Modern Infrared Spectroscopy

Analytical Chemistry by Open Learning

Author: BARBARA STUART University of Greenwich Editor: DAVID J. ANDO University of Greenwich

Published on behalf of A C O t (University of Greenwich) by JOHN WILEY & SONS Chichester New York Brisbane Toronto Singapore

Contents

Study Guide Supporting Practical Work Bibliography

xiii xv xvii

Acknowledgements 1. Introduction. . . 1.1. General Introduction 1.2. Electromagnetic Radiation 1.3. Vibrations of Molecules 1.3.1. Normal Modes of Vibration 1.3.2. Intensity of Infrared Bands 2. Instrumentation 2.1. Introduction 2.2. Representation of Spectra 2.3. Dispersive Spectrometers 2.3.1. Monochromators 2.3.2. Double-beam Instruments 2.3.3. Sources and Detectors 2.3.4. Limitations - 2.4. Fourier-transform Infrared Spectrometers 2.4.1. The Michelson Interferometer 2.4.2. Fourier Transformation 2.4.3. Advantages of Fourier-transform Infrared Spectroscopy . . : 2.4.4. Sources and Detectors 2.4.5. The Moving Mirror
IX

xix 1 1 2 6 7 13 19 19 19 20 21 22 22 23 24 24 26 27 28 28

Analytical Chemistry by Open Learning 3. Sampling 3.1. Introduction 3.2. Transmission Methods 3.2.1. Liquids and Solutions 3.2.2. Solids 3.2.3. Gases 3.2.4. Pathlength Calibration 3.3. Reflectance Methods 3.3.1. Attenuated Total Reflectance Spectroscopy 3.3.2. Specular Reflectance 3.3.3. Diffuse Reflectance 3.4. Other Techniques 3.4.1. Photoacoustic Spectroscopy 3.4.2. The Use of Temperature Cells 3.4.3. Microsampling 3.4.4. Combination Techniques 32 32 32 32 37 42 42 44 45 48 49 51 51 52 52 52

4. Spectrum Interpretation 55 4.1. Introduction . 55 4.2. Group Frequencies 55 4.2.1. The XH Stretching Region (4000-2500 cm' 1 ) . . . 55 4.2.2. Triple Bond Region (2500-2000 cm"1) 60 4.2.3. Double Bond Region (2000-1500 cm"1) 61 4.2.4. Fingerprint Region (1500-600 cm"1) 66 4.3. Complicating Factors 67 4.3.1. Overtone and Combination Bands 67 ..-- 4.3.2. Fermi Resonance 69 4.3.3. Hydrogen Bonding .70 5. Quantitative Analysis 5.1. Introduction 5.2. Spectrum Manipulation 5.2.1. Baseline Correction 5.2.2. Smoothing 5.2.3. Derivatives 5.2.4. Deconvolution 5.2.5. Curve-fitting. 5.3. Determination of Concentration 5.4. Simple Analysis 5.4.1. Analysis of Liquid Samples -. . . 75 75 75 76 76 77 79 81 81 85 85

Contents 5.4.2. Analysis of Solid Samples 5.5. Multicomponent Analysis 6. Applications 6.1. Introduction 6.2. Organic Compounds 6.2.1. Alkanes 6.2.2. Alkenes 6.2.3. Alkynes 6.2.4. Aromatic Compounds 6.2.5. Alcohols, Phenols and Ethers 6.2.6. Amines 6.2.7. Aldehydes and Ketones 6.2.8. Other Carbonyl Containing Compounds 6.2.9. Other Nitrogen Containing Compounds 6.2.10. Sulphur Containing Compounds 6.2.11. Halogen Containing Compounds 6.3. Inorganic Compounds 6.3.1. Boron Compounds 6.3.2. Silicon Compounds 6.3.3. Phosphorus Compounds 6.4. Polymers 6.4.1. Sample Preparation 6.4.2. Polypropylene 6.5. Biological Systems 6.5.1. Sample Preparation 6.5.2. Proteins 6.5.3. Lipids 6.6. Drug Analysis 6.7. Pollution Monitoring 6.8. Coal 6.9. Minerals 6.10. Catalysts 7. Identification of Unknown Samples 7.1. Introduction. . . .' > 7.2. Strategy , 7.3. Examples 7.4. Examples for Further Practice

xi 91 92 97 97 97 97 99 100 101 104 104 105 106 107 107 108 109 109 109 110 113 113 113 117 117 117 119 121 121 123 123 123 126 126 126 128 132

xii

Analytical Chemistry by Open Learning

Appendix 1. Correlation Table for Organic Molecules 2. 3. 4. Correlation Table for the Out-of-plane Bending Vibrations of Benzenoid Compounds

136 137

Correlation Table for Carbonyl Stretching Frequencies . . 138 Correlation Table for the Out-of-plane Bending Vibrations of Alkenes 139 140 171 177

Self-assessment Questions and Responses Units of Measurement Index