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What is Spectroscopy?
EMR has both electric component & magnetic component. Electric field varies in the direction of y-axis & magnetic field varies on x-axis.
Sample
may Absorb/Emit
Scattering / Reflection
Fluorescence
TYPES OF CHANGES
AFTER INTERACTION
Atomic
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
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
CHROMOPHORE
AUXOCHROME
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.
CH2
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
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
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
& R=H
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.
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