Ak Das-Vol7

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Volume 1
Atomic Structure; Wave Mechanics and Quantum Chemistry; Nuclear Structure;
Nuclear Chemisty; Nuclear Reactions and Nuclear Energy; Radiation Chemistry;
Nucleosynthesis of Elements; Chemical Periodicity of the Elements.
Volume 2
Bonding Theories (VBT and MOT) of Covalency; Strucutre and Reactivity of
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Covalent Compounds; Stereochemical Nonrigidity and Fluxionality; Molecular
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Symmetry and Point Group; Solid State Chemistry - Structure and Bonding;
Magnetic and Ferroelectric Materials.
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Volume 3
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Bonding in Metals and Metal Clusters; PSPT - Wade's Rule and Jemmi's Rule;
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Electric Conductivities of Solids; Semiconductors and Superconductors; Hydrogen
Bonding and other Weak Chemical Forces; Supramolecular Systems and
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Molecular Recognitions; Acids and Bases and Ionic Equilbria; Nonaqueous

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Solvents and Ionic Liquids; Redox Potentials, Formal Potentials and Applications;
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EMF Diagrams; Electroanalytical Techniques; Photoredox Reactions; Oscillating

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Reactions
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Volume 4
Complex Compounds - Introduction; Structure; Stereochemistry and Isomerism;
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Nomenclature, Bonding Theories (VST, CFT, LFT and MOT); Applications of CFT;
J.T. Distortion; Spectrochemical Series; Stabilities of Complexes.
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Volume 5
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Metal Complexes - Reaction Mechanisms (Ligand Substitution, Isomerisation,

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Racemisation, Electron Transfer and Photochemical Reactions); Electronic

Spectra.
Volume 6
Magnetochemistry and Magnetic Properties of Metal Complexes; Structure,
Bonding and Reactivities of Organometallics including Metal Carbonyls and
Nitrosyls; Organometallics as Catalysts.
Volume 7
Application of Metal Complexes in Analytical Chemistry and other Fields; Theory
and Applications of Spectroscopic Methods (IR, Raman, NMR, ESR, Mossbauer,
NQR, Mass Spectrometry, UV-VIS, UV-PES)
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Mahua Das
MSc (CU), PhD (VisVQ Bharati)
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Former Research Associate, Department of Chemistry

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Visva Bharatt University, Santiniketan 731235

West BengaJ (tndia)
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CBS
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eISBN: 978-93-890-1756-4
Copyright © Authors and Publisher
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All rights reserved. No part of this eBook may be reproduced or transmitted in any form or by any means,
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Fundamental Concepts of
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Published by Satish
Inorganic Kumar Jain and produced by Varun Jain for
Chemistry
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A tribute to
Prof Priyadara'1ian Ray (1888-:1982)
who made a significant contribution

in the field of chemistry
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This Page is Intentionally Left Blank

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~e present volumes 4-7 are in continuation of the existing title Fundamental Concepts
.1. of Inorganic
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Chemistry. The classnotes and valuable suggestions received from the
esteemed readers have been shaped in these volumes.
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These volumes cover the structure and bonding (VBT, CFf, and MOT), stability and
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reactivity, spectral and magnetic properties ofmetal complexes in depth. Kinetics and reaction
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mechanisms of ligand substitution, electron transfer and photochemical reactions have been
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included. Magnetochemistry and organometallic chemistry have been covered. Applications

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of different spectroscopic techniques (Raman, IR, NMR, ESR, Mossbauer, UV-VIS, UV-
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PES, etc.) have been discussed to widen the utility of the series. In developing the present
extension, we have taken all the measures to retain the basic features of the existing title.
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In preparing the manuscript, we have freely consulted the books and reviews of the earlier
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authors and have borrowed their ideas whenever it has been required. These sources are
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listed and acknowledged at the end of the text. We are grateful and indebted to these authors.
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In reality, we have picked up flowers from these gardens to prepare the garland to worship
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the goddess of learning.

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We are extremely thankful and grateful to Mr SK Jain, Managing Director, CBS Publishers
& Distributors, for his continued support. We are thankful to Mr YN Arjuna, Senior Director,
Publishing, Editorial and Publicity, and the DTP staff for taking the trouble in processing
the manuscript.
In spite of our best efforts, some mistakes and misconceptions might have crept in for
which we beg to be excused. Constructive criticism and suggestions are always welcome to
better the presentation.
Asim K. Das
Mahua Das
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11.1 Metal Complexes in Analytical Chemistry 1659
Inorganic Qualitative Analysis; Separation of Metal Ions Through Solvent Extraction;
Complexation in Spectrophotometric Analysis; Complexation in Gravimetric Analysis;
Masking or Sequestring Agents in Analytical Chemistry; Metal Complexes in Complexometric
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Titrations
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11.2 Metal Complexes in Medicinal Chemistry 1681
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11.3 Metal complexes in industrial processes 1683
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Organometallic Compounds as the Catalysts; Complexation in Water Softening; Complexation
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in Food Preservation; Complexation in the Rasching Process of Hydrazine Preparation;
Complexation in Electroplating Process; Compl~xation in Metallurgical Process;
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Complexation a.nd Photograp~y
11.4 Metal Complexes in agriculture 1687
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11.5 Metal Complexes and Solar Energy Conversion 1687

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11.6 Complexation and Stabilization of Unusual Oxidation States 1687

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11.7 Complexometric Titrations 1687

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Ethylenediaminetetraacetic Acid (called also Versene, Complexone-III): A Potential

Complexometric Agent; A quantitative Treatment of Complexometric Titration; Effect of
pH on the Complexometric Titration Curves for Ethylenediaminetetraacetic Acid as the
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Complexing Agent; Minimum Required Value of C~nditional or Effective Stability Constant

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and Suitable pH Range for Titration by Ethylenediaminetetraacetic Acid; Effect of Other

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Complexing Agents on Complexometric Titration Curves; Effect of other Complexing Ligands

on the Conditional Stability Constant; Metal Ion Buffer; Metal Ion or Metallochromic
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Indicators; Selection of Metal Ion Indicator in Complexometric Titration: A Quantitative

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Treatment; Different Types of Complexometric Titrations; Selectivity in Titration with edta

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by Controlling pH
11.8 Mercurimetric Titration of Halides: Formation of Multiple Complexes during Titration 1713
Exercise 11 1714
Appendix-lIA: Distribution of Different Species of EDTA in Different pH Values 1718
x Fundamental Concepts of Inorganic Chemistry
1719-2111
12.1 Vibrational Spectroscopy: Infra-Red (IR) and Raman Spectra 1719
Some Important Aspects of the IR and Raman Spectra; Classification of Normal Modes of
Molecular Vibration; Normal Modes of Vibration (See Appendix 12B) and Infrared and Raman
Active Modes in Some Simple Molecules; Characteristic Group Vibrations; Electronic and
Coupling Effect on Group Vibration Frequency; Limitations of the Characteristic Group
Vibrations; Application of Infrared and Raman Spectra: Determination of Structure of Some
Simple Molecules; Symmetry of the Normal Modes of Vibration (3n - 6 or 3n - 5) and Number
of ir-Active and Raman Modes (See Appendix-12B); Application of Infrared and Raman
Spectra: Determination of Structure through the Normal Mode Analysis; Application of
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Infrared and Raman Spectra: Determination of Geometrical Isomers of Coordination
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Compound~; Application of Infrared and Raman Spectra: Determination of the Structures of
Metal Carbonlys; Effect of Coordination on the Rotational-Vibrational Spectra of the Ligands;
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Application of Infrared Spectra: Appearance of New Bond Vibration for the Metal-Ligand
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Bond Formation; Application of Infrared and Raman Spectra: Appearance of New Bands of
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the Ligand upon Coordination; Application of Infrared Spectrum: Detection of Water in
Coordination Compounds; Application of Infrared Spectra: Shifting of Ligand Band Position
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to Characterise the Mode of Coordination; Application of Infrared Spectra: Identification of
Linkage Isomers; Application of Infrared and Raman Spectra: Assignment of the Coordinating
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Behaviour of the Anionic Ligands (XOr, XO,r)
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12.2 NMR (Nuclear Magnetic Resonance) Spectroscopy and Its Application 1779
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Some Basic Elements of NMR Spectroscopy; Intensity of the NMR Signals and Peak
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Broadening; Relaxation Processes: Sharp Peak vs. Intensity of the Peak; Concept of Chemical
Shifts and Solvents for PMR Studies; Factors Controlling the Magnitude and Direction of
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Chemical Shift; Chemical Shifts for the PMR Signals in Metal Hydrides and Organometallics;
Area of the NMR Peak and Number of Nuclei: Integration Principle; Spin-Spin Coupling and
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Fine Structure of the NMR Signals; Spin-Spin Coupling and Coupling Constant (J);
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Magnetically Equivalent and Nonequivalent Nuclei: Magnetic Equivalence vs. Chemical

Equivalence; Designation (i.e. Nomenclature) of Nuclei Spin System; First Order and Second
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Order NMR Spectra: Advantage of the NMR Spectrometer Operating at Higher Frequency
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(e.g. 60 MHz vs 100 or 300 MHz); Chemical Shift Reagents; Nuclear Magnetic Double
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Resonance (NMDR) and Spin Decoupling - A Way to Simplify the Complex NMR Spectra:
Noise Decoupling ~nd Nuclear Overhauser Effect (NOE); Effect of Chemical Exchange on
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NMR Spectra and Evaluation of Exchange Rate Constants; Quadrupole Effects and NMR
Studies for the Nuclei with Spin Greater than 1/2: Quadruple Peak Broadening and Decoupling;
13C-NMR Spectroscopy and Organometallics; NMR Spectroscopy for the Nuclei other than
Hydrogen: PMR Spectroscopy vs. Other NMR Spectroscopy; Application of NMR
Spectroscopy in Structure Determination: Some Representative Examples; Application of
NMR Spectroscopy in Identification of Rotational Isomerism; Application of NMR
Spectroscopy in Detection of H-bonding and in Distinction of Intramolecular and
Intermolecular H-bonding; Application of NMR Spectroscopy to Determine the Relative
Amounts of the Keto-Enol Tautomers in a Tautomeric Mixture; Application of NMR
Spectroscopy for Determination of Exchange Rate Constant; Application of NMR
Spectroscopy and MRI (Magnetic Resonance Imaging); Fluxionality through the
Intramolecular Rearrangement and NMR Studies; Two-Dimensional NMR - ROSY, COSY,
NOESY
Contents xi
12.3 Electron Spin Resonance (ESR) Spectroscopy 1870

Interaction between the Electron Spin and Magnetic Field: Some Basic Elements of ESR
Spectroscopy;' Relaxation Processes: Intensity and Bandwidths of the ESR Signals; Fine
Structure of ESR Signals: Zero-field (Crystal Field) Splitting: Kramers' Degeneracy; Zero-
field Splitting and Effective Spin (S') and Effective ESR Transitions in Different tf Systems
of the 1st Transition Series; Nuclear Spin and Hyperfine Splitting of the ESR Signals;
Mechanism of Coupling of the Electronic Spin and Nuclear Spin; Illustration of the Fine
Structure and Hyperfine Structure of the ESR Signals; ESR Spectra: Magnetically Concentrated
vs. Magnetically Diluted Complexes; Factors Affecting the g-value; Determination of the g-
value; Anisotropic Behaviour of g and Anisotropy in Hyperfine Interaction; Anisotropic
Behaviour of the g-value of the Tetragonally Distorted Copper(ll) Complexes; Anisotropic
Behaviour of the g- Value for the Tetragonally Distorted Nickel(II) Complexes; EPR Peak
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Broadening and Peak Merging and Electron Spin Exchange Rate; Applications of ESR
Spectroscopy
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12.4 MoSsbauer (MB) Spectroscopy 1943
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Isomeric Nuclides (of an Element) Differing in Energy States: Nuclear Transition
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Energy in the y-Region; Principle of Mossbauer (MB) Spectroscopy: Condition of Recoilless
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Emission and Absorption of y-Ray through the Adjustment of Doppler Shift; Source and
Absorber: MB Spectroscopy for 57Fe and 119Sn; Isomer Shift or Centre Shift or Chemical
Isomer Shift (in short, Chemical Shift) in MB Spectroscopy; Quadrupole Interaction and
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Splitting of the MB Spectral Lines; Effect of a Magnetic Field on the MB Spectrum: Magnetic
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Hyperfine Interaction; Application of MB Spectroscopy
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12.5 Electronic Spectroscopy: UV-Visible Spectroscopy 1986

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Electronic Spectroscopy of the Transition Metal Complexes; Electronic Transitions in Organic

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Molecules; Franck-Condon Principle and the Selection Rule; Designation of the UV-Bands
of Electronic Absorption; Important Terms Involved in the Electronic Spectra: Chromophores
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and Auxochromes; Bathochromic Shift (i.e. Red Shift) and Hypsochromic Shift (Blue Shift);
Hypochromic and Hyperchromic Shift; Isosbestic Point; Solvent Cutoff Points; Effect of
Resonance and conjugation on the Position and Intensity of the Absorption Bands; Solvent
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Effect (i.e. Solvatochromism or Solvatochromic Shift) on the Position of the Absorption

Bands;
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Effect of Intramolecular H-Bonding on the Positions of the Absorption Bands: Identification

of Keto-Enol Tautomerism; Characteristics of the Absorption Bands in Alkenes and Polyenes;
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Characteristics of the Absorption Bands of the Carbonyl Compounds; Characteristics of the

Absorption Bands in the Aromatic Compounds; Colour of Halogens and Different Colours
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of Iodine (12) and Bromine (Br2) in Different Solvents 2020

12.6 Electronic States of Diatomic Molecules and Electronic Spectra of Diatomic Molecules 2021
Electronic States and Term Symbols of the Diatomic Molecules and Ions; Selection Rules of
Electronic Transitions in the Diatomic Molecules: Electronic Spectrum of Molecular Hydrogen
and Oxygen
12.7 Ultraviolet Photoelectron Spectroscopy (UV-PES) and Identification of the Nature of
Molecular Orbital Energy Level 2031
12.8 Nuclear Quadrupole Resonance (NQR) Spectroscopy and Its Application 2031
Quadrupole Nucleus, Nuclear Quadrupole Moment, Electric Field Gradient (EFG)
and Asymmetry Parameter (11) ; Principles of.NQR Spectroscopy: Quadrupole Energy States
and Interaction with the Electromagnetic Radiation; NQR Transition Energies for the Axially
Symmetric Systems (i.e. 11 = 0); NQR Transition Energies for the Nonaxially Symmetric
Systems (i.e. 11 i:- 0); Effect of a Magnetic Field (Zeeman Effect) on NQR Transitions;
xii Fundamental Concepts of Inorganic Chemistry
Conditions (Summary) to observe the NQR Signals; Solid State Effect and the Magnitude of
Nuclear Quadrupolar Coupling Constant Determined from the NQR Studies; Application of
NQR Spectroscopy
12.9 Mass Spectrometry and Its Application 2059
Working Principle of a Mass Spectrometer; Ionisation and Fragmentation of the Sample:
Fragmentation Mode-a Fingerprint of the Sample; Application of Mass Spectrometry
12.10 Optical Rotatory Dispersion (ORD) and Circular Dichorism (CD) and Application of
ORD and CD Curves to Determine the Absolute Configuration 2069
12.11 Magnetic Moment and Application of the Knowledge of Magnetic Moment Data 2069
12.12 Some Important Electroanalytical Techniques Like Potentiometry, Coulometry,
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Amperometry, Polarography and Cyclic Voltammetry (CV) 2069
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12.13 Other Instrumental Methods of Chemical Analysis 2069
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Exercise 12 2078
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Appendix 12A: Character Tables of Different Point Groups (Excluding the
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Cubic Functions) 2095
Appendix 12B: Normal Vibrational Modes for Some Common Molecular Structures 2107
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Appendix 12C: Splitting of ground state T-term (octahedral and tetrahedral Fields)
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by Spin-Orbit Coupling and Magnetic Field (i.e. Zeeman Effect) 2110
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2112-2192
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13.1 Introduction to Errors in Analysis 2112

13.2 Important Terms in Error Analysis 2112
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13.3 Characteristics of Systematic Errors 2118

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13.4 Characteristics of the Random or Indeterminate Errors 2120

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13.5 Distribution of Random Errors: Statistical Treatment of Random Errors 2121

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13.6 Population Mean (m), Sample Arithmatic Mean (X), and Measures of Dispersion-
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Range, Populatiola Standard Deviation (s) and Sample Standard Deviation (s) 2126
13.7 Confidence Interval (CI) and Confidence Level (CL) and Probable Random
Analytical Error 2135
13.8 Testing for Significance (Hypothesis Testing) and Criteria for Rejection of
an Observation 2139
Comparison of the Mean Values (t-test); Comparison of Precision (Variance Ratio Test or
F-test) ; Criteria for Rejection of an Observation
13.9 Propagation of Random Error: Accumulation of Random Error in the
Compound Quantities 2143
13.10 Rounding-off Numbers, Significant Figures and Computation Rules 2153
Rounding-off Numbers and Rules of Rounding-off Numerical Values; Concept of Significant
Figures; Significant Figures in Numerical Computation of Addition and Subtraction;
Contents xiii
Significant Figures in Numerical Computation of Multiplication and Division; Significant

Figures in Numerical Computation of Logarithms and Antilogarithms
13.11 Correlation Coefficient, Regression Analysis of Straight Line Relationship (i.e. Method
of Least Squares) and Regression Coefficient 2162
Correlation Analysis and Correlation Coefficient; Linear Regression Equation: Least Squares
Method
Exercise 13 2189
Numerical Problems 2191
Bibliography 2192
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Appendices A-1-A-9
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Appendix I: Units and Conversion Factors A-I
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Appendix II: Some Physical and Chemical Constants A-3
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Appendix III: Wavelength and Colours A-4
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Appendix IV: Names, Symbols, Atomic Numbers and Atomic Weights of the Elements
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Appendix V: Some Useful Mathematical Relationships A-6
Appendix VI: Books Consulted A-9
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Subject Index 1-1-1-4

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Application of Complex Compounds
11.1 METAL COMPLEXES IN ANALYTICAL CHEMISTRY
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11.1.1 Inorganic Qualitative Analysis
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(A) Separation of AgCI from Hg2 CI 2 and PbCI2 in Gr. 1 of qualitative analysis: From the Group 1
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precipitate containing AgCI, Hg2Cl 2 and PbCI2, the components are separated as follows:
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Gr.1 precipitate is boiled with water and filtered when hot
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! 1
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Residue Filtrate contains PbCI 2

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(H9 2 C1 2 + AgCI) (PbCI 2 is soluble in hot water

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but not in cold water)

Treatment with dil. NH 3
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Residue (black) Filtrate

(Hg + Hg(NH 2 )CI) [Ag(NH 3)2l +
H
(Ammine complex)
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Reactions:
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Disproportionation of Hg~+ I I
• Hg 2Cl 2 + 2NH 3 -------~) Hg~ + Hg(NH 2)CI ~ + NH4+ + CI-
• AgCI + 2NH 3 Complexation) [Ag(NH 3)2]+ + Cl-
Thus AgCI is separated through the ammine complex formation
(B) Separation of Gr-IIA and lIB sulfides in qualitative analysis: When the mixture of precipitate
is treated with yellow ammonium sulfide, the Gr-IIB sulfides (i.e. sulfides of arsenic, antimony and tin)
produce the complex thiosalts which are soluble.
1659
1660 FUNDAMENTAL CONCEPTS OF INORGANIC CHEMISTRY
Gr-IIA sulfides (i.e. HgS, PbS, Bi 2S3 , CuS, CdS)

+
Gr-IIB sulfides (i.e. AS2S3 + Sb2S3 + SnS)
yellow ammonium sulfide

i.e. (NH 4)2 Sx solution
Residue Filtrate
(Gr-IIA sulfides) (Thiocomplex of Gr-IIB precipitate)
AS 2S 3 + 3(NH4)2Sx ~ 6NHt + 2AsSl- + (3x - 5)S ~
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As 2S S + 3(NH4)2Sx ~ 6NHt + 2AsSl- + (3x - 3)S ~
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Sb 2S 3 + 3(NH4)2Sx ~ 6NHt + 2SbSl- + (3x - 5)S ~
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SnS + (NH4)2Sx ~ 2NHt + SnS1- + (x - 2)S t
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The Gr-lIB sulfides are solubilized through the oxidation followed by the formation of thiocomplexes
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like Assl- (thioarsenate), SbSl- and SnS1-. The Gr-IIA sulfides fail to form the complexes under this
condition.
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(Note: Yellow ammonium sulfide i.e. (NH4)2Sx possesses the oxidizing action (e.g. AS IlI ~ As v ;
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Sn Il ~ Sn IV ) probably due to the presence of some sulfur in zero oxidation state. Thus, (NH4)2Sx
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may be considered as (NH4)2S + (x - I)S. Thus, the simple ammonium sulfide i.e. (NH4)2S does not
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have any oxidizing action).

The thiocomplexes of Gr. lIB sulfides are easily decomposed by acidification with HCI.
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2Assl- + 6H+ ~ As 2S S ~ + 3H2S~ As 2S S ~ AS 2S 3 ~ + 2S ~

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2SbSl- + 6H+ ~ Sb2Ss ~ + 3H2S; SnS1- + 2H+ ~ SnS2 J,. + H 2S.

(C) Separation of Cd2+ and Cu2+ in Gr. IIA analysis: In an acidic condition, both Cd2+ and Cu 2+ are
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precipitated as sulfides. They are separated as follows:

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H
1 : 1 HN03 2 2 dil. NH 3 2
~ Cu ++ Cd + - -...
CuS + CdS - - -... ~ [Cu(NH 3)4]2+ + [Cd(NH 3)4] +; (ammine complexes)
~
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Solution
! (i)KCN
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(ii) H2S
Precipitate Filtrate of
of CdS [Cu(CN)i~"
In presence of excess CN-, Cu(ll) is reduced and complexed as follows:

2Cu 2+ +4CN- ~2Cu(CN)2~2CuCN+(CN)2 i
(unstable)
2CuCN + 6CN- ~ 2[Cu(CN)4]3- (cyanido complex).

Formation of stable [CU(CN)4]3- raises the formal reduction potential of the Cu(II)/Cu(l) couple to
allow the oxidation of (CN)- to (CN)2 (i.e. cyanogen gas)
Though the solubility product of CdS is much higher than that of CU2S, in presence of H 2S (in
ammoniacal medium), [Cd(CN)J 2- decomposes to give the precipitate of CdS. It happens so due to the
ApPLICATION OF COMPLEX COMPOUNDS 1661
higher stability of [CU(CN)4]3- where CN- is a Tt-acid ligand. The metal ~ ligand Tt-back bonding is
favoured for the lower oxidation state of metal centre. It makes the complex [CU(CN)4]3- more stable.
The detailed chemistry behind the separation of Cu(II) and Cd(II) has been discussed in Sees. 14.17.3
and 16.4.4 of Vol. 3.
(Note: Separation of Cu 2+ and Cd2+ through complexation as stated above is an example of masking).
(D) Identification of metal ions by following the characteristic colour of their complexes: Very
often, the complexes possess the characteristic colour. The coloured complex may be soluble or insoluble.
These complex formation reactions are used to identify the metal ions in qualitative analysis. In most
of the cases, the characteristic intense colour originates from the charge transfer (CT) transitions.
For the J> systems (e.g. Bell, Mg II , Pbll , CrVI , AIIII , Ti lv , etc.) and metal ions of high charge to radius
ratio (e.g. FellI, COllI, etc.), the ligand to metal CT (i.e. LMCT) bands give the intense colour. For the
ry
lower valent metal ions (e.g. Fell), the intense colour may arise from the MLCT bands. However, in
ra
some cases, (e.g. tetrahedral, square planar complexes), the colour may appear due to the d-d transitions.
ib
Some representative examples are given below.
yl
ICu
em
2
+ I
ch
(i) NH3 solution: [Cu(NH3)4]2+ (deep blue solution (d-d transition)):
(ii) Salicylaldoxime (LH) (in acetic acid solution):
e al
-)Q>
th
H O----H
\ HI:
e/
C==NOH " C==N 0I
~O dO~- ;:c( _
t.m
2
y- OH + Cu 2+ _
~I
:
N-C,
I H
+2H
+
e
(LH 2) H--O
er
[CU(L)2l
H
(Greenish yellow precipitate)

bisalicylaldoximatocopper(ll)
k
lic
(Note: Pd(II) gives a similar precipitate in acetic acid solution)

C
(iii) Benzoinoxime (cupron) : In neutral or ammoniacal solution, Cu(II) produces a green complex
that precipitates (probably in a polymeric form involving the N-O-Cu bridge).
Ph Ph
'"ICH-OH
C===N-OH
+ CUll - '"I CH-O
C===N
,>CU II +2H+
Ph/ Ph/ ' "o
(iv) Rubeanic acid (i.e. dithiooxamide):

NH
S C~
+ 2LH 2 ~ Cu
2
Cu +
I
S-----C~
~NH
2+ +
or, Cu + LH 2 ~ CuL + 2H
In fact, in weakly acidic or ammoniacal solution, Cu2+ gives a polymeric and extremely insoluble
black coloured complex. This reagent is the most sensitive reagent known for the detection of Cu 2+.
It can detect Cu 2+ at a concentration of 1 ppb. This method for detection of Cu2+ was developed by
ry
Prof. P. Ray, an Indian chemist.
ra
(Note: Under the similar condition, Co(ll) gives a brown insoluble complex and Ni(ll) gives a blue to
green insoluble complex).
ib
Pd(ll) and Pt(ll) also form the coloured complex with the semi-acid form of the ligand.
yl
em
H2
N--C=S
M =Pd, Pt
I
ch
M
S--C=NH
e al
th
e/
t.m
. NH2.
/
(i) Thiourea: S=C\. z.e. tu
e
NH 2
er
In dilute nitric acid solution, Bi(lll) forms a yellow coloured (LMCT) soluble complex,
H
[Bi(SC(NH 2)2)3]3+ i.e. [Bi(tu)3]3+.

(ii) KI solution: In acidic solution, Bi(lll) gives the black precipitate of BiI 3 which dissolves in
k
lic
presence of excess KI to give an orange coloured solution.

C
Bi 3+ + 31- ~ Bil 3 (J,);BiI 3 (s) + 1- ~[BiI4J (orange)
cf. Hg 2+ + 21- ~ Hgl 2 (red) J,; Hgl 2 (s) + 21- ~[HgI4j- (colourless).
I Fe2+ and Fe3+ I

(i) 2, 2'-bipyridine (bpy): Fe2+ion produces the deep red [Fe(bpY)1J 2+complex (MLCT band: metal
to vacant 1[* -MO of ligand).
(ii) o-phenanthroline (phen): In the reaction with phen, Fe 2+ also produces the deep red coloured
[Fe(phen)3]2+ complex (called ferroin).
Note: Fe 3+ ion produces the very light blue coloured complexes with the bpy or phen ligands. In
dilute solution, they appear almost colourless. If Fe3+ is reduced by NH 20H, HCI (i.e. hydroxyl
amine hydrochloride) to Fe 2+ then the reduced Fe2+ can be detected by using the bpy or phen
ligand.
[Fe(L-L)3]3+ (almost colourless) Reduction) [Fe(L-L)3]2+ (deep red coloured)

(L-L = bpy or phen)
(i) SCN- (thiocyanate): Fe3+ gives the red coloured complex [Fe(SCN)x ](x-3)-. This colour is due
to ligand to metal charge transfer (LMCT).
Nc:'f: • Organic acids like oxalic acid, tartaric acid, etc form the colourless complexes with Fe3+.
These complexes, e.g. [Fe(C 20 4)3 ]3-, [Fe(C4H60 2)3 ]3-, etc. are colourless and such organic
chelating ligands (having the O-donors) interfere with the complexation by SCN-.
• Fluorides can discharge the red colour of [Fe(SCN)x](x-3)- due to replacement of SCN- by
P- leading to the colourless [FeF613- complex. In fact, Fe(III) being hard prefers P- compared
to SCN-.
ry
• Hg2+ being softer than Fe3+ can snatch away the Fe(III)-bound soft SCN-'ligand to discharge
ra
the red colour. In fact, Hg(ll) forms the more stable [Hg(SCN)4]2- complex.
(ii) Ferron or 7-iodo-8-hydroxyquinoline-5-sulfonic acid:
ib
yl
S03H
em
ch
Fe
al
HO
e
th
The tris-chelate is green (LMCT) coloured.

(Note: Fe2+ does not react with ferroin under the condition).
e/
(iii) With tiron (i.e. disodium 1,2 dihydroxybenzene-3,5-disulfonate).

t.m
-OaS1 6 ( 0H
-03S~0
~ Fe ~.~ 0
e
IOH + 3+ _ _ ) F e 111/3 + 2H+

er
o
H
so; SO;
k
lic
(Red complex, LMCT)

Note: 1: 1 Complex - blue; 1:2 Complex - violet; 1:3 Complex - red.
C
(iv) With hydroxamic acid, Fe(lll) also gives the characteristic colour (LMCT).
R-C=O
I ""Fell~3
HN-O/
(v) Cupferron (i.e. ammonium salt of nitrosophenylhydroxylamine)
@-j-O--NH;
Fe
N=O
(Cupferron)
In aqueous HCI solution, Fe 3+ gives a reddish-brown (LMCT) precipitate of the complex,

[Fe{C6HsN(NO)O}3l
Note: The ligand was initially used for detection of iron and copper and this is why the ligand was
named so.
(vi) Sulfosalicylic acid: Fe(II) does not give any colouration but Fe(III) gives the violet colouration.
ry
(vii) DmgH2 : In ammoniacal solution, Fe(II) gives the red coloured complex [Fe(dmgH)3]- but Fe(III)
ra
does not respond to this test (cf NiH + dmgH 2). \
ib
yl
em
(i) Alizarin and Alizarin-S: ch
o OH o OH
al
OH OH
e
th
e/
o o
t.m
(Alizarin) (Alizarin-S i.e. sodium salt of alizarin sulfonate)

e
er
AI 111/3 /A\,H)x(OH 2)6-2_X

/ \0
H
o o 0
k
OH OH
lic
C
o o
AI-Complex 1:3 AI-Alizarin Complex 1: 1
In a slightly alkaline condi~ion, A1 3+ forms a slightly soluble red coloured (LMCT) complex
(called aluminium lake) with the titled ligands.
Note: Zirconium(IV) (i.e. Zr02+, zirconyl cation) also forms a similar complex of red-violet
colour and the complex is more stable than the AI(III)-complex. In fact, the Zr(IV)-complex is
stable even in a strongly acidic condition while the corresponding AI(III)-complex is decom-
posed in an acidic medium. However, the Zr(IV)-complex is decomposed by P- giving rise to the
more stable [ZrF6 ]2- complex (cf. hard-hard matching) which is colourless.
(ii) Aluminon: This is the ammonium salt of aurine tricarboxylic acid. It gives a red coloured
(LMCT) lake of aluminium in a weakly alkaline solution of AI(III)
HO
HO CO;NH;
ry
(Aluminon)
ra
ib
~
CO;NH;
yl
HO
em
o C
ch
e al
th
e/
HO CO;NH;
t.m
AI(III)-Complex
(1 : 1 Complex)
e
It may form also the tris-complex i.e. 1:3 complex

er
H
k
lic
(i) NH4SCN: C0 2+ forms the blue coloured (d-d transition; high E-value in the tetrahedral complex)
C
complex, [CO(SCN)4]2- which can be extracted in amyl alcohol layer as H 2[Co(SCN)4]

(Note: Interference by Fe3+ can be removed by using the masking reagent P-).
(ii) KN02 solution: C0 2+ gives the yellow precipitate of K3 [Co(N02)6].3H20. The reaction is carried
out in a weakly acidic condition (say acetic acid medium). NOi oxidizes C02+ to C03+ and NOi
is itself reduced to NO. Then C0 3+ undergoes complexation with the excess ligand NOi.
Co 2+ N~~~~; ) Co 3+ excess KN0

2
) K 3 [ Co (N0 2 )6 ]
(iii) Rubeanic acid: In an ammoniacal medium, with the ligand, Co(II) forms a yellow-brown com-
plex which is insoluble.
(iv) a-Nitroso-p-naphthol: It remains in a tautomeric equilibrium. Its tautomeric oxime form makes
an inner complex of Co(III). The reagent can itself act as an oxidizing agent to oxidise Co(Il) to
Co(IIl) because it is an orthoquinoid compound and a derivative of HN0 2• But it is convenient
to oxidise Co(II) to Co(III) before applying the reagent.
NO 0~N--COIll/3
OH
I
o
co3+
---.
-H+
Of,
(Note: In presence of the title chelating ligand, oxidation of Co(ll) to Co(lll) by air is also
possible).
I VV i.e. Vanadate I
ry
(i) "202: Vanadate in aqueous sulfuric acid solution reacts with H 20 2 to give a red-brown complex
ra
which is a peroxido-complex. In presence of excess H20 2, the peroxido complex gives the yellow
ib
orthoperoxidovanadic acid. The colour of the peroxido complexes is due to the ligand
yl
(i.e. 0i-) to metal (i.e. VV) charge transfer transition, i.e. LMCT transition. This colour is not
em
discharged by P- and PO~- (cf. difference from Ti(IV».
ch
Vanadate (in dil. H2S04) _H_0_ ~.,~ (v<ol
22
)2(S04)3
al
i.e. VV
e
th
(Red) (Yellow)
e/
[ V(112 -O~- )]2(S04 )3 (wine red)+ 6H20~(=H=20=2~, 3H 2S0 4 + 2V (112-o~- )(OH)3 (yellow)
t.m
H S0 2 4
(peroxidovanadium sUlfate) (orthoperoxidovanadic acid)
In the said peroxido complexes, peroxide exists as 112-01-.

e
The wine red complex (in acidic condition) becomes yellow on addition of alkali due to the forma-
er
tion of dioxidodiperoxidovanadate(V) ion.

H
V(l1 z-O;-)3+ (wine red) + HzO z +60H-~V(O)z(l1Z-O;-)~- (yellow)+4H zO

k
lic
The reaction is reversible, i. e. on acidification, the wine red colour reappears.

Note: • Regarding the composition of the species produced in the given reactions, there is a
C
difference in opinion among the workers. However, it has been proved that nature ofthe product species
depends on the concentration ofH 20 2 and pH ofthe solution. It is suggested that in the acidic solution,
the red-brown (i.e. wine red) species is [V(0)(0"2)4(TJ2~-)]+ (an oxidoperoxido complex).
With the increase of alkalinity and concentration of H 20 2, the species like [V(0)(OH 2)2(02)2]-,
[V(0)2(OH2)(02)2]3-, [V(0)(02)3]3-, [V(02)4]3-(in all cases, peroxide as 112-0~) start to appear gradually.
From the strong alkaline solution, the blue-violet crystals of M 3[V(02)4]' nH20 (M = Li, Na, K, etc.)
are isolated.
• It may be noted that CrO~- on being treated with an acidic solution of H 20 2 produces the blue
coloured species CrOs i.e. [Crv1 (0)(112_0i-)2] which can be stabilised as erOs' py to be extracted in
ether. But in an alkaline solution of H20 2, Cr(VI) is reduced to Cr(V) which is stabilised as
[CrV(TJ2- 01-)4]3- (a red paramagnetic compound).
• The reaction of vanadate with an acidic solution of H20 2 probably occurs as follows:
VO) + H20 ~ H2V0.i ; H2V0.i + H+ ~ H3V04; H3V04 + H+ ~ vat + 2H 20
vot + H20 2 ~ V(0)(112_0~1+ (wine red) + H20; (acidic solution).

VO(02)+ actually exists as [V(O)(OH2)4(Tl 2-Oi-)]+ which may react with H 20 2 in presence of OH-
to give the different species.
[V(O)(OH 2)4 (02)r (red) + H 20 2 + 20H- ;=[V(O)(OH 2h (02hJ (yellow) + 4H 20
[V(O)(OH 2h (02)2T +20H- ;=[V(O)2(OH 2)(02ht (yellow) + 2H 20
[V(O)(OH 2h(02)2T +H 20 2 +20H- ;=[V(O)(02hJ- +4H 20
[V(O)(02)3]3- + H 20 2 ;=[V(02)4t i.e. [ V(T{~~- )4t (blue) + H 20
ry
ra
(cf. No redox reaction)
ib
yl
Peroxido Complexes: Reactions of Cr(VI), V(V) and Ti(IV) with H2 0 2
em
• Cr(VI): In aqueous solution, it remains in a pH dependent equilibrium between CrO~- and
Cr20~- (i.e. chromate and dichromate).
ch
crO~- + H+ ~HCr04; 2HCrO:; ~Cr20~- + H 20
al
,-
e
H
th
, o~/""'/
e/
2 O=Cr-O + 2H+ ~ 2 O=Cr-OH ~ O=Cr Cr=O

t.m
-I
(Td)
-/ -/"'" / "0 o
e
H
er
U
H
(Td) /0" (Td)

k
O-Cr Cr-O- + H20

lic
/11o 1I~0
C
0
(i) When Cr(VI) is treated with an acidified solution of 8 2°2' it gives a deep blue-violet colour due
to the formation of CrOs i.e. [CrvI(0)(112_022-)2] which is unstable and it decomposes with the evolu-
tion of 02. However, CrOs can be stabilized as the adduct of pyridine i.e. [Cr(0)(02)2(PY)] which can
be extracted in ether. Bipyridine and phenanthroline can also stabilize CrOs.
Cr ( VI ) acidified H"I02
°
. . ) crO s i.e. [ Cr ( ) (112 -0 2 ) ] (
2- 2 a complex of Cr VI )
(Blue, unstable)
o
1'~r/lrl]LO:- 1 ether + py
0/ "0
[CrOJ [ Cr VI( 0)(T1 2-o~- )2 (py)]
(Blue, stable, TIP = 0.5 8M)
o-------[~~
~cr--o
o
Vi""N,/
~
I
bpy or phen
(Pentagonal bipyramid)
ry
crOs in neutral or faintly acidic solution gives the explosive blue-violet species
ra
[CrvI (O)(OH)(1l2_0i-)2]- (diamagnetic or small TIP).
ib
(ii) When Cr(VI) is treated with an alkaline solution Qf H 20 2, Cr(VI) is reduced to Cr(V) and it
yl
produces the stable red paramagnetic species, tetraperoxidochromate(V) i.e. [CrV(1l2-0i-)4]3-
Cr(VI) alkaline H 20 2 >[CrV( l'\2_0~- t ch r-

em
(a complex of Cr V)
(red, paramagnetic, dodecahedral structure, J..l = 1.8 B.M.)
al
Here H20 2 acts as a both reducing agent (cf. CrVI ~ CrY) and as a complexing agent.
(iii) When the red complex ion, [Cr(112-02)4]3- is warmed (50 0 C) with an aqueous solution of NH 3,
e
th
a red brown complex of CrIV i.e. [Cr IV (NH 3)3(1l2_0 2)2] separates out on cooling the solution. Here,
Cr(V) is reduced to Cr(IV). Previously, it was wrongly interpreted as a superoxido complex of Cr(II).
e/
t.m
e
0~7°\~
er
H
/cr--7
k
[Cr(02)4r- (red)----...d~w-IU:-~-.~..,.-)--+)[ Cr(NH 3)3 (0 2)2];

lic
(a complex of Cr IV ,
C
2.28
red brown, J..l = BM)
0----____ - - - -\- - - - .NH"
3
NH 3
(Pentagonal bipyramid)
(iv) The peroxido complex of Cr(V) can be converted into the Cr(VI) complex by adjusting the pH.
Here the coordinated 0i- causes the oxidation of Cr(V) to Cr(VI).
[ Cr V(l'\2-o~-
(Red-brown)
tr- + 2H+ + H 20 =[Cr VI(O)(OH)~l'\2-o~-
(Blue-Violet)
)J- + %H20 2
(v) It is evident that the nature of reaction of H 20 2 with Cr(VI) is highly pH dependent. In acidic
condition, the unstable Cr(VI) compound (that may be stabilized as CrOs.py, CrOs.bpy) readily under-
goes redox decomposition producing Cr(III) and 02'
Cro~- +2H zOz +2H+ ~Cr(O)(T\z-Oz)z i.e. Cr0 5 (blue)+3H zO

4CrO s + 12H+ ~ 4Cr 3+ + 6H 20 + 702
The overall red-ox process (i.e. reduction of chromate by H 20 2) is:
2CrO~- + 3H 20 2 + 10H+ ~ 2Cr 3+ + 302 + 8H 20
[c/. EO (CrzO~-/2Cr3+) = +1.38 V; EO (Oz/HzO z ) = +0.695 V]

It may be mentioned that H20 2 in alkaline condition can oxidise Cr(III) to Cr(VI).
Cr(OH)3(S)+OH- ~Cr(OH)~
ry
2Cr(OH)~ +3H 20 2 +20H- boiling) 2CrO~- +8H 20
ra
[ct. EO (CrO~- /Cr(OHh) = -0.11 V; EO (CrO~- / Cr(OH)~) = -0.72 V;
ib
yl
EO (H0 2/20H-) = +0.87 V]
em
In the strong alkaline condition, the intermediate state, i. e. Cr(V), may be stabilized as
[CrV (1l2-0i-)4]3-. But under the boiling condition, the peroxido complex being thermally unstable,
ch
decomposes and chromium is converted into chromate, i.e. Cr042-.
• Vanadate(V): The nature and composition of the peroxide complex depends on pH.
e al
(i) V(V) 2 2
>[ V(O)(T\z-O~-)(OHz)4r (Red);(Not decomposed by F-)
th
acidicH 0
e/
(ii) V (V) alkaline H 20 2 ) Depending on the concentration of OH- and H 20 2, different species like
t.m
[V(0)(OH2)2(02)2]- (yellow), [V(0)2(OH2)(02)2]3- (yellow), [V(O)(02)3]3-, [V(02)4]3- (blue) exist

(in all case, peroxide coordinates as 112-0i-). On acidification, these species are converted into the red
e
species of acidic solution, i.e. the pH dependant changes are reversible.

er
• Ti(IV): In an acidic solution of H 20 2, it forms the orange-yellow coloured species,

H
[Ti(OH)(OH 2)x(1l2-0i-)]+ which decomposes in presence of P- giving rise to the more stable complex
k
[TiF6]2- (hard-hard matching). However, the orange-yellow colour of the peroxido complex can be
lic
restored by the addition of soluble Be(II)-salts or digesting with H3B03 because of the formation of
C
more stable [BeF412- complex and volatile BF3 gas.

[Ti(OH)(OH2)x(1l2-0i-)]+ (orange-yellow) + 6P- + 3H+ ~ [TiF6]2- (colourless) + H 20 2 + (x + 1)H20
2 [TiF6 J2- + 3Be 2+ ~3 [BeF4 j- (colourless) + 2Ti 4+

[TiF6 J2- +2H 3B0 3 +6H+ ~2BF3 (i) + Ti 4 + +6H 20.
Ti(aq)4+ hydrolyses to give Ti(O)(aq)2+ which undergoes complexation with H 20 2 to give the
characteristic orange-yellow colour.
I Be2+ I
(i) Quinalizarin: A slightly alkaline solution of Be(II) gives a blue-violet colour (LMCT band) or
precipitate with the chelating ligand. In the complex (i.e. basic beryllium salt), there are two
Be-centres per ligand.
HO OH
OH
(Quinalizarin)
ry
ra
OH /0
ib
(H 20)(HO)Be"
yl
° 0
"
em
/Be(OH)(OH 2)
°
ch
OH
al
c.......- _ __ __----OH----J
e
V
th
Probable Structures of the Be(II)-complex

e/
t.m
e
er
(i) Dithizone (i.e. diphenylthiocarbazone): It gives a red (LMCT) precipitate of the Pb(II)-complex
(inner complex).
H
k
lic
H H
N-N-Ph
C
2S=C
/ ~
+ Pb2+ _(-2_H_+)......J..
"'-N=N-Ph
The ligand remains in a tautomeric equilibrium and it may be also possible for coordination by
the N,S-donor sites of the ligand.
H H H
Ph-N-N Ph-N-N
~-SH "'-c=s
Ph-N=N/ Ph-N=N/
(Green)
/Ph /Ph
HN-N N=N/
I "'-Pbll/2 or I
C-S/
"'-Pb ll/2
C=S/
Ph-N-N/
H #
Ph-N=N/
(Red) (Red)
Note: Diphenylcarbazone is structurally related with diphenylthiocarbazone. Diphenylcarbazone

bears the o=c( group instead of the S=C( group. Diphenylcarbazone can be reduced
ry
to diphenylcarbazide (i.e. -N = N- is converted into -NH-NH - ). Both diphenylcarbazide
ra
and diphenylcarbazone may undergo complexation with Hg(I) and Hg(II) to give the characteristic
colour. The structures of the complexes may be formulated as in the case of Pb(II) with
ib
diphenylthiocarbazone.
yl
em
I Molybdate I ch
(i) SnCI2 + KSCN: SnCl2 reduces MovI in dB. HCI solution to MOIlI which gives the red coloured
al
complex [Mo(SCN)6]3-.
e
Mo VI ~:~~I)) Mo Ill SCN-) [Mo(SCN)6]3- (red)

th
e/
(Note: Mo vI is also reduced to Mov to some extent to generate [Mo(SCN)s] which is also red.)
t.m
I Ni2+ I
e
er
(i) Dimethylglyoxime (dmgH2): In an ammoniacal solution, Ni2+ forms a bright red complex with
the ligand.
H
k
""H ...
lic
0"" ......0
I I
C
Me-C=N, /N=C-Me
------i.~ I /Ni" I + 2H+
Me-C=N N=C-Me
I
0... ..0
I
"'H"
(Red Complex)
Note: Fe(II) also gives a red coloured complex with the ligand. This is why, Fe(II) interferes with
the test of Ni(II) by this chelating ligand. To avoid the interference by iron, it is to be oxidized to
Fe(III) and then the masking agents like tartarate or fluoride is to be added. Fe(III) does not form
any complex with dmgH 2 under the experimental condition but it gives the precipitate of Fe(OH)3
in the ammoniacal medium. This is why, it is to be masked.
~
°
(i) 8 2 2 : In an aqueous sulfuric acid solution, Ti(IV) forms a peroxido complex of orange-yellow
colour. The colour appears due to the ligand (i.e. Oi-) to metal (i.e. Ti IV ) charge transfer band (i.e.
LMCTband).
Because of the high charge/radius ratio of Ti(IV), the species [Ti(OH2)6]4+ is extensively hydro-
lysed to produce the polymeric forms having the zigzag - Ti-O-Ti-O- chain. In acidic
condition, the dilute solution of Ti(IV) may have the predominant species Ti(0)(aq)2+ (titanyl
cation) or Ti(OH)2(aq)2+.
Ti (IV) H 20. H+ )[ Ti (OH) (OH 2) x (11 2-O~- )r (orange~ yellow)
ry
ra
This colour fonnation reaction may be also utilised for 8 20 2 estimation. The colour is dis-
charged by fluorides due to the formation of more stable [TiF6]2- complex. Phosphate can also
ib
discharge the colour (cf. hard-hard interaction, 8SAB theory). It may be noted that fluoride
yl
and phosphate cannot discharge the colour of the peroxido complex of V(V).
em
Note: There is a difference in opinion among the workers regarding the composition of
[Ti(OH)(OH2t(112_0~-)]+,
ch
the peroxido-complex of Ti(IV). Different species like
al
[ Ti(OH 2t (112_0~- )J+, [ Ti(112_0~- )(112-S04)zJ2-, etc. have been proposed. The composition
e
(112-0~-)r.
th
depends on pH. Probably at pH < 1, the predominant species is [ Ti (OH) (OH 2t

e/
At higher pH, the polymeric species like [(11 2 -O~- )(aq)Ti - 0 - Ti (aq) (11 2 -O~-) r+ may exist.
t.m
This may give the yellow precipitate of Ti (0)(11 2 -0 2 ). nH 2 0 i.e. Ti0 3 . nH 20.
e
(ii) Chromotropic acid: In an aqueous sulfuric acid media, Ti(IV) fonns a red coloured (LMCT)
er
complex with the ligand.

H
5- 2-
SO;
k
lic
OH
C
Ti
OH
H03S so;
(Chromotropic acid)
"-""--------V ------)
Probable complexes of Ti(IV)
I Zirconium (IV) I
(i) a-Nitroso-~-naphthol: The ligand forms a green-yellow complex with Zr02+. The ligating
behaviour of the ligand has been .pointed out in the case of Co(lll) complex.
(ii) p-Nitroso-a-naphthol: It gives a red complex with zr0 2+.
OH O--ZrO/2
NOH 1
-ZrQ2+
I
N
2
~o or,
(iii) Alizarin: The ligand forms a red complex with Zr(IV) even in a strongly acidic condition. The
colour is discharged in presence of P- due to the formation of more stable complex [ZrF6] 2-.
ry
Ligating behaviour of the ligand has been shown in its AI(III)-complex. It may be noted that the
ra
corresponding AI(III)-complex is stable only in neutral or slightly alkaline medium only. .
ib
(iv) Phenylarsonic acid andp-dimethylaminobenzene-azo-phenylarsonic acid: Phenylarsonic acid
yl
gives a white precipitate in reaction with Zr(IV) in acidic condition but the second reagent is more
em
selective for Zr(IV). It gives a brown precipitate of Zr(IV) complex.
ch
e al
th
(brown precipitate)
e/
t.m
I Brown Ring Test I

e
In the detection of NOi, the ring test involves the brown ring complex, [Fe(NO)(H0 2)5]2+. Previously,
er
it was considered as a complex of Fe(l) with NO+ ligand. Recent evidences support it as a complex of
H
Fe(III) with NO- as a ligand (see Sec. 9.6 and Chapter 16, Vol. 3).
k
11.1.2 Separation of Metal Ions through Solvent Extraction

lic
Type-I: If the complex is uncharged, then the complexes can be extracted in organic solvents. Thus the
C
inner complexes can be extracted in organic solvents. The representative examples are:
[Ni(dmgH)J ;
H3C,
HC/
3
" c-=o
~
C--O
~CU1l/2 ;
@-I
0
-" N-O
N-O/
Fe 111/3
W Fe-O
3
i. e. ferric oxinate
i.e. [Cu(acac)2] i.e. ferric cupferrate
Type-II: Sometimes, the complex species is itself charged but it can form ion-pair which can be
extracted in organic solvents. Some representative examples of such extractable ion pairs are:
{[Cu(phen)2]2+.2CI04-}; {H+. [FeCI4]-}; H2[Co(SCN)4] i.e. {2H+ . [CO(SCN)4]2-}
CH 3 X- (R =H, neocuproin
CH 3 R = Ph, bathocuproin)
ry
R R
ra
Note: Neocuproin or bathocuproin is specific for CUI. In presence of the reducing agent like hydroxy-
ib
lamine hydrochloride, CUll is reduced to CUI which undergoes complexation with the said ligands.
yl
Depending upon the distribution coefficient of the extractable species in the organic phase, the species
em
can be separated.
Chelating agents commonly used in solvent extraction: These are:
ch
nH
al
H
e
H3C " /C~ /CH 3

,~~ /C 0-.. /CF3
th
C ":c S C ":c
II
e/
o
I
OH II I
t.m
o OH
(acacH)
(Hexafluoroacetylacetone) (TTA i. e. theonyltrifluoro-
i. e. acetylacetone acetylacetone)
e
er
H
Ha" . /CH3
©J9J #C-C~
k
N~ ~N
lic
I
C
OH
OH
I
OH
(oxinH)
(a-hydroxyquinoline i.e. oxine) Dimethylglyoxime
(dmgH 2 )
N=O N-OH
HSC2 " . /tS
/C-C~
OH
Na+
HSC2 S
(Sodium diethyldithiocarbamate)
(a-Nitroso-(3-naphthol)
Extracting Solvents: Benzene, chloroform, methylene dichloride, tri-n-butyl phosphate (n-C 4H 9 )3P04,
etc.
• The chelates of AI(III), Be(II), Cr(III), etc. formed with the complexing ligands like acetylacetone,
trifluoroacetylacetone, hexfluoroacetylacetone are volatile. Such chelates may be extracted in organic
solvents like benzene and then they can be analyzed by gas chromatography.
• Lead content in blood can be determined by using the principle of solvent extraction. Dithizone
(i.e. diphenylthiocarbazone) forms a red coloured inner complex with Pb 2+ and this complex can be
extracted into methylene chloride-solvent and analyzed spectrophotometrically at 540 nm.
• Separation of Fe(III) and AI(III) through solvent extraction using oxine, i.e. 8-hydroxy-
quinoline as the complexing ligand: Fe(III) forms a more stable complex than AI(III). In fact, in a
slightly acidic condition, complexation by Fe(III) with oxine is quantitative while the complexation by
Al(III) becomes quantitative in a slightly alkaline condition.
~
~ W
ry
M3+ + + H+, M=AI, Fe
ra
ib
OH .M..--O
yl
3
em
The Fe(III)-complex i.e. [Fe(oxin)3] is readily soluble in chloroform. If the solution containing
Fe(III) and AI(III) is treated with an excess amount of oxine at pH close to 3.0, then the Fe(III)-
ch
complex can be extracted in chloroform. Under this condition, Al(III) remains in aqueous phase. After
al
the separation of Fe(III), from the aqueous phase, [AI(oxin)3] can be quantitatively precipitated out in
a slightly ammoniacal medium.
e
th
[Fe(oxin)3l organic phase

(Amax = 470 nm)
e/
t.m
(i) excess oxinH

Fe(lIl) +AI(III)
(ii) pH adjusted to ca. 3.0
(iii) extraction in CHCI 3
e
er
1
Aqueous phase containing AI(III)
H
Made slightly ammoniacal

k
lic
[AI(oxin)3l (precipitated)
C
• Separation of Co(II) and Ni(II) through solvent extraction by using acetylacetone: Neither
Co(II) nor Ni(II) can form the extractable chelate with acac, but Co(III) forms the inner complex
[Co(acac)3] which is extractable. Thus, if Co(II) is oxidized to Co(III) then it can be separated from Ni(II).
• Separation of Zr(IV) and Hf(IV): Both Zr(IV) and Hf(IV) form the insoluble complexes with the
ligand theonyltrifluoroacetylacetone (TTA). The chelates have different solubilities in benzene. The
Zr(IV) chelate is about 20 times more soluble in benzene than the corresponding Hf(IV)-chelate.
Successive extraction of the two metal ions in benzene in presence of TTA gives a good separation of
Zr(IV) and Hf(IV).
(TIA, enol form).

11.1.3 Complexation in Spectrophotometric Analysis

Metal complexes are very often identified by their characteristic colours. For the spectrophotometric
determination of metal ions, the complexes having very high extinction coefficients are generally
selected. The d-d transitions are Laporte forbidden and the molar extinction coefficients are relatively
small. The colour due to the charge transfer bands is generally more intense and such transitions are
very often utilized for the spectrophotometric analysis. The basic requirements are:
(i) High molar extinction coefficient; (ii) Stable complex; (iii) Beer-Lambert law applicable over a
sufficient range of concentration of the complex.
If the coloured complex can be extracted quantitatively in organic solvents, then the spectrophoto-
metric analysis is carried out in organic solvent. If the complex is charged, then it is kept in aqueous
phase for spectrophotometric analysis. Some representative examples are· given below:
ry
ra
Metal ion Ligand Colour of the Complex
ib
Fe2+ phen red colour
yl
Cu 2+ NH 3 blue
em
Ni 2+ dmgH 2 rosy red
Fe 3+ SCN- red
ch
A13+ aluminon red
al
Bi3+ thiourea yellow
e
*Cr(VI) diphenylcarbazide violet

th
Ti(IV) H 20 2 orange red

e/
Fe3+ 5-sulfosalicylic acid red

t.m
**Zr(IV) alizarin, SPADNS red

Pb2+ dithizone pink
e
* It is suggested that Cr(VI) in acidic condition oxidizes diphenylcarbazide to diphenylcarbazone (colourless) and
er
finally to diphenylcarbadiazone.
H
NH---NH---Ph NH---NH---Ph /NH===NH---Ph

k
/ CrV1 , H+ / CrV1 , H+
lic
O===C ~ O=C .. O=C

"'NH---NH---Ph "'N=N---Ph "'N===N---Ph
C
(Dlphenylcarbazide) (Diphenylcarbazone) (Diphenylcarbadiazone)
In this process, it is believed that CrV1 is reduced to CrI (not to Crll ) which is stabilized by complexation
with the enol form of diphenylcarbazone. This complex of CrI gives the red-violet complex (an inner
complex).
,l'N-7--- Ph
"'N= ~---Ph
C ---0--- Cr(OH 2 )3 (Red-violet, inner complex of Crt').
However, the intense colour due to the said CrI-complex can be reasonably questioned because
Cr(II) is unstable in an aerobic condition. Moreover, the intense colour cannot be rationalised in terms
of the LMCT bands of a complex of a such low-valent metal centre (i.e. CrII) and the intense colour
is not surely due to the d-d transition in Cr(II) (If system). Thus it has been argued that during the
reduction of Cr(VI) by the ligand, the intermediate labile state like Cr(V) or Cr(N) may be stabilised
through complexation and in such complexes, the LMCT bands are probably responsible for the intense
colour. Complexation of Cr(III) (during the course of reduction of Cr(VI)) may also occur. Complexation
of Cr(VI) with the oxidised form 'Jf the ligand cannot be also ruled out.
OH OH
N=N-@-SO; Na+
Na+ -°38 80; Na +
(SPADNS i. e. 1, 8-dihydroxy-2-para-sulfophenylazo
ry
-naphthalene-3, 6-disulfonate)
ra
** In an acidic condition both alizarin and SPADNS produce the orange-red complex with Zr(IV).
ib
P- can discharge the colour due to the formation of the more stable [ZrF6]2- (colourless) complex. This
yl
property can be utilized for the spectrophotometric determination of fluoride in water.
em
11.1.4 Complexation in Gravimetric Analysis
For the quantitative precipitation of metal ions, both organic and inorganic ligands (e.g. OH-, CI-, etc.)
ch
may be used. For estimation of platinum, Ag2[PtCI6] precipitate may be used; for estimation of iron, it
al
may be precipitated as Fe(OH)3 which is subsequently converted into, Fe203. But compared to such
e
inorganic ligands as precipitants, organic ligands as the precipitants in gravimetric analysis are preferred.
th
This can be realized from the following discussions.

e/
Insoluble inner complexes (i.e. electrically neutral) can be used for the gravimetric analysis. The
advantages in such gravimetric analysis involving the organic ligands are given below.
t.m
(i) The inner complexes having the organic chelating ligands can precipitate the metal ion
quantitatively.
e
(ii) If the molecular mass of the organic chelating agent is high, then the error in the process is less.
er
In fact, high molecular mass of the precipitants compared to the atomic mass of the metal ion to
H
be estimated gives the high accuracy of the process.

k
(iii) The particle size of the precipitate of the complex is generally large. Thus the precipitate can be
lic
filtered and washed easily.

C
(iv) The precipitate bears the organic moieties of the chelating agents. Thus, the precipitate can be
dried easily because the precipitate possesses a lesser tendency to hold water.
(Note: Sometimes, the complex may undergo decomposition at the drying temperature (12Q-150°C)
and such complexes are ignited to produce the corresponding metal oxide. Complexes of cupferron (i.e.
ammonium salt of N-nitroso-N-phenylhydroxylamine) are thermally unstable.
Metal ion to be Chelating agent Complex precipitated

estimated
dmgH2, (in ammoniacal medium) [Ni(dmgHhl (rose red)

*[Pd(dmgH)2l (yellow)
oxinH, (in slightly ammoniacal solution), [AI(oxin)3l (yellow)
bphaH (pH 3.5 - 6.5) [AI(bpha)3l
(Contd.)
(Contd.)
Metal ion to be Chelating agent Complex precipitated
estimated
quinaldic acid (in dil. H2S04 media), bis-complex (dull green)
salicylaldoxime (in dil. acetic acid), bis-complex (green)
cupron (in dilute ammoniacal solution), his-complex (green)
bphaH (pH range 3.5-5.5) [Cu(bphahl
bphaH (pH range 3-5.5) [Fe(bpha)3l
oxinH [Zn(oxinhl
* [Pd(dmgH)2] is insoluble in dilute HCI while [Ni(dmgH)2] is soluble in an acidic condition. This
difference is due to the higher stability of the Pd(II) complex.
ry
ra
Common chelating agents used in Gravimetric Analysis:
ib
0 ;
yl
(i) OxioR: r()rAlN pH range: A1 3+(5-9.8), Fe 3+(3-9), Ni 2+(4.6-1O), Zn 2+(4.5-1O),
. . .'
. N'~
em
Mg 2+(8-11),
OH
ch
The different metal ions form the oxinate complexes of different stabilities and the complexation
al
occurs quantitatively for different metal ions at different pH values. For example, Fe (III) can complex
e
with oxine in a slightly acidic condition (pH ca. 3.0) while Al (III) complexes quantitatively in a slightly
th
ammoniacal medium. Thus by adjusting the pH, the metals can be separated. The separation becomes
e/
more effective in presence of suitable masking agents. The metal oxinates can be washed and dried for
the gravimetric analysis. The oxinates may be also be dissolved in dil. HCl. liberating 8-hydroxyqui-
t.m
noline which can be titrated with the standard KBr03 solution in presence of excess KBr.
Br03- + 5Br- + 6H+ ~ 3Br2 + 3H20.
e
C9H70N (i.e. oxinH) + 2Br2 ~ C9HsBr20N + 2Br- + 2H+

er
(Bromination of oxine)
H
k
r()r(Y
lic
(ii) Quinaldic acid: ,yO

~YAc
C
I
OH
2
OH
H /
C=N
(iii) Salicylaldoxime:
©C;C~II
o
Ph-C=O
(iv) N-benzoyl-N-phenylhydroxylamine (bphaH): I
Ph-N-OH
(v) Dioximes:
U
o C=N
/OH
Ryy-N-OH
I
~N-OH
U
o C=N"
OH
R = H, CH 3
(Dimethylglyoxime) (a-Furildioxime) R =H : Cyclohexanedione
- 1 2 -dioxime (nioxime)
I
R =Me : 4-Methyl-cyclohexanedione
ry
- 112 -dioxime (4-Me-nioxime)
ra
Dioximes are mainly used for Ni(II), Pd(II). In presence of the masking agent edta, selectivity of
ib
the dioxime may be increased.
yl
(vi) Cupferron and neocupferron:
em
ch
e al
th
Cupferron Neocupferron
e/
(ammonium salt of (ammonium salt of

N-nitroso-N-phenylhydoxylamine) N-nitroso-N-naphthylhydroxylamine)
t.m
The reagent can precipitate Fe(lll) (in a strong mineral acid solution) and Cu(ll) (in a weakly
acidic solution). It explains the name. Besides iron and copper, many other metal ions can be
e
er
precipitated by these chelating ligands.

H
(vii) a-Benzoinoxime (Cupron): Ph-CH-OH
I
k
lic
Ph-CH=N-OH
C
(viii) Arsenic acids: R-AsO(OH)2
Used for precipitating the quadrivalent metal ions like SnIV , ThIV , Ti IV and Zrv in presence of
mineral acids.
11.1.5 Masking or Sequestring Agents in Analytical Chemistry

Masking agent: Many desired reactions are very much unselective. It needs the removal of the inter-
fering substances which can be done without the physical separation, i. e. the interfering substances are
chemically transformed into the species which cannot participate in the desired reaction. This process
of removal of interference is described as masking which generally involves the complexation. The
ligands used for this purpose are called the masking or sequestering agents.
Demasking: In this process, the masked substance can be brought back to its original form.
The masking or sequestering agent keeps the interfering metal ions as the soluble complexes that
cannot participate in the desired reaction. The masking agents must satisfy the following conditions.
(i) The complexes of sequestering agents must be soluble. (ii) The sequestering agent must form the
more stable complexes with the interfering metal ions than the ligands in the desired precipitating or
complex forming reactions, i. e. the masked complex will not break in presence of other ligands
involved in the desired reaction.
The following examples illustrate the masking process.
(i) Volumetric titration by edta: The chelating ligand, edta, is very much unselective. At a particu-
lar condition, it can complex with different metal ions. The relatively softer metal ions like
Cd(II), Hg(II), Zn(II), Fe(II), Cul(II), Ni(II), Ag(I), etc. can be strongly complexed with the
ligands like CN- and their cyanido complexes cannot react with edta. On the other hand, the hard
ry
metal ions like Ca2+, Mg 2+, Mn 2+ etc. do not form any strong cC'mplex with CN- but with edta.
ra
Thus the softer metal ions can be masked by CN- to allow edta to complex selectively with
the hard metal centres. Without CN-, the ligand edta will undergo complexation with the both
ib
soft and hard metal ions.
yl
• For example, the metal ions in a solution containing Zn2+, Cu2+ and Mg2+can be estimated
em
by edta titration by using the suitable masking agent.
Step-I: To the solution, an excess amount of standard edta solution is to be added. The uncomplexed
ch
edta is to be back titrated with the standard Mg(II)-solution by using EBT indicator. It will give
al
the measure of total metal content.
Step-II: A portion of the solution is treated with an excess amount of KCN solution. It will
e
th
produce [Zn(CN)4]2- and [CU(CN)4]3- and Mg(ll) will remain uncomplexed that can be titrated
with edta solution. This will give the measure of Mg(ll) content only.
e/
Step-III: The titrated solution obtained at Step-II, is treated with formaldehyde-acetic acid solu-
t.m
tion to demask Zn(II).

e
er
H
[Zn(CN)4]2- + 4HCHO + 4H+ ~ Zn 2+ + 4HOCH 2CN

k
Thus the released Zn(ll) can be titrated as usual by edta. It may be noted that the said demasking
lic
agent cannot release Cu(l) from [CU(CN)4 ]3- which is highly stable. The Cu-content can be
C
obtained from the difference.

(ii) Masking of Fe(III) in iodometric estimation of Cu(II): Under the experimental condition, both
Fe(lll) and Cu(ll) can release iodine from KI solution. But in presence of excess F-, formation of
[FeF6 ]3- (having the lowered formal reduction potential) prevents the liberation of iodine by
Fe(III). Thus in presence of excess P-, the liberated 12 is due to Cu(ll) only.
(iii) Masking of Fe(III) in qualitative analysis: Detection of Co(ll) by SCN- through the formation
of blue coloured complex, [CO(SCN)4]2- is interfered by Fe(III) which produces the red coloured
complex with SCN-. However, excess fluoride or tartarate can mask Fe(III).
(iv) Edta as a masking agent: Benzimidazole forms an insoluble salt with Ag+. But other metal ions
like Cu 2+, Ni 2+, C0 2+, Cd 2+, etc. present in solution can interfere with the process. In fact, these
metal ions are also precipitated as complexes when treated with benzimidazole. However, if the
solution is first treated with excess edta, these interfering metal ions are masked as the edta-
complexes, but Ag+ does not form any stable complex with edta. Then Ag+ can be precipitated
with benzimidazole.
~) + Ag+
H
(Benzimidazole)
Be(ll) can be precipitated as Be(OH)2 in presence of Al(III) by using edta as the masking agent
which prevents the precipitation of Al(III) as AI(OH)3. In fact, AI(III) remains in solution as the
AI(III)-edta complex.
(v) Masking of Ca2+ in boiler and detergent action: Precipitation of CaC03 in boiler can be prevented
ry
if edta is used. In fact, Ca 2+ remains as a soluble Ca-edta complex in solution. In fact,
polyphosphates used in detergents act as the sequestering agents and keep Ca2+ as a soluble
ra
phosphate complex in water.
ib
yl
11.1.6 Metal Complexes in Complexometric Titrations
em
Different metal ions can be estimated volumetrically by using the suitable chelating agents in presence
of suitable metal ion indicator. These aspects will be discussed in detail in Sec. 11.7.
ch
11.2 METAL COMPLEXES IN MEDICINAL CHEMISTRY
e al
It covers a broad field (see Bioinorganic Chemistry - A.K. Das, Books and Allied, Kolkata). Some
th
important aspects are just mentioned below.

e/
(i) Chelating ligands (i.e. chelation therapy) in detoxification of metal ions: Chelating antidotes
t.m
can remove the toxic metals from our body through chelation.
CH 2-SH Na+-0 2C",

e
I
er
CH-SH
CH 2-SH
I .
H
CH 2-OH
I
CH-SH
k
Na+-o c/
lic
2, 3-dimercapto-1-propanol 2
(British antiLewisite i.e. BAL) (Disodium meso-2, 3-dimercaptosuccinate, DMSA)
C
(used in As-poisoning) (used in CH 3 Hg+ poisoning)
D-penicillamine (DPA)
\..... i. e. 3-dimercaptovaline N-acetyl-D-penicillamine (NAPA) )
~
Used in detoxification of Cu" (i.e. Wilson's disease), CH 3 Hg+
(Minamata disease), Hg2+
Sodium diethyldithiocarbamate OH
(used in Ni-poisoning) (Aurintricarboxylic acid)
i.e. aluminon
ry
(used in Be-poisoning)
ra
ib
yl
em
ch
Desferrioxamine-B (i.e.; desferal)
al
used in detoxification of iron.

e
th
Ca- and Zn-salts ofpolyaminocarboxylic acids: Na2Ca(edta), Zn2(edta) - edta-salts (used in Pb-, Cd-
poisoning); Na3Zn(dtpa) used in Pu-detoxification.
e/
t.m
CH 2C02H
H02CH 2C", /CH 2C02H H02CH2C", I /CH 2C02H
/N-(CH 2) 2 - N " , /N-(CH 2) 2 - N-(CH 2) 2 - N",

e
H0 2CH 2C CH 2C02H
er
H02CH 2C CH 2C02H
edtaH4 dtpaHs
H
(Diethylenetriaminepentaacetic acid)
k
lic
• HSAB theory and chelation therapy: Generally, the toxic metal ions remain bound with the
C
biogenic ligands and the administered chelating antidote forms the more stable complexes
with these bound metal ions. Such chelating antidote-metal complexes being water soluble are
excreted through urine. Here, matching of the hard-soft character of the toxic metals with the
binding sites of chelating drugs is of an important consideration. This is why to remove the soft
(i.e. heavy) metals (e.g. AS III , Hg II , CUI, etc.), chelating drugs should have the soft binding sites
like S, N. On the other hand, for the removal of hard metals, the chelating drugs should have
the hard donor sites. Thus, for detoxification of Fe(III), Pu(IV), Be(II), the hard donor ligands
are recommended.
• Ca- and Zn- salts of edta, dtpa: To avoid the possibility of depletion of essential metal ions
like Ca2+, Zn2+ by edta or dtpa, such salts are used. Otherwise, such essential metal ions will
be lost through complexation with the aminopolycarboxyic acids when the sodium salts like
Na2H2edta, Na3H2dtpa are used. In detoxification of lead, the following reaction occurs:
Na2[Ca(edta)] + Pb2+ ~ Na2[Pb(edta)] (excreted) + Ca2+
The details of the mechanism of detoxification by the chelating antidotes are discussed in the book,
Bioinorganic Chemistry by A. K. Das. The chelating drugs fonn the water soluble complexes with the
toxic metals and these are excreted through urine.
(ii) Metal complexes as drugs:
• As-, Sb-, Hg- complexes as the antimicrobial agents..
• Gold complexes as the antiarthritic drugs.
• Platinum complexes as the anticancer drugs.
CI" /NH 3
Pt
ry
CI/ "NH 3
ra
cls-platln
ib
cis-diamminedichloridoplatinum(ll)
Carboplatln
yl
cis-diammine-1 ,1'-cyclobutanedicarboxylatoplatinum(ll)
em
Pt(II) binds with the DNA-bases of the cancerous cells to prevent the DNA replication.
(iii) Metal complexes as the diagnostic agents:
ch
• 99mTc-complexes as the radio-imaging agents.
99mTc-complexes like [99mTc(CNR)6] are selectively absorbed in heart tissues. Similarly, the
al
phosphonate (-CH 2P0 3R) complexes are selectively accumulated in the growing bones. The
e
99mTc-based radiopharmaceuticals experience the isomeric transition and the corresponding 140
th
keV y-ray coming out from 99mTc can be detected by a scintillation camera.
e/
• GdIII(f)-, FeIII (d5)_ and MnII (d5)- complexes in MRI (magnetic resonance imaging)
t.m
The paramagnetic metal centres can cause the water proton relaxation rate enhancements. The MRI
agents are accumulated in different concentrations in the nonnal and affected tissues. Thus the PMR
e
signals of water present in the nonnal and affected tissues become different.
er
11.3 METAL COMPLEXES IN INDUSTRIAL PROCESSES

H
11.3.1 Organometallic Compounds as the Catalysts

k
lic
These are discussed in detail in Chapter 10.

C
11.3.2 Complexation in Water Softening

The hardness of water mainly arises due to the Ca2+ and Mg 2+ ions that can fonn precipitates with the
soaps. These hardness causing metal ions produce the insoluble scale of CaC03, MgC03 in boiler. By
using the suitable sequestering agents, these ions may be kept ineffective through complexation in
water. For this purpose, polyphosphates (known as calgon) and aminopolycarboxylic acids (e.g. ntaH3)
are used.
11.3.3 Complexation in Food Preservation

Decomposition process of the food stuff like fruit juice, cake, bread, etc. needs the presence of catalytic
amounts of different transition metal ions. Suitable complexing agents (e.g. citrate) when used can
complex with these transition metal ions and thus the metal ions become nonavailable in the decomposition
process. For example, the sequestrants like citric acid, edta, etc. are used for this purpose as the
preservatives. They can sequester the catalyzing centres like Cu2+, Fe2+, Fe3+, etc.
1684 FUNDAMENTAl CONCEPTS OF INORGANIC CHEMISTRY
11.3.4 Complexation in the Rasching Process of Hydrazine Preparation

In this process, hydrazine is prepared by reacting C1 2, NaOH and NH 3. The overall reaction is:
2NaOH + Cl 2 + 2NH3 ~ N2H4 + 2NaCI + 2H20.
The reaction intermediate NH2CI can destroy the product N2H4 in the following reaction.
M"+
N2H4 + 2NH2CI ) 2NH4CI + N 2
The above reaction is catalyzed by the transition metal ions Mn+ (e.g. Cu 2+). These are present at
trace quantities with the raw materials used in the process. Thus, the above undesirable side reaction
is unavoidable. To prevent this side reaction, a small amount of gelatin or albumin or glue is added to
the reaction mixture. Such an organic matter bears many functional groups to act as the complexing
sites to sequester the catalyzing metal ions. The sequestered metal ions cannot catalyze the process.
ry
11.3.5 Complexation in Electroplating Process
ra
For electroplating in the electrolytic bath, instead of free ion, complexed metal ions are generally used.
ib
It is done so, because of the following reasons.
yl
(i) Controlling of deposition potential: Due to complexation, 2-3 different metal ions can be
em
deposited at a particular decomposition potential. In free state, the deposition potentials of the metal
ions are different but through complexation (having different magnitudes of stability constants) their
ch
deposition potentials can be made almost the same. For example, the standard reduction potentials (in
aqueous solution) of the involved couples in brass deposition are:
al
° ° = -0.7 6 V
= 0.34 V> Ezn2+/zn
e
Ecu2+/cu
th
Thus electrolysis of a solution containing both Cu 2+ and Zn2+ will lead to deposition of copper on
e/
cathode first. In presence of CN-, they will produce [CU(CN)4]3- and [Zn(CN)4]2- complexes where the
stability constant of [Cu(CN)J 3- is much higher than that of [Zn(CN)J 2-. Consequently, their reduction
t.m
potentials becomes comparable, i. e.

e
EO[Cu (CN )4 J3- jCu

/ : : : EO[Zn(CN ) J3-/Zn
er
This allows the simultaneous deposition of copper and zinc. The details of simultaneous deposition
H
of copper and zinc are discussed in Sec. 16.4.4, Vol. 3.

k
(ii) Deposition of fine grain: To have a fine grain of deposit, concentration of the free metal ion to
lic
be deposited should be reduced to a small extent. In presence of a complexing agent in the electrolytic
C
bath, concentration of free metal ion is reduced to a significant extent. This allows the deposition of fine
grain. In fact, for electrodeposition of copper, silver, gold and cadmium, KCN is used as the complexing
agent.
M 2+ + 4CN- ~ [M(CN)4]2- , M = Zn, Cd.

Au+ + 2CN- ~ [Au(CN)2]-
Cu 2+ CN-) (CN)2 + [CU(CN)4]3-, (reduction followed by complexation).

Note: For deposition of copper, the object to be plated is made the cathode and a copper rod is used as
the anode. During the electrolysis, in presence of excess CN-, the following reactions occur.
Anode: Cu + 4CN- ~ [CU(CN)4]3- + e
Cathode: [CU(CN)4]3- ~ Cu + 4CN- - e
Thus during copper plating, metal is transferred from the anode to the cathode through the forma-
tion, migration and decomposition of the complex, tetracyanidocuprate(I), i.e. [CU(CN)4]3-.
• If electroplating is done by using the Cu 2+-solution (without KCN), the electrode reaction will
occur as follows
Anode: Cu ~ Cu 2+ + 2e; Cathode: Cu 2+ + 2e ~ Cu
Half mole of copper will be deposited per faraday of electricity while in presence of CN- (as a
complexing agent), one mole of copper will be deposited per faraday. Thus, electroplating by copper
in presence of CN- is economic also. However, this economic benefit is not available for Au or Zn or
Cd-plating in presence of CN-.
11.3.5 Complexation in Metallurgical Process
ry
Some illustrative examples are discussed below.
ra
(i) Extraction of gold: Gold is a noble metal (i.e. inert in chemical reactivity). But in presence of
ib
CN-, it becomes very much reactive, i.e. oxidizable and O2 (in air) can oxidize gold. In fact,
because of the formation of stable [Au(CN)2]- complex, the formal reduction potential drops.
yl
Au(aq)+ + e ~ Au, EO = 1.83 V
em
[Au(CN)2]- + e ~ Au + 2CN-, EO = ~0.60 V.
ch
-t O2 + H20 ~ 20H- - 2e, EO = 0.40 V, (at [OH-] = 1.0 mol dm- 3)
al
=0.81V(atpH=7)
e
Thus, O2 can oxidize gold to its cyanido complex. The involved reactions in the extraction of gold
th
are:
e/
4Au(s) + 8CN- (aq) + 02(g) + 2H 20(l) ~ 4[Au(CN)2]- (aq) + 40H- (aq).

t.m
Then the cyanido-complex of gold(I) i.e. [Au(CN)2]- is reduced by elemental zinc.

2[Au(CN)2]-(aq) + Zn(s) ~ [Zn(CN)4]2-(aq) + 2Au(s).
e
Because of the formation of the complex, [Zn(CN)4]2-, Zn becomes more readily oxidisable.
er
Zn 2+ +2e ~ Zn, EO = -0.76V; [Zn(CN)4]2- +2e ~ Zn +4CN-,Eo = -1.35V

H
(ii) Extraction of silver: From argentite (Ag 2S), silver is extracted in presence of CN-. The involved
k
lic
reactions are:
4[Ag(CN)2]-(aq) + 40H-(aq) + 2S(s).
C
2Ag 2S(s) + 8CN-(aq) + 02(g) + 2H 20(l) ~
2[Ag(CN)2]-(aq) + Zn(s) ~ [Zn(CN)4]2-(aq) + 2Ag(s).

(Note: In presence of CN-, because of the formati~n of stable [Cu(CN)41 3- complexes, the reduction
potential of the Cu(I)/Cu(O) couple significantly drops, i. e. Cu-becomes very much oxidizable. In
presence of CN-, copper readily dissolves in water).
(iii) Complexation and chemistry of aqua regia (cf. Sec. 16.4.5, Vol. 3): For dissolving the noble
metals like Au, Pt, etc. aqua regia (3 vol. conc. HCI + 1 vol. cone. HN0 3) is used. The individual
acids (i.e. HCI or HN0 3) cannot attack alone the noble metals. In aqua regia, the effective oxidiz-
ing agents are: H+ and NOj" and these cannot attack the noble metals in absence of the
complexing ligand like CI-. These are supported by the thermodynamic data (i.e. reduction
potentials) of the involved redox couples.
{ E~O-/NO =0.95V;
3
E~o-/NO2 =O.77V;
3
EO
H+
/12
H2
=O.OV
{E~u+/AU =1.83V; E~U3+/AU = 1.52 V; E[AUCI2J/AU = 1.15 V; E[AUCI J/AU = 1.0 V 4
{E~2+/Pt =1.2V; E[PtCI Y-/Pt =0.76V

4
{E~d2+ /Pd = 0.92 V ; E[PdClS-/Pd = 0.62 V

The reduction potentials of the couples like Au+/Au, Au3+/Au, Pt2+/Pt, Pd2+/Pd drop in presence
of CI- because of the formation of chlorido-complexes. This fall in reduction potential makes
the metals more reactive (i.e. more oxidizable) and then N0 3- can oxidize the metals. Without
this complexation, the reduction potential of the N0 3-/N0 couple lies far below the reduction
ry
potentials of the redox couples of the involved metals.
ra
(Note: For details of the chemistry of aqua regia, see Chapter 16, Vol 3)
ib
(iv) Purification of nickel by Mond's process: Nickel obtained from C-reduction of NiO is impure.
yl
It can be purified through the formation of volatile [Ni(CO)4] complex. The carbonyl complex is
decomposed thermally to obtain the pure nickel.
em
Metallurgical ) NiO _C_-r_ed_u_cti_on----+) Impure Ni +CO(SO°C) ) [ Ni (CO) 4 ] 180°C) Ni
Ni-ore
ch
processes -4 CO (pure)
al
11.3.6 Complexation and Photography

e
In photography, the fixing step involves the complexation process. To understand the importance of this
th
step, the whole process is discussed in short.

e/
Photographic plate consists of light-sensitive silver halides (mainly AgBr) as an emulsion along
t.m
with the organic dyes acting as the photosensitisers. The photosensitizers help light absorption for the
involved photochemical process. The whole process consists of the following steps.
e
(a) Exposure to light: AgX (h hv .. ) )Ag+X,2X~X2(absorbedbygelatin)

er
p otosensltlser
H
The deposition of grains of Ag produces a latent image.

(b) Developing: It intensifies the latent image by producing the more Ag-grain deposit. A mild
k
lic
reducing agent like hydroquinone can reduce only the AgX present in the exposed portion of
the film.
C
2AgX + C 6 H 4 (OH)2 ~ 2Ag + 2HX + C 6 H 4 O 2 .

~
Present on the (hydroquinone) (quinone)
exposed portion
(c) Fixing: In this step, unchanged AgX (not exposed to light) is removed through complexation by
using the sodium thiosulfate (i.e. hyposolution) as the ligand.
2AgX + 2Na2S203 ~ Na3[Ag(S203)2] + NaX
(soluble complex)
Thus a negative is produced. The portion blackened due to Ag-grain represents the area of expo-
sure to light. This is why, it is called negative.
(d) Printing: It is done from the negative on a photosensitive printing paper (coated with AgBr
emulsion) by repeating the steps a-c. Thus in printing, light is passed through the negative onto
the printing paper followed by developing and fixing.
11.4 METAL COMPLEXES IN AGRICULTURE

Because of the very low solubility products of Fe(OH)2 (Ksp ::::: 2 x 10- 15 ) and Fe(OH)3 (Ksp ::::: 2 x 10-39 ),
in alkaline soil, iron is not available to the plants. In alkaline soil, Fe(OH)2 is readily (but slowly)
oxidized to more insoluble Fe(OH)3 by aerial oxygen. In the presence of Mn02' iron is also readily
oxidized to Fe(OH)3. Thus high alkalinity, presence of Mn02 and absence of organic reducing agents,
make the soil-iron unavailable to the plants because of the formation of highly insoluble Fe(OH)3. In
such cases, farmers use the Fe(III)-edta chelate which is soluble. It makes iron available to the plants.
It may be noted that some plants like wheat, oats, etc. can grow even in the alkaline soil. Such plants
can produce the chelating agents - polyaminoacids that are utilized by the plant roots to solubilize
Fe(OH)3 present in soil. The plants like rhododendron, azelea, etc. that normally grow in soils of low
pH cannot survive in alkaline soil because of iron deficiency. Such plants cannot produce the chelating
ry
agents to solubilize iron-hydroxide.
ra
(Note: Iron is very much essential for the plants because it is required to the synthesis of cytochromes,
ib
ferredoxins, etc. Iron deficiency in plants is characterized by yellow leaves and this disease is called
yl
iron chlorosis. For the biosynthesis of chlorophyll, iron is required as a catalyst. Thus, deficiency of
iron hampers the production of chlorophyll that makes the leave green.)
11.5 METAL COMPLEXES AND SOLAR ENERGY CONVERSION

em
ch
It has been already mentioned that Ru-complexes can be utilized to harvest solar energy in many
al
reactions like photochemical cleavage of water, photochemical reduction of nitrogen, etc. These aspects
e
have been discussed in Sec. 16.16.2 (Vol. 3).

th
11.6 COMPLEXATION AND STABILIZATION OF UNUSUAL OXIDATION STATES

e/
These aspects have been discussed in Sec. 4.9 in detail. Generally to stabilize the low oxidation state,
t.m
complexation by soft and n-acid ligand is recommended. To stabilize the higher oxidation state,
complexation by nonpolarizable hard donor ligands is recommended.
e
er
11.7 COMPLEXOMETRICTITRATIONS
H
In this method, concentration of metal ion is titrimetrically determined through complexation by a

polydentate chelating ligand. Such chelating agents are called chelones or complexones. Complexometric
k
lic
titrations are also called chelatometric or chelometric titrations.

C
Nitrilotriacetic acid
(H 3 nta)
(pka(1) = 1.9, pKa(2) = 2.5 1, 2-diaminocyclohexanetetraacetic acid
pK a (3) = 9.7) (H 4 cdta or H4dcta)
Ethyleneglycol-bis-(p-aminoethylether)-tetraacetic acid (H 4egta)
Fig. 11.7.1 Structures of some common complexing agents used in complexometric titrations
Ethylenediaminetetraacetic acid (H 4edta, commonly called EDTA or edta) is the most promising
complexing agent in this field. In the most common type complexometric titration, an organic dye (a
chelating agent) is used as a metal ion indicator which forms a relatively weak complex with the metal
ion. The colour of the metal-indicator complex is different from the colour of the free indicator under
the same experimental conditions. As the complexometric ligand reacts with the last small amount of
metal-indicator complex and the indicator gets freed. The end-point is detected by the colour of the free
indicator.
Besides edta, some other chelating agents (Fig. 11.7.1) may be also used as the complexing agents.
However, edta is most widely used.
Here it may be noted that stabilities of Ca-edta and Mg-edta complexes are comparable (cf. log f3 =
10.7 and 8.7 for Ca2+ and Mg 2+ respectively) but for egta, their stabilities (cf. log f3 = 11.0 and 5.4 for
ry
Ca2+ and Mg 2+ respectively) differ significantly. Thus, by egta, calcium can be titrated in the presence
ra
of magnesium. But, by edta titration, their sum total is obtained. For estimation of calcium only,
magnesium is first precipitated out.
ib
yl
11.7.1 Ethylenediaminetetraacetic Acid (also called Versene, Complexone-III):
em
A Potential Complexometric Agent
In its structure, the four carboxylate ends and two amino nitrogens are in a suitable condition to provide
ch
the octahedral coordination symmetry. It can exist as H6edta 2+ having the successive six pKa values:
0.0, 1.5,2.0, 2.7,6.2, 10.3 (at 20°C). The first four values correspond to the 4 carboxylic acid groups
al
while the last two values correspond to the ammonium protons. The first two pKa values indicate two
e
strongly acidic protons. Thus it is reasonable to assume that in the working pH range, the first two
th
protons are almost completely lost, i. e.

e/
=[ H 2
]+[ Hsedta+ ] +[H4edta ]+[ H 3edta- ]+[ H 2 edta 2 - ] +[Hedta 3- ]
t.m
Tedta 6 edta +
+[edta 4- ] ~ [H4edta ]+[ H 3edta - ] +[H2 edta 2- ] +[Hedta 3- ] +[edta 4 - ]; (cf. Appendix ItA)
e
Thus for the sake of simplicity, we shall consider it as H4edta and its deprotonated species.
er
The acid dissociation constants of H 4edta (i.e. four dissociable protons) are:
H
pKa(1) = 2.0, pKa(2) = 2.7, pKa(3) = 6.2 and pKa(4) = 10.3, (at 20°C)
k
It indicates that there are two strongly acidic protons that lead to a Zwitterionic structure.
lic
H02C-H 2C",- /CH 2 - C 02-

C
H-N+-CH2-CH 2- N + - H
-02C- H2C/ "'-CH 2 - C 0 2H
Thus, H 4 edta acts as a diacarboxylic acid (pKa(1) = 2.0, pKa(2) = 2.7) having two ammonium protons.
(pKa(3) = 6.2 and pKa(4) = 10.3). It is commercially available as Na2H2edta i.e. disodium salt of H4 edta.
Because of its hexadentate character, it generally forms the 1: 1 complex. However, it may act as a
.flexidentate ligand. For the metal ions favouring coordination number greater than 6, it also forms the
1: 1 complex where rest of the coordination sites are occupied by H 20 (i.e. solvent). Considering the 1: 1
complex formation in the complexometric titration, the involved reaction can be represented as follows:
M n+ + H 2 edta 2- ~ [M (edta) ](4-n)- + 2H+
From the above reaction, it is evident that there is a release of protons during the complexation. Thus
at highe~pH, the equilibrium is shifted towards the right side while at lower pH, the equilibrium is
favoured towards the left. In fact, position of the equilibrium depends on the pH and complexing
power (measured by the stability constant) of the metal ion.
[Complex] [H+ ]2 [Complex] x [edta 4- ] [H+ ]2

K - - ~--=-=----=._~------=-
eq - [M n +][ H2edta2- ] - [M n+][edta4 - ][ H 2edta 2- ]
4 [ )](4-n)- [Complex]
M n + +edta - ~ M(edta ,~= .
[M n + ] [edta 4- ]
2- + 4- [edta 4- ] [H+ ]2
ry
H 2edta ~ 2H + edta ,Ka(3)K a (4) = [H edta 2- ]
ra
2
ib
~ = stability constant; Ka(3) and K a(4) are the 3rd and 4th acid dissociation constants of H4 edta respectively.
yl
Stability constants of some metal-edta complexes are given in Table 11.7.1.1.
em
Table 11.7.1.1 Stability constants (-25 C) of metal-edta complexes
ch 0
Metal ion log ~ Metal ion log ~ Metal ion log ~

al
Ag+ 7.3 Co 2+ 16.2 Cu 2+ 18.8

e
Ba2+ 7.8 Cd 2+ 16.6 Hg 2+ 21.8

th
Sr2+ 8.6 Zn 2+ 16.7 Fe 3+ 25.1

e/
Mg2+ 8.7 Ti0 2+ 17.3 A1 3+ 16.3

t.m
Ca 2+ 10.7 Pb 2+ 18.0 Ga3+ 20.3

Mn 2+ 13.8 Ni 2+ 18.6 La3+ 15.2
e
Fe 2+ 14.3 V0 2+ 18.8 Ce3+ 16.0

er
For the complexometric titration, the pH range

H
must be selected in a way so that the complex

k
formation becomes more or less quantitative (i.e.

lic
complete). For the systems having the higher

C
stability constants (P), the reaction becomes

quantitative at a relatively lower pH while for
the systems having the lower stability constants
(P), the quantitative complexation occurs at a
relatively higher pH. Compared to the bivalent
metal ions, the trivalent and tetravalent metal ions
form the more stable edta-complexes. This is why,
titration of higher valent metal ions by edta can be
carried out at a relatively lower pH.
Desired pH ranges for the quantitative formation [M(edta)] Complex
of some common metal-edta complexes. (Octahedral)
Fe3+:
pH (1-3); Pb2+, Cu2+, Zn2+,AI3+: pH (4-6), Fig. 11.7.1.1 Octahedral coordination by edta in
Ca2+, Ba2+, M g2+: pH (8-10) a 1: 1 complex.
Here it should be mentioned that besides the effects of charge and radius parameters (more
correctly, charge/radius parameter), cfse may also contribute for the transition metal ions to
determine the stability of the metal-edta complex. For example, Cu(II) forms a more stable complex
than Mg(II) though both of them are the bivalent metal, ions.
In general, we can conclude: higher the stability constant (P), lower the pH range of titration.
For the bivalent metal ions, the titrations are carried out in basic solutions while for the trivalent and
tetravalent metal ions the titrations are carried out in slightly acidic solutions.
11.7.2 A Quantitative Treatment of Complexometric Titration

Let us consider the metal ion (M, charge not shown) which is being titrated by the ligand (L).
ry
~ ML, ~ = [~1t~] ,
ra
M+L (charges not shown for the sake of simplicity)
ib
Let us consider the following parameters.
yl
V~ = initial volume of the metal ion solution to be titrated.
T~ = initial molar concentration of the metal ion.

em
ch
T2 = molar concentration of the ligand solution used in titration.
al
= volume of the ligand solution added during titration.

e
VL
th
At any stage of titration, total concentration of the metal (TM) and ligand (TL ) are given as
e/
follows:
t.m
e
er
H
and TL = [L] + [ML] = (0

V +VL
)
k
M
lic
When the stability constant (~) is very high, we can have the situations as shown in Table 11.7.2.1.
C
Table 11.7.2.1 Calculation of different concentration terms in a complexometric titration
Before the equivalence At the equivalence After the equivalence

point point point
[L]::::: 0 T~V~ = T2vL TM:::::[ML]
TM = [M] + [ML] TM ::::: TL ::::: [ML] [M] :::::0
TL ::::: [ML] [M]:::::[L]:::::O TL = [ML] + [L]
The above conditions (given in Table 11.7.2.1) are satisfied only for the very large values of the
stability constant (~). The concentration terms can be expressed in terms of ~ as shown in Table
11.7.2.2.
Table 11.7.2.2 Calculation of different concentration terms in terms of stability constant in complexometric
titration
Before the equivalence point At the equivalence point After the equivalence point
[ML]:
[M]:
T2vL -T~V~
ry
[L]:
v~ +VL
ra
ib
[ML]
. M + L;=, ML, ~ = [M][L]
yl
em
The above relation is always maintained.
• Before the equivalence point, [L] will be determined by the dissociation of ML and it will be given
ch
by the following relation.
al
[L] = [ML]
e
~[M]
th
• At the equivalence point, [M] = [L] and this will be maintained by the dissociation of the complex.
e/
12
J
t.m
i.e. or, [M]=[L]= ( 13

1 [ML] /
e
• After the equivalent point. [M] will be determined by the dissociation of ML.
er
[M]=*[~~] where [L]=(T2 vL -T~V~)/(V~ +VJ

H
k
For the following experimental conditions (when ~ is sufficiently large), T2 = T~ = 0.1 mol dm-3,
lic
V~ = 100 mL we have the relations shown in Table 11.7.2.3.

C
Table 11.7.2.3 Calculation of pM(= -log[M]) values in a complexometric titration.
Before the equivalence At the equivalence After the equivalence

point (VL < 1(0) point (VL = 100) point (VL > 100)
[ !(~)]l/2
0.1(100 - VL ) 1 0.lxl00
[M]: -x----
100+ VL P 100+100 P O.I(VL -l00)
1+log -100+
-V -L ) 1 1 200
pM: ( 100- V -logP+-Iog- logP - 2 + log(VL -100)
L 2 2 10
1
="2logP + 0.65
Note: -log [M] = pM; actually conditional or effective stability constant (~') is to be used instead of thermodynamic
stability constant (~) in all these calculations.
Thus it is evident that before and after the equivalence point, pM increases with the increase of
VL (i.e. volume of titre) and at the equivalence point it is only dependent on p. The degree of sudden
change of pM value at the equivalence point depends on the magnitude of the stability constant.
In fact, the plot of pM vs. VL (i.e. titration curve) is very much comparable with that of the acid-base
titration curve (i.e. pH vs. V). It is illustrated in Fig. 11.7.2.1 by taking some representative examples.
Titration curve (i.e. pM vs. VL ) can be constructed as shown in Table 11.7.2.4.
Table 11.7.2.4 Construction of a titration curve in a representative complexometric titration

(say log~ = 10.0)
log P= 10.0 T~ = T~ = 0.1 moldm-3 , V~ = 100 mL
ry
VL (mL): 0 10 50 90 99 99.9 100 100.1 110
ra
pM: 1.0 1.1 1.48 2.28 3.3 4.3 5.65 7.0 9.0
ib
yl
_ (100 + V pM=~log~ pM = log~-2
em
L )
pM -1 + log 100 - V 2 +log(VL -100)
L ch +0.65
e al
th
~(4) > ~(3) > ~(2) > ~(1)

e/
t.m
~(3)
e
er
~(2)
H
k
lic
~(1)
C
Equivalence point
~ Volume of edta solution
Fig. 11.7.2.1 Qualitative representation of the change of pM value at the equivalence point depending on the magnitude
of the stability constant (~) of the metal-edta complex.
Validity of the titration depends on the sharp change of pM values at the region of equivalence point
and this change depends on the stability constant ~ as evident from Table 11.7.2.5 and Fig. 11.7.2.1.
Table 11.7.2.5 Change of pM value at the region of equivalence point in the complexometric titrations
depending on the magnitude of the stability constants (B). T~ = T2 = O.IM, v~ = 100 mL
log fJ pM-value pM-value pM-value ApM

Just before the Equivalence Just after in the region
equivalence point, point the equivalence point of equivalence
VL = 99.9 mL (say) (VL = 100 mL) VL = 100.1 mL (say) point
i.e. 0.1% under i.e. 0.1% over
titration) titration)
8 4.30 4.65 5.0 5.0 - 4.3 = 0.7

10 4.30 5.65 7.0 7.0 - 4.3 = 2.7
ry
12 4.30 6.65 9.0 9.0 - 4.3 = 4.7
14 4.30 7.65 11.0 11.0 - 4.3 = 6.7
ra
16 4.30 8.65 13.0 13.0 - 4.3 = 8.7
ib
yl
11.7.3 Effect of pH on the ComplexometricTitration Curves for
em
Ethylenediaminetetraacetic Acid as the Complexing Agent ch
Ethylenediaminetetraacetic acid (H 4edta) is commonly used in complexometric titrations. Stability
constant (~) is expressed as follows:
al
M + edta 4 - ~ [M(edta)], (charges not shown for the sake of simplicity)

e
th
(Complex)
e/
~ = [Complex]
t.m
[M] [edta 4 - ]
In addition to the above equilibrium, there are number of proton-ligand competitive equilibria.
e
er
H
Note: Here it is assumed

k
that the first two strongly

lic
acidic protons of H 6 edta 2 +

C
are almost completely lost

in the working range of pH,
. eXIstence
l.e. . 0 fH 6ed ta 2+
and Hsedta + has been

ignored (cf. Appendix ItA)
3- + 4- [H+ ] [edta 4 - ]
Hedta T=': H + edta , K a (4) = [Hedta 3-]
pKa(1) = 2.0, pKa = 2.7, pKa = 6.2, pKa = 10.3 at (20
(2) (3) C) (4)
0
Distribution of different protonated species of edta is shown in Fig. 11.7.3.1. It is evident that both
the metal ion (M, charge not shown) and H+ mutually compete for edta4-. Under this condition, the
conditional or effective stability constant (~/) is more important than the thermodynamic stability
constant (J3) to understand the titration curve of complexometric titration.
edta4-
Note: In reality, at pH < 2.0, besides the

species H4edta and H3edta-, the species
Hsedta+ and H6edta2+ also exist but these
ry
are ignored here. In fact, at pH ~ 0, Hsedta
2
+
ra
is the most predominant species (see
Appendix 11A).
ib
yl
o em
ch
2 4 6 8 10 12
-----. pH
e al
Fig. 11.7.3.1 Distribution of different protonated species of edta (ignoring the H 6 edta2+ and H s edta+ species).
th
From the mass-balance, we can write:

e/
TM = [M] + [M(edta)]
t.m
TL = [M(edta)] + [H 4edta] + [H 3edta-] + [Hzedta z-] + [Hedta 3-] + [edta 4-]

e
[H+ ]4 [H+ ]3
er
TL - [M(edta)] = { K a(I)Ka(2)Ka(3)Ka(4) +
H
K a(2)Ka(3)Ka(4)
k
lic
C
=(XL [edta 4 - ], (XL depends on pH).
[edta 4-] = TL -[M(edta)]

or,
(XL
K a(4), K a(3), ••• are the successive deprotonation constants of H 4edta. Thus for a particular ligand, (XL
is a function of pH (cf. Table 11.7.3.1 and Fig. 11.7.3.2).
ry
ra
ib
yl
em
ch
e al
o
th
2 4 6 8 10
e/
t.m
Fig. 11.7.3.2 Variation of log u L as a function of pH for edta.
Thus the thermodynamic stability constant (~) can be expressed in terms of aL-
e
er
~ = [M(edta)]
H
[M] [edta 4- ]
k
lic
[M(edta)]a L .. . .
; (Ignonng the hydrolysIs of the metal Ion).
C
{TM - [M(edta) ]}{TL - [M(edta) ]}
= ~' a v (~' = conditional or effective stability constant)

i.e. log ~ = log ~' + log a L
or, log ~' = log ~ - log aL
From the known Ka-values of H 4edta, the parameter a L (which is a function of pH) can be calculated
(cf Table 11.7.3.1).
The plot of 10g(aL) vs. pH is shown in Fig. 11.7.3.2.
Note: If the metal undergoes complexation with the other ligands including OH- (i.e. hydrolysis of
the metal centre), then we have: ~ = ~'a~L i.e. log ~ = log ~' + log aL + log aM, (cf Sec. 11.7.5 and
Chapter 4). Here for the sake of simplicity, aM is taken as unity (i.e. no complexation with the other
ligands).
Table 11.7.3.1 Values of UL for edta at different values

pH uL log uL
1.0 1X 10 18 18.0
2.0 2.75 x 10 13 13.44
2.5 7.24 x lOll 11.86
3.0 3.98 x 10 10 10.60
4.0 2.75 x 108 8.43
5.0 2.9 x 106 6.46
6.0 4.46 x 104 4.65
7.0 2.13 x 103 3.33
ry
8.0 1.86 x 102 2.27
9.0 19.0 1.28
ra
10.0 2.88 0.46
ib
11.0 1.18 0.07
yl
12.0 1.02 -0.00
em
11.7.4 Minimum Required Value of Conditional or Effective Stability Constant and
ch
Suitable pH Range for Titration by Ethylenediaminetetraacetic Acid
al
For a successful complexometric titration (i.e. sufficient and sudden change of the pM value at the
equivalence point in the titration curve), conditional stability constant CB') should be atleast 108 i. e.
e
th
log p' ~ 8.0 (ef Table 11.7.2.5, L\pM ::::: 0.7 for log~' = 8)
e/
Let us consider the titration of Ca2+ by edta for which log B= 10.7, i.e.
t.m
logB= log B' + log u L

or, log u L = log B- log B' = 10.7 - 8.0 = 2.7
e
er
pH = 12
H
pH = 10
k
lic
C
pH =8
ct3
U
Q.
r
----.~ Vol. of edta solution
Fig. 11.7.4.1 Qualitative representation of the effect of the pH on the nature of titration curve for titration of Ca2+ by edta
solution.
From Fig. 11.7.3.2, it is evident the required a L (i.e. log a L = 2.7) is attained at pH = 7-8. In practice,
the maintained pH is around 10.0. At lower pH, the conditional stability constant is less and conse-
quently the change in pCa in the range of equivalence point is less. It makes the titration erratic.
For Pb 2+, log ~ = 18.0, the required condition is:
log a L = log ~ - log ~' = 18.0 - 8.0 = 10.0
This required a L is attained at much lower pH. Thus it may be concluded that, with the increase
of thermodynamic stability constant (P), the minimum required value of conditional stability
constant (log ~' ~ 8.0) is attained at a lower pH.
Note: At higher pH (i.e. higher concentration of OH-), participation of OH- as ligands may complicate
the situation. It may lead to the hydroxo-species.
[M(edta)] + nOH- ~ M(OH)n j, + edta4 -
ry
Thus to maintain the required condition (i.e. log ~' ~ 8), pH cannot be increased arbitrarily.
ra
This is why, for the systems having very low stability constants, the complexometric titration
ib
cannot be done.
yl
Illustration 1: 100 mL of 0.01 M Ca2+ solution is being titrated with 0.01 M edta solution at the
em
buffered pH 10. Calculate the change of pCa at the equivalence point.
Given: ~[Ca(edta)] =5 X 1010, a edta = 2.85 (at pH = 10),
ch
a Ca = 1 (i.e. no complexing ligand other than edta).
al
Solution: We have the relationship.

e
~[Ca(edta)] = ~'[Ca(edta)]aCaaedta
th
~[Ca(edta)] -
10
e/
(d"· 5 X 10
.
I. e. A'
fJ [Ca(edta)] con thanaI stab·l"
t tty constant ) = - - = 1.75 X 1010. (a = 1)
2.85 x l ' Ca
t.m
aCaaedta
aCa = 1 indicates that the metal ions not bound to edta remain as free ion, i.e. TM - [M(edta)] = [M]
e
pCa can be calculated at the different stages of titration as follows:

er
(i) At the start of titration (i.e. VL = 0):

[Ca2+] = 0.01 M i.e. pCa = -log[Ca2+] = 2.0
H
(ii) After the addition 30 mL of edta:

k
lic
[Ca2+) = 0.01 (100 - 30) M = 5.38 X 10-3 M

C
100+30
i.e. pCa = 2.26
(iii) After the addition 99.9 mL of edta (i.e. just before the equivalent point):
[Ca2+) = 0.01 (100 -

99.9) M = 5 X 10-6 M
100 + 99.9
i.e. pCa = 5.30
(iv) At the equivalent point (i.e. VL = 100 mL)
At this point, [Ca(edta)] z 100 x 0.01 M =5 X 10-3 M

200
~' _ [M(edta)]
[M(edta)] - [Cone. of M not bound to edta] x (Cone. of edta not bound to M)
At the equivalence point, concentrations of Ca2+ and free edta are determined by the dissociation
of the 1: 1 complex. It leads to:
[Ca2+] = molar concentration of Ca2+ not bound to edta
= molar concentration of edta not bound to Ca2+ = [edta]
, 5xl0-3 10
l3[ca(edlal] = [ca 2 + f =1.75 x 10
3
or, [Ca 2+ ] =( 5 X10- JI/2 "" 5.3 X 10-7 M
1.75 X 10 10
ry
i.e. pea = 6.27.
(v) At VL = 100.1 mL (i.e. just after the equivalence point): [Ca2+] is determined by the dissociation
ra
of the complex.
ib
[edta] = conc. of edta not bound to Ca2+
yl
em
= 0.1 x 0.01 M = 4.99 x 10-6 M
100 + 100.1 ch
[Ca (edta)2- ] = 100 x 0.01 M = 4.99 X 10-3 M
100 + 100.1
e al
M=~M=l 75xlO IO M
3
13'
th
= 4.99 x 10-
[Ca(edta)] [Ca 2 +] x 4.99 X 10-6 [Ca 2 +] .
e/
i.e. [Ca2+] = 5.7 x 10-8 M

t.m
i.e. pCa = 7.24

(vi) At VL = 110 mL: [Ca2+] is determined by the dissociation of the complex.
e
er
[edta] = 10xO.Ol M=4.76xI0-4 M

100 + 110
H
[Ca(edta)2- ] = 100 x 0.01 M = 4.76 x 1O-3 M

k
100 + 110
lic
3
13'
C
= I 75 X 10 10 = 4.76 X 10- M = _10_ M

[Ca(edta)]' [Ca 2 +] x 4.76 X 10-4 [Ca 2 +]
i.e. [Ca 2+]=

10 =5.7xI0-IOM
1.75 x 10 10
i.e. pCa = 9.24
Illustration 2: During the titration of 100 mL of 0.01 M M2+ by 0.01 M edta solution, the reaction is
supposed to be almost complete for the addition of 99.95 mL of edta solution. Then pM changes by 3
units for the addition of excess 0.1 mL (i.e. 2 drops) of edta solution. Calculate the conditional stability
constant, f)' M(edta)·
Solution: VL = 99.95 mL
M2+ = om (100 - 99.95) M = 2.5 X 10-6 M

[] 100 + 99.95
i.e. pM = 5.60
~pM = 3.0 i.e. pM = 5.60 + 3 = 8.60 when VL = 100.05 mL
It leads to: [M2+] = 2.50 x 10-9 M.
[M(edta)2-]", lOOxO.01 M=5xlO-3 M

100+100.05
[edta] = conc. of edta not bound to metal when VL = 100.05 mL
0.05 x 0.01 M = 2.5 x 10-6 M

100+ 100.05
~'
ry
= [M(edta?- ]
ra
[M(edta)] [M 2+ ] x conc. of edta not bound to M 2+
ib
yl
em
2.50 X 10-9 x 2.5 X 10--{}
=8xl0 11 •
ch
11.7.5 Effect of other Complexing Agents on Complexometric Titration Curves: Effect
al
of other Complexing Ligands on the Conditional Stability Constant

e
th
Sometimes, it may be required to raise the pH significantly high but at this higher pH, the metal ion to
be titrated may form the precipitate of hydroxide or oxide. To avoid this, it may be required to use the
e/
masking agent. When NH4CI-NH3 buffer is used to maintain the pH close to 10, NH3 as a complexing
t.m
ligand can act as a masking agent. Thus NH3 functions dual roles: buffering action to give the required
pH and masking agent action. In fact, for titration of Zn2+ by edta in presence of NH4CI + NH 3 buffer,
e
the following reaction occurs.

er
[Zn(NH 3)4]2+ + Hedta 3- r= [Zn(edta)]2- + 3NH3 + NH4+

H
In such cases, the extent of progress of the reaction depends on two factors: pH and concentration
k
of NH 3 • In other words, conditional or effective stability constant of the [M(edta)] complex depends on
lic
both [H+] and [NH 3].

C
Dependence of ~[M(edta)] on [H+] arises from the competition between 'M' (i.e. metal ion) and H+
for the complexometric ligand (L) edta (assuming no hydrolysis of the metal ion). It is expressed in
terms of a v Dependence of ~'[M(edta)] on [other complexing ligand] i.e. [NH 3] (in the present case) arises
for the competition between NH3 and edta for the metal centre. The effect of such auxiliary complexing
ligand (L') is expressed in terms of aM.
Thus a L takes care of distribution of the complexometric ligand (L) while aM takes care of the
distribution of the metal centre among the different ligands.
We have already discussed the origin and developmerit of av Now let consider the origin and
development of aM. We can write:
TM (concentration of total metal) = Concentration of the metal bound to the complexometric
ligand (L i.e. edta) + concentration of the metal bound to
the auxiliary ligand (L') + concentration of M not bound
to Land L'.
i.e. TM - [M(edta)] = ([M] + [ML'] + [ML'2] +[ML'3] + ...)

x
=I [ML;]
i=O
x
or, TM - [M(edta)] = I[ ML;] = Concentration of the metal not bound to the complexometric
i=O
ligand (L i.e. edta)
If we take: M = Zn2+, and L' = NH3, then we can write:
4
I[M(NH 3 );] = [M] + [M(NH 3)] + [M(NH3h] + [M(NH 3)3] + [M(NH 3)4]
i=O
ry
= [M] + K 1[M][NH3] + K 1K 2[M][NH3]2 + K 1K 2K 3[M][NH 3]3 + KIK2K3K4[M][NH3]4
ra
= [M] {I + K 1[NH3] + K 1K2[NH3]2 + K1K 2K 3[NH3]3 + KIK2K3K4[NH3]4}
ib
yl
=[M]{ 1 + ~/3n [L'r } , (n = 1, 2, 3, 4 in the present case)
= [M]aM em
ch
[M (edta)] = -f A
al
TM - =1 [ ,]n
It leads to: [M] Cl. M + ~""n L
e
th
/3 - [M(edta)] _
e/
[M(edta)]Cl.MCl. L
[M(edta»)- [M][edta 4 -] - {TM -[M(edta)]} {TL.,-[M(edta)]}
t.m
=~[M(edta)]aMaL
e
er
13' - Cone. of [M(edta)] complex

H
[M(edta)] - (Cone. of metal not bound to edta) x (Cone. of edta not bound to metal)
k
Illustration: ~[Zn(edta)] = 3 X 10 16 ; pH =9.0 maintained by 0.1 M NH 3 + 0.17 M NH4CI, a L = a edta = 19.0

lic
at pH = 9.0 (Table 11.7.3.1).

C
Zn 2+ + NH 3 ~ [Zn(NH3)]2+, K 1 = 190
[Zn(NH3)]2+ + NH 3 ~ [Zn(NH3)2]2+, K 2 = 210
[Zn(NH 3)2]2+ + NH3 ~ [Zn(NH3)3]2+, K 3 = 250
[Zn(NH 3)3]2+ + NH 3 ~ [Zn(NH 3)4]2+, K 4 = 110
It leads to: aM = 1 + K 1[NH3] + K 1K2[NH3]2 + K 1K2K 3[NH3]3 + KIK2K3K4[NH3]4
= 1 + 190 ~ 0.10 + 190 x 210 x (0.10)2 + 190 x 210 x 250 x (0.10)3 + 190 x 210 x 250 x 110 x (0.10)4
~ 1.20 X 105 , (using K 1 = 190, K 2 = 210, K 3 = 250, K 4 = 110)
A' _ ~[M(edta)] 3 x 10 16
- - - - - ~ 1.30 X 10 10 , (a L = 19.0, at pH = 9.0)
fJ[M(edta)] - a a
M L 19.0 x 1.20 x 10 5
Thus, the conditional stability constant is widely different from that of the thermodynamic stability
constant.
It is evident that if [NH31 is increased, f3/[M(edta)] decreases. Consequently, change of pM at the

equivalence point becomes less. It makes the titration less accurate.
Effect of buffer on the complexometric titration: Buffer is required to maintain the required pH
in a complexometric titration. But if the buffer contains the complexing ligands that can complex with
the metal ion to be titrated, then conditional stability constant (i.e. ~/[M(complexometric ligand)]) decreases.
Consequently, the extent of change of pM at the region of equivalence point becomes less i.e. change
of pM value at the equivalence point is less sharp.
Illustration: 100 mL of 0.01 M Zn2+solution is titrated with 0.01 M edta solution at pH 9.0 maintained
by NH 3 + NH4CI buffer. Calculate the change of pZn at the equivalence point for (i) [NH3] = 0.01 M,
and (ii) [NH3] = 0.1 O.
Given: At pH = 9, a L = a edta = 19.0; ~[Zn(edta)] = 3 10 16 ; step-wise stability constants for Zn2+-NH 3
ry
X
system, K l = 190, K2 = 210, K3 = 250, K4 = 110
ra
Solution: We have:
ib
~[Zn(edta)] = ~[Zn(edta)]aZnaedta
yl
(In general: ~[M(L)] = ~[M(L)]a~L)·
em
aM (i.e. a Zn ) is given by:
ch
aM = 1 + K l [NH3] + K 1K2[NH3]2 + K 1K2K 3[NH3]3 + KIK2K3K4[NH3]4
= 0.1 =1 +
al
For [NH 3] M; aM 190 x (0.1) + 190 x 210 x (0.1)2 + 190 x 210 x 250 x (0.1)3
+ 190 x 210 x 250 x 110 x (0.1)4
e
= 1.20 X 105
th
For [NH3] = 0.01 M; aM = 1 + 190 x (0.01) + 190 x 210 x (0.01)2 +190 x 210 x 250 x (0.01)3
e/
+ 190 x 210 x 250 x 110 x (0.01)4 .

t.m
= 27.82
A 16
[J- )
e
A' PZn(edta) = 3x10 zl.30x10 10 ( -

= 1.20x10 5 x19.0 ' atpH-9.0and NH 3 -O.lM
er
P[Zn(edta)] aZnaedta
H
16
3 X 10
~[Z
I
= 27.82 13
5.6 x 10 ,(at pH =9.0 and [NH 3 J= 0.01 M)
k
(d )] z
n e ta x 19.0
lic
=0.1 M)
C
Case-I (in presence of [NHal

(i) VL = 99.9 mL of 0.01 M edta solution (i.e. just before the equivalence point).
Cone. of Zn2+ not bound to edta = Tzn - [Zn(edta)2-]
= 0.01(100-99.9) M
100+99.9
= 5 x 10-6 M
.. T -[Zn(edta)2- ] -_ --1 2 10 5
B Y de fiInltIon, Zn [ ] a Zn . x
2
Zn +
-6
i.e. [Zn 2 +] = 5 x 10 = 4.16 X 10-11
1.2 X 10 5
and pZn = 10.38
(ii) For VL = 100 mL (i.e. at the equivalence point).
[Zn(edta)2- J== 100xO.01 M =5x10-3 M

100 + 100
~' _ [Zn(edta)2- J
2
[Zn(edta)] - (cone. of Zn + notJ x (cone. of edta not)
bound to edta bound to the metal
_ [Zn(edta)2- J
- {Tzn -[Zn(edta)2- J}{T J}
ry
edta
-[Zn(edta)2-
ra
At the equivalence point, TZn - [Zn( edta )2] =Tedta - [Zn(edta )2-] =X (say)
ib
5 X 10-3
yl
, 10
Thus: ~[zn(edta)] =1.3x10 = 2
em
X
3
ch
or, x 2 = 5 X 10- = 3.84 X 10-13
1.3 X 10 10
al
i.e. x = 6.2 X 10-7 M

e
By definition:
th
e/
TZn -[Zn(edta)2- ] = = 1 2 10 5
cx. Zn • x
t.m
[ 2+
Zn]
x = [Zn 2+]
e
or,
1.2 x 105
er
7
H
6.2 X 10- = [Zn 2+ ]

or,
1.2 x 105
k
lic
i.e. [Zn2+] = 5.16 x 10- 12 M

C
and pZn = 11.28

(iii) For VL = 100.1 mL (i.e. just after the equivalence point).
[Zn(edta)2- J~ 100xO.01 M==5x10-3 M
100 + 100.1
Cone. of edta not bound to the metal =T edta - [M(edta)]
0.01(100.1-100)
100+100.1
= 5 x 10-6
, [Zn (edta)2- J
~[zn(edta)] ={
T [
- Zn(edta)
2- J}{
T [Zn(edta) J}
2-
Zn edta -
3
or, 1.3 X 10 10 = 5 X 10-
{Tzn -[Zn(edta?-J}x5 x 10-6
or, TZn - [ Znedta

( )
2- J= 5 x 10-
10
3
-6=7.7xl0
-8
1.3 x 10 x 5 x 10
TZn -[Zn(edta)2- J__ <x' Zn = 1•2 x 105

[ 2+
Zn]
8
[Zn 2 + ] = 7.7 X 10- = 6.4 X 10-13
ry
or,
1.2 X 10 5
ra
i.e. pZn = 12.2
ib
Thus, pZn changes from 10.38 to 12.2 for increasing VL =99.9 mL to 100.1 mL i.e. pZn changes
yl
by 1.82 unit only at the equivalence point region.
em
Case-II (in presence of [NH 3l =0.01 M) ch
(i) VL = 99.9 mL of 0.01 M edta solution.
al
. [Zn 2+]- TZn -[Zn(edta)2- J_5xlO-6 M

e
It leads to. - (X.Zn -27.82

th
= 6.74
e/
i.e. pZn
t.m
e
er
H
k
lic
C
c
N
a.
----+ Vol. of edta solution
Fig. 11.7.5.1 Qualitative representation of the effect of [NH 3l on the change of pZn value for titration of Zn 2+ by edta
solution at pH.
1704 FUNDAMENTAL CON'CEPTS OF INORGANIC CHEMISTRY
(ii) VL = 100 mL (Le. equivalence point)

3
~' = 5.6 X 1013 = 5 X 120- ; or x = 0.94 X 10-8
X
8 8
[Zn 2 + ] = 0.94 X 10- 0.94 X 10- "" 3.4 X 10- 10
U Zn 27.82
Le. pZn = 9.46
(iii) VL = 100.1 mL of 0.01 M edta (i.e. just after the equivalence point)
3
T. -[Zn(edta)2- ] = 5 X 10'-3 = 5 X 10-
ry
Zn B X 5 x 10-6
I 5.6 x 10 13 X 5 x 10-6
ra
: : : 1.8 X 10- 11
ib
11 11
[Zn 2+ ] = 1.8 X 10- 1.8 X 10- = 6.4 X 10-13
yl
U Zn 27.82
em
Le. pZn = 12.2 ch
Thus at the equivalence point region, pZn changes from 6.74 to 12.2, i.e. by 5.46 unit.
Conclusion: If the titration by edta is carried out in [NH 3] = 0.01 M, then the change of pM at the
al
region of equivalence point is much sharper than the case of titration in presence of [NH 3] = 0.1 M.
e
Thus addition of too much buffer is a common source of error in edta-titration.

th
e/
11.7.6 Metal Ion Buffer

t.m
Bronsted conjugate acid-base pair (e.g. NH4+-NH 3 , CH 3C0 2H-CH 3COi, etc.) can act as a buffer to
resist the change of pH with the addition of strong acids or bases. Similarly, a system consisting of a
metal complex and excess complexing ligand can act as a metal ion buffer which can resist the change
e
of pM with the addition and removal of the metal ion. This can be realized by considering the following
er
equilibrium.
H
M + L ~ ML, (charges not shown for the sake of simplicity)

k
lic
A'
p =-[-]-, A' = Cond"thonaI stabOlo
[ML] p t tty constant
M CL
C
CL = Concentration of free ligand not bound to the metal ion

Here, it is assumed that there is no other ligand to complex with M. Thus we can write:
log~' = -log[M] + log [ML]

CL
or, pM CL
= logpA' + log-[M-L-]' ( [CB])
cf. pH = -log K a + log -[C-A-]
l--- --J
The above equation is similar to Henderson equation. At, CL = [ML], pM = log ~/. Introduction of
more metal ion will produce more ML Leo [ML] will increase and CL will decrease. Thus the system will
resist the lowering of pM compared to the system having no free L. If M is removed, it will be compen-
sated by the dissociation of ML, i.e. pM will not increase significantly. Thus the system consisting of
ML and free ligand can act as a buffer with respect to the change of pM.
11.7.7 Metal Ion or Metallochromic Indicators

An organic dye stuff to act as a metal ion indicator, it will have to satisfy the following conditions.
(i) The indicator as a ligand must form a suitable coloured complex with the metal ion at the same
pH range at which the metal ion complexes with the complexometric ligand. At the same pH
range, colour ofthe free indicator must be significantly differentfrom that ofthe metal-indicator
complex.
(ii) Under the experimental condition, the metal-indicator complex must be less stable than the
metal-complexometric ligand complex, so that the following reaction can occur.
metal-indicator complex + complexometric ligand ~ metal-complexometric ligand complex +
indicator.
Here it is worth mentioning that if the metal-indicator complex is of very poor stability, intensity
ry
of colouration of the metal-indicator complex will be very low because of its dissociation. Hence,
ra
it must have an optimum stability. In fact, the following conditions are to be satisfied.
ib
A' >10 8 . A' >10 4
P[ M( complexometric agent)] -
yl
, P[M(indicator)] -
em
~[M(comPlexometric agent)] > 104
and,
ch
~fM(indicator)]
al
where ~' denotes the respective conditional stability at the pH of titration.

e
(iii) All the equilibria must be attained rapidly under the experimental conditions.
th
Here we shall discuss the characteristics of two metal ion indicators - Erichrome Black-T (EBT)
e/
and Murexide.
• Erychrome Black-T (called also Solochrome Black-T): It is the sodium salt of I-(I-hydroxy-
t.m
2-naphthylazo)-6-nitro-2-naphthol-4-sulfonic acid. The sulfonic acid group (-S03H) is strongly

acidic. Thus dissociation constants of the two phenolic OH groups are to be considered.
e
It is generally represented as H2In-. For these two dissociable protons, the dissociation constants are:
er
pKa(1) = 6.3, pKa(2) = 11.5

H
OH OH
k
lic
N==N
C
(EST)
N02
H2In- can act as an acid-base indicator also as follows:

_ pKa(I) = 6.3 2 pK (2)= 11.5 In 3-
H 2 In \ >HIn - ;:::::====a======~
(Red) (Blue) , (Orange yellow)
The indicator gives the metal complexes which are wine red in colouration which is almost
identical with that of free indicator at pH below -5.5. This is why, in such low pH ranges, it cannot
be used as an indicator. At a higher pH (in the range 10 ± I), the problem does not arise. But at
pH ) 11.0, it does not work well because, colours of the [M(In)] complex and free indicator In3- are very
close.
M + H 21n- ~[M(ln)] + 2H+, pH < 5.5

(Red) (wine red)
M +Hln 2- ~[M(ln)] + H+, pH ~ 9 -11

(Blue) (wine red)
M+ In 3- ~[M(ln)], pH>12.5
(orange-yellow) (wine red)
The best pH range for EDT as a metal ion indicator is 9-10. Charges of the metal ion and metal-
indicator complex, i.e. [M(ln)] are not shown. The above indicator can be used for edta-titration of
Mg 2+, Mn2+, Zn2+, Pb 2+, Cd2+, etc.
ry
• Calmagite: EBT solution is unstable and it requires a fresh solution each day. This is the serious
ra
limitation of EDT though it is widely used. Calmagite is structurally similar to EBT and calmagite
ib
is a substitute of EBT. The indicator properties of calmagite are very much comparable with those
yl
of EBT. The main advantages of using calmagite is its stability in aqueous solution. It is also
em
represented as H 31n (i.e. triprotic acid). The sulfonic acid group is strongly acidic and this why it
is commonly represented as H 2In-.
ch
pKa ==8.1 2 pKa ==12.5 3
H2In-~<===~'Hln -~<===~ In-
al
(Red) (Blue) (Reddish orange)

e
th
OH HO
e/
t.m
N=N
e
er
H
Calmaglte
k
• Murexide: It is the ammonium salt of purpuric acid. There are four imido protons. Out of these,
lic
only two protons are dissociable havingpKa (1) =9.2 and pKa(2) = 10.5. The pH dependent equilibria
C
are shown below.
Murexide
Aqueous solution of murexide is unstable and it requires a fresh solution each day.
11.7.8 Selection of Metal Ion Indicator in ComplexometricTitration: A Quantitative

Treatment
Let us illustrate the case by taking erichrome black-T (EBT) as the representative metal ion indicator
(InH3). In InH3, the sulfonic acid group is strongly acidic while the other two dissociable protons are
weakly acidic (pKa-values 6.3 and 11.5). This is why, it is generally represented as H2In-. Thus in the
pH range, 10.5-12.0, we get the following predominant equilibrium.
M + Hln 2- ~[M(In)] + H+, pH ~ 10.5 -12.0

(Blue) (Wine-red)
The metal-indicator stability constant is given by:
ry
ra
Total concentration of the indicator in the above pH range is given by:
ib
yl
TIn = [M (In)] + [Hln 2 - ] + [ln 3- ]
= [M(ln)] + [ln 3- ] {I + [H+] }

em
ch
K a (2)(In)
where K a(2)(In) represents the following equilibrium.
e al
K
Hln 2 - < a(2)(In) ) H+ + In 3-
th
We can write:
e/
t.m
TIn - [M(ln)] = [ln 3- l{l + [H+] }

K a (2)(In)
e
In general, we can write:

er
I
H
TIn -[M(ln)]= [Inn-l{ [H+f + [H+r- +... + [H+] +l}

Ka (I)K a(2)···K a(n)
k
K a (2)K a (3) ••• Ka(n) Ka(n)

lic
= [lnn-]aIn' (cf. Sec. 11.7.3 for edta).

C
TIn - [M(ln)]
i.e. a In = [In n - ]
Ka(l)' K a(2), ••• stand for the successive deprotonation constants of the indicator Hnln. a In is a function
of pH (cf. Sec. 11.7.3 for OwL).
In the present case of EBT, we can write:
. [M(In)]
~[M(EBT)] z.e., ~[M(In)] = [M][In3~ ]
[M(In)]{l+ [H+] }
K a(2)(In)
[M] {TIn -[M(ln)]}
= ~[M(In)]<lIn
where f3'M(In) is called the conditional or effective stability constant of the metal-indicator complex.
At the transition point (i.e. the stage at which the indicator changes its colour), the following
condition is maintained.
Concentration of the metal-bound indicator ([M(ln]) = concentration of the free indicator, (at the
transition point) i.e. [M(ln)] =[In 3- ] + [Hln 2- ] .
ry
}H+] )
ra
i.e. [M(ln)l = [ln 3- ] ) 1+ = [ln 3 -1 <lIn
1
ib
a(2)(In)
yl
or, [M(ln)]t = [lnn-]t<lIn' (in general)
em
(Here 't' denotes the stage of transition point).
For EBT, the titration is generally carried out at the pH range close to 10 where the predominant
ch
indicator-proton equilibrium is:
al
Hln
2
- ~ In 3- + H+, pKa(2)(In) :::::: 11.5
e
Blue Orange red

th
[ln 3-
e/
]
pH = pKa(2)(In) + log [HIn 2- ] ' (cf. Henderson's equation)
t.m
At, pH == 10, the predominant form of the free indicator (EDT) is Hln2- that looks blue.
e
At the transition point, we can write:

er
H
k
lic
C
Of, [MJr = <lIn/~[M(In)J;
or (pM)t = log~[M(In)] -log<lln = log~[M(In)]·

(cf f3[M(ln)] = f3[M(In)]<lIn).
Now let us consider following expression of conditional stability constant of the metal-indicator
complex.
_ [M(ln)]
- [M]{[HnInJ + [ Hn_1In- ] +... + [In n- l}
[M(ln)]
[M] [Free indicator not bound to the metal]
M I [M] I R' I [Free indicator not bound to the metal]

or, p =- og = ogp[M(In)] + og [Metal bound indicator]
To detect the colour of the metal-bound indicator, its concentration must be at least 10 times greater
ry
than that of the free indicator. Similarly, for the detection of the colour of the free indicator, its concen-
tration must be atleast 10 times greater than that of the metal-bound indicator. Thus the range, where
ra
sharp colour change of the indicator occurs is given by:
ib
I(pM)t(range) = log ~[M<In)] ± 11, (cf· pHt(range) = pK In ± 1, in acid-base titration)
yl
em
and !(pM)t = log ~[M<In)] I ch
where concentrations of the metal-bound indicator and free indicator are equal.
For a successful titration, (PM)t of the indicator should lie close to (PM)equivalence i.e.
e al
(PM)t::::: (PM)equivalence, (cf. pHt i.e. pHtransition::::: pHequivalence in acid-base titration)

th
In fact, (PM)t(range) i.e. the range of pM value for the colour change (transition) of the indicator, should
e/
overlap with (PM)equivalence. It may be noted that, (PM)t(range) is governed by ~'[M(In)] while (pM)equivalence
is governed by ~'[M(Complexometricagent)]. Both these conditional stability constants are the functions of
t.m
pH and by monitoring the pH, the above mentioned condition may be satisfied.
• Illustration: Let us illustrate the case by taking EBT as the indicator for titration of Ca2+ and Mg 2+
e
by edta solution under the conditions.

er
T~ =T2 =0.1 M, vZ =100 mL

H
i.e. titration of 100 mL solution of 0.1 M Ca + or Mg 2+ solution by 0.1 M edta solution.

2
k
The results at different pH are shown in Table 11.7.8.1.

lic
Table 11.7.8.1 Results of titration of 100 mL 0.1 M Ca2+ or Mg 2+ solution by 0.1 M edta solution in presence
C
of EBT indicator at different pH values (pCa = -log[Ca2+], pMg = -log[Mg 2+])
Different parameters pH-values

7 8 9 10 11 12
log ~' [Ca(edta)] 7.3 8.4 9.4 10.3 10.6 10.7

(pCa)t = log ~'[Ca(ln)] 0.8 1.9 2.8 3.8 4.7 5.3
(pCa)equivalence = t log~'[Ca(edta)] + 0.65 4.3 4.8 5.3 5.8 5.9 6.0
log ~' [Mg(edta)] 5.3 6.4 7.4 8.3 8.6 8.7
(pMg)t = log ~'[Mg(In)] 2.4 3.4 4.4 5.4 6.3 6.8
(pMg)equivalence = t log ~' [Mg(edta)] + 0.65 3.3 3.8 4.3 4.8 4.9 5.0
log J3'[M(edta)] = log J3[M(edta)] - log u L ; for calculation of (PM)equivalence, see Table 11.7.2.3.
• Ca2+-estimation and EBT indicator: From Table 11.7.8.1, it is evident that for Ca 2+ at pH :::: 12,
the required conditions are attained:
(pCa)t :::: 5.3 and (pCa)equivalence :::: 6.0
i.e. the span of (pCa)t ± 1 i.e. 5.3 ± 1 overlaps with the pCa value of the equivalence point.
But for EBT, at pH > 11.5, the free indicator exists predominantly as In 3- which is itself red in
colour and it cannot be differentiated from that of the metal-indicator complex. This is why, EBT
is not recommended for Ca2+-estimation.
• Mg2+-estimation and EBT-indicator: Now let us consider the case of Mg 2+ estimation by using
EBT as an indicator. It is evident that at the pH range 9-10, the required condition, (pMg)t ::::
(pMg)equivalence is attained and in this range, the indicator predominantly exists as Hln2- (blue)
which is different in colour from that of the metal-indicator complex. Thus the titration is carried
ry
out at pH 9-10 (maintained by NH 3 + NH4 Cl buffer).
ra
At pH = 9, (pMg)t = 4.4 and (pMg)equivalence = 4.3
ib
At pH = 10, (pMg)t = 5.4 and (pMg)equivalence = 4.8
yl
i. e. at pH 9-10, the span of (pMg)t ± 1 covers the (pMg)equivalence
em
• Titration error in titrating Ca2+ and Mg2+ at pH == 10 by using EBT indicator: The experimental
conditions are:
ch
= TL0(.I.e., Tedta
TMo 0) = 0.1 M, VM0 = 100 mL
al
For Mg2+: (pMg)( = 5.4, (pMg)equivalence = 4.8

e
th
i. e. (pMg)t ± 1 inter~al spans (pMg)equivalence

e/
Thus colour changes after the equivalence point and at that region pMg is given by:
t.m
(pMg)t = log ~' [Mg(edta)] + log (VL - 100) - 2, (cf Table 11.7.2.3)
or, 5.4 = 8.3 + 10g(VL -
100) - 2
100) = 5.4 + 2 - 8.3 = 7.4 - 8.3 = -0.9
e
or log (VL -
er
or, VL = 100.132
H
i.e. the error is 0.132%

For Ca2+: (pCa)t = 3.8; (pCa)equivalence = 5.8
k
lic
i.e. (pCa)t ± 1 interval does not span (pCa)equivalence.

If the titration is carried out, the indicator will change the colour before the equivalence point.
C
Before the equivalence point, pCa is given by:

100+V 100+V
(pea)t = 1 + log 100 _ / ' or, 3.8 = 1 + log 100 _ / ' (cf. Table 11.7.2.3)
L L
10 100+VL =2.8
or, g 100 - V
L
100+ VL
or
, 100- VL
=631, or VL = 99.67
i.e. the error is 0.33 %. In reality, the error is much greater than 0.33 %
• Note: This difference between Ca2+ and Mg 2+ with respect to EBT arises from the fact that at pH
- 10, the Ca-EBT complex is much weaker than the Mg-EBT complex. In fact, Ca2+ cannot be
titrated by edta at pH - lOin presence of the EBT indicator. However, Ca2+ may be titrated by
using the EBT indicator at pH - 10 (maintained by NH4CI + NH 40H buffer) in presence of Mg 2+.
The Ca-edta complex is more stable than the Mg-edta complex·but the Mg-EBT complex is
more stable than the Ca-EBT complex. Thus, before the equivalence point, the Mg-EBT com-
plex gives the colour and Ca2+ is converted into the Ca-edta complex during the progress of
titration. When all the Ca2+-ions are complexed with edta, the Mg-EBT complex reacts with edta
to give the Mg-edta complex and free indicator that gives the blue colouration.
• Generally, for titration of Ca2+-solution, some amount of Mg-salt is added to the edta solution
before its standardization. Thus the titrant solution contains both the Mg -edta complex and free
edta. When the titrant is added to the solution containing Ca2+ (pH - 10 maintained by NH4CI +
NH 40H), the Mg-edta complex is converted into the more stable Ca-edta complex. Thus the
ry
liberated Mg 2+forms the Mg-EBT complex (wine red colour). When Ca2+is completely complexed
ra
with edta, additional titrant converts the Mg-EBT complex into the Mg-edta complex with the
ib
release of free indicator (blue colour).
Estimation of Ca2+ and Mg2+: Total content of Ca2+ and Mg 2+ can be estimated by edta titration at
yl
pH - 10 (maintained by NH4CI + NH40H) using EBT titration. This method is commonly used for the
em
determination of total hardness of water. To determine Ca2+ alone, pH of the solution is adjusted to
about 12 (by the addition of requisite amount of NaOH solution) and then it is titrated by a standard
ch
solution of edta in the presence of murexide indicator. The end point is detected from the colour
al
change, red to purple. Very often the colour change is not distinct. At this pH, Mg2+is precipitated out
as Mg(OH)2 and Ca 2+ is alone titrated by edta.
e
th
It has been already pointed out that Ca-egta (log ~ = 11 .0) is much more stable than Mg-egta
(log ~ = 5.5) and Ca2+ can be selectively titrated by egta in presence of Mg 2+ by using a suitable indicator.
e/
t.m
11.7.9 Different Types of Complexometric Titrations

Complexometric titration can be carried out for most of the common metal ions. In fact, complexometric
e
titrations have successfully replaced the tedious gravimetric analysis. There are several procedures of
er
complexometric titrations.
H
(i) Direct titration: In this method, the metal ion to be estimated is directly titrated at a suitable
k
buffered pH and the end point may be detected by using the suitable metallochromic indicators or by
lic
potentiometric or by spectrophotometric or by amperometric method, etc. This method is applicable

only when the said complexation reaction is fast.
C
However, complexometric titration by using the metallochromic indicators is the most convenient
way. In fact, several metal ions can be titrated by edta in this method. Very often, NH 3-NH4 CI buffer
is used to maintain the pH 9-10. Some metal ions undergo complexation with NH3 to avoid the
precipitation of metal hydroxides. In some cases, other complexing agents like citrate, tartarate, etc.
may be used to prevent the precipitation of metal hydroxides. However, it may be mentioned that
presence of such auxiliary complexing agents (that may come from the buffer also) can introduce some
titrational error because of the lowering of conditional stability constants. This aspect has been discussed
in Sec. 11.7.5.
(ii) Back titration: When the metal ion to be estimated reacts slowly with the complexometric agent
or suitable metallochromic indicator is not available, excess but known amount of the complexometric
ligand is to be added at the desired buffered pH ligand. If the metal ion to be estimated is kinetically
inert, after the addition of this excess amount of complexometric ligand, the solution is heated for some
time to ensure the complete reaction. Then, the excess (remaining uncomplexed) complexometric ligand
can be back titrated by using a standard solution of Mg 2+ or Zn 2+. This method can be applied for the
estimation of cr3+ (which reacts slowly because of kinetic inertness), Pb 2+ in insoluble PbS04, Ca2+ in
insoluble Ca-oxalate.
(iii) Substitution or replacement titration: When there is no suitable metal indicator, an excess of
a solution containing the Mg-edta complex is added to the solution of metal ion (say MO+) to be
estimated. If under the experimental conditions, the Mg -edta complex is less stable than the M -edta
complex, then the following reaction will occur to release an equivalent amount of Mg 2+.
MO+ + [Mg(edta)]2- ~ [M(edta)](4-o)- + Mg 2+
Thus the released Mg 2+ can be titrated with a standard solution of edta by using the EBT indicator.
Depending on the condition, besides the Mg-edta complex, Ca- and Zn-edta complexes may be also
used. Thus the general reaction is:
ry
Mf+ + [M(edta)]2- ~ [M 1(edta)](4-o)- + M 2+,
ra
(M 2+ = Mg 2+, Ca2+, Zn2+; Mr+ is to be estimated).
ib
The basic condition is:
yl
~[Ml(edta)]» ~fM(edta)]' and the substitution reaction is kinetically fast.
em
Then the released M 2+ can be estimated complexometrically as usual.
Sometimes, a different metal complex may be added for this purposes. For example, in estimating
ch
Ag+, [Ni(CN)4]2- can be added and the liberated Ni 2+ can be estimated complexometrically as usual.
al
[Ni(CN)4]2- + 2Ag+ ~ 2[Ag(CN)2]- + Ni 2+
e
To make the reaction quantitative, it must have:

th
~[' Ag(CN )J- »~[' Ni(CN)4 J2-

e/
(iv) Acid-base titration: When Na2H2edta reacts with the metal ion, per mole of the metal ion, two
t.m
equivalent of hydrogen ions are released.

MO+ + H2edta 2- ~ [M(edta)](4-o)- + 2H+
e
The released H+ can be determined either by alkalimetric or potentiometric titration.

er
(v) Indirect titration and estimation of anion: In this method, a number of anions can be estimated.
Sulfate in solution can be estimated by adding an excess amount of Ba2+ or Pb2+ solution. This will
H
give the precipitate of BaS04 or PbS04. Then the unconsumed Ba2+ or Pb 2+can be directly titrated with
k
a standard solution of edta. Here, it is assumed that during the titration of Ba2+ and Pb2+ by edta
lic
solution, the precipitated BaS04 or PbS04 will not react with edta. In the other way, precipitated BaS04
C
or PbS04 is separated and treated with an excess of edta solution and then heated to allow the precipi-
tate to react with edta. Then the unreacted edta is back titrated with a standard Mg2+ solution.
For the estimation of phosphate in solution, it is precipitated as Mg(NH4)(P04) which is collected
and dissolved in acid. Then an excess amount of edta solution is added and pH is adjusted to about 10
and then the uncomplexed edta is titrated with a standard Mg 2+ solution by using EBT indicator. Here
it is possible because the MgII-edta complex is more stable than the MgII-phosphate complex.
For the estimation of halides, these are precipitated as AgX which is dissolved in an excess amount
of [Ni(CN)4]2- and the released Ni 2+ is titrated with the edta solution.
2AgX + [Ni(CN)4]2- ~ 2[Ag(CN)2]- + Ni 2+
11.7.10 Selectivity in Titration with edta by Controlling pH

If the conditional stability constants «(3') of the metal-edta complexes differ significantly for the different
metal ions then the consecutive end points for a system having more than one metal ion can be obtained
(cf titration of mixed acids by alkali). However to detect these consecutive end points, it is exceptionally
difficult to obtain the suitable metal indicators.
By adjusting the pH, selectivity in titrations with edta can be attained to some extent. Metal ions
forming the more stable complexes can be titrated at a lower pH where the metal ions forming the less
stable complexes will not interfere. For example, in a solution containing Fe(lll) and divalent metal ions
like Mg(II), Ca(II), etc, Fe(lll) can be titrated at pH - 2 with a standard solution of edta without any
interference from the divalent metal ions. It is possible because at pH = 2, the conditional stability
constant of the Fe(III)-edta complex is about 10 12 while under the same condition, conditional stability
constants of the edta-complexes of the said bivalent metal ions are negligibly small. Similarly, Ni(ll)
which forms a more stable complex with edta can be titrated at pH about 3.5 in presence of Ca2+ and
Mg 2+ which form very weak complexes with edta at this pH. However at pH - 10, (i.e. NH4CI + NH3
ry
buffer) the interference will appear. In fact, in presence of NH3, Ni(ll) will form the ammine complexes
and consequently ~[Ni(edta)] will drop and in fact, the effective stability constant of [Ni(edta)]2- becomes
ra
comparable with those of the [M(edta)]2- (M = Mg, Ca) complexes at pH - 10. It may be noted that
ib
alkaline earths (being hard) do not form any stable ammine complex.
yl
em
11.8 MERCURIMETRICTITRATION OF HALIDES: FORMATION OF MULTIPLE
COMPLEXES DURING TITRATION
ch
It will be illustrated for Hg(II)-CI- system where the stepwise stability constants are given below.
al
Hg 2+ + CI- ~ [HgCI]+, log K 1 = 6.7 ; pK_ 1 = 6.7

e
log K2 = 6.5 ; pK_2 = 6.5

th
[HgCI]+ + CI- ~ [HgCI]2'

e/
[HgCI]2 + CI- ~ [HgCI3]-, log K 3= 0.8 ; pK_3 = 0.8

t.m
[HgC13]- + CI- ~ [HgCI4 ]2-, log K4 = 1.0 ; pK-4 = 1.0

K h K 2, are the successive formation constants while K_ h K_2 , •...•• are the corresponding
e
dissociation constants. It indicates that K1 and K2 are comparable but the values of K 3 and ~ are
er
drastically dropped. Thus if a solution containing CI- is titrated with Hg(II), then with the progress of
H
: titration before the equivalence point, concentration of Hg(ll) will be mainly monitored by the following
equilibrium.
k
lic
C
2
pHg = -log [Hg +] pCI = -log [cr]
Equivalence
point U
a. Equivalence
point
1 1
---+ Vol. of Hg (II) solution ---+ Vol. of cr solution
(a) (b)
Fig. 11.8.1 Qualitative representation of mecurimetric titrations

Thus [Hg(II)] i. e. pHg = -log[Hg 2+] will be determined by the dissociation of HgCl 2 which is very
much stable. Consequently, pHg will remain more or less constant up to the complete formation 0:
HgCI 2. When formation of HgCl 2 is complete., pHg will drop sharply, i.e. [Hg(II)] will increase sharply
with the addition of any excess amount of Hg2+. In fact, at the equivalence point pHg will be controlled
by the following equilibrium.
HgCl 2 + Hg 2+ ~ 2HgCI+, Keq = K/K 2 ::::: 1.8
After the equivalence point, added Hg2+ will remain free and its concentration will be determined by
the equilibrium, HgCl 2 + Hg2+ ~ 2HgCI+ and thus pUg will drop but not sharply because of its
consumption in the above reaction forming HgCI+. Similarly, if Hg(II) solution is titrated by a CI-
solution, before the equivalence point [CI-] will be determined by the dissociation of HgCl 2 which is
ry
highly stable, i.e. pCI will remain more 01 less constant. Just after the equivalence point (i.e. when
formation of HgCl 2 is complete), there will be a sharp increase of [CI-] i.e. there will be a sharp fall
ra
in the pCI value because of the formation of weak [HgCI 3]- complex. The pCI value at the equivalence
ib
point is approximately given by 1/2(pK_2 + pK_3 ) = 3.7. The equivalence point can be detected
yl
potentiometrically. This can be done also by using a suitable indicator.
em
When the titration is carried out by the addition of Hg(II)-salt, sodium nitroprusside Na2[Fe(CN)sNO]
can be used as an indicator. Sodium nitroprusside gives a white precipitate of Hg[Fe(CN)sNO] i.e.
ch
Hg(II)-nitroprusside. After the equivalence point, excess Hg(II) gives this white precipitate indicating
the end point.
al
Br-, SCN-, CN- can also be determined by mercurimetric titration. For SCN- determination,
e
th
Na2[Fe(CN)sNO] cannot be used as the indicator because the white precipitate of Hg[Fe(CN)sNO] is
obscured by the sparingly soluble [Hg(SCN)2]. In this case, Fe(III) can be used as the indicator which
e/
forms the red colour with SCN-.

t.m
Note: In Hg(II)-X- system, compared to K] and K 2 the last two stepwise stability constants K 3 and K 4
are remarkably reduced.
e
[HgX 2] + X- ~ [HgX 3]-, (K3 ); [HgX 3 ]- + X- ~ [HgX4 ]2-, (~)

er
Hg(II) has got the preferred tendency to have the linear geometry. HgX2 is linear but [Hg(OH2)X 3 ]-,
H
[HgX4]2- are tetrahedral. In K 3 , fixing of a solvent molecule produces an entropic disfavour. These
k
aspects have been discussed in Chapter 4.

lic
EXERCISE 11
C
A. General Type Questions

1. Discuss the role of complexation in qualitative analysis of Gr-I and Gr-II precipitate.
2. (a) Give the complexation reaction utilized in qualitative detection of the following metal ions.
Cu 2+, Bi 3+, Fe 2+, Fe 3+, AI 3+, Co 2+, Ni 2+, V S+, Ti4+, Z~+, M06+ (as molybdate), Pb 2+, Cr6+ (as
chromate), Cu+.
(b) Give the reactions of V(V), Cr(VI) and Ti(IV) with H 20 2 in different conditions.
3. Discuss the role of complexation behind the chemistry of ring test for NOi, and aqua regia in
dissolving the noble metals.
4. Discuss the role of complexation in solvent extraction of metal ions.
5. Discuss the role of complexation reactions in spectrophotometric analysis of metal ions.
6. Complex formation reactions are very much important in gravimetric analysis of metal ions.
Illustrate with suitable examples.
7. What do you mean by masking and demasking agents? Illustrate with examples.
8. Discuss the use of complexes in medicinal chemistry.
9. Give the examples of chelating antidotes used in detoxification of metal ions.
10. Discuss the importance of complexation reactions in (i) water softening, (ii) food preservation,
(iii) Rasching process ofhydr~zine synthesis, (iv) electroplating process, (v) metallurgical process,
(vi) photography, (vii) agriculture.
11. The phenomenon, complexation is quite important in stabilization of the unusual oxidation states
of metals - illustrate.
12. Define the terms: complexometric and chelometric titration, chelones, metallochromic indicators,
conditional or effective stability constant, complexone.
13. Give the examples of complexones used in complexometric titrations.
ry
14. Discuss the complexing behaviour of edta.
ra
15. Discuss the general nature of the titration curve (pM vs. volume of complexone) in a complexometric
ib
titration. How do you compute the pM values before the equivalence point, at the equivalence
point and after the equivalence point?
yl
16. "The change of pM value at the equivalence point in a complexometric titration depends on the
em
conditional stability constant of the metal-chelone complex" - illustrate.
17. Give the minimum value of conditional stability constant required for a complexometric titration.
ch
18. Discuss the variation of different species of edta with the change of pH. What do you mean by
al
Uedta? Give its expression in terms of the acid dissociation constants of H 4 edta.
e
19. In edta-titration, the conditional (i.e. effective) stability constant is given by:
th
log f3' = log f3 - log Uedta

e/
f3' = conditional stability of the f3 = corresponding thermodynamic stability

[M(edta)] complex,
t.m
constant
(Note: Assume, metal ion only undergoes complexation with edta).
Establish the above relation.
e
er
20. Conditional stability constant, f3'[ML] of the complex is in general given by:
H
~~L = UM(X.L
~ML , aM and a L bear the usual significance.
k
lic
Establish the above relation.

C
21. In the complexometric titrations by edta, to attain the required conditional stability constant, very
often pH is required to increase - illustrate.
22. In edta titration, very often pH is to be raised but to avoid the precipitation of the metal ion to 1)e
titrated, masking agents may be required. Explain.
23. In the complexometric titrations, the buffers (containing the complexing ligands) can introduce
the titrational errors - illustrate.
24. Discuss the role of metal ion indicators in complexometric titrations. Give the characteristic
properties of EBT and murexide indicators.
25. (a) Give the required minimum values of the following conditional stability constants in
complexometric titrations.
f3' [M(chelone)] and f3' [M(indicator)]
(b) Give the required value of pM i. e. (PM)t at which the metal indicator changes its colour.
(c) Give the relation between (PM)t and (PM)equivalence to be satisfied in a complexometric titration.
26. Mg 2+ can be estimated by edta by using the EBT indicator but Ca2+ cannot be estimated by edta
by using the EBT indicator. Explain in a quantitative way.
27. Ca2+ can be estimated by edta by using the murexide indicator. Illustrate.
28. EBT as a metal ion indicator works well only in the pH range 8-10. At lower and higher pH, it
cannot work. Explain the fact.
29. All the metal ion indicators are the acid-base indicators - illustrate.
30. How can you determine Ca2+ by edta using the EBT indicator?
31. Discuss the different types edta titration.
32. How can you determine the following anions by edta titration?
sulfate, phosphate, halide, cyanide
33. "By monitoring the pH, one metal ion can be titrated by edta in presence of other metal ions" -
ry
illustrate with examples.
ra
34. Monitoring of pH can give the selectivity in edta titration. Illustrate.
35. What do you mean by mercurimetric titration? Discuss the nature of titration curve when CI- is
ib
titrated by a soluble Hg(II) salt. Name the indicator that can be used in this titration. Discuss the
yl
nature of titration curve when Hg 2+ is titrated by CI-.
em
36. Give the structures and applications (in analytical chemistry) of: cupferron, ferron, ferroin,
bathocuproin, aluminon, neocuprion, trifluoroacetylacetone, dithizone, diphenylthiocarbazone,
ch
rubeanic acid, aluminum red lake, egta, calmagite, quinalizarin, alizarin-S, chromotropic acid,
oxine, thiourea, a-nitroso-~-naphthol, oximes, arsonic acid; peroxido complexes of Cr(VI), Cr(V),
al
Cr(IV), V(V) and Ti(IV).

e
th
B. Justify the following statements

e/
1. Hg 2Cl2 and AgCI can be separated through complexation with NH 3 •

t.m
2. In the qualitative analysis, the Gr IIA and lIB sulfide precipitates can be separated through
complexation.
3. Cu 2+ and Cd2+ are separated through the formation of cyanido complexes.
e
er
4. Sometimes, the charged complexes can also be extracted into the organic solvents.
5. Fe(lll) and AI(III) can be separated as their oxinate complexes.
H
6. Zr(IV) and Hf(IV) can be separated through solvent extraction.

k
7. Co(ll) and Ni(ll) can be separated through solvent extraction.

lic
8. Interference of Fe(lll) can be avoided by using the suitable masking agents.

C
9. Zr(IV)-alizarin reaction can be used for the estimation of P-.

10. bpy and phen give different colours with Fe(ll) and Fe(III).
11. Reaction of chromate with diphenylcarbazide gives the colour of Cr(II)-inner complex.
12. In the detection of Co(II), a-nitroso-~-naphthol is used but actually the reaction involves Co(III).
13. Oxinate complexes may be used in a volumetric analysis.
14. Cu 2+, Zn2+ and Mg 2+ in a solution can be separately estimated by edta titration.
15. Be(ll) and AI(III) can be separated by NH4 0H in presence of edta.
16. HSAB theory is important in designing the chelating antidotes in detoxification of metal ions.
17. 99mTc complexes find uses in diagnosis of some diseases.
18. Na2Caedta and Na2Znedta instead of Na2H2edta are used in chelation therapy.
19. Paramagnetic complexes of Gd(III), Fe(III) and Mn(ll) are used in MRI.
20. Complexation in the electroplating process enjoys many advantages.
21. The deposition potentials of Cu2+ and Zn 2+ are different but they can be simultaneously deposited
in presence of CN-.
22. Electroplating by copper in presence of CN- requires a less electricity consumption.

23. The noble metals like Au, Ag, Pt, etc. become quite reactive in presence of CN-.
24. Cu readily dissolves in water in presence of CN-.
25. Chemistry of aqua regia involves both the redox and complexation reactions.
26. Fixing in photography involves complexation.
27. In alkaline soil, to meet the iron deficiency of plants, Fe(III)-edta is used.
28. Conditional stability constant of the metal-edta complex depends on pH.
29. The change in pM value at the equivalence point largely depends on the conditional stability
constant of the metal-chelone complex.
30. In a complexometric titration, the metal-indicator complex should have an optimum conditional
stability constant.
ry
31. EBT is only effective in the pH range 9-10.
ra
32. Colour change of a metal ion indicator depends on a particular value of pM
i.e. (PM\ = log ~/[M(In)] ± 1
ib
2
yl
33. Mg + can be estimated by edta in presence of the EBT indicator.
em
34. EBT cannot work at pH below 6.0 and above 11.0.
35. Ca2+ cannot be titrated by edta solution in presence of EBT but in presence of murexide.
36. For the estimation of Ca2+ by edta in presence of EBT, it needs the presence of Mg 2+.
ch
37. If a mixture of Ca2+ and Mg2+ is titrated by edta in presence of murexide at pH - 11.5, then Mg 2+
al
does not interfere.

e
38. When pH is adjusted by NH 3 + NH4CI, the conditional stability constants of the M-edta complexes
th
(M = Mg 2+, Ca2+) do not depend on [NH3] at a fixed pH, but the conditional stability constant of
e/
the Zn-edta complex depends significantly on [NH 3] at a fixed pH.

39. The system constituted by ML and excess L can act as a metal ion buffer (i. e. resistant to the
t.m
change of pM).
40. Kinetically inert systems like Cr3+ can also be estimated by edta in back titration.
e
41. 50]-, HPOl-, C 20]-, halide can be estimated by edta titration.

er
42. In edta titration, sometimes other complexing ligands are required as the masking agents.
H
43. By monitoring pH, Fe(III) can be titrated by edta in presence of Mg(II) and Ca(II).
44. Ni(II) can be estimated by edta in presence of Ca(II) or Mg(II) but the reverse is not true.
k
In Hg(II)-CI- system, compared to K} and K2, the last two stepwise stability constants K 3 and ~
lic
45.
are drastically reduced.
C
46. CI- and Br- can be titrated by Hg(II) in presence of Na2[Fe(CN)5NO] as an indicator.
APPENDIX 11 A: Distribution of Different Species of EDTA at Different PH Values

It can act as a hexaprotic acid H6edta2+ (say H6L2+).
H02C-H2~ /CH 2- C 0 2H
H/N+-CH2-CH2-+N~ H (Hl+)
H02C - H2C CH 2- C02H
The successive pKa values (at -20°C) are:

o 1.5 2.0 2.7 6.2 10.3
v
4 carboxylic protons 2 ammonium protons.
ry
ra
ib
yl
em
ch
e al
th
e/
t.m
e
er
H
k
lic
C
2 4 6 8 10 12
-----+~ pH
Fig. 1 Distribution of different protonated species of edta at different pH values.

Spectroscopic Methods (IR, Raman, NMR,
ESR, Mossbauer, UV-VIS, UV-PES) and
ry
ra
other Physical Methods in Chemistry
ib
yl
12.1 VIBRATIONAL SPECTROSCOPY: INFRA-RED (IR) AND RAMAN SPECTRA
em
ch
12.1.1 Some Important Aspects of the IR and Raman Spectra
al
(A) Energy states of a vibrating diatomic molecule (A-B): The nuclei oscillate in such a way that the
e
th
internuclear distance periodically varies about an equilibrium distance (cf property of a simple harmonic
oscillator). The oscillation frequency is:
e/
t.m
ffiosc = 2~ ff Hz ,
~ (reduced mass of the system) =
k =force constant of the bond

mm
A B
(m A +m B )
e
i.e.
Jfr
er
-
00 = - - =1- -cm -1
ooose c = velocity of light.
ose C 21tc ~
H
k
Solution of the Schrodinger equation for a harmonic oscillator, gives the vibrational energy as
lic
follows:
±)
C
Ev =( v + hffiosc joules, v (vibrational quantum number) = 0, I, 2, '"
Eo (zero point energy) = .!..hffiosc joules (for v = 0)

2
Selection rule for a harmonic oscillator experiencing the vibrational energy level changes is:
~v = ±1
For the v = 0 ~ v = 1 transition, the energy change is:

- v roos -
liE = hv =hroose i.e. v = roose or v =- =__ e = roose
c c
In general, v ~ v + 1 or v + 1 ~ v i.e. ~v = ±1,
1719
i.e. v = IDose or V = IDose

when the vibrational energy levels are equally spaced, the vibrational transition between the adjacent
levels will give the same energy change.
Table 12.1.1 Vibrational wave numbers ill or V and force constants (k) for some simple diatomic molecules
Molecule ooosc or v (em-I) k (dyne/em) Molecule ooosc or v (em-I) k (dyne/em)
ry
HF 3960 8.8 x 105 F2 892 4.5 x 105
ra
Hel 2890 4.8 x 105
Cl 2 557 3.2 x 105
ib
HBr 2560 3.8 x 105 Br2 321 2.4 x lOS
yl
HI 2230 3.0 x 10 5
CO 2143 18.7 x 105
em
NO 1876 15.5 x 105
ch
v
al
t--------r-------f 8 Continuum of
e
__________ ~~v~~~~____________________ _ _
th
e/
8
t.m
7
6
Realistic
5
e
er
~
4
~
Do
H
Q)
c 3
w
De
k
i r 2 2nd overtone
lic
C
req .
- - . Internuclear
distance (r) ----+ Internuclear distance (r)
(a) Harmonic oscillator (b) Anharmonic oscillator

(Selection rule: /).V = ±1) (Selection rule: /).V = ±1 , ±2, ±3, ...)
Fig. 12.1.1.1 Morse potential diagram: Vibrational energy levels in (a) harmonic oscillator and (b) anharmonic
oscillator where at the higher values of v, the energy levels are closely spaced to give a continuum of levels.
Anharmonicity in the potential energy curves leads to the following important observations.
• Morse potential function: Ep (potential energy) = De (1 - e-ax )2; De (classical bond dissociation
energy) and a are constants; x = r (internuclear distance) - re (equilibrium distance)
SPECTROSCOPIC METHODS AND OTHER PHYSICAL METHODS IN CHEMISTRY 1721
• The energy levels are no more equi-spaced.

• The energy difference between the successive vibrational energy levels decreases for the higher
vibrational levels.
• The selection rule ~v = ±1 for the harmonic oscillator is relaxed and the transitions with ~v = ±2,
±3, ... , become also allowed.
~v = ±1 (v = 0 ~ 1; fundamental transition); ~v = ±2 (v = 0 ~ 2; first overtone); ~v = ±3
(v =0 ~ 3; second overtone); and so on.
For Hel: fundament (2890 cm- I ), first overtone (5668 cm- I ), second overtone (8347 cm- I )
Hot-band: At ordinary temperature, population density at the higher vibrational levels (v = 1, 2, 3, ... )
has been ignored but at higher temperature, population density at these higher levels become quite
ry
significant and the transitions (for (~v = + 1) like v = 1 ~ 2, v = 2 ~ 3, etc. become significant. Such
ra
bands (recorded at the relatively higher temperature) are called hot bands.
JK, i.e.
ib
(B) Effect of isotopic substitution on vibrational frequencies (cj. Sec. 5.2.2; Vol. 1): (Oose oc
yl
if
em
(Oose oc (assuming k and internuclear distance to be the same for the isotopes)
ch
For two isotopic molecules 1 and 2, we can write:
ff- ff-
al
I
rot = 2:C
e
(OJ = 2n i.e.
th
e/
t.m
:: =t;
e
er
It leads to:
H
For the isotopic molecules, A-H and A-D (H, 0 are the isotopes of hydrogen),
k
~~: ~ ~:: ~ Jf = l.~1

lic
:: =
C
Illustration: In R2AsH, VAs-H = 2080 cm- 1
- - 1 2080 -1
VAs - D =V As - H x--=--=1475 cm
1.41 1.41
-V _ 1850 -1320 cm -1
c 0- D -
1.41
-
Table 12.1.1.2 Vibrational wave number (v) and isotopic shift C~v) for
some isotopic diatomic molecules.
Molecule v (em-I) /),V (em-I)
I H35Cl} 289O}
2H35CI 2090 800
I H127I} 223O}
2H1271
1600 630
35 Cl 19 F }
ry
37 Cl19p
793} 15
ra
778
ib
(C) Combined rotational-vibrational energy for a diatomic vibrator: Assuming, Etotal = E rot + E Vib
yl
- ( 1) - () 1 Jfr -
em
E v 1 = v+- v+Bl 1+1 ; v=-- - andB=-2- h
'2 21tc Jl ch 81t Ie
I (moment of inertia) = J.!,2; 1 = (rotational quantum number) = 0, 1, 2, 3, ....
Selection rules for the combined motions: ~v = ±1, IV = ±1
al
For a particular vibrational level, the rotational energy levels (1 = 0, 1, 2, 3, ... ) exist.
e
For v = 0 ~ v = 1, we can write:

th
M 1 ,v =E1 " v=l -E1 ,v=o

e/
(%v-±v)+ ii[ 1'(1' + 1) -

t.m
= J (J + 1)J
e
= v + B [1'(1' + 1) -1(1 + I)J

er
• For IV = +1 i.e. 1 ~ l' = 1 + 1 (R-branch) IV = -2 -1 0 +1 +2

H
M 1v =v+2B(J+l);1=0, 1,2, ... (Branch) 0 P Q R S

k
For IV = -1 i.e. J ~ J' = (1 - 1) (P-branch)

lic
•
M 1 ,v =v-2B(J' +1)=v-2BJ
C
J' = 0, 1, 2, .... i.e. J = 1, 2, 3, .....

• For IV = 0 (Centre of the band; Q-Branch)
~J, v = V (fundamental vibrational frequency)
But, for a diatomic molecule, IV ~ 0 i.e. vibrational change must involve a simultaneous rotational
change. Thus a diatomic molecule gives the PR band not the PQR band. The vibration-rotation
combined spectrum consists of equally spaced lines (2B) on each side of the band origin V (i.e.
Q-branch). For CO, the band centre appears at 2143 cm- I with 2B = 3.83 cm- I . P-lines appear at
2139.43 cm- I , 2135.55 cm- I , 2131.63 cm- I , ... and R-lines appear at 2147.08 cm-t, 2150.86 cm- I ,
2154.59 cm- I , ....
Selection rules for the linear molecules:
(i) Diatomic molecule (e.g. CO): ~v = ±l, ±2, ±3 ... ; LV = ±1; LV ~ 0 i.e. no Q branch i.e. PR band)
(ii) Poly~tomic linear molecules (C0 2, HCN, N 20, C2H 2, etc.)
(a) Parallel vibrations (i.e. oscillating dipole parallel to the molecular axis, e.g. antisymmetric
°
stretching in = C = 0): ~v = ±1, ±2, ±3, ... ; M = ±1, ~J *" 0 (as in the diatomic molecule
giving the PR band).
Presence of the PR band indicates the linearity of the molecule.
(b) Perpendicular vibrations (i. e. oscillating dipole moment perpendicular to the molecular
axis, e.g. bending mode of vibration in CO 2): ~v = ±1, ±2, ±3, ... ; M = 0, ±1 (PQR band)
(iii) Nonlinear polyatomic molecules: These are of different types like spherical (e.g. CCI4 ), symmetric
top (e.g. CHCI 3, CH 3Br, NH 3, etc. C3v point group) and asymmetric top (e.g. S02, 03' S02C12,
etc.). In the symmetric top molecules, oscillating dipole moment may lie either parallel to the
unique axis (e.g. C 3 axis in CH 3Br) or perpendicular to the axis. For the symmetric top molecules,
parallel absorption band appears with the P, Q and R branches (i.e. similar to the perpendicular
ry
band of a linear molecule) and perpendicular absorption band appears with the several
ra
Q-branches (e.g. PQQR band). In CH3CI, the C-CI bending vibration give.s the perpendicular
ib
band.
yl
Q
em
ch
al
R
P
e
th
J'values
e/
} for v=1
t.m
e
i
er
H
k
---. Internuclear distance

lic
(a)
C
R
P
Q-branch
R-branch _
P-branch
r 28
.~--- v(cm- ---.~

1
)
(b) (d)
Fig. 12.1.1.2 (a) Rotational energy levels for v = 0 and 1; (b) PQR branches for rotational-vibrational spectrum;
(c) PQR branches (under low resolution) for rotational-vibrational spectrum, (d) PR branches (under low resolution)
for rotationpl-vibrational spectrum.
(D) Raman spectrum: A monochromatic beam of light illuminates the sample and the scattered light
is observed at right angles to the incident beam. If the incident light and scattered light are found to have
the same frequency (say YO) i.e. no change in frequency, it gives the Rayleigh scattering. If the
frequency of the scattered light is less than that of the incident radiation, it gives the Stokes lines
(Raman scattering) but if the frequency of the scattered light is higher than that of the incident radiation,
it gives the anti-Stokes line (Raman scattering).
When the incident light (vofrequency) induces a vibrational transition (say v = 0 ~ v = 1, the energy
requirement for this vibrational transition =hv), frequency of the scattered light becomes (vo - v) (i.e.
Stokes lines). If the vibrationally excited molecule (v = 1) interacts with the incident radiation and
transfers the excitation energy (hv) to come back to the ground state (v = 0), then the incident radiation
gains the additional energy hv and if this photon scatters, it will possess the frequency V o + v (i.e. anti-
ry
Stokes lines). There are many other ways for returning from the excited state (v = 1) to the ground state
(i.e. v =0) and consequently, intensity of the anti-Stokes line is much lower than that of the Stokes
ra
lines.
ib
yl
v'=1------
em
Upper
electronic
v'=o------ } state
ch
/-,.--_..._---- ------
e al
Virtual
th
level
e/
Virtual
level
t.m
hv o .....
e
,.,.,.,.,.,.,.,.
v v v v v v v v...
er
hv'
~
H
v') V o
k
lic
v=1
Ground
C
hv
}. electronic state
v=O----I...--....I....--
Rayleigh Raman scattering Raman scattering
scattering (Stokes line) (Anti-Stokes)
Fig. 12.1.1.3 Schematic representation of vibrational Raman scattering.

Note: Virtual energy level is not the real energy state. If the virtual energy level resides within the upper electronic state,
then Raman resonance will occur to the lines in the same way.
Thus the Raman effect may be described as an optical analogue of Compton effect. The interaction
between the incident photon and molecule may be considered as a collision process. Rayleigh scattering
(i.e. unmodified line or frequency) is the result of elastic collision while Raman scattering (i.e.
modified lines or frequencies) is the result of inelastic collisions.
The collision time (-1 0-15S) for the collision of the photon with the molecule is exceedingly small.
In an inelastic collision, there can occur an exchange of energy between the photon and the. molecule.
This will change the vibrational or rotational energy of the molecule. Principle of conservation of
energy can be applied for the collision process.
1 2 1 2
Eo +-muo +hv o = E +-mu +hv
I I
2 2
(Before collision) (After collision)
Where a molecule of mass m in the energy state Eo is colliding with a light photon of Vo frequency, it
changes the energy state from Eo to E' and velocity from Uo to u and frequency of the light photon
changes from Vo to v'. Assuming no change in temperature (i.e. no change in kinetic energy during the
collision), we can write:
'
Eo+hvo=E I +hv I .I.e. VI =v o + (Eo h- E =v o + liE J
ry
h
ra
• Elastic Collision: liE = Eo - E' = 0 i.e. v' = V o (unmodified line i.e. Rayleigh scattering)
• Inelastic Collision: Eo ( E' i.e. liE = -ve and v' ( vo. This gives the Stoke's lines.
ib
yl
• Inelastic Collision: Eo) E' i.e. liE = +ve and v' ) v o. This gives the anti-Stokes lines.
em
Note: To explain the blue colour of the sea and sky, C.V. Raman and his coworker K.S. Krishnan had
undertaken the experiment of scattering light by various liquids in 1928. They noticed the scattered
light with the modified frequencies i. e. v obs = Vo ± v m' V m is a characteristic property of the molecular
ch
system. This type of scattering with a change of frequency is described as Raman scattering to honour
al
the scientist. Some other scientists predicted this phenomenon earlier but C.V. Raman was the first to
e
prove it experimentally. For this work, C.V. Raman was awarded the Nobel Prize in Physics in 1930.
th
(E) Normal modes of molecular vibrations (see Appendix 12B): An atom has three degrees of
e/
motional freedom (i.e. x, y and z-directions). Consequently, a molecule constituted by n-atoms is expected
t.m
to have 3n degrees of motional freedom. Now let us consider the movement of all atoms in the
x-direction by the same amount. It will simply displace the centre of mass of the system in the
x-direction without making any change in the internal dimensions (i.e. bond length, bond angle, etc.).
e
Similar translational motions can also occur along the y- and z-axes. Thus, of the 3n degrees of motional
er
freedom, these three translational motions are not the genuine vibrations. Similarly, the concerted
H
motions of all the atoms in circular paths about the three axes actually represent the molecular rotations
k
not the molecular vibrations. Thus, the normal modes of vibration is given by 3n - 6 for an n-atomic
lic
molecule. For a linear polyatomic molecule, the rotation of the nuclei about the molecular axis cannot
occur, i. e. it possessses only two degrees of rotational freedom. Thus for an n-atomic linear molecule,
C
the number of normal modes of vibration is given by 3n - 5.

• These normal modes of vibration (3n - 6 or 3n - 5) can be divided into the bond stretching
(symmetric and antisymmetric) and bond angle bending or deformation (in-plane and out-of-
plane) vibrations. For an n-atomic molecule, there will be (n - 1) bonds between the atoms. This
will lead to:
(n - 1) bond stretching vibrations + (2n - 4) or (2n - 5) angle bending vibrations.
Generally, Vstretch ) Vbending; Vantisym. stretch) Vsym . stretch-
• To determine the symmetries of the normal modes of vibration, the set of three Cartesian
displacement vectors (x, y, z) is to be assigned for each atom of the molecule. These vectors (i.e.
coordinates) represent the instantaneous atomic displacements upon the application of the sym-
metry elements of the point group to which the molecule belongs.
• Number of ir-bands is found very often less than (3n - 6) or (3n - 5) (cf Table 12.1.2.1). It is due
to two reasons: all normal modes of vibrations may not be ir-active; occurrence of degenerate
bands (e.g. E and T modes). For example, in NH 3 (C3v ), the number of normal modes of vibrations
is 6 (= 3 x 4 - 6) (cf r vib = 2A 1 + 2E = 2 x 1 + 2 x 2) but the number of ir-bands observed is
4 (= 2A 1 + 2E) (cf doubly degenerate E-band).
(F) Symmetry selection rules for ir-spectra: For the vibrational transitions, Wv ----t Wv' to be allowed,
one or more of the following transition moment integrals must be nonzero.
Tx J
= WvJ.1 x'1/ v' dt; Ty = J\II vJ.1 '1/ v,dt; T = J'1/ vJ.1 '1/ v,dt
y z z
The operator Jli represents the electric dipole vector of the molecule. Intensity of the spectral tran-
sition is directly proportional to the square of the transition moment integral (T).
The integral becomes nonzero, if the direct product Wv Jli Wv' contains the totally symmetric represen-
tation. Let us consider the fundamental transition, v = 0 to v'. WV for v = 0 (i.e. ground state) is always
ry
totally symmetric. Thus, if 'IIv' (i.e. excited state) and J.1i belong to the same symmetry representa-
ra
tion, then the entire direct product will contain the totally symmetric representation. It leads to the
conclusion:
ib
if the symmetry of the normal vibrational mode is the same as that of the J1i (x, y, and z functions)
yl
components, then the direct product will definitely contain a totally symmetric representation and it
em
will make the transition moment integral nonzero (i.e. the transition is allowed).
In other words, if a particular normal mode of vibration can produce an oscillating dipole moment
ch
(i.e. oscillating electrical field) which can interact with the oscillating electrical vector of the incident
al
electromagnetic radiation, then it leads to the resonant absorption of the radiation (i. e. the oscillating
electrical vector ofthe electromagnetic radiation can interact with the oscillating electricalfield produced
e
th
by the oscillating dipole moment vector of the molecule in resonance).

The above required condition does not imply that the molecule to be ir-active should possess the
e/
permanent dipole moment but the molecular vibration must be able to produce an oscillating dipole
t.m
moment temporarily. The homonuclear diatomic molecules like H 2, C12, N2, 02' etc. have no permanent
dipole moment nor they can produce any dipole moment when vibrating. All such molecules are
e
ir-inactive. The permanent dipole moment of the heteronuclear diatomic molecules like CO, HCl, etc.
er
changes during their vibrations (cf Fig. 12.1.1.4) and such molecules are ir-active. CO 2 (linear) is
having no dipole moment but some of its vibrations (i.e. unsymmetric stretching and bending vibrations)
H
can produce an oscillating dipole moment (cf Fig. 12.1.1.5) and these modes of vibrations are ir-active.
k
For the bent triatomic molecules like H20, N0 2 and S02, the three normal modes (= 3 x 3 - 6) can
lic
produce the oscillating dipole moment and these modes of vibration are ir-active (Fig. 12.1.1.6).
C
8-y
8-y 8-y 8- 8-
------1r----~~f-----jf----- - - - I- - ~-f- -·
y
v(X-Y): -1------
8+ 8+ x 8+ 8+ +x
x X X X
8+x 8+
1I I t I I I !
X
Dipole moment:
Fig. 12.1.1.4 Changes of dipole moment (i.e. oscillating dipole moment) during the molecular stretching vibration of the
heteronuclear diatomic molecule X-Y (Y is more electronegative than X).
Dipole o o o o o o o 0 o o o
moment
ry
ra
ib
yl
o o
em
Dipole
moment
Com~onent
of dipole
axiS~
p ~
ch
~
~
al
moment along
the molecular
e
th
Bending (Perpendicular vibration) (ir-active mode)

e/
t.m
Dipole
moment o
e
er
Component
of dipole
H
moment
perpendicular
to the I'--------~~------____:l~------
k
lic
molecular
axis
C
Fig. 12.1.1.5 Changes of dipole moment (i.e. oscillating dipole moment) during the molecular vibrations of CO2 (having
no permanent dipole moment).
Bond elongation Bond Bond angle Bond angle One bond elongation and
compression opening closing other bond compression
v 1 : Symmetric stretch v2 : Symmetric bending v3 : Antisymmetric stretch
Fig. 12.1.1.6 Molecular vibrations in a nonlinear triatomic molecule ( {

X
"y e.g. H20, N02, S02, etc.).
The above condition can be stated in other words by considering the facts:
(i) The symmetry properties of the component (J.!i) of the dipole moment are the same as those of the
translation vectors along the corresponding Cartesian axis.
(ii) The symmetry properties of the first excited vibrational wave function (i.e. the transition,
v = 0 ~ v = 1) are the same as those of the irreducible representation of the normal mode of
vibration.
These considerations leads to:
A fundamental transition (v = 0 --+ v = 1) will be allowed (i.e. ir-active) if the normal mode of
vibration (which is excited) belongs to the same representation as anyone or several ofthe Cartesian
coordinates.
The above condition can be restated as follows:
ry
A vibrational mode is infrared active if it has the same symmetry as a component of the electric
ra
dipole vector.
Thus in a centrosymmetric molecule, J-li (dipole moment vector) is of u-symmetry, lfIi (vibrational
ib
ground state) is ofg-symmetry (A 1g representation) and all the u-type modes (vibrational excited mode)
yl
become ir-active (cf. g x u xu==> g).
em
(G) Symmetry selection rule for Raman spectra: For Raman scattering, at least one integral of the
following type must be non-zero.
ch
J'I' vaij 'I' v,dt,
al
Here aij is the polarisability tensor of the molecule. For the vibrational transition, there are six com-
e
th
ponents of a. These are a x2 ' a y2 , a z2 ' axy, {lyZ and {lzx. These are transformed by the symmetry
operations in the same way as x 2, y2, Z2, xy, yz and zx respectively. These quadratic polarisability
e/
functions correspond to the irreducible representations involving the given combination of the
t.m
coordinates. It may be noted that components of the polarisability tensor may be the combinations such
as x 2 - y2, x 2 + y2.
e
To have the nonzero value of the above transition moment integral for any component of the
er
polarisability tensor, the following condition must be satisfied.

A fundamental transition (i.e. v = 0 ~ v = 1) will be Raman active if the normal mode of vibration
H
belongs to the same representation as one or more of the components of the polarisability tensor of the
k
molecule.
lic
Simply it can be stated as follows:

C
A vibrational mode is Raman active, ifit has the same symmetry as a component ofthe molecular
polarisability.
IR vs. Raman Spectroscopy

• Operator for infrared spectroscopy: The operator in the transition moment integral,
fWground (operator)Wexcited d't, corresponds to translation along the Cartesian axes x, y and z.
• Operator for Raman spectroscopy: The operator transforms as the polarisability tensor which
corresponds to the quadratic functions of x, y and z. In the character tables, the representations
appear as, xy, yz, xz, r, y2, x 2 - y2, and so on.
• Infrared active: The molecular vibration must change the dipole moment of the molecule.
• Raman active: The molecular vibration must change the eletrical polarisability of the
molecule.
(H) Rule of mutual exclusion: This rule states as:

for a centrosymmetric molecule, the same vibrations cannot be active in both the infrared and
Raman spectra. But, a mode may be inactive in both.
This can be understood by considering the following facts.
(i) For a centrosymmetric molecule, the representations generated by the Cartesian coordinates
(x, y, z) belong to the u-symmetry (i.e. values of x, y and z change their signs on inversion through
the centre of symmetry). Dipole moment is of u-symmetry and it involves the Cartesian coordinates.
Thus all vibrations belonging to the u-representation will be infrared active. It can be understood
as follows:
for the transition, v = 0 ~ v', in the transition moment integral, fWv=oIlWv' dt, Wv=o is of
g-symmetry, Il is of u-symmetry. To make the integral nonzero, Wv' must be of u-symmetry.
ry
(ii) Polarisability tensor of a molecule is a quadratic function (i.e. binary function) of two Cartesian
ra
coordinates, viz. x 2, y2, Z2, xy, yz and zx which belong to the g-representations (cf. u xu=::) g)
ib
because these do not change their signs on inversion through the centre of symmetry. Thus, the
yl
vibrational modes of g-representation will be Raman active but infrared inactive. It can be
understood as follows:
em
for the transition, Wv=o ~ Wv=v', in the transition moment integral, fWv=Q(operator)Wv,dt, Wv=o is of
g-symmetry, the operator polarisability tensor is of g-symmetry. To make the integral nonzero,
ch
\IIv' must be of g-symmetry.
al
(I) Illustration of symmetry selection rule for the centrosymmetric square planar molecule (D4h
e
point group): The normal mode analysis on a square planar molecule of D 4h symmetry leads to:
th
r vib = A Ig + BIg + B2g + A 2u + B2u + 2Eu; (3n - 6 = 1 + 1 + 1 + 1 + 1 + 2 x 2 = 9)

e/
For this centrosymmetric molecule, the vibrational ground state (Wi) belongs to the totally symmetric
representation A/g. The dipole moment components f.lx and f.l y belong to E u (doubly degenerate irreduc-
t.m
ible representation) and f.l z belongs to A 2u representation (cf. see Character Table). Thus f.lx' f.ly and Ilz are
=
of u-symmetry. The direct product, r(\IIi) x r{JJ.i) x r(\IIj) r(JL;) x r(\II/) (cf. r(Wi) belongs to a totally
e
symmetric irreducible representation A Ig) contains a totally symmetric irreducible representation (A Ig)
er
for r(Wj) =A 2u and E u (cf. A 2u X A 2u =A Ig ; Eu x E u =A Ig + A 2g + Eg; A 2u X B2u = BIg; E u x B2u = Eg). It

H
indicates that only two of the u-type modes, i.e. A 2u and E u are ir-active but the B2u mode is ir-inactive.
Thus all the u-type modes are not ir-active.
k
Similarly for Raman activity (taking r(W;) =A Ig' r( (Xi) =A Ig' BIg, B2g and E g; see Character Table),
lic
r(\IIi) x r( Q.;j) x r(\IIr) =r( ay) x r(\II/) contains the totally symmetric irreducible representation A Ig for
C
r(Wj) =A Ig' BIg and B2g (cf. A Ig X A Ig =A Ig; BIg X BIg =A Ig; B2g x B 2g =A Ig) i. e. the Raman active modes
are A 19' BIg and B2g .
(J) Illustrations to identify the ir-and Raman active vibrations:
(i) Molecules of C 2v point group: The partial Character Table (see Appendix 12A) of C2v point group
is given below.
C2v Classes Infrared Raman

functions functions
A) z x 2, y2, Z2 • Bent XY2 (e.g. H20): r vib = 2A) + B 2

A2 xy • CIF3 (T-shaped): r vib = 3A) + B) + 2B2
B) x xz • cis-N 2F2 : r vib = 3A) + A 2 + 2B 2
B2 y yz • cis-[PtL2CI 2]: r vib = 4A) + A 2 + B) + 3B 2
• .cis-[ML4 X z]: r vib = 6A} + 2A z + 3B 1 + 4B z

• mer-[ML3X 3]: r vib = 6A 1 + A z + 4B 1 + 4B z
• A I-stretching vibration includes, z, x Z, yZ and zZ. Thus this mode of vibration is active in both
infrared and Raman spectra (noncentrosymmetric system).
• A z mode is Raman active but ir-inactive.
• B} and B z modes are active in both infrared and Raman spectra (noncentrosymmetric system).
(ii) Molecules of D3h point group: The partial Character Table is given below.
Classes Infrared Raman

functions functions
ry
Ai • BF3 : r yib =A~ + A; + 2E'
A~ • [ML s] (TBP): r yib = 2A; + 3E' + 2A; + E"
ra
E' (x, y) • Infrared active: E', A;
ib
A'~ • Raman active: A;, E', E"
yl
A'~ z • Both Raman and ir-active: E'
em
E" (xz, yz) (noncentrosymmetric system)
(iii) Molecules of C2h point group: The partial Character Table is given below.
ch
al
functions functions
e
th
r, y2, Z2, xy • trans-N 2F2: r yib = 3A g + Au + 2Bu

e/
xz, yz • trans-C2H 2C12 (planar): r yib = SAg + 2A u + Bg

t.m
z + 4Bu
x,y • Raman active but infrared inactive: A g, Bg
e
• Infrared active but Raman inactive: Au, Bu

er
• Mutual exclusion principle: No common line for the centrosymmetric system

H
(iv) Molecules of D 4h point group (e.g. [ML4 ]) (cf 'I' of this Section for analysis in terms of Group
Theory). The partial Character Table is:
k
lic

C
functions functions
x2 + y2, Z2
• [ML (square planar): r = + ++ ++
4] yib A Ig BIg
A 2u
B 2g
B 2u 2Eu
r- y2 • rthe polarisability
does not contain the
yib
component
mode but it represents
Eg
(uij) (xz, yz).
xy
• Infrared active vibrational modes: A 2u , E u
(xz, yz) • Raman active
A lg , and
BIg (cf
B 2g • Eg
vibrational modes:
g-symmetry
does not belong to r yib )
z
• Centrosymmetric system: No common line in the
ir-and Raman spectra (cf mutual exclusion
principle).
• u-symmetry vibr&tions: A 2u, E u ir-active (B 2u silent
mode)
x,y
• g-symmetry vibrations: Raman active.
(v) Molecules of Td point group: The partial Character Table is given here.
Td Classes Infrared Raman

functions functions
Al
A2
x 2 + y2 + Z2 • [ML 4] (Td ): r vib = Al + E + 2T2
• Infrared active mode: T2
E (2z 2 - x 2 - y2, r _y2) • Raman active mode: A I' E, T2
TI
T2 (x, y. z) (xy, yz, zx)
• spectra
T 2-mode common both in the ir-and Raman
(i.e. noncentrosymmetric system).
• Number of ir-bands: 2 (2T2 )
ry
• Number of Raman bands: 4 (AI + E + 2T2 )
ra
ib
(K) Fourier transform spectroscopy: Conventional method of recording the spectrum involves the
point-by-point scanning of the whole wavelength region of study. Thus each point of the spectrum is
yl
recorded separately and for this purpose, frequency of the incident radiation is swept smoothly for the
em
whole wavelength region of study. This method is slow and it may require several minutes to several
hours for the ir- and NMR studies. If for a sample, the spectrum gives one or two line(s) in the whole
ch
wavelength region, but we are to sweep from one end to the other end of the wavelength region to
al
record the lines. Thus, most of the time is spent in recording nothing but the background noise. The
solution to this problem is to replace point-by-point scanning ~r simultaneous and almost instan-
e
th
taneous recording of the whole spectrum in the NMR and IR-studies. In fact, this technique excites
all the transitions simultaneously and the resulting signals (found as the beating patterns) are analysed
e/
mathematically (Fourier transformations) using a computer. As the recording time is small, a large
t.m
number of scans can be taken and summed up to increase the sensitivity.

(L) Preparation of samples for recording the ir-spectra: Volatile compounds (e.g. mononuclear
e
metal carbonyls, etc) can be studied in gas phase. Solid samples are generally analysed by mull technique
er
or by pressed pellet technique.

H
In the mull technique, the finely ground solid sample is mixed with Nujol (paratin oil) to make a
thick paste (mull) which is sprayed as a thin layer between the alkali halide plates. Nujol itself absorbs
k
at 3.5 J..lm (strong) and 6.7 to 7.3 J..lm (weak) (1 J..lrn = 10-6 m = 10-4 cm == 104 cm- l in terms of v). If
lic
the sample absorbs in these regions, then with the Nujol mull, the spectrum cannot be recorded.
C
Hexachlorobutadiene has been found to be transparent in the regions where Nujol absorbs. Thus Nujol
and hexachlorobutadiene can be used in combination.
In the pressed pellet technique, finely ground solid sample is mixed with an alkali halide (generally
KBr) and then the mixture is subjected to a very high pressure to prepare a transparent disc which is
then mounted in the path of infra-red beam and the spectrum is recorded. The KBr pellet can be stored
for a long time and this method can work even with a very small amount of sample. The disadvantages
are: moisture absorption giving rise to a band at 3450 cm- l (for the OH group), possibility of reaction
between the sample and alkali halide like KBr; polymorphic changes in the sample may occu~ under the
high pressure of KBr pellet preparation. The mull method is free from such defects.
(M) Non dispersive infrared (NDIR) spectroscopy: This technique is very often utilised for the
estimation of ir-active gases like CO, COb S02, NOb etc. present (as pollutants) in air. In this method, "
the ir-radiation is allowed to pass through a long cell containing the ir-active gas under examination.
A fraction of the ir-radiation will be absorbed by the gas. Here the ir-radiation coming from the source
is not dispersed. In the detector: it uses the same compound to be estimated in the sample. The details
of this procedure have been discussed in the author's book, "Environmental Chemistry with Green
Chemistry."
12.1.2 Classification of Normal Modes of Molecular Vibration

These are of two types: bond stretching and bending or deformation.
Normal modes of molecular vibrations
I
!
Bond stretching
1
Bending or deformation
ry
I I
ra
ib
Symmetric Unsymmetric In plane Out of plane
yl
or asymmetric Symmetric (scissoring Symmetric (wagging
or antisymmetric mode), unsymmetric mode), unsymmetric
em
(rocking mode) (twisting mode)
These different modes of vibration are illustrated for the angular XV2 unit attached to a heavy
ch
portion of the molecule.
r
al
Heavy atom
or skeleton ~
e
th
e/
t.m
Y a Y Y a Y
e
er
(vs ) (vas)
Symmetric stretching (vs) Antisymmetric
H
stretch (vas)
l. _ )
k
~
lic
Stretching mode (a remains unchanged; bonds only stretch),

C
stretching along the directions of the bond.
a a.
Y Y Y Y
(a) a-decreases (b) a-increases (Rocking mode)

Symmetric in-plane bending, 8 (YXY) Unsymmetric in-plane
(a changes); bending (a-remains unchanged),
l. Scissoring mode Ps(XY2 ) j Rocking mode Pr(XY2)
~
In-plane bending; the directions of displacement of
the atoms perpendicular to the bonds
v V V
<±> <±> (t)
Symmetric (wagging
e
Unsymmetric (twisting
l. mode, Pw(XV2) mode, Pt(XV2 ) )
~ -yr
Out of plane angle bending; (±) => rising above the plane; Twisting mode for the planar XV3 unit
G => moving below the plane (e.g. BF3), leading to a pyramidal shape;
called breathing mode
ry
12.1.3 Normal Modes of Vibration (see Appendix 128) and Infrared and Raman Active
ra
Modes in Some Simple Molecules
ib
Number of normal modes of vibration: (3n - 6) or (3n - 5)
Number of bonds = Number of bond stretching vibrations = (n - 1)
yl
Number of bending vibrations = (2n - 5) or (2n - 4).
em
These are illustrated in some representative cases.
(i) Diatomic molecules (X-Y or X-X) (e.g. H-CI, C==O, H-H, 0=0, etc.): n = 2; total
ch
degrees of freedom = 3n = 6; no. of modes of vibration = 3n - 5 = 1; no. of bond stretching vibration
al
= n - 1 = 1; no. of bending vibration = 2n - 4 = O. The homonuclear diatomic molecule is ir-inactive

e
but Raman active.

th
(ii) Triatomic linear molecule (XY2 i.e. Y-X-Y) (e.g. 0= C = 0, -N=N+=O, etc.): n = 3;
e/
total degrees of freedom =3n =9; no. of normal modes of vibration =3n - 5 =4; no. of bond stretching
t.m
vibrations = n - 1 = 2; no. of bending vibrations = 2n - 4 = 2

• Symmetric stretching (breathing mode) (VI) (ir-inactive but Raman active):
.-- ----..
e
Parallel vibration: o=c=o (central atom stationary)

er
• Antisymmetric stretching (V3) (ir-active but Raman inactive):

H
Parallel vibration: 0= C= 0 (dipole moment changes parallel to the molecular axis,

k
----....--~
cf. Fig. 12.1.1.5)
lic
• Symmetric bending (V2) (ir-active but Raman inactive):

C
Perpendicular vibration in two mutually perpendicular planes; V2 doubly degenerate.
t t
o=c=o (dipole moment changes perpendicular to the molecular axis, cf. Fig. 12.1.1.5).
t
CO 2:VI (1330 em-I); :2 (667 em-I); :3 (2349 em-I)} :1 (ir-inactive; Raman active)
N20: VI (1285 em-I); V2 (589 em-I); V3 (2224 cm- I) v 2 and v3 (ir-active, Raman inactive)
X
(iii) Triatomic angular molecule (XY2 i.e. / '" ) (e.g. N0 2, H20, S02, etc.): n = 3; total degrees
V V
of freedom = 3n = 9; no. of normal modes of vibration = 3n - 6 = 3; no. of bond stretching vibrations
= n - 1 = 2; no. of bending vibrations = 2n - 5 = 1
Symmetric Antisymmetric Symmetric bending V2

stretching (VI) stretching (V3) i.e. a(yXy)
(ir-active) (ir-active) (ir-active)
a-remains unchanged a-remains unchanged a-changes
(A 1 symmetry)
ry
Molecule
ra
3652 1595 3756
ib
1320 648 1621
yl
1151 519 1361
See Fig. 12.1.1.6 for Vh v 2 and v 3; v3 ) VI ) ) v2 em

i.e. 8(YXY). Both VI and v 3 involve the bond
ch
stretching.
e al
12.1.4 Characteristic Group Vibrations

th
A large polyatomic molecule subjected to ir-study possesses a large number of normal modes of
e/
vibrations (3n - 6 for the n-atomic nonlinear molecule, 3n - 5 for the linear n-atomic molecule). Hence,
t.m
it is very often almost impossible to have a complete normal coordinate analysis for a large polyatomic
molecule. For the sake of simplicity, all the normal modes of vibration are divided into two broad
classes: the sketetal vibrations which involve all the constituent atoms to suffer the displacements and
e
the characteristic group vibrations which involve only a small portion of the molecule while the
er
remaining portion of the molecule remains almost stationary. Here we shall pay our attention to such
H
characteristic group vibrations.

k
lic
If we consider a certain functional group (e.g. )C=O , -SH, -OH, etc.) then its group frequency
C
is supposed to be almost independent of the structure of the molecules within which the functional
group exists. Thus, in acetone ( H 3C - C- CH 3 , for example), the C - 0 stretching motion (one of
II
o
the normal modes) involves the negligible motion of the other atoms, and similarly the methyl groups
can also be considered to undergo vibrations which are not affected by the motion of the carbonyl
group. The different electronic factors such as conjugation, inductive effect, etc. can slightly influence
(±150 cm- I ) the position of a particular group vibration in different molecules. Thus, in different com-
pounds, the stretching frequency of the ) C = 0 group (i. e. vco ) lies in the range 1700 ± 150 cm-1 .
The characteristic group frequencies of some common functional groups are given in Table 12.1.4.1.
Comparison of these values with those found in unknown compounds helps us to ascertain the existence
of these functional groups. In some cases, because of the overlapping of many group vibrations, the
bands cannot be assigned. In such cases (e.g. VC-H' VN-H , Va-H)' the isotopic substitution, i.e. substitution
of H by D in a particular group, may separate the peak from the overlapping region as the substitution
of H by D shifts the frequency towards the lower direction by a factor -1.3 to 1.4.
• Effect of atomic mass: Table 12.1.4.1 shows that the trends of group frequency can be logically
rationalised by considering the following relation.
v = ffi = _1_ [ cm -I, (k =force constant; 11 =reduced mass of the system)

21tc ~~
Let us consider the group frequency of a particular group, say A-X (where X may vary). With the
ry
increase of mass of the atom (X) suffering oscillation within the group, the stretching frequency
decreases as JJ. increases. Thus we have:
ra
VC- H) VC- VC-CI) VC-Br; vc=O) vc=s
ib
F )
yl
• Effect of bond length and bond order: With the decrease of bond length (i.e. increase of bond
strength) and increase of bond multiplicity (i.e. increase of bond strength), the force constant (k)
em
increases and consequently, the stretching frequency increases. It leads to:
== == N) VC=N ) VC- N; vc=o ) vc - o
ch
Vc C ) vc=c ) v c - c ; Vc
Thus in general we may conclude:
al
"-
e
the terminal groups involving the light atoms and multiple bonds (e.g. -OH, - NH 2 , - C - H,
th
/
e/
- c == N, - SR, \. c = 0, etc.) are of higher stretching frequency while the groups consti·
t.m
/ \. \.
tuted by the heavier atoms linked through the single bond (e.g. -C - CI, -C - Br,
/ /
e
er
metal-metal bond; metal-N bond, etc.) are of relatively lower stretching frequency.
H
From the standpoint of application of group frequencies in detecting the functional groups in the
unknown compounds, the generalised observations are of as follows: .
k
lic
(i) v) 2500 em-I: It occurs for the A-H bonds i.e. H bonded to other lighter elements (e.g. A = 0,
N, C). The stretching frequencies of the O-H and N-H bonds occur at -3600 cm- l and -3400
C
cm- l but these can be lowered due to H-bonding (effect of lowering of the O-H or N-H bond
strength i.e. -O-H···X or -N-H· ··X, where X is an electronegative centre and increase of
fJ. of the associated system). Very often, VN-H and VO- H (hydrogen bonded) overlap but the peak
due to the )N -H group is sharper. The H-bonding not only lowers the stretching
frequency but also broadens the peak.
The stretching frequency of the C-H bond in the aliphatic compounds lies in the range, 2850 -
3000 cm- l while for the aromatic compounds, it lies in the range 3000 - 3100 em-I. In general,
we have:
Vsp-C-H) V sp2_ C - H > Vsp3-C-H i.e., V C - H : V==C-H)V=CH 2 )V -CH 3

With the increase of s-character of C-orbital in the C-H bond, the bond becomes stronger (i.e.
shorter).
VH- F =4100 em-1, VH- H =4160 em-1 : Effect of two light atoms, small bond length and high
force constant.
(ii) v (2000-2500 em-I): Stretching frequency of the triply bonded systems
(e.g. VC==N =2200 - 2300 cm -1; VC==C = 2225 cm -1 ) lies in this range.
(iii) V (1600 - 2000 em-I): Stretching frequency of the doubly bonded systems (e.g.
VC=O = 1600-1750cm- 1 , VC=C = 1650cm-1 , Vc N = 1600 cm- 1 ) generally lies in this
range. Here it may be noted that frequency for the bending mode of vibration of the N-H group
also lies in the given range of frequency (cf. for the stretching mode of vibration of the A-H
ry
bonds where A = C, N, 0, etc. the frequency lies above 2500 cm- I but for their bending modes,
ra
the frequency lies far below except for the N-H bond).
ib
(iv) Skeletal vibrations (Fingerprints): For the organic compounds, the skeletal vibrations give
yl
several absorption bands in the range 700-1400 cm- I . These absorption bands are called the
fingerprints because from these bands, the skeletal molecular structure can be recognised. In
em
fact, these bands are highly typical of the specific molecular skeletal structure.
ch
4000 3500 3000 2500 2000 1500 1000 cm-1
e al
th
e/
IV
t.m
I
Stretching Stretching Stretching Stretching
e
C===C C-C, C-N,

O--H C_C C-O,C=F,
er
N--H C===O C-CI,C=S

C N
H
C===N Bending
C--H S--H, C-H,C-O,
P--H, N===O
k
O-H
Si--H P===O
lic
Other stretching,
C--O Bending bending and com-
C
bination bands.
N--H The fingerprint
region.
Region-I: vX- H (X = C, N, 0), single bond involving the light H-atom.
Region-II: vC==N' vC==C ' VX-H (X = S, P), Ve-o
Region-III: vx=y (X, y = C, N, 0, P) i.e. stretching of double bouds; ON-H
Region-IV: Bending vibrations (N-H exception), weaker single bonds and fingerprint region.
Fig. 12.1.4.1 Regions of ir-absorption corresponding to the stretching (v) and bending (8) vibrations of the main
functional groups and carbon skeleton bonds.
Table 12.1.4.1 Characteristic stretching frequencies of some molecular fragments
Group Approximate frequency Group Approximate frequency

(v in em-I) (v in em-I)
-OH 3600
(3200 - 3600) for H-bonded )C-O- 1100 - 1250 (vco )
3350 - 3400 )C=O 1600 - 1750
3300 \..C-C/ 1650

/ - \..
ry
@-H
ra
3050 )C=N- 1600
ib
yl
-N=C=O 2270
(isocyanate)
em
3030 -N=C=S 2125
(isothiocyanate)
ch
)S=O 1050
al
(sulfoxide)
e
th
-CH 3 (methyl) -2965* \.. /

-C-C-
e/
/ \..
-2875** \.. / 1000 - 1225
t.m
-C-N
) CH 2 (methylene) -2930* / \..
\..
-C-O-
e
-2855** /
er
H
~
-C - H (methine) -2890 (weak)
k
/
lic
-SH 2500
C
)C=S 1075 - 1120

\..pH 2400
/
\.. \..
-Si-H 2300 -C-F 1050
/ /
\..
-C==N 2260 -C-CI 750
/
\..
-C==C- 2225 -C-Br 660
/
\.. \..
-P=O 1140-1210 -C-I 560
/ /
(R3PO; Ar3PO)
*asymmetric stretch, ** symmetric stretch. Methyl (primary-C); Methylene (secondary-C); Methine (tertiary-C)
Methyl Methylene Amino Nitro Carboxylate Acid anhydride
~H. \ ~H ~H 0. 0
-N · -c·
0. 0 "
/
----+
c=o
--C-H --N
1
~ /C~ ~H ~'o ~'o
V (cm- ) ~H 0"
(Symmetric H C=O
stretch): - 2875 -2855 - 3300 -1350 -1400
/1~
~l- \ ~H ~H 'i. a J}.o " ----+

C=o
V (cm-1 )
-C-H
~H /
C
~H
-N
~H
-N ·
~·o
-C ·
~·o cI
(Asymmetric
stretch): - 2965 -2930 - 3400 -1550 -1600
"/~oC=O
ry
ra
Note: The mode generating a larger dipole moment is of higher intensity
ib
12.1.5 Electronic and Coupling Effect on Group Vibration Frequency
yl
em
These aspects are illustrated in different cases.
A
~C
ch
(A) Inductive effect on vco : (),
A/X
e al
It indicates that the electron pushing inductive effect (i.e. +1 effect) introduces the single bonded
th
character into the CO group i.e. vco decreases.

e/
vco : HCHO ) CH3CHO ) CH3COCH3

t.m
The electron withdrawing inductive effect (i.e. -I effect) enhances the veo value.
e
vco : CH3COCH3 <CICH2COCH 3 <Cl 2CHCOCH3

er
H
The electron withdrawing inductive effect of halogen in the acid halides (e.g. RCOCI) raises the
vc=o value (ca. 1800 cm- I ). Here the electron pushing mesomeric effect of the halogen towards the
k
lic
C=O group is not significant.

C
(B) Resonance and conjugation effect on vco: Conjugation between the )C=C and )C=O
groups shifts both the vc=c and v eo values. The isolated carbonyl group (e.g. R 2C=O) and ethylenic
bond (i.e. )C=C() show the stretching frequencies -1715 and -1650 cm- I respectively but in
the conjugated systems like (1, ~-unsaturated carbonyl compounds, ) C = C - C = 0 ~

I I
)C+ -C=C-O-, their frequencies are appreciably shifted to -1675 cm- l and -1600 cm- l
I I
respectively. This shifting towards the lower frequency for the both groups arises due to the fact that
the resonance introduces some single bonded character into the both C=O and C=C bonds.
In terms of intensity (measured by the degree of dipole moment change), the )C = 0 band is more
intense than the ) C = C( band but coupling of the two groups through resonance as indicated above
makes the both bands almost equally strong (i.e. intensity of the >C=C( band increases
significantly).
Conjugation in the amides

(
.
I.e. (~-NH2
n~ .--.. -I=NH +
2
)
introduces some single
bonded character into the C=O bond and some double bonded character into the C-N bond. This
lowers down the Yco value but raises the YCN value. (cf Yco ::::: 1680 cm- 1 in urea, ::::: 1715 cm- 1 in
acetone).
ry
Let us consider and compare the effect of conjugation on the vc=o value in the amides and esters.
ra
ib
n 0.
yl
I ..
O=C-O-R'
em
R
ch
Nitrogen is less electronegative than oxygen. Consequently, the O-lone pair is less readily avail-
al
able for conjugation with the carbonyl group. It makes.

e
th
vc=o (amide) ( vc=o (ester)

e/
Let us consider the positions of vc = 0 in the aliphatic esters, aryl esters and a, Ji-unsaturated
t.m
esters.
.
e
~
er
q
C-O-R'
I ..
O===C-O-R'
H
R C-
k
I
lic
C-
I
C
For the saturated aliphatic ester, there is no additional conjugation from the R-group. Thus it is
reasonable to expect:
Yco (aliphatic ester) ) vc=o (aryl ester and a, ~-unsaturated ester)

The same thing happens for the aldehydes and ketones, i. e. vc = 0 (aliphatic aldehydes or ketones)
) vc=o (aromatic aldehydes or ketones) ) vc=o (unsaturated aldehydes or ketones where the ethylenic
double bond is in conjugation with the CO group).
Unsaturation at the a-position to C lowers the v c = 0 values while unsaturation at the a-position
to 0 as in unsaturated lactones raises the v c=o value because here the O-lone pair can participate
in conjugation with the both C = 0 and C = C bonds.
o~
1735 1720
(C) Coupling or mixing (called kinematic coupling) of the adjacent individual group vibrations:
ry
Simultaneous vibration of two adjacent groups leads to the coupling or mixing of the individual group
ra
vibrations. This coupling is very much efficient between the adjacent fragments if their inherent vibra-
tional frequencies do not differ significantly.
ib
yl
To understand the coupling effect, let us consider the segment A-O=C< where the O-atom is
em
to move against the atom A to which it is coordinated. It will raise the 'C=O' stretching frequency. In
ch
other words, the C=O and A-O stretching vibrations mechanically couple to raise the vco value. This
phenomenon is described as kinematic coupling.
al
Let us consider the A-B-C segment where the coupling of the vibrational modes of A-B" and
e
B-C is being considered. The combination of v A-B and VB--{: is very much comparable to the linear
th
conbination of atomic orbitals (LCAOs) leading to the molecular orbitals (MOs). Coupling (i.e. mixing)
e/
of v A-B and v B--{: gives the resultant frequencies which are different from the non interacting group
t.m
vibrational frequencies. Due to this coupling, the lower frequency (say v A-B) is further lowered to
VI « V A-B) which consists of both the vibrational modes of A-B and B-C but predominantly enriched
in the character of A-B vibrational mode. On the other hand, the higher frequency (i.e. VB-C) becomes
e
further highered to produce VII ()v B--{:) consisting of both the modes of A-B and B-C vibrations but
er
predominantly enriched in the character of the B-C vibrational mode (cf. positions of the bonding and
H
antibonding MOs in the X-Y molecule where electronegativities of X and Y differ). The efficiency of
k
this coupling or mixing of the vibrational modes depends on the energy separation of V A-B and VB--{:'
lic
Let us consider the coupling ofvcoand vc=c in the ketene moiety, )C=C=O. In this moiety,
C
the observed values are: Yco (2100 em-I) and vc=c (1100 em-I) (cf. typical values of Yc=o and
Yc=c are about 1700 cm- I and 1650 cm- I respectively). These values are significantly deviated from
their characteristic group frequencies, i. e. YC = 0 is raised and vc = c is lowered. In fact, in such
cases, the simultaneous vibration of more than one group leads to the coupling of their of individual
vibrational modes.
Let us consider the coupling ofvc_H and vCE=N in H-C N. The observations are:
H - C==N: V C- H = 3312 em-I, VC:=N = 2089 em-I} V C- H _ 3312 _

_ - -1 - -1 - - -1.26
D-C=N: V C- D =2629 cm ,VC:=N =1906 cm V C- D 2629
If there is no coupling, we can expect: VC - H

~ 3300cm- I ) VC - D
(~ 3300 = 2357 em-I) and
1.4
VC:=N :::= 2250cm -1 . The significant shifting of VC=N towards the lower frequency in DCN indicates the
coupling between VC- D arid VC=N i.e. on deuteration, VC=N shifts to the lower frequency due to the
coupling between the adjacent vibrational modes. Generally, on deuteration, a stretching frequency gets
lowered down by a factor about 1.4 but here vC-H gets lowered down by a factor less than 1.4 (cf.
VC- H/VC-D == 1.26 < 1.4 i.e. VC-D (observed) ) VC-D (calculated)). It is due to the coupling between
I
VC-D and VC=N and this coupling leads to VC-D towards the higher frequency direction (2357 cm- to
I I I
2629 cm- ) and VC=N towards the lower frequency.direction (2250 cm- to 1906 cm- ). In H-C==N,
VC- H and VC=N differ widely and no effective coupling occurs.
Here it is worth mentioning that this type of coupling makes the weaker band stronger (cf. intensity
stealing phenomenon). This type of shifting of intensity also occurs in Fermi resonance.
• Fermi resonance: Let us consider the case of CO 2 to illustrate the mutual interaction of two
ry
vibrational frequencies. For CO 2, onefundamental transition (VI; ir-inactive, Raman active; Fig. 12.1.1.5)
is at 1330 cm- I and one overtone transition (2V2 = 2 x 667 cm- I ) is at 1334 cm- I . These close transitions
ra
in terms of energy are described as an accidental degeneracy. Due to the mulual interaction between
ib
these transitions, these are shifted to 1285 cm- I and 1388 cm- l respectively in Raman Spectrum and the
yl
overtone transition gets intensified at the expense of the fundamental transition (Fermi resonance; here
em
a fundamental resonates with an overtone). Their mean frequency is 1335 cm- I and approximately close
to 1330 cm- I .
ch
X
• Let us consider the compounds F2CO, CI 2CO and Br2CO having the structure ) C =0 with
al
X
e
the C-O stretching frequencies 1928 cm- I , 1827 cm- I and 1828 cm- I respectively. The higher
th
electronegativity of X (i.e. higher electron withdrawing inductive effect) enhances the double bonded
e/
" r" • "-+

t.m
character in the CO group, /C=O .. /C - 0 i.e. shifting of 1t electron towards oxygen
is prevented, if C is attached to the electronegative groups. But this effect cannot alone expain the
e
variation of the vco values. The significantly high C-O frequency in F2CO arises due to the coupling
er
of C-F and C-O vibrations where VC-F and vc-O are close to each other. For Cl 2CO and Br2CO, this
H
type of coupling is insignificant because, for the heavier halogens, vc- x is far away from vc=o (cf.
k
VC-F) VC-Cl ) VC- Br)· Thus coupling of the C-O and C-F vibrations shift vc=o towards the higher
lic
frequency and VC-F towards the lower frequency.

C
v
• Let us consider the po values in different phosphoryl compounds. It varies singnificantly in the
range (1100-1400 cm- I ) and it needs an explanation.
Compound: F3PO Ph3PO
vpo (em-I): 1404 1295 1285 1275 1261 1190 1176
The ir-stretching frequency (v po ) is a measure of the P-O bond strength: higher the vpo value,
higher the P-O bond strength which largely depends on the efficiency of the 2p(O) -+ 3d(P)
7t-bonding. For the halides, v po is the highest one for X =F and it is minimum for X = Br (correspond-
ing iodo-compound not known). For the electronegative substituents on P, the 3d-orbital is contracted
to favour the 7t-bonding. Thus the process gets favoured maximum for X = F (which is the most
electronegative one). It has been found that vpo is related (quantitatively) with the sum of the
electronegativities (Lx) of the substituents as follows:
vPO = 930 + 40Lx' X = Pauling electronegativity of the substituent.

The observation, vPO (Ph 3PO) vPO ( Me 3PO) indicates that the electron pushing mesomeric effect
of the phenyl ring does not work significantly. Rather, the higher electronegativity of the
Sp2_C (compared to that of the Sp3_C) explains the observation.
(D) Effect ofH-bonding: Hydrogen bonding by the O-H group gives two characteristic observations:
downward shifting of the frequency and broader peak. The downward shift of VO- H occurs due to the
O-H bond weakening and increase of effective mass in the H-bonded fragment, -O-H· ··D
(D-donor site).
ry
ra
ib
1
yl
em
ch
al
H-bonded
~---- ~Vo-H ~
e
1
... 400 (cm- ) -------. phenol in CCI 4
th
e/
3600 3500 3400 3300 3200

t.m
1
+-- v(cm- )
Fig. 12.1,5.1 Infrared spectra of non-hydrogen bonded and hydrogen bonded phenol in CCl4 solvent.
e
Intermolecular and intramolecular H-bonding can be distinguished from the ir-study. Possibility
er
of the intermolecular H-bonding decreases in solution with the decrease of concentration in aprotic
H
solvents (e.g. CCI4 ). This why, the broad peak due to the intermolecUlar H-bonding (leading to the
k
intermolecular association among the solute molecules bearing the O-H group) gradually disappears
lic
on dilution. The relatively sharp peak due to the intramolecular H-bonding remains unch~nged with
C
dilution. This prediction has been experimentally verified in different types of hydroxy compounds
(e.g. alcohols, phenols) and carboxylic acids.
Hydrogen bonding between the -OH and) C=O group i.e. -O-H ... O=C(, partially
weakens both the O-H and C=O bonds. Thus it reduces· both VO-H and vc=o. However, shifting of
the group frequency due to the resonance and coupling of vibrational modes is more important for the
diagnostic purposes.
Hydrogen bonded dimers of the monocarboxylic acids show the lowervc=o values (1680-
1720 cm- I ) than the monornor (nohydrogen bonded species). Salicylic acid, anthranilic acid, etc. can
experience the intramoleculer H-bonding to show the lower vc=o values.
(E) Keto-enol tautomerism: Enolisation lowers the vc=ofrequency. Acctylacetone is stabilised through
the intramolecular :fI-bonding in its enol-form (cf Vol. 3, Ch. 13). It further lowers the vc=o value. In
the enol form, the vc=c peak appears.
V e = 0 = 1724 cm-1 enol form

(doublet) (symmetric stretch) (Keto-enol tautomerisation in CCI 4 solvent)
= 1706 cm-1 Yeo ~ 1630 cm-1, (double bonded character reduced)
(asymmetric stretch) Y OH - 3300 cm- 1 (broad)
ry
andve=eabsent
-;OH
ve=e ~ 1600 -1650 cm-1
ra
Similar keto-enol tautomerisation has been identified in ethyl acetoacetate, CH 3COCH 2C0 2Et by
ib
ir-spectroscopy.
yl
(F) Ring size and exocyclic and endocyclic double bonds: With the decrease of ring size (i.e. smaller
em
bond angle), more p-character of the C-orbitals is involved in making the C-C bonds of the ring (ef
sp ~ 180°, Sp2 ~ 120°, Sp3 ~ 109°). It means that more s-eharaeter of the C-orbitals is involved in
ch
making the exoeyclie a-bond to strengthen the exocyclic double bond. It is illustrated in the following
al
examples.
e
th
e/
t.m
e
er
0 ~ c£H ..N-H
H
IC"\
~
N-H
k
lic
ve=o (cm -1): -1660 -1705 -1750

C
The vc=c value for the endocyclic double bond varies as:
- -1
ve=o(cm ):
o
1646 161 0 1566 (lowest) 1656
~
Increasing strain in the ring;
decreasing s-character of the C-orbitals
in the carbon-carbon a-bonds.
With the decrease of ring size, the decrease of vc = c value is quite expected in terms of the
increasing strain in the ring and decreasing of s-character of the C-orbitals in forming the carbon-
carbon a-bonds. But the increase of the value for cyclopropene is due to the strong coupling between
the C=C stretching vibration and C-C stretching vibration. For the C-C=C bond angle (a)
90°, the vibrational modes are orthogonal (as in cyclobutene) and they do not couple but the vibra-
tional modes can couple to raise the vc=c value for the bond angle less than 90° and greater than 90°.
It is illustrated in Fig. 12.1.5.2. For the bond angle a > 90° or < 90°, the C-C single bond stretching
vector can be resolved into two components and one of these two components is coincident with the
direction of the C= C stretching vector and -it allows the coupling of C-C and C=C bond
vibrations to raise the vc-c value.
-------~
i ~-\k--
1
C
I I C
ry
C
~=900 ! a> 90
~<900!
0
ra
C-C-" +-C-C----+ '+-- C-C
!
Coupling of No coupling Coupling of
ib
C-C and of C-C and C-C and
yl
C=C stretching C=C stretching C=C stretching
vibrations vibrations vibrations
em
Fig. 12.1.5.2 Resolution of C-C single bond stretching vector for different bond angles along the
C=C bond.
ch
al
12.1.6 Limitations of the Characteristic Group Vibrations
e
In discussing the Group Vibration, it is assumed that the skeletal vibration will not affect the group
th
vibration. In other words, during the vibration of a particular group/segment, the remaining portion of
e/
the molecule will remain stationary. But to retain the centre of mass of the whole system, it is not
possible to keep the remaining portion of the molecule stationary, i. e. all the nuclei of the molecule
t.m
must suffer their harmonic oscillations in a synchronous manner. If the remaining portion of the mol-
ecule contains the heavier nuclei, then their movement may be negligible to restore the centre of mass
e
of the system. Under these conditions, the concept of group frequency works well. But if the nuclei of
er
the remaining portion are comparable or lighter in mass with respect to the nuclei involved in the group
H
under consideration, then the above approximation is not valid (i.e. movements of the other nuclei
cannot be ignored) and the concept of group vibration (which is supposed to be independent of the
k
lic
nature of skeletal portion) fails.

Moreover, different electronic factors, coupling of vibrational modes, and many other factors dis-
C
cussed in Sec. 12.1.5 can shift the group frequency appreciably. In such cases, appropriate caution must
be taken to make the conclusion.
12.1.7 Application of Infrared and Raman Spectra: Determination of Structure of

Some Simple Molecules
The following principles are helpful in structure determination of the molecules.
(i) PQR vs PR branches in vibration-rotation spectra: Linear vs. nonlinear molecule: It has been
already discussed in terms of selection rule that for a linear molecule, the parallel vibrations
which preserve the linearity of the molecule give the PR branches (i.e. ~J = ±1, ~J 0). The *
perpendicular vibrations which destroy the linearity of the molecule produce the PQR branches
(i.e. ~J = 0, ±1).
Thus if the infrared spectrum contains any band of PR branches, then the molecule is linear.
Absence of any band of PR branches indicates the nonlinear structure of the molecule.
(ii) Centre of symmetry and rule of mutual exclusion principle: For a centrosymmetric molecule,
the infrared active vibrational modes are Raman inactive, i.e. for a centrosymmetric molecule,
there will be no common band in the infrared and Raman spectra.
(iii) Number of bands in both the infrared and Raman spectra: It depends on the property of the
point-group to which the molecule belongs. In general, reduction in symmetry gives the larger
number of bands. Less symmetric molecules also give the more intense bands.
(iv) Nature of vibrational mode: The observations are:
• Symmetric vibration ~ Polarised Raman line
• Antisymmetric vibration ~ Depolarised Raman line
• Vbending ( V stretching; V sym-stretching ( Vantisym-stretch.
(i.e. bond length deformation is more difficult than the bond-angle deformation).
ry
Fingerprint spectrum: The infrared spectrum of a particular substance is of unique characteristic
ra
features. This is why, ir-spectrum of a substance is called its fingerprint spectrum.
ib
Illustrations
yl
(A) CO2 (cf Fig. 12.1.1.5): The experimental findings are:
em
VI (1330 em-I) (symmetric stretch): Infrared inactive but Raman active
v
ch
2
(667 em-I) (bending): Infrared active (PQR type) but Raman inactive
v (2349 em-I) (antisymmetric stretch): Infrared active (PR type) but Raman inactive.
al
3
The v3-band (ir-active) includes the PR contour. It suggests the molecule to be linear. There is no
e
common line in the ir-and Raman spectra. It indicates that the molecule possesses a centre of symmetry.
th
Thus, the structure is:

e/
o=C=O (a linear centrosymmetric molecule).

t.m
CO2 molecule possesses 4 fundamental modes of vibration (i.e. 3 x 3 - 5 = 4). Number of bond
stretching vibration =n - 1 = 2 (one symmetric + one antisymmetric). Number of bending vibration =
e
2n - 4 = 2 (in two mutually perpendicular planes).

er
• The symmetric stretching (i.e. parallel vibration) does not change any dipole moment but
H
changes the volume of the molecule (i.e. polarisability changes). This vibration (VI) is ir-inactive
but Raman active.
k
lic
• The antisymmetric stretching (i.e. parallel vibration) changes the dipole moment but not the
polarisability (or volume). This vibration (V3) is ir-active (PR contour) but Raman inactive.
C
• The bending vibration (i.e. perpendicular vibration) changes the dipole moment but not the
polarisability. This vibration (V2) is ir-active (PQR contour) but Raman inactive.
~ f- ~ i
VI: f-O=C=O~ V3 : O=C=O V2 : O=C=O
J, J,
(Symmetric stretch) (Antisymmetric stretch) (Bending mode)
(B) S02 (cf Fig. 12.1.1.6): The experimental findings are:

VI (1151 em-I) (symmetric stretch): Infrared active (PQR type), Raman active (polarised)
v2 (519 em-I) (bending): Infrared active (PQR type), Raman active (polarised)
v3 (1361 em-I) (antisymmetric stretch): Infrared active (PQR type), Raman active (depolarised)
All the ir-bands include the PQR contour. It indicates that the molecule is nonlinear, i.e. angular. The
infrared and Raman spectra contain the common lines. It indicates that the molecule does not have the
centre of symmetry. Some of the Raman lines are polarised, i.e. the corresponding vibrations are
symmetric. In other words, these vibrations preserve the symmetry of the molecule. It is possible, if
the two O-atoms are symmetrically placed with respect to the central atom S.
S
Thus the above findings suggest the structure: / ~
o 0
No.. of modes of vibration = 3n - 6 = 3; No. of stretching vibrations = n - 1 = 2; No. of bending
vibration = 2n - 5 = 1
The stretching vibrations are: VI (1151 em-I) (sy~metric) and v3 (1361 em-I) (antisymmetric). The
symmetric bending vibration is: v2 (519 em-I).
V1 : S (Symmetric stretch) v 3 : ~ S \... (Antisymmetric stretch) v 2 : S (Bending)
" ~ ~ (Perpendicular vibration)
ry
/ '" (Parallel vibration) / '" (Parallel vibration)
00 . 00 00
ra
/ ~~
ib
(C) N2 0: The experimental findings are:
yl
VI (1285 em-I): Infrared active (PR type), Raman active (polarised)
em
v 2 (589 em-I): Infrared active (PQR type), Raman inactive
v3
ch
(2224 em-I): Infrared active (PR type), Raman active (depolarised).
Two ir-bands i.e. VI and V3 include the PR contour. It indicates that the molecule is linear. The
al
infrared and Raman spectra contain some common lines. It indicates that the molecule lacks in centre
e
of symmetry (i.e. O-atom cannot be the central atom). The structure is:
th
+ +
e/
-N= N=O ~ N - N-O

t.m
No. of modes of vibration = 3n - 5 =4; No. of bond stretching vibration = n - 1 = 2; No. of bending
vibration = 2n - 4 = 2
e
The symmetric stretching vibration (VI' 1285 em-I) maintains the linearity of the molecule. It
er
gives the ir-band with the PR contour. The corresponding Raman line is polarised.
H
VI (1285 em-I): N-N-O (symmetric parallel vibration).

~~
k
lic
The antisymmetric stretching vibration (v 3 ' 2224 em-I) maintains the linearity of the molecule.
It gives the ir-band (PR type) and .the depolarised Raman line.
C
v3 (2224 em-I): N-N-O

--. ~---.
(Asymmetric parallel vibration)
The bending vibration (doubly degenerate; perpendicular vibration in two mutually perpendicular
planes) destroys the linearity of the molecule. It gives the ir-band (PQR contour).
v2 (589 em-I): N-N-O

t (perpendicular vibration)
• +
(D) C 2H 2 : The findings are:
VI (3374 em-I): Infrared inactive, Raman active (polarised)
v2 (1974 em-I): Infrared inactive, Raman active (polarised)
V3 (3287 em-I): Infrared active (PR type), Raman inactive

v4 (612 em-I): Infrared inactive, Raman active
vs (729 em-I): Infrared active (PQR type), Raman inactive.
Existence of the PR branches in the v 3 band indicates the molecule to be linear. There is no common
line in the ir-and Raman spectra. It indicates that the molecule is centrosymmetric. The structure is:
H-C==C-H
No. of normal modes of vibration = 3n - 5 = 7; No. of stretching vibrations =n - 1 = 3; No. of
bending vibrations: 2n - 4 = 4
Symme~ric Stretches:
ry
== C -
ra
H- C==C-H H- C H} No change in dipole moment (ir-inactive);
~ ~ ~ ~ ~ ~( ~) ~
ib
Change in polarisability (i.e. Raman active)
b374 em-I) 1~4em .
yl
em
Antis)'mmetric stretch:
ch
H- C == C - H} Change in dipole-moment; linearity is maintained
f- ~ ~ ~ (i.e. ir-active, PR type); No change in polarisability(i.e. Raman inactive)
al
b287 em-I)
e
th
Be~ding vibration: (doubly degenerate)

e/
~_ C==~_H}NO change in dipole moment (i.e. ir-inactive);

t.m
J, J, change in polarisability (i.e. Raman active).

(612 em-I)
e
er
~ending vibration: (doubly degenerate)

H
i i}Change in dipole moment and linearity is not -.' .:.'

k
H- C==C-H maintained (i.e. ir-active, PQR type). No chaRge

lic
J, J,)l in polarisability (Raman inactive).

C
(729 em-
, (E) XeF4: Combined analysis of the ir- and Raman spectra has proved its square planar structure not
,;' the tetrahedral structure. This aspect has been discussed in Sec. 12.1.9.. 1..
12.1.8 Symmetry of the Normal Modes of Vibration (3n - 6 or 3n - 5) and Number of

ir-Active and Raman Modes (see Appendix 128)
Very often it is noted that the number of ir-bands is less than the number of normal modes of vibration.
It is due to two reasons:
(i) all normal modes of vibration are not ir-active (the modes which cannot make any change in
dipole moment are ir-inactive);
(ii) some modes are degenerate, e.g. E mode (doubly degenerate), T-mode (triply degenerate).
These are illustrated for some representative cases in Sec. 12.1.1.1 ~nd in Table 12.1.8.1.
Table 12.1.8.1 Symmetry of the normal modes of vibration and infrared and Raman active modes (ef
Character Tables).
Molecule T Vib (normal No. of No. of Raman
modes of vibration) ir-active bands active bands
(i) XY2(bent, C 2v ) 2A I + B 2 = 2 x 1 + 1 3 (2A I + B 2) 3 (2A I + B 2)

e.g. H 20, S02, Cl 20 = 3 = (3 x 3 - 6) .
AI(symmetric stretch)
A I(symmetric bending)
B 2 (unsymmetric stretch)
(ii) CIF3 (T-shaped, C 2v ) 3A I + B I + 2B 2 6 (3A I + B l + 2B 2) 6 (3A I + B I + 2B 2)
=3xl+l+2xl=6
ry
= (3 x 4 - 6)
ra
(iii) cis-N 2F2 (planar, C2v ) 3A I + A 2 + 2B 2 5 (3A I + 2B 2) 6 (3A I + 2B I + A 2)
=3xl+l+2xl=6 A 2 (ir-inactive) A 2 (Raman active)
ib
= (3 x 4 - 6)
yl
(iv) cis-[PtCI 2L 2J 4A I + A 2 + B I 8 (4A I + B I + 3B 2) 9 (4A I + A 2 + B I + 3B 2 )
em
(planar, C 2v ) + 3B 2 = 4 x 1 + 1 + 1 A2 (ir-inactive) A 2 (Raman active)
+3xl=9= ch
(3 x 5 - 6)
(v) CH 2Cl 2 4A I +A 2 + 2B I + 2B 2 8 (4A I + 2B I + 2B 2) 9 (4A I + A 2 + 2B} + 2B 2)
al
(tetrahedral, C2v ) =4xl+l+2xl+2xl A 2 (ir-inactive) A 2 (Raman active)
e
= 9 = (3 x 5 - 6)
th
(vi) cis-[ML4 X 2J 6A I + 2A 2 + 3B I + 4B 2 13 (6A I + 3B I + 4B 2) 15 (6A I + 2A2 + 3B I + 4B 2)

(octahedral, C2v ) =6xl+2xl A2 (ir-inactive) A 2 (Raman active)
e/
+ 3 x 1 + 4 x 1= 15
t.m
= (3 x 7 - 6)
(vii) mer-[ML3X 3J 6A I + A 2 + 4B I + 4B 2 14 (6A I + 4B I + 4B 2) 15 (6A I + A 2 + 4B I + 4B 2)
(octahedral, C 2v ) = 6 x 1 + 1 + 4 x 1+ 4 x 1 A2 (ir-inactive) A 2 (Raman active)
e
= 15 = (3 x 7 - 6)
er
(viii) NX 3, PX3 (pyramidal, 2A I + 2E = 2 x 1 4 (2A I + 2E) 4 (2A I + 2E)

H
C 3v ) (e.g. NH 3, + 2 x 2 = 6 = (3 x 4 - 6)
PCl 3 etc.)
k
lic
(ix) OPCl 3 3A I + 3E = 3 x 1 + 3 x 2 6 (3A I + 3E) 6 (3A I + 3E)

(pyramidal, C3v ) = 9 = (3 x 5 - 6)
C
(x) fac-[ML 3X 3 J 4A I + A 2 + 5E = 4 x 1 9 (4A I + 5E) 9 (4A I + 5E)

(octahedral, C3v ) + 1 + 5 x 2 = 15 A2 (ir-inactive) A 2 (Raman inactive)
= (3 x 7 - 6)
(xi) [ML5 J (square 3A I + 2B I + B 2 + 3E 6 (3A I + 3E) 9 (3A I + 2B I + B 2 + 3E)
pyramidal, C4v ) =3xl+2xl+1+3x2 B., B 2 (ir-inactive)
= 12 = (3 x 6 - 6)
(xii) C 2H 4 (planar, D 2h ) 3Ag + 2B Ig + B 3g + 5 (B lu + 2B 2u + 2B 3u ) 6 (3A g + 2B Ig + B 3g )
Au + B Iu + 2B 2u + g-modes (ir-inactive) u-modes (Raman inactive)
2B3u= 3 x 1 + 2 x 1 + 1 +
1 + 1+ 2 x 1 + 2 x 1 = 12
= (3 x 6 - 6)
(xiii) BX3 (planar, D 3h ) Ai + A;+ 2E' 3 (A~ + 2E') 3 (A~ + 2E')
= 1 + 1 + 2 x 2 = (3 x 4 - 6)
(Contd.)
Table 12.1.8.1 (Contd.)

Molecule rvib (normal No. of No. of Raman
modes of vibration) ir-active bands active bands
(xiv) [MLs] (TBP, D 3h ) 2Ai + 3E' + 2A~' + E" 5 (2A~ + 3E') 6 (2A~ + 3E' + E")
=2xl+3x2+2
x 1 + 2 = 12 = (3 x 6 - 6)
(xv) [ML4 ] (square A ig + Big + B 2g + A 2u + 3 (A 2u + 2E u) 3 (A lg + Big + B 2g )
planar, D 4h) B 2u + 2E u = 1 + 1 + 1 + 1 B 2u (silent mode)
+1+2x2=9 g-modes (ir-inactive) u-modes (Raman inactive)
= (3 x 5 - 6)
(xvi) trans-C 2H2Cl 2 SAg + 2A u + B g + 4B u 6 (2A u + 4B u) 6 (5Ag + B g)
ry
(planar, C 2h ) =5xl+2xl+l+4xl g-modes (ir-inactive) u-modes (Raman inactive)
= 12 = (3 x 6,,,- 6)
ra
(xvii) [ML4 ] Al + E + 2T2 ; 1 + 2 + 2 (2T 2) 4 (AI + E + 2T2)
ib
(Tetrahedral, Td) 2 x 3 = 9 = (3 x 5 - 6) A., E (ir-inactive)
3 (A 1g + E g + T 2g )
yl
(xviii) [ML6] A ig + E g + T 2g + 2T lu 2 (2T lu )
(octahedral, 0h) + T2u = 1 + 2 + 3 + 2 x 3 T2u (silent mode) u-modes (Raman inactive)
em
+ 3 = 15 = (3 x 7 - 6) g-mode (ir-inactive)
*
ch
Symmetries of the normal modes can be determined by Normal Mode Analysis. The method of normal mode
analysis is available in any standard book on Group Theory.
al
It is evident from the Table 12.1.8.1, that with the reduction of symmetry, the number of absorp-
e
tion bands increases. It is illustrated in the following representative cases.

th
• No. of ir-bands for the octahedral complexes: 2 (for [ML6], 0h), 9 (for fac-[ML 3 X 3 ] , C 3v ), 13 (for
e/
cis-[ML4X 2], C2v ), 14 (for m·er-[ML 3X 3], C2v ),

t.m
• No. of ir-bands for the square planar complexes: 3 (for [ML4 ], planar, D4h ), 8 (for cis-[PtCI 2L2 ],
C 2v )
• Conventions to label the vibrations (see Appendix 12B): The conventions are summarised here.
e
A ~ symmetric vibration with respect to the highest-fold Cn-axis.

er
B ~ antisymmetric vibration with respect to the highest-fold Cn-axis

H
E ~ doubly degenerate; T ~ triply degenerate; '(prime) ~ symmetric vibration with respect to the
k
horizontal plane (Oh) of symmetry; "(double prime) ~ antisymmetric vibration with respect to
lic
0h; subscript 1 and 2 (e.g. AI, A2) ~ symmetric and antisymmetric vibration respectively towards the
C 2-axis perpendicular to the en (principal axis) axis; g and u ~ symmetry of the vibration with respect
C
to the centre of inversion of the molecule.

• Inversion vibration of NH3 (C 3v ): The equilibrium configuration of NH3 is pyramidal of C 3v
symmetry. Without breaking any N-H bond, through the V2 (AI) symmetric bending (HNH)·vibra-
tion, one pyramidal configuration can be converted into its inverted pyramidal configuration. This
inversion (equivalent to an umbrella turning inside out and vice-versa) passes through the planar
geometry (i.e. D3h symmetry). In the potential energy curve (Fig. 12.1.8.1), the two identical minima
correspond to the pyramidal configurations (I and III) while the maximum corresponds to the planar
configuration (II). The central ene~gy barrier of inversion is about 23.5 kJ mol- 1 (= 1965 em-I). This
energy barrier of inversion is low and not too broad and tunnelling is possible between the pyramidal
structures (I and III) without crossing the energy barrier.· This tunnelling establishes an interaction
between the identical sets of vibrational energy levels in the two limbs of the potential energy curve.
This interaction splits the vibrational energy levels and the magnitude of splitting increases towards the
top of the barrier.
8
\Je.
Sp2_ N H
H ' ..H
Sp -N
3 --.N
/j\.. _ '/
H...
'N+- Sp -N
3
HI ... H
H H
I II
0
N"
H
'- \
\j
III
t
ry
ra
Symmetric bending
ib
(HNH)
Normal coordinate
yl
Fig. 12.1.8.1 Potential energy curve for the inversion of NH 3 through the v2(A}) nonnal mode of vibration.
12.1.9 Application of Infrared and Raman Spectra: Determination of Structure

em
ch
through the Normal Mode Analysis
al
Details of normal mode analysis for obtaining the irreducible representations of vibrational motions are
e
not discussed here. The results are given in Table 12.1.9.1.

th
e/
Table 12.1.9.1 Prediction of the number of ir-bands and Raman lines for different point groups (ef
Table 12.1.8.1 and Character Tables)
t.m
Molecule No. of No. of No. of

and point group ir-bands Raman lines coincidence
e
er
2(1t u + L u+ 1 (L g+) 0*
H
3 (2A 1 + E}) 3 (2A} + E}) 3

k
lic
C
3 (2A 1 + B 2) 3 (2A 1 + B 2)
B-A-B
B
I (C 2v )
(T-shaped)
6/1"'6B (C 3v ) 4 (2A} + 2E) 4 (2A} + 2E) 4 (2A} + 2E)

(Pyramidal)
(Contd.)

Molecule No. of No. of No. of
and point group ir-bands Raman lines coincidence
8
8-A/ 3 (A~' + 2E') 3 (A~ + 2E') 2 (2E')
"'8
(Planar)
ry
1
A
ra
8/1"'8 2 (2T z) 2 (2T z)
ib
8
yl
(Tetrahedral)
em
3 (A zu + 2E u )
0*
ch
(B zu is a silent mode)
e al
th
AB s (D 3h ) 5 (2Ar + 3E') 6 (2A~ + 3E' + E") 3 (3E')

e/
(Trigonal bipyralnid)
AB s (C 4v ) 6 (3A,+ 3E) 9 (3A 1 + 2B, + B2 + 3E) 6 (3A, + 3E)
t.m
(Square pyramid)
AB 6 (Octahedron) (Oh)
e
er
* (Rule of mutual exclusion principle)

H
Illustrative examples
A
k
lic
(A) AB2 molecule: The possible structures are B-A-B (linear as in CO 2 ) and / " (angular as in
B B
C
802)' These can be distinguished by examining their ir-and Raman spectra. These have been illustrated
in Sec. 12.1.7.
(B) AB3 molecule: The possible structures are:
8
B-A-8 A
B-A/
I
8
8/1"'8 8 "'B
(T-shaped, C 2V) (Pyramidal, C3V) (Trigonal Planar, D3h )
Example: CIF3 PCl 3 BF3

Predicted no. of ir-bands: 6 (3A 1 + B 1 + 2B z) 4 (2A 1 + 2E) 3 (Ar + 2E')
Predicted no. of Raman lines: 6 (3A 1 + B 1 + 2B z) 4 (2A, + 2E) 3 (A~ + 2E')
Common line in both ir- and
Raman spectra Yes (3A 1 + B 1 + 2B z) Yes (2A, + 2E) Yes (2E')
Experimental findings are given below for the CIF3, PCl 3 and BF3 molecules.
Molecule v (cm- J
) for ir-bands v (cm- J
) for Raman Spectra
326, 364, 434, 528, 703, 752 326, 364, 434, 528, 703, 752
(6 bands) (6 lines)
190, 258, 484, 511 190, 258(P), 484, 511 (P)
(4 bands) (4 lines)
480, 691, 1454 480, ·888(P), 1454
(3 bands) (3 bands)
482, 719, 1505 482, 888(P), 1505
(3 bands) (3 bands)
ry
(P) denotes the polarised Raman line. This can be also predicted from the concerned Character Table.
ra
For BF3, the Raman line at 888 cm-J is due to the totally symmetric vibration because there is no ir-
ib
band at 888 cm-J•
yl
All the experimental findings can be fitted for the C 2v (T-shaped), C 3v (pyramidal) and D 3h (trigonal
em
planar) symmetries of CIF 3 , PCl 3 and BF3 molecule respectively.
(C) Structure of NSF3: Different possible structures and the predicted number of ir-bands are as
ch
follows:
al
F F N
e
I I III
th
N S F-S-F No. of predicted ir-band for C 2v

e/
C 2v :
II I I (pentaatomic molecule)
t.m
N F = 9 (4A} + 3B} + 2B 2 )
/8",,-
F F F/ ""-F (Planar)
e
er
/F IF
H
N S No. of predicted ir-bands for C s (pentaatomic molecule)

Cs :
k
II II = 9 (7A' + 2A")
lic
/8",,- /"-
C
F F F F
N S
C3v :
IIIS f
N
No. of predicted ir-bands for C 3v (pentaatomic molecule)
= 6 (3A} + 3E)
F/I""-F F/I""-F
F F
Experimentally, 6 ir-bands (1515 cm- I , 775 cm- I , 521 cm- I , 811 cm- I , 429 cm- I , 342 cm- I ) for NSF3
have been noted. Out of these 6 bands, 4 bands are found to contain the PQR branches. All these
suggest the C 3v symmetry. Existence of the PQR branches indicate the symmetric top molecule.
Between the two possible geometries for C 3v symmetry, the band at 1515 cm- I indicates the presence
of S==N bond. The other possible structure of C 3v symmetry cannot explain this high vibrational
frequency (cf. VN-F = 1031 cm- I in NF 3). Thus the structure of NSF 3 is:
III
S (C 3v ' a symmetric top molecule).
F/I"'-
F F
In the same line of argument, the structure of CI03F (perchloryl fluoride) is:
I 6 ir-bands and 6 Raman bands: (1415 em-I, 873 em-I,

CI
473 em-I, 990 em-I, 485 em-I, 345 em-I)
/1"'-
ry
o 0
o
ra
For POCI3 , the 6 ir-bands common with Raman bands appear at: 1290 em-I, 581cm- l, 486 em-I, 337
ib
em-I, 267 em-I, 193 cm- l
yl
em
Note: For N==SF 3, POX3, CI03F (C 3v ), r tot =4A 1 + lA2 + 5E = 4 x 1 + 1 + 5 x 2 = 15 = 3 x 5 = 3n
and r vib = 3A 1 + 3E = 3 x 1 + 3 x 2 = 9 = (3 x 5 - 6) (ef rtot = r vib + rrot + r tran )
ch
(D) Structure AB4: There are two possibilities: square planar (D4h ) and tetrahedral (Td). By analysing
al
their ir-and Raman spectra, they can be identified.
e
• Square planar (Centrosymmetric): (3 Raman bands + 3 ir-bands; no common band):

th
9 Normal modes of vibration: A lg + BIg + B 2g + A 2u + B 2u + 2E u .

e/
'-v--------' \ V J
Raman activt:. ir-active

t.m
But B 2u appears as a silent mode, i.e. 3 ir-active modes. A 1g , BIg and E'l are the stretching modes (in
plane). B 2g and Eu are the bending modes (in plane). A zu and B2u are the deformation modes (out of
e
plane). In this centrosymmetric system, there is no common line in the ir- and Raman spectra.
er
• Tetrahedral (noncentrosymmetric): (4 Raman bands + 2 ir-bands; 2 coincident bands):

H
Al +E+2T2
9 Normal modes of vibration: ~
k
All Raman active;

lic
2T2 only ir-active.

C
Al represents the pure stretching mode. E denotes the pure bending mode. T z is a mixed mode. The
2T2 bands are coincident, i.e. two common bands in the ir- and Raman spectra.
(E) Structure of XeF4: After the discovery of XeF4, there was a debate regarding its structure. Some
workers argued in favour of its tetrahedral structure while some workers proposed its square planar
structure. The combined analysis of ir- and Raman spectra solved the problem. It gives three ir-bands
(A2u + 2E u) and three Raman lines (A Ig + B Ig+ B 2g ) and there is no coincidence (i.e. no common line
in the ir- and Raman spectra). This no-coincidence strongly supports the square planar structure. If it
were tetrahedral, there should be common lines in the ir- and Raman spectra (i.e. ir- and Raman bands
are coincidental in the noncentrosymmetric system like the tetrahedral geometry).
X~F4 (Square planar): Infrared bands: A2u (291 em-I), E u(123 em-I), E u (586 em-I). Raman lines: A Ig
(543 em-I), BIg (502 em-I), B 2g (235 em-I) and a weak band at 442 cm- I (as an overtone of the B 2u mode
which is itself both ir- and Raman inactive). The overtone representation is obtained by squaring the
irreducible representation B zu (cf B 2u X B 2u = A ig which is Raman active).
12.1.10 Application of Infrared and Raman Spectra: Determination of Geometrical

Isom,ers of Coordination Compounds
This aspect has been already discussed for the mononuclear carbonyls (cf. Table 9.4.11.1). It is illustrated
for v M- X in different geometrical isomers.
Table 12.1.10.1 Number of ir-active (M-X stretching frequency, VM-X) bands in different geometrical
isomers. (X = halogen) (cf. Character Table)
Complex Point group No. of ir-active No. of Raman

(vM- X) bands lines
cis-[ML2X 2l 2 (AI + B I) 2 (AI + B 1)
ry
trans-[ML 2X 2l ) Square planar 1 (B 3u ) 1 (Ag)
ra
trans- [ML2X 2l 1 (B u) 1 (Ag )
ib
"I • cis-[ML4X 2l 2 (AI + B 2) 2 (AI + B2 )
yl
trans-[ML4 X 2l 1 (A 2u ) 1 (A Ig )
em
cis-[ML2 X 4 l 4 (2A I + B I + B 2 ) 4 (2A I + B I + B 2)
Octahedral
trans-[ML 2X 4 l ch 1 (Eu) 2 (A lg + Big)
fac-[ML 3X 3l 2 (AI + E) 2 (AI + E)

mer-[ML3X 3l 3 (2A I + B 2) 3 (2A I+ B 2)
e al
x------------ L X------------X
~~-7i
th
!~/i !~/i
e/
i/M~j i/M~i i/M~i

t.m
L ------------X L ------------L L---------------X

e
frans-[ML 2 X2 ] (D 2h ) cis-[ML2 X2 ] (C 2V ) frans-[ML 2 X2 ] (C 2h )

er
"--------- ------_./ (Rectangular)

'V'"
H
The results are obtained through the Normal Mode Analysis for which any standard book on Group
k
lic
Theory can be consulted. For cis-[ML 2X 2], both the v(M-X) band are ir-active but for the trans-isomer
only one v(M-X) band is ir-active.
C
Examples:
(A) [PdCI2 (NH3)2]: The cis-isomer (C 2v ) is expected to give two bands (AI + B 2) due to Pd-CI
stretching while the trans-isomer is expected to give one Pd-CI band (B u or B 3u ) in ir-spectra. In fact,
experimentally, it has been found that the cis-isomer gives 2 bands (actually a doublet band) and the
trans-isomer gives one band at 333 cm- I . It may be noted that for the cis-isomer, the band due to
Pd-N stretch also splits at 490 cm- I .
Note: Tetrahedral ML 2X 2 also gives two v(M-X) bands (one symmetric stretch and one antisymmetric
stretch). These two bands are well separated. In fact, for the tetrahedral complex, the band separation
is much larger than that occurs for the cis-square planar complex where the v(M-X) band splits only.
(B) [IrCI2 (PY)4]+: The cis-isomer (C 2v ) gives two ir-bands (AI + B 2) while the corresponding trans-
isomer (D4h ) gives one ir-band (A2u ) for Ir-CI stretching. These predictions have been experimentally
verified.
.\
•
cis-[IrC1 2 (pY)4]+: V1r - C1 = 327 em -1 , 333 cm- I
trans-[Ir~12(pY)4]+: V1r - C1 = 335 em- I
(C) [PtCI4(NH3)2]: A partial normal mode analysis for the MX4 unit gives 4 ir-bands (2A I + B I + B2)
for the cis-complex (C 2v ) and one ir-band (E u) for the trans-complex (D4h ) for M-X stretching. These
predictions are experimentally verified.
cis-[PtCI4(NH3)2] : vPt - Cl (cm- I ): 206, 330, 344, 353

trans-[PtCI4(NH 3 )2] : vPt - Cl (cm- I ): 352 cm- I
ry
In general, with the lowering of symmetry, the number of ir-bands goes to increase. This is why,
in the 'cis-isomer, the number of ir-bands is higher compared to the case of trans-isomer. Moreover,
ra
the bands in the lower symmetry compound are relatively stronger. In fact, the bands in the cis-
ib
complex are relatively more intense.
yl
For example, for [CoCI2(bpY)2]CI, the trans-isomer shows only 7 ir-absorptions while the cis-
em
isomer records about 13-14 ir-absorptions. ch
(D) [ML3X3 ]: For v(M-X), the fac-isomer (C 3v ) gives two ir-bands (AI + E) while the mer-isomer
(C 2v ) gives three ir-bands (2A I + B 2). These predictions are experimentally verified.
e al
[Complex] VM - C1 (em-I), (mer-isomer) VM- Cl (em-I), (fac-isomer)

th
e/
[RuC1 3(OH 2hl 291,311,315 291, 315

t.m
[RhC1 3(pyhl 295, 322, 355 325, 340
(E) cis-trans isomers of dichloroethylene: The trans-isomer is symmetrical and the symmetric stretch-
e
ing vibration (causing no change in dipole moment) is ir-inactive. But this mode is ir-active for the cis-
er
isomer and vc=c appers at 1580 cm- I .

H
k
lic
H"" ~CI
C~ H3C - C _ C - H H3C - C - C - C H 3
C
vc:: c = 2150 cm- 1

vc:: c (absent)
II
/C~
H CI
f.l= 1.85 D f.l=o

vc=c = 1580 cm-1 vc=c (absent)
12.1.11 Application of Infrared and Raman Spectra: Determination of the Structures

of Metal Carbonyls
These aspects have been discussed in Secs. 9.4.11 - 13. The structures can be predicted by considering
the number of ir-bands for CO stretching (cf Table 12.1.11.1).
Table 12.1.11.1 Number of ir-bands and Raman lines due to the C-O stretching in different carbonyls of
different symmetries.
Molecule Point group Number and symmetry Number and symmetry
of IR bands of Raman lines
[M(CO)6] °h 1 (TIJ 2 (A Ig , Eg)

[M(CO)sL]
[M(CO)Ls]
)(OS C4v
C4v
3 (2A b E)
1 (AI)
4 (2A b B I , E)
1 (AI)
cis-[M(CO)4L 2] C 2v 4 (2A b B b B 2) 4 (2A b B b B 2)
trans-[M(CO)4L 2] D 4h 1 (Eu) 2 (A Ig , BIg)
cis-[M(COhL4] C2v 2 (AI' B I ) 2 (A b B I )
ry
trans-[M(COhL4] (Oh )* D 4h 1 (A 2J 1 (A Ig )
ra
!ac-[M(CO)3L3] C 3v 2 (A b E) 2 (A b E)
ib
mer-[M(CO)3L 3] C 2v 3 (2A b B I ) 3 (2A b B I )
yl
[M(CO)s] (SP) C 4v 3 (2A I , E) 4 (2A I , B I , E)
em
[M(CO)s] (TBP) D 3h 2 (A~, E') 3 (2A~, E')
[M(CO)4L(ax)] C 3v 3 (2A b E) 3 (2A b E)
ch
[M(CO)4L (eq)] ) (TBP)* C 2v 4 (2A b B b B 2) 4 (2A b B b B 2)
[M(CO)3L l ax)] D 3h 1 (E') 2 (Ar, E')
al
[M(CO)4] Td 1 (T2) 1 (AI)

e
th
[M(CO)3L] 2 (A b E) 2 (A b E)
!(Td )* C 3v
e/
[M(COhL2 )] C 2v 2 (AI' B I ) 2 (A b B I )
[M(CO)L3] C 3v 1 (AI) 1 (AI)
t.m
cis-[ML2 (COh] } (Square C 2v 2 (AI + B l ) 2 (AI + B I )

trans-[ML 2(CO)2] planar) * D 2h 1 (B 3u ) 1 (A g)
e
er
* Denotes the geometry

H
Note: Sometimes, weak bands due to l3CO may arise from the natural abundance of l3C. However, this
aspect has been ignored here. Sometimes, l3C-NMR becomes important for the structure determination.
k
lic
If the molecule is not fluxional (on NMR time scale), then for the inequivalent CO groups, separate
l3C-signals will appear. The terminal CO group is more shielded (ef Sec. 12.2.17).
C
• Structure determination of [Fe(CO)s] - use of infrared spectra, Raman spectra and 13C·NMR
spectra (Sec. 10.11.1 and Sec. 10.9.4, Vol. 2): It may adopt two possible geometries: square pyramidal
(C 4v ) and trigonal bipyramidal (D 3h). The predicted number of ir- and Raman bands are:
[Fe(CO)s] (C 4v , square pyramid): 3 ir-bands (2A I + E); 4 Raman lines (2A I + B I + E)
[Fe(CO)s] (D3h, trigonal bipyramid): 2 ir-bands (A'~ + E'); 3 Raman lines (2A~ + E')
Experimental findings: 2 ir bands (2028 cm- I , 1994 cm- I ) and 3 Raman lines (2114 cm- I ,
2030 cm- I , 1988 cm- I ); there are two common bands.
The observations nicely match with the trigonal bipyramidal strucuture (not the square pyramidal
structure). The totally symmetric band (Ai) at 2114 cm- I is absent in the ir-spectrum but it gives a strong
j lill,e in the Raman spectra (ef Fig. 12~ 1.11.1). Thus the ir-and Raman spectra support the two types
....
....;?~<.'-9!.~O groups (i.e. axial and.equatorial)

." 13C-NMR shows one signal due to the M-CO band (i.e. all the Fe-CO bonds appear equivalent).
indicates the molecule to be fluxional (on NMR time scale) i. e. there is a rapid interconverision
between the equatorial and axial CO groups within the NMR time scale. Thus, the 13C-NMR spectrum
is not useful here for the structure determination.
• 2 ir-bands
• 3 Raman bands
ry
Jj,
TBP
ra
ib
r r
yl
em
2200 2100 2000ch 1900
+-- v,cm- 1
al
Fig. 12.1.11.1 Infrared and Raman spectra of liquid [Fe(CO)5] (in the CO stretching region).
e
Note: Readers are suggested to go through the Secs. 9.4.11-13 and 10.6.1 to understand the use of ir-
th
spectroscopy in structure determination of metal carbonyls.

e/
12.1.12 Effect of Coordination on the Rotational-Vibrational Spectra of the Ligands

t.m
The molecular vibrational and rotational energy changes occur in the infra-red region of the spectrum.
The vibrational and rotational energy changes depend on the masses of the constituent atoms, bond
e
er
lengths and bond strength. When a ligand coordinates to a metal centre, not only its symmetry gets
reduced but the above. factors are also changed to some extent due to the metal-ligand bond formation.
H
Here it may be mentioned that the metal-ligand bond is weaker than the bonds within the ligands. The
k
metal atom is heavier. The vibration of the metal-ligand bond gives the new ir-absorption bands in
lic
the far-infrared range 150-600 cm-I • Thus the v -values of the metal-ligand bond and the bonds
C
within the ligand differ widely. Consequently, there is only a little interaction of the metal-ligand bond
vibration with the vibrational modes within the ligand. This is specially true when v for the metal-
ligand bond vibration lies in the very low frequency range.
The metal-ligand bond formation is reflected in the ir-spectrum as follows:
(a) New bond vibration: VM- D (150 - 600 cm- I ), D = donor atom of the ligand.
(b) Shifting of group frequency (v) for the bonds within the ligand: The bond length and bond
strength within the ligand may change due to coordination. It causes the shifting of v for the
ligand (compared to that of the free ligand).
(c) Appearance of new skeletal vibration for the coordinated ligand: For the polyatomic ligands
(e.g. H 20, col-, N0 3-, etc.) due to coordination with the metal centre, the symmetry of the ligand
changes. It leads to the appearance of the new bands.
The above changes in the ir-spectrum can be studied to understand the coordinating behaviour of the
ligands. These aspects are discussed in the next sections.
12.1.13 Application of Infrared Spectra: Appearance of New Bond Vibration for the
Metal-Ligand Bond Formation
The new metal-ligand bond (M-D, D = donor atom e.g. halogen like CI, Br, F, 0; N; As; P; Sb; etc.)
is produced. These metal-ligand bond vibrations generally appear in the far-infrared region (ca. 100
- 650 cm- I ). They appear in the very low energy region (compared to the v-values for the bonds within
the ligand). It is due to the two factors:
(i) the metal atom is heavy i.e the atoms constituting the M-D bond are relatively heavier; (ii) the
M-D bonds are generally much weaker compared to the bonds within the ligands.
For the x-acid ligands (i.e. M~D 1t-back bonding), the M-D bond is quite strong and VM - D
appears at the relatively higher frequency (cm 450 - 650 cm- I ). It happens so for the M-C (carbonyl
ry
complex), M-P, M-As, etc. bonds. VM - N generally appears in the range 300 - 500 cm- I ; for the 3d
ra
metal ammines, it occurs at about 450 cm- I .
ib
Sometimes, the isotopic substitution (e.g. 18 0 in the" M-O bond; D i.e. 2H in the M-H bond), may
yl
be useful for characterisation of the metal-ligand bond from the ir-spectra. Obviously, VM - H lies in the
em
higher frequency region.
• VCo-N for [CoCI(NH3)s]CI2 vs. [CoCI(ND3)s]CI2 : It is known that for the heavier isotopes, the
ch
bond energy is higher i.e. the N-D bond is stronger than the N-H bond (cf. Sec. 10.1.2, Vol. 2, for
discussion). It makes, the M-N (ND 3) bond weaker than the M-N (NH 3) bond, i.e. replacement of
al
H by D weakens the M-N bond. It is reflected in the VM - N values.

e
th
Complex: [CoCI(NH3)s]2+ [CoCI(ND3)s]2+ [Co(NH3)6]3+

e/
I
Vco - N (cm- ): 493 487 502
t.m
It indicates that among the above complexes, in [Co(NH 3)6]3+ bearing the highest cationic charge,
Co-N bond is the strongest one. In [Co(NH3)6]3+, VN - H (~3280 cm- I ) is significantly reduced com-
e
pared to that of free NH 3 (V N - H ~ 3340 cm- I ).

er
H
H
/
Free NH 3 possesses the C3v symmetry. In the metal-ligand bond formation i.e. M f- N-H, the local
k
"
lic
H
symmetry is still C 3v . In general, there are five ir-bonds: -3300 cm- I (N-H stretching),
C
-1600 cm- I (NH 3 degenerate deformation), -1300 cm- I (NH 3 symmetric deformation), -825 cm- I
(-NH 3 rocking), -500 cm- I (M-N stretching) i.e.
v(N - H) ~ 3300 cm- I , bd(NH 3) ~ 1600 cm- I , bs (NH3) ~ 1300 cm- I , prCNH 3) ~ 825 cm- I , v (M-N)
~ 500 cm- I ,
• vpt - H =P, As; X = N03, CI, Br, I, N02, SCN; R = alkyl or aryl
in trans-[Pt(AR3 )2(X)(H)] (A
v H has been found in the range 2000 - 2200 cm- I and the position of v H is correlated with
group): pt - Pt -
the trans-influence of the trans-ligand X. The trans-influence series is:
X: PR3) SCN- ) 1- ) CN- ) Br- ) CI-) NH 3.
A ligand (say X) having the higher trans-influence weakens more the bond at the trans-position, i.e.
higher the trans-influence of X, lower the v pt - H value.
• VN-H and VPt-N for trans-[PtCI2(NHRR')(L)]: Here the ligands Land NHRR' are at the trans-
position. Higher trans-influence of L weakens the Pt-N bond more (i.e. strengthens the N-H bond),
i.e. higher the trans-influence of L, lower the VPt-N and higher the V N- H •
trans-influence of L: PR3 ) SbR3 ) P(OR)3) AsR3 ) TeR2 ) SeR2 ) SR2 ) piperidine.
V N- H +-(- - - - - - - - i n - c r - e a s - i n - g - t r - e n - d - - - - - - - - - - - - - ; , . - -
VPt- N increasing trend
• VPt-N and VN-H for trans-[PtCI 2(NH 3 )(L)]: Here NH 3 and L are at the trans-positions. Higher
trans-effect or trans-influence of L makes the trans-Pt-N bond weaker (i.e. N-H bond stronger).
L = NH3 ( SEt2 ( C2H 4 (trans-effect/trans-influence)
ry
- (-1) _5_o_7(_N_H.::.,.3)_ _49_3_(S_E--=t2_)_ _4_8_1(C.....:2~H-'-4_)_
+-(
cm :
ra
V Pt - N increasing trend
ib
increasing trend
yl
and in [Co(CN)sH]3- and [Co(CN)sD]3-: = 1850 cm- I . It leads to:
em
• VC()-H VC()-D V Co - H
vCo-D : : : V Co - H ::::::1320cm- 1.
ch
1.41 '
al
1 1
cf. For the A-H and A-D bonds: - =- +- ::: - and - =- +- ::: - assuming,
e
J..lH rnA rn H rn H J..lD rnA rn D rn D

th
rnA» rnH, rnD

e/
. VA - D ~ ~ [1 1
= V;;; "" V--;;;;; = ~2 = 1.41
t.m
I.e., VA-H
• Formation of the M-OH2 bond: For the formation of M-OH2 bond in the complex, the new
e
bands for v(M-O), Pw(OH 2), plOH 2) and pt(OH2) will appear. These aspects are discussed in
er
Sec. 12.1.14.
H
12.1.14 Application of Infrared and Raman Spectra: Appearance of New Bands for the
k
lic
Ligand upon Coordination

Local symmetry of a ligand very often changes upon c~ordination. Many inactive ir-bands of the ligand
C
may become active upon coordination. Some ir-bands may undergo splitting. These changes in the ir-
spectra may help us to characterise the coordinating behaviour of the ligands. This aspect is illustrated
here in some representative cases.
(A) Homonuclear diatomic molecules (e.g. H 2, N2, O2) as the ligands: Such homonuclear diatomic
molecules are ir-inactive but Raman active. When they remain coordinated as the ligands, they be-
come ir-active because the symmetry changes upon their coordination. For example, the stretching
vibration (2331 cm- I ) of free N 2 is ir-inactive (though Raman active) but in the complex like
[Ru(NH3)s(N2)]2+ (produced in the reaction of [Ru(NH3)s(OH 2)]3+ with the azide ion), the N-N stretching
becomes ir-active (2130 cm- I ). The reduction in stretching frequency occurs due to the n-acceptance by
N 2 into its vacant n*-MO.
The shifting of stretching frequency for N2' O 2 and H 2 upon coordination in different complexes
indicates the coordinating property of these molecules and chemical state of the molecules in the
complexes. These aspects have been illustrated in Chapter 9.
(B) New skeletal vibrations of H 2 0 upon coordination: Upon coordination by H2 0 as a ligand, new
modes of vibration i.e. v M- O , Pw(OH2 ) (wagging mode), prC0H 2 ) (rocking mode), pt(OH2 ) (twisting
mode) will appear in addition to the three fundamentals. For the M-OH 2 moiety, the observed group
frequencies are:
B(HOH) ::::: 1650 em-I (ef B(HOH) ::::: 1600 cm- I for free water); Pw(OH ) ::::: 550-700 em-I; prCoH ) :::::
2 2
750-800 em-I; Pt : : : 625 em-I; v(M-O)::::: 300 - 600 cm- 1
The three fundamentals of free H2 0 (Sec. 12.1.3):

VI (symmetric stretch):
o 3652 cm- I
ry
H /'" H
V2 (symmetric bending):
ra
1595 cm- I
ib
(cf Fig. 12.1.1.6) v3 (unsymmetric stretch):
yl
M M 3756 cm- I
em
I I
0
~/O~e H/~H
ch
H H
= 755 cm- I
\/ Pw( OH 2 ) ::::: 645 cm -I, prC0H2)
al
I
e
pt(OH 2 ) 8(HOH) [Cr(OH 2)6]CI3 : VCr - O = 490 cm-

th
Pw( OH 2 )::::: 540 em -I ,prC0H2) = 800 cm- I

e/
t.m
Fig. 12.1.14.1 Modes of vibration of M-OH 2 .
(C) M~NH3: The local symmetry is C 3v (ef free NH 3 also possesses the C 3v symmetry). The charac-
e
teristic vibrations for this coordination have been discussed in Sec. 12.1.13.
er
(D) New skeletal vibrations upon coordination by the anionic ligands like COj-, NOi a~d 801-:
H
These are separately discussed in the next sections.

k
12.1.15 Application of Infrared Spectrum: Detection of Water in Coordination

lic
Compounds
C
The actual fate of H 20 in the coordinated compounds may be understood from the ir-spectra. For free
water, it shows two characteristic bands: 3600-3200 cm- I (stretching), -1600 cm- I (bending). If H20 is
present as the lattice water (held by the weak lattice forces), a band in the region 300-600 cm- I along
with the abovementioned two bands will appear. If water remains coordinated (i.e. M-OH 2 ), then the
new bands (i.e Pw(OH2 ), prC0H2 ), pt(OH2» will appear in the range 500-1000 cm- I. The vM - O will also
apear in the range 300 - 600 cm- I. The B(HOH) band occurs at about 1650 cm- I. The order is:
B(HOH) ) prC0H2 ) ) Pw(OH 2 ) ) pt(OH2 ) ) v M- O •
Due to H-bonding for the anion water, the stretching frequency (-3600 cm- I) is shifted towards
the lower frequency and the band becomes broader. This shift may be quite high (by about 300 -
400 cm- I, ef Fig. 12.1.5.1).
• Metal coodinated water: New bands appear for Pw(OH 2) (i.e. wagging mode), plOH 2) (i.e.
rocking mode) and pt(OH 2) (i.e. twisting mode) in the range 600 - 1100 cm- I. Another new band
appears for v M- O in the range 450 - 650 em-I.
• Lattice water held by weak lattice forces: A new band appears in the 300-600 cm- I range in
addition to symmetric and antisymmetric stretching frequencies in the range, 3200 - 3600 cm- I and
bending vibration in the range, 1600 - 1650 cm- I .
• Hydrogen bonded water: Sometimes, the lattice water may undergo H-bonding with the anion.
In such cases (i.e. anion water), a broad peak in the range 3100 - 3500 cm- I appears (cf Fig. 12.1.5.1).
• An exciting example of detection of water in the clathrate compound, Ni(CN)z· NH3• C6H 6 •
xHzO by the ir-spectrum: The ir-spectrum of the clathrate compound clearly indicates the presence of
water though the single crystal X-ray study fails to detect the presence of water in the clathrate compound.
In the said clathrate compound, the water molecules are placed in such a way that the frequencies of
the out of plane vibrations are increased though the in-plane vibrations are not affected.
ry
12.1.16 Application of Infrared Spectra: Shifting of the Ligand Band Position to
ra
Characterise the Mode of Coordination
ib
On complexation, the characteristic group frequency of the ligands very often undergoes a shifting.
yl
This shifting can yield a lot of information regarding the bonding mode of a ligand in a complex. This
em
shifting may occur towards the higher frequency and lower frequency depending on the condition. The
different factors to determine the magnitude and direction of shifting are discussed below.
ch
• Shifting towards the higher frequency: It may occur when the antibonding election is donated
by the ligand to the metal through the a-bond and the electron cloud is received by the ligand from the
al
metal in a bonding MO.

e
For the a-donor ligand LXn (L = donor atom), if the electronegativity ofL is less than that of X (i.e.
th
XL < Xx as in coordination through the S-end of SOj-, etc.) then upon coordination (i.e.
e/
M f- LX n a-bond formation), the L-X bond becomes stronger (compared to that of the free state of
t.m
the ligand). It makes v L- X higher upon coordination.

• Shifting towards the lower frequency: If the bonding electron of the ligand is donated and
e
electron cloud from the metal centre is received into the antibonding MO of the ligand, then the group
er
frequency of the ligand is lowered. It happens ·so for C 2H4 and H 2 coordinating in the 112-C 2H 4 and
112-H2 fashion.
H
In the case of coordination through the O-end of CO}-, urea, DMSO, etc. the double bonded character
k
in the groups like CO, SO is partially reduced and then vco and vs o decrease.
lic
For the a-donor ligand LX n (L = donor atom), if the electronegativity of L is higher than that of
C
X (i.e. XL) Xx e.g. NH 3 as the ligand coordinating through the N-end), then upon coordination (i.e.
Mf-LXn a-donation by the ligand), the L-X bond becomes weaker (compared to that of the free state
of the ligand). It makes VL-X lower upon coordination.
• Explanation for the direction of VL-X shifting upon coordination: In terms of the MO energy
diagraITl of LXn , donation of electron from the BMO of LX n and receiving of electron in the ABMO of
LX n reduce the L-X bond order (i.e. decrease of VL-X). For the COi-, NO) etc. as the ligands, the 1t-
bonding electron is donated. For the olefins as the ligands, the 1t-bonding electron is donated. Donation
of electron from an ABMO (generally weakly ABMO as in CO, CN-) strengthens the L-X bond (i.e.
increase in v L- X). But for CO and CN-, receiving of electrons from the metal centre into their 1t*-MO
will reduce VL-X (i.e. vc-o, VC-N).
To understand effect of a-donation (i.e.XnL ~ M) on the L-X bond strength, the Gutmann's rule
may be considered. If XL) Xx, then in the free state and coordinated state, the L-X bond is polarised
as follows:
(PI-) (ql +)
L-X bond polarisation: Xn_1L-X where PI> P2
When the electron is donated from L to the metal centre, the amount of negative charge is reduced
on 'L' compared to that in the free state (i.e. PI ) P2)' Thus the ionic character in the L-X bond is
decreased upon coordination, i.e. the contribution of covalent-ionic resonance to strengthen the
L-X bond is decreased upon coordination. This is why, vL-X decreases upon coordination. It hap-
pens so for the ligands like NH 3 , OH 2 , etc.
VN - H (in free NH3 ) = 3338 cm- I , VN - H (in [Co(NH3 )6](CI04 )3] = 3280 cm- I
If XL ( Xx, then in the free state and coordinated state, the L-X bond is polarised as follows:
(P 3+) (ql-) (P4+)
ry
L-X bond polarisation: Xn_1L-X M~ LX n where P3 > P4
ra
Electron donation from L makes L more electron deficient i.e. P4) P3' It enhances the ionic character·
ib
in the L-X bond, i.e. covalent-ionic resonance interaction to strengthen the L-X bond increases. It
yl
makes VL-X higher upon coordination.
em
It happens so for the ligands like SnCIi (coordination through Sn), SOj- (coordination through S),
CN- (coordination through C; n-acceptance of CN- is negligible), etc.ch
VSn - CI (in free SnClj") =297 cm- I , 256 cm- I ; VSn - C1 (in [Rh(PPh3)3(SnCI3)] = 327 cm- I , 302 cm- I
Some authors have explained the above observation in terms of the degree of covalence of the
al
L...:.-X bond. This aspect is illustrated below.

e
XL ( Xx: For XnL ~ M a-donation, L becomes more electronegative due to the increased electron
th
deficiency and consequently the electronegativity difference, i.e. XL - Xx decreases upon coordination.
e/
It enhances the degree of covalence in the L-X bond upon coordination, i.e. vL-X increases upon
t.m
coordination.
XL ) Xx: For XnL ~ M a-donation, L becomes more electron deficient, and consequently, it becomes
more electronegative. Thus the degree of covalence in the L-X bond decreases upon coordination
e
because XL - Xx (electronegativity difference) increases. It reduces vL-X upon coordination.

er
H
12.1.17 Application of Infrared Spectra: Shifting of Band Position to Characterise the

Mode of Coordination - Illustrative Examples.
k
lic
(A) Carbonato and nitrato complexes: In free carbonate (-1400, -1100, -880, -750 cm- I ) and
nitrate, there is a partial double bonded character in the C-O and N-O bonds. But coordination
C
through the O-end reduces this bond order. It is reflected in vc-o and vN- O which will be shifted towards
the lower frequency upon coordination.
/0", /0",
M C-::-=-::O M C=O
,(~'-
0' "'0/
veo::::: 850 cm- 1 veo::::: 830 cm-1
veo = 880 cm- 1
SPECTROSCOPIC METHODS AND OTHER PHYSICAL MFTHODS IN CHEMISTRY 1763
The shifting of vc-o and vN-o can help us to understand their coordinating behaviours. It has been
already mentioned that upon coordination, their local symmetry is reduced (D 3h ~ C2v , C 3v depending
on the mode of coordination) and this symmetry lowering is reflected in the ir- and Raman spectra.
These aspects have been illustrated in Sec. 12.1.19.
(B) Shifting of vc=o in the carbonyl compounds (see Secs. 9.4.11, 10.6.1): The nonbonding electron
pair (which is weakly antibonding in character) is used for a-donation to the metal centre and the
electron is received into the vacant 1t-ABMO through the n-bonding from the metal centre. Thus a-
donation, slightly enhances the C-O bond order (i.e. slight increase in vco) but the n-acceptance
(which is more important) significantly reduces the C-O bond order. In most of the cases, effect of
1Ti-aceptance to reduce the C-O bond order is more significant than the effect of c;donation causing
a slight increase in the C-O bond order. Compared to the terminal CO group, for the bridging CO
ry
groups, the reduction in the C-O bond order is more.
ra
ib
M
yl
CO (free) M-C _ 0 (terminal) ""'C===O
/
em
2143 1850-2140 M 1l2- CO
1700-1850
ch
Angular bridging CO groups (i.e. J.I.2-CO) vs. almost linear bridging CO group: When the metal-
al
metal bond distance is relatively short, the linear terminal CO groups can act as the poor bridging
e
ligands through a slight bending. The vco values of such nearly linear bridging CO groups are higher
th
than those of the angular bridging CO groups (i.e. J.l2-CO). But the veo values of such nearly linear
e/
bridging CO groups are less than those of the typical terminal CO groups. Thus in terms of the vco values,
t.m
the nearly linear bridging CO groups represent an intermediate situation and such CO groups are
described as the semibridging J.l2-CO groups, i.e.
veo : terminal CO (1850-2140 em-I) > nearly linear bridging CO > angular bridging CO (1700-
e
er
1850 em-I). It is illustrated in the following example.

)31 ~[ (11 -Cp) Mo (CO)2 ] + 2CO
H
[(11 5 -cp) Mo (CO 5

k
The vco values and structural features of the above two compounds are illustrated in Fig. 12.1.17.1.
lic
C
Nearly linear ,
co OC CO o ~ bridging CO ......---...
5I \ /5
(11 -Cp)Mo - - - MO(l1 -Cp)
/ c~~.
(11 5 -Cp)Mo, / '< MO(l1 5 -Cp)
group OC~d
~
. ·o':,pC
/ \ I ", ~
OC
-
CO CO
-1 ··.~~1 Me Me
veo = 1915,1960 em
(terminal CO group) 0 ,.
veo = 1859,1890 em- 1
(Mo)d ~ n;*(CO)
(a) (pure terminal CO group?)
(b)
Fig. 12.1.17.1 (a) Structure of [(1l5-Cp)Mo(CO)3h; (b) structure and bridging property of the CO group
in [(1l5-CP)MO(CO)2h.
The relatively low veo values in [(1l5-Cp)Mo(CO)2]2 cannot be explained by considering the existence
of pure terminal CO groups as in the proposed following structure satisfying the 18e rule.
co co
I I
(1l5-Cp) Mo_Mo (115-Cp) (satisfying the 18e rule; no bridging property
I I of the terminal CO group)
CO CO
The bridging property of the linear terminal CO groups is attained through a slight bending and the
following interactions are attained.
(i) the n-bonding electron cloud of the terminal CO-group can be donated to some extent to the other
metal centre to reduce the c-o bond order.
(ii) the n*-MO of the CO group can also receive the electron cloud to some extent from the filled
ry
metal d-orbital to reduce the c-o bond order further.
ra
Both the said actions to reduce the C-O bond order are relatively weaker than those in the angular
ib
bridging CO group. This is why, the c-o bond order in the nearly linear bridging CO group is greater
yl
than that in the J..l2-CO group but less than that in a pure terminal CO group (i.e. M-CO). .
em
On heating, [(1l5-Cp)Mo(CO)3]2 loses some CO molecules with the concomitant increase in the
metal-metal bond order from 1 to 3 (in conformity with the 18e rule). This shrinkage in the metal-
ch
metal bond distance allows the linear terminal CO group to act as a poor bridging ligand in
[(1l5-Cp)Mo(CO)2]2·
al
Here it is worth mentioning that [(1l5-Cp)Mo(CO)3]2 shows the fluxionality (see Fig. 10.9.6.5 in
e
Vol. 2 and Sec. 10.11.3) through the participation of the CO group as the bridging J..l2-CO group. But
th
in the equilibrium mixture, concentration of the structure having the angular J..l2-CO groups is negligible
e/
and the ir-data also support the fact that it predominantly exists in the structure having only the terminal
t.m
CO groups.
• For the nonclassical carbonyl complexes (i.e. carbonyl complexes of the highly electronegative
and heavier congeners, e.g. Au, Ag, Pd, Pt, etc.) where M ~ CO n-bonding is not important, the veo
e
increases slightly in the complexes due to M ~ CO (a-donation of the nonbonding electron pair having
er
some antibonding character).

H
Different factors to determine the v eo values in the carbonyl complexes have been dissussed with a
large number of exampl~s in Chapter 9, Sec. 10.6.1 and Sec. 12.8.5, Vol. 3.
k
lic
(C) Nitrosyl complexes (see Sec. 9.6): Depending on the conditions, NO can form the bent
C
(M-N i.e. NO as ·NO-) and linear (M-N=O, i.e. NO as NO+) bonds. They can be distinguished
~
o
by comparing the VNO frequencies.
/\.
M-N-O (ca. 170-180°): VN - O ~ 1660 - 1900 cm- l
(Linear)
/\.
M-N-O (ca. 120-140°) : VN - O ~ 1525 - 1680 cm- l
(Bent)
V NO (J..l3-NO) <V NO (J..l2-NO) <v NO (terminal) (as in carbonyl complexes).

(cf v NO+ (~ 2300 cm -1 )V NO (~ 1876 cm -1)V NO- (1500 -1600 cm -1)
The different factors controlling the position of VNO in the complexes have been discussed in detail
with a.large number of exa~~l~~s in Chapter 9 and Sec. 16.1 of Vol. 3).
(D) Dinitrogen complexes (see Sec. 9.11): Dinitrogen (N2) is itself ir-inactive (though Raman active)
but the coordinated dinitrogen is ir-active. 1l1_N2 cannot practically function as a a-donor ligand but it
can act is a poor 1t-acceptor ligand (M --., n* of N2). It is reflected in the lowering of V N - N upon
coordination. When it acts as a bridging ligand (i.e M-N == N-M), V N- N is further reduced compared
to that in M-N == N (i.e. terminallll-N2). The stretching frequency runs as:
VN - N (free N2) = 2331 cm- l ) VN - N (terminallll-N2) = 2200 - 1850 cm- 1 ) VN - N (bridging f.,l-lll: 1l1_N2)
Some representative examples are given below.
VN - N (cm- l) "= 2130 in [Ru(NH 3)s(N2)]2+; 2095 cm- l in [lrCI(N2)(PPh3)2]; 2088 cm- l in
[Co(H)(N2)(PPh3)3]; 1955 cm- 1 and 1890 cm- l in trans-[Mo(N2)2(Meg[16]aneS4)].
In the dinitrogen complexes, the M --., n*(N2) n-bonding is the main factor to stabilise the complex.
The n-back bonding largely depends on the chemical state of the metal centre and other ligands
ry
present in the complex. Definitely, the high oxidation state, presence of the electron withdrawing
ra
ligands, presence of the other n-acceptor ligands will disfavour the M --., n*(N2 ) n-bonding. Better
ib
M --., n*-MO (N2) n-bonding will stabilise the dinitrogen complex better, i.e. V N- N will be reduced more
yl
for the better n-back bonding.
em
All these aspects have been discussed in detail in Secs 1.7,9.11 and 10.12.10.
(E) Dioxygen complexes (see Sec. 9.13): For binding of dioxygen as a ligand, vo - o is reduced compared
to that of vo-o = 1555 cm-I(Raman stretching frequency, in free state). In fact, O2 can act as an-acid
ch
ligand. Position of v o- o in a complex can tell us the chemical state of the coordinated O2. In fact, from
al
the values of 0-0 bond length and vo-o, the chemical states of the dioxygen adducts of Vaska's
e
complex have been predicted.

th
[ Ir II (CO)CI(11 2 -0 2 )(PPh 3 )2 ] [ IrIII(CO) 1(11 -O~- )(PPh 3 )2 ]

2
e/
0-0 = 130 pm, 0-0 = 151 pm,

t.m
v - = 857 cm- l
o o v - (857 cm- l
o o
(Superoxido Complex; 0-0 in (Peroxido Complex; 0-0 in
e
free 0 22- = 149 pm)

er
free O2- = 128 pm)

Here it is worth mentioning that from the ir-data and 0-0 bond length data, it is difficult to
H
ascertain the exact oxidation state of Ir and chemical state of the coordinated O2. However, for the
k
dioxygen adducts of hemoglobin (Hb), myoglobin (Mb) and hemerythrin (Hr), the ir-data are more
lic
conclusive.
C
vo- o : 1106 cm- l (oxy-Hb), 1103 cm- l (oxy-Mb), 844 cm- l (oxy-Hr).
It suggests that O2 remains as 0i (superoxide) in the adducts with Hb or Mb; but it remains as oi-
(peroxide) in the adduct with Hr (cf vo - o = 1145 cm- l in free 0i, = 842 cm- l in free Oi-).
In the dioxygen adducts, (M-0 2), the following possibilities may arise.
~,o
0' (Superoxido complex)
I (11 1• O;)
M (Superoxido complex)
0-0 = 125 - 135 pm (f.,l-11 1 : ,,1- 02 )

vo- o = 1130 - 1195 cm- l 0-0 = 126 - 136 pm
(cf in free 0i; 0-0 = 128 pm, vo - o = 1075 - 1122 cm- 1
vo - o = 1145 cm- l as in K0 2)
0\/0
M
(Peroxido complex)
(Peroxido complex)
(11 2- 0 i-) (Jl-11 1 : 11 1 -O~- )

(Vaska's type) 0-0 = 144 - 149 pm
0-0 = 130 - 155 pm vo - o = 790 - 884 cm- I
vo - o = 800 - 930 cm- I
(cf. in free 0 22- as in Na202, 0-0 = 149 pm, vo - o = 842 em-I)
ry
The characteristic properties of different dioxygen complexes have been discussed in detail in Sees.
ra
1.7,9.13 and 10.12.9 and in Vol. 3, Sec. 14.7.5).
ib
(F) Dihydrogeo complexes (see Sec. 9.12): In the dihydrogen complexes, 112-H2 can act as a x-acid
yl
ligand i.e. a-BMO(H 2) ~ M and a*-ABMO (H 2) ~ M. Thus both the a-donation and It-acceptance
em
will weaken the H-H bond. Under the limiting situation, the H-H bond undergoes reputured and then
the dihydrogeo complex (112-H2) transforms into the cis-dihydrido complex.
ch
H
,," I
al
" I
M + H2 ~M" :
e
"" I
th
"" I
H
e/
M(1l2-H 2) cis-M(H)2
t.m
The H-H distance in the complex is remarkably elongated to about 85 - 90 pm (cf. 74 pm in free
H 2). This bond lengthening is quite expected due to the loss of a-bonding electron and gain of electron
in the a*-ABMO. It is also supported by the lowering of VH- H to the range 2635 - 3250 cm- I (cf. VH- H =
e
4160 cm- I in free H 2).

er
Sometimes, it becomes difficult to distinguish between the the M(112-H2) and cis-M(H)2 modes of
H
coordination. However, in some cases, the ir-data can help us to distinguish these possibilities. It is
k
illustrated for the Vaska's complex.

lic
[Ir(CO)CI(PPh3)2] + H 2 ~ [Ir(CO)CI(112-H2)(PPh3)2] or [Ir(CO)CI(H)2(PPh3)2]

C
v = 2100 em-I, 2190 cm- I (for the hydrogenated product)

v = 1548 em-I, 1620 cm- I (for the deuterated product)
2100 :::; 1.35 2190:::; 1.35)
( 1548 ' 1620
(In the deuterated analogue, the v-values are lowered by a factor about 1.35)
The too low v-values are not in conformity with the M(T1 2-H2 ) structure. The new sharp
ir-bands at 2190 cm-1 and 2100 cIb-1 (1620 cm-1 and 1548 cm-1 for the deuterated species) indicate
the presence ofM-H or M-D bonds (i.e. hydrido-complex). 00 deuteration, the isotopic shift by
a factor 1.35 is in conformity with the M-H and M-D bonds.
v(M-H) =~~D "" (I""1.41

v(M - 0) JlH ~1
(G) Olefinic and alkyne complexes (see Sees. 9.17, 8): Olefins and alkynes can act as the n-acceptor
ligands and this reduces the C-C bond order (cf effect donation of n-bonding electron and acceptance
into the n*-MO). This is reflected in lowering of vc-c due to complexation. This aspect has been
discussed in detail in Chapter 9. I
(H) Cyanido complexes (see Sec. 9.7): In the carbonyl and olefinic complexes, the ligand frequency
is very often decreased but in the cyanido complexes (cf CN- and CO are isoelectronic), the ligand
frequency is very often shifted towards the higherfrequency. It may happen so, if the coupling mechanism
(Sec. 12.1.5) to raise the stretching frequency is considered to be more important than the n-bonding
leading to the decrease of ligand stretching frequency. However, the observed v CN values in the complexes
can be explained by comparing the relative importance of the a-donor and 1t-aeceptor properties of
the ligand CN-. Let us compare the a-donor and n-acceptor properties of som~ isoelectronic species.
ry
ra
a-donor strength: CN- ) NO+ - CO,
ib
1t-acceptor strength: CN- ( N2 ( CO ( NO+
yl
The anionic ligand CN- is relatively more electron rich and the constituting atoms of CN- are relatively
em
less electronegative compared to those of the other isoelectronic species. It makes CN- a better a-donor
ligand and a poorer n-acceptor ligand. In a-donation, the electrons are removed from a MO which
ch
is weakly antibonding in nature. Besides this, the a-donation from the C-end which is less
electronegative than N will strengthen the C-N bond (cf Sec. 12.1.16). Thus thi~ a-donation enhances
al
the C-N bond order (i.e. increase in YeN)' The n-acceptance into the n*-MO of CN- lowers the
e
v CN- value but the effect of a-donation to raise VCN is probably more important for CN-. For CO and
th
NO+, the reverse is true i.e. effect of a-donation to increase the v eo or vNO value is less important than
e/
the effect of n-acceptance to lower the veo or VNO value.

t.m
Thus, for the CN--complexes, the -NC ~ M a-donation determines the VCN value. The higher
electronegativity of the metal centre will favour the a-donation better by the ligand and it will raise the
e
V CN value. This prediction is experimentally verified in many complexes.

er
H
Complex: [ Ni(CN)4]2- [Pt(CN)4]2-}VCN (free CN- I )

k
-V
CN
( em -1) : 2128 2150 = 2080 cm- I
lic
Increasing trend ofL~M (J-donation; decreasing trend ofM~1t'* (CN) bonding;

C
electronegativity order: Ni(II) < Pd (II) < Pt (II).
III
Complex: K 3 [Mn (CN)6] K 4 [Mn II (CN)6] K s [Mn I (CN)6]
-V ( em -1) : 2125 2060 2048
CN
Decreasing trend of ligand to metal (J -donation; increasing trend of M ~1t* (CN) bonding;
trend of electronegativity: Mn III> Mn II > Mn I
Complex: [yII(CN)6r- [yIII(CN)6r-

-V ( em -1) : 2065 2077
CN
Increasing trend ofL ~ M (J-donation; decreasing trend ofM~1t* (CN) bonding;
electronegativity order: V III >V II >V I .
Complex: [Ag(CN)4]3- [Ag(CN)3]2- [Ag(CN)2]-

-V ( em -1) : 2092 2105 2135
CN
Increasing trend of ligand ~ metal cr -donation per CN- ligand; increasing trend of M -nt *-MO (CN- )
v
bonding per CN- ligand; decreasing number of CN- ligands; order of eN values is determined by
the M ~ CN- sigma donation
Note: • M ~ n*-MO(CN-) lowers the VCN value, i.e. better the n-acceptance, lower the VCN value.
Higher electronegativity of the metal centre disfavours the M ~ n*-MO (CN-) n-bonding. Thus the
trend of vCN is also in conformity with the trend of n-acceptance by CN-. But the resultant effect is
mainly controlled by the M ~ CN- C1-donation not by M~N- n-back bonding.
ry
• In CN-, the C-end is less electronegative than the N-end. The electron pair used in a-donation
ra
is weakly antibonding in nature. Consequently, the a-donation from the C-end will raise the VCN value.
This aspect has been already discussed in Sec. 12.1.16.
ib
• CN- bridged polymeric complexes: In such cases, there are two types of CN- groups - terminal
yl
CN--group (i.e. M-C-N) and bridging CN--group (i.e. M-C:=N-M). In such cases two different
em
C:=N stretching frequencies are noted. In the polymeric complex of Na2[CO(CN)s], the corresponding
values are: VC==N (terminal) = 2205 em-I) VC==N (bridging) = 2130 cm- l
ch
(I) Isocyanido complexes (see Sec. 9.8): Depending on the condition, it can form the bent C-N-C
al
segment or linear C-N-C segment. The position of ir-stretching frequency (v NC ) can distinguish the
e
bent and linear linkage mode of coordination.

th
n.
e/
+ - jr' +
R-N_C: M===C===N ~ -M-C==N-R
t.m
(Free RNC) "'R linear C - N -C segment

v:::::: 2140 cm-1 angular C - N -C segment
e
er
\INC: Bent C-N-C linkage < Linear C-N-C linkage

H
(M-CNR) (M-CNR)
k
The behaviour of aryl isocynadides (ArNC) is different from that of alkyl isocyanides (RNC). All
lic
these aspects have been discussed and explained in Sec. 9.8.

C
(J) Effect of conjugation arising from the metal-d orbital with the unsaturation in the ligands: In
the acetylacetonate complex, the following type conjugation may arise.
(pseudo-aromaticity in the ring through the involvement of the metal d-orbital)
Better conjugation stabilises the complex more. Thus with the increase of stability of the complex,
the M-O bond strength increases and the C-C and c-o bond strengths decrease. It is illustrated in
the following acetylacetonato-complexes.
Co(ll) Ni(ll) Cu(ll) Pd(II)

9.5 10.5 15.0 27.0
Increasing stability of the M- 0 bond
-V ( cm -1) : 1602 1592 1554 1545

CO
Decreasing trend of the C-O bond strength )
-V (-1)
cm : 1601 1592 1580 1570
C- C
Decreasing trend of the C-C bond order )
In fact, the better conjugation with the metal d-orbital reduces both the C-O and C-C bond order.
ry
• Bipyridine and phenanthroline complexes: Let us illustrate the effect of metal ~ ligand (e.g.
ra
bpy, phen) n-bonding on V M - N • Obviously, the better metal~bpy/phen n-back bonding will strengthen
ib
the M-N bond (i.e. stability of the complex will increase). The less electronegative metal will act as
yl
the better n-donor to strengthen the M-N bond. It is illustrated in the following complexes.
em
M(II): Fe(ll) Co(ll) chNi(ll) Cu(ll) Zn(ll)
Increasing trend
Electronegativity of M (II) :
al
VM- N (cm- I ) (for bpy): 423 264 286 297 280
e
VM- N (cm- I ) (for phen): 530 288 299 300 288

th
The electronegativity of M(II) (measured by the ionisation energy of M(II) ~ M(III)) roughly
e/
increases along the period of the d-block metals, i. e. Fe(ll) is the least electronegative centre in the
t.m
above series. It makes the most favourable situation for M(II) ~ bpy, phen back bonding and it makes
the VFe(II)-N highest and the vZn(II)-N lowest.
e
(K) Shifting of group frequency upon coordination by some typical ligands (e.g. urea, thiourea,
er
dimethyl sulfoxide, triphenylphosphine oxide, etc.) (cf. Sec. 12.1.18):

H
(a) When urea coordinates through the O-end, veo decreases but when it coordinates through the N-
k
end, veo increases (effect of the resonance effect and electronegativity effect, cf. Secs. 12.1.5,
lic
12.1.16, 12.1.18).
C
(b) When dimethylsulfoxide coordinates through the O-end, vso deceases but vso increases when it
coordinates through the S-end (effect of the change in the n-bond of the SO group and also the
electronegativity effect of the donor atom).
(c) Coordination through the O-end of triphenylphophine oxide and pyridine-N-oxide, reduces the
v po and VNO values respectively (effect of both the n-bonding and electronegativity of the donor
atom).
f\()P~: __ M
~-/ \
Ph Ph
(d) Coordination by the S-site of SOl- raises the vso value but coordination by the O-site reduces the
vso value (effect of the electronegativity of the donor site).
12.1.18 Application of Infrared Spectra: Identification of Linkage Isomers

The ambidentate ligands like SCN-, N0 2-, CN-, S03 2-, S2032-, etc. can produce the linkage isomers
which can be identified by using the ir-spectra of the complexes.
(A) Linkage isomers of SCN- (Sec. 2.2.5): The possible linkage isomers (S-bonded and N-bonded)
are: M-NCS (thiocyanto complex) and M-SCN (isothiocyanto complex). The thiocyanto complex
experiences the higher crys~al field strength and consequently the d-d transition occurs at the
shorter wavelength compared to the case of the isothiocyanato complex. They can also be distin-
guished from their ir-spectra. Their resonating structures are given below.
.r
sp
~~r-:._
M~N===C~ s: . . .~--i~~
Sp2
•• 2-
N===C===S: .....~--i~~ M===N===C=== S:
+r sp
••
ry
/
ra
M II III
ib
1\
(M - N- C::=: 1800 -170 0 i.e., almost linear linkage)
yl
The bond angle value indicates that the resonating structure II is less important. The stretching
em
frequencies indicate that the resonating structure III contributes predominantly.
ch
sp3--.........0 0.~~--i~~
' S - C - N ....
+
S===C===N:
1\
al
( M - S - C : =: 1000 i.e., bent linkage)
- /.. /~
e
M -M ~s~
th
III IV
e/
It indicates that the resonating structure III is more important. In the structure III, the C-S bond
t.m
predominantly bears the single bonded character while the C-N bond predominantly bears the
triple bonded character.
e
_.0 C' ..'

er
:s·-
'C:=N:. ~ S===C===N: (Free ligand)
H
V VI
k
The stretching frequencies, VC-S = 750 em -1, VC-N = 2050 em -1 indicate that the resonating
lic
structure V is more important.

C
• It is evident that for the S-bonded complex, i.e. M-SCN, the C-S bond predominantly bears the
single bonded character while for the N-bonded isomer, the C-S bond gets the double bonded character
predominantly and the triple bonded character of the CN-group is decreased.
• For the S-bonded isomer, the triple bonded character in the C-N linkage is more important than
that in the N-bonded isomer.
These are strongly reflected in the v c- s and V C- N stretching frequencies (cf in free CNS-:
v c- s = 750 em-I, VC - N = 2050 em-I, 8NSC i.e. bending mode = 480 em-I).
N
M-NCS M-SCN III ~ridging mode:
vc-s (em-I): 780 - 860 690 - 720 C V C - N = 2150 - 2180 cm-
I
VC - N (em-I): ( 2000 (broad) ) 2000 (sharp) I

0NCS (bending): 450 - 500 400 - 440 /8",-
M M
The relative positions of vc-s and vC-N (with respect to those of free SCN-) for the different modes
of coordination by SCN- can be understood by considering the resonating structures of SCN-. For the
M-NCS linkage, VC-N slightly decreases but vc-s increases compared to those of free SCN-.
For the M-SCN linkage, VC-N remains almost unchanged and vc-s slightly decreases upon
coordination.
Among the above three modes of vibration, vc-s is very often used as the diagnostic one for
characterising the linkage isomers. This is illustrated in the following examples.
Complex
K2[Hg(SCN)4] 715 2107, 2114 For KSCN
ry
(soft-soft interaction) vc - s = 750 cm- 1
ra
ib
821,816 2045, 2080 VC - N =2075 cm- 1
yl
trans- [Pd(AsPh3)iSCNhl
855
em -700
ch
2090 2120
al
e
In the same way, the linkage isomers produced by SeCN-, and OCN- can be distinguished. Examples
th
of the linkage isomers for SCN- are given in Sec. 2.2.5.

e/
(B) Linkage isomers for NOi: This ambidentate ligand gives the two isomers: N-bonded (M-N0 2,
t.m
called nitro-isomer conventionally) and O-bonded (M-ONO, called nitrito-isomer conventionally).

The nitrito isomer experiences a lower crystal field strength and consequently the d-d transition
e
occurs at the longer wavelength compared to that of the nitro isomer. They can also be distinguished
er
from their ir-spectra. The N0 2- (free) ion, has the low symmetry (C 2v ) and its three vibrational modes,
i.e. symmetric and asymmetric stretching, i.e. V S (N~O) and va (N-O) and bending (8) are all ir-
H
active. The number of ir-bands do not change on coordination, i.e. vs' va and 8 bands remain present
k
in both the free ligand N0 2- and the complexes. Thus the number of ir-bands cannot distinguish
lic
correctly the linkage isomers but the positions of the ir-bands can distinguish the isomers.
C
~9
M-N I
.... 124 pm
- ~o .... 129 pm (.... 1000 -1100 cm-1)
~9
Vs
M" ,\
) ....121 pm
M-N
(VM-N::::
"',
I
o
300-450 cm- 1 ) M-N
~9
I
O-N~
o
--l
(-1400-1500cnr1 )
~,
- ",0
Va
(Relatively larger angular volume, (Relatively smaller angular volume,

i.e. more steric factor) i.e. less steric factor)
M-N02 M-DNO NOi(free)

N-O (pm): .... 124 .... 121 (terminal)
.... 129 (internal)
VS (N0 2 )(em- 1) 1310 - 1340 ....1250
Va (N0 2 ) (em-I): 1370 - 1450 -1335
Pw(N0 2) (em-I): 620 - 640 (absent)
cS(ONO) (em-I): ....830 -830 ....830
V (ONO) (em-I):
S
1040 - 1100
Va (ONO) (em-I): 1420 - 1480
ry
60 - 120 380 - 480 85
ra
The important and diagnostic observations are:
• For the M-N0 2 linkage isomer, both v lN0 2) (i.e. symmetric stretching band) and v a (N0 2) (i.e.
ib
antisymmetric stretch) are shifted towards the higher frequency significantly compared to those
yl
offree N0 2-.
em
• For the M-ONO linkage isomer Vs is shifted towards the lower frequency while va is shifted
towards the higher frequency compared to those offree NOi.
ch
• dV (= Vs - va): dV (M-ONO) ) ) dV (M-N0 2). It indicates the more inequality of the two NO
al
bonds in the nitrito isomer. In fact, for the nitro-isomer, both the N-O bonds are very much
e
comparable and it makes d v smaller. In fact, d v for the nitro isomer is comparable to that of free
th
NOi·
e/
• The wagging mode, i.e. Pw(N02 ) at about 600 cm- 1 is absent in the nitrito isomer.
t.m
• The bending mode, i.e. 8(ONO) at about 830 cm- 1 remains more or less at the same position for
the both isomers.
e
The above predictions are illustrated in the following linkage isomers.

er
H
k
(Yellow, higher lODq value) (Red, lower lODq value)

lic
VCo - = 500 cm- 1 } (strong bands) Vs = 1065 cm- 1 (strong diagnostic band)
C
= 1315 cm- 1
Vs Va = 1465 cm- 1
Va = 1430 cm- I ~V = 400 cm- I
~V = 115 cm- 1 Pw = absent.

Pw(N02) = 600 cm- I
The bending vibration, i.e. 8(ONO) for both the isomers appears at about 825 cm- I. The magnitQde
of ~v is a characteristic feature to distinguish the isomers. These are illustrated in the following
examples (values are in em-I).
Complex Va (N -0) Vs (N -0) !J.V cS(ONO) v(M-N)
[CO(N0 2 )6P- -1390 1330 - 60 835 415
[Cr(NH3)5(ONO)]2+ 1460 1050 410 840 absent
N0 2- can show its bidentate chelating action.
l1~_monomet~lliC} /~~N·
bldentate action M........... ' '/ •
va (NO 2 ) ~ 1270 em-I; V (NO )
s 2
~ 1200cm-l,~v~70cm-l
"0/ O(ONO) :== 850 cm- 1
It indicates that both the N-O bonds are almost equal.

For the bidentate chelating action, compared to the M-N0 2 mode of action, both the symmetric and
antisymmetric stretching frequencies are lowered and the bending mode is slightly shifted towards the
higher frequency.
NOi can also function as a bridging ligand.
ry
H 3+
ra
M M
/o~
ib
\ / (H 3 NbCo Co(NH 3b
yl
j,~_-;-::: 0
\\-1)
\ em
0'
(trans-form)
7~o
ch
N---O
(1l2-bimetallic
/
al
bridging action) o
e
VS (NO) ~ 1200 cm-1 V(N02): -1515 cm- 1,

th
Va (NO) ~ 1515 cm-1 -1200 cm- 1

e/
cS (ONO) ~ 830 cm- 1

t.m
H2 ~
/ N----CO(NH)
e
(H aN)4CO "
er
/ a4
N-·-O
H
o
II
k
(111-bimetallic bridging action)

v (N0
lic
2 ): -1515 cm-1
-1200 cm-1
C
(C) Linkage isomers of 801-: SOj- can coordinate either through the O-end or the S-end. Oxygen is
more electronegative than sulfur. Thus coordination through the O-end (i.e. more electronegative end)
will reduce the vso stretching frequency (i.e. S-O bond will be weaker after coordination) (cf. Sec.
12.1.16).
• vso (complex) ) vso (free SOj-) ~ Coordination through the S-end
• vso (complex) ( vso (free SOj-) ~ Coordination through the O-end.
Now let us consider the local symmetry of the M-S0 3 and M-OS0 2 linkages.
For free SO~- (C 3v), the important ir-bands are:

VI (AI) = 961 C,?-I; v (AI) = 633 cm-I; v (E) = 1010 cm-I; v (E) = 496 cm- I
2 3 4
Out of these 4 ir-bands, the v3-band is the most sensitive one towards coordination, i.e.
the V3 -band is considered as the diagnostic band to identify the coordinating behaviour of SOJ-.
C3v C3v Cs
v3(SO) (E-band): 1010 cm- I (free S03 2-) ) 1010 cm- I E-band splits into two
(for M-S0 3) components;
( 1010 cm- I
(for M-OS02).
It is illustrated in the following examples:
ry
K 6 [Pt(S03)4] (S-bonded, monodentate): V3 = 1055 - 1080 cm- I ) 1010 cm- I
v = 1110 cm- I ) 1010 cm- I
ra
[Co(NH3)s(S03)]CI (S-bonded, monodentate): 3
v (E) band spits: 862 cm- I and
ib
TI 2[Cu(S03)4] (O-bonded, monodentate): 3
yl
902 cm- I ( 1010 cm-I.
em
(D) Linkage isomers produced by urea, N, N-dimethylformamide and N, N-dimethylacetamide:
ch
H H 2N
"'c=o "'c=o
al
/ /
e
Me 2 N
Me 2 N (N, N-dimethylacetamide)
th
(N, N-dimethylformamide, i.e. DMF)

e/
The important resonating structures are:

t.m
Yeo = 1683 cm- 1

e
er
H
k
lic
V eo = 1662 cm- 1
C
(cf.veo = 1685 cm- 1 (DMF);

veo ~ 1710 cm- 1 in
free carbonyl group)
The smaller value of v eo in urea, DMF or N, N-dimethylacetamide compared to that of acetone

(-1715 cm- I) indicates that the nitrogen lone pair is engaged in resonance with the CO group in urea,
DMF or N, N-dimethylacetamide. They can coordinate either through the O-end or N-end as follows:
"'..7
~ '"c===o:
0. ~ M ~
,,+~ .
'"C - O.. - M ; M~:N
"'/
/
'" c=O
N N
/ / (More favoured)
SPECTROSCOPIC METHODS AI\JD OTHER PHYSICAL METHODS IN CHEMISTRY 1775
• Coordination through the O-end: veo and v MO differ widely and consequently their coupling
(called' kinematic coupling) to raise the vco value can be ignored. Removal of the 1t-electron
cloud from the CO group weakens the C-O bond. In the most favoured resonating structure, the
C-N bond gets the more double bonded character. Thus coordination through the O-end, will
raise the VCN value but lower the vco value (compared to those offree ligand, i.e. urea, DMF or
dimethylacetamide). The NCO bending frequency will go to increase on coordination through
the O-end. The C-O stretching frequency and NCO bending frequency are treated as the. diag-
nostic parameters because the C-N stretching frequency needs a complicated interpretation
due to the coupling-effect.
• Coordination through the N-end: The nitrogen lone pair is engaged in metal coordination. Thus
the nitrogen lone pair is not available for participation in conjugation with the CO group. It
ry
enhances the double bonded character in the CO group and reduces the double bonded character
ra
in the C-N linkage. It will raise the vco value and lower the V CN value (compared to those of the
free ligand)
ib
It has been found that in complexation of urea with the relatively harder metal ions like Fe3+, Cr3+,
yl
Zn + or Cu 2+, the veo decreases and v eN increases. It supports the coordination through the O-end.
2
em
But when urea undergoes complexation with the relatively softer metal.centres like Pd2+ or Pt2+, the
vcois found to increase with simultaneous decrease ofv CN . It supports the coordination through the
ch
N-end. These are illustrated with the experimental data.
al
U(free) [PtU2 CI2] [CrU6]CI3 }

e
Vco (em-I): 1683 1725 1505 U ==> urea

th
VCN 1471 1395 1505

e/
(em-I):
t.m
(E) Linkage isomers of thiourea (coordination by the S-end or N-end) can also be distinguished in the
same way as in the case of urea.
e
er
H
k
lic
C
~cs ~ 730 em-1 (free ligand)
NH
_ / 2
M-S-C i.e.,
"-NH 2
+
It lowers the ves value but the deformation

vibrations of the NH 2 do not change significantly.
(F) Linkage isomers of dimethylsulfoxide (Me2S=O): DMSO can coordinate either through the
S-end or O-end. Obviously, the O-end is preferred for the harder metal centres while the S-end is
preferred for the softer metal centres (e.g. PtU , Pdu).
Coordination through the O-end reduces the vso value because the double bonded character in the
S-O bond is destroyed partially upon coordination. Besides this, the O-site is more electronegative
than the S-site. Thus coordination through the O-site also reduces the vso value (cf. Sec. 12.1.16). The
coupling of v so and v MO to raise the value of vs o may be ignored because v so and v MO differ widely.
Coordination through the less electronegative S-site will raise the vso value. It may be mentioned
that in this mode of coordination, the n-bond in the SO group is not practically disturbed in resonance.
R 0 R
)s=o ' "S

+ -O- (Free R2S=0, vs- o :::: 1050 cm- 1 , R=Me)
/
R R
R\ R
M-;=0 (vs-o >1050 cm- 1
): R)S-~-M (vs-o <1050 cm- 1
).
ry
R
ra
[FeCI 2(DMSO)4] (vs-o = 950 cm-1 i.e. coordination through 0).
ib
cis-[PtCI 2(DMSO)2] (vs-o = 1134,1158 cm- 1 , i.e. coordination through S).
yl
em
12.1.19 Application of Infrared and Raman Spectra: Assignment of the Coordinating
Behaviour of the Anionic Ligands (XO~-, XO~-)
ch
(A) Coordination behaviour of COj- and NOi: These anionic ligands (free) possess the D 3h symmetry.
al
The 6 (= 3 x 4 - 6) fundamental vibrational modes are:

e
A~ (1) + Ar (1) + 2E' (2 x 2)

th
The pure stretching mode A{ (VI) is ir-inactive but Raman active while the pure bending mode Ar
e/
(v 2) is ir-active but Raman inactive. The two E' modes (v 3, V4) are both ir-active and Raman active.
These are evident from the character table of the D 3h point group.
t.m
O-M
/
e
o=x",
er
O-M
H
(Free ion, D3h ) (Unidentate, Cs ) (Bidentate, C2v) (Bridging, C2v)

k
(X=C, N)
lic
Fig. 12.1.19.1 Coordinating behaviour of XO~- i.e. coj- or NOi and change of local symmetry upon coordination.
C
Table 12.1.19.1 Vibrational modes for XO~- (i.e. coj-, NOi) in different local symmetries (R and IR denote
the Raman and ir-active bands respectively).
Point group VI V2 V3 V4
D 3h A~ (R) A~ (lR) E' (R + IR) E' (R + IR)

Cs A' (R + IR) A" (R + IR) 2A' (R + IR) 2A' (R + IR)
C 2v Al (R + IR) B i (R + IR) Ai (R + IR) Al (R + IR)
+B 2 (R + IR) B2 (R + IR)
Upon coordination, the local symmetry of NO]" or C01- is reduced to Cs (for the unidentate character)
or c 2v (for the bidentate and bridging character). These symmetry changes (i.e. D 3h to C s or C2v ) are
reflected in the ir- and Raman spectra. The ir-inactive modeA;(vI) becomes active on symmetry reduction.
The Ar mode changes its symmetry and degeneracy of the E' mode is lifted, as the symmetry is lowered
upon coordination.
These are obtained from the character tables of the respective point groups.
Here it is worth mentioning that for both the C s and C 2v symmetries of the coordinated XO~- ligand,
the numbers of bands (in both IR and Raman spectra) are the same for both VI and V2 and both the VI
and V2 modes do not split upon coordination but change their symmetries; both the v 3 and v 4 bands
undergo splitting upon coordination. The asymmetric stretch (E') undergoes splitting upon coordination
into a higher-frequency asymmetric X-O stretch and a lower-frequency symmetric X-O stretch. The
degree of splitting of the V3 and V4 bands is different for the C s and C 2v symmetry. The splitting is larger
for the C2v symmetry (i.e. biddentate and bridging mode ofcoordination) than that/or the Cs symmetry
(i.e. unidentate mode of coordination). Splitting of the v 3 band is greater than that of the v 4-band and
ry
splitting of the v3-band is monitored for characterisation of the coordinating behaviour of COj- or N0 3-.
ra
It is illustrated in the following examples.
ib
Complex Splitting of the vrband (em-I)
yl
em
[Co(C03)(NH3)5]Br 1450, 1370 80
(unidentate CO~-) (smaller ~v ~ unidentate COr, Cs )
ch
[Co(C03)(NH3)4] CI 1592, 1255 337
(bidentate carbonate) (larger ~v ~ bidentate COf-, C2v )
e al
Bidentate and bridging X0 3- are more or less similar in terms of ir- and Raman spectra but they can
th
be distinguished from the v M - O values appearing in the far-infrared region.

e/
NO; (free): VI (Ai, R) (1068 cm- I); V2 (Ar, IR) (831 cm- I); V3 (E', R + IR) (1400 cm- I); v 4 (E',
t.m
R + IR) (710 cm- I).
Complex Splilting of vrband (em-I)

e
er
[Ni(enh(N03h] 1420, 1305 115

H
(Unidentate N0 3-) (~ unidentate NOi, Cs)

1440, 1315 125
k
[Ni(dien)(N0 3)2] }
lic
(both unidentate (~ unidentate NOi, Cs )

and bidentate N0 3-) 1480, 1300
C
180
(~ bidentate NOi, C2v )
(B) Coordinating behaviour of 801-: Free sof- adopts the T d symmetry but upon coordination, its
symmetry is reduced to C 3v (for the unidentate behaviour), C2v (for the bidentate and bridging behaviour).
For the tetrahedral point group, there are 9 fundamental vibrational modes (= 3 x 5 - 6): A I(l) + E(2)
+ 2T2(2 x 3) where the E-vibration is doubly degenerate and the T2vibration is triply degenerate. The
AI(VI) and E(V2) vibrations are ir-inactive but Raman active. The two T 2 vibrations are ir-active and
also Raman active. Upon coordination (i.e. reduction of symmetry), the VI and V2 vibrations become
active in both the Raman and infrared spectra. The v2-band does not split for the C3v symmetry but it
splits for the C 2v symmetry. The V3 and V4 vibrations undergo splitting as follows:
v 3, V4 (Td) ~ Two components (AI + E) for the unidentate mode of coordination (i.e. C3v symmetry)
v 3, v 4 (Td ) ~ Three components (AI + B I+ B2) for the bidentate or bridging mode of coordination (i.e.
C 2v symmetry).
Table 12.1.19.2 Vibrational modes for XO£-(e.g. SOl-, CI04", etc.) in different local symmetries (R and IR
indicate the Raman active and ir-active bands respectively.
Point group VJ V2 V3 V4
T d (free XO£-) Al (R) E (R) T 2 (R + IR) T 2 (R + IR)

C 3y (Unidentate XO~-) Al (R + IR) E (R + IR) (AI + E) (R + IR) (AI + E) (R + IR)
C 2y (Bidentate and Al (R + IR) Al (R + IR) (AI + B I+ B 2) (AI + B I+ B 2)
bridging XOS-) +A 2 (R) (R + IR) (R + IR)
0
2- /1,,'
ry
il 0 /M", M"" /M
ra
0
'8' I 0
,8/
0
,/0
o-/'~
ib
"'0 0 /8~
~~ '\" 8
o
o~~0
yl
,,'0
'0 o~~0
em
Td (free 80;-) (Unidentate 80:-, C3) (Bidentate 80;-, C2v )
ch (Bridging sulfate C2v)
Fig. 12.1.19.2 Change of local symmetry upon coordination by SOJ-.

al
Species Local symmetry VI V2 V3 V4

e
th
SOJ- (free) Td -* * 1105 615

e/
[Co(NH 3)5(OS03)]Br C 3y 970 438 1032-1044, 645,

t.m
(monodentate SOJ-, C 3y ) 1117-1143 604
[ 2
/NH "/Co(NH )4
r
e
(H 3 N)4 Co" 3 C 2y 995 460 1050-1060, 640,610,

S04
er
1105, 1170 570

(bridging sulfate, C 2y )
H
* These two bands (983 cm- I, 450 cm- l) are ir-inactive but Raman active.
k
lic
• It is evident that after coordination by S042-, the inactive ir-bands (VI and V2) become active.
C
Td C 3v C 2v No. of ir-bands and

No.ofir-bands: 2 ~ 6 ~ 8 Raman bands and the
No. of Raman diagnostic criteria of
active modes: 4 6 9 the ligating modes of SO~- .
• For the monodentate mode of coordination by SOl- as in [Co(NH 3)s(OS03)]+, there are 6
ir-bands. The V3 band splits into two broad components: 1032 - 1044 cm- I and 1117 -
1143 cm- I. The v4-band also splits into two components at 645 cm- l and 604 em-I.
• For the bridging mode of coordination by SOl-, each of the v3 and V4 bands undergo splitting
into 3-components.
• In [Co(NH3)4(S04)]Br, sol- acts as a bidentate ligand, the V3 and V4 bands split as in the case of
bridging mode of coordination by SOl-. These two modes can be distinguished by.comparing the
frequencies of the v I and V3 bands. It has been observed that the stretching frequencies for the
· SPECTROSCOPIC METHODS AND OTHER PHYSICAL METHODS IN CHEMISTRY 1779
bidentate chelation are higher than those for the bridging mode of coordination. The v M- O
frequencies appearing in the far-infrared region may be also helpful for characterising the mode
of coordination.
The above examples illustrate that the analysis and comparison of the ir-spectra (coupled with the
Raman data) of the free ligands like X0 3-, X0 4- and their complexes can help us to understand their
coordinating behaviour.
12.2 NMR (NUCLEAR MAGNETIC RESONANCE) SPECTPlOSCOPY AND ITS

APPLICATION
12.2.1 Some Basic Elements of NMR Spectroscopy
~
ry
(A) Nuclear spin (I): The total angular momentum (I) of a nucleus arises from the orbital and spinning
ra
motion of the nucleons (i.e. protons and neutrons).
ib
I = J1(/ + 1) ~ ~ I (~); I = nuclear spin quantum number or simply nuclear spin
yl
21t 21t
em
1 357
1=0 (for even Z and even N); 1= -, -, -, -, ... (for odd A),
ch
222 2
1= 1,2, 3, ... (for odd Z and odd N) (A =mass number, Z = atomic number, i.e. number of protons,
al
N = number of neutrons, A = Z + N). Nuclear spin quantum numbers of some important nuclei with
e
their abundance are given in Table 12.3.5.1.

th
Nuclear magnetic moment (J..lI) is given by:

e/
III = gl~I(I +1) ~;gl (also represented by gN) = nuclear g-factor; mp = mass of a proton
t.m
41tm p c
e
er
H
(B) Common NMR active nuclei (abundance in %, nuclear spin, gr):

k
(99.98,~,5.585);
lic
IH 2H(0.02, 1, 0.857); 10J3 (19.6,3); liB (80.4,%);

C
13C(1.11,~,1.404);14N(99.63, 1,0.403); 15 N ( 0.37,~} 17

0 (0.04,%),
19F (100,~, 5.257); 31p (100,~)

The nuclei with 1 = ! are most conveniently used in NMR spectroscopy" Such nuclei are: IH, 19p,
2
*
l3C, 31p, 29Si, l17Sn, 119Sn, 195Pt, etc. Nuclei with the nonzero nuclear spin (I 0) behave as the spinning
=
nuclear magnets and such nuclei are NMR active. Nuclei with I 0 are NMR inactive. NMR signal
is intrinsically weak for the nuclei with I >!. However, the elements such as 14N(I = 1),
2
35.37 C1 (I = %). 1(I = %) are abundant and they are used in NMR spectroscopy.
127
(C) Frequency for NMR transition and relation with the Larmor frequency: Nuclear spin can
interact with the external magnetic field. In absence of the magnetic field, different spin states charac-
terised by m/ (nuclear spin angular quantum number) which can have values I; (I - 1), ... , (-I + 1),
(-I) (i.e. +1 to -I at intervals of unity) are degenerate. But this degeneracy is lifted in presence of an
external magnetic field.
-+~ '-2
m1--2 +1. ...:".
.:>'
No field ':.--
..::--. +1.
ry
2
-----+~
ra
2
ib
yl
1 3
em
Fig. 12.2.1.1 The allowed energy levels in presence of a fixed magnetic field (Ho) for the nuclei I = - and -.
ch 2 2
For a nucleus of I = !, the spin state mJ = +! gets oriented along the field and consequently the
2 2
al
state becomes of lower energy. On the other hand, the nuclear magnetic moment of the nuclear spin
e
= _!
th
state m J opposes the field and it gets destablised to the same extent (Fig. 12.2.1.1.).
2
e/
E=-m Y;n;h )Ho i.e. E, (m +i) =-i( Y;n;h )Ho Assuming the applied field (H 0) =
t.m
J( J = field experienced (Hex); generally,
=-i) =+i( Y;n;h )H

Hex < H 0 and in the actual expression
E
e
and 2( mJ o H 0 is to be replaced by Hex.

er
H
.. ) Nuclear magnetic moment

YN (gyromagnetlc ratio of the nucleus = - - - - - - - - - -
k
Nuclear angular momentum

lic
C
i.e., V=(YN)Ho=gJIlNHOHZ gNIlNHo Hz, (representingg J bygN)

2n h h
h
In general, !'1E =Y21t
N Hoflm J where flm J = ±1; assuming applied field (Ho) =experienced field
(Hex)·
In presence of a magnetic field, the nuclear magnetic moment (of the nucleus of nonzero I) precesses
about the direction of the field (Fig. 12.2.1.2). The angular frequency of this precessional motion is
referred to as the Larmor precessional (circular) frequency (OlL) which depends on the magnetic field
strength (Ho), (OL = yNHo.
Larmor precessional frequency OlL (rad S-I), YN (rad S-1 1 1) and Larmor frequency (v L in Hz) are
related as:
Thus, the NMR transition will occur under the condition, VL = v, i.e.
ry
Larmor frequency (vL ) becomes just to equal to the frequency (v) related
ra
to the energy separation between the energy levels for the NMR transition.
The energy difference (~) is quite small. It is illustrated for 1H.
ib
yl
M =hv = g/IlNHO i.e. v = g/IlN H O; g/ =5.585, IlN =5.04 X 10-27 JT- 1
em
h
27 1
= 5.585 x 5.04 x 10-34 JT- xl T ( HIT)
ch
Thus, v say = Fig. 12.2.1.2 Precession of
6.62 x 10- J s "0 a nuclear magnetic moment
al
under the influence of an ap-

= 4.26 X 107 Hz = 42.6 MHz (a radiofrequency)
e
plied magnetic field (Ho).

It leads to: v = 63.9 MHz for H o = 1.50 T, v = 749 MHz for H o = 17.6 T.
th
Thus with the increase of magnetic field (Ho), dE increases and V lies in the radiofrequency region.
e/
t.m
NMR VB. ESR Transition

For the NMR transition, v lies in the radiofrequency region while for the ESR transition, v
e
lies in the much higher frequency region (in the region of microwave frequency). This difference
er
occurs from the difference in JlN and JlB.

H
eh eh .
JlN = - - - andJlB = - - ; me = 9.1 10-28 g whIle m = 1.67 x 10-24 g.
k
X
41tmp c 41tm e c p
lic
It makes, J.!B/JlN :::: 103.

C
For the ESR transition, LlE = gJlBHoLlms' (Llm s = ±1), g = 2; JlB = 9.27 x x 10-24 J 11 (cf. JlN =
5.04 X 10-27 J 11).
. gJlBHO
dE = gJlBHo, z.e. hv = gJlBHo and v = ---
h
24 1
v=2X9.27Xl0- JT- XIT (forH =IT)
6.61 x 10 -34 J s ' 0
= 2.8 X 1010 Hz = 28 GHz, (a microwave frequency)
In the NMR experiments, generally a fixed operating radiofrequency (say 60 MHz) is applied and
then the magnetic field (Ho) is applied and gradually increased. When Larmor frequency (VL) be-
comes equal to the operating frequency, then resonance, i.e. NMR transition occurs. The condition
for the NMR transition is: VL = v (operating frequency) where VL oc H o.
12.2.2 Intensity of the NMR Signals and Peak Broadening

(A) Probability of the upward and downward NMR transitions: The ratio of population density at
two energy levels between which the NMR transition occurs is given by:
n~
n (-~)
=exp kBT ;
~ 1- gIJlNHO
kBT
~ = gj J.lN H o <<kBT; n2 =population density at the excited level; n 1 =population density at the lower
level.
ry
Thus in the NMR transition, the population density ratio (n2Inl) is maintained by the Boltzmann
ra
distribution law. The upward transition (i. e. lower level to upper level) needs the absorption of radia-
ib
tion. At the same time, the excited nuclei come back to the lower level (i.e. downward transition), and
it emits the radiation of the same frequency. Statistically, the rate of transition depends on the popula-
yl
tion density of the level from which the transition occurs. Generally, nl ) ) n2 and the upward transitions
em
are more than the downward transitions and it makes a net absorption of the radiation. The intensity
of the signal depends on the magnitude of net absorption. Thus to increase the intensity, the condi-
ch
tion n 1 ) ) n2 must be maintained throughout the experiment.
al
Now let us examine the ratio n/n2 (which is important to determine the intensity of the peak) for the
PMR signal. For a proton, for H o = 1.41 T, the resonance occurs at 60 MHz. The corresponding energy
e
th
difference between the states in which the PMR transition occurs is 2.4 x 10-5 kllmole, i. e.
4 x 10-26 J/molecule. The thermal energy (kBD at room temperature is sufficiently high to populate both
e/
these levels.
t.m
!!:.L = exp (- ~ ) = exp(-~), v = 60 X 106 Hz, kB = 1.38 X 10-23 JK- 1 molecule- l

nl kBT kBT
e
er
~ 4.1
2
For T = 298 K, kBT x 10-21 J/molecule, the ratio !!:.L = exp ( 4 x 10- :, J= exp (-1 x 10-
5
)
H
nl 4.1xlO-
~ 1- (1 X 10-5 ) = 0.999990 = 1,000,000 =~; N = 106
k
lic
1,000,009 N+9
C
It indicates that at 298 K, out of 2 million 1H nuclei, there are only 9 more nuclei at the lower spin
state, i.e. only a marginal difference in population density at the two levels. Thus the condition of
saturation (i.e. nl ~ n2 leading to the equal rate of upward and downward transition and no net
absorption and no signal) is likely to be attained, if the appropriate precautions are not taken.
(B) Factors controlling the nl/n2 ratio: For a particular NMR active nucleus, the ratio can be
controlled by adjusting the following factors .
• By increasing the operating frequency of the NMR spectrometer (i.e. increasing ~E), the ratio
n /n2 can increased.
!!:.L ~ -~, (N = 106 ); X = 3 (20 MHz), 6 (40 MHz), 9 (60 MHz), 16 (100 MHz), 32 (200 MHz),
nl N+x
48 (300 MHz)
It indicates why the NMR spectrometers operating at the higher frequency are more preferred to
see the more intense signals.
• Effect of the value of YN (gyromagnetic ratio) on the ratio !!.L to increase the intensity:
n2
We have:
AE = YN (~)Ho
21t
= hv, i.e. liE increases with the increase of YN' i.e. the ratio ~
n
also increases.
2
Thus for the nuclei with the lower gyromagnetic ratio (YN), the NMR signals are intrinsically weak
as in ]3C. The values of YN for some representat~ve NMR active nuclei are given below.
Nuclei: IH 2H l3e 19F 3lp
YN (radiansffesla): 267.5 41.1 67.3 251.5 108.5
The above discussion indicates that in the NMR study, AE is not too high, i.e. n. is not too large
ry
compared to n2. To increase the ratio, ntfn2' two measures may be taken:
ra
(i) lowering of temperature (i.e. kil' becomes smaller) and (ii) application of high magnetic field
ib
which makes t1E larger (cf. t1E oc H o) and consequently, it requires a higher operating
yl
frequency of the NMR spectrometers.
em
It increases the upward transition more and intensity of the signal becomes higher.
(C) Relaxation and reestablishment of the Boltzmann equilibrium: To maintain the intensity of
ch
the signal, the excited nuclei should come back rapidly to reestablish the Boltzmann equilibrium.
This return to the ground state occurs through the relaxation process. In the relaxation process, the
al
excited nuclei come back to the ground state through the loss of energy to the surroundings but without
e
the emission of radiation. If the excited nuclei do not return readily to the ground state~ then n2
th
increases (i.e. n]/n2 ratio decreases) and intensity of the signal will gradually decline.
e/
t.m
---r---;----~---Higher energy state

ir\
Downward
Upward Relaxation to reestablish the
transition
e
transition Boltzmann equilibrium

~
er
(no emission)
H
- " " ' : : ' - _ . 1 . . . . -_ _" " " - : : ' _ - - Lower energy state
k
lic
Fig. 12.2.2.1 NMR transition (in both directions) and relaxation.

C
(D) Uncertainty principle and NMR peak broadening: Natural peak broadening can be realised
from the Heisenberg's uncertainty principle.
1
~J1.t::::: h, i.e. hliv 1/2J1.t:::::: h or, i\VIj2 ::::::-
i\t
J1.t is the life period of the excited nucleus and its magnitude depends on the efficiency of the relaxation
process. J1.t is called the relaxation time and Iivl/2 is the half-bandwidth (i.e. peak width at half-
maximum intensity of the NMR signal). 1"'1he value of lit (relaxation time) depends on the efficiency of
the relaxation process. If lit is very small, the bandwidth will increase (i.e. peak will be broadened) but
intensity (measured by the increased probability oj" the upward transition) increases. If the peak is
bro~dened too much, the NMR signal will not be detected.
The uncertainty principle leads to the following conclusions.
• large L1t makes the sharp peak with the gradual decaying of intensity (i.e. gradual decaying ofthe
nj/n2 ratio);
• small L1t makes the broad peak along with the increased intensity (i.e. the ratio nJ1n2 does not
decrease with time), but the too broadened NMR signal cannot be detected.
Here it is worth mentioning that the peak broadening may also occur due to the chemical exchange
process (Sec. 12.2.15) and inhomogeneity of the field experienced by the different parts of the sample.
Thus, from the bandwidth (Llv l12 ), the relaxation time cannot be estimated.
NMR VB. ESR (cf. Secs.12.2.3 and 12.3)

Frequency of transition: Radiofrequency region (NMR), microwave region (ESR)
Intensity: (n 1ln2)ESR ) ) (n/n2)NMR and faster relaxation in ESR makes the ESR signal more intense.
Slower relaxation in NMR may cause decaying of intensity of the NMR signal during the experiment.
Width: Shorter relaxation time in ESR, makes the peak broader, i.e. bandwidth of an ESR signal is
ry
much larger than that of a NMR signal (ef 1 MHz vs. 0.1 Hz).
ra
ib
12.2.3 Relaxation Processes: Sharp Peak VB. Intensity of the Peak
yl
Relaxation process leads to the return of the excited nucleus to the ground state without the emission
em
of radiation. In terms of the uncertainty principle, to have a sharp line, the life period of the excited
state should be large (i.e. slow relaxation). If the life time of the excited state is very small (i.e. fast
ch
relaxation), then the peak is broadened and if the broadening is too high, no NMR signal is to be
al
noticed. If the relaxation process is hindered, the population density at the ground level will decrease
during the study and intensity of the signal will decrease gradually. Thus the relaxation process is a
e
th
matter of an important consideration.

The important relaxation processes are: spin-lattice relaxation and spin-spin relaxation.
e/
(A) Spin-lattice relaxation: Nuclear spin of the excited nucleus interacts with the local fluctuating
t.m
magnetic field developed from the motion of the nearby magnetic nuclei (e.g. IH) present in the lattice.
The lattice represents the atoms of the molecules which may be the same molecule or the other mol-
e
ecules including the solvent molecules. The interaction is illustrated in Fig. 12.2.3.1.
er
\ The nucleus A (from lattice) with a magnetic moment is in motion

H
around the excited nucleus B whose nuclear moment is opposed by the
~
field. Because of the motion of the magnetic nucleus A, it produces a
k
lic
fluctuating magnetic field towards the excited nucleus B. The excited

nucleus B gives up its energy to attain the more stable orientation (i.e.
C
spin alignment in the direction of the field). This released energy is
H
/ A (from lattice)
taken by the nucleus A to increase its translational or rotational energy
of the molecule containing A. Thus the excess energy of the excited
nucleus passes to the surroundings (i.e. lattice) as the rotational and
Fig. 12.2.3.1 Spin-lattice re- translational energies. The lost energy heats the surroundings. This
laxation process where the spin
process is called the spin-lattice relaxation and it occurs under the
of the excited nucleus (B) can
be oriented in the direction of condition: frequency of the fluctuating magnetic field arising from
the field by the fluctuating mag- the motion of the magnetic nucleus A of the lattice must be the
netic field from the magnetic same of the NMR transition for the excited nucleus B. The moving
nucleus A (in motion) of lattice. magnetic nucleus A (of the lattice) generally possesses a wide distri-
bution of frequency components to satisfy the condition.
The efficiency of this spin-lattice relaxation process depends on the two factors: magnitude of the
local fluctuating magnetic field and the frequency of this fluctuation due to the motion.
• Spin-lattice relaxation in presence of a paramagnetic substance: The magnetic moment of an

unpaired electron is about 103 times higher than that of a nucleus (say proton). Consequently, the
paramagnetic substances in the lattice provide the stronger magnetic field in the spin-lattice
relaxation process and consequently the paramagnetic substances can cause the said relaxation very
fast (i.e. T l becomes very small ca. 10-4 s) and the NMR peak is broadened (cf ~lit = hliv l12 T l =:: h,
i.e. Iivl/2 (half-bandwidth) =:: 1ITl ). In fact, the PMR signal of [Mn(OH2)6]2+ (5 unpaired electrons,
highly paramagnetic) is so extensively broadened due to the efficient relaxer Mn2+ (high spin, t2~ e;)
that the PMR signal cannot be detected.
Here it is worth mentioning that in 13C-NMR spectroscopy, deliberatly, the paramagnetic compound
[Cr(acac)3] (t2~) is added to favour the spin-lattice relaxation process (cf Sec. 12.2.17).
• Physical state of the substance and spin-lattice relaxation process: The efficiency of the spin-
ry
lattice relaxation process depends on the physical state of the substance. T l is generally in the order
ra
of 10-2 to 104 s for the solids while T l is in the range 10-4 to 10} s for the liquids, i.e. the spin-lattice
ib
relaxation is more efficient in the liquid state due to the greater freedom of molecular motion of the
lattice which causes a larger fluctuation of the magnetic field to the excited nuclei. In solid state, the
yl
atomic vibration is relatively less efficient to create a large fluctuation of the magnetic field.
em
• Intensity of the NMR signal and spin-lattice relaxation time: The loss of energy from the
excited nucleus (B) brings down the nucleus to the ground state (i.e. population density at the ground
ch
level increases to increase the intensity of the NMR signal) and it is available for the upward NMR
al
transition. The lost energy is converted into the thermal energy to heat the surroundings. The rate of the
e
process follows the firs-order kinetics and the rate constant for this energy decay process is related
th
with the spin-lattice relaxation time (T}) as follows:

e/
-1 = rate constant of the energy decay process

t.m
T1
The spin-lattice relaxation time (T}) (rather than the spin-spin relaxation time T2 ) determines the
e
intensity of the NMR signal because the spin-lattice relaxation time (T}) gives the measure of the rate
er
of buildup of the spin polarisation in the direction of the external field. Thus the system relaxes back
H
to the Boltzmann equilibrium (i.e. small T1 means the rapid reestablishment of the Boltzmann
equilibrium).
k
lic
The spin-lattice relaxation is also described as the longitudinal relaxation as the decay of magneti-
sation occurs in the direction of the applied field.
C
• Spin-lattice relaxation process for the 13C-nuclei: The spin-lattice relaxation process is quite
effective, if there are hydrogen atoms (magnetic nuclei) in the surrounding lattice. For the l3C-nuclei,
the relaxation process becomes very much efficient if they are directly attached with the H-atonlS as in
CH 3, CH 2 , CH. T l varies as follows:
C -*CH 3 </ <

C",.
*CH 2
C'"
C - *CH
/
< C'"
C - * C - C (*C => 13C)
/
C C C
• Nuclear overhauser effect and spin-lattice relaxation process: For the l3C-NMR spectra, nuclear
overhauser effect (NOE, Sec. 12.2.14) is very much important and NOE is related with T}. In tolune,
C} (i.e. ipso carbon) is having the highest T} (as expected) and in l3C-NMR, the ipso carbon shows the
signal of the lowest intensity.
a-C C\ C2 C3 C4
16 90 24 24 17
0.61 0.56 1.6 1.6 1.6
For the details of NOE, readers are suggested to consult any standard book on NMR spectroscopy.
• Efficiency of the spin-lattice relaxation process and size of the molecules: The spin-lattice
relaxation process is very n:zuch effective for the large molecules which tumble (i.e. rotate) slowly. Thus
the process becomes inefficient for the small molecules which tumble faster specially at the relatively
higher temperature.
• Spin-lattice relaxation for the quadrupole nucleus: The nuclei with the quadrupole moments
(I> ±) undergo the spin-lattice relaxation process very rapidly. In such cases, it becomes very much
ry
ra
difficult to have the NMR signals because the peaks are broadened (cf. hl1vl/z/'i.t "" h i.e. I1vl/ Z = ~ ).
ib
~t
However, for t4N (I = 1) and 2H (I = 1), the quadrupole relaxation is less effective and their NMR
yl
em
signals can be observed (cf Sec. 12.2.16). In fact, the nuclei with I >!
very often appear as the
2
nonmagnetic nuclei in NMR spectroscopy because of their rapid quadrupole relaxation.
ch
(B) Spin-spin relaxation process (first order process): In this process, the excited nucleus (say B)
al
interacts with another magnetic nucleus (say A) at the ground state. The energy exchange deexcites the
e
= +.! = _.!
th
nucleus B and excites the nucleus A, e.g. A goes from m/ to the excited state m/ and B
2 , 2
e/
comes down from the excited state m/ = _.! to the ground state m/ = +.! . Thus in this process, there
t.m
2 2
is no change in energy of the spin system. It is an entropy driven process (i.e. randomisation of the
spins) and the process occurs between the nuclei of the same type which are studied in the NMR
e
experiment. This spin-spin relaxation process is described as the transverse process as it occurs in a
er
plane perpendicular to the direction of the applied field. The spin-spin relaxation time (T2) is the
H
inverse of the rate constant of this first-order process.

k
lic
Intensity and Bandwidth: T1 and T2

C
• T, maintains the Boltzmann distribution equilibrium, i.e. spin-lattice relaxation brings down
the excited nuclei to the ground state to reestablish the Boltzmann equilibrium. In this
regard, T2 has nothing to do. Thus T] determines the intensity of the peak.
• Peak broadening is determined by the relation ~E~t::::: h, i.e. h~v'/2~t::::: h where ~t = life time
of the excited nucleus = T t or T2 which one is smaller. It leads to: A.Vl/2 (== half-bandwidth)
1
== T (T = T1 or T 2 which one is smaller). For solids, T2 ::::: 10-4 s « ( T t ) and it leads to:
~V'/2 ::::: 104 Hz which is a broad peak.
• Here it may be mentioned that the peak broadening is not only controlled by the relaxation
process. It is also controlled by chemical exchange process and magnetic inhomogeneity that
arises when the different parts of the sample experience the different Ho (applied magnetic
field) values from the spectrometer. A very good spectrometer can avoid this magnetic
inhomogeneity factor.
In solid, T2 is in the order of 10-4 s (i.e. T} ) ) T2 ) while in solution, T} ~ T2 • In solid, because of the
very small value of T 2, broad spectral lines are obtained.
• Precautions to minimise the peak broadening: For a better resolution, peak broadening should
be minimised (i.e. life time of the excited state should not be too small).
(i) Paramagnetic impurities such as dissolved O 2, magnetic materials, etc. which make T1 smaller
should be excluded from the sample (cf No PMR signal for the highly paramagnetic substance
[Mn(OH 2)6]2+).
(ii) In solid and viscous liquids, spin-spin relaxation is very fast (i.e. T 2 small). Solid state should be
avoided if possible.
(iii) Quadrupole nuclei (I > ±) relax fast (T. small). It should be taken into consideration.
ry
(iv) Rapid chemical exchange may broaden the peak. It should be taken into consideration.
ra
ib
12.2.4 Concept of Chemical Shifts and Solvents for PMR Studies
yl
• Requirement of the chemical shift parameter: From the relation, v = (~: )Ho (for the NM~
em
transition), it is evident that for a nucleus (in a particular compound), v for the NMR transition depends
ch
on H o. Otherwise, H o is different for the different operating v values. If a fixed operating frequency (i.e.
al
v fixed) is used, H o is fixed for the nucleus but if the operating frequency v is changed, H o is to be
changed, i.e. the peak position (in terms of the magnetic field) depends on the operating frequency
e
th
used in the study. To remove this difficulty, in expressing the peak position, the parameter chemical
shift (8) has been chosen and it is independent of the field strength or operating frequency.
e/
The chemical shift (8) is defined as:

t.m
~ 6
u = H (sample) - H (reference)
x 106 . the factor 10 is used to give the convenient numbers of b in
H (reference) , the unit of ppm.
e
er
H -H v -v 'Y H
10 6 = _ s_ _r X 10 6 ; H, YN constant for a given nucleus).
H
= s r X (cf V = _N_, i.e. v oc

Hr vr 21t
k
lic
~ V s - V r X 10 6 . (v s and v r are the large numbers which only slightly differ from v o, the operating
' frequency say 60 MHz or 100 MHz or 300 MHz).
C
V
o
• Shielding constant (a) and chemical shift (~): The electrons around the nucleus shield the
nucleus and it cannot experience the full applied magnetic field (say Ho). Under the influence of the
external magnetic field (Ho), the electrons around the nucleus (to experience the NMR transition) are
induced to produce an induced magnetic field which opposes the applied field. This effect is called the
local diamagnetic shielding. Thus the electrons around the nucleus shield the nucleus and conse-
quently it cannot experience the full applied magnetic field (Ho), i.e. Hex (the magnetic field experi-
enced) is less than H 0-
Hex = Ho - Hinduced, Hinduced oc H o, i.e. Hinduced = aHo, a = proportionality constant, i.e. Hex = HoC I - a)
a (proportionality constant) = shielding constant (a dimensionless quantity).
Here it is worth mentioning that in reality, besides the said local diamagnetic shielding (measured
by ad), local paramagnetic deshielding (measured by (Jp) and neighbouring group effect, i.e. remote
effect (measured by an) may contribute to determine a. These factors will be discussed later.
(Note: Ignoring the solvent effect and other minor effects, the main contributing factors to 0' are the
local effect (O'd and O'p) and remote or neighbouring group effect (O'n) which also includes the ring
curre~t effect, i.e. a == ad + a p + an where 0d (> 0) and op( < 0) denote the local diamagnetic shielding
and local paramagnetic deshielding effect respectively. In PMR spectroscopy, O'd> O'p == O. All these
aspects will be discussed later).
NMR spectra are recorded by using a constant oscillator frequency, i.e. probe frequency or operating
frequency (say 60 MHz) and varying the magnetic field (Ho). For the higher shielding constant (a), Hex
(experienced field) is lower than the applied field (Ho) and the resonance will occur for the higher
applied field for which v L (Larmor frequency) = yNH ej2n becomes the operating frequency (v).
We can compare the value of H (say H r ) required to produce the resonance in the reference com-
pound with the value (say H s ) required to produce the same effect in the sample compound.
ry
Hex = Hi1 - Os) and Hex = H r (1 - Or)' i.e. Hs (1 - as) = Hr (1 - O'r) where as and or denote the
ra
shielding constants for the sample and reference respectively.
ib
Hs = 1- 0' r; or Hs _ 1 = 1- 0' r _ l' or 0' s - 0' r = Hs - Hr
yl
i.e.
Hr l-O's Hr l-O's' l-O's Hr
0= (Hs;r
Hr
em
) X 106 = ( ~s_-cr~r ) x 106 '" (cr s - cr r ) X 106 ,
ch
(1)> crJ
al
• Reference in recording the PMR spectrum ofH-nuclei: For this purpose, TMS (tetramethylsilane,
e
SiMe4) is used as the reference compound. All the protons of TMS are equivalent and the shielding
th
constant is very high. They give a single peak at a very high field strength (for 60 MHz, H o = 1.4092 T).
e/
The 8-value for the TMS protons is arbitrarily set equal to zero. The larger value offJ indicates a down-
t.m
field (i.e. lower field) resonance, i.e. lower shielding constant (a).
In the tau (t = 10 - 8) scale, the reference is assigned the arbitrary position of 10.
e
• TMS as a reference one-why?: It is selected as a reference one because of its following

er
characteristic properties.
H
(i) The 12 equivalent protons give a single PMR signal.

(ii) The electronegativity of silicon is very small (cf XSi == 1.8 ( Xc = 2.5) and consequently the
k
lic
protons are highly shielded (i.e. a is very high) and they resonate at a very high field
(Ho = 1.4092 T for a 60 MHz probe). In fact, with respect to the TMS protons, almo~t all other
C
protons (in organic compounds) resonate in the downfield direction.

(iii) TMS is very much chemically inert and stable.
(iv) It has a very low boiling point (300 K) and it can be easily removed by evaporation from the
sample.
(v) TMS is not water soluble. It is a drawback. For the water soluble sample, DSS (sodium salt of 2,2-
dimethyl-2-silapentane sulfonic acid), i.e. Me3Si(CH2)3S0i Na+ or (CH3)3Si(CD2)2COi Na+ is
used as a reference one. CH3-protons of DSS resonate in the same position as those of TMS.
• Other reference compounds: TMS generally used for IH, l3C and 29Si NMR studies; CFCl 3 for
19F NMR studies; 85% H3P04 or OP(OEt)3 for 31p-NMR studies.
• a and fJ values for the different groups of protons in CH3CH20H: The proton of the OH group
is least shielded as it is attached to the highly electronegative O-atom (i.e. a is small). Thus the magnetic
field (Hex) experienced by the OH proton is more close to the applied field (Ho). This is why, among the
three types ofprotons, the OH-proton resonates at the lowestfield. On the other hand, the CH3-protons
are most shielded (i.e. a is maximum) and they resonate at the highest field. The CH 2 protons resonate
at an intermediate field.
a CH3 ) a CHz ) 00H i.e. Hex = H o (1- OCH 3 ) ( Hex = (1- 0CH z ) (Hex = H o (1- 00H)
i.e. (Hex )CH 3 < (Hex )CH z < (Hex )OH
Thus for the PMR signal H o : CH3 ) CH2 ) OH (for a particular fixed probe frequency)
Similarly for CH 30H, H o : CH 3 ) OH
For CH 3CHO, H o : CH 3 ) CHO
• Relation among CJ (shielding constant), a (chemical shift) and Ho (required field for the NMR
ry
transition at a fixed probe frequency): From the cases of CH 3CH20H, CH30H and CH 3CHO, we can
ra
conclude as follows:
ib
(i) More the shielded protons (i.e. more the positive value of a):::::) more the electron density around
yl
the proton, more the upfield signal:::::) less the B-value or more the t value (for the TMS reference).
em
(ii) More the deshielded protons as in the OH group proton (i.e. less the a-value):::::) less the electron
density around the proton:::::) more the downfield signal:::::) more the B-value or less the t-value
ch
(for the TMS reference).
(iii) For TMS, the PMR signals appear at 8 = 0, i.e. t = 10.
al
(iv) a-scale (PMR): RCOOH*(10-13) R-OH* (2-5) R-NH 2* (1-3) R-CH 3* (0.6-1.2)
e
th
e/
I
Negative shielding No shielding or Positive
I
t.m
i. e. deshielding no deshielding shielding
8:
Decreasing
Increasing
~ (Hex} Hal (Hex '" Hal J (Hex (Hal
e
0: ~
er
Increasing
't: ~ Downfield --+ Ho (applied field) Upfield
H
Increasing
Ho(app): ~
k
8: ~
Decreasing
lic
(for a fixed probe frequency) 't: ~

C
Increasing
TMS
Deshielding Shielding
4
Downfield Upfield
8 (ppm):
10 9 8 7 6 5 4 3 2
Increasing
• Solvents used in PMR studies: Aprotic solvents (having no H-atom) producing no PMR signal
are used for the solid and viscous liquid samples for their PMR studies. The common solvents ar~: D20,
CCI4 , CDCl3(deuteriochlorofonn), CS 2, C 6D 6 (hexadeuteriobenzene), (CD3)2C=O (hexadeuterioacetone),

(CD3)2S=O (hexadeuteriodimethyl sulfoxide), etc. It may be noted that the deuterium nucleus is
NMR active (I = 1) but because of its very small value of YN (= 41.1, cf YN = 267.5 for 1H), its NMR
frequency is small (cf 9.21 MHz for 2H and 60 MHz for IH in a magnetic field of 1.4 T). Thus the
NMR transition for deuterium in a 60 MHz spectrometer will appear at a very large magnetic
field (about 9.0 T). This is why, no peak for deuterium will appear in the magnetic field used for
scanning the NMR signal of tH.
12.2.5 Factors Controlling the Magnitude and Direction of Chemical Shift

The important factors may originate from the both local and remote effects and each effect may lead
to the diamagnetic shielding and paramagnetic deshielding, i.e. a ::::: alocal + aremotc (i.e. an) = ad +
ry
ap + a w
ra
(A) Local Diamagnetic Shielding (ad' an isotropic effect): Under the influence of an externally
ib
applied magnetic field (Ho), the electrons around the nucleus are induced to circulate to produce an
induced magnetic field (Hinduced DC H o, i.e. Hinduced = adH o). This induced magnetic field opposes the
yl
applied magnetic field and the nucleus (to experience the NMR transition) experiences a less magnetic
em
field. Obviously, the diamagnetic shielding constant ad is positive in the expression, Hex = H o(1 - a)
where a ::::: alocal + aremote and al ocal = ad + a p (cf in PMP spectroscopy, cr local::::: cr d i.e. cr p ::::: 0). This
ch
phenomenon leading to crd is called the local diamagnetic shielding (which is identical in all direc-
al
tions, i.e. isotropic) whose magnitude depends on the electron density around the nucleus under con-
e
sideration and the applied field strength (Ho).

th
e/
Nucleus
Electron
t.m
circulation
e
er
H
Lines of the
k
magnetic flux
lic
Revolving
electron
C
Fig. 12.2.5.1 Local diamagnetic shielding leading to ad at the nucleus due to the electron circulation around
the nucleus.
More the electron density around the nucleus, more the diamagnetic shielding, i.e. more the upfield
NMR transition and less the chemical sh~ft (8).
The magnitude of local diamagnetic shielding ofprotons is given by ad :=:: 21.51 x 10--6 where A gives
the measure of effective number of electrons in the 1s atomic orbital of hydrogen. For the common type
of protons, ad varies in the range 10~5 while it is in the order of 10-3 to 10-4 for the heavier nuclei.
The following factors determine the magnitude of the local diamagnetic effects.
(i) Electronegativity effect and inductive effect: The electronegative substituents show the electron
withdrawing inductive effect to reduce the electron density around the nucleus. It reduces the
local diamagnetic shielding (i.e. downfield NMR transition) and the chemical shift (8) becomes
higher. It is illustrated in the following examples (for the PMR signals).
CH 3-X: CH 3-F CH 3-OH CH 3-CI CH 3-Br Si(CH3)4

X(X): 4.0 3.5 3.1 2.8 X(C) = 2.5
8 (ppm): 4.3 3.4 3.0 2.7 X(H) = 2.2
X(Si) = 1.8
8=0
Effect of substitution: CHCl 3 (8 = 7.27), CH 2Cl 2 (8 = 5.3), CH 3Cl (8 = 3.0)
The electron pushing groups like alkyl groups enhance the electron density around the nucleus to
increase the diamagnetic shielding (i.e. upfield transition and lower 8-value).
R-CH 3 (8 = 0.7 - 1.2) (R2CH 2 (8 = 1.2 - 1.4) ( R3CH (8 = 1.4 - 1.7).
ry
(ii) Hybridisation state of C: The electronegativity sequence is: sp-C ) Sp2_C ) Sp3_C. Thus consid-
eration of the local diamagnetic shielding predicts the chemical shift order for PMR.
ra
ib
'"
8 (ppm): -C - H (=CH 2 (==C - H (expected order based on (Jd)
yl
/
em
But the above prediction is not supported experimentally because, another effect called magnetic
anisotropy is important. This aspect will be discussed separately. Because of this anisotropic
ch
effect, the aromatic hydrogens, vinyl hydrogens and carbonyl hydrogens experience the
al
downfield resonance (i.e. higher 8-values).

e
(iii) Effect of resonance: Aromatic hydrogens generally show the 8 values in the range 7-8 ppm. In
th
the benzene ring, electron pushing effect enhances the electron density to make 8 relatively less
e/
while the electron withdrawing groups make the chemical shift relatively larger.
t.m
x-@-x : 8 (ppm) = 7.32 (X = H), ) 7.32 (X = electron withdrawing group),

e
( 7.32 (X = electron pushing group)

er
H
k
: Order of deshielding of protons (0 ) p ) m);

lic
C
n0 n
,-~:: : Order of sheilding of protons (0 ) p ) m);
8-"==./ NH 2
8-
(iv) Hydrogen bonding: The hydrogen bonding, R-O-H···O (0 = donor, an electronegative centre)
reduces the electron density around the H-centre, i. e. H-bonding reduces the local diamagnetic
shielding, i.e. H- is deshielded. The H-bonded proton experiences the more downfield resonance,
i.e. higher chemical shift, compared to the non-H-bonded protons. The intermolecular
H-bonding of R-OH (in an aprotic solvent like CCI4 ) can be minimised by increasing the
dilution. In fact, in dilute solution, the OH proton of ROH shows the chemical shift in the range
0.5 - 1.0 ppm but in concentrated solution (where the intermolecular H-bonding occurs), the
chemical shift occurs at about 4-5 ppm.
, H H H
'. /
o "/ 0
"
0
/ " '
I I I
R R R
(Free, in dilute solution,
(Intermolecular H-bonding)
8 = 0.5-1.0 ppm)
(H-bonded ROH in concentrated solution, 8 = 4-5 ppm)
Obviously, in the case of intramolecular H-bonding, there is no effect ofdilution on the position
of the PMR signal of the OB proton.
ry
ra
R
ib
Enol form (~-diketone)
yl
(Salicylates, 80H ~ 10-12 ppm) 80H~ 10-13 ppm
em
Intramolecular H-bonding
Intramolecular ch
Keto-enol tautomerism: It occurs very often for ~-diketone and ~-ketoester. Existence of the
keto-enol tautomerism can be identified from the PMR signals.
al
Acetylacetone:
e
th
(c)
e/
/H",
. . . H,
o 0
o 0 O~ ~O
t.m
I
C
I
C I I i.e. I:, ~ CI
~ C C C .........
~C/ "C/
e
(a) / " / "(a)

(a) / "(a)
H3 C (b) C CH 3 /' I ' " CH
er
H2 H3C 3 H3C I (b) CH 3

H) H
H
(Keto form)
Two types of protons
Methine proton (enol-form)
k
i.e. CH 3 and CH 2 (methylene)

(This methine proton can Three types of protons and
lic
protons and two PMR signals

also be described as a three PMR signals of the
of the intensity ratio 6:2
vinyl proton.) intensity ratio, 6:1:1;
C
existence of the H-bonded

proton and methine proton
indicates the enol form.
Thus the PMR signals of a keto-enol tautomeric mixture show the different types of protons of
different chemical shifts. For acetylacetone, the chemical shift values of the PMR signals are:
8 (ppm) (for the enol form) = 15.5 (OH), 5.5 (vinyl or methine C-H), 2.0 (CH 3); 8 (ppm) (for
the keto form) = 2.2 (CH 3), 3.6 (CH2)
For acetylacetone, the strong PMR signals appear for 8 = 15.5 ppm, 5.5 ppm and 2.0 pm while
the weak PMR signals appear for 8 =2.2 ppm and 3.6 ppm. It clearly indicates that for acetylacetone,
the enol form predominantly exists (about 80%).
Thus positions of the PMR signal for the OH, NH, SH groups depend on the degree and strength
of H-bonding which depend on the nature of solvent, concentration, temperature and characteristics
of the substance. Greater the hydrogen bonding, greater the depletion of electron density
around the proton, greater the deshielding and greater the downfield resonance (i.e. higher
chemical shift).
(v) Effect of charge: Electron deficiency arises in the cationic species (i.e. deshielding effect and
downfield resonance) while in the anionic species, the enhanced electron density causes the more
shielding (i.e. upfield resonance). This is illustrated in the following examples.
Cp- (cyclopentadienyl
anion), 8 (H) ~ 5.4 ppm
©
Benzene Cycloheptatrienyl
All are aromatic,
4n + 2 = 6
i. e., 6 n-electrons
8 (H) ~ 7.2 ppm cation, 8 (H) ~ 9.2 ppm
ry
ra
[ CH 2 =-=-=CH=-=-=CH 2 ] + [ CH 2 =-=-=CH=-=-=CH 2 ] -
ib
yl
8 (ppm) = 8.95 9.65 8.95 8 (ppm) = 2.45 6.30 2.45
em
'"'- ----.... _---------J
V
Allyl cation: Positive charge is more concentrated on the central
ch
carbon. Ally anion: Negative charges are more concentrated on
the terminal C-centres to avoid the electrostatic repulsion. MOT
al
can explain this charge distribution pattern.
e
(vi) Acidic hydrogens of -C02" group, -803" group, etc.: Such hydrogens are the least shielded
th
ones (i.e. approximately H+ ions). They show the downfield resonance (8 : : : 10 - 14 ppm). Both
e/
the electron withdrawing inductive and mesomeric effect make the hydrogen so electron deficient.
t.m
CO yO
e
R-C-f" R-S=O
er
C~-H C~-H
H
k
lic
(B) Local Paramagnetic Interaction «(Jp, anisotropic in nature): This effect is mainly important for the
nuclei like C, N, 0, F, etc. but this effect is not discussed here in detail. The applied field can cause the
C
electrons to circulate using the low-lying unoccupied orbitals. Obviously, if the unoccupied orbitals
are ofmuch higher energy then this effect is ofno importance as in the case ofhydrogen. Paramagnetic
field at the nucleus causes deshielding (i.e. downfield resonance). Here the anisotropic effect arises
from the mixing of the ground state and excited state leading to a field induced nonspherical circulation
of electron around the nucleus.
Here the word 'paramagnetic' is not used to imply the same property of paramagnetism arising
from the unpaired electrons in a system. In the present case, it describes the field induced nonspherical
circulation of electron density through the mixing of the ground and excited states. It makes the para-
magnetic contribution to shielding (cf. the local diamagnetic shielding constant (Jd is positive while
local paramagnetic shielding constant (Jp is negative). The contribution of (Jd and (Jp to 8 (chemical shift)
can be understood in terms of Ramsey equation and Lamb equation (W.E. Lamb, 1955 Nobel Prize in
Physics for the discovery of "Lamb shift" in the hydrogen spectrum) which are beyond the scope of
the book. Qualitatively, it is concluded that the asymmetric distribution of electrons in the p- and
d-orbitals at the both ground and low-lying excited states will be ideal for the paramagnetic
contribution. The energy difference (~E) between the ground and excited states should not be large to
prevent their mixing.
CJd vs. CJp : (Jd opposes the applied magnetic field at the nucleus (i.e. the nucleus is shielded) while
•
(Jpenhances the magnetic field intensity at the nucleus (i.e. the nucleus is deshielded). Diamagnetic
shielding is favoured when the electrons are localised on a single atom or around a linear double or
triple bond while paramagnetic deshielding is favoured when the applied field causes the electrons
to circulate nonspherically throughout the molecule using the unoccupied orbitals.
• CJd and CJp for IH vs. elements of higher atomic number (e.g. lIB, 13C, 19F, etc.): For hydrogen,
to have the paramagnetic contribution, the electron is to be promoted to the 2p-orbital (cf s-orbital is
spherically symmetrical) and this transition is energetically very much unfavourable because of the
ry
large ~E value. This is why, for IH, contribution of a p is insignificant. However, for the elements of
ra
higher atomic number, AE gradually decreases and contribution of CJp increases dramatically. For
ib
the heavier halogens, contribution of (Jp is more because of the smaller values of excitation energy (~).
For IH, both (Jd and (Jp (::::: 0) are small because it involves fewer electrons and larger AE value and
yl
the chemical shift (8) covers a narrower range (ca. 20 ppm). For the elements of higher atomic
em
number involving the larger number of electrons and smaller AE values, both (Jd and (Jp are quite
high and (Jp dramatically increases with the increase of atomic number and it becomes the dominating
ch
factor to control the range of 8-values. For boron (i.e. lOB, lIB), both (Jd and (Jp are of comparable
al
values and the 8-values cover a range of about 140 ppm. For l3C and 19F, (Jp is very high and the
e
8-values cover a wide range (cf about 225 ppm for l3C, about 1000 ppm for 19F). Thus we can conclude:
th
CJp » ad (for 59CO, 14N, 13C, 19F); CJp ::::: CJd (for 10, lIB); CJd » CJp ::::: 0 (for IH); CJd (10, lIB, 13C, 19F)
e/
» CJd (IH).
t.m
• Chemical shift (8) range: ca. 1000 ppm (for 19F); ca. 225 ppm (for 13C, in organic compounds);
ca. 140 ppm (for 10,11B); ca. 20 ppm (for IH).
(C) Neighbour Anisotropic Effect (CJremote or an, Remote Effect) of the x-Electron Cloud: The
e
er
n-electron cloud is also induced to produce a magnetic field in presence of an external magnetic field
H
k
lic
C
~LineSOf
magnetic
flux
Deshielding Deshielding
region region
l )
-....y-
(a)
Shielding
region
(Diamagnetic shielding H~
r
ry
effect on both hydrogen Shiel,ding
ra
and carbon) region
(Diamagnetic (Paramagnetic
ib
H (Parallel shielding deshielding (Perpendicular
o
orientation) effect on effect on orientation)
yl
l____________ hydrogen) carbon) ~
em
~
(b)
ch
Shielding
Deshielding
al
region Deshielding
region ~ region
e
~ +
th
Circulation of
e/
1t-electron
~
t.m
Lines of
magnetic flux
e
er
H
k
lic
C
(c)
Fig. 12.2.5.2 Contribution of neighbour anisotropic effect (i.e. remote effect) from the induced circulation of tt-electron
cloud in (a) ethylene, (b) acetylene, and (c) benzene.
due to the directed circulation of the n-electron cloud. This induced magnetic field may be diamagnetic
or paramagnetic depending on the direction, i.e. anisotropic behaviour. The neighbouring nuclei
which are not directly chemically bonded to the n-system lllay also experience the induced anisotropic
magnetic field due to the circulation of the 1t-electron cloud under the influence of the external field.
This is why, this effect is also described as the remote effect. A particular nucleus may be shielded or
deshielded by this induced magnetic field depending on its orientation with respect to the n-system.
This neighbour anisotropic effect (i.e. an) is also to be considered to estimate the magnetic field
experienced (Hex) by the nucleus under investigation.
The anisotropic magnetic field generated due to the induced circulation of the 1t-electron clvud is
illustrated for alkenes, alkynes, aromatic system and carbonyl group in Figs. 12.2.5.2, 3.
The nature of neighbour anisotropic effect depends on the orientation of the molecule/group
containing the 1t-electron cloud with respect to the direction of the field. It is illustrated for some
systems.
• Ethylene: In an externally applied magnetic field, ethylene is preferably oriented in a way so that
plane of the double bond is perpendicular to the direction of the field. Thus the induced circulation of
the 1t-electron cloud produces a diamagnetic field (i.e. opposing the applied field) around the C-centres
and paramagnetic field in the region of the protons, i.e. C-centres experience the diamagnetic shielding
while the protons experience the paramagnetic deshielding from the anisotropy caused by the
induced circulation of the 1t-electron cloud of ethylene. This is why, the ethylene protons experience the
higher field and resonate at downfield, i. e. resonance at the lower applied field. It gives the higher
~-value.
ry
• Acetylene: In an external magnetic field, acetylene is preferably oriented parallel to the direction
ra
of the field (i.e. the triple bond is parallel to the field direction). In this orientation, the 1t-electron cloud
of the C == C bond is most free to circulate around the molecular axis under the influence of the
ib
yl
external field. The magnetic field generated from the induced circulati,on of the cylindrical1t-electron
cloud of the C == C bond opposes the applied field in the regions of the protons. Thus these protons
em
experience a lower field due to this dimagnetic shielding from the anisotropic effect. This is why, the
acetylinic protons resonate at the higher applied field (i.e. lower 8-value).
ch
The horizontal orientation of the molecule (i.e. perpendicular to the direction of the field) experiences
al
a hindered circulation of the 1t-electron cloud causing the paramagnetic anisotropy towards the centre
e
of the triple bond and dimagnetic shielding or diamagnetic anisotropy towards the protons. Thus both
th
the vertical and horizontal orientations of the acetylene molecule provide the shielding at the proton.
e/
However, the horizontal orientation of the acetylene molecule is less favoured.

t.m
Neighbour anisotropic
diamagnetic shielding
region denoted by
e
+ sign (cone)
er
H
(-)
c
k
'O==C,':;, (-) III H

lic
(-)
C
Neighbour anisotropic
paramagnetic deshielding
region denoted by - sign
(outside the cone)
Fig. 12.2.5.3 Neighbour anisotropic effect. Conical shaded region (denoted by + sign) represents the anisotropic
diamagnetic shielding region while the region (denoted by - sign) outside the conical region denotes the anisotropic
paramagnetic deshielding region.
• Benzene: In presence of an external magnetic field, the benzene molecule lies preferably in a
plane perpendicular to the direction of the field. The induced circular motion of the 1t-electron cloud
around the ring produces a ring current. This induced ring current produces a diamagnetic field at the
centre of the ring and a paramagnetic field outside the ring. Thus the aromatic protons at the periphery
of the benzene ring expeiience the paramagnetic anisotropic effect, i.e. paramagnetic deshielding.
This is why, the aromatic protons experience the higher magnetic field and they resonate at the lower
applied field (i.e. downtield resonance and consequently the higher chemical shift cS).
In different aromatic systems with (4n + 2)1t electrons, because of the induced ring current (under
the influence of a magnetic field), the protons lying outside the ring are deshielded (i.e. paramagnetic
anisotropy and higher cS-value) while the protons residing within the ring are shielded (i.e. diamagnetic
anisotropy and lower cS-value) (Fig. 12.2.5.4).
ry
Outer protons (downfield)
ra
Inner protons (deshielded)
(0 =9 ppm
ib
(shielded) (upfield) (
Anisotropic (0=-2 ppm) (
yl
diamagnetic
shielding H H
em
Upfleld proton \
(0 ~ -1.0 ppm) ' "
ch
CH~r2 H H
e al
CH fj ~ CH H H
th
~ 2 2
Anisotropic /
e/
paramagnetic . (6n-electrons) H H
deshielding Relatively
t.m
downfield proton H H
(o~ 2.0 ppm) Annulene [18],
(18 n-electrons)
e
er
Ring proton (deshielded)

H
(Downfield), 0 ~ 8.5 ppm.

CH 3 protons (shielded)
k
(Upfield), 0 ~ 4 ppm.
lic
C
Trans-15, 16, dimethyl-

15, 16-dihydropyrene.
Fig. 12.2.5.4 Neighbour anisotropic effect. Protons lying in the shielding region are the upfield protons and protons
lying in the deshielding regions are the downfield protons.
• Carbonyl group: The anisotropic effect indicates that the eRO proton lies in the paramagnetic
deshielding region and it shows the higher chemical shift. The carbonyl or nitro group (showing the
electron deficiency at the 0- and p- positions due to the electron withdrawing mesomeric effect) in the
aromatic ring shows this anisotropic effect for the ortho- protons (i. e. deshielding due to the aniso-
tropic effect arising from the n-electron cloud of the double bond present in the carbonyl or nitro
group).
The shielding and deshielding regions due to the different types of 1t-electron systems have the
characteristic shapes and directions (Fig. 12.2.5.3). Protons falling within the conical region are
experiencing the anisotropic diamagnetic shielding while protons lying outside the conical region are
experiencing the anisotropic paramagnetic deshielding.
(D) Chemical shift values for C2H 6, C2H4, C2H 2, C6H6 and RCHO:
H
R
H H ~
C=Q
HC==CH H/
H H
8 (ppm): -0.9 5.3 2.3 7.3 9-10
In terms of protonic character and local diamagnetic effect (controlled by the electronegativity of
ry
C-centre), among C2H6 , C2H4 , and C 2H2 , the acetylinic hydrogen is most deshielded and it should show
ra
the highest 8-value. The experimental values of 8 can be explained by considering the predominant
neighbouring group anisotropic effect generated in C 2H4 and C 2H2 • For C2H 4, both the local diamagnetic
ib
effect (controlled by Sp2_C) and remote anisotropic paramagnetic deshielding effect work in the same
yl
direction but in C2H2, the local diamagnetic effect and remote anisotropic diamagnetic effect experienced
em
by the protons work in the opposite directions (cf Figs. 12.2.5.2-3). This remote anisotropic effect is
more important than the local diamagnetic effect.
ch
• C 2H 4 vs. C 6H 6 : In terms of the local diamagnetic effect (controlled by the Sp2_C), the chemical
al
shifts of the protons should be more or less comparable in C 2H4 and C6H6 . But in reality, the C6H6
e
protons are more deshielded. Though in both C 2H4 and C 6H 6, the protons reside in the paramagnetic
th
deshielding region (remote anisotropic effect), the effect due to the ring current of C~6 is more
e/
pronounced. This is why, the C6H6 protons resonate at the much lower field.
• C2H 4 vs. RCHO: In both the cases, sp2_C is present and the protons reside in the paramagnetic
t.m
deshielding region (remote anisotropic effect). The more downfield resonance (8 = 9 - 10 ppm) for the
aldehydic proton is due to the better remote anisotropic effect and the electron withdrawing inductive
e
effect (due to the high electronegativity of oxygen) causing a strong local diamagnetic effect to reduce
er
the shielding.
H
(E) Chemical shifts for HCI vs. H-CH3 : The chemical shift parameters (8) indicate that the proton
k
in HCI (gas phase) is more shielded than those in CH4• In terms of the protonic character (electronegativity
lic
effect) and local diamagnetic effect, HCI proton should be more deshielded. It needs an explanation to
rationalise the observation.
C
The linear H-CI molecule (having the cylindrical symmetry) can experience the different types of
remote anisotropic effect (arising from the diamagnetic circulation of the electron cloud on the
remote atom CI) for different orientations of the HCI molecule with respect to the applied field
direction. If the H-CI molecule is oriented parallel to the field direction, the diamagnetic circulation
of the electron cloud on the remote atom CI will produce a field that will shield (i. e. remote anisotropic
diamagnetic shielding) the proton. But if the molecule is oriented perpendicular to the field direction,
the same effect of CI will deshield (t.e. remote anisotropic paramagnetic deshielding) the proton. The
relative importance of these two effects on H of H-CI will depend on the relative susceptibilities of CI
for the parallel (XII) and perpendicular (Xl.) orientations of HCl.
Now let us consider the relative importance of XII and Xl- for H-X (X =CI, CH 3). For the tetrahedral
molecule (i.e. X =CH 3) where the C-centre has the spherical symmetry, XII:::: Xl-, the net effect arising
from the remote anisotropic effect is zero. For the axially symmetrical molecule or cylindrical molecule
(i.e. X = CI), the electron circulation is less for the perpendicular orientation of H-CI, i.e. the remote
anisotropic diamagnetic shielding effect on H from the parallel orientation of H-CI is more
important. This remote anisotropic effect to shield the Hel proton is more important than the local
diamagnetic effect which is related with the electronegativity of X (i.e. attached atom). For CH4 (i.e.
H-CH 3), the local diamagnetic effect controls the magnitude of shielding while for HCI, the remote
anisotropic shielding effect (from the parallel orientation of the molecule) is the main contributing
factor. It explains the chemical shift values of the protons of HCI and CH4 .
Deshielding
region
Deshielding
C.
ry
~region
ra
ib
yl
em
ch
Parallel (Perpendicular
al
orientation orientation)
e
th
Fig. 12.2.5.5 Contribution of neighbour anisotropic effect for the parallel and perpendicular orientations of HCI molecule
from the field induced diamagnetic circulation of electron cloud on the remote atom Cl.
e/
(F) Chemical shifts of R-CH3 vs. Ar-CH3 : Let us consider the chemical shifts of CH3 protons in
t.m
CH 3- CH 3 and C 6H s- CH 3 (i.e. tolune). For toluene, the aromatic protons resonate at the relatively
lower field (8 = 7.2, remote paramagnetic anisotropic deshielding effect) while the CH 3-protons resonate
e
at upfield (8 = 2.3). Here it is worth noting that in toluene, the methyl group protons resonate a
er
little downfield compared to the ordinary alkyl protons (cf R-CH 3 , 8 : : : 0.9). It is due to the fact
H
that the methyl protons of toluene are somewhat deshielded by the ring current produced by the
1t-electrons of the attached benzene ring (cf this remote anisotropic paramagnetic deshielding effect is
k
more pronounced for the protons directly attached to the benzene ring).
lic
C
Table 12.2.5.1 Chemical shifts for protons (i.e. PMR signals) in different chemical environments (8 =0 ppm
for TMS).
Type ofproton ~ (ppm) 'l' Type ofproton ~ (ppm) 'r
Primary (R-CH3) 0.9 9.1 Alcoholic (R-OH) 1-5 9-5

Secondary (R 2CH2) 1.3 8.7 Phenolic (Ar-OH) 4-8 6-2
Tertiary (R3CH) 1.5 8.5 Aldehydic [ R - c( :J 9-10 1-0
Vinylic or ethylenic 5.3 4.7 Carboxylic (R-C0 2H) 10.5-12 -0.5-(-2)

(=CHR) Amino (Ar-NH 2) 3-5 7-5
(Contd.)

Type of proton S (ppm) l' Type of proton S (ppm) l'
. ( ,/C=r-r-H
Allyhc I J 1.7 8.3 Amino (R-NH2) 1-5 9-5
Acetylinic (==CH) 2-3 8-7 Carbonyl compound
Phenyl (Ph-H) 7.3 2.7

[~C_C~O]
/ I '\ 2-3 8-7
H
ry
[~ ~ ]
ra
-C-OR
Aromatic (Ar-H) (in general) 6-8.5 4-1.5 Ether 3.5 6.5
ib
yl
Ar-~- H J
em
Benzylic ( 2-3 8-7 Ester (CH3O-COR)
ch 3.7 6.3
[F ~ J
al
Alkyl fluoride C- H 4 6 Water (H2O) 5.2 4.8
e
Sulfuric acid (H2SO4) 11.5 -1.5

th
~ C - HJ
e/
Alkyl chloride [ Cl 3.5 6.5 Chloroform (CI 3CH) 7.5 2.5

t.m
a (ppm): Methyl protons (0.9 - 3.8); Methylene protons (1.5 - 3.6); Methine protons (3 - 4.5);
Olefinic protons (5.0 - 6.5); Acetylinic protons (2.0 - 3.2); Aromatic protons (6.0 - 8.5); Aldehydic
e
er
protons (7.8 - 9.9).

These are the approximate ranges of O-values for different types of protons.
H
12.2.6 Chemical Shifts for the PMR Signals in Metal Hydrides and Organometallics
k
lic
',see Example 11 of Sec. 12.2.19)

C
In the transition metal hydrides, the PMR signal due to the metal bound hydrogen very often shows the
negative values of chemical shift (0 = -5 to --15 ppm). The negative value of 0 indicates that the
concerned nucleus is more shielded (relative to that of the reference TMS protons), i.e. the NMR
transition in the upfield side of the reference (TMS).
For the metal hydrides e.g. [HMn(CO)s], [HCO(CO)4], [HRh(CN)s] 3-, etc. (where the transition
metal centres are in low oxidation states), the metal bound protons resonate 5 to 15 ppm to the high
field side of TMS (i.e. 0 = -5 to -15 ppm). It is easy to detect the M-H bond by following this
characteristic PMR signal because very few other protons appear in this range. This is a diagonostic
feature of the transition metal hydrides. In some cases, it may occur even 60 ppm upfield from the
TMS reference. The heavy shielding of the metal bound hydrogen arises from the partly filled
d-orbital electrons of the transition metals (in low oxidation states). However, the high electron
density (i.e. local diamagnetic shielding) around the H-atom bound to the transition metal centres
cannot alone explain the so upfield (i.e. too negative O-value) PMR signal. Negative O-value for the
carbonyl hydrides like [HCO(CO)4], [H2Fe(CO)4] showing the Bronsted acidity is really unusual in
terms of local diamagnetic shielding. Some authors have argued the paramagnetic contribution from
the nearby transition metal centres to explain the so upfield PMR signals of the hydride ligands
bound to the transition metals. This paramagnetic shielding occurs by the incompletely filled
d-electron subshell of the transition metal centre which may be itself diamagnetic also. This aspect has
been discussed in Examples 11 and 26 of Sec. 12.2.19.
For [HRh(CN)s]3- (I =!for Rh), the PMR signal due to the Rh-H group shows 8 = -10.6 ppm
2
(i.e. resonance occurs at 10.6 ppm on the high field side of the TMS reference). Actually, the PMR
signal appears here as a doublet one due to the splitting by Rh (I = !) and centre for the doublet
2
corresponds to 8 = -10.6 ppm. This observation strongly supports the Rh-H bond.
ry
Chemical shifts for the PMR signals of some representative organometallic compounds are given
ra
below.
ib
Complex: [W(CH3)6] [Ni(112-C2H4)3] [Fe(l1s-CsHs)2] [Cr(11 6- C6H 6)2]
yl
8 (ppm): 1.80 3.0 4.0 4.10
em
(cf. 8 = 0.9 for R-CH 3; 8 = 5.3 for C2H4 ; 8 = 5.4 for CsHs; 8 = 7.3 for C6H6)
ch
Chemical Shift for Different Types of Hydrides: (AH x)
al
a(ppm): + 10 (strongly acidic proton);- 0 (H is partially negatively charged); highly negative

e
(-10 to - 20 ppm) (organometallic hydride complexes)

th
e/
12.2.7 Area of the NMR Peak and Number of Nuclei: Integration Principle
t.m
Generally area of an NMR peak is proportional to the number of equivalent nuclei for which the peak
appears. This integration principle is widely used for the PMR signals. However, this principle is not
e
applicable for the 13C-NMR spectroscopy because the relaxation times of the different 13C-centres vary
er
widely (cf. Sec. 12.2.3)

H
12.2.8 Spin-Spin Coupling and Fine Structure of the NMR Signals

k
lic
1 1 1
(A) A-X molecule where 1= 2" for A and 1= 1 for X: For A, 1= 2" and m/ = ±2"; for X, 1= 1 and
C
m/ = ±1, O.
The nuclear magnetic moments of the nuclei are mutually interacting. Let us first consider the effect
of A on X assuming the A-X molecule to lie perpendicular to the direction of the field. There are two
possible orientations ( mJ = ± ~) of A in the magnetic field.

(i) m J = +.!. of A: For this orientation of the nuclear spin, A creates a magnetic field which opposes
2
the applied magnetic field (Ho) at X. Thus the actual field experienced (Hex) by X is less than H o.
Hex (by X) = Ho - HA , H A =the field generated by A on X. Thus the nucleus X will resonate at an
upper field.
(ii) m J = - ~ of A : For this orientation of the nuclear spin of A, it creates a magnetic field which acts
in the direction of the field at X. Thus the actual field experienced by X is greater than H o.
Hex (by X)= Ho + HA , HA = the field generated by A on X. Thus the nucleus X will resonate at a
lower applied field.
Lines of
/ __',*, ~ __, ragnetic flux

~--""""', ,,--......... ,/', /' ",
,/ ' \ 1// ", / 'VI \
/
I ml =+"2
1 t~ \, / 11
I m =-"2 l
\
t 0---0
1 \
\ ~ I
t \
0 - - - q ) H =H +H
; ,
ex o A
\ \ t /
ry
\""+-/r,,",,,-_/I r \"'·-/r:"'--~/ r
ra
H Ho H
ib
o o
yl
Ho 0
em
Fig. 12.2.8.1 Spin-spin coupling between the nuclei (A and X in AX system) having I for the nucleus A. =!
2
ch
Note: Here it is illustrated for the perpendicular orientation (with respect to the direction of H o) of the molecule
A-X. For the parallel orientation of A-X, Hex (by X) = Ho +HA (for m/ = +! of A) and Hex (by X) = Ho -
al
HA (for
2
e
m/ =_! of A). The actual mechanism of spin-spin coupling is discussed in Sec. 12.2.9.
th
2
e/
It is revealed that for two different orientations of the nuclear spins of A, the nucleus X will give two
t.m
NMR signals and these two peaks will be of equal intensity. The equal intensity of the two peaks occurs
due to the fact that the two orientations of A (Le. m/ = ±! ) are of equal probability, i.e. X can experience
2
e
the field H o + H A or H o - H A with the equal probability.

er
H
(lj (lj
c:: c::
0)
k
0)
1+-1JHO~1JHO-+l
"00 1 1 1
1+- JOH-+I 1 J HO I 1 J OH I "00
lic
0 0
:cco :cco
a:: a::
C
i i
(a) Doublet peak for
~ Ho
(b) Triplet peak for
• Ho
deuterium resonance proton resonance

in HO (splitting by 1H) in HO (splitting by 2 0 )
Fig. 12.2.8.2 Expected peaks of NMR signals for HD (lJ HO = IJOH )

Note: For a particular operating frequency, the required field for the resonance of deuterium is much higher than that
required for proton (i.e. Ho for D » Ho for H; cf. YN(D) = 41.1, YN(H) = 268).
Similarly, the NMR signal due to A undergoes splitting into three components by X for its three
possible orientations (m] = ± 1, 0) in the magnetic field. In fact, for the three different spin orientations
(m I =± 1, 0) of the nucleus X, in a magnetic field, the nucleus A experiences three different fields,
H o + H x, H o and H o - H x, i.e. A can resonate at three different fields at a fixed operating frequency. This
1
is illustrated for H-D (I = 2" for H, 1= 1 for D) in Fig. 12.2.8.2.
The peak separation is measured by the spin-spin coupling constant (J). It is: JXA (signal of X is split
by A) and JAX (signal of A is split by X).
1 1
H-D: For the HD molecule eH: 1= -, m[ = ±-; D, i.e. 2H: 1= 1, m[ = ± 1,0), the NMR signal
.22
due to H is split by D into three components and the NMR signal due to D is split by H into two
components (Fig. 12.2.8.2).
H-F: l H(1 =±' m/ = ±±) and F(1 =±' m/ = ±±). Thus the NMR signal due to
19 19F is split
ry
into two components by lH. Similarly, the PMR signal of lH is split into two components by 19p.
ra
(B) CH3CH20H where CH3CH2 represents the A3 X2 system and CH30H: In CH 3CH 20H, there are
ib
three types of protons and three PMR signals (3:2: 1 in terms of the peak areas) are expected (Fig.
yl
12.2.8.3a). It happens so under low resolution but under high resolution, the peak due to the methyl
em
protons is split into 3 components (with the intensity ratio, 1:2: 1) while the peak due to the methylene
group is split into 4 components (with the intensity ratio, 1:3:3: 1) (Fig. 12.2.8.3b). This can be explained
ch
by considering the spin-spin coupling between the CH3 and CH 2 protons (i.e. spin-spin coupling in the
A3X2 system where 1=1/2 for both A and X). Let us first consider the fate of the PMR signal of the
al
Me-protons under the influence of the two methylene protons (neighbouring protons). The different
e
combinations of the two equivalent methylene protons produce M[ = 'Lm[ = ±1, 0 as shown below:
th
'Lm[ = M[
e/
1 11 +1
t.m
Effect of the (parallel spins, 1 spin state)

CH 2 protons on 1~ ~~ 0 (antiparallel spins, 2 spin states)
the CH 3 protons ~~ -1 (parallel spins, 1 spin state).
e
er
• Thus for the three different spin orientations (M[ = ± 1, 0) of the CH2 -protons, the CH3 -protons
H
experience three different fields.

• The three possible combinations of "Lm[ can split the PMR signal of the CH3 group into 3 fine
k
components of the intensity ratio 1 : 2 : 1

lic
In the same way, the three equivalent methyl protons can split the PMR signal of the two equivalent
C
methylene protons. The three equivalent methyl protons can combine to produce to
3 1
M[ = 'Lm[ = ±- and ± - as shown below.
2 2
'Lm[ = M[
3
+- (1 spin state)
2
111 1
+- (3 spin states)
2
Effect of the 11 ~ 1~~ ~~~ 1
CH 3 protons on -- (3 spin states)
2
the CH 2 protons ~~ ~ ~~~ 1~~ 3
-- (1 spin state)
2
~~~
For the/our different spin orientations (M[ =±%,±~) of the CHrProtons, the CH2-protons
experience four different fields. Thus the CH 3- protons split the PMR signal of the CH2- protons into
4 fine components having the intensity ratio 1:3:3: 1
OH (m l = -~)
CH 2 (m l = -~)
......................... CH 3 (ml=-~)
ry
r , ~##
f~~ \~i:~:i!:; ~:.:~:.
ra
~E= hv
>-
ib
e>
Q)
c v = 60 Mhz
yl
W
em ·····················CH (ml=+~)
ch
3
CH2(ml=+~)
al
OH (ml=+~)
e
th
e/
t.m
~ Ho
- - - - - - - - - - - - - - - - - - - - - - -......
OH proton CH 2proton CH 3 proton
e
er
Fig. 12.2.8.3 (a) Schematic representation of variation of the potential energy levels of OH, CH2 and CH3 group protons
of CH3CH20H in the presence of a magnetic field (Ho) (Low resolution NMR spectrum of CH3CH20H).
H
Here it is worth mentioning that the equivalent nuclei do not split each other. Thus for the -CH3
k
group, the PMR signal due to a proton cannot be split by the remaining two protons.
lic
• Fate of the OH proton: On the basis of the above argument, the protons of the CH2 - group should
C
split the PMR signal of the OH- group proton into a triplet one. Similarly, the OH proton should split
the four PMR signals of the CH2 group into eight components. However, these predictions are not
reflected in the PMR spectrum of ethanol (Fig. 12.2.8.3b). Rather, for the OH group proton (which is
shielded minimum, cf local diamagnetic effect and electronegativity effect of oxygen), one unsplit
PMR signal appears and the PMR signal of the CH 2 group is a quartet one (i.e. splitting by the CH3
protons but no splitting effect by the OH group proton).
The observations can be explained by considering the rapid exchange of the OH proton among the
different ethanol molecules in presence of a trace amount of protonic acid which efficiently catalyses
the exchange process. This proton exchange process is much faster than the NMR transition. Due
to this rapid proton exchange among the different molecules, within a very short time interval, a number
of protons with an equal probability of the both spin states (m[ =±~) may occupy the O-site of a
particular ethanol molecule. Thus only a time average effect of the two spin states of the proton is
(Low resolution)
(Sample experiencing the
rapid OH proton exchange)
CH 3
(8 ~ 1.2 ppm)
(High resolution)
(Sample experiencing the
ry
i rapid OH proton exchange)
ra
ib
----+ Magnetic field strength (H o)
yl
Fig. 12.2.8.3 (b) PMR spectrum of CH3CH20H.
em
observed by the methylene protons and the statistical average magnetic effect is zero (i.e. I appears
ch
as 0).' This is why, the PMR signal of the CH 2 group does not experience any splitting by the OH proton.
The PMR signal of the OH group is a singlet one because each hydroxyl proton spends some time on
al
a large number of ethanol molecules within the NMR transition time and it observes an average effect
e
of the methylene proton nuclear spins of all these molecules and this average effect is statistically
th
zero. In other words, the time spent by a proton in a particular ethanol molecule is too short to allow
e/
the spin-spin interaction with the neighbouring CH2-protons. This is why, the PMR signal of the OH
t.m
proton is not split by the CH 2-protons.
Effect of rapid proton exchange among the CH aCH 20H molecules

e
• The CH2-protons in a particular molecule experience the average magnetic effect of the nuclear
er
spins of a large number of hydroxyl protons on the O-atom. This time average magnetic effect
H
is statistically zero.
k
• The each OH-proton experiences an average magnetic effect of the CH 2 proton nuclear spins
lic
of a large number of molecules. This average effect is statistically zero.

C
• As the exchange rate increases, the fine structure components of a peak (under the condition
of no exchange) gradually collapse to give a broad band and then sharpens to a single line
(cf Sec. 12.2.15) for the neucleus experiencing the exchange.
• CH30H: Similarly, for CH30H due to the rapid OH group proton exchange process, the CH3
protons give a singlet peak and the OH proton also yield a singlet PMR signal, i.e. the PMR signal of
the CH3 protons is not split by the OH proton and PMR signal of the OH proton is not split by the
CH3- protons (Fig. 12.2.8.4).
• PMR spectrum of methanol in ultrapure condition: In absence of the catalysing species (i.e.
protonic acids or bases), the OH group proton exchange process is prevented and the PMR signal of the
OH group is split into four components by the CH 3-protons. Similarly, the PMR signal of the CH3-group
protons is split into a doublet by the OH proton (cf Fig. 12.2.8.4).
• PMR spectrum of ethanol in ultrapure condition: In the ultrapure sample (having no trace of
acid or base as an impurity to catalyse the proton exchange process among the OH groups), the PMR
signal due to the OH group is split by the CH2 protons into a triplet one and each of the 4 peaks of the
CH2 group protons (splitting done by the CH3 group protons) is split into a doublet (i.e. 4 doublets
giving total 8 lines for the CH2-protons) by the OH group proton.
OH Sample experiencing
rapid OH proton exchange
CH 3 (High resolution)
Ultrapure sample
OH experiencing no OH
proton exchange
ry
i
ra
ib
yl
--+ Magnetic field strength (H o) .
em
Fig. 12.2.8.4 PMR spectrum of CH 30H.
Note: Here it may be noted that the spin-spin coupling interaction is only important between the
ch
adjacent groups (i.e. 3JH,H) and it is practically insignificant for the saturated compounds over more than
al
three bonds (i.e. nJH,H is negligible when n ) 3) (cf. Sec. 12.2.9). Thus there is no mutual splitting effect
e
between the CH3 and OH group protons in ethyl alcohol.

th
I~
e/
I
t.m
H - f - f -O - H 3J » 4J (cf. Sec. 12.2.9)

e
H H
er
~3
J 4
J
H
• PMR spectrum of ethyl alcohol in presence of 0 20: It will lead to C 2HsOD through the rapid
k
exchange process with the solvent D 20.

lic
CH 3CH 20H + D20~CH3CH20D + DOH

C
The deuterium nucleus (I = 1) is NMR active but its NMR frequency is very small (cf. YN(2H) = 41.1
and YNetH) = 267.5; 9.21 MHz for 2H and 60 MHz for IH in a magnetic field of 1.4 T). It occurs so
because the magnetic moment of the deuterium nucleus is much smaller than that of a proton. Conse-
quently, for the operating frequency of 60 MHz, the NMR transition for deuterium will occur at a very
large magnetic field (about 9.0 T). This is whY,for C2H sOD, no peak due to deuterium will be observed
in the magnetic field range applied for scanning the spectrum.
• Deuterium exchange: Basic catalysts are efficient for the phenols and acids while the acidic
catalysts are efficient for the alcohols and amines in the deuterium exchange process.
RCOOH + D20~RCOOD + DOH; ArOH + D20~ArOD + DOH; (Basic catalyst)
RNH 2 + 2D 20 ~ RND 2 + 2DOH; ROH + D 20 ~ ROD + DOH; (Acidic catalyst)

Deuterium exchange leads to the disappearance of the PMR signal of the exchanged proton.
(C) Number of fine components generated in a peak by a group of equivalent nuclei (e.g. A2X2,
A3X2, ••• systems): If an NMR signal due to A is split by nx equivalent X nuclei of the nuclear spin Ix,
then the number of fine components (NA ) is given by:
NA =2nxlx + 1, for I =!,NA =nx + 1 which is described as the (n + 1) rule.
2
The relative intensities of the fine components (caused by the n equivalent nuclei of I =.!.) is
2
obtained from the coefficients of the terms that appear from the binomial expansion of (r + l)x-I where
x = number of fine components in the split peak, r = an undefined variable. For illustration, let us take
a triplet.peak where x = 3, the expansion is: (r + 1)2 = r2 + 2r + 1, i.e. the intensity ratio is 1 : 2 : 1. For
a quartet peak, x = 4, (r + 1)3 = r3 + 3r2 + 3r + 1, Le. the intensity ratio is 1 : 3 : 3 : 1.
=.!. , the following Pascal's triangle (when n equivalent nuclei of spin
ry
For the n splitting nuclei of I
1 2
ra
2" will split a peak into n + 1 fine components) is helpful to remember the coefficients of the binomial
ib
expansion.
yl
Intensity ratio
em
n =0 (Singlet)
n =1 (Doublet) 1: 1
ch
n =2 2 (Triplet) 1: 2 : 1
al
n =3 3 3 (Quartet) 1: 3 : 3 : 1
n =4
e
4 6 4 (Quintet) 1: 4 : 6 : 4 : 1
th
n =5 5 10 510 (Sextet) 1 : 5 : 10 : 10 : 5 : 1
e/
Note: Sum of any two adjacent elements in Pascal's triangle in a row = the element between them
t.m
in the row just below (cf triangle constituted by 6, 4 and 10 or 2, 1 and 3).
Relative intensities of the said (n + 1) hyperflne lines can also be obtained from:
n n!
e
em = m! (n-m.), where m = 0, 1,2, ... , n

er
For example, n = 4 (say), relative intensities of the five lines are as 4C O : 4C 1 : 4C 2 : 4C 3 : 4C4 = 1 :
H
4 : 6 : 4 : 1. This intensity ratio for the splitting nuclei of I =.!..2 can also obtained by con~tructing a
k
lic
family free (see Scheme 12.3.5.1 and Table 12.3.5.2)

C
(D) AxMXy system: The NMR signal of M is split by both xA and yX nuclei. In such cases, the number
of fine components in the NMR signal of M is given by:
NM = (2xIA + 1)(2ylx + 1), IA and Ix are the spin numbers of A and X respectively.
Let us illustrate for AMX 2 having: A(I =~), M(I =~) and X(I =~)
where N M = ( 2 x 1x ~ + 1)(2 x 2 x ~ + 1) = 6.
The different possibilities are discussed below.
(i) JM- X ) JM - A : Two X (I =~) atoms can split the NMR signal of Minto a triplet (2 x 2 x ~ + I)
and A ( I = ~) can split each component of the triplet into a doublet, i. e. a multiplet of 6 fine lines
will be generated. Thus the NMR signal of M will give three doublet peaks for the condition
JM-X ) JM-A where JM-X denotes the coupling constant for the nuclei of M and X and JM-A denotes
the coupling constant for the M and A nuclei.
(ii) JM- A ) JM- X : A can split the NMR signal of M into a doublet and each component of the doublet
is split into a triplet by two X nuclei. It will give a multiplet consisting of two triplet peaks (i.e.
a multiplet of 6 fine components).
(iii) JM- A == JM- X: The M-A and M-X coupling constants are comparable. Then the spectral pattern
will be of an intermediate nature of the above two possibilities.
J M- A 31 P-NMR spectrum
J M- X I I of HPF2
~ ~10II ~~I
ry
(ij
c:: loll (ij
c::
ra
0)
0)
"00 "00
0
0 JM-x) JM-A'
ib
=0 =0
co co Three doublets
cr: cr:
yl
i i t7
em
ch
---+ Ho
- - + Ho
al
(a) Splitting of the NMR peak of (b) Splitting of the NMR peak of
e
M by 2X into a triplet M by both A and X

th
(i) Splitting of the NMR peak of M under the condition, J M- X ) JM-A giving rise to a three doublet peaks, i.e. triple doublets.
e/
t.m
+ - - J M- A ~
(ij
c::
0)
e
~ A
"00
er
0
=0
co
cr:
H
i
k
lic
---+
C
Ho
(a) Splitting of the NMR peak (b) Splitting of the NMR peak
of M by A into a doublet of M by both A and X
(ii) Splitting of the NMR peak of M under the condition, J M- A ) J M- X giving rise to a two triple peaks.
Fig. 12.2.8.5 Nature of the NMR peak of Min AMX 2 system (A:I = 1/2, X: I = 1/2 and M: I = 1/2) depending on the
relative values of JM- A and J M- X
Assuming JA - M ) JA - X ; JA- M ) JM - X , we can have: NMR of A (one pair of triplets), NMR of M (one
pair of triplets), NMR of X (one pair of doublets).
Let us illustrate the 31p_NMR spectrum of HPF2 (I =~ for lH, 19 F and 31 p ). The 31p_NMR signal
will produce a muliplet of (2 x I x ~ + I) ( 2 x 2 x ~ + I), Le. 6 fine components. Depending on the
relative values of Jp - H and Jp - F , the 31p NMR spectrum will show two triplet bands (if Jp - H ) Jp - F ) or
three doublet bands (if Jp - F ) Jp - H ). In reality, Jp - F ) Jp - H (ca. 1500 Hz vs. 250 Hz) and the 31p-NMR
spectrum of HPF2 gives three doublets. HPF2 represents the AMX2 system (cf. Table 12.2.11.1).
(E) NMR spectrum of vinyl fluoride (AMXZ system): Here the three protons are magnetically non-
equivalent in terms of the JHF coupling constants. The first-order 19F-NMR spectrum may be constructed
as shown in Fig. 12.2.8.6.
ry
3JHF (VI'C) ) 3J HF (trans) ) 3J HF (cis)
ra
ib
yl
em
ch
e al
th
e/
t.m
e
er
H
Fig. 12.2.8.6 Schematic representation of the stick diagram of the first-order 19F-NMR spectrum (4 doublets)
of vinyl fluoride.
k
lic
(F) Illustration (Prediction of the number of fine components): Analysis in terms of mainly
C
CHEMICAL EQUIVALENCE of the protons (ignoring their MAGNETIC EQUIVALENCE)

(i) (a) (b) (c) (a) Triplet (n = 2); (b) Multiplet (12 lines, nl = 2, n2 = 3,
H3C-CH 2 -CH 2 - B r assuming Jab '# J bc ); (C) Triplet (n = 2) - downfield resonance
o(ppm): 1.2 1.98 3.47 due to the electron deshielding effect of bromine. Peak area
~ a : b : c = 3 : 2 : 2.
(cf. Sec. 12.2.10; for the magnetic equivalence)
(a) (b) (a)
(ii) H3C-CHBr- CH 3 (a) Doublet (n = 1), (b) Multiplet (7 components, n = 3 + 3)
o (ppm): 1.75 4.3 1.75
(downfield, B = 4.3 ppm, deshielding effect of Br); Peak area
~a:b=6:1
(a) (b)
(iii) (a) Doublet (n = 1), (b) Quartet (n = 3 ) (downfield due to the
H3 C-CHO
anistropic effect of the 1t-electron cloud and electron with-
o(ppm): 2.2 9.8
drawing inductive effect of 0); Peak area ~ a : b = 3 : 1
(iv) (c) (b) At 60 MHz (probably 2nd order effect): (a) Singlet, (b) Multi-
H H
plet (ortho-protons deshielded by the anisotropic effect of the
(c) carbonyl group); (c) Multiplet (assuming two m- and one
H p~ protons equivalent) (ef benzaldehyde at 300 MHz, xix).
Here interpretation is simply given in terms of chemical
similarity/equivalence of the 5 ring protons. The 5 ring protons
8 (ppm): (c) 7.6 (b) 8.1 (a) 2.45 actually respresent the ABB'MM' spin system (Sec. 12.2.11).
(v) (a) Singlet, (b) Singlet (5 aromatic protons are of three types:
2 'J-H, 2 m-H and 1 p-H with respect to the Me-group; but
ry
y these aromatic protons are hardly affected by the Me-group)
ra
(b)
8 (ppm): (b) 7.2 (a) 2.3
ib
yl
(c)
(vi) H (a) Singlet (shifted downfield because of the electronegative
em
(b) (a) O-atom), (b) Multiplet (electron pushing mesomeric effect, 0
H O-CH 3 and p positions are more shielded and relatively upfield),
ch
(c) Multiplet (m-protons relatively downfield) (ef the problem
(C)H
al
H
(b)
of acetophenone and benzaldehyde).
e
8 (ppm): (a) 3.7 (b) 6.85 (c) 7.15

th
e/
(vii) (c) (b) Crude analysis of the ring protons in terms of chemical equiva-
t.m
H H
lence: (a) Singlet; (b) Doublet (split by the neighboring pro-
(a)
ton ortho- to the N0 2 group); (c) Doublet (split by the proton
N
°2 CH 3
e
ortho- to CH 3 group) (downfield, deshielding effect of the

er
(C)H (b) N0 2 group, both electron-withdrawing mesomeric effect and

H
anisotropic effect of the n-bond of the N02 group on the ortho-
H
8 (ppm): (C) 7.4 (b) 6.7 (a) 2.4 hydrogens).

k
Note: In terms of chemical equivalence, the 4 ring protons

lic
show (crudely) two doublets (i.e. 4 lines) in the PMR spectro-

C
scopy. This aspect is discussed later. In terms of magnetic

equivalence, the 4 ring protons actually represent AA'BB'
system (Sec. 12.2.10).
3F (equivalent, C 3 axis), one 19F(I =~) NMR signal is split
by one 31 p (I =~) into a doublet.
The 31P-NMR signal is split into a quartet (n = 3) by 3F.

12 equivalent protons, i.e. one PMR signal which is split into
a triplet by 14N(I= 1) (ef 2 x 1 x 1 + 1).
(x) CI---@-CI 4 aromatic protons are assumed to be equivalent, i.e. one
PMR signal.
(a) In terms of chemical equivalence, the 4 ring protons should
c'jQ(.(b
(b)
give two 2 PMR signals (each split into a double by the

J
other, i.e. two doublets). In reality, the observed complex
(a) multiplet PMR'signal can be explained by considering the
CI
magnetic equivalence of the ring protons representing the
p AA'BB' spin system not the AB spin system.
A
Let us compare the chemical equivalence of the 4 ring
H
protons in the given 0- and p- isomers.
The p-compound should give one PMR signal for the 4
A A
H equivalent ring protons while the o-compound should give
P 2 PMR signals (each split into a doublet by the other, i. e.
ry
two doublets) for the 4 ring protons. In reality, the p-isomer
HA
ra
gives one PMR signal while the o-isomer gives a complex
multiplet PMR signal for the ring protons.
ib
p-isomer: 8 ~ 7.2 ppm (P = CI); 8 = 7.2 ppm (ring protons)
yl
and 2.3 ppm (2 Me protons) for P = Me.
em
Note: Por finer analysis, the magnetic equivalence of the
ring protons is to be considered.
ch
(xi)
F--@-F 4 aromatic hydrogens are not equivalent in terms of
Jet
al
9
p- 1H) coupling constants; it gives a complex multiplet
e
PMR signal.
th
(a) (b) (c)

(xii) NC-CH 2-CH 2-OH: (a) Triplet (n = 2), (b) Triplet (n = 2), (c) Singlet (rapid
e/
exchange of the OH proton)

t.m
(xiii) In terms of magnetic equivalence, the 4 ring

protons actually represent the AA'BB' sys-
e
p tems (to be discussed later) and the PMR

er
A' signal is a complex one. Thus o-dichloroben-

H
H
zene gives a complex PMR spectrum. These

and aspects will be discussed later in Sec. 12.2.10.
k
B B'
lic
B'
H H H Note: H A and H A ' are chemically equivalent.
Similarly, HB and H B' are chemically equiva-
C
a
I
H
A'
lent. Both sides (with respect to the a-plane)
I
~cr of the ring are identical and consequently

(ct. Sec. 12.2.10)
both sides of the ring show the identical
splitting in the PMR spectroscopy. The PMR signal of HA is split into a doublet by H B and similarly
the PMR signal of H B is split into a doublet by H A • It gives two doublets for H A and H B • Similarly, H A'
and H B' give two identical doublets. Thus the 4 ring protons produce (crudely) two doublets (i.e. 4
lines) in the PMR spectra.
Thus considering the same chemical shifts (i.e. chemical equivalence) of H A and H A ' and similarly
the same chemical shifts of H B and H B', we can expect two doublets (i. e. 4 lines) for the 4 ring protons
in the crude PMR spectra. This characteristic 4 line PMR spectrum has been crudely observed in
many cases for the disubstituted para- and ortho- compounds as shown above. However, under high
resolution, they behave as the AA'BB' spin system for the 4 ring protons to produce a complex
spectrum (2nd order effect).
x
M M'
H H
(xiv) It represents the ABB'MM' system for the 5 ring protons
(X = F, Sr, CI)
(to be discussed in Sec. 12.2.10) and it gives a complex
B'
H PMR spectrum. Benzaldehyde, acetophenone, etc. also
belong to this spin system.
(ct. Sec. 12.2.10)
ry
ra
(xv) BrFs and IFs: Two 19F-NMR signals: one doublet (for the 4 basal F
(C4v ' square pyramidal) atoms) and one quintet (for the axial F).
ib
yl
PMR SPECTRA IN TERMS OF CHEMICAL EQUIVALENCE ONLY
em
For the PMR studies, JH,H is not very large·. Consequently, considerating the chemical equivalence
of the protons (ignoring their magnetic equivalence), the PMR spectra can be at least crudely
ch
interpreted in most of the cases.
al
(xvi) o (a) Singlet (attached to the CO group relatively

II
e
(a) (b) (c)

downfield), (b) Quartet (n = 3), (relatively downfield,
th
CH 3- C- CH 2-CH 3
effect of the adjacent CO group), (c) Triplet (n = 2) (rela-
e/
(Methyl ethyl ketone)

tively upfield).
t.m
8 (ppm): (a) 2.12 (b) 2.45 (c) 1.05
(b) (a)
e
(xvii) CI-CH 2-CHCI 2 (a) Triplet for the methine protons (downfield; attached to
er
two Cl-atoms); (b) Doublet

8 (ppm): a (-5.8), b (-4)
H
(xviii) (c) (b) (a)

(a) Triplet; (b) Multiplet: 6 lines (n = 5) (if Jab =J bc ); 12
k
°2N-CH2-CH2-CH3
lines (nl = 3, n2 = 2) (if Jab '* J bc); (C) Triplet (downfield,
lic
8 (ppm): a (-1.0), b (-2.0),

effect of the adjacentN02 group).
C
c (-4.5)
Note: At 60 MHz, H(b) - protons show 6 fine lines, i.e.
splitting by 5 protons, i.e. n =5 (3 H(a) + 2 H(b». It supports,
Jab::::: J bc • In other words, overlapping of some lines of
the 12 lines (splitting by 3H(a) and 2H(c), Jab "# Jbc ) give
the 6 lines.
(xix) Interpretation in terms of chemical equivalence of the 5

ring protons: At 60 MHz (probably 2nd order effect), 2
PMR signals (multiplets) for the ring protons; 2 ortho-
H
b protons (downfield); 2 meta-protons + 1 para-proton
(cf. acetophenone, iv)
(relatively upfield). At 300 MHz, 1st order effect and
8 (ppm): 9.9 (CHO proton), 8.1 (o-protons), n+l rule can explain the findings: He (doublet, splitting
7.5 (m- and p-protons) by Ha); Ha (triplet, splitting by Hb and HC); Hb (triplet,
splitting by two Haprotons); HC (downfield, anisotropic effect of the CHO group); between Ha and Hb,
Hb resonates slightly downfield (resonance effect).
Note: Two chemically equivalent Ha protons are magnetically nonequivalent; similarly two HCprotons
are also magnetically nonequivalent. Actually, the 5 ring protons represent the AA'BB'C system under
high resolution.
12.2.9 Spin-Spin Coupling and Coupling Constant (J)

The degree of coupling interaction (causing splitting of the NMR signal) between the nonequivalent
nuclei is measured by the coupling constant (J) which is expressed in the unit Hertz (Hz).
• Mechanism of Coupling: There are many theoretical models to explain the mechanism of cou-
pling. According to the Dirac Model, the electrons of the intervening bonds carry the spin information
ry
between the interacting nuclei through the interaction between the nuclear spin and electron spin. An
ra
antiparallel arrangement of the nuclear spin and electron spin stabilises the system more than their
parallel arrangement. In this antiparallel arrangement of the electronic and nuclear spins, the electronic
ib
magnetic dipole is opposed to that of its own nucleus. The l3C_1H coupling may be understood as
yl
follows:
em
e e
~ Nuclear spin ~ {Electron spin t+--+-t
ch
'3C 'H
t~ t ~
al
t Antiparallel Antiparallel
e
(Lower energy) (Higher energy) nuclear spins i.e. positive J-value nuclear spins
th
e/
For m/ == +.!.. of l3C, the bonding electron with spin _.!.. will have the highest probability of being
t.m
2 2
found near l3C. Obviously, the other bonding electron of +! spin residing close to IH will direct IH
2
e
_.!.. (i.e.
m/ == _.!.. for IH). Similarly, for m/ == _.!.. of
er
to adopt the nuclear magnetic quantum number

2 2 2
H
l3C, the bonding electrons will direct IH to have m/ == +.!... In this indirect spin-spin interaction, i.e.
2
k
lic
electron coupled spin-spin interaction leading to nucleus-electron-electron-nucleus with the alternate

spins, when the proton spin interacts with the l3C-spin, it 'sees' two different orientations of the l3C-
C
spin. Thus two different nuclear spin states of t3C give two different NMR transitions of tH. In
terms of m/ = ±"21 of IH, similarly two NMR transitions of l3C can be understood.
• Field independent parameter (J): It may be recalled that the direct spin-spin coupling effect as
illustrated in Fig. 12.2.8.1 depends on the orientation of the molecule (A-X) with respect to the field.
Considering all the possible orientations of the molecule (A-X), the statistical average coupling
effect becomes zero, i. e. all the orientations leading A to reinforce the field at X are just balanced by
the other orientations reducing the field at X. The electron coupled indirect mechanism of spin-spin
coupling indicates that it mainly depends on the nature of the intervening bonds between the nuclei but
not on orientation ofthe molecule in the field. This is why, J is independent of the field strength but
the chemical shift, i.e. frequency shift (Av in Hz) from the reference depends on the field strength.
If there are two peaks for the NMR signal then it can happen due to: two nonequivalent nuclei (i.e.
two different chemical shifts) or spin-spin coupling arising from a nearby nonequivalent nucleus with
1
I = "2. If the peak separation increases with the increase of the field strength then it indicates that the
two peaks are for two different nonequivalent nuclei. If the peak separation does not change with the
field strength, then the peaks are due to the spin-spin coupling.
• Sign of J: Dirac's model suggests that if the number of intervening bonds between the interacting
nuclei is odd (e.g. IJ,3J, ... ), then J becomes positive. If the number of intervening bonds is even (e.g.
2J, 4J, ... ), then J becomes negative. There is no difference in the spectral appearance of the fine
components for the negative and positive J-values but with the change of the sign of J, the .individual
lines of a multiplet are only interchanged, i.e. upfield and downfield fine components are inter-
changed.
• Homonuclear couplings: JeH-IH), J( 13C_ 13 C), J( 3I p_3I p), etc.
ry
• Heteronuclear couplings: J( 13C- IH), Je 4N- IH), Je 9F- IH), J(3Ip- IH) etc.
ra
• Magnitude of the coupling constant: The magnitude of J depends on the number and nature of
the intervening bonds and the spatial relations between the interacting nuclei. The value of J decreases
ib
with the increase of distance. Generally, one bond coupling (i.e. IJ) is stronger than two bond coupling
yl
(2J) which in tum is much larger than three bond coupling (3J), i.e. IJ ) 2J ) 3J ).... The coupling beyond
em
the three bond distances is insignificant but such long range couplings may be important in the
unsaturated compounds.
ch
J 13C _ 1H (Hz): 125 ( sp 3_C ) < 170(sp 2-C ) < 250(sp-C)
al
It indicates that the greater s-character in the C-H bond gives the better spin-spin coupling inter-
e
action (cf s-orbital electron has a finite probability at the nucleus while the p, d,forbital electrons have
th
the zero-probability at the nucleus).

e/
Coupling constants (absolute values) of some systems are given below.

t.m
e
er
H
k
lic
3J. =3 - 18 Hz < = 12 - 24 Hz '

C
3 I
CIS ..Jtrans
3 Jao(ortho) = 6 - 10Hz; 4J am (meta) = 2 - 3 Hz; 5J ap (para) =0 - 1 Hz;

5J (para)
with the increase of distance, J-decrease.
Mil = Pd", Pt"; 2Jtrans (31 p_31 P) ) 2J cis (31 p_31 P)

1J195Pt_31p (cis) > 1J195Pt_31p (trans)
Note: Splitting of the PMR signal for the N-H group by 14N(I = 1) is not generally resolved and it
gives a broad signal. The fast quadrupole relaxation (T1is very short) for the system is responsible for
this.
ry
• Karplus relationship: Vicinal coupling constant (3JH,H) depends on the dihedral angle (a) and
ra
it is minimum for the gauche conformation (a =90°) and maximum (3JH H::::: 10-12 Hz) for the eclipsed
ib
conformation (a = 0°) and anti-, i.e. trans- conformation (a = 180°). The variation of 3J with the
yl
dihedral angle (a) is mathematically expressed by Karplus equation. For a = 90°, the two adjacent
em
C-H bonds are orthogonal and at this condition, there is a minimum orbital overlap interaction
between the C-H bonds to carry the spin information. It makes J very small for a = O. For a = 0 (i.e.
parallel orientation of the C-H bonds) and a = 180° (antiparallel orientation of the C-H bonds), the
ch
good overlap interaction makes J larger.
e al
th
rh ~H
e/
12.0
)6{~
t.m
eclipsed H
trans or anti
e
8.0 H~3JHtH (gauche)

er
N $~ ,,2-4Hz
H
~ 6.0
:I: 3
JHtH
(anti)
I
k
C')J ~ 10-12 Hz
lic
4.0
t H
C
2.0
Fig. 12.2.9.1 Approximate variation of 3JH ,H with the dihedral angle ex (Karplus relationship).
• [PtX2(PR3)(PR3']: This square planar complex can have the cis- and trans- isomers.
2J p _ p (trans)2 J p _ p (cis) ; IJ195Pt_31p (Cis)1 J195Pt_31p (trans).

These coupling constants can help us to identify the cis- and trans- isomers.
• RnPFs- n (trigonal bipyramidal): The coupling constant for the equatorial fluorine is higher, i.e.
I J 31 p_19 F (eq) ) 1J 31 p_19 F (ax)·
12.2.10 Magnetically Equivalent and Nonequivalent Nuclei: Magnetic Equivalence

vs. Chemical Equivalence .
• Chemically equivalent nuclei: If the nuclei are related in terms of symmetry operation (plane of
symmetry or axis of symmetry), they are called chemically equivalent. If two centres are chemically
equivalent then substitution of each centre by some other atom will produce the same or enantiomeric
compound (i.e. mirror image). Chemically equivalent centres show the same resonance frequency for
the NMR transition (i.e. same chemical shift) and thus they are isochronous.
• Magnetically equivalent nuclei: If the chemically equivalent nuclei (related through the symme-
try operation) are isochronous (i.e. same chemical shift) and they do not mutually split each other in
the NMR spectra, then the such nuclei are both chemically and magnetically equivalent. Thus for the
magnetically equivalent nuclei, the coupling interactions (measured by the coupling constant 1) with
ry
all other nuclei of the molecule must be the same.
ra
Magnetically equivalent nuclei must satisfy the following two conditions.
(i) Magnetically equivalent nuclei must be isochronous (i.e. same chemical shifts), i.e. they must be
ib
chemically equivalent.
yl
(ii) Magnetically equivalent nuclei must have the same coupling constants (J) with all other nuclei.
em
In other words, the magnetically nuclei do not split each other and they give a single NMR signal.
Thus it maybe mentioned that the chemically equivalent nuclei may not be necessarily magnetically
ch
equivalent but the reverse is true.
al
(A) Chemically equivalent but not magnetically equivalent nuclei: (a) Let us compare 1,1- difluro-
ethene and difluoromethane. In each case the protons as well as the fluorines are chemically
e
th
equivalent.
Presence of C2 and cry containing the C 2 axis make the F-
e/
~ c atoms, i.e. F(a) and F(b) chemically equivalent. Similarly,

t.m
(a)H F(a)( 2
-~C=C:':-::--- H(a) and H(b) are chemically equivalent.

--»
(b)H/ " ' - F(b)
Both 1 H ( I ="21) and 19 F ( I 1) are magnetIcally
= "2 . actIve.
.
e
er
3
J cis = 3J H(a) p(a) '# 3J trans = 3 J H(a) p(b)
H
It implies that F(a) and are magnetically nonequivalent.

k
F(b)
lic
3J H(a) p(b) = 3 Jtrans '# 3 J H(b) p(b) = 3 J cis. It implies that H(a) and H(b) are magnetically nonequivalent.
C
In general, in alkenes, 3J trans is larger than 3J cis.

Presence of cr containing the CH2 or CF2 in CH2F2 suggests
H(a)~ that both hydrogens as well as the fluorines are chemically
2J equivalent. They are also magnetically equivalent
I . d F(b) II
/C" 2
J H(a)p(a) = 2 J H\a)p(b) I.e., F(a)
an
.
are magnetlca y
H(b) F(b) I equivalent; 2 J H(a)F(a) = 2 J H(b)F(a). i.e. jfa) and jfb) are
F(a) magnetically equivalent.
(b) In 2-methylpropene, as in the case of 1, I-difluoroethene, the hydrogens as well as the methyls
are chemically equivalent but not magnetically equivalent.
H" /CH 3
-----.C=C----( C
H/ "CH 3
2
(c) Let us consider the para- and ortho- disubstituted benzene.

P Presence of cr makes ya) andya') chemically equivalent
H(a') and also yb) and H(b') chemically equivalent.
3 J H(a)H(b) "# 5 J H(a')H(b) , i.e. ya) and ya') are not magnetically
equivalent. Thus it represents the for the four ring protons
AA'BB' spin system for the four ring protons.
3 J H(a) H(b) "# 4 J H(b) H(a') i.e. Ha) and Ha') are magnetically non-
ry
equivalent (though chemically equivalent). Similarly, H(b)
ra
and yb') are magnetically nonequivalent though chemically
ib
equivalent (i.e. AA'BB' spin system)
yl
Note: For the disubstituted ortho- and para- compounds
em
having a plane of symmetry, by considering the chemical
equivalence of Ha and Ha'; and chemical equivalence of Hb
ch
and Hb', the 4 ring protons crudely show two doublets in
PMR spectroscopy (see Sec. 12.2.8).
al
r
3
J (a)
(I = ±)
e
F
Presence of cr makes the F-atoms chemically
th
~
H(a) "-'::: H(b) c;
e/
equivalent but they are not magnetically equivalent.

---- ---- -------
t.m
(a' ~ (b') 3 J F(a)H(a) "# 4 J H(a)F(a') , i.e. F(a) and F(a') are magnetically
H H
~ nonequivalent but chemically equivalent. In the same way
e
F(a')
RCa) and HCa') are magnetically nonequivalent but
er
chemically equivalent.
(d) Let us consider, CH3-CH2-X (X = halide, alkyl group) where the three CH 3-protons are chemi-
H
cally equivalent and similarly the two methylene protons are chemically equivalent. Now let us
k
examine the magnetic equivalence of the protons. If the rotation about the C-C bond is con-
lic
sidered to be fast, then all the three methyl protons have the same time averaged magnetic
C
environment. The coupling constants of the protons of the CH2 group for each of the three methyl
J = 5-12 Hz
C
H
9
H
Hd Hd
) J=2~HZ c
HC H H
Hb
x X X
(I) (II) (III)
Fig. 12.2.10.1 Conformations (i.e. 3 rotational isomers) ofCH 3CH2X where the CH 3- protons are labeled as Ha, H b and
He. A particular proton, say Ha is anti to X in one conformation (I) and gauche in the other two conformations (II and
III) ; JH,H(gauche) :::: 2 - 4 Hz; JH,H(anti) :::: 10 - 12 Hz (cf. Karplus Rule, Sec. 12.2.9).
protons become identical only if the three possible structures (I, II, III) undergo rapid
interconversion through the rotation around the carbon-carbon single bond (cf. Fig. 12.2.10.1).
.If the rotation about the C-C single bond is locked by placing a bulky group for X and
lowering the temperature, then the magnetically equivalence will be lost because the coupling
constants will be different for the different dihedral angles (cf. Sec. 12.2.9; J HCHd J HbH d , i.e. *
Hb and He are magnetically nonequivalent in I). .
(e) Cyclohexane: If the interconversion between the two chair forms of cyclohexane is very fast (i. e.
rapid interconversion between the axial and equatorial hydrogens), then one PMR signal is
obtained. If the interconversion rate is slowed down by lowering the temperature or through
substitution then two different PMR signals for the nonequivalent axial and equatorial hydrogen
will be observed.
ry
(f) In XCU 2-CU2X, all the 4 protons are chemically equivalent (existence of a symmetry plane
ra
bisecting the C-C bond). If the rotation around the C-C bond is restricted, the protons become
magnetically nonequivalent. When the free rotation around the C-C bond is very fast (compared
ib
to the NMR time scale), each proton experiences an identical time averaged magnetic environment.
yl
The magnetically nonequivalence of the protons is evident from the coupling constants in a
em
particular locked conformation (Fig. 12.2.10.2) ch
eal
th
; JH,H (gauche) :I:- JH,H (anti)

e/
t.m
(I) (II) (III)

e
er
Fig. 12.2.10.2 Interconversion among the three rotational isomers of XCH 2-CH 2X through the C-C bond rotation.
H
x'" /X
k
(g) Similarly, it can be shown that in Y - C - C -Us, the two protons Ha and Hb are magnetically
lic
z/ "'H b
C
Cl
/
nonequivalent. This is why, in H 3 C - CHC1- C-H a , the protons Ha and Hb are magnetically
. 1ent. " Hb
nonequlva
(B) Chemically equivalent nuclei (related through the symmetry operation and same chemical
shift): For the PMR studies, specially where JH, H constant is not very large, the chemically equivalent
protons generally give one signal (which may be split by the other nuclei). However, under high
resolution, the magnetically nonequivalence (if it exists) may be noted. Chemically equivalent nuclei
in different compounds are illustrated in the following examples.
(i) CU 3-X (C3v ): All the three Me-protons are related by the C 3-symmetry operation and
0- symmetry operation. Thus the Me-protons are chemically equivalent. Assuming the free rotation
about the C-X bond, i.e. C3- axis, all the three Me-protons experience the identical time average
magnetic environment. Thus the three Me-protons are also magnetically equivalent and they give
one PMR signal.
(ii) Examples of chemically equivalent protons are given below:
CI
H3 C", '0-
I
- - - - - - - - 0- - - -. C===0 - -~ . Br-CH 2 -:-CH 2 --Br

I
I
HC/
3
CI (6 protons chemically (4 protons chemically (12 protons chemically

equivalent, one PMR equivalent, one PMR equivalent, one PMR
4 ring protons chemically
signal) assuming rapid signal)
ry
equivalent; one PMR signal signal)
rotation around the
8 = 7.2 ppm.
ra
C-C bond
ib
yl
o
em
(b)
H02C", \
\
/H
ch (a)
II
C
C=rC
H(a) ~\ (a)H / i\ H(al
~(bl
al
(a) / '" (b)
H C0 2H
C2
e
CH~b) (b)H C : CH 3
th
3
(i centre of symmetry) 10-
Two types of protons, H(a)and H(b); 1
e/
two PMR signals (6:4 intensity ratio); Two types of protons, H(a) and H(b), Two types of protons, (H(a) and H(b)).
8 = 7.2 ppm (ring protons), 2.3 ppm two PMR signals. two PMR signals, peak
t.m
(Me-protons). area ratio 6:2
(a) (b) (a) (a) (b) (c) (a) (b) (c)

e
CH 3 - CHX- CH 3 CH-CH
3 2 -OH , CH 3 - CH 2 - CHO
er
Two types of protons (~ ~) ~)

H
and 2 PMR signals CH 3 - - CH 2 --CH 2 - - X

~'- ""'" _-------J
k
V
lic
In each case, 3 types of protons ann

3 PMR signals.
C
(iii) Two vinylic protons are not equivalent: H(b) (cis- CH 3 , trans-
X), H(c) (cis- X, trans- CH 3). Three types of protons and 3 PMR
signals.
It may be noted that the substitution of the vinylic protons by A produces a pair of diastereomeric
products, i.e. vinylic protons are diastereomeric protons (not enantiomeric protons).
(iv) Two BHB bridges lying in a plane perpendicular to the plane of

the B-H terminal bonds. Two types of protons and two PMR
signals (decoupled from lIB).
Quadrupole nuclei Nand CI do not couple with the methyl
protons. Two equivalent II B (I =%) nuclei split the PMR

signal of the Me-protons (cf. Me groups are equivalent) into
7 components.
(v) C2 In the trans-isomer, the two PR3 groups are

Br- - - - - - - - -- - - PR R P------------Br
,tJ related through the C 2-axis (CI-Pt-Br) and
:~/:3 3:~/: cry (containing the C 2 axis and perpendicular
ry
to the molecular plane). Thus these two
:/Pt : :/Pt :
1 ",.
1 "I chemically equivalent PR3 groups give one
ra
1 '" 1
Cl-----------PR3
1 ,,'
CI -----------PR3 31p_NMR signal which can ·be split into a
ib
,,'
(cis-) (trans-) doublet through the 1 J 195 pt _31 p coupling
yl
1
(cf. 1=- for 195Pt).
em
2
In the cis-isomer, the two PR3 groups are not related through the symmetry element like en or cr and
ch
thus these two PR3 groups are not equivalent and they produce two different 31p NMR signals. Each
al
signal is split by both 195pt and the other nonequivalent 31p nucleus producing a double quartet.
e
The difference in the coupling constants can also distinguish the isomers,
th
1 J195Pt_31p (cis) > IJ195Pt_31p (trans)

e/
(;C
t.m
2
(vi) In each case, the two 2PR3 groups are
R P------------X R P------------X' equivalent, i.e. one 31p-NMR signal which
3:~/: 3:~/: will be split by 195pt. The two chemically
e
----:----- Pt-----f ~ :/Pt : equivalent PR 3 groups are not always

er
:/~: C 2 1
1
'"
,,'
1
magnetically equivalent and the 31p-NMR
x------------PR3
H
R P------------X
3 ,,' signals may be split.
(cis-) , (trans-)
k
lic
C2v D2h
C
The difference in the coupling constants, IJ pt _ p (cis) ) IJ pt _ p (trans) and 2J 31 p _31 p (trans»>
2 J 31 p_ 31 p (cis) can distinguish the cis- and trans- isomers (cf. the problem of [PdCI 2(PR3)2], Sec.
12.2.19).
(vii) All the F-atoms in each of the following molecules are equivalent, i.e. one 19F-NMR signal in
each case.,
(4F related
F-Be-F
by C 4 )
(3F related by C3 axis)

v v
(C 3v), 3F related by C3 axis
one quartet (strong signal) for Il BFi ;

BF- } one weak septet (weak signal) for 10 BFi
ry
19 F - NMR:pectrum
%}
ra
(see Fig. 12.2.19.8); llB(80%, 1= IOB(20%, 1=3)
ib
F
yl
..\c=ot-
em
/ C
F (C ) 2
2v
ch
(viii) Two types of F atoms, i.e. two 19F-NMR signals in each of the following two cases.
al
F
.
F
~~re4d~a~~~~_atoms) !~i7i
e
F........ ~/
th
.. F"
AFs : "
,"""/A~F
e/
• "" I \ One triplet (for 5

One quintet : / "" •. (A = Sr, I) : (A = I, Re) basal F-atoms)
t.m
11
(for 1 axial F-atom) / "" : /" :\ ', One sextet (for 2

F------------F F ... ...... .: ' " axial F-atoms)
4 basal F + ......:... F'
e
1 axial F 5 basal F + 2 axial F

F
er
(A4X spin system) A SX2 spin system

H
k
lic
: Two types of P; two 31P-NMR signals.

C
(ix) One signal doublet (split by 1 P)

3 equivalent and other signal quartet (split by 3P)
P-centres
CI
F N-=P-CI
I(b)
"'.(aV
P '" N
/ ~ (b~
F N--P-CI
(x) I
CI AB 2X2 spin system
(complex NMR spectra)
Two types of P-centres; X2 denotes for the P-atoms.
the two equivalent F-centres.
CI CI
(a) I
CI-P===N-P-NHCsH s
I (b)
I
N
I
N
p 4N4Cls(NHCsHS)2
(xi)
CI-P-N===P-CI
II <b) (a) I
I
NHCsH s CI
I A.;x2 spin system
Two types of P centres:
ry
Two triplet 31 P-NMR signals, each signal
ra
is split by two other equivalent 31 P centres.
ib
12.2.11 Designation (i.e. Nomenclature) of Nuclei Spin System
yl
em
(i) Each different nucleus is designated by a capital letter, A, B, C, ...
(ii) If the nuclei are chemically and magnetically equivalent, their number is designated as A2 , B2 ,
ch
B3 , etc.
(iii) If the chemical shift of a nucleus is well separated from that of A or B, then it is denoted by
al
a letter like X, Y or Z far away from A, B in the alphabet. It is illustrated for -CH2-CH2- .
e
th
~v ~ 10) ~v ::; 10)' I1v = chemical shift difference

e/
-CHz-CHz-: AzXz (When and AzB z (

t.m
(in Hz) for the protons of the two methylene groups; J (in Hz) = coupling constant between the
protons of the two methylene groups. The ethyl group (CH3 CH2) in ethyl acetate or ethyl alcohol
e
is designated by AY¥2 because the chemical shifts of the protons of the CH 3 and CH 2 groups differ
er
significantly (i.e. ~v ~ 10
condition is satisfied). When the ethyl group is at the end of a long
H
J
aliphatic chain, it is designated as A~2 because the chemical shifts of the protons of the CH 3 and
k
lic
CH 2 groups differ only marginally.

(iv) For the AMX system (i.e. M belonging to the middle portion of the alphabet), the chemical shift
C
of M is in an intermediate range of the chemical shifts of A and X whose chemical shifts differ
sufficiently. Thus, the chemical shifts of A, M and X are widely separated.
(v) The primed symbols are used to denote the nuclei which are chemically equivalent (i.e. same
chemical shift) but magnetically nonequivalent. Thus A and A' denote the same nuclei which are
chemically equivalent but magnetically nonequivalent.
(vi) The NMR spectra ofAX,A~z,AMX, etc. systems are of 1"1 order type (i.e., ~v ~ 10) and they
can be easily interpreted but the NMR spectra of AB, A 2B 2 , A 3B 2 , etc. systems are of 2nd order
type (i.e., ~v is small) and it is difficult to interpret the 2nd order spectra. By using the higher
probe frequency, the ~v (chemical shift difference in Hz) can be increased and the AB system
may be converted into the AX system.
Illustrations of different nuclear spin systems (cf. Sec. 12.2.10)

CH4 : A4 ; C6H6 : A6; CI 2HC-CHC12 : A 2 ; CI2HC-CHO: AX; CI 3C-CH3: A 3 ; H-F: AX; HPFCI 2 :
AMX eH, 31p, 19F); CIF3 (T-shaped): AB2 (two types of 19F); CICH2CH20H: A2B2X (X for the OH
proton); CH3CH2CI: A3X2 for the ethyl group;
(a)H (a)
'" /F
. - - - C===C- - _. cr AA'XX'
(a'H / '" F (a')
ry
(One type of F
and one type of H) H(a) and H(a) : Chemically equivalent
ra
but not magnetically. F(a) and F(a')
chemically equivalent but not
ib
magnetically equivalent.
yl
em
o 0 0 0
I I I I
ch
-O-P-O-P-O-P-O-P-O- A 2 B 2 (Two terminal 31 P-centres equivalent;
I I I I two middle P-centres equivalent).

al
-0 0 0-- 0
e
th
e/
t.m
I
I
P
e
(a')H
er
AA'BB'
H
(ring protons)
(b')H
k
lic
Q
I
I
C
I
·cr
p
cr
AA'BB'
(b')H
(ring protons)
P
H(a')
Note: For the disubstituted ortho- and para-compounds, the PMR signals for the four ring protons
crudely show 4 lines (i.e. two doublets) (ef Sec. 12.2.8).
Table 12.2.11.1 Spin-spin splitting pattern in the NMR signals (1st order spectra) in different spin systems
(taking I =!. for all the NMR active nuclei) (application of n + 1 rule).
2
(i) Spin system NMR signal of A

A singlet
A2 singlet
A3 singlet
An singlet
(ii) Spin system NMR signal of A NMR signal of X
AX One doublet (1 : 1) One doublet (1 : 1)
ry
AX 2 One triplet (1 : 2 : 1) One doublet (1 : 1)
ra
AX 3 One quartet (1 : 3 : 3 : 1) One doublet (1 : 1)
AX4 One quintet (1 : 4 : 6 : 4 : 1) One doublet (1 : 1)
ib
AXn One multiplet (n + 1 fine lines) One doublet (1 : 1)
yl
A 2X 2 One triplet (1 : 2 : 1) One triplet (1 : 2 : 1)
em
A 2X 3 One quartet (1 : 3 : 3 : 1) One triplet (1 : 2 : 1)
ArnXn One multiplet (n + 1 fine lines) One multiplet (m + 1 fine lines)
ch
(iii) Spin system NMR signal of A NMR signal of M NMR signal of X
al
AMX )(Say,JA_M) One pair of doublets One pair of doublets One pair of doublets
e
th
AMX 2 JA-X; JA-M ) One pair of triplets One pair of triplets One pair of doublets
e/
AMX 3 J M-X) One pair of quartets One pair of quartets One pair of doublets
t.m
Note: For the A",Bn spin systems, the chemical shift difference (8A ...., 8B ) and the spin coupling
constant (JAB) are comparable in magnitude and it gives the complicated 2nd order spectrum which
e
=~).
er
does not follow the simple splitting rule, i.e. n + I rule (When I
H
k
NMR signal NMR signal

lic
of A of X
C

of A
IJAXI =IJXAI :1 X I
/)\0\\
t 1:"~"':r~O O :OI
~
// "" """"
/
" ///
~
/
r; J
XA
:1 J AX XA
(Doublet) (Doublet) (Triplet) (DOUblet)
(a) NMR signal of (b) NMR signal of

an AX system. an AX2 system.
(Contd... )
(Contd... )
NMR signal NMR signal NMR signal

of X ofM of A
)
... ....., )..\
iJMXi 1 rJAX
J~ f\ f~J~ JMJAM AMX
ry
spin system
ra
t
ib
t A pair of tAPairOf A pair of
yl
doublets doublets doublets
em
NMR signal NMR signal NMR signal
of X ofM of A
ch
~
e al
th
e/
t.m
(Vinyl acetate) (Vinyl fluoride)

e
4 doublets (see Fig. 12.2.8.6)

(c) PMR spectrum of Vinyl acetate (an AMX spin system)
er
(d) 19 F_NMR spectrum of vinyl fluoride (an

(IJMXI =IJXMI; IJAXI =IJXAI; IJMAI =IJAMI, IJMXI > IJAXI > IJAMI) AMXZ system)
H
Fig. 12.2.11.1 Illustration of the (n + 1) rule by using the splitting tree for 1st order splitting of NMR signals in some
k
representative spin systems (I = 1/2 for all nuclei).

lic
C
12.2.12 First Order and Second order NMR Spectra: Advantage of the NMR Spectrometer
Operating at Higher Frequency (e.g. 60 MHz vs 100 or 300 MHz)
(A) 1st order NMR spectra (as in AX system): It occurs when the chemical shift difference ~v (in Hz)
(i.e. frequency shift difference) between the interacting nuclei is greater than the coupling constant (J)
(i.e., ~v ~ 10) and each nucleus ~f one group must interact equally with each and every nucleus of the
second group.
For the first order splitting, multiplicity of a signal arising from the spin-spin coupling interaction
from a group of n-equivalent nuclei (i.e. splitting by n-equivalent nuclei) of nuclear spin I is given by
2nI + 1 (n = number of splitting nucleus). For I = !, it is given by n + 1, i.e. multiplicity of a signal

2
is given by n + 1 (called n + 1 rule). The intensity ratio of the fine lines in the multiplet is given by the
coefficients of the binomial expression of (1 + r)n-l or by the use of Pascal's triangle (cf. Sec 12.2.8).
Separation between the adjacent fine lines gives the measure of the coupling constant (1) which does
not depend on the field strength.
(B) 2nd order NMR spectra (as in AB system): yWhen the frequency shift difference (~v in Hz)
between the interacting nuclei is comparable to the spin coupling constant (1), the condition of 1st order
splitting is not satisfied and it gives the complicated 2nd order NMR spectra which do not follow the
(2nl + 1) rule. Thus the second order NMR spectra occur when the interacting nuclei possess the
nearly same chemical shifts (but not exactly identical).
=1J= -=LL
ry
CI 2 CH CH 3
ra
~ r-"--l
ib
yl
~v ....
., ~v
...
Jl'"
em
---+
ch
~v ~
~ Ho ~ Ho ~ Ho
al
(2nd order splitting, (1 st order splitting, (for CI 2CH-CH 3 )
~v/J small) ~v/J large)
(1 st order spectra)
e
th
Fig. 12.2.12.1 Qualitative illustration of the conditions for 1st order and 2nd order NMR spectra.
e/
(C) Frequency shift difference (Av), i.e. chemical shift difference (Av in Hz) vs. coupling con-
t.m
stant (J in Hz): It may recalled that the Larmor frequency (v L or (OL) depends on the applied field (Ho)
as v L or (OL oc H o and the energy difference between the states in which the NMR transition occurs also
increases with the field strength (i.e. liE oc Ho). Thus the frequency shift difference, i.e. chemical shift
e
er
difference in Hz depends on the magnetic field strength, i.e. Av (in Hz) for the two interacting nuclei
becomes larger at the higher applied field but the coupling constant (J) which depends on the
H
structural feature or geometrical feature of the two interacting nuclei is independent of the field
k
strength. Thus at the higher field (i.e. higher operating frequency), it becomes easier to analyse the
lic
NMR spectra. In fact, in many cases, the applied higher field converts the 2nd order spectra into the
C
simple 1st order spectra.

a
(D) Av (in Hz) field dependent but (in ppm) and J field independent: Here it is to be mentioned
that by definition, B (in ppm unit) is not dependent on the field strength.
0= Hsample - B ref x 106 = V sample - V ref X 106 : : : V sample - V ref X 106

H ref V ref V operating
(E) Illustration of 60 MHz vs. 100 MHz operating frequency in PMR spectroscopy: If the
operating frequency is increased from 60 MHz to 100 MHz, then the NMR transition will require a
higher field. For example, for 60 MHz, proton can resonate at the applied field 1.41 T while the proton
will resonate at the applied field 2.35 T for the 100 MHz operating frequency. Thus for the proton, the
frequency shift (in Hz) from TMS is "35 ( = 100MHz 2.35 TJ

60 MHz = 1.41 T times larger for the 100 MHz operating
frequency than that for the 60 MHz operating frequency. The field independent parameter (0 in ppm)
remains unchanged. For 60 MHz, if the frequency shift from the TMS is x Hz (say) for a particular PMR
5x
signal, then the shift from TMS is 3 Hz for 100 MHz.
o= shift (in Hz) from TMS x 106 = ~ = 5x/3 =..!-

Operating frequency (in Hz) 60 100 60
ry
ra
ib
t
yl
TMS
60 MHz
em
spectometer
--------+~ Ho
ch
110 Hz
e al
th
CH 2
~
e/
~
eli
t.m
100 MHz c:
0)
spectometer "00
o
~v = 120 Hz :0
e
ctS
cr:
er
t
H
...--- -1
300 Hz
- - - - - - - + . Ho
I
k
180 Hz
lic
Fig. 12.2.12.2 PMR spectra of CH 3CH 2I at 100 MHz and 60 MHz operating frequencies.
C
For CH3-CH2-I (3JH,H = 7.5 Hz), frequency shifts from TMS are: 110 Hz (for CH 3 protons) and 180
Hz (for CH 2 protons) for the 60 MHz operating frequency. These frequency shifts are 180 Hz
( '" 110 x 5 HZ) and 300 Hz ('" 180 x 5 HZ) respectively for the 100 MHz operating frequency.
3 3
• For 60 MHz spectrometer: 11v = (180 - 110) Hz = 70 Hz; B = V sample -- V TMS X 10 6 ppm
V operating
6
110 X 106 180 X 10
B(CH 3 )= 6 ~1.80ppm; B(CH 2 )= 6 =3 ppm.
60x10 60x10
• For 100 MHz spectrometer: I1V = (300 - 180) = 120 Hz;
180 X 106 300 X 106

B(CH 3 ) ~ 6 = 1.8 ppm; and B(CH 2 ) ~ 6 = 3 ppm.
100x10 100x10
Thus in changing the operating frequency 60 MHz to 100 MHz, for CH 3CH2I, liv for the CH3-
and CH2 protons increases from 70 Hz to 120 Hz but the chemical shifts (8 in ppm) and coupling
constant (3JH,H = 7.5 Hz) remain unchanged.
Thus for the better resolution of the NMR spectra, and to convert the complex 2nd order NMR
spectra into the simple 1st order spectra (e.g. A2B2 system to A2X 2 system), the NMR spectrometers of
higher operating frequency (e.g. 300 MHz, 400 MHz) are preferred though these are costly.
(F) Intensity factor: Higher operating frequency needs the higher applied field and it makes the
energy difference more between the states in which the NMR transition occurs. It enhances the Boltzmann
population density at the ground state (cf. Sec. 12.2.2) and consequently the intensity of the signal is
also increased. This is an added advantage for the higher operating frequency.
(G) CIF3 (T-shaped) (10 MHz vs. 60 MHz): There are two types 19F centres (2 equatorial + 1 axial
ry
in terms of the TBP geometry) and their chemical shifts do not differ significantly. In fact, at the low
ra
operating frequency (say 10 MHz), it appears as an AB2 system giving a complex NMR spectra (2nd
order spectra) but at a higher operating frequency (say 60 MHz), it appears as an AX2 system (one
ib
doublet peak for the axial F-atom and one triplet peak for the equatorial F-atoms, in 19F-NMR
yl
spectroscopy). Equatorial F resonates at a higher field than axial F (cf. Figs. 12.2.12.3, 12.2.15.4).
(ij
em
ch
c:
.~ (2nd order spectra)
~ 10 MHz
al
(AB 2 type)
co spectrometer
a:
e
th
i
e/
Ho
t.m
----------.~ Fax-CI-Fax
I
Feq
e
er
(1 st order spectra)
60 MHz
H
(AX2 type)
spectrometer
i
k
lic
------.~Ho
C
Fig. 12.2.12.3 19F-NMR spectra of elF3 at 10 MHz and 60 MHz spectrometers.
Note: It may be noted that CIF3 is a stereochemically nonrigid molecule but not a fluxional
molecule (cf. Sec. 10.9.5, Vol. 2). At low temperature (ca. -60°C), 19F-NMR spectroscopy can distinguish
the axial and equatorial F-atoms. The quadrupole CI nucleus cannot split the 19F-NMR signal because
in this environment, the CI nucleus experiences the rapid quadrupole relaxation and the F-atoms
observe the time average magnetic field (which is zero) from the CI nucleus (cf. Sec. 12.2.16).
• BrCH2CH3 (bromoethane) vs. BrCH2CH 2CI (l-bromo-2-chloroethane): The ethyl group
(CH3CH2- ) of CH 3CH2Br behaves as an A3X2 system as in CH 3CH20H (ethyl alcohol) in PMR
spectroscopy (i.e. CH 2 group protons resonate at the relatively lower field than the CH3 group protons
because the CH2 group is directly attached to the electronegative atom). In fact, the chemical shift
difference between the CH 3 and CH2 protons is sufficiently high to meet the condition of 1st order
PMR spectra (i.e. Av> > 3Jo, 0). On the other hand, the -CH2CH2- moiety of BrCH 2CH2CI behaves
as an A2B2 system in PMR spectroscopy (Fig. 12.2.12.4). The similarity in the electronegativities of Br
and Clleads to the chemical similarity of the two methylene group protons. It reduces the chemical
shift difference between these two sets of protons. But these two sets of protons are magnetically
nonequivalent (cf. rotation around the C-C bond and rotational isomerism, Sees. 12.2.10, 12.2.20).
For these two methylene group protons, due to the decreased difference of chemical shift, the condition
of 2nd order PMR spectra (i.e. Av == 3JH, H) is attained and the -CH2CH2- moiety behaves as an
AzBz system in PMR spectroscopy.
ry
ra
ib
yl
em
~
~ Chemically almost
ch
i BrCH 2CH 2CI
~
similar but magnetically
nonequivalent
al
A 2B 2-system (~v ~ JH,H)

e
2nd order spectra

th
e/
t.m
Fig. 12.2.12.4 Qualitative representation of the PMR spectra (high resolution) of bromoethane and I-bromo-
2-chloroethane.
e
er
12.2.13 Chemical Shift Reagents

H
In some cases, the PMR signals of the organic compounds overlap and they cannot be resolved. The
k
situation can be simplified by using the higher frequency (e.g. 300 MHz, 400 MHz, etc.) NMR
lic
spectrometer but such instruments are costly. Sometimes, change of solvent (which can interact with
the sample through the H-bonding to change the position of the PMR signals) may help to simplify the
C
spectra. The use of solvents like benzene instead of CCl4 or CDCl 3 can change the position of the PMR
signals by imposing the anisotropic effect on the surrounding moieties of the sample. However, the use
of chemical shift reagents can change the positions of the PMR signals (without any peak broadening)
and it is an inexpensive technique to resolve the overlapping signals.
CMe3
CF CF
o ...<F2 2 3
o~ Eu I CH
Eu CH
o~
I
o~ CMe3
CMe3
[Eu(dpmbl [Eu(fodbl
tris-( dipivaloylmethanato)europium(lll) tris-(6, .6, 7, 7, 8, 8, 8-heptafluoro-2, 2,

dimethyl-3, 5-octanedionato)europium(lll)
The well known chemical shift reagents are the paramagnetic complexes of Ln 3+. The p-diketonate
complexes of Eu(lll) and Pr(lll) (praseodymium(III)) e.g. [Eu(dpm)3]' [Eu(fod)3]' [Pr(fod)3]' etc. are
commonly used as the shift reagents.
The Lewis basic sites (:B) e.g. )C=O, -OH, -NH 2 , -SH, -COOR, - 0 - , etc. of the
sample may interact with the Ln 3+ (which can increase the coordination number upto 8). Thus the
Ln(lll) complex is incorporated with the sample through the acid-base adduct.
2B: + [Eu(L - L)3] ~ [Eu(B)2(L - L)3]
Incorporation of the highly paramagnetic lanthanide complex (which may be considered as the
powerful little bar magnets) stretches the spectrum to separate the overlapping signals. The mag-
netic field experienced by the lanthanide bound sample is different than that experienced by the free sample
ry
(i.e. unbound sample) because the Ln(III)-bound sample remains also under the influence of the magnetic
ra
field due to the unpaired electrons ofthe lanthanide ion. It causes the shift of the resonance frequency. The
ib
shift direction depends on the nature of the lanthanide ion e.g. downfield shift for Eu(ill) and upfield shift
for Pr(III). The effect (i.e. change in resonance position) decreases inversely with the distance measured
yl
from the site of incorporation of the paramagnetic lanthanide complex. The effect also depends on the
em
ratio of the molar concentrations of the sample and shift reagent. This is why, in reporting the lanthanide
shifted spectrum, the molar concentrations of the sample and shift reagent must be mentioned.
ch
Complicated PMR spectrum of cholesterol is dramatically simplified in presence of the Eu(III)-
al
complex as an NMR shift reagent. It is illustrated for I-hexanol (Fig. 12.2.13.1). In absence of any shift
e
reagent, it gives a complex PMR spectra due to the overlapping of the signals and second order effect.
th
Only the signals of the terminal methyl group and the methylene group directly attached to the OH group
e/
are resolved. The PMR signals ofthe remaining methylene groups remain unresolved. However, in presence
of the shift reagent, [Eu(dpm)3]' the PMR spectrum is simplified and each set ofthe equivalent protons can
t.m
be identified by their own characteristic PMR signals (Fig. 12.2.13.1). The different methylene group
protons show the different multiplets which can be interpreted in terms of (n +1) rule (i.e. first order
e
spectra). Eu(III) interacts with I-hexanol through the OH group and the effect on the chemical shifts (i.e.
er
change in resonance positions) of the methyene protons gradually decreases away from the OH group.
H
Increasing distance from the binding site of Eu(llI)

•
k
Decreasing effect on the PMR signal positions A TMS

lic
FED C B A
C
HQ-CH2-CH2-CH2-CH2-CH2-CH3
(In presence of E D
[Eu(dpm)3l
TMS
(Without any shift reagent)
- - - - - - - - - . . Ho
Fig. 12.2.13.1 Qualitative representation of the 100 MHz PMR spectra of 1- hexanol in CDCl 3 in presence of the NMR
shift reagent [Eu(dpmhl (molar ratio of the shift reagent and 1-hexanol :::: 0.8) and in absence of the shift reagent (cf.
J.K.M. Sanders et al. Chern. Commun., 442" 1970; B.C. Mayo, Chern. Soc. Rev., 2, 49, 1973).
12.2.14 Nuclear Magnetic Double Resonance (NMDR) and Spin Decoupling - A Way to
Simplify the Complex NMR Spectra: Noise Decoupling and Nuclear Overhauser
Effect (NOE)
If the spin-spin coupling is destroyed then the NMR spectra become simplified. For CH 30H and
CH 3CH 20H, it has been found that due to the rapid proton exchange among the alcohols, the coupling
between the OH proton and the adjacent CH 3 or CH2 group protons vanishes due to the kinetic reasons.
Thus the neighbour CH3 or CH2 proton groups are decoupled from the OH group proton due the rapid
exchange (a kinetic reason) of the OH proton among the different alcohol molecules (cf Sec.
12.2.8, Figs. 12.2.8.3-4).
The above decoupling process can be deliberately carried out by using a second strong (i.e. high
intensity) radiofrequency (rj) radiation (i.e. decoupling irradiation). The frequency of this second
ry
rfradiation is adjusted to match with the resonance frequency (at the same field) qf a selected group of
ra
nuclei (e.g. protons) that are intended to be decoupled. This irradiation by the second rffield causes
ib
the selected group of nuclei to undergo rapid transitions among their possible nuclear spin states.
Consequently, the observing nuclei (whose NMR signal is to be split by the selected group of nuclei)
yl
experience only the time averaged nuclear spin states (which is zero) of the selected nuclei irradiated
em
by the second rf field. Thus this selected group of nuclei is effectively decoupled from the observing
nuclei and the NMR signals of the observing nuclei are not split by the selected group of nuclei
ch
irradiated by the second rf field. This decoupling technique is described as the double resonance
because the sample is irradiated by two rfs - observing rf and decoupling if.
e al
th
Rapid exchange reaction: Leading to the rapid exchange of the nuclei and decoupling.
Decoupling rf field: Leading to the rapid exchange of the nuclear spin through the rapid transi-
e/
tions among the possible nuclear spin states rather than the exchange of nuclei.
t.m
(A) (X)
e
er
(i)
H
k
lic
(A)
A
C
(ii)
- - " ' " --~-------

(X)
(iii)
(a) NMR spectrum of AX (I = 1/2 for both nuclei). (i) The normal spectrum, i.e. doublet peaks for both A and X; (ii) The
effect of decoupling if field of v x, i.e. X is decoupled; (iii) The effect of decoupling if field of VA.
a ~ y
Br~H7H~~
(Splitting by 5
protons (a-CH 2 (Splitting by two
~-CH2 protons)
+ y-CH 3)
(i) (Splitting by
~-CH2 protons)
ry
ra
ib
(ii)
yl
em
------------------.~ He
(b) NMR spectrum of BrCH 2CH2CH3• (i) The normal spectrum, assuming the splitting of the PMR signal of ~H2
ch
protons by 5(= 2 + 3) equivalent protons. (ii) The effect of decoupling if field of the resonance frequency of the
~protons, i.e. ~H2 protons are decoupled.
e al
Fig. 12.2.14.1 Illustration of decoupling technique.

th
e/
PMR spectrum
t.m
of B2He
e
1
er
H
k
---.~ He
lic
(a)
C
B-Ht
(ij
~
c:
C) PMR spectrum of B2 H6
·00 11
o (decoupled from 2 B)
is
as
a:
1
---+ He
(b)
Fig. 12.2.14.2 Qualitative PMR spectra of B 2H6 (see Fig. 12.2.19.5). (a) Complex spectrum due to llB_1H coupling
(splitting by the minor lOB isotope has been ignored). (b) IlB-decoupled PMR spectrum of B2H6 •
• Let us illustrate for the A-X system (I =.!. for both A and X) which gives two doublet peaks,
2
i.e. the NMR signal ofA is split into a doublet by X and the NMR signal ofX is split by A into a doublet.
Now, the AX sample is simultaneously irradiated by a if field of v A (resonance frequency of A) to
record the NMR signal of A and a strong if field of Vx (resonance frequency of X). The application of
this strong decoupling if field of Vx causes the nucleus X to undergo rapid transitions between its two
spin states (i.e. rapid flip-flops between the two energy states) and A observes the time averaged zero
magnetic effect from X and it is decoupled from A. Thus the spectrometer tuned at v A frequency records
a singlet NMR signal of A instead of a doublet. In the same way, A can be decoupled from X by using
a strong decoupling if field of v A.
Y ~ a .
ry
• Let us illustrate for CH 3 - CH 2 - CH 2 Br: y-H (triplet; splitting effect by 2f3-H), f3-H
ra
(multiplet of 6 fine lines, splitting effect by 3y-H and 2a-H protons), a-H (triplet; splitting effect of
ib
2f3-H). If the f3-CH 2 protons are decoupled by using a decoupling if field at the resonance frequency
yl
of the f3-protons, then the a- and y-protons are decoupled from the f3-protons. It leads to two singlet
em
PMR signals: one for the a-protons and one for the y-protons (no spin-spin splitting effect). It indicates
that the (X- and y-protons remaining at a long distance cannot split their signals (4JH,H is negligible).
ch
• B2H 6 : There are two types of protons (4 terminal protons, i.e. 4B-Ht + 2 bridging protons, i.e.
=~;
al
2B-Hb-B). lIB (I abundance about 82%) splits the PMR signal through the lIB-1Hcoupling.
e
2
th
By using a decoupling lj'field at the resonance frequency of lIB, two PMR signals (4:2 intensity ratio)
are detected. It simplifies the NMR spectra.
e/
By considering the coupling with lIB and weak coupling between the bridging and terminal protons,
t.m
the first-order effect gives: a quartet of triplets for the terminal protons and a septet of quintets for
the bridging protons. The IlB-NMR spectrum gives a triplet of triplets. These are discussed in the
e
example 17 of Sec. 12.2.19 (see Fig. 12.2.19.5).

er
• Proton decoupling in 13C-NMR spectroscopy: The 13C-1H coupling splits the NMR signal of
H
13C and this further weakens the inherent poor intensity of the NMR signal of 13C (cf. peak splitting
spreads out the intensity). Use of a strong decoupling if at the resonance frequency of IH destroys the
k
lic
coupling and simplifies the NMR spectra of 13C. For this purpose, the 13C sample is simultaneously
irradiated by a strong if at the IH resonance frequency (say 100 MHz) and a if at the 13C resonance
C
frequency (25.4 MHz in the same field) to observe the 13C-NMR signal. This noise decoupling con-
verts the multiplet signal into a singlet and the intensity is increased.
Techniques for Simplification of Complex NMR Spectra (e.g. 2nd Order Spectra)
The three techniques for this purpose are practised.
(i) Use of a higher operating frequency (e.g. 400 MHz) spectrometer to cause a higher chemical
shift difference (~v in Hz).
(ii) Use of the NMR shift reagents, i.e. suitable Ln(III) complexes.
(iii) Use of decoupling radiofrequency radiation (double resonance).
Noise decoupling also intensifies the NMR signal due to the Nuclear Overhauser Effect (NOE).
Noise decoupling radiation induces some relaxation processes by perturbing some other nuclei to
favour to maintain the Boltzmann distribution equilibrium rapidly. Thus a higher population density at
the ground level is maintained throughout the experiment (i. e. rapid transition from the excited nuclear
state to the ground nuclear state without any emission of radiation; spin pumping mechanism to
maintain the Boltzmann equilibrium). It intensifies the signal (cf. Sec. 12.2.3).
Note: INDOR (internuclear double resonance) spectroscopy is not discussed here. It is used to indentify
the coupling system.
12.2.15 Effect Chemical Exchange on NMR Spectra and Evaluation of Exchange Rate
Constants (cf. Sec. 10.9.4, Vol. 2)
Proton exchange process: Let us consider the following proton exchange process:
X-H* + Y-H ~ X-H + Y-H*
ry
When the mean life time of the proton on X and Y is much larger than the NMR transition time, i.e.
ra
proton exchange rate is much slower than the NMR transition time, two characteristic PMR signals of
X-H and Y-H protons will appear. If the proton exchange rate increases, the peaks broaden to merge
ib
or coalesce. At the condition of coalescence, a broad peak arises. After coalescence, further increase
yl
of the proton exchange rate leads to the appearance of a single sharp peak. It happens so when the
em
NMR transition time is much longer than the time required for the proton exchange. At this situation of
fast proton exchange, the NMR method cannot detect the protons in two different chemical environ-
ch
ments rather it measures the average proton environment. The average position is given by: 8avg = nx8x
+ ny8y, 8 denotes chemical shift, n denotes the corresponding mole fraction.
al
In the region of partial collapse of the two PMR signals (i. e. intermediate proton exchange rate),
e
the following equation roughly explains the results.

th
e/
t.m
e
V~ - v~ = peak separation in Hz where there is no exchange (with respect to the NMR time scale).
er
(vx - VY)obs = separation of the peaks (in Hz) in the intermediate proton exchange rate.
H
r'x = r' y, i. e. life time of the proton on X = life time of the proton on Y (i. e. probability of residing
k
the proton at the both sites is equal).

lic
r
C
In general, = r'x + r' y, i.e. average life time of the proton on X or Y == r' .
2
At the condition of coalescence, (vx - VY)obs = 0 and we get: r' ==

21t Vx -v y
(f 0 )
To detect the resonance frequencies of the exchanging protons in two different chemical environ-
ments, the following condition is to be satisfied.
r' > .fi

21t(V~-V~)
Determination of the exchange rate constant (k) at the coalescence point: When both the environ-
ments are equally populated, at the coalescence point, we have: k = J, == .fi 1t (v~ - v~ )== J2 1t ~V
r
SPECTROSCOPIC METHODS AND OTHER PHYSICAL METHODS IN Ci-iEMISTRY 1835
(bYJL (~ (~
---+ Ho ~Ho - - - . Ho ---+ Ho
(e) (f)
ry
---+ Ho
ra
Fig. 12.2.15.1 Effect of the exchange rate of a particular nucleus between two sites on the NMR spectrum of the nucleus
ib
undergoing exchange (e.g. X-H* + Y-H ~ X-H + Y-H*, exchange of proton between two sites X and Y).
yl
(a): Slow exchange or no exchange with respect to the NMR time scale; two characteristic PMR signals; (b) to (e):
em
Gradually increasing exchange rate; (e): Merging or coalescence of two peaks giving a broad peak; (£): Very rapid
exchange rate giving a sharp PMR signal. ch
(i) Effect of the proton exchange process on the PMR spectra of CH30H and CH3 CH20H:
These aspects have been discussed in Sec. 12.2.8.
e al
(ij
c::
th
C)
"w
e/
0
=0
«S OH
a:
t.m
(a)
i
H2O
f\
e
(ij
c::
er
C) (Pure CH 3C02 H)
"w
H
A
=0 (b)
«S -C0 2 H
a:
k
J\
lic
i
C
(ij
c::
C) CH 3
"w
o
=0
«S
a:
i
(c) CH 3C02H
+ H20
A
OH
fl_
~
Ho
Fig. 12.2.15.2 PMR spectra of (a) H20, (b) Pure CH 3C02 H and (c) CH3C0 2H + H2 0 mixture (cf. position of the PMR
signal for the CH 3 protons remains unchanged; position of the PMR signal of the OH protons reflects the average
environment of the proton of the two sites between which the proton exchanges).
(ii) PMR spectra of a mixture of CH3C0 2H and H 20: When the PMR spectra of CH 3C0 2H and
H20 are recorded for the pure samples, for CH 3C0 2H, two signals are noted for the OH proton
(relatively downfield) and CH3 protons; and for H 20, one PMR signal (more upfield compared to
the -C02H proton of CH3C02H) appears. In a mixture of CH 3C02H and H 20, the position of the
PMR signal of the CH3 protons remains unchanged but instead of two separate PMR signals for
the OH protons (HOH and CH 3COOH), one PMR signal for the OH groups arises. Because of the
rapid proton exchange between the -C02H group and H 20, the NMR method sees only the
average hydroxyl proton environment in the system. For a such rapid proton exchange process,
the observed chemical shift is given by:
Bobs =0avg = nCH co HOCH co H + n H OOH 0
°
3 2 3 2 2 2
where denotes the chemical shift of the OH proton, n denotes the mole fraction.
(iii) NMR spectra of an aqueous solution of CH NH at different pH:
3 2 As in the alcohols, the rapid
ry
intermolecular -NH2 group proton exchange among the different molecules of CH3NH2 and
H 2 0 decouples the spin-spin interaction between the -NH 2 protons and the protons on a-carbon
ra
atom. Thus the -NH2 protons give a singlet (unsplit) PMR signal and the PMR signal for the
ib
hydrogens on a-carbon atom is not split by the -NH2 protons. On protonation of the -NH2
yl
group, the intermolecular proton exchange rate is slowed down and it allows the spin-spin coupling
em
interaction.
In the acidic condition (pH ~ 1), CH3NH2 exists as CH 3NHj. The proton exchange between the
ch
sites, -NHj and H 20 is base catalysed. Thus in the acidic condition, the proton exchange rate is
sufficiently slow with respect to the NMR time scale. The NMR spectra give:
al
• At pH == 1.0: Quartet signal of the CH3-protons (peak splitting by the three NHt protons); a sharp
e
peak for the H 20 proton; three broad peaks for the NHt protons (splitting by 14N having I = 1).
th
The peaks for the NHt protons are not strongly split by the CH3 protons because of the quadrupole
e/
broadening (Sec. 12.2.6) by nitrogen. In fact, the peak broadening effect by the quadrupole
t.m
relaxation is more pronounced than the peak splitting by the eH3 protons determined by the
coupling constant, 3J H (CH ), H(NH ). However, a careful analysis indicates that each broad peak of
3 3
e
the triplet (for the NH 3+ protons) is weakly split into a quartet by the CH3 -protons (cf. I N-H ~
er
50 Hz; JH(N) -H(C) ~ 5 Hz)

H
k
lic
A broadened triplet; each component

weakly split into a quartet by the CH 3-protons.
C
~ (-NH;) ~
J~= 50 Hz
1--
( ~~ J ~I
i ---+ Ho
Fig. 12.2.15.3 Qualitative representation of the PMR spectrum of CH3NH 3+ at about pH =:: 1.0 (i.e. acidified CH3NH 2).
Note: A broadened triplet due to the spin-spin coupling of IH and 14N (directly attached) (cf. quadruple relaxation).
Each component of this triplet is weakly split into a quartet by the 3-methyl protons.
• At pH == 5.0: This relatively more basic solution allows the rapid proton exchange between the -
NH{ group and H 20 and the solution gives a different PMR spectrum: one singlet peak for the
CH3 protons (i.e. no peak splitting by the -NHt protons); one broad peak for the protons in-
volved in the rapid base catalysed proton exchange process between the -NHt group and H20.
The steps of base (B = H 20, OH-, RNH 2 , etc.) catalysed proton exchange are:
CH 3 NH; + B ~ BH+ + CH 3 NH 2 , BH+ + CH 3 NH 2 ~ B + CH 3NH;

(iv) SF4' SeF4' TeF4 : There are two types of F-atoms (2 equatorial F + 2 axial F, in terms of the static
TBP structure). But because of the rapid exchange between these two types of F-atoms, only
one peak (corresponding to the average environment) for 19p (I =~) is noticed.
ry
ra
,/,11i
ib
yl
Q:f~i
I -F
ch
em
\._----V
al
F ------')
e
Probable intermediate for

th
the F-exchange
e/
At very low temperature (ea. -100 C C) when the F-exchange rate is very slow (with respect to the
t.m
NMR time scale), two separate triplets for the axial and equatorial F-atoms are noted as ex-
pected. The similar results have been found for SeF4 and TeF4 and the exchange rate follows the
order: TeF4 ) SeF4 ) SF4 . The F-exchange probably involves a bimolecular path producing a
e
er
dimeric species. Thus at low concentration, the exchange process is slowed down.
(v) B3H 8-: The llB-NMR spectrum ofB 3Hg- shows a multiplet (with 9 fine components). It indicates
H
three B-atoms equivalent and eight protons equivalent due to the rapid intramolecular exchange
k
process making the 8 hydrogens equivalent (el Sec. 12.2.19).

lic
(vi) PCI2F3and other fluxional molecules (cf. Sec. 10.9, Vol. 2; Sec. 10.11): In the trigonal bipyramidal
C
geometry, the more electronegative F-atoms preferably occupy the axial positions, i.e. in PCl2F 3
two CI atoms occupy the equatorial positions, 2F atoms occupy the axial positions and one
F-atom occupies the remaining equatorial position (el Bent's rule). In the static structure, there
are two types ofF-atoms, i.e. 2 axial F-atoms (i.e. Fax) and one equatorial F-atom (Feq). This static
structure should give two 19F-NMR signals which undergo splitting due to 19F_31p coupling and
19Fax-19Feq coupling. The 19p-NMR signal of the Fax 'atom is split into a doublet by the 19Fax_ 31 p
coupling and each component of this doublet is further split into a doublet by 19Fax_ 19Feq coupling
1
(2 x 1 x 2" + 1 = 2, for one 19Feq atom). Thus the 19F-NMR signal for the axial fluorine (Fax)
gives a doublet of doublets (Fig. 12.2.15.4). The 19p-NMR signal of the equatorial F is split into
a doublet by 19Feq_31P coupling and each compon'ent of this doublet is split into a triplet (1:2:1)
1
by two 19Fax atoms (2 x 2 x 2" + 1 = 3 for two 19pax atoms).
Thus the 19F-NMR signal of the equatorial fluorine (Feq ) gives a doublet of triplets at the
relatively higher field and it gives a doublet of doublets for the axial fluorine (Fax) at the relatively
lower field (Fig. 12.2.15.4). This prediction (i.e. a doublet of doublets for the Fax atoms and a doublet
of triplets for the Feq atom) in 19F-NMR spectra is experimentally verified at very low temperature
(ca. -145°C) at which the exchange rate between the Fax and F eq atoms is sufficiently slow (with respect
to the NMR time scale) but with the increase of temperature they undergo peak broadening, merging,
disappearing (i.e. no signal)followed by the appearance ofa single doublet indicating the time average
environment ofthe F-atoms. In fact, the intramolecular exchange rate (i.e. interconversion rate between
the Fax and F eg atoms) increases with the increase of temperature and at high temperature (ca. -25°C),
the NMR technique cannot distinguish between the Fax and F eq atoms. The single NMR signal of the
(I = ~ J
ry
time averaged 19F is split into a doublet by 31 P
ra
ib
~ A single doublet
----u(- *---+I
I " - - J
-25°C)
Fav
-
P
e
ch
al
em
yl
th
(No resonance)
e/
«S
t.m
c::
C)
(Peak broadening)
en0
r
A doublet of ~
e
..
triplets a:
er
~ (For 1Feq )
H
1 (Berry's pseudorotation
causing the stereochemical
k
I
nonrigidity)
lic
I I ------------ I I
I I I I
~ / J Fax - P l+-----+l
~ ~JFeq-P
C
(Magnetic field)
Fig. 12.2.15.4 Qualitative representation of the 19F-NMR spectra of PCl 2F3 at different temperatures. (I = 1/2 for 31p
and 19F).
12.2.16 Quadrupole Effects and NMR Studies for the Nuclei with Spin Greater than
1
2" : Quadruple Peak Broadening and Decoupling
For I ~ 1, the nuclei are nonspherical and they possess the electric quadrupole moments because of the
non-spherical nuclear charge distribution (see Vol. I). For the spherical nuclei (i.e. I = 0, ), there ~
is no electric quadrupole moment. If there is an electric field gradient (q) at the nucleus, the electric
quadrupole moment (for I ~ 1) interacts with the electric field gradient (q). This electric field gradient
is produced when there is a non-spherical distribution of electron density around the quadrupolar
nucleus. The nuclear quadrupole moment will tend to lie in the electric field direction. The most
favourable orientation (i.e. coupling) will bring the largest amount of positive charge of the nonspherical
nucleus closest to the largest amount of negative charge density in the surrounding electron environment.
If this coupling interaction between the nuclear quadrupole moment and electric field gradient is
sufficiently strong then it will oppose the coherent alignment of the nuclear magnetic moment in an
applied magnetic field. Thus the quadrupole moment gives a mechanism of spin relaxation and the
process is described as the quadrupole relaxation. This is a case of spin-lattice relaxation controlling
T 1 (cf Sec. 12.2.3) where the nucleus can exchange energy with the molecule in which it is situated.
However, the nucleus can also experience randomisation of nuclear phase controlling T2 • The efficiency
ry
of this relaxation process depends on the electric field gradient (q).
ra
Actually, the interaction of the nuclear quadrupole moment with the electric field gradient causes
the rapid transitions among the possible nuclear spin states of the quadrupole nucleus (cf the
ib
effect of decoupling rf field, Sec. 12.2.14). Consequently, the adjacent NMR active nuclei see the time
yl
averaged nuclear spin state (which is equivalent to I = 0) of the quadrupole nucleus (cf the effect of
em
decoupling rf field and the rapid exchange of an NMR active nucleus, Sees. 12.2.14-15). Thus this
interaction (i.e. rapid nuclear transitions) decouples the quadrupole nucleus from the adjacent observing
ch
nuclei (i.e. no signal splitting) and the NMR signal of the quadrupole nucleus undergoes broadening.
al
If in a molecule, the groups around the quadrupolar nucleus are spherically oriented (as in the cubic
e
symmetry like 0h' Td ), then the electric field gradient (q) is zero (i.e. spherical distribution of electron
th
cloud around the nucleus). For the lower symmetry point group e.g. e3v (pyramidal shape), there is a
nonspherical distribution of electron cloud (i. e. q ~ 0) around the nucleus and the degree of deviation
e/
from the spherical symmetry is measured by q. Let us consider the NH 3 molecule having the pyramidal
t.m
geometry (C3v ).
r l+
e
Q
er
H
N 4&- N3&-
&+H/ I"'H&+ &+/1"'8+
k
vs. H H
lic
HM HO+
C
NH; (Td)
Presence of three positively charged centres (i.e. 3Ho+) on one side of the N-nucleus produces a
strong electric field gradient (q) at the N-nucleus. This electric field gradient tends to orient the nuclear
quadrupole moment axis perpendicular to the plane containing the three positively charged H-centres.
When the molecule rotates or tumbles, the N-nucleus follows this molecular rotation. It may be noted
that in NHt (Td ), the positively charged equivalent H-atoms are spherically distributed around the
N-nucleus (i.e. q = 0) and this is why the N-nucleus does not experience the quadrupole relaxation
when present in NHt ion.
Effects of rapid nuclear quadrupole relaxation (controlling T l' spin-lattice relaxation) on NMR
spectra: Because of the rapid quadrupole relaxation, only the time average spin state (i.e. I = 0) is
observed. This phenomenon can be compared with the effect of decoupling rffield and rapid exchange
process. Rapid nuclear quadrupole relaxation rate is in the range of intermediate exchange rate which
gives the broader peale Thus the relaxing quadrupolar nucleus gives the broad peaks (cf Sec. 12.2.15,
~dt : : :; h, dt : : :; T1) and the other nuclei attached to the quadrupolar nucleus experience only the time
average spin state (i.e. I = 0) of the quadrupolar nucleus which undergoes rapid relaxation and con-
sequently the peak splitting by the quadrupolar nucleus does not occur. The important effects of
quadrupole relaxation are:
• Quadrupole broadening of the NMR peak of the NMR active quadrupole nucleus (cf. NMR
signals for 1271- and 12713 ; I = 5/2 for 1271).
• The peak split by a quadrupole nucleus also undergoes broadening (cf. PMR signals of 14NH3 and
1
15NH3, I = 1 for 14N and I = "2for 15N).
• Spin-spin decoupling between the quadrupole nucleus and the adjacent NMR-active nuclei, i.e.
ry
no or very weak splitting of the NMR signal of the quadrupole nucleus by the adjacent NMR
active nuclei and no or very weak splitting of the NMR-signals of the adjacent nuclei by the
ra
quadrupole nucleus.
ib
Because of the peak broadening effect, it is in general, difficult to record the NMR signal for the
yl
nuclei with 1 ~ 1 (e.g. 2H, 1 = 1; 14N, 1 = 1; 35,37Cl, 1 =~; Br, 1 =~; 127 1 = ~ ). However, for 2H and 14N
em
2 2 2
(specially when present in the relatively smaller molecules which experience the more rapid molecular
ch
motions to hinder the quadrupolar relaxation process), their NMR signals have been recorded in many
al
cases. For the halogens (i.e. CI, Dr, I), their NMR spectra have been recorded only in very few cases.
e
It will. be shown that such nuclei (I ~ 1) can avoid the quadrupole relaxation when they are in the
th
spherical symmetry (e.g. Td, 0h) where the electric field gradient (q) is zero and in such situations, their
e/
NMR signals may be observed.

t.m
• 2H: In fact, for 2H (i.e. deuterium), the quadrupole moment is very small and the said quadrupole
moment-electric field gradient interaction is quite inefficient and its quadropolar relaxation is very
e
slow. This is why, its NMR signal can be observed and it can split the NMR signals of the adjacent
er
NMR active nuclei.

=
H
• PMR signals of NH3 and NH4+ ( 14N, I 1): For NH3 (having a nonspherical electron distribution
around N in the molecule having the C 3v symmetry), the quadrupole relaxation process is quite efficient
k
and three broad PMR signals are noted (21 + 1 = 2 x 1 + 1 = 3) (cf. a sharp doublet for !5NH3,
lic
1 .
="2
C
I for 15N). For NH4+ (Td , having the spherical distribution of the electron cloud around the N-
nucleus), the electric field gradient (q) at the N-nucleus is zero, the quadrupole relaxation process
remains absent as expected and three sharp PMR lines arise.
• PMR signals of CH3NH2: This aspect has been discussed already in Sec. 12.2.15.
• NF3 : The 19p-NMR spectrum shows that at very low temperature (ca. -205°C) a sharp single
peak (i.e. no peak splitting by 14N) appears but at high temperature (ca. 25°C), it shows a triplet peak
(2 x 1 + 1). At low temperature, the slow molecular motion (i.e. tumbling) gives an efficient path for
the rapid quadrupole relaxation process. This is why, under this condition, the 19F-NMR signal is not
split by the quadrupolar nucleus N (I = 1). At high temperature, the fast molecular motion is not so
efficient for the quadrupole relaxation process and the life time of a particular spin state of 14N is
sufficiently high to cause the spin-spin splitting (cf. Fig. 12.2.19.2).
• NMR signals for CI, Dr, I: Their NMR signals are found when they exist as free halides (i.e.
CI-, Br-, 1-) and they exist in the symmetrical environment of electron cloud in the compounds like
x0 4-. Free halides are spherical in shape, i.e. spherical charge distribution around the nucleus. Similarly,
in X04- (Td ), the electron distribution around the central atom X is also spherical. In such cases, the
electric field gradient (q) at the nucleus is zero and the quadrupole relaxation process does not operate.
Under such conditions, their NMR signals can be recorded. The NMR signal for Cl in the compounds
like TiCI4, VOCI 3, SiCI4, etc. where Cl does not reside in a cubic or spherical symmetry has been noted.
Free halides (spherical in shape) give the NMR signals but the polyhalides like 13-, 15-, etc. lacking in
spherical symmetry show the NMR signal broadel)ing phenomenon because of the rapid quadrupole
relaxation.
A solution containing free 1- gives the NMR signal but on addition of 12 , it forms 13- (1- + 12 ~
13-) which is linear (cylindrical symmetry) and the NMR signal disappears. Distribution of electron
cloud around the iodine nucleus maintains the spherical symmetry in free 1- but not in 13- (in which the
ry
cubic symmetry is lost). Thus the quadrupolar relaxation process is present for 13- but absent for 1-. This
is why, the NMR signal of 1271 of free 1- disappears on addition of 12-
ra
• CI04- (T d) vs. CI0 3 (C 3v): CI04- is symmetrical (i.e. quadrupole relaxation process is not effi-
ib
cient) and it gives an NMR signal for 35, 37Cl. CI03- being pyramidal (C 3v ) experiences the rapid
yl
quadrupole relaxation process and it does not give any NMR signal for Cl.
em
• PMR signals for BH4- and GeH4 and 19F-NMR signal for BF4-: Because of the symmetrical
tetrahedral arrangement of the ligands (i. e. H- and P-), the quadrupolar relaxation is inefficient and the
ch
=~). l1 B ( I =%). lOB (I =3) can split the NMR'signals of IH and 19p (cf Pig. 12.2.19.8).
al
nuclei 73Ge (I
e
th
12.2.17 13C-NMR Spectroscopy and Organometallics

e/
It has now become very much popular in organic chemistry and inorganic chemistry (specially in
t.m
metal carbonyls) for structure determination. There are sqme inherent intrinsic difficulties for the
BC-NMR spectroscopy.
e
The characteristic features of the BC_NMR spectroscopy are pointed out here.
er
• Dominance of the local paramagnetic contributio~ «(Jp) and large range of chemical shift: It
H
has been already mentioned that for IH, both the contributions ad and ap (z 0) are small (see Sec.
12.2.5B) but, for BC involving a larger number of·electrons and the smaller value of ~E (energy
k
lic
difference between the ground and excited electronic states), both (Jd and (Jp are quite large and (Jp
dominates over the local diamagnetic contribution «(Jd) and remote anisotropic effect (cf. Sec~
C
12.2.5B: ap (BC) » ad e 3C) » ad eH) » ap eH) z 0)..Because of these factors, the chemical shift (0)
for BC in different organic compounds varies in a wide range (0 to 225 ppm) (cf. 0 to 14 ppm for IH)
taking 0 = 0 for the carbons of the methyl groups (not the hydrogens) of TMS. Because of this large
range of O-values of BC, the signals for the different types of C-atoms do not generally overlap (cf.
PMR signals very often overlap because of the narrower range of O-values). Approximate BC-chemical
ranges as follows:
a (in ppm): 8-75 (saturated Sp3_C atoms, i.e. highfield resonance); 100-170 (alkene and aromatic
Sp2_C atoms); 155-230 (carbonyl Sp2_C atoms, i.e. lowest field resonance)
It gives the approximate order of 0 for BC (cf. almost the similar order in PMR).
0: )c=o (aldehydes, ketones) >)c=O(carbOXYliC acids, esters, amides)
) aromatic C-atoms, C=C, C==N ) C ==C) C- ° (alcohols), C- X(X = CI, Br) ) alkanes
Carbonyl-C
2"_
Sp -C, / C - O
-A-C-id-S-,-Es-t-er-s-,....,
r-I
Alkyne-C
Amides
1Aldehydes, I I I
-C==C-
ketones
Alkene and Aromatic-C Alkane-C
ry
TMS
I Sp3_ C - X
ra
(X = 0, CI, Br)
ib
Alkane-C
yl
Sp3_ C
240 200 160 120

em
80 40 o
ch
13C-chemical shift (8 in ppm)
al
Fig. 12.2.17.1 Approximate l3C-chemical shift ranges for different types of C-atoms (taking 8 = 0 for the methyl
e
th
carbons of TMS as the reference).

e/
Though (Jp is the most dominating factor to determine the 8-value for 13C, (Jd along with the remote
anisotropic effect (arising from the 1t-electrons) makes also a sizable contribution to determine the
t.m
value and order of 8. In fact, by considering the local diamagnetic effect, electronegativity effect and
remote anisotropic effect, qualitatively the 13C-8 values can be interpreted as in the PMR spectroscopy
e
(cf. 8H = m8 c + b for the IH- 13 C signal pairs; R.S. Macomber, J. Chem. Edu., 68(a), 284, 1991).
er
Electronegative substituents (X) directly deshields the 13C-centres while they deshield protons via
H
the C-centre, i.e. via two bonds (cf. C-X vs. X-C-H). Thus the electronegativity effect of X causing
deshielding is more pronounced for 13C than for 1H. The higher electronegativity of X shows the higher
k
lic
deshielding effect and more downfield resonance for BC.

Remote anisotropic effect of the 1t-electron cloud (cf. Sec. 12.2.5C) explains the large 13C-8 values
C
of the alkene and aromatic ring C-atoms. Higher 13C-8 value in ethylene compared to that of acetylene
can also be rationalised in terms of the remote anisotropic effect (cf 8-values of the PMR signals of
C2H4 and C 2H 2).
For the carbonyl C-atom, the very large 13C-8 value arises due to the electronegative oxygen
directly attached and the remote anisotropic effect of the carbonyl group (cf. IH-8 value of the -CHO
group).
• Poor sensitivity: The natural abundance of 13C (I = ~, YN = 67.3) is only 1.11 % and its nuclear
2
magnetic moment is relatively small (cf. abundance of IH = 99.98% and YN = 267.5, i.e. JlH : Jlc ~ 4 : 1,
i.e. magnetic moment of IH is about 4 times that of 13C). It makes the gyromagnetic ratio (YN) smaller
for 13C (cf. YN: IHJ 13 C ~ 4). Intensity of an NMR peak (cf. Sec. 12.2.2) depends on two factors:
abundance of the nucleus and difference in population density between the excited and ground
state. Poor abundance makes the 13C_NMR signal intrinsically weak. Because of the smaller value of
YN of 13C, the population density at the ground level is only marginally greater. The relative population
density measured by nex/ngd depends on YN as follows:
~
n =~
n = exp - - -
n1 n gd kBT
(dE) = exp (Y·
-~ hH ) i.e. lower value of YN reduces the population density at
21tk T B
the ground level (cf. Sec. 12.2.2). Thus the ratio n/n2 decreases with the decrease of YN).
Detailed calculation shows that in an NMR experiment at a constant field (Ho), the sensitivity is
proportional to the cube of YN (gyromagnetic ratio). Thus for 13C, the sensitivity of the NMR signal
is ~ (= :3) of the PMR signal. Thus the poor intrinsic sensitivity of 13C-NMR signal (due to the
ry
ra
very low abundance and low value of YN) compared to that of the PMR signal is the major drawback in
ib
13C spectroscopy.
• Failure of the integration principle: For the PMR studies, the peak area is generally proportional
yl
to the number of nuclei (i.e. integration principle). Thus it is easy to calculate the number of equivalent
em
hydrogen atoms from the peak area. But for the 13C-NMR, this integration principle is not applicable
because, the relaxation times (specially T I) differ widely for the different C-atoms depending on the
ch
chemical environment (see Sec. 12.2.3). This is another drawback in 13C-NMR spectroscopy. However,
al
by adding the paramagnetic regents, the spin-lattice relaxation process may be accelerated for all the
e
C-atoms and under this condition, the integration principle (i.e. correlation between the peak area and
th
number of nuclei) becomes approximately applicable. For this purpose, the paramagnetic compound,
[Cr(acac)3] (ti g ) (acac = acetylacetonate) is often used in recording the 13C-NMR spectra of the
e/
organometallic compounds.
t.m
Major disadvantages in 13C-NMR spectroscopy

e
(i) Poor intensity due to the very low abundance of 13C-isotope and its small YN (gyromagnetic
er
ratio of the nucleus) value.

H
(ii) Failure of the integration principle (i.e. peak area DC number of the nuclei) due to the large
differences in relaxation times for the different carbon atoms.
k
lic
The two main drawbacks of 13C-NMR spectoscopy, i.e. poor intensity (due to the very low
C
abundance and small YN value) and failure of the integration principle, are largely overcome in the
modem NMR spectrometer (using the FT analysis).
• Relative advantages in the 13C-NMR compared to that of PMR: The PMR signals of the
organic compounds give information of the C-skeleton indirectly but the 13C-NMR signals give the
direct information of the carbon skeleton. For the 13C-NMR spectroscopy, the chemical shifts (8) span
over a larger range of about 200 ppm (cf. it is less than 20 ppm for the PMR signals). Because of this
large range of 8-values, the 13C signals for the different C-centres rarely overlap. Due to the very low
abundance of 13C nuclei, it is almost improbable that in a particular compound, two 13C nuclei will
reside at the adjacent positions. Thus the peak spliting by coupling with a neighbouring 13C nucleus
is very much unlikely.
• Proton decoupling (cf. Sec. 12.2.14) in 13C-NMR spectroscopy: The peak splitting by i 13c _ 13c
is unlikely but the peak splitting by i 13C _ 1H is very much probable to complicate the 13C-NMR
signals, i. e. presence of protons will split the 13C-NMR signals to complicate the interpretation. To
avoid this, proton decoupling is done by irradiating the protons with a high intensity radiofrequency
radiation at the IHresonance frequency (say 100 MHz while observing the 13C-NMR spectrum at 25.4
MHz in the same field). Because of this irradiation, the protons will be excited to undergo rapid flip-
flops (i.e. rapid transitions among the possible spin states of the protons) among the possible
nuclear energy states of IH (i.e. the protons will change their spin states rapidly). Under this condition,
the 13C nucleus feels an average zero magnetic field from the protons, i. e. the protons are decoupled
from the 13C nuclei. This technique is described as noise decoupling (double resonance). Comparison
of the noise coupled and noise decoupled spectra can provide the more information of the structure.
The noise decoupling technique can enhance the intensity of the 13C-NMR signal through the nuclear
overhauser effect (NOE). The noise decoupling radiation" favours the spin-lattice relaxation process
(i.e. T 1 becomes smaller) and reestablishes tI1e Boltzmann distribution equilibrium very rapidly. It gives
ry
an intensity bonus of the 13C-NMR signal.
ra
Let us consider the proton decoupled 13C_NMR spectra of disubstituted benzenes.
ib
CI
yl
cab d
em
CI C1
~cv :CI
I a
~ I b
ch
.0
CI
al
(ortho) (meta) CI
e
Three types of carbon, Four types of carbon, (para)

th
3 13C-NMR signals 4 13C-NMR signals; Two types of carbon,

2 13C-NMR signals
e/
t.m
• 13C-NMR spectra of organometallics: When the organometallics contain the ligands without any
proton (e.g. CO, CN, F 3C-C ==
C-CF3), the 13C-NMR spectroscopy is very much helpful for the
structure determination.
e
er
13C-chemical shifts (0 in ppm with respect to TMS reference) for some organometallics are given
below.
H
8 (in ppm) 13C of carbonyl: [Ni(CO)4] (+191.5); [Fe(CO)5] (+212); [Cr(CO)6] (+211.4),
k
(115-Cp)Cr(CO)3]- (+247); [W(CO)6] (+191.5);

lic
In the trigonal bipyramidal structure of [Fe(CO)5]' there are two types of CO groups (3 equatorial
C
+ 2 axial). Thus two 13C-NMR signals are expected but experimentally only one 13C-NMR signal
is obtained (Sec. 10.11.1). It is due to the fluxional behaviour (i.e. rapid interchange between the axial
and equatorial CO groups).
• Metal carbonyls: M-CO (terminal) (0 = 180 to 225 ppm); bridging CO (0 slightly greater than
that for the terminal CO groups) (cf. distinction between the terminal and bridging CO groups in terms
of13C-NMR spectroscopy). 13C chemical shift depends on the C-O bond strength. In general, stronger
the C-O bond, lower the chemical shift. Thus it leads to: better the M ~ CO 1t-back bonding,
weaker the C-O bond (i.e. more single bonded character) and higher the 13C chemical shift. The
increased metal ~ ligand n-back bonding leads to the increased deshielding. This may help to
characterise the identification of the different types of CO groups. However, IR is a better tool for this
purpose.
• M-CH3 (8: -30 to 24 ppm); M=C < (8: 190 to 400 ppm); M==C- (8: 235 to 410 ppm). It
indicates that the 13C chemical shift increases with the increase of M-C bond order.
12.2.18 NMR Spectroscopy for the Nuclei other'than Hydrogen: PMR Spectroscopy VB.
Other NMR Spectroscopy .
We have already pointed out that the PMR spectroscopy faces the difficulties due to the following
reasons.
• Relatively smaller ra.cge ofchemical shift (8 = 0 to 14 ppm) causes the overlapping ofthe signals
for the common organic compounds. .
• The small values of t1v/J generate the complex spectra (i.e. 2nd order effect) in many cases.
In this regard, the other important nuclei are: 2H~ lIB, 14N, 13C, 19F, 31p, 29Si, 1I7Sn, 1I9Sn, 195Pt, etc.
For such nuclei, the chemical shift-and spin-spin coupling constants are generally much larger than for
the protons. For various protons, generally the chemical shifts (8) cover the span of 15 ppm while for
31p NMR spectra, it covers the spar\ of about 400 ppm; for 19F, it covers the span of 600 ppm. The spin-
ry
spin coupling constants are also increase~,but not to that extent of chemical shift. Thus the condition,
ra
~v/J ~ lOis also easily maintaine<;l in such cases to show the first-order effect. The gyromagnetic
ib
ratios (YN) for the nuclei like 19F, 31p, etc. are also fairly high and their NMR signals are fairly strong (cf.
yl
Sec. 12.2.2).
Because of the fairly strong NMR signals and·la,rge chemical shifts, for structural information,
em
less precise instruments can be used. The NMR spectra can be interpreted more easily because they
always show the 1st order spectra, i.e. AaM,)(x-.. typ~ rather than AjJbCc type (cf. AX system gives the
ch
1st order spectrum while AB system gives the 2nd order spectrum which is a complicated one).
al
12.2.19 Application of NMR Spectroscopy in Structure Determination: Some

e
Representative Examples
th
!
e/
1. Isomers of C2H2BrCI and 0, p-isomers of dinitrobenzene: The possible isomers of C2H2BrCI

are:
t.m
Br", /H1a)
'"
Br
/
CI
e
C=C C=C
er
IbIH/ "'CI IblH/ ' " H(a)

H
(trans) (cis)
3Jab~ 12-18 Hz 3Jab~ 6-12 Hz
k
lic
In all cases, there are two nonequivalent H-centres and each of the isomers will give two doublet
C
peaks in the PMR spectroscopy, i. e. signal for each type of proton will be split into a douplet by the
other 1H nucleus. From this peak splitting, the coupling constant (Jab) (= separation between the com-
ponents ofa doublet peak) is determined and this coupling constant is different for the three isomers.
Thus, determination of coupling constant (JH,H) can distinguish the isomers.
The dinitro-isomers are:
N0 2 I
I
CH 3
I
I
I
aH Ha aH I N02 aH Ha
cf.
a
aH Ha bH Ha aH Ha
N02 Hb CH 3
a
Two PMR signals: 8(ppm) = 2.3 (2CH 3);
7.2 for the 4 ring protons)
Under low resolution, in the p-dinitrobenzene, all the 4 ring protons appear chemically equivalent
to give a single PMR signal. On the other hand, in the o-isomer, there are two types of protons to give
two different PMR signals and each signal will be split into a doublet by the other protons (i.e.
splitting of the Ha signal by Hb and splitting of the Hb signal by Ha; see Sec. 12.2.8F). Thus, the p-isomer
gives a single singlet PMR signal (downfield than the C6H 6 protons due to the - I and - R effect of the
-N02 group). The o-isomer gives two doublet PMR signals (downfield than the C6H6 protons due to
the - I and - R effect of the -N02 groups. The aH protons are more downfield than the bH protons,
because the -N02 group dishield the ortho-protons more than the meta- and para-protons (cf. aniso-
tropic effect on the ortho-protons). The characteristic features of the PMR spectra of the four ring
protons of the disubstituted ortho- and para- compounds can be roughly explained (see Sec. 12.2.8F)
by considering only the chemical equivalence of the ring protons (ignoring their magnetic equiva-
ry
lence). It is possible because the coupling constants Ju, H are not very large. However, for the detailed
ra
analysis (under high resolution), the magnetic equivalence not the chemical equivalence is to be con-
sidered (cf. Sec. 12.2.10). The indicated chemically equivalent protons are magnetically nonequivalent
ib
and the 4 ring protons actually represent the AA'DB' spin system.
yl
2. Hypophosphorous (H3P0 2) and phosphorous acid (H3P03): The possible structures are:
em
H H
9~ 9~
ch
I I
~ P===O ~ P===O
""-
al
-.;:- / H/I"'o-H H/ ""-OH

e
Ho/I"'o-H HO OH
th
HO OH
HP(O)(OH)2 HP(OH)2 HPH(O)(OH)
e/
P(OH)3
Phosphorous acid Phosphonic acid Hypophosphorous acid (Phosphinic acid
t.m
(minor tautomer) (major tautomer) (minor tautomer) (major tautomer)

I '---- 1
e
er
The 31p_NMR spectrum of H 3P0 2 gives a triplet signal, i.e. the NMR signal of 31p is split by two
H
phosphorous bound hydrogens. It suggests the structure H 2P(O)(OH) not HP(OH)2 which actually
k
represents the minor tautomer. HP(OH)2 is expected to give a doublet peak (i.e. the NMR signal of 31p
lic
is split by the one H atom directly attached to the P-atom).

For H3P03, the 31p-NMR spectrum gives a doublet peak which indicates the structure HP(O)(OH)2.
C
The 31p-NMR signal is split into a doublet by the one H atom directly attached to the P-atom. For
P(OH)3' the 31p-NMR signal is expected to be a singlet one (i.e. no splitting by the proton). In fact,
P(OH)3 is the minor tautomer.
(Note: In this analysis, splitting of the 31p-NMR signal by the OH proton is ignored because of two
reasons: rapid proton exchange (cf. Sec. 12.2.8) of the OH proton and IJp _H » 2Jp _H ).
By using the above argument, the structures of RP(H)(O)(OH), F-P(O)(OH)2' F 2P(O)(OH) can be
confirmed.
• F-P(O)(OH)2: a doublet 31p_NMR signal (i.e. splitting by one 19F, I =! )

2
F
• \.p (O)(OH): a triplet 31p_NMR signal (i.e. splitting by two 19F centres, I=! ).
F/ 2
(Note: Position of the prototropic tautomeric equilibrium for H3P02 and H 3P03 can be rationalised
in terms of the stabilising action of the P-O bond through the O(2p) ~ P(3d) n-bonding. In fact, this
n-bonding urges the system to attain the structure preferably where the P=O bond exists (see Sec.
10.7.2, Vol. 2).
3. Ortho- and para-isomers of dichlorobenzene and para-isomer of difluorobenzene:
: 0 (a) CI
lal I lal __ ~b~~__ CJ
CI I CI (b)~
~ (a) CI
(a) I (a)
1 PMR signal 2 doublet PMR signals
ry
(actually a complex multiplet
PMR signal)
ra
Note: Under high resolution, the apparently chemically equivalent protons behave as the magnetically
ib
nonequivalent protons (in terms of the coupling constants). These are discussed in Secs. 12.2.8, 10.
yl
1
0
em
1
I
• I
I J H (a) F (a) ":t J
H
(a) (a')
F
=> F (a) an d F (a') are not magnetIca
ch . 11 . Ient
y equlva
(a')F but chemically equivalent. Similarly, H(a) and H(a') are chemically
equivalent but magnetically nonequivalent.
e al
H(b') H(a')
th
It gives a complex multiplet in both IH-NMR and 19F-NMR spectra.

e/
(a)H F(a)
----~c=C(---(C2
t.m
4. lHlalF(a) :;tlH(a)F(a') i.e. Fa) and F(a') are magnetically nonequivalent

/ '" though they are chemically equivalent (see Secs. 12.2.8, 10)
(a')H F(a') ,
e
Two protons are magnetically nonequivalent; two 19F centres are also magnetically nonequivalent.
er
It represents an AA'XX' spin system not the A2X2 system. It gives a complex NMR spectra.
H
Note. If hydrogens are considered to be equivalent and F-atoms are considered to be equivalent,
k
the single PMR signal will be a triplet one (intensity ratio 1:2: 1) due to the splitting by two F-
lic
atoms. Similarly, it would give a triplet 19F-NMR signal. But in reality, it is not so.
5. IFs, BrFs (C4v , square pyramidal): IflFs and BrFs are assumed to be trigonal bipyramidal, they
C
will have two types of 19P-centres: 2 axial F and 3 equatorial F, i.e. 2 19F-NMR signals: one triplet
for Feq and one quartet for Fax. If they possess the square pyramidal geometry, they will have also
two types of 19F-centres: 4 equatorial F and one axial F. The 19F-NMR spectrum shows two peaks:
one doublet and one quintet.
19}' (I = i) NMR spectra of IF (assuming the stereochemi-
5
_-----rJ~~ cally rigid TBP geometry): 2 Peaks should appear with the
intensity ratio 3:2. The peak due to the equivalent 3 equatorial F-
F~~[~\ centres is split by the two equivalent axial F-atoms. Thus the
F
r 'F
peak is a triplet one (2 x 2x ~ + I). The peak due to the axial
(TBP)
F-centres is split by the 3 equatorial F-centres, i.e. the peak is a
D3h
quartet one. The same conclusions prevail for IFs.
19F-NMR spectra of BrF5 for the stereochemically rigid square
r~I-7r
pyramidal geometry: Two peaks appear with the intensity ratio
4: 1. The peak due to the axial P is split into 5 five equidistant
fine components, i.e. (intensity ratio 1:4:6:4: 1, see Pascal's
i/Br~i
triangle) by the 4 equivalent equatorial P-atoms. The peak due to
the 4 equivalent equatorial P-atoms is split into a doublet (1: 1
F-------------- F intensity ratio) by the one axial P-atom. Thus the experimental
(square pyramidal) e
findings 9p NMR spectra: one doublet peak and one quintet
C4V peak) support the square pyramidal geometry not the trigonal
bipyramidal geometry.
6. elF3: It may have the three possible geometries and the 19p-NMR spectral features of the possible
ry
structures are given below.
(8)F
ra
"
(8)F-CI-F(8) CI
I" CI-F(8)
ib
(b) I (8)
F
/
(8)F F
(8)
(a)F/
yl
F
em
(T-shaped, C2V) (Pyramidal, C3V) (Trigonal planar, D3h )
Types of F-atoms: 2, (2F + 1F) 1 (3F related by the C3 axis) ch 1 (3F related by the C 3 axis)
19F- NMR peaks: 2 (one triplet for 1 1
(b)F, spliting by two
al
(a)F atoms; one doublet
for (a)F-atoms, spliting
e
by one (b)F atom).

th
e/
Note: Peak splitting by 35CI, 37CI ( I = %) has been ignored because such nuclei with a quadrupole
t.m
moment undergo relaxation very rapidly (see Sec. 12.2.16)

The experimental findings of the 19p-NMR spectra (Pig. 12.2.12.3) (one triplet peak due to the
e
equatorial P-atom, i.e. (b)p and one doublet peak due to the axial P-atoms, i.e. (a)F atoms) support the
er
T-shaped (C2v ) structure. In fact, sp3d hybridisation of the central Cl-atom places two P-atoms in the
H
axial directions (i.e. (a)p atoms) and one P-atom at one equatorial position (i.e. (b)p) according to Bent's
k
rule. The remaining two equatorial positions are occupied by two lone pairs (see VSEPR, Vol. 2).
lic
(8) F (ax)
C
l
(~)f(eq)
.... " 1
.. " 1
.. " 1
C>Cjl~: ...
...
.1
·1
.........
(a) F (ax)
Here it is worth mentioning that when the 19p_NMR spectrum of CIP3 is recorded at the lower probe
frequency (say 10 MHz), the second order spectra will result (cf. Fig. 12.2.12.3) because under this
condition, 2JF_F and chemical shift difference (~v in Hz) between the two types of P-atoms become
comparable. It complicates the interpretation. At the higher probe frequency (say 60 MHz, the chemical
shift difference (~v in Hz) becomes larger but the coupling constant 2JF_F remains unchanged (cf.
Sec. 12.2.12) and the second order spectrum is converted into the simple 1st-order spectrum (i.e.
f!.v »JF- F). Thus at 10 MHz, CIF3 appears as an AB 2 molecule (2nd order effect) but at 40-60 MHz,
it appears as an AX2 molecule (1st order effect).
It is worth mentioning that ir and Raman spectroscopy can also differentiate the three possible
structures of CIF3. This aspect has been discussed in Sec. 12.1.9.
Note: 19F-NMR spectra of PCI2F 3 (trigonal bipyramidal) is shown in Fig. 12.2.15.4.
7. Q PF3: It adopts the pyramidal structure of C 3v symmetry. The F-atoms are equivalent
P (C 3-axis) and they produce one 19F-NMR signal which is split into a doublet
F/I"F
F b y 31p (I=-i).
ry
(C 3V>
ra
The pyramidal structure of PF3 having three equivalent F-atoms is also supported from the 31p
ib
NMR spectrum. The 31p_NMR signal is split into a quartet (intensity ratio 1:3:3:1) due to the
yl
SPlitti~g by 3 equivalent F atoms ( 2 x 3 x -i + 1 =4). Here it is worth mentioning that the trigonal
em
planar structure of D 3h symmetry (where the 3F atoms are also equivalent) will also give one
ch
31p-NMR signal having four fine components (splitting by 3F atoms) and one 19F-NMR signal
split into a doublet by 31p. However, the NMR spectra can distinguish between the C 3v (pyramidal)
al
and C 2v (T-shaped) symmetries of PF3.

e
7. NF3: It also adopts the pyramidal structure (C 3v ) as in PF3. Because of the rapid nuclear quad-
th
ruple relaxation of 14N (I = 1) (cf. Sec. 12.2.16), the single 19F-NMR peak is not split by 14N. In
e/
fact, at very low temperature (say, -205°C), it gives a single unsplit peak for 19p but with the
t.m
increase of temperature, the NMR peak starts to broaden at about 20°C and it gives a sharp triplet
at the higher temperature, i.e. 19F-NMR peak is split into a triplet peak by 14N (I = 1).
e
er
H
k
19_
lic
F NMR
spectrum
C
of PF3 (One doublet peak; splitting
i by one 31 P nucleus)
'----------------+ 8
.---.~
(ij
c
C)
°Cii 31_
p NMR
o
:cn3 spectrum (One quartet peak; splitting
a: of PF3 by three 19 F nuclei)
i
'-----------------+ 8
Fig. 12.2.19.1 19p_ and 31p-NMR spectra of PP3'
(19 F_NMR) (very low

temperature) (Relatively
higher temperature)
iL.--- _ il...--- _
- - - - - . . Ho
(b)
Fig. 12.2.19.2 19p-NMR spectra of NP3. (a) Low temperature (ca. -205°C); (b) High temperature (ca. 20 - 30°C).
ry
It is suggested that at low temperature, the slow molecular motion (tumbling motion) is very much
ra
efficient for the quadrupole relaxation and the F-atoms see the time average zero nuclear spin
ib
state (i.e. 1= 0) at the N-nucleus (cf quadrupole relaxation is much faster than the NMR transition
yl
time). But at higher temperature, the rapid molecular motion is not so effective for the quadrupole
em
relaxation and the life time of a particular nuclear state of the 14N nucleus is sufficiently high to
split the 19F-NMR signal (cf Sec. 12.2.16).
Note: In the fluxional molecules, at higher temperature, the different peaks merge. But for NF3 ,
ch
the reverse situation arises because the reasons are different in the two cases.
al
8. WF6 ·L (complexes of WF6) and W20 2F9": The general formula of the complexes, tungsten
e
hexafluoride is given by WF6 ·L (L = ligand). At the early date, it was assumed to have the 7
th
coordination number. The 19F-NMR spectrum of the complex, WF6 ·L shows the three peaks with
e/
the intensity ratio 4: 1: 1. It indicates the presence of three types of 19F as: 4F, IF, IF. This is not
in conformity with the 7 coordinate structure of WF6 ·L. The NMR signals for 19F support the
t.m
structure as: [WFsL]+P-. In octahedral [WFsL]+ (C4v )' 4F atoms are at the basal plane while the
axial positions are occupied by the fifth F and L. The 4F atoms at the basal plane are equivalent
e
(related by the C4 axis) and they produce the strongest peak which is split into a doublet peak by
er
the fifth axial P (I =±). The NMR signal due to the axial P is split into a quintet (intensity ratio,
H
1:4:6:4: 1, see Pascal's triangle) by the 4 basal 19P-centres (I =±). The remaining unsplit peak
k
lic
is due to the' P- which resides outside the coordination sphere.

C
i~~~J-7i
i/Wj~i
F F
F-------- --------F
F
([WLFs]+ F-)
The 19F-NMR spectra of W 20 2F g- shows: a doublet of intensity 8 and a nonet of intensity 1 (i.e.
intensity ratio, 8:1). This observation is in conformity with the structure OWF4-F-WF40- having two
types of F atoms (8: 1) where one F-site acts as a bridging site. The 19F-NMR signal of the bridging
fluoride is split into 9 components by 8 equivalent basal fluorides. The 19F-NMR signal of the basal
F-sites is split into a doublet by the bridging F-centre.
9. HF2-: The linear structure [F ... H ... F]- is in conformity with the 19F_NMR spectrum. Here both
the fluorines are equivalent and they produce one 19F-NMR signal which is split into a doublet
by the proton.
10. SF4 and O==SF4 : Both the species show two triplet peaks in 19F-NMR spectroscopy (32S,
I =0). Their structures are related with the trigonal bipyramidal geometry (i.e. sp3dhybridisation
of S). In each case, there are two types of F-atoms: 2 axial F and 2 equatorial F. Each of them
will give two 19F-NMR signals and each signal will be split into a triplet by the other two F-
atoms. Thus the trigonal bipyramidal structure supports the NMR spectra: two triplet peaks for
ry
19F-NMR spectroscopy in both the compounds.
ra
F
ib
yl
em
ch
e al
th
e/
The other possible symmetrical structures, i.e. planar SF4 (D4h ), square pyramidal OSF4 (C4V )
t.m
should give only one unsplit NMR signal for 19F because in such cases, 4F atoms are equivalent.
32S (I = 0) is a nonmagnetic nucleus' and it does not come into the picture to split the 19F_NMR
e
signals.
er
Note: Because of the rapid exchange between the nonequivalent F-atoms, for SF4 (cf. Sec.
H
12.2.15) only one sharp signal is obtained (at room temperature). At very low temperature (ca.
-100 C C), two separate peaks are observed because at such low temperature, the exchange rate is
k
sufficiently slow with respect to the NMR time scale. It happens so for also SeF4, TeF4'
lic
11. [Rh(CN)sH]3- and other transition metal-hydrides like carbonyl hydrides (Sec. 12.2.6): The
C
PMR signal (D =- 10.6 ppm) for [Rh(CN)sH]3- is a doublet one due to the splitting by Rh (I = ~)
It indicates the existence of the Rh-H bond. Here it is worth mentioning that in the metal hydride
complexes (cf. Sec. 12.2.6), the protons are strongly shielded and their chemical shifts com-
monly lie in the range -5 to -60 ppnl relative to TMS (cf. 8 = - 7.5 ppm, -9 ppm, -11 ppm for
[HMn(CO)s], [HFe(CO)4]- and [H 2Fe(CO)4] respectively). Thus in terms of chemical shift, such
protons are typical (i. e. highly negative 8 value) and very few other protons appear in this range.
Thus the M-H protons can be easily identified.
The very high upfield resonance (8 = -5 to -60 ppm) for the hydride ligands bound to the transition
metals may arise from the diamagnetic shielding by the metal d-electrons. In such cases, the transition
metal centres generally lie in the low oxidation states and the electronegativities of such metal centres
and hydrogen become comparable and in some cases, electronegativity of hydrogen may be even larger
than that of the low valent metal centre. Thus under the condition, X(H) ~ X(M) and the hydridic
character of the transition metal hydrides, the phenomenon, diamagnetic shielding apparently sounds
well. But this diamagnetic shielding cannot alone explain the too high negative values of chemical shift.
Here it is interesting to note that in [HCO(CO)4] or [H2Fe(CO)4], the metal bound hydrogen is acidic
in character but it shows the negative value of 8 (z - 10 ppm). Acidic proton but negative 8-value!
This is unusual. '
All these observations strongly indicate that besides the diamagnetic shielding, some other factors
also contribute to make the large negative value of 8 for the hydrogen bound to the transition metal
centre. This factor has been argued as the paramagnetic shielding by the incompletely filled d-electron
subshell of the transition, metal centre (Refs. A.D. Buckgham et aI, 1 Chem. Soc., 2747, 4583, 1964;
L.A. Lalancette et aI, J. Am. Chem. Soc., 86, 5145, 1964). This paramagnetic screening can occur even
ry
when the metal centre is itself diamagnetic. This paramagnetic screening becomes quite important
ra
when there are accessible low-lying excited electronic states. It happens so in the transition metal
complexes with the incomplete d-electron subshell. Effect of the paramagnetic metal centres on the
ib
PMR signals of the ligands has been discussed in Sec. 12.2.19(26).
yl
12. [MO(CO)3H2(PPr~2]: It may lead to the two possibilities: MO(1l2-H 2) (dihydrogen complex) and
em
cis-M(H)2, (i.e. di~ydrido complex). X-ray and neutron diffraction studies could not solve the
problem without any ambiguity. However, the PMR studies on the complex, [MO(CO)3HD(PPr~2]
ch
solved the problem.
al
[ Mo(CO)iPPrj)2]~[ MO(COhH2(pprj)zJ (18e)

e
th
(16e) I HD ) [ MO(CO)3HD (pprj)2] (18e)

e/
t.m
J H-D = 33.5 Hz
The PMR spectrum of [MO(CO)3HD(PPri)2] shows the H-D coupling constant (JH- O ) about 33.5
e
Hz which is comparable to the value IJH_O (43.2 Hz) found in the PMR spectrum of free H-D.
er
H
It may be noted that the coupling constant 2J H- D is only 1 - 2 Hz as in the system like M< .
H
D
k
Thus the high JH- D constant strongly suggests that in the complex, HD remains as an
lic
M~(l]2_~D), i.e. [
C
undissociated species, i.e. Mo <!) which gives the coupling constant
IJ H_ O ' Thus the complexes are the dihydrogen complexes, i.e. [Mo(CO)3(1l2-H2)(PPr~)2]'
[Mo(CO)3(1l2-HD)(PPr~)2], not the dihydrido complexes, i.e. [MO(CO)3(H)2(PPr~)2]'
[MO(CO)3(H)(D)(PPrD2]'
13. Polyoxymetallate, [W 60 19]2-: Its structural features have been discussed in Sec. 11.14.3 (Vol. 2).
17O-NMR spectroscopy can distinguish the different kinds of O-sites, i. e. bridging O-site, terminal
O-site and encapsulated O-site. In the isopoly acids, the edges of the M0 6 octahedra are shared.
170-NMR spectrum of [W60 19 ]2- shows three signals (i.e. three types ofO-sites) (with the intensity
ratio 12:6: 1): one signal for the 12 bridging oxygen atoms, one signal for the 6 terminal oxygen
atoms and one signal for the encapsulated oxygen atom.
14. Equimolar mixture of [TiF6]2- and TiF4 in ethanol: In solution, the 19F-NMR signal shows two
peaks with the intensity ratio 4: 1 where the weaker peak is a quintet (1 :4:6:4: 1) one and the
intense peak is a doublet (1:1) one. It supports the existence of [TiFs(C 2 H sOH)]- (octahedral
structure of C4v symmetry by considering the local symmetry) where the equivalent 4F atoms
lying at the equatorial plane give the doublet 19F-NMR peak (splitting effect from the axial F) and
the axial fluorine gives the quintet peak due to the splitting by four equivalent basal F atoms (cf
48Ti; I = 0). This structural problem is similar to that of WF6 ·L.
[TiF6 ]2- + [TiF4] + 2S ~ 2[TiFsS]-, (S = EtOH).
15. [TiF4] in donor solvents (8): The 19p-NMR spectrum (48Ti, 1= 0) gives the results: two triplet peaks
of equal intensity at -30°C while one unsplit peak at the relatively higher temperature (say O°C).
[TiF4] is expected to increase its coordination number to 5, 6 in presence of the coordinating
solvent (S). The possible structures are:
i~j-7i i~f-7i r----j-7i
ry
------------f
~~. /-
ra
I~T'
I I
I I
ib
I I
i/Ti~i i/Ti~i i/Ti~i

I
yl
:/I~:
em
F------L-----oF
S
F------)------ s
F
F-------------·F
ch F-------------·F
(Trans) (D 4h ) (cis-)(C 2v) (Square pyramidal) (C 4v) (Square planar) (D 4h)

4F (equivalent, C4 Two types of F-atoms, 4F (equivalent), i.e. one 4F (equivalent) and one
al
axis), i.e. one unsplit 2 F (basal plane) and 2F unsplit 19F-NMR signal unsplit 19F-NMR signal
e
19F-NMR signal (axial direction), i.e. two

th
triplet 19F-NMR signals

e/
Appearance of two triplet 19F-NMR signals at the low temperature (say, -30°C) suggests the
t.m
cis-[TiF4(S)2] structure where there are two types of F-atoms (each group consisting of two
equivalent F-atoms). They give two peaks and each peak is split into a triplet one by the other two
equivalent F-atoms. At a relatively higher temperature, this cis-complex dissociates into the
e
5-coordinate square pyramidal complex (C 4v ) or the 4 coordinate square planar complex (D4h )
er
which gives a single 19F-NMR signal.

H
[TiF4] (D 4h) + 2S: ~ cis-[TiF4(S)2] (C 2v)

k
cis-[TiF4(S)2] (C 2v ) ~ [TiF4(S)] (C4v ) + s

lic
[TiF4 (S)] (C 4v ) ~ [TiF4] (D 4h) + S

C
The dissociation reactions leading to the 5- and 4-coordinate

complexes are negligible at low temperature but predominant at
high temperature. Thus at the lower temperature range, the six
coordinate octahedral (cis-form) complex is the predominant
species while at the relatively higher temperature, the 5 and/or 4
coordinate complexes are the predominant species and they give
one unsplit 19F-NMR signal (i.e. all the F-atoms are equivalent).
16. [RhCI3(PPh3)3]: It can have two isomersfac- and mer- which can
be distinguished by analysing the 31p-NMR spectra.
• lac-isomer with one type of 31p atoms (related through the C3
axis): Thus it gives one 31p NMR signal which is split into a doublet
by Rh(I =±).
(a)31 P ((ae)
31
p _PMR ##
signal
ry
(One doublet)
----+ Ho
ra
Fig. 12.2.19.3 Qualitative representation of the 31p-NMR spectrum of !ac-[RhCliPPh3h]
ib
yl
em
ch
• mer-isomer with two types of 31p, i.e. two trans-axial 31p
al
centres (related through 0), i.e. (a)p and one equatorial or
basal P, i.e. (b)p: Thus it gives two 31p NMR signals-one is
e
th
double doublet (for the two (a)p centres) and another is two
triplets (for one (b)p centre).
e/
t.m
e
er
H
k
lic
C
(For (a)p)
Double doublets
(For (b)p)
I I
Double triplets
r
(Double doublets) Double triplets
Fig. 12.2.19.4 Qualitative representation of the 31p-NMR spectrum of mer-[RhCliPPh3h].

In the fac-isomer, the three equivalent 3lP-atoms (related through the C 3 axis) give one NMR
signal which is split into a doublet one by Rh ( I = ±). In the mer-isomer, the two trans-axial 31p
centres give a peak which is split into a doublet one by Rh (cf ap-Rh coupling). Each component
of this doublet may be further split into a doublet by (b)p (trans to chlorine). Thus the 3Ip-NMR
signal for the trans-axial aP-centres gives two doublets (i.e. double doublets). The (b)P-centre
(trans- to CI) gives the NMR signal which is split by Rh ( I = ±) into doublet one. Each component
of this doublet is further split into a triplet by two other equivalent aP-centres. Thus it gives two
triplets, i.e. double triplets. In this way, the 3Ip-NMR spectra can distinguish the fac- and mer-
isomers of [RhCI3(PPh 3)3]:
ry
fac (doublet); and mer (double doublets and double triplets) (assuming IJp _Rh) 2Jp_p )
ra
ib
17. B2H 6 (cf Sec. 12.2.14): The lIB decoupled PMR spectrum of B 2H 6 shows the lines with the
yl
intensities 4:2 (cf. Fig. 12.2.14.2). It supports the bridged structure having 4 terminal B-H bonds
and two B-H-B bridge bonds (when peak splitting by lIB of I = ~ has been removed by
em
2
decoupling).
ch
• IIB-NMR spectrum: The two B-centres are equivalent and they give one signal which is split
al
into a triplet by the two equivalent terminal protons (H t ). Each component of the triplet
e
±+ 3)
th
can be split into a triplet ( = 2 x 2 x 1= by the two equivalent bridging protons (Hb )
e/
(ct. IJB _ H , >I JB _ Hb ). Thus the IIB-NMR spectrum ofB 2H 6 gives a triplet of triplets (Fig.
t.m
12.2.19.5).
e
• PMR spectra (considering the coupling with liB): The equivalent terminal protons give a
er
PMR signal (at low field) and the signal is split into a quartet ( = 2 x %+ 1 = 4) by II B ( I = %)
H
k
nuclei. The bridging and terminal protons are weakly coupled and each component of the quartet
lic
±1) (ct. IJ
C
is weakly split into a triplet ( = 2 x 2 x + by the two bridging protons H' _B > 2 J H' -Hb ).
Thus the PMR signal of the terminal protons consists of quartet of triplets (Fig. 12.2.19.5).
The PMR signal (at higher field) of the bridging protons is split into a septet ( = 2 x 2 x %+ 1 = 7 )
by the two equivalent lIB (I =%) nuclei. Each component of the septet is weakly split by 4 tenninal
protons into a quintet e J Hb -B > 2 J Hb -H' ). Thus, the PMR signal for the bridging protons is basically
a septet of quintets (Fig. 12.2.19.5).
The above conclusions are made by considering the 1st order effect and ignoring the presence of
lOB (which is about 19% in abundance and I = 3). However, in reality, complications arise from the 2nd
order effect and the NMR active less abundant lOB nuclei.
ry
ra
Triplet of triplets Septet of quintets
ib
b
(Stick diagram for 11 8 ) (Stick diagram for H )
yl
Fig. 12.2.19.5 Considering the 1st order effect, the stick diagrams (qualitative representation; not in scale) of the NMR
em
spectra of liB, Hb and H t ofB 2H6 • Note: For this symmetrical molecule, both sides are identical. Thus the NMR spectra
of liB and terminal hydrogen CH), of both sides are identical (cf the PMR spectra of ring protons of 0- and p- disubstituted
ch
benzene, Sec. 12.2.8F, xiii). For the PMR spectrum of the bridging hydrogen (Hb), the whole molecule is to be considered.
18. B3"8- (cf. Sec. 12.2.15): The llB-NMR spectrum gives a single peak having 9 fine components,
al
i. e. nonet. It indicates the 8 protons equivalent to split the 11 B-NMR signal. The rapid intramolecular
e
rearrangement (i. e. tluxionaiity) makes the three B-centres equivalent and 8 protons equivalent.
th
e/
t.m
e
er
H
k
lic
In the proton decoupled IIB-NMR spectrum of B3H g-, only one unsplit signal appears for the
three equivalent B-centres.
C
The 8 equivalent protons give a single PMR signal which is split into 7 fine components by
three equivalent lIB (I = 3/2) nuclei.
Note: The natural abundance of boron isotopes is: 11 B ( 1 = %) about 80%; lOB (I = 3) about 20%.
The PMR signal split by the relatively less abundant lOB isotope is of relatively poor intensity and in
many cases, the lOB-multiplet is not observable. The coupling constant for JOB is relatively smaller
than that of JJB because of the larger gyromagnetic ratio of 1JB.
19. Structure of B10"14: The IIB-NMR spectrum (decoupled from the protons) shows 4 peaks with
the intensity ratio 4:2:2:2. It indicates that there are 4 types of B-atoms in the structure. These are:
4 equivalent B nuclei; three different (i.e. nonequivalent) pairs of B-nuclei. It may be noted
that there is no B-B coupling. The skeleton structure of B 10H l4 is in conformity with the
IIB-NMR spectrum.
110---- _
(a)
Fig. 12.2.19.6 (a) Structure of B 1oH14; 4 equivalent B-centres are denoted by *B; other 3 nonequivalent pairs (a, a; b,
ry
b; c, c) are evident in the structure; (b) Proton decoupled llB-NMR spectrum of B lOH 14 .
ra
20. Ge~ C3Ge, I = ~), BH:;, BFi (lOB, 1=3; liB, 1= %): Because of the tetrahedral (i.e. symmetric
ib
yl
arrangement of the ligands, i.e. H-, P-) around the quadrupole nucleus (i.e. I > ! ), the quadrupolar
em
2
relaxation is insignificant (Sec. 12.2.6) and the quadrupole nucleus can split the IH and 19p_NMR
ch
signals. All the hydrogens in GeH4 are equivalent and the PMR signal is split into 10 fine
~ + I) B~-, the PMR signal consists of a strong quatret

al
components (2 x I x by 73Ge. For

e
(splitting by the more abundant II B nucleus of I = ~ ) and a weak septet (splitting by the less
th
2
e/
abundant lOB nucleus of I = 3) (cf abundance of lIB and lOB about 80% and 20% respectively).
t.m
Similarly, the 19p-NMR signal Of BFi consists cf a strong quartet and a weak septet (see Pig.
12.2.19.8).
e
21. [M(PR3)(PR~)X2] (M = PdII, PtII): Here the 31P-centres are non-equivalent and two 3Ip_NMR
er
signals are expected for both the cis- and trans-isomers. Each signal is split into a doublet by the
H
other nonequivalent 31P centre. The magnitude of this splitting is determined by the coupling
constants 2Jp_p which are different for the cis- and trans- isomers. The cis- and trans- isomers
k
lic
of these square planar complexes can be distinguished by considering the 2Jp _p values: 2JP-P(trans)
» 2Jp-P(cis).
C
2Jp _ p (trans)
i~--7r3 i~--7r~
.l/M~i
R3P- - - - - - - - - - - - - - - X
~/M~i
X- - - - - - - - - - - - - - - PR3
("ans~ (c~~
2J p _ p (trans) »2J p _ p (cis)
The complex, [PdCI2(PMe3)2] is quite interesting in terms of its PMR spectrum.

Me3~~-
- - - - - - - - -- / - -91
- - -- C:~--7PMe3
:
I
:/
:
I
Pd :6
~:2JI/
I
: r
1/
H
./C"
H
H
i/Pd~ 2J
CI- - - - - - - - - - - - - - - - .P
CI· - - - - - - - - - - - - - - - - - - - -PMe 3
/ "'Me
Me
(trans-isomer) (cis-isomer)
2J p _ p »2J p _ 2Jp _
p
« 2J p _ H
» 4Jp-H
H
ry
The two P-centres are chemically equivalent but they are not magnetically equivalent because
ra
2Jp_H and 4Jp_H are of different magnitudes, i.e. the two P-centres are not magnetically equivalent.
ib
• For the trans-isomer, 2Jp_p is much larger than 2Jp_H. Thus the PMR signal (for the Me-proton) is
yl
split into a triplet one (1 :2: 1) by two chemically equivalent 31P-centres (which behave as the
em
equivalent nuclei to split the PMR signal). In such cases, the two chemically equivalent but
magnetically nonequivalent 31P-centres remain virtually coupled to split the PMR signal.
ch
• For the cis-isomer, 2Jp_H is much larger than 2Jp_p and the PMR signal (Me-proton) is split into
a doublet by the attached 31p centre (i.e. 2Jp_H). Here further splitting by the other nonequivalent
al
31P-centre is ignored because 4Jp_H is negligibly small.

e
th
22. cis- and trans-isomers of [PtBrCI(PR3)2]: In the trans-isomers, the two 31p centres are equiva-
lent (related through the C 2 axis and crv) but the two 31p centres are nonequivalent in the cis-
e/
isomer. Thus the trans-isomer gives one 31p_NMR signal but the cis-isomer gives two 31p-NMR
t.m
signals (each may be split into a doublet by the other nonequivalent P-centre).
For the trans-isomer, the 31p-NMR signal may be split into a doublet through the IJp_pt coupling
e
er
1
(cf 1=2" for 195Pt). For the cis-isomer, the two 31p-NMR signals may be split by both 195pt and
H
1
the other nonequivalent 31P-centre giving rise to a double quartet (cf 1= -
for both 31p and 195Pt)
k
2
lic
whose shape depends on the relative values of 1Jp- Pt and 2Jp_p. The coupling constants
C
1 J 195 31 p (cis) 1 J 195 31 (trans) can also distinguish the isomers (see the next example).
Pt - Pt- p
22. J Pt-p for the cis- and trans- isomers of [Pt(PR3)2X2]: In each case, the 31P-centres are equivalent
1 1
producing one 31p-NMR signal. The nuclear spins are: "2 for 195pt and "2 for 31p. In general, for
such square planar complexes, Jpt_p(cis) JPt_p(trans), e.g. J(cis) =3.62 Hz and J(trans) =2.46 Hz
for [PtCI 2(PR 3)2] (R = n-Bu). This difference in the coupling constants can be understood by
considering the dJt(P)-dJt(Pt) interactions. If the complex is supposed to remain in the xy-plane
and in the trans-isomer, two trans- P atoms are along the x-axis, then the d-orbitals of two P-atoms
can overlap with the dxz and dxy orbitals (i.e. two d-orbitals) of Pt. On the other hand, for the cis-
isomer, the two cis- P atoms (along the x- and y- axes) can overlap with the dxy, d yz and dzx orbitals
(i.e. three d-orbitals of Pt). This greater x-bonding interaction between the P-d-orbitals and
Pt-d-orbitals in the cis-isomer can explain the sequence of the coupling constants, J(cis) )
J(trans).
Fig. 12.2.19.7 Schematic representation of one n-type interaction between the two trans-PR 3 ligands via the dxy
orbital of Pt(II).
ry
For both the isomers, the single 31p_NMR signal is split into a doublet through the 1 J 195 Pt_31p
ra
coupling but the difference in coupling constants 1 J Pt-P for the two isomers can distinguish
ib
the isomers.
yl
It has been noted that th~ coupling constant 1 J Pt-P is very much sensitive towards the nature of
em
the trans-ligand (with respect to the PR3 ligand). The coupling constant value depends on the
trans-influence property of the ligand (trans to PR3).
ch
IJPt_p (for the trans-ligands): CI- ~ Br- ) NH 3 ) R- ) PR3
al
Trans-influence: PR3 ) R- ) Br- ) CI- ) NH 3
e
Bond weakening by a trans-ligand at the trans-position where PR3 resides lowers the Pt-P
th
coupling constant. It is expected because the coupling between Pt and P is attained through the
e/
Pt-P bonding electron.

23. RoPF 5-0: In this trigonal bipyramidal (TBP) geometry, the more electronegative F-atoms preferably
t.m
occupy the axial positions (cf. in Me2PF3, Me groups in the equatorial plane while in (CF3)2PF3,
CF3 groups in the axial directions; Bent's rule). If the molecule is stereochemically rigid, then
e
the axial and equatorial F-atoms appear as the nonequivalent centres and these can be identified
er
by 19F-NMR spectra. The coupling constants (Jp- F) for the equatorial F-centres are relatively
H
larger, i.e. 1 J 31p_19 F(eq) » 1 J 31p_19 F{ax)' If the TBP geometry is considered to have two different
k
sets of hybrid orbitals (i.e. sp 3d == Sp2 + pd) then the equatorial bonds are formed by using the Sp2
lic
hybrid orbitals (s + px + Py' if the trigonal plane lies in the xy-plane) of P while the axial.bonds are
C
formed by the pd-hybrid orbitals (Pz + dz2, axial groups along the z-axis) of P. The equatorial
P-F bonds can use the s-orbital (which ha~ a finite probability of the existence of electron to the
closest distance towards the nucleus) of P and this gives a better coupling interaction between the
nuclear spins of 31p and 19F (cf. I JC ( )
sp -
H > IJ C (2)
sp -H
> IJ C (3)
sp -H
for I3 C, Sec. 12.2.9). It
explains, 1JP-F(eq) ) 1Jp-F(ax) and the difference in these two coupling constants is about 175 Hz.
Note: Here it may be mentioned that the 5 coordinate trigonal bipyramidal molecules are very
often fluxional in nature (see Vol. 2). For example, in PF5 though there are two types of F-atoms
(3 equatorial and 2 axial) but instead of two 19F-NMR signals, only one doublet signal is obtained.
In fact, Berry's pseudorotation leads to the rapid interchange between the axial and equatorial
F-atoms and the NMR method 'sees' only the time averaged F atoms. In other words, the NMR
method cannot distinguish between the axial and equatorial F-atoms and all the five F-atoms
appear equivalent. This is why one 19F-NMR signal is obtained and this is split into a doublet by
31 p( ±). Simil~ly,
1= other trigonal bipyramidal molecules like [Sb(CH3)s] (one~MR signal),
[Fe(CO)s] (one 13C-NMR signal) also indicate that all the 5 ligands appear identicaf in the NMR
time scale. It may , noted that the NMR studies at very low temperature may distinguish the
axial and equatorial ligands because at the very low temperature, the rate of intramolecular
j
exchange between t~e axial and equatorial ligands is slowed down.

In PCI2F 3, the 19F-NJy1R spectral studies can detect the equatorial and axial F-atoms at very low
temperature (ca. -145°C, Fig. 12.2.15.4).
24. Structures of [M3(C9)12]: For M = Ru, Os, (i.e. heavier congeners) the nonbridged structure
is favoured while for M =Fe, the bridged structure is favoured (see Ch. 9 for explanation). These
two possible structures can be distinguished by the 13C_NMR spectroscopy.
ry
ra
L
L",I/ L
ib
axL/F~
yl
em
eq
L"" I
ch
-----Fe---------- --- -~-)
c c~
eqL/I~
al
c=o
~L ~f
e
th
Fe (C 2V)
/1'"L
e/
L=CO,
(L=CO)
M = Ru, Os L
t.m
L
axL = axial CO, [Fe 3 (CO)12]
e
eqL = equatorial CO
er
For the nonbridged structure (D3h symmetry), there are two types of CO groups (i.e. axial and
H
equatorial) and two 13C-NMR peaks are expected. If the structure of [Fe3(CO)12] is supposed to
k
be stereochemically rigid, then the symmetry operation on the C 2-axis passing through the
lic
Fe-centre (bearing only the terminal groups) and between the two bridging CO groups inter-
C
changes the pairs of CO groups, i.e. 6 nonequivalent CO pairs. Thus it should give six 13C-NMR
signals.
If the bridged structure of [Fe3(CO)12] rapidly interconverts into the nonbridged structure (i.e.
fluxional character) then the axial terminal CO groups (of the nonbridged structure) and bridg-
ing CO groups (of the bridged structure) are rapidly interchanged (faster than the NMR time
scale). In this interconversion process, the equatorial CO groups remain unchanged. Thus two
13C-NMR signals (i.e. one for the equatorial CO groups and one for the axial and bridging CO
groups which cannot be distinguished by the NMR method because of their rapid interconversion)
are recorded. In fact, at very low temperature, the bridged structure predominates (and the
interconversion rate is slow), then the complex 13C_NMR spectra (consisting of 6 peaks) appear
but at higher temperature, the fluxionality (i.e. rapid interconversion between the axial and bridg-
ing CO groups) is attained and two 13C-NMR peaks are noted.
25. Structures of [Fe(COs)], [Sb(CH3)s], PFs : In terms of its trigonal bipyramidal structure of D 3h
symmetry, there are two types of CO groups (i.e. 3 equatorial CO groups and 2 axial CO groups).
Infrared and Raman spectra of [Fe(CO)s] indicate the presence of these two types of CO groups
(cf. Fig.·;12.1.11.1). The rapid interconversion between the axial and equatorial CO groups (i.e.
fluxionC;ll character) leads to one 13C-NMR signal (cf ir-spectrum Fig. 12.1.11.1). The infrared
and Raman techniques are the much faster techniques while the NMR technique is a much
slower process (compared to the interconversion rate of the axial and equatorial·CO groups) and
it actually records the time average structure of [Fe(CO)s]. Because of the same ground, the
trigonal bipyramidal molecule [Sb(CH3)s] shows only one PMR signal. A similar situation arises
for PFs where only one 19F-NMR signal (split into a doublet by 31p) is obtained.
26. Structure of [NiBr2{PMe(p-MeOC6H4)2}2] (cf L. H. Pignolet et aI, J. Am. Chem. Soc., 92, 1855,
1970; E. A. Lalancette et-al, ibid, 86, 5145, 1964): It can have two isomeric structures of [Ni(PR3)2X2]
discussed in Chapter 2). These are: paramagnetic tetrahedral and diamagnetic square planar.
ry
The chemical shifts (8 in ppm) of the PMR signal of
ra
the protons present in the phosphine ligands are highly
ib
sensitive to the magnetic character of the metal centre
to which the phosphine ligand is attached. If the metal
yl
NiBr2
centre is paramagnetic (as in the present tetrahe-
em
dral complex of NiH), the chemical shifts are enor-
mously affected.
ch
In the square planar complex, the diamagnetic character
al
of Ni(ll) cannot affect the PMR signals. For this square
planar complex, three PMR signals appear for the
e
th
methyl (CH 3), methoxy (OCH3)..a nd4 aromatic (though

they are not equivalent, they are not resolved) protons.
e/
In the tetrahedral complexes, the paramagnetism of the metal centre can differentiate the ortho-
t.m
and meta- protons (with respect to the P atom) because of their different degrees of interaction
with the unpaired electrons of the metal centre (cf p- and o-protons more upfield while m-
e
protons relatively downfield). The resonance position of the P-CH3 protons is also greatly
er
affected by the paramagnetism of the metal centre and it lies beyond range. The positions of
H
different protons in the square planar and tetrahedral complexes are:

k
lic
meta-H OCH 3 TMS ortho-H CH3 protons lie

Td comPlex} -27.5 -7.0 0 +8.2 (upfield) } beyond the range.
C
(Relative values of H o for IH resonance)

Ho :
increasing magnetic field
Ph-H (aromatic protons) OCH 3 TMS

Square planar } -7.6 (no resolution for -3.85 -1.95
o
complex the o-and m-protons)
(Relative values of H o for 1H resonance)
increasing magnetic field
At very low temperature both tetrahedral and square planar geometries are frozen out into an
equilibrium mixture and the PMR signals of the both the geometries appear. At a relatively higher
temperature, there is a rapid interconversion between the two geometries (i.e. stereochemical
nonrigidity) and the PMR spectrum reveals only the time averaged environment for the each type
of protons as follows:
meta-H OCH3 ortho-H TMS
-12.2 -4.75 -3.2 o
--------+) Ho
Increasing field
• Effect of the unpaired electrons of the paramagnetic metal centre on the PMR signals of the
ligand protons: Paramagnetic Ni(ll) (tfS) (in the tetrahedral complex, e4 ti) possesses both the
filled and half-filled dn-orbitals which can participate in the dn(Ni) ~ dn(P) interaction (cf
phosphorous bears the vacant d-orbital). In the said drc-drc interaction, if the filled Ni(ll) d-orbital
ry
and vacant P d-orbital are involved, then it will simply establish a n-bond between Ni(ll) and P.
ra
But, in the said interaction, if Ni(II) uses a halffilled d-orbital, then the unpaired electron ofNi(II)
will be partially transferred on P and this transferred electron can again be partially delocalised
ib
into the n-system of the phenyl ring through the dn(P)-Pn(C) interaction.
yl
em
ch
e al
th
Thus accumulation of higher negative spin density at the ortho- and para- positions causes the
e/
upfield shifts for the ortho- and para- protons. Because of the low negative spin density at the
meta-position, the meta-protons experience the downfield shifts. Here it is worth mentioning that
t.m
this spin transfer (i.e. unpaired electron transfer) from the metal centre to the ligand can also
occurs through the a-system but this effect rapidly decreases with the distance from the metal
e
centre.
er
Note: Paramagnetic shielding on the metal bound hydrogen (i.e. M-H) can occur even for the
H
diamagnetic metal centre having the partly filled d-shell (see example 11 of this section). It
explains the highly negative value of 8 for the hydrogen bound to the transition metal centre.
k
lic
27. [(Tl 5-Cp)Rh(Tl 2-C2H4)2]: PMR spectra (cf Fig. lO.11.3.1(b» of the ethylenic protons at different
C
temperatures indicate the rotation of the coordinated ethylene around the metal-olefin bond. At
very low temperature when the activation energy for the said rotation is not attained (i. e. rotation
is kinetically prevented), two different types of ethylenic protons are indicated by two PMR
signals but only one PMR signal for the time averaged environment of the proton appears at the
relatively higher temperature when the said rotation is kinetically allowed.
28. NMR spectral feature of the low-spin Co(III) complexes: The NMR studies of different low
. spin Co(lll) complexes (cf 1='2 for 59CO) indicate that the chemical shift (8), i.e. resonance
2
frequency depends on the energy difference (~E) between the diamagnetic ground state eAIg)
e
and the paramagnetic excited state T 1g ). The chemical shift occurs due to contribution from
this paramagnetic excited term. This is why, contribution of this excited state to the chemical shift
increases with the decrease of the energy difference (~) between the IA lg and ITlg spectroscopic
states and this energy difference can be easily obt~ined from their electronic spectra.
In fact, the external magnetic field allows the mixing of the wavefunctions of the ground state
eAIg) and excited state eTIg). The induced current generates a magnetic field and deshields the
nucleus (i.e. local paramagnetic deshielding measured by op which is inversely proportional to
Llli, i.e. op oc 1/dE). Thus with decrease of dE, 8 (59 CO) increases.
With the decrease of Llli, contributon of op (-ve) increases, i.e. Hex (experienced magnetic field by
the nucleus) increases to make the resonance frequence larger (cf. vres oc Hex).
It has been noted that the resonance frequency increases with the decrease of the energy differ-
ence (.1£) for the IA lg ---) ITlg spectroscopic transition.
Complex: K 3[Co(CN)6] [Co(en)3]CI3 [Co(NH3)6]CI3 [Co(acac)3]
Llli (em-I): 32,100 21,400 21,000 16,900
v res (MHz): 4.417 4.449 4.453 4.737
ry
8 (59CO):
ra
Increasing trend
29. Distinction of cis- and trans- isomers of [Ti(acac)2(OEt)2]:
ib
yl
em
ch
e al
th
e/
t.m
CH 3
e
er
(trans) (cis)
H
In the trans-isomer, the CH2 protons of the ethoxide group are equivalent in terms of the mirror
k
plane (0) and they give a single PMR signal. In the cis-isomer lacking in the mirror plane, the
lic
CH 2 groups (of DEt) are not equivalent and they give two separate PMR signals. The CH3 protons
of the DEt groups also give the separate PMR signals for the cis-isomer.
C
30. Distinction between the fac- and mer- isomers of [Pt(CH3)3(NH3)3] (cf. Example 16 of
[RhCI3(PPh3)3]: In the fac- isomer of [Pt(CH3)3(NH3)3] all the Me-groups are in cis-configuration
and they are equivalent (related through the C 3 axis). These methyl protons give one PMR signal
which is split by 195pt (I = ~ )(cf. 2 J I H_ 195pt "" 75Hz). In the mer- isomer, there are two types
of Me-groups (1:2) and two PMR signals (intensity ratio 1:2) for the methyl protons are found.
Df course, these two signals are also split by I95pt.
31. BF4-, BH4- (isotopic shift for lIB and lOB): Boron is present in a symmetrical tetrahedral
environment of the ligands (i. e. H-, P-) and consequently, the electric field gradient (q) is zero.
This is why, the quadrupolar relaxation of 11 B (1= ~) or lOB (I = 3) is not significant and the
I9p-NMR signal or IH-NMR signal is split by boron.
The 19F-NMR spectrum shows a well-resolved quartet (strong signal) and a septet multiplet
(weak signal) (Fig. 12.2.19.8). The quartet ( = 2 x %+ 1) signal i~ due to the predominant iso-
topic species 11BF4- (ca. 80%, I = ~ ) while the weak septet (= 2 x 3 + 1) signal is due to the less
2
abundant isotopic species lOBF4- (ca. 20%, 1=3).
The separate signals of lOBF4" and lIBF4" show the isotopic shift of about 0.048 ppm. The isotopic
shift occurs because the vibrational states of the two isotopic species slightly differ and conse-
quently the electron distribution patterns in loB_F and lIB-F bonds are also different.
The coupling constants are: 1 J 19p_llB = 1.2 Hz, I J 19 F _lO B = 0.4 Hz. The bigher coupling constant
ry
for lIB is due to its higher gyromagnetic ratio (cf. YN(lIB): YNeoB) ::= 3.0).
ra
Similarly, for BH4-, a strong quartet PMR signal due to the more abundant species 11BH4-
ib
appears and a weak septet PMR signal occurs due to the less abundant 10BH4- species. Here these
two multiplets overlap (cf. chemical shift values for 19F cover a much wider range than those for
yl
1H; Sec. 12.2.5B).
em Quartet
ch
for BF4-
al
Isotopic
e
shift
th
e/
t.m
e
Septet
10 -
er
for BF41--~
H
k
lic
----+ Ho
C
Fig. 12.2.19.8 19F-NMR spectrum (qualitative representation) of BFi ion in aqueous solution.
32. Structure of Al(B~)3: The 27Al ( I = %) decoupled PMR spectrum shows a 1:1:1:1 quartet
(Fig. 12.2.19.9) due to splitting by llB (80%, I = ~ ) (ignoring the splitting by the less abundant
2
isotope lOB). The lIB-NMR spectrum (decoupled from 27 AI) shows a 1:4:6:~:1 quintet (Fig.
12.2.19.9) due to coupling by 4 equivalent protons around the B-centre. It indicates the rapid
exchange between the terminal and bridging H-atoms. The lIB-decoupled PMR spectrum
shows a broad signal composed of six broad lines of equal intensity (cf. splitting of the PMR
signal by I = ~ of 27 AI). It indicates that all the 12 hydrogen atoms are equally coupled to AI.
2
Thus the AI-centre retains three rapidly tumbling BH4 units.
(a) 27AI-decoupled (b) 27 AI decoupled 11 B _NMR spectrum (c) 11B-decoupled PMR spectrum
PMR spectrum
Fig. 12.2.19.9 NMR spectra (qualitative representation) of AI(BH4)3o
The exchange of terminal and bridging H-atoms probably occurs through the singly or triply bridged
intermediates (Fig. 12.2.19.10).
/ H, , /
~ H
ry
(H 4 B)2 AI" / ' B "
ra
H H
ib
yl
em
ch
Fig. 12.2.19.10 Probable mechanisms for the exchange of bridging and terminal H-atoms in AI(BH4)3o
e al
33. Fischer carbene (OC)sCr=C(Ph)(OMe): The resonance in this carbene introduces a partial
th
double bonded character in the C-O linkage (cf. observed bond length 133 pm is shorter than
the typical C-o single bond of about 143 pm but significantly lon~r than the typical C 0
e/
bond of about 116 pm). But this double bonded character can sufficiently slow down the rotation
t.m
around the C-O bond at low temperature to cause the cis-trans orientation of the Me-group.
In fact, at low temperature, two PMR signals for the Me-protons "are recorded. But at higher
e
temperature, the said rotation becomes faster and the cis-trans interconversion rate becomes faster
er
than the NMR time scale, i.e. NMR records only an average signal producing a single PMR peak
H
for the Me-groups.

k
lic
C
Ph Ph
/
(OC)sCr=-=-=-=c, (oc)cr==c(
"'.O -CH 3
(cis-form)
5
HC/'
3
"'.
o ,
(trans-form)
12.2.20 Application of NMR Spectroscopy in Identification of Rotational Isomerism

(cf.Sec.12.2.10, Figs. 12.2.10.1-2)
(i) BrCI2C-CBrF2: Let us consider, BrCI2C-CBrF2 which can adopt three different conforma-
tions in which the 19p centres are not equivalent (cf Pig. 12.2.20.1) but if the free rotation around
the C-C bond can occur rapidly (at a relatively higher temperature), then the F-atoms experience
a time averaged environment and one 19F-NMR signal appears. At a lower temperature, the
available thermal energy is less than the internal rotational energy barrier and then the rotational
isomers can be frozen and two different 19F-NMR signals appear. These signals are mutually split
and a complex spectrum is observed.
CI Br CI
F
F F F
~
~
~
~
Br CI
CI
ry
Br Br Br
ra
(I) (II) (III)
ib
Fig. 12.2.20.1 Rotational isomers of BrCI 2C-CBrF2 _ In (i) and (iii) two Br atoms are in gauche; and these two
yl
conformations are enantiomers and they have the same NMR spectra in an achiral solvent.
em
(ii) BrCH2-CH2Br: In terms of the PMR signal, the rotational isomers (see Fig. 12.2.10.2) of
BrCH2-CH2Br (where the four protons are chemically equivalent) can be detected at very low
ch
temperature when the rotation around the C-C bond is locked.
al
(iii) CH2CI-CHCICH3 : Let us illustrate the detection of the rotational isomers of 1,2-dichloro-
propane, i.e. CH2CI-CHCICH3 in terms of the PMR spectra. There are 4 types ofH-atoms and
e
th
one C-centre can act as an stereocentre. The aH and bH atoms are chemically equivalent but they
are magnetically nonequivalent (see Sec. 12.2.10) when the free rotation around the C-C
e/
centre is locked. These two hydrogens (i.e. aH and bH) are the diastereotopic hydrogens.
t.m
bH
I I.
cH
J
e
P .A Diastereotopic
d
er
aH-C-C-CH '" * ,,' A groups

I I C-C~
"'x·
H
CI CI 0"'1
k
R
(* stereocentre)
lic
C
In 1,2 dichloropropane, the 4 PMR signals appear (at very low temperature) for the four types of
hydrogens (cf. Fig. 12.2.20.2).
CH 3
b c
H H
aH -
I
C - C - C H3
I
CI
I I
CI
CI
CI
(Contd... )
(Contd... )

of a H of b H
3
J(CH -H c)
3
~ 6 Hz
2J
ba
=
2Jab ~ 11 Hz
3JbC~ 6 Hz
3Jac~ 8 Hz
! Jbc
I I
JUl
ry
ra
ib
Two doublets Two doublets
yl
(i.e. quartet) (i. e. quartet)
em
Fig. 12.2.20.2 Qualitative representation of the origin of the PMR signals of the two diastereotopic protons (in terms
of splitting tree) in 1, 2-dichloropropane.
ch
a H: Its signal is split by b H and cH. It gives two doublets
al
Diastereo - i.e. double doublets or a quartet.

e
topic b H: It signal is split by aH and cH. It gives two doublets

th
i.e. double doublets or a quartet.

e/
t.m
cH: It couples with aH, bH and three Me-protons. Me-protons split the signal into a quartet and each
of the components of this quartet is split separately by aH and bH. Thus it gives a complex multiplet
signal.
e
dH (i.e. Me-proton): Its signal is split into a doublet by CR.

er
H
NMR Signal
H ofH
k
lic
cF Br c
F CI
C
I
Br-C--C-H
I
b
I I
a
F
} Splitting by one
F diastereotopic b F
CI a
F
} S.plittin g by ~n~ther
dlastereotoplc F
b
F (Two doublets of doublets)
Fig. 12.2.20.3 Qualitative representation of the origin of the PMR signals of I-bromo-2-chloro-l, 1, 2-trifluoroethane
(splitting caused by three nonequivalent F-atoms, aF, bF and cF; bF and CF are diastereotopic in nature).
(iv) F2BrC-CHCIF: Let us illustrate the PMR spectrum of I-bromo-2chloro-l, 1, 2-trifluoro ethane,
F2BrC-CHCIF where the two F-atoms attached to a C-centre are diastereotopic in nature. If
the rotation around the C-C bond is locked, the rotational isomers can be detected and the
magnetic nonequivalence of the diastereotopic P-atoms can be identified by 19p-NMR spectroscopy.

The characteristic features of the PMR spectrum of this compound (cf. Fig. 12.2.20.3) are as
follows:
The PMR signal is split into a doublet by the P-atom attached to the same C-atom; then each of
the component of this dou~let is split by the diastereotopic P-atoms separately; thus the resultant
PMR signal shows two doublets of doublets (i.e. simply two quartets).
The 19p-NMR spectrum of this compound is a complicated one. Three nonequivalent P-atoms are
expected to give three NMR signals and each signal is split by the two other nonequivalent
P-atoms and one H-atom.
(v) FCI2C-CCI2F: 1, 2-difluorotetrachloroethane can have three possible conformations. Two of
these conformations are magnetically equivalent. At room temperature, when the rotation about
ry
the C-C bond is very fast, only one 19p-NMR signal is recorded. However at a very low tempera-
ra
ture (about -120°C), two 19p_NMR signals are obtained.
ib
b
F
yl
CI
em
CI
ch
CI
al
CI CI
b
F
e
b
~
F
th
CI CI CI
~ CI CI ~
~
e/
CI
CI
t.m
e
er
H
(i) (ii) (iii)

k
Fig. 12.2.20.4 (a) Three possible conformations of FCI 2C-CCI 2F; (ii) and (iii) are magnetically equivalent. At room
lic
temperature, one 19F NMR signal (rapid rotation about the C-C bond; time average environment of F). At low tempera-
C
ture, two different 19F_NMR signals.
F
J
3 F,F
(anti)
CI$b CI~ CI$CICI --::.CI$CICI
--;- ~
CI CI CI b
F b CI
F
SF' SF
-.-.-J~ 3
J F,F
SF
(gauche)
(i) i (ii) (iii)
3JF,F (anti) *- 3JF,F (gauche)
Fig. 12.2.20.4 (b) F-F coupling constant elF, F) differing in different rotational isomers (cf. Karplus Rule, Sec. 12.2.9).
12.2.21 Application of NMR Spectroscopy in Detection of H-bonding and in

Distinction of Intramolecular and Intermolecular H-bonding
These aspects have been discussed in Sec. 12.2.5.
12.2.22 Application of NMR Spectroscopy to Determine the Relative Amounts of the

Keto-Enol Tautomers in a Tautomeric Mixture
Detection of the keto-enol tautomerism by using the PMR spectroscopy has been discussed in Sec.
12.2.5. For the tautomerism in ~-diketones or ~-ketoesters, to determine the keto-enol ratio, the relative
intensities of the PMR signals of the )CH2 group (keto form) and the = CH- group (enol form) are
to be determined from their PMR spectra. For acetylacetone, the intensity (in terms of area) ratio of the
methyl and methylene protons in the pure keto form is 6:2, i.e. 3: 1 while the intensity ratio for the
ry
methyl and methine protons in the pure enol form is 6: 1. By measuring the peak areas of the meth-
ra
ylene and methine protons for a tautomeric mixture of acetylacetone, it has been found as: keto form
ib
20% and enol form 80%.
yl
12.2.23 Application of NMR Spectroscopy for Determination of Exchange Rate Constant
em
This aspects have been discussed in Sec. 12.2.15. The solvent exchange rate constant can be determined
by considering the NMR peak broadening phenomenon due to the exchange process (cf Chapter 5).
ch
al
12.2.24 Application of NMR Spectroscopy and MRI (Magnetic Resonance Imaging)
e
This aspect has been discussed in the author's book, Bioinorganic Chemistry.
th
12.2.25 Fluxionality through the Intramolecular Rearrangement and NMR Studies

e/
t.m
These aspects have been discussed in detail in Sec. 10.9 (Vol. 2) and Sec. 10.11. Some examples are
mentioned.
1. Fluxionality of PFsand PCI2F3in terms of 19F-NMR spectroscopy: These are discussed in Sec.
e
10.9 (Vol. 2) and Sec. 10.11. The 19F-NMR sectra of PCl2F 3 at different temperatures are given in
er
Fig. 12.2.15.4.
H
2. Fluxionality and rotational isomerism by PMR and 19F-NMR spectroscopy: These are discussed
k
in Sec. 12.2.20.
"8-
lic
3. Fluxionality of B3 in terms of PMR and I1B-NMR spectroscopy: This has been discussed
in Sec. 12.2.19.
C
4. Stereochemical nonrigidity of [NiX2(PR3)2] (polytopal rearrangement, tetrahedral ~ square

planar) by PMR spectroscopy: This has been discussed in Sec. 12.2.19.
5. Fluxionality of [M3(CO)12] and [Fe3(CO)12] in terms of 13C-NMR spectroscopy: This aspect
has been discussed in Sec. 12.2.19.
6. Fluxionality of Tl 3-allyl organometallic complexes by PMR studies: This aspect has been
discussed in Sec. 10.9.6 (Vol. 2) and Sec. 10.11.3.
7. Fluxional behaviour of [Ti(Tl s-Cp)2(Tl 1-Cp)2] in terms of PMR studies: This aspect has been
discussed in Sec. 10.9.6 (Vol. 2) and Sec. 10.11.3.
8. Fluxional behaviour of [(Tls-Cp)2Fe2(CO)4] and [Mo2(CO)6(lls-Cp)2] in terms of PMR and
13C-NMR spectroscopy: This aspect has been discussed in Sec. 10.9.6 (Vol. 2) and in Sec.
10.11.3. See Fig. 12.1.17.1 for the Mo-complex for the veo values.
9. Fluxionality of [Fe(CO)s)] in terms of the 13C-NMR spectroscopy: This aspect has been discussed
in Sec. 10.11.1.
10. Fluxionality of [RU(CO)3(Tl 4-CsH s)] in terms of the PMR spectroscopy: This aspect has been
discussed in Sec. 10.11.3.
11. Fluxionality of [(Me2C=C=CMe2)Fe(CO)4] in terms of the PMR spectroscopy: This aspect
has been discussed in Sec. 10.11.3.
12. Fluxionality of [Ta2(OCH3)10]: There are two bridging MeO groups.
(ax) CH 3 (ax)
(eq) HaCO"" 1./

OCHa./0"""
"""IOCHa
/OCH a (eq)
/Ta Ta
1""'- / I
ry
(eq) HaCO "'OCH a (eq)
OCH a""'- OCH a
(8H
ra
(ax) (ax)
a
ib
Bridging group
yl
There are 3 types of OCH3 groups: 2 bridging; 4 axial and 4 equatorial. In terms of the symmetry
em
operation, the 2 bridging groups are equivalent. Similarly, the 4 axial groups are equivalent and
the 4 equatorial groups are also equivalent. If the structure is stereochemically rigid, there will be
ch
3 types of PMR signals having the relative intensities 6: 12: 12, i.e. 1:2:2. It happens so at very low
temperature. But at high temperature, all these three types of OCH3 groups mutually interchange
al
rapidly (with respect to the NMR time scale) through the rupture of the bridging bond and only
e
one PMR signal is obtained.

th
13. Scrambling of Me-groups in A12Me6: In this dimeric form, there are two types of Me-groups:
e/
bridging and terminal. At low temperature, two PMR signals indicate the two types of Me-groups
t.m
but at high temperature, the rapid scrambling (through the formation of monomers followed by
their recombination, i.e. Al2Me6 ~ 2AIMe3 ~ A12Me6) of the Me-groups is indicated by one
e
PMR signal. This aspect has been discussed in Sec. 10.10.

er
14. Rotation of the coordinated olefin in [(Tl 5-Cp)Rh(C2H 4)2] (cf Fig. 10.11.3.16): Two different
H
PMR signals for C 2H 4 at low temperature suggest two different types of ethylenic protons but the
rapid rotation of the coordinated ethylenes around the Rh-C 2H4 bond at a higher temperature
k
lic
makes all the ethylenic protoris equivalent and one PMR signal is noticed. This has been discussed
in Sec. 10.11.3.
C
15. Fluxionality of [(Tl 5-Cp)Fe(CO)2(Tl 1-Cp)] (cf. Fig. 10.11.3.3b): In this tetrahedral molecule, the
ring whizzing of the a-bonded Cp (i.e. 1l1_Cp) can make the three different types of protons
equivalent. It is proved by the PMR studies at different temperatures (cf. Sec. 10.11.3).
12.2.2.6 Two-Dimensional NMR - ROSY, COSY, NOESY

Two dimensional NMR techniques like H/H, HlC, CtC COSY (2D-correlated spectroscopy); H/H,
HlC, ROSY (2D-J-resolved spectroscopy); NOESY (2D-nuclear overhauser exchange spectroscopy)
etc. have been found quite useful for structure determination specially in organic chemistry. The principles
and application of these advanced NMR techniques are beyond the scope of this present book.
12.3 ELECTRON SPIN RESONANCE (ESR) SPECTROSCOPY

A molecule or ion bearing the unpaired electron(s) absorb electromagnetic -radiation in the microwave
region under the influence of an external magnetic field. This electromagnetic radiation causes the
transition between the electron spin energy states. This phenomenon is described as the electron spin
resonance (ESR) or electron paramagnetic resonance (EPR) or electron magnetic resonance (EMR
cf PMR). It occurs for the paramagnetic substances, e.g. radicals, molecules (e.g. NO, 02, N0 2, etc.)
and transition metal complexes bearing the unpaired electron (s) e.g. Cu(II)-complexes.
12.3.1 Interaction between the Electron Spin and Magnetic Field: Some Basic Elements
of ESR Spectroscopy
The principle of ESR is very much similar to that of PMR. In PMR, the external magnetic field (Ho)
interacts with a positively charged proton while in ESR, the magnetic field interacts with a negatively
charged electron.
For an electron of spin quantum number, s = 1/2, the magnitude of spin angular momentum (Ps) is
ry
given by:
Ch1t}= S(zh1t )
ra
Ps =~s(s + 1)
ib
ms(z:) ~s(s+l) (z:)c0se
yl
The z-component of the spin angular momentum is given by i.e.
em
= ms (:1t) where e is the orientation angle of the spin angular momentum. It leads to:
ch
ms = ~s(s + 1) cosS. From the knowledge of quantum restriction, m s can have the two values ±1/2 and
al
m s is called the magnetic spin quantum number. The m s values (±1/2) indicate the two possible orientations
e
of the electron spin. In absence of any external magnetic field, these two orientations are degenerate.
th
But in presence of an external field, the spin degeneracy is removed. The low energy state is character-
e/
ised by the quantum number m s = -1/2 in which the spin magnetic moment (J..ls) is oriented in the
t.m
direction of the field. On the other hand, the higher energy state corresponds to m s =+ 1/2 where the spin
magnetic moment opposes the field.
The magnetic moment due to the spinning motion of an electron is given by (see Sec. 1.10.17,
e
er
Vol. 1):
~s = -~ Ps = -~ x ~s(s + I) x!!.-; ~s
H
(the negative sign indicates that the direction of

2m e c 2me c 21t
is opposite to that of Ps)
k
lic
=-2~s(s+1) (~J
C
41tm c e
= -2~s(s + 1) JiB'
In general, J..l s =- g ~ s(s + 1) J..l~; g (called Lande splitting factor) :::= 2 (for a free electron)
A eh (4.8 X 10-10 esu) (6.62 x10-27 erg s)

Jl B (ca11e d B 0 hr magneton ) = tJ =--- =---------.;.------~
41tm e c 4 x 3.14 x 9.1 x 10-28 g X 3 X 10 10 cm S-1
= 9.27 X 10-21 erg a-I
In SI unit, ~B = f3 = ~ =9.Z74 X 10-24 JT- 1

41tm e
Energy of an electron in a magnetic field (Ho) is given by:
E=-ll z Ho =-(llscose)Ho =-(-gIlBJs(s+l)cose)Ho

= gJIBmsHO = g~msHo' (denoting JIB by~)
1
For the ±- values of m s, the energy values are:
2
( IJ 1
E 1 forms =-- =--gJIBHO =--g~Ho; E 2
2 2 2
1 (forms =+-2IJ =-gJIBHO
1
2
1
2
=-g~Ho
Thus energy for + 1/2 spin (a-spin) linearly increases with the field Ho while the energy for -1/2 spin
(f3-spin) linearly decreases with the field H o (Fig. 12.3.1.1). For the a-spin, magnetic moment arising
ry
from the spinning motion of the electron has an unfavourable orientation (i.e. north pole of the magnetic
ra
field produced by the spinning electron comes nearer to the north pole of the external field). On the
other hand, for the ~-spin, the magnetic moment arising from the spinning motion has a favourable
ib
orientation in the external magnetic field.
yl
em
MJ = +...L
(Free ion 2
ch
state) ""~
------t::::",,- hv = g~Ho
al
J= ..!- ""
2
i'
e
~-----.~Ho ms =+ a-spin (t)

th
MJ =-....:!-.
(E = + .1 g~Ho)
e/
2
2
t.m
e
er
r
H
ms = - i '~-spin (t)
k
1
lic
(E = -"2 g~Ho)
C
No field Ho-------+~
Fig. 12.3.1.1 Variation of electron spin energy with the externally applied magnetic field strength and ESR transition
(selection rule: ~ms =±1). Inset represents splitting of the state J =1/2 by a magnetic field and ESR transition (selection
rule: ~J = ±1); here J is assumed to be a good quantum number (see Vol. 1).
Note: For a proton, the lower energy state corresponds to m/ = +1/2 while the higher energy state
corresponds to m/ = -1/2. This difference for the electron and proton arises for their opposite charge
bearing properties.
• Energy difference and frequency of ESR transition: The mechanism of ESR transition is
similar to that of PMR transition. The spinning magnetic moment vector of an electron precesses
around the magnetic field. ESR transition occurs when the frequency of the oscillator electromagnetic
radiation matches with the precessional frequency. The energy difference (~E) for the two states char-
acterised by + 1/2 and -1/2 is given by:
~ = E 2 - E 1 = g~BHo = g~Ho, (denoting ~B by ~).
24
g~Ho 2x9.274x10- JT- I H o 10 -I -I
For~=hv,orv=--= 34 =2.86x10 s T xHo
h 6.26 x 10- Js
For, H o = 0.5 T (i.e. 5 x 103 G), V = (2.86 X 1010 x 0.5) Hz = 1.43 X 10 10 Hz
Generally, the ESR frequency lies in the range 3 x 106 to 3 X 10 10 Hz (microwave region of
electromagnetic spectrum). The higher ESR frequency compared to that of PMR frequency is due to
the smaller mass of an electron (cf. Sec. 12.2.1) (cf. magnetic moment values, JlN and JlB values, Sec.
12.2.1).
• Method of ESR studies: As in the case of PMR studies, it can be done in two ways: varying the
magnetic field strength for a fixed oscillator frequency or varying the oscillator frequency for a
fixed field strength. As in the case of PMR studies, in the ESR studies, generally magnetic field is
ry
varied for a fixed oscillator frequency. There are two types of ESR instruments-X- and Q-band
ra
spectrometers. In the X-band spectrometer, the operating microwave frequency is around 9400 MHz
ib
and the magnetic field around 3000 gauss is varied. In the Q-band spectrometer, the operating frequency
is around 35,000 MHz and the magnetic field around 12,500 gauss is varied. Obviously, the ESR
yl
spectrometer at higher operatingfrequency (i.e. Q-band) is more sensitive. The higher operating frequency
em
requires the higher magnetic field for the ESR transition. The higher field makes the energy difference
(~ higher, i.e. the Boltzmann population density ratio (ntln2) becomes higher at the higher field. It
ch
enhances the intensity of the ESR signal (cf. intensity of an NMR signal at higher field, Sec. 12.2.2).
e al
Energy change (dE) in ESR and PMR transitions (cf. Sec. 12.2.1)
th
ESR: !i.E = hv = g.f3po i.e. v ESR = ge~eHo ; ge = 2, ~e = 9.27 X 10-21 erg a-I
e/
h
t.m
PMR:!i.E = hv = gpfJ/fo i.e. V pMR = gp~pHo;

h
gp =5.5854,
.)
~p = 5.05 X 10-24 erg a-I
e
er
21
V ESR = ge~eHO = 2 x 9.27 X 10- "" 660
H
V pMR gp~pHo 5.5854 X 5.05 X 10-24

k
Thus for a particular magnetic field, resonance frequency for an electron is about 660 times
lic
higher than that for a proton and VPMR lies in the radio-frequency region while VESR lies in the
C
microwave region.
• Intensity of an ESR signal: The relative distribution of the electrons between the two electronic
spin energy states is determined by Boltzmann law.
n
n
2
(
(_~)
+~) = exp (- liE
kBT
J= exp (- g~Ho J
kBT
l
liE (for ESR) is much larger than ~ (for PMR) i.e.
nl population density at the lower level (n l J (n l J because ~E (ESR) » ~ (PMR)

-;;; = population density at the higher level' -;;; ESR» -;;; PMR
Thus for ESR, the ground level is more populated compared to that in PMR. It makes the ESR
signal more intense (cf. Sec. 12.2.2). The rapid relaxation reestablishes the Boltzmann equilibrium to
maintain the intensity of the signal throughout the experiment.
• Width of an ESR signal and representation of the ESR signal: The bandwidth (i.e. natural peak
broadening) is determined by the Heisenberg's uncertainty principle (liE x ~t ~ h). A shorter relaxa-
tion time (i. e. time required for the electron to revert from the excited level to the ground state)
compared to that in PMR reestablishes the Boltzmann equilibrium fast (to favour to maintain the
intensity of the ESR signal, cf. Sec. 12.2.2) but the peak is broadened (cf. ESR bandwidth == 1 -10
MHz; PMR bandwidth == 0.1 Hz).
It is more difficult to analyse a broad peak of an ESR signal and to avoid this difficulty, the signals
are recorded as the derivative ofthe absorption curve with respect to the magnetic field (Fig. 12.3.1.2).
ry
At the point of maximum absorption, the derivative curve crosses the abscissa. It may be noted that the
ra
shoulders in the curve (c) do not pass through a maximum and consequently, the corresponding derivative
ib
peaks do not cross the abscissa. The total number of peaks and shoulders present in the absorption
yl
curve can be obtained by the number of maxima or minima in the corresponding derivative curve.
em
The total area covered either by the absorption peak or the derivative curve is proportional to the
number of unpaired electrons. In order to calculate the number of unpaired electrons, a standard sample
ch
having a known number of unpaired electrons is used for comparison.
e al
th
(A single
i
e/
/bsorptlon peak)
t.m
~
c:: ~ Absorption curve
o
E-
e
o
en
..-J
er
~
< Shoulder
H
k
(a)
lic
(c)
C
First derivative (2 shoulders and

curve 2 peaks)
(1 Peak)
Ho ---+
1 Maximum (*)
4 Maxima (*)
1 Minimum (**)
4 Minima (**)
(b) (d)
Fig. 12.3.1.2 Presentation of an ESR signal. (a) An ESR absorption curve. (b) First derivative of the spectrum in (a).
(c) Four equally spaced overlapping peaks (absorption curve). (d) First derivative of the spectrum in (c).
12.3.2 Relaxation Processes: Intensity and Bandwidths of the ESR Signals

For the ESR transition, liE =hv =g~Ho. For Ho =3300 gauss =0.33 T, liE:::: 6 X 10- 17 erg per molecule
= 6 x 10-24 J per molecule, kB = 1.38 X 10-23 J K-1 per molecule; at 300 K, kBT:::: 4.2 X 10-21 J per
molecule. Applying the Boltzmann distribution law, we get:
n2 population density at the higher level (!ill )

~ = population density at the lower level = exp - kBT
=exp ( J
6xl0-24 ::::exp (-3)
-10 (-3) ::::0.999=--
~ 1-10
999
4.2 X 10-21 1000
=~,(N=104);(ForPMR,!!2=~,N=106J
ry
:::: 10000
10,009 N +9 n1 N +9
ra
It indicates that for every 1000 electrons at the ground state, there are 999 electrons at the
ib
excited state. This small difference (though much greater than that in PMR) may lead to saturation (i.e.
yl
n1 :::: n2), if the excited electron in ESR transition does not rapidly come back to the ground state to
em
maintain the Boltzmann equilibrium. It may be mentioned that for the saturation condition (n1 :::: n2),
the rate of upward transition (energy absorption) :::: rate of downward transition (i.e. energy emission of
ch
the same frequency) and there will be no net absorption (i.e. no signal).
al
To maintain the intensity (which is determined by the ntln2 ratio), the Boltzmann equilibrium should
be rapidly reestablished after the upward transition. This is attained by the relaxation process (i.e.
e
th
return from the excited state to the ground state without any emission of radiation).
Relaxation process not only controls the signal intensity but also the bandwidth. According to the
e/
uncertainty principle, IiElit ~ h i.e., hliv 1/ 2 lit :::: h or, ~V1/2 (measuring the half bandwidth) ~ 1/lit
t.m
where lit gives the life time of the excited state. If the relaxation process is very fast (i.e. lit small), the
bandwidth becomes large. If the bandwidth is increased too much, then the signal cannot be studied. A
e
similar problem also arises in the NMR studies (Sec. 12.2.2).

er
For the higher intensity, the ratio n 1ln2 should be higher. It is attained by using the higher
H
operating frequency (i.e. higher field, cf, X-band vs. Q-band spectrometer) and lowering the working
temperature. The same principle is also practised in the NMR spectroscopy (cf Sec. 12.2.2).
k
lic
As in NMR, the important relaxation processes in ESR are:

(i) spin-lattice relaxation, (ii) spin-spin relaxation and (iii) exchange interaction.
C
(A) Spin-lattice relaxation and EPR peak broadening: This involves the interactions of the
paramagnetic substance with the thermal vibrations of the lattice (framework of the molecule, i.e.
surroundings). The excess energy of the excited paramagnetic substance is transferred to the vibrational
degrees of freedom of the lattice (cf Sec. 12.2.3). Thus in spin-lattice interaction, the excess energy
of the excited spin state is transferred (during the return to the lower energy spin state) as the added
translational, vibrational or rotational energy of the lattice. If the temperature is lowered, the thermal
violence in the interatomic motions of the lattice is decreased, and the spin-lattice relaxation process
becomes less efficient, i.e. the spin-lattice relaxation time (T1) becomes larger. At room temperature,
T 1 is about 1(J"4-1 0-6 s but at the temperature of liquid nitrogen or helium, T 1 may be in the scale of
several minutes.
• Dependence on the physical state: In liquid state, T 1 is approximately in the range 10 1 to 10-4 s
while in solid state it lies in the range 10-2 to 104 s. The higher efficiency of the spin-lattice relaxation
process in liquid state is due to the greater freedom of molecular motion.
• Dependence on the ground state term: Spin-lattice relaxation process is favoured if there are
electronic energy levels lying above the ground state by the energy in the order of kBT (available
thermal energy). This aspect is ofan important considerationfor the transition metal complexes. Let us
consider the octahedral complexes having the Ag, E g and T g ground states. For the A g and Eg ground
states, there is no excited level lying -kBT above the ground energy level. Consequently, in such cases,
the spin-lattice relaxation time is relatively longer (i.e. peaks are relatively sharper) and the ESR
signals can be recorded even at ordinary temperature (provided the spin-spin interaction and exchange
interaction are controlled by proper dilution).
On the other hand, for the octahedral complexes having the Tg ground state, the spin-orbit coupling
(Appendix 12C and Fig. 12.3.2.1) and low symmetry ligand field (cf. chapters on Electronic Spectra
and Magnetic Properties) can split the Tg state.
ry
ra
ib
yl
em
ch
e al
th
e/
t.m
e
er
H
k
lic
C
(a)
(Spin-orbit
coupling)
Ho
Fig. 12.3.2.1 (cf. Appendix 12C) Spin-orbit coupling splitting of the T-ground state (energy states not in scale).
(a) High spin octahedral complex of d' system e.g. Co(ll) (cf. Chapters 7 and 8; Figs. 8.20.3.6, 8.21.1).
Note: Spin-orbit coupling splits the 4T1g ground state into 12 low lying energy states and the 3T1g
ground state into 9 low lying energy states (cf. Appendix 12C; Fig. 12.3.2.1). These closely spaced
electronic energy states make the spin-lattice relaxation faster.
Splitting of the T 1 and T 2 levels on distortion or introduction of lower symmetry (cf. correlation
diagram):
0b Symmetry D4b D 2d C 4v C 2v D3d D3
T Ig A 2g + Eg A2 + E A2 + E A2 + B I + B 2 A 2g + Eg A2 + E
T 2g B 2g + E g B2 + E B2 + E Al + B I + B 2 A ig + Eg Al + E
These split electronic energy levels are very often separated from the ground energy level by the
order of 200 em-I. This energy difference is thermally available and the spin-lattice relaxation proce·
becomes very much favourable (i.e. spin-lattice relaxation time T I becomes very small and consequen'
the signals are broadened). Consequently, for the octahedral complexes having the Tg ground state, 1
ESR signals can hardly be obtained at room temperature. For such systems, the ESR studies are to be
carried out at very low temperature (e.g. liquid He and N 2 temperatures) so that the thermal energy
(kBT) becomes in the order ofonly few cm-1 (i.e. at this low temperature, T I becomes sufficiently large
ry
to generate the ESR signals). Here, it is worth remembering that for the Tg ground state because of the
ra
existence of the energy levels (due to spin-orbit coupling) separated from the ground level by the order
ib
of kBT, the magnetic moment becomes a complicated function of temperature (see Chapter 8).
yl
;
1
em
1
I
1
1
1
1
ch
1 J=O
1
1 1'------+-------
al
1 ,,' 1
T29
e
I~""
" """ 3 1"
------<~\ "
th
1
\ 1
J=1 +1
e/
\ 1
" "
\ 1
\ 1 , . - - - - -..........~----- o
t.m
\ 1 ,.,. ,.,.,.
\ 1 ,. .f -1
\ 1 ,.
\ 3..- 1 ,.,.
e
" 1 19
\ ( I,.
er
( (L = 1, S =1) " ,
H
(Oh crystal '"

+2
field) " ,,
k
,, J=2 +1
lic
,------...E------- o
• (Spin-orbit
C
(b)
coupling)' -1
-2
Ho
Fig. 12.3.2.1 (Appendix 12C): Spin-orbit coupling splitting of the T-ground state (energy states not in scale) (b)
Octahedral complex of t:P system e.g. V(III) (cf Figs. 8.20.3.6, 8.21.1).
• Dependence on the degree of covalence in the metal-ligand bond: Spin-lattice relaxation process
depends on the degree of covalence in the metal-ligand bond. For the higher covalence, the vibrational
frequency o.f the metal-ligand bond increases and the spin-lattice relaxation process becomes less
efficient. In [Ti(acac)3]' higher covalence (i.e. T1 is large) allows its ESR studies but [Ti(OII 2)6]3+ having
a less covalence in the Ti-O bond fails to give the ESR signal because its T1 is small.
Broad ESR signal: Octahedral complexes of d1(ZT zg ), ~(3Tlg), tr(low spin, 3T 1g ), tP(low spin,
ZT zg ), tF(high spin, 5T zg ), J7(high spin, 4T 1g ) ofTg ground state; can be studied only at very low
temperature.
Sharp ESR signal: Octahedral complexes of d 3 (4A zg ), high-spin ~ (5Eg), high spin tP (6A tg ), tJ8
(3 A zg ), cP (ZEg); can be studied even at room temperature. However, if the excited T-state lies
close to the ground A or E state, then spin-orbit coupling mixing with the excited T-state makes
the ESR studies difficult at room temperature. It happens so for the tetrahedral complexes
(e.g. d 1 system having the zE ground state and zTz excited state; d' system having the 4A z ground
state and 4T z excited state; etc) where the excited T-Ievellies close to the ground level and in some
octahedral complexes (e.g. tJ8 system mixing with the excited 3T zg state).
ry
(B) Spin-spin relaxation and EPR peak broadening: In this process, the excess energy of the
ra
paramagnetic substance is transferred to the neighbouring electron spins. The local magnetic field
ib
produced by an electron at a distance of r is proportional to ~. This local field that exists on the
yl
r
em
neighbouring paramagnetic substance influences the electron spins.
In general, the spin-spin relaxation process is more efficient (cf. spin-spin relaxation time
ch
Tz ::::: 10-6-10-8 s; T 1::::: Tz in liquid state but T 1» Tz in solid state) than the spin-lattice relaxation process
provided the sample is not extremely magnetically diluted. In such cases, Tz controls the bandwidth, i.e.
al
~Vllz'=~+~'=~(TI
e
»Tz ). Taking Tz = 1O-7s (found in this range for the most samples),
T} T2 T2
th
~V1I2 (,= ;2)

e/
becomes 10 MHz (which is much larger than that found in the PMR signals having
t.m
~VllZ ::::: 0.1 Hz).

The local magnetic field produced by the paramagnetic substance is inversely proportional to the
e
third of the distance (i.e. ?). Thus the efficiency of the spin-spin relaxation process can be reduced if
er
the distance (r) between the paramagnetic centres is increased. This is done by magnetically diluting the
H
paramagnetic sample by using a large amount of a diamagnetic isomorphous host lattice. This dilu-
k
tion technique minimises the proximity of the paramagnetic sample centres, i. e. spin-spin relaxation
lic
process is disfavoured to increase Tz. This magnetic dilution (dilution factor) 100) is illustrated,in the
C
following examples.
(i) For the ESR studies of Cr3+(d3), it is doped (about in 1% concentration) in the diamagnetic
o
substance KAI(S04)2·l2H20 where Cr3+ isomorphously substitutes A1 3+ in this solid solution.
Here it is worth mentioning that though KCr(S04)z·12H zO is isomorphous with the host substance
KAl(S04)z,12H zO, their unit cell parameters are not identical. This factor must be taken into
consideration for the analysis of the ESR signal.
(ii) [Cu(bigH)zl (s =~) can be magnetically diluted when it is isomorphously crystallised in the
host lattice of the diamagnetic square planar complex, [Ni(bigH2l. This allows the ESR studies
of [Cu(bigH)zJ
(iii) For the ESR studies of Na2[IrC16l (t i g, S= ±). it is doped into the diamagnetic host lattice of
Na2[PtC16l
(iv) For the ESR studies of (NH4)2Ni(S04)2· 6H20 bearing [Ni(OH2)6]2+, it is doped into the diamagnetic
host lattice of (NH4)2Zn(S04)2· 6H20.
Question: For an ESR study of a paramagnetic substance, it is incorporated as a trace impurity

in an isomorphous diamagnetic compound-why?
(C) Exchange interaction and EPR peak broadening: It is basically a spin-spin relaxation process (a
bimolecular process) but it generally prevails in the magnetically concentrated systems through the
overlap of the orbitals bearing the unpaired electrons. However, this process can be minimised through
the magnetic dilution as discussed above.
As in NMR, the rapid exchange process (cf. Secs. 12.2.15 and 12.3.14) leads to peak broadening
ry
(called exchange broadening) of the EPR signal. At a certain exchange rate, the peaks will coalesce to
ra
produce a single peak to give a weighted-average of the peaks. In fact, the peaks due to hyperfine
splitting will experience peak broadening and but they undergo merging to give a single peak when the
ib
electron spin exchange rate becomes quite fast. This is called exchange narrowing (see Sec. 12.3.14).
yl
Thus hyperfine splitting leads to peak broadening but the rapid electron spin exchange leads to
em
peak broadening (i.e. exchange broadening) and then to merging of the hyperfine peaks into a single
sharp peak (i.e. exchange narrowing) if the electron spin exchange process is sufficiently fast. This
ch
aspect has been illustrated for some free radicals like DPPH, nitroxides etc. which show the hyperfine
al
peaks at very low concentration (when the bimolecular spin exchange rate is sufficiently slow) but at
the relatively higher concentration, the hyperfine peaks merge into a single peak. These are discussed
e
th
in Sec. 12.3.14.
e/
(D) Motional broadening of the EPR peaks: If the paramagnetic molecule is large, its motion (tum-
bling motion) is restricted, specially in a viscous medium. It leads to a residual anisotropy causing a
t.m
peak broadening of the EPR signal. This is called the motional broadening of the EPR peak. In fact,
rapid tumbling can average out the anisotropies and this peak broadening can be avoided.
e
(E) EPR peak broadening due to hyperfine and superhyperfine interaction: Splitting of the EPR
er
peak due to the hyperfine and superhyperfine interaction causes the peak broadening in general.
H
Hyperfine lines generated for the different isotopes of a particular metal may not overlap and then
the broad signals appear. Anisotropic g-values leading to the parallel and perpendicular hyperfine
k
lic
lines can cause the broadening of the ESR signal. Slow tumbling rate of the paramagnetic sample fails
to average out the anisotropies and it broadens the ESR signal.
C
12.3.3 Fine Structure of ESR Signals: Zero-field (Crystal Field) Splitting: Kramers'
Degeneracy
Fine structure of the ESR signals arises when the sample bears more than one unpaired electron. It
happens so, very often in different transition metal ion complexes. It is illustrated in some representa-
tive systems.
(i) Two unpaired electrons (e.g. tfl, tIS): Let us illustrate for a crystal containing the molecules or
ions with two unpaired electrons. It gives: S = 1 where S denotes the total spin quantum number, and
M s = ±1, O. In presence of an external magnetic field, the enegy state for M s = +1 is raised; the energy
state for M s =-1 is lowered in energy and the state corresponding to M s = 0 remains unaffected. It may
be mentioned that for the nuclei with I = 1, the energy state corresponding to M1 = + 1 is lowered; the
energy state corresponding to M1 = -1 is raised; and the energy state corresponding to M1 = 0 remains
unaffected in presence of an externally applied magnetic field. This difference in splitting pattern
occurs because of the opposite nature of charge for the nuclei and electrons. In terms of the ~election
rule of AMs =±1 (or AM) =±1) for the ESR transtion, the possible transitions are:
Ms =-1 ~ Ms=O;Ms=O ~ Ms =+l.

For each of these two ESR transitions, the energy change (I1£) is the same, i.e. these two spectral
transitions will give a single ESR signal. But in reality, it gives two different ESR signals (fine
structures). It indicates that the energy levels are not symmetrically split as shown in Fig. 12.3.3.1a.
The dipolar interaction arising from the spin-spin interaction (similar to spin-spin coupling between
the nuclei, cf Sec. 12.2.9), spin-orbit coupling and noncubic crystal crystal field effect (e.g. trigonal,
tetragonal, rhombic, etc.) can perturb the energy states for Ms = ±1 even in absence of an external
magnetic field. This phenomenon is called zero-field or crystal-field splitting (measured by 8) which
ry
raises the energy states for Ms = ±1 (maintaining the degeneracy) with respect to the energy state for
Ms =0 in the absence of any external magnetic field. This zero-field splitting which removes the spin
ra
degeneracy becomes very much important for the transition metal complexes experiencing specially
ib
the ligand field components of low symmetry and spin-orbit coupling splitting of the T-ground state.
yl
The zero-field splitting for the energy states corresponding to M s = ±1 and M s = 0 is shown in Fig.
em
12.3.3.1b, c. ch
al
Ms =+1
e
>-
~
th
Q)
c:
W
e/
1
t.m
Ms = ±1, 0
e
- - - ---I-'fIl.'-------+------ Ms = 0
er
No field
~E= hv
H
~Ms =±1
k
Note: One transition (denoted by

lic
solid arrow) at fixed operating

frequency (v).
C
Ms =-1
---+ Ho
(a) No zero-field splitting
Fig. 12.3.3.1 Zero-field splitting and its effect on ESR transitions for a triplet state (S = 1 i.e. Ms = 0, ±1). (a) No zero-
field etTect, two ESR transitions for !:!Ms = ±1 at the same field for a fixed operating frequency, i.e. one strong ESR
signal (assuming no hyperfine splitting).
Under the influence of an external magnetic field, the degenerate energy states for M s = ±1 are
separated out (i.e. M s = -1 state is lowered and M s = + 1 is raised). Thus considering the moderate zero-
field splitting (i.e. hv » 8), two ESR transitions occurring at different Ho values for a fixed probe
frequency (v) (Fig. 12.3.3.1 b) can be explained. This explains the origin of fine structure components
of the ESR spectrum. The forbidden transition (i.e. 8Ms =±2, transition between the states of M s =+ 1
and -1) gives a weak signal. If the zero-field is splitting is very high (i.e. 8» hV) (Fig. 12.3.3.1c), then
only the forbidden transition (i.e. a weak signal) is observable in the microwave range of frequency.
The condition, S = 1 is present for the Ni(II) complexes (If, 3A 2g ); V(III) complexes (tP, 3T1g ); triplet
state of the dimeric complexes of Cu(II) (tP) and oxovanadium(IV) (d 1).
(ii) Kramers' degeneracy and odd number of unpaired electrons (n ) 1 i.e. n =3, 5, etc.): It has
been shown that for S = 1 (i.e. n = 2), the zero-field splitting can remove the degeneracy of the states
corresponding to Ms = ±1, 0 and it explains the origin of two fine structure components of the ESR
signal.
For the systems bearing an odd number of unpaired electrons (as in high spin MnII octahedral
complexes, t/ge; i.e. 6S ground state term), the zero-field splitting cannot remove the total spin degeneracy
ry
and in such cases, the zero-field splitting produces the doubly degenerate spin states. This phenomenon
ra
is called Kramers' degeneracy.
(iii) Zero-field splitting in different systems: It is present in absence of an external magnetic field
ib
for n (number of unpaired electrons) ) 1 and it introduces the fine structure in the ESR spectrum. It is
yl
illustrated for the different values of n.
em
Ms = +1
E+ 1 =8 + g~Ho
ch
Note: The total 3 transitions (denoted by
solid arrows) at a fixed operating frequency.
al
Two allowed transitions at a fixed field are
e
denoted by dashed arrows (v2 > V1). The

th
frequency of the corresponding forbidden

transition (~Ms = ±2) is (v 1 + v2).
1
e/
t.m
~Ms = ±1
Ms = ±1
~Ms= ±2 ~E =hv
v (microwave or - - hv » ~-I--- ~E= hv
e
ESR frequency) M =0
s
er
.......----~--t--------.----_- Ms = 0
(Zero field Eo =0
H
splitting, ~E = hv
independent
k
of Ho)
lic
C
Zero-field splitting Ms =-1

removes the spin E_ 1 = 8 - gJ3H o
degeneracy
-+ Ho
(b) Moderate zero-field splitting
Fig. 12.3.3.1 Zero-field splitting and ESR transitions for the triplet state (S = I, Ms = 0, ±I). (b) Moderate zero-field
splitting (8); two allowed ESR transitions (tiMs =±I) at different fields for a fixed operating frequency producing two
strong ESR signals; in addition to these two intense ESR signals, the forbidden transition (tiMs = ±2 i.e. transition
between Ms = + 1 and Ms = -I) producir..g a weak signal.
n =2 (i.e., S =1, Ms =±1, 0): The energy states are: M s =±1 ) M s = 0 (Fig. 12.3.3.1b, c)
n = 3 (. 3 3 1) 3 1
l.e.,S=-,M s =±-,±-: The energy states are: Ms=±-)Ms =±- (Kramers
2 2 2 2 2
,
degeneracy) (cf. Fig. 12.3.3.2).

n = 4 (i.e., S = 2, M s = ±2, ±1, 0): The energy states are: M s = ±2 ) Ms = ±1 ) Ms = 0 (cf.
Fig. 12.3.4.2).
. 5 5 3 1)
n =5 ( I.e., S =-, M s =±-, ±-, ±- : The energy states are: Ms =±-5 > M s =±-3 > M s =±-1
2 222 2 2 2
(Kramers' degeneracy) (cf. Fig. 12.3.3.3).
Thus for, n =even, except for M s =0, all other energy states are doubly spin degenerate. For n =odd
ry
(>1), all the energy states are doubly spin degenerate (Kramers' degeneracy).
ra
ib
yl
Ms =+1
Ms =±1
em
~Ms
ch
= ±2 (Forbidden transition)
e al
v (microwave or
th
ESR frequency) hv« 8 Ms =-1

e/
t.m
Ms=O
(Zero-field (v 1 and V 2 » microwave frequency)
e
splitting NO ESR Signal

er
independent
of Ho)
H
----. Ho
k
lic
(c) Large zero-field splitting
Fig. 12.3.3.1 Zero-field splitting (removing the spin degeneracy) and its effect on ESR transitions for a triplet state (i.e.
C
S = 1, Ms =~ ±1) (c) Large zero-field splitting (8) and the energy change for the allowed ~s =±1 transitions becomes
too large to be observed in the microwave region; only the forbidden transition (tJMs = ±2) may produce a weak ESR
signal.
On application of an external magnetic field, all the doubly degenerate spin states will undergo
further splitting.
(iv) ESR transitions for S = 1 and M s = ±1, 0: For the Ni ll (t2~ei), V1II(tfg), Fe(VI) (tP) (i.e. FeOl-
in K2Cr04 host lattice), dimeric complexes of CUll (cP) and oxovanadium(IV) (d l ), the allowed ESR
transitions (~s = ± 1) are:
M s = -1 ---7 M s = 0 and M s = 0 ---7 M s = +1 (cf. Fig 12.3.3.1b)
Besides these two allowed ESR transitions, there is a forbidden ESR transition (AMs = 2) i.e.
M s =-1 ---7 M s =+1
These ESR fine peaks may undergo further hyperfine and superhyperfine splitting depending on the
condition. This aspect will be illustrated later.
Ms = ±.3. , ±1.
2 2
ry
ra
ib
yl
em
ch
Ho
al
(a) One allowed ESR transition at a fixed operating frequency (v)

e
th
3
Fig. 12.3.3.2 (a) No zero-field splitting and one ESR signal for S = 2"
e/
t.m
Ms=+l
2
4 3
T1g E = 8 + 2g~Ho
i
+
e
>. I
~ I
",'"
",'
en I
er
I
",'" Co I
",'" C I
4 ",'"
",'"
8DQo w I
I
H
F ",'" 4
T2g I
I
~Ms = ±1 hvs
(t~g)
(~----------
, t I
I
I
I
k
" "",, I
I
lic
I
,, I
, 3 I
I
I
" 10DQo MS =±2 Ms =+l

C
I
I 2 1
'" ,.... (4
A29 )
'
,.'"
.....
",'"
, 8
\
\
\ ,.,." ,."
,.,." f
I
E =2g~Ho
S=~ ~Ms = ±1
..... ..... ,.~,.,. I
I
2 ,,~~ I hV2
I
1 \', I
(Oh crystal MS =±2 \ " " Ms =_l I
I
\ 2 1
field) (Tetragonal field)
(Zero-field
\
\
\
\
\
"
~Ms = ±1
f
I
I
E = -2g~Ho
I
splitting and \
\ I hV 1
\ I
Kramers' \ I
Zero-field splitting \
\ Ms=_l I
degenracy)
removing the spin \
\ 2 + E = 8 _lg~Ho
degeneracy 2
(b) Three allowed (~Ms = ±1) ESR transitions (v 1, v2, v s) at a fixed field
Ms=+~
2
Note: • 8 is called zero-field splitting or tetrago-

nal splitting parameter: If hv « 8, (v = operating
frequency in the microwave region) then the transi-
/ tion, M s = +.!~ M s = +~ is not observed at

--;-", 8 2 2
A29 '--&_-<
i\M s = ± 1 any attainable field (Fig. 12.3.3.2b).
MS =±"21 • If the zero-field splitting (8) is very high, then
the energy levels corresponding to Ms = ± ~ lie so
ry
(Zero field
splitting
ra
and Kramers' high above the energy levels corresponding to
degeneracy) 1 3
ib
Ms = ±"2 that the energy levels for Ms = ±"2 do
yl
not participate in producing the ESR signal at any
em
attainable magnetic field (cf. Fig. 12.3.3.1 b, c). Un-
der this conditions, only one ESR transition for the
1
ch
energy levels of M s = ±"2 is noted (i.e. effective
1
al
electronic spin S' becomes "2' though the calcu-
e
3
lated spin is "2).
th
----+ Ho
e/
(c) Three allowed (L\M s = ± 1 ) ESR transitions

at a fixed operating frequency
t.m
Fig. 12.3.3.2 (b) and (c) Tetragonal splitting or Zero-field splitting (8) and Kramers' degeneracy for Cr(III) (d3, in
octahedral complexes) and splitting of the M s levels on the application of a magnetic a magnetic field showing the three
e
allowed (~s = ±1) ESR transitions at a fixed operating frequency.

er
Here it may be mentioned that if the zero-field splitting (measured by 8) is very high (i.e. » hv) a
H
(Fig. 12.3.3.1c), the allowed (~s = ±1) ESR transitions may not lie in the microwave regjon and in
such cases only the forbidden ESR transition (~s = ±2) produces a very weak signal.
k
lic
(v) ESR transitions for S =3/2 as in the octahedral complexes of Cr(III): Without the zero-field
splitting, it produces only one ESR transition (Fig. 12.3.3.2a). But it does not support the experimental
C
finding. It needs the consideration ofthe zero-field splitting. Here, S == l, M s == ±l, ±! and the zero-
2 2 2
field splitting energy order is: M s == ±l ) M s == ±! (Kramers' degeneracy). All these doubly degenerate
2 2
spin states undergo splitting in an external magnetic field (cf. Fig. 12.3.3.2b, c) and there are three
allowed ESR transitions (L\M s = ±1).
3 1 1 1 1 3
M s =-2~Ms =-2"; M s =-2"~Ms =+2"; M s =+2"~Ms =+2"
Here it is worth mentioning that all these three allowed ESR transitions may not lie in the microwave
region (-30,000 MHz). The exact energy change in the allowed ESR transitions depends on the magnitude
of zero-field splitting. For many Cr(III) complexes, instead of three ESR fine peaks, only one peak is
obtained because the energy states for M s == ±l fail to participate in the ESR transitions. It happens
2
so for very high zero-field splitting (ef Fig. 12.3.3.1b, c). The ESR spectrum for er(III) has been
discussed in Sec. 12.3.4 (ef Fig. 12.3.4.1).
(vi) ESR transitions in the high-spin octahedral complexes of dS system e.g. Fe(III), Mn(II):
There are five unpaired electron (~g ei
i.e. S =2. andMs =±2., ±l, ±-.!..). According to Kramers'
2 2 2 2
degeneracy, the zero-field splitting produces the three doubly spin degenerate energy states and the
5 3 1
energy order is: M s =±2" > M s =±2" >M s =±2"
It leads to five allowed ESR transitions (i.e. 5 fine components; Fig. 12.3.3.3a, c) following the
selection rule ~s = ±1.
ry
5 3 3 1 1 1
Ms = -2~Ms =-2"; M s = -2"~Ms =-2"; Ms = -2~Ms =+2";
ra
ib
133 5
M s =+2~Ms =+2"; Ms =+2"~Ms =+2"
yl
em
The high spin (octahedral) d 5 system gives the 6A 1g ground state which is orbitally nondegenerate.
This state can mix with the excited 4T 19 state (orbitally degenerate and it can be split by crystal field)
ch
e al
th
I
e/
I
I
t.m
hv s :
~ I
El
Q)
I
+~
I
c: 2
v (ESR frequency)
e
W
er
(0 1 «hv)
Ms=±~
H
l +..1
2
k
S 1
(d 3 20
lic
Ms =±"2
6 )
S6 ---I----IC
(A19) -_...Ioo---foII~
C
(Weak zero-field
splitting)
-~
2
~Ms =± 1
-..§.
2
---+ Ho
(a) 5 allowed (~Ms = ± 1) ESR transitions (denoted by solid arrows) at a fixed operating
frequency (v); 5 allowed ESR transitions (denoted by dotted arrows) at a fixed field.
S
(Small zero-field splitting i.e. 81 « hv; weak tetragonal field for the high spin d system)
~
e>
(J)
v (ESR frequency) c:
W
(8 1 »hv)
ry
-~
2
ra
+1-
--M-s-=...!+~_-:;-1 ----lr-===:====-_~h~v~ 1
ib
_ _
yl
- 2 (gil = 2, g-1- = 6) 2
em
(Strong zero-field
splitting) ch Ho
(b) Large zero-field splitting (8 1 » hv) and one ESR signal noted between the
Ms = +i -iand states (i.e. S' = i); Strong tetragonal field for high spin
al
S
d system) (cf. Fig. 12.3.7.15) for splitting in rhombic symmetry)
e
th
e/
t.m
Hyperfine
e
structure
er
transitions
H
k
lic
C
(Zero-field
splitting)
Kramers' Hyperfine
degeneracy; structure
(Small zoro- transitions
field splitting)
(8 1 «hv)
(Hyperfine splitting)
(c) 5 allowed ESR transitions (v 1 , v2 , v 3 , V4 and vs ) at a fixed field and hyperfine

splitting of each ESR transition by Mn (I = 1)
Mn(lI)
_--------------======::::::::;:/I·'<:..:·:::~~:~:::-----------------_
------ / 1 (5-1Ine peaks) '1 ~'l"
L..--y---J L..--y---J L..--y---J ~ L..--y---J

llII Most intense ~
Decreasing intensify signal Decreasing intensify
ry
ra
(d) Hyperfine splitting of 5 ESR signals by Mn (I = -%-)
ib
yl
2 3 4 5 6
em
ch
e al
th
e/
t.m
e
er
H
~ Ho
k
lic
(e) 6 hyperfine components of an ESR peak of high spin Mn(lI)

C
Fig. 12.3.3.3 (a) and (b): Kramers' degeneracy and zero-field splitting of high-spin tF (~g ei) and further splitting of M s
levels on applic"ation of field (Ho); (c) and (d): 5 ESR signals of Mn(II) (high spin) and hyperfine splitting (i.e. hyperfine
splitting by the nuclear spin, I = 5/2); (d) Five ESR signals of Mn(II)---each consisting of 6 hyperfine lines; A Mn called
hyperfine splitting constant. (e) Hyperfine splitting (derivative plot) of an ESR signal (i.e. one fine component) of Mn(II)
into 6 hyperfine components by the Mn-nucleus (I = 5/2).
through the second order spin-orbit coupling and this mixing produces a relatively small zero-field
splitting (i.e. hv> > a). Moreover, the dipolar interaction of the electron spins to cause the zero-field
splitting is small. Thus, because of the small zero-field splitting (i.e. hv » a), all the allowed ESR
transitions (i.e. ~s = ±1) are detected. The predicted 5 ESR peaks are experimentally verified for the
high spin octahedral complexes of Mn(II).
Here it is worth mentioning that because of the small effect of the second order spin-orbit coupling
(leading to the inefficient mixing of the ground and excited state), the spin-lattice relaxation time is
larger (i.e. ESR spectra can be recorded at room temperature), zero-field splitting is small (i.e. S' =S),
and g value is close to 2.0.
Further hyperfine splitting by the Mn-nucleus (I =%) leads to equally strong 6 hypertine compo-
nents (2 x %+ I = 6 ) in each of the major 5 peaks. All the 6 hyperfine components in a fine peak are
equally strong because all the nuclear spin states (i.e. M[ = ±~, ±l, ±.!.) are nondegenerate. Thus
2 2 2
there are 30(= 5 x 6) total lines in the ESR spectrum.
Here it is worth mentioning that under the condition of strong zero-field splitting (i.e. 8 » hv)
occuring in a strong tetragonal field, there is only one observable ESR signal appearing from the
lowest spin-doublet (M s =±.!. i.e. transition between the

Ms = and states in presence of a +.!. _.!.
ry
2 2 2
ra
magnetic field). It leads to S' =! (cf. Fig. 12.3.3.3b).
ib
2
yl
(vii) Magnitude of zero-field splitting in excited naphthalene: Its magnitude (B) depends on the
em
system under consideration. In the excited naphthalene (obtained by irradiating with the ultraviolet
radiation) (S = 1), the magnitude of zero-field splitting (measured by the energy difference between the
Ms = 0 and Ms = ±1 in absence of any external magnetic field) is about 3000 MHz which is comparable
ch
to the energy involved in the ESR transition.
al
(viii) Number of fine components in the ESR spectrum due to the zero-field splitting: If there are
e
th
n unpaired electrons electrons (i.e. S =!!.- ), there will be n equally spaced fine structure components
2
e/
in the ESR spectrum under the condition of zero-field splitting (B « hv) due to the n allowed ESR
t.m
transitions under the selection rule (dMs = ±1). There may be some weak ESR signals due to the
forbidden transitions (lll1s = ±2). Again all these ESR transitions (for both Ill1s = ±1 and forbidden
e
transitions Ill1s = ±2) leading to the fine peaks may undergo hyperfine and super-hyperfine splitting
er
depending on the condition.

Here it is worth mentioning that if the zero-field splitting (i.e. B) is very large (i.e. B » hv), all the
H
predicted allowed ESR transitions (i.e. dMs = ±1) may not lie in the microwave region of the ESR
k
spectrometer, i. e. such high energy transitions are not detected in the spectrometer. For example, in the
lic
V(III) complexes (tP), the zero-field splitting is very large and the allowed two ESR transitions
C
(AMs = ±1) lie beyond the microwave frequency region (i.e. ESR frequency region). For the Cr(III)
complexes (d3 systems), sometimes only one peak instead of the predicted 3 peaks is observed in the
ESR spectrum (cf. Fig. 12.3.4.1) because of the same ground. To understand this, we are to consider
the effective electronic spin (S') in terms of ESR transitions instead of the calculated electronic spin
(s =%). This aspect is discussed separately in Sec. 12.3.4.
For the transition metal complexes having the A-ground state level (i.e. orbitally nondegenerate as
in high spin tF-system) and cubic symmetry, the magnitude of zero-field splitting is small (i.e. hv » B)
and all the predictedoallowed ESR transitions (i.e. dMs = ±1) are noticed as in the case of high spin
Mn(II) complexes (6A 1g ground state). On the other hand, for the transition metal complexes having the
T-ground state (i.e. orbitally degenerate) experiencing the spin-orbit coupling (cf. Appendix 12C and
Fig. 12.3.2.1) and distortion (i.e. low symmetry ligand field components), the magnitude of zero-field
splitting is quite large (i.e. B » hv) and all the predicted ESR transitions may not be observed (cf.
Figs. 12.3.3.1c and 12.3.3.3b). In such cases, very often the ESR transitions for ~s = ±1 are not
noticed because the energy change in such transitions is too large to be covered by the microwave range
(cf Fig. 12.3.3.1c). Instead of these allowed transitions, the forbidden transition (~s = ±2) may
produce a weak ESR signal. It happens so for V(III) (d 2 system) and the forbidden transition gives a
weak signal which is split by the 51 V(I =f) nucleusinto 8 components of equal intensity.
For the large zero-field splitting removing the spin degeneracy (i.e. 8 » hv; v in the microwave
range), the conclusions are:
• For n =even, the lowest spin energy state (Ms =0) is nondegenerate and the higher energy states
are separated from this lowest state by the energies which are much higher than the microwave
energy causing the ESR transition, and consequently, no ESR transition is observed (i.e. S' = 0)
ry
(cf. Fig. 12.3.3.1c)•
ra
= ±~) which splits in an external
ib
• For n = odd, the lowest level is doubly spin degenerate ( M s
yl
magnetic field; leading to theM s = -..!..~Ms = +..!.. ESR transition, i.e. ESR active. It gives
em
2 2
on~ ESR signal (i.e. S' =~)
ch
only irrespective of the value of S because the other spin states for
3 5
al
Ms = ±2" and ±2" are of too high energy to participate in the ESR transitions (Fig. 12.3.3.3b).
e
th
(ix) Relative intensities of the fine structure components: Out of the n-possible ESR transitions
e/
(n = number of unpaired electrons and 8 « hv), the intensity is highest for the central peak and
t.m
smallest for the outermost peaks.
12.3.4 Zero-field Splitting and Effective Spin (S') and Effective ESR Transitions in
e
Different d n Systems of the 1st Transition Series

er
n
H
For the n-unpaired electrons, the resultant electronic spin (S) is 2" but sometimes, due to the large zero-
k
field splitting (i.e. 8» hv, v =ESR frequency), for the ESR transitions, the effective spin (S') becomes
lic
different (i.e. S' < S) from the calculated electronic spin (S). ~)
C
It has been already mentioned that for the cubic crystal field and orbitally nondegenerate ground
state (i.e. A-ground state level), the magnitude o/zero-field splitting (S) is relatively small but/or the
noncubic crystal field (i.e. crystal field of low symmetry), and the spin-orbit coupling splitting the~T-
ground state, the zero-field splitting (S) is relatively large.
(A) Small zero-field splitting (i.e. 8 « hv): When the cubic crystal field provides an orbitally non
degenerate (i.e. singlet) ground state (e.g. A ground state), the zero-field splitting removing the spin
state degeneracy is generally small and the effective spin (S/) is the electronic spin (S = S') and it will
produce the n (= 2S) ESR transitions (for L1Ms = ±1) within the microwave region, i.e. nfine peaks are
observed in the ESR spectrum. For example, in Ni 2+(tf) octahedral complexes, the ground state is 3A 2g
and two ESR signals are noted in many cases (cf Fig. 12.3.3.1b). In fact, in the octahedral complexes
of Ni(II), the spin-orbit coupling allows the mixing of the orbitally nondegenerate ground state (3A 2g )
to a only small extent with the excited orbitally degenerate 3T2g state which can experience the crystal
field splitting (Fig. 12.3.4.3). This phenomenon causes only a small zero-field splitting.
i)
The high spin octahedral complexes of Mn(ll) (~g e (6S ground term leading to the lowest energy
state 6A 19) maintains the spherically symmetrical electron distribution. There is no other sextet state.
The second order spin-orbit coupling mixes the excited 4T1g state only to a small extent and this
excited state (4T1g ) may also undergo splitting by the crystal field, but the effect causing the zero-field
splitting is small. The spin-spin interaction (i.e. dipolar interaction) is not much important to deter-
mine the zero-field splitting. Because of these reasons, the magnitude of zero-field splitting is small and
in terms of ESR transitions, S = S' (i. e. all the 5 allowed ESR transitions are to give the 5 fine peaks)
(cf Fig. 12.3.3.3).
(B) Large zero-field splitting (i.e. 8 » hv): When the cubic crystal field produces an orbitally
degenerate T-ground state, the effect of spin-orbit coupling (cf Appendix 12C and Fig. 12.3.2.1) and
low symmetry ligand field components will remove both the orbital degeneracy and spin degeneracy.
ry
In such cases, the zero-field splitting is relatively large.
If such a system contains an odd number of unpaired electrons, the lowest spin state (Ms = ±1/2)
ra
remains doubly degenerate (Kramers' degeneracy). If the next higher doubly degenerate spin state is
ib
well separated (i.e 8 is high) from the lowest doubly degenerate spin state, then the higher energy states
yl
will not contribute to the ESR transitions at any attainable magnetic field generally used in the ESR
em
studies (cf Fig. 12.3.3.3b). In other words, the ESR transition will involve only the lowest doublet state
(Ms = ±1/2) which will split under the influence of an external magnetic field. In such cases, the
ch
effective spin (8') becomes 1/2 irrespective of the electronic spin (S).
This is illustrated for the high-spin complexes of Co(II) (~gei, n =3, S =3/2) having the ground state
al
4T1g which arises from the ground state term 4F. Here the spin-orbit coupling (Fig. 12.3.2.1a) and low
e
symmetry ligand field can produce a large zero-field splitting and the lowest spin doublet is charac-
th
terised by M s = ±1/2 (cf Figs. 12.3.3.2b, c and 12.3.3.3b; Kramers' rule). Here, the lowest doublet
e/
M s = ±1/2 is separated from the next higher doublet (Ms = ±3/2) by about 200 cm- 1 in absence of any
t.m
external magnetic field. It may be mentioned that the ESR transition occurs between the states for which
the energy difference lies within a few cm-l in presence of the magnetic field generally applied in the
ESR studies. Thus for the ESR transitions, the higher energy states are of no importance and the ESR
e
transitions effectively involve the levels for M s = +1/2 and M s =-1/2 (in presence of a magnetic
er
field). Thus it leads to the effective spin S' = 1/2.

H
Thus for the odd number of unpaired electrons, from the lowest Kramers' doublet (Ms = ±1/2), there
k
will be always one EPR signal (i.e. S' = 1/2) irrespective of the value of electronic spin (S). On the
lic
other hand, for the even number of unpaired electrons, the zero-field splitting leads to the energy states
C
characterised by Ms = 0, ±1, ±2, ..., i.e. the lowest state is singlet. If the zero-field splitting is very large
then the singlet lowest state (Ms = 0) is separated from the next higher states by the energies which
cannot be covered by the microwave region (i.e. M s = 0 ~ Ms = -1 transition energy lying outside the
microwave region). Consequently, then no EPR spectrum is observed (i.e. S' becomes 0). However,
the forbidden EPR transition (j),Ms = ±2) between the levels for M s = ±1 may appear (Fig. 12.3.3.1c).
In fact, such a weak EPR signal may be obtained for the V(III) (cP) octahedral complexes.
• Large zero-field splitting: For the odd number of unpaired electrons (i.e. n is odd), only one
ERR peak (i.e. S' =~); For the even number of unpaired electron, no EPR peak (i.e.
S' = 0).
• Small zero-field splitting: For the n-unpaired electrons, there will be n EPR peaks (i.e.
S' = S).
(C) ESR transitions in the metal complexes of 3d-series: Before to discuss the EPR spectrum of
the different transition metal complexes, we should pay attention to the following points already discussed.
• Spin-lattice relaxation time (Tl) and temperature of EPR studies (ef. Sec. 12.3.2): For the
orbitally degenerate T(g) ground state (which can be split by the spin-orbit coupling and low
symmetry ligand field), because of the very rapid spin-lattice relaxation (i.e. T 1 is very small), the
EPR studies can be done only at very low temperature (i.e. liquid He or N 2 temperature). On the
other hand, for the A(g) (orbitally nondegenerate) and E(g) ground state, T} is relatively large and
the EPR studies can be made at room temperature. But, sometimes, as in the case of octahedral
Ni(II) complexes, spin-orbit coupling mixing of the first excited state, i.e. 3T2g with the ground
3A 2g state, makes the spin-lattice relaxation process fast and the EPR studies are to be carried out
at very low temperature. In the tetrahedral complexes, very often, the energy difference between
ry
the ground A-state and excited T-state is small and mixing between these two states causes spin-
ra
lattice relaxation fast and it requires low temperature for the EPR study.
In general, for most of the cases, low temperature is needed for the EPR studies of the
ib
transition metal complexes (exceptions: oxidovanadium(IV) complexes; copper(II) complexes,
yl
low-spin octahedral complexes of d'-system; high spin octahedral complexes of tF system; etc.)
em
• Spin-orbit coupling and the magnitude of zero-field splitting: It leads to the favoured spin-
lattice relaxation causing the peak broadening (Sec. 12.3.2). It also causes the zero-field split-
ch
ting of higher magnitude making the effective spin (S') less than the electronic spin (S).
• Zero-field splitting and Kramers' degeneracy: If the zero-field splitting is very high then for
al
the even number of unpaired electrons, no EPR spectrum is noted i.e. S' = 0 (ef. the lowest
e
singlet spin state, i.e. Ms = 0, is nondegenerate). In such cases, for the odd number of unpaired
th
electrons, the lowest doubet spin degenerate state (Ms = ± 1/2) may participate to give the one
e/
EPR signal, i.e. S' = 1/2.

t.m
• 1st transition series vs. 2nd and 3rd transition series metal complexes: The spin-orbit cou-
pling interaction is much stronger for the 2nd and 3rd transition series. It causes the spin-lattice
relaxation process very fast (i.e. T} is very small and no EPR peak, ef. Sec. 12.3.2) and very high
e
er
zero-field splitting. This is why, it is very often difficult to study the ESR transitions for the metal
complexes of the 2nd and 3rd transition series.
H
1. dl-system: In the octahedral complex, the ground state is 2T2g which undergoes splitting by spin-
k
orbit coupling and low symmetry ligand field components (ef. Correlation Table). The energy levels
lic
created from the 2T2g level through the spin-orbit coupling (see Appendix 12C) are close in energy (i.e.
C
energy separation::::: kBT) and it makes the spin-lattice relaxation time very short (ef. Sec. 12.3.2). Thus
the EPR study can be made only at a very low temperature.
In the tetrahedral complex, the ground state 2E does not split through the first-order spin-orbit
coupling but the 2T2 excited state is split through the spin-orbit coupling (see Appendix 12C) and the
energy difference between the 2E and 2T states is not too large. In fact, the second order spin-orbit
coupling allows the mixing between the 2E ground state and excited 2T state. In this process, E-
component of the split T-state mixes with the ground E-state. This mixing favours the spin-lattice
relaxation process (ef. octahedral complexes of Ni(II» and the EPR study for the tetrahedral complexes
is also to be carried out at low temperature.
The oxovanadium(IV) complexes are highly distorted and the ground state becomes orbitally singlet
(i.e. nondegenerate) (ef Fig. 7.14.1.2) and the excited states are well separated (Le. energy separation
» kBn energetically from the ground state. In such cases, the spin-lattice relaxation process is
slowed and the EPR lines are quite sharp even at room temperature (ef. Cull-complexes experiencing
the strong J.T. distortion show the sharp ESR lines even at room temperature).
2. d 2-system (cf. Fig. 12.3.3.1): For the octahedral complexes, the ground state is 3TIg which
experiences splitting by the spin-orbit coupling (see Appendix 12C and Fig. 12.3.2.1). It leads to the
fast spin-lattice relaxation and the EPR study becomes difficult. For the tetrahedral complexes having
the 3A 2 ground state (orbitally nondegenerate), the spin-lattice relaxation time is relatively longer and
the EPR spectra can be recorded.
For the octahedral complexes of V(III) (tP), because of the very large zero-field splitting, the
allowed two ESR transitions (lll1s =±1) are not very often detected but the forbidden transition (lll1s = ±2)
is noted (Fig. 12.3.3.1c). This weak signal is further split into 8 hyperfine lines by SIV (I = 712).
3. d 3-system (cf. Fig. 12.3.3.2): Octahedral complexes bear the 4A 2g ground state (orbitally
nondegenerate and experiencing no spin-orbit coupling) and the spin-lattice relaxation time is relatively
longer. The next higher state 4T2g state may undergo splitting due to the low symmetry crystal field and
ry
spin-orbit coupling.
ra
The ground 4A 2g state and excited 4T2g state can interact to some extent through the spm-orbit
ib
coupling. This may enhance the zero-field splitting to some extent. The zero-field splitting leads to the
spin degenerate lowest state (Ms = ±1/2) and if the zero-field splitting energy is not very high, three
yl
ESR transitions are noted (cf. Fig. 12.3.3.2). However, if the zero-field splitting is larger than the
em
energy of the operating microwave radiation (i.e. 8» hv), then only a single EPR transition involving
the M s = ±1/2 state is noted (i.e. S/ = 1/2). Here the higher doublet state (Ms = ±3/2) does not contribute
ch
to the ESR transitions at any attainable magnetic field applied for the ESR studies.
e al
th
e/
t.m
e
er
H
(4 hyperfine peaks of
equal intensity for 53Cr)
k
lic
C
Fig. 12.3.4.1 ESR spectrum (Derivative signal) of Cr3+ in a single crystal of MgO. (The intense singlet signal is for the
nonmagnetic abundant nuclei 52Cr, 54Cr).
In fact, in many Cr(lll) complexes (d3 ), instead of 3 ESR signals, only one signal is noticed. Cr(lll)
when placed in a single crystal of MgO shows only a single intense line (Fig. 12.3.4.1) with g = 1.98
which is found to be isotropic. The slight" reduction in g-value from 2.0 indicates a small interaction
between the 4A 2g (ground state) and 4T2g (excited state) through the spin-orbit coupling. This effective
,magnetic moment is given by:
Jleff = geff~S(S + 1) BM = 1.98~S(S + 1) BM = 3.83 BM
However, in terms of the ESR spectrum, the effective spin is S' =! not ~. The single intense peak
2 2
without any hyperfine splitting (Fig. 12.3.4.1) is due to the abundant nonmagnetic 52Cr, 54Cr (I = 0)
isotopes. For the magnetic isotope 53Cr (9.54% abundance) having I = 3/2, four weak hypertine
splittings of equal intensity (cf. M I = ±l, ±.!..

are nondegenerate) appear. It may be noted that the
2 2
intensity of an ESR signal is proportional to the abundance of the isotope and inversely proportional to
ry
the number of hyperfine lines (2nI + 1) present in the signal.
ra
. f ESR· I abundance of the Cr-isotope causing the hyperfine splitting
ib
IntensIty 0 an sIgna oc - - - - - - - - - - - - - - - - - - - - -
number of the hyperfine components (21 + 1)
yl
em
. '.c 52 54 (90.5) x (2 x l + 1) 90 5 4
IntensIty lor ' C r::::: 2 =. x : : : 40
ch
i.e.
intensity for 53 Cr (9.5) x (2 x 0 + 1) 9.5 x 1
al
Here it is worth mentioning that for the ~-system, the unpaired electrons reside in the t2g orbitals (Oh
e
complex) and consequently superhypertine splitting by the ligand atoms is not important (cf. the
th
importance of superhyperfine splitting in the Cull-complexes).

e/
For the octahedral ~-system, the g-value is given by:

t.m
2
4k
g = ge ( 1- 10D
A.) ::::: 2.0023 - (4 8A.
_4A )' (taking k ::::: 1, cf. Sec. 12.3.9.)
q ~ T
e
2g 2g
er
It gives: for [V(OH 2)6]2+having ~= 11,800 cm- l and A =56 cm- I , g = 1.964 (cf. experimental value
H
1.972); for [Cr(OH 2)6]3+having ~ = 17,400 cm- I , A = 91 cm- I , g = 1.96 (cf. experimental value 1.98).
k
4. d 4-system: For the high-spin octahedral complexes, the ground state is 5Eg and the zero field
lic
splitting gives the energy states: M s(±2) ) M s(±I) ) Ms(O). It gives four allowed ESR transitions (~s
= ±1) when the zero-field splitting is not large (Fig. 12.3.4.2).
C
Ms(O) ~ M s(+I); Ms(+l) ~ M s(+2); M s(-2) ~ M s(-I); M s(-I) ~ Ms(O).

Large Jahn-Teller distortion and large zero-field splitting will lead to the situation of no EPR
spectrum (i.e. S' = 0). In fact, for the large zero-field splitting, in the case of even number of unpaired
electron, no ESR transition is noticed (cf: Fig. 12.3.3.1c).
The low-spin d 4 complexes (3TIg ) lead to the situation of d 2 system (i.e. S = 1 for both systems).
5. d 5 -system (cf. Fig. 12.3.3.3): For the high spin complexes as in Fe(lll) or Mn(ll) (~g ei, 6A Ig
ground state; and the excited state 4TIg ), the zero-field splitting is small and 5 allowed ESR transitions
are noted. This aspected has been discussed in Sec. 12.3.3. For Fe-S proteins, see Fig. 12.3.7.14-15.
6. d 6-system: The high spin complexes are similar to those of the d 4 systems having 4 unpaired
electrons (i.e. S =2). The high spin octahedral complexes possess the 5T2g ground state which experiences
the spin-orbit coupling (see Appendix 12C) and thereby mixing with the excited state becomes possible.
When the zero-field splitting is large as in a distorted octahedral complex, there will be no EPR signal
(cf. lowest spin state M s = 0 is spin nondegenerate). However, when the zero-field splitting is not
large, it will be EPR active.
Ms =+2
Ms =±2
Ms =±1
ry
Ms=O
--------+---Io.---~~-----__r_----M s =0
ra
(Zero-field
ib
splitting)
Ms = -1
yl
em
ch Ms =-2
al
Fig. 12.3.4.2 Zero-field splitting and magnetic field splitting of the spin states arising from the 5Eg ground state (i.e. et
e
high-spin octahedral complexes) and the 4 allowed ESR transitions.

th
7. d'-system: For the high spin complexes, the ground state 4T 19 undergoes spin-orbit coupling
e/
giving rise to 12 low-lying spin states (Fig. 12.3.2.1). For such systems, the spin-lattice relaxation time
t.m
is very short (Sec. 12.3.2) and to observe the ESR spectrum, a very low temperature is needed. Because
of the large zero-field splitting, the effective spin is S' = 1/2 and only one ESR transition is noted
e
involving the lowest spin doublet energy state (Ms = ±1/2, Kramers' degeneracy). It may be realised in
er
another way: because of the rapid spin relaxation, only the lowest spin state (doublet) is populated to
make S' = 1/2.
H
For the tetrahedral complexes, the ground state is 4A 2 and the excited state is 4T2 which undergoes
k
splitting through the spin-orbit coupling. The system is similar to the tetrahedral complexes of tF-
lic
system for which the ground state is 4T1 and the excited state is 4T2• In both cases, the number of
C
3
unpaired electrons is there (i.e. S = "2)' However, the energy difference between the 4T2 and 4A 2 states
is relatively smaller for the d' system. It favours the spin-lattice relaxation to broaden the ESR peak.
For the low-spin octahedral complexes of cP-system (s = ~), the lowest state 2Eg does not
experience any spin-orbit coupling to split. Besides this, there is no nearby doublet excited state (see
Tanabe-Sugano diagram) to allow mixing with the ground 2Eg state. Consequently, the spin-lattice
relaxation time (T1) is relatively longer and it becomes easier to observe their ESR spectrum (even at
room temperature in some cases).
8. d 8-system (cf Fig. 12.3.3.1): The system is similar to the d 2 system (i.e. S = 1 in both cases) and
three ESR transitions are expected by considering the moderate zero-field splitting.
For the octahedral complexes of Ni(II), the ground state is 3A2g (which is orbitally nondegenerate)
but through the spin-orbit coupling it can mix with the excited state 3T2g (orbitally degenerate) which
can be split by the crystal field (see Fig. 7.14.4.3 and 12.3.4.3). This spin-orbit coupling mixing causes
the zero-field splitting which is not large and it gives an efficient mechanism of relaxation of the
spin state. This is why, to study the ESR spectra of the octahedral complexes of Ni(II), liquid helium
or nitrogen temperature is to be employed. However, because of the small zero-field splitting, all the
predicted allowed and forbidden ESR transitions (see Fig. 12.3.3.1b) are noted.
9. d 9-system: The ground state is 2Eg in the octahedral complexes. A strong J.T. distortion disfavours
the spin-lattice relaxation process and the ESR signals are noted even at room temperature (cf. the
complexes ofV0 2+ and Ti 3+). In fact, a strong J.T. distortion splits the ground 2Eg state and the ground
state becomes orbitally nondegenerate singlet (Figs. 7.14.2.1 and 12.3.4.4) and the excited states are
well separated from the ground state (i.e. energy separation l\E » k B T) and the spin-lattice re~axa
tion is disfavoured to make the relaxation time T1 longer. It makes the EPR studies easier. In fact, the
ry
said J.T. distortion splits the orbitally doublet state (2Eg ) into two orbitally singlets (2B 1g and 2A 1g ) which
ra
are still doubly spin degenerate (i.e. M s = ± ! ). Application of an external magnetic field will remove
ib
2
the spin degeneracy and the one EPR signal is developed from the lower spin doublet (cf. Fig.
yl
12.3.4.3). It may be noted that for the dimeric complexes of Cu(II), the triplet state (S = 1) gives two
em
allowed strong EPR signals and one forbidden weak signal (cf. Fig. 12.3.3.1b). ch
--------
al
3
Note: When the cubic crystal field is distorted,
~~ ........ Eg the orbitally triplet states (T2g and T 1g) undergo
e
........
~19 ........
........ splitting. The interaction of these triplets with
th
3 the ground orbitally singlet state removes

A29
the spin degeneracy of singlet state. It gives
e/
8DQo the zero-field splitting (8).

t.m
,," ,,' 3
,,",,"
829
~,
<'........ 2 EPR peaks Ms = + 1
e
~ ~ ........ ,,'---
~29 ...............
/E'~
er
Distortion 8
-;--A --(;~y;t;i<', Ms = ± 1 Ms = - 1
3
Eg
H
2g • ------
field effect) ~ ~
10DQo
k
(On field) . 3
8 Magnetic
(b) Tetragonal field field
lic
19
C
_____ <{;;;;~.~. ._g_J3H_ o_ _ ~::: 1}1~::

3 819 Ms =-1
Tetragonal
Magnetic field
field (D 4h)
(ignoring the effect
(a) of zero-field splitting)
Fig. 12.3.4.3 Crystal field splitting of the energy levels of Ni(II)(ttS) (cf Fig. 7.14.4.3). (a) No zero-field splitting of the
spin states. (b) Zero-field splitting of the spin states (drawn as inset in the box). 0 is called the zero-field splitting or
tetragonal splitting parameter.
In terms of Fig. 12.3.4.4, the g-values are expressed as follows (cf.Secs. 12.3.9, 12.3.12):
- (1-
gll-ge E4k-E
2
"
2
0
-E ,g.l --ge (I - E k-E J-
J-- 2 - E 8A.
2
- 2 - E 2A
-E
0 3
2
"
0 3 0
ry
ra
ib
yl
Cubic
em
field (Oh) ch
Fig. 12.3.4.4 Crystal field splitting of the energy levels of Cu(II) (cP) in absence and presence of magnetic
al
field.(cf Fig. 7.14.2.1).

e
th
Here the orbital reduction factor (k) is taken as unity. The energy differences, i.e. E2 - Eo and
E3 - Eo are obtained from the electronic spectra, gil and g.l. values are obtained from the EPR studies, and
e/
the spin-orbit coupling constant (A) can be evaluated from the abose relations. When splitting of the
t.m
energy levels is very high (i.e. mixing of the excited states with ground state is negligible), the
g-value approaches to the ge value (::::: 2.0). For, Cu-metalloproteins (see Fig. 12.3.7.13), the these
e
aspects have been taken into consideration.

er
It may be noted that if distortion is weak, then the electronic energy levels are not separated much
H
from the ground state and if the energy separation lies in the range kBT, then the spin-lattice relaxation
process is favoured and it becomes difficult to follow the ESR signal.
k
lic
12.3.5 Nuclear Spin and Hyperfine Splitting of the ESR Signals

C
(A) Origin of the hyperfine splitting: Nuclei can have the nonzero nuclear spin (I) (cf. Sec. 12.2.1).
An unpaired electron can interact with the nuclear spin which can have the m/ values +1 to -I i.e. m/ can
have the 21 + 1 values. For 1 =2, the possible m/ values are: +2, +1, 0, -1, -2. The energy states for the
different m/ values are degenerate in absence of any external magnetic field but their degeneracy is
destroyed when a magnetic field is applied (cf. Sec. 12.2.1).
When an unpaired electron comes in the vicinity of a nucleus of the nuclear spin I, due to the
interaction between the nuclear spin and electron spin, the ESR absorption signal will undergo splitting
into the (21 + 1) components (called hyperfine splitting).
This interaction energy is expressed as amsm/ where a (in the unit of joule) is described as the
hyperfine splitting constant or the hyperfine constant. It may have either positive or negative value.
Thus the energies of the levels are given by:
E =g(3Homs + amsmb (cf. the nuclear spin-electron spin interaction energy, i.e. amsmb is independent
ofHo)
Table 12.3.5.1 Nuclear spin quantum number of the important nuclei relevant to the ESR studies.
Nucleus Abundance (%) I Nucleus Abundance I
1 3
IH 99.98 - 65CU 30.9 -
2 2
3
2H 1.56 x 10-2 69Ga 60.2 -
2
3 3
7Li 92.55 - 75As 100 -
2 2
3 3
9Be 100 - 79Br 50.6 -
2 2
5
ry
lOB 18.8 3 95Mo 15.8 -
2
ra
3 5
lIB 81.2 - 97Mo 9.6 -
ib
2 2
1 5
yl
13C 1.1 - 99Ru 12.8 -
2 2
em
5
14N 99.62 IOIRu 17.0 -
2
ch
1 1
15N 0.36 - I03Rh 100 -
2 2
al
1 1
19F - -
e
100 107Ag 51.35

2 2
th
5 11510
9
17
0 0.04 - 95.85 -
e/
2 2
5 5
t.m
- 127 -
27AI 100 1 100
2 2
1 7
31p 100 - 133CS 100 -
e
2 2
er
3 7
335 0.74 - 139La 99.9 -
2 2
H
3 5
35CI 75.4 - 14lpr 100 -
k
2 2
lic
7 7
5lV 99.75 - 175Lu 97.5 -
C
2 2
3 1
53Cr 9.55 - 183W 14.3 -
2 2
5 5
55Mn 100 - 187Re 62.92 -
2 2
1 3
57Fe 2.24 - 1911r 38.5 -
2 2
7 3
59CO 100 - 1931r 61.5 -
2 2
3 1
61Ni 1.25 - 195pt 33.7 -
2 2
3 1
63CU 69.1 - 197Au 21.1 -
2 2
9
209Bi 100 -
2
For interaction with more than one nuclus, we can write in general:
E = g~Homs + almsm I I + a 2 m sm I 2 +...
n
=g~Homs + LaimSm Ij
i=l
The magnitude of hyperfine splitting constant (a) depends on the factors: (i) the ratio of the nuclear
magnetic moment to the nuclear spin, (ii) the unpaired electron spin density in the immediate vicinity
of the nucleus under consideration and (iii) the anisotropic effect.
The split energy levels arising from a particular ms state are closely spaced. Such energy levels are
almost equally populated and consequently, the lines due to the hyperfine splitting by a single
nucleus are of equal intensity and these are of equal spacings. Here it is to be rembered that if
ry
hyperfine splitting is caused by more than one nucleus (e.g. CH3 radical), the hyperfine peaks are not
ra
vI equal intensity (cf. Fig. 12.3.5.3) determined by the degeneracy of the spin states (MI ).
ib
(~) General features of the hyperfine splitting of the ESR signal: In general, the results can be
yl
summarised as follows:
em
(a) Number of hyperfine lines: If the ESR signal is split by a set of n equivalent nuclei of nuclear
spin Ii' the number of hyperfine lines is given by: (2nl; + 1)
ch
(b) Number of hyperfine lines: If the ESR signal is split by a set of n equivalent nuclei of spin
Ii and a set of m equivalent nuclei of spin Ii' the total number of hyperfine lines are given by
al
(2nl; + 1)(2mlj + 1).

e
• Thus, if the odd electron gets delocalised on three nuclei of nitrogen (I = 1) sites, the hyperfine
th
split lines are: 2nNI N + 1 = 2 x 3 x 1 + 1 = 7.

e/
If there are n equivalent nuclei of 1 = 1/2, the hyperfine splitting will produce the n + 1 lines
t.m
(= 2n x 1/2 + 1).
If there are n nonequivaient nuclei of I = 1/2, there will be 2 n = (2 x 1x ~ + 1)(2 x 1 x ~ + 1) ...

e
er
hyperfine lines.
H
(c) Energy states for a particular m s value and population density: intensity of the hyperfine
n
k
components: The nuclear spin-electron spin interaction energy, i.e. LaimSm Ij is independent of the
lic
i=l
C
magnetic field (Ho). The split energy levels for a particular m s value are closely spaced and
consequently the population density for a particular energy level (characterised by ms and m I ) is
proportional to the number of degeneracy of the mI. value. Thus intensity of a hyperfine transition
from a particular ms·state is directly proportional t~ the number of degeneracy of the corresponding
nuclear spin state (i.e. M I ). The hyperfine lines are also equally spaced because, the split energy
levels for a particular m s value are equally and closely spaced.
Obviously, all the nuclear spin states (m/) values developed from a particular single nucleus
are nondegenerate and the hyperfine lines are equally spaced and equally strong. It happens so
when the hyperfine splitting is done by a single nucleus like 55 Mn (I = ~; the nuclear spin states
2
531
m/ = ±-, ± -, ± - are nondegenerate; 6 hyperfine components are equally strong and equally spaced;
222
cf Fig. 12.3.3.3e).
(d) Intensity of the hyperfine lines produced by two or more equivalent nuclei: For the two
equivalent nuclei of I= 1/2, M] =+ 1, 0, -1, M] =0 arises in two ways for the arrangement of m] values
i. e. +!, -! and _!, +! i. e. the energy state corresponding to M] = 0 is doubly degenerate. For
2 2 2 2
M] = + 1 or -1, there is only one way of arrangement (i.e. +!, +! or _!, _! ). It makes M] =0 two
2 2 2 2
times more probable than M] = ± 1. The relative intensities for the corresponding transitions are in the
ratio 1:2: 1 and it is experimentally verified. Similarly for the three equivalent nuclei (I = 1/2) as in the
CH 3 radical, the energy state corresponding to M] = ± 1/2 is three times more probable than the energy
state corresponding to M] = ±3/2. Thus the observed relative intensities for the corresponding transi-
tions are in the ratio 1:3:3: 1. In such cases (i.e. 1= 1/2), the relative intensity ratio of the hyperfine lines
ry
can be obtained by using the Pascal's triangle (cf. Sec. 12.2.8). The relative int~nsities of the (n + 1)
ra
ib
hyperfine lines produced by n-nuclei of I =! can also be obtained from:
2
yl
em
n
em = C
h
n! ) , were m = 0,1, 2, ..., n.
m! n-m!
ch
For illustration, n =4 (say), relative intensities of the five lines are as 4C O: 4C 1: 4C 2: 4C 3 : 4C4 =
al
1:4:6:4:1.
e
The relative intensities of the hyperfine lines for the n equivalent nuclei of different nuclear spin
th
quantum numbers (I) are given in Table 12.3.5.2.

e/
t.m
Table 12.3.5.2 Relative intensities of the hyperfine peaks produced by n equivalent nuclei of nuclear
spin/.
e
1=1/2
er
n= 1
H
n=2 2 Icc!. Pascal's triangle, Sec. 12.2.8)

k
lic
n=3 3 3
C
1= 1
n=1
n=2 2 3 2
n=3 3 6 7 6 3
1=3/2
n=1
n=2 2 3 4 3 2
n=3 3 6 10 12 12 10 6 3
For I = 1/2 of the splitting nuclei, the intensity ratio of the hyperfine peaks can be also obtained from
thefamily tree illustrated in Scheme 12.3.5.1.
Intensity ratio (i.e. degeneracy ratio)
1 :1
1 :2 :1
ry
ra
ib
1 : 3: 3: 1
yl
em 1 :4:6:4:1
ch
al
Scheme 12.3.5.1 Schematic representation of spin degeneracy of each nuclear magnetic energy level of a system involving
!.
e
the interaction of different number of equivalent nuclei with I =

th
2
(e) Intensity of the hypertine lines caused by a single nucleus: 2H(I = 1) gives the two hyperfine
e/
%) gives the 4 hyperfine peaks of equal intensity while for the

t.m
peaks of equal intensity. 63 Cu ( I =
= ±±' ±%). the 4 hyperfine peaks are of unequal intensity. In fact, all the nuclear
e
CH3 radical ( M[
er
spin states, i.e. m[ = ±I, 0 for 2H; m[ =±l, ±! for 63CU are nondegenerate (cf. for the CH3 radical,
H
2 2
k
M[ = ±l (nondegenerate); M[ = ±! (3 fold degenerate), cf. Fig. 12.3.5.3). Thus all the hyperfine
lic
2 2
(e.g. I =1, %,~, etc.) are of equal intensity.
C
peaks caused by a single nucleus
(C) Illustrative examples: The hyperfine splitting of an ESR signal is illustrated in some representative
cases.
1. Interaction with a proton (I =1/2) (e.g. lH-atom): Here one unpaired electron interacts with the
nuclear spin of a proton. Thus it can simply represent the H-atom. The spin state ms = -1/2 is stabilised
and the spin state m s = + 1/2 is destabilised to the same extent in an externally applied magnetic field
(Ho). Now due to the mutual interaction between the nuclear spin and the electron spin, for each value
of the electron spin magnetic quantum number ms , the nuclear spin quantum number m/ can have the
values ±1/2. Thus there will be 4 energy levels (cf. 2 energy levels in absence of the interaction between
the nuclear spin and electron spin).
1 1
E( m s , m/ ) = E( +_1+_1) =-gpH
2 o +-a
4
2' 2
1 1
E( ms,m/ )=E( +-1 --1)=-g~HO--a
2 4
2' 2
1 1
E( m s ' m/ ) = E( __1 __1) = --g~Ho
2 +-a
4
2' 2
1 1
E( ms,m/ ) =E( --1+-1) =--g~Ho
2 --a
4
2' 2
It is evident that if a is positive, the energy stated corresponding to m s = -1/2 and m/ = +1/2 is
ry
the lowest energy state. If a is negative, then the lowest energy state corresponds to ms = -1/2 and
ra
m/ = -1/2.
The allowed transitions under the conditions, Ams = ±1 and AmI =0 are (cf Fig. 12.3.5.1):
ib
yl
( m s =-! m =+!J
em
2' / 2
=__21J_M_=_hV_l_=_g~_H_o-_-=-~a---t)(m =+!
ch
m =--21 ,m/ m =_!J
( s (V2) s 2'/ 2
e al
• At a constant magnetic field (Ho), the ESR transition frequencies are:

th
g~Ho a g~Ho a. a
e/
VI = - - + - and v 2 =----l.e., 8.V =v 1 -v 2 =- MHz

h 2h h 2h h
t.m
• At a fixed operating microwave frequency (v), the required magnetic fields for the ESR transi-
tions are:
e
hv a hv a . a
er
HI = - - - - andH2 = - + - - l.e., 8.8=H1 -H2 =-gaussortesla

g~ 2g~ g~ 2g~ g~
H
k
Hyperfine splitting constant (a and A)

lic
The hyperfine splitting constant a is expressed in the unit of energy, i.e. joule. Generally, the
C
hyperfine splitting constantA is expressed from the separation ofhyperfine components. Thus A is
expressed either in the unit of frequency (i.e. MHz) or the unit of magnetic field strength (i.e.
gauss or tesla) (cf 1 gauss = 2.8 MHz). A and a are related as follows: A = a/h or A = a/gf3.
Thus separation between the hyperfine split lines is generally measured by A either in the units of
frequency (cf A = a/h) or magnetic field strength (cf A = a/gf3) (cf. 1 gauss = 2.8 MHz) and A is
generally described as the hyperfine coupling constant. In Fig. 12.3.5.1, the energy levels are dis-
played assuming a = +ve, for a = -ve, the state defined by m s = -1/2 and m/ = -1/2 would be the lowest
energy state. The hyperfine splitting measured by A or a does not depend on the magnetic field
strength.
2. Deuterium atom (iH): It contains one unpaired electron which can interact with the nucleus
having the nuclear spin, 1= 1. Thus it represents the system: m s = ±1/2 and m/ = ±1, O. The interaction
between the electronic spin and nuclear spin gives the following 6 energy levels.
1
m'=+"2
ml =_J..
2
m
s
=±.!
2 -------------------------------- (Assuming no
interaction with
No the nuclear spin)
ry
field --------------------------------
ra
ib
ml =- J..
yl
2
=_J..2
em
m
1 s
ch ml =+"2 }
al
o --------.~ Ho
e
th
Fig. 12.3.5.1 (a) Variation of electron spin energy (assuming a to be positive) due to the interaction with the nuclear spin
of a proton (m/ = ±1/2); two ESR transitions at different fields (HI and H 2) for a fixed operating frequency; hypo-
e/
thetical ESR signal (shown by dotted curve) where there is no interaction between the electronic spin and nuclear spin.
t.m
E
e
er
H
Ho
-2 +J..2 g~Ho -..14 a
1
k
~
lic
+-A;-+
C
v2
1 _J.. g~Ho +J.. a

2 2 4
m s =_ J..
2
(External field
and no hyperfine (Hyperfine
splitting) splitting)
(i) (ii) (iii)
Fig. 12.3.5.1 (b) (i) Splitting of electronic spin energy levels (assuming a to be positive) of hydrogen atom in presence
of a magnetic field without any hyperfine splitting. (ii) Effect of nuclear spin (mI = ±1/2) on these states, i.e. hyperfine
splitting (whose magnitude is independent of the field strength); two ESR transitions (VI and V2) at a fixed field.
(iii) Two derivative ESR signals (intensity ratio 1: 1) for a fixed operating frequency.
1 1 1 1
E( ms,m/ ) =E+-1 +1
=-g~Ho +-a
2 2 E(m m)
s' /
=E 1
-- -1
=--2 g~H0 + -2 a
2' 2'
1 1
E( ms,m/ ) = E +-1 0
=-2 g~H0 + 0 E( ms,m/ ) =E--1 0
=--g~Ho
2
2' 2'
1 1 1 1
E( ) =E 1 =-g~Ho --a E( mS'm/ ) =E_! =--g~H
2 --a
2
ms,m/ +- -1 2 2 +1 0
2' 2'
Under the selection rule, I1m s = ±1, 11m[ = 0, it can lead to three ESR transitions (Fig. 12.3.5.2).
(m s=-±' m/ =+1)~( ms=+±' m/ =+1)
ry
ra
(ms=-±,m/=o)~(ms=+±,m/=o)
ib
yl
(m s=-±' m/ =-1)~( ms=+±' m/ =-1) em
ch
These three hyperfine lines will be of equal intensity because there is no coincidence of states, i. e.
al
all the nuclear spin states (i.e. m/ =±1, 0) are nondegenerate.

e
th
e/
+1
ms =+.1
2 ,,",," l
t.m
,,",," v3
,---rt-~(~----- - ~~
o
/// "
, " V2
e
(No magnetic // " -1

er
field) /
l/
--~,
,
H
v1
m =±...!.2 '\\
k
s
,, ,,""
lic
'" """"
\_----~~~----- o
C
"
""
+1
(Hyperfine
(External
splitting)
Magnetic field
but no hyper-
fine splitting)
(a) (b)
Fig. 12.3.5.2 (a) Hyperfine splitting (assuming a to be positive) leading to three ESR transitions (Vb V2 amd V3) at a fixed
field in deuterim eH). (b) Qualitative representation of three hyperfine peaks (at a fixed operating frequency) in the ESR
spectrum (derivative signal) of deuterium atom; 3 peaks of the intensity ratio 1: 1:1.
3. Interaction of an unpaired electron with three hydrogen nuclei as in CH3 radical: Here the
unpaired electron is delocalised over the three hydrogen nuclei (each having I = 1/2). The combination
of the individual m] values gives the four resultant M] values ±1/2 and ±3/2 as shown below.
M1 (resultant)
+ ~ (nondegenerate state)
111 2
1
1~I 11 ~ JII +-
2
(3 fold degenerate
1 states)
JI~ JJ I 1~~ 2
JJJ - ~ (nondegenerate)
ry
2
ra
It is evident that the states ±1/2 can be obtained in three ways while the states ±3/2 are obtained in
a single way. It leads to four allowed (~ms = ±1, ~[= 0) transitions (Fig. 12.3.5.3) having the relative
ib
yl
intensities 1:3:3:1. Here it is worth mentioning for a nucleus of 1=1. (as in the case of 63CU), the
em
2
. states (.I. e. mI
nuc1ear spin 1 ± -3) are nond egenerate, I.. e.
= ±-, eac h
nuc i
ear · . 0 b·
spin state IS talned·In
2 2
ch
a single way. Consequently, in such cases, the 4 hyperfine peaks are of equal intensity.
al
M,
e
A
th
+3/2 ~
" A
e/
.A~
+1/2
t.m
.A~
-1/2
.A
-3/2
e
V1 V2 V3 V4
er
" -3/2
H
-1/2
k
+1/2
lic
H0 --+
+3/2
C
(Hyperfine
(Magnetic field
splitting)
but no hyperfine
splitting)
(a) (b)
Fig. 12.3.5.3 (a) Hyperfine splitting (assuming a to be positive) leading to 4 ESR transitions (V., V2' V3 and V4 at a fixed
field) in CH 3 radical. (b) Qualitative representation of the ESR spectrum at a fixed operating frequency (derivative signal)
of the CH 3 radical; 4 peaks of the intensity ratio 1:3:3: 1.
Energies of the 4 ESR transitions (~ms = ±1, ~[ = 0) in the CH3 radical are as follows:
(i) m
s
=_!2' M 1 =+1.~m
2 s
=+!2' M[ =+1.2
1 3 [1
LlE=hV=2g~Ho+4a- -2g~Ho-4a =g~H+4a
3] 6
1 1 1 1
(ii) m - - -
2 'M
I
=+-~m
2 s -
-+ 2"' M I -+-
- 2
1 1 [1 1] 2
AE'=-gBHo +-a- --gBHo --a =gBHo +-a
2 4 2 4 4
1 1 1 1
(iii) ms =-2"' M 1 =-2"~ms =+2"' M 1 =-2"
1 1 - [1 1] = gBH --a
AE' =-gBH o --a --gBHo +-a o 2
2 4 2 4 4
ry
1 3 1 3
(iv) ms =-2"' M 1 =-2"~ms =+2"' M 1 =-2"
ra
1 3 [1 3] 6
ib
AE'=-gBHo --a- --gBHo +-a =gBHo --a
yl
2 4 2 4 4
em
4. CsH; (i.e. cyclopentadienyl radical): The unpaired electron residing in the pure p-orbitals can
delocalise throughout the ring through the n-bond formation. Thus, there are five equivalent protons to
ch
split the ESR signal. It produces the 6 hyperfine components (2 x 5 x ~ + 1 = 6) of the intensity ratio
al
1:5: 10: 10:5: 1 (Fig. 12.3.5.4).

e
th
3 4
e/
t.m
2
e
H
er
H
H
H~
k
lic
C
(i.e. 5 protons are equivalent)
---.~ Ho
Fig. 12.3.5.4 EPR spectrum of cyclopentadiene (CsH;) radical rapidly rotating in a single crystal of cyclopentadiene.
s:
C6H; vs. CsH In the phenyl radical (C 6H;), the unpaired electron is localised in a sp2-hybridised
orbital and it cannot delocalise through the 7t-bond formation. But, in the CsHs radical, the unpaired
electron can delocalise through the n-bond formation and all the hydrogens are equivalent. Thus the
ESR spectrum of the phenyl radical is of different type (cf Fig. 12.3.5.10). J
• In the anion, CsH s- (i.e. CsHs- + e ~ CsHs-), n-delocalisation leads to the aromaticity.
5. C6H 6- (benzene anion radical): This is formed in THF solvent when an alkali metal reacts
with benzene. The unpaired electron resides in the LUMO (n*-MO) and it can interact with the six
CH-protons equally. The ESR signal is split by 6 equivalent protons (i.e. 1= 3, M] = ±3, ±2, ±1, 0) into
7 hypertine components (2 x 6 x ~ + 1) having the intensity ratio 1:6: 15:20: 15:6:1 and the coupling
constant 3.76 G (Fig. 12.3.5.5).
ry
ra
2 6
ib
yl
7
em
ch
e al
th
e/
t.m
----------------------.~ Ho
e
Fig. 12.3.5.5 ESR spectrum of C6H6- (benzene anion) produced in the reaction of alkali metal with benzene.
er
6. (CH3)3C· (t-butyl radical): The nine equivalent protons split the ESR signal to give 10 hyperfine
H
components in the intensity ratio 1:9:36:81:126:126:81:36:9:1.

7. CH3CH2• radical: Here the methyl and methylene protons are magnetically nonequivalent. It is
k
lic
quite interesting to note that the hyperfine coupling constant for the CH 3 protons is slightly higher than
the hyperfine coupling constant for the CH2 protons though the unpaired electron is primarily located
C
on the CH2-carbon. However, the coupling constants do not differ much (27 G vs. 22.5 G). Thus the 3
methyl protons splits the signal into 4 hyperfine components having the intensities 1:3:3: 1. Then each
of this quartet is split by the 2 methylene protons into three components (intensity 1:2: 1). It gives 12
(= 4 x 3) lines under high resolution (Fig. 12.3.5.6). But if the ESR study is done in a rigid matrix,
which prevents the resolution, it gives 6 hyperfine peaks (closely spaced) with the intensities 1:5: 10: 10:5: 1
(i.e. 5 protons appear equivalent).
Note: In reality A CH 3 /A CH 2 ~ 1 and in fact, in a rigid matrix trapping the ethyl radical, it shows 6
hyperfine components under the low resolution (i.e. splitting by 5 equivalent protons). A similar situation
arises for DPPH where AN(I) ~ A N (2) (cf. Fig. 12.3.14.2)
8. H 2C·(OCH3) (methoxymethyl radical): Two methyl protons and three methoxy protons are
magnetically different. The unpaired electron is primarily located on the CH2-carbon atom and the
hyperfine coupling constant for these two protons is relatively higher (cf CH 3CH2 - a notable exception).
These two equivalent CH 2-protons split the ESR signal into 3 components (intensity ratio 1:2: 1).
Splitting by
CH 3-protons
Splitting by
ry
CH 2-protons
ra
ib
(6 peaks under low resolution) i.e. merging!
yl
overlapping of some components.
em
Fig. 12.3.5.6 ESR spectral lines of C2Hs• (ethyl radical) assuming A CH3 > ACH2 •
ch
e al
(H 2COCH 3 radical)
th
(3 quartets)
e/
t.m
e
er
(a)
H
.
k
17.5 G
lic
(CH 2 0H radical)
~1.15G
(3 doublets)
C
Ho
-------------------.~
(b)
Fig. 12.3.5.7 (a) ESR spectrum (at a fixed operating frequency) of methoxymethyl radical H2C(OCH 3) (3 quartets).
(b) ESR spectrum (at a fixed operating frequency) of CH20H radical (3 doublets).
Each of these three hyperfine peaks undergo further splitting by the three methoxy protons into 4
components (intensity ratio 1:3:3:1) to give the total 12 (= 3 x 4) lines, i.e. three quartets (Fig 12.3.5.7a).
9. ·CH20H: Three doublets (A = 17.5 G, 1.15 G) (Fig. 12.3.5.7). The two CH2 protons split the
signal into a triplet (1 :2: 1) (A = 17.5 G) and each of this triplet component is further spit into a doublet
by the OH proton (A = 1.15 G). Thus it gives a three doublets.
10.p-Nitrobenzoate dianion: The unpaired electron residing in the LUMO (cf C6H6 anion radical)
can interact with different sets of magnetic nuclei to give a complex ESR spectrum. Here 14N (I = 1)
splits the ESR signal into a triplet of equal intensity. There are two sets of hydrogens having different
hyperfine coupling constants. The two hydrogens having the higher fine constants will split each of the
triplet components (produced by 14N) into a triplet of the intensities 1:2: 1 giving the total 9 lines. Each
of these 9 lines will be further split by the other two equivalent protons into a triplet (intensity 1:2: 1)
ry
giving rise to total 27 lines (i.e. 9 triplets) (Fig. 12.3.5.8). It is obtained as: (2 x 1 x IN + 1) (2 x 2 x
ra
I H + 1) (2 x 2 x I H + 1) = (2 x 1xl + 1)( 2 x 2 x ~ + 1)(2 x 2 x ~ + 1) =27.
ib
yl
2-
o
;;? em (H and bli protons magnetically
ch
nonequivalent)
-----------r- N
(J "\
c-~-------
al
// '\,.o
e
//
o
th
e/
t.m
e
er
H
k
lic
C
l____________ ~
_-----------.-J
9 triplets (* triplets are more intense)
Fig. 12.3.5.8 ESR spectral lines of p-nitrobenzoate dianion (cf 19p-NMR spectrum of p-difluorobenzene).
Note: (i) Hydrogens (aH, aH) ortho- to -C0 2-and meta- to -N02 are different from the hydrogens
(bH, bH) ortho- to -N0 2 and meta- to -C0 2 (cf PMR spectra of p-disubstituted benzene) (ii) It is
difficult to predict which set of hydrogens show the higher hyperfine splitting constants. (iii) The
common technique to identify the protons: One pair of equivalent protons can be deuterated. The
nuclear spin (I) of deuteron is 1 and this pair of deutrons will give 5-hyperfine components (== 2 x 2
x 1 + 1) in place of 3 hyperfine components.
= =
11. 13CH3 (A 13c 41 G, A H 23 G): The unpaired electron is primarily housed on the C-centre and
it makes the hyperfine coupling constant higher for 13C. Thus the ESR signal is split by 13C (I = 1/2) into
a doublet of equal intensity. Then each of this doublet is split by the three equivalent protons into
4 components (intensity 1:3:3: 1) giving rise to 8 (= 2 x 4) lines (i.e. two quartets) (Fig. 12.3.5.9)
(cf. 12CH3: Quartet signal).
ry
ra
ib
yl
em
ch
e al
th
Fig. 12.3.5.9 ESR spectral lines for the 13CH3 radical (two quartets) (Magnetic field not in scale; two quartets are
e/
expected to overlap)
t.m
12. eCF2H vs. 13eCF2H: For ·CF2H, the number of hyperfine lines = (2 x 2 x IF + 1)(2 x 1 x IH + 1)
=( 2 x 2 x ~ + I J(2 x I x ~ + I) = 6. The number of hyperfine lines for CF H = (2 x I x I Be + 1)

e
13 2
er
(2 x 2 x IF + 1)(2 x I x I + I) = (2 x I x ~ + I J( 2 x 2 x ~ + I J( 2 x I x ~ + I) = 2 x 3 x 2 = 12.
H
H
k
13. Hyperfine lines for 3sCI (I = 3/2): The possible m/ values are: ±l, ±!. Thus there will be 4
lic
2 2
hyperfine lines (2 x 1 x I + 1) of equal intensities (i.e. 1: 1: 1: 1).
C
14. Phenyl radical (C 6H se) (cf J.E. Bennett et aI, Chem. Comm., 265, 1965):
Phenyl radical is extremely reactive and it can be obtained and trapped by the
photolysis of iodobenzene. The unpaired electron remains localised in the
sp2-hybrid orbital to give this a-type radical. The unpaired electron cannot
delocalise through the n-bond formation though it is possible for the
cyclopentadienyl radical (CsH.t/) (see Fig. 12.3.5.4).
In terms of the hyperfine coupling constant, the two ortho-hydrogens (OH)
are different from the two meta-hydrogens. The hyperfine coupling constants
of the ortho- and meta-hydrogens are 18.1 and 6.4 oerested respectively. The
para-hydrogen (PH) is too far away from the localised unpaired electron to
interact, i.e. AHP ::::; O.
Thus the two ortho- hydrogens split the ESR signal into a triplet (1 :2: 1 intensity ratio) and each
component of this triplet is further split by the two meta-hydrogens into a triplet (1 :2: 1 intensity ratio).
Thus the ESR spectrum consists ~f 9 lines [= (2 x 2 x IHo + 1)(2 x 2 x 1If' + 1) = 3 x 3] which constitute
the three equally spaced triplets (Fig. 12.3.5.10) having the intensity ratio 1:2:1. The lines in each
triplet are equally spaced having the intensities in the ratio 1:2: 1.
ry
ra
ib
yl
em
ch
Fig. 12.3.5.10 Stick spectrum of phenyl radical (3 triplets).
al
Note: In CsHs• radical, the unpaired electron can delocalise through the n-bonding and 5. hydrogen are equivalent (cf.
Fig. 12.3.5.4).
e
th
12.3.6 Mechanism of Coupling of the Electronic Spin and Nuclear Spin

e/
The magnitude of hyperfine coupling constant (A) depends on the period of time which is spent by the
t.m
unpaired electron at the nucleus to be coupled. This electron-nuclear interaction is called the Fermi
contact interaction. It is expressed as follows:
e
A oc p i.e. A = Rp (McConnell equation), p = the unpaired electron density at the vicinity of the
er
nucleus, R = proportionality constant = A for p = 1. For the H-atom, R = 50 mT.

H
Now let us consider the CH3 radical which gives 4 hyperfine peaks (intensity ratio; 1:3:3: 1) sepa-
k
rated f rom eac h other by 2.3 mT. i.e. A = 2.3 mT and P -_ A -_ 2.3 -- 0.046. It indicates that the
lic
R 50
unpaired electron of the methyl radical spends about five per cent of its time in the vicinity of each
C
hydrogen nucleus through its 1s orbital. Thus, the electron spends about 85% of its time in the vicinity
of C-centre and 5% of its time to each H-centre. Now let us consider the orbital picture of the CH3
radical where the unpaired electron resides in a pure p-orbital of the C-centre and the p-orbital remains
perpendicular to the plane bearing the nuclei of the C- and H-atoms. This plane is the nodal plane of
the p-orbital bearing the unpaired electron, i.e. the H-nuclei do not experience any electron density
from the unpaired electron. It should make p = 0 and consequently A = O.
The nonzero value of A can be explained through the participation of the intervening bonding
electrons as in the case of spin-spin coupling of the nuclei (i.e. J value, cf Sec. 12.2.9). The unpaired
electron will try to orient the nearest bonding electron (close to the C-nucleus) parallel (to earn the
exchange energy, cf. Hund's rule). Consequently, the other bonding electron (close to the H nucleus)
with the opposite spin, i.e. downward orientation (Pauli's exclusion principle) will try to orient the
nuclear spin of the H-centre in the upward direction (i.e. spin polarisation). Thus the unpaired
electron sends the instruction through the intervening bonding electrons for orientation of the
nuclear spin of the H-centre. This is called spin polarisation. The long range coupling beyond the one
bond can also rationalised (cf Sec. 12.2.9, IJ, 2J, etc.).
For the one intervening bond, the electronic spin (of the unpaired electron) and the nuclear spin of
the H-centre orient in the same direction (i.e. parallel orientation) then the coupling constant A be-
comes positive. For the two intervening bonds, the electronic spin (of the unpaired electron) and the
nuclear spin of the H-centre will orient in the opposite directions (i.e. antiparallel orientation) and it
makes the coupling constant (A) negative (cf Sec. 12.2.9 for the positive and negative J values). These
are illustrated in Fig. 12.3.6.1.
McConnell equation can be used to calculate the spin density of the unpaired electron near the
magnetic nuclei causing the hyperfine splitting. Thus this idea can be used to map the molecular
orbital bearing the unpaired electron.
ry
ra
r---------- -----------,I
ib
, '!iii; I
,,"
~!~
H
yl
,,, - - H/ (Planar CH 3 radical)
em
I
I
I
I
LII H _ I
ch
-~-j
al
p-orbital
Nodal
perpendicular
e
to the nodal plane

(a)
th
plane
e/
Exchange energy
t.m
p-orbital
LOS~~
eXCh:nO~e~ NUcI,ear)
e
'-. r,..---"-, spin

er
energy
H
Nuclear spin
/ ~ electron cHcHH+
k
.~ .t.rSPin
"."
~ / '--:-v-J L..-.y--J
lic
~pauli's/
~
~
'-v---' '-v---'
C
(lower energy) (higher energy)

Pauli's (c) principle (d)
(b) principle
Parallel orientation of the nuclear spin of Antiparallel orientation of the nuclear spin
H and unpaired electron spin on C of H and unpaired electron spin on C
Fig. 12.3.6.1 (a): CH 3 radical housing the unpaired electron in a pure p-orbital whose nodal plane contains the a-bonded
planar CH 3 framework. (b) and (d): The unpaired electron on C directing the orientation of the nuclear spin ofH-nucleus
(spin polarisation) through the Hund's rule (i.e. exchange energy) and Pauli's exclusion principle involving the bonding
pairs of electrons. (b) Positive coupling constant between the unpaired electron on C and the H-nuclear spin; (d) Negative
coupling constant between the C-electronic spin and H-nuclear spin through two intervening bonds. (c) Loss of exchange
energy and less stable situation than (b). .
• Hypertine splitting constant and structure of the CH3 radical (planar vs. pyramidal): The
ESR spectrum of the CH 3 radical shows 4 hyperfine lines separated from each other by 2.3 mT (i.e. A
= 2.3 mT). It yields p = 0.046. If the methyl radical is supposed to have the planar structure, the
unpaired electron is housed in a pure p-orbital. On the other hand, if the radical adopts the pyramidal
structure, the unpaired electron is housed in a Sp3 hybrid orbital (i.e. 25% s-character). At this situation,
the unpaired electron is expected to interact better to give the higher hyperfine coupling constant.
If the l3CH3 radical is subjected to an ESR study, a splitting by 13C (I = 1/2) with A = 41 G (i.e.
A =4.1 x 10-3 T = 4.1 mT) is obtained. This value is reasonable for the planar structure of the CH3
radical where the unpaired electron resides in a pure p-orbital. Theoretically, it has been shown that if
the unpaired electron resides in an sp3-hybrid orbital (25% s-character), the splitting by l3C would give
the separation value of 300 G (= 30 mT) because the unpaired electron having 25% s-character can
interact with the BC nucleus more strongly (cf. an s-electron has a finite probability of its existence at
the nucleus).
• Hyperfine splitting constants of CH3-radical and C 6H 6--anion radical: A CH »A c H- - this
ry
3 6 6
aspect has been discussed in Sec. 12.3.7(9).
ra
12.3.7 Illustration of the Fine Structure and Hyperfine Structure of the ESR Signals
ib
yl
1. Hydrogen atom eIH): It is having one unpaired electron (s = 1/2) and a proton (nuclear spin I =
em
1/2) i.e. it represents the system m s = ±1/2 and m/ = ±1/2. It gives two ESR peaks of equal intensity
(cf Fig. 12.3.5.1) and it has been discussed in Sec. 12.3.5 (1).
ch
2. Deuterium atom (1H): It represents the system: s = 1/2 and 1= 1 i.e. ms = ±1/2, and m/ = ±1, O.
al
It gives three equally spaced hyperfine ESR peaks of equal intensity (cf. Fig. 12.3.5.2). The equal
intensity of the peaks arise because the nuclear spin states (m/ = ±1, 0) are nondegenerate, i.e. each of
e
the states is obtained in a single way (cf M, = ± 1, 0 for two protons). This aspect has been discussed
th
in Sec. 12.3.5 (2).

e/
3. CH3 radical: It represents the system, ms = ±1/2 and M/ = ±3/2, ±1/2. It gives 4 hyperfine ESR
t.m
lines (equally spaced) having the intensity ratio 1:3:3: 1 (cf Fig. 12.3.5.3). This aspect has been discussed
in Sec. 12.3.5 (3).
e
4. CD3 radicals (I = 1 for D) and 13CD3 radical: It represents the CD 3 system as: ms = ±1/2,
er
M, = ±3, ±2, ±1, O. The number of hyperfine ESR lines is simply given by: (2 x 3 x ID + 1) = (2 x 3
H
x 1 + 1) = 7. The relative intensities of these 7 lines are as 1:3:6:7:6:3: 1.

For l3CD3 (I = 1/2 for l3C, 1= 1 for D), the number of hyperfine components is given by:
k
(2 x 1 >'.1/2 + 1)(2 x 3 x 1 + 1) = 14. If A( 13 C) ) A(D) i.e. hyperfine splitting constant for l3C is higher,
lic
then the ESR spectrum will show 2 septets. Similarly for ·CH2D, the number of hyperfine components
C
is given by: (2 x 2 x 1/2 + 1) (2 x 1 x 1 + 1) = 9.

ESR spectra of many other radicals like 13CH3, 13CHF2, -CH2(OCH3). -C(CH3)3' etc. have been
discussed already in Sec. 12.3.5.
5. Ethyl radical (CH3CH 2-) and methoxymethyl radical (-CH20CH3) (cf Figs. 12.3.5.6-7): The
unpaired electron of the ethyl radical interacts with the two types of protons viz. 2 methylene protons
and 3 methyl protons. The three methyl protons will split the ESR signal into four lines (cf
n + 1 rule) of the intensity ratio 1:3:3: 1. Each of these four lines will undergo splitting into 3 lines
(cf n + 1 rules) by the two methylene protons and these 3 lines will have the relative intensities 1:2: 1
(cf Pascal's triangle). Thus, the ESR spectrum of the ethyl radical will show 12 lines (= 4 x 3) i.e.
quartet (1:3:3:1) of triplets (1:2:1) (see Fig. 12.3.5.6), under the condition, splitting by the
CH3-protons is larger than splitting by the CH 2-protons. This result can also be easily attained by using
the working relation (2nI; + I) (2mI j + I) =( 2 x 2 x ~ + 1) ( 2 x 3 x ~ + 1) = 3 x 4 = 12. Here it may be

mentioned that the coupling constants of the methyl and methylene protons do not differ much (27 G
vs. 22.5 G) and when the C2Hs radical is trapped in a rigid matrix, it prevents resolution and gives
6 hyperfine peaks (i.e. 5 equivalent protons) with the relative intensities 1:5:10:10:5:1. The
methoxymethyl radical gives three quarters (see Fig. 12.3.5.7).
M 1
+2
+1
o
.... -1
.4
....
>- -2
e>
Q)
c
W
r
ry
-2
ra
-1
o
ib
+1
(External
yl
+2
Magnetic field
(Hyperfine
em
but no hyper-
splitting)
fine splitting)
ch
(a)
e al
th
e/
t.m
e
er
H
k
lic
C
------------------+~ Ho
(b)
Fig. 12.3.7.1 (a) Hyperfine splitting (assuming A to be positive) leading to 5 ESR transitions (at a fixed field Ho) in
p-benzosemiquinone radical anion. (b) ESR spectral pattern (1 st derivative at a fixed operating frequency) (5 hyperfine
peaks of the intensity ratio 1:4:6:4: 1) of p-benzosemiquinone radical.
6. Para-benzosemiquinone radical anion: This anion radical has the following structure.
o~ ~o ~ -o~· ~o o~ ~o- o~O~o- or i.e.
H H H H H H H H
It has one unpaired electron (s = 1/2) to interact with the 4 equivalent protons (i.e. M[ =±2, ±1, 0).
It gives 5 ESR transitions (under the condition, ~s = ±1, dM[ = 0). These five lines (= 2 x 4 x 1/2 + 1
i. e. n + 1 rule) are equally spaced having the relative intensities 1:4:6:4: 1.
In the quinone-hydroquinone redox system (i.e. Q + 2H+ + 2e ~ QH2), the ESR studies indicate
a five-line spectrum of the intensity ratio 1:4:6:4: 1. It undoubtedly proves the existence of the semi-
quinone free radical anion as an intermediate in the redox couple.
Q + H+ + e ~ QH, QH + H+ + e ~ QH 2 •
H H H H
H H
o~ ~o- ~ o~ ~OH ~OH

°9 0 Hoi
ry
H H H H + H+ H H H H
ra
(Q) (QH 2)
QH (semiquinone)
ib
ESR spectrum of p-nitrobenzoate dianion (27 hyperfine lines; 9 triplets)
yl
l em
a
H 2- (See Sec. 12.2 for the PMR spectra of such
ch
p-disubstituted benzene)
(cf. Fig. 12.3.5.8)

e al
th
e/
ESR hyperfine splitting for the radical intermediate produced in the oxidation of
t.m
phenol (cf. delocalisation of the unpaired electron in semibenzoquinone).

·0 ·0 ·0
e
H3C~CH3 (CH 3)3 C ~ C(CH3)3 (CH3)3C ~ C(CH 3)3

er
'7 '7 '7

1 1 1
~ ~ ~
H
C(CH 3)3 CH 3 C(CH 3)3

k
lic
Splitting by 6 ortho-Me protons Splitting by 3 protons of Splitting by only

into a septet; each line of the 4-Me group and 2 ring 2 ring protons
C
septet splitting into a triplet protons i.e. (2 x 3 x! + 1) i.e. 3 lines

by 2 ring protons; i.e. (2 x 6 x ~ + 1) 1 2
x 2 x 2 x - + 1) = 12 lines
x 2 x 2 x ~ + 1) = 21 lines 2
7. Naphthalene negative ion: There is an unpaired electron in the LUMO to interact with the two
types of protons (4a-protons and 4p-protons).
H~-
CLH CLH
PH
PH 10
4 HP
CLH CLH
Thus its ESR spectrum consists of ( 2 x 4 x i + 1) ( 2 x 4 x i + 1) = 5 x 5 = 25 hyperfine lines.

The unpaired electron of the naphthalene negative ion resides in the LUMO (nodal points at 9 and
10 positions) of the naphthalene. LUMO of the naphthalene molecule is:
'l'LUMO = O.4253[ 'I' 2p,{I} + 'I' 2p,{4} - 'I' 2p,(5) - 'I' 2p,(8) ]
+O.2629[ -'I' 2p,(2) - 'I' 2p, (3) + 'I' 2p,(6) + 'I' 2p,(7) ]
The 1t-electron spin density (i.e. probability) of the unpaired electron residing in the 'VLUMO on each
of the a-C atoms (i.e. 1,4,5 and 8 positions) is given by (0.4253)2 = 0.1809. Similarly, the 1t-electron
ry
spin density (i.e. probability) of this unpaired electron on each of the ~-C atoms (i.e. 2, 3, 6 and 7) is
ra
given by (0.2629)2 = 0.06912.
ib
Thus the total probability density is: 4 x 0.1809 (a-C) + 4 x 0.06912 (f3-C) = 0.7236 + 0.276::::: 1.0.
Thus the hyperfine splitting constants (A =Rp, cf Sec. 12.3.6, McConnel equation) at the a- and ~
yl
positions are (R = 25 x 10-4 T):
A(a) = RPa = 25 x 10-4 T xO.1809 = 4.52 x 10-4 T

em
ch
A(~) = Rp~ = 25 X 10-4 T x 0.06912 ~ 1.73 x 10-4 T
al
•• 1
e
8. A radical like .NH 2 having 14N (I = 1, A = 1.03 mT) and two equivalent protons (I =- ,
th
2
A =0.35 mT): The 14N nucleus will split the ESR signal into a triplet where all the three components
e/
are equally intense (cf all the nuclear spin states m/ = ± 1, 0 are nondegenerate) with the separation of
t.m
1.03 mT. Each line of this triplet will further undergo splitting into three lines by the two equivalent
protons (i.e. M1 =±1, 0). These equally spaced (separation 0.35 mT) three lines are of intensities 1:2:1.
e
The total hyperfine splitting lines are given by: (2 x 1 x IN + 1)(2 x 2 x IH + 1) = (2 x 1 x 1 + 1) (2 x

er
2 x 1/2 + 1) = 9. (Fig. 12.3.7.2).

H
AH AN = 1.03 mT
k
.... lIlI • 1:2:1

lic
C
AN
lIlI •
- - - - - - - -... Ho
..
Fig. 12.3.7.2 ESR spectrum of the -NH z radical showing three triplets. Each signal due to splitting by 14N is again split
by 2H into a triplet (intensity ratio 1:2: 1).
9. Benzene anion radical (C 6H 6-), cyclopentadiene radical (C 6H s-) and phenyl radical (C 6H s-):
The unpaired electron in the LUMO of C6H6 interacts with the 6 equivalent protons to produce 7
hyperfine peaks of the relative intensities 1:6: 15:20: 15:6: 1 (cf Fig. 12.3.5.5) with the separation of
0.375 mT (i.e. A = 0.375 mT). The unpaired electron in C6H6- resides in the LUMO which is a 1t-
ABMO having a node in the plane of the molecule, i.e. no electron density from the unpaired electron
in the H-nuclei lying in the plane of the molecule. However, this 1t-antibonding electron can polarise
(i.e. spin polarisation) the bonding electrons to orient the nuclear spin of H-nuclei (cf Fig. 12.3.6.1).
This aspect has been illustrated for the CH3 radical (cf Sec. 12.3.6). The hyperfine splitting constant (A)
(3.75 x 10-4 T) of ·C 6H6- less than that of the CH3 radical (A = 2.3 x 10-3 T). In C6H6-, the unpaired
electron is delocalised over the whole molecule while in the CH3 radical, it is delocalised over the
relatively smaller number of the nuclei. Thus, the average probability of finding the electron on a H-
ry
nucleus is relatively smaller in C6H 6- compared to that in the CH3 radical. It explains the higher value
of A in the CH3 radical (cf A oc p Le. A = Rp, Sec. 12.3.6).
ra
Cyclopentadiene radical (CsH s·) gives an ESR signal which is spilt by the 5 equivalent protons to
ib
give the 6 hyperfine components of the intensity ratio 1:5: 10:5: 1 (cf Fig. 12.3.5.4). Here the unpaired
yl
electron residing in a pure p-orbital can delocalise over all the C-centres through the 1t-bonding. On the
em
other hand, in the phenyl radical (C6H s), the unpaired electron is localised in an sp2-hybrid orbital
(i.e. a-type radical). Thus the ESR signal is split by two ortho-protons and two meta-protons to give
ch
9-hyperfine lines (ignoring the splitting by the para-proton) (cf Fig. 12.3.5.10).
10. N0 2, CO 2- and CI0 2: The unpaired electron of N0 2 interacts with the 14N (I = 1) nucleus to
al
produce three equally spaced lines of equal intensity. In fact, the unpaired electron is localised on the
e
N-centre. In terms of MOT, the unpaired electron resides in the MO which is basically concentrated on
th
the N-centre (cf Chapter 9; Vol. 2). CO 2- being isoelectronic with N0 2 shows a similar ESR spectrum.
e/
The unpaired electron of CI0 2 gives 4 hyperfine lines from 3sCI (I = 3/2).
t.m
11. Nitroxides (stable radicals) - [(S03)2NO]2-, TEMPO, TEMPOL: The unpaired electron
interacts with the nitrogen nucleus (I = 1). It is mainly localised in a pure p-orbital of nitrogen. It gives
the three equally spaced hyperfine lines (2 xl x 1 + 1 = 3, triplet) of equal intensity (cf all the nuclear
e
spin states m/ = ± 1, 0 are nondegenerate). However, at a relatively higher concentration, the rapid
er
electron spin exchange through the bimolecular collision process leads to the merging of the peaks
H
into a sharp single peak (cf Sec. 12.3.14). A similar situation arises for the DPPH radicals also.
k
lic
t r
o
QM~O AMe
C
p-orbital
C>N<D
/\ HO~~---O
Me 3 C CMe 3
Me Me Me Me
Di-t-butyl Nitrosyl disulfonate
nitroxide radical TEMPOl
TEMPO
(2, 2, 6, 6-tetramethyl (2, 2, 6, 6-tetramethyl
-piperidin-1-yl)oxyl -piperidinol-N-oxyl
radical radical)
Nitroxide molecules (stable ra~icals used in ESR studies)

ESR signal: 3 lines (hyperfine splitting by 14N of I = 1) and the unpaired electron in a p-orbital is mainly localised
on the N-centre. It may be noted that in a relatively concentrated solution, rapid spin exchange (bimolecular collision
process) leads to the merging of the hypertine peaks into a single peak (cf Sec. 12.3.14, Figs., 12.3.14.1-2).
m = +..1.. "",,------ +1
s 2 ,,"
----~~~----- - - - - . . - - - - - 1 1 - - - 0
////// """". ,~ -1
--~'"
ms =±..!. '" _---4.-+--_+_- -1

2 '" """"
(No magnetic ""---.-r::t'~:-------.........--+-- 0
field) m = _..1.. .
s 2 -------.;--+1
ry
(Magnetic field (Hyperfine
ra
but no hyperfine splitting)
splitting)
ib
(a)
yl
em
13 G (for S03)2N02-
III ~
Note: The hyperfine peaks undergo merging in
ch
a relatively concentrated solution due to the rapid
electron spin exchange in the bimolecular
al
process, cf. Sec. 12.3.14).

e
th
e/
t.m
(b)
Fig. 12.3.7.3 (a) Hyperfine splitting (by 14N, I = 1 and ignoring the effects of 15N and 33S whose abundances are
e
negligibly small leading to three ESR transitions (at a fixed field) in the nitroxide molecules (assuming A to be positive)
er
(b) ESR spectral pattern (at a fixed frequency) (3 hyperfine peaks of equal intensity) of the nitroxide molecules.
H
Here it is worth mentioning that the nitrosyldisulfonate radical present in Fremy's salts i. e.
k
Na2[NO(S03)2], K2[NO(S03)2] is widely used as a stablellong-Iived radical in EPR studies. Similarly,

lic
other stable nitroxide radicals relevant in the EPR studies are TEMPO and TEMPOL. TEMPOL as a
spin label can attach to the macromolecules like proteins and menbranes and then the ESR spectral
C
features reflect the chemical environment of the site to which the spin label attaches.
Nitroxides can also act as the effective quenchers of fluorescence. Thus the combination of spin-
labelling and fluoresence techniques may be quite helpful to study the structure of membranes.
12. Bissalicylaldiminecopper(II): Because of the strong distortion in the d 9-system, the spin-
lattice relaxation time (T t ) is relatively longer and it makes the ESR studies easier (see Sec. 12.3.4).
The unpaired electron of Cu(ll) (d 9 system) interacts with the nuclear spin I = 3/2 of copper (63, 65CU,
I = 3/2). It gives four major hyperfine peaks (2 x 1 x 3/2 + 1 =4) of equal intensity. The equal
'"',,-
intensity of the 4 hyperfine pe~saPses because all the 4 nuclear spin states (i.e., m[ == ±%, ±~) are
nondegenerate (Le. each of the spin states is obtained in a single way) (ef M[ == ±~, ± ~ for the CH3
22
radical; Sec. 12.3.5, Fig. 12.3.5.3 where the peaks are of unequal intensity).
From the structure of the his-complex, it appears that the coupling may also occur with the two
e
equivalent nitrogen nuclei 4N, 1 = 1), with the two equivalent H" (I = 1/2) and with another two
equivalent H' (I = 1/2) of the ligand, if the unpaired d-electron is believed to get delocalised over the
whole ligand moieties. The splitting by ligand nuclei is called superhypertine splitting which is an
indication of the metal-ligand covalent interaction (contradicting the basic idea of idea CFT).
Hyperfine splitting by 63CU and 65CU

The relative abundances of the 63CU and 65CU isotopes are about 69% and 31 % respectively and
both have the nuclear spin I = ~. The gyromagnetic ratios of these two isotopes are very much
2
similar and consequently only one characteristic hypertine splitting into 4 lines is observed
ry
(i.e. A(63Cu) ::::: A( 65 CU).
ra
ib
If we ignore the superhyperfine splitting by the H' nuclei (directly attached with the N-centre) then
each of the major 4 hyperfine peaks (caused by the nuclear spin of Cu) will undergo splitting by two
yl
equivalent ligand nitrogens (I = 1) and two equivalent ligand hydrogens H" (I = 1/2) of the two ligands
em
giving rise to 15 peaks, i.e. (2n NIN + 1)(2nH"IH,,+ 1) = (2 x 2 x 1 + 1)(2 x 2 x 1/2 + 1) = 5 x 3 = 15.
In reality, 11 superhyperjine peaks having the relative intensities 1:2:3:4:5:6:5:4:3:2: 1 are observed.
ch
Probably, some of the 15 superhyperfine peaks undergo overlapping to reduce the number to 11. It may
al
be noted that A cu » A H ".
e
The superhyperjine splitting by the ligands indicates the delocalisation of the metal electron into
th
the ligand orbitals (i.e. evidence in favour of the metal-ligand covalent interaction as proposed in
e/
ACFT and against the ideal CFT).

That the H' atom (directly attached to the N atom) atom does not participate in splitting the ESR
t.m
signal is evidenced by the fact that deuteration of the N-H' group does not change the ESR spectrum.
If the H" atoms are replaced by the Me Groups, then each of the major 4 hyperfine peaks (caused
e
by I = 3/2 ofCu) is split into 5 components by two 14N (i.e. M] = ±2, ±1, 0). There is no further splitting.
er
It indicates that the methyl protons do not split the ESR signal.
H
Note: Superhypertine splitting (i.e. splitting by the ligand atoms) becomes quite important when
the unpaired electron resides in the eg-orbitals (i.e. the orbitals which are directly interacting with the
k
lic
ligands) as in the Cu(II) complexes (t~g e~). When the unpaired electron resides in the t2g orbitals (as in
the CrIll-complexes, t~g or oxidovanadium(IV) complexes, t~g) (i.e. the orbitals not directly interacting
C
with the ligands), the superhyperfine splitting is not of much importance.

13. Bis-salicylaldoximatocopper(II): The characteristic features of the ESR spectrum are:
4 major hypertine peaks of almost equal intensity (cf. all the nuclear spin states i.e. m] = ±1/2 and ±3/
2 are nondegenerate) and each of these 4 peaks consists of 5 superhyperfine splittings (relative intensities
1:2:3:2: 1)
The unpaired electron of Cu(II) (cP system) interacts with nuclear spin 1 = 3/2 of 63, 65CU to produce
4 major hyperfine peaks (= 2 x 1 x 3/2 + 1 = 4). If the metal unpaired electron is considered to
delocalise over the ligand, then the superhyperfine splitting of each of the hyperfine peaks by two
equivalent ligand nitrogen nuclei (I = 1) can give 5 components (= 2 x 2 x 1+ 1) having the intensity
ratio 1:2:3:2: 1. It explains the splitting of each major hyperfine peak into 5 superhyperfine components.
The relative values of the hyperfine coupling constants (A cu ) for hyperfine splitting by 63, 65CU
(I = 3/2) and superhyperfine coupling constant (AN) for splitting by 14N of the ligand depend on the
nature of the substitution on the ligand. This is illustrated below.
Acu (for bis-salicylaldoximatocopper(ll) complexes) ) Acu (for bis-5-chlorobissalicylaldoximatocopper

(II) complexes); AN remains more or less unchanged for the said two Cu(ll) complexes.
Hyperfine and Superhyperfine Splitting in the ESR Spectrum of Cu(II)-triglycine

Complex, i.e. Cu(II)-glycylglycine Complex
• 4 Major hyperfine splittings by I = l of

2
63, 65 CU.
• Superhyperfine splitting of each major

hyperfine peak by the 3 N-sites (I = 1) into 7
ry
components (= 2 x 3 x 1 + 1). However these
are not well resolved.
ra
o
ib
yl
em
ESR signal
split into 4 components
ch
by Cu of I=!
2
e al
th
e/
t.m
(Hypefine splitting by Cu)

........ Intensity 1:1:1:1
e
er
H
Splitting into
5 components
k
by two 14N (i.e.

lic
M, = ± 2, ± 1, 0) (Superhyperfine splitting
Intensity 1 :2:3:2:1 =
C
by 14N-nuclei of I 1)
/1\
" 1\
I" II \\
I I \
Splitting into
~~A"
3 components
(Superhyperfine
by two H" (i.e.
splitting by tw0
M, = ± 1,0) 1
Intensity 1 :2:1
=
H" nuclei of I 2)
H
l )
~
15 components
in each major
hyperfine peak
(a)
1920 FUNDAMENTAL CONCEPTS O~ INORGANIC CHEMISTRY
6
5 6 5
4
4 4
8
ry
ra
ib
yl
em
ch
al
(b)
e
th
Fig. 12.3.7.4 (a) Splitting tree (hyperfine and superhyperfine splitting) of the ESR signal of bis-salicylaldiminecopper(II)
e/
(b) Qualitative representation of 4 the hyperfine ESR peaks experiencing the suprehyperfine splitting.
t.m
In terms of McConnell equation (A = Rp), the coupling constant (A) is directly proportional to the
residence probability (p) of the unpaired electron concerned in the immediate vicinity of the atomic
nucleus whose nuclear spin causes the splitting of the ESR signal. Presence of the electron withdrawing
e
group like the chloro-group on the ligand moiety reduces the electron density (i.e. residence probability)
er
(p) of the unpaired electron in the immediate vicinity of the Cu(II) centre. It reduces the coupling
H
constant Acu . For the chloro-substituted ligand, AN is expected to increase but this is not reflected
much because A cu » AN.
k
lic
14. V0 2+ (3d l ) i.e. oxidovanadium(IV) complexes: The oxidovanadium(IV) complexes i.e.

oxidovanadium(IV) complexes experience a strong J. T. distortion and the orbitally singlet ground
C
state is widely separated from the immediate excited electronic state (see Fig. 7.14.1.2) (i. e. energy
separation, D£ » kBD and consequently, the spin-lattice relaxation process is disfavoured (i.e. spin-
lattice relaxation time T1 is relatively longer) (see Secs. 12.3.2,4). It makes their ESR studies easier and
it can be studied even at room temperature. Because of the same ground (see Sec. 12.3.4, Fig. 12.3.4.4),
the EPR studies of the Cu(II) complexes can be made even at room temperature.
In the monomeric oxidovanadium(IV) complexes, the unpaired electron interacts with the nuclear
spin I =7/2 of vanadium. It splits the ESR signal into equally spaced 8 hyperfine peaks (2 x 7/2 + 1 = 8)
(FIg. 12.3.7.6). This has been experimentally verified in different oxidovanadium(IV) complexes like
[VOFs]3- bis(N,N'-diethyldithiocarbamato) oxidovanadium(IV), [VO(5-chloro-salicylaldehyde-aniline )2],
etc.
In the dimeric oxidovanadium(IV) complexes, there are two unpaired electros (i.e. M s = ±1, 0) and
the zero-field splitting (Sec. 12.3.3) will give the ESR lines for both the allowed two Ilifs =±1 transitions
and one forbidden Ilifs = ±2 transition (i.e. weaker signal) (see Fig. 12.3.3.1b). Both the Ilifs = ±1 and
j)Ms = ±2 transitions will experience the hyperfine splitting by two 51V (I = 7/2) nuclei giving rise to
15 components (= 2 x 2 x 7/2 + 1). The transition for dMs = ±2 indicates the spin-spin exchange.
In (NH4)4[{VO(d-tartarate)}2]' the forbidden transition (j)Ms = ±2) appearing at 16000 gauss and
the allowed transitions (dMs = ±1) appearing at about 3200 gauss show the hyperfine splitting of 15
components.
Note: For y3+ (dl) complexes, the magnitude of zero-field splitting exceeds the energies of ESR
transitions in the range of attainable magnetic field (cf. Sec. 12.3.3). Consequently, the ESR transitions
corresponding to AMs = ±1 are not observed and only a weak signal for the forbidden j)Ms = ±2
transition (between the M s = ±llevels) is observed (Fig. 12.3.3.1c). This signal is split into 8 hyperfine
components by 1= 7/2 for 51y.
O--H
ry
HI!
ra
""c= N"
ib
/0
Cu
yl
o / " N~C
I em"'H
ch
I
H--O
e al
th
e/
t.m
e
er
(a)
H
k
lic
C
(b)
Fig. 12.3.7.5 Splitting tree (hyperfine and superhyperfine splitting) of the ESR signal of bis-salicylaldoximatocopper(II)
(Acu ) AN)' (b) Qualitative representation of the ESR spectrum of bis-salicylaldoximatocopper(II).
15. CuCI2 . 2H20 and CUS04 · 5820: The strong J.T. distortion makes the spin-lattice relaxation
time (T I ) relatively longer and the ESR studies becomes easier for the d 9 system (see Sec. 12.3.4). For
the given Cu(II) complexes, in each case, there is an unpaired electron (3d 9 ) which interacts with
I = 3/2 of 63, 65CU. Thus the ESR signal is split into 4 hyperfine peaks (ef Figs. 12.3.7.4, 5) by I =
3/2 (i.e. Ms = ±3/2, ±1/2).
// .4
/
H
ms =+1
2
'" .4~
- .4~
~
....
.4~
ry
.4~
ra
ib
yl
/
/
em
/
ch '"
e al
....
th
(Magnetic field
but no hyperfine
e/
splitting) (Hyperfine
splitting)
t.m
6
e
er
H
• Squarepyramidal geometry (C4V)

k
and distortion leading to symmetry

lic
reduction =:) Anisotropic EPR

spectrum.
C
• For axial symmetry, 8 parallel

and 8 perpendicular lines.
• In solution, anisotropic coupling
averaged to zero i.e. isotropic
hypertine interaction measured by
A0 (see Sec. 12.3.11).
-----------------.~ Ho
Fig. 12.3.7.6 (a) [Hyperfine splitting (assuming A to be positive) by the vanadium nucleus (I = 7/2) leading to 8 ESR
transitions (in a fixed field) in the oxidovanadium(lV) complexes like [VO(acach], [VO(glycolatehf-, etc. (considering
no superhyperfine splitting). (b) ESR spectral pattern (8 hyperfine peaks) for [VO(5-chlorosalicylaldehyde-anilineh] at
a fixed operating frequency.
7 10
15
ry
ra
Fig. 12.3.7.7 ESR spectrum (15 hyperfine components) at a fixed frequency for the forbidden tiMs = ±2 transition in
ib
[{VO(d-tartarate) }2]4-.
yl
em
These 4 hyperfine lines are equally spaced and equally intense. The equal intensity of the hyperfine
components arises because all the four nuclear states (i. e. m I = ± l, ±!) are nondegenerate, i. e. each
ch
2 2
of these four states can be obtained in only one way. Here it may compared with the. CH3 radical
e al
having M I =± l and ±! where the nuclear states corresponding to M I =± -21 are triply degenerate
th
2 2
= ±l are nondegenerate. In fact, 4 peaks in the ESR signal of the
e/
and the states corresponding to M I

2
t.m
CH3 radical are of the relative intensities 1:3:3: 1 (cf. Fig. 12.3.5.3).
16. Dichlorido(l, lO-phenanthroline)copper(II) i.e. [CuCI2(phen)]: For the ESR studies, this dis-
e
torted tetrahedral complex is incorporated as a trace impurity in the isomorphous diamagnetic host
er
lattice of [ZnCI 2(phen)]. The hyperfine coupling between the unpaired electron and the copper nucleus
H
(I = 3/2 for 63, 65CU) produces 4 major hyperfine peaks (=2 x 1 x 3/2 + 1).
k
lic
C
Each of these 4 major hyperfine peaks undergoes superhyperfine splitting by two equivalent 14N
(I = 1) ligand nuclei of phen into 5 components (2 x 2 x 1 = 5). Here it is worth mentioning that 35CI
has a nonzero nuclear spin (I = 3/2) but it does not split the ESR signal because the superhyperjine
coupling constant for Cl in a Cu(Il) complex is very small.
17. [Cu(bigH)2]Br2: For the ESR studies of this complex, it is taken as an impurity into the diamag-
netic isomorphous [Ni(bigH)2)]Br2 host lattice. The unpaired electron of Cu(ll) (tf) of the square planar
complex interacts with the nuclear spin I = 3/2 of 63, 65CU. It splits the ESR signal into 4 major
hypertine peaks (2 x 1 x 3/2 + 1 = 4) of equal intensity. In the two biguanide ligands coordinated to
=
Cu(II), there are 4 equivalent N-centres coordinating the metal centre. The nuclear spins (I 1) of these
e
4 equivalent ligand nitrogens 4N) lead to superhypertine splitting of each of the major 4 major
hyperfine peaks into 9 components (= 2 x 4 X IN + 1 = 2 x 4 x 1 + 1). Thus the ESR spectrum of
[Cu(bigH)2]2+ shows 4 hyperfine peaks (Cu-hyperfine splitting) and each hypertine peak consists of
9 lines (N-superhyperfine splitting).
ry
ra
ib
(i) 4 *N causing the superhyperfine splitting
yl
(ii) The N-H protons do not participate in superhyperfine splitting. A similar situation arise for the
em
bis-salicylaldiminecopper(II) complex (cf. Fig. 12.3.7.4).
Note: Nitrogen superhyperfine splitting in oxidovanadium(IV) vs. copper(ll) complexes: For
ch
the nitrogen donor ligands, the nitrogen superhyperfine splitting is commonly noted for the Cu(II)
(d 9 ) complexes but it is not usually noted for the analogous oxidovanadium(IV) (d t ) complexes
al
because of the very small superhyperfine coupling constant for the oxidovanadium(IV) complexes. In
e
th
the copper(II) complex, the unpaired electron residing in the d 2 2 orbital can directly interact with
x -y
e/
the ligand atoms but in the oxidovanadium(IV) complex, the unpaired electron residing in the d xy
t.m
orbital (a component of the t 2g set; cf. Fig. 7.14.1.2) does not interact directly with the ligand atoms.
It makes the superhyperfine splitting constant for the oxovanadium(IV) complex relatively less. Besides
this, the effect of the quadrupole moments of the Cu and V nuclei may be another factor. The quadrupole
e
moment of the Cu and V nuclei broaden the ESR signals. The quadrupole moment of the V nucleus
er
is twice that ofthe Cu-nucleus and it may be the reasonfor not observing the nitrogen superhyperfine
H
splitting for the oxidovanadium(IV) complexes.

18. Dimeric copper(ll) acetate monohydrate, i.e. [Cu2(CH3C02)4] · 2H20: The two equivalent
k
lic
Cu(II) (I = 3/2 for 63, 65CU) centres interact strongly giving rise to M[ = ±3, ±2, ±1, O. There are two
unpaired electrons (one in each Cu(II) centre) to give Ms = ± 1, 0 which experience the zero-field
C
splitting (cf. Fig. 12.3.3.1). The ESR forbidden transition ~s = ±2 gives a weak signal at wavelength
of 3 cm (= 104 MHz) at 90 K. It is an evidence of the zero-field splitting in this magnetically
concentrated complex.
When a magnetic field is applied along the z-axis, the ESR signal of copper(II) acetate monohydrate
shows 7 hyperfine peaks of the relative intensities 1:2:3:4:3:2: 1 and these are equally spaced (spacing
= 42 gauss). These 7 hyperfine components appear due to the splitting by two equivalent Cu(II)-centres
(cf 2 x 2 x ~ + 1 = 7). The relative intensities of the hyperfine peaks can be explained by considering
2
the degeneracy of the nuclear states characterised by MI.
M[ = ± 3 (nondegenerate, i.e. these can be attained through one combination)
=
M[ ± 2 (doubly degenerate, i.e. these can be obtained in two possible ways of combination)
M[ = ± 1 (triply degenerate, i.e. these can be attained in three possible ways of combination)
M[ = ± 0 (four fold degenerate, i.e. this can be obtained in four possible ways of combination).
1
c::
o
E-
oen 7
..c
<
ry
ra
--.~ Ho (along the z-axis)
ib
yl
(a)
em
Fig. 12.3.7.8 (a) ESR spectrum (7 hypertine peaks) pattern of the dimeric form of copper(II) acetate monohydrate in
a single crystal along the z-axis. (b) Singlet and triplet spin states for the two interacting Cu(II) centres, each bearing an
ch
unpaired electron in the d x2 _ orbital.
l
al
It has been found that intensity of the ESR signals of the dimeric form of copper(II) acetate mono-
hydrate increases with the increase of temperature (cf. magnetic susceptibility also increases with the
e
increase of temperature). It indicates that the spin singlet state is the ground state (S =0) while the spin
th
triplet state (S = 1) is the excited state whose population density increases with the increase of tempera-
e/
ture. It may be noted that the singlet (8 =0) ground state is E8R inactive and the excited triplet state
t.m
(8 = 1) is E8R active.
19. Dimeric fprm of bis(dimethylglyoximato)copper(II) i.e. [{Cu(dmgH)2}2]: The system repre-
e
sents: M s = 0, ±1 (experiencing the zero-field splitting) and M] = ±3, ±2, ±1, O. In addition to the
er
allowed transitions (i.e. IiMs = ±1), there is a forbidden transition (i.e. IiMs = ±2) giving a weak ESR
H
signal. Each of the IiMs = ±1 and IiMs = ±2 transitions experience the hyperfine splitting by the two
(I =%) into 7 components (2 x 2 x 3/2 + I). The appearance of zero-field
k
equivalent copper nuclei

lic
splitting and ESR transition for IiMs = 2 indicate the spin-spin exchange interaction.
C
Fig. 12.3.7.9 ESR spectrum (7-hypertine peaks) pattern for ~s = 2 transition, in the dimeric form of bis(dimethyl-
glyoximato)copper(II) i.e. [{Cu(dmgHh}2l in ethanol solution.
20. Ag(II) species: This cP system bears an unpaired electron and the g-value is quite anisotropic.
1 = 1/2 for 107Ag can split the ESR signal into two hyperfine components.
ry
ra
ib
yl
em
Fig. 12.3.7.10 ESR spectrum of Ag(II) in nitric acid.
The anisotropic character of the g-value of Ag(II) in [Ag(PY)2]S20g diluted in [Cd(PY)2](S20g) shows
ch
gil = 2.18 and g.l.. = 2.04 with gay = 2.09.
21. [C03(CO)9Se]: The EPR signal of this paramagnetic trinuclear complex (as an impurity doped
al
in the single crystal of [FeCo2(CO)9Se]) shows 22 hyperfine components. This can be explained by
e
considering the equivalent positions of the three Co-centres (I = 7/2). If the unpaired electron is sup-
th
posed to delocalise equally over the three cobalt centres then they will split the signal into 22 hyperfine
e/
components (2 x 3 x 7/2 + 1 = 22). The equivalence of the Co-centres suggests the average oxidation
t.m
state +2/3 per each Co-centre. It may be noted the ESR spectra of the reduced forms of [FeCo2(CO)9S]
and [PRCCo3(CO)9] show 15 lines (= 2 x 2 x 7/2 + 1) and 22 lines (= 2 x 3 x 7/2 + 1) respectively.
e
er
H
11 9 7
k
lic
C
Co
oc/I"'co CO ~ Ho
[Co3(CO)gSe]
Intensity ratio: 1 : 3 : 6 : 10 : 15 : 21 : 28: 36: 42: 46 : 48 : 48 : 46 : 42 : 36 : 28 : 21 : 15 : 10 : 6 : 3 : 1
Fig. 12.3.7.11 Structure of [COiCO)9Se] and the ESR peak (with 22 hyperfine components).
22. K 3[Mo(CN)s]: Mo(V) (4d 1) possesses one unpaired electron. Before to discuss the hyperfine
splitting, we should know the nuclear spins (I) of the different Mo-isotopes and their abundances.
I = 0 for 94Mo and %Mo; I = 12 for 95 Mo (15.78%) and 97Mo (9.6%)

ry
ra
------------+~ Ho
ib
Fig. 12.3.7.12 ESR spectrum (6 hyperfine peaks for 95Mo, 97Mo with I =5/2; and the central intense peak without any
hyperfine splitting for the more abundant isotopes 94Mo, 96Mo with I =0) of K3[Mo(CN)s], 13C-superhyperfine splitting
yl
not shown.
em
Thus, 94Mo and 96Mo isotopes do not split the ESR signal. But each of the 95Mo and 97Mo isotopes
ch
split the ESR signal to produce the 6 hyperfine lines (= 2 x 1 x 5/2 + 1). The 6 hyperfine peaks
developed by 95Mo overlap with the 6 hyperfine peaks generated by 97Mo. (cf. A for 95Mo::::: A for 97Mo).
al
Consequently, only 6 hyperfine peaks (instead of two different sextets) are observed. In addition to
e
these 6 hyperfine peaks, an intense singlet peak corresponding to the nonmagnetic isotopes (94Mo,
th
96Mo) appear at the central position. A similar situation arises for Cr(lll) when the central intense
e/
singlet peak appears for the nonmagnetic Cr-isotope (cf. Fig. 12.3.4.1).
t.m
Here it is worth mentioning that the superhypertine splitting by 13C (1.11 % abundance) has been
noted in the ESR spectrum of K3[Mo(CN)s]. It supports the Mo-CN bond. If there were Mo-NC
bonds, the number of superhyperfine splitting (by 14N) components would be different (cf. I = 1 for 14N;
e
1
er
2"
1 = for 13C).
H
The relative intensities of the ESR signals, i. e. sextet (by 95Mo, 97Mo) and singlet (by 94Mo, 96Mo)
k
can be estimated as follows:

lic
• intensity oc natural abundance of the isotope

• and intensity oc (number of hyperfine lines i.e. 21 + 1)-1
C
The combined abundance of the magnetic isotopes (I = 5/2) 95Mo and 97Mo is approximately 25%
while the combined abundance of the nonmagnetic isotopes (I = 0) 94Mo, 96Mo is about 75%. It leads
to:
Intensity of the singlet ESR signal due to the nonmagnetic isotopes oc 75 x 1
Intensity of sextet ESR signals due to the magnetic isotopes oc 25 x 1/6.
Thus intensity of the ESR signals due to the magnetic isotopes (I = 5/2; 95Mo, 97Mo) is J.-(= 25 x!)
18 75 6
times of the ESR signal due to the nonmagnetic isotopes (I = 0, 94Mo, 96Mo).
Note: If 13C enriched [Mo(CN)s]3- is used for the study, then carbon superhypertine splitting
becomes quite important and instead of the intense singlet line (due to the abundant nonmagnetic
isotopes), 9 lines will appear (cf. 13C of 1 = 1/2, 2 x 8 x 1/2 + 1 = 9), i.e. the singlet intense peak
undergoes 13e superhyperfine splitting into 9 components.
23. High spin octahedral complexes of Mn(II): There are five unpaired electrons to produce three
doubly degenerate spin states (Ms = ±1,2±~,

22
±!) (Kramers' degeneracy). The ground state level is
5 3 3
6A 19 and the zero-field splitting is small to observe the 5 allowed ESR transitions ( - 2" ~ - 2"; - 2" ~
1 1 1 1 3 3 5) . .
- -; - - ~ - ; - ~ -; - ~ - . These WIll constItute 5 fine components of the ESR sIgnal and each
.
2 2 2 2 222
of these 5 components will undergo hyperfine splitting by the Mn nucleus (I =%) to produce 6 hyperfine
components of equal intensity (cf. Fig. 12.3.3.3). This aspect has been discussed in Sec. 12.3.3.
24. Hexachloridoiridate(IV) ion: It has been discussed in detail in Sec. 3.16.
ry
25. [(H3N)sCo--O-0-Co(NH3)s]s+: The hyperfine structure of the ESR signal can help us to deter-
ra
mine the structural composition of the complex. The different possibilities are:
ib
(i) two equivalent COllI centres (t~g) interacting equally with the superoxide bridge (0 2) bearing an
yl
unpaired electron.
(ii) COllI (~g) and Co lV (ti g ) centres connecting the Of- (peroxidio bridge) bearing two unpaired
em
electrons. ch
(iii) nonequivalent interaction of the unpaired electron of the bridging superoxide with the cobalt
centres.
al
For (i), the ESR signal of the bridging ° 2- moiety undergoes splitting by the nuclear spin 7/2 of two
e
(= 2 x 2 x f + I) components. For
th
equivalent cobalt centres, i.e. splitting of the ESR signal into 15

e/
(ii), the unpaired electron of Co(IV) (~g) gives the ESR signal which is split into 8 components by the
t.m
Co(IV) centre (I =f for Co, 2 x f + I =8)' Complication may arise from the further splitting by the
e
other Co-centre (I = 7/2). For (iii), the ESR signal is split by two nonequivalent Co-centres into 64
er
components [ =( 2 x I x f + I) ( 2 x I x f + 1) ] . The experimentally found ESR signal is found to con·

H
k
sist of 15 lines. It supports the structure (i) having two equivalent low spin Co(III) centres bridged by
lic
O2- (i.e. supperoxide). If the unpaired electron of the bridging superoxide were assumed not to interact
with the Co-centres, it would give a single ESR line without any hyperfine splitting.
C
26. ESR Spectroscopy for the metallobiomolecules":"-copper proteins and iron proteins: ESR
studies of different metalloproteins involving the metal ions like Cu(ll) (cP), Fe(ll) (tf», Fe(lll) (tP),
Mn(ll) (tP), Mn(lll) (d4 ), Co(ll) (tP), Mo(V) (d l ) have been found quite helpful for their structural
information. However, the copper-proteins and iron-proteins have been widely subjected to the ESR
studies to extract their structural information.
Hyperfine splitting of the EPR spectra of Cu vs. Fe: Isotopes with the nonzero nuclear spin are:
63, 65 CU (I = 3/2, natural abundance .... 100%); 57Fe (I = 1/2, natural abundance .... 2%). Thus for the EPR
spectra of copper, hyperfine splitting is important but it is insignificant for iron because of the
very poor abundance of s7Fe.
(A) Copper proteins: The important characteristic features of the EPR spectroscopy of Cu(ll) are
given below:
• Cu(ll) (cP) bearing an unpaired electron is EPR active and because of the strong J. T. distortion,
the electronic spin-relaxation, i.e. spin-lattice relaxation is disfavoured (i.e. T 1 is relatively longer).
Because of this longer spin-lattice relaxation time (T I), the EPR studies may be carried out even at room
temperature. This aspect has been already discussed (see Sec. 12.3.4). This special property can allow
us to follow the EPR signals of the copper-biomolecules at the physiological temperature.
• If the EPR studies are not carried out for the frozen solutions, the molecular tumbling will
average out the anisotropy of the g-tensor. Thus, it may be required to carry out the EPR studies of the
frozen solution to know the anisotropy of the g-values and hyperfine interaction. These information
are very much essential to understand their structural features.
• The nuclear hypertine splitting by 63.65 CU( I = %) into 4 components (cf. A(63CU) "" A(65CU)) is
a characteristic feature of the ESR spectrum of Cu(II). It is mainly noted for the gil resonance.
• The g- values reflect the coordination geometry around the Cu(II) centre. For the tetragonal geometry,
ry
g-tensor is anisotropic and for the D4h symmetry (axially symmetric), it is in the following order:
ra
gz<= gil) > gx = gy (= g-L) > ge = 2.002J (see Sees. 12.3.11-12)
ib
Here the z-axis is considered to be perpendicular to the plane of Cu(II) containing four ligands at the
yl
basal plane. The anisotropic hyperfine interaction leads to the different values of hyperfine coupling
em
constants All and A.L.
• The gil resonance experiences a hyperfine splitting into 4 components due to the coupling
ch
between the unpaired electron and I = 1. (nuclear spin of 63, 65CU).
al
2
• The larger line-width in the region of gl.. resonance indicates the distorted environment around
e
Cu(II).
th
The qualitative nature of the EPR spectra of some important copper proteins are given in
e/
Fig. 12.3.7.13. For comparison, the EPR spectra of [Cu(OH 2)6]2+ and the structurally relevant complex
t.m
bis-(histidinato)copper(II) are included in the same figure.

There are three types of copper-proteins found in the biological system. These are (see the book,
Bioinorganic Chemistry by A.K. Das, for details):
e
er
• Type-I: EPR active (tP); an intense characteristic LMCT (S ~ Cu) band at about 625 nm (E
::::: 4000 mol- I em-I); distorted tetrahedral geometry around copper; present in blue proteins (e.g.
H
plastocyanin).
k
Plastocyanin is a representative electron transport blue protein where copper is present in a distorted
lic
tetrahedral geometry having coordination with two imidazole-N atoms of histidines, one cycteine-S and
C
one methionine-So Here the two Cu-N bond lengths are normal (205 - 210 pm); the Cu-S (cysteine)
bond is very short (ca. 210 pm) and the Cu-S(methionine) bond is very long (ca. 290 pm).
• Type-2: EPR active (d9); normal tetragonal complex; present in galactose oxidase, amine oxidase,
dopamine ~-hydroxylase, Cu-Zn superoxide dismutase, etc,
• Type-3: Two Cu(II) centres antiferromagnetically coupled (i.e. S = 0) and EPR inactive.
(i) ESR spectra of Type-l copper(II): The common characteristic features of the Type-l
copper(II) (e.g. plastocyanin) are:
• gz > g y > gx > ge ; A z > Ax ::::: A y } =) the unpaired electron is in the d xy orbital;
in general, gil > g1- > ge; All> A1- distorted geometry (cf. Sec. 12.3.12)
The typical values are: gz = 2.227, gy = 2.058, gx = 2.035; A z = 45 G, Ax ::::: A y = 4.5 G

• Small hyperfine splitting by I =1. of 63, 65CU
2
+
911
~ Ho
- - - - - - - -..
(a) bis(histidinato)copper(lI)
see Fig. 1.7.2.3 for structure)
ry
8(met)
ra
~I
<
ib
N(lm)
&l
yl
All: AJ. ~ 10:1 (CyslS210 CU'-!205-210 pm
em
pm N(lm)
---------+~ Ho
(Pastocyanin)
ch
(c) Type 2 CUll (d) Plastocyanin (Type 1 CUll)
e al
CU(d 7t)-S(P,rl bonding in plastocyanin:

th
e/
t.m
OH 2 (cys)
(Im)N, I ,/N(lm) (glu)O, / 8 , /N(his)
e
Cu Cu, /Cu"'-..
(his)N/ 8 8(met)
er
(Im)N'/ "N(lm) (cys), •

---------+
H
(e) Type 2 CUll (in Cu, Zn-SOD) (f) CU A cluster (oxidized form) in cytochrome
k
coxidose
lic
Fig. 12.3.7.13 Qualitative nature of the ESR spectra of the biologically important molecules of copper. (a) bis(histidinato)-
C
copper(II); (b) [CU(OH)6]2+; (c) typically Type-2 copper(II) found in different Cu-proteins; (d) Type 1 Cu(II) protein as
in plastocyanin; (e) Type 2 Cu(II) present in Cu,Zn-superoxide dismutase; (f) CUA (oxidised form) present in cytochrome
c oxidase, nitrous oxide reductase.
The small copper hypertine splitting is a characteristic property of the Type 1 copper present as the
distorted mononuclear tetrahedral Cu(ll) complexes. It is due to the large covalence in the metal-
ligand bond, i. e. metal d-electron is delocalised over the ligands. Consequently, the Cu-nucleus interacts
weakly with the unpaired d-electron (i.e. residence probability of the unpaired electron in the vicinity
of the Cu-nucleus is reduced and Acu is reduced; cf MeConnell equation, A = Rp). In plastocyanin,
there is a large electron delocalisation (i.e. large covalence) along the Cu-S(cysteine) bond
which has become too short in length. This preferential delocalisation of the d-electron along this
bond reduces the superhyperfine splitting by the N-nuclei (I = 1). In other words, the LMCT
(i.e. Cull -SR H CUI- ·SR) may lead to the accumulation of the unpaired electron on sulfur and
it reduces the hyperfine splitting by copper and superhyperfine splitting by nitrogen.
(ii) ESR spectra of Type 2 copper(II): The typical anisotropic g-values are: gil =2.244, gl. =2.054,
All = 170 G. The ESR signal (gil> g.l) indicates the tetragonal distortion placing the unpaired electron
in the d x2 _ y2 orbital. Type 2 Cu(II) present in Cu, Zn-SOD (superoxide dismutase) maintains a dis-
torted 5-coordinate geometry and it allows the mixing between the d Z2 and d X2 _ y2 orbitals to some
extent. It introduces some sort of anisotropy in the gl. components.
(iii) ESR spectra of CUA (binuclear copper-core) in nitrous oxide reductase and cytochrome c
oxidase: In the oxidised form, the binuclear copper core shows S =! (i.e. ESR active). In the reduced
2
form constituted by 2Cu(l) (dID) centres, it is ESR inactive (i.e. S = 0). In the oxidised form, Cu(ll) (tP)
ry
and Cu(I) (d lO ) centres are coupled (s =~) , The oxidised form of CUA gives an ESR signal which is
ra
ib
split into weak 7 hyperfine components (observed under high resolution) by two equivalent
yl
63,65 eu (I = %) centres (2 x 2 x %+ 1 = 7)' This equivalent character of the Cu-sites (evidenced by
em
the number of hyperfine components) suggests the mixed valence species.
ch
The very weak hyperfine splitting indicates that the metal centres are bonded to the ligands in a
al
highly covalent fashion. It may allow the delocalisation of the unpaired electron to the ligand moiety.
e
It may also allow the electron transfer interaction with the Cys-S moiety, i.e. CUll - SR H CuI_·SR
th
leading to the accumulation of the unpaired electron on sulfur. In fact, under low resolution, the ESR
e/
signal of CUA (oxidised) resembles the signal (without any hyperfine splitting) of an organic free
t.m
radical. It may be noted that the weak hyperfine splitting also occurs for Type I copper(II).
B. Fe-S proteins (ferredoxins): In rubredoxin (Rb), iron is tetrahedrally coordinated by four
e
(d 5
S= %) and it
er
cysteine-S sites and the geometry is distorted. The oxidised form contains Fe(III) ,
H
is EPR active but hyperfine splitting is insignificant due to the poor abundance of 57Pe (cf. 57pe, I = 1/2;
k
natural abundance - 2.3%). At low temperature, it gives two characteristic peaks (Pig. 12.3.7.14) at
lic
geff z 4.3 (strong signal) and geff Z 9.5 (single peak) which correspond to the EPR transitions within the
first excited and ground state Kramers' doublets repectively. These Kramers' doublets (for S = 512),
C
arise in a rhombic symmetry (Fig. 12.3.7.15). The separation due to zero-field splitting between the
Kramers' doublets is too large to observe the ESR transition between the different doublets. However,
at most temperatures, all the three Kramers doublets in rhombic symmetry for S =~ may be significantly
2
populated to observe the ESR transitions within the each doublet. This large rhombic zero-field splitting
is common for the distorted tetrahedral system with S = ~ .

2
In contrast to rubredoxin (oxidisedform, S =~), for other Fe-S proteins (to be discussed later),
2
they are characterised by S' =! with the g-values close to 2.0.
2
S(cys)
1 111
l-
Fe
!
(CYS)S/ \S(CYS) i. e. Fe(S-cys)4-
(cys)
9 = 2.05
9aff::::: 4 .3
(Strong signal)
gaff::::: 9.5
ry
Rbox
ra
ib
------------+~Ho
yl
(a) (b)
em
Fig. 12.3.7.14 Qualitative representation of the EPR spectra (recorded at low temperature) of Fe-S proteins: (a) Oxidised
ch
form of rubredoxin; (b) Reduced form of Fe2S2 ferredoxin.
Note: For Rbox, geff (isotropic) ::::: 4.3 indicates the signal that arises from the ESR transition within the middle doublet,
al
i.e. first excited Kramers' doublet. But geff(anisotropic) ::::: 9.5 is expected when the applied field (Ho) is parallel to the
e
y and z axes (cf. gy::::: 9.67, bottom doublet; gz::::: 9.67, topmost doublet; see Fig. 21.3.7.15). However, at low temperature,
th
the topmost doublet is not populated sufficiently to show the ESR signal. Thus the observed geff ::::: 9.5 reasonably
e/
corresponds to g y of the bottom doublet.

t.m
8 »hV ESR ; 8 >/ ksT (depending on T)

e
er
H
gx = 0.86, gy = 0.6, gz = 9.67

(anisotropic transitions)
k
lic
gx = 4.3, gy =4.3, gz = 4.3

C
(isotropic transitions)
gx = 0.86, gy = 9.67, gz = 0.6

(anisotropic transitions)
~--------------.Ho
o
Fig. 12.3.7.15 Splitting of three Kramers' doublets for S = 5/2 in rhombic symmetry (see Fig. 12.3.3.3b for splitting
in a tetragonal field) by the effect of zero-field splitting (0) and magnetic field. The transitions within each Kramers'
doublet are allowed. The g-values within the three Kramers' doublets are indicated.
Here it is worth noting that the reduced form of Rb possesses 4 unpaired electrons (Fell, tf, S = 2)
but it is EPR silent (cf. large zero-field splitting for S = 2; Fig. 12.3.4.2).
The FezSz-ferredoxins (having two ll2-sulfide) is ESR active (s =±) in its reduced form in which
Fe(III) (d 5
,S = %) ,and Fe(II)(tf', S =2) are antiferromagnetically coupled. The oxidised form is ESR
inactive (S = 0). In the oxidised fOlTI the two Fe(II1) centres ( S = %) are antiferromagnetically coupled
(i.e. S = 0).
The Fe~3 ferredoxin (void cubane structure) is EPR active in its oxidised form (s =±' 3Fe
III
).
For the Fe4S4 protein (cubane structure), the oxidised form (HiPIPox) constituted by the coupled 3FeIII
ry
and 1FeII centres is EPR active ( S = ±) and the 2e- reduced form (i.e. Fdred) constituted by the coupled
ra
(s = ±).
ib
IFelII and 3FeII centres is also EPR active The intermediate form i.e. 2Fe(lII) + 2Fe II (i.e.
yl
em
HiPIPred or Fdox ) is EPR inactive (S = 0).
The g-values (::::: 2.0) of the common Fe-S proteins are given below (from the ESR spectra recorded
ch
at low temperature)
Rubredoxin (Rb) 2Fe-ferredoxin 3Fe-ferredoxin 4Fe-ferredoxin
al
(lFe-OS) (2Fe-2S) (3Fe-4S) (4Fe-4S)

e
g-values: -4, -9.5 1.89, 1.95, 2.05 1.97, 2.00, 2.02 2.04, 2.04, 2.12
th
(oxidised form) (reduced form) (oxidised form) (oxidised form)

e/
(s ~)
t.m
3FellI , 1Fell, = (HiPIPox)
(Reduced form)
e
g ~ 1.88, 1.92, 2.06

er
(s =~)
H
(Rhombic EPR (Rhombic EPR (Rhombic EPR IFeIII,3Fe ll , (Fd.-oo)

k
Signal) Signal) Signal) (Rhombic EPR Signal)

lic
The condition, gx =t= gy =t= gz' indicates the rhombic symmetry (cf Sec. 12.3.11). The structural details
C
of Fe-S proteins are given in the author's book, Bioinorganic Chemistry.
12.3.8 ESR Spectra: Magnetically Concentrated vs. Magnetically Diluted Complexes

The nature of magnetic exchange interaction can be understood by following the ESR signal. Let us
take the case of S = 1/2 (e.g. 3d l , V0 2+; 3cf, Cu 2+; etc.). If the binuclear complex is taken into consid-
eration then coupling of the two S = 1/2 centres (i.e. Sl = S2 =1/2) leads to the resultant values: S = 0 .
(singlet) and S = 1(triplet). The singlet state (i.e. S = 0) is the ground state for the antiferromagnetic
exchange interaction while the triplet state (S = 1) is the ground state for the ferromagnetic exchange
interaction (cf Chapter 8).
Antiferromagnetic exchange: Ground state (S = 0), excited state (S = 1).
Ferromagnetic exchange: Ground state (S = 1), excited state (S = 0).
The population density (determined by Boltzmann distribution) at each state is determined by the
relative magnitudes of the energy difference (t1£) between the states and available thermal energy
(kBT). dE can be expressed in terms of the exchange integral (1).
The singlet state (bearing no unpaired electron) is ESR inactive while the triplet state is ESR
active. Thus, when an antiferromagnetic exchange prevails, with the increase of temperature, the
population density at the triplet state (i.e. excited state bearing the unpaired electrons) increases and
consequently, intensity of the ESR signal increases. On the other hand, when the ferromagnetic
exchange interaction prevails, with the increase of temperature, the population density at the singlet
state increases and consequently, intensity of the ESR signal decreases.
8 1 =8 2 =1/2: By taking into the consideration of zero-field splitting, two allowed ESR transitions
(liMs = ±1) are expected along with a forbidden ESR transition (1ll1s = ±2) of weak intensity (cf.
Fig. 12.3.31b). Existence of this forbidden transition supports the interaction between ihe two
centres of 8. = 8 2 = 1/2. In fact, in the dimeric complexes of copper(II) and dimeric complexes of
oxidovanadium(IV), the characteristic forbidden transition (l!.Ms = ±2) with a poor intensity is
ry
noticed. For the dimeric oxidovanadium(IV) complexes, this weak ESR signal is split into 15 hyperfine
(I =~' 2 x 2 x ~ + 1= 15) (cf Fig. 12.3.7.7). For the dimeric
ra
components by two equivalent V-centres
ib
yl
copper(II) complexes, the said weak ESR signal is split by two equivalent Cu-centres into 7 hyperfine
em
components (I =%, 2X2X%+1=7) (see Fig. 12.3.7.8). ch
12.3.9 Factors Affecting the g-value (ct. Secs. 8.15,8.17,8.18)
al
For an unpaired electron residing in a gaseous atom or ion obeying the Russel-Saunder Coupling (i.e.
e
spin-orbit coupling constant is large), the g-value is given by:

th
=1+ J (J + 1) + S(S + 1) -
e/
L(L + 1)
g 2J(J + 1)
t.m
where the symbols bear the significance as usual. For the halogen atoms, the ground state term is
e
1 3 4
i.e. L = 1, S =-and J =-. By using the above equation, we get g =- which is experimentally
er
3P312
2 2 3
H
verified. For a free electron, S = 1/2, L = 0, (i.e. no orbital contribution to the magnetic moment)
J = 1/2 and it leads to g = 2.0. Taking into the consideration of the relativistic correction, the g-value
k
lic
for a free electron becomes 2.0023.

When the unpaired electron is placed in a chemical environment (e.g. in a transition metal com-
C
plex), the orbital motion of the electron is perturbed. In other words, in a chemical environment, the
orbital degeneracy which exists in a gaseous state or in a spherical field is, at least, partly destroyed (i.e.
orbital motion is partly quenched). Specially, the low symmetry crystal field and Jahn- Teller distortions
are extremely important in removing the orbital degeneracy. This is why, the orbital contribution to the
magnetic moment is partially quenched in a crystal field. On the other hand, the spin-orbit coupling
phenomenon (leading to some orbital contribution to J.!obs) tends to restore the orbital degeneracy to
some extent. Thus the crystal field effect destroying the orbital degeneracy is opposed by the spin-
orbit coupling effect. Because of these two opposing contributions, the orbital degeneracy is only
partly removed and a partial contribution of the orbital magnetic moment is retained. Thus the g-value
is different from 2.0023. In absence of spin-orbit coupling, the expected g-value is 2.0023.
The unpaired electron in a free radical is not generally localised or confined in a particular
orbital, i. e. it can freely move over the orbitals encompassing the whole molecule. In this sense, the
electron behaves like a free electron in space (i.e. L = 0). For most of the free radicals, the orbital
contribution is very small because of the lower molecular symmetry or the loss of degeneracy of the
energy levels by Jahn-Teller distortion. Moreover, the spin-orbit coupling is not also important for the
free radicals. Consequently, the isotropic g-value for the free radicals is generally close 2.0 i.e. free
electron g-value. Such typical organic free radicals show no hyperfine interaction indicating the
complete delocalisation of the electron.
The unpaired electron in a free radical is not localised in a particular orbital but in a transition metal
complex, the unpaired electron is localised in a particular orbital. In different transition metal complexes,
depending on the different governing factors, g can have different values. These different values arise
for the different degrees of crystal field effect and spin-orbit coupling effect. For the both cubic
symmetry producing the orbitally nondegenerate ground state (e.g. high spin d 5, 6S, having the 6A 1g
ground state) and highly distorted symmetry (where all the orbital contributions to the magnetic
ry
moment are quenched), g value becomes close to 2.0.
ra
For the rare earth metal ions, the spin-orbit coupling interaction is much stronger (i.e. J is a good
quantum number) than the crystal field effect on the (n- 2)f orbitals which are deeply seated. This is
ib
why, the lanthanide ions behave like the free ions and the g-value can be calculated by using the given
yl
relation.
em
For the transition metal ions (specially the 1st transition series), the crystal field effect on the
(n-l)d orbitals is more important than the spin-orbit coupling interaction (i.e. J is no longer a good
ch
quantum number). In such cases, the orbital degeneracy is lifted by the predominant crystal field effect.
al
This is why, the g value is very close to 2.0 and the magnetic moment is very often given by the spin-
e
only value. But for the systems where the orbital angular momentum exists to some extent as in the
th
cases where the ground state level is designated by T(g), the spin-orbit coupling operates and the g-value
deviates from the spin-only g-value of 2.0. For the systems like Fe3+ (high spin, L = 0, J = S, 6S) and
e/
Mn2+ (high spin, 6S) which are having the orbitally nondegenerate ground states, the g-value is very
t.m
close to that of a free electron.

To measure the quantitative effects of the spin-orbit coupling process and the crystal field effect
e
on the g- value, we are to recall the following relations.

er
2
J=ge (1- lODq
a'Ak J, ge =
H
a'Ak2
geff =gspin-only ( 1- lODq gspin-only =2.0 (cf. Sec. 8.17)
k
lic
. - (1- 4k AJ=2(1_ 4k AJ
2 2
C
For A 2(g) ground state. geff - ge 10Dq 10Dq
2
2k2'A
For E(g) ground state: geff = ge ( 1- lODq J=2 (1- lODq
2k 'A J
k = orbital reduction factor; A = spin-orbit coupling constant

A = +ve (for the d l -4 systems), A = -ve (for the tf'-9 systems).
It indicates that geff tends to be ge for the higher crystal field splitting (i.e. higher 10Dq value)
and the smaller spin-orbit coupling constant.
For the A and E ground states, the spin-orbit coupling mixes the ground state and the excited T state
which retains the orbital angular momentum to some extent. For the Ni(II) octahedral complexes, the
ground state is 3A zg which mixes with the excited 3TZg state through the spin-orbit coupling mechanism
and geff is given by:
g iff
4k2A
= 2 ( 1- - J 8A
- ::::: 2 - - -
.
assumIng k ::::: 1
e 10Dq 10Dq'
In [Ni(OH2)6]2+, A = -270 cm- l , 10Dq = 8,500 cm- l (estimated from the electronic absorption
spectrum) and these lead to gejf = 2.25
12.3.10 Determination of the g-value

The g-value can be obtained from the condition of ESR transition (assuming no hyperfine and
superhyperfine splitting) i.e. hv =g~Ho or g =hV/~Ho, if the microwave frequency of the ESR transition
is known. In fact, an ESR spectrometer works at a particular operating frequency (called probe fre-
quency) and the magnetic field is varied to find the field strength at which the resonance works. If the
ry
microwave frequency is not known accurately, then the spectrum is calibrated by using a reference
ra
sample whose g value is accurately known. For this purpose, 2, 2-diphenyl-l-picrylhydrazyl (DPPH)
radical having g = 2.0036 is used.
ib
yl
~...02N ch
em
@N-N
al
02N
e
th
e/
(DPPH)
t.m
The g-value of the sample is calculated by using the following relationship.
(1- ~) 1- ~)
e
gsample = gDPPH = 200036(

er
where ~H gives the difference between the resonating fields required for the sample and DPPH radical.
H
The positive value of All indicates the sample to resonate at a higher field while the negative value of
k
All indicates the sample to resonate at a lower field. ~H is a small number compared to the resonance
lic
magnetic field H (obtained from the range used for the ESR study) and consequently the approximate
value of H does not significantly affect the g-value. The negative value of ~H indicates gsample ) gOPPH
C
while the positive value of ~H indicates gsample ( gOPPH'

In actual practice, the standard sample DPPH is placed along with the unknown sample in the same
chamber of a dual cavity cell to record the ESR signals of both the standard and unknown sample. From
their ESR signals, the field separation ~H is obtained.
The standard sample DPPH can also be used to estimate the number of unpaired electrons partici-
pating in producing the ESR signal. The peak area covered by either the absorption or derivative
curve is proportional to the number of unpaired electrons responsible for the ESR transition.
DPPH contains one unpaired electron per molecule. It leads to 1.53 x 1021 unpaired electrons per gram
of DPPH.
K2[NO(S03)2] (Fremy's salt, bearing the nitrosyldisulfonate radical, g = 2.0057) can also be used
as an standard substance to determine the g-value of the unknown substances.
To determine the g-value of other free radicals, DPPH or K 2[NO(S03)2] cannot be llsed as the
standard sample because for most of the free radicals, the g value is close to 2.0. Consequently, ~H
cannot be determined accurately. In such cases, a trace amount of Cr(III) entrapped in a tiny chip of
ruby crystal is used as the internal standard. This Cr(III)-standard sample shows a strong ESR signal
. having the g value 1.4.
12.3.11 Anisotropic Behaviour of 9 and Anisotropy in Hyperfine Interaction

The g-value depends on the direction of the paramagnetic species with respect to the direction of the
applied magnetic field. When the paramagnetic substance is rotated to all directions with an equal
probability, the obtained g-value is averaged over all the possible orientations and it is denoted by gave
It occurs so lvhen the measurement is carried out in the solution or gas phase where free rotation ofthe
species is not restricted. However, if the paramagnetic centre lies in a symmetric cubic field (e.g.
octahedral or tetrahedral site), the g-value does not depend on the direction, i.e. g is isotropic. The
ry
isotropic nature exists in the perfectly octahedral complexes. But for the crystal field of lower symme-
ra
try, the g-value is dependent on the direction and g becomes anisotropic.
ib
(Isotropic spectrum) (Axial spectrum) (Rhombic spectrum)
yl
em
gil gz
9.1 ch 9x
911) 9.1
eal
±).
th
Fig. 12.3.11.1 Qualitative representation of the ESR spectra of a frozen solution or a polycrystalline solid state (for S =
e/
t.m
In the anisotropic systems, the resultant g can be expressed in terms of the components gx' gy and gz
which are mutually perpendicular. The z-direction is defined along the highest fold rotation axis (en).
Then gz is consider to be gil (i.e. gz = gil) and it is obtained when the z-axis is parallel with the magnetic
e
field direction. The g-values along with the x and y axes are gx and gy respectively. In a cubic crystal
er
field (as in the perfectly octahedral complexes), all the metal-ligand bond lengths are the same along
H
the three Cartesian axes and it leads to gx = gy = gz. In such cases, g is said to be isotropic. In a
k
tetragonal symmetry (D4h), the metal-ligand distances along the x- and y-axes are the same but different
lic
from the metal-ligand distance along the z-axis. Thus the g-value shows an anisotropic behaviour i.e.
gz = gil -:t gx = gy = gl.. gl. is obtained when the external magnetic field is perpendicular to the z-axis. Thus
C
the notations, II and 1. refer to the directions along and perpendicular to the C4 axis in D4h symmetry
(i.e. tetragonal symmetry). Similarly, lilies along the C3 axis and 1. lies perpendicular to the C3 axis
in D 3h (i.e. trigonal) symmetry. For a complex of rhombic symmetry, the metal-ligand distances along
the three Cartesian axes are different and the g value shows an anisotropic behaviour, i.e. gx -:t gy -:t gz.
Magnetic moment measurement of a powdered sample determines an average value of g i.e. gave On
the other hand, if a single crystal is used for an ESR study, depending on the direction of orientation
of the crystal with respect to the magnetic field, the directional g values (i.e. gx' gY' gz) can be determined.
For a tetragonal symmetry grms and gay are expressed as follows:
2 1( 2 2 2) ="31(2g.l+
grms="3gx+gy+gz
2 g112)
Similarly, the anisotropy in the hyperfine interaction is averaged to zero when the sample is
present in a solution and the isotropic hyperfine splitting constant is denoted b~T A o or A iso . The
anisotropy in the hyperfine interaction exists when the sample is present in a polycrystalline state or
frozen solution. Then the hyperfine-splitting constant (A) is gives by:
1
Aav = "J(A II + 2A-L).
If e is the angle between the direction of the external magnetic field and the z-axis (i.e. highest fold
en axis) then the resultant g-value is given by:
g;esultant = gn cos 2 e + gi sin 2 e
The anisotropic behaviour of g indicates the deviation from the cubic crystal field symmetry. A
ry
very small distortion can also be determined from the ESR studies which show the inequality for the
g- values in different directions.
ra
• T(g) ground terms and anisotropic g-values: Spin-orbit coupling and low-symmetry ligand field
ib
components (e.g. J.T. distortion) lead to splitting of the T(g) ground state. It makes the g-value highly
yl
anisotropic. Here it is worth mentioning that if the distortion is very large (i.e. low symmetry ligand
em
field component is large) and splitting of the T(g) term is larger than Athen the orbital angular momen-
tum is fully quenched. Then it leads to g approximately isotropic and its value is close to 2.0 i.e. free
ch
electron value.
It may be again mentioned that the spin-orbit coupling and low symmetry ligand field components
al
split the T(g) ground state and this splitting is in the order of 200 cm- l (which is comparable to kBT at
e
room temperature). The energy levels lying about by kBT above the ground level favours the spin-lattice
th
relaxation. This is why, to record the ESR spectrum for the sample having the T (g) ground state,
e/
the temperature is to be reduced (so that kBT becomes of a few cm-I ) to the liquid He or N2
t.m
temperature. Such a problem does not arise for the A(g) and E(g) ground states for which presence of
the energy levels separated from the ground level by the order of kBT is unlikely. In fact, their ESR
signals can be recorded at room temperature (cf. Sec. 12.3.2).
e
er
12.3.12 Anisotropic Behaviour of the g-value of the Tetragonally Distorted Copper(lI)

H
Complexes
k
It has been already mentioned that the free electron g-value i.e. ge (= 2.0023 ::::: 2.0) is modified under
lic
the influence of spin-orbit coupling. The effective g-values can be mechanically computed with the
C
help of the Magic Pentagon (Fig. 12.3.12.1) for the S =! systems. m,

z o
n'A n'A n'A 2 6 /d '", 6
g = ge - M =2.0023 - M "" 2.0 - M / ~
d ~ 2 ~
where ~ = energy difference between the orbital containing the xz dyz
±1
unpaired electron and the orbital with which it may mix by the
2 2
spin-orbit coupling; A = spin-orbit coupling constant of the free
ion; n is an integer obtained from the magic pentagon (e.g. n = 8 2 2
for the interaction between the d 2 2 and dxy orbitals; n = 6 for

x -y
the interaction between the d Z2 and dyz orbitals; cf. Fig. 12.3.12.1).
±2
In the magic pentagon, the three rows represent the orbitals in
terms of the ml values i. e. d Z2 for ml = 0; dxz and d yZ for ml = ± 1; Fig. 12.3.12.1 Magic pentagon
dxy and d x 2 _y2 for ml =±2. Application of the magic pentagon will be illustrated for the Cu(II) complexes
(d 9 system).
Cu(II) (d 9) system can experience both the tetragonal compression (i.e. z-in) and tetragonal elon-
gation (i.e. z-out) distortions depending on the situation.
ry
ra
(z-in) (z-out)
ib
- Tetragonal Tetragonal
yl
compression elongation
em
Fig. 12.3.12.2 Electronic configuration of tP system for z-in and z-out distortion.
ch
Tetragonal compression (i.e. z-in): The ninth unpaired electron is in the d z2 orbital (energy order:
d z2 > d x2 -y 2, cf. Chapter 3).
al
For the tetragonal compression, the g-values are:

e
th
=2-~
e/
10Dql.
t.m
i.e. gl. ) gil = 2.0 (cf. A = -ve)

Tetragonal elongation (i.e. z-out): The ninth unpaired electron is in the d x 2 -y 2 orbital (energy
e
er
order: d x 2 -y 2 > d z2 , cf. Chapter 3)

For the tetragonal elongation, the g- values are:
H
_ _ =2_ 8A =2-~=2-~
8A
k
gz = gil =2
lic
Ed 2 - Ed dEli 10Dqo 10Dqll

x -i xy
C
i.e. gil ) g.l ) ge = 2.0 (cf. A = -ve; 10Dq.l) 10Dqll)·

Tetragonal compression (i.e. z-in distortion) is rarely found for the Cu(II) complexes but tetragonal
elongation (i.e. z-out distortion) is very much common for the Cu(II) complexes. For the Cu(II)-porphyrin
complexes, the g-values, gil = gz = 2.70 > gx = gy = g.l = 2.04> ge = 2.0 indicate the z-out distortion. In
some cases, the dynamic Jahn-Teller distortion may lead to the time averaged perfect octahedral structure.
It is obvious that for high splitting energy (i.e. 10Dq large), g-value approaches to zero.
Let us illustrate the effect of crystal structure on the g-value by taking the example of CuSiF6 . 6H20
i.e. [Cu(OH 2)6]SiF6 which is doped as an impurity into the isomorphous diamagnetic host crystal,
ZnSiF6 · 6H20 for an ESR study. The ESR spectrum (cf. Fig. 12.3.7.13) at different temperatures gives
the following results:
gIl =2.45±0.01} 20K gIl = 2.220 ±0.005}90K

g-t = 2.10±0.01 (-253°C) g-t = 2.230±0.005 (-183°C)
(i.e., anisotropic behaviour of g) (i.e., isotropic behavi~ur of g)
The anisotropic behaviour of g (gil) g.l ) 2.0) at low temperature indicates the tetragonally elongated
structure of [CU(OH Z)6]z+. But the isotropic behaviour of g at the higher temperature indicates the
undistorted (i.e. cubic symmetry) structure of [CU(OH Z)6]Z+.
[CU(OHZ)6]z+ is expected to have a tetragonally distorted structure in terms of Jahn-Teller distor-
tion. The tetragonal distortion (i.e. elongation of the trans-metal-ligand bonds) can occur along the
three mutually perpendicular axes with an equal probability in the present case where all the six ligands
ry
are identical. If these three distorted forms are frozen out within the ESR time scale, we can expect three
ESR signals. At the higher temperature (90 K), one ESR transition (with the hyperfine structure, i.e. 4
ra
lines due to 63CU having 1= 3/2) with an isotropic g-value is noted. It suggests that the three distorted
ib
species are in a rapid dynamic equilibrium and it is referred to as the dynamic Jabn-Teller distortion
yl
which in turn gives the time averaged perfect octahedral structure of [Cu(OH 2)6]z+. It leads to the
em
crystal field to resonate rapidly among the three possible distorted structures.
At the tower temperature (say 20 K), the three distorted forms (1: 1: 1) are frozen out as the available
ch
thermal energy is not sufficient to overcome the kinetic barrier for the interconversion process and it
leads to the static Jahn-Teller distortion supported by the anisotropic ESR spectrum consisting of
al
three sets of lines. The dynamic J.T. effect is observed in the EPR spectrum of Cu(ll) doped into
e
Zn(II)-Thttons salt (double sulfates M2'(Cu/Zn)(S04)2· 6H zO, having [CU(OH Z)6]Z+).

th
A similar observation of the resonating crystal field (i.e. dynamic Jahn-Teller distortion) at an
e/
elevated temperature has been noted for [Cu(bpY)3]z+, [Cu(phen)3]2+, etc.

t.m
12.3.13 Anisotropic Behaviour of the g-Value for the Tetragonally Distorted Nickel(lI)
Complexes
e
is the ground state and 3Tzg is the next higher state for the octahedral complexes of Ni(ll) (cf
er
3A 2g
system). Tetragonal distortion in the Ni(ll) complexes splits the 3Tzg level into the 3Eg (two fold orbital
H
degeneracy) and 3B zg (orbitally nondegenerate) levels (see Fig. 12.3.4.3). The deviation of the g-value
k
from the free electron value (= 2.0) for the A(g) and E(g) ground states occurs due to the interaction with
lic
the higher Tz(g) state through the spin-orbit coupling. The g-values for the Az(g) terms are as follows:
C
2 2
g,,=g
e
(1- 10Dqll
4k A.J=2(1_ 10Dqll
4k A.J
2 z
-
gl. - ge
(1- 4k A,
10Dql.
J-- 2(1- 10Dql.
4k A, J.
EPR studies of (NH4)2Ni(S04)z· 6HzO diluted in the diamagnetic host lattice of (NH4)z Zn(S04)Z . 6H zO
indicate the nearly isotropic g-value 2.25 (i.e. gil ::::: g.l = 2.25). Using 10Dq = 8,500 cm- I (obtained
from the electronic spectrum of [Ni(OH z)6]2+), we get: 2.25 = 2(1- ~), (taking k = 1). It leads to:
10Dq
A = -266 cm- I which is considerably less than the free ion value (= -324 cm- I ). Lowering of the A value
due to complexation is quite expected.
12.3.14 EPR Peak Broadening and Peak Merging and Electron Spin Exchange Rate
It has been noted that with the increase of proton exchange rate, the PMR signals undergo broadening
and at a certain proton exchange rate, they undergo merging to give a sharp single peak (cf Sec. 12.2.15).
Similarly, with the increase of electron spin exchange rate, the EPR hyperfine peaks may
undergo broadening (i.e. exchange broadening) and finally merging into a single peak (i.e. exchange
narrowing).
(i)
ry
ra
ib
(ii)
yl
em
ch
(iii)
al
-----.~ Ho
e
th
Fig. 12.3.14.1 EPR spectra of (Me3C)2NO at different concentrations in ethanol at 25°C. (i) 10-4 M
(ii) 10-2 M, (iii) 10- 1 M.
e/
The electron spin exchange process is very common for the free radicals and in solution it is a
t.m
bimolecular process in which two radicals collide and exchange their electrons. Thus at low
concentration, the spin exchange process is slow with respect to the EPR time scale and the hyperfine
e
EPR peaks (as in DPPH, nitroxides) are distinctly observed. B.ut at high concentration, the bimolecular
er
spin exchange process becomes quite fast and the hyperfine peaks undergo merging to give a sharp
H
single peak. From the knowledge of EPR peak broadening and peak merging with increase of electron
spin exchange rate, the rate constant of the exchange process can be estin1ated. It is illustrated in some
k
lic
representative cases.
(i) Di-t-butyl nitroxide, (Me3C)2NO: The unpaired electron giving the ESR signal is expected to
C
undergo hyperfine splitting by 14N (I = 1) to produce 3 (= 2 x 1 x 1 + 1) hyperfine peaks which

are noted at very low concentration (10-4 M in ethanol at 25°C). But with the increase of concen-
tration, the three hyperfine peaks merge to give a weighted average single peak (at about .10- 1 M
concentration in ethanol). It is illustrated in Fig. 12.13.14.1. The estimated second order rate
constant is 7 x 109 dm3 mol- I S-I.
(ii) DPPH (diphenylpicrylhydrazyl radical): The EPR signal due to the unpaired electron shows
the hyperfine peaks (5 components, splitting by two 14N nuclei, 2 'x 2 x 1 + 1 = 5) in a dilute
solution (ca. 10-3 M in xylene) but in a concentrated solution it gives a sharp .singlet peak (Fig.
12.13.14.2).
(iii) Electron exchange between naphthalene and naphthalene negative ion: When naphthalene is
added to a solution of naphthalene negative ion, the electron exchange between the species leads
to broadening of the hyperfine components (25 lines) of the EPR signal (cf Sec. 12.3.7 (7». The
estimated second order electron exchange rate constant in THF is 6 x 107 dm3 mol- 1 S-I.
(DPPH)
ry
ra
ib
-----.~ Ho -----.~ Ho
yl
(i)
em
(ii)
Fig. 12.3.14.2 ESR spectra of DPPH (i) concentrated solution in xylene, (ii) Dilute solution (ca. 10-3 M).
ch
Note: The two 14N nuclei to cause the hyperfine splitting are nonequivalent and the ESR spectrum should contain 9
lines: (2 x 1 x I N I + 1) (2 x 1 x IN2 + 1) =3 x 3. The appearance of Slines = 2 x 2 X IN + 1 = 2 x 2 x 1 + 1 instead of
al
9 lines may be explained in two ways: assuming the nitrogen nuclei to be equivalents (at least under low resolution)
e
or their hyperfine coupling constants (i.e. ANt and A N2) to be comparable. In fact, it has been noted that the ratio
th
ANI: A N2 is close to unity. A similar situation arises for the CH3CH 2 radical where A CH3 / A CH2 ~ 1 (cf Fig. 12.3.5.6).
e/
12.3.15 Applications of ESR Spectroscopy

t.m
(i) Structural information: It can provide the information: • regarding the location of the unpaired
electron; • location of the nuclei to split the signal; • summation of the intensities leads to the
e
evaluation of the number of unpaired electrons; • comparison of the g-value with free electron
er
value providing the relative importance of crystal field effect and spin-orbit coupling effect;
H
• distortion in the complex; • magnetic properties of the species; etc.

k
ESR studies can be made in solutions, in solid powdered forms and in single crystals. In solution
lic
or solid powdered forms, all the possible orientations of the paramagnetic sample with respect to
the rrlagnetic field are equally probable. The results from the ESR studies in solution or powdered
C
phase can provide the information of the magnetic properties. However, the ESR studies in single
crystals can give the details of the symmetries of the complex.
Several examples have been already discussed in the previous sections.
(ii) McConnell equation and residence probability of the unpaired electron to the magnetic
nuclei to cause splitting of the ESR signal: Determination of the hyperfine coupling constant
(A) and the use of McConnell equation can calculate the unpaired electron spin density at the
immediate vicinity of the nuclei to cause splitting of the signal. This calculation can lead to the
mapping of the orbital to house the unpaired electron.
(iii) Detection of free radical: When the concentration of free radical is very low, the paramagnetism
cannot he detected by a Gouy balance but the ESR studies can detect the free radicals even at
extremely low concentrations (e.g. DPPH radical can be detected even when its amount is lO-12 g
in the spectrometer). In the quinone-hydroquinone redox couple, existence of the semiquinone as
an intermediate has been proved from the ESR studies. This aspect has been already discussed.
(iv) Nitroxide molecules as the spin labels: The long-lived stable nitroxide molecules like TEMPO,
TEMPOL (discussed earlier) can attach with the large biomolecules like proteins and membranes
at some specific sites which can change the characteristics of the ESR signal of the nitroxides.
Thus studies of the ESR signals of these spin labels can provide the information regarding the
structural features of the biomolecules.
(v) Rate determination of electron exchange reactions by EPR studies: PMR studies can deter-
mine the proton exchange rate (ef Sec. 12.2.15), if the process is not too fast. The proton ex-
change leads to the PMR peak broadening which has been interpreted by considering the uncer-
tainty principle (h~v~t:::::: h). Similarly, the electron spin exchange process i~ads to the broadening
of the hyperfine components of the ESR signals. This allows the rate determination of the electron
exchange process (ef Sec. 12.13.14).
ry
(vi) Structural information of the inorganic compounds from the ESR studies: This aspect has
ra
been already illustrated by taking some representative examples.
(vii) Determination of oxidation state of a metal centre: Cu(ll) (cP) is EPR active while Cu(l) (d lO )
ib
is EPR inactive. This technique has been utilised in determining the oxidation states of copper in
yl
different copper proteins.
em
(viii) CFT vs ACFT or MOT: Superhyperfine splitting of the ESR signal by the magnetic nuclei
present in the ligands supports the fact that the metal d-electron is delocalised over the ligands
ch
through the metal-ligand orbital overlap interaction. It indicates that the ideal CFT is not applica-
al
ble in the metal complexes. This aspect has been already illustrated.
(ix) Double resonance technique: Double resonance technique has been found important in NMR
e
th
spectroscopy. Similarly, the double resonance techniques like ENDOR (electron-nucleus double
resonance), and ELDOR (electron-electron double resonance) are found important in EPR
e/
spectroscopy. In the ENDOR technique, one ESR transition is followed when the nuclear spin
t.m
transition is made saturated while in the ELDOR technique, one ESR transition is followed when
another electron spin transition is made saturated. Like the nuclear overhouser effect of NMR
e
spectroscopy, here also the enhanced intensity of the signal is also gained. The details of the
er
ENDOR and ELDOR techniques are not discussed here.

H
(x) Characterisation of metalloproteins: The iron and copper proteins are very often found ESR
active. Their ESR studies can help us to characterise their structural features.
k
lic
12.4 MOSSBAUER SPECTROSCOPY

C
12.4.1 Isomeric Nuclides (of an Element) Differing in Energy States: Nuclear Transition
Energy in the y-Region
When the nuclide jumps down from the excited state to its ground state, it emits y-radiation which may
be absorbed by a nuclide (generally of the same element) at the ground state to get excited to the upper
energy level. The energy difference (~) between the nuclear ground state and excited state depends
upon the chemical environment around the nucleus of the same element.
If the source, i.e. enlitter (at the excited state) and the absorber, i.e. sample (at the ground state) are
of the same element then the chemical environment induced energy changes at the sample nuclide are
very much small but quite important to understand the chemical environment. In the recoilless transi-
tion, adjustnlent of the Doppler shift to the emitted y-radiation can allow it to be rightly absorbed by
the sample nuclide. The direction and magnitude of the Doppler shift required to bring about the
absorption of the emitted y-radiation by the sample nuclide gives us the information regarding the
chemical environment around the sample nuclide. This y-ray spectroscopy (i.e. nuclear transition
occurring in the y-region) is commonly known as the Mossbauer (MB) spectroscopy to tribute the
discoverer who was honoured Nobel Prize in 1961 for this work.
12.4.2 Principle of Mossbauer Spectroscopy: Condition of Recoilless Emission and

Absorption of y-Ray through the Adjustment of Doppler Shift
(a) Nuclear resonance absorption: When a nucleus jumps down from its excited state, it emits a
y-radiation which is to be absorbed by another nucleus for its excitation. If the energy of the emitted
y-radiation matches with the energy required for the nuclear energy transition of the sample nucleus
then, the condition of nuclear resonance is attained i. e.
Ey-source (energy of the emitted y-rays from a source nucleus) = Ey-sample (energy of the y-ray
required for the nuclear transition in the sample nucleus)
ry
(b) Energy of the emitted y-radiation from a source nucleus: If the energy difference between the
ra
excited (Eex ) and ground (Egd ) nuclear states is dE, then the energy of the emitted radiation (for the
transition from the excited state to the ground state) is given by:
ib
Ey (source) = dE + ED - ER ; dE = Eex -- E gd = Eo (say)
yl
= Eo + ED - ER ~ Eo - ER , E R » ED
em
where ED = Doppler shift (due to the translational motion of the emitter nucleus), ER = recoil energy
of the nucleus.
ch
• Recoil energy (ER): A photon of very high energy (v z 1018 Hz i.e. y-photon) is associated with
al
h
a large momentum (cf. p = i' de-Broglie relationship). Thus when a y-photon comes out from a
e
th
nucleus, to maintain the principle of conservation of momentum, the nucleus will recoil (i. e. move-
e/
ment in the opposite direction). The similar phenomenon is experienced when a bullet comes out from
a gun. Thus the recoil energy represents the kinetic energy of the recoil nucleus.
t.m
2
ER (recoil energy) = = recoil momentum of the nucleus.
PR , PR
e
2M
er
M = mass of the nucleus.

H
According to the law of conservation of momentum,

recoil momentum of the nucleus = momentum of the emitted y-radiation.
k
lic
E E
i.e. PR = P y =-cy, (c = -velocity of light and Py = -cy)
C
It leads to: ER
p~ =-E~- : : : -E6
=-- _2. Ey =energy of the emitted y-photon.
2
2M 2Mc 2Mc '
=Eo-ER::::::Eo,Eo»ER
• Doppler shift (En): When the emitted y-radiation from a nucleus present in a gaseous molecule
moves in the same direction of the molecule, it possesses the energy which is different from the energy
of the' emitted y-radiation moving iQ the opposite direction of the molecule. The Doppler effect is
realised in a very common phenomenon: when a moving body emits a radiation or sound, a stationary
observer experiences a shifted frequency (called Doppler shift). Here the Doppler shift arises because
the radiation comes out from the moving (i.e recoiling) nucleus (cf. recoil velocity ~ 102 m S-1).
However, in general, ER » ED.
(c) Energy of the y-radiation for the nuclear transition (ground level to the excited level) in the
sample (i.e. absorber): It is given by:
E y (sample) = ~ + ED + ER = Eo + ED + ER ::::: Eo + ER , E R »ED

For the same nuclei of the source and sample, ~E i.e. Eo is the same. ED has the same significance.
When the y-radiation will be absorbed, the absorbing nucleus will also recoil. Thus the exciting
y-radiation will have to provide this translational energy to the absorbing nucleus.
Source Sample
(Emission) ! (Absorption)
I
Movement of the I
I
nucleus during I
y-emission I Line width

hv I
I (.1v 1)
I ~--+---&..---1~
E -~ 2"
ry
R - 2Mc2
ra
Nucleus
ib
(a)
yl
(b)
em
Fig. 12.4.2.1 (a) y-ray emission from a nucleus (at rest before y-emission) of mass M and imparting of recoil energy (ER ).
(b) Distribution of energies of the y-radiation emitted and absorbed by the same nuclei assuming Eo (source) = Eo
ch
(sample), E R (source) = E R (sample).
al
(d) Distribution of energies of the emitted and absorbed y-radiation: Distribution of energies of
e
the emitted and absorbed y-rays are shown in Fig. 12.4.2.1. The breadth of the distribution curve arises
th
from the Doppler broadening that occurs due to the t~anslational motion of the nuclei in different
directions. The shaded area (i.e. overlapping region) gives the measure of the probability of the absorption
e/
of the emitted y-radiation.

t.m
It is evident that the probability (measured by the shaded area in Fig. 12.4.2.1) of absorption of the
emitted y-radiation is very small. It is due to the recoil energy (E R). The energy distribution curve for
e
the emitted y-radiation is centered at Eo - ER while the energy distribution curve for the absorbed
er
y-radiation is centred at Eo + ER , i.e. the energy mismatch factor is 2E R• This energy mismatch factor
H
cannot be overcome by Doppler effect because E R is mach larger than ED. If the Doppler effect is
to overcome the energy mismatch factor due to E R, the source .will.have to move with a velocity of
k
2 x 104 cm S-l which is not attainable.

lic
C
E2
Energy mismatch factor = Ey(sample) - Ey(source) = 2ER =~
Mc
It is evident that this energy mismatch factor is directly proportion to E~ and it is very much important
in y-spectroscopy (cf optical region vs. y-ray region of the electromagnetic radiation: ca. 2 eV vs. 30
keV). If E R can be reduced, then the probability of absorption of the emitted y-radiati~=- ;l1creases.
Obviously, the probability of absorption will be maximum when ER becvtnes zero (i.e. recoilless
transition). E R can be reduced by increasing the mass M. This can be attained by placing the
emitting nucleus (i.e. source) and the absorbing nucleus (i.e. sample) in a matrix crystal so that the
effective mass (M*) becomes the mass of the crystal. Because of this effective large mass, the recoil
energy (ER ) becomes less (in other words, recoil energy is readily dissipated in the matrix lattice). Thus
the energy mismatch factor (2ER ) becomes less and probability of the y-ray absorption increases.
Developl1ient of this technique to reduce E R was the main contribution of Mossbauf'r to develop this
spectroscopic technique.
If the source and sample are placed at low temperature, then the thermal motions of the lattice
atoms (i.e. lattice vibrations) will be reduced and it will favour the recoilless transitions. This is why,
MB spectroscopic studies are very oftell carried out at low temperature.
(e) Natural bandwidth of the v-ray emission: Half-life of the excited Fe* nucleus is about 1.5
x 10-7 s. Using the uncertainty principle: Mx Lll=:: h, i.e. hLlV x Llt=:: h, i.e. LlV =:: ~ = 1 7 =:: 106 Hz
~t 1.5 x 10- s
(cf associated y-ray frequency - 10 18 Hz). It indicates that the uncertainty in energy is very small i.e.
very small bandwidth. (~v/v ::::: 10- 12 which is much smaller than that found in other spectroscopic
techniques e.g. LlV =:: 10-8 for NMR; LlV =:: 10-5 for IR). From Fig. 12.4.2.1, it is evident that greater
v v
ry
the bandwidth, greater the probability (measured by the overlapping area) of nuclear resonance absorption.
ra
Thus the y-ray emission of very sharp frequency (i.e. narrow bandwidth) creates a problem for its
ib
reabsorption by the sample nucleus even in the condition of recoilless transition, because the different
yl
chemical environment around the sample nucleus (to absorp the y-radiation) compared to that of the
em
source nucleus makes Eo (difference in energy between the excited and ground nuclear energy levels)
of the sample slightly differentfrom the Eo of the source (to emit the y-radiation) i.e. centres of the two
ch
curves are separated by the difference of the Eo values of the source and sample nuclei even when
E R = 0 (cf Fig. 12.4.2.1 where Eo is taken the same for source and sample).
al
(f) Effect of temperature: We have already mentioned that the natural line width (determined by
e
the uncertainty principle) of the emitted y-ray is exceedingly small (::::: 106 Hz, Vy ::::: 10 18 Hz). It minimises
th
the possibility of overlapping between the distribution of the emitted and absorbed y-rays. At higher
e/
temperature, Doppler broadening due to the thermal motion of the emitting and absorbing nuclei in
different directions is expected to increase the probability of overlapping of the two curves (Fig. 12.4.2.1)
t.m
i.e. increase of the probability of MB nuclear transition in the sample nucleus. However, contrary to this
expectation, it has been experimentally found that at the lower temperature, the resonance causing the
e
MB nuclear transition becom,es favoured. It is because of the fact that at lower temperature, the reduced
er
thermal vibration favours the recoilless transition. This aspect has been already discussed.
H
(g) Adjustment of Doppler shift for the absorption ofy-radiation (under the condition of recoilless
transition): Under the condition of E R ::::: 0, the energy mismatch for absorption of the emitted
k
lic
y-radiation arises for the slight difference in the Eo values of the sample and source nuclei. This energy
mismatch factor ~o = Eo (source) - Eo (sample) can be adjusted by Doppler shift.
C
If the source is moved with a higher velocity towards the sample, energy of the emitted y-radiation
from the source becomes higher and vice-versa.
The energy change i.e. Doppler shift (dEs) of a photon is given by:
uhv uE y cose
h~vs
=l1Es =--cose=----
c c
Where ~vs = frequency shift, u = relative velocity of the source with respect to the sample, Ey =
stationary energy of the photon; e = angle between the direction of the velocity of the source and the
line connecting the source and sample; c = velocity of light (3 x 10 10 cm S-I). Under condition of e =
o i.e. source directly moving in the direction of the sample,
uE y . UV
~s = - - I.e. ~vs = - Hz; (E y =hv)
c c
For u = 1 cm S-I i.e. 10-2 m S-·I, the frequency shift ~vs becomes about 108 Hz.
I8
ef. Avs '" 1 ems-I XlO HZ)
r 1
3xl0 0cms- 1
This ~vs is about 102 times greater than the natural bandwidth (== 106 Hz). In fact, varying the relative
velocities from +1 cm S-1 to -1 cm S-I, a reasonable range of frequencies can be made available for
scanning.
Adjustment of Doppler shift to satisfy the energy condition of the y-ray absorption by the sample,
generally the source is moved and the sample is kept fixed. The positive Doppler velocity or
positive relative velocity means that the source is moving towards the sample while the negative
Doppler velocity or negative relative velocity means that the source is moving away from the sample.
Por 57Pe emitting 14.4 ke V y-ray, the energy change for the Doppler velocity of 1mm S-1 is equivalent
ry
to 4.8 x 10-8 eVe
ra
3
AE = uEy = 1 mm S-I x14.4x10 eV =4.8xlO-8 eV
ib
s
c 3xl0 11 mms- 1
yl
em
4.8xl0-8 eV 4.8 x 1O-8 eV = 11.6 MHz
4.14xl0- 15 eVs
-
heVs
ch
34
al
E 662 10-34
( C/.v=h,andh=. x
6.62 x 10-
JS= 1.6xlO- 19 eVs=4.l4xlO
-15)
eVs
e
th
Under the condition of recoilless transition, generally the energy difference (i.e. ~o) for the same
e/
nuclear transition between the sample and source nuclei is small which can be adjusted by the Doppler
t.m
velocity. This magnitude and direction of the Doppler velocity give an idea regarding the chemical
environment around the sample nuclei (with reference to that of the source nuclei). Obviously, if the
sample and source nuclei are in the same chemical environment then for the zero Doppler velocity, the
e
er
MB signal will occur provided E R = 0 i.e. recoilless transition.

(h) Important conclusions:
H
----~------ Eex
k
lic
C
Emitter (Nuclear transition)

Absorber
~ (sample)
~
(y-absorption) (Nuclear transition)

(Source) (y-emission)
_ _ _ _....z...... E
gd
Eex - Egd = Eo (source)::= hv + ER (source) E y (sample) = hv::= (Eex - E gd ) + E R

2 2
= E y (source) + EtL(source) = Eo (sample) + ?R (sample)
2M 2M
2
i.e., E y (source) = hv = Eo (source) - EtL(source)
2M
(cf. in other optical spectroscopy, Eo =hv because E R is exceedingly small)

Fig. 12.4.2.2 Characteristics of the y-ray emitted and absorbed by the same nuclei.
(i) Because of the recoil energy (E R), energy of the emitted y-radiation (Ey) is less than the energy
change (Eo) during the nuclear transition from the excited state to the ground state (cf in
other spectroscopic techniques, hv = f1E = Eo, where the recoil energy is negligible). For the
y-photons (very high energy) emission, recoil energy is accountable (Fig. 12.4.2.1).
(ii) During the excitation by absorption of y-radiation, the energy of the exciting y-radiation will
have to provide the energy ofexcitation and also the recoil energy ofthe absorbing nucleus i.e.
E1 (sample) = hv = Eo + E R = Eo +p~-
2M
(iii) It indicates that for the same nuclear transition, energy of the emitted y-radiation is Eo - E R
while it is Eo + E R for the y-ray absorption. Thus, the emitted radiation cannot cause the same
ry
transition and the energy mismatch factor is 2ER assuming E R (source) = E R (sample). Doppler
ra
broadening cannot overcome this energy mismatch factor. .
ib
(iv) By placing the source and sample nuclei in a solid crystal (i.e. effective mass is enormously
yl
= 2MP~ = E~ 2].
em
increased), the recoil energy can be made almost zero [cf. E R It gives the
2Meff c
eff
condition of recoilless transition i.e. for the same transition, Ey(source) : : : Eo : : : E y (sample).
ch
(iv) Due to the difference in chemical environment around the source and sample nuclei, EJ
al
(source) :t EJ (sample). This small energy difference between EO(source) and EO(sample) can be
e
adjusted through the Doppler shift (~v s) of frequence.

th
~v s = UV Hz; u = relative velocity of the source with respect to the sample;

e/
c
t.m
(v) Avs vs. natural bandwidth: In the MB spectroscopy, natural bandwidth of the y-ray emission
is extremely narrow (cf ~v/v : : : 10- 12 ) and ~vs (Doppler frequency shift:::::: 108 Hz when
u = 1 cm S-I) is quite large compared to the natural bandwidth (:::::: 106 Hz). Thus, by adjusting the
e
er
Doppler shift (i. e. relative velocity of the source), MB spectrum can be recorded.
H
(i) Experimental set-up: The source nucleus (i. e. excited nucleus to be generated in situ, very short
life-time) is placed in a solid matrix next to the sample matrix (sample is the same nucleus but at the
k
lic
ground state). A relative movement of the source will cause the appropriate Doppler shift to cause the
absorption of the emitted y-radiation by the sample. A y-ray counter is placed behind the sample. The
C
y-ray counter records the weakest signal when the sample absorbs the y-radiation. Thus a plot,
signalintensity (at the y-ray counter) vs. the Doppler velocity between the source and sample gives the
MB spectrum (Fig. 12.4.2.3).
y-Ray
counter
velocity drive
(a)
ca Q)
mE
~
_ 5
(.J
c:
r.1
~ (isomer shift)
I
::s ?-
o m
0=
-2 -1 0 +1
ry
1
u (mm/s- )
ra
(b)
ib
Fig. 12.4.2.3 (a) Schematic set-up of a MB-spectrometer. (b) Representation of the Mossbauer line.
yl
12.4.3 Source and Absorber: MB Spectroscopy for 57Fe and 119Sn
em
For the successful MB studies, life-time of the excited nucleus (to act as the source of y-emission),
ch
should lie in the range 10-6 to 10- 10 s.
(a) 57Fe: The 57Pe* isotope is conveniently synthesised from 57CO = eQ < through the (I ~, 0)
e al
electron capture. The excited nucleus 57Fe* comes to ground state (stable 57Fe) through the y-emission
th
(i.e. isomeric transition, IT). 57CO is prepared by electrodeposition. The complete energy diagram
e/
leading to the generation of 57Fe* which acts as the source of y-radiation in studying the MB spectrum
t.m
of Fe-compounds is shown in Fig. 12.4.3.1.

1=7
- 57 11
2 27
CO
2
e
(89.5 keV)
er
Electron
capture
H
Y1
(t 1/2 :::; 270 days)
k
(t 1/2 :::; 245 days)

lic
5 , :;Fe*(136.4 keV)
C
2
Y2 (100/0) Y1 (90%)
I =1. ~--'-~,---_1~~Sn*
9 2
(t 1/2 :::; 8.5 x 10- s) (23.9 keV)
YMB
'VV\N\I\/\I\I\r
8
(t 1/2 :::; 1.9 x 10- s)
, ~~Fe·(14.4 keV) 1=1- - - - - - - 1~~Sn (0)
2
(Ground state)
7
YMB (t 1/ 2 :::; 1.5 x 10- s)
~
18
~ ~
(y ray, _10 Hz) 57
26 Fe (0)
(Ground state)
Fig. 12.4.3.1 Energy diagrams for the isomeric transitions giving the sources of the y-radiation (YMB) in the studies of
MB spectroscopy for iron and tin compounds.
In the transition, 57Fe*(14.4 keY) ~ 57Fe, the energy change (J1.E =Eo) per nucleus is: 14.4 keY
= 14.4 x 103 x 1.6 X 10- 19 J = 2.30 x 10- 15J. It leads to:
15
2.30 X 10-15 2.3 X 10- J __ 3.5 x 10 18 Hz (i.e. y-radlatlon).
. .
hv = J1.E = 2.30 X 10-15 J; or v =- - - -
h 6.62 x 10-34 J s
(b) 119S0: It is prepared in the form Pd3Sn or BaSn03.' It is shown in Fig. 12.4.3.1
Some important nuclei used in MB spectroscopy are given in Table 12.4.3.1
Table 12.4.3.1 Some important Mossbauer isotopes with their precursors and nuclear characteristics.
Nuclear spin Natural Lifetime of the Gamma energy Precursor
ry
Nucleus Abundance first excited change (half-life) of
ra
Ground First excited (%) state i.e. AE the y-ray
state state (x 10-9 s)* (keV) source
ib
57Fe 57CO
yl
1/2 3/2 2.2 98.0 14.4 (270 d)
119Sn 119mS n (245 d)
em
1/2 3/2 8.6 18.00 23.8
1291 7/2 5/2 -0 16.30 27.8 129Te (33 d)
1251
ch
129Te 1/2 3/2 6.7 1.40 35.6 (57 d)
197Au 3/2 1/2 100 1.80 77.3 197pt (18 h)
al
151Eu 5/2 7/2 47.8 9.80 21.6 15 1Sm (90 y)

e
166Er 0 2 1.83 80.6 166HO (27 h)

th
169Tm 1/2 3/2 3.90 8.41 169Er (9.4 d)

e/
Life-time (t112) of the excited state should lie in the range: 10-6 s to 10- 10 s. If 11/2 > 10-6 s, the natural bandwidth
t.m
*
becomes too narrow (i.e. overlapping region becomes too small, cf. Fig. 12.4.2.1) to cause the nuclear resonance
absorption. If 11/2 < 10- 10 s (i.e. too short life period), the natural bandwidth becomes too broad to be useful in
e
hyperfine studies.
er
H
12.4.4 Isomer Shift or Centre Shift or Chemical Isomer Shift (in short, Chemical Shift)
in MB Spectroscopy
k
lic
It has been already mentioned that even in the recoilless transition, the y-radiation emitted by the source
nucleus cannot cause the nuclear excitation in the sample nucleus of the same element. It is due to the
C
fact, that the nuclear transition energies for the sample and source nuclei are different (slightly) if their
chemical environments differ. The electrostatic interaction between the nuclear charge distribution
and electron charge distribution in the nucleus brings about a change in the positions ofthe nuclear
energy states. This electronic charge density at the nucleus depends on the chemical environment
around the nucleus. This difference (in chemical environment) between the source and sample nuclei
causes the difference in the Eo values (i.e. nuclear transition energies) of the source and sample but this
energy mismatch (i.e. J1.Eo = Eoource - Eoample) can be adjusted by the Doppler velocity. This energy
difference t£o gives the measure of isomer shift (sometimes called centre shift, chemical shift) which
is expressed in terms of Doppler velocity. It can adjust the energy mismatch to allow the nuclear
transition at the sample nucleus. Thus the isomer shift (8) is expressed in em S-l or mm S-l (i.e. Doppler
velocity).
For [Fe(CN)6]4-, the sharp MB absorption peak arises at the Doppler velocity, ca. -0.15 mm S-I (i.e.
8 = -0.15 mm S~I) (cf. Fig. 12.4.4.2) with reference to 57Fe*, a 57Co source.
Due to the electrostatic interaction between the nuclear charge distribution and electronic charge
distribution at the nucleus, the shift (m in the nuclear energy state is given by:
dE = KR21\11e(O)1 2
where K is a nuclear constant; R = radius of the nucleus; R is different for the excited and ground state
in a particular nucleus; l\IIe(O)1 2 = total electron density at the nucleus;
Thus the total energy change in a particular nuclear transition due to the above interaction is given
by:
8(m = dEex - dEgd = K1\11e(O)1 2 (R;x- Rid)
Thus the isomer shift (8) which gives the measure of the difference in the nuclear electrostatic
energy changes of the source (i.e. y-ray emitter) and sample (i.e. y-ray absorber) is given by:
ry
. 8 = 8(msample - 8(dE)source
ra
.=K(R;x - R2d ) { 2
1\11 e(O)1 1
2}
-1\11 e(O)1 source ; K
2
= -1tZe 2
ib
g samp e 5
yl
It is obvious that if the sample (i.e. absorber) and source (i.e. emitter) are the same nucleus with the
em
same chemical environment then ~ becomes zero.
~---r-----~r--- (ex),1 = ~
ch
/ 2
// ~Eex
t
al
I= (ex) -----r----------------------------
e
th
e/
t.m
e
er
H
2 2
(a) l'Vs(O)1 (b) l'Vs(O)1
k
= x (say) = y (say)
lic
Fig. 12.4.4.1 Schematic representation of the energy change in MB transition for 57Fe depending on the values of I'll/0)1 2
C
i.e. electron density at the nucleus (M 1 ) 11£2 i.e. higher electron density at the nucleus reduces the MB transition
energy).
For a particular element, a fixed and standard source is used, e.g. 57CO for Fe; Ba119mSn0 3 for Sn; etc.
Thus, l\IIe(O)I~ource may be taken as a constant, P (say). When (Rex - Rgd ) is very small, we can reasonably
write:
It gives:
i.e. B=K,(BR)[I
R 'Ve (0)1
2
sample
-P].,K'=!1tZe
5 R 2 2
where K' = 2KR 2 (a constant and positive); oR or dR is also a constant for a given nucleus.
R R
Now let us consider the electron density at the nucleus. For the different orbitals like s, p, d, f, 000'
except the s orbital, all other orbitals have the node at the nucleus (cf. Figs. 4.1.4.1-2, Vol. 1). Thus
only the s-electron can interact directly with the nuclear charge. However, other orbital electrons
can indirectly control the s-electron density through their shielding properties. Thus we can write:
I", e(0)!2 ." I", ,(0)1 2

and 0 = K'( 0; )[1'" s(o)l:amPle - P]
ry
ra
ib
~
u (Rex < Rgd)
·S
yl
() ()
11) Q) Q)
czi ..c en dR or 8R = -ve en dR or8R = +ve
em
~ u
11) Co Chemical term = +ve Co
0-
U 11)
en en Chemical term = +ve
~
cI
-5 "E [Fe(CN)6t- "E
ch
C ~ ~ Sn(C2Hs)4
~ 0 0
(,)
(S7 Fe) 0
(,)
~
00
"'0
al
C C
11)
11)
e
;;> ~
'So 11) 
0 mm/s mm/s
t.m
~
11) ~
00 ~ 8 = -0.15 8 = +1.21
;;>
I ..
~ 11)
~ (a) (b)
~
0
(1)
~
::3
e
clj
e
11) N ~ 00
;;> ~
a
er
+ 3~
'-' 0
"'0 ~ tt:
H
11)
00 dR or 8R = -ve
>
lic
~
E ()
~ N ~ ~
Q)
~ en
--- ~
C
~ i- '-~
""-' Co
0- (Rex) Rgd)
11) en
~ "E
a ~
dR or 8R = +ve
= ......=
'-' o
1-1 clj (,)
~ 00
1-1
~ 11)
...... e; -5
1-1 Chemical term = -ve
= ·5
~
CJ CoM
0 for both 1271 and 129 1
~ ~ 11)
=
~
~
Z U £3
00
• • .--.....
8(129 1)
Relative velocity (mm/s)
(c)
Fig. 12.4.4.2 (a) Negative isomer shift for [Fe(CN)6]4-; (b) Positive isomer shift for Sn(C 2H s)4; (c) Positive isomer
shift for Na3H2127I06 (Source: Zn l27 Te i.e. zinc telluride containing l27mTe) and negative isomer shift for Na3H2129I06
(Source: Zn 129mTe).
Nuclear term and chemical term: The isomer shift 8 depends on the nuclear term K'(8R1R) and
chemical term [Iv s(O)1 2
samp1e - p] i.e. [Iv s(o)1 2
samp1e -Iv s(O)1 2
source ]. Thus the chemical term indicates
the difference in the electron densities at the sample (i.e. absorber) and source (i.e. emitter) nuclei. The
nuclear term is a constant for a particular Mossbauer transition and consequently, isomer shift depends
only on the chemical term. This is why, the isomer shift is called the chemical isomer shift.
• If 8R is positive and chemical term is positive, i.e. l'Vs(O)I~arnple) l'Vs(O)I~ource' then 8 (isomer shift)
is positive; but for the negative value of 8R and positive value of chemical term or vice versa, 8 becomes
negative.
(A) Sign of 8R (= Rex - R gd ), sign of chemical term and sign of isomer shift: Sign of 8R depends
on the relative magnitudes of Rex and Rgd • For 57Fe, Rex ( R gd i.e. SR is negative and increase in
ry
s-electron density in the sample will produce the isomer shift more negative (cf. Fig. 12.4.7.1, Table
ra
12.4.7.1). For 119Sn, Rex ) R gd i.e. 8R is positive and increase in s-electron density gives a more
positive chemical shift.
ib
Sign of the chemical term depends on the relative magnitudes of l'lfs(O)I~arnpleand l'Vs(O)I~ource i.e. it
yl
becomes positive for IWs(O)I~ample) IwS<O)I;ource and it becomes negative for IWS<O)I;ample ( IWs(O)I;ource'
em
• Sign of isomer shift (8): It is positive when 8R (i.e. nuclear term) and chemical term are of the
sign (i.e. both are +ve or -ve). Isomer shift becomes negative when the nuclear term and chemical term
ch
are of opposite signs.
It is quite interesting to note that for 1271 (source: ~-decay of 127rnTe i.e. zinc telluride Zn 127rn Te; YMB
al
of 57.5 keY from 1271) and 1291 (source: ~-decay of 129Te i.e. zinc telluride Zn 129Te; YMB of27.8 keY from
e
1291), the 8R values are of opposite sign. 8R is negative. for 1271 (i.e. Rex < R ) and 8R is positive for
th
gd
129
1 (i.e. Rex> R gd ). But, for both the 1271 isotopes, the chemical term (when Na3H2106 is taken as the
e/
sample or absorber) is negative i.e. IWs(O)I~ample ( IWs(O)I~ource' Thus for 1271 and 1291, resonances of
t.m
Na3H2I06, the isomer shifts are expected to be positive and negative respectively. In fact, the MB
spectrum of 1271of Na3H2127106 shows a positive isomer shift while the MB spectrum of 1291of Na3H2129106
shows a negative isomer shift (cf. Fig. 12.4.4.2). It is noteworthy that 1291 isotope contains two addi-
e
er
tional neutrons which can modify the nuclear structure.

• 8R (+ve) (e.g. 119Sn, 1291, etc.): More the s-electron density at the san1ple, more the positive value
H
of isomer shift (i.e. 8 moving towards the positive direction).

k
• 8R (-ve) (e.g. 57Fe, 1271, etc.): More the s-electron density at the sample, more the negative value
lic
of isomer shift (i.e. 8 moving towards the negative direction).

C
(B) Determination of the sign of 8R: To determine the direction of the isomer shift, it is required
to know the relative values of Rex and Rgd • It is obtained in an indirect way. If the MB spectrum, is
recorded at a high pressure, then it is expected that the electron density near the sample nucleus will
increase, i. e. the chemical term will be more positive or moving towards the positive values and the
direction of the isomer shift will tell us the sign of 8R, i. e. the relative values of Rex and Rgd •
• If with the increase of pressure, 8 runs towards the negative direction (as in 57Fe, 1271, etc.), then
it indicates 8R negative (i.e. Rex ( Rgd ).
• On the other hand, if with the increase of pressure, 8 runs towards the positive direction, (e.g.
119Sn, 1291, etc.), then it indicates 8R positive (i.e. Rex) Rgd ).
Here it is worth mentioning that sometimes, the redox reaction (as in [Fe(acac)3] to be discussed
later) and high spin ~ low spin equilibrium in the transition metal complexes are controlled by the
external pressure and then to conclude regarding the sign of 8R from the directions of the shift of 8 with
the change of pressure, the said chemical phenomena are to be taken into consideration.
(C) Significance of the direction and magnitude of isomer shift (8) to understand the chemical
environment around the MB nucleus (i.e. absorber): It has been already mentioned that the
s-electron density directly interacts with the nuclear charge density because the s-orbital shows a finite
probability region at the nucleus (cf. Fig. 4.1.4.1-2, Vol. 1). Other orbitals (e.g. p, d, f, ...) possess the
nodal zone at the nucleus (see Figs. 4.1.4.1-2, Vol. 1) and they can control the s-electron density (to be
experienced by the nucleus) through the screening (i. e. shielding) effect (cf. the penetrating power of
the p, d, f orbitals which can screen the s-orbital, see Vol. 1). It has been noted that the increase of
p- and d-electron density can reduce the s-electron density at the nucleus through screening. This
change in s-electron density is reflected in the direction and magnitude of 8. It is illustrated for the 57Fe_
and 119Sn_ compounds.
(a) Fe2+(3d6) vs. Fe3+(3ds) (in the high spin state): For 57Fe, 8R is negative and consequently, with
ry
the increase of s-electron density, the isomer shift (8) runs towards the more negative direction
ra
(i.e. less positive direction). The increase in 3d-electron density causes the more screening of
ib
the 3s-electrons to be experienced by the nucleus (i.e. increase in the number of d-electron
yl
makes the s-electron density less at the nucleus) and consequently, the isomer shift runs to-
wards the more positive direction. For the comparable ligands and the high spin state, Fe(ll) (tf)
em
(bearing the higher number of d-electrons to screen the s-electron more) shows the less negative
(i.e. more positive) isomer shift than Fe(lll) (~). In fact, 8 follows the sequence (for the high spin
ch
complexes):
al
8: Fe(VI) (tP) <Fe(IV) (tr) <Fe(lll) (~) <Fe(ll) (tf) <Fe(l) (d7 )
e
Thus the direction and magnitude 8 can help us to predict the oxidation state of iron in its high
th
spin complexes.
e/
t.m
Position of isomer shift: Sign of the nuclear term and chemical term
For a particular MB-isotope, sign of the nuclear term (detennined by the sign of 8R) is fixed
but sign of the chemical term may vary from sample to sample, i.e. it is positive for l'Vs(O)I~ample)
e
er
l'Vs(O)I~ource = constant (for a particular source) and it is negative for l'Vs(O)I~ample < l'Vs(O)I;ource =
constant.
H
In fact the s-electron density at the sample nucleus depends on the chemical state of the MB-
k
isotope. For example, for 57Fe-MB spectroscopy (where sign of 8R is negative i.e. Rex < Rgd ), it
lic
has been found that for the low oxidation state, when the 3s-electron density at the nucleus is
C
less, sign of the chemical term is negative while for the high oxidation state when the 3s-electron
density at the nucleus is more, sign of the chemical term is positive. It makes the isomer shift
positive for the low oxidation states of iron and negative for the high oxidation of iron (cf.
Fig. 12.4.7.1).
Here it is worth mentioning that sign of the nuclear term of the different isotopes of a particular
element may be different (e.g. 8R = -ve for 1271, but 8R = + ve for 1291) but sign of the chemical
term of a particular sample is fixed (e.g. negative chemical term for both Na3H2127106 and
Na3H}29106 having the same chemical state of I). It makes 8 positive for 1271 resonance and 8
negative for 1291 resonance (cf. Fig. 12.4.4.2c).
(b) Fe2+(3d6) vs. Fe3+ (3d5) (in the low-spin state): In the low-spin complexes, characterisation of
the oxidation state in terms of isomer shift is not so straight-forward. Generally, in the low-spin
complexes of Fe(ll) and Fe(III), the ligands are the 1t-acid ligands (i.e. strong field ligands)
which remove the metal d-electron through the metal ----+ ligand 1t-back bonding. This 1t-back
bonding is more favoured for the lower oxidation state of the metal centre. This is why, in the
low spin complexes of Fe(II), depletion of d-electron through this n-back bonding is more
pronounced than in the comparable low spin complexes of Fe(III). Thus there are two opposing
factors to determine the effective d-electron density: number of d-electrons (i.e. 6 vs. 5) and
efficiency of 1t-back bonding reducing the d-electron density. In fact, Bvalues of the low-spin
complexes of Fe(ll) and Fe(lll) are very much comparable (cf [Fe(CN)6]3- and [Fe(CN)6]4-; Table
12.4.7.1).
Electronic Configurations
Feo: [Ne]3s 3p 6 3£i6 4s 2 ; Fe2+: [Ne]3s 2 3p 6 3£i6; Fe3+: [Ne]3s 2 3p 6 3tP
2
8no: [Ar]3d 10 4s 2 4p 6 4d 10 5s 2 5p 2 == [Kr]4d 10 5s2 5p 2; 8n2+: [Kr]4d 10 5s2 ;
ry
8n4+: [Kr]4d lO ; 8n(4 covalency): [Kr]4d 10(5sp3)4
ra
ib
(c) l19Sn-compounds (OR positive, i. e. more positive isomer shift for the more s-electron density):
yl
R
em
The relative values of isomer shift for some representative compounds of Sn are given below:
ch
Valence state isomer shift (mm S-l)
Sn4+(5so 5p o) o
al
Sn (4-covalent bonds, 5(Sp3)4) 2.1

e
th
Sn2+ (5s 2 5p o) 3.7

e/
In the Sn(IV)-compounds (i. e. Sn4+), there is no 5s-electron while there are two electrons in the
t.m
5s-orbital for Sn2+, i.e. s-electron density is more for Sn(II). It gives the more positive value of isomer
shift. In the covalent compounds, the 5s-orbital can be considered to possess one electron i. e. an
intermediate situation between Sn 2+ and Sn4+. Thus the 5s-electron density changes in the order:
e
Sn2+ ) Sn-covalent compounds) Sn4+ and the isomer shift follows the same sequence: Sn2+ ) Sn-
er
covalent compounds) Sn4+.

H
Thus the determination of the isomer shift allows us to understand the relative s-electron density
k
which in turn gives an idea regarding the chemical state, bonding character, etc. of the sample (i.e.
lic
absorber).
C
12.4.5 Quadrupole Interaction and Splitting of the MB Spectral Lines

Generally the Mosbauer active nuclei are having the half integral spins. The nuclear spin in the excited
state is invariably different from that of the ground state. Consequently, one or both of the states will
~
have the quadrupole moment (eQ) (for I > ). The quadrupole moment will interact with the electric
field gradient (EFG) (eq) at the nucleus. Thus the noncubic electron or ligand distribution produces an
electric field gradient (EFG) at the nucleus and it interacts with the quadrupole moment to remove the
1
degeneracy of the nuclear energy levels for the nuclei with I > - . For a nucleus with the spin quantum
2
number I, the possible m/ values are: +1 to -I. The quadrupole interaction does not remove the
± degeneracy of the mI values for the nonintegral spin. The energy value due to the quadrupole
interaction is:
E = (eQ){eq) [3m 2 _ 1 (I + I)J(1 + 21)1/2

±m/ 41(21 -1) J 3
11 = asymmetry parameter of the electric field gradient (EFG) and it is defined as:
qxx - qyy
11 = when qzz :f. qxx :f. qyy (i.e. rhombic symmetry)
qzz
11 = 0 for the axial symmetry i.e. qzz :f. qxx = qyy
3 1
For the nuclei (e.g. 57Fe, 119Sn, 129Xe, etc.), the nuclear spin at the excited state is "2 while it is "2
ry
i,
ra
for the ground state. For the excited state, there are four possible orientations (21 + 1) given by ± ±!.
2 2
ib
3 1
The doubly degenerate energy states corresponding to m J = ±"2 and ±"2 are separated due to the
yl
em
quadrupole interaction arising from the electric field gradient (for the noncubic electron or ligand
distribution) at the nucleus. The split energy levels for m/ = ±l are degenerate; similarly, the energy
ch
2
= ±! are degenerate. Thus the quadrupole interaction cannot remove the total
al
levels for m/
2
e
degeneracy of the nuclear spin energy states. The energy values are:
th
2 2
e/
E - (
eq ) ( eQ ) 3 x ~ _ ~ ~ + 1 1 + 2L2 J1/ - 3e 2 qQ ( 1 + 2L2J1/
t.m
±% - 41(2/-1) [ 4 2( 2 )] (
3 - 41(2/-1) 3
e
/2
(eq )( eQ ) 2J1/2
3 x ! _~ ~ + 1 1 + 2L 3e 2qQ (1 + 2L2J1
er
E -
±k - 4/(2/-1) [ 4"2 ( 2 )]( 3 -- 4/(2/-1) 3
H
k
It is evident that the degenerate energy states for = ±l are raised in energy and the degenerate
lic
m/
2
1
C
energy states for m J = ±- are lowered in energy for the nuclei having the quadruple moment
2
positive (i.e. eQ ) 0) as in the case of 57Fe. For the negative quadrupole moment (i.e. eQ ( 0), the
reverse situation arises.
For 1 = ~ (i.e. ground state), there is no question of splitting of the energy level because the quadrupole
2
moment (eQ) is zero.
The splitting of nuclear spin energy levels due to the quadrupole interaction for 57Fe having 1 = ~
2
(ground state) and 1 = ~ (excited state) is shown in Fig. 12.4.5.1. This quadrupole splitting will split
2
the MB peak into a doublet peak and the isomer shift is measured from zero to the centre of the
doublet peak.
ml Energy
1
+~
2
,.,.,.",,~----:-~----~---_.+ 2
3e qQ ( 11 )2
41(21 _ 1) 1 + 3
2
,."
,.",."
I =~ (Excited state) ,.,.,."
2 ,."
------~--:::,."
.......... o
.......... W
.......... <J
..........
..........
, 1
3e qQ (1 + .I )2
2
. . . . . . . . . . . . . . . - - - - - r - - - - + - - - - - +.1 _
- 2 41(21-1) 3
ry
ra
ib
yl
em
------&------------------------------&----- o
I = .1 (ground state) (Quadrupole interaction)
2
ch
(a)
e al
th
e/
t.m
e
o
Q)
er
~
c;:,
H
o
U
k
lic
-1 I 10 +1
C
1.....-.1 ---. Relative

8 velocity (mm/s)
(b)
Fig. 12.4.5.1 (a) Splitting of nuclear energy levels at the excited state for 57Fe due to the quadrupole interaction. (b)
Schemetatic representation of isomer shift (8) and quadrupole splitting energy (~EQ) for 57Fe of a typical low-spin
complex of Fe(II).
For 57Fe, the energy separation between the levels corresponding to m I =±l and ± .!.. (generated
2 2
from the excited nuclear state 1 = 2 through the quadrupole interaction) is:
2
fill
Q
=
2
6e qQ
41 (21 -1) (
1+ ~
3 J
l/2
=e
2
qQ
2
(
I +~
J1/
3'
2
(1 =2)
2
2
For an axial symmetry of the electric field, T) =0 i.e. M Q = e qQ. Under the selection rule AmI =0,
2
± 1, the following two transitions will lead to the two MB spectral lines (cf. one spectral transition when
there is no quadrupole splitting of the excited level, I =i )

2
From these two MB transitions, it is not possible to determine the value of 11 and the sign of
quadrupole coupling constant.
ry
ra
ib
yl
em
o 57 Fe-MB Spectrum
Q)
en
Q)
ch
0-
en
'E
:;, 1
al
o B= -0.165 mm 5-
o .1Ea =1.76 mm 5-
1
e
i
th
e/
t.m
-3 -2 -1 o +1 +2 +3
Doppler velocity (mm/sec)
e
er
(a)
H
k
lic
197 _
Au MB
C
spectrum
g [Au 4(PPh 3)412]
en
8. .1Ea = 6.6 mm/s
E
:;,
8 = + 1.25 mm/s
o
o
i
[Au(PPh 3)4 12]
-10 -5 o +5 +10
EFG-:t=O
Doppler velocity (mm/5)
(b)
(.)
Q)
en
Q; 57 Fe _Mb spectrum
a.
en 8
'E [Fe(CO)5l; EFG "* 0
H
::J
o
U
ry
r
ra
ib
yl
em
-2 -1 o ch +1 +2
Doppler velocity (mm/s)

(c)
e al
Fig. 12.4.5.2 Quadrupole splitting into a doublet peak. (a) Na2[Fe(CN)5(NO)], (b) [AuiPPh3)4I2]; (c) [Fe(CO)5].
th
If there is a nuclear spin level I > ~ (involved in MB transition), there would be more than two MB
e/
2
t.m
spectral transitions and it would be possible to determine 11 and sign of the quadrupole coupling constant.
Here it must be remembered that splitting of the nuclear energy level (by the quadrupole interaction)
will occur when there is an electric field gradient (eq) at the nucleus and it is created by the asymmetric
e
er
s-electron distribution. This asymmetric electric field may be generated by the noncubic distribution
of the electron density around the nucleus or by the noncubic ligand field (i.e. introduction of low
H
symmetry ligand field component).

k
Thus the electric field gradient (EFG) at the nucleus is determined by the asymmetry of the chemical
lic
environment (i. e. noncubic distribution of electron density or noncubic ligand field). Some illustrative
C
examples are given here for the Fe-compounds.

• 197Au-MB spectrum of [Au4(PPh3)412]: In this cluster, there is a tetrahedron of Au-atoms with the
I-atoms bridging the opposite (i.e. nonadjacent) edges. All the 4 gold atoms are structurally equivalent
but the noncubic distribution of the ligands around the Au-centre gives a single quadrupole doublet
(see Fig. 12.4.5.2b).
• [Fe(CN)6]4- vs. [Fe(CN)6]3-: [Fe(CN)6]4-(~g) is spherically symmetric in terms of both electron

distribution and ligand distribution around Fe(II) and it cannot split the energy levels for the excited
state (I =%). It gives one MB spectral transition (see Fig. 12.4.7.2). On the other hand, [Fe(CN)6]3-
(~g) gives a doublet peak (see Fig. 12.4.7.2) in the MB spectrum because the electron distribution in
the t Zg level is not symmetric. Rather the Jahn-Teller distortion due to the asymmetric electron
distribution at the tzg-Ievel intensifies the electric field gradient (EFG) at the nucleus.
• [Fe(CN)s(NO)]2-: The nitroprusside ion, [Fe(CN)5(NO)]2- being structurally asymmetric (C 4v
symmetry i.e. noncubic symmetry) splits the excited level (I =%) through the quadrupole interaction
to give a doublet peak in the MB spectrum (see Fig. 12.4.5.2).
• Low spin vs. high-spin Fe(II) complexes: For the low-spin complexes of Fe(II) (l1g ) having the
cubic ligand field symmetry there will be no quadrupole splitting if the six ligands are identical as in
[Fe(CN)6]4-. However, the noncubic ligand field for the low-spin Fe(II) complexes can lead to the
quadrupole splitting. On the other hand, for the high-spin complexes of Fe(II) (tie;), the quadrupole
splitting occurs due to the asymmetric electron distribution at the t2g -level and the inherent Jahn-Teller
distortion which produce the electric field gradient (EFG) at the nucleus. If the Jahn-Teller splitting
energy separation in the t 2g level is comparable to kBT, then the temperature dependent quadrupole
ry
splitting is observed.
ra
• [Fe(CO)s] (D3h): An electric field gradient exists for this trigonal bipyramidal compound (i.e.
ib
(I =%) giving rise
yl
noncubic and lower symmetry ligand field) and it splits the nuclear excited state
em
to a doublet peak in the MB spectrum (Fig. 12.4.5.2). ch
12.4.6 Effect of a Magnetic Field on the MB Spectrum: Magnetic Hyperfine Interaction
al
The nuclei with the non-zero nuclear spin (i.e. I ~ 0) split into 21 + 1 states in presence of a magnetic
e
field (H) and the interaction energy is given by:

th
= -gN~NHm/
e/
Emf
where gN = nuclear g-factor; ~N = nuclear magneton; m/ = nuclear magnetic quantum number having
t.m
the values +1 to -I. Thus the magnetic field splits both the ground and excited nuclear energy levels into
(21 + 1) nondegenerate equally spaced levels. This is illustrated for I' (ground state) ="21 and I"
e
er
. 3
(excIted state) =-.
H
2
k
-i):
lic
Ground nuclear energy state ( I' =

C
Excited nuclear energy state I (

/I 3)
="2- :
Taking both g~ (ground state) and g.;{ (excited state) positive, the energy level diagram and the
allowed transitions (tlm[ = 0, ±1) are shown in Fig. 12.4.6.1. This splitting of the MB spectrum by the
'magnetic field is called magnetic hyperfine splitting (Zeeman Splitting)
ml
3
",'"
",'" 2
I ~~
I
I
9N (+ve) I
I
I
I
I
I" = 3/2 I I ,,""
" ~ ~ .. ................ 1
--------{/,," 2
(Excited state) ~............
\\ ........
\ ~~ ~~ ................ 1
\
\
+-
2
ry
\\
\ ",'"
",'" +~
2
ra
ib
yl
9N (+ve)
em
ch
",,,,,,,,,,
I' = 1/2
- - - - -.........
",'"
al
(Ground state) ................
e
(Magnetic field splitting) (Splitting by both

th
magnetic and
electric field)
e/
(a) (b) (c)

t.m
Fig. 12.4.6.1 Schemetic representation of splitting of the nuclear energy levels (for I = 1/2 and g N =+ve at the ground
state; I = 3/2 and g N =+ve at the excited state) by (b) the magnetic field and (c) the simultaneous magnetic and electric
e
field (i.e. Quadrupole interaction) leading to 6 possible transitions.

er
Thus splitting of the energy levels at both the ground state (I' = 112) and excited state (I" = 312) by
H
the magnetic field, will lead to the following 6 MB transitions.

k
Transition .1m[ Transition energies*

lic
C
1 3 1
--~--
2 2
-1 2" ~NH(3gZ - g~)
1 1 1
--~--
2 2
o 2" ~NH(gZ - g~)
1 1 1
--~+-
2 2
+1 -2" ~NH(gZ + g~)
1 1 1
+-~--
2 2
-1 2" ~NH(gZ + g~)
1 1 1
+-~+-
2 2
o -2" ~NH(gZ - g~)
1 3 1
+-~+-
2 2
+1 -2" ~NH(3gZ - g~)
* Ignoring the effect of quadrupole splitting

The quadrupole splitting (relatively smaller compared to the splitting done by the magnetic field)
may be incorporated to have the resultant energy level diagram (Fig. 12.4.6.1) which also predicts 6
MB transitions (cf. transition energies are modified slightly) and the intensity ratio is 3:2:1:1:2:3.
Now let us consider the case of 57Fe for which gN at the excited state (i.e. I" = %) is negative (i.e.
g;J = -0.103) and at the ground state (i.e. I' =~), it is positive (i.e. g~ = + 0.180). Thus, for 57Fe, the
order of energy levels at t~e excited level (I" = 3/2) will be reversed in Fig. 12.4.6.1 (which is drawn
assuming both g;'; and g!J to be positive). For 119Sn, the gN values are positive at the excited state but
negative at the ground state (i.e. for I' = 1/2, g!J = -2.09; for I" = 3/2, g;'; = 0.507). Thus for 119Sn, in
Fig. 12.4.6.1 (drawn assuming both g~ and g; positive), the excited state energy levels (i.e. I" = 3/2)
ry
ra
will lie in the same order but the ground state energy levels (i.e., I' = ~) will be in the reversed order.
ib
yl
For 57Fe, the nuclear energy level diagram (considering the effect of the magnetic field and quadrupole
interaction) is shown in Fig. 12.4.6.2 (where g~ is positive and g;'; is negative). Fig. 12.4.6.3 shows the
em
MB spectrum (6 peaks) of a representative ferromagnetic compound or soft iron. ch
al
I
I ~~ 6 +1-
3 2
gN (negative) 5
e
- - ~ ~~
1
+-
th
1=3/2 .4~ .4~

2
e/
2 4 1
....
- -' .4 ~~
t.m
.4~
2
~
,,
e
............................ 1 3
er
~~
2
H
k
lic
gN (positive)
- --
C
I = 1/2 ~,.,.,.,.,."
----_.....
(Ground state) ....
(Magnetic field
(Quadrupole splitting)
splitting)
(a) (b)
Fig. 12.4.6.2 Magnetic and quadrupole splitting of the nuclear energy levels of 57Fe (ground state: I = 1/2, g = +ve;
N
. d state: I
eXCIte ="2'
3 gN = -ve) and 6 pOSSI·bIe tranSItIons.
..
Splitting of the nuclear energy levels may occur by the externally applied magnetic field or the
intrinsic magnetic field. Splitting by the internal magnetic field (i. e. intrinsic magnetic field) arises
from the interaction of the electrons with the nuclear angular momentum. This electron-nucleus interaction
depends on the dipolar terms and Fermi contact term (cf. ESR spectroscopy). The Fermi contact
interaction depends on the electron density in the s-orbital which has a finite probability of its existence
in the nucleus (cf. for the other orbitals, there is a nodal region at the nucleus, see Figs. 4.1.4.1-2,
Vol. 1). The magnetic hyperfine splitting (by the internal magnetic field) is very often noted for the
ferromagnetic and antiferromagnetic crystals (i.e. magnetically ordered crystals). Figure 12.4.6.2
illustrates splitting of the nuclear energy levels by the internal magnetic field in a ferromagnetic
57Fe-compound.
oQ)
en
ry
Q)
a.
en
ra
'E
::J
o
ib
()
yl
em
6
-5.0 -2.5 0 2.5 5.0
ch
al
Fig. 12.4.6.3 MB spectrum of a ferromagnetic 57Fe sample (e.g. soft iron foil). The transitions 1,2,3,4,5,6 are defined
in Fig. 12.4.6.2.
e
th
12.4.7 Applications of MB Spectroscopy

e/
The nuclides to be taken into consideration for MB spectroscopic studies should satisfy the following
t.m
requirements.
(i) Energy of the VMB radiation: The y-radiation should have the energy in the range 10-200 keV.
e
(ii) Half-life period of the precursor nuclide generating the YMB-emitter nuclide: The half-life of
er
the parent nuclide generating the v-emitter nuclide (i.e. source) should be sufficiently high (in the
H
order of a year) so that the same source with a reasonably constant activity may be used for a
k
reasonably long period of studies.

lic
(iii) Half life period of the excited state: The half-life period of the excited source emitting the
y-radiation should be within the range 10-6 to 10-10 s which will determine the natural bandwidth
C
of the y-radiation (cf. hAy x t 1/2 ~ h).

(iv) Isomeric transition of the excited nuclide: The excited nuclide should decay (i.e. isomeric
transition) to the ground state predominantly via the path emitting the y-radiation used for the
study, i. e. if the excited nuclide decays in different routes of comparable importance, the nuclide
is not suitable for the MB studies.
(v) Natural abundance of the sample nuclide: The absorber nuclide should have the high natural
abundance. If its abundance is not so high then the sample enriched (artificially) with the desired
nuclide is to be used.
1. Electronic structure of the Fe-compounds and isomer shift: It has been shown that the isomer
shift depends on the s-electron density directly. Thus the p, d and f-electron which can screen the
s-electron density to be observed by the nucleus can only indirectly influence the isomer shift. Thus
effect of the s-electron density has a primary effect on the isomer shift while the effect of the electron
density in the p, d and f-orbitals has a secondary effect on the isomer shift.
Thus the estimation of isomer shift gives an idea regarding the s-electron density from which the
bonding character and oxidation state of iron can be realised.
For iron (i.e. 57Fe), Rgd ) Rex (i.e. the nuclear term fJR/R in the expression of isomer shift is
negative, cf. Sec. 12.4.4), and increase of s-electron density makes the chemical term more positive
and consequently, the isomer shift more negative. For the elemental iron, the electronic configuration
is: [Ne]3s 23p 6 3cf 4s 2 • For Fe(II), it is: [Ne]3s23p 6 3cJ6; for Fe(III), it is: [Ne]3s 2 3p 6 3tP; and so on. Thus
for the Fe-compounds, the higher oxidation state reduces the 3d-electron density (cl Fell: cJ6; FellI: d 5 ;
Fe IV : cf; Fev : d 3 ; FeVI (in ferrate FeOl-) : ~). Reduction in the 3d-electron density screens the
3s-electron less (i.e. removal of the 3d-electrons leads to decrease the shielding or screening of the
3s-electrons). Consequently, with the increase of the oxidation state, the 3s-electron density at the
nucleus increases and it makes the isomer shift more negative. It is illustrated in Fig. 12.4.7.1.
ry
I 21
ra
0 2 6 6
(d 7 ) Fe : [Ne] 3s 3p 3d 4s
ib
Fe(l)
yl
II
em
-1 .6 -0.8 a 0.8 1.6 2.4 8 (mm s-1)
Increasing trend of 3d-electron density (i.e. decreasing trend of 3s-electron density
at the nucleus due to the screening effect of the 3d-electrons)
ch
al
Fig. 12.4.7.1 Isomer shift (8 in mm S-I) relative to stainless steel for different oxidation states of iron (in high
e
spin-state, except for K3 [Fe(CN)6) and K4 [Fe(CN)6]); 8 :::: 0.1 mmls for Fell (low spin, S = 0); 8 :::: 0 mmls for FellI
th
1
(low spin, S =-2 ); 8 :::: 0.5 mmls for Fe I (S = 1/2, low spin); (ef dR or 8R is negative i.e. R gd ) Rex)'
e/
R R
2. Spin-free vs. spin-paired Fe(II) octahedral complexes: The spin-free (i.e. high-spin) complexes
t.m
e;
of Fe(ll) are having the electronic configuration fig while the electronic configuration of the low-spin
complexes of Fe(ll) is 4g • Thus even for the six identical ligands, in the high spin complexes (e.g.
e
[Fe(OH 2)6]2+ present in Mohr's salt), the asymmetric d-electron distribution in the t 2g level and
er
consequently, the Jahn-Teller distortion produces an electric field gradient (EFG) at the nucleus to
H
cause the quadrupole splitting of the MB signal into a doublet. For the low-spin complexes, if the six
ligands are identical (e.g. [Fe(CN)6]4-), there will be no quadrupole splitting of the MB signal because
k
lic
the symmetric electron distribution around the nucleus fails to produce any electric field gradient at the
nucleus. In fact, [Fe(CN)6]4- gives a singlet line in MB spectrum (Fig. 12.4.7.2). If the ligands are
C
nonequivalent as in [Fell(CN)5L]3-(C4v symmetry) (L = NH 3, H 20), then the noncubic ligand field

symmetry produces an electric field gradient at the nucleus to cause the quadrupole splitting of the MB
signal into a doublet even for the low spin Fe(ll) complex.
Thus we can conclude that the high spin complexes of Fe(II) always show the doublet signal (i.e.
quadruple splitting) and the low-spin complexes of Fe(II) show the doublet signal only when the
ligands are nonequivalent (see Figs. 12.4.5.2, 12.4.7.2).
In terms of the isomer-shift, the high-spin complexes of Fe(ll) bearing the a-donor ligands (i.e.
weak field ligands) like H 20, oxalate, CI-, etc. show the isomer shift in the range (0.9 to 1.4) mm S-I.
On the other hand, the low-spin complexes of Fe(ll) bearing the n-acid ligands (i.e. strong field ligands)
like CN-, NO+, etc. show the isomer shift in the range (0 to -0.3) mm S-I. Thus, the isomer shift for
the low-spin complexes are more negative while the isomer shift for the high spin complexes are
more positive. In fact, in the low-spin complexes, the n-acid ligands like NO+, CN- withdraw the
3d-electrons through the metal ~ ligand n-back bonding. It reduces the 3d electron density and
consequently, their screening effect on the 3s-electron is decreased. Thus, indirectly it enhances the
s-electron density at the nucleus and it makes the isomer shift more negative. On the other hand, the
a-donor ligands (generally present in the high spin complexes) enhance the d-electron density and it
makes the chemical shift more positive. "
FeCI 3 (anhydrous)
~c:
:3
ry
o
o (Spin-free) (Spin-free)
~I
ra
ib
-2.0 0 +2.0 +4.0 -1.0 0 +1.0 +2.0
yl
Doppler velocity (mm/s) Doppler velocity (mm/s)
em
(i) (ii)
ch
e al
th
e/
(Spin-paired) (Spin-paired)
t.m
e
-0.3 -0.2 -0.1 0 +0.1 +0.2 -0.4 -0.2 0 +0.2 +0.4

er
Doppler velocity (mm/s) Doppler velocity (mm/s)

(iv)
H
(iii)
Low-spin
k
lic
High-spin {
'---+ Fe3+[Fe (CN)6llll
C
(Berlin green)
~
en
(8 ~ 0.03 mm/s) (8 ~ 0.54 mm/s) 'E
:3
o
o
-1.0 0 +1.0 -4.0 0 +4.0

(v) (vi)
Fig. 12.4.7.2 Qualitative representation of the MB spectra of some representative high-spin and low spin Fe(II) and
Fe(III) complexes. (Note: For ferric ferricyanide (i.e. Berlin green) Fe[Fe(CN)6], quadrupole splitting of FellI in
[Fe(CN)6]3- not shown).
3. Spin-free vs. spin-paired Fe(III) octahedral complexes: In the high-spin complexes (~g ei), if
the ligands are identical, i. e. [FeIII L6], then the electron distribution and ligand distribution around the
metal centre are of cubic symmetry and there will be no quadrupole interaction to split the MB peak
(i.e. singlet peak will be noted). Of course, for the nonequivalence of the ligands, the high spin
complexes (e.g. [FeIIILsL'] will show the quadrupole splitting of the peak into a doublet. On the other
i),
hand, for the low-spin complexes (t2 even for the six identical ligands as in [Fe(CN)6]3-, there will
be a quadrupole splitting of the peak (i.e. doublet peak) because of the asymmetric distribution of the
electron clound around the metal centre and consequently the Jahn-Teller distortion.
• The isomer shift for the high-spin Fe(III)-complexes (where the ligands are mainly the a-donor
,ligands to increase the d-electron density on the metal centre and it will screen the 3s electron
density more i.e. 3s electron density at the nucleus will be decreased), is positive in the positive
ry
range (0.4 to 0.85) mm S-1 (cf. Rex < Rgd , dR or 8R is negative, i.e. more the s-electron density, more
ra
the positive value of the chemical term of the expression of chemical shift and more the negative
value of isomer shift for iron).
ib
• The isomer shift for the low-spin Fe(III) complexes (where the ligands are the 1t-acceptor
yl
ligands like CN-, NO+ etc. to decrease the d-electron density on the metal centre and it will
em
decrease to screen the 3s-electron to be experienced by the nucleus, i. e. 3s-electron density at the
nucleus is increased), is in the negative side (ca. -0.10 to -0.20 mm S-I).
ch
• Fe(III) (ds) vs. Fe(II) (d6) (both in high spin state): For the Fe(III) complexes (tP system), the
number of d-electron is less than that in the Fe(II) complexes (tf system). Consequently, in the
al
Fe(III) complexes, the 3s electron is relatively less screened by the 3d electrons and it makes the
e
3s electron density more available at the nucleus and it makes the isomer shift more negative (or
th
less positive) for the Fe(III) complexes compared to those for the Fe(II) complexes. This prediction
e/
is verified for the high spin Fe(III) and Fe(II) complexes. The isomer shift (8) (in mm S-I) relative
t.m
to the stainless steel at ordinary temperatures for the different Fe-compounds are:
high-spin Fe(II): -0.03 to + 1.35; high-spin Fe(III): -0.10 to +0.85
e
er
Table 12.4.7.1 Isomer shift (8 in mm S-I) for some Fe(II) and Fe(III) compounds.
H
High-spin Fe(II) (~g ei) Low-spin Fe(II) (l1g)

Compound ~ (mm S-l) Compound ~ (mm S-l)
k
lic
[ ~:~~
+1.18
C
-0.12
FeS04, (NH4hS04 . 6H 20 +1.2 - +1.3 Na3[Fe(CN)5(NH3)] -0.05 - -0.15
FeCI 2 ·4H20 +1.35 Zn[Fe(CN)5(NO)] -0.27
Fe(C 20 4) . 2H 20 +1.25 Na2[Fe(CN)5(NO)] -0.17
FeC 4H 40 6 +1.25 K2[Fe(CN)5(NO)] -0.27
High-spin Fe(III) (~g ei) Low-spin Fe(III) (tslg)

FeCl 3 ·6H20 +0.85 --0.15 )

FeCl 3 (anhydrous) +0.58 [ --0.10 - -0.15
Fe(N03)3 . 9H20 +0.42 -0.17
- 0.5 to 0.7
FeiC 20 4h +0.42
Fe203 +0.45
Fe2(C4H406h +0.42
Isomer shift direction for the iron complexes

• Rex < Rgd Le. nuclear term dR or 8R is negative.
• More the 3d-electron density, more the screening of the 3s-electron, less the 3s-electron density
experienced by the Fe-nucleus, less the positive value of chemical term, less the negative value
of isomer shift (8) i.e. more the positive value of isomer shift (8) (cf Fig. 12.4.7.1).
4. Low-spin Fe(II) complexes (t~g) vs. low-spin Fe(III) complexes (t~g): Low-spin Fe(III) (tig )
complexes always experience the quadrupole splitting of the peak while the low-spin Fe(II) complexes
experience the quadrupole splitting only when the ligands are nonequivalent to destroy the cubic
symmetry. It is expected that the isomer shift should be more negative for the low-spin Fe(III) com-
plexes (d5 ) compared to those found for the low-spin Fe(II) complexes (cf) because there are more d-
ry
electrons in the Fe(II) complexes but their isomer shifts are found very often in the same negative range
ra
and sometimes it may be more negative for the Fe(II) complexes (against the expectation in terms of the
ib
number of d-electrons) (cf. 8 values for K3[Fe(CN)6] and K4 [Fe(CN)6])'
yl
The above finding can be explained by considering the relative efficiency of the metal ~ ligand
em
x-bonding in the low-spin complexes of Fe(II) and Fe(III) (cf low-spin complexes are formed generally
for the strong n-acceptor ligands). The higher positive charge on Fe(III) disfavours more this n-back
ch
donation and definitely, this n-bonding metal ~ ligand is always favoured more for the lower oxidation
state. This is why, removal of 3d electron from the metal centre in this route is more in the Fe(II)
al
complexes to make the isomer shift more negative.

e
th
a(isomber shift): Low-spin complexes of Fe(lI) and Fe(lIl)

e/
(i) Number of d-electrons (3d6 vs. 3d5): The higher number of d-electrons in Fe(II) should
t.m
make a more positive for the Fe(II) complexes (compared to that of the Fe(III) complexes).
This prediction has been verified for the high spin of complexes of Fe(II) and Fe(III) but
e
not for their low-spin complexes.

er
(ii) Metal ~ Ligand x-bonding: In the low-spin complexes of Fe(II) and Fe(III), the ligands
H
(e.g. CN-, phen, etc.) are generally the n-acid ligands which withdraw the metal d-electrons
through the said n-back bonding. This n-bonding is more favoured for the lower exidation
k
state (+2). Thus the more d-electron depletion in this route from Fe(II) makes 8 less positive
lic
(i.e. more negative) (compared to that of the Fe(III) complexes).

C
(iii) Comparable a-values: Because of the above mentioned two opposing factors, the isomer
shift for the low-spin complexes of Fe(II) and Fe(III) becomes comparable.
(iv) a (Fell, I.s.) == a (FellI, I.s.) (negative value, generally found)
a (Fell, h.s.) ) a (FellI, h.s.) (positive value, generally found).
a(Isomer shift): Low-spin and high spin complexes of Fe(l) and Fe (IV)
(i) Fe(I): 8 '" 2.2 mm1s for high spin (tige;, s = %); 8 '" 0.5 mmls for low spin (t~ge~ ,S = ~) .
(ii) Fe(IV): 8 '" 0 mmls for high spin (t1g e~. S = 2); 8 '" -0.2 mm1s for low spin (ti g, S= I) ;
(values relative to metallic iron); difficult to distinguish the h.s. and I.s. states; for Fe(IV),
metal to ligand n-bonding is not important.
• [Fe(CN)6]3- vs. [Fe(CN)6]4-: In terms of the formal oxidation states, [Fe(CN)6]3- bears Fe(III)
while [Fe(CN)6]4- bears Fe(II) but in terms of isomer shift (8) (~- 0.15 mm S-I, Table 12.4.7.1),
the real oxidation states in these two complexes do not differ so much.
5. Determination of the order/sequence of n-acceptance property of the ligands: It has been

already pointed out the importance of metal~ligand n-back bonding to determine the isomer shift. To
determine the relative efficiency of the n-acceptance of the different n-acid ligands (L), the isomer shift
of the low-spin complexes of [FeII (CN)5(L)]n- is to be considered. Better the Fell (d) ~ L n-back
bonding (i.e. more the removal of the metal d-electron), more the negative isomer shift. This
principle may exploited to determine the relative n-acceptance properties of the ligands (L). From the
observed isomer shift, the following order of n-accepting efficiency of the ligands has been noticed.
ry
NO+ ) CO ) CN- ) 5032- ) PPh3 ) N0 2- ) NH3
ra
(Strong n-acceptor ligands: NO+, CO)
ib
6. Magnitude of quadrupole splitting (AEQ) and n-aceptance/a-donor property of the ligands:
yl
Let us take the following examples:
em
Fe-complex ch
(i) FeCI 2 · 4H 20
1.35 3.0
al
i.e. [FeCI2(OH2)4](tigei)
(ii) Na2[Fe(CN)5(NO)] (t~g)
e
-0.17 to -0.28 1.76

th
(iii) Na3[Fe(CN)5(NH3)] (t~g) -0.05 0.60

e/
Isomer shift (8) is generally more negative for the low-spin complexes (compared to that of the high-
t.m
spin complexes) because of the d-electron removal from the metal centre through the metal ~ ligand
n-back bonding. This aspect has been already discussed.
e
In all the above mentioned complexes, the noncubic ligand environment (due to the nonequivalence
er
of the ligands) leads to the nonspherical (i. e. asymmetric) distribution of the electron cloud around the
H
Fe-nucleus to cause the quadrupole spilitting of the MB signal (i.e. splitting into a doublet peak).
The magnitude of quadrupole splitting (~Q) is mainly determined by the electric field gradient
k
lic
(EFG) produced at the nucleus due to the asymmetric distribution of the electron cloud around the
nucleus. In the high spin complex, FeCl 2 . 4H 20 (t~gei) having the good a-donor ligands, the electron
C
density around the nucleus is not only high but the degree of asymmetry in the electron cloud
distribution is also very high. Here the asymmetry in electron cloud distribution arises due to the
following factors:
(a) The electron distribution (t~g ei) is itself asymmetric.
(b) The asymmetric distribution of electron cloud in the 12g level (i.e. t~g) causes the inherent Jahn-
Teller distortion which makes the electron distribution more asymmetric.
(c) The degree of nonequivalence in ligand distribution in the complex (i) is 4:2 while it is 5: 1 in the
remaining two complexes. Thus the degree of ligand nonequivalence in the complex (i) is more.
Because of this higher degree of asymmetry in electron distribution in FeCI 2 • 4H20, and higher
electron density at the metal centre (due to the good a-donor ligands), the EFG is high and
consequently, the magnitude of quadrupole splitting is higher. In the low-spin cumplexes (ii and iii),
the n-acceptor ligands like CN-, NO+ deplete the d-electron density around the nucleus. Here the
electron distribution in the t 2g -level is itself symmetric (i.e. rqg). Here the asymmetry in electron
distribution arises only from the ligand nonequivalence which gives the C4v symmetry. Thus, in the
complexes (ii) and (iii), not only the electron density around the nucleus is less but the degree of
asymmetry in electron distribution is also less. These make the quadrupole splitting less (compared to
that in the compound (i».
Between the complexes (ii) and (iii), NH3 (in complex iii) is a a-donor ligand to enhance the electron
density in the d-orbitals around the metal centre but NO+ (in complex ii) is a very powerfuln-acceptor
ligand (probably one or-the strongest ones) to reduce the electron density in the d-orbitals around the
Fe-nucleus. It makes 8 (isomer shift) for the complex (ii) more negative (compared to that of iii). The
electron withdrawal through the Fe ~ NO linkage causes an imbalance in the electron distribu-
tion around the Fe-nucleus. This asymmetric electron distribution around the Fe-nucleus mainly due
to the heavy electron withdrawal in one direction (i.e. along the Fe~N-O linkage which is almost
ry
linear) produces a higher electric field gradient (EFG) at the nucleus to cause the higher quadrupole
ra
splitting (compared to that of iii). The above arguments. explain the order of dEQ.
AEQ : FeCl2 . 4H20 ) Na2[Fe(CN)5(NO)] ) Na3[Fe(CN)5(NH3)]
ib
yl
Explain: ~EQ (Fell) ) ) ~Q (FellI) in Fe-S proteins; (see Sec. 12.4.7; Example 23)
em
7. Structure of Prussian blue and Thrnbull blue: Prussian blue is obtained by the reaction of a
ch
Fe(III)-salt with ~[Fe(CN)6] in an aqueous solution while Turnbull blue is obtained by the reaction of
a Fe(II)-salt with K3[Fe(CN)6] in an aqueous solution. The MB spectra of both the blues are identical
al
and it indicates that the compounds are identical. The MB studies indicate that in these two compounds,
e
Fe(II) remains in a low-spin state (~g) while Fe(III) remains in a high-spin state (~g ei'). The structural
th
features of this polymeric compound have been discussed in Secs. 1.12, 1.14.
e/
8. Structure of sodium nitroprusside Na2 [Fe(CN)s(NO)]: To explain the diamagnetic behaviour of

the complex, it was proposed the existence of low-spin Fe2+(~g) and NO+. The ligand nonequivalence
t.m
in [Fe(CN)5(NO)]2- (C 4v ) leads to the quadrupole splitting of the MB signal into a doublet. The MB
spectroscopy of the complex anion shows a doublet (~Q : .: : in the range 1.76 to 1.85 mm S-I, separation
e
between the peaks of the doublet) and the isomer shift (8) in the range -0.165 to -0.28 mm S-l which
er
indicates the existence of low spin Fe(IV) (tig ). Existence of Fe(IV) leads to conclude the existence of
H
NO as NO-. Thus the MB spectroscopic data support the nitroprusside complex ion to be constituted
k
by NO- (two unpaired electrons in the ABMO of NO) and Fe(IV) (tig , two unpaired electrons). The
lic
prediction of this composition faces the following problems:

(i) Oxidation of Fe(III) by NO (i.e. FellI + NO ~ Felv + NO-) should be strongly discouraged in
C
the presence of so many n-acid ligands (i. e. 5 CN- ligands) which do not prefer the higher
oxidation state because for the higher oxidation state, the metal ~ ligand n bonding is disfavoured.
(ii) The diamagnetic character of the complex cannot be explained as such. It needs the consideration
of antiferromagnetic coupling between the two unpaired t2g -electrons and two unpaired n*-electrons
of triplet NO- (isoelectronic with O2) to explain the diamagnetic character.
(iii) The high NO stretching frequency in nitroprusside, v N- O = 1939 cm- 1 (cf. v N- O = 1876 cm- 1 in
free NO; =2300 cm- 1 in NO+;::.::: 1500 - 1600 cm- 1 in NO-) does not support the existence ofNO-
in the complex. .
To tackle the above theoretical objections, it has been proposed that in the nitroprusside ion, NO
exists as NO+ to cause the reduction of Fe(III) to Fe(II) (i.e. NO + FellI ~ NO+ + Fell) and this lower
oxidation state of iron is strongly favoured by the n-acid ligands (i.e. 5 CN- and NO+ which is a very
powerful1t-acceptor ligand). It makes a linear Fe-N-O linkage (bond angle::.::: 178°) which allows
an extensive n bonding between the filled metal t 2g -orbital and the vacant n*-MO ofNO+ (Fig. 12.4.7.3).
This allows the removal of metal d-electron. In fact, this n-bonding interaction produces the BMO
which is enriched in the character of n*-MO of NO+ and thus the placement of the electrons into this
n-BMO effectively leads to the loss of metal d-electron and gain of electron by NO+. This efficient
removal of d-electron (more correctly t2g -electron) through the n-bonding leads to the decreased shielding
(i.e. screening) of the 3s electron by the 3d-electrons' and effectively 8 (isomer shift) approaches to
that of Fe(IV) (as found in the MB studies).
~~ [)
~!\~l=
V ~ \J
0""
ry
ra
Fig. 12.4.7.3 Fe lI (t2g ) ~ NO+(n*) back bonding leading to the removal of metal d-electrons
ib
Existence of the paired electrons in the n-BMOs (ef t~g, and vacant n* of NO) explains the diamag-
yl
netic character. Gain of electron from the metal centre by NO+ through the n-bonding explains the
lower v NO value (1939 cm- I ) compared to that of free NO+ (v NO = 2300 cm- I )
em
9. Identification of the oxidation state of iron in terms of isomer shift (B) (relative to that of
Na2[Fe(CN)s(NO)] · 2H20): The Fe(II)-salicylaldoximate chelates originally proposed are now identified
ch
as the Fe(III)-salicylaldoximate chelates by considering their isomer shifts ea. 0.65 mm S-I relative to
al
that of nitroprusside. Similarly, brown ring complex, previously supposed to be a complex of Fe(l) is
e
now believed to be a Fe(lll) (high spin) complex.

th
e/
Table 12.4.7.2 Isomer shifts (8 in mm S-l) for different oxidation states (high spin) of iron (relative to that
of Na2[Fe(CN)5(NO)]. 2H 20 i.e. SNP)
t.m
Oxidation state: +6 +4 +3 +2 +1
-8: -0.6
e
+0.2 +0.7 +1.4 +2.2

er
10. Brown ring complex, [Fe(NO)(OH 2)s]2+ (ef R. van Eldik et al., Inorg. Chern., 41, 4-10, 2002) :
H
This complex is prepared by the reaction of NO with Fe(aq)2+. There are two propositions regarding the
composition of the complex. These are: complex of Fe(I) and NO+ (i.e. reduction of Fell by NO);
k
complex of Fe(III) and NO- (oxidation of Fell by NO). The ir-data and magnetic data are v NO = 1777
lic
cm- 1 and J.!obs = 3.8 BM. If it is considered to be constituted by high spin Fe(I) (cfl i.e. ~g ei having
C
3 unpaired electrons leading to J.!spin:::::: 3.87 BM) and NO+ (no unpaired electron), then the magnetic data
can be explained and the relatively lower v NO value compared to that of free NO+ (ef
v N- O = 2300 cm- 1 for free NO+) arises due to the metal ~ n*-MO (NO+) back bonding i.e. gain of
electron into the n*-MO of NO+ reduces the vNO value. But there is a strong theoretical objection
against composition of Fe(l) and NO+, i.e. reduction of.Fe(ll) by NO. The other remaining 5 ligands are
the good a-donor ligands (5H 20) which should strongly discourage the reduction of the metal centre
(ef in nitroprusside, presence of the 5 n-acid ligands i.e. 5 CN- encourages the reduction of FellI to Fell
=
by NO). Moreover, the isomer shift ofMB spectral data (doublet peak with AEQ 2.1 mm S-l, 8 0.76 =
mm S-l) does not support the +1 oxidation state ofiro'.' but supports the +3 oxidation state (high-spin)
of iron (ef Fig. 12.4.7.1, Tables 12.4.7.1-2).
It has been suggested that the brown ring complex is containing Fe(III) (high spin i.e. ~gei bearing
5 unpaired electrons, S = ~ ) and triplet NO- iso~lectronic with O2 (two unpaired electrons in the
SPECTROSCOpiC METHODS AND OTHER PHYSICAL METHODS IN CHEMISTRY 1971
n*-MO, S = 1) and these two centres (S =~ and S = 1) are antiferromagnetically coupled to give the
2
spin quartet ground state (s =%) which can explain both the ESR data and magnetic data. This anti-
ferromagnetic coupling removes partially the electron cloud from the n*-MO of NO- to the metalcentre.
This makes the VN-O (1777 em-I) relatively higher than that expected for free NO- (VNO = 1500-
1600 em-I).
11. Identification of cis-trans isomers: The electric field gradient (EFG) at the nucleus can cause
the quadrupole splitting. The higher EFG value can cause the higher quadrupole splitting (i. e. LlliQ
becomes higher for the higher EFG value). The higher EFG value for the trans-compounds probably
/arises from the higher inequivalence of the hybrid orbitals holding the ligands (ef cis-[R2SnX4J vs.
ry
trans-[R2 SnX 4 J, discussed later). Generally it has been found for MA4B2 (cis: C 2v ; trans: D4h ) that the
ra
I ratio of the EFG values in the cis- and trans- isomers is 1:2 and the EFG values are of opposite sign.
It makes:
ib
yl
tiEQ (cis) 1
em
tiEQ (trans) - 2
It helps to identify the cis- and trans isomers of iron and tin compounds. Some examples are given
ch
below.
al
cis- [FeC12(CNAr)4] -0.78

e
th
trans- [FeC1 2(CNAr )4] +1.58

e/
cis- [Fe(CN)2(CNEt )4] +0.30

t.m
trans-[Fe(CN)2(CNEt)4] -0.60
cis-[Fe(CNAr)iSnC1 3h] 0.50 , (predicted value -0.52)
trans-[Fe(CNAr)4(SnC1 3h] +1.10
e
er
12. [Fe(acac)3]: MB spectroscopic data at an ordinary pressure indicate the presence of Fe(III) but
H
at high pressure (ca. 165 kbar), it indicates the presence of Fe(II). This change is reversible i.e. release
k
of pressure gives back Fe(III). Probably, at high pressure, the acae moiety transfers its electron to the
lic
metal centre i.e. Fe(III). :

13. [Fe3(CO)12]; [Fe2(CO)9] and [Fe(CO)s] (Refs. R.H. Herber et aI, [norge Chern., 2, 153, 1963; 3,
C
101, 1964): [Fe(CO)5J (TBP, D 3h ) shows a doublet MB signal (see Fig. 12.4.7.2) due to the quadrupole
splitting. In [Fe2(CO)9)], both the Fe-centres are equivalent arid the noncubic ligand environment gives
the quadrupole splitting of the peak. The MB spectrum of [Fe3(CO)12J (Fig. 12.4.7.4) shows 4 lines
i.e. two doublets (one large doublet i.e. outer doublet and a small doublet i.e. inner doublet) with the
approximate ratio of the areas of the doublets, 2: 1.
The important features of the MB spectrum of [Fe3(CO)12] are:
(i) The large outer doublet having a large quadrupole splitting (i.e. ~EQ:::: 1.2 rom S-I) represents
the Fe-nuclei having the relatively more asymmetric electron cloud distribution.
(ii) The inner two peaks represent the inner doublet having ~EQ :::: 0.2 mm s-I(i.e. very small
quadrupole splitting) corresponds to the Fe-centre having the less asymmetric electron cloud
distribution.
(iii) Peak area ratio, outer doublet: inner doublet =2 : 1, LlliQ (outer doublet) (-1.2 mm » LlliQ (inner
doublet) (:::: 0.2 rom S-I)
It indicates that in [Fe3(CO)12] there are two types of Fe-centres in the ratio 2: 1. The MB spectrum
(Fig. 12.4.7.4b) clearly rules out the structure having three equivalent iron centres which could produce
maximum two MB lines (i.e. one doublet) in absence of magnetic hyperfine splitting. However, there
may be more than one structure to maintain the two types of iron-centre in the ratio 2: 1.
Thus the theoretically proposed structures (i and ii in Fig. 12.4.7.4a) having all the three Fe-centres
equivalent cannot explain the MB spectrum. In the proposed structure (iii), there are two types of iron
centres but Fe(b) remaining in an octahedral ligand field is expected not to undergo the quadrupole
o
II
oc'" /C"'" /co
> ."c
ry
OC- Fe~Fe-CO :> Bridging CO
ra
OC/ "':::::..C-::/' "'co I.e./=o
ib
II
yl
o
em
[Fe(CO)s] [Fe 2(CO)g], equivalent iron centres
(One doublet MB peak) (One doublet MB peak)
ch
e al
Bridging CO
."c
th
e/
I.eo/ =0
t.m
(i) [Fe 3 (CO)12]' one type of Fe (ii) [Fe 3 (CO)12]' one type of Fe
(i. e. one doublet MB peak is expected) (i.e. one doublet peak is expected)
e
er
OC CO
OC~~co
H
OC CO
OC~Vco \..:> Bridging CO
k
/Fe~
lic
Fe (b) /
I.e./c= 0
."
.", ~
OC"'/~ /co
C
/Fe(b)
,)-/JFe (a)
~Fe
OCOC /' (a)~• /(ai'. CO
Fe-CO
OC 7\'co (v) (crystal structure)

oc CO
\.......__(_iv_) ----..., _--------J
V
(iii) [Fe3 (CO)12]' two types of iron (a) [Fe3(CO)12], two types of iron (a, b);
and (b); Fe(b) almost in an octahedral two doublets are expected.
geometry (i.e. no quadrupole splitting)-
single line; Fe(a) - one doublet peak
Fig. 12.4.7.4\ (a) Structures of [Fe(COh], [FeiCO)9] and probable structures of [Fe3(CO)12]'
Outer doublet
with a larger ~Ea
Peak area ratio

Outer doublet:
Inner doublet = 2:1
ry
ra
ib
yl
-0.5 o +0.5 +1.0 +1.5
em
Relative velocity (mm/s)
ch
Fig. 12.4.7.4 (b) MB spectrum of [Fe3(CO) 12]
splitting, i.e. structure (iii) is expected to give a doublet (for the Fe(a) centres) and a singlet peak (for
al
Fe(b») (ef observed MB spectrum indicates two doublets). Both the structures (iv) and (v) having two
e
th
different types of Fe centres (with the noncubic ligand fields) can produce two doublet peaks. Thus
the MB spectrum cannot distinguish these two possibilities. However, the actual crystal structure (v)
e/
explains the two doublets in the MB spectrum.

t.m
14. High-spin ~ Low-spin equilibrium in Fe(II) and Fe(III) complexes: The equilibria are:
(tige; ) ~ Low-spin (tgg)

e
Fe(II): High-spin
er
(Quadrupole splitting) (No quadrupole splitting,

if the ligands are identical)
H
k
Fe(III): High-spin (tige;) ~ Low-spin (t~g)

lic
(No quadrupole splitting, (Quadrupole splitting)

C
if the ligands are identical)
The isomer shifts are also different for the high-spin and low-spin states (8: more negative for the
low-spin states, ef earlier discussion). Thus the MB spectral features can be exploited to identify the
existence of high-spin ~ low-spin equilibrium for the Fe(II) and Fe(III) complexes. Here it must be
mentioned that to characterise the both forms in an equilibrium mixture by the MB spectroscopy, the
isomers must be long-lived in the Mossbauer time scale, i.e. the life time of the species to be characterised
by the MB spectroscopy must be greater than 10-9s.
15. Characterisation of the oxidation state of So in its different compounds: The electronic
configuration Sn in its elemental state is: [Ar]3d 10 4s2 4p6 4d lO 5s2 5p 2. The amount of 4s and 5s electron
density experienced by the Sn nucleus depend on the chemical state of Sn. It has been already pointed
out (Sec. 12.4.4) that with the increase of s-electron density, the isomer shift (8) becomes more
OR
positive (ef - is positive i.e. Rex> Rgd ). For the Sn(IV) (5so 5po) compounds, the isomer shift is about
R
1974 FUNDAMENTAL CONCERtS OF INORGANIC CHEMISTRY
2.7 to 3.5 mm S-1 less positive than that found for the Sn(ll) (5s 2 5p O) compounds. The magnitude of
isomer shift depends on the electronnegativity of the groups or atoms attached with the metal centre.
Higher electronegativity of the group withdraws the more electron density from the metal centre to
decrease the 8-value more (ef. less the s-electron density, less the posi~ve 8-value, i.e. shifting of 8
towards the negative direction). Empirically, the following relations have been established.
[SnX 4 ](sp3_Sn): 8 (mm S-I) = 4.82 - 1.27Xp (X)
[SnX 6 ]2-(sp 3£i2-Sn): 8 (mm S-I) = 4.27 - 1. 16Xp (X)
• 0 ([SnX4]) ) 0 ([SnX6]2-): Addition of two extra ligands (i.e. X") to SnX4 is expected to increase
the electron density around Sn to enhance the isomer shift. But the experimental findings do not
support this prediction. It can be rationalised by considering the bond lengthening effect (ef Sn-X
ry
bond is longer in [SnX 6]2- than that in [SnX4]) and the change of hybridisation (ef. approximately Sp3,
i.e. 25% s-character, in SnX4, and approximately sp3£i2 i.e. 16.6% s-character, or the multicentred
ra
bonding by using the p-orbitals in [SnX 6]2-, ef Chapter 9, Vol. 2). The bond lengthening in [SnX 6]2- due
ib
to the increased steric crowding and average less s-orbital character of Sn in the Sn-X bond of
yl
[SnX 6]2- leads to the less electron receiving by Sn in its Ss-orbital from the ligands in [SnX 6]2-
em
(compared to SnX4). This explains the observed isomer shifts.
The relative increase in the p-character of the hybrid orbitals of Sn in [SnX 6]2- enhances the electron
ch
density in the p-orbitals of Sn through the receiving electron from the ligf'.nds (i.e. Lewis bases).
This causes more screening of the 5s electrons by the increased p-electron density of Sn to decrease the
al
isomer shift in [SnX6]2-. This also explains the isomer shift order.
e
• 0 (trans-[R 2SnX4 ] ( 0 [R2SnX2]: This order can be explained in the same way as in the case of
th
[SnX4] vs. [SnX6]2- (i.e. sp3 vs. sp3J2). Here it is to be mentioned that the 5s electron density of Sn is
e/
mainly concentrated along the Sn-C bonds. Use of the sp3£i2 hybrid orbitals (16.6% s-character)
t.m
indicates the relatively less electron receiving in the 5s-orbital of Sn from the ligands compared to the
compounds where Sn uses the sp3-hybrid orbitals (25% s-character). This less electron receiving in the
Ss-orbitals of Sn in [R2SnX4] makes 0 relatively less. Use of more p-character and d-character in the
e
er
hybrid orbitals (projected towards the Sn-X bonds in trans-[R 2SnX4 ] , cf Bent's rule) of Sn in [R2SnX4]
causes an enhanced electron density in the p- and d- orbitals and this causes more screening of the
H
Ss electrons. It makes also the isomer shift (0) less for trans-[R 2 SnX4 ].
k
• Relative isomer shifts in [SnBr4X2]2- (X = F, CI, Br, I): In these 6-coordinate complexes of
lic
Sn(IV), the metal centre (Sn IV ) receives electron from the ligands which act as the Lewis bases. Obvously,
C
Sn(IV) receives less electron in its valence orbitals (4d, 5s and 5p; probably sp3J2 hybrid orbitals) from
the more electronegative ligands. The effect of electronegativity of the groups attached to Sn on the
isomer shift (8) is illustrated in the following examples:
Complex 0 (mm S-l) 'XP (X)
(Et4N)2[SnBr4P2] on 0.53
c:
(Et4N)2[SnBr4CI2] Or;) ~ 0.77
~ ~
(Et4N)2[SnBr6] b.... 0.84
~
(Et4N)2[SnBr412] 0.96
The complex anion, [SnBr4X2]2- is supposed to bear the sp3J2 hybridised Sn(IV) i.e. all these anions
where X- = P-, CI-, Br-, 1- are structurally similar. In moving from X- = P- to X- = 1-, the electron
accumulation at the metal centre gradually increases (ef electronegativity order: P ) Cl ) Br ) 1). Thus
the electron density and consequently the s-electron density (which determines the magnitude of 8) is
maximum in the iodido complex while it is minimum in the fluorido complex. It explains the order of
8 i.e. highest value for the iodido complex and the lowest value for the fluorido complex.
Note: No equadrupole splitting is found in the MB spectrum of [SnBr2CI4]2- and [SnBr4CI2]2-.
It indicates that the unsymmetrical ligand substitution in the present octahedral species is not suffi-
ciently high to cause the electric field gradient (EFG) big enough to cause any detectable quadrupole
splitting.
• Sn(II) vs. Sn(IV) compounds: In Sn2+ (5s 2 ), the 5s-electron density at the nucleus is more than
that in the Sn-atom (5s 2 5p2) because the screening effect of the p-electrons in Sn 2+ is absent. In Sn4+
(5so), the 5s-electrons have been removed and the s-electron density at the nucleus is reduced. In
general, for 119Sn (8R/R is positive), the isomer shift of the Sn(II) compounds becomes greater than
2 mm S-l while it lies below 2 mm S-l for the Sn(IV) compounds (both relative to Sn02)' This may
ry
qualitatively help to identify the oxidation states of So.
ra
ib
SnF4 -0.47 SnS 3.15
yl
Na2[SnF6] -0.49 SnS04 3.90
em
SnC1 4 0.85 SnF2 (orthorhombic) 3.20
SnBr4 1.15 SnCl 2 4.05
ch
SnI4 1.55 SnBr2 3.95
al
SnMe4 1.20 SnI 2 3.85
SnPh4 1.22 Sn(CsHsh 3.75
e
th
Isomer shifts relative to Sn02'

e/
The isomer shift of (SnPh2)n (polymeric form) is 1.55 mm S-l which indicates the oxidation state of
t.m
Sn as +4 not +2 (though apparently indicated so). Thus comparison of the isomer shift helps to identify
the oxidation state of tin.
• Order of isomer shifts in R 2SnX2 and R 3SnX (X = F, CI, Br, I): It follows the order: 8 (I) )
e
8 (Br) ) 8 (CI) ) 8 (F) i.e. with the increase of electronegativity of X, the isomer shift decreases as
er
expected.
H
Note: If the electronegativity of X can direct Sn to change its state of hybridisation, then the
k
prediction of the direction of Dfrom the knowledge of electron depletion by the electronegativity
lic
effect of X will not be correct. It will be illustrated below, by taking the mixed ligand organotin
C
compounds).
• 8: [R4Sn] ( [R3SnX] ( [R2SnX2] (X = F, CI, Dr, I): With the increase of the number of the
electronegative substituent X, the isomer shift increases. It is illustrated:
[Me4Sn] [Me3SnCI] [Me2SnCI2]
8 (mm S-l): 1.20 1.47 1.56
If we consider the additive effect of the electronegativity of X, then with the increase of he number
of X, there will be a more electron depletion from the Sn-centre to decrease the isomer shift more.
How0ver, the experimental findings do not support this prediction from the additive effect of
electronegativity. To explain the experimental finding, it is required to consider the inequivalence of the
ligands (specially in the mixed ligand organotin complexes) to change the mode of hybridisation at
the Sn-centre.
According to Bent's rule (cf Chapters 9, 8; Vol. 2), the more-electronegative groups (i.e. X) will try
to use the more p-orbital enriched (i.e. less s-orbital enriched) hybrid orbitals of Sn. Consequently, the
more s-orbital enriched hybrid orbitals of Sn will be projected towards the less electronegative R
groups. It is indicated by the increase of C-Sn-C bond angle (from 109° ~ 180°) with the increase
of the additive electronegativity of X, i. e. with the increase of the number of X and increase of
electronegativity of X, the C-Sn-C bond angle opens up. This opening of the C-Sn-C bond
angle indicates the localisation of the 5s-electron on Sn along the Sn-C bonds. This explains the
trend of isomer shift:
[R4Sn] ( [R3SnX] ( [R2SnX2] (cf C-Sn-C bond angle sequence: [R4Sn] ( [R3SnX] ( [R2SnX 2])
• cis-[R2SnX4l (8 = 0.7 - 1.0 mm/s) vs. trans-[R2SnX 4 l (8 = 1.2 - 1.6 mm/s): According to the
Bent's rule, the more s-character enriched hybrid orbitals of Sn are projected towards the less
electronegative R-groups while the more p-character enriched hybrid orbitals of Sn are projected
towards the more electronegative X-groups. It leads to: localisation of the 5s-electrons on Sn
ry
along the Sn-R bonds and receiving of electrons by Sn in its p-character enriched hybrid
ra
orbitals from the X-groups (i.e. ligands) (cf increase in the p-electron density screens the
s-electrons more). Now let us compare the said cis- and trans- isomers.
ib
In the trans-compound, the C-Sn-C bond angle is close to 180° (i.e. 5s-electrons of Sn more
yl
concentrated on Sn along the Sn-C bonds) while the corresponding bond angle in the cis-
em
isomer is far less than 1800 • In the trans-compound (C-Sn-C bond angle -- 180°), approximately
the sp-hybrid orbitals of Sn are involved to make the two trans- Sn-C bonds, i.e. the 5s electron
ch
of Sn gets almost completely localised along the two trans-axial Sn-C bonds. On the other
hand, for the cis-compounds (C-Sn-C bond angle « 180°), the hybrid orbitals making the
al
Sn-C bonds bear relatively less 5s-orbitals of Sn i.e. the 5s-electron of Sn in the cis-compound
e
is less localised. This inequivalence of the hybrid orbitals of Sn towards the different ligands
th
leading to the localisation of 5s-electron density of Sn to different degrees in the cis- and trans-
e/
isomers can explain the order of isomer shift.

t.m
Sn-Compounds: Additive electronegativity effect vs. inequivalence of the hybrid

orbitals in controlling the isomer shift.
e
er
(a) It has been evident from the above discussion that for a giv~n coordination number, if all the
H
ligands are similar in electronegativity or hardness and mode of hybridisation of Sn remains

the same for the series of compounds, then the effect of additive electronegativity will determine
k
the order of isomer shift as in the cases of (i) [SnX4]; (ii) [SnX6]2-; (iii) [R2SnX 2]; (iv) [R 3SnX];
lic
(v) [SnBr4X2]2-, etc. for X = F, CI, Br, I

C
(b) In the mixed ligand organotin compounds, as for the series (i) [R4Sn], [R3SnX] and [R2SnX2];
(ii) cis- and trans- isomers of [R 2SnX4], the inequivalence of the hybrid orbitals towards the
different ligands becomes the important factor to control the isomer shift. In such cases, locali-
sation of the 5s electron on Sn will increase the isomer shift and the demand of additive
electronegativity may be denied.
16. 12CI 6 vs. I2Br2CI4 (Ref. M. Pasternak et aI, J. Chem. Phys. 48, 1997, 1968): The covalently
bonded 12Cl6 possess a planar bridge structure where both the I-centres are equivalent. For 1291,
the ground and excited states are characterised by I = '2 (i.e.

2
m/ = ±2,2 ±~,2 ±~,2 ± -.!..)
2
and
25 (.I.e., m/ = ±2'
5 3
±2' ±21) respectively. Thus the noncubic chemical environment gives a complex
pattern of quadrupole splitting into 8 components for the transition I = '2 ~ I = ~ maintaining
2 2
CI~/B~/CI
/I~/I~
CI Br CI
(b) D2h
ry
ra
ib
yl
em
Fig. 12.4.7.5 (a) Structures of I2Cl 6 and some possible structures of I2Br2C14'
ch
• One set of lines ~ both the I-atoms equivalent
al
• Two set of lines ~ I-atoms nonequivalent.
• 8 ~ 3.5 mm/s • 8 (I a ) ~ 3.5 mm/s; 8 (I b) ~ 2.8 mm/s
e
(structure d, Fig. 12.4.7.5a)

th
e/
r
t.m
u
Q)
en
e
Q5
er
0-
en
'E
H
::::J
o
()
k
lic
Q
Q
C
Doppler velocity
Fig. 12.4.7.5 (b) Comparison of the partial 129I_MB spectrum of I2Cl6 and 12Br2C14'
Note: 3 quadrupole splitting components (P, Q, R) out of the 8 quadrupole components are shown for I 2C1 6 • Both the
I-centres being equivalent shows only one signal which is split into 8 components (P, Q, R, ... ) due to the quadrupole
interaction. In I 2Br2C1 4 , two I-centres being nonequivalent show two MB signals and each signal is split into 8 compo-
nents (P, Q, R, ... ; p', Q', R', ... i.e. P, Q, R, ....... represent one I-centre identical to the I-centre of 12Cl 6 and p', Q', R'
...... represent the other I-centre). R' remains hidden under the shoulder of Q.
~ml = 0, ±1 (ef Fig. 12.4.5.1). For 12Br2C1 4, different possible bridge structures may be proposed (Fig.
12.4.7.5a) but the correct one may be identified by the MB spectroscopy for 1291. MB spectroscopy
results indicate that in 12Br2C14, the two iodine centres are in different environments (i.e. two
different sets of signals having appreciably different isomer shift values) and one I-centre in
12Br2CI4 is identical to the I-centre present in 12C1 6 -
In the possible structures (b) and (c) of I2Br2C14, the I-centres are equivalent and they cannot explain
the MB spectrum of 12Br2C14. The structure (d) shows the presence of two iodine centres in different
environments and it is in conformity with the observed MB spectrum (Fig. 12.4.7.5b). Here it may be
noted that in the structure (d) of 12Br2C14, one iodine centre (Ia ) is approximately identical to the iodine
of 12C1 6 •
17. IF6+vs. IF6-: The MB spectrum of 1291for (IF6)+(AsF6)- shows a single line without any quadrupole
splitting. It indicates the octahedral symmetry of the cation 1Ft. The MB spectrum of 1291 for IF6- in
CsIF6 (supposed to be Cs+ IF6-) shows the quadrupole splitting (expected into 8 components) which
is almost symmetrical. It indicates the noncubic symmetry in IF6-. IF6- actually represents a pentagonal
bipyramidal structure where one basal position is occupied by a stereochemically active lone pair.
This noncubic symmetry causes the quadrupole splitting which indirectly supports the presence of a
ry
stereochemically active lone pair. If the lone pair were stereochemically inactive (to be housed in the
ra
inner s-orbital which is spherically symmetric) then IF6- would have adopted the cubic symmetry to
deny the quadrupole splitting of the MB signal.
ib
• TeF~- vs. IF6" (stereochemically inactive lone pair vs. stereochemically active long pair):
yl
129Te-MB spectrum of TeX 62- indicates no quadrupole splitting. It supports the perfect octahedral
em
structure of TeX~- Le. the stereochemically inactive lone pair is housed in the inner 5s orbital. But the
quadruple splitting in the 1291_MB spectrum of IF6- (isoelectronic with XeF6) indicates the presence of
ch
the stereochemically active lone pair, i.e. structure of IF6- is not octahedral.
e al
th
e/
t.m
IF;(EFG = 0)
c.> No quadrupole splitting
e
Q)
en
er
Q5
a.
en
H
C
::J
o
k
()
lic
IF~ (EFG ~ 0) F
(Quadrupole splitting)
C
Stereochemically
F- - - - - - - - - - - -- active lone pair
//~
Doppler velocity
i
(a)
I
F\ , ,
,,
I --------
........
........
~
........ F
........
,, ...
, .... ........
F ....
(b)
129
Fig. 12.4.7.6 (a) Partial 1 MB spectra ofIF6+ and IF6-; (b) structures ofIF6+ (octahedral i.e. cubic symmetry) and IF6-
(noncubic symmetry).
18. Structure of 13-: MB spectroscopic study of 1291 in the compounds like Cs1 3, indicates the
presence of two types of l-centres, i. e. two different signals having the intensity ratio 2: 1. Thus any
structure proposing the equivalent I-centres is not acceptable. The linear structure of 13- is in conformity
with the MB studies and it is also supported by the crystal structure.
19. XeCI4 and XeF4 : The ~-decay product of K[129ICI4]·H20 is XeCI4. Comparison with the
129Xe-MB spectrum of XeF4 suggests XeC14 to be planar.
129 1C I- -~-) 129 XeCI (planar)·'129 10- -~-) 129 XeO (tetrahedral)
4 ,4 4 4
Quadrupole splitting is expected for the planar geometry but not for the tetrahedral geometry.
Both XeF4 and XeCl4 (obtained from 129ICI4-) show the characteristic quadrupole-split doublet
(tillQ = 41 mmls for XeF4 and 26 mmls for XeCI4) with the characteristic isomer shift ea. 0 mmls
(Fig. 12.4.7.7). Xe04 obtained from 129104- shows no quadrupole splitting in the 129Xe-MB spectrum
ry
because Xe04 is tetrahedral (EFG = 0).
ra
20. SnX4 : With the increase of electronegativity of X, there will be more electron depletion from the
ib
s-orbital of Sn (assuming the Sp3 hybridisation) and consequently, the isomer shift (for the MB spectrum
yl
of 119Sn) becomes more negative (i.e. less positive) with the increase of electronegativity of X (ef dR
is positive for, i. e. Rex:> Rgd ).
em
ch
L
al
(Tetrahedral)
129 Xe _MB spectrum
I
e
EFG=O
/7/
(XeCI 4 )
~x~ ~~ quadrupole
th
~litting
e/
t.m
L L
L
e
er
()
Q)
~
129 Xe _MB spectrum
(J)
(XeF4 ) L L
H
C
,:::J
o ~ /(Planar)
o ~
k
EFG=t=O
lic
Qu~~rupole
i xe""
" " splitting
C
L/ L
-40 -20 0 +20 +40
Fig. 12.4.7.7 129Xe-MB spectra ofXeF4 and XeCl4 (obtained from the r3-decay of 12YIC14-). Electric field gradient (EFG) = 0
for the tetrahedral geometry (i.e. no quadrupole splitting), =I:- 0 for the square planar geometry (i.e. quadrupole splitting).
21. SnF4 vs. SnCI4 : The MB spectra of 119Sn indicates the quadrupole splitting for SnF4 but no
such quadrupole splitting is noticed for SnCI4 • In fact, SnCl4 exists as a tetrahedral monomeric
species (m.p. -33°C) while SnF4 exists as a 2 D-Iayer polymeric species (high m.p.) where the octahedral
coordination around Sn is maintained by sharing the 4 equatorial apexes of the octahedral 'SnF6'
units. Thus, in the polymeric structure of SnF4, the octahedral 'SnF6 ' units are joined into the planar
layers by corner sharing of the four equatorial F-atoms (which act as the bridging ligands). The
trans-axial Sn-F bonds (terminal Sn-F bonds, 188 pm) are shorter than the equatorial bridging
Sn-F bonds (202 pm).
188 pm
CI
\.~ / F /
202pm~I / F I/F I
Sn
i
-F-M-F-M-F-
/1 F /1 CI/ I "'CI
~F F~~/F F~
CI
_ F- (Tetrahedral)
/1 /1 ~
/F F /F F L/12-F
(SnF )x
4
=
(MF4)x (M Sn): 2D-layer structure (Sharing
of 4 equatorial apexes of MF6 octahedra)
ry
Thus, in the polymeric structure of SnF4 , there are two types of Sn-F bonds and it gives an
asymmetric distribution of electron cloud around the Sn-nucleus and it causes the quadrupole splitting
ra
of the MB spectral signa~ of lI9Sn. On the other hand, in SnCl4 (monomeric form), the tetrahedral (i.e.
ib
cubic ligand field symmetry) structure maintains the spherical distribution of the electron cloud
yl
around the Sn nucleus and consequently, the MB spectral signal does not experience the quadrupole
em
splitting.
22. (a) [SnCI4] vs. [SnR4]; (b) [SnR4], [SnR3X], [SnR2X2]; (c) [SnX4] vs. [SnX6]2-; (d) [SnR2X4]
ch
(cis- vs. trans isomers); (e) SnR2X2 (X = F, CI, Br, I): The relative values of isomer shift for such
compounds of tin have been discussed and explained earlier in this section.
al
23. Biological system: Iron-proteins (heme-proteins, non-heme proteins, Fe-S protein etc.) have
e
been widely subjected to the MB spectroscopic study to identify the oxidation states. Some examples
th
are given below:

e/
• Deoxy- and oxy-hemerythrin: The MB spectrum clearly indicates the two types of Fe-centres in
t.m
the oxy-Hr form but MB spectrum cannot distinguish the Fe-centres in the deoxy-Hr form. It is reasonable
because in the deoxy form, the two Fe-centres are in the slightly different environments (basically
in terms of the amino acids) but the Fe-centres are in the widely different environments in the
e
oxy-form where one Fe-centre binds with the peroxide moiety while the other centre remains almost
er
in the same environment as in the deoxy form.

H
Mossbauer data and Deoxy-Hr Oxy-Hr

Magnetic properties
k
lic
Isomer shift (8 in mmls): 1.14 ] 0.52] 0.48]

Quadrupole splitting One doublet Two doublets
C
(dEQ, mmls): 2.76 1.92 1.00

J (cm- I ): .... -10 .... -80
Here it is worth mentioning that in deoxy-Hr, the ~-hydroxido moiety (Jl-OH) brings about a
weaker antiferromagnetic coupling interaction (J::::: -10 cm- I ) while in the met-Hr or oxy-Hr having
the J..I.-oxido grdup (i.e. Jl-O), the antiferromagnetic coupling interaction is stronger (J ::::: -80 em-I).
In fact, compared to the J..I.-OH group, the J..I.-O group is more efficient in bringing about the
antiferromagnetic coupling (see Chapter 8).
• Oxidation state of iron in the active form of catalase and peroxidase: The enzyme in its resting
condition represents the Fe(III)-heme protein, which on being treated with H20 2 produces two
compounds described as compound-I (green, Amax = 405, 655 nm) and compound-II (red,
Amax = 429, 536, 568 nm). The compound-I is more reactive than the compound-II.
Fe III _ P ~ Red compound~ Green Compound
(p for porphyrin) (Compound II) (Compound-I)
H
(H~S) !i'O ' 0
(His)N I /6~ /N(HiS)
~FIIIe e III
(HiS)N/ I ""0/ I~
O~ON(HiS)
J,!-hydroxidodiiron(lI) system, weak J,!-oxidodiiron(llI) system, strong

antiferromagnetic coupling (J ~ -10 cm- antiferromagnetic couping (J ~ -80 cm -1)
1
ry
),
paramagnetic; high spin Fe(II). diamagnetic; high spin Fe(III).
ra
Fig. 12.4.7.8 Structures of the deoxy- and oxy-hemerythrin.
ib
(See the author's book, Bioinorganic Chemistry for details).
yl
em
Isomer Shift in Iron-Porphyrin Systems: Identification of the Oxidation State of Fe
ch
FeIII(TPP) ~ FeII(TPP) +_le_ _~) [Na(THF)3J[Fe(TPP)]
(Reduction by sodium
(0=O.65mm/s)' (Fe!, S = ~).IOW spin
al
(0 = O.45mm/s) (0 = O.S2mm/s) naphthalide in THF)
e
t~:duction
1
th
by sodium
naphthalide)
e/
t.m
[Fe (TPP)J2- (diamagnetic)

(<> = 0.48 mm/s)**
e
(Fell) (not Fe 0 )
er
FeII(TPP) i.e. Fe(TPP) is the tetraphenylporphyrinate complex of Fe(II).

H
* The isomer shift (0.65 mmls) indicates that the added electron is taken by Fe(ll) to give the
k
-i)
lic
low-spin Fe(l) ( S = (cf. Fig. 12.4.7.1; 8 '" 2.2 to 2.3 mm/s for high spin Fe(I».
C
** The isomer shift (0.48 mmls) indicates that the t'wo electrons added to Fell(TPP) are probably
taken by the porphyrin ligand not by the Fell-centre. However the single electron reduction
occurs at the metal centre.
• Isomer shift of Fe IV -haemproteins: - 0 mmls
Compound-II is a compound of FeIV as FeIV(p)(O) i.e. oxido-complex of Fe(IV). But the complex-I
may be described either as a compound of Fe(V) like Fev(p)(O) i.e. oxido-complex of Fe(V) or as a
compound of Fe(IV) like FeIV(p+)(O) i.e. oxido-porphyrin radical complex of Fe(IV). The MB spectra
of the compound-land compound-II can be best interpreted in terms of the Fe(IV) oxidation state
(<>Fe ~ 0.05mm/s, dE Q ~ 1.6 mm/s). These MB-parameters nicely agree with those of the authentic
FeIV-porphyrin complexes (Fig. 12.4.7.9). Thus the green compound i.e. compound-I is a ferryl complex
i.e. Fe(IV)-complex not Fe(V)-complex and in generation of the green complex from the red complex,
the electron is lost from the porphyrin moiety not from the metal centre.
1v
Fe -porphyrin complex
(EFG * 0)
8 ~ 0 mm/s (cf.Fig.12.4.7.1)
~EQ ~ 2 mm/s
I
I
·+-
ry
--+~I
ra
ib
-3 -2 -1 o +1 +2 +3
yl
em
Fig. 12.4.7.9 Qualitative representation of the zero-field MB-spectrum of a representative FeIV -prophyrin complex.
ch
• Fe-S proteins (ferredoxins denoted by Fd, in general): The simplest Fe-S protein is rubredoxin
(Rb) where the iron centre is tetrahedrally surrounded by four cysteine-S sites. The structure is distorted
al
and the oxidised form bears FeIIl ( d 5 ,S = %) while the reduced form bears FelI(tfi, S = 2). In the other
e
th
Fe-S proteins e.g. Fe2Sb Fe3S4, Fe4S4 etc. there are more than one Fe-centre and these remain coupled
e/
(see the author's book, Bioinorganic Chemistry for details). In these multinuclear Fe-S proteins,
t.m
Fe 3+(d5 ; e2ti) and Fe 2+(tf : e3ti) reside also in the

distorted tetrahedral geometries having the mixed
ligands (i.e. inorganic sulfur and cysteine-S). The MB spectral studies of the Fe-S proteins have been
found quite helpful in understanding the structure and activity of the different Fe-S proteins. The MB
e
spectra of some Fe-S proteins are given in Figs. 12.4.7.10-11.

er
It is expected that in general, in the Fe-S proteins, the quadrupole splitting of Fe 3+ (having the
H
symmetric distribution ofd-electrons i.e. e2 t1) will arise only from the distorted tetrahedral structure
k
(slight distortion; measure of deviation from the cubic ligand field symmetry) and inequivalence of
lic
C
s/ Cys 'VVVV'v-
(Rb) I [Fe(S-Cys)J
Fe
Doublet for
Fe(lI)
-./VVVV'
r/sl ~S-CYS ~
Cys " Cys'VVVV'v-
-4 -2 o +2 +4

(a)
(Contd... )
fYS~ IYS~
8 8 8
"'-/"'-/
+- Doublet for Fe(lII) Fe /Fe
o 8/ ' "-8/ " 8
Q)
~
E
::J
I
Cys'VVVVV-
I
Cys'VVVVV-
o
()
-4 -2 0 2 4
ry
Doppler velocity (mm S-1)
ra
(b)
ib
yl
em
Doublet for Fe(lII) ch
(,)
Q)
~
al
"E Outer doublet

:J
for the delocalised
e
o
()
th
Fel"-Fe" (coupled
unit) Le. Fe2.5+
e/
t.m
-4 -2 o +2 +4
1
Doppler velocity (mm 5- )
(c)
e
er
Fig. 12.4.7.10 Qualitative representation of the MB spectra of some representative Fe-S proteins. (a) Oxidised and
reduced forms of rubredoxin (lFe-OS i.e. no inorganic sulfur) denoted by Rb; Rb (Felli) and Rb d (Fell). (b) Oxidised
H
and reduced forms of 2Fe-2S ferredoxin denoted by Fe2S2-Fd; Fe 2S2-Fdox (2Fe IIl ) and Fe 2S;-Fdred (Felli + FeU).
(c) Oxidised and reduced forms vf 3Fe-4S ferredoxin denoted by Fe 3S4-Fd; Fe 3S4-Fd ox (3Fe llI ) and Fe3S4-Fdred
k
(FellI + coupled FellI-Fell unit not 2FellI + IFell ).

lic
the ligands (i.e. inorganic sulfur and cysteine sulfur). On the other hand, for Fe2+ (having the asymmetric
C
d-electron distribution, e 3tl), the quadrupole splitting arises from the asymmetric d-electron distribution
itself, distortion (J.T. effect) and ligand nonequivalence. Thus it is quite reasonable that the magnitude
of quadrupole splitting will be more for Fe(II) i.e. ~EQ (Fell) » ~EQ (FellI) in Fe-S proteins. This
prediction has been supported experimentally.
(i) For rubredoxin (Rb), [Fe(SR)4]' in the oxidised form, the MB spectrum of 57Fe shows a small
quadrupole splitting (ca. 0.7 - 0.8 mm/s) with the isomer shift 0.25 mm S-1 while the MB
spectrum at the reduced state shows the higher magnitude of the quadrupole splitting (ca.
3 - 3.5 mm/s) with the isomer shift 0.65 mm/s. It indicates that in the oxidised form of Rb (i.e.
Rb ox ), Fe(III) is present while in its reduced form (i.e. Rb red ), Fe(II) is present.
(ii) For Fe2S2 ferredoxin, the 57Fe-MB spectrum of the ,oxidised form shows a single doublet with
a small quadrupole splitting and isomer shift 0.26 mm/s (cf. 8 = 0.25 mm/s for the oxidised form
of Rb), a characteristic feature of Fe(III). It indicates that in its oxidised from, both the Fe-centres
are as the Fe(III) centres in equivalent positions. In the reduced form, the MB spectrum shows
a smaller inner doublet (i. e. smaller quadrupole splitting, characterising the Felli-centre) with the
isomer shift 0.25 mmls and a larger outer doublet (i.e. higher quadrupole splitting, characterising
the Fell-centre) with the isomer shift 0.55 mmls. The peak area is in the 1: 1 ratio. The isomer shift
0.55 mmls with a higher quadrupole splitting supports the +2 oxidation state of iron (el
8 = 0.65 mmls for Fell of rubredoxin).
Thus the MB spectroscopy proves that in the oxidised form of Fe2S2(Fd), both the Fe-centres are as
=
the equivalent FellI-centres which are antiferromagnetically coupled (i.e. S 0) while in the re-
duced form it contains localised one FellI-centre and one Fell centre; and these localised FellI and
Fell centres remain antiferromagnetically coupled (i.e. S = !).
2
Table 12.4.7.3 Isomer shifts (8) of some Fe-S proteins.
ry
ra
Fe-S protein: Rubredoxin (Rb) 2Fe-2S Fd 3Fe-4S Fd
(lFe-OS) (i.e. Fe2SrFd) (i.e. Fe3S4-Fd)
ib
0.27 (oxidised form, 3FellI )
yl
0.25 (oxidised form, FellI) { 0.26 (oxidised form, 2FeIH ) {
em
8(mmls): 0.65 (reduced form, Fell) 0.25 and 0.55 0.29 and 0.45 (Reduced form,
{ (Reduced form, 2Fe llI + Fell)
Fe JII + Fell) Probably IFe3+ + 2Fe2.S+
ch
(iii) For Fe3S4 (denoted by Fd-II having the void cubane structure), the 57Fe-MB spectrum of the
al
oxidised form shows one small doublet (i.e. smaller quadrupole splitting, ~EQ = 0.53 mmls) with the
e
isomer shift 0.27 mmls and it supports the presence of three equivalent FellI-centres. On the other
th
hand, the reduced form (produced by the addition of one electron to the oxidised form constituted by
e/
3Felll -centres) shows an outer doublet (larger quadrupole splitting) with 0.45 mmls isomer shift and an
t.m
inner doublet (i.e. smaller quadrupole splitting) with the isomer shift 0.29 mmls. If the reduced form
is assumed to be constituted by 2Fe lll and 1Fell centre, then inner doublet should correspond to the FellI
centres and the outer doublet should correspond to the Fell centre. But this assignment raises two
e
er
questions:
• 8 = 0.45 mmls for Fell is too small (ef 8 = 0.65 mmls for Fell of Rb).
H
• if the outer doublet corresponds to the Fell-centre, then the peak area ratio of the outer doublet and
inner doublet should be 1:2 (ef assuming the reduced form constituted by 1Fell and 2Fe lll centres)
k
lic
but experimentally the observed peak area ratio of the outer doublet and inner doublet is 2:1.
C
It needs an explanation. In fact, the isomer shift 0.45 mmls of the reduced form of the Fe3S4 protein
lies between the values of FellI (0.25 mmls) and Fell (0.65 mmls) of rubredoxin (Rb). It indicates that
probably, the added electron during the reduction of the oxidised form of the Fe3S4-protein, is
shared equally by two ~elll-centres i.e.
3Fe 3+ ~ Fe 3+ , 2Fe 2.S+ (not 2Fe 3+, Fe 2 + )
It leads to the mixed valence state intermediate between ferric (Fe3+) and ferrous (Fe2+). In fact,
0.25 +0.65
the calculated isomer shift ( =- - - - = 0.45 mmls by using the 8-values found for the mononuclear
2
species Rb) value for Fe 2.5+ nicely agrees with the experimental value 0.45 mmls. It supports the fact
that in the reduced form of the Fe3S4-protein, the FellI-Fell unit remains coupled to give the average
oxidation state +2.5 of iron.
(iv) For the Fe4S4-protein (i.e. 4 Fe-4S cubane protein), the MB spectroscopic data are quite
interesting. Crystal structure determination cannot give any information regarding the oxidation states
of iron in the different forms of the Fe4S4 protein. But the MB spectroscopic data can do the task. The
isomer shifts (8) for the different forms of Fe4S4 protein are as follows:
Composition: HiPIPox (3Felll + IFell) HiPIP red or Fdox Fdred (lFelll + 3Fell)
2 7S
(Probably 4 Fe . +) III
(2Fe + 2Fe ) ll (Probably 4 Fe2.2S+)
(Probably 4 Fe2.S+)
8 (mmls): 0.32 0.42 0.57
(HiPIP stands for high potential iron protein; depending on the Eo values, the Fe4S4 protein can act
either as HiPIP or ferredoxin (Fd) i.e.
HiPIPox ~HiPIPred or Fdox ~Fdred;

£0 (reduction potential at pH ::::: 7.0) = +0.35 V for HiPIP and 0 - 0.6 V for Fd.
ry
These aspects have been discussed in the author's book, Bioinorganic Chemistry.
ra
The MB spectra (Fig. 12.4.7.11) of the different forms of Fe4S4 protein show only one signal in each
ib
case and it indicates that it does not possess the localised FellI and Fell centres. For example, if Fdox
yl
is supposed to bear the 2Fe lll and 2Fe ll centres, then it should show two MB signals with the expected
em
8-values about 0.25 mmls (for FellI) and about 0.60 mmls (for Fell) in comparison with those of the MB
data found for Rb. But it shows one signal with the isomer shift 0.42 moos. The experimentally found
ch
isomer shift values can be interpreted by considering the average oxidation state of iron which
represents the mixed valence state intermediate between FellI and Fell. In fact, by using the 8-values
al
of Rb, the calculated average 8-values of the different forms of the Fe4S4 protein nicely agree with the
e
experimental values. It strongly indicates that in any form of Fe4S4 protein there is only one kind of
th
Fe-centre.
e/
HiPIPoX< 4Fe2•7s+) HiPIPred or Fdox

t.m
8 (mnlls): 3 x 0.25 + 0.65 = 0.35 2 xO.25 + 2 xO.65 = 0.45 0.25 + 3 x 0.65 = 0.55
(Calculated 4 4 4
e
value)
er
8 (mmls): 0.32 0.42 0.57

H
(Experimental
value)
k
lic
C
8 .............. ~e/8-·CYS
.......................... ~/I
"-,,,Cys-8, / ................ 7 I
Fe.......... " I
"\ ' '"" 8 I
Fe4S4 HiPIPred \~', ,,/ I
g
en
or Fd ox \ \ " X""" II
en
/ '.. . . ', IyS

c Fe' " I
::)
..-.., Cys-- 8 ............ ',
8 Quadrupole split doublet for the ........ ~, I
lll
delocalised 2Fe -2Fe" coupled 8 Fe .
centres. "- 8-Cys
Cubane structure
-4 -2 o +2 +4 (Fe4S4 protein)
Fig. 12.4.7.11 Qualitative representation of the MB spectrum of the oxidised form of Fe4 S4-Fd or the reduced form of
HiPIP. constituted By 2Fe III and 2Fe" centres strongly coupled giving rise to the average oxidation state +2.5 per iron.
It supports the fact that in each fonn of the Fe4S4 protein, all the Fe-centres are equivalent and the
equivalent Fe-centres are antiferromagnetically coupled to register an average oxidation state.
Conclusions regarding the oxidation state and equivalence of the Fe-centres in Fe4S4 protein:
The MB-spectroscopic data indicate:
• in any fonn of the Fe4S4 protein, only one kind of iron exists and gives one MB signal,
• in sharp contrast to the Fe2S2 and Fe3S4 proteins, in Fe4S4, the Fe(ll) and Fe(lll) centres are
completely delocalised and they are antiferromagnetically coupled.
• average oxidation state of iron is in conformity with the MB data.
• magnitude of quadrupole splittings and isomer shifts are the averaged values for a particular
combination of the oxidation states of 4 Fe-centres.
24. Alloy and ore analysis: Presence of the MB active elements like Fe, Sn, etc. in any sample can
ry
be detected by the MB spectroscopy. Their oxidation states can also be identified from the
ra
MB-spectroscopy.
ib
12.5 ELECTRONIC SPECTROSCOPY: UV-VISIBLE SPECTROSCOPY
yl
Each electronic level is associated with a number of vibrational energy levels and each vibrational level
em
is associated with a set of rotational energy levels. The energy order f<?r transitions is: electronic
transition» vibrational transition» rotational transition. The electronic transition (occurring in the UV-
ch
visible range) can also lead to the vibrational and rotational transitions.
al
12.5.1 Electronic Spectroscopy of the Transition Metal Complexes

e
This aspect has been discussed in detail in Chapter 7.

th
e/
12.5.1 Electronic Transitions in Organic Molecules

t.m
To understand the electronic transitions, it is required to know the MO energy diagram of the molecule.
Here the MO energy diagram of formaldehyde is shown in Fig. 12.5.1.1 as a representative one. For
e
Px Px
er
Lone pairs
Jx
H
k
~z
lic
C
y
sp
Px Px
c c o o
DTIJIJ OJ
~Px
[]Jill
L--y----J
2 sp
sp
(s + Py + pz) (s + pz)
. Fig. 12.5.1.1 (a) The orbitals in formaldehyde; Px ± Px leading to the n-BMO and n*-MO; p,,(O) housing one lone pair
(to participate in the n ~ n"'"transition); sp-hybrid orbital to house another lone pair on the ·O-atom.
Enriched with the character Enriched with the character

of the 2p orbital of 0 of the 2p orbital of C
~
~.-/
H~
H
~~n IOn
H 7lC---~---_. H ~r-----------I'~----
(1t-ABMO)
(1t-BMO)
ry
H~C~O.<3D
x
ra
HI
ib
z
n(sp)
yl
(NBMO) y
em
(NBMO)
ch
H~ ~sp H
'---' " cr' (C~) ~ ~
~C<GOO
al
0c O(]
SPJ~1
2 +
l' / +
e
th
cr~o (cr-ABMO) '---./

e/
H i.e. Sp2(C) + sp(O) H crco i.e. Sp2(C) - sp(O)

(a-BMO)
t.m
(b) Shapes of the n-BMO, n-ABMO (n*), a-BMO (0'), a-ABMO (0'*) and NBMOs in formaldehyde.
e
c 'C = 0 (yz plane) 0

er
,/
1t-ABMO~
H
,,// \1t Enriched with x

k
""""" \ the character

lic
1 ~,,,,,,, " \, of the 2p-orbital

Px ---r-. '\ of carbon
,, ,, z
,
C
,
'\ n~1t 1t~1t. Y
,, '\
,,
Note: The lone pair residing in the sp- ,, ,,
hybrid orbital of oxygen is tightly '\~BMO ----------,,~_4_
bound and this lone pair is not avail- '\ (Py) n "",.""" Px
able for the n ~ n* transition. The other \, ,,"
,
lone pair residing in a pure p-orbital of 1t-BMO Enriched with the character
oxygen is relatively weakly bound and of the 2p orbital of oxygen
it participates in the n ~ n* transition. (NBMO) ~----------- ~
~ sp
(sp)
(c) Partial MO-diagram (neglecting the a-skeleton) showing the relative positions of n-BMO (n), n-ABMO (n*) and
NBMOs (n) of formaldehyde; i.e. partial MO energy diagram of the carbonyl group.
Fig. 12.5.1.1 Molecular orbital picture of formaldehyde and carbonyl group (in general)
the MO energy diagrams of the other representative molecules like C2H4, butadiene, benzene, Vol. 2
may be consulted.
The energy order of the MOs is: a* ) n* ) n ) n ) a. .. a-ABMO
The possible transitions are:
7t
a~a*, 1t~1t*, n~a*, n~1t*; ~~
7t-ABMO
n stands for the NBMO, i.e. p-orbital of 0

280 nm
(VI) V2 ; V3 ) V4). The commonly observed transition
V1 V2 V3 V4 (weak)
energy order is:
v: a ~ a* >n~a* >1t~n* >n~1t* n NBMO
(a) O~ 0* (ca. 120-170 nm): This highest energy tran- 180-200 nm
ry
(strong)
sition occurs in the saturated hydrocarbons like
ra
methane, propane, cyclohexane, etc. 7t 7t-BMO
ib
'\ / 120-170 nm
yl
"
-C··C (strong)
em
(b)
/ (ca. 180-200 Dm): This transition occurs in
7t ~ 7t* ch a-BMO
the molecules bearing the unsaturation, i. e. double Fig. 12.5.1.2 Electronic energy levels (in general)
bond, triple bond, aromatic rings, azo group, carbo- and the possible electronic transitions.
al
nyl group, etc.

e
• The molar extinction coefficient (c max ) 10,000) for the transition is very high because the 7t-
th
BMOs and n-ABMOs are situated in the same plane, i.e. xz-plane when the a-frame resides in
e/
the yz-plane. Consequently, probability of this electronic transition is very high.

t.m
• Conjugated n-electrons are excited at the lower energy compared to those in the nonconjugated
systems (cf. 180 nm for ethylene, 217 for butadiene) because in the conjugated systems, the
electron delocalization (cf. 'Particle in a Box' model, Vol. 1) reduces the energy gap between the
e
HOMO (n-BMO) and LUMO (n-ABMO). In such conjugated systems, the lowest energy n ~ n*
er
transition actually represents the HOMO ~ LUMO transition.

H
(c) n ~ 7t* (ca. == 280 nm; weak, forbidden): This transition generally occurs in the compounds
containing the unsaturation, e.g. double bonds and involving the heteroatoms bearing the unshared
k
Q
lic
~."." 1.~.~
,
C
.;..;.i.•.•;. .•;.;.\.•i. .•. 7t*

',l;iLL
" .'It 7t - - - - : - - - -
"C--l
x ~6.
)-.z
"" /11fJ10;
~~(n)
y " ~7t
"'~ (7t* and 7t in the same plane,
e--O i.e. xz-plane when the Px orbitals
<7'@g$Wg$%tA%W~ 7t form the 7t-bond)
(a)
(Contd... )
(b)
Fig. 12.5.1.3 Schematic representation of the n ~ n* transition in (a) carbonyl group and (b) ethylene. Note: For the
ry
.."
actual shapes of the MOs, Fig. 12.5.1.1 may be consulted.
""
ra
.. .... ' etc.). The carbonyl group in the
ib
electron pairs (e.g. /C=9." /C=~., -N=~
yl
em
"
aldehydes and ketones bearing the /C=Q.. group show the strong 1t --+ 1t* (ca. 180-200 nm)
and the weak n -+ 'It* (ca. 280 nrn) transitions.

ch
• This n ~ n* transition is symmetry forbidden (i.e. weak intensity) because the NBMO and 'It-
al
ABMO are in the perpendicular planes preventing their overlap. However, the molecular
e
vibration can bring about a partial overlap between these orbitals to allow the transition to
th
some extent.
e/
t.m
1t
e
er
H
k
lic
C
. ."" ""
....
....
G9~ (1t. and n in the
perpendicular planes)
"c---o n---.r..---
~
Fig. 12.5.1.4 Schematic representation of the n ~ n* transition in the carbonyl group.
Note: If the c-o a-bond lies in the z-direction and "'C- 0 a-frame resides in the yz-plane, then the Px orbitals of
/
C and 0 participate in forming the nand n* MOs; O-atom uses the sPz hybrid orbitals to form the C-O a-bond and houses
one lone pair (which is tightly bound and not available for transition). The other lone pair of electrons on oxygen resides
in the py-orbital. This electron pair is commonly described as the nonbonding pair and available for the n -+ 'It.
transition. Thus the piO) and n*(px) reside in the perpendicular planes, i.e. the nonbonding electron pair resides in the
yz-plane while n*-MO lies in the xz-plane.
(LUMO)
hv hv
>. +--- >.
E>
Q)
Allowed Forbidden E>
Q)
c: c:
W W
--+- -ib-
Excited state Ground state
HOMO
Excited state
(8=0), (8=0), (8 = 1),
ry
Singlet Singlet Triplet
ra
(28 + 1 = 1) (28 + 1 = 0) (28 + 1 = 3)
ib
(a)
(b)
yl
em
ch
al
(i)
e
th
hv
e/
t.m
e
er
H
(c)
k
Fig. 12.2.5.1 (a) Illustration of spin selection rule.

lic
Note 1: Organic compounds are generally in the singlet state (S = 0; i.e. no unpaired electron) in the ground state (So)
C
and the excited state may be singlet (S = 0) or triplet (S = 1) which is more stable than the singlet (cf. exchange energy).
The n ~ 7t* transition can produce the S} singlet excited state and T} triplet excited state. The 7t ~ 7t* transition gives
the S2 singlet excited state and T2 triplet excited state. According to the spin selection rule, the allowed transitions are:
So ~ S\ and So ~ S2. The So ~ T\ and So ~ T2 are the forbidden transitions.
Note 2: If the energy difference between the HOMO and LUMO is less, then the better spin-orbit coupling (see Sec. "
7.5.2) can mix the singlet and triplet states better. Consequently, the excited state bears some singlet character even in the,
so called triplet state. It relaxes the spin forbidden transition (see Fig. 9.9.2.3, Vol. 2). '
Fig. 12.2.5.1 (b) Relative positions of the singlet and triplet energy levels.
Note 3: In some cases, T2 may be of lower energy than T\. (Fig. 12.2.5.12)
Fig. 12.2.5.1 (c) Fate of the excited state. (cf. Sec. 6.9; Jablonski diagram). (i) photoexcitation, (ii) fluorescence,
(iii) internal conversion, (iv) intersystem crossing (ISC), (v) internal conversion, (vi) phosphoresence.
Triplet state: Splitting into 3 energy levels in the presence of a magnetic field depending on the three possible orientations
of the spins of two electrons. Singlet state: There is only one possible orientation of the electrons, i.e. no splitting by
the magnetic field.
(d) n --+ 0*: The unshared electrons on the heteroatoms (X) participate in the transition as in CH 3QH
(183 nm), Me3N: (227 nm), etc.
'\.
-C-X:
/
..
) '/" .
C-X: .
12.5.2 Franck-Condon Principle and the Selection Rule

According to the demand of the Franck-Condon principle, the internuclear separations in the excited
and ground state should not differ significantly. This aspect has been illustrated in Chapter 7.
Illustrative examples of selection rule in terms of group theory
ry
The selection rules (i. e. spin selection rule and orbital selection rule) have been discussed in Chapter
ra
7. In formaldehyde, (O=CH 2, C 2v ), the n ~ n* and n ~ n* transitions actually represent the
ib
IA I ~ IA 2 and IA I ~ IA I transitions respectively. The IA I ~ IA 2 transition is forbidden but the transi-
yl
tion, IA I ~ IA I is allowed in terms of the transition moment integral. Vibrionic coupling partially
em
relaxes the IA I ~ IA 2 transition.
For an electronic transition, ('If~f ~ 'lfclX), to be allowed, the transition moment integral (TMI),
f'lf~ff.l\lf~fd~ (where f.l denotes the electric dipole moment operator) must be nonzero (see Secs. 7.4.2,
ch
7.5). The TMI has the three following components:
al
f\lf~df.lx\If~fd~; f\lf~df.ly'lf~fd~ and fWlidf.lzW:id~.

e
The electronic transition to be allowed, at least one of these three integrals must be nonzero.
th
For the nonzero value of TMI, the direct product of the irreducible representations in the integrand
e/
must contain the totally symmetric At species. Formaldehyde belongs to the C 2v point group in
t.m
which the dipole moment components f.lx~ f.l y and f.lz transform as the B I' B 2 and A I representations
respectively (see Appendix 12A). Thus, f.lz is Al (i.e. dipole moment vector lying along the z-axis is the
Al species). Consequently, in formaldehyde, for the spin allowed n* ~ n* transition (i.e. IA I ~ IA I ),
e
the direct product Wgff.lz 'If~i = A I X A I X A I is A I' Thus the transition is allowed.
er
• For the spin allowed n --+ 1t* transition (i.e. IA I ~ IA 2) in formaldehyde, the excited state is IA 2
H
but no dipole moment component has the A2 symmetry. The direct product Al x f.l X A 2 can
contain the A I species if f.l is A 2 (cf. A 2 X A 2 =A I)' Thus all the three integrals become zero for the
k
lic
n ~ n* transition, i.e. the tAt --+ tA 2 transition is forbidden. However, this electronic transition
is partially allowed through the vibronic coupling (i.e. coupling of the electronic state with the
C
out-of-plane -CH 2 bending vibration).

• Let us take the case of ethylene (D2h point group) where the spin allowed n ~ n* transition
represents the lAg ~ IB lu transition. The TMI for this transition is nonzero because the f.lz (i.e. z-
component of the transition dipole moment) is the B lu species (see Appendix 12A) of the D2h
point group. It makes the transition allowed.
• For trans-butadiene, (C 2h point group), the lowest energy spin allowed transition, n* ~ n* i.e.
(a u)2 (b g)2 ~ (a u)2(bg)l(a u)1 represents the lAg ~ IBu transition and it is allowed (x, y polarisation)
(cf. f.lx' f.l y belong to the Bu species; Appendix 12A; result of the direct product: A g x Bu x B u;
u xu==> g, g x g ==> g, Chapter 7).
12.5.3 Designation of the UV-Bands of Electronic Absorption

The absorption bands can be defined in terms of the electronic transitions mentioned in Sec. 12.5.1.
However, they can also be designated as follows:
(a) R-Bands: (German, radikalartig): The weak n --+ 1t* transitions (Emax ( 100) of the chromophoric
groups like carbonyl or nitro group are referred to as the R-bands which experience the hypso-
chromic shift with the increase of solvent polarity.
(b) K-Bands: (German, konjugierte): The strong 1t --+ 1t* transitions (Emax ) 10,000) in the molecules
having the conjugated 1t-bonds as in butadiene are described as the K-bonds.
(c) B (Benzenoid) bands: This represents the 1t ~ 1t* transitions (in the region of 250 to 280 mm)
of the aromatic and heteroaromatic systems. This is a characteristic band (having the fine
structure components; Fig. 12.5.10.2) of the aromatic compounds. For symmetric C 6H6, this is
a forbidden transition but it is partially allowed through the vibronic coupling.
In, general the K-bands are more intense than the B-bands because the relatively high energy
K-band lies close to the very strong E-band and thus the K-band enjoys the intensity stealing
ry
phenomena (see Sec. 2.5.10).
(d) E (Ethylenic) bands: This represents also the 1t ~ 1t* transitions (in the range of 180-225 nm)
ra
in the aromatic structure.
ib
yl
12.5.4 Important Terms involved in the Electronic Spectra: Chromophores and
em
Auxochromes; Bathochromic Shift (i.e. Red Shift) and Hypsochromic Shift (Blue
Shift); Hypochromic and Hyperchromic Shift; Isosbestic Point; Solvent Cutoff
ch
Points
(A) Chromophores: Chromophore (chroma: colour; photos: bearer) is a Greek word meaning colour
al
bearer. Colour of the organic compounds arises from the presence of the unsaturated groups
e
th
like )C=C(, -C==C-, )C=O, -C==N, etc. which absorb the electromagnetic radiation
in the UV-visible range intensely. Such functional groups are called the chromophores.
e/
t.m
Table 12.5.4.1 Absorption characteristics of some representative chromophores, Emax in dm3 mol- l em-I.
n ~ 0* transition
e
Chromophore Compound A.max (nm) Emax

er
H
-O-H Water 167 7000

-O-H Methanol 177 200
k
-S-H R-SH 210 1000

lic
'\ Acetone 188 1850

/C=O
C
-NH 2 R-NH 2 190 3000

-0- R-O-R 180 3000
n ~ n* transition
'\ Acetone 280 15
/C=O
'\ Acetophenone 320 15
/C=O
-N=N- Azobenzene 450 10
-N0 2 Nitromethane 280 22
-N=O Nitrosobutane 300 100
'\ Thioacetamide 360 18
/C=S
'\ Thiobenzophenone 620 75
/C=S
(Contd... )
n ~ cr* transition
Chromophore Compound Amax (nm) Emax
-C==N R-C==N 160 10

- CONH 2 R-CONH 2 210 30
-C0 2 H R-C0 2H 205 30
X ~ x* transition
"
/ C = C/"
-C==N
Ethylene
Acetonitrile
165
190
10,000
9,000
-C==C- Acetylene 175 10,000
")c=?-c=c(
ry
/C=O Acetone 210 900
ra
1,3-Butadiene 217 21,000
ib
-N=N- Azobenzene 250 9,500
yl
"
em
/C=S Thioacetamide 266 12,500
-CHO R-CHO ch 190 1,000
(B) Auxochromes (auxo meaning increase): Certain groups can enhance the colouring power of the
al
chromophores and such groups like -OH, -NH2, -OR, -CH3 are called the auxochromes.
Presence of the auxochromes generally shifts the absorption maxima (of the intense bands) towards the
e
th
longer wavelength (i.e. bathochromic shift). Nitrobenzene is colourless but presence of the -NH2
group (an auxochrome) makes nitroaniline coloured.
e/
In most of the cases, the electron donating effect (specially the mesomeric effect) of the auxochromes
t.m
causes the more electron delocalization (cf. Sec. 12.5.8-10) to reduce the electron transition energy.
Illustration: Combination of the two chromophores like C=C and C=O can change the position
e
of the absorption bands.

er
-b (Jlb~
H
............. -+c-c=c-o
k
I I II I-----' I I I
lic
10.....-
C
Chromophore Chromophore
Stabilization of the excited state (i. e. 1t*) through the electron delocalization reduces the energy
difference between the 1t-BMO (i.e. HOMO) and 1t*-MO (i.e. LUMO) and it shifts Amax towards the
longer wavelength. This shift can be understood in terms of the MO energy diagram (Figs. 12.5.8.1-2).
(C) Bathochromic shift (Red shift): Shift of the Amax towards the longer wavelength is called the
bathochromic or red shift. Bathochromic shift causes the absorption to change in the order,
Violet ~ blue ~ greenish blue ~ bluish green ~ green ~ yellowish green ~ yellow ~ orange
~ red (cf VIBGYOR)
(A: increasing from violet to red)

This is why, the bathochromic shift is called the red shift. The 1t ~ 1t* transition experiences the red
shift with the increase of solvent polarity or through the attachment of an electron donor auxochrome
"
to the / C = C /\. chromophore.
Phenol in presence of alkali experiences the red shift because the nonbonding electrons of the
phenolate anion (produced in presence of alkali) interacts with the n-system of the benzene ring to
cause the more electron delocalization.
Phenol (A max = 210 nm, cmax = 6,200 dm3 mol- I em-I); phenolate anion (A max = 235 nm,
cmax = 9,400 dm3 mol- I em-I).
Hyperchromic shift
Hypsochromic shift
----. Bathochromic shift
(blue shift) .--
(red shift)
Q)
ry
u
c:::
Ct1
.c
1
ra
o
en
.c
ib
« Hypochromic shift
yl
em
----+ A (wavelength) (nm)
ch
Fig. 12.5.4.1 Illustration of hypsochromic shift and bathochromic shift; hyperchromic and hypochromic shift.
According to the principle of the model, particle in a box (cf Sec. 3.5.5, Vol. 1), with the increase
al
of delocalization (i.e. increase in conjugation length), the energy difference between the successive
e
levels decreases. It causes the red shift in the conversion of the phenol to phenolate anion (cf Sec. 3.5.5,
th
Vol. 1 for more examples).

e/
(D) Hypsochromic shift (Blue shift): The shift of Amax towards the shorter wavelength is called the
t.m
hypsochromic shift or blue shift. It imparts an opposite effect of the bathochromic shift.
The n ~ n* transition experiences the blue shift with the increase of solvent polarity. A more polar
e
solvent stabilizes the nonbonding electrons through the interactions like H-bonding and it causes the
er
lowering of energy of the NBMO. It leads to the blue shift.

H
(E) Hyperchromic and hypochromic shift or effect: The increase of intensity (i. e. cmax ) is called
the hyperchromic effect while the decrease in intensity is called the hypochromic effect.
k
lic
(F) Isosbestic point: When a compound remains in an equilibrium of two different forms having the
different Amax values, there is an isosbestic point at which absorbances of the both species (remaining
C
in an equilibrium) are the same.
Spectral Shift in the lon-Pair Charge Transfer (IPCT) Band

Ion-pair formation does not affect the d-d bands of the cationic transition metal complexes but the
spectrum in the CT region is affected. For the more oxidisable and polarisable anions residing
in the outer sphere, the intense CT band shifts towards the longer wavelength (i. e. red shift) for
the ion pair [M(NH 3)6]3+ . X- (M = Co, Ir).
[M(NH 3)6r+ , X- (I:~T) >[ M(NH 3)6J+, X

(Ion pair) (X = CI, Br, I)
v: CI- ) Br- ) 1-.
In fact, [Ir(NH3)6]3+ is itself colourless but it becomes yellow coloured in presence of X- = 1-.
From the measurement of intensity of the IPCT band, the, ion-pair formation constant, i.e.
outer-sphere association constant (Kos) can be estimated.
4.0
I: [Co(NH 3)6t+; II: [Co(NH 3)6t+, cr
III: [Co(NH 3)6t+, B(; IV: [CO(NH 3)6t\ r
3.0
ry
C')
.Q 2.0
ra
1
ib
yl
em
1.0
ch
al
250 300 350

e
-+
th
Wavelength (A.) (in nm)

e/
Fig. 12.5.4.2 Spectral shift in the IPCT band of [Co(NH 3)6]3+. x-

t.m
Illustration: Let us assume that for A + H+ ~ AH+, the Amax values of A and AH+ are different.
Distribution of the concentrations of the species AH+ and A depends on pH but at all pH-values,
e
absorbance at the isosbestic point of the equilibrium mixture is the same. This has been illustrated in
er
Sec. 7.8 (cf. Fig. 7.8.1).

H
(G) Solvents for UV-spectroscopy and solvent cutoff points: The solvents to be used in ultraviolet
spectroscopy should satisfy the following conditions:
k
lic
(i) Transparency to UV-radiation: The solvent itself should not absorb the UV-radiation, specially
in the same range of absorption by the sample under study. For this purpose, the solvent should not bear
C
the chromophores, e.g. unsaturation, carbonyl group, etc. However, different solvents remain
transparent to the UV-radiation up to different ranges, i.e. the shortest wavelength values up to which
they remain transparent. In other words, below the cutoff point, the solvent starts to absorbs. The cutoff
points (i.e. minimum regions of transparency) of some solvents are given below.
Solvent: Water Acetonitrile Cyclohexane Isooctane 95% Ethanol
Cutoff point (nm): 190 190 195 195 205
Solvent: n-Hexane Methanol 1, 4-dioxane Trimethyl Phosphate Chloroform
Cutoff point (nm): 201 205 215 210 240
(ii) Solvent effect on the fine structure of an absorption band: In a nonpolar solvent, the specific
solute-solvent interaction (e.g. H-bonding) is absent and the recorded spectrum of the sample (i.e.
solute) approximately mimicks the spectrum recorded in the gaseous state in which fine structure of the
peaks is observed. Thus to see thefine structure ofan absorption band, nonpolar solvents (e.g. isooctane)
are to be used.
(iii) Solvent induced shifts to characterise the nature of the absorption band: Polar solvents
(capable of making the H-bond) give a red shift of the n ~ n* transition and a blue shift of the n ~ n*
transition. Thus to characterise the nature of the peak, appropriate solvents are to be used (Sec. 12.5.6).
12.5.5 Effect of Resonance and Conjugation on the Position and Intensity of

the Absorption Bands
(A) Particle in a box model for the conjugated polyene systems: With the increase of the conjuga-
tion, the n ~ n* transition occurs at the longer wavelength (i.e. red shift). It can be interpreted in terms
of the principle of the model, particle in a one dimensional box. The energy difference between the
HOMO (nth n-MO) and LUMO i.e. (n + l)th n-MO is given by (cf. Fig. 12.5.5.1):
ry
ra
ib
yl
J1£ (2n + l)h .. . ..
i.e. v =- = 2 =:::) V decreases with the Increase of a (I.e. length of conJugation)
em
h 8ma
= = =
In moving from butadiene (n; 2 ~ nf 3) to vitamin A (n; 5 ~ nf 6) to carotene (n; 11 ~ = =
ch
nf= 12), the length of conjugation measured by a increases and consequently vtransition decreases. In fact,
al
butadiene is colourless, vitamin A is orange yellow and carotene is ruby red (see Fig. 12.5.5.2). This
aspect has been illustrated and discussed in detail in Sec. 3.5.5, Vol. 1.
e
th
The decrease of transition energy with the increase of the length of conjugation can also be under-
stood in terms of the relative stabilization of the excited and ground state. The greater conjugation
e/
stabilizes the excited state more (relative to the ground state) because the excited state possesses
t.m
a large number of charge-separated structures which bring about the stabilization through the
e
er
H
k
lic
C
LUMO
hv hv
---+-
(Allowed) (Forbidden)
--+-
Excited state
--4-- HOMO 4 -
Ground state Excited state
(8 = 0), Singlet (8 = 0), Singlet (8 = 0), Triplet
Ethylene Butadiene Hexatriene Octatetraene (28 + 1 = t) (28 + 1 = 0) (28 + 1 = 3)
N N\f
(b)
(a)
Fig. 12.5.5.1 (a) Decreasing trend of transition energy for the HOMO(1t) --+ LUMO(1t*) transition in the polyenes with
the increase of the length of conjugation. (b) Spin allowed and spin forbidden transition between HOMO and LUMO.
(n = 2)
Butadiene (A max = 217 nm)
CH 20H
~ ~ ~ ~
(n = 5)
Vit A1 (A max = 325 nm)
CH20~
ry
(n = 6)
ra
Vit A2 (A max = 351 nm)
ib
yl
H3 C
em
H3 C
(n = 11)
~ ~ ~ ""::: ~ ~ ~ ~
ch
CH 3
CH 3
=452 nm) (I)
al
CH 3 J3-carotene (A max
e
Fig. 12.5.5.2 Change in the position of Amax for the n ~ n* transition with the increase of the number of conjugated
th
double bond (n)

e/
Note: • Emax can be calculated by: Emax = (1.74 x l(4)n. For ~-carotene, it leads to: Emax = 1.74 X 104 x 11 = 19.4 x 104
(cf. observed value of Emax = 15.2 X 104 )
t.m
• Amax can also be theoretically calculated.

resonance. It may be noted that the excited state is more polar than the ground state. It is illustrated
e
for butadiene.
er
H
CH 2=CH-CH=CH 2 (hV. )[ +CH 2 -CH=CH-CH; H

1t~1t j
k
-CH 2 - CH=CH - CH; H +CH 2 - -CH - CH=CH 2 H etc.]

lic
Charge-separated species of the excited state

C
It may be mentioned that the bathochromic or red shift with the increase of conjugation, is also
accompanied with the increase of intensity (i.e. longer Amax.and higher £max) .
• Amax for the 7t ~ 7t* transition in conjugated diene vs. nonconjugated diene: It is illustrated for
the following two isomeric dienes.
H 2 C=CH-CH 2 -CH 2 -CH=CH 2 H 3C-CH=CH-CH=CH-CH 3
(1,5-Hexadiene, nonconjugated diene) (2, 4-Hexadiene, conjugated diene)
178 nm 227 nm
• "-max for ethylene and conjugated alkenes:
-C=C--C=C-C=C- -C=C-C=C-C=C-
Amax(n·~ n*): 175 nm 217 nm 258 nm
cmax (dm3 mol- I em-I): 15,000 21,000 35,000
... ,.,,1
(B) HOMO and LUMO energy difference (AE) and transition probability of the spin allowed
transition: The HOMO ~ LUMO transition leading to the triplet excited state (S = 1) is forbidden but
the transition leading to the singlet excited state (S = 0) is allowed. The said spin forbidden transition
can be malie partially allowed through the spin-orbit coupling mechanism. This spin-orbit coupling
mechanism allows the mixing between the singlet ground state and triplet excited state. Consequently,
the so-called excited triplet state bears some singlet state character and it allows the singlet ~ triplet
transition to some extent. Thus the spin-orbit coupling mechanism relaxes the spin selection rule
(see Sec. 7.5.2; Fig. 9.9.2.3. in Vol. 2).
The efficiency of the spin-orbit coupling mixing depends on the energy difference (~E) between the
ground state and excited state, i.e. energy difference between the HOMO and LUMO. When the energy
gap (~) is less, the spin-orbit coupling mixing becomes more efficient. It concludes:
ry
less the energy difference between the HOMO and LUMO, better the spin-orbit coupling, better
ra
the relaxation ofthe spin selection rule, higher the transition probability and higher the intensity
ib
of the transition, i.e. longer the ArntzX:' higher the £17UlX"
yl
(C) Illustrative examples: Effect of conjugation on Vtransition is illustrated in the following examples.
(i) C 6 H s- (CH= CH)x- C 6 H s (x = 1,3,5): C 6H s- CH= CH- C 6H s (colourless,
em
Amax = 319 nm), C6Hs-(CH=CH)3-C6HS (pale yellow, Amax = 377 nm), C6Hs-(CH=CH)s -
ch
C6H s (orange, Amax = 424 nm).
(ii) Acid base indicators like methyl red, methyl orange and phenolphthalein: Depending on the
al
protonation/deprotonation equilibrium, they can bear the benzenoid or quinonoid structure. The
e
benzenoid and quinonoid structures are having the different colours.

th
In the quinonoid structure, the more extensive delocalization gives the red shift (i.e. higher AmaxJ.
e/
• Ph~nolphthalein is colourless but in an alkaline solution, it becomes pink coloured due to the
t.m
increased conjugation. In a strong alkaline condition, hydroxylation prevents the conjugation and it
becomes colourless.
e
• Methyl orange and methyl red undergo protonation (pH ~ 4.0) in an acidic condition and the
er
protonated form is a charged species. Resonance gives an extra stability to the excited state of the
protonated species (i.e. charge delocalization through resonance). Thus protonation stabilizes the
H
LUMO (i.e. excited state) more than the HOMO. It makes the HOMO ~ LUMO transition energy less
k
(i.e. bathochromic shift on protonation).

lic
• Phenolphthalein vs. methyl red and methyl orange: Here it may be mentioned the extensive
C
delocalization prevails in both the protonated form (i.e. in acidic condition) and deprotonated form (i.e.
in alkaline condition) of methyl red and methyl orange and both the protonated and deprotoned forms
of these indicators are coloured. But on protonation, the excited state is stabilised better through the
delocalisation of charges, i.e. the LUMO is stabilized more, to cause the red shift. On the other hand,
for phenolphthalein, in the deprotonated form (i.e. alkaline condition), the more extensive delocalization
gives the colour (cf the protonated form at lower pH is colourless due to the less conjugation).
(iii) Extended conjugation through the benzene ring: Amax (phenol) ( Amax (nitro-phenolate);
Amax (nitrobenzene) ( Amax (nitro-aniline); Amax (nitro-phenol) ( Amax (nitro-phenolate), etc.
~ LO
.(V
D
< >rv +~
_
....
N",. (-D=-NH 2 • ~H. ~:-.etc.)
..
o
Extended conjugation
(iv) Conjugation with the heteroatom (as in phenolate):

CHz CH-QCH 3 (Amax = 190 nm), CH2= CH- NMe 2 (Amax =230 nm).
(D) Effect of resonance delocalisation on the charge separated excited state vs. charged and
uncharged ground state: This aspect is illustrated by taking some representative examples.
(i) Naphthalene vs. azulene (isGmeric compounds): Resonance stabilizes the ground state more
(compared to the excited state) for naphthalene while resonance (leading to the aromaticity along with
the charge separation)
ry
ra
ib
yl
em
(Benzenoid form) (Benzenold form colourless)
t
ch
(colourless)
alkaline medium
al
°'QN°-
e
th
C"
e/
-OH
H
&
strong
t.m
./~/
'/
I CO; .. alkaline
medium
(Hydroxylation)
e
er
(Benzenoid form) Quinonold form

H
(colourless) (pink)
k
lic
(a) Colour of phenolphthalein (weakly acidic due to the phenolic OH groups) depending on the acidity and
alkalinity of the medium.
C
(Benzenoid form)
Yellow in alkaline medium
(Methyl Orange)
(Quinonoid form)
Red in acid medium
(b) Colour of methyl orange (a weak base) depending on the acidity and alkalinity of the medium.
(Contd... )
(Benzenoid form)
Yellow in alkaline medium
(Methyl Red)
(Quinonoid form)
ry
Red in acid medium
ra
(c) Colour of methyl red (a weak base) dep~nding on the acidity and alkalinity of the medium.
ib
Fig. 12.5.5.3 Colours of som~ representative acid-bas~ indicators.
yl
Note: (a) In the quinonoid from of phenolphthalein, colour appears in the visible range (i.e. Amax is shifted in the visible
em
region) due to the extended conjugation. Protonated form (i.e. benzenoid from) of phenolphthalein is colourless due to
the less delocalization. (b) For methyl red and methyl orange, both the protonated and deprotonated forms enjoy the
extensive delocalization and their both forms are coloured. But the protonated from stabilizes the LUMO more to cause
ch
the red shift.
al
stabilizes the excited state (charge-separated structure) more for azulene. It makes: ~ (naphtha-
e
lene, colourless) ) ~ (azulene, deep blue).

th
e/
(0
t.m
1"-':::
~ . .0- Red shift
Naphthalene
e
Azulene (deep blue)

(colourless)
er
(ii) Benzene vs. fulvene: Resonance stabilizes the ground state more for benzene while resonance
H
stabilizes the excited state more (charge-separated structure) for fulvene (an isomer of benzene).
k
o ©
lic
i.e.
C
(Benzene) (colourless)
(Uncharged ring is aromatic)
D=
__
1t~1t*
CH 2 Red shitr [[J-CH2~D-CH2~ -----~ ]

(Fulvene) I.e. ~-
V CH 2
(Yellow)
Aromatic ring
is charged
It makes: ~ (benzene, colourless) ) (fulvene, yellow).

Note 1: More resonance stabilization of the excited state (compared to that of the ground state)
which is more polar and charge-separated (as in the case of conjugated linear polyenes, fulvene,
azulene etc.) causes the bathochromic shift while more resonance stabilizatio~ of the ground state
(compared to that of the excited state) as in the cases of benzene, naphthalene etc. causes the hypso-
chromic shift.
Note 2. The charge-separated excited state of the trans-form of indigotin (Sec. 12.5.7) is stabilised
by H-bonding and thus the transition energy is reduced and it looks blue coloured.
(iii) Hyperconjugative effect (cf Sec. 12.5.8): Like the resonance effect~· the hyperconjugative
effect can also stabilize the polar excited state more to cause the red shift. Thus if the. H atoms on a
chromophore (e.g. )C=C-r=O) are substituted by the primary or ~econdary alkyl groups (to
ry
participate in hyperconjugation) then they will cause the red shift.
ra
(iv) Sterically hindered resonance (Fig. 12.5.5.4): Steric factors may lead to the loss of coplanarity
ib
of a system to prevent the resonance. If the excited state is charge-separated then its stability largely
yl
depends on the resonance. In such cases, if the resonance is hindered, it will primarily affect the
em
stability of the excited state (compared to the ground state) and it will make the transition energy
larger (i.e. blue shift). This higher transition energy, i.e. higher dE, arises from the fact that the excited
state is raised more energetically. This is illustrated in Fig. 12.5.5.4. On the other hand, if the ground
ch
state is itself charged (see Fig. 12.5.4.5), then prevention of resonance win arrest the charge delocalisation
al
and it will cause the red shift.

e
H H
"c=c
th
/
e/
t.m
Blueshift )
e
Amax = 280 nm
er
(trans-stilbene) (ci9-stilbene)
H
(delocalisation sterically hindered)

-+ 1t* (trans) ) (cis); Emax trans- > cis-
k
1t : Amax Amax :
lic
(a)
C
N=N
Blue shift )
(cis-azobenzene)
(delocalisation sterically hindered)
1t ~1t* (A max = 320 nm) 1t ~1t* (A max = 281 nm)

n ~ 1t* (A max = 443 nm) n ~ 1t* (A max = 443 nm)
1t ~ 1t* and} Amax (trans) ) Amax (cis)

n ~ 1t* Emax :trans- )cis- (1t ~ 1t*)
(b)
H
H Blue shift
H
H R
(trans-cinnamic acid) (cis-cinnamic acid)
(delocalisation sterically
hindered)
7t ~ 7t*: Amax (trans) = 272 nm ) Amax (cis) = 268 nm; Emu: trans-) cis-
ry
(C)
ra
ib
Blue shift
yl
(R=Me)
em
ch
(I) Biphenyl (II) 2-Methylbiphenyl
al
(Steric hindrance slightly hinders the resonance (delocalisation sterically

e
due to the slight loss of coplanarity) hindered)

th
7t ~ 7t* : Amax (I) = 250 nm ) Amax (II) = 237 nm; £max : I ) II

e/
(d)
t.m
For the bulky R (= CMe 3 ) group, conjugation is lost

due to the loss of planarity.
Amax (1t ~ 1t *); 225 nm (R = Me) ) 180 nm (R =CMe 3 )
e
er
i.e. R= Me Blue.hllt) R=CMe 3

H
(e)
k
lic
Fig. 12.5.5.4 Blue shift arising from the steric hindrance to resonance delocalization (affecting more the stability of
the excited state; cf. stability of the charge-separated excited state largely depends on the resonance).
C
Note: (1) For the cis- and trans- isomers, the trans (E)-isomer shows the higher Emax value due to its higher magnitude
of transition moment integral (TMI) compared to that of the cis (Z)-isomer.
(2) Effect of steric hinderance to resonance: Some examples:
(a) 2,3-di-tert-butyl-l,3-butadiene O\'max ::= 180 nm); 2, 3-dimethyl-l, 3-butadiene O\.max ::= 225 nm)
(b) Ortho-nitro-toluene (A max ::= 250 nm); nitrobenzene (Amax ::= 252 nm)
(c) Amax : trans> cis for 1,3,5 hexatriene.
(3) Butadiene and cyclic dienes: The s-cis (i.e., cis-oid) form experiences the steric hindrance but it shows the higher
A..nax
for the n ~ n* transition compared to the s-trans- (i.e. transoid) form which does not experience the steric
hindrance. Thus these diene systems appear as the exceptions. These are discussed later.
(v) Charged ground state: It may be noted that if the ground state is having the charge and
resonance delocalization of the charge is prevented sterically then stability of the ground state is
primarily affected (i.e. ground state is raised more). Then such sterically hindered compounds will
show dE less (i. e. energy difference between the excited and ground state will be less because the
ground state is raised) and it wi~l experience the red shift (Fig. 12.5.5.5).
(Compound I)
(A max ~ 470 nm)
~CH~ ~CH
~ \QJ --- ~N( "'fJ
ry
ra
~ ~
ib
yl
(Compound II)
em
(A max ~ 510 nm)
ch
Amax : Compound II > Compound I, i.e. Compound 1 (Red shift) ) Compound II
al
Fig. 12.5.5.5 Resonance to stabilize the charged ground state facing an stene hindrance in compound II (raising of the
ground state energy, i.e. Amax higher).
e
th
e/
Transition energy (AE) VB. Resonance Delocalization

t.m
• Ground state having no charge separation but excited state having the charge-separation:
In such cases, stability of the charge-separated excited state largely depends on the feasibility
of the resonance. If the resonance is prevented, the energy of the excited state is raised, i. e. the
e
transition energy becomes higher (i.e. blue shift).

er
Butadiene system is an exception.

H
• Ground state having the charge: In such cases, if the resonance is prevented (i.e. charge
k
delocalisation is prevented), energy of the ground state is raised. It makes the transition energy
lic
less, i. e. red shift.

C
(E) Acyclic diene, homoanular and heteroanular dienes:

• Butadiene (cisoid vs. transoid) In butadiene (a representative conjugated diene), the middle
C-C single a-bond links the two ethylenic moieties. Rotation of one ethylenic moiety around the
C-C single bond can generate two forms: s-cis (cisoid) and s-trans (transoid) (Fig. 12.5.5.6) where
s denotes the geometric isomerism with respect to the C-C single bond. In the s-cis form, the hydrogen
atoms on C2 and C3 are eclipsed and the hydrogen atoms on C 1 and C 4 are in steric strain. It makes the
s-trans form more stable than the s-cis form. This is why, butadiene predominantly exists in the
s-trans form.
• Acylic diene vs. monocyclic diene and polycyclic diene: The corresponding monocyclic diene
adopts the cis-oid structure (structural compulsion) and absorbs at the longer wavelength than the
transoid acyclic form. However, intensity of the peak of the transoid acyclic form is higher than that of
the cisoid monocyclic form. It is due to the higher transition moment integral (TMI) value of the trans-
oid structure.
o
A
max
::::: 238· nm Amax
o ::::: 256 nm
Amax ::::: 217 nm Emax ::::: 3500 Emax ::::: 8000
Amax ::::: 270 nm
Emax ::::: 21,000 Cyclopentadiene 1,3-cyclohexadiene
s-cis (cisoid) (Monocyclic diene, cis-oid) (Monocyclic diene, cis-oid)
s-trans (transoid)
Butadiene (acyclic conjugated diene)
.. 00
ry
Red shift
ra
ib
(Heteroanular diene, trans-oid) (Homoanular diene, cis-oid)
yl
Amax ::::: 234 nm Amax ::::: 273 nm
em
Emax ::::: 20,000 Emax ::::: 10,000
ch
Fig. 12.5.5.6 Acyclic vs. monocyclic and polycyclic (i.e. homoanJlar and heteroanular) dienes. ("-max given for the
7t ~ 7t* transition).
al
In the homoanular dienes, the cis-oid structure is the structural compulsion but the heteroanular
e
dienes adopt the trans-oid structure and they absorb at the shorter wavelength as in the case of
th
trans-oid butadiene. The higher intensity of the trans-oid form is due to its higher transition moment
e/
integral (TMI) value. .

t.m
(F) Butadiene vs. alkylsubstituted butadienes: Unsubstituted butadiene preferably adopts the s-trans
conformation rather than the s-cis conformation which is less stable. Their absorption characteristics
are:
e
er
Amax (1t ~ 1t * ) : s-cis ) s-trans; E max : s-trans ) s-cis

H
The higher transition probability for the s-trans conformation makes the higher intensity.
k
Considering the electron pushing effect of the alkyl groups, the alkyl substituted butadienes are
lic
expected to rexperience the red-shift with a hyperchromic effect (cf. Sec. 12.5.8, effect of alkyl groups
on the 1t-n* transition). In fact, it happens so in many cases when the s-trans conformation is main-
C
tained. But, the 1,3-dialkylbutadienes show a large red-shift with a hypochromic effect. In fact, in
their s-trans conformation, the steric crowding between the alkyl groups destabilises the system and to
avoid the steric crowding, it undergoes isomerisation through the rotation about the carbon-carbon
Red-shift'·
(A max : s-cis > -s-trans)

s-trans
(sterically crOWded) s-cis (1, 3-dialkylbutadiene)
(sterically relieved)
single bond to adopt the s-cis conformation. The conversion s-trans to s-cis produces the red shift. The
electronic effect of the alkyl groups also contributes to the red-shift. But, inherently, the transition
probability for the s-cis form is less and consequently the intensity is decreased.
Conclusion: To understand the effect of alkyl substitution on butadiene on Amax and Emax of the
n ~ n* transition, it is important to know whether the substitution can lead to the s-cis conformation
as in the 1,3-dialkyl-substituted one.
12.5.6 Solvent Effect (i.e. Solvatochromism or Solvatochromic Shift) on the Position of

the Absorption Bands
The solvent effect (i.e. solvatochromism or solvent induced shift of Amax ) is very little for the conjugated
dienes and aromatic hydrocarbons but it is quite important for the carbonyl compounds and
ry
a, p-unsaturated carbonyl compounds for which the observations are:
ra
• 1t--+ 1t* transition moves towards the longer wavelength (i.e. red shift) with the increase of
polarity of the solvent.
ib
• n --+ 1t* transition moves towards the shorter wavelength (i.e. blue shift) with the increase of
yl
polarity of the solvent.
em
(A) Electron distribution pattern and polarity of the excited state: Let us consider the character
of the n, n* and n MOs in the carbonyl group (cf Fig. 12.5.1.1). The n-BMO is more enriched with the
ch
character of the 2p-orbital of oxygen while the n* -MO is more enriched with the character of the
al
2p-orbital of carbon. The so-called nonbonding electron pair participating in the n ~ n* transition is
e
housed in a pure p-orbital of oxygen (cf other lone pair on the O-atom is housed in a very low energy
th
sp-hybrid orbital and it does not participate in the n ~ n* or n ~ 0* transition). Thus for the n ~ n*
and n ~ n* transitions, in the excited state, the electron placed in the 1t*-MO is largely concentrated
e/
on the C-centre and it gives the polarity: C&--O~+ (cf opposite polarity in the ground state). Thus
t.m
in the n ~ n* or n ~ n* transition, in the excited state, the O-centre becomes relatively electron
deficient. The transitions can be roughly represented as follows:
e
er
rr'~r:~ , . p-Ione pair

H
~
c-o
.::
"'~I----
hv ' " 8+
C=O
•• ~ hv
.-
k
/ 7t*+-7t / •• (np~7t*)
lic
'--- sp-Ione pair

C
(1t~n;1t *1 ) (1t~n~1t *')

(Excited state) (Excited state)
1 1 1
(1t bond order ="2 (1 - 1) =0) (n-bond order ="2 (2 - 0) = 1) (1t-bond order ="2 (2 - 1) = "2)
(1tb =1t => 1t-BMO; np = or n => NBMO, 1t* => 1t-ABlVIO)
Thus in the excited state, opposite IJolarity is developed and placement of an electron in the
n* -MO makes the n-bond order 0 or ! i.e. C-O bond is elongated in the excited state. This bond
2
length elongation tends to make the dipole moment larger in the excited state. In general, the
excited state (i.e. transition to 1t*) having the longer bond distance shows the higher dipole moment
and the electron distribution is changed in the reverse direction (compared to that in the ground
state as in the 'CO' group). '
(B) Formation of diradical in the excited state: Once again, it may be mentioned that the unpaired
electron in the n*-MO is largely localized on the C-centre in the carbonyl group. Thus the excited state
in the n ~ 1£* transition produces a triplet (S = 1) diradical (See Question No. 31) where one
uppaired electron resides on the O-atom in its p-orbital and another unpaired electron resides on the
C-atom in the n*-MO which is mainly localised on the C-centre. Similarly, the excited state in the
1£ ~ 1£* transition is approximately a diradical where one unpaired electron resides in the n-BMO
mainly concentrated on the O-atom and the other unpaired electron in the n*-MO i.e. on the C-atom.
• Crotonaldehyde (CH3CH CHCHO): "'max = 214 nm (petroleum ether solvent), 220 nm

(ethanol solvent) for the n ~ n* transition; "'max = 329 nm (petroleum ether), 322 nm (ethanol)
for the n ~ n* transition. It indicates that with the increase of solvent polarity, the n ~ n*
ry
transition experiences· the red shift while the n ~ n* transition experiences the blue shift.
ra
(C) Change of energy of the MOs with the change of polarity of the solvent: The solvent induced
ib
shift of "'max for the n ~ n* and n ~ n* transitions can be explained by considering the fact that the
yl
more polar solvents stabilize the n, nand n* -MOs to different extents (see Fig. 12.5.6.1).
em
(i) l£-BMO vs. l£-ABMO (i.e. 1£*-MO) and 1£ ~ 1£* transition: In the n ~ n* transition, in general,
the excited state is more polar (i.e. higher dipole moment) and the excited state is more stabilized
ch
(compared to the ground state) by the more polar solvents through the dipole-dipole interaction and
hydrogen bonding interaction (for the hydroxylic solvents). In other words, by the polar solvents, the
al
n* -MO is stabilized more (compared to the n-MO) and it explains the red shift (i.e. till = Ere* - Ere
e
becomes less due to the lowering of the energy of n* -MO).

th
That the excited state is more polar than the ground state can be clearly understood by taking
e/
the examples of enone and butadiene where the excited state can be represented by a number of
t.m
charge-separated structures (canonical forms).

'\ hv '\ + -
e
/ C=C-C=O~-~)
I I (1t~1t*)
/C-C=C-O
I I
~
er
(Enone)
H
[rn rn
k
CH _ CH - GI 2 H TH 2 CH=CH -
lic
hv ) 2- - 2]
CH 2 =CH-CH=CH 2
(1t~1t*)
(Butadiene)
C
H+CH 2 -CH-CH=CH 2 H ...

(More polar excited state)
Here it is worth mentioning that in the ground state (for the n ~ n* transition), the l£-bonding
electrons are unlikely to participate in the H-bonding interaction because the tightly bound
l£-bonding electrons reside between the nuclei. On the other hand, in the excited state, the unpaired
electron (mainly localized on the C-cetitre) "[n the n:-MO is m~re likely to participate in the
H-bonding interaction.
(ii) NBMO vs. l£-ABMO (i.e. l£*-MO) and n ~ 1£* transition: In the ground state, the nonbonding
electrons are housed in the pure p-orbitals of the electronegative heteroatoms like N, 0 but the
promoted electron into the n*-MO is mainly concentrated on the less electronegative C-atom. 'fhe
nonbonding electrons on the heteroatoms like N, 0 are stabilised more in the ground state (relative to
the excited state) by the polar hydroxylic solvents (e.g. water, ethanol). In other words, the NBMO is
stabilised more compared to the n*-MO by the polar hydroxylic solvents and it makes the transition
energy ~ for n ~ n* larger (cf ~ = E1t*- ENBMO becomes larger because energy of t~e NBMO is
lowered more). It explains the blue shift of the n ~ n* transition for the more polar solvents.
p-Ione pair
(Here, it has been assumed that
~ 0+
" \... •• ----H-OR hv ". • ----H-OR both the lone pairs of O-atom
"C=O
/"C=O
f .. ---·H-OR / ··----H-OR participitate in H-bonding inter-
action. But in reality, one lone
sp-Ione pair
pair housed in the sp-hybrid or-
(H-bonding interaction with (H-bonding interaction with bital is less readily available for
the solvent R-QH at the the solvent R-QH at H-bonding).
ground state) the excited state)
In the ground state, two lone pairs of the carbonyl oxygen are available for H-bonding interaction
ry
with the protic solvent. On the other hand, in the excited state (for the n ~ n* transition), one nonbonding
ra
electron is placed in the n*-MO which is enriched with the character of the 2p-orbital of carbon. Thus
ib
the loss of one electron from oxygen and gain of the electron in the n*-MO make the oxygen centre
yl
slightly electron deficient and the carbon centre slightly electron rich. Thus in the excited state (for
em
n ~ n* transition) the H-bonding interaction by 0 is less efficient because of two reasons:
• less number of nonbonding electrons (1.5 V.s. 2 pairs) are available for H-bonding;
ch
• oxygen is relatively more electron deficient.
Here it is quite reasonable to assume that participation of the unpaired electron in the n*-MO
al
(present in the excited state) in the H-bonding interaction with the solvent is relatively less important
e
in the case of n ~ n* transition.

th
This is why, the H-bonding interaction with the protic solvent relatively stabilises the ground state
e/
more than the excited state. It makes the transition energy f1E larger (i.e. blue shift).
t.m
Note: • Number of nonbonding O-electrons available for H-bonding: In terms of the more
correct MO diagram, it can be shown that the two lone pairs on oxygen are residing in two different
NBMOs differing in energy (ef Fig. 12.5.1.1). Approximately one lone pair resides in a pure p-orbital
e
of oxygen and the other lone pair resides in an sp-hybrid orbital. The sp-lone pair of lower energy is
er
relatively less readily available for H-bonding. In fact, the nonbonding pair in the p-orbital more
H
readily participates in the H-bonding interaction and this nonbonding electron participates in the n ~
n* transition.
k
lic
Thus, out of the two lone pairs, the lone pair residing in the higher NBMO (i.e. almost pure p-orbital)
is more readily available for H-bonding. Thus in the ground state, one lone pair is more readily
C
available for H-bonding interaction with the solvent while in the excited state, the relatively
electron deficient O-centre can provide only one electron for the H-bonding. It makes the more
stabilisation of the ground state (compared to that of the excited state) through the H-bonding with the
polar solvent.
(D) Electronic transition time (i.e. Franck-Condon principle) vs. solvent rearrangement time:
Some workers have suggested that in the polar solvent, the excited state is energetically raised (rather
than lowered) while the ground state is lowered. It explains the blue shift. In the ground state, the
solvent dipolar molecules are properly oriented but the excited state needs a different pattern of orientation
of the solvent molecules for solvation (ef for the CO group, in the ground state, negative pole resides
on 0 while in the excited state, negative pole appears on C i.e. mode of charge separation in the
excited is different from that of the ground state). It is believed that during the time of electronic
transition, the solvent molecules cannot find time (ef Franck-Condon principle: electronic transition
is much faster than the rearrangement process of the solvent molecules) to rearrange to solvate the
excited state and consequently, the excited state is energetically raised in the more polar solvent
(i.e. solvent of higher dielectric constant).
n-ABMO --:.4~--.4-:-~---';':"':':~~~'~"""""""""""""""""················1 ..····················..····..···..····........

(n*-MO) "" ~E2> ~E1
"'" ( n*)
.4~
n~n
n~n
NBMO _+--_ _..a...-_ _~ .
'" .4~
ry
"" (v 2') ~E3 > ~E2
'"
ra
"
'" _-+-_ _--l-_-lI~~- (n)
ib
n~n
yl
(v/ <v1) (red shift)
em
n~n
ch (v 1 ') •
n-BMO---'--------~'"'<:==~~===~~~~ ·······································l~·E;~:)
al
(Less polar (More polar

e
solvent) solvent)
th
Fig. 12.5.6.1 Effect of solvation by the polar solvents on the n ~ n* and n ~ n* transition energies in carbonyl
e/
compounds. (dE 3 ) M 2 ) dEl)'

t.m
Solvent shifts of the n ~ n* transition in acetone are as follows:

Solvent: C6 H 14 CHCl 3 C2 HsOH CH 30H H2 0
e
er
Amax(nm): 279 277 272 270 264

Solvent polarity increasing and Amax decreasing (i.e. blue shift).
H
k
(E) Different possible factors to cause the solvent induced blue shift: Blue shift may occur under
lic
the different possible conditions: • lowering of energy of the ground state; • raising of energy of the
C
excited state; • relative 1/ more lowering of energy of the ground state; • relatively more raising of
energy of the excited state. Spectral measurement only gives the value of ~E. Thus it is difficult to
predict the exact reasons causing ~E higher (i.e. blue shift). Similarly, for red shift, different possibili-
ties also prevail.
(F) Fate of the n ---+ 1t* transition in acidic solution: The. nonbonding electrons on the carbonyl
oxygen is strongly stabilised through the protonation and ~E3 (Fig. 12.5.6.1) becomes very large. It
makes V2' too large and the absorption band for the n ~ n* transition may disappear. In fact, in acidic
condition, the n ---+ 1t* transition disappears for pyridine because of the protonation of the lone pair
on nitrogen.
12.5.7 Effect of Intramolecular H-Bonding on the Positions of the Absorption Bands:

Identification of Keto-Enol Tautomerism
The excited state is more polar than the ground state in the 1t ---+ 1t* transition. Thus the excited state,
in the n ~ n* transition can strengthen the H-bonding interaction better than the ground state. The
n-bonding electron tightly placed between the nuclei can hardly participate in H-bonding interaction
with the solvent but the excited electron present in the n*-MO (predominantly localised on the
C-centre) is more readily available for H-bonding interaction with the solvent. This is why, the excited
state is more stabilised than the ground state through the H-bonding interaction. It gives the red
shift.
• Intramolecular vs. intermolecular H-bonding: It is illustrated for the ortho- and para- isomers
of nitrophenol and nitroacetanilide. In the ortho- isomer, the intramolecular H-bonding leads to the
red shift with a higher cmax for the 1t ~ 1t* transition, i.e. cmax and Amax(ortho) ) cmax and Amax (para)
(no intramolecular H-bonding in the para-isomer).
OH C0 2CH 3
©C°"H ©rN_ I
ry
a : .. N--~ ..
ra
+/0
Red
a Red
Shift
ib
Shift
N
II
yl
II ~N~
+
~N~
em
0 o 0 0 o 0
o-nitrophenol p-nitrophenol o-nitroacetanilide p-nitroacetanilide
ch
(yellow) (pale yellow) (yellow) (pale yellow)
In fact, in the ortho-isomer, the better intramolecular H-bonding in the excited state stabilises the
al
excited state more compared to the ground state. It reduces the transition energy (AE). Stabilisation
e
of the excited state through H-bonding is better for the ortho-isomer experiencing the intramolecular
th
H-bonding than for the p-isomer experiencing the intermolecular H-bonding. For the smaller ~E
e/
value, Amax is higher and the transition probability is also higher (cf. Sec. 12.5.5) due to the better
t.m
relaxation of the spin forbidden transition. It explains the higher intensity of the colour of the ortho-
isomer.
• Keto-enol tautomerism in fi-diketones and fi-ketoesters: They remain as the mixtures of keto
e
er
and enol forms. The keto-form shows only the n ----; rc* weak transition due to the keto-carbonyl group
at about 275 nm. while the enol form shows both the rc ~ rc* transition (strong) due to the conjugated
H
double bond and n ~ rc* transition (weak) due to the carbonyl group. Presence of the strong 1t ~ 1t*
k
transition indicates the existence of the enol form. In acetylacetone, the enol form is strongly stabi-
lic
lised by the intramolecular H-bonding and the 1t ~ 1t* transition due to the conjugated double bond
C
experiences the red-shift. For acetylacetone, in aqueous solution, there is about 15% enol form while
in the nonpolar solvent, the enol content is about 90%.
Because of the competitive resonance in the enol forms of ~-ketoesters, the enol forms are relatively
less stable compared to the enol forms of the ~-diketones (see Sec. 13.1.7, Vol. 3). The enol forms
are characterised by the n ~ n* strong transitions of the (l, fi-unsaturated carbonyl system (cf.
Table 12.5.9.2).
Characteristics of the isolated carbonyl group and a, fi-unsaturated
carbonyl group (cf. Table 12.5.9.2).
1t --+ 1t* (strong) n --+ 1t* (strong)
)C=O:
l~~ l~:a
180 -200 nm 270-290 nm
:a
~ ~
"'C "0
)C=C-r=O: 220-230 nm -320 ~

QJ
The n-n* transition band in the a, ~-unsaturated carbonyl system experiences a further red-shift
through an intramolecular H-bonding in the enol form of ~-diketones and ~-ketoesters. The degree
of red-shift depends on the stability of the said H-bonding interaction. In acetylacetone, the
intramolecularly H-bonded structure is more stable than that for ethyl acetoacetate (see Sec. 13.1.7,
Vol. 3). This is why, red-shift for the 1t ~ 1t* transition in the enol form of acetylacetone is very
high (shifted to about 275 nm). The corresponding shift (to about 245 nm) for ethylacetoacetate is less
because of the less stability of its enol form.
Ethylacetoacetate: (A max ::=: 245 nm, smax::=: 18000)
ry
ra
(Two competitive resonance)
ib
yl
o 0 ",H ..
0.... '0
II II ~
em
Acetylacetone: I, II (A max '" 277, Emax '" 2000, in water)
~3C
AA CH3 HC3
~ CH ch 3
1t~1t*
~
al
n, p-unsaturated carbonyl
system in the enol-form
e
:l
th
H3C CH 3 H3 C CH 3
X
AA "'-X-'.:
e/
Dimedone:
(A '" 255 nm, E '" 1700)
~ OH 1t~1t'
t.m
max max
o 0 o
e
(Incapable of forming the chelation

er
through the intramolecular H-bonding)

H
In fact, position of Amax for the enol form of dimedone is in agreement with the calculated value from
the Woodward-Fieser rule.
k
lic
• Solvent effect - acetylacetone and ethyl acetoacetate: The keto form of ethylacetoacetate shows
a weak (Emax == 20) n --, 1t* transition at about 275 nm (characteristic band of an isolated keto-
C
carbonyl group) while the enol form of ethylacetoacetate shows a high intensity band at about 245
nm (E max -20000) for the 1t ~ 1t* transition due to the conjugated double bond. In the case of
keto-enol tautomerism (e.g. ~-diketone like acetylacetone, ketoester like acetoacetic ester), the keto
form is stabilised in the protic solvents through the intermolecular H-bonding with the solvent while
in the aprotic solvent, the enol form stabilised by the intramolecular H-bonding predominates.
yy.. 0 0,
In the protic solvents, the keto-
form predominates while in the
O---H" aprotic solvents, the enol form
predominates and the 1t ~ 1t*
H
/ transition becomes strong.
(Intermolecular H-bonding (intramolecular

with the solvent) H-bonding)
This is why, the band at about 275 nm (7t ~ 7t*) for acetylacetone becomes more intense in
nonpolar solvents. Similarly, for ethylacetoacetate, the band at about 245 nm (n ~ n*) becomes more
intense in nonpolar sovents.
The excited state in the n ~ n* transition is relatively more polar than the ground state and the
excited state is relatively more stabilised for the more polar solvent. Thus the n ~ n* transition for the
conjugated double bond in the enol forms of ~-ketoesters and ~-diketones experiences the red shift
with the increase of solvent polarity (see Fig. 12.5.6.1). It is illustrated below: (Emax in dm3 mol-l em-I)
Acetylacetone Ethyl acetoacetate

(n ~ n* transition in the enol form) (n -t n* transition in the enol form)
Solvent Amax (nm) % Enol Solvent Amax (nm) % Enol
ry
Hexane 269 1 ~ 12,000 96 Hexane 2441 ~ 8000 51
ra
Alcohol 273; 10,500 85 Alcohol 246; 1900 12
~ ~
ib
Water 277 ~ 2000 15 Water 255 ~ 125
yl
• Tautomerism in 2-hydroxy pyridine and cyclic a-diketones: In these cases, the enolic forms are
em
more stable and the absorption is related to that of an a, tJ-unsaturated carbonyl system. It may be noted
that in the acyclic a-diketones (e.g. biacetyl, benzil, etc.) no such enolisation is possible (see Q. No. 22).
ch
al
OH
~ (\
e
~N~OH
(Enolisation)
th
N 0
o
I
e/
2-hydroxy H
t.m
pyridine (pyridone-2) A cyclic a-diketone (called diosphenol)

• Indigotin: Its trans- fonn is stabilised through the intramolecular H-bonding and the excited state
e
is stabilised more because the excited state is more polar. It makes the LUMO of lower energy and the
er
electron transition occurs at low energy and indigotin looks blue coloured. See Sec. 12.5.5 for more
H
examples where the charge separated excited state is stabilised, i. e. transition energy (11E) is reduced.
k
lic
C
trans-form of indigotin:
(Weaker intramolecular H-bonding (Stabilised more through the stronger

intramolecular H-bonding in the
in this structure having no charge
,separatiOn) charge separated structure) )
V
12.5.8 Characteristics of the Absorption Bands in Alkenes and Polyenes
(i) Effect of conjugation: We have already mentioned (Sec. 12.5.5) that with the increase of the length
of conjugation, Amax and Emax increase.
(ii) Effect of the electron donor auxochrome: The electron donor groups (-b) like -OR, -SH,
-NH 2 etc. can extend the length of the conjugated system to reduce the transition energy (i.e.
bathochromic shift for the 7t --+ 7t* transition). In fact, resonance of the lone pair on the heteroatom
with the double bond(s) increases the length of the conjugated system.
"'~
C=C-D r. ' "C- - C = D+
/ 1 / I
In terms of MOT, the lone pair (i. e. nonbonding electron) on the auxochromic groups participates in
the Tt-MO formation leading to the extension of delocalisation (Fig. 12.5.8.1).
LUMO)
(LUMO) -_-_-_...._-_-_-_-_-_-_....__ \-----------.--~E < ~E
~ V ~---------y- 2 1
2
\ r--------------,
ry
//' " \\ V1 >v 2; ~E1 >~E2
ra
V1 // '" \ Both the HOMO and LUMO
/// ~E '" '\ are raised but energy of the
ib
~~~::~:------------------- '<::\L-H_O_M_t_~_~~_~_:_~_etd_he_m_~U_r~_r_~_la_tiv_e.....l
yl
_--+-+-:--_ _ '
,' "~'-*-
em
{HOMO)
~
1t
" //"#
'\ /// n (i.e. NBMO)

ch
"'C-C/
"'" //// 0
/-'" , / (Nonbonding
al
"'~// electron on D)
e
th
"'c=c-o
/ I
e/
t.m
Fig.,l2.5.8.1 Formation of new MOs through the interaction of the nonbonding electrons on D (auxochrome) with
1t-system of the ethylenic chromophore (v I ) v 2 i.e. red-shift due to the participation of the nonbonding electron on
aU~9chrome).
e
er
(iij) Hyperconjugative effect: The alkyl groups like Me on being attached with the ethylenic
H
chromophore can also cause the red shift. It is believed that the C-H bonding pair of the CH 3 group
participates in resonance with the double bond.
k
lic
"'~ ("I
C
C=C-C-H
"
"C - C = C / '
-
H+ H
/ 1 1
/ "-H
H
Thus the hyperconjugation can also lead to increase the length of conjugation. It introduces the red
shift in the same way (Fig. 12.5.8.1) done by the electron donor (:D) auxochromes.
(iv) Woodward-Fieser rules for dienes: By using these rules, it is possible to calculate the Amax for
different dienes. For these rules, the readers are suggested to consult any standard textbook on organic
chemistry.
Combination of Chromophores: Extension of Conjugation: Red shift

for the 7t --+ 7t* Transition
The model, 'particle in a one dimensional box' can also explain the result.
12.5.9 Characteristics of the Absorption Bands of the Carbonyl Compounds

The isolated carbonyl compounds show the two characteristic transitions, i.e. n ~ n* transition (.... 190
nm, allowed) and n ~ n* transition (-280 nm, forbidden) (ef. Fig. 12.5.1.1)
(i) Effect of the electron donor auxochromes (:D= - NR 2 , - QR, - QH, - NH 2 , - g:, etc.):
Substitutiun on the carbonyl group by such auxochromes as in acids, esters, amides, acid chlorides
gives two important effects.
• n ~ n* transition experiencing the hypsochromic shift (i.e. blue shift).
• n ~ n* transition experiencing the bathochromic shift (i.e. red shift).
(0
11r:. ,,~ n.
ry
-C-D (cf. / C = , - D , Fig. 12.5.8.1)
ra
ib
yl
• 1t ---+ 1t* transition: Participation of the nonbonding electrons of D in resonance with the n-bond
em
extends the length of conjugation (ef. Fig. 12.5.8.1) and it explains the bathochromic shift in the
1t ---+ 1t* transition (actually HOMO is raised, see Fig. 12.5.8.1).
• n ---+ 1t* transition: The auxo'chromic group bears the electronegative atoms like 0, N, Cl, etc.
ch
which show the electron withdrawing inductive effect. Consequently, the lone pair on the carbonyl
al
oxygen is less readily available for the n ~ n* transition. This is the major cause for the observed
e
hypsochromic shift. In addition to this, the 1t*-MO (i.e. LUMO) is also slightly destabilised due to
th
the participation of the lone pair on~D.(i.e. auxochrome) in resonance with the carbonyl group (ef Fig.
e/
12.5.8.1). This is also partly responsible for the observed hypsochromic shift.
t.m
Table 12.5.9.1 Hypsochromic shift of the n ~ n* transition in H 3 C - C- X due to the auxochromes (X).
II
o
e
er
x Amax (om) Emax Solvent

H
H 293 12 Hexane
k
CH 3 279 15 Hexane
lic
CI 235 53 Hexane
C
OH 204 41 Ethanol
NH 2 214 41 Water
OCH2CH 3 207 41 Ether
OCOCH 3 225 47 Isooctane
(ii) Effect of the substitution by alkyl groups: The alkyl groups like Me can show the hyper-
conjugative effect in which the a-bonding electron pair of the C-H bond will participate in resonance
with the carbonyl group to raise the 1t*-MO (ef. Fig. 12.5.8.1) but the nonbonding electrons on the
oxygen of the carbonyl group will not be affected.
o
~I ,1
-C-C-H ~ -C=C
I H+ /H
(i.e.,n~1t*,blueshift)
H
I "H
Thus here the observed hypsochromic shift (i.e. blue shift) for the n ~ n* transition mainly arises
from the destabilisation of the n*-MO.
(iii) ) C= Q vs. )C = ~ : Sulfur is less electronegative than oxygen, i.e. the nonbonding electrons
lying with the S-atom are less tightly bound (i.e. NBMO is of higher energy). It makes the n ~ n*
transition at the longer wavelength for )C=§.
c~9°
/ (Enone) " "
ry
""c=o
ra
ib
;(carbOnYI)
yl
em
ch
-165 nm
al
(n)
e
th
-190 nm (K-band)
1t-BMO
e/
(1t)
t.m
e
er
Fig. 12.5.9.1 Effect of combination of two chromophores ) C=C( and )C=O. on the positions of n ~ n* and
H
n ~ n* transitions. Compared to the noninteracting chromophores, in the interacting chromophores (i.e. combined
chromophore) both the n ~ n* and n ~ n* transitions experience the red shifts (see Particle in a Box Model).
k
C)
lic
Table 12.5.9.2 Bathochromic shifts in enones.

C
n ~ 1fl< (strong) n ~ ~ (weak, forbidden)

(nm) (nm)
"'c=o 190 280-290

/
-c=c-c=o 220-240 320
I I
-C=C-C=C-C=O 270 350
I I I I I
o=< )=0 245 435 (visible range)
(iv) Attachment of an ethylenic double bond giving rise to enone: The a, ~-unsaturatedcarbonyl
compound is the representative example. Here both the n ~ n* and n ~ n* transitions experience the
bathochromic shift but the degree of bathochromic shift for the weaker n ~ n* transition is relatively
less. The bathochromic shift in the enones can be best explained in terms of MOT (Fig. 12.5.9.1).
(v) Woodward's rules for enones: Enones exhibt the intense n ~ n* transitions of the carbonyl
group in the range 220-270 nm and the n ~ n* transition (weak) in the range 300-350 nm. From the
structural modifications, the "'max for the n ~ n* transitions can be calculated from the Woodward's rule.
(vi) Enolisation in p-diketones, cyclic a-diketones, 2-hydroxy pyridine producing the a,p-
unsaturated carbonyl system: This aspect has been discussed in Sec. 12.5.7.
(vii) Acyclic a-diketones (e.g. biacetyl, benzil): In such cases, enolisation is not possible. Success
of conjugation between the carbonyl groups depends on the dihedral angle (see Q. No. 22).
ry
B~nds in
ra
12.5.10 Characteristics of the Absorption the Aromatic Compounds
ib
In terms of MOT, the HOMO of C6H6 (benzene) is degenerate (n2' n3) and LUMO is also degenerate
(n 4 *, n 5*). The one electron transition from HOMO ~ LUMO can occur in 4 possible ways but the
yl
transition energy is expected to be the same for these four n ~ n* transitions in terms of HMO
em
(Buckel's molecular orbitals) where the electron-electron repulsion has been ignored. But in terms
of electron-electron repulsion and symmetry considerations, the transition energies are different.
ch
1 ()2 ( )4 255 nm, £:::::200 1 (B - band)
al
A1g i.e. a 2u e1g (forbidden» B2u
(Ground state)
e
th
205 nm, £:::::7,500 IB (E K b d)· l

AIg 180 nm, £==60,000
(forbidden) ) lu 2- or - an,
e/
(allowed)
The ground state configuration (a2u)2 (el g)4Ieads to the lA 1g ground electronic state but the n ~ n*
t.m
transition leads to the electronic configuration, (a2u)2 (el g )3 (e2u)1 which leads to the energy states B 1u '
B 2u and E 1u • In terms of HMO, these three energy states are degenerate but incorporation of the
e
interelectron repulsion terms shows that these three states are of different energies. It leads to
er
three different transitions.

H
The allowed IA 1g ~ IE 1u transition is very intense (Emax ::::: 60,000). Between the forbidden transi-
tions, the lA 1g ~ IB 1u transition is relatively more intense (Emax ::::: 7,500). The IA 1g ~ IB2u transition
k
lic
is very weak (Emax ::::: 200). Why?

Intensity stealing and mixing of the energy states: Energetically, the 1B lu state is closer to the 1E 1u
C
state (Fig. 12.5.10.1) i.e. degree of mixing between the IE 1u and IB 1u states is more compared to the
degree of mixing between the lEI u and I B 2u states (admixture of the 1E 1u state). It indicates that the
transition IA 1g ~ IB 1u bears the more proportion of the allowed IA 1g ~ IE 1u transition. In fact, a
forbidden transition energetically close to an allowed transition gains some intensity in this route called
intensity stealing phenomenon (see Chapter 7).
The IA 1g ~ IB 1u (K-band) and IA 1g ~ IE 1u (E 1-band) transitions give the primary bands while the
!A 1g ~ IB 2u (B-band). transition (lowest energy transition) gives the secondary band (bearing the
vibrational fine structure) called the benzenoid band. The band due to the IA Ig ~ IE lu transition is
highly intense (Emax ::::: 60,000, allowed transition). The other two bands are partially allowed through the
vibronic coupling. For the aromatic compounds (i.e. benzene derivatives), the benzenoid fine struc-
ture band (i.e. B-and) appears in the range 250--280 nm. This benzenoid band is a characteristic
band of the benzene derivatives. The benzenoid band moves towards the longer wavelength (i.e. red
shift) in the polynuclear aromatics with the increase of the number of the rings.
180
mm
11:~ - - - - r ~-
1
.4~
1
" .4
205 25 5
mm mm
ry
1~ 11: 1 (a2U ) ------'------------- -
ra
(a 2U )2 (e 19)4
(Huckel's 11:-MOs
ib
and 4 transitions) (HOMO)
yl
Fig. 12.5.10.1 The lowest energy n ~ n* transitions in benzene (D 6h symmetry). (See Chapter 9, Vol. 2 for the details
em
of the MOs).
Note: The highest energy transition (i.e. \A\g ~ lE 1u ) is allow·ed·(x, y polarisation) but the other two forbidden
ch
transition are partially allowed through the vibrionic coupling. How?
Hints: • Character Table of D 6h point group (see Appendix 12A):

al
~x, ~y ~ E lu
and ~z ~ A 2u-
e
~x, My,
the direct product A Ig x ~ X E lu contains the totally symmetric species A Ig i.e.
th
• For
IA Ig ~ IE lu transition is fully allowed in D6h symmetry.
e/
• The direct products, A Ig x ~ X B lu and A Ig x ~ X B 2u are lacking in the species A Ig i.e. the
t.m
IA Ig ~ IB Iu and IA Ig ~ IB 2u transitions are symmetry forbidden.
• rf.!rex = (A 2u + E lu )
X B lu = B 2g + E 2g ; rf.!r ex = (A 2u + E Iu ) X B 2u = BIg + E 2g .
e
• 30 normal modes of vibration of C6H 6 are: 2A Ig + A 2g + A 2u + 2B lu + 2B 211 + E Ig + 2B2g+ 3E lu

er
+ 4E2g + 2E2u . It indicates that the IA Ig ~ IB Iu transition is vibronically allowed through the
coupling of the B 2g and E2g modes of vibration. The symmetry forbidden IA Ig ~ IB 211 transition is
H
also allowed vibronically through the coupling of the E 2g vibration (i.e. E 2g vibrational mode is
k
simultaneously excited).
lic
C
Q)
c..>
c
0 Q)
c..>
c
0
(lj (lj N
.0 .0
0en 0en
.0 .0
« «
1 1
280 260 240 220 280 260 240 220
. - Wavelength . - Wavelength
Fig. 12.5.10.2 Benzenoid band in benzene and pyridine in 95% ethanol.
Note: • The bezenoid band (7t --+ 7t*, i.e. B-band, lA lg --+ IB lu .symmetry forbidden) is vibronically
allowed and it has the characteristic vibrational fine structure. This vibrational fine structure is more
pronounced in vapour phase and nonpolar solvents but less evident in the polar solvents.
• The said benzenoid band in pyridine is more intense because incorporation of 'N' reduces the
symmetry. Because of the N-Ione pair, n ~ n* (at - 270 nm) transition occurs and this band experi-
ences the blue shift with the increase of polarity of the solvent. In acidic solution, this n ~ n*
transition disappears due to protonation by the N-lone ,pair.
• Substituents (both electron donor and electron withdrawing) on the benzene ring produce the red
shift. This aspect is discussed separately. .
(a) Effect of the electron donor substituents(:D = -QR, - NH 2 , - QH, etc.): Such electron
donor groups can utilise their nonbonding electrons to·extend the conjugation. It gives the bathochromic
ry
shifts of both the primary and secondary bands. This bathochromic shift can be understood in terms of
ra
Fig. 12.5.8.1. Participation of the nonbonding electrons of D with the 7t-system of the benzene ring
ib
raises the energy of the HOMO more relative to that of the LUMO. It causes the bathochromic shift.
yl
em
ch
al
For aniline (i.e. - b = -NH 2 ) , the benzenoid band (i.e. lA 1g ~ IB 2u transition) experiences the
e
bathochromic shift (Amax ~ 280 nm) noted in ethanol solution. Other bands also experience the similar
th
red shift (cf. K-band, 205 ~ 230 nm). On protonation (i.e. Ph-NH3+), the N-Ione pair is no longer
e/
available for extension of delocalisation and then the benzenoid band appears at about 255 nm, i.e.
t.m
anilinium cation behaves like the benzene itself. In fact, aniline in an acidic aqueous solution shows
the K-band at 203 nm and B-band at 255 nm. In water, the lone pair of nitrogen of aniline also is
heavily engaged in H-bonding interaction with water, i.e. aniline behaves partly as the anilinium cation.
e
er
<
b-
o
H
Aniline + H+ - - }-NH;;
8+/
H " H8+
k
: (H-bonding with the solvent water

lic
makes the N-Ione pair less readily
0-
I
- N"'"H available for conjugation with the

C
\\\ III 2
rr-system of the benzene ring.)
The nonbonding electron of D can also lead to the n ~ n* transition which is absent in benzene.
<}-O_hV .. ~
(n~1t*)
Here one nonbonding electron of D is excited into the n*-MO to cause a charge separation.
The alkyl groups can act as the electron pushing groups through the hyperconjugation with the
n-system of the ring to cause the red shift. This effect is sterically hindered for the o-isomer.
(b) Effect of the electron withdrawing group: It also increases the conjugation but the direction of
charge separation is opposite (compared to the case of electron donor substituent).
o
()= c"
+ /
If
- R
The mesomeric electron withdrawing groups also cause the bathochromic shift (an effect of the
extended conjugation).
(c) Disubstituted benzenes: Here position of the absorption band depends on the relative orientations
of the disubstitution. For example, for the para-disubstitution, the groups like NH2 (electron donation
ry
through the mesomeric effect) and N02 (electron withdrawal through the mesomeric effect) electroni-
ra
cally assist to shift the Amax towards the longer wavelength, i.e. bathochromic shift. But the groups
ib
like NH2 and OMe being placed at the para-positions electronically oppose. Here both the groups are
yl
electron donor groups (mesomeric effect).
(Ex~enSi~n of
conJug~tlo.n, H2N
.02QD..
ch
em
r ~
(Electronically
OMe opposing
synergistic . - •• substituents)
action)
e al
For the para-disubstitution, if both the groups are electron donor or electron withdrawing, the
th
group causing the stronger shift will solely determine the value of Amax. For example, in para-
e/
nitrobenzoic acid, the Amax is the same as that of nitrobenzene (cf the N0 2 group causes the stronger
shift compared to the C02H group).
t.m
Table 12.5.10.1 Effeet of substituents (causing red shift) on Amax for C6Hs - X (E max in dm3 mol- I em-I)
e
er
-X Primary band (K-band) Secondary band (B-band)

H
Amax (om) Emax Amax (om) Emax

k
-H 205 7,500 255 200

lic
-CI 210 7,400 264 200

C
-CH 3 207 7,500 261 225

-OH 210.5 6,100 270 1450
-0- 235 9,400 287 2600
-NH 2 230 8,600 280 1450
-+NH 3 203 7,500 254 160
-C0 2H 230 11,600 273 970
-C02 - 224 8,700 268 550
-OCH 3 217 6,400 270 1500
-N0 2 252 10,000 280 1000
-CHO 249.5 11,500 280 1400
-COCH 3 246 10,800 280 1200
-CN 224 13,000 270 1000
For the ortho- and meta- disubstitution, the shift effects are additive. For the ortho-complounds,
the bulky groups may sterically hinder the mesomeric effect. This aspect should be considered (for
example: Amax : nitrobenzene> ortho-nitrotoluene; prevention of resonance causing the blue shift; cf
Fig. 12.5.5.4).
The above mentioned effects are illustrated below for the K-band:
Amax (in nm) : o-nitroaniline (283); m-nitroaniline (280) < p-nitroaniline (380)
Amax (in nm) : o-nitrophenol (279); m-nitrophenol (274) < p-nitroaniline (318)
Amax (in nm) :p-dinitrobenzene (261)
ry
(d) Solvent effect: With the increase of the polarity of the solvent, the n ~ n* transition experiences
the red shift. In the ground state, distribution of the n-electron cloud is symmetrical and the molecule
ra
is nonpolar. Excited state bearing one electron in the n*-MO does not have the symmetrical distribution
ib
of the electron cloud and this excited state is polar. Thus the excited state will be stabilised more in the
yl
presence of more polar solvents. It makes the HOMO-LUMO energy separation less (cf n*-MO is
em
lowered in energy, see Fig. 12.5.6.1).
For the substituted benzene derivatives, solvation of the substitution is of an important consideration.
ch
Aniline shows Amax = 230 nm for the K-band in ethanol but this Amax is shifted to 203 nm in an acidic
al
aqueous solution (cf 204 nm for unsubstituted benzene). In an aqueous solution, the nitrogen lone pair
is also engaged in H-bonding interaction with the solvent water molecules imparting the character of
e
the anilinium cation and this nitrogen lone pair is less readily available for ~onjugation with the
th
benzene ring. In ethanol, the said H-bonding interaction is relatively weaker and the nitrogen lone
e/
pair is more readily available for the said conjugation to shift the Amax towards the longer wavelength
t.m
(compared to that of benzene). Thus the 1t ~ n* transition energy in the anilinium cation (i.e.
Ph-NHj) or strongly H-bonded aniline is almost the same as in the unsubstituted benzene.
e
R
er
o
H
Red
k
Shift
lic
(R = CH 3)
R
C
ortho-xylene
Benzene Biphenyl
2,2'-Dimethylbiphenyl
Amax (K-band) Amax (K-band) Amax (B-band)
Amax (B-band)
~ 205 nm ~ 252 nm ~ 264 nm
~ 270 nm
Emax ~ 8000 E ~ 20,000 Emax ~ 800 E max ~ 280
max
R H R H
Planar conformation Twisted conformation

(Predominant for R = H) (Predo~inant for
R = Me)
(e) Resonance interaction between the aromatic rings: Conjugation between the rings leads to the
greater delocalisation of the 1t-electron cloud and it causes the red shift. However, if the conjugation
between the rings is sterically prevented because of the loss of coplanarity, then the effect will be less.
It is illustrated in the examples, benzene vs. biphenyl.
For the favoured conjugation between the rings, the rings should be coplanar and it is totally
prevented if the rings are at 90 0 • In biphenyl, to avoid the steric hindrance (see Fig. 12.5.5.4), the rings
are at about 40° and conjugation between the rings is slightly prevented. However, this extended
conjugation leads to the red shift. For the bulky ortho-substituents (say R =CH 3 in place of H), to avoid
the steric repulsion between R (of one ring) and H (of another ring) (see Fig. 12.5.5.4), the twisted
conformation having a large deviation from coplanarity of the rings is preferably adopted. In the stable
twisted conformation (twisting angle close to 90 conjugation between the rings is severely af-
0
ry
),
fected. In absence of the conjugation between the rings, 2, 2'-dimethylbiphenyl is structurally equiva-
ra
lent to two molecules of ortho-xylene. In fact, the UV-spectral data of ortho-xylene and 2,
ib
2-dimethylbiphenyl are very much comparable. If the benzene rings are linked by a methylene group,
yl
then there is no conjugation between the rings and it gives the spectral behaviour of benzene.
Diphenyl methane
ch
em o
al
Amax (B-band)
e
Amax (B-band) ::::: 262 nm ::::: 260 nm

th
Emax ::::: 500 nm Emax ::::: 200

e/
(No conjugation between the rings)

t.m
(f) Condensed systems (e.g. naphthalene, anthracene, etc.): The Amax increases with the increase
of the degree of condensation. The benzenoid band for the benzene derivatives appears in the 250-280
e
nm but for the polynuclear aromatics like naphthalene, anthracene, phenanthrene, etc. this benzenoid
er
band shifts towards the longer wavelength (ef effect of the extended conjugation).
H
0 (0 OCO
k
lic
~ h- ~ ~ ~
C
No. of rings (n): 2 3 5 ..
Amax (B-band): 255 286 375 580 (blue; n = 5

(nrn) pentacene)
~
Red shift
12.5.11 Colour of Halogens and Different Colours of Iodine (1 2) and Bromine (Br2) in
Different Solvents
Different colours of the halogens (X2) have been interpreted and discussed in terms of the n*(HOMO)
to cr*(LUMO) transition energies in Sec. 9.9.2 (Vol. 2). 12 or Br2 forms an adduct with the solvent where
X 2 acts as a Lewis acid. It causes a blue shift in the n* ~ 0* transition and the extent of blue shift
depends on the donor strength of the solvent. This aspect has been discussed in detail in Sec. 14.7.5
(Vol. 3).
12.6 ELECTRONIC STATES OF DIATOMIC MOLECULES AND ELECTRONIC SPECTRA

OF DIATOMIC MOLECULES
12.16.1 Electronic States and Term Symbols of the Diatomic Molecules and Ions
(cf. M.L. Campbell, J. Chern. Educ., 73,749,1996)
To describe the electronic states of the diatomic molecules by the term symbols, we can follow a
procedure analogous to the Russel-Saunders coupling scheme applied for the polyelectronic atoms. The
electronic state of a molecule is described in terms of the total spin and orbital angular momenta of the
electrons.
(A) Total orbital angular momenta of all the electrons along the direction of the internuclear axis
of the molecule: The ~rbital angular momenta of all the electrons of the molecule combine to give a
ry
resultant vector ([) which is strongly coupled to the electrostatic field produced by the two nuclear
ra
charges of the diatomic molecule. The component of the resultant vector along the internuclear axis
direction is quantised and its magnitude is given by:
ib
yl
h
axial component of the orbital angular momentum =1ML I = An, ( n = 21t)
em
The quantum number A can have the values like 0, 1,2,..., L - 2, L - 1, L, i.e. A = IMLI (absolute
ch
value of M L ).
Note: The quantum number A is not analogous to the atomic quantum number L (which is required
al
to express the resultant orbital angular momentum of the atom) but to the atomic quantum number IMLI
e
of the atom when the,re is an electric field along a particular axis.

th
• For the one-electronic diatomic systems, the magnitude of the component of the orbital angular
e/
momentum of the electron about the internuclear axis is given by Imll = An where A = 0, 1, 2 ,.... The
t.m
quantum number A is given by Imll (cf. an electron in an atomic orbital can have 21 + 1 possible
orientations along the axis).
• The molecular orbitals (MOs) can be designated in terms of the values of the quantum number
e
A (= Imll) (for the one electronic system) or A (= IMLI) (for the multielectronic system) which gives the
er
number of nodal planes containing the molecular axis.

H
Molecular System Atomic System

k
lic
m/ 0 "±l ±2 ±3 m/ 0 ±1 * ±2*
C
A= 1m" 0 1 2 3 Atomic orbital s, Pz' d Z2 Px' Py' d xz' d yz d x)" d x2 _

l
(a) Molecular cr 1t & <t> * Combination of the wave functions for m/ =± 1 or ±2
orbital
Note: (a) Except the a-MO, all other MOs are doubly degenerate. These are: 1t+b 1t- 1; 8+2, 8_2; <1>+3' <1>-3'
• For the multielectronic diatomic molecules, the quantum number A can be obtained as follows:
A = I~)"il = 11.. 1 + 1.. 2 +1.. 3 +···1; M L = ~ml;; A = IMLI

Note: (i) The possible combinations of Ai giving the positive values of A are only to be considered.
Thus for a 1t (i.e. A::= 1) and a 8-electron (i.e. A= 2), the combination leading to A = 1 (i.e. O-state) and
3 (i.e. -state) are acceptable. But the combination giving A = -1 is not acceptable.
(ii) Illustration:
Lml = +1 -1 = O,A =·0
+ (1t+ I): M L = +2, A = 2; +
(1t-I): M L = -2, A = 2; (1t+ I) + + (1t-I): M L =
(B) Characteristics of the quantum number A: (i) All the electronic' states with A > 0 are doubly
degenerate. For A = 0, there is no net orbital angular momentum and consequently there is no degen-
eracy. (ii) A is related with the symmetry of the electron cloud distribution with respect to the internu-
clear axis. (iii) A = 0 indicates the cylindrical symmetry of the electron cloud about the internuclear axis
and the corresponding tenn is designated by the symbol I, (capital sigma, Greek letter). (iv) The tenn
symbols can be designated in tenns of the values of A.
(C) Term symbols of the diatomic molecules and A-values:
A: 0 1 2 3
Term Symbol: L (sigma) IT (pi) ~ (delta) (phi)
ry
Note: For the atoms, L = 0, 1,2,3,... correspond to the states S, P, D, F, respectively. I" 0, L\, <1>, •••
ra
used for the diatomic molecules are the Greek equivalents of S, P, D, F, used for the atomic states.
(D) Spin angular momentum of a diatomic molecule: The electron spin momenta of a molecule
ib
couple to give the resultant vector (S) . The component of this resultant vector along the direction of the
yl
internuclear axis is quantised and the component is given by I,n where the quantum number L (italic
em
font) is analogous to the atomic quantum number Ms. The quantum number I, can have the values: S,
S - 1,..., -S where S denotes the total spin quantum number. The spin multiplicity of the state is given
ch
by (2S + 1).
Note: The code I, (upright) is used in the tenn symbol for A = 0 while the code L (italic) as a
al
quantum number is used to represent the component of the resultant vector Salong the internuclear
e
th
axis.
e/
(E) Total angular momentum (orbital plus spin): The component of the total angular momentum
along the internuclear axis is given by On where the total angular quantum number 0 is given by
t.m
o = A + L. The tenn symbol of a diatomic molecule is primarily represented by: 2S + lAg.

(Note: The filled MOs do not contribute to detennine A and S because they have the zero resultant
e
spin (i.e. S = 0) and zero angular momentum (i.e. A = 0) (cf. filled atomic orbitals do not contribute to
er
detennine the atomic state).

H
Illustration: The 30 state indicates: A = 1, S = 1 i.e. L = 1,0, -1 and 0 =2, 1,0 (cf. 0 =A + I).Thus
k
the corresponding tenn symbols are: 302, 30 1 and 300'

lic
(F) Symmetry properties of the electronic wave function (Wei): To describe the atomic states, we
C
need three quantum numbers L, Sand J but to describe the electronic state of a diatomic molecule, the
three quantum numbers A, Sand 0 are not sufficient. Here we must consider the symmetry properties
of the electronic wave functions to determine the electronic state of the molecule.
• Designation with respect to the symmetry element, centre of inversion (i): For the homonuclear
diatomic molecules (e.g. H 2 , O2 , etc.), the electronic wave function (Wei) may be labelled as g or u.
Presence of i (as in cr-BMO, 1t*-MO) ~ g; Absence of i (as in cr*-MO, 1t-BMO) ~ u.
For the different electronic wave functions of the MOs, we may write:
gxg=g;uxu=g;gxu=u
The g or u symbol appears as the right hand subscript of the term symbol.
Note: For the heteronuclear diatomic molecules, the question of g or u symbolism does not
arise.
• Designation with respect to the symmetry plane (av ) containing the internuclear axis: With
respect to the symrnetry element cry, the electronic wave functions of the MOs may be labelled as +
or-.
Presence of O'v (i.e. reflection does not change the sign of 'lieI) => +; Absence of O'v (i.e. reflection
changes the sign of 'IIel) => -
The sign + or - appears as the right hand superscript of the term symbol (e.g. Lg+, Li, L:, Li).
This + or - symbol is generally used for the I states.
Note: For most of the electronic wave functions corresponding to the sigma (i.e. L) states, the +
symmetry prevails. The I- symmetry appears only when there are two unpaired parallel electrons
(i.e. S =1) in the 7t or 8 MOs. This aspect can be better rationalised by a group theoretical approach
which lies beyond the scope of the book.
• Term symbols of diatomic molecules:
A Homonuclear Heteronuclear
ry
(Dooh ; i-present) (Coov ; i-absent)
ra
0 Lg+' Lg-, Lu+' Lg- L+' L-
ib
IIg , IIu II
yl
2 li g, li u Ii
em
ch
(G) Illustrative examples to determine the term symbol for some simple homonuclear
diatomic molecules:
al
(a) 8 2 molecule: Its ground state electronic configuration is cr~(ls)' i.e. (lcrg)2. The cr-electrons do not
e
contribute to the angular momentum (cf. A=0 for cr-MO) and it gives A =0 (i.e. L-state). The electrons
th
e/
are paired up, i. e. M s =L m s =+.!.2 - .!.2 =0 gives S =O. The two electrons are in the grade MO and it
t.m
gives: g x g = g. The crg-MO, i.e. D'g(ls) does not change its sign on reflection in a plane containing the
internuclear axis (i.e. crv exists). It gives the + sign (cf. + x + =+) as the right superscript. Thus the term
e
L = 0 + 0 = 0, but it is not shown.

er
symbol of H2 (in the ground state) is: lL; and Q = A +

H
Let us consider the excited states of 8 2 where one electron from (1 crg)2 is excited to the higher
energy MO. ~et us illustrate the excited H 2 having the electronic configuration (IO'g)l (20';)1 for which
k
A = 0 and S = 1 (i.e. parallel spins) or S = 0 (i.e. antiparallel spins). The MO (i.e. cr-BMO) is of
lic
g-symmetry while the other MO (i.e. cr-ABMO) is of u-symmetry and it leads to g x u = u. Both the
C
MOs are of + symmetry (i.e. Uv symmetry plane bearing the internuclear axis exists for both the
cr-MOs). Thus the possible terms are: lL~ and 3L~. This excited state having the bond order zero
dissociates immediately into two H-atoms.
Similarly, for the other possible excited states, we can determine the terms. These are given below
for some representative excited states.
• (lcrg)1(3crg)1, i.e. cr~(lS) cr~(2S) => lL g+ and 3L;
• (lcrg)1(5crg)1, i.e. cr~(ls) cr~(2p) => lL u+ and 3~~
Note: Here apparently, the overall state should be of g-symmetry (cf. g x g = g) but actually the
overall state is of u-symmetry. It may be rationalised by considering one electron in the Is-orbital
(g-symmetry) of a H-atom while the other electron in the 2p-orbital (u-symmetry) of the other
H-atom (cf. g x u = u).
• (lcrg )l(l1tu )l, i.e. O'~(lS) 1t~(2p) => A = 0 + 1 = 1, i.e. TI-state and lIl u and 3TIu
Term symbols of some homonuclear diatomic molecular species

. . 1
• He2+: cr~(1s) cr~(1s) ~ M L = Lml = 0 + 0 = 0; i.e. A = 0; S =-. It leads to: 2Lu+
2
• B2: cr~(ls) cr~(ls) cr~(2s) cr~(2S) 1t~(2p); ml = ±1 for the n-MO.
Case i: When both the 1t-electrons remain paired up either in the 1t+ 1or 1t_1-MO ~ M L = Lml =
+2 or -2, i.e. A = IMLI = 2 and S = O. It leads to: l~g, (ef u x u = g)
Case ii: When the two electrons in the 1tu-MOs remain uppaired with the parallel spins in the 1t+ 1
and 1t_1-MOs ~ M L = Lml = +1 -1 = 0, i.e. A = IMLI = 0 and S = 1. It leads to: 3 L g-, (ef
u x u = g)
Case iii: When the two electrons remain unpaired with the antiparallel spins in the 1t+1 and 1t- 1
ry
MOs ~ M L = Lml = + 1 - 1 = 0 i.e. A = IMLI = 0 and S = O. It leads to: IL;; (ef u x u = g).
ra
Obviously, for B 2, the ground state is 3Li having the highest spin multiplicity (Hund's rule). It
may be noted that O 2 molecule also gives the electronic states, i. e. 3Lg -, 1~g and 1L;.
ib
yl
em
ch
e al
th
e/
t.m
e
....
.... ....
.... ....
er
.... ....
______ ~ 2a9(2S)
....
H
....
--
k
--- ,20"9(25) ,
lic
____________---r 10":(15)
C
~ x-axis
(a)
(b)
Fig. 12.6.1.1 (a) Simple molecular orbital diagram (for the homonuclear diatomic molecules except for "2; see Fig.
12.6.2.1a for H2. (b) Symmetry interaction (i.e. noncrossing rule) among the energy levels obtained from the simple
molecular orbital diagram (Fig. 12.6.1.1a) to produce reordering of the energy levels.
Note: This symmetry interaction reordering the energy levels is important for Be2' B2, C2 and N2 where the energy
difference between the 2s and 2p orbitals is not very high but this interaction is not important for O 2 and F2 where the
energy difference between the 2s and 2p orbitals is very high and simple MO diagram i.e. Fig. 12.6.1.1a is applicable for
O2 and F 2 (see Chapter 9, Vol. 2 for details).
(b) O 2 molecule: The case is comparable to the case of B 2 • The ground state electronic configuration
of O 2 is:
crios) cr:~ls) cri(2S) cr:~2s) cri(2p) 1t~(2p) 1t~~2p) (see Fig. 12.6.1.1a and Chapter 9, Vol":'2).
Here we are to consider only the HOMOs (i.e. n*-SOMOs) because the lower filled MOs contribute
zer~ to A and S. The two unpaired electrons reside in two degenerate n;-MOs having the mrvalues +1
(i.e. 1t+~-MO) and -1 (i.e. n_~-MO). It leads to: M L= 'Lm[ = + 1 -1 = 0, i.e. A = 0 indicating the 'L-state.
These two n* -MOs are of g-symmetry and consequently, the total electronjc wave function will be of
g-symmetry (ef g x g = g).
To determine the + or - sign of the overall state, let us consider the x-axis as the molecular axis and
the n*-MOs are: 1t;(2Pz) and 1t;(2py). Now reflection from the O'xz plane (as the O'v-plane) will change the
sign of the 1t;(2py)-MO while the n;(2Pz)-MO will not change its sign for the reflection from the same
. plane (i.e. O'xz-plane). Thus with respect to the O'xz-plane, the n;(2p y )-MO is of - symmetry while the
n;(2Pz)-MO is of + symmetry. Thus, the overall state will be of - s-ymmetry (i.e. + x - =-). The two
1t; -
ry
unpaired electrons will bear the parallel spins in the two degenerate MOs to give the spin multi-
plicity 3 (i.e. S = 1). Thus the ground state term of O 2 is: 3'Li.
ra
Now let us consider some excited states (II and III) of O 2 •
ib
yl
I II III
em
cr:(2p):
1t;(2p):
4-
(1t:I)
4-
(1t~1)
-4{,
ch
(1t: I) (1t~I)
4-
(1t:I)
+
(1t~I)
al
1tu(2p): -4{, -4{, -4{, -4{, -4{, -4{,

e
-4{, -4{, -4{,

th
crg (2p):
3 I~g L;
e/
Term symbol: Li I
Relative energy
t.m
(kJ mol-I): 0 92 155
• For the excited state (II), the electrons in the HOMO are paired up (i.e. S = 0, singlet state) and
e
orbital angular momenta of the electrons lead to: M L= 'Lm[ = ±2, i.e. A = IMLI = 2 indicating the ~-state
er
for which it is not required to consider the ± symbolism. The MO is of g-symmetry, i.e. the overall
H
electronic state is of g-symmetry (ef g x g = g). Thus term symbol is: l~g.
k
• For the excited state (III), M L = 'Lm[ = 'Lm[ = +1 - 1 = 0, i.e. A = 0 indicating the 'L-state; and
lic
Ms = +! _! = 0 i.e. S = 0 indicating the singlet state. The MOs bearing the unpaired electrons (with
C
2 2 '
the antiparallel spins) are of g-symmetry giving rise to the overall g-symmetry. It leads to the term, 1'L;.
(Note: Without the group theoretical treatment, it is difficult to rationalise the origin of this + sign.)
Energy order (Hund's rule): 3'Li (ground state, highest spin multiplicity) < l~g(A = 2, S =0) < 1'L;
(A = 0, S = 0).
• Excited state of 02: 1t~(2p) n;~2p) will generate the following electronic states:
3'L;, 3'L~, 3~u, 1'L;, 1'L~ and l~u. It is illustrated for 3~u and 3'Lu.
1t~ : ---4P- -4- • 1t~: ---4- ---4P- 1t~ (+ or -) and 1t u (-)
'Lm, = + 1 + 1 - 1 + 1 + 1 - 1 = 2 ( * ) * i.e. resultant symmetry + or-
(1t: 1 ) (1t: 1 ) 1t+ 1 (1t- 1 )
ML = 'Lm,= 2, i.e. A = 2; ML = 'Lm, = 0; A = 0;
1t u : ---4P- -4- S = 1, => 3~u 1tu : ---4P- -4- S = 1, => 3'L~-
The allowed transition, 3Li ~ 3L~ in 02-molecule gives the strongest band at about 200 nm (called
Schumann-Runge band) (cf. Fig. 12.6.2.2).
Note: Atomic term symbol of oxygen.
Ground State: lsz 2sz 2p4 [jIJ [1[ill]
L = (ML)(max) = +1+1+0-1 = 1
+1 0-1 ~3p
Excited state: [jIJ illIillJ L = (ML)(max) = +1+1+0+0 = 2

+1 0-1 ~ID
The ground state O 2 molecule (3 Li , l/ig, IL;) dissociates into two ground state O-atoms (3p) while
the excited O 2 molecule (3 Lu-) dissociates into one 3p O-atom and one ID O-atom (190 kJ mol- l above
ry
the 3P state).
ra
• Let us consider the electronic states .of the 0; species. The ground state of O2+ possesses the
cr~(2s)cr~(2s) (Ji(2p)1t~(2p) 1t~(2p) (i.e. one electron is lost from the HOMO
ib
electronic configuration:
yl
which is 1t;(Zp»)' It leads to: A = I (i.e. n-state) and S =! and the ground state term of 0t is : zng.
em
. 2
The excited state of 0; arises due to the removal of one electron from the ch 1tu(2p)-MO of O2. Thus
the electronic configuration of the excited 0t species is: cri(2s)(J~(2s) cr~(2p)1t~(2p) 1t~(2p). It leads to:
="23 (i.e. three unpaired electrons with parallel spins) and M L = Lm/ = +1+1-1+1-1 = +1 (assum-
al
S
e
th
ing the electrons paired in the 1tu-MO of m/ = +1) or -1 (assuming the electrons paired in the 1tu-MO
of m/ =-1); i.e. A = IMd = 1 indicating the ll-state. Thus term symbol of the first excited state of 0t
e/
t.m
is 4ll u • The excited state (with three unpaired electrons) can also lead to S =..!.. giving rise to the term
2
2llu • Other excited states of 0t of higher energy can be generated through the removal of electron
e
from the lower energy levels like cr g(2p), cr u(2s), etc.

er
O2 (ground state) 0; (ground state) 0; (excited state) 0; (excited state)

H
O:(2p):
k
4-
lic
1t;(2p):
4- 4- 4- 4- 4- 1-
C
1tu(2p):
41v 41v 41v 41v 4- 41v 4- 41v
Og(2p):
41v 41v 41v 41v
Term Symbol: 3I,; 2n g
4n u 2nu
• Distinction marks for the ground and excited electronic states of the linear molecules: The
letter X denotes the ground electronic state while the letters A, B, C, ... denote the excited electronic
states of the same spin multiplicity in order of increasing energy. The lowercase letters a, b, c, ... denote
the excited states with different multiplicity. It is illustrated for 0t and 02.
Energy order for Or: A2nu)a4nu)X2ng;Energy order for 02: B 3 L~)blL;)al/ig)X3L;;
(see Fig. 12.6.2.2)
The photoelectron spectrum (cf. Sec. 9.11.3, Vol. 2) of O2 indicates the ionisation energy values
12.1 eVand 16.2 eV corresponding to removal of an electron from the 1t;-MO and 1tu -MO respectively.
(c) B 2 molecule: cr~(1s)cr~(1s)cr~(2s) 1t~(2p) (cf. Fig. 12.6.1.1b). The term symbol is determined by 1t~(2p)
and the case is similar to the case of O 2 molecule whose term symbol is determined by 1ti(2p). In fact,
for B2 , the possible electronic states are also the same 3L;, 1f1. g and 1L; as in the case of O 2. Let us
illustrate the origin of the ground state term.
Two unpaired electrons with the parallel spins in the 1t+ 1 and 1t_ 1 MOs give M L = Lml = + 1-1 = 0,
i.e. A = IMLI = 0 and S = 1. It gives: 3Lg (cf. u x u = g).
To determine the + or - sign, let us consider the cryZ plane (as the cry plane assuming the z-axis as the
molecular axis) and the 1tu-MOs as 1tu(2py) and 1tu(2px). Reflection from the yz-plane (i.e. cry plane) will not
change the sign of the 1tu(2py)-MO but it will change the sign of the 1tu(2Px)-MO. Thus with respect to the
crYZ-plane, 1tu(2py)-MO is of + symmetry while 1tu(2Px)-MO is of - symmetry. Thus the overall symmetry
will bear the - sign (cf. + x - =-). It gives the electronic state as: 3Li .
ry
(d) N{ molecule: The ground state electronic configuration of N 2 is: cri(1s)cr:~ls) cr~(2s)cr:f2p) 1t~(2p)cr~(2p) -
ra
(cf Fig. 12.6.1.1b and Fig. 9.10.1.1, Vol. 2). The electronic configuration of N{ is: ... cri(2s) cr*;(2s) 1t~(2p)
ib
<J~(2p) which will lead to the term 2Lg+ (cf S =.!. ; A =0; presence of <J v containing the internuclear axis
yl
2
for the This is the ground state term of Nt. If, the Nt
em
crg(2p)-MO). species possesses the electronic
configuration cri(2s)cr*u~2s) 1t~(2p)cri(2p) then it will lead to the term 2IT u which is determined by the
ch
number of holes in the 1tu(2p)-MO. The one hole in the 1t-MO leads to M L = ±1, i.e. A = IMLI = 1
indicating the IT-state and S = ~ , i.e. singlet state.
al
2
e
Note: When ionisation occurs for a closed shell molecule, the term symbol of the ionised species
th
corresponds to the symmetry of the MO from which the electron is lost. If the electron is lost from the
e/
completely filled MOs of symmetry crg , cru, 1tu' •.• , the term symbols are 2Lg+, 2L ,:, 2IT u .•• respectively.
It is illustrated for N 2+ (cf the case of 01 also).
t.m
(e) Term symbols of some common homonuclear diatomic molecular species: The procedure
discussed above leads to the following results for the different electronic configurations (cf Table
e
9.10.2.1, Vol. 2).

er
crg2 =:) I~ +. cr 1 =:) 2~ +. cru1 =:) 2~ +. cru2 =:) I~ +. 1t 1 =:) 2ITu'. 1tu3 =:) 2IT u'. 1t2g/u =:) 3~ -. I~ + and 1f1. •
H
LJ g , g LJ g , LJ u ' L.Jg' u LJ g , LJ g , g'

1ti,u =:) I L ;.
k
H 2: cr~(1S), i.e. lcr; =:) I Lg+; Hi: lcr; =:) 2Lg+; H2": lcr; 2 crJ
lic
=:) 2Lu+;
He2·• lcrg2 2cru2 =:) I~+. 2

2 • lcrg 2cru1 =:) 2~
He+·
C
LJ g ,
+.
LJ u ,
Li2 : [He2]3cr; =:) lLg+; Be2: [He2]3cr;4cr; =:) I Lg+;

B 2: [Be2] I1t; =:) ~L;; 1L g+, 1f1. g ; C2: [Be2] I1t: =:) 1L;
N 2: [C 2]5cr; =:) I L;; N{: [C2]5cri =:) Ni: [C 2]5cr; 21ti =:) 2ITg ;
2L ;;
O2: [N2]21t; =:) 3 L;, I L ;, lf1. g ; O{: [N2]21ti =:) 2ITg ; O 2: [N2]21t; =:) 2IT g , Of-: [N2]21ti =:) I Lg+;
F 2: [N2]21ti =:) I Lg +; Ne2 = [F2J6cr; =:) lL;.

(I) Term symbols of some representative heteronuclear diatomic species: Electronic configurations
of the heteronuclear diatomic species in terms of MOT have been discussed in Sec. 9.11, Vol. 2.
Obviously, the g/u symbolism does not appear in such cases. By following the same procedure applied
for the homonuclear diatomic molecules, we can determine the term symbols of the heteronuclear
diatomic molecular species. Some examples are given here.
HF (cf Figs. 9.11.1.2-3, Vol. 2): (crl)2 (0'2)2 (1t nb)4 =:) IL+
HF* (excited state): (0"1)2(0"2)2 (nnb)3 (0'3)1 :::::) Lmz = + 1 + 1-1 + 0 = 1 or -1-1 + 1 + 0 =-1, i.e.
A = IMLI = 1; S = 0,1, i.e. III, 3n states.
NO (cf. Fig. 9.11.2.2a, Vol. 2): 0"2(2p)n12p) n*(~p) :::::} 2n
NO (cf. Table 9.11.2.1, Vol. 2): In4 50"22 n *1 :::::} 2n

CO (cf. Table 9.11.2.1, Vol. 2): 11[4 50"2 :::::} IL +
CO (cf. Fig. 9.11.2.3a,3c, Vol. 2): n: O"~b :::::} I L+
CO* (excited CO): I1t4 50"12n *1 (cf. Table 9.11.2.1) :::::} In, .3Il
CO* (excited CO): 1[:O"~bn*l(cf. Figs. 9.11.2.3a, 3c) :::::} In, 3n
12.6.2 Selection Rules of Electronic Transitions in the Diatomic Molecules: Electronic

Spectrum of Molecular Hydrogen and Oxygen
ry
The selection rules are:
ra
(a) AA = 0, ±1 (cf. M = 0, ±1 in atomic spectroscopy).
nH
ib
Thus the allowed transition are: L H L, L H n, II H n,' L\,
yl
etc. and the forbidden transitions are: n $ <1>, L $ L\, etc.
em
O'g(ns)
, * \
L:
,,
, O'u(2p) \
ch 1
\
\
I \
"
al
" ,e.========~\
, , 1t~(2P) \ \
e
" \ \
,",
th
\
\ \\
", * \ \\
e/
""" ,,,
'" O'u(2S) \ \ \
\ \\
\ \\
t.m
"" ,,
\ \\
",'
\ \\
\ \\
\.
2s,2p ",
,~
~
2s,2p
e
\~\
er
\\\ ,I
~\ ,N
0\ ,n
H
\\ \ , 11
\\ \ , II
\\\ 'II
k
\ \ \ '
II
\ \ \ ' 11
lic
\ \ J 11
\ \ O'g(2S) "
"
C
,','
\\ \
\\
,",,
\
\
\
\
\
1tU(2p) .4
,,,
,
,
r (1,2,3,4, ... denote
the respective
principal quantum
\ number)
~
O'g(2p)
V
/
/
,,
/
/ 0':(1S)
'v
,,
1s //
/
V1
v2 /1' ,,
1s
------(c ,, 1 - '- - -
,, /
/
,, /
/
/
/
\c I'll /
IvO'
g(1s) 1
Ground state
(a) (b)
(Contd... )
H(1 s) + H(2p)
Emission in hydrogen are lamp:

~+ (.
3
L +g (.I.e. 1 1
0g(1S) 0g(2S)) ~ L
1 1)
u I.e. 0g(1S) 0U(1S)
ry
ra
ib
yl
H(1 s) + H(1 s)
i em
ch
al
----. Intermolecular distance

e
th
(c)
e/
Fig. 12.6.2.1 (a) Molecular orbital energy level diagram for H2. (Note: This diagram differs from the MO energy level
diagrams of other diatomic homonuclear molecules, cf Fig. 12.6.1.1) (b) Singlet ~ singlet electronic transitions in H2
t.m
molecule; (c) Schemetaic representation of the potential energy diagram of the ground state and some excited states of
H2 molecule.
e
(b) AS =0, i.e. the allowed transitions are: singlet ~ singlet; triplet ~ triplet etc.;
er
and the forbidden transitions are: singlet ffl triplet, etc.

H
(c) .M1 =0, ±1 (result of the rule, Q, b)

k
(d) Restriction on symmetry change: There will be no change in the ± symmetry, i.e. the allowed
lic
transitions are: + ~ +; - ~ -; etc. and the forbidden transitions are: + ffl -

C
(e) Change of parity: The allowed transitions in terms of g and u symmetry are: g ~ u and the
forbidden transitions are: g ffl g, U ffl U (i.e. g ~ U, g ffl g, U ffl u).
Some representative allowed transitions: L u+ ~ L g+; n u H Lg+; etc.
Some representative forbidden transitions: Lg+ ffl Lg+; TI u ffl L';; etc.
(A) Electronic transitions in "2: The ground state a~(ls) gives the electronic state IL;. To understand
the electronic transitions, we are to consider the excited states where one electron is prmoted to a BMO,
because promotion to an ABMO will lead to the bond order zero and the molecule will dissociate into
two H-atoms. It happens so for the excited states like (lag)1 (20:)1 having the zero bond order.
Now let us consider the excited states where the bond order is not zero and such states are important
for the spectroscopic studies. Term symbols of some of the excited singlet and triplet states of H 2 have
been shown in Sec. 12.6.IG. The energy order of the excited triplet states of H 2 is:
3~ +.
£.J u '
1 1
l.e. a g(ls) a g(2p)
(3n· 1 1 (
u' l.e. a g(ls) 'Tt u(2p)
3~ + .
£.J g ,
1 1
l.e. a g(ls) a g(2s)
For the allowed electronic transitions, the excited singlet states are important.· The energy order of
the excited singlet states is:
I~ + . I I (In' I I (I~+' I I
LJu , l.e. cr g(1s) cr g(2p) u' l.e. cr g(1s) 1t u(2p) LJg' l.e. cr g(ls) cr g(2s)
In fact, for the lightest molecule H 2 , the energy order of the MOs is different from those of the other
diatomic homonuclear molecules (cf. Figs. 12.6.1.1 and 12.6.2.1). For the separate H-atoms, the vacant
2s- and 2p-orbitals have the identical energies. The energy order of the MOs of H2 molecule is:
crg (1s) ( cr:(1s) ( crg (2p) (1t u(2p) ( crg (2s) ( cr;(2s) ( 1t;(2p) ( cr:(2p)
Promotion to the excited state (having bond order zero) can dissociate into two H-atoms in excited
states (see Figs. 12.6.2.1,2).
The electron may be excited to the MOs produced by the nd orbitals (n =3,4, ....) of H-atoms. Energy
order of such excited singlet states is:
ry
I~+' I I
LJg' l.e. cr(1s) cr(3d)
(In' I I
g' l.e. cr(1s) 1t(3d)
(IA' I ~I
Ll.g , l.e. cr(1s) U(3d)
ra
The ground state is singlet and the excited singlet states important for the electronic transitions are
as follows:
ib
IL; (ground state): cri(1s); I L ; (excited state): cr~(1S) cr~(ns)' n = 2, 3,...
yl
(excited state): cr~(1s) cr~(np), (n = 2, 3, )
em
IL;
In u (excited state): cr~(1s) 1t~(np), (n = 2, 3, )

I L; (excited state): cr~(1s) cr~(nd)' (n = 3, 4,
ch
)
The allowed electronic transitions are:
al
I~+ ~ I~+ In. I~+ ~ I~+

e
LJg LJu , U' LJu LJg ,

(B) Electronic transitions in 02: The electronic states are as follows:
th
O2 (ground state): I~g, lL;

e/
(1t u, 2p)4 (1t;, 2p)2 ::::) 3 L ;,
O 2 (excited state): (1t u• 2p)3 (1t;. 2p)3 ::::) 3 L :, 3L~, 3~w IL:, IL~ and I~u
t.m
(cf. Electronic states of 0;: 2ng , 4n u ' 2n u )

e
er
H
k
lic
C
(200 nm)
b L;
1
2p
i a1~g
2s
0(1 D): -I- -I- -I- -
X3L~
0(3 p): * 4- (-1)
* (+1){O)
4-
---+ Itnernuclear distance
Fig. 12.6.2.2 Potential energy diagram of the ground state and excited states of 02' The allowed transition is shown.
Note: The ground state dissociates into two ground state O-atoms ep) and the excited state dissociates into one ID
(excited atomic state) and one 3P (ground atomic state) O-atoms.
According to the selection rules, the most important electronic transition (at about 200 nm; called
Schumann-Runge band) is :
3L; (ground state) ~ 3L~, (strongest band)
The weak bands in the infrared region (i.e. forbidden transitions) are:
3 L; ~ lL; (760 nm == 13,195 em-I), 3L; ~ lL\g (1300 nm == 7,918 em-I).

The above mentioned forbidden transitions (tripet ~ singlet) in the infrared region in gas phase
are not important. However, in the condensed phase (i.e. liquid state), a single photon can excite two
colliding molecules simultaneously causing absorption of energy in the visible range. In fact, the said
forbidden transitions are responsible for the blue colour of liquid oxygen.
202eL;)~202e~g); v"'2x7,918cm- 1 =15,836 cm- 1 ",631 nm
ry
ra
ib
yl
v~ 7,918 cm- 1 + 13,195 cm- 1 = 21,113 cm- 1 = 473.7 nm
em
Note: Here it is important to mention that during the electronic transition, the Franck-Condon
Principle must be obeyed (cf. Figs. 12.6.2.1, 2).
ch
12.7 ULTRAVIOLET PHOTOELECTRON SPECTROSCOPY (UV-PES) AND IDENTIFICATION
al
OFTHE NATURE OF MOLECULAR ORBITAL ENERGY LEVEL

e
th
This aspect has been discussed in Sec. 9.11.3 (Vol. 2).

e/
12.8 NUCLEAR QUADRUPOLE RESONANCE (NQR) SPECTROSCOPY AND ITS

t.m
APPLICATION
12.8.1 Quadrupole Nucleus, Nuclear Quadrupole Moment, Electric Field Gradient (EFG)
e
and Asymmetry Parameter (TI)

er
(A) Shape of the nucleus (See Sec. 5.1.5, Vol. 1 for details):" The shape of a nucleus depends on the
H
value of nuclear spin (I) and electric quadrupole moment described also as the nuclear quadrupole
k
moment (eQ). The nuclear quadrupole moment is different from the nuclear magnetic dipole moment.
lic
The major conclusions are given below.

C
The nuclear quadrupole moment arises from the unsymmetrical distribution of nuclear electric
charge (i.e. positive charge) in the nucleus. Thus it is an electric moment rather than the magnetic
moment.
• 1=0, !
and eQ =0: It indicates the spherical shape of the nucleus, i.e. spherical symmetry of
2
the nuclear charge distribution.
1
• I ~ "2 and eQ '¢ 0: It indicates the nonspherical shape of the nucleus.
For eQ ) 0 (i.e. positive value), the nucleus becomes prolate shaped (i.e. egg-shaped) and for
eQ ( 0 (i.e. negative value), the nucleus becomes oblate-shaped (i.e. discuss-shaped).
Thus the parameter, nuclear quadrupole moment (eQ) gives the measure ofdeviation from the spherical
symmetry of nuclear charge distribution. Here it should be remembered that in all cases, i.e. spherical
*
nucleus (eQ = 0) and nonspherical nucleus (eQ 0), the nuclear charge density within the nucleus is
uniform.
The dimension of quadrupole moment (Q) is cm2 or m 2 and it is very often expressed in the unit
10-24 cm2, i.e. 10-28 m 2 (= 1 bam). For example, deuteron (2H) shows Q = 2.86 X 10-27 cm2 = 2.86 x
10-3 bam. Examples of some representative quadrupolar nuclei with their Q-values are given in Table
12.8.1.1. More examples of the quadrupolar nuclei are given in Table 12.4.3.1.
Thus the unit of eQ is: unit of charge x (unit of distance)2
Table 12.8.1.1 Some representative examples of the quadrupolar nuclei with their Q-values.
Nucleus Nuclear Q (barn)* Nucleus Nuclear Q (barn)*
(% Natural Spin (1) (% Natural Spin (1)
abundance) abundance)
ry
2H(0.016) 1 + 2.86 X 10-3 63CU(69) 3/2 - 0.21
+ 8.5 X 10-2
ra
lOB(19.5) 3 65Cu(31) 3/2 - 0.19
IIB(80.5) 3/2 + 4.4 x 10-2 69Ga(60.5) 3/2 + 0.17
ib
14N(.... 100) 1 + 1.9 X 10-2 71Ga(39.5) 3/2 + 0.10
yl
23Na(100) 3/2 + 0.10 75As(100) 3/2 + 0.31
em
27Al(100) 5/2 + 0.15 79Br(50.5) 3/2 + 0.33
35Cl(75.5) 3/2 -8.2 x 10-2 81Br(49.5) 3/2 + 0.28
ch
37Cl(24.5) 3/2 -6.4 x 10-2 121Sb(57) 5/2 - 0.40
51V(-100) -5.0 x 10-2 123Sb(43)
al
7/2 7/2 - 0.50
55Mn(100) 5/2 + 0.33 127I( 100) 5/2 - 0.7
e
59Co(100)
th
7/2 + 0.40 197Au(lOO) 3/2 + 0.55

e/
* 1 barn = 10-24 cm2 = 10-28 m2; +ve indicates the prolate ellipsoidal shape; -ve indicates the oblate ellipsoidal shape.
t.m
(B) Electric field gradient (EFG): Let us consider the nucleus to remain at the origin of an arbitrarily
chosen coordinate system x, y, z. A point charge e at a distance r = (x 2 + y2 + z2 )1/2 from the nucleus
e
will produce the time averaged electrostatic potential V(r) = efr at the nucleus. Then we can define the
er
electric field at the nucleus as the negative gradient of the potential: Ex = -aVlax = x-component of the
time averaged electric field and similarly Ey = -aVldy, E z = -aVldz.
H
The EFG is the gradient of the electric field (i.e. EFG oc 11r 3 ) and is a tensor quantity with 9
k
lic
components and it can be given by a 3 x 3 matrix (tensor) as follows:

C
aEx a2v a2v a2v

i.e. eqxx = Vxx = iJx = iJx 2 ; eqxy = Vxy = iJxiJy' , eqzz = iJ 2
z
In the real and symmetric matrix, Vxy = Vyx' Vzx = Vxz' ••• • For the real, symmetric and traceless
matrix, the diagonal elements will obey the Laplace equation, L Vii = O. It leads to:
i=x,y,z
2
V (Laplacian operator) = --2 +
a2 -a22 + -a22
ax ay az
It gives: qxx + qyy + qzz = O.
The coordinate axes x, y and z may be selected in a way so that the cross components (i.e. Vij' e.g.
Vxy) become zero. This type of coordinate system is described as the principal axis system of the EFG
tensor. Under this condition, it transforms the tensor into a diagonal one where only the non-zero
elements are the diagonal elements. In this principal axis system, out of Vxx' Vyy and Vzz' only two are
independent and the EFG tensor can be described by only two independent parameters:
Vxx - Vyy qxx - q yy
Vzz = eqzz = eq (conventionally chosen) and the asymmetry parameter 11 =- - -
Vzz qzz
ry
(C) Asymmetry parameter ('1): In the appropriate coordinate system (i.e. principal axis system),
ra
the EFG tensor has three components Vxx' Vyy and Vzz along the x, y and z axes respectively and they are
ib
related as:
yl
Vxx + Vyy + Vzz = 0 or, qxx + qyy + qzz = 0, (cf. Laplace equation).
em
(cf. Vxx = eqxx' Vyy = eqyy' and Vzz = eqzz)
Case I (spherically symmetric electric field gradient): It has the situation, Vxx = Vyy = Vzz' i.e. qxx
ch
= qyy = qzz. In this condition, EFG =0, i.e. the interaction of nuclear quadrupole moment (eQ) with EFG
vanishes and it makes the nuclear quadrupolar energy levels degenerate. In fact, EFG becomes zero
al
when two C 3 - or higher fold rotation axes are mutually perpendicular (e.g. cubic symmetry).
e
Case II (axially symmetric electric field gradient): It has the situation, qxx = qyy ~ qzz. The EFG is
th
defined by Vzz = eqzz = eq, i.e. q = Vzle where qzz is denoted by q. It makes EFG nonzero (i.e. EFG i:- 0)
e/
but 11 = 0 when the highest-fold symmetry axis (C4 or C 3) passes through the quadrupolar nucleus and
t.m
coincids with the Vzz direction. Thus for axial symmetry of EFG (i.e. 11 = 0), it lies along the z-axis
which is the highest fold symmetry axis of the molecule. For the axially symmetric molecules Cl 2 and
CH 3CI, the bond axis of Cl 2 and C-CI bond of CH 3CI are taken as the z-axes of the molecules
e
er
respectively.
Case III (nonaxial symmetry of EFG): It has the condition, qxx ~ qyy ~ qzz and to measure the
H
deviation of EFG (i:- 0) from the axial symmetry, the asymmetry parameter is defined as:
k
V -V q-q
lic
11 = xx yy = xx yy ,Iqzzl ) Iqxxl ) Iqyyl (by convention)

C
Vzz qzz
Thus it is evident that 11 can vary in the range 0 to 1 (i.e. 0 ~ 11 ~ 1).
11 = 0 indicates qxx = qyy (i.e. axial symmetry) and it leads to:
1
qxx = qyy = -2"qzz (cf. qxx + qyy + qzz = 0)
Thus it shows that for the axial symmetry, EFG is defined by only VzzC= eq) while for the nonaxial
symmetry, a second parameter, i.e. 11 (asymmetry parameter) is also needed.
11 = 1 indicates: qxx = 0, qyy = -qzz
12.8.2 Principles of NQR Spectroscopy: Quadrupole Energy States and Interaction with
the Electromagnetic Radiation
A quadrupole nucleus (I'? 1 and ellipsoidal shape) will interact with the asymmetric electric field (i.e.
EFG i:- 0) arising from the asymmetric distribution of the electron cloud around the nucleus. The extent
of interaction is different for the different possible orientations of the ellipsoidal quadrupolar nucleus.
The allowed orientations are quantised. The quadrupole nucleus may adopt the 21 + 1 orientations. The
lowest quadrupole energy level corresponds to the orientation that brings the largest amount of the
positive nuclear charge of the nonspherical (i.e. ellipsoidal) quadrupolar nucleus closest to the
largest electron density of the negative charge of the asymmetric electric field surrounding the
nucleus.
If the interacting nucleus is spherical (I = 0, 112) (i.e. having the spherical and uniform distribution
of nuclear charge) or the electronic environment around the nucleus is spherical (i.e. EFG = 0), then all
the nuclear orientations are energetically equivalent and it makes the quadrupolar energy levels degenerate.
The above discussion indicates that the irteraction of a quadrupole nucleus (I ~ 1) with the asymmetric
*
electric field (i.e. EFG 0) surrounding the nucleus leads to a set of quantised energy levels. The energy
ry
difference between the different levels is very small and the electromagnetic radiation of radiofrequency
ra
region (ca. 100 kHz to 1000 MHz) can cause the transition between the quadrupolar energy levels (cf.
ib
the case of NMR, where also the radiation of radiofrequency region causes the transition).
• Solid samples in NQR studies-why? The NQR spectroscopy is carried out on a solid crystal
yl
because in a gaseous or liquid phase, the random molecular motion averages the electric field gradient
em
to zero (i.e. qxx = qyy = qzz) and consequently, splitting of the nuclear quadrupolar energy levels does not
occur.
ch
• NMR vs. NQR: The frequency region of electromagnetic radiation causing the transition, line-
al
width, intensities, and saturation effects are the same both in NMR and NQR spectroscopy. The major
e
difference between NMR and NQR rests on the origin of the nondegenerate sets of nuclear energy
th
levels. In NMR, an external magnetic field is used to split the degenerate nuclear energy levels while
e/
in NQR, splitting of the degenerate quadrupolar energy levels occurs from the interaction of EFG (* 0)
with the quadrupolar nucleus. Thus in NMR, splitting of the nuclear energy levels occurs from a
t.m
magnetic origin while in NQR, it occurs from an electrical origin.

In NMR, spacing (i. e. energy difference) of the nuclear energy levels is proportional to the magnetic
e
field strength (Ho) applied externally and thus the NMR transition energy can be controlled externally
er
by varying the applied magnetic field strength. In NMR, the transitions are usually studied at a fixed
H
operating radio-frequency while varying the magnetic field strength. In NQR, the eQ value of a
nucleus is its own characteristic property and the EFG is a fixed property of the sample and it is
k
determined by its molecular geometry and electric field generated in the solid crystalline state. Thus
lic
the interaction between EFG and eQ causing the splitting of the nuclear energy levels cannot be
C
controlled externally in NQR. In NQR, a variable frequency detection system is used to follow the
NQR transitions.
12.8.3 NQR Transition Energies for the Axially Symmetric Systems (i.e." =0)
(A) Energy of the quadrupolar nuclear states: For the axially symmetric systems (11 = 0), the interaction
between the nuclear quadrupole moment (eQ) of the nucleus and the electric field gradient (EFG = eq)
at the nucleus, leads to the energy values of the quadrupolar nuclear states as follows:
eq x eQ[3m; - 1(I + 1)] e 2 qQ[3m; - 1(I + 1)]

E±m] = 4/(21-1) = 4/(21-1)
where 1 = nuclear spin quantum number; eq = eqzz = d2Vldz 2 = magnitude of EPG in the direction of the
highest fold symmetry axis; eQ = nuclear quadrupole moment; m/ = nuclear magnetic quantum number
which can take up the 21 + 1 values given by:
m[ = I, 1 - 1, ..., 0 , -I + 1, -I
It is evident that the energy states for ±m[ are degenerate because the expression bears the square m;
term. Thus for 1 = 312, the possible values of m[are: +3/2, +1/2, -1/2, -3/2 and E+ 3/2 =E_312 ; E+ 1I2 =E_
1/2. It/leads to the doubly degenerate sets of quadrupolar energy states. Thus the said interaction
cannot remove the total degeneracy of the nuclear quadrupolar energy states.
For, T) = 0, m[ is a good quantum ~umber and the selection rule for NQR transition is: fun[ = ± 1.
According to this selection rule, for the quadrupolar nucleus having the half-integral spins (e.g.
1 = 312, 512, etc.), there will be (I - 112) NQR transitions (cf. Fig. 12.8.3.3) and for the quadrupolar
nucleus having the integral spins (e.g. 1 = 1, 3), there will be 1 NQR transitions (cf. Fig. 12.8.3.3).
(Note: The given selection rule may relax for T) ;;:. 0).
Under the selection rule, tim[ = ±1, for the NQR transition, m[~ m[ + 1, we have:
ry
ra
2 2
till = e( qQ )[3( m/ + 1)2 - 3m/2] = e (qQ X3) 2 m/ + 1 (I I )
ib
41 21 -1 41 2/-1
yl
em
i.e. ch
al
where
e
th
The NQR transition frequencies generally lie in the range, 100 kHz to 1000 MHz. The quantity
(e 2qQ) or (e 2qQ/h) is called the nuclear. quadrupolar coupling constant which can be either expressed
e/
in the unit of energy (i.e. e2qQ) or in the unit of frequency (i.e. e2qQ/h). The nuclear quadrupolar
t.m
coupling constant can be determined from the NQR transition energy.

e
er
H
k
lic
C
(Spherical
field)
(EFG = 0)
Fig. 12.8.3.1 Nuclear quadrupole energy levels for I =3/2 in a spherical and an axially symmetric electric
field (i.e. 11 =0).
(B) NQR transitions for the quadrupolar nuclei of half-integral spins: According to the selection
rule (dm/ = ±1), there will be (I - 1/2) NQR transitions (Figs. 12.8.3.1, 3). Here we shall illustrate for
e
1= 312 1B, 35, 37CI, 63, 65CU, 69, 7lGa, 75As, 79, 81Br); 1 = 512 (27 AI, 55Mn, 121Sb, 1271, etc.) and 1=712 (51 V,
59CO, 123Sb, 181Ta, etc.) which will show 1 (= 312 - 112), 2 (= 512 - 112) and 3 (= 712 - 112) NQR
transitions respectively. These are illustrated in Figs. 12.8.3.1, 3.
• For I =3/2, the allowed NQR transition, m/ = ±1/2~m/ = ±3/2 will lead to:
!ill = E±3/2 _ E±1/2 = e2iq _ ( _ e :Q)=

2
e
2
~Q
dE e 2 qQ
ry
Le. V=-=--
h 2h
ra
• For I = 512, the two allowed transitions are:
ib
2
= ±~~m/ = ±%, !ill = E±3/2 _ EH / 2 =_ e:~Q _ ( _ e ;Q ) = 3e~~Q
yl
m/
em
3e 2qQ #-"
i.e. ="2Oh
VI
ch
2 Q
= ±%~m/ = ±%,!ill = E±5/2 _ E±3/2 = e : e:~Q ) = 6e~~Q
al
m/ _ (_
e
th
6e 2 qQ
="2Oh
e/
i.e. v2
t.m
• For I = 712, the three allowed transitions are:
= ±~~m/ = ±%, !ill = E±3/2 - :8 2

:8 e2qQ ) = 1~ (e 2qQ)
e
m/ E H / 2 =- e qQ - ( -
er
e 2 qQ
H
i.e. VI = 14h
k
lic
=±~~ml =±~, !ill = E+5/2 -E+3/2 =~(e2qQ)_(_ 3e

2qQ 2
m/ )= 2e14qQ
C
2 2 - - 28 28
2e 2qQ
i.e. V2=~
m/ = ±5/2~m/ = ±7/2, !ill = E±7/2 - E±5/2 = ±(e2qQ )_ ;8 (e qQ) = 1~ (e qQ)

2 2
3e 2qQ
i.e. V ---
3 - 14h
(C) NQR transitions for the quadrupolar nuclei of integral spins: For the integral spins like I = 1
(6Li, 14N), I = 3 eOB), there are doubly degenerate (m/ = ±1, ±2,...) and one nondegenerate (m/ = 0)
nuclear energy states. There are I allowed NQR transitions. The most studied nucleus in this group is
14N (abundance -100%, Q =1.9 x 10-2 bam). Other nuclei in this group are not suitable for NQR studies
because of their poor natural abundance and/or small quadrupole moment values.
~~~~~~~~~~~~~~~~~L
1=1
============~"",,,
,,
,,
,,
,,
ry
,,
,,
ra
(Spherical field, ,,
EFG = 0) ,,
ib
,,
,,
yl
,
em
,--------
2
E = _ e qQ
o
ch
2
(Axially symmetric field)
al
*
i.e. 11 = 0, EFG 0
e
Fig. 12.8.3.2 Nuclear quadrupole energy levels for / = 1 in a spherical and an axially symmetric electric
th
field (i. e. 11 = 0).

e/
t.m
e
er
a..
<o1~
H
II
C\J
>
k
a..
lic
~
,.../(\1
C) II
C
Ci5 a.. >

c Mlv
w
II
>
1= ~
2
0
1= 1
3 5 7
Fig. 12.8.3.3 Nuclear quadrupole energy levels for / = 1, 2' 2 and 2 in the axially symmetric electric field (i.e. EFG;f. 0,
but 11 = 0) and the allowed NQR transitions, (P = Nuclear quadrupolar coupling constant = e2qQlh).
v = vQ(2lmJ! + 1) for. the mJ ~ mJ + I transition where v Q = 4/ ~e2Qq )

2/ -1 h
For 1= 1 (Fig. 12.8.3.2), the lowest nondegenerate energy level is characterised by m/ = 0 and the
upper doubly degenerate energy level is characterised by m/ = ±1. The allowed NQR transition (m/ =
o ~ m/ = ±1) leads to:
2 2
AD_E -E _ e qQ _(_ e 2qQ )_ 3e qQ
ilL - ±1 0 - 4 2 - 4
3e 2 qQ
i.e. V=--
4h
12.8.4 NQR Transition Energies for the Nonaxially Symmetric Systems (i.e. TI '¢ 0)
ry
Sometimes, the axial symmetry of the free molecule may be lost in the solid crystalline state (e.g.
ra
BrCN, 12, etc. to be discussed later) due to the intermolecular interaction.
(A) NQR transition energies for the quadrupolar nuclei with the half-integral spins: For nonaxial
ib
EFG (i.e. 11 *0), the energy expression for the quadrupolar energy levels is a complex one. For
yl
I ) 3/2, the exact solution cannot be obtained. For I = 312, the energy value is given by:
em
1/2
(eQ)(eq) 2 11 2
ch
E+ m
- I
= 41 (21 -1 )[3m/-/(/+1)] (1+-
3 )
,(cf.Sec.12.4.5),
al
It indicates that for the nonaxial symmetric systems (i.e. qxx qyy qzz and 11 0), the asymmetry * * *
e
parameter (11) is incorporated in the energy expression.

th
From the above given energy expression, energy of the quadrupolar levels for I = 312 is given by:
e/
2
1+.!f.)1/2 =3e Qq (1+.!f.)1/2 =e qQ (1+.!f.)1/2
2 2
t.m
E = 3e Qq
±3/2 41(2/-1) ( 3 12 3 4 3
e
2
1+.!f.)1/2 = -3e Qq ()1/2
1+.!f. =_ e qQ ()1/2
2
1+.!f. 2
er
E = -3e Qq
±1/2 41 (21 - 1) ( 3 12 3 4 3
H
k
The NQR transition, m/ = ±1/2 ~ m/ = ±3/2 leads to:

lic
C
2 1/2
i.e. V = !ill = e qQ
( 1+.!f.)
h 2h 3
Here, there is a single transition for 1 = 312 and from this single NQR transition frequency, two
unknown quantities, i.e. asymmetry parameter (11) and nuclear quadrupolar coupling constant (e 2qQ)
cannot be determined (cf. for II = 0, the parameter e2qQ can be determined from the v-value). However,
*
if the NQR transitions for I = 312 with 11 0 are followed in presence of a weak magnetic field (Sec.
12.8.5) (gN~NHo« e2qQ), then the degeneracy of the states (m/ = ±3/2 and ±1/2) will be lifted (cf. Fig.
12.8.5.1) and all the quadrupolar energy states become nondegenerate leading to 4 NQR transitions
(+1/2 ~ +3/2, +1/2 ~ -3/2, -1/2 ~ +3/2 and -1/2 ~ -3/2). From these four transition energies, 11 and
nuclear quadrupole coupling constant (e 2qQ) can be determined. This aspect will be discussed later.
I=~
2
~E = e qQ
2
2 e qQ ( 2
11 2)~
~E =-2- 1 +"3
ry
(Spherical '==~===""""""""
field) e2qQ ......................
ra
E±l = - - - ..........
4 ........ =::::::::====
ib
2
(EFG = 0)
2Q (1 + 212)~
yl
E+l =-~
em
-2 4 3
(11 = 0) (11 :;to)
EFG:;tO EFG:;tO
ch
(Axially (Nonaxially
symmetric field) symmetric field)
al
Fig. 12.8.4.1 Nuclear quadrupole energy levels for 1= 3/2 in a spherical field (EFG = 0) and in an asymmetric field (EFG
e
"* 0) - *
th
axially symmetric (11 = 0) and nonaxially symmetric (11 0).

Note: (i) For the half integral spins (Le. 1= 3/2, 5/2, 7/2) degeneracy of the pairs of energy levels is not lifted for both
e/
11 = 0 and 11 "* 0 but for 11 "* 0, energy of the levels changes.

t.m
(ii) For I = 3/2, there is one NQR transition and consequently the two NQR parameters, i.e. (e 2qQ) and 11 cannot be
determined but for other systems like 1= 5/2,7/2 experiencing more than one NQR transition, both the NQR parameters
can be determined. To determine the NQR parameters for 1= 3/2, ~QR transitions in presence of a magnetic field are
e
to be followed (cf. Fig. 12.8.5.1)

er
(iii) For 1= 1 and 11 "* 0, there are 3 NQR transitions and both the NQR parameters can be determined even without the
H
application of a magnetic field.
(B) NQR transition energies for the quadrupolar nuclei with the integral spins: This is illustrated
k
for 1 = 1 (e.g. 14N) for which the energy states of m/ = ±1 are degenerate when 11 =0 (axially symmetric)
lic
but their degeneracy is lost for 11 ':t 0 (ef Fig. 12.8.4.2). The energy levels are:
C
2 2Q 2 2
E = - 2 e Qq =-2A=~ where A = e q Q ~Q
o 41(21 -1) 2 41(21 -1) 4
2 2qQ
E = e Qq(I±11)=A(1±11)=e (1±11)=l(e2qQ)(I±~)
±1 41(2/-1) 4 4 3
There are three allowed transitions (vo, V+l and V-I).
(i) m/ = -1 ~ m/ = + 1 (ef fun/ = +2, allowed only when 11 is appreciably high)

AE = E+ 1 - E_ 1 = A (1 +" -) A( )
1-11 = 2A11 =
211e2Qq
4
e 2Qq11
=- 2 -
2
e Qq"
i.e. Vo =--v;-
i.e.
(iii)m/=O~m/=-l (cf. ~m/=-l)
M=E_ 1 -Eo =A(I-11)-(-2A)=A(3-11)= e2iq (3-11)
ry
2
ra
= e:~q (3 -11) = ~( e;q)(1- ~)
ib
i.e. V_I
yl
Here it is important to mention that when the value of Tl is. appreciable (i.e. significantly deviated
em
from the axial symmetry), m/ is no longer ~ good quantum number and the selection rule is relaxed.
It makes the forbidden transition of ~m/ = ±2 allowed. This is why, the V o transition is noticed for
ch
I = 1 when 11 is significantly large.
e al
th
e/
t.m
e
er
H
k
lic
C
----K. - - - - - - - ---'- . . & - - _ - - 1 . . -_ _ m =0

ml=O l
2
E = _ e qQ e2 qQ Eo = -2A
o Eo = - -2- = -2A
2
(11 = 0, Ho = 0) (11 * 0, Ho = 0) (11 * 0, Ho * 0)
(8) (b) (c)
Fig. 12.8.4.2 Nuclear quadrupole energy levels for 1= 1 under different conditions. (a) 11 = 0 and H o = 0 (i.e. no external
magnetic field applied); (b) 11 *- 0, H o =0 and (c) relative positions of the energy levels for 11 *- 0 and Ho *- 0 (i.e. a fixed
magnetic field applied).
e1 = 1 vs. 3/2: For 11 = 0, in both cases, there is a single NQR transition (Fig. 12.8.3.3) from which
the nuclear quadrupole coupling constant (e 2qQ) can be determined. But, when 11 =1= 0, there is still one
NQR transition (±1/2 ~ ±3/2) for I = 3/2 while there are three NQR transitions (~m/ = +2 leading to
Vo and lim] = ±1 leading to v+ 1 and V-I) for I = 1. Thus for I = 312, from one NQR transition, it is not
possible to find both 11 and (e 2qQ) and to get these values, it needs to study the NQR transitions in
presence of a magnetic field (cf. Fig. 12.8.5.1). On the other hand, for I = 1, from the three NQR
transitions (Fig. 12.8.4.2), we can estimate both 11 and (e 2qQ).
• NQR studies of 14N (I = 1): Its natural abundance is about 100% but its nuclear quadrupole
coupling constant (e 2qQ/h) is relatively small (ca. 4-6 MHz) because of its relatively small value of Q
(cf. Table 12.8.1.1). This is why, Vo is noticed when only the value of 11 is appreciably large. It is
illustrated in the following example.
Illustration 1: The NQR resonance frequencies of 14N in a compound are: 2.495, 3.500 and 5.997 MHz.
It indicates: Vo = 2.495 MHz; v+ I = 5.997 MHz; V-I = 3.500 MHz (cf. Fig. 12.8.4.2).
ry
2qQ 2qQ
(e J (e J( 1+"311) = 5.997 MHz
ra
1 -h- 11 = 2.495 MHz; V+1 ="4
It leads to: Vo ="2 3 -h-
ib
2qQ
yl
3 (e
and V-I ="4 -h- J( 1- 11) =3.500 MHz
em
3
(e 2qQ J. or e2qQ -_6331
ch
_ 2x3 {5.997 +3.500)x4 _ MH
i.e. V I
+
+V- I -
4 h' 6
-
h
. z
al
e
2
Q
th
and 2v o =Tl( e : } or, 2 x 2.495 = Tl x 6.331; or'Tl = 0,788

e/
t.m
Illustration 2: It may be noted that even ifvo is not noted, then from the V+I and V_I values, the constant
(e 2qQ) and 11 can be estimated. It is illustrated by considering the NQR spectrum of 14N (at 77 K) of
solid pyridine showing two lines at about 2.95 and 3.90 MHz. It indicates:
e
er
~(e2:Q ](1 +~) = 3,90 MHz and V-I = ~(e2:Q ](l-~) = 2,95 MHz
H
V+1 =
k
_~(e2qQJ' (3,90+2,95)x2 _ e2qQ e2qQ -456 MH

lic
i.e. v+ I +v- I - h ,or 3 - h or, h - . z

C
2
2q
and V +1 - V I
-
= ~(e2qQ)x
4 h
211 = !(e Q)11 = (3.90 - 2.95) = 0.95 MHz
3 2 h
i.e. = 2xO.95 =0.42

11 4.56
Here it is worth mentioning that if the I4N-nucleus maintains the axially symmetric EFG (i. e.
11 =0), there will be one NQR transition whose transition frequency is given by:
1 1
V(Tl = 0) = "2(V +1 + v -d = "2(3,90 + 2,95) MHz = 3.425 MHz
The NQR parameters at 77 K (cf. Y.N. Hsieh et.al. J. Am. Chern. Soc., 99, 1384, 1977) for 14N present
in free pyridine (py) and coordinated pyridine are given in Table 12.8.4.1.
Table 12.8.4.1 NQR parameters for 14N present in pyridine

2
Compound vo(MHz) v+I (MHz) (MHz) e qQ (MHz)
V-I
h Tl
py (free ligand) 0.908 3.892 2.985 4.585 0.395

[ZnCI 2(pyh]*
{ 0.308
0.295
2.387
2.331
2.078
2.038
2.978
2.912
0.207
0.202
[CdCllpyh] 0.552 2.850 2.298 3.432 0.320
* Crystallographic nonequivalence exists.

It indicates that due to coordination by the nitrogen lone pair of pyridine, the nuclear quadrupole
ry
coupling constant significantly drops and consequently the NQR transition frequencies of 14N drop.
ra
The reduction in the coupling constant (e 2qQ/h) is due to the reduction of the EFG value (= eq) because
the eQ value is a characteristic value of a quadrupolar nucleus. Here EFG at the nitrogen centre
ib
decreases on complexation (i.e. more symmetric electric field around 14N after coordination) and it
yl
may reveal the coordinating behaviour of nitrogen.
em
12.8.5 Effect of a Magnetic Field (Zeeman Effect) on NQR Transitions (cf. Sec. 12.4.6)
ch
The applied magnetic field will interact with the nuclear quardrupolar energy states and the interaction
energy is given by : -gN~JNHom] (See Sec. 12.4.6) where IlN= nuclear magneton; gN(+ve or -ve) =
al
nuclear g-factor, H o = applied magnetic field. This interaction in a weak magnetic field (i.e. gN~NHo (
e
th
( e 2qQ) will destroy the degeneracy of the doubly degenerate quadrupolar energy levels (i.e. doubly
degenerate nuclear energy levels will undergo splitting in presence of a magnetic field, Zeeman effect).
e/
It will also shift the energy of a nondegenerate energy level (m] -:t 0). This is illustrated in Figs. 12.8.4.2,
t.m
12.8.5.1 for 1= 1 and 3/2.

e
~~
er
H
V3
k
lic
....
~~
C
V1 V2
E+l = _ e 4qQ (1 + 2l)~

2 ....
-2 3
(rpt: 0, Ho = 0)
(a) (b)
Fig. 12.8.5.1 Nuclear quadrupole energy levels for 1= 3/2 under different conditions: (a) 11 ;;; 0, H o= 0 (i.e. no magnetic
field applied). (b) 11 ;f:. 0, Ho ;;; 0 (i.e. a fixed magnetic field is applied along the z-axis) lending to 4 NQR transitions in
which the VI (highest) and V4 (lowest) transitions (Ami = ±2) are the weakest ones.
• Identification of the origin of NQR transitions for 1= 1: If it shows two NQR lines, then it may
originate in two ways.
(i) Two nonequivalent 14N-nuclei (i.e. having the different EFG values but 11 =0 in both cases) -
chemically nonequivalent and/or crystallographically nonequivalent and each centre producing one
NQR line (0 ~ ±1).
*
(ii) One type of nucleus (i.e. EFG same) but 11 0: It may produce three NQR transitions (v o, V±l;
Fig. 12.8.4.2) but always the Yo-peak (-1 ~ +1 i.e. lim] = +2) may not be noticed and then only two
NQR lines (V±l) will be noticed (ef. Illustration-2, Sec. 12.8.4).
The crystallographic nonequivalence can be identified by the X-ray studies. However, the said
possibilities can be discriminated by following the NQR spectra in presence and absence of a weak
magnetic field.
ry
In presence of a magnetic field, for 11 ~ 0, three transitions (i.e. Yo, v+ 1 and V-I; ef. Vo will be noted
ra
even when 11 is not sufficiently large) will be observed but their transition energies will be different
compared to those observed in absence of a magnetic field (i. e. Vo and V+ I will be higher in presence
ib
of a magnetic field while V-I will be lower in presence of a magnetic field, ef. Fig. 12.8.4.2). If the
yl
origin is due to the two nonequivalent nuclei with 11 = 0, then for each type of nuclei, the doubly
em
degenerate levels (±1) will undergo splitting in presence of a magnetic field giving rise to two NQR
transitions (i.e. 0 ~+1, 0 ~ -1). Thus the two nonequivalent nuclei will produce 4 NQR signals in
ch
presence of a ma~netic field.
al
12.8.6 Conditions (Summary) to observe the NQR Signals

e
(i) It must be a quadrupolar nucleus (i. e. I ~ 1) in an asymmetric electric field for which EFG 0 *'
th
(i.e. symmetry around the quadrupole nucleus must be less than cubic or tetrahedral).
e/
(ii) The sample size must be sufficiently large and the target NQR nucleus must have its high
t.m
natural abundance and high electric quadrupole moment (el small value of eQ will reduce
the NQR transition frequency).
e
(iii) To produce the observable NQR signals, it is to be stu(iied at very low temperature (el NMR
er
spectroscopy).
H
(iv) The NQR signals are generally very weak and broad (el NMR spectroscopy). The broad peak
(ef. rapid relaxation by the quadrupolar nucleus) may span in the range of 10 kHz (i.e. a wide
k
range of frequency for a particular NQR transition). This is why, the choice of detection system
lic
is very much important.

C
(v) The sample should be diamagnetic because the unpaired electrons lead to the rapid relaxation
(ef. the problem for NMR spectroscopy of the paramagnetic substance).
(vi) The sample must be present in sdlid state because the random tumbling motions of the molecules
in the liquid or gaseous phase will average out the EFG and it will make the time average EFG
zero. It may be noted that the solid state effect (to be discussed later) may change the (e 2qQ)
value significantly.
(vii) Each chemically distinct quadrupolar nucleus surrounded by an asymmetric electric field (i.e.
asymmetric ligand environment) will produce a single NQR signal or a set NQR signals depend-
ing on the val~es,of I (el Fig. 12.8.3.3). However, the crystallographic nonequivalence of the
chemically equivalent nuclei may split the signals (to be discussed later).
(viii) Determination of the nuclear quadrupolar coupling constant (e 2qQ or e2qQ/h) and asymmetry
-~ ( parameter (11) will provide the structural information of the substance subjected to NQR
spectroscopy.
12.8.7 Solid State Effect and the Magnitude of Nuclear Quadrupolar Coupling Constant
Determined from the NQR Studies
NQR studies are made only on solid state and the quadrupole coupling constant (e 2qQ) obtained from
the NQR studies is a characteristic property of the solid. It has been found that the value of e 2qQ of
a quadrupole nucleus present in a particular compound depends on the physical statre of the compound.
The value of e2qQ obtained from the fine structure of the microwave spectrum is different from the
value obtained from the NQR spectrum. This difference may be about by 10-25%. The value from the
microwave spectrum refers to the gaseous state value while the value from the NQR spectrum refers to
the solid state value.
It has been argued that in solid state for a particular compound, more ionicity is introduced
compared to that in vapour phase. This enhanced ionicity in a bond can stabilise the solid state through
ry
an enhanced electrostatic attaraction between the cationic and anionic centres throughout the lattice
ra
network. Sometimes, the enhanced ionicity can stabilise the solid state through the H-bonding interaction
ib
as in solid HCI, NH 3 (cf Sec. 12.8.8E). In the vapour or liquid phase, such an extensive condensed
association or aggregation is not possible to earn the favourable electrostatic intermolecular interaction.
yl
The enhanced ionicity in solid state may lead to a more symmetric electronic configuration
em
around the NQR nuclei. Then the magnitude of EFG will go to decrease. Let us illustrate for the NQR
active halogen (X) present in the bond A-X. If the ionicity accumulates negative charge on X, then
ch
X becomes electronically close to X- (having the symmetric electronic configuration, ns 2np6) for which
EFG = O. Thus, more the ionicity of the A-X bond, more the anionic character of X, less the EFG
al
value and consequently less the e2qQ value. In such cases, the NQR value of e2qQ is less than the
e
th
microwave spectrum value.

However, if the enhanced ionicity in solid state introduces a more asymmetric electronic configu-
e/
ration around the NQR nucleus, then EFG increases and the e2qQ value is raised. If the ionicity
t.m
produces the cationic character on a halogen then it becomes electronically close to X+ (having the more
asymmetric electronic configuration, ns 2np 4) for which the EFG value is raised (i.e. e 2 qQ value is
e
increased). Thus we can conclude:

er
e2qQ: X cS+ (cationic) ) XO (neutral) ) X cS- (anionic), (X = CI, Br, I).

H
For 79Br, the e2qQ values (NQR studies) are: 790 MHz (Bro), 58 MHz (NaBr) and 877 MHz (BrCI)
(cf the polarisation: cS+NaBrcS-, 8+BrClcS-).
k
For BrCI, e2qQ (79,81 Br): NQR value (solid state, more ionicity) ) microwave spectrum value. While
lic
for 35,37 CI, the reverse ord~r is true, i.e. NQR value ( microwave spectrum value.
C
12.8.8 Application of NQR Spectroscopy

Compared to other spectroscopic techniques, NQR is relatively less frequently used because its field of
application is relatively narrow. Yet it is important to study the solid state physics and chemistry of the
materials which fail to give the large single crystats. It can extract the information regarding the nature
of chemical bonding and crystal structure.
(A) Important Characteristic Features of NQR Spectroscopy:
(i) Conditions for observing the NQR signals: A quadrupolar nucleus (I ~ 1) experiencing an asym-
metric electric field (i.e. EFG ~ 0) can give the NQR signal. For our practical purpose, the sample
should be solid and diamagnetic and natural abundance of the NQR isotope should be high and its
nuclear quadrupole moment should be fairly high.
NQR isotope: I ~ 1, EFG ~ 0 (Le. less than cubic and tetrahedral symmetry around the NQR
nucleus), high natural abundance of the isotope with a high eQ value; solid and diamagnetic sample.
(ii) Contributing factors to EFG (eq): There are two sources of contribution to q:
q = qvalence electrons + qlattice
'-For the symmetric electronic configurations (e.g. Sl, S2, p6, S2p 6, (Sp3)8, etc. around the NQR
nucleus, there is no contribution from the valence electrons to EFG. qlattice is determined by the lattice
symmetry around the NQR nucleus.
(iii) Number of allowed NQR transitions: Under the selection rule, ~I = ±1, we have:
• for 1 = half-integral (e.g. 3/2, 5/2, etc.) and 11 = 0 (i.e. axially symmetrical EFG), there are
(I - 1/2) NQR transitions (see Fig. 12.8.3.3), i.e. 1, 2, 3, ... NQR transitions for 1 = 3/2, 5/2,
7/2, ... respectively.
• for I =3/2 even for 11 *" 0 (i.e. nonaxially symmetric EFG), the number of NQR transition is
one (cf. Fig. 12.8.4.1).
ry
e
• for the integral nuclear spin 1 = 1 4N), there is one NQR transition when 11 = 0 while there
ra
are three NQR transitions (vo and V±l) when 11 *" 0 (Fig. 12.8.4.2) but sometimes instead of
ib
three NQR lines only two lines (i.e. V±l but Vo remains absent) are obtained.
yl
The most widely studied NQR nuclei are associated with 1 = 3/2 (e.g. 35, 37CI, 79, 8I Br, 75As, etc.) and
em
let 4N); the NQR signals for 35CI generally appear in the range 20 - 45 MHz.
(iv) Number of NQR signals for a particular NQR nucleus (in a compound) depending on the
ch
EFG values experienced: For each chemically distinct NQR nucleus experiencing EFG *" 0, there will
be a NQR line or a set of NQR lines depending on the value of 1 (see Fig. 12.8.3.3).
al
Considering the contributions of qvalence electrons and qlattice to EFG, we can summarise as:
e
• For a particular NQR nucleus, the chemically nonequivalent centres (i.e. experiencing the different
th
EFG values) will give different NQR signals widely spaced (i.e. generally the NQR resonance frequencies
e/
differ widely for the chemically nonequivalent NQR centres).

t.m
• Chemically equivalent NQR nuclei occupying the nonequivalent .Iattice sites (i.e. qvalence electrons
same but qlattice different) will give the different NQR lines but closely spaced (i.e. the NQR resonance
frequencies cover a narrow range). In such cases, the EFG values slightly differ. In fact, the
e
er
crystallographic inequivalence for the chemically equivalent nuclei leads to split the signal producing
a multiplet like signal.
H
• For 1 = 1, multiple NQR lines may appear when 11 *" 0 (cf. Fig. 12.8.4.2).
k
• Multiple NQR lines may appear due to the splitting of degenerate quadrupolar energy states by a
lic
magnetic field (cf Fig. 12.8.5.1). In some rare cases, this splitting may occur by the other magnetic
nuclei present in the molecule (e.g. splitting of the quadrupolar energy levels of 1271 by the magnetic
C
field of proton in HID 3).

However in the present context, we are mainly interested with the first two factors, i.e. chemical
inequivalence and crystallographic inequivalence to determine the number of NQR lines.
(v) Nuclear quadrupolar coupling constant (e 2qQ) and asymmetry parameter (Tl): These are
obtained from the NQR studies. But because of the solid state effect (cf. Sec. 12.8.7), the value of e2qQ
obtained from the NQR studies differs significantly from the value obtained from the fine structure of
microwave spectrum that originates from the fact that the different nuclear orientations produce the
slightly different values of moment of inertia. Sometimes, this parameter may be obtained from the MB
and NMR spectra. The solid state effect enhances the degree of ionicity in a compound and it changes
the e 2qQ value of a NQR nucleus.
(vi) Different sets of NQR lines for the different NQR active isotopes: Sometimes, for a particular
element, there may be more than one NQR active isotope having different the eQ values. The NQR
active isotopes may have different 1 values (e.g. 121, 123 Sb). In such cases, different sets of NQR lines
for the different isotopes will' be noticed. Intensity of the lines will be proportional to their natural
isotopic abundance.
Let us consider the NQR active isotopes: 35, 37CI; 69, 61Ga; and 79, 81Br as the representative examples.
35CI (I = 3/2; abundance- -75%; Q = - 8.2 x 10-2 barn)
{
37CI (I = 31); abundance -45%; Q =- 6.4 X 10-2 barn)
Thus for the CI~NQR studies, there will be two sets of lines for 35CI and 37CI and the lines for 37CI
will be less intense. The separation between the 35CI and 37CI NQR lines is determined by the ratio
of their Q-values.
For
ry
2
)1/
ra
2 2 ( 2
V=e qQ (forTI =0) and = e qQ 1+21..- (forTI *0); (see Fig. 12.8.4.1)
2h 2h 3
ib
yl
v (35 CI) Q( 35 CI) -8.2
em
i.e. --= =-=132
v (37 CI) Q( 37 CI) -6.4 . ch
Similarly for the Ga-NQR or Br-NQR spectra, ther~ will be two sets of NQR lines.
69Ga (I = 3/2; abundance -60%; Q = + 0.17 barn)
al
{
71Ga (I = 3/2; abundance -40%; Q = + 0.10 barn)
e
79Br (I = 3/2; abundance -50%; Q = + 0.33 barn)

th
{
81Br (I = 3/2; abundance -50%; Q = + 0.28 barn)
e/
(B) NQR Spectroscopy to Identify the Chemically Inequivalent and Crystallographically

t.m
Inequivalent NQR Active Sites:

The asymmetric electric field (i.e. EFG ~ 0) around a particular NQR nucleus is determined by the
nature of its valence electron distribution and lattice site. But the effect of valence electron distribution
e
er
which determines the chemical equivalence of a particular site is more important than the effect of
lattice site to determine the magnitude of EFG.
H
Chemical f;'i:~I: ~~I~I1\:e (i.e. equivalence in the electron distribution around the NQR nucleus) can be
k
easily understood fro111 the molecular geometry (i.e. point group to which it belongs). It is illustrated
lic
for the species like SiCI4 , SeBr~-, SnBti-, PtCI~-, etc. in which the halogens in each case are chemically
C
equivalent. Thus in such cases, for the halogens (I = 312, i.e. one NQR transition), only one NQR line
is expected in each system. But, always this expectation is not experimentally satisfied because the
NQR studies are not made on the free molecules (i.e. gas phase or in noncoordinating solvents) but on
their solid crystalline state in which the chemically equivalent halogens may occupy the nonequivalent
lattice positions. Thus in such cases, the resultant EFG experienced by the chemically equivalent
centres will be slightly different. This crystallographic inequivalence may be originated from the inter-
molecular interaction in solid state. In such cases, even the chemically equivalent nuclei will experience
the slightly different EFG values due to their crystallographic inequivalence and they will produce the
different NQR lines but closely spaced and appearing like a multiplet signal. This signal splitting by
the crystallographic inequivalence will reveal the symmetry of crystal structure.
Here it is to be again mentioned that for the chemically inequivalent centres, the NQR resonance
frequencies ofthe NQR lines widely differ because their EFG values differ widely. On the other hand,
t!te NQR resonance frequencies producing the different lines (appearing as a multiplet signal) only
for the crystallographic inequivalence of the NQR nuclei cover a narrow range.
The above mentioned aspects are illustrated in the following representative examples.
• 1. SiCI4 : This tetrahedral species (i.e. Sp3 hybridisation of Si) bears the four chemically equiva-
lent CI-centres in vapour phase. In the solid state (used for the NQR studies), if the Cl-centres occupy
the equivalent lattice sites, then one NQR signal for 35CI (I = 312, one NQR transition) is expected to
be observed. But in reality, it gives 4 closely spaced NQR signals (i.e. appearing as a quartet) of equal
intensity for 35CI having the frequencies:
NQR (35 CI): 20.273 MHz, 20.408 MHz, 20.415 MHz, 20.464 MHz.
The existence of these 4 NQR lines indicates that the Cl-atoms of SiCl4 occupy different types of
nonequivalent lattice positions experiencing different electric fields (i.e. the effect of crystallographic
in equivalence). It may be noted that there will be another set of less intense 4 NQR lines for the other
isotope, 37Cl which is less abundant.
ry
• 2. TiCI4 and SnCI4 : In each case, 4 NQR lines (closely spaced) of equal intensity for both 35CI
(I =312) and 37CI (I =312) are observed as in the case of SiCI4 • It can be explained as in the case of SiCI4 •
ra
• 3. PhAsCI4 : It possesses the trigonal bipyramidal structure where two axial positions are
ib
occupied by two chlorines and the three equatorial positions are occupied by 2CI and one Ph group (cf
yl
Bent's rule). Thus there are two types of chemically nonequivalent CI-atoms-axial and equatorial.
em
The axial Cl-atoms are bound by the pd-hybrid orbitals (i.e. s-character 0%) while the equatorial
Cl-atoms are bound by the sp2-hybrid orbitals (i.e. about 33.3% s-character) of the central atom As (cf
ch
sp 3d == Sp2 + pd, see Chapter 9, Vol. 2). It indicates that the axial Cl-atoms can withdraw more electron
al
cloud from the As-CI axial bonds compared to the equatorial Cl-atoms withdrawing the electron cloud
from the As-CI equatorial bonds. Thus, we can conclude that the axial Cl-atoms are more close to Cl-
e
th
electronically compared to the equatorial Cl-atoms. In other words, the axial As-CI bonds are more
ionic than the equatorial As-CI bonds. .
e/
CI- having the symmetric electronic configuration, 3s 2 3p 6 experiences EFG = O. Thus we can
t.m
conclude:
EFG (axial-CI) ( EFG (equatorial CI)
This is why, the magnitude nuclear quadrupole coupling constant (e 2qQ) for the axial-CI is relatively
e
less compared to that of the equatorial-Cl. Consequently, the NQR signal (35 CI, 1 = 312) for the
er
axial-CI atoms appears at the lower frequency (cf v oc e2qQ). The experimental findings are:
H
NQR-frequency in MHz (35 CI): 24.00,25.00, 34.18 and 34.68.

k
lic
Peak splitting due to

C
crystallographic inequivalence
Less ionic bond ~ ____________

C~ ~
Cleq " " ' " More ionic bond
/r ~~t~~~i~)
(34.18 MHz
and 34.68 MHz; ..... As Ph (24.00 MHz, 25.00 MHz;
1:1 intensity)
for Cl eq
Less ionic bond V

Cl eq
Cl ax
Fig. 12.8.8.1 Structure of PhAsC14 and NQR eSCI) frequencies.

The NQR-frequencies 24 and 25 MHz (to constitute a doublet) are assigned for the axial 3sCI-atoms
while the NQR frequencies 34.18 and 34.68 MHz (to constitute a doublet) are assigned for the equa-
torial-3s CI atoms (Fig. 12.8.8.1)
In solid state, the chemically equivalent two axial-CI atoms occupy the nonequivalent lattice sites
and they give two closely spaced NQR (3S CI) signals (differing by 1 MHz). Similarly, the chemically
equivalent two equatorial-CI atoms occupy two nonequivalent lattice sites to give two closely spaced
NQR signals (differing by 0.5 MHz). It may be noted that the NQR frequencies (3sCI) for the axial and
equatorial chlorine atoms differ by about 10 MHz. This larger difference is due to their chemical
inequivalence.
• 4. PFCI4 vs. PCI 4Ph: The NQR (3s CI) spectral features are:
PFCI4 : two signals (1:3 intensity ratio); PCI4Ph: two signals (1: 1 intensity ratio). These NQR (35 CI)
ry
spectral features can be explained by considering the trigonal bipyramidal structures (in conformity
ra
with the Bent's rule) (Fig. 12.8.8.2). In each case, there are two types of Cl-atoms but their numbers
differ.
ib
yl
Cl ax
(NQR) frequency: 35 Cleq ) 35Clax
I
em
Q)
eq (,)
Cl "'"
c
Cl3
ch
.0
o
CI~/r-Cleq ~ en
.0
al
«
t
e
th
F
v
e/
2 NQR (35CI ) signals 2 NQR (35 CI ) signals

t.m
Intensity: 1 (axial): 3 (equatorial) Intensity: 1 (axial): 1(equatorial)

v(NQR): equatorial) axial
e
Fig. 12.8.8.2 Structural and NQR eSCI) spectral features of PFCl4 and PC14Ph.
er
Here it is worth noting that the molecular symmetry is maintained in the crystal, i.e. all the
H
chemically equivalent 3sCI centres give one NQR signal and no peak splitting indicating the
crystallographic equivalence of the lattice points.
k
• 5. PCls: The NQR (35 CI) spectrum of solid PCIs shows 10 NQR lines: one group consisting of 4
lic
closely spaced lines (like a quartet) of equal intensity while the other group (appearing at the lower
C
frequency region) consists of closely spaced 6 lines (appearing as a sextet) of equal intensity. This can
be explained by considering the fact that PCIs crystallises as PCIt PClie In PClt (tetrahedral, Sp3
hybridisation of P), all the 4 Cl-atoms are chentically equivalent but crystallographically nonequivalent
producing 4 closely spaced NQR signals. In PCli (octahedral, sp3Jl hybridisation of P), all the 6 CI-
atoms are chemically equivalent but crystallographically inequivalent producing 6 NQR signals closely
spaced.
The NQR (3SCl) frequencies for the PCl4+ moiety are higher than those found for the PCli moiety.
This difference can be explained by considering the fact that the anionic character of CI in PCli (where
P uses the sp 3cP hybrid orbitals having the 16.6% s-character to bind the Cl-atoms) is more compared
to that of CI in PCI4+ (where P uses the Sp3 hybrid orbitals having the 25% s-character to bind the CI-
atoms). Moreover, electron withdrawal by CI from the P-CI bond is easier in the anionic species PCI6"
compared to that in the cationic species PClt because the effective electronegativity of P in the
cationic moiety PCLt is more compared to that in the anionic moiety PCI6 . In fact, in PCI6, CI withdraws
the bonding electron more compared to that in PCI4+ and it makes the P-CI bond more ionic in PCI6 •
In other words, CI in PCI6- is electronically more close to CI- (having the symmetric electronic
configuration, S2p 6, i.e. EFG = 0) compared to that in PClt. It makes the NQR (3S Cl) frequencies of the
Cl-atoms of PCI 6- relatively less than those found for CI in PClt.
I l+ c,~I/c,l- CI................
....
CI
I
.... ~p-- CI
CI~'~CI CI/jl~CI CI/
ry
ra
CI CI
ib
( -_ _-----.J)
yl
em
Constituents of the Constituents of the
Solid state phase ch Meta-stable phase
Fig. 12.8.8.3 Constituent units of PCIs in solid crystalline phase and in metastable phase.
al
If PCIs vapour is rapidly cooled, a metastable phase constituted by the trigonal bipyramical molecular
e
PCIs species is obtained. This metastable phase shows three NQR (3SCI) lines out of which two lines
th
(appearing at the lower frequency region) are closely spaced. These fwo lines correspond to the two
e/
axial-CI atoms which are chemically equivalent but crystallographically nonequivalent. The remaining
NQR line (3S Cl) appearing at the higher frequency region corresponds to the three equatorial-CI atoms
t.m
which are both chemically and crystallographically equivalent.

= = =
• 6. R3MXz (M 77As, lZI, 123Sb, z09Bi; X 3S,37CI, 79, 81Br; R CH3, C 6H s, C 6H sCHz): The NQR
e
spectra of this type of compounds reveal the D 3h symmetry, i. e. in the trigonal bipyramidal geometry,
er
the R-groups occupy the equatorial positions while the more electronegative X-groups occupy the axial
H
positions (cf Bent's rule). Thus the two X-groups are chemically equivalent but they may occupy the
nonequivalent lattice sites depending on the condition.
k
lic
Among the said compounds, (CH3)3AsBrz is an exceptional one and it shows the C 3v symmetry
indicating the compound to exist as [(CH3)3AsBr]+Br-. The Br-centre (having the symmetric electronic
C
configuration, S2p 6, i.e. EFG =0) is NQR inactive but the Br-atom (79, 81Br, 1= 312) present in the cation
is NQR active and it gives a NQR signal.
• 7. Composition of the adducts 2ICI · AICI3 and 2ICI · SbCls : The NQR spectra (3s, 37CI, 1271,
27AI, 121Sb) suggest their composition as: ICltAICI4- (two types Cl-centres in terms of chemical
equivalence in the ratio 2:4) and IClt SbCI6" (two types of Cl-atoms in terms of chemical equivalence
in the ratio 2:6).
• 8. Composition of the adductAICl3· TeCI4 : The NQR (3s CI) spectrum shows 7 lines (approximately
one triplet and one quartet) in which 4 lines (i.e. quartet) of equal intensity appear at the lower
frequency. This can be explained by considering the adduct to exist as TeClt AICl4". The 4 lines of lower
frequency correspond to the Cl-centres of AIClt" while the 3 lines of higher frequency correspond to the
Cl-centres of TeCI!. In the anionic moiety AIClt", the Cl-centres withdraw the bonding electron more
compared to the electron withdrawal by the Cl-centre in the cationic species TeCI! (i.e. electron withdrawal
by CI: AlII1_CI in AICI; ) TeIV-CI in TeClt). The more anionic character of CI in AICli explains the
lower NQR (35 Cl) frequency. In AIC14-, the chemically equivalent Cl-centres occupy the nonequivalent
lattice sites to produce a quartet signal. Similarly, the three chemically equivalent Cl-centres of TeCl;
occupy the nonequivalent lattice sites to produce a triplet signal.
• 9. K 2[PtCI6], K 2[SeCI6], CS2[SeBr6], (NH4)2[SnBr6] and (NH4)2[TeCI6]: The octahedral symme-
try of the anionic moiety MX~- indicates that the halogens in each species are chemically equivalent.
The halogen NQR spectrum (35, 37Cl, 79, 81Br; 1= 312, one NQR signal) indicates one signal (no splitting)
in each case. It supports that the octahedral symmetry of the anions MX1-
is preserved in the solid
crystal.
• 10. K 2[PtI6], K2[TeBr6] and K2[SnBr6]: The anions MX~- here also maintain the octahedral
symmetry in free state and the halogens. in each species are chemically equivalent. The halogen NQR
spectrum of each compound indicates three lines (to constitute a triplet). It supports that the chemically
ry
equivalent six· halogens are distributed in three different types of lattice sites.
ra
Note: The examples given in (10) and (11) indicate that the crystal symmetry is very much sensitive
to the nature of cations and anions (ef K 2[PtCI6] vs. K2[PtI6], K2[SnBr6] vs. (NH4)2[SnBr6]).
ib
e
• 11. BrCN 4N, 1= 1): The NQR studies of 14N (/= 1,100% natural abundance) are difficult to
yl
follow because of the very low value of quadrupole moment (Q = + 1.9 X 10-2barn; ef Q = - 8.2 X
em
10-2 barn for 35Cl). However the NQR studies of 14N for BrCN reveal the structural features of BrCN.
e
The NQR 4N) spectrum of BrCN shows a doublet signal which may be originated in two ways:
ch
*
(i) II 0 (nonaxial symmetry), two NQR signals for / = 1 (ef V+l and V-I and ignoring v o, Fig.
al
12.8.4.2).
(ii) II = 0 (axial symmetry), but two crystallographically nonequivalent N-centres, and each pro-
e
th
ducing a NQR signal (ef Fig. 12.8.3.2).

These two possibilities can be discriminated either by following the effect of a weak magnetic field
e/
on the NQR spectral transitions (ef. Sec. 12.8.5) or by X-ray studies. The X-ray studies indicate that
t.m
crystallographically the N-centres are equivalent. Thus the doublet signal arises from the asymmetry
*
parameter (ll 0). The solid structure of BrCN is constituted by the following linear chains.
e
----Br-C N----Br-C N----Br-C N----

er
In the individual linear chain, the axial symmetry (i.e. II = 0) of the N-centre is maintained. But in
H
solid state, the interaction among the different chains introduces the nonaxial asymmetry (i.e. II 0) *
k
around the N-centre. It causes the splitting of the line into a doublet (ef V+1 and V-I) and both the
lic
parameters e2qQ and II can be estimated (see Ilustration 2; Sec. 12.8.4).

C
The 79, 81Br (I = 3/2, one transition) NQR spectra of BrCN indicate that the Br-centre bears a formal
positive charge (ef e 2qQ value obtained from the NQR studies of solid BrCN is higher than that
obtained from the microwave spectrum of gaseous BrCN) favouring the Br+CN- constituents in the
solid state. It should be pointed out that EFG for Br-(s2p 6) is zero but for Br+(s2p 4) the value of EFG is
high. It explains the higher value of e 2qQ in solid state (ef. Sec. 12.8.7). In the solid state, the stabilisation
is earned by the coordination of CN- around Br+. Such an ionic interaction is not possible in the gaseous
phase.
• 12. 12 : In the 12 molecule (vapour phase), the axial symmetry (i.e. II = 0) is maintained but the
1271_NQR spectra of solid 12 indicate a large assymmetry (ll * 0) arising due to the intermolecular
interaction among the 12-molecules- in solid state.
• 13. NH413, Rbl3 and Cs13 : The 1271 (/ = 5/2 and two NQR transitions) NQR studies indicate that
the three I-centres are nonequivalent. Here it is worth mentioning that in free Ii (linear), there are two
types of I-centres: two terminal and one central. The NQR studies indicate that the chemically equivalent
terminal I-centres are crystallographically nonequivalent. Here it may be pointed out that in Ii, the
central atom is sp 3d hibridised and in the TBP-geometry, the two axial positions are occupied by the two
terminal I-atoms a/nd three equatorial positions are occupied by three lone pairs.
• 14. 81°3 : Theoretically it may have two possible structures:
I
H HI0
I
3
and
e
••
I02(OH)
/ ~, (C3v) o/' ~ ""OH (CJ

The HI0 3 structure (C 3v , C 3-axis exists) indicates the axial symmetry, i.e. qxx = qyy leading to II = O.
But the NQR spectrum of 1271 (I = 512) indicates a large value of 11 and it supports the structure I02(OH)
ry
of Cs symmetry. It has been reported that the magnetic field of the proton can split the NQR signal of
ra
1271. Such a situation is rarely noticed in NQR spectroscopy.
ib
= =
• 15. Group-13 halides (MX3, M AI, Ga, In; X CI, Dr): The halogen NQR spectrum of MX 3
yl
indicates a doublet signal (i.e. two closely spaced lines) lying well above the other singlet signal. Thus
em
it shows 3 NQR lines i.e. a doublet of higher frequency and a singlet of relatively lower frequency. This
observation can be explained by considering the halogen bridged dimeric structure (Fig. 12.8.8.4).
ch
Here there are two types of halogen: bridging (2) and terminal (4). The bridging halogen (i.e.
fl2-X) is more anionic (i.e. electronically more close to X- having the symmetric electron distribution
al
S2p 6; thus fl2-X experiencing the less EFG value) than the terminal halogen. This is why, the NQR
e
frequency of the bridging halogen is less.

th
Crystallographically equivalent
e/
I I
t.m
Crystallographically
x~ /x~ /x Higher NQR
e
x/Mrx~M~x
nonequivalent frequency
er
(doublet)
H
k
lic
Lower NQR
frequency
C
(singlet)
Fig. 12.8.8.4 Structure of dimeric MX 3 .
The molecular structure indicates that the 4 terminal halogens are chemically equivalent but the
halogen NQR spectra indicate that they are distributed in two types of crystallographically
nonequivalent lattice sites in solid state giving rise to two closely spaced NQR lines (i.e. appearing as
a doublet). On the other hand, the two bridging halogens are both chemically and crystallographically
equivalent giving rise to a single NQR line (i.e. singlet). The NQR frequencies for AIBr3 and GaCl 3
are as follows:
NQR-nucleus v (NQR) MHz v (NQR) (MHz)
terminal-X bridging-X
A1Br3 79Br 113.790, 115.450 97.945
GaCl3 35CI 19.084, 20.225 14.667
The equivalent sets of NQR lines for the isotopes 37CI, 81Br are also recorded.
• 16. Na+GaCI4- vs. Cs+GaCI4-: Their crystal symmetries are different and this difference is reflected
in the 35CI-NQR spectra. The anionic moiety GaCl.i is tetrahedral and all the Cl-centres are chemically
equivalent. The 35CI-NQR spectrum of Na+GaCLl" shows 4 NQR lines while that of Cs+GaCli shows
8 NQR lines.
The NQR spectrum of Na+GaCli indicates that the chemically equivalent 4 Cl-centres occupy 4
nonequivalent lattice positions in solid state giving rise to 4 NQR lines closely spaced (i.e. appearing
as a quartet). For Cs+GaCI4-, the number NQR (35CI) lines is more than the number of Cl-atoms. It
happens so only when two or more molecules occupy the asymmetric site of the unit cell.
• 17. Ga+GaCli: The 35CI-NQR spectra show 2 NQR lines (i.e. appearing as a doublet) at low
temperature but 4 NQR lines (appearing as a quartet) at higher temperature. It indicates that at lower
temperature, the 4 chemically equivalent Cl-centres are distributed in two types of nonequivalent lattice
ry
sites while at higher temperature these are distributed in four types of nonequivalent lattice sites. In fact,
ra
there is a phase change (at about 47°C, Le. 320 K) of the crystalline solid Ga+GaCI4" with the change
of temperature. The appearance of more NQR lines for 35CI at higher temperature indicates that the
ib
crystallographic inequivalence increases in the phase stable at higher temperature, Le. crystal symmetry
yl
drops at higher temperature (cf. 2 NQR lines vs. 4 NQR lines).
em
• 18. Na+[Ga2C1,]-: It shows 2 NQR signals of 69Ga and 7 NQR signals of 35CI out of which 6 lines
are closed spaced (i. e. appearing as a sextet) while the remaining 7th signal (i. e. appearing as a singlet)
ch
appears at substantially lower frequency compared to the group of 6 lines. The spectrum also records
al
the equivalent sets of NQR lines for the NQR active isotopes 71Ga and 37Cl. The NQR spectra of
e
Na+[Ga2CI7]- can be explained by considering the Cl-bridged structure of Ga2Cl7- which is constituted
th
by two corner shared GaCl4-tetrahedra (Fig. 12.8.8.5).

e/
CI CI
t.m
e
Ga Ga
er
H
k
lic
CI CI
C
Fig. 12.8.8.5 Structure of Ga2Cl-7'

The 6 terminal Cl-centres are chemically equivalent but crystallographically nonequivalent giving
rise to 6 NQR lines closely spaced (i.e. appearing as a sextet). The bridging CI (i.e. J.!2-Cl) centre is
chemically different and it is more anionic (Le. more close to CI- in terms of electronic environment)
compared to the terminal-CI atoms and consequently, the NQR frequency of the bridging-CI appears at
the lower frequency region. It happens so for the halogen bridged dimeric species like (AIBr3)2,
(InCI 3)b (GaCI 3)2 discussed earlier.
• 19. TeCI4: It shows 6 NQR (35 Cl) lines of equal intensity. The crystal structure can explain the
NQR spectrum. The TeCl4 crystal is constituted by the Te4C116, i.e. (TeCI4)4 units. The Te4Cl16 unit is
described by a cube in which the alternate comers are occupied by the TeCI; cations while the remaining
corners are occupied by the CI- anions which bridge the adjacent TeCI; cations (Fig. 12.8.8.6). The
bridging Cl- anions (S2p 6 electronic configuration) are NQR inactive because their symmetric electronic
configuration (3s 23p 6) makes EFG =O. In the cationic moiety TeCI!, all the three Cl-centres are chemically
equivalent but two pairs of TeCI; ions in each Te4Cl16 unit are crystallographically nonequivalent giving
rise to 6 NQR (35CI) lines. 37Cl isotope also produces another set of NQR lines (1 sextet) which are
relatively less intense.
XI
,.,."
/ x-----------..
I ,."
.-:.l.. /~}
I
TeX;
X- Te-:--- - f--- - - X ,. :
/I I I I
X I I I I
: : : : X = CI, Br
I I I I
I I X I I
1/
ry
I I I
I X -Te o
- - L - --- - X} X-
: ,,""--1 : ,.,."
ra
X~----t-----Te ~x
ib
X x/I
X
yl
em
Fig. 12.8.8.6 Structural unit Te4XI6(X = CI, Br) to constitute the solid crystal of TeCl4 and TeBr4.
• 20. TeBr4: Its crystal structure is also similar to that of TeCI4. In fact, TeBr4 gives one set of 6 NQR
ch
lines of equal intensity for 79Br and another set for 81Br.
• 21. AS2S3 : The NQR spectrum of 75As (I = 312, i.e. one NQR transition) shows two lines of equal
al
intensity for the y-phase of As zS 3 • It indicates the presence of two nonequivalent As-centres.
e
th
• 22. CI3CCOCI and CI-<Q(:CCI3 : The 35Cl-NQR spectral studies of these compounds indicate
e/
CI
t.m
the presence of different types of chemically equivalent Cl-atoms and the crystallographic inequivalence
of the three CI-atoms of CCI3 group. This aspect has been discussed in Sec. 12.8.8E.
• 23. 14N-NQR spectra for pyridine vs. metal coordinated pyridine: The change in the NQR
e
frequency on metal coordination occurs due to the reduction in the value of EFG (= eq) of 14N and
er
consequently in the value of nuclear quadrupole coupling constant (eZqQlh). This aspect has been
H
discussed in Sec. 12.8.4.

k
(C) NQR Spectroscopy to Study the Phase Change in Crystalline Solids:

lic
Phase change leading to the change of crystal symmetry may be identified by following the NQR
C
spectra of a substance at different temperatures. This is illustrated in some representative examples.

• 1. K2[SeBr6]: The NQR (79Br) spectrum of K2[SeBr6] changes with the change of temperature as
follows:
Temperature:
No. of NQR C9Br) lines:
In the octahedral anionic moiety SeBrl-, all the Br-centres are chemically equivalent but their
crystallographic equivalence depends on the phase of crystallisation of K2[SeBr6]. The number of NQR
lines 1, 2 and 3 indicates the distribution of chemically equivalent Br-centres in 1, 2 and 3 types of
lattice positions, i.e. at temperature above -33°C~. all the lattice sites occupied by the Br-centres are
equivalent; in the temperature range of -52°C to -33°C, the Br-centres are distributed in two types of
crystallographically inequivalent positions; and it occurs in three types of crystallographically inequivalent
sites in the temperature below -52°C. It indicates that with the lowering of temperature, the crystal
symmetry gradually drops (e.g. cubic ~ tetragonal ~ orthorhombic).
• 2. Ga+[GaCI4 ]-: At the lower temperature ( 47°C), there are two NQR (35 Cl) lines but at the
higher temperature, it shows four NQR (35 CI) lines. Here the phase transition (n ~ ~) occurs at 47°C.
The stable phase at the higher temperature distributes the chemically equivalent Cl-centres in 4 types
of lattice positions while at the lower temperature, the distribution occurs in two types of lattice points.
It indicates that here at lower temperature, the crystal structure is more symmetric.
=
• 3. Ml[MIVX 6] (X CI, Br, I): Phase transition in such complex halides has been noticed by
following the halogen NQR spectra at different temperatures. The general conclusion is:
phase transition causing reduction in crystal symmetry leads to the larger number
of halogon NQR lines.
(D) NQR Spectroscopy to Identify the Nature of Chemical Bonding and Determination of
Electronegativity DitTerence between the Combining Atoms:
ry
Chemical state of an element in a compound is determined by its effective electronic configuration
ra
attained in the compound. For the NQR-active nucleus, its nuclear quadrupolar coupling constant
ib
depends on the effective electronic configuration around the nucleus. The nuclear quadrupolar coupling
constant is e2qQ where Q is a characteristic property of the nucleus but q- varies depending on the
yl
nature of the chemical environment around the NQR nucleus (cj. Sec. 12.8.1; q oc ~ where the potential
em
r
= e/r).
ch
at the nucleus due to the point charge e residing at the distance r It indicates that only the
electrons residing close to the nucleus are important to determine the value of q. Thus from the
al
radial distribution function (RDF, see Volume 1) of the different orbitals, the s, and p orbitals appear
e
important to interact with the nucleus but the s-orbital being spherically symmetric does not contribute
th
anything to determine EFG (= eq). Thus distribution of the valence electrons in the p-orbitals is the
e/
most important factor to be considered to determine EFG (Townes and Dailey).

t.m
• Here it should be pointed out that the closed valence shell being spherically symmetric will
contribute nothing to EFG. Thus the electronic configurations like Sl , S2, p6, (Sp3)8, S2p6 will not contribute
to EFG, i.e. qxx = qyy = qzz and EFG = o.
e
• The d- and f- orbitals cannot penetrate close to the nucleus and their electron occupancy is not of
er
much importance to determine EFG. However, the electrons present in the d-orbitals may produce an
H
asymmetric field to some extent at the nucleus.

k
Let us consider the EFG in the qua~rupolar halogen nucleus (say CI) in the compound A-CI where
lic
chlorine is more electronegative than A. In the atomic state, the electronic configuration of CI is:
C
Is22s22p63s23p5 where the asymmetrically filled 3p s electronic configuration produces a large

quadrupolar coupling constant. If CI is more electronegative than A, then the electron density around
the quadrupolar nucleus CI is increased in A-CI compared to that in the isolated atom Cl. If A is highly
electropositive, then CI becomes almost CI- having the almost symmetric electronic configuration
Is22s22p63s23p6 producing EFG ~ O. Thus ifA-Cl bond is perfectly ionic, then Cl experiences EFG
= =
0, i.e. e2qQ O. From this, we can conclude:
with the increase ofthe ionic character in the A-CI bond (i.e. CI bears the more anionic character),
the EFG at CI goes to decrease, i.e. the nuclear quadrupolar coupling constant (e 2qQ) of CI goes to
decrease.
Now let us consider the B-X bond where B is more electronegative than X (halogen). Here the
bond polarisation will produce the cationic character on X, i.e. X will be electronically close to X+
having the asymmetric electronic configuration ns 2np4 producing a high EFG. Thus in such cases, the
enhanced ionicity in the B-X bond will make value of quadrupolar coupling constant higher for the
NQR nucleus X.
The above predictions are illustrated by taking the examples: TICI vs. FCI and FBr vs. NaBr.
e 2 qQ(MHz) for 35CI* : -16( 0+ TICl o- ) ( -110(free 35 CI ) (-146( 0- FCl o+)
e 2 qQ(MHz) for 79Br: + 58( 0+ NaBro- ) ( + 770 (free 79 Br ) ( + 1090( o-FBr o+)
i.e. e2 qQ: X o- ( XO ( X o+ (X = halogen)

(*Here the magnitude has been considered to determine the order).
Solid state effect and enhanced ionicity in solid state (Sec. 12.8.7)
Here it should be pointed out that the solid state effect may lead to an enhanced ionicity in the
solid state to stabilise the system through an extended electrostatic attraction throughout the
ry
lattice network (cf. Sec. 12.8.7). Thus the NQR value of e 2qQ may be significantly different from
ra
the value obtained from the microwave spectrum. Thus to compute the different molecular properties
ib
like % of ionic character in a bond, difference of electronegativity between the combining atoms,
yl
etc. from the NQR values of e2qQ, the solid state effect must be taken into consideration.
em
Thus the measurement of the nuclear quadrupolar coupling constant can estimate the ionic character
ch
of the bond. The degree of ionic character of a particular bond can also be estimated from the knowledge
of electronegativity difference (see Vols. 1 and 2). Both the results are in good agreement in many cases.
al
Thus, measurement of the nuclear quadrupolar coupling constant can also estimate the electronegativity
e
difference of the combining atoms. However, we should be cautious regarding the solid effect on the
th
NQR data to make any conclusion (cf. Sec. 12.8.7).

e/
The above ideas will be illustrated in the following representative cases.

t.m
• 1. Degree of covalency in the halides: For the A-X bond where X (halogen) is more electro-
negative than A, with the increase of the covalency, the nuclear quadrupolar coupling constant (e 2qQ)
of the quadrupolar nucleus X goes to increase. In other words, with the increase of ionic character in
e
the A-X bond, the e2 qQ value of X goes to decrease.

er
H
Compound: 2
BrCl ICI TICI KCI} e qQ = -110
2
e qQ(MHz) : -104 -82 -16 o MHz for free
k
lic
(35 CI) 35CI-atom.

C
( Increasing trend of covalence in the A-CI bond
It may be noted that if X is less electronegative than A then with the increase of ionic character in
the bond, the nuclear quadrupolar coupling constant (e2 qQ) of X goes to increase. This aspect has been
already illustrated.
• 2. NQR group frequency and fingerprint application: In the A-X bond (halogen X is NQR
active), for the higher covalence, the nuclear quadrupolar coupling constant is higher when X is more
electronegative than A. In other words, the NQR resonance frequency of X increases (almost linearly)
with the increase of the degree of covalence in the A-X bond, i.e. more the NQR frequency, more
the covalence, i.e. less the electronegativity difference between A and X.
If A is varied then the NQR frequency of X changes and it depends on the character of A. It leads
to the conclusion:
when the halogen X is attached to a particular element A (in different compounds having the more
or less comparable electronic environment around A), the NQR frequency of X remains more or less
fixed and it covers a certain range. Thus the NQR frequency of X is a characteristic feature (i.e.
fingerprint) of the A-X bond (cf group frequency in IR-spectroscopy). The 35CI-NQR frequency
of some particular bonds are:
Si-CI (15 - 22 MHz), S-CI (30 - 40 MHz), N-CI (43 - 56 MHz).
The variation of NQR group frequency can be explained by considering the electronic factors
controlling the covalency in the A-X bond. By considering the NQR frequency tables for A-35 CI,
A-79Br, etc. (A = different elements), the A-X bonds can be characterised.
In organic compounds, the element carbon may remain in widely different electronic environments
and the NQR group frequency (35 Cl) of the C-35CI bond is fixed (within a certain range) for a particular
type of carbon. The electron releasing substituents on C make CI more anionic (i.e. the C-CI bond
becomes more ionic) and consequently the e 2qQ value becomes smaller, i.e. the 35CI-NQR frequency
ry
becomes lower. The effect will be opposite when the electron withdrawing groups are attached on the
ra
C-atom of the C-CI bond (cf. Table 12.8.8.1). This aspect has been discussed in detail in Sec. 12.8.8F.
• 3. Determination of electronegativity order: The NQR frequency of X for the M-X bonds
ib
(M = C, Si, Ge, Sn; X = CI, Br, I) has been analysed and % of ionic character in the M-X bond has
yl
been estimated from the e 2qQ values. From this estimated % of ionic character in the M-X bond, the
em
electronegativity order is found as:
X: C ) Ge ) Sn :::; Si (cf secondary periodicity, Sec. 8.20, Vol. 1).
ch
• 4. Distinction of linkage isomers RNC and RCN; RNCS and RSCN: The NQR frequency for
al
14N is different for the R-C=:N and R-NC groups. The e2 Qq values for 14N are: -4.2 to -4.6 MHz
e
(R-CN group); ,.,. +0.5 MHz (for R-NC). The observed e 2qQ value of +1.2 MHz for 14N in HNCS
th
supports the structure H-NCS and excludes the other possible linkage isomer H-SCN. More studies
e/
are needed for further development in this direction.

• 5. Distinction between the cis-trans isomers: The e2qQ value is higher for the trans-isomer
t.m
compared to that of the cis-isomer (cf MB spectroscopy; Sec. 12.4.7). It is illustrated for the cis-trans
isomers of [CoCI 2(en)2]Cl. The e 2qQ values are: 33.6 (cis) vs. 60.6 (trans). A similar conclusion is made
e
from the MB-spectra (cf Sec. 12.4.7).

er
• 6. Detection of 1t-bonding to introduce the double bonded character in the A-X bond (X =
H
NQR active nucleus halogen): This can be done from the measurement of the asymmetry parameter
k
11 obtained from the NQR spectroscopy. The single a-bond leads to the axially symmetric field gradient
lic
(i.e. 11 = 0) around X but the n-bonding introducing the double bonded character leads to the nonaxially
'*
symmetric field gradient (i.e. 11 0). It has been established that the degree of n-bonding is related
C
with 11.
The degree of carbon-halogen 1t-bonding in vinyl halide (H 2C=CH-X, X = CI, Br, I) can be
estimated from the measured 11-values obtained from the halogen NQR spectra. The n-bonding occurs
as follows:
~ n·.
H2C-CH-X· ~ H2C - CH-X·
- _~
Here it is worth mentioning that the n-bonding in M-X (M = Si, Ge, Sn) will reduce the ionicity
of the bond (cf. X(p) ~ M(d) n-bonding reduces the anionic character of X) but the solid state effect
(Sec. 12.8.7) will try to enhance the ionicity of the bond. In fact, the very small double bonded character
(ca. 1%) found from the NQR spectroscopy for 1271 in MI4 (M = Si, Ge, Sn) is probably due to the solid
state effect.
The NQR data for X of the MH 3X type compounds (M = C, Si, Ge, Sn; X = 35, 37CI, 79, 81Br) indicate
the highest double bonded character in the Si-CI bond of SiH3Cl. The increased double bonded
character reduces the charge separation (i.e. decrease of the ionicity of the bond) and shortens the bond
length and consequently the the dipole moment (more correctly the bond moment) goes to decrease. In
fact, it has been found that the dipole moment of GeH 3CI is larger than that of SiH3CI having the highest
amount of double bonded character in the M-CI bond.
(E) NQR Spectroscopy to Identify the Hydrogen Bonding in Solid state:
It has been already discussed that the solid state effect (Sec. 12.8.7) leading to the more ionicity in
the A-X bond reduces the magnitude of nuclear quadrupolar coupling constant of halogen (X) when
X is more electronegative than A. In fact, the e 2qQ values determined from the NQR data are less than
the values determined from the fine structure of microwave spectrum by about 10 to 25%. The e 2qQ
value for 35CI in HCI in solid state is about 20% smaller than the value found in the vapour state
(microwave spectroscopy). A similar situation is found for 14N in NH 3. The strong H-bonding interac-
ry
tion (intermolecular) in solid HCI or NH 3 introduces an enhanced ionicity in the bond to reduce the
ra
coupling constant of 35CI or 14N.
The 35CI NQR spectrum of solid Na+AuCI4- • 2H20, i.e. sodium tetrachloridoaurate(III) dihydrate
ib
shows 4 NQR lines in which one line (i.e. singlet signal) appears at 2.5 MHz lower (at 77 K). In fact,
yl
the band appears to consist of a triplet signal (1: 1: 1 intensity) and a singlet signal. The singlet signal
em
is due to the Cl-centre which is involved in H-bonding interaction with the two lattice water molecules.
With the increasing of temperature, the H-bonding interaction decreases and the NQR frequency of the
ch
4th line (i.e. singlet signal) starts to shift towards the higher frequency.
Thus the NQR spectroscopy may appear as a promising tool to investigate the H-bonding interaction
al
in the solid state.

e
(F) NQR Spectroscopy of the Organo-halogen Compounds:

th
It is illustrated in the following examples:

e/
t.m
Compound Type ofCI Number of

(in terms of chemical equivalence) NQR eSCl) bands
e
er
@-CI
H
2
CI-@-CI (crystallographically two
k
nonequivalent Cl-atoms)
lic
CI-@-CH 2CI 2 2
C
CI-<Q(-CH 2CI 3 3
CI
C-CI NQR group frequency: The NQR frequency for 35CI depends on the type.ofthe C-centre and
its electronic environment. The electron pushing substituents on C introduces the more anionic character
on Cl to reduce the e2qQ values. In fact, the following linear relationship has been found for the chloro
substituted benzenes:
v (MHz) (for 35CI) = 34.83 + 1.0240,0 = Hammett constant.
In fact, the C-CI NQR (35, 37Cl) group frequency is a fingerprint or characteristic property of the
C-centre (cf. Table 12.8.8.1).
The C-35 CI and C-37 CI NQR group frequencies are available in literature and comparison of the
experimental values with the literature value can help us to identify the nature of C-CI bonds.
Table 12.8.8.1 Some representative C-37CI NQR group frequencies.

Group NQR frequency Group NQR frequency
(MHz) (MHz)
I
-C-CI
I
30.0 - 43.0 o-CI 34.5 - 40.0
I
-C-CI
I
34.5 - 42.5
"
/'
C-CI 36.5 - 39.5
CI
ry
I
"
ra
CI-C-CI 37.8 - 42.0 C-CI 28.8 - 34.5
O~
ib
I
yl
CI
em
I 29.7 - 32.8
-O-C----:.CI
I
ch
al
• (1) Chloromethanes: Nuclear quadrupolar coupling constants for 35CI of the substituted
chloromethanes vary as follow.~:
e
th
CH3CI ( CH2Cl 2 ( CH2Cl 3 ( CCl4

e/
It indicates the least ionic character in the C-CI bond for CCI4 . In fact, with the gradual substitu-
tion by CI, the effective electronegativity of the C-centre increases to reduce the electron flow towards
t.m
chlorine and it reduces the ionicity of the C-CI bond (i.e. less anionic character of CI) and enhances
the e2qQ value a:~d consequently, the NQR frequency of 35Cl.
e
• (2) Trichloroacetyl chloride (CI 3COCI): The 35CI NQR spectrum shows 4 NQR lines-3 closed
er
spaced lines to constitute a triplet and a single line appearing at a relatively lower frequency. The NQR
H
(35 Cl) frequencies are:

k
40.60,40.48,40.13,33.72 MHz
lic
From the knowledge (Table 12.8.8.1) of 35CI group frequency, the 35CI nuclei of the CCl3 group
should show the NQR frequencies in the range 38-42 MHz. Thus the three NQR lines appearing at
C
about 40 MHz correspond to the chemically equivalent but crystallographically nonequivalent

CI-atoms of the tricholoromethyl group, i.e. CCI3 group. The 4th NQR signal at 33.72 MHz arises
for the Cl-centre of the CaCI group. The higher NQR frequency for 35CI of the CCl3 group is rationalised
by considering the electron withdrawing effect of the chloro groups.
35CI_NQR: 33.72 MHz
~
Chemically equivalent
but crystallographically
nonequivalent 3CI-centres.
CI-C
'"
CI"" /C=O
35CI_NQR: Triplet in the range
40 MHz 1:1:1 (intensity) CI/
• (3) 2, 4-dichlorobenzenetrichloride: It has the following structure.
In terms of chemical equivalence,

two types of CI-atoms in the ratio 2:1
i.e. CI in the CCl a group.
35CI-NQR: One doublet and one singlet

(in the range of 39 MHz)
It indicates the three types of Cl-centres in the ratio 3: 1: 1. Thus, it is reasonable to expect three 35CI
NQR bands with the intensity ratio 3:1:1. The actual 35CI NQR spectrum shows three bands as ex-
pected. The band appearing at about 39 MHz corresponds to the CCl3 group and this band is expected
ry
to constitute a triplet with the intensity ratio 1: 1: 1. But this band shows a doublet and a singlet with
the intensity ratio 2: 1. It is believed that the ortho-chloro group sterically hinders the. free rotation of
ra
the trichloromethyl (CCI 3) group and the two chlorine atoms of the CCl3 group being nearer to the
ib
ortho-chloro group are different from the third chlorine atom which remains relatively further away
yl
from the ortho-group. It explains the doublet and singlet peak: with the intensity ratio 2: 1.
em
• (4) Isomers of hexachlorocyclohexane: The different isomers can be identified by following 35CI
NQR spectra.
ch
In fact, the NQR spectroscopy is being widely utilised by the organic chemists to extract the struc-
tural information.
e al
12.9 MASS SPECTROMETRY AND ITS APPLICATION

th
12.9.1 Working Principle of a Mass Spectrometer

e/
It has been discussed in detail in Sec. 1.2, Vol. 1. It is used to determine the ratio M/q of a positively
t.m
charged species (in vapour phase) where M = mass of the ion and q = charge of the ion and the ratio
is given by:
e
M = H5 r2
er
q 2V
H
r = radius of curvature of the trajectory followed by the positively charged ion and r is a characteristic
k
property of a particular instrument; H o = applied magnetic field and it is k~pt constant; V =accelerating
lic
electrostatic field for the positively charged ion.

C
The positively charged particles are generated in the spectrometer through the bombardment of an
acclerated electron beam (having energy in the range, 8 eV to 100 eV) on the sample at vapour phase
kept at a very low pressure in the range 10-5 to 10-7 mm of Hg to provide a long mean free path for
the ions. It reduces the possibility of reactions among the ionised and fragmented species through
mutual collisions.
The electrical signal produced by the positively charged ions reaching the electrometer is amplified.
The amplified current (I) is plotted against the variable electros~ic potential V and the pe~s correspond
to the different values of M/q. To determine the M/q value, the instrument is first calibrated with respect
to some known M/q values. Then the unknown M/q value is obtained from the V value for the peak.
• Each peak: of the plot I vs. V corresponds to a particular M/q value.
• In the calibrated spectrometer, actually, the plot, I vs. M/q is made.
• For the same value of q, a more massive particle will show the signal or peak: for the lower value
1
of V, cf M oc - •
V
• For a particular value of q, the heights of the peak in the plot (I vs. V) represent the relative
abundances of the corresponding particles.
12.9.2 Ionisation and Fragmentation of the Sample: Fragmentation Mode - a Fingerprint

of the Sample
When a compound in vapour phase is subjected to an electron beam (EB), different processes like
ionisation, bond breaking leading to fragmentation, etc. will occur depending on the energy of the
electron beam.
For the electron beam of energy in the range 8 to 15 eV, it mainly leads to the formation ofunipositive
molecular ions through the ionisation of the molecules. Intensity of the peak corresponding to the mass
of the unipositive molecular ion goes to increase with the increase of energy of the bombarding electron
ry
beam till the excess energy of the molecular ion causes the fragmentation through the bond breaking.
ra
The minimum accelerating potential of the bombarding electron beam required to initiate the
fragmentation process· is called the appearance potential of the fragmentation. If energy of the
ib
electron beam is further increased, then more than one bond may break and even the doubly charged
yl
molecular ions may be produced.
em
Generally, the fragmentation process starts for electron energy greater than 15 eV. However, the
electron energy of about 70 eV (i.e. far above the appearance potential) has been found to produce
ch
the good fragmentation of reproducible intensity. The electron energy more than 70-80 eV has been
found to produce the doubly charged molecular ions.
al
The ionisation and fragmentation process can be illustrated by taking the hypothetical molecule
e
PQRS.
th
e/
(i) Ionisation (EB energy, 8-15 eV): PQRS ( EB ) ) (PQRS)+ + e; EB denotes the bombarding
8-15 eV
t.m
electron beam.
(ii) Fragmentation of (PQRS)+ (when EB energy) 15 eV):
e
EB
er
p" + (QRS)+
H
EB +
EB EB r ( p ) + Q"
k
(RS)+ +"Q+--(QRS)+ + p" 4olIlI--- (PQRsf t - - - - - -... (PQR)+ + S·

lic
l ~(PQ(
C
EB EB + R"
+ - - QR++S· !
(PQ)+ + RS·
Fragmentation mode - a characteristic property (i.e. fingerprint) of the substance: Apparently,

the fragmentation process can go on in many possible ways but it is not a random process. Stability
of the fragmented cationic species is the deciding factor to determine the mode of fragmentation. The
species which can delocalise the positive charge better will be produced more preferably during the
fragmentation process. It is illustrated by considering the fragmentation of the molecular ion
HOCH2-CH2 NHi. It can occur in two probable routes.
HOCH; (M/q =31) + .CH 2NH 2 ~HOCH2-CH2NH;

~HOCH2. + CH 2NH; (M/q = 30)
Nitrogen is less electronegative than oxygen and this is why, the cationic species CH 2NH 2+ is better
resonance stabilised (H2C NH 2+) compared to +CH20H (i.e. H 2C=OH+). Consequently, fragmenta-
tion of the molecular ion preferably produces the CH 2NH2+ species (Mlq = 30). Thus the mode of
fragmentation producing the cationic species is a characteristic property of the compound and it can
be treated as a fingerprint of the compound.
12.9.3 Application of Mass Spec~rometry

(A) Determination of molecular formula: Determination of molecular mass of the parent compound
and fragmented species (fingerprint application) can help us to establish the molecular formula when
the elemental analysis data are available. This procedure is widely applied for the organic compounds.
(B) Determination of ionisation potential and bond dissociation energy: Formation of the unipositive
ry
molecular ion (i.e. A ~ A+ + e) by the bombarding electron beam of energy 8-15 eV is the most
ra
common process. Thus the ionisation potential of a molecule can be obtained from mass spectrometry.
ib
The appearance potential initiates the fragmentation process through the bond breaking. It can help
yl
us to estimate the bond dissociation energy. It is illustrated for CH4 subjected to the mass spectrometric
em
study.
The result indicates: appearance potential ofCH; = 14.4 eV (for CH4) and 9.8 eV (for CH3 radical), i.e.
ch
CH 4 14.4 eV ) CH; + H· + e; ·CH 3 9.8 eV ) CH; + e
al
Let us construct the Born-Haber cycle
e
CH4~H· + ·CH 3 9.8 eV ) H· + CH~ + e

th
I 14.4 eV j
e/
i.e. x = (14.4 - 9.8) eV =4.6 eV

t.m
1 eV = 1.6 x 10- C x 1 V = 1.6 x-t0- 19 J

19
4.6 x 1.6 x 10- 19 x 6.02 X 10 23

e
Bond energy = 4.6 eV/molecule = kllmole

er
1000
H
= 443.8 kllmole.
k
lic
i.e. bond dissociation energy of CH4 = 443.8 kllmole.

C
(C) Determination of natural abundance of isotopes: The isotopic element can be subjected to the
mass spectrometric study. From the positions of peaks of the I vs. V plot (cf. Fig. 12.9.3.1), mass
numbers of the isotopes can be obtained. The heights of the peaks give the measure of their relative
abundances (assuming q is the same). This has been qualitatively illustrated for magnesium in Fig.
12.9.3.1.
Conventionally, the height of the most intense peak (corresponding to the most abundant isotope) is
taken 100 (called base value) and heights of other peaks are measured with respect to this base
value.
79,SlBr isotopes: Isotopes of an element will be distributed in its different compounds according to
the natural abundance of the isotopes. Let us consider the mass spectrum of CH3Br to find the distri-
bution of the isotopes of bromine. It shows two peaks (in the plot I vs. V) corresponding to the M/q
values 94 and 96 which represent the species CH~9Br+ and CH381 Br+respectively. The peak height ratio
is almost 1:1 (i.e. 50% abundance for both the isotopes, 79Br and 81Br; cf. actual abundance 50.5% and
49.5% for 79Br and 81Br respectively).
100 A=24
In the mass spectrometer, singly charged
Mg-ions i.e. Mg+ (cf. Mg + e ~ Mg+ + 2e)
(A = atomic mass of Mg-isotopes) are produced and it makes M/q = atomic
mass of the isotope.
E
e (Peak heights for
:; 50 A = 24, 25 and 26)
u 100: 12.8:14.1
i
(approx).
ry
ra
'-----..;...,"'---L~ ---"'----'-~ _ _""--_....I.__ ____"l_ ___. V
M+: 26 25 24
ib
Fig. 12.9.3.1 Current strength I (measured by electrometer) vs. electrical field strength V (i.e. I vs. V plot) in a mass
yl
spectrometer to measure the relative abundance of the isotopes of the element magnesium having the isotopic abundances
em
78.60%, 10.11 % and 11.29% for 24Mg, 25Mg and 26Mg respectively.
13
C isotopes: For CH4 , the observed two peaks correspond to the M/q values 16 and 17 which
12,
ch
represent the species 12CH! and BCHt. The peak corresponding to M/q = 18 representing the species
al
12C1H22H! is insignificant due to the very poor natural abundance of 2H (about 0.015%). The peak
e
height ratio for the M/q values 16 and 17 is about 90: 1. It gives the natural abundance of 12C and BC
th
as 98.9% and 1.1 % respectively.

e/
Illustration 1: Find the peak height ratio for the masses M and M + 1 (M corresponds to the parent ion
t.m
peak) in the case of acetone (C 3H 60). (See Table 5.2.4.2, Vol. 1 for isotopic abundance of the concerned
elements).
The M + 1 peak may represent the molecular ion species containing BC, 2H or 170 (i.e. the species
e
are respectively: 12Ci3C1HJ60+, 12CjHs2HI60+ and 12CjHJ70+).

er
Height of the parent peak (M) !!.M.- probability of occurrence of 12 C3H6 0

H
For 13C: - - - - - - - - - - -
Height of the M + 1 peak hM + 1 1
probability of occurrence of 12 C 3cH 60
k
lic
Natural abundance of 12 C
C
Number of C-atoms x Natural abundance of 13C
98.892 . hM
= = 29.75 l.e. - - =-100- = 29.75, l.e.
.
hM +1 = 3.36
3xl.l08 hM + 1 hM + 1
Thus if peak height for M is taken as 100 (i.e. base value) then the peak height for M + 1 is 3.36
Similarly the peak height ratio for 2H and 17 0 can be calculated by using their natural abundance values.
2 • h M +1 = 6xO.015 ~9xI0-4. For 17 0 : h M +1 = lxO.037 ~3.7xI0-4

For H. hM 99.985 99.759
' hM
17
It indicates that the contributions of 2H and 0 substitution to the peak height of M + 1 are negligible
compared to the contribution of BC substitution.
Illustration 2: An organic compound (Molecular mass = 196) consisting of C, Hand 0 shows: peak
heights of the masses M (i.e. parent peak), M + 1 and M + 2 = 100 (base value), 13.4 and 0.4 respectively.
Find its molecular formula.
Let the compound be CxHyO z• The peaks for M + 1 and M + 2 correspond respectively to 13C and 180.
The possibility of incorporation of 17 0 for M + 1 can be reasonably ignored because of its poorer
abundance compared to that of 13C (cf. 0.037% vs. 1.108%). Here the M + 1 peak for the incorporation
of 2H is also ignored because of its very poor abundance (0.015%). Similarly, M + 2 corresponding to
the simultaneous presence of 13C and 17 0 is a rare possibility.
Thus we can write for 13C substituion:
Peak height for M _ hM _ Natural abundance of 12C

Peak height for M + 1 - hM +1 - Number of C-atoms x Natural abundance of 13 C
100 98.892 98.892 x 13.4 11 96 12 ( . )

i.e. -- = ; or x = = . ::: nearest Integer
ry
13.4 x x 1.108 100 x 1.108
Similarly, for 18 0 substitution:
ra
ib
~=100 Natural abundance of 16 0
yl
h M +2 0.4 Number of O-atoms x Natural abundance of 18 0
em
= 99.759 x 0.4 : : : 2 .0 ( nearest Integer
100 99.759. . )
or, - = ; I.e. Z
ch
0.4 z x 0.204 100 x 0.204
We have: 196 = 12 x 12 + y x 1 + 2 x 16; or y = 196 - 144 - 32 = 20
al
i.e. the compound is C 12H 20 0 2.

e
th
Probability of Isotopic Substitution in a Compound

e/
t.m
RAn: For the molecule RAn' if the element A is considered to possess two isotopes IA and IIA
having the relative probabilities of natural abundance p and q respectively (i.e. p + q = 1), then
the probability of occurrence of the species RIA~IAn_x is given by: nCx(PY(q)n-x
e
Thus we can write:

er
Probability of occurrence of the species R1 An

H
Probability of occurrence of the species R1 An_III A

k
lic
C
nCn (pf (q)o =L; (cfne =1 and ne =ne =n).

ne - ()n-l
p
()1
q n q n . n-l 1
n 1
Illustration 3: Find the relative population densities of the species having mass M, M+ 1 and M+2 for
an organic compound CaHbNcO d •
M +1: For an organic compound constituted by.C, H, Nand 0, the mass spectrometric peak for
M + 1 may arise due to substitution by a 13C-atom or by a 2H-atom or by a 15N-atom or by an 170-atom.
The relative natural abundance of the isotopes are:
12C : 13C:::::: 100 : 1.12; IH : 2H:::::: 100 : 0.015; 14N : 15N::::: 100 : 0.37; 160 : 17 0 ~ 100 : 0.037 ; 160 :
18 0::::: 100 : 0.204.
The substitution by 13C makes the largest contribution to the peak for M + 1 (cf. natural abundance
of 13C is relatively large compared to that of 2H, 15N and 1~0). Thus if the effect of 13C is considered
only then, the peak height ratio is given by:
a x natural abundance of l3e = a x 1.1Q8 = 1.12 x 10-2a

natural abundance of 12 C 98.892
i.e. (h:;1 x 100) (for 13e) = 1.12a
Considering the combined effect of substitution by l3C, 2H, IN5 and 170, we can write:
hM + 1 x 100 = 1.12a + 0.015b + 0.37c + 0.037d

hM
M +2: The peak for M +2 may arise due to the species:
ry
12Ca_213C21Hb14Nc160d (I)~ 12Ca_113CIHb_12H14Nc160d (II); 12Ca_113CIHb14Nc_115N160d (III);
ra
12Ca_ll3ClHb14Nc160d_1170 (IV); 12CalHb14Nc160d_1180 (V). Other probable species due to the simul-
ib
taneous substitution by 2H and 15N; 2H and 170; 15N and 170, etc. are less important.
yl
The species representing the mass Mis 12CalHb14Nc160d (VI).
em
Relative contributions of the different species having the mass M + 2 are as follows:
ch
Population density of the species I aC (100)a-2 (1.12)2 aC2 X (1.12)2
a
al
Population density of the species VI (100)a (100)2
e
(cf. the relation nCx(P)x(q)n-x, relative abundance, 12C : l3C = 100 : 1.12)
th
e/
h M +2 x 100) (for l3e) = a C 2 X (1.12)2 X 100 = a (a -1) x (1.12f = a(a -1) x 6.3 x 10-3
i.e.
t.m
( h (100)2 2 x 100
M
Population density of the species II ax1.12 bxO.015

e
---x---
Population density of the species VI
er
100 100
H
i.e. (h:;2 x 100}for l3e and 2H ) = ab x 1.7 X 10-4

k
lic
Similarly,
C
hM+2 x 100) (for 13C and 15 N ) = ac x 1.12 x 0.37 x 100 = ac X 4.1 X 10-3
( h 100 x 100
M
h M + 2 x 100) (for 13C and 170) = ad x 1.12 x 0.037 x 100 = ad x 4.1 X 10-4
( h 100x 100
M
hM + 2 x 100) (for 18 0 alone) = d x 0.204 x 100 = 0.204d; (16 0 : 18 0 = 100: 0.204)

( h 100
M
Thus we can write:
h
M+2 X 100::= 0.204d +6.3 X 10-3 a(a -1)+4.1 X 10-3 ac + 1.7 X 10-4 ab +4.1 X 10-4 ad
hM
The species V (i.e. substitution by 18 0) makes the largest contribution to the M + 2 peak and we can
reasonably write:
hM +2 ~ 0.204d.
hM
Illustration 4: Find the peak height ratio (h M+ 1 : hM ) for two compounds C 6H 4N 20 4 and C 12H 24 having
the same molecular mass (M) 168. How can you distinguish them?
For C6H 4N 20 4 , we can write:
hM +1 X 100 =6 x 1.12 + 4 x 0.015 + 2 x 0.37 + 4 x 0.037 ~ 7.67

hM
ry
i.e. peak height for M +1 will be 7.67% of the peak height for M.
ra
(c/. h:;2 x 100 "" 4 x 0.204 = 0.82)
ib
yl
For C 12H 24 , we can write:
em
hM +1 x 100 ~ 12 x 1.12 + 24 x 0.015 = 13.8
ch
hM
Thus, measurement of the peak height ratio for the species M + 1 and M can identify the two com-
al
pounds having the molecular mass M.

e
th
Illustration 5: Peak height ratios for the organo-halogen compounds.

e/
For RIAxIIAn_x eA and IIA are the isotopes of the element A and their relative probabilities of occur-
t.m
rence in nature are p and q respectively), its probability of occurrence is given by: nCx(P)x(q)n-x. The
binomial expression of (p + q)n can also calculate the relative population densities of the species.
(i) RCI3 (n =3, p =0.75 for 35CI and q =0.25 for 37CI i.e. p:q = 3: 1): The binomial expression gives,
e
(p + q)3 = p3 + 3p2q + 3pq2 + q3. The relative population densities of the different species are
er
given by:
H
R 35 Cl 3 (M) : R35Cl237CI (M + 2 ) : R35Cl37Cl2 (M + 4) : M 37 Cl 3 (M + 6) = 33 : 3 x 3 2 xl: 3 x 3 X

12 : 13 = 27 : 27 : 9 : 1
k
lic
(ii) RBr2 (i.e. n = 2, p ~ 0.5 for 79Br and q ~ 0.5 for 81Br i.e. p:q = 1:1): We can write, (p + q)2 =p2
+ 2pq + q2. The relative population densities of the different species are given by:
C
=
R79Br2(M): R 79 Br81 Br (M + 2): R81Br2(M + 4) 12 : 2 x 1 xl: 12 1 : 2: 1 =
(iii) RCI 2 (i.e. n = 2, p = 0.75 for 35CI, q = 0.25 for 37CI i.e. p:q = 3:1): We have the binomial
expression, (p + q)2 = p2 + 2pq + q2. Thus we have:
R 35CI2 (M): R 35 Cl 37 CI (M + 2): R 37 C1 2 (M + 4) = 32 : 2 x 3 xI: 12 = 9: 6: 1.
(iv) RCIBr: R 35 Cl 79Br and R 37 Cl 81 Br represent the mass M and M + 4 respectively while both the
species R 35 Cl 81 Br and R 37 Cl 79 Br represent the mass M + 2. Thus we can write:
M : M + 2 : M + 4 = 3 xl: (3 x 1 + 1 x 1) : 1 x 1 = 3 : 4 : 1
(cf. natural abundance ratios, 35CI : 37CI = 3:1, 79Br : 81Br = 1:1)
h
M+2 (i.e. peak height ratio for M+2 and M) for the organo-halogen and organo-sulfur
hM
compounds: The ratio is usually very small for the organic compounds constituted by C, H, Nand 0
only but the ratio is high for the organo-halogen and organo-sulfur compounds where the relative
abundance of the more massive isotope is fairly high (cf. 37Cl -- 25%, 81Br -- 50%, 34S -- 4.3%). It has
been illustrated for RCI 3, RCI 2, RBr2, RBrCl. The ratio hM+2 : hM can tell as the number of halogen atoms
in the compound (cf. the ratio is 1 : 1 for RCl 3 while it is 6 : 9 for RCI 2).
(D) Mass spectra of metal carbonyls: In the mass spectrometer, during the fragmentation, all the CO
=
groups are lost gradually (cf. loss of a CO group loss of mass by 28 units) and all the resultant species
can be characterised.
Illustration 1: Mass spectrum of [ReBr(CO)s] (isotopic abundance of the isotopes: 185Re -- 37%, 187Re
-- 63%; 79Br -- 50%, 81Br -- 50%; 12C -- 99%, 13C -- 1%; 160 -- 100%). Its fragmentation products can be
explained by considering the following two routes.
-co )[ReBr(CO)4]+ -co )[ ReBr(CO)3]
ry
(a) [ReBr(CO)5]~[ ReBr(CO)5]+
(M=404,406, 408) (M=376,378, 380) (M=348,350,352)
ra
l-
ib
co
(Triplet patterns of peaks)
yl
em
Re+ ( -Br
[ReBr]+ (
-co [ReBr(CO)]+ ( -co [ReBr(CO)2]+
(M=185,187) (M=264, 266, 268) (M=292, 294, 296)
ch (M=320, 322, 324)
al
[Re Br (CO)5] ~[Re Br (CO)5]+ _-B_r~) [Re (CO)5]+ -co ) [Re(CO)4]

e
(M=404,406,408) (M=325,327) (M=297,299)

th
l-
e/
(Doublet patterns of peaks) co

(b)
t.m
Re+ (-co [Re(CO)]+ ( -co [Re(CO)2]+ ( -co [Re (CO)3]+

(M=185,187) (M=213,215) (M=241,243) (M=269,271)
e
er
Here mass of CO has been taken as 28 (i.e. ignoring the effects of 13C, 17 0 and 180 isotopes having
H
the very poor abundance). Thus for [ReBr(CO)5]+' we can have the following combinations:
[185Re79Br(CO)5]+ (M = 404), [185Re81Br(CO)5]+ (M = 406),
k
[187Re79Br(CO)5]+ (M = 406), [18 7Re 81 Br(CO)5]+ (M = 408).

lic
In this way, mass of each species can be calculated. Considering the natural abundance 50% for each
C
isotope of 79, 81 Br, the relative abundance of the species of M = 406 (joint contribution of two species),
408 and 404 is 100 : 63 : 37.
It is evident that for the species bearing the ReBr unit, there will be the triplet patterns of peaks
while for the species containing rhenium lacking in bromine, there will be the doublet patterns of
peak. For the doublet peaks, the intensity ratio (measured by the relative peak heights) will be 63:37
(i.e. the isotopic abundance ratio of 187Re and 185Re; e.g. for [Re(CO)]+, the peak height ratio for
M = 215 and 213 is 63:37) (cf. Fig. 12.9.3.2). On the other hand, the peak height ratio of the components
of a triplet peak will be 100:63:37; e.g. for [ReBr(CO)4]+' it is 100:63:37 for M = 378, 380 and 376 (Fig.
12.9.3.2). For M = 378, both the Re-isotopes contribute; for M = 380, the 187Re isotope having the
natural abundance 63% contributes; for M =376, the 185Re-isotope with the abundance 37% contributes.
Here it may be mentioned that because ofthe 1:1 isotopic abundance ofthe 79Br and 81 Br isotopes, their
distribution in the species [ReBr(CO)xJ+ (x = 0, 1,2, ...,5) does not affect the relative abundance of the
species.
[ReBr(CO)J+
ry
ra
ib
yl
M/q = 380 J i \. M/q = 376
em J \.
ch
M/q = 378 Mlq =243 M/q =241
al
Fig. 12.9.3.2 A representative triplet peak (a) and a representative doublet peak (b) noted in the mass spectrum of
e
[ReBr(CO)5l.
th
(a) Triplet peaks are noted for the fragments, [ReBr(CO)x]+ (x = 0, 1, 2, 3, 4, 5). [ReBr(CO)5]+
e/
(M =404, 406, 408) (parent); x =4 (M =376, 378, 380); x =3 (M =348, 350, 352); x = 2 (M =320,
322, 324); x = 1 (M = 292, 294, 296); x = 0 (M = 264, 266, 268).
t.m
(b) Doublet peaks are noted for the fragments [Re(CO)y]+ (y =0, 1, 2, 3,4, 5). y =5 (M =325, 327);
y = 4 (M = 297, 299); y = 3 (M = 269, 271); y = 2 (M = 241, 243); y = 1 (M = 213, 215); y = 0
e
(M = 185, 187).
er
Illustration 2: Mass spectrum of [HMn(CO)s]. Its fragmentation can go on in two possible routes.
H
[HMn(CO)5]~[ HMn(CO)5]+ (M = 196);

k
55 Mn (i.e. monoisotopicl00%)
lic
C
(a) [HMn(CO)5]+ -co )[HMn(CO)4]+ -co )[HMn(CO)3]+ -co )[HMn(CO)2]+

(M=196) (M=168) (M=140) (M=112)
l-co
Mn+ ~ [MnH]+ ( -co [HMn(CO)]+
(M=55) (M=56) (M=84)
[HMn(CO)5]+ ~[Mn(CO)5]+ -co )[Mn (CO)4]+ -co )[Mn (CO)3]+

(M=196) (M=195) (M=167) (M=139)
(b)
l-co
Mn+ ( -co [Mn(CO)]+ ( -co [ Mn(CO)2]+
(M=55) (M=83) (M=lll)
M/q (route b): 196 195 167 139 111 83 55

M/q (route a): 196 168 140 112 84 56 55
4 sets, each set differing by 1 unit;

H-containing species (route a) vs.
species without H (route b).
Illustration 3: A carbonyl halide [M(CO)xXn] in its mass spectrum shows the M/q values: 232, 230,
195, 167, 139, 111,83, 67, 55, 16 where the value 67 corresponds to the metal carbide. Find the values
of x and n; and the intensity ratio of the M and M + 2 peaks; and identify the carbonyl halide.
Solution: The value 195 differs from the values 232 (M + 2) and 230 (M) by 37 and 35 units respectively.
It indicates X = 35,37 Cl. No other successive fragments differ by 37 and 35 units. It indicates n = 1. The
ry
peaks for M/q = 167, 139, 111, 83 and 55 differ successively by 28 units and it indicates the successive
ra
loss of 5 CO groups (i.e. x = 5).
ib
The peak at Mlq = 55 corresponds to 55Mn (100% abundance). The peaks at M/q = 67 and 16
yl
correspond to 55Mn 12C+ (metal carbide) and 160+.
em
Thus the carbonyl halide is: [Mn(CO)5Cl]. ch
The isotopes are: 55Mn(100%), 35Cl(-75%), 37Cl(-25%), 12C(_ 99%), 160(-100%). Thus the M and
M + 2 peaks correspond to [55Mn(CO)535Cl] and [55Mn(CO)537Cl] having the intensity ratio 75:25 =::
al
100:33 (i.e. determined by the isotopic abundance of 35Cl and 37Cl because Mn is monoisotopic).
e
th
The fragmentation routes are as follows:

e/
[Mn(CO)5Cl]+ ~[Mn(CO)5]+ -co ) [Mn (CO)4]+ -co ) [Mn (CO)3]+

t.m
(M=232,230) (M=195) (M=167) (M=139)

o + MnC+(
l-co
e
o+~
(M=67)
er
H
Mn+ ( -co [Mn(CO)]+ ( -co

(M=16)
[ Mn(CO)2]+
(M=55) (M=83) (M=llI)
k
lic
Illustration 4: Mass spectrum of [Re2(CO)sCI2] shows the successive loss of 8 CO groups (loss of
C
mass by 28 units at each step). The existence of peak for the unit Re2C12+ indicates that· the atoms in the
cluster are strongly bonded to each other. In fact, in the given carbonyl compound, the two chlorine
atoms are bridging the metal centres.
Illustration 5: Fragmentation routes for [Mn2CO)10] in a mass spectrometer.

It is having the structure: [(OC)5Mn-Mn(CO)5]. Thus fragmentation (i.e. successive loss of CO
group) can occur in both the binuclear and mononuclear ions.
It is illustrated below.
[ Mn 2 (CO)10]+
-co )[Mn2(CO)9]+--C-O~)[Mn2(CO)8]+~···"·~ Mn;
(M=390) (M=362) (M=334) (M=110)
1-[ Mn(CO)4]
L....-_-_[M_n_(C_O)...;...5]~[ Mn (CO)5]+ -co )[Mn(CO)4]+ ~ ~ Mn+

(M=195) (M=167) (M=55)
12.10 OPTICAL ROTATORY DISPERSION (ORD) AND CIRCULAR DICHORISM (CD)

AND APPLICATION OF ORD AND CD CURVES TO DETERMINE THE ABSOLUTE
ry
CONFIGURATION
ra
These aspects have been discussed in Sec. 2.7 (cf Figs. 2.7.9-12) of Vol. 4.
ib
12.11 MAGNETIC MOMENT AND APPLICATION OF THE KNOWLEDGE OF MAGNETIC
yl
MOMENT DATA
em
These aspects have been discussed in Chapter 8. ch
12.12 SOME IMPORTANT ELECTROANALYTICAL TECHNIQUES LIKE POTENTIOMETRY,
COULOMETRY, AMPEROMETRY, POLAROGRAPHY AND CYCLIC VOLTAMMETRY
al
(CV)
e
th
These have been discussed in Sec. 16.22. (Vol. 3).

e/
12.13 OTHER INSTRUMENTAL METHODS OF CHEMICAL ANALYSIS

t.m
The instrumental methods like atomic absorption spectrophotometry (AAS), X-ray fluorescence
spectroscopy, nondispersive infrared (NDIR) spectroscopy, gas chromatography (GC), high performance
e
(pressure) liquid chromatography (HPLC), etc. have been discussed in the authors' book, Environmental
er
Chemistry with Green Chemistry, Books and Allied, Kolkata.

H
SOLVED NUMERICAL PROBLEMS

k
= 2080 cm- 1 , find vAs-O; (b) = 3300 cm- 1,

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Problem 1: (a) In R 2AsH, VAs-H In CH 30H, VO- H

v YCo - H = 1850 cm- 1, find YCo - o .
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find o - o ; (c) In [Co(CN)sH]3-,

Solution: For the A-H and A-D bonds, we have:
~ A-D =~~AH IlAH =

mHm A 1 1 1 1 .
or --=-+-::::::-,(assunnngmA»m H )
V A- H IlAD m H +m A IlAH mA mH mH
· ·1 ary,
SIml 1 --::::::-
1 1
IlAD mD
1 1 1 2
=-::::::- m H =-g,m D = - g
J2 1.41 No No
- - 1 2080 4 5 -1
(a) V As-D :::::: V As-H X - = - - : : : 1 7 em
1.41 1.41
(b) Vo D
- -
~vo H
1
x-=--~
3300 2340 em -1
- - 1.41 1.41
More correctly, we can write:
VO- H =~~OD = 16x2 x 16+1 =

VO- D flOH 16+216x1
- - 1 3300 2 -1
i.e. Vo D =V o H x--=--~ 402 cm
- - 1.374 1.374
-V - 1 1850
=- - ~ 1320 cm -1
(c) Co D ~ V Co H X -
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- - 1.41 1.41
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Problem 2: For HCI, the fundamental band arises at 2886 cm-I. Find the v values of the first two lines
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of P and R branches of HCl. (Internuclear distance in HCI = 127.5 pm)
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Solution: We have, for J ~ J/, v = Vo + B[ J' (J' + 1) - J (J + 1)]
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For R-branch, M = +1, i.e. J ~ J' = j + 1 ch
i.e. VR = Vo + 28J' = Vo + 28(J + 1), J = rotational quantum number = 0, 1, 2, 3, ...
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For P-branch, M = -1, i.e. J ~ J' = J - 1
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i.e. vp =vo -28J=v o -2B(J'+1), J'=0,1,2,3, ...

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e/
- h 2
B=- - I=flr
81t 2Ie '
t.m
1 35.5
-x--
e
mHmCI No No 35.5
er
~HCI = m H + mCI = 35.5 + 1 = 36.5 x 6.02 x 1023 g

H
No
k
J
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. gram atomic mass

( mass of an atom III gram = No
C
= 35.5 ~ 1 62 X 10-24
flHCI 36.5 x 6.02 x 10 23 g . g
27
Ii = h 6.62 X 10- erg s
2 r2 2
81t fl e 8 x (3.14)2 x 1.62 x 10-24 g x (1.275 x 10-8 cm) x 3 x 1010 cm s-1
~ 10.62 cm- I
Thus we get:
v P1 =v o -2B(J' +1)=vo -2B, j' =0
= 2886 cm- I - 2 x 10.62 cm- I = 2864.76 cm- I
vP2 =v o -2B(J' +1)=v o -48, j' =1
= 2886 cm- I - 4 x 10.62 cm- I = 2843.52 cm- I
V R\ =vo +2B(J+l)=vo +2B,J=0

= 2886 cm- I + 2 x 10.62 cm- I = 2907.24 cm- I
VR2 =vo +2B(J+l)=vo +4B,J=1
= 2886 cm- I + 4 x 10.62 cm- I = 2928.48 cm- I
Problem 3: Find the spacing between the lines of rotational spectrum of HCl. Use the data given in
Problem 2.
Solution: B = 10.62 cm- I (see Problem 2).
Spacing between the lines ~v=2B=2xI0.62 cm- I =21.24 cm- I .
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Note: Compare the line spacing in the rotational spectra of H35 CI and H37 CI and find the isotopic
shift, i.e. ~v (H 35 CI) - ~v (H 37 CI) (see Sec. 5.2.2, Vol. 1).
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Problem 4: A sample was excited by a radiation of 4500 A wavelength. A Raman line was observed
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at 4600 A. Calculate the Raman shift in cm- I . Comment on the nature of Raman line.
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c
Solution: Frequency of the exciting radiation, v 0 =:;:
o
ch
Vo = _1_ = 1 = 22222 cm-I
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i.e.
Ao 4500 x 10-8 cm
e
th
VR (wave number of the scattered photon giving the Rarrlan line)

e/
1 1 =21739cm- 1
t.m
AR 4600 x 10-8 cm
Raman shift, !1V R =(22222-21739) cm- I =483 cm- I

e
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VR < Vo ' i. e. the observed line is the Stokes line.

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Problem 5: Using the exciting radiation of wavelength 4 x 103A, the first Stokes line appears with a
k
spacing of 300 cm- I from the Rayleigh line. Find the frequency of the first anti-Stokes line in cm- I .
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Solution: Raman shift ~v R = 300 cm- I

C
Vo (exciting radiation) = _1_ == 3 1 8 == 25,000 cm- 1

Ao 4xl0 xl0- cm
VR (first Stokes line) = (25000 - 300) = 24,700 cm- I

VR (first anti-Stokes line) = (25000 + 300) = 25,300 cm- I
Problem 6: Acetylene (H-C==C-H) shows vs (C-H)=3375 cm- I and vas(C-H)

= 3290 cm -I. Identify the Raman and IR active vibrations. Calculate the frequency of the Raman line
when acetylene is excited by a radiation of wavelength 4355 A.
Solution: The molecule has a centre of symmetry. Thus according to the rule of Mutual Exclusion
Principle, the IR active vibrations are Raman inactive. For the asymmetric vibration (vas)' there is a
dipole moment change and consequently it is IR active but Raman inactive. It concludes that vs is
Raman active but IR inactive.
Vs = 3,375 cm- I (fundamental vibration and Raman active).
vex (i.e. wave number of the exciting radiation)
1 = 22,962 cm- I
4355 x 10-8 cm
Vs = Vfund (for the fundamental vibration) = 3,375 cm- I

Thus, wave numbers (v R) of the Raman line are ± Vfund ' i.e.
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vex
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vR = 22,962 + 3,375 = 26,337 cm- I (anti - Stokes line)
ib
vR = 22,962 -3,375 =19,587 cm- I (Stokes line)
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Problem 7: For a molecule, a particular vibration mode is both Raman and IR active. When it is excited
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by a radiation of wavelength 4358 A, it shows a Raman line at 4600 A. Find the v for the IR band.
ch
Solution: -v ex (excItIng
.. rad")
latton = - 1 = 1 8 =22, 946 cm -I
Aex 4358 x 10- cm
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vR (Raman line) = = 21,739 em -1 < vex; (i.e. Stokes line)

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i.e. 1 8
4600 x 10- cm
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The Raman shift, i. e. change in frequency of the light, gives 'the energy difference between the
t.m
vibrational levels.
It gives: ~V R (Raman shift) = 22,946 - 21,739 = 1207 cm- I
e
er
vIR = 1207 em-I i.e. AIR = 1 8 A = 82,850A

H
1207 x 10-
k
Problem 8: Calculate the magnetic field strength required for a proton to resonate (resonance frequency
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220 MHz).
Oiven: gN = 5.585, JlN = 5.04 X 10-24 erg 0- 1.
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Solution: We have: ~ = hv = gNJlNHo;
H = ~ = 6.62 X 10-27 erg s x 220 X 106 s- 1

i.e. o
gNJlN 5.585 x 5.04 x 10-24 erg a-I
Problem 9: Find the gJ or gN value of 19 F (I = ±) having the nuclear magnetic moment (IlJ) 2.6273 IlN.
Problem 10: Find the required magnetic field for a proton and l3C nucleus to resonate at the operating
frequency 30.5 MHz of an NMR instrument. Given, nuclear magnetic moments (f.lI) of IH and l3C are
1
2.7927 f.lN and 0.7022 f.lN respectively; 1="2 for both IH and 13C; f.lN = 5.05 X 10-27 J II.
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_ hvI
i.e. H 0-
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JlI
ib
6.62 X 10-34 J s x 30.5 X 106 (1/2) .
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S-l X
For IH: H = 27 l
=0.71T
em
o 2.7927 x 5.05 x 10- J T-
ch
6.62 X 10-34 J s x 30.5 X 106 S-l x (1/2)
For l3C: H = =2.84 T
0.7022 x 5.05 x 10-27 JT- l
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o
e
th
Problem 11: Calculate the chemical shift in ppm (B and 't) for a proton that resonates at 130 Hz
downfield from TMS on a spectrometer operating at 60 MHz.
e/
t.m
V sample - V TMS (in Hz) 6

Solution: 0 ( chemical shift ) = ( ) x 10
Operating frequency in Hz
e
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6 6
i.e.
0= /),.vHzxlO 130 X 10 =2.16 m.
H
Operating frequency (Hz) 60 x 10 6 pp

k
i.e. 't = (10 - 2.16) ppm = 7.84 ppm

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C
Problem 12: A peak separation of 40 Hz is maintained when the NMR spectrum is recorded at 60 and
100 MHz operating frequencies. Comment on this.
Solution: As the peak separation remains unchanged, the two peaks are originated from the spin-spin
coupling (i.e. splitting of a signal due to the spin-spin coupling). Here the coupling constant (1) is
given by 40 Hz.
Note: If the peaks were two different signals then the peak separation would increase on changing .
the operating frequency 60 MHz to 100 MHz.
Problem 13: For CH3-CH 2-I, frequency shifts (downfield) from TMS are: 110 Hz (CH 3-proton) and
180 Hz (CH 2-proton) (for the operating frequency 60 MHz). What will be the frequency shifts for the
operating frequency 300 MHz? (see Fig. 12.2.12.2).
. 110 x 106 180 x 106

Solution: B(CH 3 )= 6 =1.83ppm;B(CH 2 )= 6 =3ppm
60xlO 60xl0
For the operating frequency of 300 MHz, we can write:
f).y x 10 6
O(CH 3 ) = 1.83 ppm = 6 i.e. f).y = 549 Hz (from TMS)
300 x 10
f).y X 106 .
O(CH 2 ) = 3.0 ppm = I.e.
f).y = 900 Hz (from TMS)
6
300x 10
Note: (1) For the change of operating frequency, chemical shift of a particular signal does not change.
(2) For the 60 MHz operating frequency, the PMR signals of the CH 2- and CH 3- protons are
separated by 180 - 110 or 70 Hz while for the 300 MHz operating frequency, these signals
are separated by 900 - 549 or 351 Hz (ef Fig. 12.2.12.2).
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Problem 14: A mixture containing methyl bromide and tert-butyl bromide shows two PMR singlet
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signals of the chemical shifts 2.20 and 1.8 ppm having the relative intensity integrals 5: 1. Find the
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composition of the mixture.
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. H 3C",
Solution: H 3 C-C-Br(O=1.8 ppm); H 3C-Br(O=2.2 ppm). ch
H 3C/
(I) (II)
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In (II), Br is directly attached to the Me-group, i.e. the three Me-protons are more deshielded
e
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compared to the nine Me-protons of (I) in which Br is attached to a C-centre which is linked to the
Me-groups. Thus the chemical shift 0 = 2.2 ppm (downfield) corresponds to the Me-protons of (II)
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while 0 = 1.8 ppm (upfield) corresponds to the Me-protons of (I).

t.m
9 equivalent protons of (I) give a singlet signal while 3 equivalent protons of (IIj give the singlet
signal. If the mixture contains x mole of (II) and y mole of (I), then we can write:
e
Intensity integral for (II) =3x =2. (given), i.e. .::. =.!2.
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Intensity integral for (I) 9y 1 y 1

H
. y 1 y 1 y + x 16
k
It gIves: ~ = 15 or, ~ + 1= 15 + lor, -x- = 15

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C
x 15
or, -+- = mole fraction of (II) = -
x Y 16
15 x 100
i.e. mole percent of (II) (i.e. CH 3Br) = = 93.75%
16
and mole percent of (I) = (100 - 93.75) = 6.25%
Problem 15: Calculate the proton exchange rate constant for the OH-proton of ethanol when the
OH-triplet just coalesces into a broad peak from the following data:
For the ultrapure ethanol, the peak separation in the triplet = 5.0 Hz.
Solution: We have: average residence time of the proton (r') = .fi

21tL1Y
(at the condition of coalescence)
L1V = peak separation (in Hz) when there is no exchange = 5 Hz

It gives r' = .J2 1 =0.045 s

2x3.14x5 s-
At the point of coalescence, k = J, = _1_:::::: 22 S-1 , i.e. the OH-proton changes its site 22 times
r 0.045
per second.
Problem 16: Calculate the ratio of the heights of the PMR signals of CH3CH20H.
Solution: Peak area ratio is given by, CH3 : CH2 : OH = 3:2:1
i.e. peak height (total) ratio is given by, CH 3 : CH2 : OH = 3:2:1
OR-proton: singlet peak, peak height = 1 unit (say).
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CH2-proton: quartet peak (splitting by three CH3 protons into 4 components) with the intensity ratio
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1:3:3:1.
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Total peak height = Ix + 3x + 3x + Ix = 2 unit, i.e. x = 0.25 unit.
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Thus the peak heights of the components of the quartet signal are = 0.25 unit, 0.75 unit, 0.75 unit and
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0.25 unit.
CH3-proton: triplet (splitting by the two CH2 protons) signal, intensity ratio = 1:2: 1
Total peak height = Ix + 2x + Ix = 3 unit, i.e. x = 0.75
ch
Thus the peak heights are: 0.75 unit, 1.5 unit and 0.75 unit.
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th
Triplet
e/
-OH 3 unit
t.m
Singlet
'"
/CH 2
e
1 unit
Q~rtet
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2 u~it
H
0.75 0.75
I
k
0.75 0.75
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C
or 0 25
1 .
--------------------.~ Ho
Fig. 1 PMR signals of CH3CH20H. Integral trace analysis indicates, 1 unit, 2 unit and 3 unit for the singlet, quartet and
triplet signals respectively.
Problem 17: ESR signal is noted for atomic hydrogen with an instrument operating at 9.0 GHz. What
is the strength of the magnetic field. Given: g for the electron in H-atom = 2.0026, JlB = 9.274 X
10-24 J 11
Solution: We have, hv = gJ.l.BHo = gJ:lHo, i.e. H o = hv

gp
6.62 X 10-34 J s x 9.0 X 109 s- 1

i.e. H = = 032 T
o 2.0026 x9.274x 10-24 JT- 1 •
Problem 18: Calculate the g-value of the benzene radical anion (C 6H6") if it shows the ESR signal at
0.332 T in a spectrometer operating at 9.302 GHz.
. g~Ho. hv
SolutIon: We have: v = - - , l.e. g = -R-
h pHo
hv 6.627 X 10-34 J s x 9.302 X 10 9 S-1

g=-= =2.002
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~Ho 9.274xl0-24 JT- 1 xO.332 T
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Problem 19: Calculate the ESR frequency of an unpaired electron in a magnetic field of 3000 G.
ib
Solution: We have: ~ = hv = g~H
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g = 2, ~ = 9.2732 X 10-21 erg G- 1, H = 3000 G, h = 6.62 X 10-27 erg s
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v = gl3H = 2 x 9.2732 X 10-21 erg G -I X 3000 G = 8.4 X 109 Hz
i.e.
ch
h 6.62 x 10-27 erg s
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=8400 MHz
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Problem 20: 57Fe* (14.4 keY) emits y-ray (t 1/ 2 = 9.6 X 10-8 s). Find the frequency uncertainty, natural
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line width, relative line width and doppler velocity corresponding to the natural line width.
e/
t.m
• . t1/2 9.8 X 10-8 s

Solution: Average hfe-period (tav ) = - = ----
In2 0.693
e
= 1.4 x 10-7 s
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H
Taking, fill x !it "'~, i.e. Mv x !it "'~, we get:

21t 21t
k
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~v (frequency uncertainty) = _1_ ~ _1_ = 1 7 = 1.13 X 106 Hz

C
21t~t 21ttav 2 x 3.14 x 1.4 x 10- s

(Taking ~t = uncertainty in the life time of the excited state ~ tav)
It gives: Natural line width = ~v = 1.13 X 106 Hz (i.e. very small bandwidth)
E y (energy of the y-ray) = 14.4 keY = 14.4 x 103 x 1.6 X 10- 19 J = 23.04 X 10- 16 J
i.e. hv = 23.04 X 10- 16 J
. . 23.04 X 10- 16 J
It gIves, v (frequency of the emItted y-ray) = -34
6.62 x 10 J s
= 3.48 X 10 18 Hz
=-~v
6
· I· I" .
It gIves, re alIve Ine WIdth
1.13 x 10 Hz
= 18
v 3.48xl0 Hz
::::: 3.2 X 10- 13 •
Doppler velocity u (corresponding to natural line width) is given by:

Iiv
u=-c
v
(1.13 X 10 6 s- l ) x (3 x 108 m S-I)

3.48 X 10 18 s-1
= 9.7 X 10-5 m S-1 = 9.7 X 10-3 cm S-1
Problem 21: Calculate the recoil velocity, recoil energy and Doppler shift of the y-ray radiation (3.5 x
10 18 Hz) emitted by a free 57Pe atom. Compare the values when the 57Pe atom is held in a matrix of
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10 g mass.
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Solution: Momentum of the y-ray photon =!!.- = hv
ib
A e
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Conservation of momentum leads to:
hv = momentum of the recoiling nucleus = mu

em
ch
e
(m = mass of the nucleus, u = recoil velocity).
e al
hv
th
i.e. u=-
me
e/
gram atomic mass of 57 Pe 57 g mol- 1

t.m
m=m = = - - -23- - -
Fe NO 6.02 x 10 mol- 1
e
er
H
27
u= hv = 6.62xlO- ergsx3.5xlQI8 s -1 ::::8.2xI0 3 cms-I
k
me 9.47 x 10-23 g x 3 x 10 10 cm S-I

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C
1 18 1
. ~ _ uV
3
H _ 8.2xI0 cms- x3.5xI0 s-
Doppler shIft, vs - Z - 10 -I
e 3 x 10 cm s
~9.6x101IHz
= 3.2 X 10- 15 erg = 3.2 x 10-22 J
Taking M = 10 g, we get the recoil velocity:

27 18 1
u = ~ = 6.62 X 10- erg s x 3.5 X 10 s- = 7.72 x 1O-2ocms-1
Me 1
10gx3x10 0cms- 1
Ere (recoil energy) =.!.. Mu 2 =.!.. x to x (7.72 X to-20 em S-I)2 '" 0

2 2
uv 7.72x10-2ocms- 1 x3.5x10 18 s- 1
Doppler shift, Av s =-Hz = 10 -I
C 3 x 10 em s
=9x10- 12 Hz
Note: Par 57Pe*emitting the y-radiation, frequency uncertainty z 106 Hz (See Problem 20).
Av s (Dapper shift) = 9.6 x lOll Hz » 106 Hz (for free 57Pe-atom)
= 9 x 10-12 Hz « 106 Hz (57Pe-atom held in matrix of 10 g mass).
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Problem 22: The MB nucleus 57Pe* makes the isomeric transition from the excited state of energy 14.4
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keY. What is its recoil energy?
ib
E 2 E2
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· · '"IT
SoIU t Ion. yye have Pre -- - -Y.
Py - , E re -
- Pre Y
- --- - 2
2m 2mc
em
C
£2
ch
(recoil energy) = ~
Ere
2mc
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Ey = 14.4 X 10 eV = 14.4 x 10 x 1.6 X 10- J = 23.04

3 3 19
X 10- 16 J
e
th
57 X 10-3 kg mol-I
m = mFe (mass of the 57Pe nucleus) = 23 -I
e/
6.02x10 mol
t.m
= 9.47 x 10-26 kg
E = (23.04xto- 16 J)2
e
()2
er
re
2x9.47x10-26 kgx 3xl0 8 ms- 1
H
k
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C
Problem 23: The source (i. e. 57Co) of 57Pe* is moving at a speed of 2 mm S-I. Calculate the frequency
shift (y-ray frequency 3.5 x 10 18 Hz).
Solution: The Doppler shift (Av s ) due to the u-velocity of the source is given by:
2 10 -3 -I 3 5 10 18 -I
AVs=uv Hz = x ms:. ~ s =2.33xto 7 Hz=23.3MHz
c 3 x 10 ms-
Por numerical problems on NQR Spectroscopy and Mass Spectrometry, see text (Sees. 12.8, 12.9).
EXERCISE 12
A. Questions on Infrared and Raman Spectra
1. Raman scattering is an optical analogue of Compton effect - explain.
2. Give the selection rules of ir- and Raman spectra.
3. What is the rule of mutual exclusion? Explain it.

4. What are the different types of normal modes of vibration? Explain the inversion of NH3 through
a vibrational mode. Illustrate the modes: vs' vas' 8, Ps' PP Pw' Pt. Show the symmetric and asym-
metric stretches in methyl, methylene, amino, nitro, acid anhydride (CO group).
5. What are the normal modes of vibration for: CO 2, S02, N 20, C 2H 2 and C 2H 4.
6. Comment on the positions of vc=o in the following cases: isolated carbonyl group; CH3CHO,
HCHO, CH3COCH 3, CICH 2COCH3, C12CHCOCH3; CH3COCH 2COCH3; )C=C-C=O;
exocylic )c=o group of rings of different sizes, amide and ester; aliphatic es~er; ~omatic
ester and u, B-unsaturated ester; aliphatic aldehyde and aromatic ketone; )C=C=O (ketene);
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X 2CO (X = F, CI, Br), saturated and unsaturated lactones and lactams.
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7. Coment on VC==N of HCN and DCN.
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8. What is Fermi resonance?
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9. Comment on vp=o in F 3PO, CI3PO, Br3PO, Ph3PO, Me3PO.
10. Comment on VOH for the free OH group and H-bonded OH group.
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11. How can you predict the linearity and nolinearity of the molecules from the ir-spectra?
12. How can you determine the structures of BF3, CIF3 and PF3 from their ir- and Raman spectra?
ch
13. How can you determine the structures of SF4, XeF4 and CF4 from their ir- and Raman specta.
al
14. How do you establish the structures of NSF3, POCl 3 and CI03F from their ir- and Raman spectra?
e
15. How can you determine the structure of PFs from its ir- and Raman spectra?
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16. How can you distinguish (by using the ir- and Raman spectra): cis- and trans- isomers of
e/
[PtCI 2(NH 3)2]; cis- and trans- isomers of [CoCI 2(NH 3)4]+;fac- and mer- isomers of [CoCI 3(NH3)3],
cis- and trans- isomers of [PtCI4(NH 3)2].
t.m
17. How can you distinguish (by using the ir- and Raman spectra): cis- and trans- isomers of
[MO(CO)4(PR3)2], fac- and mer- isomers of [MO(CO)3(PR3)3]'
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18. How can you establish the tetrahedral structure of [Ni(CO)4] and trigonal bipyramidal structure
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of [Fe(CO)5] from their ir- and Raman spectra?

H
19. Explain the order of VCo- Nin [CoCI(NH3)s]2+, [CoCI(ND 3)s]2+ and [Co(NH3)6]3+.
20. Explain the order of VN-H in free NH 3 and in [Co(NH3)6]3+.
k
Predict the order of Vpt-H in trans- [PtII (PR 3)2(X)(H)] for X = PR3, SCN-, I, CN-, CI-, NH 3.
lic
21.
22. Predict the order of v Pt- N and VN-H in trans- [PtCI2(NHRR')L] for L = PR3, P(OR)3' AsR 3, TeR2,
C
SeR2, SR2·
23. Predict the order of VPt-N and VN-H in trans- [PtCI 2(NH 3)(L)] for L = NH 3, SEt2 and C 2H 4.
24. Calculate VCo - D in [Co(CN)sD]3-if VC- H = 1850 cm- l for [Co(CN)sH]3-.
25. What are the characteristic features of ir- spectra for coordination by H 20 and NH 3?
26. How can you predict the chemical state of H 20 present in coordination compounds from the ir-
spectra.
27. IR- spectra can detect the presence of water in the clathrate compound, Ni(CN)2' NH 3 · C 6H6 .
xH20 -explain.
28. "The direction of shifting of ligand ir-band upon coordination depends on many factors"-
explain and illustrate with the examples.
29. Explain:
VN-H: NH 3 ) [Co(NH3)6]3+; VSn-CI: SnCI 3- ( [Rh(PPh3)3(SnCI 3)]
v po : Ph 3P=O) Ph 3P=O ~ M; VN=N: N 2 ) [Ru(NH3)5(N 2)]2+;
VNO : M-N-O (linear) ) M-N-O (bent); vc=c: C 2H4 ) [PtCI3(C 2H4)]-

vc=c: [M(C 2H4)] ) [M(C 2F4)]; VCN: [Pt(CN)4]2- ) [Pd(CN)4]2- ) [Ni(CN)4]2-;
VCN: [Mn(CN)6]3- ) [Mn(CN)6]4- ) [Mn(CN)6]5-; VCN: [Ag(CN)2]- ) [Ag(CN)3]2-) [Ag(CN)4]3-;
vco values in the carbonyl compounds involved in the following reaction:
[(11 5 -Cp)MO(CO)3 J2 ~2[ (11 5 -Cp)MO(CO)2J + 2CO

VNC : M-CNR (linear) ) M-CNR (bent); M-CNR vs. M-CNAr.
30. How can you determine chemical state of coordinated O 2 and H2in the coordination compounds?
31. How can you determine chemical state of O 2 in the adducts of Hb, Hr, Hc and Vaska's complex
from the v o- o values?
32. How can you distinguish the possibilities, [M(1l2-H 2)] and cis-[M(H)2] from the ir-spectra?
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33. [Ir(CO)CI(PPh 3)2] + H2 ~ adduct (showing v at 2100 cm- I , 2190 cm- I ). Predict whether the
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adduct is a dihydrogen complex or a dihydrido complex.
ib
• How does v co vary for the different oxidative addition products of Vaska's complex?
yl
34. Generally, on complexation by CO, v co decreases but VCN increases when CN- undergoes
em
complexation but both are isoelectronic-explain.
35. In the CN--bridged polymeric complexes, there are two VCN values-explain.
ch
36. For [M(acac)2]' v co and v c- c : Co ) Ni ) Cu ) Pd
37. For [M(bpy)]2+ and [M(phen)]2+: VM - N: Fe(II) ) Cu(II).
al
38. How can you distinguish the linkage isomers: M-SCN and M-NCS; M-CN and M-NC;
e
M-N0 2 and M-ONO; M-S0 3 and M-OS0 2?

th
39. How do you distinguish the O-bonded and N-bonded linkage isomers for urea as a ligand?
e/
40. How can you distinguish the different modes of coordination by NOi and soj- by considering
t.m
the ir-spectra?
41. Explain: vco: [PtU 2CI 2] ) [CrU6]CI3 and VCN: [CrU6]CI3 ) [PtU 2CI 2]
vso: [PtIl(dmso)] ) [CrIII(dmso)].
e
42. See Chapter 9 for the questions on Carbonyl and Nitrosyl Complexes.
er
H
B. Questions on NMR Spectroscopy

k
1. What is the frequency of NMR transition? How is it related with the Larmor frequency?
lic
2. Find the range of electromagnetic radiation required for the NMR and ESR transition. Why do
they differ?
C
3. What is the nuclear gyromagnetic ratio (YN)? How does it control the resonance frequency of the
NMR transition?
4. What are the effects of (i) temperature, (ii) gyromagnetic ratio, (iii) operating frequency of the
NMR spectrometer, and (iv) spin-lattice relaxation on the intensity of the NMR signal?
5. What are the factors to control the width of a NMR signal? What are the common solvents used
in NMR studies?
6. What are the different ways of relaxation process? How does it control the intensity and width of
an NMR signal?
7. Spin-lattice relaxation controls the intensity of an NMR signal-why?
8. Efficiency of spin-lattice relaxation depends on the nature of carbon (i.e. primary, secondary and
tertiary) in 13C-NMR spectroscopy-explain.
9. Spin-lattice relaxation process is relatively more efficient for the large molecules-explain.
10. Paramagnetic substances can enormously favour the spin-lattice relaxation process-explain.
11. Spin-lattice relaxation is more efficient in the liquid state than in the solid state----explain.
12. In an NMR experiment, the dissolved O 2 should be removed-why?
13. Spin-spin relaxation is an entropy driven process----explain.
15. For the solid sample, very often the NMR peaks are too broadened----explain.
16. In IR and electronic spectroscopy, the transition frequency is the characteristic parameter of the
sample but in NMR spectroscopy, the NMR transition frequency is not the characteristic parameter
of the sample-why?
17. Why do we need the parameter 'chemical shift' in NMR spectroscopy?
18. What is the shielding constant? How is it related with the chemical shift?
19. Why do you use TMS as a reference one in NMR spectroscopy of IH and BC? What are the
alternatives to TMS?
ry
20. What is the local diamagnetic shielding effect? What are the factors to control this parameter?
ra
• What is the local paramagnetic shielding? What are the factors to control this contribution?
Does it contribute to PMR spectroscopy? If not, why not? Does it contribute to lIB, BC, 19F?
ib
If so, why so?
yl
• Be and BH increase in the sequences: methyl (MeCH3) < methylene (Me 2CH2) < methine
em
(Me3CH) < quarternary-C (Me4C).
(Hints: Gradual substitution of hydrogen by the more electronegative carbon).
ch
21. How does H-bonding affect the B-chemical shift? How can you detect the intermolecular and
al
intramolecular H-bonding, keto-enol tautomerism by NMR spectroscopy?
e
22. Comment on the chemical shifts of the protons in: (a) CH 3X (X = H, CI, Br, I) and SiH4,
th
(b) different types of hydrides; (c) C 2H4, C 2H 2 and C 2H 6 ; (d) CH3CH20H and CH3CH2C0 2H;
(e) C 6H 6 and C 6H sCH3; (0 cyclopentadiene and cyclopentadienyl anion (Cp-); (g) cycloheptatriene
e/
@-X (= NOz, OH; CHO) and

t.m
and cycloheptatrienyl cation; (h) allyl cation and allyl anion; (i)
cinnamaldehyde; U)
RC0 2H and RS0 3H; (k) metal hydrides and organometallic hydrides;
e
(1) alkyl fluorides in liquid S02 in presence and absence of SbFs

er
(Hints: (CH 3 ) C - F (0 = 1.35 ppm, doublet) _+_Sb_F5~)(CH 3 )3 C+SbFi

H
(0=4.4 ppm, singlet)

k
(m) cis- trans- isomers of stilbene.

lic
C
Ph (a)
(Hints: '" c===c /H cis: H(b) deshielded by one Ph-ring

trans: H(a) deshielded by two Ph-rings.
(a) H/ '" Ph
23. What do you mean by neighbour anisotropic effect? How does it affect the chemical shifts of the
protons in (a) C 2H 4, (ii) C 2H b (iii) C 6H 6 , (iv) -CHO.
24. In gas phase, chemical shift indicates that HCI proton is more shielded than the CH4 proton-
explain.
• [HCO(CO)4] shows the acidic character but the O-value of the PMR signal is negative----explain.
25. How can you identify the transition metal hybrides from the chemical shift of the PMR signal?
26. Give the characteristic features of the PMR spectra of (i) CH30H, (ii) CH 3CH 20H, (iii) HD,
(iv) HPF 2, (v) H 2C=CF 2, (vi) B 2H 6 . (vii) BH 4-; (viii) CH 3CH 2Br vs. BrCH 2CH 2CI;
(ix) CH3CH2CH 2N02; (x) C 6H sCHO; (xi) 0- and p-isomers of dichlorobenzene.
",
27. Give the PMR spectra of the ultra-pure samples of CH30H and C2HsOH. What will happen if their
PMR spectra are recorded in 0 20 solvent? Give the PMR spectrum of C 2HsOD.
28. Compare the PMR spectra of: 0- and p- dichloro benzene; 0- and p- difluoro benzene.
29. Give the mechanism of spin-spin coupling? Discuss the factors to determine the coupling constant
(J). What is Karplus relation?
30. There are two close spaced PMR lines. How can you distinguish whether these are due to spin-
spin coupling or due to two different protons?
31. What do you mean by chemically and magnetically equivalent nuclei? Illustrate with the suitable
examples.
32. How can you distinguish the rotational isomers (i) Br2CH-CHBr2, (ii) CH3CH 2Br,
(iii) BrCI2C-CBrF2, (iv) (X)(Y)(Z)C-CH 2(A).
ry
33. How can you determine the structures of the followings by NMR spectroscopy:
(a) PF3, (ii) NF3, (iii) BF3, (iv) NH 3, (v) CIF3, (vi) BrFs, (vii) IF7, (viii) P 3N 3C1 4F2, (ix) P4S3,
ra
(x) P4N4CI6(NHC6Hs)2, (xi) B 2H6 (decoupled PMR signals), (xii) B 10H 14 , (xiv) B3Hi, (xv) BFi,
ib
(xvi) disubstituted ortho- and para-compounds.
yl
34. Illustrate the principle of designation of nuclei spin system in terms of A, B, C, M and X.
em
35. What do you mean by AB and AX system? How can you convert the AB system into the AX
system?
ch
36. Gives the representative examples of: (i) A3X 2 (ii) A 3B 2 (iii) A 2B 2 (iv) AMX, (v) AA'BB'
(vi) AA'XX' system, (vii) A 2X 2, (viii) A 2B2X2.
al
37. What do you mean by 1st order and 2nd order NMR spectra?
e
38. Why do we prefer the NMR spectrometer of higher operating frequency like 300 MHz, instead of
th
40 MHz, 60 MHz?
e/
39. How can you simplify the complex NMR spectra?

t.m
40. Depending on the operating frequency, CIF3 can act as an AB 2 molecule or as an AX 2 molecule
in terms of 19F-NMR spectra-justify.
41. Give the dependence of spin-spin coupling constant (J) and frequency shift (~v) on the applied
e
er
field.
42. What do you mean by the chemical shift reagents? How do they modify the PMR spectra?
H
Illustrate with an example.

k
43. What is nuclear magnetic double resonance (NDMR)? What is the principle of spin decoupling?
lic
How does the noise decoupling technique give the nuclear overhauser effect (NOE)?
C
44. What are the advantages of the proton decoupled l3C-NMR spectroscopy?
• In l3C-NMR spectroscopy, chemical shift (8) values cover a very wide range while, in PMR
spectroscopy it covers a narrow range-why?
• What are the advantages in lIB, l3C and 19F NMR spectroscopy over the PMR spectroscopy?
45. Discuss the effect of chemical exchange on the NMR spectra.
46. Give the characteristics of the PMR spectra: (i) ultrapure CH30H; (ii) ultrapure CH3CH20H;
(iii) mixture of CH30H and H 20; (iv) mixture of CH 3C0 2H and H20; (v) CH 3NH 2 at different pH
values; (vi) SF4 at very low temperature and room temperature; (vii) B3Hg-,
47. What do you mean by quadrupole relaxation? How does it affect the NMR spectra?
48. Quadrupole nuclei very often appear as the nonmagnetic nuclei in NMR spectroscopy-justify.
• 2H is a quadrupole nucleus, but it gives the NMR spectra-explain.
49. Comment on the NMR spectra of: NH 3 (PMR), NH4+ (PMR), CH 3NH"3 (PMR), CH3NH 2 (PMR),
NF3 e9F-NMR)~ 1- vs. 13- e 271-NMR); CI- vs. CI04- (3s CI-NMR); CI03- vs. CI04- (35 CI-NMR);
low-spin complexes of Co(lll) (59 CO) of the ligands of different crystal field strength.
50. What are the intrinsic disadvantages in 13C-NMR spectroscopy in comparison with the PMR
spectroscopy?
51. How can you identify the bridging and terminal CO groups by using the 13C-NMR spectroscopy?
52. Explain the chemical shifts (8 for the CO group) of 13C-NMR spectra of the followings:
[Cr(CO)6](8 = +211.4), [(l1 S-Cp)Cr(CO)3]- (8 = +247);
[W(CO)6] (8 =+191.5); [(Ph3P)W(CO)s] (8 = +221.3 for cis position; +216.5 trans-position (cis,
trans-positions with respect to PPh3).
53. How can you determine the structure of the followings by using the suitable NMR spectroscopy.
isomers of C2H 2BrCI; tautomers of H 3P03 and H 3P02; P and 0- dichlorobenzene; F 2P02H; BrFs;
CIF3; PF3; NF3; WF6 • L; HF2-; SF4; SeF4; OSF4; [Mo(CO)3H2(PPr3i)2]; TiF4 in coordinating
solvents; [RhCI3(PPh3)3] (lac and mer isomers); B 2H 6 ; B 3H g-; B10H14; W20 2F 9-; [NiBr2(PPh2Me)2]
ry
(square planar and tetrahedral); [Pt(CH3)3(NH3)3] (lac-mer isomers); [PdCI2(PMe3)2] (cis- and
ra
trans- isomers); [PtCI 2(PR 3)2] (cis- and trans isomers); RnPFs- n ; [Fe3(CO)12] (bridged and
nonbridged structures);
ib
54. How can you identify the rotational isomersim in the following cases by using the NMR
yl
spectroscopy?
em
BrCI2C-CBrF2; CH2CI-CHCICH3; F2BrC-CHCIF; FCI2C-CCI2F
54. How can you detect (i) H-bonding; (ii) intramolecular and intermolecular H-bonding, and
ch
(iii) keto-enol tautomerism by PMR studies.
55. How can you determine the exchange rate constant by NMR method?
al
56. Discuss the application of NMR studies to follow the fluxional behaviour of different molecules.
e
57. CI04 gives a NMR signal for 3sCI but CI0 3 does not give any NMR signal-explain.
th
58. PMR spectra of dimethyl formamide and Fischer carbene can indicate the cis-trans- isomerism
e/
specially at low temperature.

n
t.m
(b)H CH(a)
(I): 2 PMR signals
" ••/ 3 (intensity; 6: 1)
C-N
e
(Hints:
06
er
""-CHiO
) (II): 3 PMR signals
H
(I) (intensity; 3:3: 1)

k
For Fischer carbene (see text).

lic
c. Questions on ESR Spectroscopy

C
1. What is the condition for an ESR transition?

2. Intensity of an ESR signal is generally higher than that of an NMR signal--explain.
3. ESR transition occurs in the microwave region while NMR transition occurs in the radio frequency
region-why?
4. Discuss the factors to control the intensity and bandwidth of an ESR signal.
5. Bandwidth of an ESR signal, in general, is higher than that of an NMR signal-why?
The NMR peaks are sharper than the ESR peaks-why?
6. The Q-band ESR spectrometer is a better choice than the X-band ESR spectrometer-why?
7. For the ESR studies, very often dilution by the isomorphous diamagnetic host is essentially
required-explain.
8. For the transition metal complexes, if the ground state level is A(g) or E(g), then their ESR studies
can be done even at room temperature (maintaining the proper magnetic dilution), but if the
ground state level is T(g), then for the ESR studies, a very low temperature is required-explain.
9. Octahedral complexes of d 1, dl, tf (low spin), tF (low spin), cfS (high spin) and d' (high spin)
systems give the broad ESR signals even at very low temperature but the octahedral complexes
of J3, tf (high-spin), tF (high spin), tJ8 and lP systems give the sharp ESR signals even at room
temperature--expain.
• Tetrahedral complexes having the A or E ground states (e.g. 2E for d 1; 4A2 for d') require low
temperature for their ESR studies--explain.
• Octahedral complexes of Ni(ll) possess the 3A 2g ground state but they need very low tempera-
ture for the ESR studies-why?
.~ Oxidovanadium(IV) and Cu(ll) complexes can be subjected to even room temperature for their
ESR studies-why?
• Presence of unpaired electrons cannot always ensure the appearance of ESR signal--explain.
ry
[Hints: Large zero-field splitting (ef S = 2); rapid spin-lattice relaxation).
ra
10. [Ti(acac)3] gives the ESR spectrum but (Ti(OH 2)6]3+ fails to give the ESR spectrum--explain.
• [Ti(acac)3] in neutral solution gives the ESR spectrum but on acidification, the ESR spectrum
ib
disappears--explain.
yl
11. In general, for the n-unpaired electrons, there will be n ESR signals--explain.
em
12. Illustrate the zero-field splitting, Kramers' degeneracy and number of ESR transitions for 2, 3, 4
and 5 unpaired electrons.
ch
13. For the high spin Mn(ll) (ds) complexes, all the five expected ESR transitions are experimentally
verified-why?
al
• For the Cr(lll) complexes, there are three expected ESR transitions but generally they show
e
th
only one ESR transition. Explain.

• The rhombic and tetragonal distortion in high spin complexes of tF-system reduce the number
e/
ESR signals-why?
t.m
14. For the V(III) (dl) complexes, a very weak (forbidden) ESR signal (~Ms = ±2) arises. The allowed
ESR transitions (~Ms = ±1) are not observed. Explain.
15. The ESR transition for ~Ms = ±2 is an indication of magnetic exchange-illustrate.
e
er
16. What do you mean by effective spin (S') and electronic spin (S) in terms of ESR transitions?
Illustrate.
H
17. Cr(lll) placed in a single crystal of MgO shows a strong intense ESR signal with two small peaks
k
on either side--explain.
lic
18. What do mean by hyperfine and superhyperfine splitting of an ESR signal? Illustrate.
C
• Superhyperfine splitting is important for the Cu(ll) complexes but not so important for the
Cr(lll) and oxidovanadium(IV) complexes-why?
• Hyperfine splitting components generated by a single nucleus are of equal intensity but if they
are generated by more than one equivalent nucleus, they are of unequal intensity--explain.
• For the DPPH radical, instead of 9 hyperfine components, 5 hyperfine components are found-
explain.
• Oxidised form of rubridoxin (s =%) is EPR active but the reduced form it (S = 2) is EPR
silent though both the systems possess the unpaired electrons--explain.
19. Predict features of the ESR spectrum of:
(i) H-atom, (ii) D-atom, (iii) Cl-atom, (iv) NO and N02, (iv) NHzradical, (v) 13CH3, CH 2D, CHF2,
CH3 radicals, (vi) CH3CH 2 radical (vi) CD3, 13CD3 radicals, (vii) naphthalene negative ion, (viii)
benzene radical anion (C 6H6-), (ix) p-benzosemiquinone radical anion, (x) nitroxide molecules-
NO(S03)1-, di-t-butyl nitroxide, TEMPO and TEMPOL, (xi) CsHs radical, CsHs-, CsHs+.
(cf. CsHs: radical 1 unpaired electron; anion no unpaired electron; cation: 2 unpaired electrons
CI CI
in terms of MOT); (xii) C6~' C6H6+, C6~- (cf. MO diagram), (xiii) 0 * 0 radical anion
H H
(cf. 2H to split the signal; a triplet signal), (xiv) ·CH20H, (xv) ·CH2(OCH 3), (xvi) C6Hs• vs. CsHs•.
20. Give the features of the ESR spectrum of the following complexes.
(i) bis-salicylaldiminecopper(II), (ii) bis-salicylaldoximatocopper(II), (iii) [Cu(bpY)2]2+,
(iv) [Cu(bigH)2]' (v) [CuCI 2(phen), (vi) [VOFs]3-, (vii) [VO(dtc)2], (viii) CUS04· 5H20,
(ix) [CU2 (CH 3C0 2)4] . 2H 20, (x) [{Cu(dmgH)2}2]' (xi) [Ag(PY)2]S208; (xii) [C0 3(CO)9Se],
(xiv) K3[Mo(CN)8], (xv) Na2[IrCI6], (xvi) [(H3N)s Co-O-O-Co(NH3)s]s+, (xvi) [VO(acac)2];
ry
(xvii) blue proteins and Fe-S proteins; (xviii) Type 3 copper.
21. How can you distinguish the magnetically dilute and magnetically concentrated systems from the
ra
ESR studies?
ib
22. What are the factors to control the g-values? How can you determine the g-value from the ESR
yl
studies?
em
• Free radicals generally record the g-value close to that of the free electron g-value (i.e. ge) -
why?
ch
• Crystal field effect and spin-orbit coupling effect show the opposing contributions to determine
the g-value-why? .
al
• Perfectly octahedral and tetrahedral complexes show the g-value close to 2-why?
e
• Complexes having the strong J.T. distortions and low symmetry ligand field show the g-value
th
close to 2.Q-why?
e/
• Complexes having the T-ground state show the g-value different from 2.Q-why?
t.m
23. What do you mean by the anisotropic and isotropic behaviour of the g-value? What do they
indicate? What do you mean by isotropic and anisotropic hyperfine interaction?
• How can you express the gil and gl. values for the Cu(II) complexes (both z-in and z-out
e
er
distortions) from the use of magic pentagon?

• How can you distinguish the tetragonally compressed and tetragonally elongated Cu(II)
H
complexes from the g-values?

k
• Give the expressions of g-value for the complexes having the A and E ground state.
lic
24. ESR spectrum of CuSiF6 · 6H20 (doped in ZnSiF6 · 6H20) indicates the isotropic behaviour of g
C
at a relatively higher temperature but it gives the anisotropic behaviour of g at a relatively lower
temperature-explain.
25. What are the different applications of ESR spectroscopy?
26. Ni2+(S = 1) and Mn 2+ (S = 5/2) produce the 2 and 5 ESR signals but Cr(III) or Co(II) (S = 3/2)
produces only one ESR signal-explain.
27. What do you mean by McConnell equation? What is the use of it?
• What are the factors to determine the intensities of the hyperfine components?
28. How can you interpret the electronic spin-nuclear spin interaction? Define the hyperfine cou-
pling constant (a, A).
29. What do you mean by spin label? What is its application?
30. A slight distortion in the structure can be evidenced by the ESR data-illustrate.
31. Both the cubic and highly distorted geometries lead to g ~ 2.O-explain.
32. The ESR studies can distinguish between the ferro- and antiferromagnetic exchange interaction-
explain.
33. The dimeric form of copper(II)- acetate gives 7 ESR lines-explain. Intensity of its ESR signal
depends on the temperature of study-why?
34. The first transition metal complexes give the g-values very close to 2.0, but for the different
lanthanides, the g-values differ-explain. Intensity of its ESR signal depends on the tempera-
ture-why?
35. The monomeric and dimeric forms of the complexes of Cu(ll) and oxovanadium(IV) can be
distinguished from the ESR studies-explain.
36. Hyperfine splitting (i.e. superhyperfine splitting) of an ESR peak by the ligand nuclei is an
indication of metal-ligand covalence-explain.
37. There are many systems bearing more than one unpaired electron to show only one ESR signal-
illustrate.
ry
38. Without the concept of zero-field splitting, the J2 and cJ8 systems should produce a single ESR
ra
signal-illustrate.
• Number of ESR signals for the high spin tF-systems depends on the degree of distortion-
ib
explain.
yl
39. ESR data can prove the planar shape not the pyramidal shape of the CH3 radical-explain.
em
40. DPPH and nitroxide radicals show only a single sharp peak at a relatively higher concentration
but at a relatively lower concentration, they show the hyperfine splitting peaks-explain.
ch
41. The magnitude of zero-field splitting in the transition metal complexes is very high for the
T-ground state level but it is small for the A-ground state-why?
al
42. For the even number of unpaired electrons, if the zero-field splitting is large, there will be no ESR
e
spectrum. On the other hand, for the odd number of unpaired electron, even if the zero-field
th
splitting is large, there will be an ESR spectrum-explain.

e/
1
43. Octahedral complexes of Ti(III), oxovanadium(IV) and Cu(II)-all are represented by S = "2. It
t.m
is extremely difficult, even at a very low temperature, to study the EPR spectrum for Ti(III) but
oxovanadium(IV) and Cu(ll) give the sharp ESR signals even at room temperature-why?
e
er
44. In general, it is difficult to make the ESR studies for the 2nd and 3rd transition series metal
complexes but it is quite easy for the many metal complexes of the 1st transition series-explain.
H
45. For the high-spin octahedral complexes of tf system, there are 4 allowed ESR transitions but in
k
many cases, there is no ESR spectrum-explain.

lic
46. For the high-spin octahedral complexes of Co(II), it becomes difficult to record the ESR spectrum
C
at room temperature. There are 3 unpaired electrons, but it gives only a single ESR signal in most
of the cases-explain.
47. How can you distinguish between the peaks and shoulders of the ESR spectrum?
48. The magnitude of the zero-field splitting is very small for the high-spin octahedral complexes of
tP -system-why?
49. Hyperfine splitting components produced by 63 Cu ( m[ = ±%, ±~) are of equal intensity but the
hyperfine splitting components for CH3 ( M[ = ±%, ±~) are of unequal intensity--explain.
50. The hyperfine splitting components are of equal spacing and the components may be or may not
be equally strong. Illustrate and explain.
51. In K3 [Mo(CN)8], the Mo-C or Mo-N linkage can be established from the ESR studies-
explain.
52. Intensity of the hyperfine lines depends on the abundance and nuclear spin values of the isotopes
causing the splitting. Illustrate for Cr and Mo.
53. How do we determine the g-value of a sample from the EPR studies?
54. Discuss the EPR spectra of Cu- and Fe-proteins.
55. Give the characteristic features of the EPR spectra of Cu(II).
56. Compare the g-values obtained from the EPR spectra of rubridoxin, Fe2S2, Fe3S3 and Fe4S4
proteins.
D. Questions on Mossbauer Spectroscopy

1. What are main differences in the principles of y-ray spectroscopy and other optical spectroscopy?
2. If the energy difference between the nuclear energy levels is ~, then the radiation of frequency
ry
v( = ~).;annot cause the nuclear excitation-why?
ra
ib
• If the nucleus deexcites, the frequency v of the y-emission is less than the calculated one
(v= ~)-WhY?
yl
em
3. What do you mean by recoilless nuclear transition? What are the conditions to satisfy for the
recoilless nuclear transition?
ch
4. The natural line width of y-emission for the nuclear deexcitation is very small-why? How does
al
it affect the MB spectroscopy?
5. What do you mean by Doppler shift and Doppler peak broadening?
e
th
6. At the higher temperature, Doppler peak broadening is expected to make the absorption of the
y-radiation by the sample more probable but in reality, intensity of the MB signal decreases with
e/
the rise of temperature-why?

t.m
• For the better MB spectral signal both the source and sample are to be kept at low tempera-
ture-why?
e
7. In the MB spectroscopy, life period of the excited nucleus (i.e. y-emitter as the source) should lie
er
within the range 10-6 to 10- 10 s-why?

H
8. Give the energetics and isomeric transitions for 57Fe and 119Sn in terms of their MB spectroscopy.
9. What do you mean by isomer shift? Discuss the factors to control the value of the isomer shift.
k
lic
10. Even for the recoilless transition, the emitted y-radiation may not be absorbed by the sample
nucleus (due to the energy mismatch) though both the source and sample nuclei experience the
C
same nuclear transition-explain.

11. The s-electron density directly controls the isomer shift while the electron density in the other
orbitals like p, d, f, indirectly determines the isomer shift-explain.
12. In some cases, with the increase of s-electron density the isomer shift moves towards the negative
direction (as in 57Fe) and in some cases (as in 119Sn), it moves towards the positive direction-
explain.
13. For the 1271 and 1291 isotopes, the isomer shifts vary in different ways with the s-electron density-
explain.
• Explain the contributions of the nuclear term and chemical tern to determine the position of
isomer shift (8).
14. For the Fe-complexes, with the increase of d-electrons, the isomer shift moves towards the posi-
tive direction while with the increase of s-electron density, the isomer shift moves towards the
negative direction-explain.
2088 FUNDAMENTAL.. CONCEPTS OF INORGANIC CHEMISTRY
15. Oxidation state of iron in its high-spin complexes can be more or less correctly predicted from the
isomer shift of their MB spectra----explain.
16. For the low-spin complexes of iron (in +2 and +3 oxidation states), the formal oxidation states
cannot be predicted from the isomer shifts----explain.
17. The real oxidation states of iron in [Fe(CN)6]3-and [Fe(CN)6]4- do not differ so much as indicated
by their formal oxidation states----explain.
18. For the same oxidation state of the Fe-complexes, the isomer shift is generally more negative for
the low-spin complexes (compared to that of the high spin complexes)----explain.
19. What do you mean quadrupole splitting of a MB signal? What are the conditions for such quadrupole
splitting?
20. Illustrate the nature of quadrupole splitting of the MB signal for 57Fe and 119Sn.
ry
21. What do you mean by magnetic hyperfine splitting (i. e. Zeeman splitting) of a MB signal? Illus-
ra
trate for 57Pe.
22. How can you distinguish (i) high-spin Fe(II) and Pe(III) complexes; (ii) high-spin and low-spin
ib
complexes of Fe(II); (iii) high-spin and low-spin complexes of Fe(III), (iv) low spin complexes of
yl
Fe(II) and Fe(III) from the MB spectroscopy?
em
23. Comment and compare the constitution of nitroprusside ion and brown ring complex from the
MB and ir spectral studies.
ch
24. MB spectral data do not support the existence of high-spin Fe(I) in the brown ring complex-
explain.
al
• Existence of Fe(I) and NO+ in the brown ring complex cannot be also supported theoretically-
e
explain.
th
25. How can you determine the positions of the n-acid ligands in the spectrochemical series from the
e/
MB spectral studies of the Fe-compounds? Explain and illustrate.

t.m
25. Comment on the structural composition of (i) Prussian and Turnbull blue; (ii) oxy- and deoxy-
hemerythrin; (iii) active iron compound in the catalase and peroxidase activity; (iv) different
Fe-S proteins from the MB spectral studies.
e
er
26. How can you identify the cis- and trans- isomers of [FeA4B2] and [SnR2X4] from the MB spectral
studies?
H
27. Give the important features of the MB spectra of (i) [Fe(CO)5]' [Fe2(CO)9] and [Fe3(CO)12]; (ii)
k
[Fe(acac)3].
lic
28. MB spectral studies can identify the existence of the low-spin ~ high-spin equilibrium in the
C
Fe(II) and Fe(III) complexes-illustrate.

29. How can you identify the Sn(II) and Sn(IV) compounds from the MB spectral studies?
30. Comment on the isomer shift sequence for [SnBr4X2]2- for X = F, CI, Br and I.
31. How can you determine the structure of I2Br2Cl4 from the MB spectral study of 129I?
32. How can you determine the structures of IF6+and IF 6- from the MB spectra of 129I?
33. How can you determine structure of 13- from the 129I_MB spectrum?
34. SnF4gives a quadrupole splitting but SnCl4 does not show any quadrupole splitting----explain.
35. The relative extents of n-bonding in the Sn-O and Sn-S linkages of R3SnOCH3and R 3SnSCH3
can be predicted from the quadrupole splitting in their MB spectra----explain.
36. The magnifude of quadrupole splitting varies in the following complexes as follows:
~Q: FeCI2 · 4H20 ) [Fe(CN)5(NH 3)]3-) [Fe(CN)5(NO)]2-
37. Give the MB spectral features of rubredoxin, Fe2S2 ferredoxin, Fe3S3 ferredoxin and Fe4S4 protein
in their both oxidised and reduced forms.
• In the MB spectra of Fe4S4 ferredoxin, there is a one MB signal (with a small quadrupole
splitting) in each of its different forms-explain.
• In Fe2S2 ferredoxin, the Fe-centres are different (in terms of MB spectroscopy) in its different
forms-explain.
• How can you characterise the chemical state of the Fe-centre in hemerythrin, catalase and
peroxidase from their MB studies?
• How can you identify the oxidation states of iron in Fe-porphyrins from the MB study?
38. Predict and explain the order of isomer shift in the following Sn-compounds:
(i) [SnX4] vs. [SnX6]2-; (ii) [SnMe4] VS. [SnX4]; (iii) [R4Sn], [R3SnX], [R2SnX2]; (iv) cis- and
trans- isomers of [R 2SnX4]; (v) [R3SnX] (X = F, CI, Br, I), [SnX4] (X = F, CI, Br, I)
39. How can you determine the oxidation states of Sn in its different compounds from the MB study?
ry
What is the oxidation state of Sn in (SnPh 2)x?
ra
40. How can you prove whether the lone pair in XeF6, TeF62- or IF6- is stereochemically active or not
from the MB studies?
ib
41. How can you distinguish the tetrahedrah and square planar structures of XeL4from the MB study?
yl
em
E. Questions on Electronic Spectroscopy
1. What are the common electronic transitions in organic molecules?
ch
2. The n ~ n * transition is stronger than the n ~ n* transition-why?
al
3. Illustrate: chromophore, auxochrome, bathochromic shift (red shift), hypsochromic shift (blue
shift), hypochromic and hyperchromic shift, isosbestic point, benzenoid band, ethylenic band, R-
e
th
band, K-band, solvatochromism and solvatochromic shift.

4. Draw the molecular orbitals of formaldehyde and show the electronic transitions.
e/
5. Compare the colours and Amax positions:

t.m
(i) nitrophenol vs. nitrophenolate, (ii) aniline vs. nitroaniline; (iii) phenolphthalein in acidic and
alkaline condition; (iv) methyl red and methyl orange in acidic and alkaline condition; (v) polyenes
e
having the different conjugation lengths; (vi) butadiene, vit. A and carotene; (vii) naphthalene vs.
er
azulene; (ix) benzene vs. fulvene; (x) s-cis and s-trans forms of butadiene, (xi) cis- and trans
H
forms of stilbene; (xii) cis- and transforms of cinnamic acid; (xiii) biphenyl vs. 2-methylbiphenyl;
(xiv) cis- and trans forms of azobenzene; (xv) cis- and transforms of indigotin; (xvi) ortho- and
k
para- nitroaniline; (xvii) > C=Q vs. >C=~; (xviii) aniline vs. anilinium cation; (xix) pyridine
lic
C
vs. pyridinium cation; (xx) benzene vs. substituted benzene; (xxi) carbonyl group vs. enone;
(xxii) benzene; biphenyl; 2,2'-dimethylbiphenyl; (xxiii) cyclic and acyclic a-diketones;
(xxiv) cyclic vs. acyclic dienes; (xxv) homoanular diene vs. heteroanular diene; (xxvi) cis- and
trans- isomers of 1, 3, 5-hexatriene; (xxvii) K-band vs. B-band of benzene; (xxviii) substituted
butadiene vs. unsubstituted butadiene; (xxix) o-nitrophenol vs. p-nitrophenol; (xxx) biphenyl and
diphenylmethane.
6. Prevention of resonance may cause both the red shift and blue shift depending on the condition.
Illustrate and explain with the suitable examples.
7. In the n ~ n* transition, the excited state is more polar than the ground state. Explain and
illustrate with the suitable examples.
8. In the n ~ n* transition in the carbonyl chromophore, the polarity of the 'C=O' group changes-
explain.
9. Compare the polarities of the ground and excited states of enones and butadienes in the n ~ n*
transition.
10. Compare the C-O bond lengths (in the chromophore) in the excited and ground states for the
n ~ n* and n ~ n* transition.
11. In the chromophore )C=Q, there are two lone pairs on the O-atom, but only one lone pair
participates in the so called n ~ n* transition-explain.
12. Explain the solvent effect (i.e. solvent shift) for the n ~ n* and n ~ n* transition in terms of
MOT.
13. With the increase of solvent polarity, generally the n ~ n* transition experiences the blue shift
while the ~ n n: transition experiences the red shift-explain.
14. The n ~ n* transition in the chromophore, )C=O, leads to an excited state which may be
destabilised even in a polar solvent though the excited state is sufficiently polar-explain.
ry
(Hints: Change of polarity during the electronic transition and relatively slower solvent reorientation
ra
process.)
15. The blue shift or red shift can not tell us the actual energy change of the states between which the
ib
electronic transition occurs-explain.
yl
• The IPCT (ion pair charge transfer) band in [M(NH3)6]3+ X- (M = Co, Ir; X- = CI-, Br-,
em
1-) experiences the spectral shift as; AI ) ABr ) Acl . Explain
• [Ir(NH 3)6]3+ is colourless but it becomes yellow coloured in presence of 1-. Explain.
ch
16. In the chromophore, ) C = Q, the two lone pairs on the O-atom are not equally available for the
al
intermolecular H-bonding with the solvent-explain.

e
17. How can you identify the keto-enol tautomerism by using the UV-spectroscopy.
th
• For acetylacetone, intensity of the band at about 270 nm decreases with the increase of solvent
e/
polarity-explain.
t.m
• For acetylacetone, the band at about 270 nm experiences the red shift with the increase of
solvent polarity-explain.
• For ethyl acetoacetate, the band at about 245 nm shows the red shift and hypochromic effect
e
with the increase of solvent polarity.

er
18. For acetylacetone, the n ~ n* transition (in the enol form) experiences a much larger red shift
H
compared to that of ethylacetoacetate.

k
19. The n ~ n* transition in pyridine disappears in an acidic solution.

lic
20. In H-bonding interaction, the n ~ n* transition experiences the blue shift if it acts as the donor-
explain.
C
21. Electron donor auxochromes (e.g. - QR, - NH 2 ) and hyperconjugative effect can lead to the
red shift for the n ~ n* transition-explain in terms of MOT.
• The auxochromic groups like -QR, - NR 2 etc. can cause the red shift for the n ~ n*
transition but the blue shift for the n ~ n* transition in the chromophore )C=O. Explain.
• The n ~ n* transition in H 3C - C- X experiences the blue shift as follows:
II
o
X H CH 3 OH NH 2 OCOCH 3
Amax (nrn) = 293 279 204 214 225
22. Attachment of an ethylenic double bond with the carbonyl chromophore causes the red shift for
both the n ~ n* and n ~ n* transitions.
• )c=O )c=c-c=O 00=0

I I
1t~1t*(nm): 190 230 250
n ~ 1t* (nm): 285 320 430
• Cyclic a-diketones (called diosphenols) and 2-hydroxy pyridine show the "-max value characteristic
to that of an a, ~-unsaturated carbonyl system--explain.
• Explain: "-max::::: 450 nm (biacetyl) > 370 nm (benzil).
ft R=CH 3 (i.e. biacetyl), dihedral angle'" 1800
R
R/C"C/ R= Ph (i.e., benzil), dihedral angle'" 90 0
ry
ra
U (Effect of coplanarity on resonance between the CO-groups) .
ib
23. In benzene, the 1t ~ 1t* transition (HOMO ~ LUMO), in terms of HMO (Huckel Molecular
yl
Orbitals), there should be only one band, but in reality there are three bands--explain.
em
24. The benzenoid band of the aromatics shows the fine structure components and these fine structures
are more pronounced in vapour phase and nonpolar solvents--explain.
ch
• The benzenoid band is more intense in pyridine compared to that in benzene.
25. Attachment of an electron donor group with the benzene ring causes the red shift in the n ~ n*
al
transition and a new band (n ~ n*)--explain.

e
• Attachment of an electron withdrawing mesomeric group with the benzene ring can causes the
th
bathochromic shift for the n ~ 1t* transition.

e/
26. The n ~ n* transition of benzene experiences the red shift with the increase of solvent polarity-
t.m
explain.
27. Position of the "-max in the disubstituted benzenes, depends on the relative orientations of the
disubstitution--explain.
e
• The - NH 2 and -N02 groups being placed at the para- positions cause the red shift in a
er
synergistic fashion--explain.
H
• If the electron donor and electron withdrawing groups are placed at the p- positions, then the
k
red shift becomes pronounced but if one group is electron donor and another group is also
lic
electron donor, then no such pronounced red shift is noticed--explain.

C
28. The n ~ n* transition of aniline appears at about 230 nm in ethanol but this band position is
shifted to about 203 nm in an acidic aqueous solution--explain.
• The band also shows a blue-shift with the increase of solvent polarity.
29. The n ~ n* transition follows the sequence:
'\ .. '\ .. .
Amax : /C=Q < /C=~; ExplaIn.
30. Explain the origin and intensity of colour of halogens (X 2) in terms of MOT. Explain the origin
of different colours of Br2 and 12 in different solvents in terms of MOT.
31. Ph 2C=O hv(:n;j') Ph 2C(OH) - C(OH)Ph 2 (pinacol) + R - R + Ph 2C(OH)R: explain
the products.
(Hints: Ph2C=O-n-:-v1t~*-+) Sl ~Tl (Ph 2 c=6:) long-lived diradical, n-bond order
= 1/2.
The diradical => Ph 2C-g: (assuming n-BMO predominantly enriched with the 0-2p orbital
and n*-MO i.e. n-ABMO predominantly enriched with the C-2p orbital).
2R·~R-R; R·+Ph2C-OH~Ph2C-OH)
I
R
32. Phenol is more acidic in the excited state while benzoic acid is a weaker acid in the excited state.
ry
ra
ib
yl
em
33. The n ~ n* transitions in C 2H 4 , trans-butadiene and formaldehyde are allowed. The n ~ n*
transition is forbidden in formaldehyde but it is vibronically allowed. Explain all these qualitatively
ch
and in terms of group theory (i.e. in terms of transition moment integral).
al
34. In benzene, the lowest energy n ~ n* transition should give a single peak in terms of Huckel's
Molecular Orbital (HMO) theory but in reality it gives three peaks-Explain.
e
th
• Out of the three possible transitions, one is symmetry allowed but the other two transitions are
e/
symmetry forbidden-explain.
t.m
• The two symmetry forbidden transitions are vibronically allowed-explain.

• Between the two forbidden transitions, one is more intense-why?
35. In hexane, chloral hydrate shows Amax Z 270 nm but in aqueous solution, the band disappears-
e
explain.
er
(Hints: In hexane, it is CCl3CHO . H20 but in water it is CCI 3CH(OH)2).

H
36. How can you distinguish the cis- and trans- isomers of 1, 3, 5-hexatriene?
k
lic
R H
(Hints: )c=c( R (tran~) (R = -CH=CH 2); Amax : trans> cis, (steric hindrance in the
C
H
.cis-isomer.)
37. The following diene gives Amax 220 nm but the calculated value is 237 nm.
X
Z
"'max ",220 nm. (Hints: Blue shift due to the loss of conjugation, i.e. loss of coplanarity).
38. Alkyl substitution on butadiene causes a red-shift along with a hyperchromic effect but in some
cases, it may lead to a red-shift with a hypochromic effect--explain.
Hints: For unsubstituted butadiene, stability: s-trans > s-cis; Amax : s-cis > s-trans; cmax : s-trans >
s-cis; electron pushing effect of alkyl group causes a red-shift; alkyl substitution at the 1,3-
positions sterically favours the s-cis conformation.
Red-shift
Blue-shift
F. Questions on NQR Spectroscopy
ry
1. Illustrate the terms: nuclear quadrupole moment, electric field gradient (EFG) and asymmetry
ra
parameter in connection with the NQR spectroscopy.
ib
2. What are the conditions for observing the NQR signals?
yl
3. Why do you carry out the NQR studies on solid state only?
em
4. Compare the characteristics of NMR and NQR spectroscopy.
5. Find the expression of NQR transition frequency for (a) I = 1, 312, 512 and 712 when II = 0;
'*
ch
(b) 1= 1 and 312 when II O.
6. How can you determine the nuclear quadrupole coupling constant (e 2qQ) and the asymmetry
al
parameter (ll) for I = 312 and 1.

e
7. Give the effect of a weak magnetic field on the NQR spectra of 3S, 37CI and 14N.
th
8. What do you mean by solid state effect? Very often the e2qQ value obtained from the NQR spectra
e/
differs significantly from the value obtained from the fine structure of microwave spectrum-
explain.
t.m
9. Solid state effect must be considered to compute the molecular properties from the NQR data-
illustrate.
e
10. For the A-X bond where X = halogen, the NQR value of e2qQ for X depends on whether X or
er
A is more electronegative--explain.
H
11. Compare the e2qQ values of 3S, 37CI and 79, 81Br in the compounds NaCI, FCI, BrCI, FBr, NaBr.
12. Give the number of NQR lines and their characteristics for:
k
lic
MCl4 (M = Si, Ti, Sn); R 3MX2 (M = As, Sb; X = CI, Br); PFCl4 vs. PCI4Ph; AsCI4Ph; PCIs;
2ICI· SbCIs; AICI 3·TeCI4; TeX4(X = CI, Br); Me3AsBr2; BrCN; 12; HI0 3; Group 13 and 14 halides;
C
M+GaCI4- (M = Na, Cs, Ga); NaGa2CI7; AS 2S3; py and [CdCI2(pY)2]; CI 3CCOCI;
CI ~CCI3; CI ~ CH CI; 2 K2[SeBr6] (at different temperatures); GaGaC14 (at
CI CI
different temperature); BrCN; dichloro benzene (0, m and p isomers)
13. How can you follow the phase transition from the NQR studies?
14. How can you estimate the % of ionic character and electronegativity difference from the NQR data?
15. How can you study the H-bonding interaction in solid state from the NQR studies.
16. What do you mean by NQR group frequency? Can it be treated as a fingerprint?
17. Illustrate the isotope effect on the NQR transition frequencies.
18. For BrCI; e2qQ (79Br): NQR-value ) microwave spectrum value, but for NaBr, the reverse order
is true--explain.
G. Questions on Mass Spectrometry

1. Give the working principle of mass spectrometry.
2. How can you determine (a) Ionisation energy of a molecule; (b) Bond dissociation energy;
(c) Isotopic abundance of an element from the mass spectrometry.
3. Fragmentation mode in mass spectrometry is a characteristic property of a compound-illustrate.
4. Find the peak height ratios of M, M + 1 and M + 2 for the compounds C 6H 120 6, C 2HsOH;
CH 3CHO; C2H sNH2·
(For isotopic abundance of the elements, see Table 5.2.4.2; Vol. 1).
5. An organic compound consisting ofC, Hand 0 shows the peak height ratioM : M + 1 = 100 : 13.4.
Find the number of C-atoms per molecule of the compound.
6. Find the peak height ratios, hM, hM+ 1 and hM+2 for an organic compound (CxHyNzOp) subjected to
ry
a mass spectrometric study.
ra
7. Find the peak height ratios, hM , hM +2 and hM+4 for the organo-halogen compounds RCI 3, RBr2'
ib
RCl 2 and RCIBr subjected to the mass spectrometric studies.
8. How can you apply the mass spectrometric data for getting the structural information of metal
yl
carbonyls?
em
9. Give the characteristic observations in the mass spectra of [Fe(CO)s], [ReBr(CO)s], [HMn(CO)s],
[Mn(CO)sCI], [Re2(CO)8CI2]; [Mn2(CO)10]'
ch
e al
th
e/
t.m
e
er
H
k
lic
C
APPENDIX 12A: CharacterTables of Different Point Groups (Excluding the Cubic Functions)
Characteristic Features of the Character Tables: Symmetry properties, characteristic operations and
irreducible representations are displayed in a Character Table.
• Point group (see Sec. 10.14, Vol. 2) is indicated at the left top comer.
• The column headings indicate the classes of symmetry operations. Symmetry operations (see
Sec. 10.14, Vol. 2) are grouped into classes of closely related operations such as for the D6 point
group: 2C 6 = C 6 and C~ ; 2C 3 = C~ i.e., C 3 and C~ i.e. C~. For example, in the C2v point group, the
4 classes of symmetry operations are: E (identity operation), C 2 (rotation), cry and cr~ (two
reflections).
• Symmetry operations are replaced by numbers or matrices that multiply in the same way as
the operations themselves. In the C2y point group, the symmetry operations E, C 2, cry and cr~ can
ry
be replaced by unity in 4 possible ways (+1, +1, +1, +1), (+1, +1, -1, -1), (+1, -1, +1, -1), (+1,
ra
-1, -1, +1).
ib
• Irreducible representations are listed at the extreme left column. An irreducible representation
yl
cannot be decomposed into a simpler or more fundamental form.
em
• The characters +1 and -1 correspond to the symmetric and antisymmetric behaviour. In C 2y
point group, the characters (+1, -1, + 1, -1) of the operations correspond to the irreducible
ch
representation B I.
• In a particular point group, the number of irreducible representations is equal to the number
al
of classes of symmetry operations. For example, in the C 2y point group, there are 4 classes of
e
symmetry operations (E, C b cry and cr~) and 4 irreducible representations (AI' A 2, B I and B2).
th
• Basis functions: x, y an z (represent the coordinates) relevant to infrared vibrational spectra;

e/
Rx ' Ry and Rz (rotations about the specified axes) relavant to infrared rotational spectra; x 2, y2,
t.m
Z2, xy, yz, zx (squares and binary products of the coordinates according to their transformation
properties) relevant to Raman spectra.
• . All one dimensional representations (rotation by 2n/n about the principal C n axis) are desig-
e
er
nated either by A (symmetric i.e. + 1 character) or by B (antisymmetric i.e. -1 character). The

Subscripts 1 and 2 attached to A's and B' s indicate, respectively, the symmetric and antisymmetric
H
with respect to C~ (perpendicular to the principal axis Cn) or, in absence of such an axis (i.e. C 2
k
perpendicular to Cn), a vertical plane of symmetry (cry).

lic
• Primes (') and double primes (") indicate, respectively, the symmetric and antisymmetric behav-
C
iour with respect to a horizontal plane of symmetry (crh).

• The subscripts g (gerade) and u (ungerade) denote, respectively, the symmetric and antisymmetric
behaviour with respect to the inversion (i.e. presence of i indicates g; absence of i indicates u).
• Two dimensional and three dimensional representation are denoted by E (not to be confused
with the identity operation E) and T respectively.
1. The Nonaxial Groups (i.e. Groups of Low Symmetry)
~
A I 1
Cs E °h Cj E i
A' 1 1 x, y, Rz x 2, I, Z2, xy Ag 1 1 RX' Ry, Rz xl, I, Z2, xy, xz, yz

A" 1 -1 z, RX' Ry yz, xz Au 1 -1 x, y, z
2. The en Groups (i = H ;e* = e with - i substituted for i)

C2 E c2 C3 E c3 C 32
A 1 1 z, Rz x 2, y2, Z2, .xy A 1 1 1 z, Rz x 2 + y2, Z2
{~ :*}
£
B 1 -1 x, y, RX' Ry yz, xz E (x, y), (RX' Ry ) (x 2 - y2, xy), (yz, xz)
£*
£ = exp(2ni/3)
ry
C4 E C4 C2 cl
ra
A 1 1 1 1 z, Rz xl + y2, Z2
ib
B 1 -1 1 -1 X2 _ y2,xy
yl
n i -1
em
E -i -1 -a (x, y), (Rx, Ry ) (xz, yz)
ch
e al
th
Cs E c5 c/ cl C54
e/
t.m
A 1 1 1 1 1 z, Rz xl + y2, Z2
{~
2*
E1
£
*
£2
2*
£
:* } (x, y),(R x ' R y ) (yz, xz)
e
£ £ £2
er
{~
£2 £* £
*}2
H
E2 E (Z2 _ y2, xy)

2* * £2
£ £ £
k
= exp(21ti/5)
lic
£
C
C6 E c6 c3 c 2 cl C 65 c6 =c3 X c2
A 1 1 1 1 1 1 z, Rz r + y2, Z2
B 1 -1 1 -1 1 -1
-£
*
-1 -£ (x, y),
E1
G
£
£
*
-£ -1 -£ * :*} (Rx,R y ) (xz, yz)
-£ * -£ *
E2
G -£
-£
-£ *
1
1 -£
-E*}
-£
(r - y2, xy)
£ = exp(21ti/6)
C, E C7 cl cl C74 ci C76
A 1 1 1 1 1 1 1 z, R z xl + y2, Z2
{~
3* 2* (X, y),
:* }
£ £2 £3 £ £
EI * 2* 3* £3 £2 (XZ, yZ)
£ £ £ (R x ' Ry )
e *}
{~
£2 3* * £3 2
£ £ £
E2 £
2* £3 £ £
* 3* £2
(r - y2, xy)
£
E3 {~
£3
3*
£
* £2
2*
£
£2
2*
£
*
e
£3
3
*}
ry
£ £ £ £
ra
£ = exp(21ti/7)
ib
yl
Cs E Cg C4 C2 cl Cg3 Cg5 Cg7 Cg = C4 X C2
em
A 1 1 1 1 1 1 1 1 z, Rz r + y2, Z2
B 1 -1 1 1 1 -1 -1 -1
ch
{~
-£ *
i -1 -i
:*} (x, y)
al
£ -£
EI * * Rx,R y (xz, yz)
£ -i -1 i -£ -£
e
th
n -~}
i -1 1 -1 -i i
e/
E2 -i -1 1 -1 i -i (r - y2, xy)
t.m
E3 {~
-£
*
i
-i
-1
-1
-i
i
£
*
£
*
-e*}
e
-£ £ £ -£
er
£ = exp(21ti/8)
H
k
3. The Cnv Groups

lic
C2v E C2 alxz) a'lyz)

C
Al 1 1 1 1 z xl , y2, Z2
A2 1 1 -1 -1 Rz xy
BI 1 -1 1 -1 x, Ry XZ
B2 1 - 1 - 1 1 y, Rx yz
C3v E 2C3 3av
Al 1 1 1 z x2 + I, Z2
A2 1 1 -1 Rz
E 2 -1 0 (x, y), (Rx' Ry ) (r - I, xy), (xz, yz)
C4v E 2C4 C2 20 v 20d
Ai 1 1 1 1 1 Z x2 + y2, Z2
A2 1 1 1 -1 -1 Rz
Bi 1 -1 1 1 -1 x2 _ y2
B2 1 -1 1 -1 1 .xy
E 2 0 -2 0 0 (x, y), (R x ' Ry ) (xz, yz)
I
CSv E 2Cs 2cl 50v
Ai 1 1 1 1 x2 + y2, Z2
ry
Z
A2 1 1 1 -1 Rz
ra
E] 2 2 cos 72 0
2 cos 144 0
0 (x, y), (R x ' Ry ) (xz, yz)
ib
E2 2 2 cos 144 0 2 cos 72 0 0 (x2 _ y2, xy)
yl
C 6v E 2C6 2C3 C2 30v 30d
em
ch
A] 1 1 1 1 1 1 Z x 2 + y2, Z2
al
A2 1 1 1 1 -1 -1 Rz
e
B] 1 -1 1 -1 1 -1
th
B2 1 -1 1 -1 -1 1
e/
E] 2 1 -1 -2 0 0 (x, y), (R x ' Ry ) (xz, yz)

t.m
E2 2 -1 -1 2 0 0 (xl - y2, xy)

e
4. The Cnh Groups (i =H ; £* =£ with -i substituted for i)

er
H
C2h E C2 i
°h
k
Ag 1 1 1 1 Rz xl ,y2, Z2, xy
lic
Bg 1 -1 1 -1 Rx' Ry xz, yz
C
Au 1 1 -1 -1 z
Bu 1 - 1 - 1 1 x, y
C32 5
C3h E C3 °h S3 S3
A' 1 1 1 1 1 1 Rz xl + y2, Z2
{~
E* 1
E'
E
E* E 1
E
E*
:*} (x, y) (x2 - y2, xy)
A" 1 1 1 -1 -1 -1 z
E"
{~
E
E*
E*
E
-1
-1
-E
-E *
-E*}
-E
(Rx' Ry ) (xz, yz)
E = exp(2ni/3)
C4h E C4 C2 C] i s]
°h S4
Ag 1 1 1 1 1 1 1 1 Rz r + y2, Z2
Bg 1 -1 1 -1 1 -1 1 -1 r-r,xy
Eg
Au
U 1
i
-i
1
-1
-1
1
-i
i
1 -1
1
1
i
-i
-1
-1
-1
-1
-n
-1
(R» R)
z
(xz, yz)
Bu 1 - 1 1 - 1 - 1 1 - 1 1
Eu
U i
-i
-1
-1
-i
i
-1
-1
-i
i
1
1
-n (x, y)
ry
ra
ib
CSh E C5 CS2 C53 C/ °h S5 S/ sl S5 9
yl
A' 1 1 1 1 1 1 1 1 1 1 Rz r + y2, Z2
{~
em
2*
:"2}
£2 2* * £2
£ £ £ 1 £ £
EI ' £
*
£
2* £2 £ 1 £
*
£
2* £2
ch (X, y)
{~
2* *
£2 £* £ £ 1 £2 £ £
E{ e "} (r - y2, xy)
al
2* * £2 2* * £2
£ £ £ 1 £ £ £
e
A" 1 1 1 1 1 -1 -1 -1 -1 -1 z
th
e
2* *
EI "
£ £2 £ £ -1 -£ -£ 22* -£ 2"2 -£ "} (R» R y ) (XZ, yZ)
e/
* 2* £2 *
£ £ £ -1 -£ -£ -£ -£
{~
* 2*
-£ *
t.m
£2 _£2
E2" 2*
£ £
*
£ -1
2*
-£
*
-£
_£2
2"}
£ £ £ £2 -1 -£ -£ -£
e
£ =exp(21ti/5)
er
H
E C6 C3 C2 C/ C65 i S3 5 S6 5
k
C6h crh S6 S3
lic
Ag 1 1 1 1 1 1 1 1 1 1 1 1 Rz r + y2, Z2
C
Bg 1 -1 1 -1 1 -1 1 -1 1 -1 1 -1
Eig g £
£ * -E
-£ * -1
-1
-£
-E*
£*
£
1
1
£
E*
-£*
-E
-1 -£
-1 -E* :"} (R» R y ) (xz, yz)
(r - y2, xy)
{~ -E * -E 1 1
-E -E 1 -E* -E -E*
E2g -E }
-E -£* 1 -£ -E* 1 -E -E* 1 -E -£ *
Au 1 1 1 1 1 1 - 1 - 1 - 1 - 1 - 1 -1 z
Bu 1 - 1 1 - 1 1 - 1 - 1 1 - 1 1 - 1 1
Elu
{~ E
E*
-E*
-E
-1
-1
-E
-E*
£*
E
-1
-1
-£
-£*
£*
E
1
1* E*
E -e" }
-E
(x,y)
{~
1 -1 -1 E*
E2u
-E* -E
-E -E * 1
-E* -E
-E -E* -1
E*
E
E
E* -1 £
£
£* }
£ = exp(21ti/6)
5. The D n Groups
D2 E Cz(z) Cz(y) Cz(x)
A 1 1 1 1 x2 , yZ, ZZ
B1 1 1 -1 -1 z, Rz xy
Bz 1 -1 1 -1 y,Ry XZ
B3 1 -1 -1 1 x, Rx yz
D3 E 2C3 3Cz
1 1 1 r + yZ, ZZ
ry
Al
Az 1 1 -1 z, Rz
ra
E 2 -1 0 (x, y), (RX' Ry ) (r - yZ, xy), (xz, yz)
ib
(x axis coincident with Cz)
yl
D4 2C4 Cz (= C4 2)
em
ch
E 2C2' 2Cz"
1 1 1 1 1 r + y2, ZZ
al
Al
Az 1 1 1 -1 -1 z, Rz
e
r- y2
th
B1 1 -1 1 1 -1
e/
B2 1 - 1 1 - 1 1 xy
E 2 0 -2 0 0 (x, y), (Rx , Ry ) (xz, yz)
t.m
(x axis coincident with Cz')

e
er
Ds E 2Cs 2CS2 5C2

H
Al 1 1 1 1 r + y2, Z2
k
Az 1 1 1 -1 z, Rz
lic
E1 2 2 cos 72° 2 cos 144° 0 (x, y), (RX' Ry ) (xz, yz)

(r - y2, xy)
C
E2 2 2 cos 144° 2 cos 72° 0
(x axis coincident with C2)
D6 E 2C6 2C3 Cz 3Cz' 3Cz"
Al 1 1 1 1 1 1 r + yZ, Z2
A2 1 1 1 1 -1 -1 z, Rz
B1 1 -1 1 -1 1 -1
B2 1 -1 1 -1 -1 1
E1 2 1 -1 -2 0 0 (x, y), (RX' Ry ) (xy, yz)
Ez 2 -1 -1 2 0 0 (r - y2, xy)
(x axis coincident with Cz')
6. The D nd Groups
DlJl E 2S4 C2 2C2' 2ad
Al 1 1 'I 1 1 xL- + y2, Z2

A2 1 1 1 -1 -1 Rz
BI 1 -1 1 1 -1 xL--y2
B2 1 -1 1 -1 1 z xy
E 2 0 -2 0 0 (x, y), (R» Ry ) (xz, yz)
(x axis coincident with C2')
ry
DJd E 2C3 3C2 i 2S6 3ad
ra
A ig 1 1 1 1 1 1 xL- + y2, Z2
ib
A 2g 1 1 -1 1 1 -1 Rz
yl
Eg 2 -1 0 2 -1 0 (R» Ry ) (xL- - y2, xy), (xz, yz)
em
A lu 1 1 1 -1 -1 -1
A 2u 1 1 -1 -1 -1 1 z
ch
Eu 2 -1 0 -2 1 0 (x, y)
al

e
th
D4d E 2Ss 2C4 2Ss3 C2 4C2' 4ad

e/
Al 1 1 1 1 1 1 1 xL- + y2, Z2
t.m
A2 1 1 1 1 1 -1 -1 Rz
BI 1 - 1 1 - 1 1 1 - 1
e
B2 1 -1 1 -1 1 -1 1 z
er
EI 2 fi 0 -fi -2 0 0 (x, y)
H
E2 2 0 -2 0 2 0 0 (x 2 - y2, xy)
k
-fi fi
lic
E3 2 0 -2 0 0 (R» Ry ) (xz, yz)

C
D Sd E 2Cs 2CS 2 SC2 i 2S 103 2S lO Sad
A ig 1 1 1 1 1 1 1 1 xL- + y2, Z2
A 2g 1 1 1 -1 1 1 1 -1 Rz
E ig 2 2 cos 72° 2 cos 144 0 0 2 2 cos 72° 2 cos 144 0 0 (R» Ry ) (xz, yz)
E2g 2 2 cos 144° 2 cos 72° 0 2 2 cos 144 0 2 cos 72° 0 (xL- - y2, xy)
A lu 1 1 1 1 -1 -1 -1 -1
A 2u 1 1 1 -1 -1 -1 -1 1 z
E 1u 2 2 cos 72° 2 cos 144 0
0 -2 -2 cos 72° -2 cos 144° 0 (x, y)
E2u 2 2 cos 144° 2 cos 72° 0' -2 -2 cos 144° -2 cos 72° 0

2102 FUNDAMENTAL CoNCEPTS OF INORGANIC CHEMISTRY
D 6d E 2S 12 2C6 2S4 2C3 2S 125 C2 6C{ 6crd
Al 1 1 1 1 1 1 1 1 1 xl + y2, Z2
A2 1 1 1 1 1 1 1 -1 -1 Rz
BI 1 - 1 1 - 1 1 -1 1 1 - 1
B2 1 -1 1 -1 1 -1 1 -1 1 z
EI 2 J3 1 0 -1 -J3 -2 0 0 (x, y)
E2 2 1 -1 -2 -1 1 2 0 0 (xl - y2, iy)

E3 2 0 -2 0 2 0 -2 0 0
E4 2 -1 -1 2 -1 -1 2 0 0
ry
E5 2 -fj 1 0 -1 J3 -2 0 0 (R» Ry ) (xz, yz)
ra
ib
yl
em
ch
7. The D nh Groups
al
D2h E C2(z) Ciy) C2(x) i cr(xy) cr(xz) cr(yz)

e
th
Ag 1 1 1 1 1 1 1 1 xl, I, Z2
e/
BIg 1 1 -1 -1 1 1 -1 -1 Rz xy
t.m
B 2g 1 -1 1 -1 1 -1 1 -1 Ry XZ
B 3g 1 -1 -1 1 1 -1 -1 1 Rx yz
e
Au 1 1 1 1 -1 -1 -1 -1
er
B Ju 1 1 -1 -1 -1 -1 1 1 z
H
B 2u 1 -1 1 -1 -1 1 1-1 1 y
k
B 3u 1 -1 -1 1 -1 1 1 -1 x
lic
C
D 3h E 2C3 3C2 crh 2S3 3crv
AI' 1 1 1 1 1 - 1 Xl + y2, Z2
A 2' 1 1 -1 1 1 -1 Rz
E' 2 -1 0 2 -1 0 (x, y) (Xl - y2, xy)
AI" 1 1 1 -1 -1 -1
A 2" 1 1 -1 -1. -1 1 z
E" 2 -1 0 -2 1 0 (R» Ry ) (xz, yz)

D 4h E 2C4 C2 2C2' 2C2" i 2S4

°h 20v 2ad
A tg 1 1 1 1 1 1 1 1 1 1 x 2 + y2, Z2
A 2g 1 1 1 -1 -1 1 1 1 -1 -1 Rz
BIg 1 -1 1 1 -1 1 -1 1 1 -1 r- y2
B 2g 1 -1 1 -1 1 1 -1 1 -1 1 xy
Eg 2 0 -2 0 0 2 0 -2 0 0 (R» Ry ) (xz, yz)
A lu 1 1 1 1 1 -1 -1 -1 -1 -1
A 2u 1 1 1 -1 -1 -1 -1 -1 1 1 z
B lu 1 -1 1 1 -1 -1 1 -1 -1 1
B 2u 1 -1 1 -1 1 -1 1 -1 1 -1
ry
Eu 2 0 -2 0 0 -2 0 2 0 0 (x, y)
ra
ib
(x axis coincident with C{)
yl
em
D Sh E 2Cs 2CS2 5C2
°h 2Ss ch 2SS3 50 v
AI' 1 1 1 1 1 1 1 1 r + y2, Z2
A 2' 1 1 1 -1 1 1 1 -1 Rz
al
E I' 2 2 cos 72° 2 cos 144° 0 2 2 cos 72° 2 cos 144° 0 (x, y)
e
(r - y2, xy)
th
E 2' 2 2 cos 144° 2 cos 72° 0 2 2 cos 144° 2 cos 72° 0

1 1 1 1 -1 -1 -1 -1
e/
AI"
A 2" 1 1 1 -1 -1 -1 -1 1 z
t.m
E I" 2 2 cos 72° 2 cos 144° 0 -2 -2 cos 72° -2 cos 144° 0 (R» Ry ) (xz, yz)
E 2" 2 2 cos 144° 2 cos 72° 0 -2 -2 cos 144° -2 cos 72° 0
e
er
(x axis coincident with C2 )

H
D6h
k
E 2C6 2C3 C2 3C{ 3C2" i 2S3 2S6 ah 30d 30v

lic
A lg 1 1 1 1 1 1 1 1 1 1 1 1 x 2 + y2, Z2
C
A 2g 1 1 1 1 -1 -1 1 1 1 1 -1 -1 Rz
BIg 1 -1 1 -1 1 -1 1 -1 1 -1 1 -1
B 2g 1 -1 1 -1 -1 1 1 -1 1 -1 -1 1
E lg 2 1 -1 -2 0 0 2 1 -1 -2 0 0 (R» Ry ) (xz, yz)
E 2g 2 -1 -1 2 0 0 2 -1 -1 2 0 0 (r - y2, xy)
A lu 1 1 1 1 1 1 -1 -1 -1 -1 -1 -1
A 2u 1 1 1 1 -1 -1 -1 -1 -1 -1 1 1 z
B lu 1 -1 1 -1 1 -1 -1 1 -1 1 -1 1
B 2u 1 -1 1 -1 -1 1 -1 1 -1 1 1 -1
E tu 2 1 -1 -2 0 0 -2 -1 1 2 0 0 (x, y)
E 2u 2 -1 -1 2 0 0 -2 1 1 -2 0 0
(x axis coincident with C{)

D Sh E 2Cg 2Cg3 2C4 C2 4C2' 4C2" i 2si 2Sg 2S4 crh 4crv 4crd
A Ig 1 1 1 1 1 1 1 1 1 1 1 1 1 1 xl + y2, Z2
A 2g 1 1 1 1 1 -1 -1 1 1 1 1 1 -1 -1 Rz
BIg 1 -1 -1 1 1 1 -1 1 -1 -1 1 1 1 -1
B 2g 1 -1 -1 1 1 -1 1 1 -1 -1 1 1 -1 1
E Ig 2 fi -12 0 -2 0 0 2 fi-fi 0 -2 0 0 (RX' Ry ) (xz, yz)
E 2g 2 0 0 -2 2 0 0 2 0 0 -2 2 0 0 (xl - y2, xy)
E 3g 2-fi fi 0 -2 0 0 2 -fi fi 0 -2 0 0
A lu 1 1 1 1 1 1 1 -1 -1 -1 -1 -1 -1 -1
1 1 1 1 1 -1 -1 -1 -1 -1 -1 -1 1 1
ry
A 2u z
1 -1 -1 1 1 1 -1 -1 1 1 -1 -1 -1 1
ra
B lu
B 2u 1 -1 -1 1 1 -1 1 -1 1 1 -1 -1 1 -1
ib
E lu 2 fi -fi 0 -2 0 0 -2 -fi fi 0 2 0 0 (x, y)
yl
E 2u 2 0 0 -2 2 0 0 -2 0 0 2 -2 0 0
em
E 3u 2-fi fi 0 -2 0 0 -2 fi-fi 0
ch 2 0 0
(x axis coincident with C 2')

e al
8. The groups Coov and D ooh for Linear Molecules

th
c_v E 2Coo¢> ... oocrv

e/
t.m
At==L+ 1 1 ... 1 z xl + y2, Z2

A 2 == L- 1 1 ... -1 Rz
E I == IT 2 2 cos ... 0 (x, y), (RX' Ry ) (xz, yz)
e

(xl - y2, xy)

er
E 2 == 6- 2 2 cos 2<1> ... 0

E 3 == 2 2 cos 3<1> ... 0
H
k
lic
D_h 2Coo¢> oocrv 2Soo¢> ... ooC2 D ooh = D oo

C
E ... i X Cj
A tg : L g+ 1 1 ... 1 1 1 ... 1 Xl + y2, Z2

A 2g : L g- 1 1 ... -1 1 1 ... -1 Rz
E tg : IT g 2 2 cos ... 0 2 -2 cos ... 0 (RX' Ry ) (xz, yz)
E 2g : 6- g 2 2 cos 2<1> ... 0 2 2 cos 2<1> ... 0 (xl - y2, xy)
... ... ... ... ... ... .. . .. . .. .
A lu : L u+ 1 1 ... 1 -1 -1 ... -1 Z
A 2u : Lu- I 1 ... -1 -1 -1 ... 1
E tu : nu 2 2 cos ... 0 -2 2 cos ... 0 (x, y)
E 2u : ~u 2 2 cos 2<1> ... 0 -2 -2 cos 2<1> ... 0
E 3u : <l>u 2 2 cos 3<1> ... 0 -2 2 cos 3<1> ... 0
9. The S2n Groups (i = ~ , E* =E with -i substituted for i)

84 E S4 C2 sl
A 1 1 1 1 Rz r + y2, Z2
B 1 -1 1 -1 z x2 _ y2, xy
i -1
E
D -i -1 -a (x, y), (RX' Ry ) (xz, yz)
86 E C3 cl i sg S6 S6 = c3 X Ci
ry
Ag 1 1 1 1 1 1 Rz r + y2, Z2
ra
{~ :*}
E E* 1 E
(r - y, xy), (xz, yz)
ib
Eg E* E 1 E*
(RX'R y )
yl
Au 1 1 1 -1 -1 -1 z
{~ em
Eu
E E* -1 -E -EO} (x, y)
E* E -1 -E * -E
ch
= exp(21ti/3)
al
€
e
th
88 E Sg C4 sl C2 Sg5 C4 3 S87
e/
A 1 1 1 1 1 1 1 1 Rz x 2 + y2, Z2
t.m
B 1 -1 1 -1 1 -1 1 -1 z
{~ :O}
E i -E * -1 -E -i (x, y),
e
E1 E* -E *
er
-i -E -1 i (Rx,R y )
H
i -1 -i 1 i -1
E2
D -i -1 i 1 -i -1 -a (x2 - y2, xy),
k
{~
lic
E3
-E *
-E
-i
i
E
E*
-1
-1
E* i
-i
-Eo}
-E
(xz, yz)
C
€ = exp(21ti/8)
10. The Higher Order Groups (i.e. Cubic Groups - Tetrahedral, Octahedral and
Icosahedral Groups)
T E 4C3 4C/ 3C2
A 1 1 1 1 r+y2+ z2
{~ ~}
E E*
E
E* E
(2z 2 - x 2 - y2, r- y2)
T 3 0 0 -1 (RX' R)'l Rz), (x, y, z) (xy, xz, yz)
E = exp(21til3); i= H, €* = € with -i substituted for i)

0 E 6C4 3C2 (= Cl) 8C3 6C2
Al 1 1 1 1 1 r + y2+ Z2
A2 1 -1 1 1 -1
E 2 0 2 -1 0 (2z 2 - r- y2, x2- y2)
TI 3 1 -1 0 -1 (R;p RY' Rz), (x, y, z)
T2 3 -1 -1 0 1 (xy, xz, yZ)
Td E 8C3 3C2 6S4 60d
Al 1 1 1 1 1 r + y2+ Z2
A2 1 1 1 -1 -1
ry
E 2 -1 2 0 0 (2z 2 - x2- y2, x2 _ y2)
ra
TI 3 0 -1 1 -1 (R;p RY' Rz)
ib
T2 3 0 -1 -1 1 (x, y, z) (xy, xz, yZ)
yl
E 8C3 6C2 6C4 3C2 (=cl) i 6S4 8S6 30h 6crd
em
°h
A ig 1 1 1 1 1 1 1 1 1 1 x 2 + y2 + Z2
ch
A 2g 1 1 - 1 - 1 1 1 - 1 1 1 - 1
2 -1 0 0 2 2 0 -1 2 (2z 2 - x 2 _ y2, x2 _ y2)
al
Eg 0
T ig 3 0 -1 1 -1 3 1 0 -1 -1 (R;p RY' Rz)
e
th
T 2g 3 0 1 -1 -1 3 - 1 0 -1 1 (xz, yz, xy)

e/
A lu 1 1 1 1 1 - 1 - 1 - 1 - 1 - 1
A 2u 1 1 - 1 - 1 1 - 1 1 - 1 - 1 1
t.m
Eu 2 -1 0 0 2 -2 0 1 -2 0
T lu 3 0 -1 1 -1 -3 -1 0 1 1 (x, y, z)
e
T2u 3 0 1 - 1 -1 -3 1 0 1 - 1
er
H
lh E 12C5 12C52 20C3 15C2 i 12S Io 125 103 20S6 150

k
Ag 1 1 1 1 1 1 1 1 1 1 r + y2+ Z2
lic
3 !(1+.J5) !(l- .J5) 0 -1 3 !(1-.J5) !(1+.J5) 0 -1

C
T ig 2 2 2 2
(R;p RY' Rz)
T2g 3 !(1-.J5) !(1+.J5) 0 -1 3 !(l +.J5) !(1-.J5) 0 -1

2 2 2 2
Gg 4 -1 -1 1 0 4 -1 -1 1 0
Hg 5 0 0 -1 1 5 0 0 -1 1 (2z 2-r-f,
r- y2, xy,
yz, zx)
Au 1 1 1 1 1 - 1 - 1 - 1 - 1 -1
T lu 3 !(1+.J5) !(l- .J5) 0 -1 -3 -!(1-J5) -!(1+J5) 0 1 (x, y, Z)

2 2 2 2
T 2u 3 !(1-.J5) !(1+.J5) 0 -1 -3 -!(l +.J5) -!(1-J5) 0 1

2 2 2 2
Gu 4 -1 -1 1 0 -4 1 1 -1 0
Hu 5 0 0 -1 1 -5 0 0 1 ~1,
APPENDIX 128: Normal Vibrational Modes for Some Common Molecular Structures
tA
/ I1 " 1~+
c/J.~ r/).~
)/~ B~ vj"'v
v1(A1) v2 (A1) v3 (E) (doubly degenerate) v4 (E) (doubly degenerate)
Sym. stretch (A-B) Sym. bend (BAB) Unsym. stretch (A-B) Unsym. bend (BAB)
Normal vibrational modes of pyramidal AD3 molecules (C3v)
ry
ra
t 0
f: r:
ib
OB
I t
yl
• A
• •
em
~/ "-0 B~
~/ "-0,& 0/ "-0 0/ "-0
B
"- e e
ch
,/
v1(A;) v3 (E') v4 (E') v2 (A;)
e al
(a) In-plane stretching modes (A; + E') (b) In-plane bending mode (c) Out-of-plane deformation mode
th
e/
Normal vibrational modes of planar AD 3 molecules (D3h)

t.m
e
er
H
k
lic
C
v1(A 1) V3 (T2) v2 (E) v4 (T2 )

(a) Stretching modes (A 1 + T 2) (b) Angle-bending modes (E + T 2 )
Normal vibrational modes of tetrahedral AD 4 molecules (Td)
JI ~
",, -------- ,
B, ,8
-------- JI
" -------- JI
,, ,
,,,
I
, A
+
8' 8
--------- ~
--------- ---------
v 1(A 1g) v2(8 1g) " v6(E u) "
(a) Stretching modes, in-plane (A1g + 8 1g + Eu)
/'
--------
, -------- +
I I
I I
I I
I
I
I
I
+
I 1
~I 1/1
--------- ---------
'& ~ +
v 4 (829) v 7 (Eu) v 3(A2u ) v S(B2u )
(b) In-plane bending modes (8 29 + Eu) (c) Out-of-plane deformation modes (A2u + 8 2u)
Normal vibrational modes of square planar AB 4 molecules (D4h )
ry
ra
~0 t 0
ib
0
'\
cr",
08
cr", cr", "cr",
yl
8 I
1 I " 1
1 I
I1 A __ " "
em
I
----ilU 1
1
1
I
1
1 +-
","
1
,,'",,"
I 1 I
1 1
/1
I I
1 ,," 1
,,'",," I 1 ,,"
,," ","
","
ch
08 0 0
,/ 0
t t
e al
v2(A~) v3(A~) vs(E')

th
e/
(a) Stretching modes (2A~ + P:~ + E')

t.m
0 +-0 +-0
0
cr", er", tier"~,
e
(downwardT I
tier"~, I " "
er
I " I
" I
~ ~
I I
movement) I
I
I
I
I ","
,,'"
I
I ~","
I
I """,,,,,,,,,...
H
I I "," I ,," ~l ,,"

~l
I ",'"
"",,,,
(downward ~""", '(j"'"
,,'" C;""
k
+ 0 movement)
+-0 0
0-+
lic
C
v4(A~) v 7 (E') v 6 (E') ve(E")
(b) Angle-deformation modes (A; + 2E'+ E")
Normal vibrational modes of trigonal bipyramidal ABs molecules (D3h)
Jf
r~t/l
" 0
1 I
If'
I/""!
~--------~
~
(E)
(a) Stretching modes (2A 1 + 8 1 + E)

° tot /,0'
°
K tt
I
71 I
r~r7! r~t71
I I
~r~t71~
I I
I/""!
o--------~ I/""!
o--------~
,! /+""!"" ,!/""!""
O--------~ O--------~
t (A1)
t t (E) t (E)
(b) Bending modes (A 1 + 8 1 + B2 + 2E)
Normal vibrational modes of square pyramidal ADs molecules (C 4v)
ry
ra
i i
ib
yl
em
/'
B B
ch
e al
th
e/
t.m
e
er
H
i
k
lic
C
(downward
movement)
~,::~-r,~:~>~
~
i (downward
movement)
v3(T1u)
Normal vibrational modes of octahedral AD6 molecules (Ob)

APPENDIX 12C: Splitting of Ground StateT-term (octahedral and tetrahedral fields) by

Spin-Orbit coupling and magnetic field (i.e. Zeeman effect) (cf. Sees. 8.20.3, 8.21)
Note: For the negative values of spin-orbit coupling constant (A), the I-levels will be inverted in a
particular diagram.
9 MJ gJ
d (Tdl A. -ve)
1 +.1
d (Ohl A. +ve) J =.1 ;';'
;';'
2
,,
2 <.;' 2
,,,
........
5 ........... _.1
d (Oh l A. -ve) (A.)
, 2
,,
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(-fA. )
(Splitting by (Splitting by
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spin-orbit magnetic
coupling) field)
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J =.1 +.1-
<::::::~
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3
d (Tdl A. +ve) 1 3
7 (tAA.) -"2
d (Ohl A. -ve)
/' +l
// 2
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spin-orbit magnetic
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8 I
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The Theory of Errors and Statistical
Treatment of Analytical Data
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13.1 INTRODUCTION TO ERRORS IN ANALYSIS
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Every experimentally measured value experiences some uncertainties (commonly called errors) and
thus the observed mean value of an experimental quantity should be considered as an estimate of true
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value. The deviation of the experimental value from the true value gives the measure of error. Here it
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should be noted that mistake is not an error.
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13.2 IMPORTANTTERMS IN ERROR ANALYSIS

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(A) Replicate Measurements: For a chemical analysis of a sample, generally several measurements of
the sample are done in the same way. These measurements are called the replicate measurements of the
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sample.
(B) Mean (M), Mode (Mo) and Median (Me)-Measures of Central Tendency: Generally, the values
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of replicate measurements are distributed in a range. The individual values.of the replicate measure-
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ments constitute a set of values and the best estimate of the true value is considered to be the central
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value of the set. In fact, some observed values are larger and some others are smaller than the central
value which is more reliable than any individual value.
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If a large number of replicate measurements are done, then it would be evident that there is a
tendency of the individual values to cluster around the central value, i. e. most of the individual values
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lie in a small interval about the central value. This is called the central tendency of a frequency
distribution. The central value actually averages the individual values. The different forms of average
are the measures of central tendency. Mean (i.e. arithmatic mean), Median and Mode are the 3 measures
of central tendency.
• Mean (M): It is obtained by dividing the sum of the values of replicate measurements by the
number of measurements. It is actually the arithmatic mean (A.M.) denoted by x for the variable
parameter x.
_-( 1)- Xl +X2 +X3 + ... +Xn _ 1~

Jl- X Mean va ue - - - ,£.Jxj
n ni=l
Xi denotes the individual value of ith observation.
2112
THE THEORY OF ERRORS AND STATISTICAL TREATMENT OF ANALYTICAL DATA 2113
The weighted mean is given by:
-( 'hdAM)- J1
f
Xl 1'1 +x 2 2 +x3 3 + ... +X f 1 p
PP _ _ ~I'.
f p
_~I'
X weIg te .. - - £.JJixi' n - £.JJi
!I + !2 + /3 +... + !p n i=I i=I
where Xb X2' •.. , x p denote the distinct values of the variables x and!l' !2"'" /p denote their respective
p
frequencies and n = Lh
i=I
Note: The geometric mean (G.M.) and harmonic mean (H.M.) are also considered as the measures of
central tendency, but these are not important in terms of error analysis and analytical data treatment.
n
. (n )1/ . 1 n
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xG (sImple G.M.) = ~XIX2 ,,,xn = II xi ' z.e. logx G =- Llogxi
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i=I ni=I
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(simple H.M.) = l I n
n
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ch
XH 1
n 1
-+-+.... +- L-
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xl X2 Xn i=IX i
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th
n p
X H ( weighted H.M.) =- - where n = Lh
f 1;
e/
i=1
t.m
i=Ix i
It may be noted: A.M. ~ G.M. ~ H.M.

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IDustration 1: A car travels along the four sides of a square ground with the speeds 50 km/h, 25 km/h,
40 km/h and 20 km/h respectively. Find the average speed of the car.
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. total distance
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Solution: Average speed = .

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total tIme
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1 1 41 1 l ' 1 =length of each side.

-+-+-+-
vI V2 V3 V4
4
1 1 1 l ' i.e. H.M. of the speeds.
-+-+-+-
vI V2 V3 v4
where 1Ian being the length of each side of the square ground; VI, V2' V3 and V4 be speeds (in km/h) to
travel along the 4 sides of the square ground. Thus we can write:
4 800
Average speed = 1 1 I 1 = 27 = 30 km/h (cj. A.M. cannot give the average speed)
-+~+-+-
50 25 40 20
Illustration 2: If the car travels with the speeds VI' V2' V3 and v4 for t hours each, then the average speed
is given by:
total distance vIt + v 2t + v 3t + V 4t
Average speed = =- ------
total time 4t
VI + v2 + v3 + V4
--- - - - , i.e. A.M. of the speeds.
4
• Median (Me): When the replicate data are arranged in the ascending or descending order of value,
the middle-most value is called the median (Me). Thus the median divides the whole set of values into
two parts such that half of the observations are more than or equal to it and half are less than or equal
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to it.
For an odd number of observations (i.e. n =odd), there exists only one middlemost value which
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1 1
is the "2 (n+ 1)th value in the ordered arrangement of the observations, i.e. the "2 (n+ 1)th value represents
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the median of the values.
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n
For an even number of observations (i.e. n =even), there is a middle pair constituted by the "2 th
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and (% +I) th values in the ordered arrangement of the values. The arithmatic mean of this middle pair
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is taken as the median of the set of values.

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th
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Gaussian curve
(Bell shaped)
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H
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f Mean, mode
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t and median same

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_ _ _~_ _" : " ' - - _ - - - '_ _---L._ _- ' - -_ _"'--_---I-=-----' variable

- .~------ 0 --------+~ +
(Deviation from mean, X-f.!)
Fig. 13.2.1 (a) Normal error curve (Gaussian curve). For normal distribution: mean, mode and median same.
• Mode (Mo): For a set of replicate observations, the value which occurs with the maximum
frequency (i.e. highest frequency density) gives the mode (Mo).
• Relation between mean (i.e. A.M.), mode and median: In an ideal case where the number of
replicate observations is very large (i. e. n very large) and the observations follow the Gaussian
distribution, the mean, mode and median are identical (Fig. 13.2.1 a) but for the smaller number
of observations (i.e. n is relatively small), the values of mean, mode and median differ.
• Asymmetric frequency curve and skewness: Normal distribution curve, i.e. Gaussian curve, is
symmetric and bell-shaped but sometimes the distribution curve may be asymmetric and the
departure from the symmetry is measured by skewness. The skewness may be positive or negative
in accordance with the longer tail of the distribution is towards the higher or the lower values of
the variable (Fig. 13.2.1b). It may be noted that the skew curves look approximately like the
normal curves when the frequency is plotted against the logarithm of the variable rather than
against the variable itself. Such a distribution is described as the log normal distribution.
~
~ 0
0 cQ)
cQ)
:J Mode) Mean :J (Sk = +ve) Mean) Mode
C'" (Sk = -ve) C'"
Positive
~
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~ Negative skewness
~ skewness ~
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~ ~
CD CD
a:
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a:
t t
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Variable
-~ 0 • + - ~ 0 • +
(Deviation from mean, X-J.l) (Deviation from mean, X-J.l)
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Fig. 13.2.1 (b) Asymmetric distribution curve: positively and negatively skew distribution.
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Normal distribution (i.e. symmetrical distribution): Mean (M) =Median (Me) =Mode (Mo).
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th
Positive skew distribution: Mean (M) ) Median (Me) ) Mode (Mo).

Negative skew distribution: Mean (M) < Median (Me) < Mode (Mo).
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. Mean - Mode M - Mo x--Mo

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Skewness (Sk) IS measured as: Sk = - -

Standard deviation s s
Illustration: The replicate analysis of a sample shows the % of Pb-content as follows:
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er
14.3, 14.1, 14.7. 14.5, 15.0, 14.9, 15.7, 15.2, 15.3 15.0, 16.0, 15.5
H
Find the mean, mode and median for the data set.
Let us first arrange the value in the increasing order.
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14.1, 14.3, 14.5, 14.7, 14.9, 15.0, 15.0, 15.2, 15.3, 15.5, 15.7, 16.0
'--.r----'
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The number of observation is 12, i.e. n = 12 (even number).

The middle pair consists of the values 15.0 and 15.0 and their A.M. is 15.0, i.e. median
=.!.(15.0 + 15.0)% = 15.0%
2
The frequency of observation is maximum for the value 15.0% (twice in 12 observations), i.e. mode
of the set is 15.0%
Mean (A.M.) = 14.1 + 14.3 + 14.5 + 14.7 + 14.9 + 15.0 x 2 + 15.2 + 15.3 + 15.5 + 15.7 + 16.0
12
= 15.016 ::= 15.02%
(C) Absolute error: It gives the measure of deviation of the experimental value from the true or
accepted value. It is given by:
Ea = Xi - Xl (for a single measurement)
=X - x t (for the replicate measurements where X is the mean value of observed values).
Xt denotes the true or accepted value.
The sign of Ea (absolute error) indicates whether the measured value is higher (i.e. + sign of E a ) or
lower (i.e. -sign of Ea ) than the true or accepted value. In general we can write:
measured value = true value ± error.
i.e. true value = measured value ± error
(D) Relative error: It is more frequently used than the absolute error. The relative error (Er ) expresses
the error relative to the magnitude of the amount to be determined. E r is either expressed in percent or
parts per thousand (ppt).
x-x E x-x E
E r = _ _t x 100% =_a x 100%, or E r = _ _t x 1000 ppt =_a x 1000 ppt
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x t
x t x t x t
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(E) Fractional error: It is actually the relative error. It is given by:
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Et -- Ea i.e. 100E! and 1000E! give the percentage and ppt error in X t respectively.
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xt .
We can write: ch
x=xt +Ea =x, (I+E/); ct. E/ = E a
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xt
e
~=l+Et ~x=(-J
th
t
i.e. or, IE JX[ll- E J= l-E; ",,1-E/; (cf E/« 1).
x .+ t - Et 1- Ef
e/
t
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(F) Systematic or determinate errors: These remain constant in a particular analysis. They may also
vary according to a definite law. The systematic error in a particular analysis is reproducible and
unidirectional with respect to the true value and it can be corrected.
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(G) Random or indeterminate errors: These are indeterminate and their occurrence does not obey
any definite law and this cannot be avoided (cf. systematic errors can be avoided). In contrast to
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determinate error (which is generally unidirectional), the indeterminate error leads to both positive and
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negative error with an equal probability,

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Etotal = Esystematic + Erandom == Erandom when the systematic error is negligible or absent.
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(H) Accuracy and precision: In an ordinary sense, these two words are often used synonymously but
in a scientific sense, they are different.
Accuracy describes the correctness of a result. In other words, it gives the measure of closeness of
the result to the accepted or true value. Obviously, we can conclude: the smaller the error, the
greater the accuracy.
In fact, in absence of any systematic en-or, the accuracy is high when the precision is high.
Here it should be mentioned that accuracy is a relative term. For example, for determination of
mercury in fish-tissues (Hg-content, about 10-20 parts per billion), accuracy within ±10% is quite
satisfactory but accuracy within ±10% for determination of mercury in its ore (that normally contains
~ 20%) is not at all satisfactory.
Precision is determined by the reproducibility of results, i. e. closer the results of the replicate
determinations to each other, more the precision. Thus precision refers to the mutual agreement among
the replicate data but it has no relation with the accepted or true value.
Accuracy vs. precision: Random errors determine the precision and it is measured by the parameters
like average deviation, range, standard deviation, variance and coefficient ofvariation. These parameters
will be discussed later. Good precision indicates the absence of any considerable amount of random
error.
If there is a constant systematic error in an analysis, the results may be precise but inaccurate. In
such cases, the systematic error will affect each measurement or observation equally and the precision
of the data will not be affected.
Thus we can say that precise values are accurate only when there is no systematic error.
Here it is important to mention that precision of the results can be easily determined by comparing
the replicate data but to determine the accuracy, we need the true value which may not be known
always.
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Illustration 1: Accuracy vs. precision
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Measuring the systematic error
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Accuracy ( , ) Accuracy
+ve error
.. -ve error
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(i.e. +E a) (i.e. -Ea)
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th
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True or Observed True or

accepted mean value accepted
1 value \ (X or Jl) / value (><t)
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L.....-_..;...(><t..;...}_"a----l'---_ _~_ _~_ __..;~---I-II'--- ...... (value)

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Spread measuring the

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precision or the
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random error
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Fig. 13.2.2 Illustration of accuracy vs. precision; systematic error vs. random error, (Ea denotes the absolute error).
Illustration 2: In determination of the strength of a KMn04 solution by a standard oxalic acid solution,
the replicate titre values are covering a very narrow range, i.e. the titre values are quite precise. But if
the standard oxalic solution is prepared erratically, then the strength of the KMn04 solution determined
from the knowledge of strength of the oxalic acid solution will be inaccurate. Thus, in spite of the good
agreement among the replicate results, the strength of KMn04 solution is inaccurately determined here.
Illustration 3: Kjeldahl method is very often utilised to determine the nitrogen content in an organic
compound. In this method, the organic compound is decomposed in hot concentrated H2S04 and it
produces (NH4)2S04 from the nitrogen present in the given organic compound. The amount of NH3
released from the (NH4)2S04 is determined through an acid-base titration. It has been found that for the
organic compounds bearing the pyridine ring as in nicotinic acid is incompletely decomposed under
the experimental condition. Thus the estimated N-content is less than the true value. In such cases, the
results may be precise but they are inaccurate producing a negative error.
Reference or
true line
x •
x
i ( Experimental value
Accurate but not precise
1 Both accurate and precise
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--+y --+y
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Measuring the
Reference or • "
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~ .
s~stematiC error true line ""
Reference or "
".,,, "
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true line
x
Observed
..... "
.,," x
ch
. ,,""t· ·
"
,,"
1 line~"."
i ."",,;" .
• "",,,,,,, • Observed line
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"""",.:
,,, ". Precise but not accurate
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r" Neither accurate nor precise

..1
th
---+y
e/
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Fig. 13.2.3 Illustration of accuracy vs. precision. Plot of the observed values (x) vs. the corresponding variable
parameter (y) free from error.
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Both accurate Accurate but Precise but Neither accurate

and precise not precise not accurate nor precise
Fig. 13.2.4 Illustration of accuracy and precision using the target of darts (i.e. small arrows) on a dartboard.
13.3 CHARACTERISTICS OF SYSTEMATIC ERRORS

When the systematic or determinate error exists in an analysis, the mean value of the replicate results
differs from the accurate or accepted value. Thus existence of the systematic error produces the incorrect
result and the absolute error (E a = X - X t ) may be negative or positive depending on the condition.
Thus the systematic error gives the measure inaccuracy ofthe results (cf Fig. 13.2.2). It does not matter
whether the replicate measurements are precise or not. In a particular analysis, the systematic errors are
reproducible and unidirectional with respect to the true or accepted value. Existence of systematic error
may be identified by comparing the results with the results obtained by other authentic methods of
analysis.
(A) Classification of systematic errors on the basis of their origins: _On the basis of origin, the
systematic errors may be classified as instrumental error, errors due to reagents, methodic error, operative
error and personal.
• Instrumental error: The important sources are:
(i) Measuring devices-use of uncalibrated balance and weights; use of uncalibrated volumetric
glass apparatus like burets, pipets, volumetric flasks, etc. can introduce the systematic error.
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Proper calibration can eliminate such errors.
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(ii) Electronic instruments-use of electronic instruments under the nonideal conditions
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introduces the systematic error.
• Errors due to reagents-impurities in the reagents used in the analysis can introduce a systematic
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error.
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• Methodic errors: It is illustrated by taking some examples.
(i) In weighing a hygroscopic substance, some error is always expected and it depends on the
ch
humidity of environment.
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(ii) Analysis of a volatile substance is expected to be accompanied with some error due to the
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loss of the substance.

th
(iii) In iodometry, if appropriate precaution is not adopted, some amount of 12 may be liberated
due to the aerial oxidation.
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(iv) Instability of the species (e.g. MnDi if generated in analysis of manganese) introduces some
t.m
error.
(v) Slowness and incompleteness of the reaction can introduce the error. It has been already
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illustrated that in estimation of nitrogen (by Kjeldahl method) of an organic compound bearing
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the pyridine ring, the incomplete decomposition introduces a negative error. In such cases,
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some correction factor may be introduced to nulify the error.

(vi) Coprecipitation and postprecipitation are the origins of methodic error.
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(vii) Solubility of a precipitate in solution and loss of a precipitate due to peptisation during
lic
washing are also the common sources of error.

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(viii) Unavoidable induced reactions and side reactions can make the results inaccurate.
(ix) Decomposition or volatilisation of a precipitate during heating introduces a methodic error.
The determinate or systematic errors can be identified and they are reproducible and suitable corrective
measures may be adopted.
• Operative error: It is associated with the ineptitude of the analyst.
• Personal error: It varies with the individuals. In measurement or taking readings, sometimes, it
requires the personal judgement. Sometimes, the personal error may originate from the personal
prejudice or bias.
(B) Classification of systematic error based on the effect on the result: On the basis of the effect on
the result, the systematic errors may be classified as constant error or proportional error.
• Constant error: In such cases, the magnitude of error is almost constant regardless the sample
size of analysis. Obviously, this constant error seriously affects the result when the sample size is
small. Some examples of constant error are given below:
(i) Indicator end-point error-the excess amount of reagent needed to cause the noticeable
change in colour is constant. If the end-point error is 0.1 ml (say) (i.e. 0.1 ml excess titrant
to be added to bring about the needed colour change), it introduces 10% error (relative error)
when the sample requires 1 ml titrant but it introduces 1% error for the sample requiring
10 ml titrant. It indicates that the effect of constant is serious when the sample size is small
because for the smaller size of the sample, the relative error becomes larger.
(ii) Loss ofprecipitate due to solubility-it remains constant and does not depend on the amount
of precipitate remaining in equilibrium with a certain volume of solution from which the
precipitation has been done.
• Proportional error: The magnitude of such error depends on the sample size in such a way that
the relative error remains constant. Such an error may happen when the interfering substance
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remains present within the sample. It is illustrated in the following examples.
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(i) Iodometric determination of copper(II) (say in brass): The liberated 12 by Cu(ll) is estimated
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to determine the Cu-content. But Fe(III), if present, in the sample will liberate 12 (if not
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prevented) and it will cause a positive absolute error. If the sample size is doubled, the error
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due to Fe(III) is doubled but the relative error remains fixed because the amount of Cu(ll) is
also doubled in the sample. Thus for the larger sample size, the magnitude of absolute error
ch
is also larger but the relative error is the same.
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(ii) Iodometric determination of chlorate: Besides the chlorate, other oxidants like bromate and
iodate present in the sample will liberate 12 to introduce the positive error.
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th
13.4 CHARACTERISTICS OFTHE RANDOM OR INDETERMINATE ERRORS

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The values of replicate measurements always differ to some extent even when the measurements are
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done by the same person with great care under the identical conditions as nearly as possible. The values
are found to be distributed within a certain range. In other words, due to the accumulated random
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errors, the values ofreplicate measurements fluctuate randomly around the mean value. With respect
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to the mean value, the low and high results (by a certain amount) appear with an equal probability, i.e.
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both the negative and positive deviation from the mean value are symmetrically distributed. These
symmetric deviations are due to the indeterminate or random errors. Because of the symmetrical
k
distribution of the replicate data, the random errors tend to cancel one another and the effect of
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random errors on the mean value is minimum. It may be pointed out that in contrast to the indeterminate
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error, the determinate error is generally unidirectional (i.e. either the positive or negative deviation in
a particular method of analysis).
The random or indeterminate errors cannot be corrected in the same way as practised for the
determinate errors because the law of variation of indeterminate error is unknown. But it is possible to
have the idea regarding the most probable result and its degree of reliability in terms of statistical
treatment.
Probable sources of random error: It is illustrated in the calibration of a pipet. The probable
sources are: visual judgement in locating the level of liquid; variations in the liquid drainage time;
variations in the retention of liquid in the pipet after drainage; variations in drainage time and angle of
pipet for drainage; temperature fluctuation causing the fluctuation of pipet volume and viscosity of the
liquid to be drained; etc. Thus even the simple pipet calibration process is affected by so many
uncontrollable variables which produce a cumulative effect to the observed results scattering
symmetrically around the mean value.
13.5 DISTRIBUTION OF RANDOM ERRORS: STATISTICAL TREATMENT OF RANDOM

ERRORS
(A) Frequency distribution - histogram, frequency polygon: The individual values of replicate
measurements are to be arranged in an order (ascending or descending). Then the difference between
the lowest and highest value gives and range of observations. Then the range is split into a convenient
number of equal cells (say 10-20) where each cell accommodates the data within the specified boundaries
or intervals. It would be noticed that the cells residing at the boundaries of range accommodate the
fewer data while the cells residing at the middle position of range accommodate the larger number of
data, i. e. the observed data show a tendency to cluster at the central position of range (cf. central
tendency). In other words, the frequency of occurrence of the observation increases in the cells moving
towards the central position of the range. The cell heights (proportional to the number of observations
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appearing within the cell) represent the frequency distribution. The bar graph of the continuous (i.e.
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adjoining) cell heig~ts representing the frequency distribution of data is called histogram (Fig. 13.5.1).
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A frequency polygon may be constructed by connecting the mid-points of cell-roofs (measuring the
frequency) with the straight lines (Fig. 13.5.1). At the limiting situation (i. e. a very large number of cells
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of very small cell-widths are constructed to accommodate a very large number of replicate measurements),
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the frequency polygyon represents the normal or Gaussian distribution curve.
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Histogram
bars
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\~ Normal
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curve
~
t.m
·enc: (Gaussian curve)

Q)
'lJ \
\
~
0 \
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c:
Q)
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::J
c:r \
~ I \
H
I \
Q)
I
> I
~
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Q) I
cc I
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20.030.0 40.0 50.060.0 70.080.0

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Marks -+ " Most probable value

(a) (b)
Fig. 13.5.1 (a) Histogram and frequency polygon for the distribution of % of marks in an examination among the
students (showing the largest fraction of students securing marks in the range 50-60%). (b) Histogram and the corresponding
normal curve for distribution of measurements of a particular parameter.
(B) Characteristics of the normal (Gaussian) error curve: It shows the symmetrical distribution of
data of replicate measurements around the mean value of an infinite set of data. It may be noted that
the corresponding curve for a smaller number of observations is called the frequency polygon which
is generally irregular in shape. The bell-shaped regular normal curve for an infinite set of data is
the locus of a well known mathematical function. The normal error curve (strictly valid for a hypothetical
infinite set of date) is taken as a model curve to treat the finite number of replicate data.
The normal error curve indicates the probability of occurrence of a particular observation and
thus it shows the distribution of random errors and follows the normal probability law:
y = fix) = A exp[-h2(x - J.l)2]; (A, hand J.l constants) ... (13.5.1)

where y = frequency of occurrence of a deviation from the population mean J.l; (x - J.l) representing
simply the deviation of an individual value from the population mean J.l.
Area under the curve

-0' to +0': 68.3%; 0 to +0': 34.15%
0.4 -20' to +20': 95.40/0; +0' to +20': 13.6%
-30' to +30': 99.7%; +20' to +30': 2.1 %
~
()
c:
Q)
::J
0-
-30'
~
ry
Q)
> 0.2 +30'
~
ra
Q)
a:
ib
i
yl
0
em
ch
-4 -3 -2 -1 0 2 3 4
z= x-f.l
al
cr
e
Fig. 13.5.2 Normal error curves (Gaussian distribution curve). Relative frequencies of deviations (x - f.l) from the
th
cr(cf z = x ~ 11 ).
e/
population mean (11) where abscissa measuring the deviation (x - 11) from 11 in the units of
t.m
The normal error curve is symmetrical about J.l, i.e. positive and negative deviations by a certain
amount are equally probable. The smaller deviations occur much more frequently than the larger
e
deviations (cf Fig. 13.5.2), i.e. the frequency of observation decreases exponentially as the magnitude
er
of deviation increases.
H
The total probability is unity for the whole set of data, i. e. the distribution function is normalised
by setting the area under the curve equal to unity. It is evident that for the larger deviations (i.e. large
k
lic
values of x - J.l), the curve runs asymptotically to the abscissa on either side of J.l (cf Fig. 13.5.2). Under
the condition of normalisation, we can write:
C
+OOJ
Aexp [-( x-fl )2 h 2] dx=--=l,l.e.A=
AJn. hC
~ h vn
The above result is obtained as follows by using the standard integral of r -function.
(Standard integral)
Let
Putting r = x - J.l, we get: dr = dx

x = r + J.l, i.e. as x ~ - 0 0 , r ~ -00 and as x ~ +00, r ~ + 00
Thus we can write:

+00
I = A f exp(-r 2 h 2 )dr
= Ajf;-, (using the standard integral)
A£
h
Thus the equation of normal error curve is:
ry
y = j(x) = Jx 2
exp[ -h (x - ~.ll] ... (13.5.2)
ra
ib
It indicates that for a normal distribution, the probability of appearance of an observation having the
Jx
yl
value between x and x + ax is yox, i.e. exp[ -h 2(x -Ilf] ax.
em
In other words, the fraction of popu-
0:) ax is given by yax i.e

ch
lation of observations (say having the values in the range x and x ±
al
oN =j(x)ax =yax = ~exp[-h2(x-~.lfJox ... (13.5.3)

e
N ,,1t
th
~ =j(x)dx= Jnexp [ -h 2(x-Il)2Jdx

e/
or ... (13.5.3)
t.m
This is why, Eqn. 13.5.2 is called the equation of probability density or relative frequency density
of the distribution of observation. It is evident that the normal distribution of probability density is
e
determined by two parameters hand J.! where J.! gives the population mean (which is equivalent to the
er
arithmatic mean of the observations when the number of observations is very large) and h is called the
H
precision constant which is related with cr (called population standard deviation to be discussed
later) as follows:
k
lic
C
Thus Eqn. 13.5.2 reduces to:
y=_I_ exp [- (x- Il )2] ... (13.5.4)

crJ2X 2cr 2
For x=ll±cr: y= cr~exp(-~)~~5

1 0.135
For x=J.!±2cr: y= ~exp(-2)~ ~
cr" 21t cr" 21t
The absolute deviation of the individual values of x from the mean value J.! is given by (x - J.!) and
it can be measured in the unit of a single of variable z defined by:
X-Jl
Z =--, i.e. z = 1 when x -
a
f.! =a; z = 2 when x - f.! = 2a.
.
PuttIng
d
z =-dx , we can write:
a
dN =ydx=f(x)dx= ~exp[ (x-Jl)2]dx=_I_exP[_~]dZ ... (13.5.5)

N av 21t 20 2 J2n 2
(C) Area under a Gaussian curve: The area under the curve between any two values of (x - J.l) gives
the probability or the measure of the fraction of total population of observations having the values
ry
between the limits.
ra
In other words, probability of an observation to lie between the values XI and X2 is given by:
ib
1 x-Jl
[ ( )2]
yl
X2 X2
exp --
2 --
Jj(x)dx = J
em
area = 0 dx
Xl Xl oJ2n ch
+oexp[-~(x~~ J]
e al
= f J2n dx ; say Xl = -0' and x2 = +0'

th
-0 0 21t
e/
The above integral gives the area under the curve between -la and +la of the mean, i.e. area
t.m
between the limits f.! - 1a = x I and f.! + 1a = X2' It is easier to handle the above equation in terms of the
X-Jl)
single variable z ( =- - ,i.e. x_-Jl
= _1 and Z2 x _-Jl
= _2
e
Zl _ _.
o 0 a
er
It gives:
H
k
+1 exp ( -Z2)
lic
-
Jv~
1
exp(-~JdZ = ~± 10', z = ±1
Z2 2
area = f = J2n2 dz; forx

C
Zl21t 2 -1 21t
= J2n L
1 +1 exp ( -~ 2 Jdz = elf 2 (12) = (12 = erf 1 ) 0.683
1 +a
[ cf. J2n exp L
(Z2 ) dz = erf (afi)
-2 -2- =erf ( 12
a )]
The integral has been numerically evaluated because it does not have any closed form of solution.
The error function, erf(1) is defined as follows:
erf(T) = ~ +f exp(-t 2 )dt = ~ Jexp(-t 2 )dt; (cf. symmetric distribution in Gaussian curve).
v1t -T v1t 0
The values of error functions for different values of T are given in mathematical tables.
Error function
1
,fiit iT exp
+T
T Jdt =erf (.fiTJ; cf· ,fiit1 Iexp ((2
((2 T
-2 Jdt =21 erf (T
.fi J
T o 0.674 2 3
o 0.500 0.683 0.954 0.997
Similarly, it can be shown:
ry
f exp ( -~2 Jdz =0.954
ra
1 +2
x = f..l ± 20, i.e. z = ±2; area = ~
ib
v21t -2 2
yl
f exp ( -~2 Jdz =0.997
em
1 +3
x = f..l ± 30, i.e. z = ±3; area = ~
v21t -3 2
ch
kI ~ Jdz =total probability =1
al
and area = exp ( -

e
th
It indicates that about 68.3% of the total area under the curve is enclosed in the range z = -1 to
e/
z = + 1, i. e. limits of f..l ± 10 or -0 to +0 around the population mean fl. It means that about two-thirds
t.m
(i.e. 68.3%) ofall the observations (when the number ofobservations is infinitely large) will lie within
the limits JJ ± 1 a Similarly, about 95.5% of the total observations will fall within the JJ ± 2 a limits
and the limits JJ ± 3awill practically include all the observations (actually 99.7%) (Fig. 13.5.1). Thus
e
the probability of recording an observation beyond the limits f..l ± 30 is negligibly small (i.e. 0.3%
er
probability or 1 in 300).
H
Here it is worth mentioning that in reality, it is not possible to find 0 (standard deviation) for an
k
infinite set of data and the sample standard deviati0'l (s) obtained from a finite set of data is taken
lic
as an estimate of (J to predict the conclusions, i.e. ~e magnitude of precision or random error.

The major conclusions are given below:
,
C
(i) The most probable value is taken as the weighted arithmatic mean (x), i.e. x replaces f..l in
a practical sense.
(ii) Mean, mode and median (measures of the central tendency) are the same for the normal error
law (i.e. Gaussian distribution of random error).
(iii) Positive and negative deviations of the same ihagrlltude from the most probable value are equally
probable and consequently, these deviations do not affect the arithmatic mean x but they determine
the degree of precision. It gives:
n n
L(xi-x)=Ldi=O.
i=1 i=1
(iv) Frequency of occurrence decreases exponentially as the deviation from the most probable value
increases; statistically, about 68.3% of the observations lie in the range x ± 10; similarly about
95.5% of the observations fall in the range x ± 20 and about 99.7% of the observations lie in the
limits x ± 30 . The observed values beyond the limits x ± 30 may be neglected (cf. Fig. 13.5.2).
Here the said conclusions are made assuming x to represent the population mean Jl (i.e. x:::::: Il).
(v) The probability of the magnitude of random error associated with a single measurement can also
be predicted from the normal error curve. For example, the probability of random error associated
with a single measurement to lie within the range ±10 is 0.683 (i.e. 68.3%). Similarly, for the
random errors within the range ±20 and ± 30 associated with a single measurement, the corre-
sponding probabilities are 0.955 (i.e. 95.5%) and 0.997 (i.e. 99.7%) respectively.
13.6 POPULATION MEAN (J1), SAMPLE ARITHMATIC MEAN (x), AND MEASURES OF
DISPERSION-RANGE, POPULATION STANDARD DEVIATION (0) AND SAMPLE
ry
STANDARD DEVIATION (s)
ra
(A) Mean: In practice, central tendency of a finite set of data is taken as the arithmatic mean about
ib
which the individual values tend to cluster.
yl
em
~
-
= Xl +X2 +X3 =-1 £...ix
+ ... +x n
X i ~ Il as n ~ 00
n ni=1
ch
'.;.,
p p
al
Lh x . LJ:·x.
_ ( . ) f1x1 + f2x2 + ... + f p X p
= .-1 = "-I
e
weIghted mean =
I I I I ( • • • )
X _1-_ _ _1-_ _ ; for frequency dIstnbutton
f
th
f 1 + f 2 + ... + f p n
£...if;
e/
i=1
t.m
(f; denotes the frequency of the observed value Xi).

When the number of observations is very large (i.e. n ~ 00), x tends to Il (i.e. x ~ Il). Statistically,
Il is a better parameter than x but x obtained from a finite set of observations is taken as an estimate
e
er
of J1.
H
(B) Measures of dispersion: It indicates the extent to which numerically the individual observations
vary around the most probable value (i.e. x). Range, mean deviation and standard deviation are the
k
lic
measures of dispersion.
C
(C) Range (R): It is given by the difference between the maximum and minimum observed values, i.e.
R = X max - Xmin
In a practical sense, xmax = Il + 30 and Xmin = Il - 30, i.e. range = 60 which can accommodate about
99.7% of the observations.
(D) Mean deviation (MD) or average deviation (dav ): It is given by the average of individual deviations
from the mean value. Here, signs of the deviations are ignored.
n n
It may be noted: L(xi - x) = Ldi = 0, i.e. the positive and negative deviations of the same magnitude
i=1 'i=1
are equally probable (cf. bell-shaped curve for the distribution of random errors).
Weighted average deviation may be expressed for frequency distribution as follows:
where
[Note: Peters formulae - for a sample of n data taken from a normal distribution, day is given by:
dav =iii Id4(Jn(n - 1)), n =iii, [cf. cr vs. s.]

i=1 i=1
1*
ry
d
Average deviation of the mean =
ra
d
ib
Relative average deviation (%) = ~v x 100
yl
x
em
Relative average deviation (%) is also described as the coefficient of mean deviation.
d
~v x 1000
ch
Relative average deviation (ppt) =
x
al
• Significance of dav : The magnitude of day is determined by the random errors, i.e. the smaller value
e
of day indicates the .smaller random errors, i. e. higher precision.

th
It can be shown that:

day :::: 0.8s, i.e. s :::: 1.25dav
e/
(E) Root mean square deviation (s) called sample standard deviation: To measure the effect of
t.m
random errors, statistically, root mean square deviation is more meaningful. It is given by Bessel's
formula:
e
er
n 2
L(Xi - x)
H
s= \/...;....i=....;;..1 _ d 12 + d 22 + d23 +... _

k
n-1 n-1
lic
2/
C
s=
r
Lh (Xi - x) (n -1) =
r
Lh d; /(n -1) where Lh
r
= n.
i=1 i=1 i=1
The quantity (n - 1) is called the degrees of freedom which is defined by the number of individual
observations that can be varied for a fixed x value. Thus when the mean (i.e. x) is kept constant, all
but one observation can be varied, i.e. the last value of x is automatically fixed by x and all other Xi
values. Thus for n observations (for a fixed x value), the degrees of freedom is (n - 1).
The expression of s can be simplified as follows:
f(x i _X)2 = f(x i -x)(xi -x)= f(x i -x)xi - f(x i -x)x

i=1 i=1 i=1 i=1
=fx; - xfxi - xf(x; - x) = fx; - n(x)2; f(x i - x) =0 and fX i =rii

i=1 i=1 i=1 i=1 i=1 i=1
2128 FUNDAMEN1,' 'RGANIC CHEMISTRY
It gives: ~ )[±x;-nCx)2] =
s= -(
n 1 1=1
~ )[~x;-n(~Xi)nJ2]
-(
n 1 1=1 1=1
1
= - -[LX;
n 2
--n1 (LX;
n 2]
(n - 1) ;=1 ;=1 J
It needs the evaluation of ~X; and (~Xi r·
• Significance of s: It gives the measure of precision. The smaller value of s indicates that the
ry
observed values are clustered closely to x, i.e. the higher precision is reflected (Fig. 13.6.1). In other
ra
words, the magnitude of random error is small for the small values of s. Figure 13.6.1 illustrates the
ib
spread of random errors, where the standard deviations are in the ratio 1:2:4. Here, s is taken as a ,good
yl
estimate of o.
em
A ch
e al
Precision: A ) B ) C
th
Spread of random error: A ( B ( C

e/
Range: A ( B ( C
t.m
e
i
er
H
k
lic
- -II 0 ~ +
(Deviation from mean, x-J!)
C
Fig. 13.6.1 Normal error curves having the same central tendency f..l but with different standard deviations, i.e. with
different precisions or spreads.
(F) Population standard deviation (0): It gives the measure of precision of population data, i.e. an
infinite set of data. Statistically, 0 is more important than sand 0 is defined as follows:
fid~ + f2 d i +... =
±.fi(Xi-J.l./ r
0=
/1 + /2 +...
;=1 r ' L/; =n ; (for frequency distribution)
~ E ;=1
£..JJ;
;=1
• Difference between s and a: In defining a, the sample mean x (obtained from a finite set of
observations) is replaced by population mean J..l and the number of degrees of freedom (n - 1) is
replaced by n (known as Bessel's correction). It is quite reasonable that for the large values of n, x ~ J..l
and n - 1 ~ n, i.e. s ~ a (cf. a 2 =s2(n - 1)/n ::::: S2 for n > > 1). In fact, s is taken as a good estimate of a
when the value of n is fairly large.
(cf. Peters' correction for dav : d == Lld;1 "" Lld;1 when n» 1)

av ~n(n -1) n
Taking, n - 1 ::::: n and x = J,!, we can write:
ry
ra
ib
yl
For frequency distribution,
1 (1
em
0
2
~ s2
r - - LXih
=- LX;h
r)2 where n = Lh
r
n i=l n i=l i=l
ch
• Significance of a: It is determined by the magnitude of random errors. The smaller value of (j
al
indicates the higher precision of the results (Fig. 13.6.1). The analytical results may be shown as:
e
x ± 0 which indicates the probability (P) of an observation to lie in the range x- cr to X + 0 is 0.683
th
(i.e. 68.3%). In other words, the range x ± 0 covers the 68.3% zone of total observations. Similarly,
e/
significance of other representations of the analytical results can be understood. These are:
t.m
x ± 0.670 ~ p = 0.50 i.e. 50.0% zone

x ± 10 ~ p = 0.683 i.e. 68.3% zone Assuming x ~ Jl(cf. normal
e
x ± 20 ~ p =0.955 i.e. 95.5% zone

er
error curve, Fig. 13.5.2)

x ± 30 ~ p = 0.997 i.e. 99.7% zone
H
The normal error curve can give another interpretation of random errors in terms of a (standard
k
deviation). We can say:

lic
for a single measurement, the probability of random error associated with it to lie within the
C
range ±la is 0.683 (i.e. 68.3%); similarly for the random errors within the range ±2a and ±3a
associated with a single measurement, the corresponding probabilities are 0.955 (i.e. 95.5%) and
0.997 (i.e. 99.7%) respectively.
Thus the standard deviation (a) is a useful parameter to measure the random error (i.e. precision)
involved in the analytical method.
(G) Relationship between MD (mean deviation) and SD (standard deviation): dav(i.e. MD)::::: 0.8a.
MD is defined as follows:
_MD_Llxi-lllh
d av- _Llxi-Illpi -~I - I ~ -1
- Lh - LPi -kJXi IlPi'kJPi-
where f denotes the frequency and P denotes the corresponding probability of the deviation from the
population mean J..l.
i.e. MD = mathematical expectation or expected value of Ix - III = Elx - III = Llxi - III Pi
+00
It leads to: MD = Elx - JlI = f Ix - Jllf(x)dx; (for the normal error curves)
where for the normal error curves (i.e. Gaussian curves),
f(x)=_l exp [_!(x- Jl ]2]

crJ2n 2 0
+00 ~ +00
It gives: MD= f IX-Jllf(x)dx= f Ix-ulf(x)dx+ f IX-Jllf(x)dx
~
ry
+00
(cf symmetric distribution of random
= 2 f (x -
ra
Jl )f(x)dx;
errors around the mean value Jl).
ib
~
yl
em
ch
· x- Jl
Putting, - - = z, we get: (x - Jl) = oz, or dx = odz; x ~ Jl then z ~ 0 and
al
" 0
'.. x ~ then z ~ 00
e
00
It leads~ to:
th
e/
2
MD=--
2
f crzexp (Z2
+00 ) 20 (Z2 )
- - crdz=-- f zexp - - dz
+00
t.m
oJ2n 0 2 crJ2n 0 2
=a~ T ~ }z ~ O.8a Tzexp ( - ~ )dZ

e
zexp ( -
er
H
2
Putting, ~ = u, we get: 2zdz =2du; or, zdz
k
= duo
lic
,2
It gives:
C
4 4
dav =MD ~ 0.80 Jexp(-u)du ~ 0.80[ -exp(-u)J~ = 0.80 = -0
+00
55
or -s
0
(Cf f exp(ax)dx = ~exp(ax»)

Sometimes dav is denoted by 11.
Idavorl1 =al =~a =o.sa·1

(H) Standard deviation of composite group: If two groups contain nl and n2 observations with means
xl and x2 having the standard deviations Sl and S2 respectively, then S.D. of the composite group (i.e.
combined data) is given by:
THE THEORY OF ERRORS AND STATISTICAL TREATMENT OF ANALYTICAL DATA ,2131
2 nIs; + n2S~ ni (Xl - X)2 + n2 (X2 - X)2

S = +---------
n i +n2 n i +n2
where, X (pooled filean) = nI XI +n

,
2x 2
n l +n2
2
2 + n s 2 n n (-
nIsI
_)2
Xl - X2
= 2 2 +l -2 - ---
It gives: S
n i + nz (n I + n2 )2.
Illustration: For a group of 50 persons, the mean and standard deviations of their weights are 59.5 kg
ry
and 8.38 kg. For another group of 40 persons, the corresponding values are 54 and 8.23. Find the mean
ra
and standard deviation of the combined group of 90 persons.
ib
Solution: S (standard deviation of the combined group) is given by:
yl
2 nIs; + n2s~ . ni (Xl - x)2 + n2 (X2 - x)2
em
S = +_....:..---~----~
n i +n z n i +n 2 ch
X = nixi + n Zx2 = 50 x 59.5 + 40 x 54 = 5135 = 57.06
where,
al
nl +n2 50+40 90
e
Xl - X = 59.5 - 57.06 = 2.44 and x2 - X = 54.0 - 57.06 = -3.06

th
e/
50 X (8.38)2 +40x(8.23)2 +50x(2.44)2 +40 X (-3.06)2

Thus,
t.m
50+40
50 x 70.22 + 40 x 67.73 + 50 x 5.95 + 40 x 9.36
e
90
er
H
= 6892.74 = 76.58
90
k
lic
i.e. s = ~76.58 = 8.75

C
Note: Sometimes, pooled standard deviation for different groups of observations can be expressed as
follows:
where nl is the number of observations in Set-I, nz is the number of observations in Set-2, nt is the
number of observations in Set-t; t denotes the numbers data sets or groups.
(I) Some important properties of the standard deviation (0):
• Standard deviation is independent of the change of origin: Let crx be the standard deviation for the
set of values, Xh Xz, X3' ..., Xn • If each of the Xi -values is shifted by a fixed quantity (say c), then it leads
to new set of values, Yh Yz, Y3' ..., Yn which give the standard deviation cry (say).
Xl' X2' X3' ..., Xn :::::} ax; YI' Y2' Y3' ..., Yn :::::} ay
where Yi = Xi - C, C = constant, i.e. YI' Y2' Y3' ... are derived from Xb X2' X3' ... by shifting the origin to
an arbitrary constant c. Now we can write:
cr; = L,(x -xf In where x = !L,X

i
n
j
Yi = Xi - c and it gives: y = x - c; or, x = y + c

(Xi -X)=(Yi +C)-(Y+C)=Yi-Y
2 i L,(X -X)2
i.e. ax = - - --
ry
n n
ra
Note: This principle makes the computation to find a easier and it is illustrated in the solved numerical
problem 13.
ib
• Relation between ax and ayfor the relation, y = a + bx: ax and a y denote the standard deviations
yl
of the two variables X and Y respectively and they are related as follows:
em
Yi =a+bxi i.e. y=a+bx ch
It gives: Yi -y=b(xi -x)
al
I.(Yi -)if =b2I.(xi _x)2

e
Then we can write:

th
i=1 i=1
e/
1~ ( _)2 ~ ( Xi - _)2
or, - £.JYi - Y = b 2x -1 £.J X
t.m
n n
or, a~ =b 2a;: or, cry =Ibla x.

e
er
• Variance (S2, 02): The sample variance is denoted by S2 while the population variance is denoted
bya2 •
H
• Coefficient of variation (CV): It is the percent relative standard deviation (RSD) (i.e. standard
k
deviation is expressed as of the mean). Thus CV is give by:

lic
For s For (J
C
RSD = ~ and CV(= RSD in %) = ~x 100 RSD= a, CV(=RSD in %)= a xl00

x x Jl Jl
RSD (inppt)=~XlOOO RSD (in ppt) = cr x 1000

X Jl
(J) Standard error or standard deviation of the mean, probable error of the mean and standard
error of the standard deviation: We have already mentioned that Jl and a refer to the infinite population.
· If f:-om the infinite set of data, a finite set of n-data is selected at random, the mean (x) of the sample
set (finite set) will not be the same as the population mean Jl. If size of the sample set increases (Le. n
becomes larger) then the difference between x and Jl decreases. If such different random sets are made
from the infinite population, then means of such sample sets of the given size (n data) will follow the
distribution of normal curve and their mean equals the true mean or population mean Jl and the standard
a
deviation is given by .j;, where n is the number of data in each sample set and cr is the standard
deviation of the whole population constituting the infinite set.

• Standard error or standard deviation of the mean: The distribution of means of the random
sample sets follows the normal curve and the dispersion decreases as the sample size increases (i.e. n
increases). In other words, the magnitude of random error depends on the sample size and standard
error of the mean is given by:
ry
The standard emor of the mean denoted by cr x or ~ is a good estimate of the uncertainty in and
the result is very often expressed as:
ra
ib
x ± ~ where ~ or cr x = ~ =standard error of the mean.
yl
em
In a more general way, the result is expressed as (cf. Sec. 13.7):
± ±:;;
x z~ =x
ch
where the value of z depends on the probability (ex) of the population mean or true
n mean (Il) to lie within the given range. This probability indicates the confidence
al
level (CL, cf. Sec. 13.7).

e
x ± z~ gives the confidence interval (CI) of J.L (cf.

th
In fact, Sec. 13.7).

e/
For z =~ or 0.67 (i.e. ex = 0.50, 50% probability zone), 0.67~ =0.67 cr/.j;, is called the probable
t.m
3
error of the mean. But this parameter is not very much meaningful and it is not presently used in
presenting the analytical data. For z = 1 (i.e. a =0.683), ~,i.e. a/.j;, is called the standard error of
e
the mean.
er
Illustration: Let us say that 100 replicate measurements of a physical parameter gives: x = 67.475
H
with the standard deviation 0.46.

k
It gives the standard error of the mean given. by:

lic
1 x cr _ 0.46 - 0 046 ( - 1)
C
A _
ZtJ - .j;, - J100 -. ,Z -
Thus the result may be written as: 67.475 ± 0.046 which means that the probability of the true value
(Il) to lie in the range 67.475 ± 0.046, i.e. 67.475 - 0.046 to 67.475 + 0.046 is 0.683 (i.e. 68.3%
probability zone).
If the result is written as: 67.475 ± 2~ = 67.475 ± 0.092 (i.e. z = 2 for which a = 0.955) then it
indicates that the probability of the true value (Il) to lie in the range is 0.955 (i.e. 95.5% probability zone).
It is evident that the magnitude of f3 (i.e. standard error of the mean) depends on the number of
observations and its magnitude decreases with the increase of the number of the observations
( cf cr x or ~ ~). Thus it is reasonable to mention the number of observations to express the standard
oc
error of the mean and the present result should be written as:
67.475 ± 0.046 (for 100 observations)
• Uncertainty in the standard error of the mean (OX or ~ = 0 / ~): It is given by
~/~(2 (n -I») ::= ~/~ when n is quite large. Thus the standard error of the mean is expressed as
follows:
Standard error of the mean = ~±J ~

2(n-I)
::= ~± t-
'\j2n
(when n » I); where ~ = ';-
'\jn
For the above mentioned result, f3 = 0.046 (for n = 100), it is to be written as:
Standard error of the mean = ~ ± J2 (n~ -1) = ~ (I ± J2 (n1 -1) J
ry
ra
=~(1+ 1 J
ib
~ - ~2(n-l)
yl
=0.046(1 ±
~2(100-I)
1
em
J
ch
al
= 0.046(1 ± 0.07)
e
It indicates the 7% uncertainty in the standard error of the mean.

th
• Standard error of the standard deviation: It is given by 0/ ~2(n -1). Thus the standard deviation
e/
(0) may be written as:

t.m
Standard deviation = 0" ± J 0" =0"(1 ± J 1 J

e
2(n -1) 2(n -1)

er
.Jk-)
H
=0"(1± when n» 1.
k
i
lic
~--------==----
----+ n (number of observations)
C
For the above mentioned result, i.e. 0 =0.46 and n = 100,

the standard deviation may be written as: Fig. 13.6.2 Qualitative representation of
variation of relative error in s (sample
Standard deviation = 0"(1 ± J2(1~ -I) J= 0.46(1 ± 0.07). standard deviation) with the number (n) of
observations.
Note: For the finite set of observations, we can use the sample standard deviation (s) to express the
standard error or standard deviation of the mean (~= s/~) and its uncertainty (= ~/~2(n -1) ).
i.e. standard error of the mean = ~ ± J2(n~ -1) = r

s
'\jn
s
± r x
'\jn
T--
1
2(n -1)
~ J;(1± J2(~-I)]-
Similarly, the sample standard deviation with its uncertainty may be written as:
sample standard deviation = s ± ~2 (: _ I) = s (1± ~2(~ _ I) )-

Obviously, uncertainty in s de~reases as the value of n increases. It has been graphically represented
in Fig. 13.6.2. In most of the cases, it has been noted that for n > 20, sand cr become practically the
same (i.e. s ::::: cr).
13.7 CONFIDENCE INTERVAL (CI) AND CONFIDENCE LEVEL (CL) AND PROBABLE
RANDOM ANALYTICAL ERROR
We have already seen that Jl (population mean) and cr (standard deviation) correspond to an infinite set
ry
of replicate measurements but in reality, we deal with a finite set of replicate measurements giving x
ra
and s which are only the estimates of Jl and cr respectively. Obviously, for a large number of replicate
ib
observations, they are the good estimates of Jl and cr. Statistically, we can find the probability of J.l to
yl
lie within a certain range or interval surrounding the x -value (experimentally determinedfrom afinite
em
set of replicate measurements). This interval is called the confidence limits and the probability of Jl to
lie within the CI is called the confidence level (CL denoted by a) which is often expressed as a
ch
percentage. The probability beyond the confidence level is called the significance level.
Illustration: Replicate measurements of Fe-content (x) in a sample gives the value, x = 25.75%. The
al
true value (i.e. population mean value Jl) lies in the interval 25.75% ±0.25% with a probability 0.95 (i.e.
e
95% probability). Then we can say: CI for Jl is 25.50% to 26.00% with CL = 95%. (i.e. a = 0.95), i.e.
th
Jl is expected to lie in the range 25.50 to 26.00% (Fe-content) with the 95% probability. In other words,
e/
95 times out of 100, the true mean Jl will appear in the interval (25.75 ± 0.25) % Fe.
t.m
(Note: The common misconception is: 95% of the experimental means would lie in the range (25.75
± 0.25)% Fe. Thus the meanings of CI and CL should not be confused.)
e
CI: The size of CI is obtained from the sample standard deviation s and the size of CI depends on
er
the relationship between s and cr. If s is determined from a large number of observations (i.e. s is a good
H
estimate of cr), then CI is relatively narrower and CI is relatively larger (for a desired CL) when s is
obtained from a fewer number of observations.
k
Let us consider the following two cases for CI.

lic
(A) Case-I (a is known or s is a good estimate of a): It happens so when a large number of replicate
C
measurements is done (i.e. s ~ cr or s::::: cr). In such cases, we can use the normal error curves (cf. Fig.
13.5.2) showing the plot, relative frequency vs. (x - J.1)/cr = z, i.e. deviation from Jl. divided by cr. The
area under the curve between the limits -z to +z indicates the percentage of observations lying between
the limits.
For example, for z = ±1, i.e. x - Jl = ±lcr, i.e. deviation of x from Jl by ±lcr, the curve under the limits
-1 to + 1 (i.e. -lcr to + lcr around Jl) covers about 68% area of the total area under the curve (limits: -00 to
+00) (cf. Fig. 13.5.2). It indicates that about 68% of the total observations will lie in the limits Jl ± lcr
i. e. -1 cr to + 1cr around J.1. If one experimental value is x from a data set with the standard deviation
cr, then we can say that the probability of the true mean Jl. to lie within the interval x ± lcr is -0.68 (i.e.
-68%). It gives the confidence level (CL) 68% and confidence interval (CI) x ± 1cr and the significance
level (probability beyond the CI) 32%.
In general, for a particular observed value x (when cr ::::: s, i.e. cr is known), the probability (CL or
a) of true mean II to lie within the range x ± zcr depends on the value z (Table 13.7.1).
X-fl
CI for fl = x ± za, i.e. ±z =- -
a
Table 13.7.1 Values of z and confidence interval (CI) depending on the confidence level (CL)
CI: x ± 0.670 x ± 10 x ± 1.280 x ± 1.640 x ± 1.960 x ± 2.580 x ± 30

z: 0.67 1.00 1.28 1.64 1.96 2.58 3.00
CL or a: 50% 68% 80% 90% 95% 99% 99.7%
Table 13.7.1 indicates that for the smaller degree of confidence (i.e. smaller value of a), the limits
for possible fluctuation of x become smaller (i.e. CI becomes smaller).
ry
If we use x (mean of n number of replicate measurements) which is a better estimate of fl, then we
ra
can write:
ib
CI for ~ =x± Ji; where J;, = standard error or standard deviation of the mean.
yl
i.e. ±z = (-x -fl )~
-
em
ch
a
It indicates that for a desired confidence level (i.e. a fixed), the confidence interval decreases as
al
the number of replicate observations increases.

e
th
(B) Case-II (a is unknown, i.e. s is not a good estimate of a): It happens so when a fewer replicate
observations are obtained and s is calculated from a small set of replicate measurements and conse-
e/
quently, s possesses an appreciable uncertainty (cf. Fig. 13.6.2) and classical theory of error is not
t.m
applicable in such cases. In reality, we deal with a finite number of observations and we do not know
fl and a. The observed x and s values are only the estimates of fl and a respectively.
e
Here we define the statistical quantity t (called student's t) in the same way as done for z (cf.
er
Case-I).
H
X-fl x-fl
±t =- - (for a single observation); cf. ± z = - -
k
s a
lic
x - fl ~ x - fl (- )~
C
and ±t = / r = (x - fl)- (for n observations); cf ± z = / r = x - fl -

s \In s a \In a
It gives: CI for fl = x ± ts (for a single observation); (cf. CI = x ± za)
_ ts _ za
and CI for ~ = x ± ~ (for n measurements); CI = x ± ~
t s
The equation, CI (for ~) = x ± J;; indicates the probability (a) of population mean (~) to lie within
a certain region around x (experimental mean).

(C) z vs. t: It has been already shown that the value of z depends on the value of confidence level (Table
13.7.1). Similarly, the value of t also depends on the choice of confidence level (Table 13.7.2). In
contrast to z, the t-value not only depends on the CL (i.e. a) value but also it depends on the number
(~f observations (cf Table 13.7.1 vs. Table 13.7.2). For a particular CL or a-value, the t-value decreases
as the number of observations (n) increases and the limiting value of t (i.e. too) becomes identical with
the z-value for a certain CL or a-value, i.e.
too(i.e. n ~ 00) = z
The inverse relationship between the t-value and n (number of observations) is quite expected. For
the smaller number of observations (i.e. smaller value of n), the less information is· available for esti-
mating the population parameters and it is compensated by the increase of t-value.
In using Table 13.7.2, we must consider the degrees of freedom (K) given by: K = n -1, i.e. degrees
of freedom is less than the number of observations by unity. The degrees offreec.!lJm is defined as the
number of individual observations that can vary for the fixed values of x and s in a particular finite
set of observations. Obviously, all but one observation can be varied (i.e. out of n values of x,
(n - 1) values are varied), and the last remaining value of x is automatically determined by the fixed
ry
value of x and other (n - 1) values varied. It gives the degrees of freedom n - 1.
ra
Table 13.7.2 Critical t-values (fer;t) for various levels of probability or confidence and different numbers of
ib
observations (n).
yl
em
No. of No. of degrees terit values at different probability levels/confidence levels
observations offreedom =
(a 0.5) =
(a 0.8) =
(a 0.9) (a = 0.95) (a = =
0.99) (a 0.999)
=0 -
ch
(0) (K 1) 50% 80% 90% 95% 99% 99.9%
al
2 1 1.00 3.08 6.31 12.71 63.66 637.0
3 2 0.82 1.89 2.92 4.30 ~.92 31.60
e
th
4 3 0.76 1.64 2.35 3.18 5.84 12.94

5 4 0.74 1.53 2.13 2.78 4.60 8.61
e/
6 5 0.73 1.48 2.02 2.57 4.03 6.87

t.m
7 6 0.72 1.44 1.94 2.45 3.71 5.96

8 7 0.71 1.42 1.90 2.36 3.50 5.41
e
9 8 0.71 1.40 1.86 2.31 3.36 5.04

er
10 9 0.70 1.38 1.83 2.26 3.25 4.78

H
11 10 0.70 1.37 1.81 2.23 3.17 4.59

21 20 0.69 1.32 1.73 2.09 2.84 3.85
k
41 40 0.68 1.30 1.68 2.02 2.70 3.55

lic
61 60 0.68 1.30 1.67 2.00 2.62 3.46

C
0.67 1.28 1.64 1.96 2.58 3.29
(D) Probable random analytical error (~) for a certain confidence level (CL or a): It is given by:
(i) L.= ± ~:' (Cf. CI for Il = x ± ~ } (when (J ... s)
(ii) L. =± ~, (Cf. CI for Il = x ± ~ } (when (J is unknown)
In real analysis (i.e. (j is unknown), we are interested with the second relationship where ta gives the
student's t-value for the confidence level (1" s = sample standard deviation and n = number of experi-
mental observations. The value of L gives the measure of precision in the analysis. In ether words, it
gives the measure of influence of random error on the result. Thus confidence interval (el) of the true
mean valu.e of x is given by: x ± ~
It is evident that with the increase of the number of observations (i. e. n increases), ta rapidly decreases
(cf Tabl~ 13.7.2) and J;, increases and thus they jointly reduce the magnitude of I (probable random
error) and it narrows the confidence interval of the true value. However, this effect is pronounced most
for the smaller values of n. After a certain value of n, the effect becomes almost constant. At such
saturation point, there is no need to spend time and reagents to increase the value of n.
Illustration: In a given brass sample, volumetric method of analysis of Cu-content gives the results
(%): 67.40,67.48,67.37,67.43 and 67.47 (i.e. 5 replicate measurements).
It gives:
x =!(67.40 + 67.48 + 67.37 + 67.43 + 67.47)%

5
ry
= 67.43%
ra
%ofCu Deviation from Square deviation
ib
Ix
mean i.e. -xii = Idil (x -Xi )2 =df
yl
67.40 0.03 0.0009
em
67.48 0.05 ch 0.0025
67.37 0.06 0.0036
67.43 0.00 0.0000
al
67.47 0.04 0.0016

e
th
Lld;1
x = 67.43 d av = -5- = 0.0360/0 I d;2 = 0.0086
e/
t.m
average deviation of the mean =~ = 0~6 % = 0.016%.

e
er
s = ~Ld; = ~0.0086 . . of the mean = AtJ = 0.046 = 0.0 20-10)

H
-- - - % = 0.046%; (standard devIatIon S

r = ~% 01.
n-l 4 . "n ,,5

k
~ 1.25 x dav = 1.25 x 0.036% = 0.045%)

lic
(cf s
x ± ~ = (67.43 ± 0.02)%
C
The result is very often expressed as
· f .. ( ) s x 100 0.046 x 100

CoeffiICIent 0 vanatlon CV =- - - = = 0.068
x 67.43
Probable analytical error (~) = ± Ji;

Let us consider a = 0.95 (i.e. confidence level is 95%).
For degrees of freedom =5 - 1 = 4, ta = 2.78 (see Table 13.7.2). It gives:
1: = ± 2.78 x 0.046 % = ± 2.78 x 0.046 % = ± 0.057%

15 2.236
Thus the confidence limits to contain the true value (J.l) is given by: (67.43 ± 0.057)% when confidence
level is 95%.
For a = 0.99, ta = 4.6 and we get:

_ 4.6 x 0.046 01. 0 09501
I - ± 15 70 -
-
±. 1'0
It gives the confidence limits of the true value as: (67.43 ± 0.095)% when the confidence level is
99%. It indicates that CI increases as the a-value increases.
For n ~ 00, too ~ z and s ~ 0', i.e. classical theory of error becomes applicable. In this condition, for
a = 0.99 (i.e. 99% confidence level) we get:
2.58 x 0.046
E= ± 15 % = ± 0.053% ; (cf t~ = 2.58; see Table 13.7.2)
If gives the CI for the true value = (67.43 ± 0.053)%
ry
It gives the narrower confidence interval (cf. ±0.053 vs. ±0.095).
ra
ib
13.8 TESTING FOR SIGNIFICANCE (HYPOTHESIS TESTING) AND CRITERIA FOR
yl
REJECTION OF AN OBSERVATION
em
13.8.1 Comparison of the Mean Values (t-test)
When a particular sample is analysed by two different methods, the mean values obtained are different.
ch
Statistics cannot tell us which value is right or wrong. Now the question is: is the difference between
the mean values significant?
al
If the random errors are responsible for this difference, the sample t-test can tell us whether the mean
e
values differ significantly or not. The statistical aid to this problem is to use the principle of null
th
hypothesis which states that the two observed mean values are identical. The t-test can verify the
e/
correctness of the null hypothesis with a certain confidence level (say 95% or 99%). It is illustrated for ,...
t.m
two sets of data. I), -
Set-I: xl (mean value), Sl (standard deviation), nl (number of observations), ~l (standard deviation of

e
2
i:- and ~~ (variance of the mean) =~.n
er
the mean) =
Vnl
H
S s2
Set-II: x2 ' ~2 = d:- and ~~ =- l . We are interested to determine the difference between the
k
s2' n 2 ,
Vn n2
lic
2
means.
C
tli=!(x) ±~))-(X2 ±~2)1 = Ix) -x21±~=lx) -x21±~~~ +~~

J3 = standard deviation of the difference of the means. If the replicate data are collected in the same way
for the both sets, then it is reasonable to assume that the standard deviations of both the data sets are
more or less comparable (i.e. Sl ::::: S2). It gives:
=lx -x 1 ~
l 2
S nl +n 2
Thus the calculated t-value can be compared with the critical t-value for a degree of freedom
nl + n2 - 2 (see Table 13.7.2) at the desired confidence level. If the calculated t-value is smaller than
the critical t-value at the desired confidence level (i.e. t ealc (t erit ), then the null hypothesis is substantiated,
i.e. there is no significant difference between the mean values (Xl and x2 ) of two sets of data at the
desired confidence level. On the other hand, for the condition, tealc ) terit (i.e. calculated t-value is greater
than the critical t-value at the desired confidence level), the null hypothesis is incorrect, i.e. Xl and x2
differ significantly and then we should find out the reason behind this significant difference.
ry
13.8.2 Comparison of Precision (Variance Ratio Test or F-test)
ra
This statistical test can tell us whether there is any significant difference between Sl and S2 which are
ib
-+
s2
yl
the sample standard deviations of two sets of data. For this purpose, the ratio F = (where Sl > S2 to
em
s2
make F > 1) is evaluated and compared with the critical F-value at the desired confidence level (see
Table 13.8.2.1). If the calculated F-value is greater than the critical F-value (i.e. F eale ) F erit) at the
ch
desired confidence level then it is concluded that 81 and 82 (measuring the precisions of two sets of
al
observation) differ significantly. Under the condition, F cale ( F erit, the sample standard deviations do
e
not differ significantly at the desired confidence level.

th
e/
Table 13.8.2.1 Critical F-values at the 95 % confidence level.

t.m
(n -1)for Degrees offreedom (n -1) for larger S2 (i.e. numerator)

smaller S2
(i.e. denominator) 2 3 4 5 6 10 20
e
er
2 19.00 19.16 19.25 19.30 19.33 19.40 19.45 19.50

H
3 9.55 9.28 9.12 9.01 8.94 8.79 8.66 8.53

4 6.94 6.59 6.39 6.26 6.16 5.96 5.80 5.63
k
lic
5 5.79 5.41 5.19 5.05 4.95 4.74 4.56 4.36

6 5.14 4.76 4.53 4.39 4.28 4.06 3.87 3.67
C
10 4.10 3.71 3.48 3.33 3.22 2.98 2.77 2.54

20 3.49 3.10 2.87 2.71 2.60 2.35 2.12 1.84
3.00 2.60 2.37 2.21 2.10 1.83 1.57 1.00
Illustration: A brass sample was analysed by two different methods to find out the Cu-content. The
results are:
Analysis-I: Xl (Cu-content) = 64.35%; Sl = 0.25%, nl = 6
Analysis-II: x2 (Cu-content) = 64.65%, S2 = 0.20%, n2 = 5
(a) Are the mean values significantly different at the 95% confidenc~ level? (b) Are the standard
deviations significantly different?
Solution: (a) t-test can give the answer. The t-value can be calculated using either Sl or S2 value. Here
it is done by using the Sl value (0.25%).
tcalc _IXI - X21 J ~1lz

-~-~
s n1 +~
t )64.65 - 64.351 )6 x 5 = 0.30 [30 =1.2 x .J2.73 =1.98

i.e. calc 0.25 6+5 0.25 '111
terit (for the degree of freedom = nl + n2 - 2 = 6 + 5 - 2 = 9) at the 95% confidence level = 2.26 (see
Table 13.7.2). It gives: t eale = 1.98 ( terit = 2.26
i. e. the null hypothesis is correct and the difference between the mean values is not significant at the
95 % confidence level.
s; (0.25)2 ( )
ry
(b) Fcalc =2"" =- - - 2 = 1.56; cf. sl > s2
ra
s2 (0.20)
Sl (larger value): n - 1 = 6 - 1 = 5 and for S2 (smaller) = n - 1 = 5 - 1 = 4
ib
For
F erit = 6.26 (see Table 13.8.2.1).
yl
It indicates: Ferit ) Fealc (at the 95% confidence level), i.e. the standard deviations are not significantly
em
different. ch
13.8.3 Criteria for Rejection of an Observation
al
Sometimes, an outlying result (that appears to reside outside the range of random errors) appears to be
e
out of the range of other replicate data. The outlier may appear due to some undetected gross error or
th
mistake and the outlier must be rejected. However, there must be some criteria for rejection or retention
of a suspected result (i.e. outlier). For this purpose, some empirical rules have been formulated.
e/
(i) 2.5dav rule: Mean value of the reliable or good results is calculated (excluding the suspected
t.m
result) and average deviation (dm ,) of the good results is determined. If the deviation of the suspected
result from the mean of the good results is greater than or equal to 2.5dav' then the suspected result is
e
to be rejected for further consideration.

er
Illustration: Let the replicate results be:

H
Xl' X2' X3' X4' Xs and X6 where X3 appears to be an outlier.

k
X ( for the good results ) = Xl +X2 +X4 +XS +X6

lic
5
Llx; - xl; i = 1, 2, 4, 5, 6; i:t- 3
C
day (for the good results) =.-. ;,-'- - - - - - - - - -

5
i.e.
IXI - xl + IX2 - xl + IX4 - xl + Ixs- xl + IX6 - xl
day = 5
It gives:
d (for the outlier) = IX 3 - xl
If, d ~ 2.5dav ' then X3 is to be rejected and if d < 2.5dav ' then X3 is to be retained.
Limitation of the 2.5dav rule: The limit for rejection under this rule is very small and many valid data
may be rejected and it will introduce an 'error of first kind'. To avoid this, the limit has been extended
in the 4dav rule.
(ii) 4dav rule: Here the limit of 2.5dav rule has been extended and the condition of rejection of the
suspected result is: d ~ 4dav•
Note: There is no statistical justification behind the 2.5dav or 4dav rule. The 2.5dav or 4dav rule is
applicable for rejection of one result from a large group of data say 4 to 10 replicate data (i.e. n ~ 4),
but not for the smaller group of data (e.g. rejection of one result from a group of 3 replicate data cannot
be done).
(iii) Q-test: This test for rejection of the outlier is statistically justified. The Q-parameter is calculated
as follows:
the difference between the suspected result (say x s ) and its nearest neighbour (say xn ) is divided by
the range (R) of the entire set of results, i.e.
ry
The calculated value of Q (i.e. Qeale) is compared with the critical value of Q (i.e. Qerit) at the desired
ra
confidence level (Table 13.8.3.1). If Qealc) Qcrit' then the suspected result is to be rejected with the
ib
indicated degree of confidence. On the other hand, for the condition, Qeale ( Qerit' the suspected result is
not to be discarded.
yl
em
Table 13.8.3.1 Critical values of the rejection quotient (Qerit) at different confidence level.
ch
No. of Critical Q- values
Observations QO.99
al
QO.90 QO.95
e
3 0.94 0.97 0.99

th
4 0.76 0.83 0.93

e/
5 0.64 0.71 0.82

t.m
6 0.56 0.62 0.74

7 0.51 0.57 0.68
8 0.47 0.53 0.63
e
er
9 0.44 0.49 0.60

10 0.41 0.47 0.57
H
Condition of rejection: or
k
Qcalc Qobs ) Qclit

lic
Statistical Tests: Comparison of the mean values and sample

C
standard deviations; and rejection of a data.

• I-test (comparison of the mean values): t ealc ( terit ==> the mean values are not significantly
different at the desired confidence level (i.e. the null hypothesis is substantiated).
• F-test or variance ratio test (for comparison of the sample standard deviations or
precisions): F ealc ( Ferit ==> the standard deviations are not significantly different at the desired
confidence level.
• Q-test (rejection of a result of an observation): Qeale ( Qerit ==> the result is not to be rejected
at the desired confidence level.
Illustration: A sample of soda ash (Na2C03) was analysed and the percentage of Na2C03 was found
for 5 replicate estimations as follows:
40.55, 40.58, 40.50, 40.62, 40.70
The last value appears to be a suspected one. Apply the different tests to discard or not the data.
Solution: Let us find the mean value of the good results.

x (%) 40.55 40.58 40.50 40.62 x = 40.56%
deviation (%) = 0.01 0.02 0.06 0.06 = 0.0375%
dav
I
=:: 0.038%
Deviation of the suspected result from the mean of the good results =d = 140.56 - 40.701% =0.14%
• 2.5dav rule: 2.5 x 0.038 = 0.095 < 0.14, i.e. the suspected result is to be rejected.
• 4dav rule: 4 x 0.038 = 0.152 > 0.14, i.e. the suspected result is not to be rejected.
• Q-test: For n =5, Qcrit =0.64 (90% confidence level) and =0.71 (95% confidence level) (cf. Table
13.8.3.1).
Q
calc
= lx, - x I n = 40.70 - 40.62 = 0.08 = 0.4
x max x min 40.70 - 40.50 0.20
ry
-
It indicates: Qcalc = 0.4 < Qcrit (for both the 90% and 95% confidence level).
ra
Thus the suspected result is not to be rejected at the both 90% and 95% confidence level.
ib
yl
13.9 PROPAGATION OF RANDOM ERROR: ACCUMULATION OF RANDOM ERROR IN
em
THE COMPOUND QUANTITIES
Let us first consider the simplest case, y = f(x), i.e. y is a function of one variable x which is an
ch
experimental quantity with the random error Bx (say). Let the error in y be by due to the error Bx in x.
The error By can be estimated by using the principle of calculus as follows:
e al
. By dy. by dy ~. .
11m ~ =-, I.e. ~ ~ -when uX IS sufficIently small.
th
ox~O uX dx uX dx
e/
It gives: By "" ( : )Bx

t.m
The fractional or relative errors in y and x are:

e
by bX
f y =- andfx =- respectively.
er
y x
H

y =f(a, c, b, ... ), i.e. y is a function of the experimental variables which are independent.
k
The error in the compound quantity y is by and it is determined by Ba, Bb, Bc,... present in the
lic
experimental quantities a, b, c, ... respectively. We can determine By by taking the partial derivative of
C
y with respect to each variable.
By "" (~: ) xBa + (~~) xBb + (~~) xBe +...

b,c,... a,c, ... /' a,b, ...
i.e. BY""(~:)xoo + (~~)XBb + (~~)xBe +...... ... (13.9.1)

(expressed so for the sake of simplicity)
Here (~:) x Ba (= partial derivative with respect to the variable a x uncertainty in the variable
quantity a) is the error in y due to the error 00 in a only. Similarly, (~~) x Bb is the error in y due to
the error Bb in b only.
The above expression of By is described as the principle of superposition of errors.
Here 8a, 8b, 8c, ... are the respective random errors and they are independent. Consequently, they
can have any value between -Ea and + Ea , -Eb and +Eb , -Ec and + Ec "" respectively. Thus, if y is a
function of more than one variable, then their respective random errors may combine in different
possible ways (Illustration 1). The maximum error (SY)max may be obtained as follows:
... (13.9.2)
To find the standard deviation in y from the standard deviations of a, b, C, ••• for n-replicate
determinations or observations, Equation 13.9.1 (i.e. expression of 8y) is to be squared, summed up for
n-replicate observations, divided by (n-l) and then square root of the result is to be taken (cf definition
of standard deviation, Sec. 13.6E).
ry
<=[(~~r (8a)2 +(~~r (8b)2 +(~~r (8c)2 + ]+
ra
(8y)2
ib
yl
2[ (~~)( ~~ }&) (8b) + (~~)(~~ }&H&) +
em
]
= sum of square terms + 2 x sum of cross terms.
ch
... (13.9.3)
Here, 80, Db, 8c, ... are the respective random errors and they are independent. The square terms are
al
always positive. In the cross terms (i.e. covariances), the products such as (8a) x (8b) are just likely
e
to be negative as positive in anyone determination or observation, i.e. some of the cross terms are
th
negative and others positive. When average of a large number of determinations (i.e. n is sufficiently
e/
large) is taken, the sum of all the cross terms approaches to zero. Under this condition, the sum of
Equations for n-determinations (i.e. i = 1 to n) can be expressed as follows:
t.m
L(8Yi/ =(~~r L(&i)2 +(~~r L(8bi/ +(~~r I(8c )2 + .

e
i
er
It leads to:
H
... (13.9.4)
k
lic
We can write:
C
L(8y; )2 L( __ )2
y; Y =Sy2 ( I.e.
. .
vanance if Sec. 13 .6) ,
0 f y; c.
n-l n-l
L(8a;)2 L(a;-a)2
-~-~ = s~ (i.e. variance of a), and so on.
n-l n-l
Thus, Equation 13.9.4 may be represented as follows:
s~ =(~~ y +(~~ rsi +(~; r +.. .

s; s;' ... (13.9.5)
In general, the most probable random error (E.v) in y is given by:
da db
l
E y2= (-dy ')2 E a2+ (-dY )2 Eb2+ -dy )2 Ec2+
,dC
. ... (13.9.6)
where E a , E b , E c ' ••• denote the largest random error associated with the experimental variables a, b, C, •••
respectively. Thus we can say that the most probable random error (Ey ) is the square root of the sum
of squares of the largest error [e.g. (~~ x E a J] due to an error in each variable.
Illustration 1: y = na + mb; nand m free from error; a and b are the experimental quantities with
errors.
y y
By =( a ) Ba + ( a ) Bb
aa b ab a
ry
y
a ) = n(aa)+m(ab) = n xl +m xO = n
( aa
ra
b aa aa
ib
y
a ) = n x 0 + m X 1= m
yl
Similarly, ( ab
em
a
·
I t gIves: ~ = nua
~ + mu~b ; or -By (i.e.
. re I·
atlve error ) = nBa + -mob
--
ch
uy
Y na+mb na+mb
al
Assuming covariance between a and b to be zero, we can write:

e
For y( ±Sy) = na(±sa) + mb(±sb)

th
e/
t.m
e
er
y y
H
For, y=na-mb,(a ) =n and (a ) =-m

aa b ab a
k
lic
It gives: s2y = n 2s2a + (_m)2 s2b = n 2s2a + m 2s2b

C

For, Y = na ± mb ± pc, i.e. y(±Sy) = na(±sa) ± mb(±sb) ± pc(±sc)
or, Sy -_\jIn 2 Sa2 + m 2 Sb2 + P2 Sc2' ·i.e. E y -_ ~ 2E 2

n a
2 2 2
+ m Eb + P Ec
2
Let us take the case, y = a - b + c where the values are:

a = 4.25 ± 0.06, b = 2.50 ± 0.02, c = 7.45 ± 0.04
Ey (max) = +0.06 + 0.02 + 0.04 = 0.12; or - 0.06 - 0.02 - 0.04 = -0.12
Ey (min) = +0.06 - 0.02 - 0.04 = 0; or - 0.06 + 0.02 + 0.04 = 0
However, the standard deviation of y or the most probable value of the random error in y will be
between the above two extreme values and it is given by:
Sy or E y = ~(0.06)2 + (0.02)2 + (0.04f = ~5.6 x 10-3 "" 0.07

It gives: y = (4.25 - 2.50 + 7.45) ± 0.07 = 9.2 ± 0.07
Illustration 2: y = nab, (n = free from error)
y
Oy =( a ) Oa + ( dY ) ob = nb x Oa + na X ob
aa b db a
Oy nbOa naOb Oa Ob
or, -=--+--=-+-
Y nab nab a b
ry
(ef In y = In n + In a + In b; taking differential of the equation, we get:
ra
ay = aa + ab, i.e. oy "" Oa + Ob; c/. ~(lnx) =~, i.e. a(lnx) = ax
ib
y a b y a b ax x x
yl
i.e. fractional error in y ::::: fractional error in a + fractional error in b
em
To find the standard error or most probable random error in y, we can write:
For, y (±Sy) = na (±sa) x b (±Sb)
ch
2 ( dy )2
al
2 ( dy )2 2 22 22
SY = aa b Sa + ab a Sb = (nb) Sa + (na) Sb
e
th
e/
or,
t.m
2
(~) +( ~ )
2 2]1/
e
i.e. ; (i.e. relative standard deviation of y) = [

er
H
k
or,
lic
C
Ef(y), Ef(a) and Ef(b) denote the respective fractional errors.

Let us take the case of a rectangle whose the lengths of sides are measured with 2% and 3% error.
Thus in the calculated area, the maximum possible error is 5% (assuming the addition of errors with
the same sign) and the minimum possible error is 1% (assuming the additions of errors with the
opposite sign). But the most probable error will lie between these two extreme values.
Now let us calculate the most probable fractional error in the calculated area of the rectangle
having the relative fractional errOiS 2% and 3% in the measurements of lengths (say a, b), i.e.
y (area) = ab; Ef(a) = 0.02 and Ef(b) = 0.03
Ef(y) = ~(0.02)2 + (0.03)2 =0.036
i.e. the most probable fractional error in the calculated area is 3.6% (ef Ef(y)(max) =5% and Ef(y)(min) = 1%
but the most probable value of Ef(y) = 3.6%).
THE T' ''=ORY C'F ERRORS AND STATISTICAL TREATMENT OF ANALYTICAL DATA 2147
ltIustration 3: y = n ( ~ ) where n is free from error, i. e. In y = In n + In a - In b
It gives: Oy = Oa _ ob = Oa +(_ Ob);

Y a b a b
Y
[ e!.oy=(dda ) b.oa+(dY)
db a
Bb;(dY)
da b
=~,(ay)
b db a
i.e. By = ~x Ba +(- naJBb, or By = nb x Ba +(- nabnab x BbJ or, ByY = Baa +(- Bbb)]
ry
b b2 y bna 2
ra
ib
. For Y = n (a)
We can wrIte: - ,y (±Sy ) = n-(--)
a(±sa) ,
yl
b b ±sb
i.e.
em
ch
al
2s2 2 2
n a n a 2
e
=-2-+-4- Sb
th
b b
e/
2 22 222 2 2
Sy n b 2 nab 2 Sa Sb
2 = 222 Sa +224 Sb =-2 +2
t.m
i.e.
Y bna nab a b
It gives:
e
er
H
k
lic
or,
C
ab ( ) a (±sa) X b(±sb)
In the same way, for y = - , we can write: y ±Sy = (+)
e e _sc
Iny = Ina+lnb-Ine, l.e. By Oa Bb ( -Be)

. -=-+-+ -
Y abe
Dlustration 4: y = ntr (where n and x free from error)
It gives: Iny=lnn+xlna, i.e. oy zx Oa

y a
It gives: s; x(s; ). or ; x( ~a i.e. relative error in y = xx relative error in a

:= := ).
Illustration 5: y = nax!JY where n, x and y are free from error. It gives: In y = In n + x In a + y In b

By Ba Bb
. -~x-+y-
I.e. y a b
ry
i.e.
ra
ib
yl
or,
em
Illustration 6: Let us take some specific cases. ch
• Ideal gas law: PV = nRT, i.e. P = nRT, R = gas constant (free from error). Let us calculate the
V
al
accumulated error in P due to the errors in n, T and ~ We have:

e
th
op:= (~= jon + (~~ JOT + (~~ )ov

e/
-l'
t.m
or, 2
Sp -
ap )2 2 (ap)2
an Sn + aT
2+ ( av
ST
ap)2 2
Sv
e
er
Here, ap ') = RT (ap) = nR(ap) =_ nRT

( an V2
H
V' aT V' aV
k
2_(-RT)2 Sn2+ (-nR )2 ST2+ (- -nRT)2 2

lic
It gives: Sp - 2- Sv
V V V
C
or,
i.e. Ep:=(~) T2E;+n2Ei+n2T2(~J

In terms of relative error, we can write:
S~ =( RT)2 x (~)2 s2 + ( nR)2 x (~)2 s2 + (_ nRT)2 (~)2 s2

p2 V nRT n V 2 nRT T V nRT v
i.e.
~ [c:=r i r ~ rr +( +(
2
; =[(~ r+(i r+(~ rr

2
or,
It may be noted that the above relation can be attained more easily as follows:
P= nRT, i.e.lnP=lnn+lnR+lnT-lnV
V
ry
oP = On +oT +(_ OV)
ra
It gives:
P n T V
ib
(~r =(5nn r+(5;r+(5:r
yl
i.e.
r r r]
~n +(i + (~ em
ch
i.e. ; =[(
e al
• Area (y) of a circle of radius (r): y = n,J-

th
e/
It gives: dy =21tr, i.e. 5y == 21tr5r (assuming 5r small).

dr
t.m
The relative or fractional error in area (y) is given by:
=2 5r , i.e. 2 =2~ or, Ey = 2 Er

e
5y == 21tr5r
'Itr 2
er
y r Y r Y r
H
It indicates: fractional error in area is approximately twice the fractional area in radius. For example,
if the uncertainty in the measurement of radius is 3%, the uncertainty in area becomes about 6%
k
(d)3 = 4
lic
4 3 = -'It
• Volume of a sphere (y) = -1tT
4 - 1 d 3 = _d
-'It X - X
'It 3
C
3 3 2 3 8 6
(r = radius, d = diameter)
dy =
dr 3
±1t x 3r 2
= 41tr 2 , i.e. Oy ~ 4'Itr 2 0r
2
5y == 41tr X3 5r =3(Or),i.e. E
y =3(Er )
or,
y 41tr 3 r y r
It indicates: fractional error in volume = 3 x fractional error in radius. When the error in diameter is
considered,
5y 31tlP X6 5d =3 &l
or, y ~ 1td 3 X6 d
i.e. fractional error in volume ~ 3 x (fractional error in diameter)

• Volume of cylinder (y) = nr'lh, r = radius and h = height

Oy::::;(aY)or+(aY)Oh; ay =2rcrh and ay =rcr 2
ar ah ar ah
: : ; (2rcrh) Or + (rcr 2 )Oh
i.e.
cf. Iny = Inrc + 2lnr + lnh, l.e. Oy 2Or- +Oh)

. -::::; -
ry
( y r h
ra
It leads to:
ib
yl
Say, r = (4.5 ± 0.1) em and h = (10.7 ± 0.2) em
em
ch
J2 = (2 x 0.1)2 +( 0.2 )2 = 1.97
al
Ey X 10-3 + 3.49 X 10-4

i.e. ( y 10.7
e
4.5
th
e/
E
--l'- = 4.82 X 10-2 or, E y = rc(4.5)2 (10.7) x 4.82 x 10-2 ::::; 32.8 em 3
t.m
or,
y
i.e. Volume =y ± Ey = y ± y x 4.82 10-2 = y(l ± 4.82 x 10-2)

e
X
er
It gives: volume = n(4.5)2(10.7) ± 32.8 = 680.4 ± 32.8 em3

H
• Determi.nation of g from the oscillation of simple pendulum:

k
4rc 2Z 2 ag 81t 2 Z
lic
.. ag 4rc
g = -- and It gIves: - = - -2 , - = - - 3-
2
T az T aT T
C
We ean write: Bg~(~nBI+(~: )BT
i.e.
or,
cf. lng = In ( 2 + InZ- 21nT, l.e.

4rc) Og -oZ - 2oT
. -::::; -)
( g Z T
THE THF0RY OF ERRORS AND STATISTICAL TREATMENT OF ANALYTICAL DATA 2151
It leads to:
i.e.
Exponential function: y = exp(mx) (say), i.e. : = m x exp(mx), i.e. Oy = myOx

. by . Ey
ry
It gIves: - = mbx, l.e. - = mEa
y y
ra
• Determination of viscosity coefficient (11) from Poiseullie's equation:
ib
4
yl
T\ = 1tPr t where I = length of the cylindrical tube of radius r;
em
81m
m = mass of the liquid passing through the tube in time t,
ch
P = pressure difference.
al
i.e. In T\ = In( i) + InP + 4lnr + lnt -lnl-Inm

e
th
It gives:
e/
bTl bP 4br bt b1 bm
-::::::::-+--+-----
t.m
Tl P r t 1 m
Here r is very small and consequently its fractional error is the most important term to determine the
e
error is ll.
er
From the above equation, the most probable error can be calculated as usual.
H
Illustration 7 (trigonomeric function): y = sina, i.e. dy = cosa

k
da
lic
Oy"" (cosa)&z ; or Oy "" (c~saJba = (cota)ba

C
It leads to:
y SIna
E
i.e. -y =Eacota
y
In the same way, it can be shown:
E
for y = cosa, - y = Ea tan a
y
dy ~ ~
for Y = tana, - = sec 2
a, .l.e. uy:::::::: 2
uasec a
da
2
and by =ba(sec a)=ba( 1 )
y tan a sinacosa
[cf ~(sin X) = cosx, ~[sin (X + a)] = cos(x + a); ~(cosx) = -sinx

~ ~ ~
~[cos(x+a)] = -sin(x + a); ~(tanx) = sec 2 X,

dx ~
~[tan(x + a)] = sec 2 (X + a); ~[cot(x + a)] = -cosec 2 (X + a);

dx dx
~[sec(x + a)] = sec(x + ahan (X + a);

dx
ry
~[cosec(x + a)] = -cosec(x + a)cot(x + a).]
ra
dx
ib
yl
Illustration 8: y = logIoa, i.e. y = logiO a, i.e. y = _I-Ina
2.303
dy =_l_~(lna)=_l_x!, i.e. oy=_l_ x oa;

em
ch
It gives:
da 2.303 da 2.303 a 2.303 a
al
= _ 1 (!.E.-J. E = _ 1 (E a J
e
Of, S
th
y 2.303 a ' y 2.303 a .

e/
3
For example: y --I og [2 .00(+0
_. 02) x0- 1_ x 0.02 x 10-3
t.m
l3 ,
].
I.e. Sy -
__
2.303 2.00 x 10-
e
= 4.34 X 10-3 ~ 0.004.

er
It gives: log[2.00(±O.02) x 10-3 ] = -2.699 (±0.004)

H
k
Illustration 10: y = anti loglOa = loa, i.e. log y = a

lic
~(Iny) = 2.303(da J; or, ~(Iny) dy = 2.303

C
It gives: _l_ Iny = a; or, Iny = 2.303a, i.e.

2.303 da da dy da
Of,
dy = 2.303da, i.e. Oy ~ 2.3030a (when oa small).
y y
Sy Ey
It gives: - = 2.303 sa ; Of - = 2.303Ea
y y
S
For example: y = antilog 1o [7.45 (±0.05)], i.e. --Z. = 2.303 x (0.05) = 0.115
y
i.e. Sy =2.82xl0 7 xO.115=0.32x10 7
It gives: antilog [7.45(±O.OS)] = 2.82(±O.32) X 107 .

Illustration 9 (exponential function): y = A exp(mx), (say)
It gives: dy =~[Aexp(mx)] =Aexp(mx)~(mx) =[ Aexp(mx)]m =my

dx dx dx
i.e. Oy = mOx', or ~ =msx'. or E = myEx

y y .V
(
Cf. Iny =InA + mx, i.e. ~(Iny) =m; or ~(Iny) dy =m; or.!.. dy =m; or dy =myJ.
dx dy dx ydx dx
ry
Table 13.9.1 Some representative working formulas to calculate the propagated random error in y due to the
random errors in the experimental quantities a, b, C, •••
ra
Function Propagated e"or in y Function Propagated e"or·in y
ib
yl
(i) y=a±b±c = ~ Ea2 +Eb2 +Ec2 (viii) y = ncr E; =x(~ )
em
Ey
Ev
= na Ey =~n2E2a
+m 2b
E 2 +p 2E 2 = sin a -=- = Ea cota
ch
(ii) y ± mb ± pc c (ix) y
y
al
(~r+(~r
Ey E
= cos a ~= Ea tan a
e
(iii) y = nab y
(x) y
y
th
e/
(~ar+(~r
Ey
y=n(~)
Ey Ea
(iv) (xi) y = tan a
t.m
y y sinacosa
Ey
r r
(X~a +(Y:b (E-;;a)
e
(v) y = ncrbY (xii) y = loglOa 1

Ey = 2.303
er
(~a r+(~ r+(;r

H
Ey Ey
(vi) y = abc (xiii) y = antilog1oll -=2.303Ea
k
y y
lic
(~r+(~r+(;r
Ey
C
ab . Ey
(vii) y=- (iv) y = A exp (rna) Ey =myEa , I.e. - = mEa
c y y
n, x, y free from error. Ey, Ea, Eb, Ec,'" denote the random error associated with y, a, b, c, ... respectively. These errors may
be taken as the standard deviations.
13.10 ROUNDING-OFF NUMBERS, SIGNIFICANT FIGURES AND COMPUTATION RULES

13.10.1 Rounding-off Numbers and Rules of Rounding-off Numerical Values
Rounding-otT numbers: It generally means retaining upto a certain number of digits after the decimal
point and discarding the other decimal points. For example, to round-off J7
(= 2.64575131 ...) to two,
three and four places of decimal, we get 2.64, 2.646 and 2.6458 respectively.
In rounding-off the numerical data, the general rules are:
(i) If the last digit to be dropped is less than 5, then it is simply dropped without any modification
of the preceding digits.
(ii) If the last digit to be dropped is greater than 5, the preceding digit is increased by one.
(iii) If the last digit to be dropped is 5, then the preceding digit is rounded to the nearest even number.
This convention eliminates the tendency to round-off the data in one direction only.
Illustration: The numerical values 15.573 and 15.578 are rounded at the second decimal point as 15.57
(cf. at the 3rd decimal point: 3 < 5) and 15.58 (cf. at the 3rd decimal point: 8 > 5) respectively.
The values 15.575 and 15.565 are rounded at the second decimal point as 15.58 (cf. 8 is the nearest
next even number to the digit 7 at the second decimal point) and 15.56 (cf. the digit 6 at the second
decimal point is itself even) respectively.
The following data are rounded at the first decimal point:
5.63 ~ 5.6, 5.66 ~ 5.7, 5.75 ~ 5.8, 5.85 ~ 5.8, 5.09 ~ 5.1, 5.04 ~ 5.0, etc.
ry
13.10.2 Concept of Significant Figures
ra
In a numerical value of a parameter, all the certain digits and the last digit which is uncertain to
ib
some extent make the significant figures.
Each of the digits 1, 2, 3, ..., 9 in the decimal system is a significant figure. 0 (zero) is also a
yl
significant figure except when it is used to fix the decimal point.
em
Illustrations:
ch
(i) In the common analytical weighing balance, the recorded value is uncertain at the 4 th decimal
point (i.e. uncertainty = ±0.1 mg or ±O.OOOI g). If it records the weight of a substance as 15.6584 g then
al
it indicates that its exact weight lies between 15.6583 g and 15.6585 g, Le. the digit 4 at the 4 th decimal
e
th
point is uncertain but the remaining 5 digits are certain. It indicates that the number of significant
figures in this numerical data is 6 (i.e. 5 certain digits + 1 uncertain digit).
e/
15.6584g ~ 15.658 4y ~ 6 significant figures.

t.m
Certain digits uncertain digit
(ii) In the common 50 ml buret, the graduations are at

e
19
0.1 ml interval (Fig. 13.10.2.1). Thus the buret reading 20.24
er
ml (say) indicates that the last digit 4 is uncertain and it is

H
obtained by eye approximating between two graduations. In

k
fact, the observer can estimate a reading to 0.01 ml by mentally Meniscus

20
lic
dividing the smallest division into 10 equal parts. The observer ~-~- Eye level
similarly can estimate a reading to 0.02 ml by mentally dividing
C
the smallest division into equal 5 parts. Thus the value of last
digit (at the second decimal point) depends on the choice of
the observer and the maximum uncertainty in a single buret
reading is ± 0.02 ml. In the present case, the actual buret reading
22
is between the values 20.2 ml and 20.3 ml and in the buret
reading 20.24 ml, the first 3 digits are certain and the last digit
(L e. 4 at the second decimal point) is uncertain. Thus the reading
contains 4 significant figures (i. e. 3 certain digits + 1 uncertain Fig. 13.10.2.1 Buret section showing the
digit). meniscus of liquid level: illustration of
uncertainty level in a reading when a 50
(iii) In a microburet having the graduations at the 0.01 ml
mL buret used. (Note: Conventionally, it
interval, for the buret reading 1.354 ml (say), the third decimal is assumed that the maximum uncertainty
point (L e. digit 4) is obtained by eye approximating between in a single buret reading using a 50 ml
the graduations. Thus in this buret reading, the last digit at the 3rd buret is ± 0.02 ml).
decimal point is uncertain while the remaining digits are certain and the above buret reading contains
4 significant figures. It may be noted that the reading becomes 1.35 ml when an ordinary 50 ml buret
is used and the reading bears three significant figures (i.e. 2 certain digits + 1 uncertain digit).
(iv) What is the difference between the reported analytical data 10.7 ml and 10.70 ml?
The data 10.7 ml and 10.70 ml contain 3 and 4 significant figures respectively. The value 10.7 ml
indicates that the actual value lies in the range 10.6 ml to 10.8 ml while the value 10.70 ml indicates
that the actual value lies in the range 10.69 ml to 10.71 ml. Thus the uncertainties of the data 10.7 ml
and 10.70 ml are ± 0.1 ml and ± 0.01 ml respectively.
Here it should be noted that for the value 10.70 ml, the actual value is closer/nearer to 10.70 ml than
is either to 10.69 ml or 10.71 ml.
(v) What are the uncertainties in the reported values 20 g, 20.0 g and 20.00 g?
ry
In the analytical sense, the meanings of the data 20 g, 20.0 g and 20.00 g bearing the significant
ra
figures 2, 3 and 4 respectively are different. The relative absolute uncertainties in the values 20 g, 20.0 g
X2~00}
ib
and 20.00 g are ±1 g, ± 0.1 g and ±O.Ol g respectively. It gives the relative uncertainties 5%( = I
yl
em
0.5%(= 1 x 100J and 0.05%(= 1 x 100 J respectively in the values 20 g, 20.0 g and 20.00 g respectively.
200 2000 ch
(vi) An analytical balance shows 8.2400 g as the weight of a substance. Can you represent the data
as 8.240 g or 8.24 g?
al
If the analytical balance (showing uncertainty at the 4 th decimal point) records the weight 8.2400 g,
e
then it should not be written as 8.240 g or 8.24 g. The value 8.2400 g indicates the uncertainty in the
th
order of 0.1 mg (i.e. 0.0001 g) while the values 8.240 g and 8.24 g indicate the accuracy of a milligram
e/
(i.e. 0.001 g) and a centigram (i.e. 0.01 g) respectively. The number of significant figures in the values
t.m
8.2400 g, 8.240 g and 8.24 g are 5, 4 and 3 respectively.

(vii) Function of zero (0) in determining the significant figures: It may be a significant figure or
not depending on its function in numerical representation of a value. Initial zeros just to locate the
e
position of decimal point are not the significant figures but the terminal zeros (measuring the precision)
er
are the significant figures. If the terminal zeros are merely used to locate the decimal point, then such
H
zeros are not also the significant figures.

k
Thus the initial zeros are not the significant figures but the terminal zeros may be or may not be the
lic
significant figures depending on their roles. To find out the number of significant figures, it is to count
from the first non-zero digit.
C
For example, the data 5.0030 g, 0.0030 g and 02.550 g possess five, two and four significant figures
respectively.
• Floating point representation mode involving mantissa and power of ten: The terminal zeros
merely used to locate the decimal point are not the significant figures. The power of ten will be used
to avoid the confusion regarding the role of terminal zeros in determining the significant figures. In
general, any scientific number can be expressed in the following form (called floating point
representation):
? a-Ia-2~-3 .. ·.. ·a_k, x IOn (n = an integer; a_I "# 0).

mantissa
In the above mode of representation, the fraction, 0.a_la_2 a_k and the integer n are known as the
mantissa and its exponent respectively. The above number bears k significant digits. It is illustrated
below.
3.02456 = 0.302456 x 10 1 (i.e. 6 significant figures);

0.4805 = 0.4805 x 10° (i.e. 4 significant figures);
28200 = 0.28200 x 105 (i.e. 5 significant figures) = 0.2820 x 105
(4 significant figures) = 0.282 x 105 (i.e. 3 significant figures)
In the last case dealing with a whole number, the number of significant figures is 5 or 4 or 3
depending on the mode of representation. Thus in such cases of whole number, the number of
significant figures is not fixed.
• Change of unit and role of terminal zero: For example, 25.0 kg (3 significant figures) should
not be written 25000 g that will apparently indicate 5 significant figures. But the last two digits are not
the significant figures. To avoid this confusion, it should be written as 25.0 x 103 g (3 significant
figures) or as 2.50 x 103 g (3 significant figures) or as 0.250 x 103 g (i.e. 3 significant figures). Thus,
ry
in the change of unit, the number of significant figures does not change.
ra
We can conclude:
ib
zeros are the significant figures when they are used to measure the precision. but they are not the
yl
significant figures when used merely to locate the decimal point (i.e. such zeros may be omitted by
em
the choice of proper units or by the floating point representation mode involving mantissa and
powers of ten).
Thus 260.00 kg should be written as 2.6000 x 102 kg (5 significant figures) or 2.6000 x 105 g (5
ch
significant figures). The quantity 0.0045 kg (2 significant figures) =4.5 x 10-3 kg (2 significant figures)
al
=4.5 g (2 significant figures) =4.5 x 103 mg (2 significant figures) illustrates the role of zero when the
e
values (in different units) are expressed in terms of the powers of ten.
th
(viii) How many significant figures?

e/
In the final result, there will be only one uncertain figure. Thus, if we know the estimated error or
t.m
uncertainty, then we can decide how many significant figures to use in reporting the result. This aspect
has been illustrated in the next section for different types of numerical computations.
e
13.10.3 Significant Figures in Numerical Computation of Addition and Subtraction

er
There may be two possible cases and the relevant rules are discussed below.
H
Case I: In the process of addition or subtraction of numbers bearing the same number of digits after the
k
decimal points, the results so obtained are not to be rounded-off.

lic
Case II: If the number of digits after the decimal point in the given numbers for addition or subtraction
C
differ, the results so obtained are to be rounded off at the decimal point which is equal to the minimum
number of digits after the decimal points of the given numbers entering into the computation. In other
words, the final result will retain only as many decimal points as present in the original given number
which bears the fewest decimal points.
Illustrations
(i) 4.152 + 2.2257 + 5.017 + 8.34567 = 19.74037 === 19.740
Here the minimum number of digits after the decimal point is 3 in the original numbers used in
addition. Thus in the sum, the digits beyond the 3rd decimal place cannot be significant. This is
why, the final result is rounded-off at the 3rd decimal point, i. e. the sum is rounded-off at the third place
after the decimal point. It may be noted that the result contains 5 significant figures while the original
numbers bear 4, 5, 4 and 6 significant numbers and it does not matter.
(ii) 10.4 + 2.458 + 15.4750 - 8.4285 = 19.9045 === 19.9
Here the final result is rounded-off to one decimal place.
(iii) 5 + 1.15 = 6.15 :::; 6 (cf. the number 5 does not contain any digit after the decimal point);
5.0 + 1.15 = 6.15 :::; 6.1 (cf. the number 5.0 contains one digit after the decimal point); 5.00 + 1.15 =
6.15; 5.0 - 2.35 = 2.65 :::; 2.6 (cf. the number 5.0 contains only one digit after the decimal point).
Note: To avoid the accumulation of rounding errors in the final result, the rounding will be done
only at the final result. However, the use of guard digit can minimise the excerise (see sec. 3.10.4).
(iv) Let the replicate measured values of a particular parameter be 25.1,24.8,24.6,24.7 and 25.0.
The mean value (x) is 24.84 :::; 24.8. The standard deviation (s) is given by:
ry
Standard deviation or standard error of the mean (~ or Sx ) = j;; = ~
ra
ib
= 0.0894 :::; 0.1
yl
Thus the result should be reported as: x ± ~ =24.8 ± 0.1 (5 observations). Here, the first decimal
em
point is rounded off for both the mean value and its uncertainty.
(v) If we add the values 5.12 ± 0.10, 20.2 ± 0.3, 8.357 ± 0.012 and 0.5276 ± 0.0001, then the
ch
maximum uncertainty in the final result is given by:
Emax = 0.10 + 0.3 + 0.012 + 0.0001 =0.4121 :::; 0.4 (rounded-off at the first decimal point).
e al
(cf. 0.3 contains only one digit after the decimal point).
th
Emax contains only one uncertain digit.

e/
(vi) 4.856 x 104 + 7.285 X 106 - 2.225 X 105 = 0.04856 X 106 + 7.285 X 106 - 0.2225 X 106 = 7.11106
t.m
X 106 :::; 7.111 x 106 (rounded-off at the third decimal point and the result contains 4 significant figures).
In such cases, the numbers are expressed to the same power of 10 before the numerical computation.
e
3.10.4 Significant Figures in Numerical Computation of Multiplication and Division

er
Thumb rule: In multiplication or division of numbers having the different numbers of significant
H
figures, the result so obtained will be rounded-off in a way so that it bears the significant numbers equal
k
to the minimum number of significant figures in the given numbers entering into the computation.
lic
It may be noted that the least precise number bears the fewest significant figures and the same number
C
of significant figures is retained in the final result. This thumb rule is illustrated below.
(i) Calculation of density (p = mlv): For m = 10 g and v = 3 cm3, p = 10 g3 =3.333 .... g cm-3 ::= 3g
3cm
cm-3 (cf. 3 bears one significant figure).
For m = 10.0 g and v =3.0 cm3, p = 10.0 g3 =3.33 g cm-3 ::= 3.3 gcm-3 (cj. there are 2 significant
3.0cm
figures in both 3.0 and 3.3).
(ii) 4.01234 x 0.02035 = 0.0816511 :::; 0.08165
The minimum number of significant figures in the given numbers is 4 (cf. 0.02035 bearing 4 significant
figures) and this is why, the result of product is rounded-off to generate 4 significant figures.
(iii) y = (0.1290) x (35.453) ::= 0.1290 x 35.45 =0.3817 ::= 0.382.

(143.32) x (0.0836) 143.3 x 0.0836
Here the least precise number into the computation is 0.0836 bearing 3 significant figures. Thus
the final result should not bear the significant figures more than 3. The other numbers (having
significant figures more than 3) entering into the computation are rounded-off to one additional
significant figure (called guard digit) before computation (e.g. 5 significant figures are rounded
off to the 4 significant figures).
(iv) 685695.0 x 0.388 = 0.6856950 x 106 x 0.388 = 0.6857 x 106 x 0.388 = 0.266 x 106 = 2.66 X 105
l....-.;---.J Guard~ , . ,
3 sigmficant digit J 3 significant
~~ ~~
• Caution: It may be noted that the above thumb rule may lead to an incorrect rounding because
the relative precision of the result (i.e. product or quotient) cannot be greater than the precision of
the least precise number entered into the computation. This restriction originates from the fact that
ry
the relative random errors are directly transmitted into the result of multiplication or division.
ra
Illustration
ib
• 5.2x32.86 .( . .)
yl
(I) = 1.709 = 1.71 rounded-off at the second deCimal pOint.
100.0
em
Assuming a unit uncertainty in the last digit of each number, the relative uncertainties in the
ch
numbers 5.2, 32.86 and 100.0 are:
lxl00 lxl00 lxloo .
al
---%, ---% and - - - % respectively.

52 3286 1000
e
th
It indicates that the number 5.2 is the least precise one, i.e. possessing the highest uncertainty. Thus
e/
thereI atIve . .In the fiInaI resuI t cannot be Iess than ---%.
· uncertainty 1x 100 A ssuffilng
. - 1x-100
- 01 •
-/0 uncertainty
52 52
t.m
in the final result, the absolute uncertainty (Ea ) in the result becomes:
1
e
E a =1.709x-=0.03.
52
er
Thus the product 1.709 is to be rounded (at the 2nd decimal point) to 1.71 which bears 3 significant
H
figures. Here it may be noted that the smallest number of significant figures in the entering number is
k
2 (cf. the number 5.2). Thus, if the thumb rule is applied here, the result is to be rounded to 1.7 (2
lic
significant figures). It indicates that the thumb rule should be used with a caution.
(Note: The relative un~ertainties of 1.7 and 1.71 are -6% and -0.6% respectively while relative uncer-
C
tainty associated with 5.2 is about 0.5%. Thus the result 1.71 possesses the relative uncertainty (-0.6%)
which is very close to the largest uncertainty associated with the entering numbers).
.. . 3.2 x 30.75 8
(II) Let us consider: = 0.9 4 = 0.98
100.0
IXI00 )
Here the largest fractional uncertainty ( ----n-% is present in the number 3.2. Assuming the same
fractional uncertainty in the result, the absolute uncertainty (Ea ) in the result is:'
1
= 0.03075 ~ 0.03
E a = 0.984 x -
32
Thus the result 0.984 is rounded (at the 2nd decimal point) to 0.98 which bears 2 significant figures
(cf. the smallest number of significant figures in the entering number is also 2). Thus the thumb rule
is maintained here.
Note: Relative uncertainties in 0.984 and 0.98 are - 0.1 % and -1 % respectively while the relative
uncertainty in 3.2 is about 3%. Thus the result 0.98 bears the uncertainty close to the uncertainty
associated with 3.2.
(iii) P = -109 3 333 ...... g cm -3 ~ 3 g cm -3

- 3 =.
3cm
. uncertaInty
Largest reI atIve . among th · numb
e entenng ers·IS -
1x-100 . d WIt
% ~ 33.3% aSSocIate . h 3. The
3
relative uncertainties associated with 3.33, 3.3 and 3 are: -0.3%, -3% and 33.3% respectively. This is
why, the result is rounded to 3 which also bears the relative uncertainty 33.3% (cf. same prediction from
ry
the thumb rule).
ra
p= 10.0 g3= 3.....
333 gcm -3 33
~. gcm
-3
ib
3.0cm
yl
(cf. relative uncertainties of 3.0 and 3.3 are very much comparable).
em
(iv) Let us take the following examples of multiplication:
(a) (2.15 ± 0.01) x (0.95 ± 0.02) = x } x =2.0425?

ch
(b) (1.85 ± 0.01) x (1.54 ± 0.01) =y y = 2.849 ?
al
In (a), the maximum uncertainty remains with 0.95 among the entering numbers and it is given by:
e
th
2 x 1000 '" 21 ppt. Hence the product (x) should contain uncertainty close to 21 ppt. Let Ea be the
95
e/
absolute uncertainty in x (= 2.0425), i.e.

t.m
E a x 1000 =21. or E ~O.04

2.0425 "a
e
er
It indicates that the result is to be rounded at the second decimal point and x is rounded as 2.04. It
may be noted that the thumb rule fails here (cf. the least number of significant figures for the entering
H
numbers is 2 while the result bears 3 significant figures).

k
lic
For (b), the relative uncertainty in the product should be close to 1x 1000 i. e. 6.5 ppt. It gives the
154
C
absolute error (Ea ) in the product as follows:
E a x 1000 =6.5 or, E a '" 0.02

2.849
It indicates y to be rounded at the second decimal point and it becomes y ~ 2.85 (cf. thumb rule also
predicts the same thing).
(v) Let us calculate the following expression.
(12.00 ± 0.04) x (5.000 ± 0.003) = 15.0 (not 15, 15.00 or 15.000)
(4.00 ± 0.02)
The relative uncertainties of the entering numbers are:
4x1000
12.00'± 0.04 => = 3.33 ppt; 5.000 ± 0.003 => 3x1000 =0.6 ppt
1200 5000
2x1000 .
4.00 ± 0.02 ~ = 5 ppt (maxImum).
400
Thus the result must have relative uncertainty at least (or close to) 5 ppt. The result may be written
as, 15, 15.0, 15.00, 15.000, ... having the absolute uncertainties ±1, ±0.1, ±0.01, ±0.001 ... respectively
1x1000 1x1000 1x1000
and the corresponding relative uncertainties are: 15 ('" 66.7 ppt), 150 ('" 6.7 ppt), 1500
('" 0.7 ppt), I x 1000 ('" 0.07 ppt) , :... Thus the value 15.0 possesses the relative uncertainty which is
15000
close to the largest uncertainty associated with the entering number (i.e. 4.00 ±0.02). This is why, the
result is rounded to 15.0.
ry
(Note: Some authors suggest that the relative uncertainty of the final result should be close to the
sum of the relative uncertainties [i.e. 8.93 ppt in the present case] of the associated numbers.)
ra
ib
Illustrative Example
yl
Problem: 0.9804 g Mohr's salt was dissolved in 5% H 2S04 solution and titrated with 0.1004 (N)
em
K2Cr207 solution. It required 24.54 ml K2Cr207 solution. Find the % of Fe(II) in the given Mohr's salt.
. 55.850 x 0.1004 x 24.54 ( )
Solution: 24.54 ml 0.1004(N) K2Cr207 solution: g Fe (II)
ch
1000
al
(ct. 103 ml1.0000(N) K 2 Cr2 0 7 solution: 55.850 g Fe(II))

e
%Fe(ll) = 55.845 x 0.1004 x 24.54 x 100

th
i.e.
1000 x 0.9804
e/
= 14.03425% (?)
t.m
:::: 14.03%
(i) 100 and 1000 are the whole numbers and they are free from error.
e
(ii) For a 50-ml buret, the maximum uncertainty in a single buret reading is ±0.02 ml (cf. Sec. 13.10.2
er
and Fig. 13.10.2.1). The value 24.54 ml is obtained from the measurement of final and initial buret
readings, i. e.
H
(Final buret reading ± 0.02) ml - (Initial buret reading ± 0.02) ml = 24.54 ± 0.04 ml
k
Here the maximum uncertainty is taken as 0.04 ml

lic
(Note: The most probable uncertainty is given by:

C
Ev =~(0.02)2 + (0.02)2 =0.028 ml '" 0.03 ml, i.e. 24.54 ± 0.03 ml).
(iii) The weight of a sample is obtained from the difference to two weights. In the common analytical
balance, the uncertainty of a weight = ± 0.1 mg or ± 0.0001 g.
(Initial weight ± 0.0001) g - (Final weight ± 0.0001) g = 0.9804 ± 0.0002 g
Here, again the maximum uncertainty (= ±0.0002 g) rather than the most probable uncertainty is
taken.
(iv) The uncertainty in normality is generally given by 1 ppt, i.e. we can write: (0.1004 ± O.OOOI)N
(v) The atomic weight (= 55.845) is generally with ±1 uncertainty at the last decimal, i.e. it is 55.845
± 0.001
Considering the uncertainties of the involved quantities, we can write:
Fe(n)(%) = (55.845 ± 0.001) x (0.1004 ± 0.0001) x (24.54 ± 0.04)
(0.9804 ± 0.0002) x 10
The relative uncertainties (in ppt) of the involved quantities are:
24.54 ±0.04 mL ~ 0.04 x 1000 "" 1.6ppt; 0.1004 ± O.OOOl(N) ~ 0.0001 x 1000 "" 0.99 ppt.
24.54 0.1004
0.9804 ± 0.OO02g ~ 0.0002 x 1000 "" 0.2 ppt; 55.845 ± 0.001 ~ 0.00 x 1000 "" 0.02 ppt.
1
0.9804 55.845
Among the entering quantities in the computation, the buret reading value 24.54 m1 bears the maximum
relative uncertainty (= 1.6 ppt) and consequently, the relative uncertainty in the result will be close to
1.6 ppt.
If Ea be the absolute error in the final result then, we can write:
ry
E x 1000 _ . _
-a- - - - 1.6, or Ea - 0.02
ra
14.03425
ib
It indicates that 14.03425 is to be rounded as 14.03 (i.e. rounded at the second decimal point).
yl
(Note: More rigorous calculations involving the most probable error into the final result may be
em
considered, i. e.
(relative error in the final result)2 = (relative error in atomic weight)2
ch
+ (relative error in normality of the solution)2 + (relative error in buret reading)2
+ (relative error in weight of the sample)2.
al
Thus the uncertainty in the final result may be calculated but the conclusion remains the same in both
e
approaches).
th
e/
13.10.5 Significant Figures in Numerical Computation of Logarithms and Antilogarithms

t.m
Let us illustrate for log(3.5 x 104) = 4.544068 which consists of two parts: characteristic (i.e. whole
number 4) and mantissa (i.e. decimal fraction .544068) i.e.
e
log (3.5 X 104 ) =1f4· 544068

er
. . ~. ~
ch aractensti~. mantissa
H
I I
6 significant
figures
k
lic
Characteristic is determined by the exponent (i.e. power of ten). This characteristic locates the
position of the decimal point in the number whose logarithm is being taken. The mantissa does not
C
depend on the exponent, i.e. for log (3.5 x Ion) (where exponent n is an integer), the mantissa is the
same though the characteristic may vary depending on the value of n. This is why, the digits constitut-
ing the characteristic are not considered as the significant figures but all the digits of mantissa are
the significant figures.
Rule I: The number of digits in the mantissa contributes to determine the number of significant figures
and the mantissa will bear the number of digits same as the number of significant figure of the original
number whose logarithm is being taken. It is illustrated below.
log (3.5 x 104) =4.5441 (using 4 place log table) ~ 4.54 (i.e. rounded at the
X ~ ~ 2nd decimal place)
2 significant 4 significant 2 significant
figures figures figures
Here the result should contain two significant figures.

3
log (4.000 x 10- ) = 3.6021 = -2.3979 (i. e. no rounding required)
~ ~~
Here the result should contain
' - - 4 SignifiCan1figures /
4 sigaificant figures.
log (4.00 x 10-3) =3.6021 =-2.3979 ~ -2.398 (i.e. rounded at the
'---J
" "fi '-----.J
~
~
11
'------'
~
3rd deCIma . t)
. I pOin
3 sIgnI Icant ."- ./ . ."-
figures 4 significant 3 significant
figures figures
Rule II: When taking the antilogarithm, retain as many digits as there are in the mantissa of the original
number. It is illustrated bellow:
ry
antilog (3.5) =3.16227 x 10 3
~ 3 X 10
3
; (result should contain 1 significant figure)
ra
'--.-J '-
, " 1 significant
ib
1 SIgnIficant figure
figure
yl
em
antilog (4.975) =94406.09 ~ 9.44 x 10 4
; (result should contain 3 significant figures)
~ ~
'- '-
ch
3 significant 3 significant
figures
al
figures
e
13.11 CORRELATION COEFFICIENT, REGRESSION ANALYSIS OF STRAIGHT LINE

th
RELATIONSHIP (i.e. METHOD OF LEAST SQUARES) AND REGRESSION

e/
COEFFICIENT
t.m
13.11.1 Correlation Analysis and Correlation Coefficient

e
Correlation means the nature of interdependence between two variables (say x and y). The correlation
er
may be linear or nonlinear. If one variable increases and the other variable, on the average, increases
then the variables are said to be positively correlated. On the other hand, if one variable increases and
H
on the average, the other variable decreases, then the variables are said to be negatively correlated. A
k
third possibility arises, when one variable changes but the other variable remains constant on the
lic
average. This is the case of zero correlation, i. e. the variables are uncorrelated.
C
Positive correlation Negative correlation
... •
•• Zero correlation
.....
\
y
• ••• •••
• •• y •• •
• •• • •••
••
i .:~
•• t ••••
y
•• • ••
•••••
••••
i • •••••
• •• • •
•
•
----+ x -----+ x ---. x
(a) (b) (c)
Fig. 13.11.1.1 Different types of correlation between two variables y and x.

The correlation coefficient of two variables x and Y is denoted by r xy (or simply, r) and is defined as:
cov(x,y) cov(x,y)
r-r - -------
- xy - ~var(x) ~var(y) - 0" x 0" y (13.11.1.1)
or, cov(x, y) = rxyoxoy (13.11.1.2)

where cov(x, y) = covariance of x and y; var(x) = = variance of X; var(y)0; = 0; = variance of y.
For the n-pairs of values i.e. (Xl' YI), (X2' Y2),···, (Xm Yn)
i.e. (Xi' y) where i = 1, 2, ..., n.
ry
ra
(Cf.; L(Xi -X)(Yi - y)) =; L(XiYi -xiy -Xyi +xy)
ib
yl
1 ~ __
em
1 YLx i XLYi
-- =- LXiYi - - - - - - - - + - £..Jxy
n n n n
ch
1~ __ __ __ 1 ~ __)
=-n £.JxiYi - Y X - X Y + X Y =- £.JxiYi - X Y
al
n
e
th
2 1 ~( Xi-X_)2 =-£.J
var (X) =O'x=-£..J 1 ~( Xi-X-)( Xi-X_) =-£..JXi
1 ~ 2 -------+-£..J
XLXi XL Xi 1 ~-2
X
e/
n n n n n n
t.m
1 ~ 2 -2 -2 1 -2 1 ~ 2 -2
=- £.JXi -x -X +-xnx =- £..JXi -X
n n n
e
er
H
Thus using the expressions of cov(x, y), var(x) and var(y), we can write:
k
lic
r= L(xi-x)(Yi-Y) = :LxiYi-nxy
C
~:L(Xi _x)2 (Yi - y)2] ~[(:Lxl-nX2 )(:Ll- ny2)J
... (13.11.3)
~1- £..Jx
~ i2 - (_)2
X ~ 2 - (_)2
-1 ~Yi Y
n n
Multiplying both the numerator and denominator by n and using the relations,
nx = LXi and ny = LYi' we get.
... (13.11.4)
r can be expressed also as follows:
where
p. = X· -x
_1_ _ and q. = y.-y
_I_ _
I (J' I (J'
X Y
2
It can be shown that the standard error in correlation coefficient is given by 1 ~ .
ry
Here it should. be mentioned that correlation coefficient gives a measure of only linear association
ra
of the variables. For example r = 0 for Y = x 2 relationship.
ib
13.11.2 Linear Regression Equation: Least Squares Method
yl
em
The word regression is used to denote the estimation or calculation of one variable for a particular given
value of the other variable. The necessary equation for this estimation is called the regression equa-
ch
tion. The linear regression indicates the linear relationship between the variables.
Let the equation be Y = a + bx, (a, b constants) ... (13.11.2.1)
al
.Here Y is taken as the dependent variable and x is taken as the independent variable. Let us consider
e
the pair (Xi' y;). For Xi' the calculated or estimated value of Y is a + bXi while the observed value of Y is
th
Yi. The difference between the estimated value and observed value of Y gives the error ei' i.e.
e/
ei = Yi - (a + bXi) =Yi - a - bXi

t.m
According to the principle of least squares method, the linear relation will best fit the data when
the constants a and b are so chosen as to minimise the sum of the squares of the errors, i.e. the sum of
the squares of the errors will be least. It gives:
e
er
Le; = L(Yi - a - bxi )2 is minimum.

H
i i
The conditions to determine the values of a and b are to take the partial derivatives of the sum of the
k
squares of the errors with respect to a and b and equating them to zero. It gives:
lic
aaa (Len =0 or, ~

C
L(Yi -a -bxi)2 =0
aa
and, ;b(Len=OOr, ;b L (Yi- a- bxi)2=O
L(Yi-a-bxi)(-2)=O {L(Yi-a-bxi)=O ... (13.11.2.2)

i.e.
{ L(Yi -a-bxi )(-2xi )=0 or LXi(Yi -a-bxi)=O ... (13.11.2.3)
The equations 13.11.2.2-3 are called the normal equations which can be written as:
LYi = na +bLXi
2
... (i)} .
.. l = 1, 2, ..., n
LXiYi =aLxi +blxi ... (11)
To eliminate a from the above two equations, we may write:
(ii) xn-(i)xLXi i.e.
nLxiYi - (LXi )(LY;) =b[nLx; - (Lx i )2 ]

1~ __
or b= nLxiYi -(LXi)(LYi) = ;""XiYi -xY.
~ 2_ (~)2 1 2 -2 ' (obtained by dividing both the denominator and
n~xi ~xi - LXi - x numerator by n 2 )
n
... (13.11.2.4)
ry
ra
(b) is called the regression coefficient of Y on x and is denoted by byx ).
ib
From Eqn. (i), we can write:
J-
yl
1 ~na 1 ~ . -
b x-x~xi,l.e.y=a+ b- - b- - (<J y ... (13.11.2.5)
em
-~Yi=-+ xor,a=y- x=y-r - x
n n n <J x
ch
al
or, ... (13.11.2.6)
e
th
e/
(obtained by using, X=~LXi andY=~LYi)'

t.m
• Special Case: When a = 0, i.e. y = bx ... (iii)

e
The corresponding normal eq~ations are:

er
LYi = bLxi ... (iv) and LxiY; = bl:x? ... (v)

H
b = LYi and b = LXiYi

k
It gives:
lic
LXi LX;
C
i.e. LX'Y' Ly· ... (13.11.2.7)

b ( regression coefficient ) = - - '2-' = ~
LX; ~X;
• Linear regression equation of y on x: Y = a + bx (say)

where Y is the dependent variable and X is the independent variable. It gives:
Y =(y - bx) + bx =Y + b(x - x); cf. a = y - bx
=Y+r(:: }X-X) = y +by)x-x);
. (b = byx = regression coefficient of Y on X = r(:: ))

• Linear regression equation of x on y: x = a' + b'y (say)

where x is the dependent variable and y is the independent variable. To estimate a' and b', the sum of
the squares of the errors in the estimation of x should be minimum (cf. principle of the least squares
method) i.e.
L(xi - a' - b'Yi)2 should be minimum.

The corresponding normal equations are:
Lx.I =a'n+b'LY,I and Lx·y· I I
=a'Ly·I +b'LY~ I
By following the same procedure as before, the regression equation of x on y is obtained as follows:
= cov(~.y) =r(O'x)
ry
x=x+bxy(Y-Y) wherebxy (bxy = regression, coefficient of x on y)
O'y O'y
ra
ib
• Properties of linear regression: The two linear regression equations are:
yl
y = -y + byx ( X - -). y (
y - - =r - x and x
x -- J = -x + bxy (Y - -). X =r ( -
x -- y -- y)
em
X ,I.e. - Y ,I.e. -
O'y O'x ch O'x O'y
where byx -_cov(x,y)_

- r
(O'y) _cov(x,y)_ (O'x.)
and bxy - - r
al
2 2
O'x O'x O'y O'y
e
th
e/
t.m
Regression line
• of x on y
e
y \..
er
y
t =a' + b'y)
H
(x
•
t ..
k
•• • ' - - Regression line • \.. Error

lic
of y on x
i.e. y =a + bx
C
--+ x --+ x
(a) (b)
Fig. 13.11.2.1 Two regression lines: (a) regression line of yon x (where sum of squares of the vertical distances of he
observed points from the regression line is minimised); (b) regression line of x on y (where sum of the squares of the
I)orizontal distances of the observed points from the regression line is minimised).
'Th~ said two regression lines intersect at the point (x, y) i. e. both the equations are satisfied for
x = x and y = y. The angle between the two regression lines depends on the value of correlation
coefficient r.
• For r = 0, the two lines are mutually perpendicular but they coincide for r = +1 or -1. It
indicates that as the numerical value of r increases from 0 to 1, the angle between the lines
decreases from 90° to 0°.
r= 0
• • • •
y
• • •
i •
•
•
•
•
•
--+x ----+x
y
• r =-0.89
ry
t • •
ra
•••
ib
•
yl
em
--+ x
Fig. 13.11.2.2 Qualitative representation of regression lines with different correlation coefficients.
ch
It indicates: for r = ±1 the two lines become identical but for i '::: 0, the regression equations reduce .
al
to y = y and x = X, i.e. neither y nor x can be estimated from the linear equations.
e
• The deviation of r from the value of ± 1 indicates the degree of scattering of the experimental
th
values with respect to the regression line (cf. Fig. 13.11.2.2).

e/
• Uncertainty in the coefficients (a, b): By using the most probable values of a and b (obtained
t.m
by least squares method), we can calculate the error in y as: d = (a + bXi - Yi) which is the
deviation of each experimental point from the regression line and it is called a residual (denoted
by also ds ).
e
er
The mean square error (a';) is given by:

H
2 L(a+bxi -Yi)2
2 2 i Ld
s =0. = - -
k
r y n-2 n-2
lic
a.y is also described as the standard deviation about regression and it is denoted by s r which actually
C
represents the standard deviation for y when the deviations are measured notfrom the mean value (y)
but from the regression line. sr or a y is also the standard error of estimate.
Here for a y or Sn the number of degrrees of freedom is n - 2 because two degrees offreedom have
been used in calculating the coefficients a (intercept) and b (slope).
If a.a and ab denote the standard errors in the values of a and b, then we get:
2
0. 2 0. 2 0. s2
__ a_=_b _Y -L..
LX; n ~ ~
where tJ. is given by the following determinant,
LX; LXii =nLx; -(Lxi )2

ILXi n
The above relationships are obtained by using the normal equations (i and ii). The results are:
fl~ (= uncertainty in slope)2 = fl~n x { 21 2}

nLxi -(LXi)
aa2 = ( uncertaInty
. .In.Intercept )2 = fly2 X { 2LX; 2 }
nLXi -(LXi)
The results are shown as follows:
=
slope b ± <Xt, and intercept =a ± <Xa
where b and a are their least square values.
ry
Note: Student's t-value may be used here. It is illustrated for 90% confidence limit of the slope.
CL(90%) = b + to.90fl b
ra
The value of to.90 at (n - 2) degrees of freedom is obtained from the standard table.
ib
yl
SOLVED NUMERICAL PROBLEMS
em
Problem 1: (a) For a titration, the initial and final buret readings are 2.54 ml and 46.46 ml. Find the
relative uncertainty in the titre value.
ch
(b) For weighing a substance in an analytical balance, the observations are:
al
1st weight (weighing bottle + sample) = 35.4268 g
2nd weight (after transfer of the sample) = 10.2578 g
e
th
Find the relative uncertainty in the weight taken.

e/
Solution: (a) In a 50.0 ml buret, the smallest graduation is 0.1 ml (i.e. 10 divisions for 1 ml). An analyst
can record a reading of 0.01 ml by mentally dividing the smallest division into further 10 divisions.
t.m
Thus the recorded buret reading 2.54 ml actually lies in the 2.53 - 2.55 ml range. The observer can also
estimate a reading of 0.02 ml by mentally dividing the smallest division into equal 5 parts. Thus the
e
value of last digit (at the second decimal point) depends on the choice of the observer and the maximum
er
uncertainty is ± 0.02 ml, i.e. maximum uncertainty in a single buret reading is ± 0.02 ml (cf Fig.
H
13.10.2.1 ).
Thus titre value (V) is obtained as follows:
k
lic
V = (46.46 ± 0.02 ml) - (2.54 ± 0.02 ml) = 43.92 ± ~(0.02)2 + (0.02)2

C
= 43.92 ± 0.028 ml
. reIatIve
I.e. ' uncertaInty
. .In th '
e tItre vaI ue =-
0.028 000 0 64 ppt.
- xl:::::.
43.92
(b) In an analytical balance, the uncertainty in a single weighing is about ± 0.0001 g i.e. ± 0.1 mg.
Thus the recorded value 35.4268 g actually lies in the range 35.4267 to 35.4269 g.
The weight (w) of the substance taken is:
w = 35.4268 ± 0.0001 g - (10.2578 ± 0.0001 g)
=25.l690±~(0.000l)2 +(0.0001)2 ",,25.l690±0.000l g
0.0001
i.e. relative uncertainty in w = x 1000 = 0.00397 ppt.
25.1690
Note: (i) Some analysts consider the errors in buret reading and weighing in an analytical balance as
the determinate errors (see Quantitative analysis by R.A. Day, Jr, and A.L. Underwood, 5th Edition).
In such cases, the resultant error in the titre value = 0.02 + 0.02 = 0.04 ml
. . 0.04
i.e. re1atIve error In V =- - x 1000 = 0.91 ppt.
43.92
. . . . 0.0001 +0.0001 0.0002
SImIlarly, relatIve error In w = x 1000 = x 1000 :::: 0.008 ppt.
25.1690 25.1690
(ii) In fact, the error ± 0.028 ml in the titre value is the most probable error while the maximum
possible error is ± (0.02 + 0.02) ml Le. ± 0.04 ml. Similarly, in the weight of the sample taken, the
maximum possible error is ± (0.0001 + 0.0001) g = ± 0.0002 g.
ry
Problem l(c): In a gravimetric analysis, washing of the precipitate by 100 ml washing liquid leads to
ra
the loss of precipitate of 0.40 mg. If the precipitate weighs 100 mg and 500 mg, compare the relative
ib
error for the said two cases.
Solution: E a (absolute error) = -0.40 mg in both cases.
yl
em
. ~ 100 . . -0.40 x 100
R e1atIve error lor mg preCIpItate = =- 0.4%.
100
ch
. ~ 500 . . - 0.40 x 100
R e1abve error lor mg precIpItate = = -0.08%.
al
500
e
Note: The constant error affects more when the sample size is small.
th
Problem 2: What is the maximum absolute uncertainty in the volume measured from the initial and
e/
final readings of a 50 ml buret? What is the most probable u:lcertainty in the value? Calculate the
t.m
minimum volume (to be measured) having the maximum uncertainty 1 ppt?

Solution: We have already mentioned (ef Sec. 13.10.2, Problem 1a) ~hat the maximum uncertainty in
e
a single buret reading is ± 0.02 ml in a 50-ml buret. Thus we can wn:e:

er
measured volume (V) = Final buret reading - Initial buret reading

H
=(~l ± 0.02) ml - (Vi ± 0.02) ml

=(~t'- VJ ± 0.04 ml
k
lic
Here the maximum uncertainty in the measured volume is ± 0.04 ml

EV(n~ax) = ±0.04 ml
C
Le.
The corresponding relative uncertainty is given by:
±0.04 1000 ±0.04

EV(max)
=- -x ppt = ( ) x 1000 ppt.
V V Vf-V;
The most probable uncertainty is given by:
Ev = J(0.02)2 + (0.02)2 = 0.028 ml

The corresponding maximum relative uncertainty is given by:
Ev(max) ±0.04 1000 ±0.04x1000

V = -V- x ppt = (V _ V; ) ppt
f
Let the minimum volume be Vrnin for which the maximum uncertainty is 1 ppt, Le.
0.04 .
--x 1000 = 1 ppt, l.e. Vrnin = 40 ml
Vmin
Thus in volumetric analysis, to make the uncertainty ~ 1 ppt in the titre value, it should be at least
40 ml.
Problem 3: The number 20.71264 is rounded at the 3rd decimal point. Find the absolute and relative
error in rounding the value.
Solution: The number is rounded as 20.713.
Absolute error (Ea ) = 120.713 - 20.712641 = 3.6 x 10-4
. Absolute error -5
= 20.71264 =1.74 x 10
ry
Relative error (E r )
ra
= 1.74 X 10-5 x 100 = 1.74 x 10-3% = 0.00174%
= 1.74 x 10-5 x 1000 = 1.74 X 10-2 = 0.0174 ppt
ib
yl
Problem 4: The observed value (x) is 67.84 having 1% uncertainty. Find the absolute error.
em
Solution: Let the true value be Xt, i.e. ch
Xt-XI
- I xxl
x
- =0.01; or 1 - - =0.01; or, 1--=±0.01
al
Ix t t
xt
e
th
x x 67.84
or, -=1 =+= 0.01; or, x t = - - - = - - -
e/
xt 1 =+= 0.01 1 =+= 0.01

t.m
The absolute error (Ea)=lx t -xl=1 1~7084

0.01
-670841
+
e
er
i.e. Ea = 1
67 84
~
. -67. 84 1 ±0.672, i.e. E ( . ) ~ ±0.672
H
1.01 a mm
k
67 84
~ ± 0.685, i.e. Ea(max ) ~ ± 0.685
lic
or, Ea = 1 . - 67.84 1
0.99
C
Problem 5: x = 4.275 ± 0.105 and y = 2.235 ± 0.012. Find the maximum absolute error and relative
x
error in the results, x + y, x - y, xy and -. Find also tile range of error and most probable error in each
y
case.
Solution: (i) x + y = (4.275 ± 0.105) + (2.235 ± 0.012) = 6.510 ± 0.117
It gives: maximum absolute error, i.e. Ea(max) = ± 0.117
±0.117
and maximum relative error = E ( ) = - - - x 100 ~ 1.8 %
r max 6.510
Similarly, Ea(min), i.e. minimum absolute error = ± (0.105 - 0.012) = ± 0.093
It gives: range of absolute error = ± 0.093 to ± 0.117
Most probable error = ±~(Oo105)2 + (OoOl2? "" ±O.105

(ii) x - y = (4.275 ± 0.105) - (2.235 ± 0.012) = 2.040 ± 0.117

±0.117
i.e. E ( ) = ± 0.117 and E (max) = - - - x 100 = ± 5.73%
a max r 2.040
Ea(min) = ± 0.093 and range of absolute error = ± 0.093 to ± 0.117
Most probable error = ±~(0.105)2 + (0.012)2 '" ± 0.105
(iii) For xy, the maximum relative error in the product is given by:
Er(max) = relative error in x + relative error in y
= 0.105 x 100 % + 0.012 x 100 % = 2.456% + 0.537% === 3%
ry
4.275 2.235
ra
i.e. Er(max) ::= ± 3%. It gives the absolute error (Ea ) as follows:
ib
Ea =
4.275 x 2.235 . I(
- 4.275 x 2.235; see Problem 4)
yl
1 1±0.03
em
9 554
E . =1 . _9.5541=19.554 -9.5541='9.276-9.5541=±0.278
ch
a(mm) 1 + 0.03 1.03 Corresponding to
al
Er(max) === ±3%

= 9.554 I
=19.849 - 9.5541 = ±0.295
e
and Ea(max) 0.97 - 9.554

th
= ± (2.456 -
e/
Er(min), i.e. minimum relative error 0.537)% ::= 1.92%

t.m
It gives: range of relative error = ±1.92% to ±3.0%
Most probable fractional error =±~(0.537)2 + (2.456)2 '" ±2.52%

e
er
2
E
(p) q) ;
Ep 2 Eq 2]1/ 2 2 1/2
H
(cf. For z = pq (say), - : = [ +( or Er(z) = [ Er(p) + Er(q) ]

k
lic
Er(z), Er(p) and Er(q) denote the respective fractional errors)

C
x
(iv) For -, the relative error in the quotient is given by:
y
Er = relative error in x - relative error in y = ± 2.456% - (± 0.537%)
i.e. Er(max) === ± 3% and Er(min) ::= ± 1.92%; range of error = ± 1.92% to ± 3.0%
Ea(max) can be calculated as usual and it is ± 0.295 and Ea(min) = ± 0.278 for Er(max) ::= ± 3%
Problem 6: 2.5250 g of a substance (weighed in an analytical balance) was dissolved in a volumetric

flask of 250.0 ml capacity. Precision of the analytical balance is ± 0.0004 g and uncertainty in the
volume of volumetric flask is ± 0.50 ml. Find relative error in the concentration of the solution
prepared.
. .
SolutIon: ConcentratIon (C) = Weight taken(w) w
() = -gjrnl
Volume V V
relative error in w = ±0.0004 x 100 ~ ±0.016%

2.5250
. .
reIatlve error In V = ±0.5x100 = ±0201.
. -/0
250
relative error in C = relative error in w - relative error in V = (± 0.016)% - (± 0.2)%
i.e. relative error in C lies in the range ± 0.216% to ± 0.184%
The most probable error in C is given by
±~(0.016i +(0.2)2 "" ±0.2

Note: If the absolute error in V is + 0.50 ml, then relative error in C =(± 0.016) - (+ 0.2), i. e. it can vary
ry
in the range -0.216% to -0.184%
ra
Problem 7: For a rectangle, the lengths of sides are measured with the uncertainties 3% and 5%. Find
ib
the error in the area.
yl
Solution: Area (A) = length x breadth = xy (say).
em
Relative or fractional error in the area = EftA) (say)
= fractional error in x + fractional error in Y = Ejtx) + Efty)
ch
i.e. EftA) = E ftx ) + Efty) = ± (3%) + (± 5%)
al
It gives: EjtA)(max) = ±8% and EjtA)(min) = ±2%

e
th
. 2 2 ~
The most probable error In area = E f(x) + E f(y) = ± '\/3- + 5- % = ± 5.83%
e/
Problem 8: For the linear relationship, 2x + 5y = 15 between the variables x and y, if the mean,
t.m
deviation of x about its mean is 4, then find the mean deviation (MD) of y about its mean.
e
Solution: Let us consider the general relationship,

er
y = a + bx, i.e. Yi = a + bxiand y=a+bx

H
Then we can write:

k
Yi -y=b(x j -x)
lic
; Lh -yl =Ihl; Llx xl

C
or, i -
i.e. MDof y=lbl MDofx
Now, for 2x + 5y = 15, i.e. y = 3 -~x = 3 +( -~)x

i.e. MD ofy = I-~IMD of x = ~X4 =1.6
Problem 9: For the relationship, 5x + 12y = 80 between the variables x arid y, if the standard deviation
of y is 2, find the standard deviation of x.
Solution: For y = a + bx, we can write:
Yj =n+bxj; y=a+bx, i.e. (Yj -y)=b(xj -x)
It gives:
or,
For, 5x +12y =80 or, y= 80~5X = ~~ +( -1~)x

5I
Oy=lblcrx; or Oy= --ox; 12 =-x2=4.8
or, 0x=-cr 12
i.e. y
I 12 5 5
ry
Problem 10: Find the mean deviation of the following results.
ra
x 1.0 1.1 1.2 1.3 1.4
ib
I = 3 12 18 12 3
yl
Solution:
em
x f Ix ch d =lx-xl Ilx - xl =Iidl
1.0 3 3.0 0.2 0.6
1.1 12 13.2 0.1 1.2
al
1.2 18 21.6 0 0
e
th
1.3 12 15.6 0.1 1.2

1.4 3 4.2 0.2 0.6
e/
t.m
~=48 U;Xi = 57.6 ~Idil = 3.6
x = Lf;x;
e
= 57.6 = 1.2
er
"'if; 48
H
. d . . ) Lfild;1 3.6
dav (I.e. mean eVlatlon = -~-- =- =0.075
k
~fi 48
lic
C
Problem 11: Find the mean and standard deviation of tQ.e first n natural numbers.
Solution: cr 2 = -1 ~(
~ Xi - X
_)2 =-1 ~(2
~ Xi -
2 XiX- + -2)
X
n n
=![LX;
n
-L2xi x+1iX 2 J=![LX;
n
-2XLXi +1iX 2 J
1[~
=- ~xi -
2
2-( -) +nx
X nx -2J ; - 1~
X =-~xi
n n
1
=-LX; -
2 (_)2
X
1
=-LX;
2-2
1 (LX; )2
n n n
The first n-natural numbers are: 1, 2, 3,..., n.

n(n + 1)
LXi =1+2+3+ ...+n=---
2
_ LXi n(n+1) n+1

i.e. X=--= =--
n 2n 2
ry
ra
ib
(n + 1)(2n + 1) (n + 1)2 2(n + 1)(2n + 1) - 3(n + 1)2
yl
6 4 12
em
(n + 1)(4n + 2 - 3n - 3) (n + l)(n -1)
ch
12 12
al
i.e. 0'= ~( n2)/

-112 and -X=-;;LX
1 n+1
i =-2-.
e
th
Problem 12: Fe-content of a substance is 25.05%. Two analysts report their replicate observations:
e/
Analyst-I : 25.01 %; 25.07% and 25.15%

t.m
Analyst-II: 25.55%; 25.50% and 25.52%

Comment on the accuracy and precision of their results:
e
er
Solution: For Analyst-I, the mean value = !(25.01 + 25.07 + 25.15)% = 25.08%
3
H
. (25.08 - 25.05)
k
i.e. relatIve mean error = x 100 = 0.12%

lic
25.05
C
·· 125.01-25.081+125.07-25.081+125.15-25.08I m
M ean d eVIatIon = -/0
3
= 0.07 + 0.01 + 0.07 % =0.05%

3
Relative mean deviation = 0.05 x 100 z 0.2%

25.08
Standard deviation z 1.25 x mean deviation = 1.25 x 0.05% z 0.06%
1
Analyst-II: Observed mean value ="3 (25.55 + 25.50 + 25.52)% = 25.52%
25.52 - 25.05)
Relative mean error= ( x 100 = 1.87%
25.05
·· 125.55 - 25.521 + 125.50 - 25.521 + 125.52 - 25.521

M ean d eVlatlon = - - - - - - - - - - - - - - - - -
3
= 0.03 + 0.02 + 0 ~ 0.02%

3
R e1atIve .. = -
. mean d eVlatIon 0.02
- x 100 ~ 0 .08 %
25.52
Standard deviation ~ 1.25 x mean deviation = 1.25 x 0.02% = 0.025%
Relative mean error gives the measure of accuracy while relative mean deviation and standard
deviation give the measure of 'precision.
ry
Thus the result of analyst-I is more correct/accurate than that of the analyst-II but precision is more
ra
for results of analyst-II. For the analyst-II, a small constant error (i.e. systematic error exists) exists.
ib
~
yl
Note: Check the standard deviation value by using the fonnula ~H'
em
Problem 13: Calculate the standard deviation of the values: 46, 63, 49, 59, 65, 54, 52 and 60.
ch
Solution: Standard deviation remains unchanged by the change of origin. To facilitate the calculation,
= 0;. 0;
al
let each value be reduced by 50, i.e. we can write: Yi = Xi - 50 where
e
x: 46 63 49 59 65 54 52 60 = 8
n
th
y = x-50: -4 13 -1 9 15 4 2 10 = 48
~Yi
e/
y2: 16 169 1 81 225 16 4 100 ~y? = 612

t.m
2 1 2 1 2 612 ( 48 )2 2
cry =;LYi -~(LYi) =-8--"8 =76.5-6 =76.5-36=40.5
e
er
i.e. y = ~ 40.5 = 6.36

H
Ox = Oy = 6.36
k
lic
Problem 14: For a group of 50 persons, the mean and standard deviations of their weights are 59.5 kg
C
and 8.38 kg respectively. For another group of 40 persons, the corresponding values are: 54 kg and 8.23
kg. Find the mean and standard deviation of the combined group of 90 persons.
· 2 nloi + n2o~ + n 1 (Xl - x)2 + n2 (X2 - x)2 -( led ) nlxl + n 2x 2

S oIutlon: 0 = ; X poo mean = ~~---...;;;;~
nl + n2 n1 + n2 n1 + n2
See text for its solution.

Problem 15: (a) Find the relative uncertainties in the values 2 g, 2.0 g and 2.00 g.
(b) Find the error in Y for Y = a2 and Y = ab where a = 5.0 ± 0.2 and b = 5.0 ± 0.2
Solution: (a) Let us assume the uncertainty in the last digit by one unit. It gives the values: (2 ± 1) g,
(2.0 + 0.1) g and (2.00 ± 0.01) g. Thus the relative errors are:
1 . 1 1x 100
(2±1) g: -xl00=50%; (2.0+0.1)g:-xI00=5%;(2.00±0.01) g: --=0.5%
2 20 200
dy da. Oy Oa
(b) For y = a2 , i.e. In y = 2 In a and - = 2-, l.e. -::::: 2 -
yay a
. Ey Ea 0.2
l.e. -::::: 2 - =2x- = 0.08 ; or Ey = y x 0.08 = 25 x 0.08 = 2.0
y a 5
It gives: y = 25.0 ± 2.0. It should be written as: 25 ± 2 (cf. 2 significant figures in the product.)
dy da db. E y Ea Eb
Fory = ab, i.e.lny = Ina + lnb; or -=-+-b ,l.e·-=-+-b
yay a
J=(~a r +(~ r =(~:~r +(~:~r =16.0XlO-4;; =4xlO-
ry
2
It gives: ( ;
ra
ib
and Ey =yx4x10-2 =1.0
It gives: y = 25.0 ± 1.0, i.e. y = 25 ± 1 where the product bears 2 significant figures.
yl
Note: y = a2 = ab when a = b but the error is different for the two different functions.
em
Problem 16: 4 students have analysed a sample of haematite to determine the Fe-content by using the
ch
same procedure. The values are: 20.41, 20.43, 20.49 and 20.39%. Analyse the data in terms of standard
parameters used in error analysis and analytical treatment of data. Find also the 95% confidence inter-
al
val of the true value.

e
th
4 1
(a) Mean value (x) = LXi =-(20.41 + 20.43 + 20.49+ 20.39)% = 20.43%
e/
i=l 4
t.m
(b) The values (%) (arranged in an order) are: 20.39,20.41,20.43,20.49; (cf. even number of
~ observations).
e
Median (Me) = 20.41 + 20.43 % = 20.42%

er
2
H
(c) Range (R) = Highest value - Lowest value = 20.49% - 20.39% = 0.10%
( ) Ilxin-xl =__
Id.
k
(d) Average deviation dOl' =

lic
I
11
C
= 120.41 - 20.43\ + 120.43 - 20.431 + 120.49 - 20.431 + 120.39 - 20.431 %

4
= 0.02 + 0 + 0.06 + 0.04 % = 0.03%

4
Average deviation of the mean is given by:
d av 0.03 01 - 0 01501
~-
_
14 -/0-. -/0
dav 0.03 x 100

(e) Relative average deviation: -x100= %:::::0.15%
X 20.43
d av x 1000 = 0.03 x 1000 = 1.5 t

x 20.43 pp
· · (s) = ~- ~ 0.0056 ot
2
(f) Stand ard d eVlatlon 2. d-
j
= 0.0004 + 0 + 0.0036 + 0.0016 ot
-/0 = - - -/0 ~
0 •04 01
-/0
n-l 3 3
s ~ 1.25dav = 1.25 x 0.03% = 0.0375% ~ 0.04%
•
(g) Coef1i Clent f··
0 variation: CV
s 100 = -0.04
=-x - x 100 ~ 0.2%
x 20.43
s 0.04 0.04
(h) Standard error or standard deviation of the mean (~) = r = r-;% =--% =0.02%
\In \14 2
i.e. the most probable value of Fe-content = x ± ~ = (20.43 ± 0.02)%, (4 observations)
ry
There are only 4 observations and consequently the uncertainty in the value of standard error of the
ra
~ ~
ib
mean is significant and the uncertainty in the standard error of the mean is
2(n -1)
yl
Thus the standard error or standard deviation of the mean is to be expressed as:
~+ ~ ~[1 + 1 )=_S_(1 em
+ --;:==1==-)
ch
=
- )2(n-l) - ~2(n-l) f;t - )2(n-l)
e al
= 0.02 ( 1 ± ~)% = 0.02(1 ± 0.41)%, (4 observations)

th
e/
t.m
(i) Standard error of the standard deviation ('Y) = ~ s

2(n -1)
i.e. the standard deviation should be written as:
e
er
s + 'Y = s + S(1 +- --;:==1==-)

H
S =
- - )2(n-l) )2(n-l)
k
lic
=0.04( 1± ~) =0.04(1 ± 0.41)%, (4 observations)

C
(j) Probable analytical random error (2.) = Jf;

For 95% confidence level, to. = to.95 = 3.18 (see Table 13.7.2)
(n = 4, i.e. degrees of freedom = n - 1 = 3)
2. = 3.18~0.04 % "" 0.06%
Thus the probability of the true value of lie within the range x± J;;'s i.e. 20.43 ± 0.06% is 95%
t
i.e. J.! (95% confidence interval) = (20.43 - 0.06) % to (20.43 + 0.06) %

If the uncertainty in s is negligible, i.e. s is a good estimate of (J' then t a ~ z and s ~ (J' (i.e. classical
theory of error is applicable) and we get: to. = to.95 = 1.96 at the limiting condition (Table 13.7.2).
~ _ tas _ 1.96 x 0.04 lJ1. 004 0l

~ - .f;, - 14 -/0 -
_
• -/0
It gives the narrower confidence interval (cf ± 0.06% vs. ±0.04%).

Note: In old literature, the precision of a result is measured by the parameter like probable deviation
(i.e. probable error) given by 0.674s. It means that probability of an observation to lie in the range
x ± O.674s is 50% (cf normal error curve). Thus the probable error (p) is given by:
P 0.027
P = 0.674s = 0.674 x 0.04% "" 0.027% and probable error of the mean =.f;, = 14 %.
ry
ra
Problem 17(a): The mean of 5 replicate determinations of eu-content in a sample is 65.35%. The
ib
deviations of the determinations from the mean are: -0.40%,0.20%,0.50%, -0.15% and 0.25%. Find
yl
the standard deviation and coefficient of variation.
Solution: dav =! (0040 + 0.20 + 0.50 T J.15 + 0.25)%

em
=0.30%
ch
5
s (standard deviation) = 1.25dav = 1.25 x 0.30% = 0.375% ::::: 0.38%
e al
. f .. s x 100 0.38 x 100

vanatlon =- - - = =0.58%
th
coeffilClent 0
x 65.35
e/
Note: From the values of deviations (d = x - x) and x, the individual values of x can be obtained. From
t.m
these Xi values, s can be calculated by using the standard formula. This is illustrated in the next problem.
. Problem 17(b): Pb-content in a sample was found 6.12,6.15,6.12,6.11 and 6.16% (5 replicate
e
measurements). Find the most probable value of Pb-content, the standard error and coefficient of
er
variation. Find the 99% CI of the true value.

H
Solution:
k
lic
No. of observations Ph-Content (%) Idl =Ix-xl(%) Square deviations

(d2 )
C
(x) (deviation from the mean)
6.12 16.12 - 6.131 = 0.01 1 x 10-4

2 6.15 16.15 - 6.131 = 0.02 4 x 10-4
3 6.12 16.12 - 6.131 = 0.01 1 x 10-4
4 6.11 16.11 - 6.131 = 0.02 4 x 10-4
5 6.16 16.16 - 6.131 = 0.03 9 x 10-4
1
Lxi = 30.66 day =5'Ld; 'Ldl = 19 x 10-4
- 30.66 6 1
i.e. x = - - = .13% =-x(0.09)%
5 5
=0.018%
s(staDdard deviation)::::: JLd?

n-1
: : : J19 X 10-4
4
%::::: ~4.75 X 10-4 % = 2.18 x 10- % ::::: 0.022%
2
~
1.25dav = 1.25 x 0.018% ~ 0.022%)
(cf. s
Standard error or standard deviation of the mean
(~)::::: :-::::: 0.0;.2 ::::: 0.022 ::::: 0.0098 ::::: 0.01 %, (for five observations)
'\In '\15 2.236
It gives the most probable value of the Ph-content = x ± p = (6.13 ± 0.01)%
Note: The number of observation is only five and consequently the uncertainty in J3 is not ignorable and
it should be given by:
ry
~(1± ~2(~ -1) )::::: 0.01(1± Js)%::::: 0.01(1± 0.35)%
ra
ib
yl
_
± stj;,
o99
: :.: ( 6.13 ± 0.022X4.60)
J5
em
99% CI of the true value::::: x %
ch
= (6.13 ± 0.022 x 4.60)% = (6.13 ± 0.045)%
2.236
e al
(cf. to.99 = 4.60, Table 13.7.2).

th
Problem 18: Calculate the weighted mean and its standard error of a given quantity measured as
e/
follows:
t.m
Value of the measured Frequency Ix Idl =/x; -xl tP ftP

parameter (x) (j)
e
er
5.16 2 2 x 5.16 0.15 225 x 10-4 450 X 10-4

1 x 10-4 2 10-4
H
5.32 2 2 x 5.32 0.01 X
5.43 4 4 x 5.43 0.12 144 x 10-4 576 X 10-4

k
lic
5.25 1 1 x 5.25 0.06 36 x 10-4 36 X 10-4

5.27 3 3 x 5.27 0.04 16 x 10-4 48 X 10-4
C
_ 'Lfix; 2 x 5.16 + 2 x 5.32 +4 X5.43 + 1X5.25 +3 X5.27

x --------------------
- Lfi - 2+2+4+1+3
=63.74~5.31· L+.=n=12
12 'Ji
S
2 = L/;d; = Lfid;2 = 1112 X10-4 = 101.1 X 10-4·I.e. s = 0 . 1
L/; -1 12-1 11 .
Standard error of the mean :::::~::::: :-::::: O~ ::::: 0.10 ::::: 0.03
'\I n '\112 3.46
Thus the most probable value is: x ± ~ = 5.31 ± 0.03, (for 12 observations)
Problem 19: Analysis of a soda-ash sample shows the Na2C03 content 90.50, 90.58 and 90.43%. Find
the confidence limit within the 95% range.
Solution: Mean value (x) = !(90.50 + 90.58 + 90.43)% = 90.50%

3
Id; =(90.50-90.50)2 +(90.58-90.50)2 +(90.50-90.43)2 =0+0.0064+0.0049= 0.0113
i.e. S = ~Ld;
n-l
= )0.0113 % = 0.075%
3-1
Confidence interval (CI) ofthe true value = x ± to;;/;(to.
ry
95 = 4.3 for n -1 = 2, Table 13.7.2)
ra
=90.50± 4.3~075 = (90.50 ± 0.19)%
ib
yl
em
i.e. probability of the true value to lie within the range (90.50 ± 0.19)% is 0.95.
If s is considered as a reliable estimate of the population standard deviation cr then to.95 ::::: Z = 1.96
ch
(Table 13.7.2) (assuming n ~ 00), then CI of the true value is given by:
al
1.96 x 0.075 1.96 x 0.075
CI of J..l (95% confidence) = 90.50 ± ~ = 90.50 ±
e
'13 1.732
th
= (90.50 ± 0.085)%
e/
::::: (90.50 ± 0.08)%

t.m
It gives the narrower CI (cf. ± 0.08 vs. ± 0.19)

Problem 20: A standard brass sample was analysed by a group of 6 students and the result is: Cu-
e
content (average) x = 60.65% and s = 0.22%

er
H
The certificate value is 60.95%. Are the results different at the 95% and 99% confidence level?
J!;s ,i.e. 60.95 = 60.65 ± t x 0.22

k
t
Solution: I.l. = x ± J6
lic
0.95
C
= 60.65 ± to.95 x 0.09
It gives: calculated value of t o.95 = ~~ = 3.33) critical value of to.95 = 2.57 (Table 13.7.2)
From Table 13.7.2, for 5 degrees of freedom (i.e. n = 6), the critical to.95 value is found 2.57 which
is much smaller than the calculated value (= 3.33). It indicates that at 95% confidence level, the
students' result is significantly different from the certificate value.
At the 99% confidence level, critical t-value is 4.03 (see Table 13.7.2) which is greater than the
calculated value (= 3.33), i.e. at the 99% confidence level, there is no significant difference between the
students' value and certificate value.
Problem 21: An iron sample was analysed independently by 30 students and the estimated mean value
is 47.25% with the standard deviation ±1.85%. (The certificate value is 48.20%). Are the reported
values acceptable at the 95% and 99% confidence level?
THE THEORY OF ERRORS AND STATISTICAL TREATMENT OF ANALYTICAL DATA 218·1
Solution: Here the number of replicate measurements is sufficiently high (i.e. n = 30) and s can be
taken as a good estimate of 0'. To find the CI for the true value (Il), we can use the following equation:
Z x 1.85
or, 48.20 = 47.25 ± ~
v30
. Z x 1.85
or, 0.95 = ± , z.e. z = 2.8.
5.48
From Table 13.7.1, we get Zerit = 1.96 for 95% confidence level (CL) and = 2.58 for 99% CL. The
observed value (= 2.8) is greater than Zerit (i.e. Zealc ) ZeriJ and it indicates that the result is not acceptable
at both 95% and 99% confidence level.
Note: For the quite large value of n (say 30), the critical t-value may be considered to have the limiting
ry
value. Under this condition, we can also use the following relationship.
ra
toos
ib
f.l=x± J;;
yl
Problem 22: The two variables x and y bear a linear relationship. Find the linear equation from the
em
following data. Find the uncertainties in the slope (i.e. regression coefficient) and intercept. Find the
value of correlation coefficient.
ch
x: 1 2 3 4 5 6
al
Y: 17.2 19.5 21.5 23.8 26.0 28.5

e
Solution:
th
x Y xy r y2 Y(caled) Idl = IY(caled) - yl Idl

2
e/
t.m
1 17.2 17.2 1 295.84 17.15 0.05 0.0025

2 19.5 39.0 4 380.25 19.39 0.11 0.0121
3 21.5 64.5 9 462.25 21.63 0.13 0.0169
e
er
4 23.8 95.2 16 566.44 23.87 0.07 0.0049

5 26.0 130.0 25 676.00 26.11 0.11 0.0121
H
6 28.5 171.0 36 812.25 28.35 0.15 0.0225

k
lic
Ui = 21 ~Yi = 136.5 UiYi = 516.9 u'f = 91.0 ~yl = 3193.03 'Ul'f = 0.0710
=== 3193.0
C
For the linear equation, y = a + bx, we have (cf. Sec. 3.11.2):
b= nLxiYi -(LXi)(LYi) = 6x516.9-21x136.5 = 3101.4-2866.5 = 234.9 =2.24

nLx; - (LX i )2 6 x 91- 21 x 21 546 - 441 105
y = a +bx, i.e. a = y -bx
y =.!.(136.5) = 22.75 and x =.!.(21) = 3.5

6 6
.. a = 22.75 - 2.24 x 3.5 = 22.75 - 7.84 = 14.91
i.e. the equation is: y = 14.91 + 2.24x
Slope (b) i.e. regression coefficient = 2.24
Intercept (a) = 14.91
() !I.XjYj-(X)(Y)
r(correlationcoefticient) = ~covx~' Y n
= --;==:::::::::::::::==---;::::::=====-, (cf. Sec. 3.11.1)
var ( x ) var (Y) 1 ~ 2 (_)2 1 ~ 2 (_)2
- ~ xi - X - ~ Yi - Y
n n
1
- x 516.9 - 3.5 x 22.75
r= 6
~!6 x 91-3.5 x 3.5 !6 x 3193 - (22.75)(22.75)
ry
= 86.15 -79.62 = 6.53 = 6.53 ~10
ra
"'15.16-12.25"'532.16-517.56 "'2.91"'14.60 1.70x3.82 .
ib
We have:
yl
Ycalc = 14.91 + 2.24x and Idl = IYcalc - Yexpl
em
2
sr
2
oray =n-2i
Ld 2 0.0710 -3 (
=6=2=17.75X10 ; cf.Sec.3.11.2
)
ch
al
3
a2=a2n[
e
1 ]=17.75X10- X6[ 1 ]
b Y nI.x; _(I.x )2 6x91-21x21
th
j
e/
6 x 17.75 X10-3 6 x 17 75 x 10-3

t.m
=. =10.14x10-4
546 -441 105
ab (uncertainty in slope or regression coefficient) = ~10.14 x 10-4 ~ 0.03

e
i.e.
er
LX~]
H
a~ =a; 2 =17.75x10- [ - 91 ] ~154x10-4

3
I
[ nLX; - (LXi) 105
k
lic
~154 x 10-4 = 0.124 ~ 0.12

C
i.e. aa (uncertainty in intercept) =

Thus the regression equation is:
Y = (14.91 ± 0.12) + (2.24 ± 0.03)x
a
Problem 23: Prove: for Y = ab, /y = fa + fb and for Y = b' f y = fa - f b where /y, fa and fb denote the
fractional e~ors in y, a and b respectively.
E
Solution: Ea (absolute error in a) =a - a p i. e. fa (fractional error in at) = ---.E-
at
(i) For Y = ab, a = at + Ea and b = bt + Eb and it gives:

y = (at + Ea)(bt + Ea) = (at + faat)(b t + fbb t)

=at (1 + };)bt (1 + fb)
=:: apt (1 + fa + fb); fa' fb « 1
= apt + apt ifa + fb)
i. e. error in y = Ey = apt (fa + fb)
Ey (
-
)
fractional error in y = f y = atbt (fa + f b ) = fa + f b
y atbt
ry
ra
ib
'" :1 (1+ fa - fb);(fiPfb« 1, i.e.n« 1)
yl
t
em
ch
e al
It gives:
th
e/
= a + b, f y '" fa + ~b (fb -
t.m
Problem 24: Prove: for y fa) =:: f b + _a- (fa - fb), (fy, fa and fb denote
a+ a+b
the fractional errors in y, a and b respectively). Show,h =:: fa when a » b andh::::: fb when b » a.
e
= (at + Ea) + (b t + Eb), i.e. Ey= Ea + Eb

er
Solution: y = a + b, i.e. y
H
Ey =/ = Ea +Eb = aJa +bJb = aJa +bJa -bJa +bJb

and
k
y Y at +bt at +bt at +bt

lic
= fa(at+b t ) +---...;..-
bt(fb-fa)
C
at +bt at +bt
=:: fa when a » b
Similarly, it can be shown: h =:: fb when b >> a
ai+bf a ) a
f y = t a t b =fb+--t-(fa-fb =::fb+--(fa-fb)=::fbwhenb»a
at +bt at +bt a +b
Problem 25: The sides of a rectangle are: 25.50 ± 0.05 cm and 15.30 ± 0.04 cm. Find the error in the
calculated area.
Solution: Area = length x breadth, i.e. y =a x b (say).
y = 25.50 x 15.30 ± Ey = 390.15 ± Ey
We have:
i.e. ( ~J2
390.15
=( 0.05 )2 + ( 0.04)2 =3.84
25.50 15.30
X 10--6 + 6.81 X 10--6 =10.65 X 10--6
ry
-E -
ra
or,
y
= 3.26x 10 -3 ; or, E y = 1.27
390.15
ib
Thus the area is: 390.15 ± 1.27 cm2
yl
em
Problem 26: If the error in the measurement of radius of a circle is 5%, what is the error in the
calculated area of the circle. ch
Solution: y (area) =Ttr-, i.e. dy = 21tr
al
dr
e
Oy ~ -21tr (or)
th
It gives: Oy ~ 2TtrOr or, - 2 Or = 2 -

Y 1tr r
e/
t.m
i.e. E; =2 ( ; ) =2 x 0.05 = 0.10 i.e. error in the calculated area is 10%

e
Problem 27: For a cylinder, the measurements are:

er
r (radius) = 4.5 ± 0.1 cm; h (height) = 10.7 ± 0.2 cm.

H
Find the volume of cylinder and the error in the calculated volume.
Solution: V (volume) = Ttr-h, i.e. In V = Inn + 2Inr + Inh
k
lic
It gives: VOV ~ 2 (or) Oh

-; + h; (Sec. 13.9; Illustration 6).
C
Then for the most probable random error (E v) in ~ we can write:
(~ r=e: r+( ~h r=e=.~·lr +C~~ r

r
= 1.97 x 10-3 + 3.49 X 10-4 = 23.2 X 10-4

E
or, ~ = 4.82 X 10-2 or, E v = 4.82 X 10-2 x V
V
Thus the calculated volume = V ± E v = V ± 4.82 x 10-2 V
=V (1 ± 4.8 x 10-2) = Tt (4.5)2(10.7)(1 ± 4.82 x 10-2) cm3
:::= 680.36 (1 ± 4.82 xl 0-2 ) cm3 ~ (680.4 ± 32.8) cm3

Problem 28: The measured diameter of sphere is 4.25 ± 0.05 cm. Find the error in the calculated
volume.
dV
2
3rr.d I.e.
dd =-6-' .
2
31td-Bd; ( cf·lnV=ln
BV::::::- (1t"6J+3Ind,l.e·
. BV =3 &i)
6 V d
It gives: Ev = 31UP x6 E =3(Ed J= 3xO.05 =0.035

V 6 x 1td 3 d d 4.25
ry
E v = 0.035 x V
ra
= V ± E v = V(l
ib
Thus, calculated volume ± 0.035)
yl
= ~(4.25)3(1 ± 0.035) cm3
em
6
= 40.2(1 ± 0.035) cm3 =(40.2 ± 1.4) cm3

ch
al
Problem 29: If the standard errors in mass (m) and volume (V) are 1% and 4% respectively of a
substance. Find the standard error in the calculated density (p).
e
th
·
Solutlon: We have: p =-m , i.e. inp = inm -in V
e/
V
t.m
It gives:
e
er
H
or,
k
lic
i. e. 4.1 % error in the calculated value of volume.

C
Problem 30: A particle freely falls from rest. After some time, its measured velocity is 6.5 ± 0.2 mls.
Find the error in the measured time.
Solution: u = 0, v = 6.5 ± 0.2 mls; g = 9.8 mls 2•
v = U + gt = gt, i.e. dv = g and av "" gat, i.e. E I =.!.Ev

dt g
i.e. E t ( error . .)
In tIme =- 1 x error In
. veIoClty
· =± ( 0.2 ms -12 J
9.8 9.8 ms-
= ± 0.02 s
Problem 31: The initial (Xi) and final (xf) positions of a particle are: 10.5 ± 0.2 cm and 30.2 ± 0.4 cm
(distances are measured in a certain direction). Find the displacement and its uncertainty.
Solution: Displacement (x) = XI - Xi = 30.2 - 10.5 = 19.7 cm
The error in displacement =~(0.2)2 + (0.4)2 = JOi = 0.44 '" 0.4cm

i.e. displacement = 19.7 ± 0.4 cm
Problem 32: The solubility product of Ca3(P04)2 is (2.1 ± 0.2) x 10-33 at 25°C. Find the solubility of
this salt in water.
Solution: Ca 3 (P0 4 )2 (s) ~ 3Ca 2+ (aq) + 2PO~- (aq)
If solubility of the salt is x molenitre, then [Ca 2+(aq)] and [PO]- (aq)] will be 3x and 2x molenitre
respectively.
i.e. K sp (solubility product) = [Ca2+]3[PO~-]2 = (3x)3(2x)2 = 27 x 4.0 = 108.0
ry
33 33 5
ra
2.1 x 10- (2.1 X10- )1/
i.e. 108.0 = 2.1 x 10-33 or, x 5 or x=
ib
108' 108
yl
33
em
1 (2 1 X 10- ) = -log(1.94
logx = -log· 1 35
X 10- )
or,
5 108 5 ch
. =.![ log 1.94 + log 10-35 ] = .![0.287 - 3S] = -6.94 = log(1.1S x 10-7)
al
5 5
e
i.e. x = 1.15 X 10-7 moVlitre.

th
e/
1 J1/5
P ( an error free quantity) = ( -
t.m
108
1
e
i.e. lnx = lnp + SlnKsp

er
H
33
It gives: Ox "'.! o( K sp ) ,i.e. Ex '" .!(0.2 X 10- )
k
X 5 K sp x 5 2.1 X 10-33
lic
C
or, Ex '" 0.02 or, Eierror in solubility) = US x 10-7 x 0.02 '" 0.02 x 10-7 molllitre.
x
It gives, solubility = (1.15 ± 0.02) x 10-7 moVlitre.
Problem 33: Find the standard deviation in the following result.
y = [(205 ± 2) + (65 ± 3)] x (0.050 ± 0.002)

~---:::------~-----::::----
[(45.8 ± 0.4) - (15.3 ±0.2)]

Solution:
y-
(270±~22 +3 2 )(0.050±0.002) - (270±3.6)(0.050±0.002)
--
ab
- (30.S ± ~(0.4)2 + (0.2)2 ) - (30.5 ± 0.44) - c
i.e. 2
y
3.6)2
( 270 + +
(0.002)2
0.050
(0.44)2 =
30.5
~(1.77 ++
16.0 2.07) x 10-4
= ~19.84 X 10-4 = 4.45 X 10-2

y = 0.442 10-2 and
=44.2 x Sy =0.442 x 4.45 x 10-2 = 1.96 X 10-2
It gives: y = (44.20 ± 1.96) x 10-2
Problem 34: For an ideal gas, the measured quantities are:
P =0.272 ± 0.015 atm, V =2.25 ± 0.05 L, T =298.4 ± 0.4 K
ry
Find the error in the calculated value of number of moles of the ideal gas (Given R = 0.082 L atm
mol-1K- 1).
ra
ib
PV
Solution: We have, PV = nRT or, n =- =-0.272
- -x -
2.25
-
yl
RT 0.082 x 298.4
=
em
= 2.5 x 10-2 0.025 moles
We can write: Inn = InP + In V -lnR -In T
ch
on=oP +OV +(_OT)
al
i.e.
n P V T
e
th
or, (~ r ~(3:r +(3:r+(3:r

e/
t.m
It gives:
(~ r =(; r +(~ r+(i r
e
er
0.015)2 (0.05)2 (0.4)2

H
=( 0.272 + 2.25 + 298.4

k
= 30.3 x 10-4 + 4.9 X 10-4 + 1.8 X 10-6 z 35.2 10-4

lic
X
C
E
i.e. _n z 5.93 X 10-2 and En (error in the number of moles) = 0.025 x 5.93 x 10-2 z 0.15 X 10-2
n
i.e. number of moles = (2.50 ± 0.15) x 10-2
Problem 35: Find the relative error in y due to the 4% error in x for the relations:
(i) y = 4x -~; (ii) Y = Ax 2 ; (iii) y 3 = r; (iv) y = _x_; (v) y = A exp(mx)

x l+x x+4
3 . dy. 3
Solution: (i) y=4x--, l.e. -=4+ 2
x dx x
y 3 3
i.e. E = (4X: + J x 0.04, i.e. relative error in y = (4X: + J x 0.04
y 4x -3 4x -3
2
.. A x . dy
(11) y = ( 2) , I.e. - = A [1+X -X(2X)] 2
1+ x dx (1 + x 2 )
ry
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ib
yl
em
ch
al
2 2 2 2
e
E y = A(1-x ) X (1+x ) Ex =(I-X JE x =(I-X JXO.04

th
i.e. 2 2
Y (1 + x 2 )2 Ax 1+ x X 1+ x
e/
dy 2 -1/3. ~ 2 -1/3~
t.m
3 2. 2/3
(iii) y = x ,I.e. y = x or, dx ="3 x , I.e. uy = "3 x uX
e
oy 2 x-l/3 2 Ox Ey 2E 2
x =-xO.04
er
-=---Ox=--, i.e.- = _ _
y 2
3 x / 3 3 x y 3 x 3
H
, x . dy (x + 4) x 1- x x 1 4
k
(iv) y=--, I.e. - = 2 = 2

lic
x+4 dx (x+4) (x+4)

C
or, x dy ~ 4x =_x_x_4_=y{(X+4)-X}=y(l_y)
dx (x+4)2 (x+4) (x+4) (x+4)
dy =(l_y)dx
or,
y x
-Oy( Ox or, -Ey = ( 1- y)--!..

= 1- y)-; E
= (1- y) x 0.04
It gives:
y x y x
i.e. relative error in y = (1 - y) x 0.04
(v) y=Aexp(mx)=Ae mx , i.e.lny=lnA+mxlne=lnA+mx
~(lny). dy =O+m· or ! dy =m· or dy =mdx

dy dx "ydx" y
y
It gives: OY""mOx; or, E ""mEx =mxxxO.04=mxxO.04
y y
i.e. relative error in y = mx x 0.04
EXERCISE 13
1. Define and illustrate the following terms:
mean; mode; median; skewness; determinate and indeterminate errors; relative errors; mean
deviation; standard deviation; standard error of the mean and the uncertainty of the standard error;
standard deviation with its uncertainty; correlation coefficient; regression coefficient; t-test;
F-test; Q-test; variance; coefficient of variation; confidence interval (CI).
ry
2. Compare: constant error vs. proportional error; systematic error vs. random error; absolute error
vs. relative error; normal curve vs. skew curve; population mean vs. sample mean; population
ra
standard deviation vs. sample standard deviation; accuracy vs. precision; simple harmonic mean
ib
(SHM) vs. arithmatic mean (AM); histogram vs. frequency polygon.
yl
3. What is the relationship between the absolute error and relative error?
em
4. What are the possible sources of systematic or determinate errors? Discuss with illustration.
5. What are the characteristic features of random errors? How can you estimate this? What· are the
ch
probable sources of this error?
6. What do you mean by the measures ofcentral tendency and measures ofdispersion? High precision
al
does not always ensure accuracy-illustrate.

e
7. Discuss the characteristics of normal error curve.

th
8. Give the equation of distribution of random error. Systematic error affects the accuracy but ran-
e/
dom error affects the precision-explain.

t.m
9. Calculate the area between the following limits for a normal error curve.
(a) J..l ± la, (b) J..l ± 2a, and (c) J..l ± 30
10. How can you measure the precision of a result?
e
11. Prove that standard deviation is independent of the change of origin.

er
12. What are the standard errors of the mean and standard deviations? What are the uncertainties of
H
these standard errors?

0; 0;
k
14. For y = a + bx, prove that = b2

lic
4
=5" 0
C
15. Prove: mean deviation (dav or 11)

16. How can you calculate the standard deviation of a composite group? What do you mean by pooled
standard deviation?
17. What do you mean by confidence interval (CI), confidence level (CL) and probable random error
at a certain confidence level?
18. How can you measure the confidence interval (CI) of true mean from the knowledge of 0 and s?
19. What is student's t? What are the factors to determine the t-value?
20. How can you use the t-test to compare the two mean values obtained by two different methods?
21. How can you use the F-test or variance ratio test to compare the precision of two methods?
22. What are the criteria for rejection of an observation?
23. Compare the limitations of the 2.5dav and 4dav rule to reject an observation.
24. What do you mean by rejection quotient in Q-test? How can you apply the Q-test to reject an
observation?
25. In terms of propagation of random errors, what do you mean by maximum error, minimum error
and most probable error in the compound result?
26. Find the error (Ey ) in y in terms the errors E a, E b and E c •
(i) y(±Ey ) = a(±Ea) x b(±Eb)/c(±Ec );
(ii) y(Ey ) =a(±Ea) ± b(±Eb) ± c(±Ec );
(iii) y(±Ey )= [a(±Ea)]n; (iv) Y(±E.y) = log a(±Ea);
(v) y(±Ey ) = antilog[a(±Ea)]; (vi) y(±Ey ) = exp[a(±Ea)]
27. Find the relative error in y in terms of the relative error in r:
4
(a) y = m2 (b) y =-1tr 3
3
ry
28. What are the rules to round-off a number? Illustrate with the examples.
ra
29. What do you mean by significant figures of a number.
ib
30. How can you determine the significant numbers in the results of different types of computations
yl
like (i) addition and subtraction, (ii) multiplication and division, (iii) logarithms and anti-
em
logarithms.
31. What do you mean corr~lation coefficient? Give its mathematical expression.
ch
32. What is the principle of least square method applied to have the linear regression equation?
33. What are the normal equations for y = a + bx and y = bx. What is regression coefficient? Give
al
the least square values of a and b. What are the uncertainties in a and b?
e
34. What is the range of the value of correlation coefficient (r)? What does it signify? What is the
th
limitation of this parameter?

e/
J
t.m
. b) =r (cry
35. For y = a + bx, prove byx(l.e. Ox .
e
36. Find the error (Ey) in y in terms the error (Ex) in x for the following functions:
er
Ax 2
B A (1 - x )
H
. ( B) ..
(i) y = Ax - - and (ii) Y =-1--2 [ADS. (z) E y ~ A +2" Ex; (u) E y = 2 Ex]
x +x x (1 + x 2 )
k
lic
37. Find the limits of Ey for y = AT 2

C
l+x
-AE ~
[ADS. Ey(max) =AEx when x = 0; Ey(min) =~ when x =±v3
2
1- x ..]
for which the factor 2 becomes mInImum
(1 + x 2
)
B
38. Find the limits of error (Ey ) for y = Ax - -
x
y y
[Hints: E =(AX: +BJEx ; E becomes maximum when Ax2
Y Ax -B x Y
- B "" 0 i.e. x""± !BB ;
VAA
E y(max) "" 2AEx when x '" ±~ ;EY(min) "" AE and ( ; )
x min '" ; when x is large]
NUMERICAL PROBLEMS
1. Find the mean, median and mean deviation for the following sets of values.
(i) 89.83,89.68,89.25 and 89.61;
(ii) 20.41, 20.43, 20.39 and 20.49
[ADS: (i) Mean = 89.59, Median = 89.64, Mean deviation: 0.17]
(ii) Mean = 20.43, Median = 20.42; Mean deviation: 0.03
2. Find standard deviations and coefficient of variations (CV) of the data sets given in Problem 1.
[ADS: (i) s ::::: 0.21; CV ::::: 0.23%; (ii) s ::::: 0.04;
CV = 0.195% ::::: 0.2% (cf. s ::::: 1.25dav )]
3. Find mean deviation and standard deviation of the following replicate values of Pb-content in a
sample.
ry
1.16 ppm, 1.12 ppm, 1.11 ppm, 1.12 ppm and 1.15 ppm.
ra
Find also the 95% confidence interval (CI) of the true value.
[ADS. day = 0.018 ppm::::: 0.02 ppm, s = 0.022 ppm::::: 0.02 ppm,
ib
CI(a = 0.95) = (1.13 ± 0.027) ppm::::: (1.13 ::::: 0.3) ppm.]
yl
4. What is the value of random error at 99% and 95% confidence level of the analysis given in
em
Problem 3.
[Ans. Lo.99 = ±0.05 ppm (99% confidence level)
ch
Lo.95 = ±0.03 ppm (95% confidence level)]
al
5. Replicate determinations of Cr-content of an alloy gives the results (%): 8.20, 8.25, 8.08, 8.15 and
e
8.02.
th
Find the confidence interval of the true value at the 95% confidence level and random error at this
[ADS. CI(a = 0.95) = 8.14 ± 0.10%, LO.95 = ± 0.10%]
e/
confidence level.
6. An over titration of 0.05 ml is required to notice the colour change of an indicator. Compare the
t.m
relative errors when the titrant volumes are 25.0 ml and 50 ml. [ADS. 0.2% and 0.1 %]
7. Replicate determinations of Fe-content in a sample gives the results (%): 11.8, 11.2, 11.9 and
e
11.5. The certificate value is 12.3%. Are the results significantly different at the 95% and 99%
er
confidence levels.
H
[ADS. Yes (at the 95% confidence level);

No (At the 99% confidence level); cf. s ::::: 0.32%,
k
t ealc = 4.38, terit = 3.18 (a = 0.95) and 5.84 (a = 0.99)]

lic
8. Analysis of an alloy to determine the Fe-content was carried out by two methods. The results are:
C
Method I: Xl = 12.61 %, nl = 6, Sl = 0.07%

Method II: x2 = 12.53%, n2 = 4, S2 = 0.072%
Are the results significantly different at the 95% confidence level?
[ADS. No (cf. t ealc = 1.77 using S = 0.07; terit = 2.31 for 8 degrees of freedom)]
9. Assuming the uncertainty 0.02 ml in each buret reading, find the volum~ of solution to be meas-
ured by a such buret so that the maximum error in the measured volu~e is 1 ppt.
[ADS. 40 ml]
10. Find the least square values of slope and intercept for the (Xi' y;) pairs:
(Xi' y;): (1.00, 4.96), (2.00, 7.05), (3.00, 9.03), (4.00, 10.92), (5.00, 12.94) (y is the dependent
variable) [ADS. Slope = 1.98, intercept = 3.04]
11. Compare the errors in Yl and Y2 defined as follows:
Yl = a 2 and Y2 = ab where a = b = 4.0 ± 0.2
[ADS. Yt = 16.0 ± 1.6 ::::: 16 ± 2, Y2 = 16.0 ± 1.1 ::::: 16 ± 1]
12. The solubility product of PbS04 is (4.0 ± 0.4) x 10-8 • Find the solubility of PbS04 with the
uncertainty. [ADS. (2.0 ± 0.1) x 10-4 mol dm- 3 .]
13. Find the values with error:
(a) x = 100 ± 1 [ADS. 50 ± 25]
2+1
(b) log(2.00 ± 0.02) x 10-6 [ADS. -5.699 ± 0.004]
14. Express the results with the significant figures.
(a) log (2.4 x 106 ) [ADS. 6.38]
(b) antilog (10.5) [ADS. 3 x 105 ]
(c) 2.12 g + 0.88 g + 5.27 g + 3.8 g [ADS. 12.1 g]
ry
15. The mean value of 5 replicate determinations of Pb-content in an alloy is 5.13%. The deviations
(i.e. IdiD of the determinations from the mean value are: 0.01 %, 0.02%, 0.01 %, 0.02% and 0.04%.
ra
Find the standard deviation and coefficient of variation.
ib
[ADS. S = 0.03%, CV = 0.58%; cf. S :::: 1.25 x dav ]
yl
BIBLIOGRAPHY
em
1. J.R. Taylor, An Introduction to Error Analysis: The Study of Uncertainties in Physical Measurements.
ch
2. P.R. Bevington and O.K. Robinson, Data Reduction and Error Analysis for the Physical Sciences.
3. J. Topping, Errors of Observation and Their Treatment.
al
4. R.A. Day (Jr) and A.L. Underwood, Quantitative Analysis.
e
5. D.A. Skoog, D.M. West, F.l Holler and S.R. Crouch, Fundamentals ofAnalytical Chemistry.
th
e/
t.m
e
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H
k
lic
C
APPENDICES
APPENDIX I
Units and Conversion Factors
Table 1: Basic physical quantities in 81 units
Physical quantity Symbol for quantity lVame of unit Symbol for unit
Length metre m
Mass m kilogram kg
Time t second s
Electric current I ampere A
ry
Temperature T kelvin K
ra
Amount of substance mole mol
Luminous intensity candela cd
ib
yl
em
Table 2: Derived physical quantities in 81 units
Physical quantity Name ofSI unit Symbol and definition Named after
ch
ofSI unit
al
Force, weight newton (N) N = kg m S-2 = J m- I Isaac Newton (1642-1727)

e
Work, energy, joule (J) J=Nm James Prescott Joule (1818-1889)

th
quantity of heat
Power watt (W) W = J S-I James Watt (1737-1819)
e/
Pressure pascal (Pa) Pa = N m-2 B. Pascal (1623-1662)

t.m
Electrical charge coulomb (C) C=As Charles Auguste de Coulomb (1736-1806)

Electrical potential volt (V) V =kg m2 s-3 A-I Allesandro Volta (1745-1827)
= J A-I S-I
e
=JC-I=W A-I
er
Electric capacitance farad (F) F=C V-I Michael Faraday (1791-1867)

Electric resistance ohm (0) 0= V A-I Georg Simon Ohm (1787-1854)
H
Electric conductance siemens (S) S =0- 1 W. von Siemens (1816-1892)

k
Magnetic flux weber (Wb) Wb=.Vs W. Weber (1804-1891)

lic
Magnetic flux density tesla (T) T=Wbm-2 Nikola Tesla (1856-1943)

Inductance henry (H) H =V S A-I Joseph Henry (1799-1878)
C
Frequency hertz (Hz) Hz = S-I Heinrich Hertz (1857-1894)

Radioactivity becquerel (Bq) Bq = S-I A. Henri Becquerel (1852-1908)
Absorbed dose of gray (Gy) Gy =m2 s-2 Louis H. Gray (1905-1965)
radiation =J kg- 1
Area (A) square metre m2
Volume (V) cubic metre m3
Density (p) kilogram per kg m-3
cubic metre
Velocity (u, v, w, c) metre per second
Acceleration metre per square
second
*Concentration (c) mole per cubic metre mol m-3
*for concentration (c ) in mol per litre, it is given by mol dm-3
A.1
A.2 FUNDAMENTAL CONCEPTS OF INORGANIC CHEMISTRY
Table 3: 81 prefixes
Fraction PrefIX Symbol Multiple Prefix Symbol
10- 1 deci d 10 deka da
10-2 centi c 102 hecto h
10-3 milli m 103 kilo k
10-6 micro Jl 106 mega M
10-9 nano n 109 giga G
10- 12 pico P 10 12 tera T
10- 15 femto f 10 15 peta P
Table 4: CG8 and 81 units for some common physical quantities
Physical CGS units Sf Units
ry
quantity Name Symbol Name Symbol
ra
Length centimetre cm metre m
Angstrom (10-8 cm) A
ib
Mass gram g kilogram kg
Time second sec second s
yl
Temperature celsius °C kelvin K
em
kelvin oK
Energy calorie cal joule J
kilocalorie kcal kilojoule kJ
ch
litre-atmosphere ergs lit-atm erg
al
* tonne (t) = 103 kg, lb =453.59 g, Btu = 1.055 X 10 10 erg =252 cal
e
th
Table 5: Conversion of CG8 units to 81 units

e/
Physical quantity Relation between the units

t.m
Length Angstrom (A) = 10- 10 m = 10- 1 nm = 102 pm

micron (Jl) = 10-6 m
Volume llitre (L) = dm 3
e
Force dyne = 10-5 N

er
Energy * erg = 10-7 J

cal = 4.185 J
H
eV = 1.602 x 10- 19 J; eV/molecule = 96.484 kJ mol- 1

atm = 1.013 x 106 dyne cm-2 = 101.33 kN m-2
k
Pressure
lic
atm = 760 torr

mm Hg or torr = 133.32 N m-2
C
bar (106 dynes/cm2) = 105 N m-2

Viscosity poise = 10- 1 kg m- 1 S-1
Magnetic flux density gauses = 1Q-4 T
* 1 cm- 1 (wave number) = 2.86 cal mol-I, reciprocal centimetre is known as Kayser (K) 1 kK (kilo
Kayser) = 1000 cm- 1, 1 eV per molecule = 23.06 kcal mol-I, 1 erg = 2.39 x 10-11 kcal. 1 eV = (charge
of an electron) x 1 V = 1.6 X 10- 19 C X V = 1.6 X 10- 19 J,
1 23
leVImolecule = 1.6 x 10- : ;:;02 x 10 kJ/mole =96.488 leI mol-I,
1 kK molecule- 1 = 103 cm- 1 molecule- 1
=he x 103 cm- I molecule- t (Cf . E = hv = ~ )

= 6.62 X 10-34 J s x 2.99 X 108 m S-1 x 105 m- 1 molecule- 1
= 1.985 x 10-20 J molecule = 11.96 kJ mol- 1

Table 6: Atomic Units (see text, Vol. 1, Chapter 1, Sec. 1.8.2)
ApPENDICES A.3
APPENDIX II
Some Physical and Chemical Constants
Table 1: Values of some physical and chemical constants
Constant CGS and other units Sf units
Acceleration due to gravity (g) 980.665 em sec-2 9.80665 m s-2

Avogadro's number (NA ) 6.02217 x 1023 molecules mole- 1 6.02217 x 1023 mol- 1
Bohr magneton (f.1B) 9.274 x 10-21 erg gauss- 1 9.274 x 10-24 J T-1
Nuclear Magneton (f.1N) 5.04 x 10-24 erg G-1 5.04 X 10-27 J T-1
Bohr radius (ao) 0.52918 A 5.2918 X 10- 11 m
Boltzmann constant (kB or k) 1.3806 x 10-16 erg (degree K)-I 1.3806 x 10-23 J K-1
ry
Debye 10- 18 esu em 3.3356 X 10-30 C m
4.80298 x 10- tO esu 1.60216 x 10- 19 C
ra
Electronic charge ( e)
Electronic rest mass (me) 9.10953 x 10-28 g 9.10953 X 10-31 kg
ib
Faraday (F) 96487 coulomb equiv- 1 9.6487 X 104 C mol- 1
Gas constant (R) 8.3144 x 107 erg (degree K)-l mole- 1 8.3144 J K-1 mol- 1
yl
8.31441 Joules (degree K)-l mole- 1 8.3144 N m K-1 mol- 1
em
82.053 x 10-3 litre-atm (degree K)-l mole-I 8.3144 Pa m 3 K-1 mol- 1
1.987 cal (degree K)-l mole- 1
8.854188 X 10-12 C V-I m- 1
ch
Permitivity of vacuum (Eo)
(C V-I m- 1 =C2 N-1 m-2)
41t x 10-7 H m- 1
al
Permeability of vacuum (f.1 o )
Planck's constant (h) 6.62618 X 10-27 erg sec 6.62618 x 10-34 J s
e
Rest mass of proton (m p ) 1.672648 x 10-24 g 1.672648 x 10-27 kg

th
Rest mass of neutron (m n ) 1.674954 X 10-24 g 1.674954 X 10-27 kg

Atomic mass unit (u) 1.660565 x 10-24 g 1.660565 X 10-27 kg
e/
=
(l u 10-3 kg mol- 1INA ) (= 931.48 MeV)
t.m
Vacuum speed of light (c) 2.99793 X 10 10 cm sec- 1 2.99793 x 108 m S-l

Standard atmospheric pressure 76 cm Hg 101.325 kPa
760 mm Hg (or torr) 1.01325 bar
e
1.1032 x 106 dyne cm-2

er
Hartree energy (Eh) 4.3597 X 10-18 J

Zero of the Celsius scale 273.15 K
H
k
lic
C
APPENDIX III
Wavelength and Colours
Table 1: Spectral wavelength and colours

Range of the wavelength Colour of the radiation Complementary
absorbed (nm) absorbed colour observed
400-450 Violet Green-yellow
450-470 Indigo Yellow
470-490 Blue Orange
490-500 Blue-green Red
500-560 Green Purple
ry
560-575 Green-yellow Violet
ra
575-590 Yellow Indigo
590-640 Orange Blue
ib
640-730 Red Blue-green
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em
ch
e al
th
e/
B
t.m
e
er
G
Artist's Colour Wheel: Colours and complementary colours.
H
k
Colours that stand opposite each other on the colour wheel are called as the complimentary colours. The amount of a colour in
lic
a particular image can be decreased by increasing its complimentary colour and vice-versa.
C
RGB colour model: In this model, red (R), green (G), and blue (B) are considered as the three primary colours that can generate
all the colours of the visible spectrum when mixed together in different proportions. Mixing of these three primary colours in equal parts
gives white and complete absence of these three colours results in black. Computer monitor devices use these three additive primaries
to produce the different colour shades.
ApPENDICES A.5
APPENDIX IV
Names, symbols, atomic numbers and atomic weights* of the elements
Element Symbol Atomic Atomic Element Symbol Atomic Atomic

number weight number weight
Actinium Ac 89 227.03 Lead Pb 82 207.19

Aluminium Al 13 26.98 Lithium Li 3 6.94
Americium Am 95 (243) Lutetium Lu 71 174.97
Antimony Sb 51 121.75 Magnesium Mg 12 24.31
Argon Ar 18 39.95 Manganese Mn 25 54.94
Arsenic As 33 74.92 Mendelevium Md 101 (258)
ry
Astatine At 85 (210) Mercury Hg 80 200.59
Barium Ba 56' 137.34 Molybdenum Mo 42 95.94
ra
Barkelium Bk 97 (247) Neodymium Nd 60 144.24
Be Ne
ib
Beryllium 4 9.01 Neon 10 20.18
Bismuth Bi 83 208.98 Neptunium Np 93 237.05
yl
Boron B 5 10.81 Nickel Ni 28 58.71
em
Bromine Br 35 79.91 Niobium Nb 41 92.91
Cadmium Cd 48 112.40 Nitrogen N 7 14.01
Calcium Ca 20 40.08 Nobelium No 102 (259)
ch
Californium Cf 98 (251) Osmium Os 76 190.2
Carbon C 6 12.01 Oxygen 0 8 16.00
al
Cerium Ce 58 140.12 Palladium Pd 46 106.4

e
Cesium Cs 55 132.91 Phosphorus P 15 30.97

th
Chlorine CI 17 35.45 Platinum Pt 78 195.09

Chromium Cr 24 52.01 Plutonium Pu 94 (244)
e/
CGbalt Co 27 58.93 Polonium Po 84 (209)

t.m
Copper Cu 29 63.54 Potassium K 19 39.10

Curium Cm 96 (247) Praeseodymium Pr 59 140.91
Dysprosium Dy 66 162.50 Promethium Pm 61 (145)
e
Einsteinium Es 99 (252) Protactinium Pa 91 231.04

er
Erbium Er 68 167.26 Radium Ra 88 226.03

Europium Eu 63 151.96 Radon Rn 86 (222)
H
Fermium Fm 100 (257) Rhenium Re 75 186.2

Fluorine F 9 19.00 Rhodium Rh 45 102.91
k
Francium Fr 87 (223) Rubidium Rb 37 85.47

lic
Gadolinium Gd 64 157.25 Ruthenium Ru 44 101.07

Ga Sm
C
Gallium 31 69.72 Samarium 62 150.35

Germanium Ge 32 72.59 Scandium -Sc 21 44.96
Gold Au 79 196.97 Selenium Se 34 78.96
Hafnium Hf 72 178.49 Silicon Si 14 28.09
Helium He 2 4.00 Silver Ag 47 107.87
Holmium Ho 67 164.93 Sodium Na 11 22.99
Hydrogen H 1 1.008 Strontium Sr 38 87.62
Indium In 49 114.82 Sulfur S 16 32.06
Iodine I 53 126.90 Tantalum Ta 73 180.95
Iridium Ir 77 192.2 Technetium Tc 43 (99)
Iron Fe 26 55.85 Tellurium Te 52 127.60
Krypton Kr 36 83.80 Terbium Tb 65 158.92
Lanthanum La 57 138.91 Thallium Tl 81 204.37
Lawrencium* Lr 103 (260) Thorium Th 90 232.04
(Contd.)
* Previously it was represented by Lw. Now as per IUPAC recommendation, it is represented by Lr.
Element Symbol Atomic Atomic Element Symbol Atomic Atomic

number weight number weight
Thulium Tm 69 168.93 Xenon Xe 54 131.30

Tin Sn 50 118.69 Ytterbium Yb 70 173.04
Titanium Ti 22 47.90 Yttrium Y 39 88.91
Tungsten W 74 183.85 Zinc Zn 30 65.37
Uranium U 92 238.03 Zirconium Zr 40 91.22
Vanadium V 23 50.94
* Values are based on the presently accepted physical scale of 12C = 12.00000 as the standard. The ratio of these atomic weights to
those on older chemical scale assuming the value 16.0‫סס‬oo for the atomic weight of natural oxygen (composition: 160, 99.757%;
17 0,0.039%; 18 0,0.204%) is 1.000279. The values given within the parentheses are the mass numbers of the most commonly known
isotopes.
ry
The true atomic weight of natural oxygen is given by : 16 x 0.99757 + 17 x 0.00039 + 18 x 0.00204 = 16.00447.
ra
. . Physical atomic weight 16.00447 = 1.000279
It gIves. Chemical atomic weight 16.0‫סס‬oo
ib
Presently the term atomic weight is replaced by atomic mass or relative atomic mass (RAM). These are expressed in terms of amu
yl
or u or Da (Dalton). These aspects have been discussed in Sec. 5.2.3.
em
** For the translawrencium elements with Z> 103, the currently used names (cf. Chemistry of the Ele~ents by N.N. Greenwood and
A. Earnshaw and IUPAC, 1997) are : I04Rf(rutherfordium), lOsDb (dubnium), I06Sg (seaborgium), 107Bh (bohrium), lOSHs (hassium),
100Mt (meitnerium). However, other names to these elements have also been suggested from time to time. These are : Z = 104
ch
(kurchatovium, Ku; dubnium, Db), Z = 105 (hahnium, Ha, neilsbohrium, Ns, joliotium, Jl), Z = 106 (rutherfordium, R/), Z = 107
(neilsbohrium, Ns), Z = 108 (hahnium, Hn). The IUPAC (1977) recommendation, Le. a hybrid Latin-Greek numerical method (cf.
al
Sec. 8.6), is free from such confusions. The elements with Z = 110, Ill, 112, 114, 116, 118 have been characterised.
e
th
e/
APPENDIX V
t.m
Some Useful Mathematical Relationship

e
(A) Differentials
er
(u and v are the functions of x; a and m are constants).

H
dx =1 d du d du dv
(i) (ii) dx(au)=a (iii) dx (u+v)-= dx + dx
dx dx
k
lic
m m 1 dlnu 1 du
(iv) !!...x =mx - (v) !!...lnx=.!. (vi) - - = - -
dx
C
dx x dx udx
d ..!!... (eU) = eU du d dv du
(vii) _(eX)=e x (viii) (ix) dx (uv) = u dx + v dx
dx dx dx
v(:)-u(:) ~ (sin x) =cos x !!...

(x)
~(~)= v2
(xi) (xii)
dx
(cos x) = - sin x
d
(xiii) -(tan x) = sec 2 x (xiv) -d ( . ) =cosu-
slnu du (xv) -d (cosu ) =-slnu-
. du
dx dx dx dx dx
(8) Integrals
(u and v are the functions of x; a and m are constants; for the indefinite integrals, there should be an addition of arbitrary constant
of integration).
ApPENDICES A.7
(i) Jdx=x (ii) Jaudx = aJudx (iii) J(u + v)dx = Judx + Jvdx
x m+1
(iv) Jx m dx=--,(m=t-l)
m+l
(v) Jdx =inx
x
(vi) JeXdx=e x
(vii) (viii) JIn ax dx = x In ax - x (ix) Jsin x dx = - cos x

(x) Jcos x dx = sin x (xi) fuvdx = u f vdx - f[: fvdx] dx, (by parts)
Judv = uv - Jvdu Jxne-
00 ,
(xii) (xiii)-
ax
= a=~l ' (n positive integer)
ry
o
ra
(C) Trigonometric relationship
ib
(i) sin (900 - 9) = cos 9 (ii) cos (900 - 8) = sin 9
yl
(iii) exp (± im9) = cos (m9) ± i sin (mS), (Demovier's theorem)
em
1
cos (m9) =.!. [exp(imS) + exp(-im9)] sin (m9) = 2i [exp(im8) - exp(-im9)]
2
ch
(iv) sin 2 9 + cos 2 9 = 1 (v) sin 28 = 2sin 8 cos 8
al
2 2 2 2
(vi) cos 29 = cos 9 - sin 9 = 2cos 9 -1 = 1- 2sin 9 (vii) sin (a. ± (3) = sin a. cos 13 ± cos a. sin 13
e
th
(viii) cos (a. ± (3) = cos a. cos 13 + sin a. sin 13 (ix) sin a. ± sin 13 = 2 sin.!. (a. ± (3) cos.!. (a. :+ (3)
2
e/
2
t.m
(x) coso. + cos~ = 2 cos 2"1 (a. +~) cos 2"1 (a. - (3) (xi) coso. - cos 13 = - 2sin.!. (a. + (3) sin.!. (a. - (3)
2 2
sin a. sin ~ = .!. cos (a. - (3) - .!. cos (a. + ~) cos a. cos ~ = .!. sin (a. - ~) + .!. cos (a. + (3)
e
(xii) (xiii)
er
2 2 2 2
H
(xiv) sin a. cos 13 = .!. sin (a. + (3) + .!. sin (a. - ~)
2 2
k
lic
(0) Some Useful Expansions (Xl ~ 1)

C
(l + x)-l = 1 - x + x 2 -x3 + ..... (1 - x)-l = 1 + x + x 2 + x 3 + .... (l - x)-2 = 1 + 2x + 3x2 + 4x 3 + ....
x2 x3 x4
in (l+x)=x-2"+"3-4+ ....
x2 x3 x4
in (l-x)= -x-2"-"3-4 ....
x 2 x3 x4
exp(x)ore X =l+x+- +-+-+ .... , (for all x)
2! 3! 4!
3 5 7
. X X X
SIn X = X - 3! + 5! -7T + ...., (for all x)
2 4 6
x x x
cos X = 1- 2! + 4T - 6! + ...., (for all x)
In x! = x In x- x or x! = ~ (Stirling approximation, 1730)

eX
(for x > co. 10)
(E) Progressions
ry
(i) Arithmatic progression: a, a + d, a + 2d, ....
ra
n-th term (Tn) = a + (n - l)d;
ib
Sum of first n terms (Sn) =!!.. (1} + Tn) =!!.. {2a + (n -1)d}
yl
2 2
em
n(1 + n)
Sum of first n-natural numbers = 1 + 2 + 3 + .... + n = --2- ch
(ii) Geometric progression: a, ar, ar2, ....
al
a(1- r n )
n-th term (T ) = am - 1. Sum of first n terms (Sn) = - - - when r < 1
e
n ' (1-r)
th
a(r n -1)
e/
Sn =~ when r> 1; sum to infinity (Soo) = 1: r when Irl < 1

t.m
I
(iii) Useful results :
e
er
Lx 2
= - (n + 1) (2n + 1)
H
n
x=l 6n
n [ n ]2 For first n natural numbers, 1, 2, 3, ...., n
Lx 3
k
= -(n+l)
2
lic
x=l
C
(F) Permutations and combinations
n!= 1 x 2 x 3 x x (n - 2) x (n - 1) x n; O! =1
(G) Logarithms
log(mn) =log m + log n; log ( -;) =log m -log n,

) =n log m; log 1 =0; loga a =1; In(x) = 2.3 log x
n
log (m
Natural logarithm (base e); common logarithm (base 10).
(H) Mathematical Constants

1t = 3.14159265 ....., e = 2.71828...., In x =2.30258 ... loglOX
ApPENDICES A.9
APPENDIX VI
Books Consulted
Akhmetov, N.: General and Inorganic Chemistry Huheey, lE.: Inorganic Chemistry-Principles of Structure and
Akitt, J.W.: NMR and Chemistry Reactivity
Anantharaman, R.: Fundamentals of Quantum Chemistry Huheey, J.E., Keiter, E.A., Keiter, R.L. and O.K. Mehdi: Inorganic
Aruldhas, G.: Molecular Structure and Spectroscopy Chemistry-Principles of Structure and Reactivity
Ballhausen, C.J.: Introduction to Ligand Field Theory Jolly, W.L.: Principles of Inorganic Chemistry
Banerjea, D.: Inorganic Chemistry-Elements and Compounds Jorgensen, C.K.: Absorption spectra and Chemical Bonding in
Banerjea, D.: Coordination Chemistry Complexes
Banerjee, D.: Inorganic Chemistry (Principles) Kalshi, P.S.: Spectroscopy of Organic Compounds
Banerjea, D.: Fundamental Principles of Inorganic Chemistry Kapoor, K.L.: A Textbook of Physical Chemistry (Vol. 1-4)
Banwell, C.N.: Fundamentals of Molecular Spectroscopy Kettle, S.F.A.: Coordination Compounds
Berrow, GM.: Introduction to Molecular Spectroscopy Langford, C.H. and Gray, H.B.: Ligand Substitution Processes
ry
Basolo, E and Pearson, R.G: Mechanisms of Inorganic Reactions Laidler, K.J. and Meiser, J.H.: Physical Chemistry
Bertini, I., Gray, H.B., Lippard, S.J. ara' Valentine, J.S.: Lee, J.D.: Concise Inorganic Chemistry
ra
Bioinorganic Chemistry Lever, A.B.P.: Inorganic Electronic Spectroscopy
Carlin, R.L.: Magnetochemistry Lippard, S.J. and Berg, J.M.: Principles of Bioinorganic Chemistry
ib
Chanda, M.: Atomic Structure and Chemical Bonding Mackay, K.M. and Mackay, R.A.: Introduction of Modern
yl
Chatwal, GR. and Anand, S.K.: Spectroscopy Inorganic Chemistry
Connelly, G, Damhus, T. (Editors): Nomenclatute of Inorganic Mahan, B.H.: University Chemistry
em
Chemistry: IUPAC Recommendations 2005. Miessler, G.L. and Tarr, D.A.: Inorganic Chemistry
Cotton, EA. and Wilkinson, G: Advanced Inorganic Chemistry Mohan, l: Organic Spectroscopy: Principles and Applications.
ch
-Cotton, EA. and Wilkinson, G: Basic Inorganic Chemis'ry Mukherjee, G.N. & Das, A.: Elements of Bioinorganic Chemistry
Cotton, EA. and Wilkinson, G., Murillo, C.A. and Bochmann, Nakamoto, K.: Infrared Spectra of Inorganic and Coordination
al
M.: Advanced Inorganic Chemistry Compounds
Cotton, EA.: Chemical Applications of Group Theory Orchin, M. and Jaffe, H.H.: The Importance of Antibonding
e
Das, Asim K.: Bioinorganic Chemistry Orbitals

th
Das, Asim K.: Inorganic Chemistry: Biological and Environmental Pavia, D.L., Lampman, G.M. and Kriz, GS. : Introduction to
Aspects Spectroscopy
e/
Das, Asim K.: Environmental Chemistry with Green Chemistry Potterfied, W.W.: Inorganic Chemistry: A Unified Approach
t.m
Das, A.K.: A Textbook on Medicinal Aspects of Bioinorganic Purcell, K.F. and Kotz, J.C.: Inorganic Chemistry
Chemistry Rakshit, P.C.: Physical Chenlistry
Day (Jr), D.A. and UnderWood, A.L.: Quantitative Analysis Rao, C.N.R.: Chemical Applications of Infrared Spectroscopy
Rao, C.N.R.: Ultraviolet and Visible Spectroscopy
e
Day, M.C. and Selbin, l: Theoretical Inorganic Chemistry

Dorain, P.B.: Symmetry in Inorganic Chemistry Ray, R.K.: Electronic Spectra of Transition Metal Complexes
er
Douglas, B.E. McDaniel, D.H. and Alexander, J.J.: Concepts and Reddy, K.V.: Symmetry and Spectroscopy of Molecules
H
Models of Inorganic Chemistry Shriver, D.E, Atkins, P.W. and Langford, C.H.: Inorganic Chemistry
Drago, R.S,: Physical Methods in Chemistry Sarkar, R.: General and Inorganic Chemistry (Part I and II)
k
Drago, R.S.: Physical Methods for Chemists Satyanaryana, D.N.: Electronic Absorption Spectroscopy and
lic
Dyer, J.R.: Applications of Absorption Spectroscopy of Organic Related Techniques

Compounds Satyanarayana, D.N.: Vibrational Spectroscopy - Theory and
C
Dutta, P.K.: General and Inorganic Chemistry Applications

Dutta, R.L. and Syamal, A.: Elements of Magnetochemistry Sharpe, A.G.: Inorganic Chemistry
Dutta, R.L.: Inorganic Chemistry (Part. I and II) Skoog, D.A., West, D.M., Holler, EJ. and Crouch, S.R.:
Earnshaw, A.: Introduction to Magnetochemistry Fundamental of Analytical Chemistry
Ebsworth E.A.V., Rankin, D.W.H. and Cradock, S.: Structural Solomon, E.I. and Lever, A.B.P.: Inorganic Electronic Structure
Methods in Inerganic Chemistry: and Spectroscopy
Emeleus, H.J. and Anderson, J.S.: Modern Aspects of Inorganic Steed, lW. and Atwood, J.L.: Supramolecular Chemistry
Chemistry Topping, J.: Errors of Observation and Their Treatment
Figgis, B.N.: Introduction to Ligand Fields Vogel, A.I.: A Textbook of Quantitative Inorganic Analysis
Glasstone, S.: Textbook of Physical Chemistry Wilkins, R.G.: The study of Kinetics and Mechanism of Reactions
Griffith J.S.: The Theory of Transition Metal Ions of Transition Metal Complexes
Greenwood, N.N. and Earnshaw, A.: Chemistry of the Elements Wulfsberg, G.: Inorganic Chemistry
Acknowledgement
The above listed references and sources have been freely consulted to borrow their views and ideas. The present authors are
indebted to all these authors to an endless extent. The present author expresses his heartiest thanks and grateful acknowledgement
to all of them.
ry
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ib
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Subject Index
13C_NMR spectroscopy 1841 Chelation therapy 1681, 1682

1st order NMR spectra 1824, Chelometric titrations 1687
1825 B (Benzenoid) bands 1992 Chelones 1687
2nd order NMR spectra 1826 ~-Nitroso-a-naphthol 1673 Chemical equivalence 1809
Bandwidth 1786 Chemical isomer shift 1950
Bathochromic shift 1993 Chemical shift reagents 1829
Bathocuproin 1674 Chemical shifts 1787
Benzene 2016 Chemical term 1954
Benzenoid band 2015 Chromophores 1992
a-Benzoinoxime 1679
ry
Benzenoid form 1999 Chromotropic acid 1672
a-Nitroso-~-naphthol 1665, 1672
Benzimidazole 1681
ra
Absorption bands in the aromatic Circular dichorism (CD) 2069
Benzoinoxime 1661, 1679 Cis-platin 1683
compounds 2015
ib
Biphenyl 2002 Coefficient of variation 2132
Abundance of isotopes 2061
yl
Blue shift 1994, 2005 Complexometrlc titrations 1681,
Accuracy 2116, 2117
BphaH 1678
em
Accuracy vs. precision 2117 1687
British antiLewisite 1681 Complexones 1687, 1688
Alizarin 1664, 1673
Brown ring complex 1970 Conditional or effective stability
ch
Alizarin-S 1664
Brown ring test 1673, 1970 constant 1693, 1695, 1699
Aluminon 1664
al
Aminopolycarboxylic acids 1683 Confidence interval 2133, 2135
Confidence level 2133, 2135
e
Amperometry 2069
th
Analytical chemistry 1659 Constant error 2119

Anharmonic oscillator 1720 Calgon 1683 Correlation coefficient 2162,
e/
Anisotropic g-values 1938 Calmagite 1706 2163, 2166

t.m
Anti-Stokes line 1724 Carbonyl compounds 1763 Coulometry 2069

Appearance potential 2061 Carboplatin 1683 Coupling 1740
Aqua regia 1685 Catalase 1980 Coupling constant 1813, 1814
e
Arsenic acids 1679 Central tendency 2112, 2126 Coupling mechanism 1767
er
Asymmetry parameter (11) 2031, Centre shift 1950 Covalent-ionic resonance 1762
H
2033 Character tables 2095 Cupferron 1663, 1674, 1679

Aurintricarboxylic acid 1682 Characteristic group vibrations Cupron 1661, 1679
k
Auxochromes 1993 1734 Cyanido complexes 1767

lic
Average deviation 2126 Characteristic stretching Cyclic voltammetry 2069

C
Azulene 2000 frequencies 1737 Cytochrome c oxidase 1931
1.1
1.2 FUNDAMENTAL CONCEPTS OF INORGANIC CHEMISTRY
Electroplating process 1684 Gravimetric analysis 1677

ENDOR 1943 Group vibration frequency 1738
D-penicillamine (DPA) 1681 Enones 2014 Gutmann's rule 1761
Decoupling 1838 Error function 2124, 2125 Gyromagnetic ratio of the
Decoupling if field 1831 Errors in analysis 2112 nucleus 1780
Demasking 1679 Erychrome black-T 1705
Deposition potential 1684 ESR 1871
Desferal 1682 ESR spectroscopy 1871
Desferrioxamine-B 1682 ESR studies 1873 Harmonic oscillator 1720
Detergents 1681 ESR transition 1872 Hemerythrin 1980
Diamagnetic shielding 1790, 1796 Ethylenediaminetetraacetic Hexafluoroacetylacetone 1674
Diastereotopic hydrogens 1866 acid 1688 HiPIP 1985
Dihydrogen complexes 1766~
ry
Exchange broadening 1879, 1941 Histogram 2121
1852 Exchange interaction 1879
ra
Homoanular diene 2004
Dimethylglyoxime 1671 Exchange narrowing 1879, 1941 Hot bands 1721
ib
Dinitrogen complexes 1765 Exchange rate constants 1834 HSAB theory 1682
Dioximes 1679
yl
Extraction of gold 1685 Hydrazine preparation 1684
Dioxygen complexes 1765 Extraction of silver 1685
em
Hydrogen bonding 1791
Diphenylcarbadiazone 1676
Hydroxamic acid 1663
Diphenylcarbazide 1676
Hyperchromic shift 1994
ch
Diphenylcarbazone 1671, 1676
Diphenylthiocarbazone 1670
[J Hyperfine splitting constant 1896
al
Hyperfine splitting of the ESR
Distribution of random errors 2121 F-test 2140 signals 1896
e
Dithiooxamide 1661 Fenni contact term 1962 Hypochromic effect 1994

th
Dithizone 1670 Fermi resonance 1741 Hypochromic shift 1994

e/
DMSA 1681 Ferredoxin 1931, 1933, 1982, Hypsochromic shift 1994

Doppler broadening 1946 1983
t.m
Doppler shift 1943, 1944, 1946 Ferroin 1662, 1663

Double resonance 1831 Fine structure and hyperfine
DPPH 1936, 1941
e
structure of the ESR 1912

Indigotin 2011
er
Fine structure of the NMR

signals 1801 Inelastic collisions 1724
H
Infrared spectroscopy 1728

~ Fingerprints 1736
Floating point representation 2155 Intermolecular H-bonding 2010
k
E (Ethylenic) bands 1992 Inversion vibration 1749

lic
Force constants (k) 1720

EDTA 1688 Fourier transform Ion-pair charge transfer (IPCT)
C
Effective spin (S') 1889 spectroscopy 1731 band 1994

EFG 1971, 2031, 2032 Fractional error 2116 IR-active and Raman modes 1747
Elastic collision 1724 Franck-Condon principle 1991, Iron proteins 1928
ELDOR 1943 2007 Isochronous 1816
Electric field gradient (EFG) 1971, Fremy's salt 1936 Isomer shift 1950
2031, 2032 Frequency polygon 2121 Isosbestic point 1994
Electron paramagnetic resonance Fulvene 2000 Isotopic shift 1722
(EPR) 1871 Fundamental transition 1721
Electron spin resonance (ESR)
spectroscopy 1870 [K]
Electronic spectroscopy 1986 K-bands 1992
Electronic transitions in H2 2029 Karplus equation 1815
Electronic transitions in O2 2030 "(-ray spectroscopy 1943 Keto-enol tautomerism 1742,
Electronic transitions in the g-value 1934, 1936 1792, 2008
diatomic molecules 2028 Gaussian curve 2114, 2121 Ketone moiety 1740
SUBJECT INDEX 1.3
Kinematic coupling 1740 Neocupferron 1679 Paramagnetic interaction 1793

Kramers'degeneracy 1879, 1881 Neocuproin 1674 Paramagnetic shielding 1852,
Nitroprusside 1970 1862
Nitrosyl complexes 1764 Pascal's triangle 1807, 1899
Nitrosyldisulfonate radical 1936 Peak broadening 1782
Laplace equation 2032 Nitrous oxide reductase 1931 Percent relative standard
Larmor frequency 1780, 1781 Nitroxide molecules 1916, 1943 deviation 2132
Least squares method 2164 Nitroxides 1916, 1941 Peroxidase 1980
Linear regression equation 2164 NMR active nuclei 1779 Peroxido complexes 1666, 1667,
Linkage isomers 1770 NMR spectroscopy 1779 1765
Noise decoupling 1833 Phase change 2052, 2056
Nonclassical carbonyl Phenolphthalein 1998, 1999
ry
complexes 1764 Phenylarsonic acid 1673
Normal (gaussian) error curve 2121 Phosphoryl compounds 1742
ra
Magic pentagon 1938
Magnetic equivalence 1810 Normal curve 2121 Photoelectron spectroscopy 2031
ib
Magnetic hyperfine Normal equations 2164, 2165, Photography 1686
2167 Plastocyanin 1929
yl
interaction 1960
Normal modes of molecular Polarography 2069
em
Mantissa 2155, 2161
Masking 1661 vibrations 1725, 1733, 2107 Polyaminocarboxylic acids 1682
Masking agent 1679 NQR group frequency 2056 Polyphosphates 1681
ch
Mass spectrometry 2059 NQR spectroscopy 2033 Population mean 2122
Nuclear magnetic double resonance Population standard
al
McConnell equation 1910, 1916,
1920, 1930 (NMDR) 1831 deviation 2123, 2128
e
Mean 2112 Nuclear magnetic resonance 1779 Potentiometry 2069

th
Mean deviation 2126 Nuclear overhauser effect Precision 2116

e/
Median (Me) 2114 (NOE) 1785, 1831, 1833, Principle of superposition

1844 of errors 2143
t.m
Medicinal chemistry 1681

Mercurimetric titration 1713 Nuclear quadrupolar coupling Probable error of the mean 2132
Metal carbonlys 1755 constant 2035 Probable random analytical
e
Metal ion indicator 1706, 1707 Nuclear quadrupole moment 2031 error 2137
er
Metal-edta complexes 1689 Nuclear quadrupole resonance Propagated random error 2153
(NQR) spectroscopy 2031 Propagation of random error 2143
H
Metallochromic indicators 1705

Metallurgical process 1685 Nuclear spin (I) 1779, 1896 Proportional error 2119, 2120
k
Methylorange 1998, 1999 Nuclear term 1954 Proton decoupling 1843

lic
Methyl red 1998 Nuclei spin system 1822 Proton exchange 1805
Nujol 1731 Proton exchange process 1834
C
Mode 2114
Mond's process 1686 Null hypothesis 2139 Prussian blue 1969
Morse potential diagram 1720 Pseudo-arolnaticity 1768
Mossbauer spectroscopy 1943
Most probable random error 2144
Motional broadening 1879 Optical rotatory dispersion
MRI (magnetic resonance (ORD) 2069 Q-test 2142
imaging) 1683 Overtone 1721 Quadruple peak broadening 1838
Murexide 1706 OxinH 1678 Quadrupole broadening 1840
Quadrupole effects 1838
Quadrupole interaction 1955
Quadrupole moment 2032
N-acety 1-D-penicillamine P. Ray 1662 Quadrupole nucleus 2031
(NAPA) 1681 Paramagnetic deshielding 1794, Quadrupole relaxation 1839
Neighbour anisotropic effect 1794 1796 Quadlupole splitting 1958, 1971
1.4 FUNDAMENTAL CONCEPTS OF INORGANIC CHEMISTRY
Qualitative analysis 1659 Selection rules for ir-spectra 1726

Quinaldic acid 1678 Sequestring agents 1679
Quinalizarin 1669 Shielding constant 1787 t-test 2139
Quinonoid form 1999 Shift reagents 1830 Term symbols of the diatomic
Significant figures 2153, 2154, molecules 2021
2156, 2157 Tetramethylsilane 1788
Sketetal vibrations 1736 Thiocomplexes 1660
Skewness 2115 Thiourea 1662
Sodium nitroprusside 1969 TMS 1788
R-Bands 1992
Solar energy conversion 1687 ITA 1674, 1675
Radio-imaging agents 1683
Radiofrequency 1781 Solid state effect 2044, 2055 Tunnelling 1749
Raman spectra 1719, 1724 Solochrome black-T 1705 Turnbull blue 1969
ry
Random or indeterminate Solvent cutoff points 1995 Tuttons salt 1940
Solvent extraction 1673 Twisting mode 1733
ra
errors 2116, 2120
Range 2126 Solvent shifts 2008
ib
Rasching process 1684 Solvents used in PMR
yl
Rayleigh scattering 1724 studies 1789
em
Recoil energy 1944 SPADNS 1677 UV-Bands 1991
Recoilless transition 1947, 1948 Spectrophotometric analysis 1676 UV-PES 2031
Red shift 1993, 2005 Spin decoupling 1831 UV-Visible spectroscopy 1986
ch
Regression analysis 2162 Spin labels )943
Spin-lattice relaxation 1784, 1839,
al
Regression coefficient 2165
Regres~ion equation 2164 1875
e
Regression line 2166 Spin-orbit coupling 2110

th
Variance ratio test (F-test) 2140

Hejection of an observation 2141 Spin-orbit coupling splitting 1876 Versene 1688
e/
R~Jative error 2116 Spin-spin coupling 1801, 1813 Vibration-rotation combined

t.m
Relative standard deviation 2132 Spin-spin relaxation 1784, 1878 spectrum 1722
Relaxation 1783, 1875 Stability constants 1689 Vibrational spectroscopy 1719
Relaxation prolcsses 1784 Stabilization of unusual oxidation Volumetric titration by edta 1680
e
Remote e1f~c1 1795 states 1687

er
Rhombic symluetry 1886, 193~ Standard deviation 2127

Standard en'or of the mean 2133
H
Ring current 1797

Rocking mode 1732 Standard en'or of the standard
Wagging nlode 1733
k
Root mean square deviation 2127 deviation 2134

Water softening 1683
lic
Rotational isomerisnl 1865 Statistical tests 2142

Wilson's disease 1681
Stereochemicallyactive
C
Rotational-vibrational energy 1722 Woodward's rules 2015

Rounding-off numbers 2153 lone pair 1978
Rubeanic acid 1661 Stcreochcmically inactive
Ruberidoxin 1931, 1983 lone pair 1985
Rule of nlutual exclusion 1729 Stilbene 2001
Stokes lines 1724 Yellow ammonium sulfide 1659,
Student's t 2136 1660
Sulfosalicylie acid 1664
Superoxido complex 1765
Salicylaldoxime 1661, 1678 Symmetries of the normal
Schumann-Runge band 2031 modes 1725 Zeeman effect 2042
Scissoring mode 1732 Systematic or determinate Zero-field (crystal field) splitting
Selection rules 2028 errors 2116, 2118 1879, 1880, 1889
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Molecular Recognitions; Acids and Bases and Ionic Equilbria; Nonaqueous

EMF Diagrams; Electroanalytical Techniques; Photoredox Reactions; Oscillating

Metal Complexes - Reaction Mechanisms (Ligand Substitution, Isomerisation,

Racemisation, Electron Transfer and Photochemical Reactions); Electronic

Former Research Associate, Department of Chemistry

Visva Bharatt University, Santiniketan 731235

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Prof Priyadara'1ian Ray (1888-:1982)

who made a significant contribution

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included. Magnetochemistry and organometallic chemistry have been covered. Applications

the goddess of learning.

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11.5 Metal Complexes and Solar Energy Conversion 1687

11.6 Complexation and Stabilization of Unusual Oxidation States 1687

11.7 Complexometric Titrations 1687

Ethylenediaminetetraacetic Acid (called also Versene, Complexone-III): A Potential

Complexing Agent; Minimum Required Value of C~nditional or Effective Stability Constant

and Suitable pH Range for Titration by Ethylenediaminetetraacetic Acid; Effect of Other

Complexing Agents on Complexometric Titration Curves; Effect of other Complexing Ligands

Indicators; Selection of Metal Ion Indicator in Complexometric Titration: A Quantitative

Treatment; Different Types of Complexometric Titrations; Selectivity in Titration with edta

Magnetically Equivalent and Nonequivalent Nuclei: Magnetic Equivalence vs. Chemical

12.3 Electron Spin Resonance (ESR) Spectroscopy 1870

12.5 Electronic Spectroscopy: UV-Visible Spectroscopy 1986

Electronic Spectroscopy of the Transition Metal Complexes; Electronic Transitions in Organic

Effect (i.e. Solvatochromism or Solvatochromic Shift) on the Position of the Absorption

Effect of Intramolecular H-Bonding on the Positions of the Absorption Bands: Identification

Characteristics of the Absorption Bands of the Carbonyl Compounds; Characteristics of the

of Iodine (12) and Bromine (Br2) in Different Solvents 2020

13.1 Introduction to Errors in Analysis 2112

13.3 Characteristics of Systematic Errors 2118

13.4 Characteristics of the Random or Indeterminate Errors 2120

13.5 Distribution of Random Errors: Statistical Treatment of Random Errors 2121

Significant Figures in Numerical Computation of Multiplication and Division; Significant

Subject Index 1-1-1-4

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11.1 METAL COMPLEXES IN ANALYTICAL CHEMISTRY

Residue Filtrate contains PbCI 2

(H9 2 C1 2 + AgCI) (PbCI 2 is soluble in hot water

but not in cold water)

Residue (black) Filtrate

Gr-IIA sulfides (i.e. HgS, PbS, Bi 2S3 , CuS, CdS)

yellow ammonium sulfide

AS 2S 3 + 3(NH4)2Sx ~ 6NHt + 2AsSl- + (3x - 5)S ~

have any oxidizing action).

2Assl- + 6H+ ~ As 2S S ~ + 3H2S~ As 2S S ~ AS 2S 3 ~ + 2S ~

2SbSl- + 6H+ ~ Sb2Ss ~ + 3H2S; SnS1- + 2H+ ~ SnS2 J,. + H 2S.

precipitated as sulfides. They are separated as follows:

In presence of excess CN-, Cu(ll) is reduced and complexed as follows:

2CuCN + 6CN- ~ 2[Cu(CN)4]3- (cyanido complex).

C==NOH " C==N 0I

(Greenish yellow precipitate)

(Note: Pd(II) gives a similar precipitate in acetic acid solution)