You are on page 1of 33

Guided by

Asst. Prof. Tathagata & Asst.Prof. Sarvana bhavan

Prepared by
S.M.FARIYAZ

What is Spectroscopy?

What is Electromagnetic Radiation?

WAVE PROPERTIES OF EMR

EMR has both electric component & magnetic component. Electric field varies in the direction of y-axis & magnetic field varies on x-axis.

What is Electromagnetic Spectrum?

INTERACTION OF RADIATION WITH MATTER


What happens EMR interacts with matter?

Sample

may Absorb/Emit

radiation Absorption spectra Emission spectra

Scattering / Reflection
Fluorescence

TYPES OF CHANGES
AFTER INTERACTION
Atomic

level Molecular level

TYPES OF SPECTROSCOPY

UV-VISIBLE THEORY
When a molecule absorbs ultraviolet radiation the electron in that molecule undergoes transition from lower to higher energy level.

Three types of electrons are involved in organic molecule-electronsInvolved in the saturated bonds. Found in the carbon, hydrogen in the paraffin. Energy required to excite electrons in -bonds is more than that produced by the UV-light. - electronsInvolved in unsaturated hydrocarbon. Present in trienes & aromatic compounds. n-electronsIt does not involve in the bonding of the molecules. Eg. N,O,& other halogens

Types of transition in the organic molecule


transition -* n-* -*
n-* usually allowed
* anti bonding * anti bonding

forbidden

energy

n*

non bonding
bonding bonding

Allowed transition:- having max 104 or more. This transition due to -* transition. In 1,3-butadiene exhibits absorption at 217 nm & has max 21000 represent allowed transition. Forbidden transition:- transition having max less than 104 .
Occurs due to n-*

transition .

Fig. 1 The order of orbital energies and approximate order of electronic transition energies in a hypothetical unsaturated molecule containing a heteroatom with a nonbonded electron pair (n).

BANDS
K-bands(kanjugierte)
Eg: butadiene,mesityl oxide

-* n-*

R-bands(radical) B-bands(benzenoid)

Eg: compounds with single chromophoric group Characteristic of aromatic & heteroaromatic compounds

E-bands(ethylenic)

BEERS LAW:
When light is incident upon a homogeneous medium,a part of the incident light is reflected ,a part is absorbed by the medium & the reminder is allowed to trasmit as such.

Intensity of incident light decreases exponentially as the concentration of absorbing medium increases arithmetically. It = I0 e-k' c It = I0 10-0.4343 k' c It = I0 10 K' c . . . . . . . . . .(4) Where, K and K' = a or c = concentration t or b = thickness of the medium log I0 / It = bc . . . . . . . . . .(5) = absorptivity

When a beam of light is allowed to pass through a transparent medium, the rate of decrease of intensity with the thickness of medium is directly proportional to the intensity of light. Mathematically, the Lamberts law may be expressed as follows. - dI / dt I -dI / dt = KI . . . . . . . . . .(1)

Where I = intensity of incident light t = thickness of the medium K= proportionality constant By integration of equation (1), and putting I=I0 when t=0, I0/ It = kt or It= I0 e-kt

TYPES OF TRANSITION IN THE INORGANIC MOLECULE


Inorganic molecules also exhibit the same kind of phenomenon
Eg:

CHROMOPHORE

AUXOCHROME

What is Electromagnetic Radiation?

SHIFTS
What is shift?

WOODWARD-FEISER RULE
It is used for calculating the absorption maxima Woodward (1941) gives certain rule for correlating max with the molecular structure These rules are modified by Scott & Feiser. This rule for calculating max in conjugated dienes, trienes, polyenes. Homoannular dienes:cyclic dienes having conjugated double bonds in the same ring. CH e.g.

CH3

Hateroannuler dienes:cyclic dienes in which double bonds in conjugation are present in the different ring. Endocyclic double bonds:it is the double bond present in ring as shown. Exocyclic double bonds:double bond in which one of the double bonded atom is the part of ring system.

e.g. Heteroannuler dienes

CH2

Endocyclic double bond

Exocyclic double bond

Woodwards-Fieser rule for conjugated dienes


a)Parent values1. Acyclic & Heteroannuler conjugated dienes 2.Homoannular conjugated dienes 3.Acyclic trienes 215 nm 253 nm 245 nm

b)Increments1.Each alkyl substituent or ring residue 2.Exocyclic double bond 3.Double bond extending conjugation 4.auxochromes-OR -SR -Cl , Br -NR2 -OCOCH3 5 nm 5 nm 30 nm 6 nm 30 nm 5 nm 60 nm 0 nm

Woodwards-Fieser rule for ,unsaturated carbonyl compounds


a)Parent values:1.,-unsaturated acyclic or six membered ring ketone 2.,-unsaturated five membered ring ketone 3.,-unsaturated aldehyde 215 nm 202nm 207nm

b)Increments:1.Each alkyl substituent or ring residue at , position at ,position at ,position 2.Each Exocyclic double bond 3.Double bond extending conjugation 4.Homoannular conjugatated dienes 5.Auxochromes. -OH 35 -OR 35 -SR -OCOCH3 6

10nm 12nm 18nm 5nm 30nm 39nm Positions 30 30 85 6


50 17 6

Problems:1) 1,4- dimethyl cyclohex-1,3,-diene


H3C CH3

Parent value for Homoannular diene = 253 nm Two alkyl substituent's 2 5 = 10 nm Two ring residues 2 5 = 10 nm Calculated value Observed value 2) Parent value for Heteroannuler diene = Four ring residue 4 5 Calculated value Observed value 215 nm = 20 nm = 235 nm = 236 nm = 273 nm = 265 nm

Woodwards rule for principal band of substituted benzene derivative


R-C6H4-COG parent chromophore:G=alkyl/ring residue G=H G=OH or O alkyl Add for R: Alkyl or ring residue max (nm) 246 250 230 o,m p 3 10

& R=H

-OH, OMe, -O-Alkyl


O-

o,m p
o m p

7 25
11 20 78

Cl
Br NH2 NMe2

o,m p
o,m P o,m p o,m p

0 10
2 15 13 58 20 85

1) Para chloroacetophenone
O C CH3

Cl Basic value Cl substitution at p- position Calculated value Observed value = 246 nm = 10 nm = 256 nm = 254nm

Gurdeep R. chatwal; Sham K. Anand; Instrumental Methods Of Chemical Analysis. Y. Anjaneyulu; K. Chandrasekhar; Valli Manickam; Text book of analytical chemistry. Y. R.Sharma; Elementary organic spectroscopy. P.S.Kalsi; Spectroscopy of organic compound. B.K.Sharma; Instrumental methods of chemical analysis.

Any Questions

You might also like