Organic Spectroscopy

CHE 203 1.0

Prof. B. Asiri Perera

Department of Chemistry
University of Sri Jayewardenepura
 What is Spectroscopy ?

SPECTROSCOPY, is known as the study

of interaction between electromagnetic
radiation and matter

SPECTROMETRY is the quantitative

measurement of these interactions
SPECTROMETER is an instrument
which perform the measurement

SPECTRUM is the plot or graph that

shows the intensity or the response of
the atomic or molecular system to
different wavelengths of the radiation.
2
 MAIN METHODS OF SPECTROSCOPY
Ultra Violet (UV)
A technique used to identify characteristic of
the molecular structure and bonding patterns
based on electronic transitions.

Infra Red (IR)

Which reviles the presence or absence of key
functional groups based on bond vibration
frequency.
Nuclear Magnetic Resonance 1
(H
NMR &
13C NMR)

A technique which analyze H and C

environments using magnetic fields and
frequency pulses.

Mass Spectroscopy (MS)

A technique which gives the molecular
weight and formula both of the molecule
itself and various structural units within it.
 Electro Magnetic Radiation
Electromagnetic radiation is a form of energy that
is transmitted through space at very high velocities.

It propagates as both electric and magnetic waves

(wave property) traveling in packets of energy
called photons (particle property).
It takes many forms, such as radio waves,
microwaves, x-rays, sunlight etc

Covers a wider range of wavelengths from 10-16 m

5
- 10 m.
Electro Magnetic Spectrum

6
 Schematic Absorption Spectrum -
In organic chemistry mainly deal with molecular spectroscopy.

λmax
A spectroscopic transition takes a molecule
from one state to a state of higher energy.
Energy gap of a transition is a molecular
property and characteristic of molecular
structure. 8
 Special Terms in UV Spectroscopy
Chromophore
A band or group of bands, is due not to the whole
molecule, but to an identifiable part of the
molecule, call a chromophore. (light absorbing
groups in a molecule)

may correspond to a functional group. ( hydroxyl group

OH, or the double bond in a carbonyl group).

it may equally well correspond to a single atom within a

molecule or to a group of atoms (methyl CH3 ) which is
not normally associated with chemical functionality9
β-carotene is a strongly colored orange-red
pigment found in yellow and orange fruits,
such as carrots, pumpkins, and yams.

The long, extended series of conjugated

double bonds (shown in red) is the
chromophore.
10
Degree of Unsaturation ( D.O.U )

There can be double bonds, triple bonds or

rings in the structure.
The degree of unsaturation indicates the
number of π bonds or rings that the
compound contains
n−r+2
Cn Hn+r D.O.U =
2

11
 C6H12 n−r+2
Cn Hn+r D.O.U =
2
n=6,
n+r =12 6 −(12−6) + 2
6+r =12 D.O.U =
2
r =12-6 = 6
6 −(6) + 2
= =𝟏
2

Can be a single double bond structure or a ring

CH2 = CH-CH2CH2CH2CH3 or

( Check for IR band C=C peak at between 1680 – 1620 cm-1 )

C3 H7Br n − r + 2−𝐡𝐚𝐥𝐨𝐠𝐞𝐧
Cn Hn+r D.O.U =
2
n=3, 3 −(7−3) + 2 −𝟏
n+r =7 D.O.U =
2
3+r =7
r =7-3 = 4 3 − 4 + 2−𝟏
=
2
5−5
= =𝟎
CH3-CH2CH2-Br 2

Subtract number of halogen

 C2 H5NO n − r +2 +𝐧𝐢𝐭𝐫𝐨𝐠𝐞𝐧
Cn Hn+r D.O.U =
2
n=2,
n+r =5 2 −3 + 2+𝟏
2+r =5 =
2
r =5-2 = 3
5 −3
O = =1
2
C

CH3 NH2

Add number of Nitrogen.

Neglect Sulphur or Oxygen atoms
14
C7 H6Cl2 n − r + 2−𝐡𝐚𝐥𝐨𝐠𝐞𝐧
Cn Hn+r D.O.U =
2

n=7, 7−(6−7) + 2 − 𝟐
n+r = 6 D.O.U =
2
7+r = 6
r = 6-7 = -1 7 −(−1) + 2 −𝟐
D.O.U =
2
Cl
c 7+1) + 2 −𝟐
Cl D.O.U = =4
2

Most probably an aromatic ring.

1 for the ring and 3 for 3 double bonds. All 4
15
 Connectivity
A molecular formula of C3H5OCl contains the
structural elements -CH3 , -CI, -C=O, and -CH2-
this leaves two possible structures:

IR Spectroscopy determine whether there is a ketonic

carbonyl group (1) or an acid chloride ( 2).

NMR determine whether the methyl (-CH3) and

methylene(-CH2-) groups are separated(1) or adjacent(2)
16
 Sensitivity
It signifies the limits of detectability of a
chromophore.
e.g. 'H NMR) detect all chromophores with
equal sensitivity.
UV, the range of sensitivity towards different
chromophores spans many orders of
magnitude.
Generally, overall sensitivity, i.e. the amount of
sample required,
MS > UV > IR > 1H NMR > 13C NMR
Sensitivity decreases.
17
 ULTRA VIOLET SPECTROSCOPY
"UV spectroscopy" generally refers to
electronic transitions occurring in the
region of the electromagnetic spectrum (λ
in the range 200-380 nm)

Electronic transitions are also responsible

for absorption in the visible region
(approximately 380-800 nm)
18
 Basic Instrumentation for UV and IR-
consists of an energy source,a sample cell, a dispersing
device (prism or grating) and a detector 19
 Possible Transitions
The absorption bands are characterized by the wavelength
of the absorption maxima 𝝀max.
σ*
π * } Antibonding orbitals
n Non bonding orbital
π
σ } Bonding orbitals
The electronic transitions possible
σ σ*
π π *
n π *
n σ *
 σ *
σ Transitions
Compounds such as Methane (CH4) has C-H bond
𝝀max at 125 nm. Do not show absorption in UV
region. Energy required is large.

*
π Transitions
π
Compounds with multiple bonds like alkenes,
alkynes, carbonyl, nitriles, aromatic compounds.
Alkenes in the region 170 to 205 nm.
 *
σ Transitions
n
Saturated compounds containing atoms with
lone pair of electrons like O, N, S and halogens.
Transitions at 150 – 250 nm.

*
π Transitions
n
Compound with double bond involving hetero
atoms C=O, C=N, N=O Normally at 300 nm 22

22
 UV Transitions
*
π Transitions n *
π Transitions
π

Electronic transitions show absorption

in region above 200nm which is
accessible to UV-visible
spectrophotometer
23
Non bonding electrons do not form bonds . Lone pairs
of O , S , N and halogens.
Transitions to antibonding π* orbitals are associated
with the unsaturated centers of the molecule.
• Conjugated System
π π *
CH3 – CH = CH – CH = CH2

• Aldehydes and Ketones

O O *
n π 285 nm
C C *
H R R R
π π 185 nm
24
A molecule may show more than one band because
it may contain several chromophores or more than
one transition of a single chromophore is observed.

e.g. - Acetophenone

25
 Special Terms in UV Visible Spectroscopy
Auxochromes ( Auxiliary Chromophores )
Groups which have little UV absorption by themselves but
which often have significant effects on the absorption ( both
𝝀max and 𝛆 ) of a chromophore to which they are attached.

e.g. - Atoms with one or more lone pairs like OH, OR, NR2,
Halogen
OH NH2

𝐁𝐞𝐧𝐳𝐞𝐧𝐞 𝐏𝐡𝐞𝐧𝐨𝐥 𝐀𝐧𝐢𝐥𝐢𝐧𝐞

𝝀max 255 nm 𝝀max 270 nm 𝝀max 280nm
26
Hypsochromic Shift (Blue Shift)
Phenomenon where the 𝝀max of a compound shift
to a shorter wavelength (high E) due to an
attachment of an auxochrome or change of
solvent.
NH2 NH3+Cl-

H+ Acidic medium

𝐀𝐧𝐢𝐥𝐢𝐧𝐞
𝝀max 265 nm
𝛌max 280 nm

Aniline loses its conjugation. result Blue shift 27

Bathochromic Shift (Red Shift)
Phenomenon where the 𝝀max of a compound shift
to a longer wavelength due to an attachment of
an auxochrome or change of solvent.

OH- Alkaline medium O

OH NO2 O
-
N
O
-
𝐩 − 𝐧𝐢𝐭𝐫𝐨𝐩𝐡𝐞𝐧𝐨𝐥
𝝀max 400nm
𝝀max 310 nm

Negatively charged oxygen delocalizes more effectively

than in p-nitrophenol. result Red shift
Upon adding a base absorption peak wavelength
shifted toward the long wavelength region and the
absorption peaks tend to be larger.

𝐈 OH NO2
𝐈𝐈

OH-
𝐈
H+
O
𝐈𝐈 O
-
N
O
-

Two states of PNP

310 nm 400 nm in different conditions
Two characteristic peaks were observed. 29
Attachment of auxochrome in benzene to aniline

NH2

Red shift

𝐁𝐞𝐧𝐳𝐫𝐧𝐞 Aniline
𝝀max 255 nm 𝝀max 280 nm
Conjugate

30
 Hyperchromic Effect
Here the absorption intensity (ϵ molar absorptivity) of
the compound is increases. If auxochrome introduced
to the compound the intensity of absorption increases

Pyridien 2-methyl Pyridien

𝜆max 257 nm 𝜆max 260nm
ϵ = 2750 Lmol-1cm-1 ϵ = 3560Lmol-1cm-1

N pulls the electrons, CH3 donate electrones

reducing the π to N. π electron cloud
electron cloud present as it is
Hyporchromic Effect
Here the absorption intensity (ϵ) of a
compound is decreases.

naphthalene 2-methyl naphthalene

ϵ = 19000 Lmol-1cm-1 ϵ = 10250 Lmol-1cm-1

Due to the distortion of

the geometry by methyl
group
Shifts and Effect

Hyperchromic shift

Blue Red
shift shift
Absorbance

Hyporchromic shift

Wave lenth
 The effect of Solvent on absorption
Solvent polarity may affect the absorption
characteristics, in particular λmax .

non polar compounds

π π *

Have only π π* transition. In 95% ethanol

(polar) or hexane(non polar) solvents these non
polar compounds have very little effect on λmax .
Polar compounds π*
H

:
: π*
n
β E E
α n
α β unsaturated
: π π
carbonyl compounds
When change the solvent from non polar(hexane) to polar
solvent (ethanol) H bonding occur in non bonding electrons
and stabilizes bonding n level more than anti bonding π*
level. Energy gap n π* increases. Blue shift result.

But in π π* H bonding stabilizes π bonding level to a

lesser extend than π* level. Energy gap in π π* decreases.
Red shift result
 Larger Smaller
ΔE ΔE

Highly conjugate the system the lower the energy

difference (ΔE ) between molecular orbitals, lower the
required energy of light needed to exited the electrons.
36
1,5-Hexadiene 2,4-Hexadiene
𝝀max 178nm 𝝀max 227nm

Conjugation in a carbon chain will

increase the band intensity and also
shift 𝝀max into a longer wavelength.
 Important UV Chromophores
Dienes and Polyenes

Woodward Rules can be used to calculate the positions of

absorption maxima of conjugated alkenes and conjugated
carbonyl compounds. 38
 Woodward-Fieser Rules

Empirical rules (Woodward's Rules) of

good predictive value are available to
estimate the positions of the absorption
maxima in conjugated alkenes and
conjugated carbonyl compounds.

39
Each type of diene or triene system is having
a certain fixed value at which absorption
takes place which is the BASE VALUE or
PARENT VALUE.

The contribution by various alkyl

substituents or ring residue double bond
extending conjugation and polar groups such
as –Cl, –Br etc are added to the base value to
obtain 𝝀max for a particular compound.
40
 Calculation of 𝝀max using Woodward
Rules
According to Woodward rules the 𝝀max can be
calculated using,

𝝀max = Base Value + 𝜮 Substituent contributions

+ 𝜮 other contributions

41
 Parent Value/ Base value Conjugated dienes

Acyclic buta dienes 215 nm

Hetero annular conjugated

dienes (Conjugated diene in 215 nm
two rings)

Homo annular conjugated dienes 253 nm

(Conjugated diene in single ring)

Acyclic trienes 245 nm

 Auxochrome
Each alkyl substitute or ring residue 5 nm

Exocyclic double bond (onesp2

carbon of the bond is not a part 5 nm
of same ring

Double bond extending conjugation 30 nm

(two conjugated systems)

Increments
-OR 6 nm
-SR 30 nm
-Cl / Br 5 nm
-NR2 60 nm
-OCOCH3 0 nm 43
 CH3 CH2
C C

CH2 CH3

Acyclic conjugated diene = 215 nm

2 Alkyl substituents 2 × 5 = 10 nm

Calculated 𝝀max 225 nm

 CH3 H
CH3 C =C
C= C H
CH3 H

Parent conjugated = 215 nm

Alkyl Groups 3 × 5 = 15 nm

Calculated 𝝀max 230 nm

Observed 𝝀max 228 nm

46
47
48
49
 INFRA-RED SPECTROSCOPY
Study of the interaction between infrared
radiation and matter. Basic Instrumentation is
same as UV Spectroscopy.
𝝀 Range 2.5 𝜇m – 15 𝜇m

Wave number ν -1
(cm ) = 1/λ
-1 1
ν (cm ) = −4 −4
2.5×10 cm – 15×10 cm

ν (cm-1) = 4000 – 666 cm-1

50
 INFRA-RED Active compounds
For a particular vibration to result in the
absorption of IR energy, that vibration
must cause change in the dipole
moment (measure of polarity) of the
molecule.
The dipole moment should interact with
the electric vector to give a IR band. If
no dipole moment no interactions
would occur and no IR band.
Polar bonds are associated with strong IR
absorption while symmetrical bonds may
not absorb at all

CH3 – C ≡ C – CH3 CH3 CH3 H H

C=C C=C
CH3 CH3 H H

No net dipole of any of these symmetric 52

molecules due to symmetrical stretching.

Therefore no IR bands 52
IR bands are due to molecular vibrations which
are periodic motions involving stretching or
bending of bonds.

Shorter and stronger bonds (= or ≡ ) have

stretching vibrations at the higher energy
(shorter wavelength) longer and weaker bonds
(- bonds) have stretching vibrations at the lower
energy (longer wavelength)

Also bonds to lighter atoms (e.g.- hydrogen),

vibrate at higher energy than bonds attached to
heavier atoms. 53
 Sampling method
Material for cuvette should be
transparent and inert over this region.
Alkyl halides are widely used.(NaCl,
NaBr)

Solids dissolve in chloroform or carbon

tetrachloride can be examined in
compressed discs of KBr, KCl, NaCl)
54
55
Gas cells

IR radiation passes through a sample and

chemical vapors present in the gas sample
will absorb IR energy at different wave
lengths. 56
 Molecular Vibrations
Stretching Bending
Distance between Position of the atom
2 atoms changes changes relative to
the original bond axis
Vibrational = degrees of – translational – rotational
modes
,
freedom modes modes

= 3n – 3 – rotational
modes
n = number of atoms in the molecule 57
 Vibrational modes
non linear molecule with n no. of atoms

Vibrational modes = Degrees of freedom

– 3 translational – 3 rotations
= 3n – 3 -3
= 3n – 6

Methane CH4 3(5) – 6 = 9 modes of vibrations

Benzene C6H6 3(12) – 6 = 30 modes of vibrations

linear molecule with n no. of atoms

Vibrational modes = degrees of freedom

--3 translational – 2 rotations
= 3n – 5

Ethylene C2H2 3(4) – 5 = 7 modes of vibrations

59
 Mode of vibrations
CH4

In Plane
Symmetric stretching Asymmetric stretching

C H
 In Plane
Scissoring Rocking

Out of Plane
Wagging Twisting
 Distinct IR Bands

C=O - 1850-1630 cm-1

C=C -

C=C - 1680-1620 cm -1

sharp peak closer to C =O

esters
62
 Peak shift in carbonyl
-
C=O C O
+
C=C C C
Shift toward lower frequency associated with
the α,β-unsaturation. (Ketones 1700 – 1725,
α,β-unsaturated ketones 1660 – 1715(cm )-1

carbonyl band in an enone has more single

bond character and is therefore weaker 63
O-H Groups
N-H and O-H regions normally
overlap.

O-H 3500-3300 cm -1

One band usually broad.

Non hydrogen-bonded
-1
("free") 3600 cm Sharp

Hydrogen-bonded
3100 - 3200 cm -1
N-H Groups

N-H 3650-3200 cm-1

Primary amine (R-NH2)

two absorption bands.

2ryamine (R2-NH) one

band.
Aromatic Rings
Mono substituted Ring.
2 peaks
Near 690 and 750 cm-1

Mono

Meta Substituted Ring

3 band
690 ,780 and 880 cm-1

Meta
 Ortho Substituted Ring
1 strong band
near 750 cm-1

Ortho

Para Substituted Ring

1 strong band
800 – 850 cm-1

Para
67
 Alkenes

C=C double bonds in unconjugated

alkenes exhibit weak to moderate
absorptions due to C=C stretching in
the range 1660-1640 cm .-1

Alkenes conjugated with an aromatic

ring absorb strongly near 1625 cm -1

lower frequency .
 Fingerprint region
Region from about 1500 to 500 -1
cm .
Contains a very complicated series of
absorptions. Mainly due to bending
vibrations within the molecule.

Much more difficult to pick out individual

bonds in this region. Each different
compound produces a different pattern in
this part of the spectrum. 69
CH3CH2CH2OH

CH3CHCH3
OH

70
 Summary

O-H C ≡C C-Cl
C=C
C ≡ 𝐍 Very few C-O
C-H C=O C=N
X-C ≡C-Y bands C-N
N-H
(C,O,N,S) N=O C-C

4000 2500 2000 1800 1650 1550 650

 stronger weaker
≡ > = > -
2300-2000 1900-1500 1300-800

single bonds involve very small

motions C-H , O-H , N-H and
72

vibrations occur at a very high

frequency between 3700- 2630 cm -1

72
IR Spectrum

73
Important IR Chromophores

74
75
Other polar functional groups

76
Other polar functional groups

77
Chromophores absorbing in the region between
1900 - 2600 cm-1

78
79