Engineering Chemistry

MODULE 2
• Spectroscopic Techniques And Applications
 Spectroscopy deals with the interaction of atoms or
molecules or matter with electromagnetic (EM)
radiations.
 All molecules possess different quantum mechanical
energy states such as Electronic, vibrational, rotational
and nuclear.
 Transitions can occur between these states by absorption
or emission of EM radiations. Only those transitions that
comply with or follow quantum mechanical rules are
allowed.
 Spectroscopy provides information of the details
regarding the structure and bonding.
 The instrument used for spectroscopic study is called
Spectrometer.
 The plot obtained from a spectrometer is called Spectra.
 A spectrum provides atomic and molecular information
on the interaction of EM radiation with atoms and
molecules.
 Spectroscopic study (i) Gives accurate and reliable results
(ii) Requires less time, (iii) sample unaltered.
 Electromagnetic radiation is a form of energy transmitted
through space with velocity of light.(c= 3x108ms-1).
 EM radiations are a bundle of radiations of different
wavelengths ranging from Gamma, X-rays, Ultraviolet, visible,
infrared and radio waves.

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 On the basis of interaction of atoms/molecules with EM
radiation, the spectra can be divided as, (i) Absorption
spectrum,(ii) Emission spectrum.
 Absorption spectrum:
Atom or molecule undergo transition from lower energy state
(Ei) to a higher energy state(Ef),absorption of energy (hʋ) takes
place E.g UV visible, IR, Microwave .and NMR

Ef

hʋ

EI

 Emission spectrum:
Atom or molecule undergo transition from higher energy state
(Ef) to a lower energy state (Ei),emission of energy (hʋ) takes
place. E.g Hydrogen spectrum, Atomic emission spectrum,
Atomic fluorescence spectrum.

hʋ

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MOLECULR ENERGY LEVELS
• Electronic Energy (Eel)

• Associated with electrons of molecules, Molecular Orbital may

be bonding or antibonding, The energy gap between the
electronic energy lies in the UV-Visible region.

• Vibrational energy (Evib)

• Associated with vibration of atom/molecules about the center

of mass.The energy gap between the vibrational energy level
lies in the Infrared region.

• Rotational energy (Erot)

• Associated with rotation of atoms/molecules in space about an

axis. Possessed by molecules of gas or liquids. Energy gap lies in
the microwave region.

• Translational Energy (Etrans)

• Associated with transition of atoms /molecules with change in

center of mass.

• Etotal =Eel + E vib + Erot +ETrans and

• Eel > Evib > Erot > E Trans

• Electronic transitions are always accompanied by vibrational
and rotational transitions.
• Vibrational transitions are always accompanied by rotational
transitions.

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• Different molecular energy levels are shown below.
Electronic energy level E1 Electronic energy level E2
Vibrational level ʋ3
Rotational levels
level Vibrational level ʋ2
Rotational levels
Rotational Levels
Vibrational level ʋ1

Vibrational level ʋ3
Rotational levels
Rotational Levels
Vibrational level ʋ1
Rotational levels
Rotational Levels
Vibrational level ʋ0

Electromagnetic Radiation
• Properties
• Consists of Electrical and Magnetic waves.propagating on
mutually perpendicular directions.
• EM radiation has both particle and wave character.
• The particle is called Photon
• The frequency (ʋ) and wave length (λ) are related to
ʋ = c/ λ. & ʋ = 1/ λ
• Energy of a photon of EM radiation E = h ʋ = h c/ λ where h is
called Planck’s constant equal to 6.63 x 10-34Js

Beer-Lambert Law
 This law governs the absorption of electromagnetic radiation
by matter
 When a beam of monochromatic electromagnetic radiation is
passed through a solution of concentration (c),the rate of

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 decrease in intensity (-dI) of radiation with thickness of the
solution (dx) is proportional to the intensity of incident
radiation (I) at that point and also to the concentration ( c ) of
the solution.
 Mathematically expressing the law, we have
- dI α Ic
dx
ie- dI = k I c ,----------(1) where k is proportionality constant
dx .
Above equation (1) is the differential form of the law. From this
we can derive as follows.
- dI /I = kcdx
- On iintegratin between the intensity of incident radiation (I0 )
and intensity after passing through the solution,(I) we have
∫ -dI/I = ∫kcdx ;
ln [I0 / I ] = kcx ;
2.303log [I0 / I ] = kcx
log [I0 /I ] = ε c x, ====== (2) where ε is k /2.303 called
molar extinction coefficient which depends on (i) nature of
absorbing molecule,(ii) type of absorption.
Thus log [I0 /I ] = ε c x, ====== (2) – integrated form of the
law.
We know , Absorbance(A) is lograthmic ratio of intensities of
incident light (I0) to the transmitted light (I)
A = log [I0 / I ] ======== (3)
From (2) and (3) we can write,
A= εcx. =========== (4) (simplified form of the law
Above equation (2 ) can be expressed in exponential form as
I = I0 e-kcx ========= (3) –exponential form of Beer-Lambrt
law

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 Transmittance is defined as ratio of intensities of transmitted to
incident light ie
T= I / I0
Therefore, A = ε c x = -log T
Molar Absorbtivity: (ε) :
ε = A/cx;: unit of molar absorptivity is moles/dm3.

Limitations of the law:

1. Law is invalid at high concentrations
2. Turbid solutions cannot be measured due to scattering of
light.
3. Fails if the light is not monochromatic
4. Deviation is observed if there is fluorescence or
phosphorescence is observed or different form of molecule.

Numericals:
1. The percentage transmittance of a 0.01M dye solution in
ethanol is 20 in a 2 cm cel for a light of wave length 5000 A 0 .
Find the absorbance (A) and molar absorption coefficient.
Let the incident intensity (I0)be 100, then form the given date
we can write ,(I) shall be 20.
Therefore , A= log I0/I ,
A= log 100/20, A= 0.6989
From equation, A = ε c x , wher x= 2 cm = 0.2dm,
Therefore , Molar extinction coefficient ε = A/ εx = 0.6989/0.1
* 0.2 = 349.4 mol-1dm2
2.A Dye solution of concentration 0.04M shows absorbance of
0.045 at 530nm while a test solution of same dye shows
absorbance of 0.022 under same conditions. Find the
concentration of the test solution.

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 UV –Visible spectroscopy
(Electronic spectroscopy)
Principle:
 EM radiation in the range of 10-800nm region capable of
interacting In the wave ength range 10-800nm,gives these type
of electronic transitions.
 UV Visible specroscopy involves the study of electronic
transitions that occur from lower to higher electronic state .
 UV region 200-400 nm, (10-200 nm not measurable) ,Visibl e
region : 400-800 nm .
 UV visible spectroscopy occur between the energy levels
corresponding to the molecular orbitals of the system.
Classification of Electronic Transition
Three distinctive types of electrons are involved in electronic
transitions.
1. Sigma electrons(σ)2.Pi electrons(π)3.Nonbonding
electrons(n).
Both bonding and anti-bonding electrons are associated with
(σ),and (π) electrons.
Electronic transitions are classified into four types
 σ σ* ; ∏ ∏* , n σ* and n ∏*
 σ σ* : Exhibited by saturated hydrocarbons which are
transparent to UV light only- C-C sigma bond, C-H sigma bond
– λ at 150 nm-not detectable.
∏ ∏*: Exhibited by unsaturated hydrocarbons containing
double or triple bond. -C=C can give absorption at 169nm-not
detectable.E.g 1,3 Butadiene,1,3,5 hexatriene,Benzene.

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n ∏ *: Exhibited by compounds containig a C=O group ie
aldehydes and ketones which contain both ∏ electronsand
nonbonding electrons. These are low intensity transitions.
 n σ* : Exhibited by compounds containing S,N,O etc
which contain non-bonding e-. weak transitions hence
forbidden – λ below 200 nm .
 Electronic transitions in Formaldehyde molecule:

σ*
π* LUMO

n ↑↓ HOMO
π ↑↓
σ ↑↓

PI-Pi* transition in Ethene molecule

σ*
∏* LUMO
λ = 169 nm

∏ ↑↓ HOMO

σ ↑↓

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Pi-Pi* transition in 1,3 Butadiene molecule

Ψ4
ψ3 LUMO
λ = 217 nm

ψ2 ↑↓ HOMO

Ψ1 ↑↓

Pi-Pi* transitions of Benzene

ψ6
ψ5
ψ4 LUMO
λ = 247 nm

ψ3 ↑↓ HOMO
ψ2 ↑↓
ψ1 ↑↓

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Instrumentation in UV Visible spectroscopy

UV source
Slit 1
Mirror 1

Visible source

Slit 2

Filter
Lens 1
Reference cuvette Detector 2
Reference beam 1
I0

Half mirror
Mirror 2
Lens 2 Detector 1

I
Sample beam
Sample cuvette

UV-Visible spectrum:

It is a plot of Absorbance (A) aginst wave length (λ) of light. The

wavelength maximum (λmax) is characteristic value .Different
compounds have different (λmax) value, which is obtained by scanning
a sample in the UV region. Discrete lines are not obtained in the
spectrum since electronic transitions are accompanied by vibrational
and rotational transitions.Hence it appears as a band spectrum. A
typical UV visible spectrum is shown below.

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Applications of UV-Visible spectroscopy:

1. For identification of unknown compounds: By comparing the

spectrum its spectrum with the spectra of known compounds.
2. For detecting impurities in organic compounds.
3. For characterization of dyes and colorants.
4. For detection of conjugation in aromatic compounds
5. Determination of unknown concentrations in quantitative
analysis.
6. Study of kinetics of chemical reations in which the a reaction
shifts the absorption wave length.
7. Used in clinical laboratories for quantitative estimation of blood
sugar and in other medical diagnostic purposes.
8. Determination of structure of compounds
9. Determination of molecular weight of compounds.
10. Determination of ozone and other pollutants in environment.
******

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 Engineering Chemistry
MODULE 2 : INFRA RED SPECTROSCOPY
(VibrationalSpectroscopy)
 Infra-red spectroscopy (IR) involves the transitions between
vibrational energy levels of a molecule having change in dipole
moment with vibrations of a bond.
 These transitions are brought about by absorbing IR radiations
in the range of 400 to 4000 cm-1
 Used to establish identity of a compound
 To predict functional group of a compound.
 Photons in IR regions are not energetic to cause electronic
transitions but can cause rotational transitions.
 IR radiations are absorbed by molecules, thereby causing
different type of vibrations like stretching, bending of bonds.
 An IR spectrum is a plot of %Transmittance (Y axis) against
wave number (ʋ) in x axis.

Number of vibrational n modes in a Diatomic molecule:

 To describe position of an atom in a molecule, it requires three
degrees of freedom, thus for a molecule with ‘n’ atoms the
number of freedom is equal to 3n.
 Linear molecule:
For a linear molecule, there are three translational, two
rotational degree of freedom. Thus for a linear molecule of “n”
atoms, the vibrational degree of freedom can be (3n-5).
A diatomic molecule like HCl, there are (3x2-5) = 1, mode of
vibrations are possible ie stretching vibration.
For e.g, HCl molecule can have (3x2-5) =1 can undergo only
stretching vibration, which is IR active.

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A triatomic linear molecule like CO2, has (3x3-5) =4 vibrational
modes, which includes symmetric stretching, Asymmetric
stretching, Bending (in-plane) and Bending (out of plane) as
depicted as follows.

O=C=O O=C O
Symmetric stretching Asymmetric stretching,
No change in dipole Change in dipole moment,
moment, IR Inactive -1
IR active (2349 cm )

O=C=O O=C=O
Bending in plane, Bending out of plane,

Change in dipole moment Change in dipole moment

-1 -1
IR active (667 cm ) IR active,( 667 cm )

Of the four modes, only asymmetric stretching, in-plane

bending and out of plane bending are IR active as they involve
change in dipole moment during the vibration. Symmetric
stretching does not produce any change in dipole moment, it is
IR inactive. Also the two bending vibrations modes are
equivalent,(degenerate),only two absorption signals are
observed in the case of CO2 at 2349 cm-1 , for asymmetric and
667 cm-1 for bending vibration.
For HCN also (3x3-5) =4 modes,and all are IR active.

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Non-Linear molecule: For a non-linear molecule, there are
three translational, three rotational degree of freedom. Thus
for a non-linear molecule of “n” atoms, the vibrational degree
of freedom can be (3n-6).
For example, molecules like (H2O),(SO2), (NO2) are non-linear
triatomic, there are 3 atoms and hence (3x3-6) =3 modes of
vibrations are possible which includes, symmetric stretching,
asymmetric stretching and a bending mode. All the three
vibrations are IR active as there is change in dipole moment
during the vibration. So IR spectrum of water exhibits three
absorption bands.

O O
O
H H H
H H
H
Bending vibration
Asymmetric stretching
Symmetric stretching

Mechanism of interaction:
A vibrating molecule if it results in change in dipole moment,it
generates electric and magnetic field and act as a source of EM
radiation.Similarly when a photon of frequency interacts with
the frequency of the vibrating molecule absorption of photon
takes place.

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 Vibrational Energy of a Diatomic molecule:
A vibrating diatomic molecule is similar to a simple harmonic
oscillator.
Consider two atoms of masses m1 and m2, connected by means
of a chemical bond of force constant k.
Acc to classical mechanics,
Fundamental frequency of vibration ( ʋ0 ) = 1 x √(k/μ)
2π ------ (1)
Where μ is reduced mass given by (m1 x m2)
m1 + m2
Consider the bond stretch by a distance of ‘x’ m from the mean
position,the potential energy (V) is given by
V = - 1x kx2
2π ------------(2)
Substituting this iin the schrodinger equation and solving we
get the eigen value
E = (v +1/2)hʋ0, ----------(3)
where ‘v’ s called the vibrational quantum number which has
values 1,2,3…
In the ground state (v=0), E= hʋ0, called Zero point
energy,implying that even at absolute zero,there will be
vibration,

Consider a molecule undergoing transition from lower

vibrationary state (V1) to a higher vibrationary state, (V2),
ΔE = hʋ
(V2 + ½) hʋ0 – (V1 + ½) hʋ0 = hʋ
(V2 - V1) hʋ0 = hʋ-------- (4)
According to quantum mechanics, for the transition of
vibrationary levels, Δv = ± 1
V2 - V1 = 1

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 Therefore eqn 4 becomes hʋ0 = hʋ,
ʋ0 = ʋ,
ie,the frequency of absorbed IR radiation (ʋ) is equal to the
fundamental frequency of the molecule(ʋ0).
Thus there should only a single line in IR spectrum of a diatomic
molecule. But a band is observed. Due to unharmonicity of
vibrations at higher quantum levels.
Expression for Force constant:
(1)Can be rearranged as
ʋ 0 = 1/2π (k/μ)1/2
or (k/μ)1/2 = 2π ʋ0
squaring both sides and rearranging for k,
k= 4 π2 ʋ02 μ or k= 4 π2 c2 ʋ02 μ is an expression for
force constant.

Problem

CO molecule absorbs at 2140cm-1 .Calculate the force constant

of the molecule, given atomic masses of C, and O are 12amu
and 16 amu respectively
We know from (1) above.
ʋ 0 = 1/2π (k/μ)1/2
and subsequently rearranging after squaring we get,
k= 4 π2 ʋ02 μ
frequency of absorbed radiation (ʋ) is equal to fundamental
frequency (ʋ0)
k= 4 π2 ʋ2 μ but ʋ =c ʋ,
k= 4 π2 (cʋ)2 μ and μ = (m1 x m2)
m1 + m2
μ = 12 x1.66 x 10-27 x 16x x1.66 x 10-27 Kg
(12+16) x 1.66 x 10-27
since1amu=1.66 x 10-27 Kg

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Therefore
k= 4(3.14)2 x(3x108ms-1)2 x (214000m-1)2 x 1.138 x10-27 kg
k= 1849 Kgs-2 = 1849 Nm-1 (1 N= kms-2)

Practice problem:
If the fundamental frequency of HCl molecule is 8.667 x 107,s-1,
calculate the force constant of HCl bond [H=1.008,Cl=35045]
roy
IR spectra is recorded employing Fourier-Transform technology.
Solid samples are mixed with potassium bromide and the
mixture is pressed into a thin wafer, which is placed in the path
of the IR beam.
Drop of liquid sample is placed between two sodium chloride
discs through which IR beam is irradiated.
A typical IR spectrum:

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Applications of IR spectroscopy:
1. Determination of Force constant:
2. Identification of Functional groups in organic molecules

From the stretching vibrations of the bonds present in the

functional group the presence of functional groups can be
detected.(for e.g,the stretching frequency of C=O group in
saturated ketones is 1700-1725cm-1 etc
3. Identification of unknown compounds: By comparing the IR
spectrum of unknown compound with that of a known
compound, by finger print (700-1500cm-1)region matching.
4. Determination of Purity
5. To detect and distinguish between intra, inter molecular
Hydrogen bonding.
Detection: OH stretching frequency (33000-3600cm-1 ) is
lowered due to hydrogen bonding. From the decrease, the
presence of hydrogen bonding can be detected.
Distinction: After detecting the presence of hydrogen bonding,
noted the frequency of absorption. Dilute the sample. Then
record the IR spectrum of the diluted sample and noted the
absorption frequency of the diluted sample.
Intermolecular hydrogen bonding does not alter the absorption
frequency on dilution while ther will be a shift in the absorption
frequency.
e.g o-hydroxy phenol-No shift in absorption frequency is
observed since there is intramolecular hydrogen bonding.,while
for p-hydroxy phenol, absorption frequency shifts due to inter
molecular hydrogen bonding.

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6. To understand shape and symmetry of molecules.
7. Study of chemical reactions
8. Study of tautomeric equilibrium : amido-imido tautomerism
can be studied by noting the absorption frequency of hydroxyl
or carbonyl group in the compound.
9. Study of coordination compounds
10. To find Molecular symmetry and dipole moments.
******

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 ENGINEERIG CHEMISTRY
MODULE-2 : Nuclear Magnetic spectroscopy (NMR)

H1 NMR Spectroscopy.

NMR is the study of the properties of molecules containing magnetic

nuclei by means of the application of a magnetic field and the
observation of the frequency at which they come into resonance
with applied radiofrequency electromagnetic field.

Principle: Radiofrequency waves of the electromagnetic spectrum

induce transitions between magnetic energy levels of nuclei of a
molecule, which are created by keeping the nuclei in a magnetic
field. It depends on the absorption of energy when the nucleus of an
atom is excited from its lowest energy nuclear spin state to the next
higher one. The energy reqired for transition falls in radiofrequency
region (60 to 500 MHz).

Theory: Nuclei of atoms and molecules spin, and develops magnetic

field and act as a tiny magnet with a magnetic moment (μ).

Subatomic particles spin on their own axis. These spins in most of the
atoms (12C) are paired against each other, such that the nucleus has
no overall spin. The rules for determining the net spin can be
explained as follows.

It has been found that any nucleus consisting of either an odd

number of protons or an odd number of neutrons or both has the
property of nuclear spin and is NMR active.

If the mass number is even.( two cases arise )

,(a) Both np and nn are even, (b) Both np and nn are odd

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 (a) Both np and nn are even
Protons and neutrons separately pair up inside nucleus, then
4
the nucleus has no net spin. e.g He,12C,16O. Hence, such nuclei
are NOT NMR active.
(b) Both np and nn are odd
Protons and neutrons separately pair up inside nucleus, leaving
a half integral spin in each kind of particles giving a net integral
spins for the nucleus.( I= 1,2,3….) such nuclei are NMR active.
E.g 2 1H,(I=1/2+1/2=1) ,147N,(I=1),105B,
If mass number is odd ;( two cases arise)
(a) If np is odd , and nn is even- net spin of neutrons is zero, and
protons pair leaves odd half integral spin.
I=1/2, 3/2,5/2…., such nuclei are NMR active.
E.g :11H;I=1/2,31P(I=1/2). 15N , 3717Cl,I = 115B = 3/2,
(b)If np is even, and nn is odd.- Net spin due to protons is zero,
neutrons pairing leaves odd half integral spins,- such nuclei are
also NMR active E.g 136C (I=1/2).
According to quantum mechanics a nucleus of spin ‘I’ will have
(2I +1) orientations.
I=1/2 will have 2 orientations. 1H and 13C are examples.
For I=1,there are 3 orientations.
Energy levels of a nucleus with I=1/2,
Nuclear spin and energy levels in Magnetic field:
Applied field (H0)

No Field I=-1/2
Energy

ΔE

I=+1/2

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Larmor Frequency :
H0
H0

600

600

Flipping of Spining Nucleus

Imagine a hydrogen nucleus (I=+1/2) in a magnetic field. Here
the nucleus is in lower energy level (magnetic moment vector
align with the applied magnetic field. When the nucleus spins
on its axis, in the presence of an external magnetic field
(H0),the axis of spin precess around the magnetic field (similar
to the precessional motion of a spinning top in gravitational
field). The frequency of precission of the spinning nucleus in a
magnetic field is called Larmor frequency.( ʋ = (γ /2π) H0 )
When this frequency becomes identical to the radiofrequency,
resonance occurs and flipping of spinning nucleus takes place
with the absorption of radiation and spin orientation of nucleus
becomes -1/2 from +1/2.and now the nucleus is at higher
energy level ,also its magnetic moment is aligned against the
applied magnetic field.
Relation between radiofrequency and field strength:
The frequency of radiation needed is determined by the
difference in energy between the energy levels. According to

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 quantum mechanics, the spinning nucleus can have only those
spin angular momentum values permitted by the equation,
Spin angular momentum = I (I+1)1/2 h/2π, where h is Planck’s
constant, I is the spin quantum number of the nuclei, which can
have zero. Integral or half integral values.
But the magnetic moment of the nucleus (μ), can be equated to
the spin angular momentum as μ = γ x I(I+1) 1/2 h/2π.
On introducing the nucleus having a magnetic moment into
external magnetic field H0 , as shown in the above fig whose
energy states can have energy given by the equations,
E1 = -1/2(γ h/2π) H0 --------- (1).and
E2 = +1/2(γ h/2π) H0 -------(2) ,there by
When a nucleus absorbs energy equal to the difference
between E2 and E1 ie ΔE = E2 – E1
჻ ʋ = ΔE / h ,
= +1/2(γ h/2π) H0 –(-1/2(γ h/2π) H0)
H
ʋ = (γ /2π) H0 is the relation between radio frequency and
field strength.
From the above equation, it is clear that
(1)The frequency of absorbed or emitted radiation by a nucleus
in moving from one energy state to another is directly
proportional to the applied magnetic field.
(2)When the radiofrequency is kept constant and the strength
of magnetic field is varied, at some filed strength the energy
required to flip the proton matches with the energy of
radiation, when absorption occurs and we get absorption
signal.
(3)The resultant signal (spectrum) obtained is called NMR
spectrum.

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Note : A magnetic field of 4.7 T ( about 100,000 > earth’s
magnetic field) separates the two spin states of 1H nucleus by
an energy difference of 200 MHz in the radiofrequency range of
the electromagnetic spectrum.
Chemical shift (δ): Dependence of resonance frequency of a
nucleus that results from its molecular environment is called its
chemical shift.
ie the shift in the NMR signals due to shielding and deshielding
by electrons is called chemical shift.
Chemical shifts are measured in relative to a reference.
The position of the NMR signals relative to the reference signal
is also called as chemical shift.
(ʋsample-ʋref) Δʋ in Hz
6
δ= X 10 ppm; Or δ =
ʋref ʋop (MHz)

Chemical shift is dimensionless. Expressed in ppm

Alternate system of defining position of NMR signals is by a
scale called tau “τ” scale.
τ = 10 - δ
Different kind of protons in a molecule give different signals at
different frequency.

Theoretical concept of chemical shift:

Shielding and De-shielding

When a nucleus is placed in a magnetic field (applied field), its

electrons are caused to circulate and produce a secondary
magnetic field. This induced secondary magnetic field may
oppose or reinforce the applied magnetic field. Thus two
possibibilities arise.

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They are as follows.

1. When induced secondary magnetic field oppose applied field

Here the net field felt by the nucleus (e.g 1H) in a molecule
will be less than the actual applied magnetic field and hence
we can say that the hydrogen nucleus is shielded.
A more shielded hydrogen nucleus absorbs RF radiation at a
lower frequency. E.g Field felt by the hydrogen nucleii of
methane is less than that of free hydrogen nuclei.
When induced secondary magnetic field reinforces applied
field, the net field felt by the nucleus (e.g 1H) in a molecule
will be greater than the actual applied magnetic field and
hence we can say that the hydrogen nucleus is de-shielded.
A more de-shielded hydrogen nucleus absorbs RF radiation at
a higher frequency.
Measurement of chemical shift in NMR spectroscopy
involved the use of a reference standard- Tetramethylsilane
(CH3)4Si. Called as TMS.TMS is the most commonly used
reference compound because of the following reasons.
1. TMS is chemically inert
2. Do not interfere with other compounds under study
3. IT is highly volatile (b.pt 270c) hence samples can be
recovered after analysis.
4. TMS gives a single sharp absorption peak due to twelve
equivalent protons, at a lower frequency than samples,
due to lower electronegativity of Si than C.
5. Soluble in most organic solvents.

Factors affecting chemical shift:

1. Shielding and de-shielding: Compared with an isolated
proton, a shielded (diminishing of applied magnetic field

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 by the electrons of the atom) proton requires higher
applied field strength and therefore a more shielded
proton absorbs at lower frequency of RF radiation.
While a de-shielded (increasing of applied magnetic field
by the p electrons of the atom) proton requires a lower
applied field strength. Therefore a more deshielded
proton absorbs at higher frequency of RF radiation.
Thus shielding and de-shielding of protons by electrons
causes chemical shift.

De shield Sheild

Down fileld Upfield

10 9 8 7 6 5 4 3 2 1 0
δ(ppm)
2. All aromatic protons and olefinic protons differ widely
because of the deshielding due to the circulation of π
electrons. Deshielding effect increases the chemical
shift. (δ lies between 6.5 to 8.5).

3. Electronegativity of the attached atoms: Presence of

electronegative atom attached to aliphatic compounds
influences chemical shift. When an electronegative atom
is present in the –CH system, and there is less shielding
(more deshielded) and chemical shift increases.
Foe e.g,in the compound CH3X ( X=F,Cl,Br,I),the shielding
of the methyl protons decreases as the electronegativity
of X becomes more and more.

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 Thus chemical shift depends on the degree to which an
electronegative atom draws electrons towards it from the
methyl group.

Compound Chemical shift(δ) ppm for X

F Cl I
CH3X
4.3 3.1 2.2
Deshielding effect of electronegative substituents is
cumulative

Compound
Chemical shift(δ) ppm CH3Cl CH2Cl2 CHCl3
3.1 5.3 7.3
Shielding effect decreases when an electronegative atom
substituted in the hydrocarbon chain, the electron density
around the protons decreases as the proton gets closer
towards the electronegative atom.ie δ value increases
e.g: 1-chloropropoane
H3C-CH2-CH2Cl
δ (ppm) : 1.0 1.4 3.4
4. Hydrogen Bonding: Protons that are involved in hydrogen
bonding typically change the chemical shift. More the
hydrogen bonding, more protons are deshielded, and the
chemical shift is higher.
Chemical shift of some of protons
Proton type Chemical Proton Chemical
shift(δ) ppm type shift
H-R (aliphatic) 0.9-1.8 H-C-Br 2.7-4.1
H-C = C-(alkynal) 2.5 H-C-Cl 3.1-4.1
H-C=C-(alkenyl) 4.5-6.5 H-C-O-R 3.3-3.7
H-Ar(aromatic) 6.5-8.5 OH-R 0.5-5
H-CO-R 9.10 H-O-CO-R 10-13

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Interpretaion of chemical shift
1. Number of NMR signals indicate the no of types of protons
present
2. The position of the signal indicates about the protonic
environment.
3. The intensity of the signal (peak area) indicates how many
protons of the same kind are present. Also the relative peak
ratios of different kinds of protons in the molecule can be
understood.
For e.g. there are two kinds of protons in CH3-oCH2-CN,NMR
spectrum will have two signals, apart from that of
reference(TMS),and the two signals will be at different
position due to their different environment. There relative
intensities are also different since they have three protons of
one kind and two protons of another kind.
A typical NMR spectrum of CH3-oCH2-CN is given below.
(A) (B)

TMS
(A)

(B)

5 4 3 2 1 0
0

Spin-spin Splitting (coupling): Fine splitting of the NMR signals

due to the interaction between protons on adjacent atoms is
referred as Spin-spin Splitting or Spin-spin coupling.

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Each nucleus in a molecule spins and possess its own magnetic
moment. The electronic environment of each proton
distinguishes it from all others in the molecule and the
magnetic field associated with a given proton be affected by
the magnetic field of an adjacent proton.
At low resolution, the NMR spectrum is broad and at higher
resolution, splitting of NMR signal is caused by Spin-spin
interaction.
Rules for spin-spin splitting
1. Chemically equivalent protons do not show Spin-spin
splitting.
2. Only nonequivalent protons couple and split
3. Protons on adjacent carbons normally will couple.
4. Splitting of signal is based on (n+1) rule .ie The multiplicity
(No of peaks into which a particular proton is split) of a
proton is calculated. .If “n: number of protons are present in
an adjacent nucleus, the signal will split into n(n+1) peaks.
Zero hydrogen as neighbor it will split into (0+1) ie singlet
One hydrogen as neighbor it will split into (1+1) ie doublet
Two hydrogen as neighbor it will split into (2+1) ie Triplet
Three hydrogen as neighbor it will split into (3+1) ie Quartet
and so on.
5 If a set A of nA equivalent protons and another set X of nx
set of equivalent protons both spin couple with a particular
set M with are present, nm equivalent protons; then the
signal for M is split into (nA+1) (nx+1) component lines.

Let us take the following compounds as example and discuss

the spin –spin coupling in these molecules.

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1. The NMR spectrum of CH3-oCH2-CN gives two signals, both
are singlet.
2. In the case of CH3CHCl2, a doublet at δ=2.1 ppm for methyl
proton and a quartet at δ=5.9 ppm for CH proton. The CH3
proton split into a doublet under the influence of one CH
proton while the CH proton splits into a quartet under the
influence of three CH3 protons. The intensity ration of the
quartet of CH proton is 1:3:3:1,while that of the doublet is
1: 1.
3. n-propane: CH3CH2CH3
Two different kinds of protons. The two terminal methyl
protons are of same kind, will generate one signal (a), and
the CH2 protons will generate another signal(b).
‘a’ will split into a a triplet under the influence of the two CH 2
protons with an intensity ratio of 1:2:1,and ‘b’ signal will split
into a septet ( as per n+1 rule 4 above) (6+1=7) under the
influence of six equivalent protons, with an intensity ratio of
1:6:15:20:15:6:1.

CH3

CH2

1.8 1.6 1.4 1.2 1.0 0.8 0.6

NMR spectrum of propane

Predict the 1H NMR signals ,their relative positions and

multiciplities for ethylacetate.

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 O
CH3 C O CH2 CH3
C b a
Three types of protons-(a,b,c)-
The δ for methyl proton ‘a’ is closer to TMS,(low δ value),
because the H atoms are far away from the electronegative
oxygen atom.
“c” type methyl proton appears next and the ‘b’ type
methylene proton appear last with high δ value

b a

6 5 4 3 2 1 0

Ppm
1
H NMR spectrum of ethyl acetate.

Explain the 1H NMR spectrum of ethanol.

A: The NMR Structure of pure ethanol is CH3CH2OH shows
(i) A triplet for methyl protons (due to their coupling with
methylene proton) at around δ=1.15 ppm.
(ii) An octet for methylene proton (due to their coupling with
methyl proton and hydroxyl proton) at δ= 3.6 ppm,the
multiplicity observed being in accordance with (nA+1)
(nx+1) formula.
B: The NMR spectrum of acidified ethanol or 20% solution
of ethanol shows,

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A triplet for methyl protons as expected (due to their
coupling with methylene proton) at around δ=1.15 ppm,
but the CH2 signal is a quartet and the OH signal is a
singlet only.NOspin –spin coupling takes place between
OH proton and CH2 protons.
This is due to chemical exchange ie there is rapid
excahange of protons between the ethanol molecules.

CH3CH2OHA + CH3CH2OHB CH3CH2OHB+CH3CH2OHA

Coupling constant (J): The magnitude of separation

between (ie distance or spacing) the between the peaks in
a multiplet arising from spin-spin coupling constant or
coupling constant. It is denoted by the letter ‘J’.,
expressed in HZ. J value is independent of the applied field
strength or operating frequency of the instrument.
It is a measure of how strongly a nucleus is affected by the
spin states of its neighbor.
For example, in t he NMR spectrum of ethanol, the
coupling constant between the methyl triplet is equal. In
the case of methylene signal,the spacing between the
signals is not constant due to the difference in coupling
constants of –OH and CH3 protons.
Applications of NMR spectroscopy:
1. In magnetic resonance imaging for medical diagnosis
2. For identification of atomic configuration in molecules.
3. Used in quantitative analysis of materials for isotope
content determination
4. A rapid non-destructive method for analyzing protein
content of oils and fats.

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 5. For determination of water in Liquid N2O4 and in heavy
water.
6. Used in the structural diagnosis and study of Keto-enol
tautomerism.
7. In the study of hydrogen bonding
8. In the study of reaction kinetics
9. In sample Purity determination.
10. For data acquisition in petroleum industry for
exploration an drecovery of petroleum and Natural
gas.

Magnetic Resonance Imaging (MRI)

 Used in Radiology to visualize internal structure of the
body in detail.
 Make use of the property of nuclear magnetic resonance
to image the nuclei of atoms inside the body.
 Make use of the water present in the body tissues.
Working When the person is inside a powerful magnetic
field of the scanner, average magnetic moment of protons
becomes aligned with the direction of the field.
A radiofrequency current is briefly turned on, producing
resonance frequency and the radio waves are absorbed
and flip the spins of the protons. After the
electromagnetic field is cut off, the spins of the protons
reach thermodynamic equilibrium called relaxation. Due
to this a radio signal is generated from the body, which is
measured with a receiver coils and recorder.
Once the RF signal is removed, the nuclei realign
themselves and treturn to equilibrium by emitting their
own RF signal. This signal is called free-induction decay.
Relaxation time for molecules to regain their natural

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 alignment vary depending on the type of tissues being
scanned. This allows thw scan to detect different type of
tissues.
Applications Of MRI
1 Diffusion MRI is useful for diagnosis of neurological
disorder and also to understand central nervous
system.
2 Used to measure the different metabolites.
3 To generate picture of arteries (Magnetic resonance
angiography)
4 Functional MRI is used to measure signal changes in
brain.

https://youtu.be/nFkBhUYynUw?t=2

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