Contents ... 4, INTRODUCTION TO SPECTROSCOPY 1.4-1.8 11 Introduction 11 12 Types of Spectroscopy 11 13 Nature of Electromagnetic Radiations 12 14 Electromagnetic Spectrum 13 15 Terms Used in Spectroscopy 13 * Summary 16 + Exercise 16 2. ULTRA-VIOLET AND VISIBLE SPECTROSCOPY 2.1 - 2.20 2.1 Introduction 21 21.1 Electromagnetic Radiations 22 2.12 The Absorption Spectrum 22 2.13 Nature of Bands obtained in UV Spectra 24 22. Electronic Transitions 25 23. Terms Used in Ultra-Violet Spectroscopy 27 23.1 Chromophore 27 23.2 Auxochrome 27 2.33 Bathochromic Shift (Red Shift) 28 234 Bathochromic Shift (Red Shift) 28 235 — Hyperchromic Effect 28 236 — Hypochromic Effect 29 24 Applications of Visible and Ultra-Violet Spectroscopy 29 25 Applications of Electronic Spectroscopy and Woodward's Rules 29 25.1 Conjugated Dienes 2.10 25.2 Conjugated Carbonyl Compounds 2u 25.3 Calculation of Ama by Woodward and Fieser Rules for Dienes and Enones 2.12 * Summary 216 * — Bercise 217 3. INFRA-RED SPECTROSCOPY 3.1-3.20 3.1 Introduction 31 32 Infra-Red Radiations and Types of Vibrations 31 33 Divisions of IR 34 oa Infra-Red Spectroscopy in Organic Molecules 3S . ‘aracteristic LR. Absorption of Some Groups 3.5 35.1 Simple Alcohols, Ethers and Phenols 36 26 coc esos rata : 37 Applications of Spectroscory | — GTOUP eu * Summary 4 _ 2 Brercise 3.15Chapter ul Introduction to Spectroscopy 1.1. Introduction 1.2 Types of Spectroscopy 1.3 Nature of Electromagnetic Radiations 1.4 Electromagnetic Spectrum 1.5 _ Terms Used in Spectroscopy * Summary * Beercise INTRODUCTION Whenever an unknown compo first and the foremost Job of a mod the physical and chemical pro, Upto the early of 20" cer chemical methods. These und is synthesized or isolated lern organic chemist is to dete erties are directly dependent on th ntury, determination of mol methods were tedious, ti from natural sources, the rmine its structure; since all 'e structure of the m lecular structure was based m: imi olecule. inly on tives, degradation of laboratory by an fe been 'roscopic methods are the most them. They provide accurate information about the structure of the molecule in a very short time. These methods can be Used to detect intermediates during the Course of a reaction the reaction, The Spectroscopic methods sui Resonance (NMR), Mass, X- Of organic compounds. More TYPES OF s ich as Ultravi tay diffraction etc, eover, this informati PECTROSCopy the molecule i ~ le are eae exposed to some kinds Of radiations and the responses ect’ its porns Seal in the fon 8 graph called as spectrum. By ioSOPY is the study of responses OM light on the structure of molecules. Therefore, Of radiations= 'SeS of the Molecule when it is exposed to certain kinds iolet (WV), Inf Provide good ion is More a Red (.R), Nuclear Magnetic information about the structure accurate and reliable,ON [Link]. Organic Chemistry-Il (Sem. VI) (PU) __1.2 Introduction to Sey (a) Absorption Spectroscopy : A given molecule when exposed to radiations absorbs part of it and gets excited ay goes to higher energy. The amount and the type of wavelength of radiations absorbey ° the molecule in order to reach the excited state depends upon structural features of the molecule. Therefore, by studying the type of radiation absorbed, it is possible to predict wha kind of structural features are present in the molecule. The absorption of different types oy radiations such as UV, visible, infrared, microwave, radio waves produce different kinds of excitations of the molecule and each excitation provides some important information abou, the structure. Since, in all these methods, the nature of the radiation absorbed is studied, the spectroscopic methods are designated as ‘absorption spectroscopy’. (b) Emission Spectroscopy : Once the molecule absorbs radiations, it goes to the higher energy state or the excited state. However, the life time of this state is very small and molecule would loose absorbed energy in the form of heat or other kinds of radiations and comes back to the ground state. The radiations emitted by molecules can also be studied to reveal the structure of a molecule. This is called as ‘emission spectroscopy’. e.g. Phosphorescence and fluorescence emission of certain colours when inorganic salts are directly heated in a flame. However, emission spectroscopy has not provided much information about the structure of the molecule as absorption spectroscopy, hence it is not very popular. 1.3 NATURE OF ELECTROMAGNETIC RADIATIONS Radiations exhibit dual nature i.e. particle and waveform. In studying spectroscopy our emphasis is more on the ‘waveform’ of the radiation. The electromagnetic waves have the same velocity as that of light. These waves also show the properties of visible light. All radiations when propagate in waveform produce electric field and magnetic field. Thus, electromagnetic radiations consist of waves composed of an electric vector and 4 magnetic vector. Both these vectors are mutually perpendicular to each other and also perpendicular to the direction of propagation of light (Fig. 1.1), only the electric vector is responsible for the absorption of light. Electric vector 9074, 90° Direction of Propagation of light ‘Magnetic vector Fig. 1.1.[Link]. Organic Chemistry-II (Sem. VI) (PU) 1.3 Introduction to Spectroscopy 4.4 ELECTROMAGNETIC SPECTRUM The electromagnetic spectrum covers a very wide range of wavelengths. The most familiar electromagnetic radiation is the visible light. It lies between 400 - 800 nm (ie. 4000 to 8000 A’). The electromagnetic spectrum extends on both sides of the visible spectrum. It has microwaves and radio waves of longer wavelength at one end and X-rays and v-rays of very short wavelength at the other end. The region beyond red is called infra-red while that beyond violet is called as ultraviolet. Table 11 shows the whole electromagnetic region. Table 1.1 : Electromagnetic Spectrum Ranges 3 : g > 5 | 2 e 2 s ele |2/2/a |e |dslé |ggagee & x &/?3 > g = & 25/253 . . < ° 2 < =< s| 3s I< & & = x \s 7 3 | |e) 88) 88 e]e]% 8 zl/a las fe /F fe 2 |e is 8 8.)3 [8 ja] s ee 3% ages AS we move from left hand side to right hand side (Table 1.1), the wavelength goes on increasing, hence energy and frequency go on decreasing. 1.5 TERMS USED IN SPECTROSCOPY ] Electromagnetic wave is characterized by the following parameters : (1) Wavelength (A) : The distance between two successive crests (or troughs) is known aS wavelength. It is denoted by the symbol A. Direction of propagation Trough : Wave motion and wavelength (A)Introduction o Spectr, ‘ee Onan chat om V0 (PU . in which wavalongth ts measured are Angstrom (A°} millmieran (y waves passing through a certain Pont er secon (2) Frequency () bya symbol called as frequency and it id a8 wave number and itis and maximum disturbance ig to describe Electromagnetic Radiation Unit and Symbol Conversion Wavelength (A) | Micron (i) Ape lo%em Lm # 10° m (or 10" em) Limp = 20” em L ngstrom (AY) 1A® = 10 cm (or 1 AY = 0.1 nm) Frequency (0) | Cycles per sec (eps) LHe = Leps Werte (he LMHE ® 208 eps Freshell = 10! Wave number (| Resiprocal centimeter oe L em Lemay a Kayser 1 a 7 __| tkaysee #2 emt phoma Tees a ates ‘edation is made up of discrete particles called «an be described in ters of fe bye sles {tore propery electromagnetic radiation touch other bythe velocy of ight Rake unten ath The two parameters are elated Eatal : “yk E nergy of radiation erg) - he Man’ constant (627 x 10°? Frequency of radiations (2) ‘em see ‘aslation increases with increasing erg. sec) a NL Le ee latter are exposed to radiations. $ molecules, the molecules absorb part of it. The wavelength or lures of molecules. As a result ‘When radiation frequency of radiation absorbed depends upon struct microwaves are used (2 = 10° to 10” nm), molecules red is minimum, ns are used they bring about vibr than microwaves, along with vi (b) Molecular Energy Leve ray leads to different kinds of excitations of rotational, vibrational ‘These energy levels of molecules are known as ly represented in Fig, 1.3. ected — > va ——— | — & Eneroy Grand t serene ‘so 7 —+- t t & Fig, 1.3 : Molecular energy levels