1

Spectroscopy
Introduction:
Determination of molecular structure is one of the central scopes of organic
chemistry. For this purpose, chemists today rely almost exclusively on
instrumental methods, four of which we discuss in this course. Infrared (IR) and
nuclear magnetic resonance (NMR) spectroscopy will be discussed in details,
while a brief introduction to ultraviolet (UV) and mass spectroscopy is also
contained.
Electromagnetic radiation (emr):
Gamma rays, X-rays, UV, visible light, IR, microwave and radio wave are all
types of Electromagnetic radiation. Because Electromagnetic radiation
behaves as a wave traveling at the speed of light, it can be described in terms of
wavelength () and frequency (v) according to the law: E = hv = hc/ . (page
474).
Theory of spestroscopy:
A molecule can undergo a transition (excitation) from energy state E1 to a higher
energy state E2 by irradiating the molecule with emr corresponding to the energy
difference between E2 and E1 energy states. When the molecule returns, it emits
equivalent amount of energy.
Molecules absorb energy to make several bond vibrations in IR radiation region.
Molecules absorb energy to make electronic transition in UV radiation region.
Molecules absorb energy to make nuclear spinning in NMR radiation region.
Molecular spectroscopy:
It is the instrumental process of measuring which frequencies of radiation are
absorbed or emitted by a particular compound and attempting to correlate
patterns of energy absorption or emission with details of molecular structure.
Infrared Spectroscopy
Introduction:
Infrared spectroscopy provides a direct method of detecting:
Certain functional groups in the molecule
- IR region 0.8-200 by wavelength but the fraction used in IR spectroscopy lies
between wavelength from 2.5 -16
- We use wave number ( =1/ cm
-1
) to describe IR
- Wave number is directly proportional to energy of IR





2
v IR spectrum:
Is a plot of transmittance against wave number
wave length in
IR peak
0
1.5
1
625
1000
2000
3000
50%
4000
100%
v
cm
-1
2.5
16
%T
A [absorbance]

Theory:
atom
atom

1) Molecules are in a continuous state of vibration. Different chemical bonds have
different vibrational frequencies & the energy associated with these frequencies
are quantized( have certain allowed energy)
2) When a molecule absorb IR radiation , the energy absorbed is used to induce
vibrational energy transition
3) In IR spectroscopy, we can identify a molecule by the presence of absorption
band at certain frequencies. e.g. the strong band at 1700-1725 cm
-1
is of
C=O ketoninc stretching.

the frequency of stretching vibration depends on:
1) Strength of the vibrating bond:
The stronger the bond the higher the frequency of the stretching vibration
e.g. CC is shorter than C=C so it is stronger and needs high energy, occur at
higher frequency
2) Masses of the atoms connected by the bond:
The smaller the atoms, the shorter the bond, the higher the frequency of
stretching vibration
E.g. C-H , N-H ,O-H bonds occurs at high frequency due to hydrogen atom.
3) hybridization
alkyne>alkene>alkane in IR: as alkynes has sp orbital which make short bond
so more IR frequency, also sp
2
orbital in alkenes make shorter bond than alkane
so alkenes has more IR frequency
+ Modes or types of vibration:
a) Stretching vibration: 4000-1400 cm
-1

- It occur for function group so called fuctional group region
- The distance between the 2 atoms increase or decrease but atoms remain in the
bond axis(same plane)
It may be symmetric or asymmetric as shown:
3

sym asy


b) Bending(deformational)vibrations: 1400-650 cm
-1

- It is called finger print region as It is rich in absorption bands and shoulders
- The position of the atoms changes relative to the bond axis.
- it may be:
a) In plane b) Out of plane
Scissor

Rock

Twist

Wag



The stretching energy is higher than bending energy so of higher frequencies.
- Identification by fingerprint:
- The region (1400-650 cm-1) containing many absorption caused by
bending vibration as well as absorption caused by C-C,C-O,C-N
- Substance gives the same spectra(same finger print) are the same










4


Application of IR spectroscopy:

1) The identification of characteristic absorption bands caused by
different functional group.
IR frequencies of functional gp
group Frequency range cm
-1

O-H str. Of alcohols & phenols 3600-3200
N-H str. 3600-3200
OH str. Of carboxylic 3500-2500
-CC-H( alkyne C-H) 3300
=C-H( alkene & aromatic C-H) (peaks) 3100-3000(>3000)
-C-H( alkane C-H) (peaks) 2950-2850(<3000)
C-H str. Of aldhyde(-CO-H) 2850-2700
CC str.(alkyne) &CN( nitrile) 2300-2100
C=O str.( aldhyde ,ketones, acids) 1800-1650
C=C str. Of aromatic ring (peaks) 1600-1450
C=C str. Of alkene (peaks) 1650-1600
C-O bond str
1100-1250 e.g. C-O of
CH3OH


Carbonyl stretching frequencies
Aldehyde RCHO (saturated) 1740-1720
Acid RCOOH(saturated) 1725-1700
Ketone RCOR(saturated) 1725-1700
RCOOR Ester (acyclic= no
cycle)
1750
Acid halide
R C X
O
x = halogen
1815-1720
Acid anydrides
2 bands separated by 60 cm
-1
at
1850-1800 cm
-1
& 1780-1740 cm
-1

R C NH
2
O

amides
1700-1650
C
O
C
O
O
R
R

5

1000
3000 2000 1800 1650
1600
OH
NH
CH
C C
C N
CH
CH
2
O
C
C
C
C
C
a
r
o
m
a
t
i
c
a
l
k
e
n
e
o
u
t

o
f

p
l
a
n
e

b
e
n
d
i
n
g

- NOTES ON IR:
1) OH &
NH str
OH & NH appear at lower frequencies and broader if it is
hydrogen bonded
2) amines
Primary amines give 2 peaks in 3500-3300 cm
-1
(forked peak)
Secondary amines gives one peak in same region
Tertiary amines gives no peaks in the region of 3500-3300 cm
-1
















Factors which cause minor shift in IR region:
1) electronic effect(inductive & resonance effect):
- resonance lower the frequency of C=O & C=C str.because it decrease the
double bond character of C=O &C=C
O
O
O
C=o v
1700
1720 1700
C=C v
1650
1610


- C=O frequency is changed also due to:
6
- -I effect increase double bond character so Increasing frequency

2) H-bonding:
-intermolecular hydrogen bonding:
*alcohols & phenols form H-bond in condensed phase (solid or conc. Liq.) so
appear as broad absorption bands with lower frequencies (3500-3300)
R OH O H O H
R R


E.g. acetic acid it form a dimmer & a polymer so decrease v of OH &C=O

H
3
C C
O
OH
CH
3
C
O
HO

3) Ring strain:
- Why Carbonyl gp in strained cycle (ketones) have higher frequency
?
e.g. C=O in cyclobutane 1775cm
-1
& in cyclopentane 1746 cm
-1

In cyclohexane 1715 cm
-1


answer: in strained ring the carbonyl bond angle is reduced below 120
o
so lead
to more p characters in C-C bond & more s character in C=O
So C=O is shortened & becomes more stronger & have higher v
> >
O
O
O
more s character
more p- character


Some notes on IR:
a) how can you differentiate between acetone & allyl alcohol?
C
H
3
C
CH
3
O
H
2
C
CH
H
2
C
OH
OH str. at 3600-3300
c=c str. at 1650-1600
c-h str. alkene at 3100-3000
C=O str. at 1725-1705
c-H str. aliphatic 2950-2850

b) how can you differentiate between propanal & 2-propenal?
C
C
H
2
H
O
H
2
C
H
C CH
O
C=O str. at 1680 due to conjugation
c=c str. at 1650-1600
c-H str. alkene at 3100-3000
C=O str. at 1720
C-H str. aliphatic 2950-2850
H
3
C




7

Ultraviolet Visible spectroscopy
It is also called electronic spectroscopy because energy absorbed E induce
electronic transition[one electron is transferred from low molecular orbital to
higher one]
UV-Vis spectrophotometer measures absorption of UV radiation between (200-400
nm) and Visble light (400-800 nm)

ground state
exited state


Electronic transition:
Absorbed E in the UV & Vis region produces changes in electronic energy of the
molecule[resulting from transition of valence electrons in the molecule]
Transition of electron means excitation of an electron from filled molecular orbital
(non-bonding p or bonding t or orbital) to the next higher energy orbital (anti-
bonding t
*
or
*
)
Types of electronic transition :
1)
*


- Is the only transition in alkanes
- it needs high energy & require very short UV light (around 150)
2) n
*


- ocuur in compound have nonbonded electrons( lone pair of electrons )&
electrons (e.g OH,NH2, halogen).
e.g alcohols , amines & alkyl halides
- it occurs at longer wavelength than
*
but it has high energy & low
( below 200)
3)
*
- occurs in compounds containing unsaturated groups e.g C=C ,C=O
a. in simple alkene & non-conjugated diene transition occurs at below 200
nm
b. in conjugated multiple bonds compounds the region is above 200 nm
due to
*

4) n
*


- occurs when non-bonded electrons is adjacent or conjugated to a multiple
bond e.g. C=O , C=C-OH
- is the lowest energy transition
- Occur at longer wavelength in region 270-300 nm but its intensity is low
(<100)







8
o
t
t-
o-
n

A
or E
or logE
in nm
n t
t t
*
*


problem: what are the possible electronic
transition in acetaldehyde CH3CH=O
answer:

1)
*

2) n
*

3)
*

4) n
*

only n
*
takes place above 200nm with
low intensity


The UV-vis spectrum:
It is the plot of absorption intensity(A or or log) versus wavelength
The absorption band due to
*
and n
*

Absorbance ranges from zero(no absorption) to 2 (99% absorption)












Conjugation effect in electronic spectra (imp.)

The more conjugation the higher the max

Examples
H
2
C
H
C
C
H
2
CH
2
H
2
C CH
2

OH

max =171 max =217 max =253 max =256 max =282 max=270

polyenes with more than 8 conjugated double bond absorb in the visible region e.g.
-caroten

Terms:
a) chromophore :
it is covalently unsaturated gp e.g C=C ,[C=O , NO2(has n-t* & t-t*)]
b) auxochrome
it is a gp having lone pair of electron & when attached to chromophore cause
increase of both wavelength and intensity of absorption e.g OH , NH2 , Cl
9

c) bathochromic shifts ( red shift)
it is the shift of absorption to longer wave length due to substitution or solvent
effect
d) hypasochromic shifts(blue shift)
it is the shift of absorption to shorter wavelength due to substituent or solvent
effect
e) hyperchromic effect
it is the increase in absorption intensity
f) hypochromic effect
it is the decrease in absorption intensity



Uv-Vis spectroscopy of aromatic molecule:
Benzene shows 2 absorption bands:
a) max =204 (=7400) called primary band
b) max =256(=200) called secondary or benzenoid band(low
intensity band)
Effect of substituents on benzene ring:
1) alkyl gp: alkyl gp in benzene cause slight bathochromic shift by 5 n.m e.g.
toluene has max 261nm
2) auxochrome: e.g. OH , NH2 ,OR
the interaction of non-bonding electrons with electrons of the benzene
increases conjugation and causes bathochromic shift
3) chromophore :e.g CHO,COR, NO2 [increase conjugation & max increase]


UV spectral change on converting aniline to aniline hydrochloride

Give reason: why addition of HCl to aniline cause hypsochromic shift?
Addition of acids to aniline cause attachment of H
+
to the non-bonded electrons
on N removing it from conjugation with the t electrons of benzene so cause
hypsohromic shift
NH
2
HCl
NH
3
Cl

UV spectral change on converting phenol to phenate anion
Give reason: why addition of alkali to phenol cause bathochromic shift?
10
Addition of alkali to phenol e.g NaOH cause removal of H
+
so form phenate anion.
the Oxygen in the phenate anion contain addition lone pair of electrons so more
conjugation so cause bathohromic shift
OH
NaOH
O

Application of UV-Vis spectroscopy to organic chemistry & pharmacy:
UV spectroscopy can differentiate conjugated dienes from non conjugated dienes
[ the greater the conjugation , the greater the wavelength i.e. conjugated trienes
absorb at longer wavelength than conjugated dienes]
.>

Woodward Rule for calculation of max
1] for simple conjugated system :
parent
alkyl substituent
extra or extension
homoanular diene
exocyclic
exocyclic

a) parent diene system = 217nm
b) homoanular diene = 36 nm
c) alkyl substituent or ring residue = 5nm
d) exocyclic C=C =5nm
e) double bond extension( extra double bond in conjugation)= 30nm
2] for simple conjugated ketones or aldhydes
R
O
R H
O
O
O
parent acyclic or 6 membered
ring ketones =215 nm
parent 5 membered
ring ketone =202 nm
aldehyde =207 nm
R

exocyclic
O
parent
homoanular diene
extra or extension
o
|

o

a) parent acyclic or 6 membered ring ketones =215 nm
OR parent 5 membered ring ketone =202 nm
Or aldehyde =207 nm
b) double bond extension( extra double bond in conjugation)= 30nm
c) exocyclic C=C =5nm
11
O
d) homoanular diene = 39 nm
e)alkyl substituents =10 nm
=12 nm
or =18
Example
Parent = 215 [6 membered ketone]
Homoanular = 39
Exocyclic = 3x5=15
Extension = 30
Substituent:
=10 =12
=18 =18
Total = 357 nm
Woodward rule is not applied for:
1-aromatics (benzene) 2- Crossed conjugation 3-more than 4 conjugated double bonds
12
homoanular diene = 36 nm
alkyl substituent or ring residue = 4 x 5= 20nm
exocyclic C=C =5nm
double bond extension = 30nm
parent diene system = 217nm
308 n.m
max
=
alkyl substituent or ring residue = 2x 5= 10nm
exocyclic C=C =5nm
parent diene system = 217nm
232 n.m
max
=
alkyl substituent or ring residue = 4 x 5= 20nm
exocyclic C=C =2 x 5 = 10nm
double bond extension = 30nm
parent diene system = 217nm
277 n.m
max
=
homoanular diene = 36 nm
alkyl substituent or ring residue = 5 x 5= 25nm
exocyclic C=C =3 x 5 = 15nm
double bond extension = 30nm
parent diene system = 217nm
323n.m
max
=
O
O
CH
3
parent = 215
extension = 30
homoanular diene = 39
exocyclic 5 x 3 = 15
o
|

o
= 10
= 18
= 12
= 18
357n.m
max
=
parent = 215
extension = 0
| = 12
227n.m
max
=
O
O
parent = 215
exocyclic 5 x 2 = 10
o
|
= 10
= 12 x 2 = 24
259n.m
max
=
parent = 202
o
|
= 10
= 12 x 2 = 24
236n.m
max
=