensities 1 : 2 : 1.
Each of these three lines will split into four lines due to methyl protons with relative intensities
1 : 3 : 3 : 1. Thus the ethyl radical will show twelve lines, i.e. quartet (1 : 3 : 3 : 1) of triplets
(1 : 2 : 1).
PROBLEM 14.10 Give your comments on ESR spectrum of 1, 4-benzosemiquinone radical ion
and 2-methyl 1, 4-benzosemiquinone radical ion .
Solution 1, 4-benzosemiquinone radical ion.

It has four identical protons. Thus we may expect five absorption lines with relative intensities
4C , 4C , 4C , 4 C , 4C , i.e. 1 : 4 : 6 : 4 : 1.
0 1 2 3 4
When one H at 2-position is replaced by methyl group, 2-methyl1,4 benzosemiquinone radical
ion is obtained. It is found that the spin density is the same at the methyl protons as at the ring
protons, and the spectrum consists of seven lines with an intensity ratio of 1 : 6 : 15 : 20 : 15 : 6 : 1,
corresponding to the interaction with six equivalent protons given by Binomial coefficient 6C0,
6C , 6C , 6C , 6C , 6C , 6C .
1 2 3 4 5 6
PROBLEM 14.11 How many ESR lines can be expected for the 1, 2-, 1, 3- and 1,
4-difluorobutadiene radical anions I = 1/2 for 19F and 1H.
Solution For 1, 2- and 1, 3-compounds (no HS or FS are equivalent) hence, there are six number
of nuclei giving ESR lines according to 2n rule. As n = 6 the number of ESR signal is 26, i.e. 64.
For 1, 4-compound if FS are trans-trans, then two FS are equivalent and one set of 2HS and another
set of 2HS are equivalent giving (2 + 1) (2 + 1) (2 + 1) = 27. However, if FS are trans-cis, then all
the substituted FS and HS are non-equivalent giving 26 = 64 lines.
PROBLEM 14.12 How many ESR lines can be expected for 33S19F6 radical anion and radical
cation I = 3/2 for 33S, and I = 1/2 for 19F.
Solution The number of lines is given by the formula (2n1I1 + 1) (2n2I2 + 1). In the above problem
n1 = number of S which is 1 and I1 = 3/2
n2 = number of FS which is 6. I2 = 1/2
So the number of lines = (2 ´ 1 ´ 3/2 + 1) (2 ´ 6 ´ ½ + 1) = 4 ´ 7 = 28 lines

(i) In ESR, radiation having frequency of
(a) Microwave region is absorbed (b) Radio frequency region is absorbed
(c) UV region is absorbed (d) Visible region is absorbed
(ii) The magnetic moment associated with a spinning electron is given by the relation
(a) mm = g E S ( S 1) (b) mm = g E S ( S 1)
(c) mm = g E I ( I 1) (b) mm = g E I ( I 1)
(iii) The ESR spectrum of hydrogen atom gives
(a) Two ESR signal (b) One ESR signal
(c) Four ESR signal (d) None of these
(iv) The selection rule for ESR is
(a) DMS = 0 and DMI = ±1 (b) DMS ¹ 0 and DMI ¹ 0
(c) DMS = ±1 and DMI = 0 (d) DMS = ±1 and DMI = ±1
(v) The intensities ratio of four ESR signals in case of methyl radical correspond to
(a) 1 : 2 : 2 : 1 (b) 1 : 3 : 2 : 1
(c) 1 : 3 : 3 : 1 (d) None of these
(vi) The ESR spectrum of oxovanadium(IV) is expected to contain
(a) Four lines (b) One lines
(c) Eight lines (d) None of these
(vii) The ESR spectra of CuSO4·5H2O is expected to contain
(a) One measure peak (b) Two measure peak
(c) Three measure peak (d) Four measure peak
(viii) The ESR spectrum of S = 1 system shows
(a) Only one allowed transition (b) Only two allowed transition
(c) Only three allowed transition (d) None of these
(ix) The number of Kramer degeneracy level for d3 system having S = 3/2 is
(a) One (b) Two
(c) Three (d) None of these
(x) The value of Bohr magneton in SI unit is

(a) 9.2741 ´ 1024 JT1 (b) 5.047 ´ 1027 JT1
(c) 1.38 ´ 1023 J (d) None of the these
2. Write whether the following statements are true or false. If false, write the correct answers
(i) The value of g is not constant but it is a tensor quantity.
(ii) ESR has been applied to the study of chemical, photochemical and electrochemical reactions
which proceed via free radical mechanisms.
(iii) For a d1 system, the occurrence of DMS = 2 transition in the ESR spectrum is considered as
due to magnetic exchange.
(iv) In the complex [Fe(H2O)4(NO)2]2+, the number of ESR lines is five.
(v) ESR spectrum of the complex ion [Mo(CN)8]3 enriched with 13C contains nine lines.
(i) The electron is a charged spinning particle with a spin equal to .............. .
(ii) The intensity of absorption line is .............. to the number of unpaired electrons.
(iii) The best standard used in ESR spectroscopy is .............. .
(iv) The magnetic ratio of electrons is .............. Rad G1sec1, protons have a comparable value
of .............. Rad G1sec1.
(v) Usually ESR spectra are recorded in the .............. form to enhance sensitivity and resolution.
(vi) For hydrogen atom, the hyperfine coupling constant is .............. .
(vii) In ESR, a transition between two different energy levels occurs by absorbing a quantum of
radiation of frequency in the .............. region.
(viii) g, the proportionality factor, is also called .............. or .............. .
(ix) p-benzosemiquinone radical ion is expected to give .............. number of ESR lines.
(x) ESR spectrum of CD3 radical will show .............. number of ESR lines.

(i) Which of the following system will show ESR spectrum?
(a) H, (b) H2, (c) Na+,
(d) N2, (e) NO, (f) Cu+,
(g) Cu2+, (h) CH3, (i) CO2.
(ii) Why C12 and O16 nuclei do not interact with the electron?
(iii) Vanadyl acetylacetonate shows eight lines in the hyperfine structure of its ESR spectrum.
Calculate the spin of the V51 nucleus.
(iv) Predict the number of lines in ESR spectrum when an unpaired electron interacts with three
equivalent protons.
(v) The interaction of an unpaired electron with N14 causes a splitting of three lines while with
Mn55 it gives six lines. Why?
(vi) Predict the number of lines in the ESR spectrum of p-benzosemiquinone.
(vii) Name the best known free radical used in caliberating ESR spectra.
(viii) What is the value of g in case of (a) free electron, (b) organic radical, (c) transition metal
ions, (d) DPPH powder.
(ix) Will the radical anions and cations of naphthalene, anthracene, tetracene and pentacene
shows ESR spectrum?
(x) How many lines are expected in ESR spectrum of radical anion derived from p-xylene?
(xi) The ESR spectrum of free radical C3H7 shows 14 lines. Whether this radical is n-propyl or
isopropyl radical? Explain.

(i) Predict the ESR spectrum of NH2 radical.
(ii) Sketch the ESR spectrum arising from the interaction of an unpaired electron with three
equivalent protons.
(iii) Explain the mechanism of hyperfine interaction in the ESR spectra of organic radicals.
(iv) Draw an energy level diagram showing ESR spectrum of an odd electron.
(v) Why water and alcohol are not suitable solvent for ESR studies?
(vi) Why the instrumentation of ESR is quite different from that of NMR while their basic
principles are closely related to each other?
(vii) Why ESR spectroscopy is widely used in the study of chemical and electrochemical reaction,
which proceed via free radical mechanism?
(viii) Calculate the g value of the methyl radical showing ESR peak at 3290G (0.329 T) with a
spectrometer working at 9230 MHz.
(ix) An ESR spectra operating at 9300 MHz. Shows two lines at 3570 and 3044 g. Calculate the
hyperfine splitting constant (MHz) for the system.
(x) How many ESR lines can be expected for Cu(S2PF2)2 and VO(S2PF2)2 (I = 3/2 for Cu;
I = 7/2 for V; I = 1/2 for F) if the metal, phosphorous, and fluorine hyperfine splitting were
observable in solution spectra?
(xi) How many ESR lines can be expected for the tetrahedral P4 radical I = 1/2 for 31P? What
would be the theoretically expected relative intensities of the lines?

6. (a) Prove that DE = gbH for an electron in presence of magentic field.
(b) Calculate the value of Bohr magneton.
(c) Calculate the energy difference between the two levels of a magnetic field of 3000
gauss. In what range of electromagnetic radiation does the energy difference lies?
7. Using the Boltzmann distribution and the energy difference between the two levels of
electron, calculate the relative distribution of electrons in the two levels. Explain relaxation
process and line width in ESR transition.
8. The interaction of the unpaired electron with the magnetic active protons of a molecules
produces hyperfine structure in the ESR spectra. If there are n protons in a molecule and if
they are equally coupled with the electron then
(a) How many lines will be observed in the ESR spectra?
(b) How are the relative intensities of the lines related to each other?
(c) Discuss the ESR spectra of deuterium.
9. (a) How many lines will be observed in the ESR spectrum of benzene anion radical?
What will be their relative intensities?
(b) The ESR spectrum of C3H7 radical shows 14 absorption peaks with relative intensities
of 1, 1, 6, 6, 15, 15, 20, 20, 15, 15, 6, 6, 1 and 1. Is this n-propyl or an isopropyl
radical?
(c) How many ESR peaks are expected for ethyl radical?
(d) Sketch the ESR spectrum of cyclopentadienyl radical C5H5.
10. (a) The ESR spectrum of atomic hydrogen was recorded on a spectrometer working at
9.302 GHz. The value of hyperfine coupling constant was found to be 50.7 mT.
Find the value of H at which two lines of atomic hydrogen will be observed?
(b) Predict the appearance of the ESR spectrum of CD3 and CH3CH3 mentioning their
intensity distribution in the hyperfine lines.
11. (a) A radical, containing two non-equivalent protons with splitting constants 2.0 mT and
2.6 mT, give a spectrum centred in 332.5 mT. At what field do the hyperfine lines lie
and what are the relative intensities?
(b) Predict the form of ESR spectrum of the radicals containing 14N nucleus (I = 1,
a = 1.03 mT) and two equivalent protons (I = 1/2, a = 0.35 mT).
12. Explain zero field splitting and Kramers degeneracy giving suitable examples.
13. Discuss the ESR spectrum of bis-salicylaldiminato Cu(II) complex, Explain why this complex
shows 11 ESR peaks instead of theoretically expected 15 peaks.
CHAPTER 15
Mass Spectral Method
15.1 INTRODUCTION
In this technique, the compound under investigation is bombarded with a beam of energetic
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
charged ions are produced only rarely relative to singly charged ions, the charge can normally
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
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
method are:
(i) High sensitivity, reproducibility and accuracy,
(ii) Materials present in concentrations less than 1 ppm can be easily detected by this technique,
(iii) In addition to elucidation of molecular structure, mass spectra are useful for determining
molecular weight, investigating reaction mechanisms, identifying a functional group and
in tracer technique etc.
The instrument used for investigation is known as mass spectrometer which is designed to
perform the following functions:
1. To vapourize compounds of varying volatility.
2. To produce ions from the neutral compounds in the gas phase.
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
greater than its ionizational potential so that the removal of electron takes place by the following
process:
M(g) + e M
70 eV + (g) + 2e
This ionisation reaction requires energy (in the form of electrons, photons, electric fields, heat or
electrical discharge) in the order of 70 eV (~ 1600 Kcal mole1). This is greater than the typical
bond energies encountered in organic molecules. When the energy of the bombarding electron is
just equal to the ionization potential. This energy must be used to remove an electron form the
molecule orbital of the molecule M to form the parent ion or molecular ion M+. With the increase
in energy of the bombarding electron, the probability of the collision inducing ionization increases.
If the energy of the electron is quite high, then M+, the parent ion may retain excess energy sufficient
enough to rupture the bond and form a new ion N+ and a neutral fragment, O. Neutral particles, O
produced in the process of fragmentation (e.g. M+® N+ + O ) cannot be detected in the mass
spectrometer. This is illustrated taking the example of neopentane.
Fragmentation mode of neopentane.
Each compound yields a characteristic series of fragments called the fragmentation pattern or
cracking pattern. The mass spectrum of a compound is thus a record of the masses and relative
abundance (intensity) of the molecular ion and the positively charged fragment formed by electron
bombardment. The mass spectrum of neopentane corresponding to its molecular ions and
fragmentation products is shown in Figure 15.1.
The spectrum is presented in the form of a bar graph in which abscissa represents the m/e ratios
of the various ions formed by ionization and fragmentations and ordinates indicate their relative
abundance. The most intense peak (bar of maximum height) arbitrarily assigned a value of 100%
is called the base peak. The intensities of other peaks are represented relative to the base peak. The
molecular ion obtained after removal of one electron from the original molecule (known as parent
molecule) is known as parent ion designation M+ and the peak obtained corresponding to its m/e
value is called parent peak. Thus in neopentane, C5H12+ ion obtained after removal of one electron
from C5H12 molecule is the parent ion giving parent peak at m/e = 72. The set of ions (daughter
ions or fragment ions) are analysed in such a way that a signal is obtained for each value of m/e.
The intensity of each signal represents the relative abundance of the ion producing the signal.
In neopentane, the base peak is due to C4H9+ at m/e 57, whereas the molecular ion peak is of very
low abundance (~10%) at m/e 72. Thus, parent peak may not be confused with the base peak.
The relative abundance is expressed at the percentage of base peak given by the relation
Spectroanalytical Techniques—Mass Spectral Method 527
Peak height × 100

% of Relative Abundance =
Height of base peak
Figure 15.1 Mass spectrum of neopentane.
15.3 INSTRUMENTATION
Common mass spectrometer consists of

1. Sample introducing system
2. The ion source and accelerating chamber
3. Mass analyzer and magnets
4. Ion-collector detector
5. Signal sensor and recorder.
The schematic diagram of the mass spectrometer is shown in Figure 15.2. The whole system, from
ion source to the collector electrode is maintained at high vacuum. The only difference among
various types of spectrometers lies in the means for separating the ions according to their m/e ratio.
Figure 15.2 Schematic diagram of mass spectrometer

15.3.1 Sample Introducing System

Its consist of a device for introducing the samples, a micro manometer for determining the amount
of sample to be introduced and a device (molecular leak) for entering the samples to the ionization
chamber and a pumping system.
15.3.2 Ion Source and Accelerating Chamber

The first and an important step in obtaining the mass spectrum is to ionize the sample under
examination. The common technique used for the production of ions in mass spectrometer is by
the bombarded of electrons produced from an electrically heated tungsten filament. A few milligram
of the substance is introduced as a vapour in the source at an operating pressure of 106 mm.
The vapour is allowed to pass through a slit A into the ion chamber as shown in Figure 15.3.
Here it is bombarded by a stream of electron produced from a tungsten filament. The bombarding
electrons have energy of about 70 eV. Due to bombardment, the molecule generally lose one
electron to form a parent ion radical. The bombardment of the electron may result in the following
types of ions.
AB(g) + e ® AB+ + e
® AB+ + 2e (most probable)
® AB+n + (n + 1)e (least probable) n = 2, 3, etc.
® A+ + B + e (ion pair production less probable)
® A+ + B + 2e
® AB (electron capture) less probable
Figure 15.3 Ionization of sample and accelerating of ions.
The energy required for removing one electron from the neutral parent molecule is usually
10 eV. With this much energy, no ions are formed, i.e. no fragmentation of the parent ion takes
place. But if the energy of the bombarding electrons is around 70 eV then additional energy is
consumed in fragmenting the parent ions. This results in the formation of fragment ions or daughter
ions. The positive ions are detected in the mass spectrometer whereas the neutral molecules or the
radicals are left undetected. The efficiency of negative ions formation is lower by about a factor of
1000 as compared to positive ions and cannot be studied by this method.
15.3.3 Mass Analyzer and Magnet

The positively charged ions (parent or fragment ions) produced in the ion chamber are accelerated
by applying an acceleration potential. These ions then enter into the mass analyzer. Here the fragment
ions are differentiated on the basis of their m/e ratio. The positive ions are directed through a slit
B. Repeller potential is applied between A and B. The ions are accelerated by applying an
acceleration potential through the slit C. It is applied between the plates B and C. The positive
ions travel through whole of the analyser portion with high velocity and are separated according to
their m/e ration. Dempsters mass analyzer as showin in Figure 15.4 is used for this purpose.
The positive ions accelerated by electric field travel in a circular path through 180° under a
magnetic field H and fall on a collector (Figure 15.4).
Figure 15.4 Dempsters mass analyzer.
Mathematical calculation
Suppose an ion having a charge e is accelerated through a voltage V. Then the kinetic energy of the
ion is expressed as:
1 2
mv eV (15.1)
2
where v = velocity of the ions after acceleration, V = potential applied.
It may be noted that a massive ion will travel slowly in a circular path compared to the lighter
fragment. In a magnetic field H, any ion will experience magnetic centripetal force (Fm = Hev).
It produces an acceleration of v2/r in a circular path of radius r. Then centrifugal force is given by
v2
Fc = m (15.2)
r
In order to traverse in a circular path to the collector, Fm = Fc
v2
Hev m
r
Squaring both sides, we get
H2e2v2 = m2 v4/r2
or H2e2 = m 2 v 2 r 2 (15.3)
But 1/2 mv2 = eV (from Eq. 15.1)
m ¹ 2eV
H2e2 =
r2
2 mV
or H 2e =
r2
m H 2r 2
= (15.4)
e 2V
Equation (15.4) indicates that at a given magnetic field strength and accelerating voltage, the ions
of m/e value will follow a circular path of radius r. The ions of various m/e values reach the
collector, amplified and recorded. The mass spectrum can be obtained either by
(a) Changing H at constant V,

(b) Changing V at constant H.
When magnetic field is varied, the method is called magnetic scanning. It is known as electric
voltage scanning when potential is varied at constant field strength, H. In most spectrometer H and
r are fixed. Therefore, the mass to charge ratio of the particles reaching the slit is inversely
proportional to the accelerating voltage V. As most particles possess single unit of positive charge
so that any desired mass can be focussed on the exit slit by suitable adjustment of the accelerating
voltage, V.
15.3.4 Ion Collector/Detector and Amplifier

The ions which are separated by the analyzer are detected and measured electrically or
photographically. The ions pass through the collector slit one after the other and fall on the ion
collector/detector. A typical ion collector consists of one or more collimating slits and a Faraday
cylinder. The ion beam impiges axially into the collector and the electric signal obtained is amplified
by an electron multiplier and fed into the recorder.
15.3.5 Recorder
Ion currents are ordinarily small and over a range of 1017 to 1019A. (The former current corresponds
to about 60 ions reaching the detector per second).
In order to record peaks of such diverse sizes, most mass spectrometers are equipped with
several pens, with each responding to a different peak size. Thus, a peak of convenient size can
always be found on the chart.
Some instruments incorporated a set of mirrored galvanometer which records the spectrum on
sensitized paper. Each galvanometer has a different sensitivity to permit the recording of peaks of
widely different size.
Resolution of mass spectrometer
The ability of a mass spectrometer to separate two ions of different m/e values that gives just
separable peaks of nearly equal size is described by its resolving power. The resolving power
necessary to separate two ions of masses M and M + DM is defined as M/DM. Two peaks are
considered to be separated if the height of peak of valley between them is no more than 10% of
their height as shown in Figure 15.5.
Figure 15.5 Resolution of two ions with a 10% value.
Need for double focussing mass spectrometer

The resolving power of Dempsters mass spectrometer is limited by initial spread of translational
energy of the ion leaving the source. The resolution of particles differing by small fraction of a
mass unit is not possible by using this type of instrument. This problem can be overcome by
passing the ions through radial electric field (perpendicular to the direction of flight of the ions)
and magnetic field. The electric field is an energy analyzer instead of a mass analyzer and thus
serves to limit energy spread of the ion beam before it enters the magnetic field.
The electric fields effect will cause focussing of the ions by placing a slit between the electrostatic
and magnetic analyzer as shown in Figure 15.6. The instruments in corporating such system are
called double focussing mass spectrometers. These instruments are capable of attaining much
higher resolving power then single focussing instrument like Dempsters mass spectrometer.
By using this type of instrument, it is possible to resolve the ions which have the same integral
mass but differ in exact masses. For examples, though CO, N2 and CH2 == CH2 all have same
integral mass (28). However exact masses of four species are different. By using double focussing
instrument, it is possible to separate the positive ions corresponding to CO, CH2 == CH2, N2, etc.
15.4 INTERPRETATION OF MASS SPECTRA
The mass spectrum of a compound consists of a series of lines corresponding to the masses of the
ion fragments and relative abundance of these ions and also that of parent ion. Once the spectrum
of a compound is recorded, all the prominent ion peaks, stating from the highest, are tabulated
along with the group lost to give these ion peaks. The most intense mass peak (i.e., the base peak)
is assigned a value of 100 and other peaks are recorded as percentage of the base peak.
Peak intensities are also indicated as being in one of the classes, 02%, 220%, 2050% or
50100% of the base peak. From the available mass spectral data, all possible structures are listed
and checked against the actual spectrum. The various types of ions produced are as follows.
15.5 TYPE OF IONS PRODUCED IN A MASS SPECTROMETER
15.5.1 Molecular Ion or Parent Ion

The electron bombardment with energy 1015 eV usually removes one electron from the molecule
of the organic compound in the vapour phase. It results in the formation of molecular ion, which is
a radical cation M+. The highest occupied orbital of aromatic system and non-bonding electron
orbital on oxygen and nitrogen atoms readily lose one electron. An electron from double bond
(2-p electron) or triple bond (4-p electrons) is usually lost. In alkanes, the ionization of C C
sigma bond is easier than that of C H bonds. Some examples are:
The mass of the parent ion gives the molecular ion peak which is the peak of the highest mass
number for the non-isotopic molecules. It is important to locate the molecular ion at the high mass
region of the spectrum. The mass of the ion gives the molecular mass of the samples. It is also
possible to determine the molecular formula. Information on the number and the nature of the
atoms present in the molecule is obtained from the molecular ion peak. Hence, the molecular ions
are considered to be most important of all types of ions in the mass spectrum. The stability of the
parent ion decides its relative abundance. In some cases, parent ion peak is not formed which
means that the rate of decomposition of parent ion is too high for its detection. The rate of
decomposition of the parent ion increases with the molecular size in the homologous series, since
larger molecular ions provide more possible reaction pathways.
Important features of the parent ion peak
1. The molecular ion peak in aromatic compounds is relatively much intense due to the presence
of p-electron system.
2. Unsaturated compounds give more intense peak as compared to the saturated or the cyclic
molecule.
3. The relative abundance of the saturated hydrocarbon is more than the corresponding branched
chain compound with the same number of atoms. For example, the molecular ion peaks for
n-pentane is more intense than that of neopentane.
4. Absence of molecular ion peak in the mass spectrum means that the compound is highly
branched or tertiary alcohol.
5. Primary and secondary alcohols give very small molecular in peaks.
6. Conjugated olefins show more intense molecular ion peak as compared to the corresponding
non-conjugated olefins. Conjugated olefins are more stable than the corresponding non-
conjugated olefins.
7. The substituent groups like NH2, OH, OR, etc. with lower the ionization potential
increase the relative abundance in case of aromatic compounds while the groups such as
NO2, CN, etc. with higher the ionization potential, decrease the relative abundance
of aromatics.
8. Nitrogen containing compound with an odd number N atoms in the molecule must have an
odd molecular mass. For example aniline has odd molecular mass, i.e. 93 as it contains 1 N
atom which is odd number. On the other hand, nitrogen containing compounds with even
number of N atoms in the molecule must have even molecular mass. For example, 2, 4-
dinitrophenol has even number molecular mass, i.e. 184 as it contains 2 N atoms which is
even. Absence of N atom in the compounds also shows the molecular mass of the compound
to be even. For example toluene has a molecular mass of 92 which is even. This rule is
known as Nitrogen rule. It is due to the fact that nitrogen is the only element with an odd
valency and even mass number.
General rules for predicting prominent peaks in a spectrum
1. The relative height of the parent peak is usually greatest for the straight-chain compound
and decreases as the degree of branching increases.
2. The relative height of the parent peak decreases with increasing molecular weight in a
homologous series. Fatty esters appear to be an exception.
3. Cleavage is favoured at branched carbon atoms. The more branched, the more likely is
cleavage. This is due to the increased stability of a tertiary carbonium ion over a secondary,
which in turn is more stable than a primary.
4. The largest substituent at a branch is eliminated most readily as a radical because a long
chain radical can acquire some stability by delocalization of the lone electron.
5. Double bonds, cyclic structures, aromatics or heteroaromatic ring stabilize the parent ion
and thus increase the probability of its appearance.
6. Double bonds favour allylic cleavage and give the resonance-stabilised allylic carbonium
ion.
7. Saturated rings tend to lose side chains at the a-bond. The positive charge tends to stay
with the ring fragment.
8. In alkyl-substituted aromatic compounds, cleavage is very probable at the bond beta to the
ring, giving the resonance-stabilized benzyl ion or the tropylium ion directly.
9. Compounds containing ring give peaks at mass numbers characteristic of the ring. Thus in
case of benzene and naphthalene, the parent peak at m/e 78 and m/e 128 respectively, are
also the base peaks.
10. Carbonyl compounds break at the carbonyl group carrying positive charge with it
11. Cleavage is often associated with elemination of small stable neutral molecules such as
H2O, CO, NH3, H2S, HCN, olefins, ketones, alcohols or mercaptans. These cleavages often
take place with rearrangement.
In general, the relative stability of the parent ion decreases in the following order:
Aromatics > Conjugated olefins > Alicyclics > Unbranched hydrocarbons > Ketones > Amines
> Easters > Ethers > Carboxylic acids > Branched hydrocarbons > Alcohols.
15.5.2 Isotope Ions

Most elements are mixture of two or more stable isotopes differing by one or two mass units.
Fluorine, Phosphorus and iodine are mono isotopic whereas, chlorine consists of Cl35 and Cl37 in
the ratio of 3:1 and bromine contains Br79 and Br81 in the ratio of 1:1. Similarly, elements like
carbon, hydrogen, oxygen, sulphur, etc. have one major isotope, which is more than 90% abundant
and minor isotope. The presence of isotopic elements in a molecule is recognized by the
characteristics isotopic clusters (also known as satellite peaks) in the spectrum corresponding to
M + 1 and M + 2 peaks. Compounds containing chlorine and bromine will clearly have M + 2
peaks besides parent peak M. Thus, in the spectrum methyl bromide the molecular ion is a doublet
consisting of two equally intense peaks, one at m/e 94 (C3 79Br) and the other at m/e 96 (C3 81Br) as
79Br and 81Br are in the ratio of 1:1. The isotopic clusters are very much useful to determine the
presence of such elements in a molecule. It is also possible to calculate the elemental composition
of unknown substances from the abundance of the isotopic peaks M + 1, M + 2.
15.5.3 Metastable Ions or Peaks

Some of the ions formed in ion source by electron bombardment of the samples are metastables.
These are stable enough to be withdrawn from the ionization chamber but their lifetime is only of
the order of few micro-seconds. So many of them dissociates during their passage to the detector.
The formation of such ions is described below.
Formation of metastable ions

Consider that M1 is the parent ion and m1 is the daughter ion. If the reaction M 1 m 1

takes

place in the source, then the daughter ion, m1 may travel the whole analyzer region and is recorded

as m1 ion. If the transition M1 to m1 occurs after the source exist and before arrival at the
collector, then m1 is called a metastable ion. We know that in double focussing mass spectrometer,
there are two field regions called drift regions. The ions pass through the regions after acceleration.
The first field region refers to the portion of the ion path immediately before the electrostatic
analyzer. The second field region lies between electrostatic analyzer and magnetic analyzer.
Suppose the reaction, M 1 m1 occurs in the second field free region (Figure 15.6),
of the double focussing mass spectrometer.
Figure 15.6 First and second field free region.
The daughter ion (m1+) will decompose to m2 in the magnetic field so that the peak for the
daughter will not appear at the normal position for m1+ on the mass scale but appears as low
intensity broad peak at apparent mass m*. The numerical value of the m* is given by,
2
m* = m2 / m1 .
Thus the peak at mass m* is called the metastable peak. This peak appears as broad and diffused
peak generally at positions corresponding to non-integral masses lower than the mass of the daughter
ion. Some typical metastable peaks are shown in Figure 15.7.
Figure 15.7 Formation of metastable peaks.
Important characteristic of these peaks are:

(i) These are of relatively low abundance and much broader and diffused peaks.
(ii) They generally occur at the non integral m/e values lower than the mass of the daughter ion.
(iii) The peaks are not always symmetrical.
Importance of metastable peaks
1. The metastable peaks in the mass spectrum generally provide information about the
structure of many intermediate ions formed during the fragmentation of organic ions.
2. From the positions of the parent ion and the daughter ion, the position of the metastable
ion can be calculated. For example, in the spectrum of toluene, the formation of less
intense metastable peak at 46.4 indicates the structure of toluene. It is due to the
fragmentation of C7 H 7+ ion to C5H5+ ion in the second field free region.
3. For ions containing poly isotopic elements, it is possible to find out whether the poly
isotopic element is present in the neutral fragments or in the resulting daughter ions from
the study of meta topic peak.
PROBLEM 15.1 Calculate the position of metastable peak in case of toluene.
Solution Mass spectrum of toluene exhibits two strong peaks at m/e 91 and m/e 65. The peak at
m/e 91 is due to the formation of tropylium cation (stable) which loses a molecule of acetylene
(26 mass units) to give C5 H 5+ (m/e 65).
Suppose the transition C7 H 7+ (91) to C5 H 5+ (65) occurs in the second field free region, then a
metastable peak is formed. The position of the broad metastable peak is determined by:
m22 65 65
m 46.4
m1 91
A metastable peak in case of toluene appears at 46.4 in the mass spectrum.
PROBLEM 15.2 Predict the position of metastable peaks in the spectrum of p-amino anisole.
The molecule or parent ion appears at m/e 123. Give your comments on the results.
Solution Suppose the fragmentation of molecular ion into daughter ion, (due to the loss of
CH3 radical, i.e. loss of 15 mass units) takes place between the electrostatic and the magnetic
analysers, i.e. in the second field free region.
The position of metastable peak

m22 108 108
m 94.8
m1 123
The position of metastable peak (94.8) below m1 ion (108) is nearly the same as m1 ion below
M 1 (123) on the mass scale which is linear. The position of the metastable peak due to the following
fragmentation in the second field free region can be determined.
The position of metastable peak
m22 80 80
m 59.2
m1 108
15.5.4 Fragmented Ion and Fragmentation Modes
When an electron beam of energy of 70 eV is used the molecular ion is produced by the loss of a
single electron which undergoes splitting to form many fragments. The four major fragmentation
modes are:
(i) Simple cleavage
(ii) Retro Diels-Alder reaction
(iii) Hydrogen transfer rearrangement
(iv) Skeletal rearrangement
The stability of the ion can be judged by stabilization of the charge which depends upon
(a) Resonance
(b) Inductive effect
(c) Polarizability, etc.
(i) Simple cleavage
This process involves homolytic or heterolytic cleavage of a single covalent bond. The ionization
of a molecule results in a formation of molecular ion having an unpaired electron (radical site) and
a positive charge (positive site).
Homolytic cleavage The homolytic cleavage is initiated by a radical site. Odd electron ions
have an unpaired electron which is capable of new bond formation. When a bond is formed,
energy is released. The energy released by bond formation can help offset the energy required for
the cleavage of some other bond in the ion. These reactions may occur according to the following
modes.
(a) Mode I This fragmentation mode operates in compounds in which a heteroatom is
singly bonded to a carbon atom. Parent ion is formed by the removal of one electron form
the heteroatom. A new bond is formed with the adjacent atom through the donation of the
unpaired electron and transfers of an electron from the adjacent bond. A single-barbed
fishhook ( ) designates the shift of single electron. Cleavage of a bond requires the
movement of two electrons. However, to prevent the clutter, only one of the pairs of the
fishhooks will be drawn. This practice is illustrated for cleavage of C C bond next to a
heteroatom as shown below:
Abundant peaks are formed by the cleavage of C C bond which is in the a-position
to the heteroatom in the mass spectra of amines, alcohols, ethers, sulphides and mercaptans,
etc. as shown below.
This has been discussed in the later section.

(b) Mode II When a heteroatom is attached to a carbon atom by double bond, a-cleavage
is the preferred fragmentation.
This type of fragmentation is shown by ketones, esters and amides, etc. In ketones,
significant peaks are observed due to the cleavage of C C bond which is alpha to the
carbonyl group. Unsymmetrical ketones show two types of peaks since either alkyl group
can be lost.
The elimination of a bigger alkyl radical is preferred. In the same way, the fragmentation
mode in aldehydes, esters and amides leads to the cleavage of C H, C O and
C N bond respectively. However, compounds containing C == N or C == S groups do
not show this type of fragmentation.
The presence of amino and hydroxyl groups which are electron donating in nature reduce
the relative abundance of acylium (R C ºº O+) ion. The presence of electron
withdrawing substituent such as nitro and cyano increase the relative abundance of the
ion. This has been discussed in details while discussing the fragmentation modes of
aldehydes, ketones, carboxylic acids, esters and amides in the sections to follow.
(c) Mode III (Allylic cleavage) It is a favoured mode of unsaturated compound in which,
an allyl cation is resonance stabilized leading to fragmentation of a C C bond b- to a
double bond as shown below.
This type of cleavage has been further discussed in olefins.

(d) Mode IV (Benzylic cleavage) It is an energetically preferred fragmentation mode.
It involves the cleavage of a C C bond which is beta to the aromatic ring.
It is to be noted that benzylic cleavage leads to formation of tropylium cation structure

rather than the less symmetrical benzyl structure.
(ii) Heterolytic cleavage
It takes place at the cationic site. The cleavage of C X (X == O, N, S, Cl) bond is more
difficult than that of a C C bond. In such a case, the positive charge is carried by the carbon
atom and not by the heteroatom.
The fragmentation modes for n-butyl halide and di-n-propyl ethers are shown below.
(iii) Retro Diels Alder reaction

The reaction is characteristic of cyclic olefins which involve multicentred fragmentation.
Here the cleavage of two bonds of a cyclic system occurs resulting in the formation of two stable
unsaturated fragments in which two new bonds are formed. The highly substituted or more
conjugated fragment which has a lower ionization potential carries a charge. In simple system, the
charge is carried by a diene.
(iv) Hydrogen transfer rearrangemnts

Electron impact induced reactions result not only in bond cleavage but also lead to a new bond
formation. The new bond formation reactions induced by electron impact are known as
rearrangements. They are generally multicentred fragmentation reactions. If hydrogen is involved
in the rearrangement in which it is transferred from one part of the molecule to other, then it is
known as hydrogen transfer rearrangement. Such rearrangements involve specific bonds and specific
atom in the molecule. It is classified into four types:
1. Scrambling; 2. Elimination; 3. Ortho effect; 4. McLafferty rearrangement
Rearrangement
1. Scrambling: The simplest hydrogen transfer rearrangement is the scrambling of hydrogen
atoms. The formation of tropylium ions from benzyl derivatives is a good example of
hydrogen scrambling.
2. Elimination: Elimination reactions involve the abstraction of hydrogen by hydroxyl,
halogen or acetate function. This process leads to elimination of neutral molecules such as
H2O from alcohol, HX from alkyl halide, Ketene (C2H2O) from n-phenyl acetamide and
phenyl acetate and CH3COOH (HOAC) from methyl ester. The elimination mode is shown
below:
It is to be noted that HOAC elimination occurs either through 1, 2- or 1, 4 mechanism.

3. Ortho effect: In ortho substituted aromatic compound or in cis olefin, the substituent
and a hydrogen atom can come close proximity so as to help the elimination of a neutral
molecule as exemplified below:
As the ortho substituents are involved in such rearrangements, it is known as ortho-effect.

Such an elimination of neutral molecule by ortho effect distinguishes
(i) cis and trans isomers and
(ii) Ortho substituted compound from meta and para substituted isomers.
4. McLafferty rearrangement ion (MR): McLafferty rearrangement involves the cleavage
of a b-bond followed by a g-hydrogen transfer. The rearrangement leads to the elimination
of neutral molecules from aldehydes, ketones, acids, esters, olefins, alkyl benzene, phenyl
ethanol, aryl ethers, amides, nitriles, etc. The rearrangement proceeds through a sterically
hindered six-membered transition state. This is illustrated by taking ketone, an olefin and
aldehydes as examples.
The structural requirement for this rearrangement is a side chain containing at least three
carbon atoms, the last bearing a hydrogen atom and a double bond which may be a carbonyl
group, an olefinic bond or an aromatic system.
(v) Skeletal rearrangement
Rearrangement involving migrations of groups heavier than hydrogen are called skeletal
arrangements. Such rearrangements are bond forming reactions between atoms other than hydrogen.
In such process, neutral molecule which bridges the terminal of a molecule is expelled as shown
below:
Besides the above ions, there are possibilities of formation of multiple charged ions, negative
ions, odd and even ions, ions formed by ion-molecule reactions. However, mass spectra methods
deal with only uni positive ions.
(vi) Fragmentation mode as per nitrogen rule for the compounds containing N atoms
According to this rule, the fragmentation at a single bond gives an odd numbered ion fragment
from an even numbered molecular ion.
Similarly, an even numbered ion fragment results from odd numbered molecular ion. However,
the fragment ion must contain all the nitrogen atoms of the molecular ion. For example, nitrobenzene
(C6H5NO2) which contains one N atom (odd number) gives molecular ion of odd number molecular
mass such as at m/e 123. Two important ion fragments appear at even mass number. These are
(a) NO2+ at m/e 46 and
(b) NO+ at m/e 30.
If we consider a compound containing even nitrogen atoms such as 2, 4-dinitrophenol (in this
number of N atoms is 2) it give molecular ion of even mass number such as at m/e 184.
The fragmented ions appear at (M+ H) m/e 183 and at (M+ H CO) m/e 155. Thus the
fragment ion containing both N atoms appear at odd mass number.
15.6 MASS SPECTRA OF SOME ORGANIC COMPOUNDS
15.6.1 Straight Chain Alkanes

1. Alkanes require high energy for ionization. The ions so formed undergo random
rearrangement.
2. The molecular ion peak M of a straight chain saturated hydrocarbons is always present.
However, the relative height of the parent peak decreases as the molecular mass increases
in the homologues series.
3. Clusters of peaks in the spectrum are observed 14 (CH2) mass units apart. The largest peak
in each cluster represents CnH2n + 1 fragment. This is also accompanied by CnH2n and
CnH2n 1 fragments.
4. The most intense peaks are due to C3H7+ and C4H9+ ions at m/e 43 and m/e 57 respectively.
5. The relative abundance of fragment ion formed depends upon the
(i) Stability of the ion formed and
(ii) Stability of the radical which is lost.
The stability of the carbonium ion has the order: Allylic > Tertiary > Secondary > Primary > Methyl.
The stability of the free radical lost depends upon
(i) Nature of the free radical, whether primary, secondary or tertiary.
(ii) Length of the straight chain since it allows greater dispersal of the odd electron.
The n-butyl free radical is more stable than n-propyl free radical. Greater the stability,
easier the formation.
PROBLEM 15.3 Mention the various fragmentation modes of n-butane.
Solution The fragmentation modes of n-butane are given below.
PROBLEM 15.4 Write the various fragmentation modes of n-Nonane (C9H20).

Solution
The C3H7+ (m/e 43) is the base peak (100% abundance). It is due to the formation of most stable
secondary carbonium ion and the elimination of most stable free radical. Peaks are formed at 14
mass units apart with decreasing abundance. C4H9+(m/e 57) peak is much abundant. The relative
abundance goes on decreasing from m/e 57 to 85 and so on. As expected, the molecular ion peak
is much less intense.
15.6.2 Branched Chain Alkanes

The important features of mass spectra of branched chain alkanes are:
1. Generally, the largest substituent at a branch is eliminated readily as a radical. The radical
achieves stability by the delocalization of lone electron.
2. The relative abundance of the parent ion is least and is mostly not observed.
3. Bond cleavage occurs preferably at the site of branching, resulting in a more stable secondary
or tertiary carbonium ion.
4. Greater numbers of fragments result from a branched chain compound compared to the
straight chain compound. It is due to more sites available for cleavage.
PROBLEM 15.5 Predict some important peaks in the mass spectrum of 2, 2-dimethyl pentane.
Solution The fragmentation mode of 2, 2-dimethyl pentane.
(i) No parent ion (M+) peak is expected in this compound.
(ii) Peaks due to C3 H 7+ ion and C4 H 9+ ion at m/e 43 and 57 are formed in substantial
abundance due to the removal of most stable radical.
(iii) A much abundant peak at m/e 71 is also seen due to the formation of tertiary carbonium
ion.
PROBLEM 15.6 Explain the formation of peaks at m/e 43, 57 and 71 on the mass spectrum of
3, 3-Dimethyl heptanes.
Solution
(i) A peak due to C4 H9+ at m/e 57 is expected due to the loss of tertiary, free radical. Also
the loss of n-butyl free radical results in the formation of tertiary carbonium ion at
m/e 71.
(ii) The much abundant peak at m/e 43 ( C3 H 7+ ) is formed due to the loss of most stable free
radical.
15.6.3 Alkens (Olefins)

Some characteristic features of the mass spectra of olefins are:
1. The parent peak of olefins, especially poly olefins, is usually distinct and more intense than
the corresponding alkanes. This is due to better resonance stabilization of the charge on the
cation formed by the removal of one of the p-electons.
2. The relative abundance of the molecular ion peak decreases with increasing molecular
mass.
3. Acyclic olefin also shows cluster of peaks which are 14 mass units apart due to formation
of C n H 2 n 1 ions which is more intense than C n H 2 n 1 peaks as observed in alkane.
4. The general mode of fragmentation induced by a double bond is the allylic cleavage as
shown below resulting in resonance stabilized allylic cation. Resonance stabilization of
allyl cation leads to increase probability of fragmentation of a b-to double bond.
5. Another mode of fragmentation is observed in olefins giving more intense peaks.

This mode is due to McLafferty rearrangement as follows.
McLafferty rearrangement
In this arrangement, a g-hydrogen atom is transferred through a six-membered transition state to an
electron deficient centre followed by cleavage of b-bond. The reaction results in elimination of a
neutral molecule. Thus McLafferty rearrangement ion is formed at m/e 42 in the spectrum of
1-pentene due to the loss of ethylene molecules as shown below.
This type of fragmentation mode is also characteristic of aldehydes, ketones, acids, esters, amines,
etc. to be discussed in the following sections.
PROBLEM 15.7 Write the various fragmentation modes of 1-hepetene.
Solution
15.6.4 Cycloalkanes
The important features of mass spectrum of cycloalkanes are:
1. The relative abundance of the molecular ion of cycloalkane is more than that of corresponding
alkane.
2. Fragmentation of the ring is usually characterized by the loss of two carbon atoms as C2H4
(28 mass units) and C2H5 (29 mass units).
3. The stability of the fragment ion depends upon the size of the ring.
4. It favours cleavage at the bond connecting the ring to the rest of the molecule.
5. Fragment ions are observed by the loss of alkenes or alkenyl ion. The side chain on the ring
breaks and the lone electron remains on the ring.
PROBLEM 15.8 The mass spectrum of n-Propyl cyclohexane is given below (Figure 15.8).
How do you interpret the spectrum?
Figure 15.8 Mass spectrum of n-Propyl cyclohexane.
Solution
1. The molecular ion peak is quite abundant and occurs at m/e 126.
2. The base peak at m/e 83 is formed by the loss of the side chain. The lone electron remains
on the ring. This positively charged ion radical appears at m/e 83.
3. A fragment ion of large abundance is formed at m/e 55.
4. The ion radical shows retro-Diels-Alder reaction. The various fragmentation modes are
shown below:
15.6.5 Cyclo Olefins

The fragmentation for cyclo olefins has already been discussed in retro Diels Alder reactions.
15.6.6 Alkynes (Acetylenes)

1. The relative abundance of the molecular ion peak decreases as the molecular mass of the
alkyne increases.
2. The fragment ions are generally formed by the loss of alkyl radical. Hence M+ 15,
M+ 29, etc. peaks are observed in the spectra of alkynes.
3. For 1-butyne and 2-butyne, the molecular peak is the base peak.
15.6.7 Aromatic Compounds

1. The molecular ion peak in aromatic compounds is fairly abundant as compared to the
corresponding alkanes and alkenes containing the same number of carbon atoms. Since the
positive charge is stabilized by p-electron of benzene ring, Benzene shows molecular ion
peak at m/e 78 due to formation of C6H6+ ion.
2. The molecular ion peak is usually accompanied by small isotopic peaks, M+ + 1 and
M+ + 2 because of fairly large abudance of molecular ions peak.
3. In case of polynuclear hydrocarbons, doubly or triply charged ions (M2+, M3+ ions) are
possibly formed. Doubly charged molecular ions (m/2e) appear at integral m/e values.
4. Cleavage of a C C bond which is in the b-position to the aromatic ring is an energetically
favoured fragmentation mode. This is known as benzylic cleavage. A prominent peak

at m/e 91 is indicative of an alkyl substituted benzene ring. Here the benzyl (C6 H 5 C H 2 )
cation formed rearranges to more stable tropylium cation ( C7 H 7+ ) which appears at
m/e 91.
5. Tropylium cation in turn loses a molecule of acetylene to form C5 H 5+ at m/e 65.
6. A characteristic cluster of ions due to a-cleavage and hydrogen rearrangement of monoalkyl
benzenes appears at m/e 77 ( C6 H5+ ), 78 ( C6 H +6 ) and 79 ( C6 H +7 ).
7. McLafferty rearrangement operates in alkyl benzene having propyl or longer alkyl
chain, e.g. n-propyl benzene loses a neutral molecule of olefin to produce a peak at m/e 92
due to C7H8+ ion.
The various fragmentation modes of methyl benzene (tolune) and benzene are given
below.
PROBLEM 15.9 Write the various fragmentation modes of benzene and methyl benzene (tolune).
Solution
Phenyl cation loses a molecule of acetylene as below:
Thus parent peak is benzane is formed at m/e 78 along with the other important peaks
at 77 (C6H5+), 51 (C4H3+) and 39 (C3H3+)
PROBLEM 15.10 The mass spectrum of ethyl benzene is given below. How do you interpret its
spectra?
Figure 15.9 Mass spectrum of ethyl benzene.

Solution The fragment ion appears at m/e 91 and it is a base peak. It is due to formation of
tropylium cation, which loses a molecule of acetylene, i.e. 26 mass units to form a peak at m/e 65
due to C5H5+.
PROBLEM 15.11 Mass spectrum of n-propylebenzene is given below. Write the various
fragmentation mode of this compound and assign the position of their peaks from its mass
spectra.
Solution m/e = 91 prominent peak is identified with tropylium cation.

15.6.8 Alkyl Halides

This has been discussed in heterolytic cleavage.
For the shake of convenience, organic compounds are included in separate group taking the
similarity in their fragmentation modes as follows.
15.6.9 Alcohols, Ethers and Amines

These compounds can be represented as
R CH2 X
For primary alcohol X == O
H (hydroxyl group)

H (Amino group)
For primary amine X == N 2
For ether X == O
R (Alkoxy group)

Formation of parent ions and fragmentation modes
The C C bond adjacent to the X group is involved in cleavage. A new bond is formed with the
adjacent atom (containing unpaired electron) in the parent ions through donation of unpaired electron
and transfer of an electron from the adjacent C C bond. If there is no C C bond adjacent to
C C bond, then C H bond cleavage takes place as in the case of CH3OH and CH3NH2. This
type of mode of formation is known as a-cleavage (C C or C H bond).
1. Cleavage of C H bond
(a) In case of Methyl Alcohol
(b) In case of Methyl Amines
(c) In case of Dimethyl Ether
2. Cleavage of C C bond
Primary Alcohols
Secondary Alcohols
Tertiary Alcohols
Primary Amines
Secondary Amines
Tertiary Amines
Ethers
Mass Spectral Method 553
In ether besides the C C bond cleavage, C O bond cleavage also takes place in which the
charge remains on alkyl fragment as shown below:
Some other characteristics of alcohols, amines and ethers are given below.
For alcohol:
(a) Formation of M 2 and M 3 peaks: Primary alcohol shows M 2 ( R CH == O
) and
+
) peaks due to loss of 2 and 3 hydrogen atoms directly from the parent
M 3 (R C ºº O
+
ion.
(b) Formation of M 18 peaks due to loss of water molecule as shown below.
This path way is consistent with loss of OH and g-hydrogen (n = 1) or d-hydrogen

(n = 2).
(c) Formation of peaks of M (olefin + H2O), i.e. peak at M 46, M 74, M 102, etc.
according to McLafferty rearrangement.
For amines:
(a) In case of secondary and tertiary amine the decomposition of first formed ions results peak
at m/e 30, 44, 58, 72, etc due to the following type of rearrangements.
Thus we see that in case of all types of amines a peak due to CH2 == NH+ at m/e = 30
occurs. However, it is less intense in case of secondary and tertiary amines whereas in case
of primary amines this peak is considered as base peak (most intense).
(b) Formation of M 1 peak: This peak occurs due to loss of one hydrogen atom especially for
primary amine.
For ethers:
The first formed fragment decomposes by the following process analogous to primary amine to
give even a base peak. The decomposition is very important when a-carbon is substituted.
PROBLEM 15.12 Write the various fragmentation modes of methanol indicating its base peak.
+
Solution CH3OH + e ¾® CH3OH (m/e 32) + 2e
+
CH3OH+ ¾® CH2OH (m/e 31) + H
CH3OH+ ¾® CH3+ (m/e 15) + OH
CH2OH+ ¾® CHO+ (m/e 29) + H 2
PROBLEM 15.13 The mass spectrum of butanol-2 is presented below. How will you interpret
the spectrum? Mention its various fragmentation mode.
Solution
PROBLEM 15.14 The mass spectrum of Pentanol shows peak at m/e 31, m/e 70, m/e 55 and
m/e 29. How do you explain these peaks?
Solution
PROBLEM 15.15 Write the various fragmentation mode of 1-hexanol.

Solution
PROBLEM 15.16 The mass spectrum of an ether shows prominent mass peaks at m/e 59,
m/e 31 and a weak peak at m/e 74. Write the structural formula of ether.
Solution The weak peak at m/e 74 indicates the parent ion peak. The compound may be
di-ethyl ether as it indicate from its fragmentation mode as follows.
PROBLEM 15.17 Write the important fragmentation mode of sec-butyl ether.

Solution
PROBLEM 15.18 The mass spectrum of ethyl amine is given below. How will you interpret the
spectra writing its various fragmentation mode.
Solution
15.6.10 Fragmentation Mode of Aromatic Alcohols, Phenols, Aromatic Amines,

Aryl Ethers
Aromatic alcohols
Some characteristics of mass spectrum of aromatic alcohols are:
1. Aromatic alcohols show fairly intense molecular ion peaks.
2. Some of the fragment modes of benzyl alcohol involve loss of one, two or three H atoms.
3. The (M+ H) fragment of benzyl alcohol also rearranges to form hydroxy tropylium ion.
4. Removal of CO group results in formation of [C6H7]+ (m/e 79) and further removal of
two hydrogen gives [C6H5]+ (m/e 77) which ultimately leads to formation of [C4H3]+
(m/e 51) with elimination of acetylene molecule as shown below in case of benzyl alcohol.
5. A moderate benzylic peak (M OH) is also expected from cleavage beta to ring (Benzylic
cleavage).
6. Another characteristic peak due to loss of water (peak M-18) is a common feature especially
in the case of ortho-substituted benzyl alcohol like 2-benzyl alcohol by the following
rearrangement.
The above arrangement is known as ortho effect.

Phenols
The characteristic features of mass spectrum of phenols are:
1. The parent peak (M+) is intense and base peak.
2. The signal due to the loss of hydrogen radical, M+ H is small.
3. A rearrangement peak at m/e 77 and the peaks resulting from loss of CO(M 28) and loss
of CHO(M 29) are usually found in phenols. The fragmentation mode is given below:
Aromatic amines
1. A parent ion is formed by the loss of one electron from the lone pair present on N atom.
2. Loss of HCN followed by loss of H atom gives prominent at m/e 66 and 65 respectively.
3. In primary aromatic amines, M+ 1 signals are often seen. The elimination of 27 mass due
to HCN give a signal due to cyclopentadienyl cation.
The fragmentation mode of aniline is given below
Aryl ethers
The molecular ion peak is prominent. Primary cleavage occurs at the bond beta to the ring and the
first-formed ion can decompose further. Loss of methyl gives an ion M 15 which further splits to
lose CO. Methyl phenyl ether (anisole) shows the following main fragmentations peaks at
m/e 93, 65, 78 and 77.
Fragmentations mode of anisole
PROBLEM 15.19 The mass spectrum of 2-ethyl-4-methyl phenol is given below. How will you
interpret the spectrum? Write the different fragmentation ion modes.
Solution
PROBLEM 15.20 Explain the occurrence of peak at m/e 94 in case of phenyl ethyl ether.
Solution The fragmentation mode showing peak at m/e 94 is presented below:
15.6.11 Aliphatic Aldehydes and Ketones

Aliphatic aldehydes
The important features of mass spectra of aldehydes are:
1. The main fragmentation processes are cleavage of and resulting
in M 1 peak and M R peak (m/e 29 CHO+). The M 1 peak is good diagnostic peak
even for long chain aldehyde, but the m/e 29 peak present in C4 and higher aldehydes is due
to the hydrocarbon C2H5+ ion.
2. For higher molecular weight aldehydes, containing g -H atom beta cleavage or McLafferty
rearrangement ion is most significant to yield a enol of m/e 44 ( CH2 == CH OH)+ and at
58 or 72 depending on the alpha substituent. The fragmentation modes of butanal are given
below to explain the facts.
In aldehydes, methyl or alkyl radical is preferably lost compared to hydrogen radical.

Aliphatic ketones
1. The molecular ion peak is usually quite pronounced.
2. In ketones, the cleavage of C C bond adjacent to oxygen atom takes place, with the
charge remaining with the oxygenated fragment. The loss of large group is brought about
by a-cleavage.
The cleavage gives rise to a peak at m/e 43 or 57 or 71... . The base peak very often results
from loss of the larger alkyl group.
3. When one of the alkyl chains attached to C == O group is C 3 or longer, (McLafertty
rearrangement reaction) occurs to give major peak at 58, 72 or 86, etc. The fragmentation
mode of ethyl n-butyl ketone is presented here to explain the above facts.
PROBLEM 15.21 Write the different fragmentation modes of butanal.

Solution
PROBLEM 15.22 Write the various fragmentation mode of 3-heptanone.

Solution
PROBLEM 15.23 Write the various fragmentation mode of 2-hexanone.

Solution
15.6.12 Aromatic Aldehydes and Ketones

1. Aromatic aldehydes are characterized by large molecular ion peak and by an M 1 peak

due to the ion Ar C ºº O (base peak)

2. The ion Ar C ºº O eliminates CO to give the phenyl ion (m/e 77) which in turn eliminates

CH ºº CH to give C 4 H3+ ion (m/e 51). The fragmentation mode of benzaldehyde is given
below. In which M 1, M 28 are formed by the removal of CO.
The molecular ion peak aromatic ketones is prominent. Cleavage of aryl alkyl ketones

occur at the bond beta to the ring leaving a characteristic ArC ºº O fragment which is

usually the base peak. Loss of CO in that fragment gives the aryl ion (m/e 77). For example,
when the alkyl chain is C3 or longer, McLafferty rearrangement occurs as follows:
3. In ketones, the loss of larger group is preferred by a alpha-cleavage. For example,

fragmentation of alkyl phenyl ketone occurs as follows:
15.6.13 Carboxylic Acids, Esters and Amides

These compounds can be represented as
R –– C == O
|
X
For carboxylic acid X == O

H (hydroxyl group)

R (Alkoxy group)
For carboxylic ester X == O

H (Amino group)
For amide X == N 2
Formation of parents ion and fragmentation mode

In all the above cases parent ion is formed by removal of one electron from carbonyl oxygen.
In this cases the C C bond adjacent to the carbonyl group is involved in cleavage. A new bond
is formed with the adjacent atom (containing unpaired electron) in the parent ions through
donation of unpaired electron and transfer of an electron from the adjacent C C bond. If there is
no C C bond adjacent to C C bond, then C H bond cleavage or rearrangement leading to
loss of CO takes place as given below.
1. Cleavage of C H bond
(a) In case of Formic acid
(b) In case of Formamide
(c) In case of Methyl formate

In methyl formate a base peak at m/e 31 is obtained indicating a rearrangement with
loss of carbon monoxide as shown below.
Similar process operates in ethyl and iso-propyl formate.

2. Cleavage of C C bond
(a) In case of carboxylic acid: Alkyl (R) group acid is directly eliminated by this type of
cleavage giving a signal at m/e 45.
(b) In case of amide: In this case also a strong peak at m/e 44 is obtained due to this type
of cleavage.
(c) In case of carboxylic ester: C C cleavage may resolve to two different types of
ions as shown below:
Homolytic cleavage:
Heterolytic cleavage: There is also possibility of heterolytic cleavage forming R+.
Some other characteristics of carboxylic acids, esters and amides are given below.
For carboxylic acid: Some other characteristic features of mass spectra of carboxylic acids are:
1. In lower chain acids, M+ OH and M+ COOH peaks are prominent. These represent
cleavage of bonds next to C == O as shown below.
Homolytic cleavage of C O bond:
Heterolytic cleavage of C C bond:
2. In aliphatic acids, if a carbon atom containing a g-H atom is not substituted, a McLafferty
rearrangement ion is formed at m/e 60. It is often the base peak as shown below.
3. In long chain acids, the spectrum consists of two series of peaks resulting from cleavage
at each C C bond with retention of charge either on the oxygen containing fragment
(m/e 45, 59, 73, ) or on the alkyl fragment (m/e 29, 43, 57, etc.). The hydrocarbon
pattern also shows peaks at m/e 27, 28; 41, 42; 55, 56, etc. For example, hexanoic acid
(m.m. 116) cleaves as follows:
For esters Some other characteristic features of mass spectra of esters are
1. Besides the C C cleavage, C O cleavage may result in two different types of ions as
shown below.
The acyl ion R C ºº O+ gives an excellent diagnostic peak for esters. In methyl ester it
occurs at m/e M 31. It is a base peak in methyl acetate
2. The methyl esters containing gamma H atom show McLafferty rearrangement ion at
m/e 74. Methyl substitution at a-C atom shifts the position of MR peak at m/e 88.
The fragmentations modes of methyl butanoate showing the base peak at m/e 74 are as
follows.
3. Esters of long-chain alcohols show a diagnostic peak at m/e 61, 75 or 89 resulting from
elimination of alkyl moiety and transfer of two hydrogen atoms to the fragment containing
the oxygen atoms.
Thus 1-propyl ethanoate can be distinguished from methyl butanoate by a peak at 61 due
to above type of rearrangement.
4. Esters of fatty alcohols (except methyl esters) eliminate a molecule of acid as shown
below.
For amides Some other important features of the mass spectrum of amides are:
1. The McLafferty rearrangement peak is the base peak as shown below.
Branching at aC (CH3, etc.) gives a homologous peak at m/e 73 or 87.

2. A moderate peak at m/e 86 results from g, d C C cleavage accompanied by cyclisation.
15.6.14 Aromatic Acids

The parent peak of aromatic acids is large. Some other prominent peaks in aromatic acids are
M+ 17 and M+ 45 formed by loss of OH and COOH group respectively. A signal due to M 18
(loss of H2O) is also noticed if a hydrogen-bearing ortho group is present. It is called ortho-effect,
i.e. the substituent can form a 6-membered transition state by H-bonding to facilitate loss of a
neutral molecule like H2O, ROH or NH3 as shown below:
Benzyl and phenyl ester: Benzyl acetate and phenyl acetate eliminate the neutral molecule
ketene and this gives rise the base peak as shown below:

Of course, the m/e peak (CH3 C O) and m/e 91 (C7H7+) peak are prominent for benzyl acetate.
Some of the important fragmentation modes of nitro compounds, aliphatic nitriles, aliphatic nitrites,
aliphatic nitrate are given below.
15.6.15 Fragmentation Modes of Nitro Compounds

Some important features of the mass spectra of nitro compounds are:
1. The molecular ion peak in (odd number) of aliphatic mononitro compound is usually absent
but it is prominent in aromatic mononitro compound.
2. The presence of a nitro group is indicated by an appreciable peak at m/e (NO+) and a
smaller peak at m/e 46 (NO2+). The main peaks are attributable to the hydrocarbon fragments
up to M NO2.
3. Besides the molecular ion peak in aromatic mononitro compound, strong peaks are observed
by elimination of nitro (NO2) radical due to (M 46)+ and by elimination of nitrosonium
radical (NO) due to (M 30)+, (M 30)+ ion corresponds to phenoxy cation. Further loss
of HC ºº CH from (M 46)+ accounts for a strong peak due to (M 72)+ and loss of CO
from the (M 30)+ gives a peak due to (M 58)+.
4. The isomeric o, m, and p-nitroanilines give a strong peak (even number). They all give
prominent peaks resulting from two sequences:
5. When a substituent is present in the meta or para position, the fragmentation modes are
similar to those as observed in nitrobenzene. But when the substituent is present in the
ortho position, then it interacts with nitro group as follows:
15.6.16 Fragmentation Modes of Aliphatic Nitriles R CH2 C ºº N

The important features of mass spectra of aliphatic nitriles are:
1. The molecular ion peak of aliphatic nitriles is weak or may be absent.
2. A weak but diagnostically useful (M 1) peak is formed by the loss of a-H atom to form
the stable ion.
3. The base peak of straight chain nitriles between C4 and C9 is m/e 41. This peak is due to the
ion resulting from hydrogen rearrangement in a six-membered transition state.
4. A peak at m/e 97 is characteristic and intense in straight chain nitriles C8 and higher.
The following mechanism has been depicted.
15.6.17 Fragmentation Modes of Aliphatic Nitrites

1. The parent peak of aliphatic nitrites is weak or absent. The peak due to NO+ at m/e 30 is
large and often the base peak.

2. A peak at m/e 60 (CH2 == O NO) is seen due to cleavage of C C bond next to ONO

group in all nitrites un-branched at the a-carbon.
3. An a-branch can be identified by a peak at m/e 74, 88, 102, etc. The absence of a large peak
at m/e 46 permits differentiation from nitro compounds.
15.6.18 Fragmentation Modes of Aliphatic Nitrates

1. The parent peak is weak or absent.
2. A prominent peak is observed by cleavage of C C bond next to ONO 2 group with loss of
the heaviest alkyl group attached to the a-carbon.

3. The N O 2 peak at m/e 46 is also intense.

(i) Ion analyzers typically operate at pressures
(a) ~106 mm Hg (b) ~102 mm Hg
(c) ~10 mm Hg (d) ~5 mm Hg
(ii) In a single focussing analyzer the separator has a circular beam
(a) 180°, 120° or 60° (b) 90°, 120° or 60°
(c) 90°, 180° or 60° (d) 180°, 120° or 90°
(iii) In mass spectrometer if H (magnetic field) and v (particle velocity) are fixed, then mass-to-
charge ratio of the particle is
(a) Directly proportional to the acceleration voltage
(b) Inversely proportional to acceleration voltage
(c) Numerically equal to acceleration voltage
(d) None of these
(iv) In mass spectrometry, the base peak is:
(a) Farthest to the right of the plot (b) Farthest to the left
(c) Tallest peak (d) Peak preceding the isotope peaks
(v) Mass spectrometry is a
(a) Low pressure technique (b) High temperature technique
(c) High pressure technique (d) Low temperature technique
(vi) Any aromatic molecule containing a benzyl group will show a very important fragment at
m/e values
(a) 92 (b) 78
(c) 77 (d) 91
(vii) The peak arising out of reaction that occur outside the ionization chamber but before the
magnetic analyzer of the mass spectrometer is known as
(a) Isotope peak (b) Metastable peak
(c) Base peak (d) Molecular ion peak
(viii) A very weak parent ion peak and a prominent (M+ 18) peak would probably indicate
(a) Alcohol (b) Ketone
(c) Aldehyde (d) Presence of heavier isotope of oxygen
(ix) A small peak in the natural abundance of an ion is called
(a) Metastable peak (b) Isotope satellite peak
(c) Base peak (d) None of these
(x) McLafferty rearrangement involves
(a) Clevage of a beta bond followed by gamma hydrogen transfer
(b) Clevage of a gamma bond followed by beta hydrogen transfer
(c) Clevage of alpha bond followed by beta hydrogen transfer
(d) None of these
2. State wheather the following statement are true or false. If false write the correct statements
(i) The additional peaks appearing one or two mass units higher than the parent peak are
known as isotope peaks.
(ii) The relative abundance peak of n-hexane is more compared to that of n-butane.
(iii) In n-alkane, the most intense peaks often apper at m/e 43 and m/e 57.
(iv) In alcohols, a-cleavage results in the formation of an ion at m/e 31 which is often a base
peak.

(v) For primary amines, the base peak is formed at m/e 30 due to H2 C N H2 .
(vi) The stability of molecular ion decreases in the order: Aromatic, conjugated olefins, ketones,
amines, ethers and carboxylic acids.
(vii) Secondary alcohols give more intense peak than that of tertiary alcohol.
(viii) Neutral fragments and molecules can reach to the detector.
(ix) The energy required for removing an electron from a molecule varies in the order:
Lone pair < conjugated < Non-conjugated p < Non-conjugated p < s.
(x) Alcohols generally fail to give a visible molecular ion peak.
(i) The higher the .............., the more easily the mass spectrum obtained.
(ii) The molecular ion peak gives the .............. of the compound.
(iii) Mass spectrum is a record of the relative abundance versus ..............
(iv) Fragmentation that involves a six-membered cyclic transfer of hydrogen atom is called
..............
(v) The molecular ion will appear at an even-valued mass if the molecule has .............. number
of nitrogen atoms.
(vi) In the mass spectrum, broad peaks arise at the non-integer m/e values due to .............. .
(vii) In a mass spectral measurement, the ion current is proportional to the .............. .
(viii) Metastable peaks are .............. than the normal peaks.
(ix) If the pair of peaks appear in the intensity ratio of 1:1, then it must be ..............
(x) In amines, loss of the largest branch from .............. is preferred.

(i) Mention the basic component of a mass spectrometer.
(ii) What do you mean by metastable peak?
(iii) What is the average energy possessed by an electron to break the bond in the molecule?
(iv) How mass spectra are recorded?
(v) What is meant by M+ + 1 peak?
(vi) The base peak at m/e 91 corresponds to which ion in case of ethyl benzene?
(vii) Calculate the position of metastable peak in case of toluene.
(viii) How would you distinguish straight chain and branched chain compound from mass spectra?
(ix) What will happen to the relative height of the parent peak with increasing molecular weight
in a homologous series?
(x) Explain nitrogen rule.

(i) 1-Hexanol shows very weak molecular ion peak at m/e 102 in the mass spectrum. Other
prominent peaks appear at m/e values of 100, 99, 84, 56 (base peak) and 31. Write most
probable species responsible for these peaks.
(ii) Predict the structure of a compound showing m/e peaks at 88, 70, 55, 42, 31 (much intense)
and 29.
(iii) Determine the structure of the compound whose peaks in mass spectrum have m/e values
57 (100% abundance), 41, 29 and 27.
(iv) Determine the structure of compound whose peaks appear at m/e values 124, 122, 81, 79,
43 (base peaks), 41, 29 and 27 in the mass spectrum.
(v) Predict the structure of a saturated hydrocarbon showing signals at m/e 99, 71, 57, 43, 41
and 29.
(vi) An aromatic compound forms peaks in the mass spectrum at m/e values 162, 134
(MR ion), 120, 91 and 65. Confirm its structure.
(vii) Determine the structure of compound that shows peaks at 102, 85, 60 (MR ion), 57, 41 and
29. The compound on heating with alcohol in the presence of concentrated sulphuric acid
gives fruity smell.
(viii) An aliphatic aldehyde exhibits its peaks at m/e 86, 85, 44 (MR ion), 57 and 41. Predict its
structure.
(ix) An organic compound of formula C6H14O shows peaks at 100, 87, 73, 59, 45 (base peak)
and 29 in its mass spectrum. Deduce its structure.
(x) An organic compound reduces Tollens reagent. When its mass spectrum is scanned, the
various signals appear at m/e values are 100, 71, 58, 44, 41 and 29. Write the compound.
(i) Write some important features of mass spectra of methyl amine.
(ii) How would you distinguish 1-butanol and 2-butanol from mass spectra.
(iii) Write the various fragmentations of n-butane.
(iv) The mass spectrum of isobutene shows a peak at m/e 29 while that of methane has a small
peak at m/e 17. Explain these observations.
(v) What is McLafferty rearrangement? Illustrate.
(vi) The mass spectrum of ethyl alcohol shows fragments at m/e 46, 45, 31, 29, 17 and 15. Draw
the structures of these fragments.
(vii) Write most probable species for the peaks at m/e 106, 91, 65 in the mass spectrum of ethyl
benzene.
(viii) The mass spectrum possesses a strong peak at m/e 122, 92, 91 (100%) and 65. There are
metastable peaks at 46.5 and 69.4 mass units. Deduce the structure of the compounds.
(ix) The molecular ion peak in the mass spectrum of a compound appears at m/e 108.
Other peaks appear at 93, 65, 78, 77, 51. Determine the structure of the compound.
(x) The various m/e values for a hydrocarbon are given as below:
100, 43 (100%), 57, 85, 71, 41, 29.
Write the structure of the compound and also show its various fragmentation modes.

7. Describe some basic principles of mass spectrometry.
8. What do you understand by metastable ions or peaks? How these are recognized in a mass
spectrum and what is their importance?
9. Write some important features of the mass spectra of aromatic hydrocarbons with examples.
10. Give some important features of the mass spectrum of primary, secondary and tertiary
alcohols.
11. Describe some important features of the mass spectra of the hydrocarbons (only alkanes
and alkenes).
12. Describe some important features of the mass spectra of amines. Give examples.
13. Describe some important features of the mass spectra of
(i) Aldehydes,
(ii) Ketones, and
(iii) Acids.
14. Discuss some important features of the mass spectra of n-propyl cyclohexane, 1-hexanol
and phenol.
15. Discuss some important features of the mass spectra of carboxylic esters with reference to
methyl butanoate, methyl salicylate, benzyl and phenyl acetate.
16. Give your comments on mass spectra of amides and nitro compounds.
17. Give your comments on mass spectra of the following:
(i) Aliphatic nitrile,
(ii) Aliphatic nitrites,
(iii) Aliphatic nitrates and
(iv) Ethers.
Index
Absolute errors, 148 Basis of separation, 213
Absolute method, 352 Benzylic cleavage, 539
Absorbing species involving d or f electrons, 380 Brown ring test
Absorption law, 367 for nitrate, 29
Accelerating chamber, 528 for nitrite, 27
Accuracy, 147 Bush Densen equation, 220
Acid-base titration, 62
theory, 62
Action of Calcon indicator, 86
methyl orange, 63 Calculation of ESR splitting, 508
phenolphthalein, 63 Captive zero, 140
Activation overpotential, 297 Cation exchange resin, 235
Additivity of absorbance, 386 Cation-release method, 107
Allylic cleavage, 538 Characteristic of gas chromatography peak and
Analysis of mixture of ions by polarography, 354 resolution, 254
Analysis of oils and fats, 197 Charge transfer spectral absorption, 380
Anion exchange resin, 235 Chemical method of separation and purification, 277
Anion-releasing method, 105 Chi-square test, 159
Application of ESR, 514 Chromatographic methods and their classifications,
determination of g value, 514 225
electron transfer reaction, 516 Chromophore, 383
study of free radicals, 515 Clapeyron-Clausius equation, 273
study of internal motion, 516 Classical description of NMR, 462
Application of UV-visible spectral method, 390 Classification of
composition of coloured complex, 400 group II cations into group IIA and IIB, 6
determination of pK value of indicator, 398 group III cations, 7
multiple analysis, 397 group II cations into group IIIA and IIIB, 8
quantitative analysis, 404 group IV cations, 9
structural analysis, 390 group V cations, 9
Auxochrome, 384 Classification of chromatographic methods, 226
based on contact, 226
Base peak, 526 based on physical state, 226
Based on based on physical or chemical mechanism, 227
molarity, 60 Classification of electroanalytical technique, 287
normality, 60 Classification of errors, 142
575
576 Index
Colour change interval of indicator, 64 bromide and iodide in presence of each other, 33
Column (or adsorption) chromatography, 228 bromide ion, 28
application, 233 carbon and hydrogen, 179
characterization of the chromatography peak, 229 carbonate ion, 23
chromatographic resolution, 229 chloride in presence of bromide and/or iodide, 31
theory and principle, 228 Cl, Br and I in presence of each other, 33
Column efficiency, 231 CO32 and SO32 in presence of each other, 24
Common ion effect, 4 F , SiF62 and SO42 in presence of each other, 39
Comparison between single and multiple extractions, chloride ion, 27
217 end point by visual method, 63
Complexometric titration theory, 79 ferricyanide, 36
Concentration polarization, 297 ferrocyanide, 36
Conditional stability constant, 81 Group I anions (CO 32, SO 32, S2O32, NO2), 23
Confidence limit, 154 Group II anions, F , Cl, Br, I, NO3, borates,
Constant current coulometry, 320 SCN, Fe(CN)64, Fe(CN) 63, 27
Constant errors, 142 chromylchloride test, 28, 31
Contamination of precipitate, 107 floride ion, 27
Controlled potential coulometry, 327 Group III anions (Precipitation group) (SO 42,
application, 329 AsO33, AsO43, PO43), 38
Convection current, 340 halogens, 181
Co-precipitation, 107 impurities, 404
Coulometers, 318 Iodide and iodate in presence of each other, 34
gas (hydrogen-oxygen coulometer), 319 magnesia mixture, 42
iodine-coulometer, 319 nitrate in presence of bromide and iodide
silver coulometer, 318 (Devardas alloy test), 30
Coulometric calculation, 316 nitrate in presence of nitrite, 30
Coulometric titration, 322 nitrite ion, 26
complexometric, 326 nitrogen, 180
neutralization (acid-base), 324 oxalate in presence of fluoride, 43
precipitation, 325 phosphate, arsenate and arsenite in presence of
primary, 322 each other, 41
redox, 326 phosphate ion, 40
secondary, 323 phosphorous, 181
Coulometry, 316 S and N in presence of each other, 181
Counter (or back) potential, 295 S2, SO32 and S2O32 in presence of each other, 25
Coupling constant (J), 489 silicate ion, 39
Criteria of purity, 280 silicofluoride ion (fluosilicate), 39
Crystallization, 263 sulphate ion, 38
Current flow in polarographic cell, 339 sulphide ion, 24
sulphite ion, 24
sulphur, 180
d and tÿ(tau) scales, 470 thiocyanate, 35
Decomposition potential, 295 thiocyanate, ferrocyanide and ferricyanide in pres-
Definition of chromatography, 225 ence of each other, 37
Dempsters mass analyzer, 529 thiosulphate anion, 25
Depolarizer (or potential buffer), 300 Determinate errors, 142
Anodic depolarizer, 301 causes, 143
Cathodic depolarizer, 301 Determination of charge, Q, 317
Detection of Determination of dissolved oxygen, 355
arsenate ion, 41 Determination of formation constant of complex, 353
arsenite ion, 41 Diffusion current-concentration plot, 350
borate, 35 Digestion (ageing), 111
Index 577
Dimethyl glyoxime, 19 carbon and hydrogen (Leibigs combustion
Distillation under reduced pressure, 272 method), 181
Distribution coefficient (KD), 215 aniline, 195
and their relation, 215 glucose, 191
ratio (D), 215 halogens (Carius method), 190
Double focusing spectrometer, 531 nitrogen, 185
Dropping mercury electrode (DME), 349 phenol, 193
advantage and disadvantage, 349 phosphorous (Carius method), 191
Drying and/or incineration of the precipitate, 114 sulphur (Carius method), 190
Dumas method, 185 copper by iodometry, 76
Experimental setup, 348
factors influencing group vibrational frequencies,
Effect of conjugation of chromophore, 386 430
Effect of electron withdrawing, and electron donating for column chromatography, 232
groups in NMR, 474 Extraction of metal chelates, 224
Effect of solvent polarity, 388
Effect of substitution of auxochrome, 387
Electric dipole mechanism, 371 Fehling solution, 192
Electrical circuit, 291 Fermi resonance, 424
Electrical components, 288 Filtration, 111
electrochemical cell, 290 Finger print region, 434
Fractional crystallization, 266
electrode and electrode potential, 288
Fractional distillation, 270
electrolytic, 291
Fragmentation modes, 537
galvanic, 290
of aliphatic nitriles, 569, 570
Electrogravimetry, 292
Fragmented ions, 537
calculation, 293
Freundlichs law, 251
problems involved, 305
F-test, 158
theory and principle, 292
Electrolysis at
anode, 304 Galvanostat and potentiostat, 292
constant current, 299 Germinal coupling, 490
constant voltage, 302 Gibbs phase rule, 214
controlled potential, 302 Gravimetric calculation, 101
spontaneous or internal electrolysis, 304 Gravimetric factor, 101
Electrolysis in simple cell, 294 Group I cations, 5
galvanic cell, 298 Group II cations, 5
non-galvanic cell, 294 Group vibrational frequencies, 429
Electron spin resonance method, 497 factors influencing group vibrational frequencies,
basic principle, 497 430
techniques, 502 Gyromagnetic ratio, 462
Electropotential method, 78
End point and equivalence point, 57
End point for redox titration, 73 Half bandwidth and oscillator strength, 372
Eriochrome Black T, 85 Half-wave potential (E1/2), 344
Errors and their causes, 142 Hanus method, 199
Errors in precipitation, 110 Hanus reagent, 198
ESR studies of inorganic compounds mainly Henrys law of partition, 251
complexes, 517 Heterolytic cleavage, 539
Estimation of High resolution NMR spectrum of
calcium and magnesium by complexometric ethyl alcohol, 480
titration by EDTA, 85 methyl alcohol, 480
578 Index
Homogeneous precipitation, 105 IR spectrophotometer, 429

Homolytic cleavage, 537 Isomorphic inclusion, 108
Hydrogen bonding in NMR, 475 Isotope ions, 534
Hydrogen transfer rearrangement, 540
Hyperfine splitting, 504
for H atom, 505 Jobs method of continuous variation, 400
for deuterium, 506
for methyl radical, 506
Kjeldahls method, 187
Kramers degeneracy, 512
Ignition, 115
Ilkovic equation, 342
its derivation, 343 Lamberts law, 367
Inclusion, 108 Lambert-Beer law, 368
Indeterminate errors, 145 Langmuirs law, 251
Inductive effect, 473 Laporte rule, 372
Infrared (IR) spectral method, 415 Large-range coupling, 491
Instrumental errors, 144 Larmor precesion, 462
Intensity of NMR signals, 463 Leading zero, 140
Interferring radical, 43 Line width of ESR transition, 501
Interpretation of derivative curve, 503
Iodimetry, 74
Magnesia mixture, 42
Iodine value and its determination, 197
Magneson regent, 22
Iodometry, 75
Magnetic anisotropy, 471
Ion collector, 530
Magnetic moments of the nuclei, 458
Ion-exchange capacity, 237
Magnetic properties of nucleic and their angular
Ion-exchange chromatography, 234
momentum, 457
application, 238
Masking agent, 13
experiment setup, 238
Mass analyzer, 528
principle, 234
Mass spectra of
Ion-exchange equilibria, 237 alcohols, ethers and amines, 551
Ion source, 528 aliphatic aldehydes and ketones, 560
IR characteristics of some organic compounds, 435 alkenes (olefins), 545
acid amide, 445 alkyl halides, 551
acid anhydride, 445 alkynes (acetylenes), 548
acid halides, 445 aromatic acids and esters, 568
alcohols and phenols, 439 aromatic alcohols, phenols and aromatic
aldehydes and ketones, 442 (amines), ether, 557
amines, 441 aromatic aldehydes and ketones, 563
carboxylic acids, 443 aromatic compounds, 548
esters, 445 branched chain alkanes, 544
hydrocarbons, 435 carboxylic acids, esters and amides, 563
alkanes, 435, 436 cyclo alkanes, 547
aromatic hydrocarbons, 438 cyclo olefins, 548
cycloalkanes, 438 straight chain alkanes, 543
cyclo olefins, 438 Mass spectral method, 525
IR spectra of inorganic compounds especially metal Mass spectrometer, 527
complexes, 448 Maximum suppressor, 347
carbonato and nitrato complexes, 449 McLafferty rearrangement, 541
nitro and nitrite complexes, 449 Mean and medians, 150
oxalato complexes, 451 Measurement of diffusion current, 341
sulphato and perchlorato complexes, 450 Mechanism of ion exchange, 236
Index 579
Mediator, 324 Percentage of extraction, 216
Metal chelates, 79 Personal or human errors, 144
Metal ion indicator, 84 pH method, 64
Metastable ions or peaks, 534 Pilot ion method (internal standard method), 352
Methodic errors, 144 Polarographic cell, 348
Methods of expressing precision, 150 Polarographic maxima, 346
Methods of solvent extraction, 221 Polarography, 339
batch extraction, 221 principle, 339
continuous extraction, 221 Position of the signals and chemical shift, 468
countercurrent extraction, 222 Post precipitation, 110
Microcosmic salt bead test, 39 Potential energy of a nucleus in a magnetic field, 459
Migration current, 340
Potential energy of electron in magnetic field, 498
Migration parameters, 240
Potential energy of a proton in a magnetic field, 460
Milions base, 22
Precipitation, 103
Mixed melting point, 280
Precipitation gravimetry, 101
Molar absorption coefficient and its unit, 369
Molecular vibrations and vibrational frequency, 415 Precision, 147
Multiple extraction, 217 Prediction of number of NMR signals, 466
Multiplicity of NMR peaks, 491 Presentation of ESR spectra, 503
Primary standard, 58
Problems involved, 355
Nature of electronic spectrum, 370 Problems involving chemical shift and spin-spin
Nernst distribution law, 214 splitting, 482
Nesslers reagent, 22 Propagation of errors, 146
Nitrogen rule, 542 Propelling force, 240
Non-isomorphic inclusion, 108 Proportionate errors, 143
Nuclear magnetic spectral method, 457 Purification techniques, 262
principle, 457 for liquid, 269
technique involved, 464 for solid organic compounds, 262
Nucleation and particle growth, 103
Q-test, 160
Occlusion, 108
Ohmic potential or IR drop, 296
One dimensional paper chromatography, 243
Range, 151
ascending chromatography, 243
Recrystallization, 265
descending chromatography, 244
Redox indicator, 76
radial (circular) paper chromatography, 244
Operational errors, 144 Reductant primary standard, 71
Organic precipitants, 116 Reichert-Meissel value (RM value), 200
Ortho effect, 541 Rejection of result, 159
Overvoltage (overpotential), 295, 297 Relative average deviation, 152
Overtones, combination and different band, 423 Relative error, 148
Oxidant primary standard, 71 Relative standard deviation, 153
Relative standard deviation of the mean, 154
Relaxation process and line width in ESR transition,
Paneth-Fajans-Hahn law, 108 500
Paper chromatography, 240 Residual current, 340
application, 246 Resolution of mass spectrometer, 530
principle, theory, 240 Resonance condition in ESR, 499
technique, 242 Retarding force (RF), 240
Parent peak, 526 Retro-Diels Alder reaction, 539
Pascals triangle, 482 Rocking vibration, 420
580 Index
Sample injection system, 252 Steam distillation, 274

Saponification value and its determination, 199 experimental setup, 276
Saturation and relaxation process, 464 theory, 274
Scissoring vibration, 420 Stereochemical factors, 389
Secondary standard, 58 Students test, 156
Selection rules for absorption, 371 Study of EDTA complex formation, 83
Selection rules for IR absorption, 422 Study of redox titration by electrochemical method,
Selectivity factor, 230 72
Separation and detections of Sublimation, 266
Group I cations (Ag+, Hg 22+, Pb2+), 10 technique, 267
Group IIA cations (Pb2+, B 3+, Hg2+, Cd2+, Cu2+), 11 under reduced pressure, 267
Group IIB cations (As3+ or 5+, Sb3+ or 5+, Sn2+ or 4+), 14 Supporting electrolyte, 340
Group IIIA cations (Fe3+, Al3+, Cr3+), 16 Surface adsorption, 108
Group IIIB cations (CO2+, Ni2+, Mn2+, Zn2+), 18 Symmetries of vibrations and their IR activity, 424
Group IV cations, (Ca2+, Ba2+, Sr2+), 20 for H2O, 424
Group V cations (Na+, K+, Mg2+, NH 4+), 21 CO2, 425
Separation factor, 220 SO2, 425
Separation techniques, 213 octahedral molecule, 428
basis of, 213 pyramidal molecule, 426
Seque stering (or masking) agent, 120 square planar molecule, 427
Shifting of absorption band and change in intensity, tetrahedral molecule, 427
385 trigonal planar molecule, 426
bathochromic shift, 385
hyperchromic shift, 385
hypochromic shift, 385 Tautomeric equilibria, 405
hypsochromic shift, 385 Test for I, 29
Significant figures, 139 for NO3, 29
Simple cleavage, 537 Test of significance, 155
Simple distillation, 269 Theories of precipitation, 103
Skeletal rearrangement, 542 Theory of redox titration, 71
Slope ratio method, 403 Thin layer chromatography (TLC), 246
Sodium carbonate extract (SCE), 23 application of TLC, 249
Sodium nitroprusside, 24 development of chromatogram, 248
Solubility product, 4 experimental technique, 247
Solvent extraction, 268 gas chromatography, 250
Solvent extraction of metal ions by chelation, 223 Titration, 57
Solvent extraction method, 213 Titration of
principle, 214 strong acid with strong base, 65
Specific and selective precipitant, 116 weak acid with strong base, 65
Specific visual indicator, 74 weak acid with weak base, 69
Spectral regions in infrared, 433 weak base with strong acid, 67
Spin labelling of biomolecules, 517
Spin-spin coupling (or splitting), 477 Trailing zero, 141
Stability constant of EDTA complex, 81 Transition of involving s , p and n (non-bonding
Standard addition method, 353 electrons), 376
Standard deviation, 153 n-ÿp*, 378
Standard deviation of the mean, 154 n-s *, 377
Standardization of sodium thiosulphate by K2Cr2O7, p -p *, 378
75 s-s *, 377
Index 581
Troutans rule, 273 Variance, 154
Twisting vibration, 420 Vibration of
Two dimensional paper chromatography, 245 diatomic molecule, 415
Types of absorption bands, 381 polyatomic molecule, 418
B-band, 381 Vicinal coupling, 490
E-band, 382 Volumetric (titrimetric) calculation, 59
K-band, 381 von Weimarns theory of relative supersaturation, 104
R-band, 381
Types of electrogravimetry, 293
Types of electronic transition, 376 Wagging vibration, 420
Types of molecular vibrations, 418 Washing of the precipitate, 113
bending, 419 Weighing, 115
(in plane), 420 Wijs
(out of plane), 420 method, 198
stretching, 418 reagents, 198
Types of UV-visible spectrophotometer, 374
Yoes mole ratio method, 400
Ultraviolet and visible spectral method, 365

principle, 366 Zero field splitting, 511
technique involved, 373 Zirconyl nitrate method, 44

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Analytical Chemistry

Dhruba Charan Dash

3. Quantitative AnalysisPrecipitation Gravimetry 101135

4.4 Propagation of Errors 146

6.6.7 Experimental Set-up 238

7. Purification Techniques 263284

9. Electroanalytical TechniquesCoulometry 316338

9.7 Coulometric Titration 322

10. Electroanalytical TechniquesPolarography 339362

11.9 Some More Problems Involved in UV-visible Spectral Method 405

12. Spectroanalytical TechniquesInfrared (IR) Spectral Method 415456

13. Spectroanalytical TechniquesNuclear Magnetic Resonance

14. Spectroanalytical TechniquesElectron Spin Resonance

15. Spectroanalytical TechniquesMass Spectral Method 525574

15.3 Instrumentation 527

Dhruba Charan Dash

Method of analysis Quantity of the sample

1.1.1 Solubility Product Principle

1.1.2 Common Ion Effect

1.2 SEPARATION OF CATIONS INTO GROUPS

Substances Solubility product

Substances Solubility product

Explanation for inclusion of Pb2+ in group I as well as group II

SnS2 + (NH4)2S2 ¾® (NH4)2SnS3 + S

As2S3 + (NH4)2S2 ¾® 2(NH4)3AsS4 + S

[NH 4 ]  [OH  ] = 1.8 ´ 105 ´ [NH4OH]

Classification of group III cations into IIIA and IIIB

Fe2+ + K3[Fe(CN)6] ¾® KFe[Fe(CN)6] + 2K+

1.3 DETECTION AND SEPARATION OF CATIONS OF EACH GROUP

1.3.1 Separation and Detection of Group I (Silver Group) Cations

PbCrO4 + 4NaOH ¾® Na2[PbO2] + Na2CrO4 + 2H2O

Solution containing Ag+, Pb2+ and Hg 22 ions

Redox reaction of HgCl2 with SnCl2

2HgCl2 + SnCl2 ¾® SnCl4 + Hg2Cl2 (White ppt.)

Separation and detection of Pb2+

PbSO4 + 2CH3COONH4 ¾® Pb(CH3COO)2 + (NH4)2SO4

Separation and detection of Bi3+

Cd2+ + 4NH3 ¾® [Cd(NH3)4]2+ tetraammine cadmium(II) ion

Separation and detection of Cd2+

Detection of Cd2+ in presence of Cu2+

[Cd(NH3)4]2+ + 2CN ¾® Cd(CN)2 + 4NH3

Solution containing group II cations

1.3.4 Separation and Detection of Group IIB Cations

Separation of As2S5 from Sb2S5 and SnS2

As2S3 + 6NH3 + 3H2O ¾® (NH4)3AsO3 + (NH4)3AsS3

The arsenite is oxidized to arsenate when treated with H2O2

(NH4)3AsO4 + MgSO4 ¾® Mg(NH4)AsO4 + (NH4)2SO4

The presence of arsenic is further confirmed as follows:

5(2HNO3 ¾® 2NO + H2O + 3O)

Separations and detection of antimony (Sb3+ or Sb5+)

H[SbCl4] + 3C2O42 ¾® [Sb(C2O4)3]3 + 4Cl

Detection of tin (Sn2+ or 4+)

Table 1.3 Separation and detection of group IIB cations

Detection of Fe3+ by analysis of the residue Fe(OH)3

2(HNO3 + 3HCl ¾® NO + 2H2O + 3Cl)

Co2+ + 4SCN ¾® [Co(SCN)4]2

Analysis of the filtrate containing (ZnCl2 + MnCl2)

Detection of Zn2+ from its zincate solution

1.3.7 Separation and Detection of Group IV Cations (Ca2+, Ba2+, Sr2+)

BaCO3 + 2CH3COOH ¾® Ba(CH3COO)2 + CO2 + H2O

Separation and detection of Ba2+

Ba(CH3COO)2 + K2CrO4 ¾® BaCrO4 + 2CH3COOK

On filtration, the filtrate contains Ca2+ and Sr2+.

3. Quantitative AnalysisPrecipitation Gravimetry 101135

7. Purification Techniques 263284

9. Electroanalytical TechniquesCoulometry 316338

10. Electroanalytical TechniquesPolarography 339362

12. Spectroanalytical TechniquesInfrared (IR) Spectral Method 415456

13. Spectroanalytical TechniquesNuclear Magnetic Resonance

14. Spectroanalytical TechniquesElectron Spin Resonance

15. Spectroanalytical TechniquesMass Spectral Method 525574

[NH 4 ] [OH ] = 1.8 ´ 105 ´ [NH4OH]

Solution containing Ag+, Pb2+ and Hg 22 ions

[Cd(NH3)4]2+ + 2CN ¾® Cd(CN)2 + 4NH3

H[SbCl4] + 3C2O42 ¾® [Sb(C2O4)3]3 + 4Cl

Co2+ + 4SCN ¾® [Co(SCN)4]2

2K 2 HgI 4 2NH 4 2OH ¾® NH 2 Hg 2 I3 4KI NH 4 I 2H 2 O

Reason for detection of CO32 and SO32 in presence of each other

The presence of S2 is confirmed by sodium nitroprusside test given below.

S2 O32 + 2HCl ¾® H2S2O3 + 2Cl

S2 + CdCO3 ¾® CdS + CO 2

Detection of SO32 by the analysis of residue (SrSO3 )

Detection of S2O32 from the filtrate containing S2O32

Table 1.7 Separation and detection of (S2, SO 32 , S2O 32 )

Detection of NO2 ion

Detection of Fluoride (F)

2HNO3 + 2H+ + 2e ¾® 2NO2 + 2H2O

NO3 4Zn 7OH ¾® NH 3 4ZnO 22 2H 2 O

CrO2Cl2 Na CrO

(NH4)2 CO3 + H2O 2(NH

[Ag(NH3)2]+ + Br ¾® AgBr + 2NH3

Detection of thiocyanate (SCN)

SCN + Fe3+ ZZX

Detection of ferrocyanide [Fe(CN)6]4 ion

Detection of ferricyanide [Fe(CN)6]3 ion

2[Fe(CN)6]3 + 3CdSO4 ¾® Cd3[Fe(CN)6]2 + 3SO42

Detection of silicate ion (SiO32)

SO42 + Pb(CH3COO)2 ¾® PbSO4 + 2CH3COO

SiF62 + Pb(CH3COO)2 ¾® PbSiF6 + 2CH3COO

Detection of F and SO42 by analysis of the residue

Detection of phosphate (PO43)

PO43 + 3HNO3 ¾® H3PO4 + 3NO3

The detection of PO43 is further confirmed by AgNO3 test as follows.

AsO43 + 2H+ + 2e ¾® AsO33 + H2O

Detection of AsO43 from analysis of the residue containing

Detection of PO43 from the filtrate

or ZrO(NO3)2 + PO43 + H+ ¾® ZrO(HPO4) + 2NO3

pH = log[H+] = log K a [acetic acid]

CH3COOH + OH ZZX H 2O(1) + CH3COO

p(OH) = log[OH] = log[excess NaOH]