CHAPTER 3

INTRODUCTION TO
SPECTROSCOPY

By
Dr Rizana Yusof
 2
Introduction to Spectroscopy

u Spectroscopy: the study of the interaction of matter with

electromagnetic radiation (energy)
u Energy applied to matter can be absorbed, emitted,
cause a chemical change, or be transmitted
u Spectroscopy can be used to elucidate the structure of
a molecule
u Types of spectroscopy:
§ Infrared (IR) Spectroscopy
§ Nuclear Magnetic Resonance (NMR)
§ Mass Spectrometry (MS)
 Principle of spectroscopy

3. Absorption or
emission occurred
(electron transition)

1. Energy from electromagnetic radiation

strike sample 4. Detector measure
2. Bond in molecule stretch, bend or energy (E) differences
rotate at certain frequencies
 4
Principle of spectroscopy

u Electron transition between two energy level can cause absorption

or emission

u The energy of the photon ( E = hν) is equal to the energy gap

between the excited state and the ground state
 5
Principles of Spectroscopy

u The relationship between energy, frequency and wavelength

E=hc
l
u Where E = energy
h = plank constant
v = frequency
c = speed of light
l = wavelength of light

u the higher the frequency, the higher the energy.

u the shorter the wavelength of light, the higher its energy.
 6
Electromagnetic Radiation (EM)
 7
F.T.I.R
 8
Fourier transform Infrared
Spectroscopy

u FTIR Spectroscopy: method for detecting functional groups

u Electromagnetic (EM) radiation in IR frequency range as an
energy strike a molecule
u The atom of molecule vibrate, increase amplitude and
change dipole moment
u if the frequency of EM being absorb is similar to frequency of
molecule, the molecule vibrate and cause bond bending and
stretching.
u Hence, the absorption cause the energy do not pass through
molecule and percentage transmittance low
PEAK APPEAR
 9
Fourier transform Infrared
Spectroscopy

u However, if the energy strike the molecule with different

frequency to molecule, the energy was not absorb and the
molecule do not vibrate
u Hence, the energy pass through molecule (not being absorb)
and cause percentage transmittance almost 100%.
NO PEAK
 10
Fourier transform Infrared
Spectroscopy

INFRARED SPECTRUM PLOT OF ABSORPTION

VS FREQUENCY
100%
High transmittance
= do not absorb

low transmittance
= absorbance happen

0%
WAVENUMBER (CM-1)
 11
Fourier transform Infrared
Spectroscopy

u However, not all the bonds in a molecule are capable of

absorbing IR energy.
u Only those bonds that have a dipole moment are capable
of absorbing the IR radiation.
u Thus, a symmetric bond which has identical or nearly
identical groups on each end will not absorb in the infrared .
A symmetric bond which has identical or nearly identical
groups on each end will not absorb in the infrared.

symmetric bond
 12
Fourier transform Infrared
Spectroscopy

u When the molecule absorb energy, a vibration such as

stretching and bending happen:

Symmetrical stretch Asymmetrical stretch Scissoring

Wagging Twisting Rocking

 13
Fourier transform Infrared
Spectroscopy

u The vibration only happen when the frequency of EM similar

to frequency of molecule.

u For example:
The sample perfume is strike with the EM of IR radiation at ~3300
cm-1. The sample absorb the energy because the OH bond in
perfume sample also have same frequency. Hence, the
absorption cause the energy do not pass through molecule
and percentage transmittance low, peak appear at ~3300 cm-1
 14

u IR spectrum is usually measured as wave number (cm-1), as they

are directly proportional to energy
u The wavenumbers of IR extends from 4000 to 400cm-1.
u The frequency range is related to the
1. Mass of atom - Lighter atom vibrate faster at higher
frequencies
2. Strength of bond –stronger bond(triple bond) are stiffer than
weaker bond(single bond), therefore require more force to
stretch. Thus, stronger bond vibrate faster at higher
frequencies.
 IR spectrum

Bonds to H Triple bonds Double bonds Single Bonds

stretching Bending
Functional group
region Fingerprint
Region

O-H C≡C C=O C-C

N-H C≡N C=N C-N
C-H C=C C-O

4000 cm-1 2700 cm-1 2000 cm-1 1400 cm-1 600 cm-1
High frequencies
Stronger, lighter
high wavenumbers
higher E
 Hydro- Frequency
carbon Vibration (cm-1 ) Intensity 16
Alkane
H H
C-H Stretching 2850 - 3000 Medium
H __C __C __ H Bending 1450-1475 Medium
H H CH 3 Bending 1375 and 1450 Weak to medium
C-C (Not useful for interpretation - too many bands
Alkene
H H C-H Stretching 3000 - 3100 Weak to medium
H __C=C__ H C=C Stretching 1600 - 1680 Weak to medium
Alkyne
C-H Stretching 3300 Medium to strong
H __CΞC __ H C C Stretching 2100-2250 Weak
Arene
C-H Stretching 3030 Weak to medium
C=C Stretching 1450-1600 Medium
C-H Bending 690-900 Strong
IR spectrum of Alkane

CH3 bending
CH2 bending 1360-1390 cm-1
1450-1475 cm-1
If two peaks appear,
slightly on the right of
sp3 C-H 1400 and slightly on left
2850-3000 cm-1 of 1400, CH3 is presence
IR spectrum of Alkenes

If the band is
slightly
above > 3000 it is C=C stretch
alkene sp2 C-H or 1600-1680 cm-1
alkyne sp C-H

CH2 bending
1450-1475 cm-1
sp2 C-H
3000-3100 cm-1

3000
IR spectrum of Alkynes

CΞC stretch
Sharp 2100-2250 cm-1
spike
CH2 bending
1450-1475 cm-1
sp C-H
3300 cm-1
(terminal alkynes) 3000

sp3 -C-H 2850-3000 cm-1

sp2 =C-H 3000-3100 cm-1 C=C 1600-1680 cm-1
Sp ΞC-H 3300 cm-1 CΞC 2100-2250 cm-1
IR spectrum of aromatics

Due to the
delocalization
u combination of C-C, vinyl C-H, C=C bonds of e
- in the ring,

stretching
frequency for
these bonds is
sp2 C-H slightly lower in
C=C stretch C-H bending
3030 cm-1 energy than
1600, 1500, 1480 690-900 cm-1
(aromatic) normal C=C
cm-1(aromatic) (aromatic)
 IR spectrum of C=O stretching 21

u Generally the carbonyl group gives a strong peak which occurs

at 1630-1780 cm-1
u The exact location depends on the actual functional group
present

C=O stretch

Amide 1630-1690 cm-1

Ketone 1680-1750 cm-1
Aldehyde 1690-1740 cm-1
Carboxylic 1710-1780 cm-1
Ester 1735-1800 cm-1
The effect of electron donation on amide

Single
bond

1630-1690 cm-1 1660 cm-1

Ability N to donate e by resonance

cause C-O as a single bond.
Hence, a single bond appear at lower
frequency (1660 cm-1) compare to original
(1630-1690 cm-1)
 IR spectrum of Amides (1°)
O Amides
RCNH2 C=O Stretching 1630-1680 Strong
N H Stretching 3200, 3400 Medium
(1° amides have two N-H stretches)
(2° amides have one N-H stretch)

O Carboxylic esters
u 1° Amides
RCOR' C=O show two N-H absorptions
Stretching 1735-1800 Strong
2
sp C O Stretching 1200-1250 Strong
3
sp C O Stretching 1000-1100 Strong

O O Acid anhydrides
RCOCR C=O Stretching 1740-1760 and Strong
1800-1850
C O Stretching 900-1300 Strong
N-H
RC N Nitriles C=O stretch
3300-3500 cm-1CºN Stretching 1630-1690 cm-1
2200-2250 Medium
1° (2 peaks)

sp2 C-H
2720-2820 cm-1
 IR spectrum of Amides (2°)

u 2° Amides show a single N-H absorption

N-H
3300-3500 cm-1
C=O stretch
2° ( 1 peak) 1630-1690 cm-1

sp2 C-H
2720-2820 cm-1
IR spectrum of Amides (3°)

u 3° amides do not show N-H absorption

C=O stretch
1630-1690 cm-1

sp2 C-H
2720-2820 cm-1
 IR spectrum of Aldehydes & Ketones
Frequency
Carbonyl Group Vibration (cm-1 ) Intensity
O Ketones
RCR' C=O Stretching 1680-1750
1630-1820 Strong
O Aldehydes
RCH C=O Stretching 1690-1740
1630-1820 Strong
C-H Stretching 2720 Weak

O Carboxylic acids
RCOH C=O Stretching 1700-1725 Strong
O H Stretching 2500-3300 Strong (broad)

C=O stretch
Aldehyde appears as 1690-1740 cm-1
a doublet – ‘fermi
doublet’ ’
at 2700 & 2800 cm-1

sp2 C-H
2720-2820 cm-1
 O Ketones
RCR' C=O Stretching 1630-1820 Strong
O
RCH
IRC=O of Carboxylic
spectrumStretching
Aldehydes
1630-1820
acids
Strong
C-H Stretching 2720 Weak

O Carboxylic acids
RCOH C=O Stretching 1710-1780
1700-1725 Strong
O H Stretching 2500-3300 Strong (broad)
C-O Stretching ~1200-1320

O-H C=O stretch

2500-3300 cm-1 1710-1780 cm-1
C-O stretch
1210-1320 cm-1
RCNH2 1630-1680 (1° amides have two N-H peaks)
(2° amides have one N-H peak)
O
IR spectrum of
O-H
Esters
stretching at 2400-3400
RCOH 1700-1725
C-O stretching at 1210-1320
O C=O Stretching 1735-1800
RCOR C -O
1735-1800 Stretching ~1200-1320
C-O stretching at 1000-1100
and 1200-1250

u Absorption of C=O and C-O stretch

C=O stretch
1735-1780 cm-1
C-O stretch
1000-1250 cm-1
 IR spectrum of Alcohols

Bond Frequency, cm-1 Intensity

dilute O-H (free) 3600-3650 Weak
concentrated O-H (H bonded) 3200 - 3500 Medium, broad
C-O 1000 - 1250 Medium

Broad
U-shape
peak

C-O stretch
O-H sp3 C-H 1000-1250 cm-1
3200-3500 cm-1 2800-3000 cm-1
 IR spectrum of Amines
• 1o amines give two peaks
• 2o amines give one peak
• 3o have no N-H bonds (no peak)
****concentrated amines broader peaks

W or V-shape
peak

CH3 bending
N-H CH2 bending 1360-1390 cm-1
3300-3500 cm-1 1450-1475 cm-1
sp3 C-H
1° (2 peaks)
2800-3000 cm-1
2° ( 1 peak)
3° ( no peak)
 IR spectrum of Ethers

sp3 C-H
2800-3000 cm-1 C-O stretch
1050-1150 cm-1

C-O carboxylic acid ~1200

C-O alcohol /ether/ester ~ 1000
 32
IR Frequency range
Exercise 1:
Predict the possible functional group of FTIR spectra band 33
N.M.R 34
 35
Introduction to NMR

• To identify carbon-hydrogen framework within molecules

• 2 common types of NMR spectroscopy:
1. 1H NMR – type and number of H atom
2. 13C NMR – type of C atom

• The main sources of electromagnetic radiation in NMR s

radio waves

• The interaction between radio wave and sample can

change the nuclear spin of atom
 36
Principle of NMR

• 1H ,13C, 19F and 31P ( odd atomic number/mass )

= spin quantum number = 1/2

• electron (-ve) move around nuclei (+ve), behave as

spinning charges generates a magnetic field

• With external magnetic field, they orient either

ü align, +1/2
ü against, -1/2

• 12C and 16O (spin quantum 0) do not respond to an

external magnetic field
 NMR Principle
37
Principle of NMR
Tiny magnetic bar

No applied magnetic field magnetic field is applied, Bo

nuclear spin move

randomly
nuclear spin nuclear spin
align to Bo against to Bo
(low energy) (high energy)
 NMR Principle
38
Principle of NMR

u electromagnetic radiation strike sample at correct frequency,

the nuclear magnetic flip from lower to higher level and
absorb energy.

u The energy absorb = energy difference between two states.

u NMR apply an external magnetic field (B0)and measure the

frequency at which the nucleus achieves resonance.
 39
Principle of NMR
 40

“
1H NMR
”
 Spectrum of NMR

u The information contained in a common NMR

spectrum typically falls into four categories:

i. chemical shift

ii. number of signals present

iii. relative signal intensities,

iv. signal multiplicities.

41
 Chemical shift of NMR
u “chemical shift” = position of the signals in the spectrum.

u measured on a delta (d) scale in units of parts per million (ppm)

u The small signal at d 0 used to calibrate the chemical shift scale

= internal standard (tetramethylsilane, TMS)
 Chemical shift of NMR
u The chemical shift are depend on the atom around H

u electronegative atom pull electron away from H, decrease the

electron on H, cause H deshielded – “shielding effect”

u H come to down fields / higher value of ppm

Cl- CH2-CH3

a b

Deshielding 1.5 0.9

Shielding
/Downfield 0 ppm (δ) /Upfield
 44

Chapter 9
 Number of signal in NMR spectrum
u Number of signals = how many sets of equivalent/similar protons.
u Similar environment of protons will produce same signal.

Cl

2 signals 3 signals 2 signals

1 signal 4 signals
 Number of signal in NMR spectrum

Cl
Example: 2 set of H = 2 signals

CH3- CH-CH3

b
a

Deshielding
/Downfield 0 ppm (δ) Shielding
/Upfield
 Number of signal in NMR spectrum

u Example: 3 set of H = 3 signals

Cl- CH2- CH2-CH3

a b c

Deshielding
/Downfield 0 ppm (δ) Shielding
/Upfield
EXERCISES 1 : How many signal of NMR spectrum produced from the
following compounds?

1) Cl - CH2 - CH3 5) Cl - CH2 – CH2 - Br

CH3
2) Cl - CH2 – CH2 -Cl

6) CH3 - C – CH2 - Cl
Cl
CH3
3) CH3 - C – CH3

Cl 7) Cl - CH2 – CH2 - CH2 - Br

Cl

4) CH3- CH2 - C – CH3

Cl

48
EXERCISES 2 : How many signal of NMR spectrum produced from the
following compounds?

(a) (b) (c)

Butane 2-Methylpropane 2-Methylbutane

(d) (e) (f)

Cl H 3 C Cl CH
O
CH 3 CCH 3 CH 3 Cl
ClCH 2 CH CHCl O C CC C
2
H3 C H CH
1,1-Dichloro- Cyclopent- (Z)-1-Chl
Propanone 1,2-Dichloro-
ethane Cyclopentane
anone 2,3-Dimethyl
propen
(Acetone) ethane
(2 signals) (2 signals)
2-butene
(3 signa

49
 Signal intensities (Integration)
u Integration /signal intensities = number of equivalent protons in
each set (unique environment) within a molecule
u The numbers are not exact number of H
~ relative number or ratio of the amount of equivalent

9H

3H
 Signal intensities (Integration)

Example: peak a : peak b

1H : 6H Cl

CH3- CH-CH3

b
6H
a

1H

3H
 Peak pattern / Signal multiplicities

u peak patterns = the number of protons on adjacent carbons

u This is called signal multiplicity
- singlet, doublet, triplet, quartet, pentet, and multiplet
zoom out NMR
spectrum
To see the
multiplicities
Signal multiplicities
u Signal split into N+1 peaks , where N= neighboring protons

Example 1:
u For CH , it attach to C with 3H neighbours, split into 3+1 = 4
(quartet)
u For CH3 , it attach to C with 1H neighbor, split into 1+1 = 2
(doublet)

Cl2 - CH- CH3

Signal multiplicities

Example 2:
u For CH2 , it attach to 3H neighbours, split into 3+1 = 4 (quartet)
u For CH3 , it attach to 2H neighbor, split into 2 +1 = 3 (triplet)

Cl – CH2- CH3
Signal multiplicities

Example 3:
u For CH , it attach to C with 2H neighbours, split into 2+1 = 3
(triplet)
u For CH2 , it attach to C with 1H neighbor, split into 1 +1 = 2
(doublet)

Cl Cl

Cl – CH- CH2
 Signal multiplicities for –OH or -NH

triplet
quartet
c
singlet
c

u Spin decoupling is typical in the 1H NMR spectra of alcohols,

amines and carboxylic acids
u The proton attached to the oxygen or nitrogen normally appears
as a singlet because of rapid exchange processes
56
Pascal’s Triangle
The Pascal's triangle is a splitting pattern used to predict the ratio
of heights of lines in a split NMR peak.

57
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1 2 1 1 1
EXERCISES 3 : State how many signal, multiplicities and integration of NMR
spectrum produced from the following compounds?
a b Number of signal = 2 ( label a & b)
1) Cl - CH2 – CH2 - Br Multiplicities: a =triplet , b = triplet
Integration ; a = 2H, b = 2H
2) Cl - CH2 – CH2 -Cl

3) CH3 - CH2 – CH3

4) Cl - CH2 – CH2 - CH2 - Br

CH3

5) CH3 - C – CH2 - Cl

CH3
MULTIPLET

Cl - CH2 – CH2 - CH2 - Br

CH2 Cannot apply N+1 rule

Cl-CH2 is not equal to CH2-Br

so signal at CH2 ~ (2+1) x (2 + 1) = 9

Called as triplet of triplet

MULTIPLET

Cl - CH2 – CH2 - CH2 - Cl

If both H is equal, Cl-CH2 (on left) is equal to CH2-Cl (on right)

so signal at CH2 ~ (2 + 2 + 1) = 5

Called as multiplet
 PROBLEM
EXERCISES 4 : State how many signal, multiplicities and integration of NMR
spectrum produced
u predict fromofthe
the number following
signals compounds?
and the splitting pattern of each signal in
the 1H-NMR spectrum of each compound

O O O
(a) (b) (c)

61
u : Sketch
EXERCISES 5Sketch
Problem: and
and draw
draw the
the 1H H
1 NMR spectrum of the following
NMR spectrum of each of the
(from exercise
following 3 question 1 & 5):
compounds?
a.
Cl -2-pentanone
CH2 – CH2 - Br

CH3

CH3 - C – CH2 - Cl

CH3
 Important Rules
u v

Equivalent H do not split each other

Cl - CH2 – CH2 -Cl

O H3 C
CH 3 CCH 3 ClCH 2 CH 2 Cl C
H3 C
Propanone 1,2-Dichloro- Cyclopentane 2,3-D
(Acetone) ethane 2-
63
 64

“
13C NMR
”
Introduction to 13C NMR
u 12C has no magnetic spin and produces no NMR signal
u One Peak for each unique carbon atom
u Since the 13C isotope of carbon is present in only 1.1% natural
abundance, there is only a 1 in 10,000 chance that two 13C
atoms will occur next to each other in a molecule
u The low probability of adjacent 13C atoms leads to no
detectable carbon-carbon splitting
u 1H and 13C do split each other, but this splitting is usually
eliminated by adjusting the NMR spectrophotometer accordingly
u Most 13C NMR, therefore, consist of a single peak for each unique
carbon

65
 Chemical shift 13C NMR

u Just as in 1H NMR spectroscopy, chemical shifts in 13C NMR

depend on the electron density around the C nucleus
ü Decreased electron density causes the signal to move
downfield (desheilding)
ü Increased electron density causes the signal to move
upfield (sheilding)

u Because of the wide range of chemical shifts, it is rare to

have two 13C peaks coincidentally overlap

66
67
 PROBLEM
EXERCISES 5 : State how many signal of NMR spectrum produced from the
following compounds?
u predict the number of signals and the splitting pattern of each signal in
the 1H-NMR spectrum of each compound

O O O
(a) (b) (c)
O

CH2 CH3

(d) (e)

68
FINAL PROBLEM
EXAM QUESTION JUNE 2019:
u predict the number of signals and the splitting pattern of each signal in
the 1H-NMR spectrum of each compound

FINAL EXAM QUESTION JUNE 2018:

FINAL PROBLEM
EXAM QUESTION JULY 2017:
u predict the number of signals and the splitting pattern of each signal in
the 1H-NMR spectrum of each compound

FINAL EXAM QUESTION DEC 2016