Unit-V: A): UV Spectroscopy

Contents:

I) Introduction
II) Woodward-Fischer Rules for……
A) Conjugated Dienes
B) Conjugated α,β-Unsaturated Carbonyl Compounds
III) Applications of UV spectroscopy

I) Introduction:
➢ Electromagnetic spectrum:

UV spectroscopy is a spectroscopic technique that is used for the detection of conjugation that is
present in an organic compound. This UV region ranges from 200-400nm. It is used to differentiate
conjugated and isolated dienes and trienes. Similarly, it is used to differentiate saturated and
unsaturated carbonyl compounds. It also throws light on the stereochemistry of cis-trans compounds.
UV region have lower wavelength than Visible and IR region therefore it has higher energy and
frequency than Visible and IR region.
➢ Principle of UV spectroscopy:
When electromagnetic radiation having wavelength in the UV region is incident on organic compound
then there is excitation in organic molecules is taking place from BMO to AMBO by absorption of light
radiation of suitable wavelength. When transmitted light is passed through the spectrophotometer,
which then compared the wavelength of transmitted light and absorbed light by an organic molecule
and then record the wavelength which is absorbed by the organic molecule in the form of graph (A
v/s λ) called as UV spectrum.
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➢ Beer-Lambert’s Law:
The UV spectroscopy is based on Beer-Lambert’s Law, which states that, “The fraction of incident light
absorbed is directly proportional to the number of molecules in the path length”.
Mathematically it is given by equation as follows,
A = elc
Where,
A= is the absorbance
e= is the molar attenuation coefficient or absorptivity of the attenuating species
l= is the optical path length in cm
c= is the concentration of the attenuating species.
➢ Nature of UV band:
UV region is more energetic. Absorption of UV radiation by organic molecule brings about the
electronic excitation from BMO to ABMO. The overall process of electronic excitation in a molecule is
takes place by the simultaneous change in vibrational and rotational energy levels of organic
molecule, therefore the UV spectrum is broad.
➢ Absorption of UV radiation by Organic Molecules/Types of Transitions:
The absorption of light radiation by an organic molecule in UV and Visible region involves the
promotion of electrons from BMO to ABMO in a molecule. Depending on the transition of electrons in
a molecule, there are following four types of transitions are observed,
1) Sigma→Sigma* (σ→σ*) Transition
2) pi→pi* (π→π*) Transition
3) n→Sigma* (n→σ*) Transition
4) n→pi* (n→π*) Transition

1) Sigma→Sigma* (σ→σ*) Transition:

In this type of transition, there is a transition of electron is taking place from bonding σ-orbital to
higher energy antibonding σ*-orbital. In σ-bond σ-electrons are tightly held therefore, this type of
transition required higher energy and it takes place at a very short wavelength of UV radiation
(150nm). In alkanes, there are only sigma bonds are available. Therefore, alkanes are showing this
type of transition.
2) pi→pi* (π→π*) Transition:
In this type of transition, there is a transition of electron is taking place from bonding π-orbital to
higher energy antibonding π*-orbital. In π-bond π-electrons are loosely held therefore, this type of
transition required lesser energy than σ→σ* transition and it takes place at high wavelength of UV

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radiation (170-205nm). The unsaturated hydrocarbons and carbonyl compounds shows this type of
transition.
3) n→Sigma* (n→σ*) Transition:
In this type of transition, there is a transition of non-bonding electrons is taking place to higher energy
antibonding π*-orbital. This n→σ* transition is takes place at less energy than π→π* transition
therefore occurs at higher wavelength (above 205nm). This type of transition involves saturated
compounds with one hetero atoms like oxygen, nitrogen, fluorine, chlorine, etc. Normally, saturated
halides, alcohols, ethers, aldehyde, ketones, and amines shows this type of transition.
4) n→pi* (n→π*) Transition:
In this type of transition, there is a transition of an electron in unshared pair on a hetero atom is
excited to higher energy antibonding π*-orbital is taking place. This type of transition requires the
least amount of energy than all types of transition in UV spectroscopy. Therefore, the n→π∗ transition
gives the absorption with a longer wavelength (around 280nm). Normally, unsaturated compounds
containing heteroatoms such as aldehyde, ketone, ester, carboxylic acid and nitriles shows this type
of transition.

Figure: Various Electron Transitions

➢ Terms used in UV spectroscopy:
1) Chromophore:
Chromophore is an unsaturated functional group that absorbs light and reflects it at specific angle to
give the hue. e.g., azo (-N=N-), keto (-COC-), nitro (-NO2), nitroso (-NO), ethylene (-C=C-), carbonyl (-
C=O) etc.

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2) Auxochrome:
It is a functional group which does not absorb radiation longer than 200nm, but when it is attach to
auxochrome then it causes shift in absorption to longer wavelength. e.g., hydroxy (-OH), methoxy (-
OCH3), amino (-NH2) etc.

3) Bathochromic shift/Red shift:

Absorption to a longer wavelength (lower frequency) is called as Bathochromic shift. Because
the red color in the visible spectrum has a longer wavelength than most other colors, the effect is also
commonly called a red shift.

This can be explained as, in case of phenol alone the electron pair that is present on the phenolic
oxygen atom is shifted towards nitro group by resonance effect, but during such shifting there is
separation of charges (+ve and -ve) is taking place in 4-nitrophenol molecule and hence it becomes
unstable (high energy) due to which it absorbed at lower wavelength.
While, on addition of alkali in 4-nitophenol, it forms phenoxide ion which is more stable (lower
energy) as compared to original molecule and hence absorbed at higher wavelength.
4) Hypsochromic shift/Blue shift:
Absorption to a shorter wavelength (higher frequency) is called as Hypsochromic shift. Because
the blue color in the visible spectrum has a shorter wavelength than most other colors, this effect is
also commonly called a blue shift.

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This can be explained as, in case of aniline alone the electron pair that is present on the nitrogen atom
is shifted throughout the ring by resonance effect and it is stable (lower energy) and hence absorbed
at higher wavelength.
While on addition of acid in aniline the lone pair on nitrogen atom abstract proton from acid
molecule and because of which there is separation of charges (+ve and -ve) is taking place in original
molecule and hence it becomes unstable (high energy) due to which it absorbed at lower wavelength.
➢ Effect of conjugation on position of UV band (peak):
UV spectroscopy is most effective in detection of conjugation. The conjugation in organic molecule
shifts the UV spectrum towards longer wavelength. If 1 -C=C- is increases in conjugated parent
molecule, then its λmax value increases by 30nm.
The conjugated system mainly divided into two classes as follows,
1) Conjugation with like or same chromophore involving π→π conjugation:
In this type of molecules, the two -C=C- are present in conjugation with each other.
e.g., dine (-CH2=CH-CH=CH2-), triene (-CH2=CH-CH=CH-CH=CH2-) etc.
Conjugated dienes are again classified in to two types as follows,
I) Open chain dienes (-CH2=CH-CH=CH2-).
II) Cyclic dienes: When two -C=C- are present in cyclic system.

These cyclic dienes are again classified in to two types as follows,

A) Homoannular diene: In this type of diene the two -C=C- are present in one and the same ring/
cyclic system.

B) Heteroannular diene: In this type of diene the two -C=C- are present in different ring/ cyclic
system.

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Exocyclic double bond: The exocyclic double bond is a bond which is present outside of the ring.
Endocyclic double bond: The endocyclic double bond is a bond which is present inside the ring.

2) Conjugation with unlike or different chromophore involving n→π conjugation:

In this type of molecules, the -C=C- is present in conjugation with -C=O. e.g., enone (-CH2=CH-CO-CH3).
II) Woodward-Fischer Rules for….
A) Conjugated Dienes:
Woodward's rules, named after Robert Burns Woodward and also known as Woodward–Fieser
rules (for Louis Fieser) are several sets of empirically derived rules which attempt to predict
the wavelength of the absorption maximum (λmax) in an ultraviolet–visible spectrum of a
given compound.
According to Woodward’s rules the λmax of the conjugated dienes can be calculated using a formula:
λmax = Base value + Σ Substituent Contributions + Σ Other Contributions

Sr. Structural feature λmax

No. (In nm)
1 Base value for parent acyclic or Heteroannular diene 215
2 Base value for Homoannular diene 253

Increments
1 Double bond extending conjugation 30
2 Exocyclic double bond 5
3 Exocyclic double bond for two rings 10

Substituents
1 Substituent-H 0
2 Substituent-R (alkyl) 5
3 Substituent-Cl, Br 5
4 Substituent-OH, -OR (alkoxy) 5
5 Substituent-OCOR (ester), OAc (acetate) 0
6 Substituent-ROR (ether) 6
7 Substituent-SR (sulfide) 30
8 Substituent-NR2 (secondary amine group) 60
9 Substituent-cis or trans diene 40

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B) Conjugated α,β-Unsaturated Carbonyl Compounds:
Woodward-Fieser rules can be extended to calculate the λmax of α,β-unsaturated carbonyl
compounds (enones). In a similar manner to Woodward rules for dienes discussed previously, there
is base value to which the substituent effects can be added and the λmax can be calculated using the
formula:
λmax = Base value + Σ Substituent Contributions + Σ Other Contributions

Sr. Structural feature λmax

No. (In nm)
1 Base value for parent six-member cyclic α,β-unsaturated 215
carbonyl compound

2 Base value for parent five-member cyclic α,β-unsaturated 202

carbonyl compound
3 Base value for parent cyclic α,β-unsaturated aldehyde 207

5 Base value for parent α,β-unsaturated aldehyde 210

(R=-H)
6 Base value for parent α,β-unsaturated ketone 215
(R=-alkyl)
7 Base value for parent α,β-unsaturated ester 195
(R=-OR)
8 Homoannular diene 39

Increments
1 Double bond extending conjugation 30
2 Exocyclic double bond 5
3 Exocyclic double bond for two rings 10

Substituents
Substituent present at α-position
1 Substituent-H 0
2 Substituent-R (alkyl) 10
3 Substituent-Cl 15
4 Substituent-Br 25
5 Substituent-OH, -OR (alkoxy) 35
6 Substituent-OCOR (ester) 6
Substituent present at β-position
1 Substituent-R (alkyl) 12
2 Substituent-Cl 12
3 Substituent-Br 30
4 Substituent-OH, -OR (alkoxy) 30
5 Substituent-OCOR (ester) 6
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 6 Substituent-SR (sulfide) 85
7 Substituent-NR2 (amine) 95
Substituent present at γ/δ-position
1 Substituent-R (alkyl) (both γ and δ) 18
2 Substituent-Cl (both γ and δ) 12
3 Substituent-Br (both γ and δ) 30
4 Substituent-OH (only γ) 50
5 Substituent-OR (alkoxy) (only γ) 30
6 Substituent-OCOR (ester) (both γ and δ) 6

III) Applications of UV spectroscopy:

UV spectroscopy have broad range of applications in various fields. Some of them are described as
follows,
1) Detection of Impurities:
It is one of the best methods for the determination of impurities in organic molecules. Additional
peaks can be observed due to impurities in the sample, and it can be compared with that of standard
raw material. By also measuring the absorbance at a specific wavelength, the impurities can be
detected.
2) Detection of Conjugation:
UV spectroscopy is used for the detection of conjugation that is present in an organic compound. As
we know that, the increase of one -C=C- in conjugated dienes increase its λmax value by 30nm.
UV spectroscopy is also used for differentiating conjugated and non-conjugated (isolated) dienes. It is
observed that conjugated dienes absorbed at higher wavelength than isolated dienes.
e.g., 1) 1,3-cyclohexadiene (conjugated diene) absorbed at higher wavelength than 1,4-
cyclohexadiene (non-conjugated/isolated), because in 1,3-cyclohexadiene two -C=C- are present in
conjugation and it required less energy for π→π* transition and therefore absorbed at longer
wavelength (λmax=265nm). While, in case of 1,4-cyclohexadiene two -C=C- are not present in
conjugation and it required more energy for π→π* transition and therefore absorbed at shorter
wavelength (λmax=190nm).

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3) Detection of Stereochemistry:
UV spectroscopy is also used for determination of stereochemistry i.e., to differentiate cis and trans
isomers.
In a pair of geometrical isomers cis-isomer (λmax=280nm) is absorbed at lower wavelength than
trans-isomer (λmax=296nm).
e.g.
1) cis-stilbene absorbed at lower wavelength than trans-stilbene due to two reasons,
i) In cis-isomer there are two bulky groups (phenyl ring) which are present in close vicinity of each
other due to which steric interactions are increases, planarity of molecule is disturbs because of which
the delocalization of electrons is difficult and therefore it required more energy for delocalization of
electrons and hence absorbed at lower wavelength.
ii) In cis-isomer the length of chromophore decreases due to which π→π* transition required higher
energy and hence absorbed at lower wavelength.
While, in case of trans-stilbene the two bulky groups (phenyl ring) which are present apposite to
each other due to which no steric interactions are present, planarity of molecule is not disturbs
because of which the delocalization of electrons is takes easily and therefore it required less energy
for delocalization of electrons and hence absorbed at higher wavelength.

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 Unit-V: B): IR Spectroscopy

Contents:

I) Introduction
II) Characteristics vibrational frequencies of,
1) Alkanes
2) Alkenes
3) Alkynes
4) Aromatic compounds
5) Alcohols
6) Phenols
7) Aldehydes
8) Ketones
9) Carboxylic acids
10) Esters
11) Amides
12) Anhydrides
13) Lactones
14) Lactams
III) Effect of……
1) Hydrogen bonding
2) Solvent effect on vibrational frequencies
IV) Applications of IR spectroscopy

I) Introduction:
➢ Spectroscopy:
It is the branch of science that deals with the investigation and measurement of spectra produced
when matter interacts with or emits electromagnetic radiation.
➢ Electromagnetic spectrum:

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➢ IR spectroscopy:
Infrared spectroscopy (IR spectroscopy or vibrational spectroscopy) is the measurement of the
interaction of infrared radiation with matter by absorption, emission, or reflection.
It is most widely used tool for the detection of function groups in organic compounds. IR region have
higher wavelength than UV and visible region and therefore it has lower energy and frequency than
UV and visible region.
➢ Principle:
A molecule is not rigid in nature. In molecule different atoms joins to each other by chemical bonds.
In molecule these bonds acts as a spring of various strength. The bond in the molecule continuously
stretches, contract or bend due to which the molecule is continuously vibrating. The various
vibrations of a bond take place at a definite frequencies. When the IR radiation of definite frequency
is incident on a molecule, the molecule absorbs only those frequency which is responsible for
stretching or bending vibration of a molecule, therefore when IR radiation is incident on a molecule
then vibration of a bond is takes place and the magnitude of vibration increases, and molecule shows
an absorption spectra known as IR spectra. An IR spectrum can be visualized in a graph of infrared
light absorbance (or transmittance) on the vertical axis (Y) vs. frequency or wavelength on the
horizontal axis (X).
The method or technique of infrared spectroscopy is conducted with an instrument called an infrared
spectrometer (or spectrophotometer) which produces an infrared spectrum.
➢ Types of vibrations:
There are two kinds of fundamental vibrations for a molecule as follows,
1) Stretching vibration
2) Bending vibration

1) Stretching vibration:
In stretching vibration, the distance between two atoms increases or decreases but the atoms remain
in same plane.
Stretching vibration is further divided in to two types as follows,
A) Symmetrical stretching vibration
B) Asymmetrical stretching vibration

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1) Bending vibration:
In bending vibration, the position of the atoms changes relative to the original bond axis.
Bending vibration is further divided in to four types as follows,
A) Scissoring (In plane bending)
B) Rocking (In plane bending)
C) Wagging (Out of plane bending)
D) Twisting (Out of plane bending)

➢ Divisions of IR:
For systemic study the whole IR region is divided into three parts as follows,
1) Near IR region [14000-4000 cm-1, (0.8-2.5 μm wavelength)]
2) Mid IR region [4000-400 cm-1, (2.5-25 μm)]
3) Far IR region [400-10 cm-1, (25-1000 μm)]
An organic chemist is mainly concerned with Mid IR region [4000-400 cm-1, (2.5-25 μm)]. This Mid IR
region is subdivided into three parts depending on the vibration of a molecule.
A) Functional group region: The functional group region runs from 4000-1450 cm-1. These are
typically associated with the stretching vibrations of functional groups.
B) Finger print region: The region between 400-1500 cm-1 in an IR spectrum is known as the
fingerprint region. It is very complex, usually contains a large number of peaks, making it difficult to
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identify individual peaks. However, the fingerprint region of a given compound is unique and,
therefore, can be used to distinguish between compounds.
C) Aromatic region: The region between 667-400 cm-1 in an IR spectrum is known as the aromatic
region. This region is very useful for the detection of aromatic character of a molecule. The absence of
absorption in this region shows the non-aromatic character. The bands occur in this region is due to
the bending vibrations in the molecule.
II) Characteristics vibrational frequencies for various functional groups:

Sr. No. Function group Unit IR frequency in cm-1

C-C 1200
1 Alkane (C-C)
C-H 2850-2960
C=C 1640-1680
2 Alkene (c=c)
C-H 3000-3100
c C 2180
3 Alkyne (c C)
C-H 3300
4 Alkyl halide (R-X) C-X 500-700
O-H 3550-3600
5 Alcohol (R-OH)
C-O 10-1050, 20-1100, 30-1150
O-H 3200-3600
6 Phenol (Ar-OH)
C-O 1250
C=O 1725
7 Aldehyde (R-CHO)
C-H 2720-2860
8 Ketone (R-CO-R) C=O 1715
C=O 1730
9 Carboxylic acid (R-COOH)
O-H 2700-3300
1060-1150 (alkyl)
10 Ether (R-O-R) C-O-C
1250 (aryl)
C=O 1735-1750
11 Ester (R-COO-R)
O-C 1180-1200
C=O 1800
12 Acid chloride (R-CO-Cl)
C-Cl 500-700
C=O 1754
13 Acid anhydride (R-CO-O-CO-R)
C-O-C 1825
N-H 10-3350-3500, 20-3250-3450
14 Amine (R-NH2)
C-N 1560-1640
C=O 1660
15 Amide (R-CO-NH2)
N-H 3300
C=C 1600 and 1450-1500
16 Aromatic compounds (Ar-OH)
C-H 3030-3050
17 Nitrile (C N) C N 2210-2260

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III) Effect of……
1) Hydrogen bonding on IR absorption:
The presence of hydrogen bonding changes the position and shape of an infrared absorption band.
Frequencies of both stretching as well as bending vibrations are changed because of hydrogen
bonding. The X-H stretching bands move to lower frequency usually with increased intensity and band
widening. Stronger the hydrogen bonding, greater is the absorption shift from the normal values.
The compounds alcohols and phenols show IR absorption in the range of 3550-3600cm-1 and
3200-3600cm-1 respectively. If hydrogen bonding is present then band is very broad. The hydrogen
bonds are of two types intramolecular (Intra-molecular hydrogen bonds are formed when the proton
donor and acceptor are present in a single molecule) and intermolecular (Inter-molecular hydrogen
bonding involves association of two or more molecules of the same or different compound, and it may
result in dimer molecules). Both intra and intermolecular hydrogen bonding lowers IR absorption
frequency of -OH group due to increase in bond length of -O-H bond.
The intramolecular and intermolecular hydrogen bonding is distinguished by dilution. If on
dilution band becomes sharp and absorb at 3550-3600cm-1 indicates presence of intermolecular
hydrogen bonding, while if there is no change in position (3200-3600cm-1) of band 1 indicates
presence of intramolecular hydrogen bonding.

2) Solvent effect on IR absorption:

The polarity of solvent will have an influence on the IR spectra of organic compounds due to the
interactions between solvent and compounds, which is called solvent effects. If we place a compound,
which contains n, pi and pi* orbitals, into a polar solvent, the solvent will stabilize these three orbitals
in different extent. The stabilization effects of polar solvent on n orbital are the largest one, the next
larger one is pi* orbital, and the effects on pi orbital is the smallest one. The spectra of n→pi* transition
will shift to blue side, which means it will move to shorter wavelengths and higher energies since the
polar solvent causes the energy difference between n orbital and pi* orbital to become bigger. The
spectra of pi→pi* transition will shift to red side, which means it will move to longer wavelengths and

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lower energies since the polar solvent causes the energy difference between n orbital and pi* orbital
to become smaller.
IV) Applications of IR spectroscopy:
IR spectroscopy is used for the following,
1) Identification of functional group and structure elucidation:
IR spectroscopy is the most useful tool for the detection of functional groups. As most of the organic
compounds (functional groups) shows absorption in this region, hence it is useful for the detection of
various kinds of functional groups.
2) Study of kinetics or mechanism of reaction/ Studying the progress of the reaction:
As the majority of chemical reactions involved change in the function group during the course of
overall reaction, thus IR spectroscopy helps us to follow the course of reaction. In this method the
sample of reactants is drawn from time to time during the reaction and its IR spectrum is studied
which is useful to determine how far the reaction is progressed.
e.g. The conversion of Benzaldehyde to Benzyl alcohol

3) Detection of impurity:
It is generally observed that particular functional group absorb IR radiation of particular frequency
known as functional group frequency. If some impurities are present in pure compound then it can be
easily detected by IR spectroscopy.
e.g.
If some impurity ketone is present in hydrocarbon (alkane), then it can be easily detected by the IR
spectroscopy. As pure hydrocarbon shows IR absorption band at 1200cm-1 (C=C) and 2850-2960cm-
1 (C-H), while ketone shows IR absorption band at 1715cm-1 (C=O) from that we can be easily detect
the ketone impurity that is present in pure hydrocarbon (alkane).
4) Ring size:
It is observed that in case of smaller ring, ring strength is high, while in case of big ring the ring
strength is low.

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It is observed that as ring size decreases, angle strain (ring strain) increases and hence IR absorption
frequency is also increases.
e.g.

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 Unit-V: C): 1H-NMR Spectroscopy

Contents:

I Introduction
II Principle of 1H-NMR (Nuclear Magnetic Resonance) Spectroscopy
III Magnetic and non-magnetic nuclei
IV Shielding-Deshielding
V Chemical shift
A) Measurement of chemical shift
B) Factors influencing chemical shift
VI Peak area
VII Spin-spin coupling (n+1 rule)
A) Rules of Spin-spin coupling
VIII Pascal triangle
IX Coupling constant (J)
X Factors affecting on coupling constant

I) Introduction:
➢ Electromagnetic spectrum:

1H-NMR spectroscopy is another form of absorption spectroscopy. 1H-NMR spectroscopy radiation of

very long wavelength (1010-1011nm) is used. This region is also called as radio wave region. This
region (radio waves) has very-very less energy (no energetic) due to very high wavelength therefore
it does not affect rotational, vibrational, or electronic energy levels of molecule, but they (radio waves)
are able to interact with nuclei of certain atoms when placed in strong magnetic field. Hence this

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spectroscopy is called as nuclear magnetic resonance spectroscopy. This spectroscopy is used for
structure determination of organic molecules, as it detects environment around the functional group.
II) Principle of 1H-NMR spectroscopy:
The NMR spectroscopy deals with the nucleus of an atom that possess magnetic moment. The nucleus
of an atom contains protons and neutrons. The neutrons are electrically neutral, while protons +vely
charge, hence nucleus of an atom is +vely charged. And here we are concerned with protons only.
Like electrons nuclei of certain atoms also spin about their own axis. The spinning of these
charged particles around its own axis generates a magnetic field and posses’ magnetic moment
around the spinning axis, so these nuclei act as a tiny bar magnets. Individual proton and neutron
have spin quantum number (I) +1/2 and -1/2 respectively. Therefore depending on the number of
nucleons (protons + neutrons) certain nuclei possess some spin.
The total spin quantum number is a characteristics of a nucleus. The nuclei which have spin
quantum number is equal to one (1) or greater than zero (0) possess a spin and such nuclei are called
as magnetic nuclei, while the nuclei which have spin quantum number is equal to zero (0) do not
possess a spin and such nuclei are called as non-magnetic nuclei.
III) Magnetic and non-magnetic nuclei:
The spin quantum number, which is denoted by “I”, is a characteristics of a nucleus of an atom. The
following rules are used to find out the nuclear spin quantum number.
1) The nuclei which have odd mass number and odd or even atomic number have half integral spin
i.e. I = 1/2, 3/2, 5/2……etc. then these nuclei are called as magnetic nuclei.
e.g. 1H1, 6C13, 7N13, 9F19, 15P31 etc.
2) The nuclei which have even mass number and even atomic number have zero spin quantum
number (I = 0), such nuclei do not have spin angular momentum and magnetic property. These
nuclei are called as non-magnetic nuclei.
e.g. 6C12, 8O16, 16S32 etc.
3) The nuclei which have even mass number and odd atomic number have integral spin quantum
number i.e. I = 1, 2, 3……etc. then these nuclei are called as magnetic nuclei.
e.g. 1H2, 7N14 etc.
IV) Shielding-Deshielding:
When the molecule is placed in the external applied magnetic field (Ho) the electrons around the
protons are force to circulate; due to the circulation of electrons a secondary magnetic field (δHo) is
produced around the nucleus, which is known as induced magnetic field.

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So, from figure it is observed that, the secondary induced magnetic field (δHo) is in opposite direction
to that of external applied magnetic field (Ho). This secondary induced magnetic field (δHo) tries to
protect the nucleus from the external applied magnetic field (Ho).
This type of protection of nucleus from external applied magnetic field (Ho) is called as
diamagnetic shielding or shielding.
And when the nucleus is not protected from external applied magnetic field (Ho) by the
secondary induced magnetic field (δHo) then it is known as deshielding.
The shielding and deshielding of the nucleus are depends upon the density of electrons around
the nucleus.
1) If there is more the electron density around the proton, more is secondary induced magnetic field
(δHo) and therefore more is the shielding of proton from external applied magnetic field (Ho) and
vice-versa.
The shielded protons required more external applied magnetic field (Ho) to produce
heff/resonance and therefore the position of the signal is shifted to higher value i.e. absorption occurs
at up-field (i.e. closer to zero).
2) The deshielded protons required less external applied magnetic field (Ho) to produce
heff/resonance and therefore the position of the signal is shifted to lower value i.e. absorption occurs
at down-field (i.e. far from zero).

Shielding and deshielding is depends upon electronic effect.

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e.g.
The proton attached to the oxygen (-O-H), and the proton attached to the carbon atom (-C-H) are
different from each other. As the oxygen atom is more electronegative, the electron density around
this proton is deshielded and hence the absorption occurs at down-field.
While, in case of proton attached to the carbon is more protected by the electron cloud (as
caron is less electronegative) from the external applied magnetic field (Ho) then such protons are
shielded and hence the absorption occurs at down-field.
Let us consider the examples of shielding and deshielding,
1) Shielding: Acetylene molecule (C2H2)
When the acetylene molecule is placed in uniform external applied magnetic field (Ho), then it may
be oriented in such a way that, its molecular axis is parallel to the external applied magnetic field (Ho).

Pi (π) electrons are force to circulate because of external applied magnetic field (Ho) and these
circulating electrons produces secondary induced magnetic field (δHo), which opposes the external
applied magnetic field (Ho).
Thus, the acetylene protons are highly shielded and absorb at up-field (i.e. closer to zero). And
they are absorbed at 2.5δ.
2) Deshielding: Benzene molecule (C6H6)
When benzene molecule is place in external applied magnetic field (Ho), then this molecule is oriented
in such a way that, this planer hexagonal ring remains perpendicular to the external applied magnetic
field (Ho).

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The pi (π) electrons are force to circulate because of external applied magnetic field (Ho) and these
circulating electrons produces secondary induced magnetic field (δHo), which reinforces the external
applied magnetic field (Ho) i.e. secondary induced magnetic field (δHo) do not oppose the external
applied magnetic field (Ho) hence they are said to be deshielded and absorb at down-field (i.e. far
from zero). And they are absorbed at 7-7.5δ.
V) Chemical shift:
We know that each nucleus in different environment requires different external applied magnetic
field for resonance and we get picks. These picks occur in different regions along the spectrum.
Chemical shift is the position of signal along the NMR spectrum where there is resonance is
takes place for a particular nucleus.
For 1H-NMR spectra of organic compounds the single resonance peak of the methyl group in
tetramethyl silane (TMS) is taken as internal reference standard. Most of the protons in organic
compounds absorb to left or down-field form TMS in NMR spectrum.
Chemical shift can be defined as, “The distance in the δ values from TMS to each signal
(absorption/peak) in NMR spectrum is called as the chemical shift for proton or protons giving that
signal”.
A) Measurement of chemical shift:
Chemical shift is measured in terms of frequency, and it has unit Hertz indicated by symbol Hz. Most
of the routine instrument operates at 300MHz, while the more sophisticated instruments operate over
300MHz.
The chemical shifts measured in Hz may vary with the spectrophotometer i.e. NMR instrument
so, to avoid this complication the chemical shifts are measured/expressed in terms of δ (delta) or 𝛕
(Tau) scales which are independent of the field strength.
The chemical shifts in the δ (delta) scale are expressed in ppm. (1MHz = 106ppm)

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 The chemical shifts for most of the protons lie to the left i.e. downfield from TMS within the
range of 0-10ppm. The low δ (delta) value represent up-field absorption while, high δ (delta)
represent down-field absorption.
The chemical shifts can also be expressed in another unit called as Tau (𝛕) scale. In this scale
TMS peak gas 𝛕 value 10δ.
The relation between 𝛕 (Tau) and δ (delta) scale is as follows,
δ (delta) = 10-𝛕
OR
𝛕 (Tau) = 10-δ

B) Factors influencing chemical shift:

Important factors influencing chemical shift are electron density, electronegativity of neighboring
groups and anisotropic induced magnetic field effects.
✓ Electron density shields a nucleus from the external field.
✓ A nucleus in the vicinity of an electronegative atom experiences reduced electron density and
the nucleus is therefore deshielded.
✓ Anisotropic induced magnetic field effects are the result of a local induced magnetic field
experienced by a nucleus resulting from circulating electrons that can either be paramagnetic
when it is parallel to the applied field or diamagnetic when it is opposed to it.
VI) Peak area:
We know that in 1H-NMR spectra we get peaks, and these are not of equal intensity. Actually, the area
under each signal or the peak height is directly proportional to the number of magnetically equivalent
protons giving that signal.

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e.g.
Consider the 1H-NMR spectra of ethyl chloride.

It has two sets of protons (a) and (b), so we get two signals in the NMR spectrum. From visual
comparison of NMR spectrum we can say that the area ratio for these protons is 2:3, but for the
accurate analysis i.e. what is the actual area ratio to find out this; these picks are integrated by an
electronic integrator.
Such an integration appears on the NMR spectrum in t6he form of step-up curve, and the height
of these integration is proportional to the area of that particular peak.
But it should be noted that integration curves do not tells us the number of protons under
different peaks, but it indicates the ration in which they exist in the molecule.
The area under the peak is directly proportional to the number of protons.

VII) Spin-spin coupling (n+1 rule):

When the NMR spectra is recorded under low resolution the number of broader absorption peaks are
observed. The area under the peak is directly proportional to the number of protons giving that
particular peak. These peaks provide considerable information about the structure of the molecule.
But when these NMR spectra were recorded on high resolution NMR instrument then number
of lines were observed in place of original broad peaks. This multiplicity of lines is due to the spin-
spin coupling.
The spin-spin coupling is the interaction between spin of two adjacent protons. The bonding
electrons tends to pair its spin with the spin of nearest proton. The spin-spin coupling gives us
information about the number of protons that are present on the adjacent carbon atom. But during
such splitting it should be noted that the area the signal remains same.
Dr. Kamlesh R. Desale Page 23 of 28
A) Rules of Spin-spin coupling:
1) The spin-spin coupling is takes place between the protons on the adjacent carbon atoms. It is
known as first order coupling.
2) The magnetically same protons (i.e. having same environment) do not couple with each other. The
coupling/splitting takes between magnetically non-equivalent protons.
3) The number of line i.e. multiplicity of the signal is generally given by equation,

Proton (a) gives triplet and proton (b) gives quartet.

4) The intensities of multiplicity are symmetrical near the midpoint; this point represents chemical
shift.

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VIII) Pascal’s triangle:
Pascal's triangle is a triangle of numbers bordered by ones on the right and left sides. Every number
inside the triangle is the sum of the two numbers above it.
You can use Pascal's triangle to predict the intensity ratios of proton NMR multiplets.
Thus, a doublet has 1:1 or equal intensities. A triplet has intensity ratios of 1:2:1. A quartet has 1:3:3:1
ratios, etc.

IX) Coupling constant:

It is defined as, “The distance between the centers of two adjacent peaks in a multiplet”.
The coupling constant is indicated by “J”, and it is the measure of effectiveness of spin-spin
coupling. The magnitude of J is usually expressed in units of Hz and never in δ (ppm) values. The value
of J remains constant and does not depend on magnetic field that means it is independent of field
strength (Ho). Therefore the separation between two peaks in a multiplet remains always constant
but if this separation changes that means that they represent different signals or does not belong to
the same peak/multiplet.
The value of J is generally varying in the range of 0-18Hz. If the value of Δν/J is greater than 6 (six)
then it represents simple pattern of splitting. While, if the value of Δν/J is greater than 6 (six) then it
represents complex pattern of splitting.
X) Factors affecting on coupling constant:
Coupling constant is a measure of the effectiveness of spin-spin coupling. The value of J depends upon
the number, type and geometrical orientation of bonds separating the coupled nuclei. One bond
coupling is greater than the two-bond coupling which in turn is larger than the three-bond coupling
and so on. The coupling constant unlike the chemical shift expressed in Hz, does not depend on the
applied field strength (Ho). This is because the strength of the magnetic moment of a neighboring
proton, which is the source of the spin-spin coupling phenomenon, does not depend on the applied
field strength. In general coupling constant is designated as nJab. The superscript indicates the number
Dr. Kamlesh R. Desale Page 25 of 28
of bonds through which interaction occurs. For example 1J, 2J, 3J means that the one, two or three
bonds are involved in coupling interaction. The subscript (ab) tells about the nuclei (Ha and Hb) which
are taking part in the coupling. The important factors which affect the magnitude of coupling
constants in various types of coupling are discussed as follows.
1) Geminal Coupling (2JHH):
Protons attached to the same carbon are called as germinal protons and these are separated by two
bonds. If geminal protons are chemically non-equivalent then only they show coupling. The germinal
coupling (2JHH) constant values are usually negative or near to zero. In the present discussion we
have ignored the negative sign for the convenience.
The germinal coupling (2JHH) in general depends on the hybridization of carbon atom and the
bond angle and the substituent such as electronegative atoms. When s-character is increased, the
absolute value of geminal coupling constant is decreased (move to positive value) i.e. 2Jsp3 > 2Jsp2 >
2Jsp. If an electronegative group is attached nearby the coupled protons, the geminal coupling
constant decreases (move to positive value).

The bond angle (HCH) also gives rise to change in 2JHH value. In general, the value of 2J coupling
constant increases as the bond angle between the coupling protons decreases. As the angle decreases,
the two atoms come closer and hence the interaction between the electron spin become greater.
Therefore geminal coupling constant can also help in determining the ring size. As the ring size
increases, the absolute value of geminal coupling constant also increases (as shown below). As the
CCC bond angle in the ring increases (from 3 membered to 6 membered), the complementary HCH
bond angle decreases (from 3 membered to 6 membered) and consequently the germinal coupling
constant increases.

2) Vicinal coupling (3JHH):

Protons attached to the adjacent carbon atoms are called as vicinal protons and thus are separated by
three bonds. Vicinal coupling constant always has the positive value and depends on the dihedral
angle (angle of rotation, HCCH), the carbon-carbon bond length, and the effects of electronegative
atoms.
Dr. Kamlesh R. Desale Page 26 of 28
3) Long range coupling:
Coupling The magnitude of J decreases sharply with the distance. It is very less through more than
three covalent bonds but in some cases the coupling is observable even in case of more than three
bonds. Such coupling is most common in systems such as olefins, acetylenes, aromatics,
heteroaromatics, and strained ring systems (small or bridged rings). This kind of coupling which
occurs beyond three bonds, are called as long-range coupling.
3.1) Allylic coupling:
In addition to the germinal and vicinal coupling, alkenes also show small coupling between protons
substituted on carbons α to the double bond and those on the opposite end of the double bond. This
four-bond coupling is called allylic coupling. Allylic coupling constant are very less about 0-3Hz. The
π-electrons of the double bond apparently help in coupling the concerned nuclei and the magnitude
of this depends upon the extent of overlap of the carbon-hydrogen σ-bond with the π-bond. This type
of coupling also occurs in acetylenes.
3.2) Homoallylic Systems:
In some alkenes, coupling can occur between the C-H σ-bonds on either side of the double bond.
Homoallylic coupling is weaker than the allylic coupling because it occurs over a greater distance (five
bonds). This type of coupling (5J) is generally very small or even non-existent in most molecules but
sometimes it appears in NMR spectrum.
3.3) Aromatic coupling:
In aromatic systems also, coupling occurs beyond the adjacent carbon atoms (more than three bonds).
The ortho, meta and para protons can all interact but the ortho coupling is maximum, followed by
meta and then para. In fact, the para coupling is rarely observed.

Dr. Kamlesh R. Desale Page 27 of 28

3.4) Hetero-aromatic coupling:
The hetero-aromatic systems also show long range coupling analogues to the aromatic systems. For
example, in furan coupling occurs between all of the ring protons. The values of the coupling constant
are given as follows,

3.4) Rigid systems:

The long-range coupling occurs in compounds without π-systems also, but it is less common. This
unusual long-range coupling in saturated systems occurs through an arrangement of atoms in the
form of ‘W’ in which hydrogens occupy the end positions. The magnitude of coupling constant is
usually small except in highly strained ring systems. Apparently these rigid strained arrangements
somehow have a favorable geometry for the overlaps involved. Most of the W type couplings give rise
to the peak broadening rather than apparent splitting.

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