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Engineering Chemistry
Spectroscopy (Tutorial)

UV-Visible spectroscopy

Woodward-Fieser rules (Calculation of 𝝀max (nm) in conjugated dienes

Woodward–Fieser rules predict the value of λmax for a given structure by adding the
contributions from various substituents to a base wavelength, which remains fixed for a given
class of dienes or trienes.

Base value 𝜆max (nm)

Parent value for Butadiene system or a cyclic conjugated diene 217

Acyclic or heteroannular dienes 215

Homoannular dienes 253

Increments for:

Double bond extending conjugation 30

R alkyl substituent or ring residue 5

Exocyclic double bond 5

Polar groupings:

OCOCH3 0

OR 6

Cl, Br 5

NR2 60
Explanation of terminologies used in Woodward-Fieser rules

Examples
Example 1:
Calculate the absorption maximum (max) in the ultra-violet spectrum of 2, 4- Hexadiene:

Solution:
Basic Value = 217 nm
2-alkyl substituents (2 5) = 10 nm
Calculated value = 227 nm
Example 2:
Calculate the absorption maximum in the UV spectrum of

Solution:
It is a butadiene system. There are two alkyl substituents and two ring residues on the double
bonds. Moreover, there is an exo-cyclic double bond.
The value of absorption maximum is calculated as follows:
Basic value = 217 nm
2-alkyl substituents (2  5) = 10 nm
2-Ring residues (2  5) = 10 nm
1-Exocyclic double bond = 5 nm
Calculated value = 242 nm
The observed value is also found to be 242 nm.

Example 3:
Calculate max for

Solution:
It is an example of heteroannular diene and there are four ring residues on the double bonds.
Thus,
Basic value = 215 nm
Four Ring residues (4  5) = 20 nm
Calculated value = 235 nm

Example 4: Calculate the absorption maximum for the compound

Solution:
It is an example of homoannular conjugated diene and there are three ring residues on it.
Moreover, it contains an exocyclic double bond in it. Thus,
Basic value = 253 nm
3-Ring residues (3  5) = 15 nm
1-exocyclic double bond = 5 nm
Calculated value = 273 nm

Example 5: Calculate the absorption maximum for the compound

Solution:
It is an example of heteroannular diene and there are three ring residues in it. Moreover, it
contains one exocyclic double bond in it. Thus,
Basic value = 215 nm
3-Ring residues = 15 nm
1-exocyclic double bond = 5 nm
Calculated value = 235 nm

Example 6: Following the Woodward-Fieser rules, calculate the absorption maximum

for each of the following compounds:

Solution:
i) It is an example of butadiene system,
Basic value = 217 nm
2-Ring residues = 10 nm
1-exocyclic double bond = 5 nm
Calculated value = 232 nm

ii) It is an example of heteroannular diene system,

Basic value = 215 nm
4-Ring residues = 20 nm
Calculated value = 235 nm

iii) It is an example of homoannular conjugated diene system,

Basic value = 253 nm
4-Ring residues = 20 nm
 2-exocyclic double bond = 10 nm
1-double bond extending conjugation = 30 nm
Calculated value = 313 nm

iv) It is an example of heteroannular diene system,

Basic value = 215 nm
3-Ring residues = 15 nm
1-exocyclic double bond = 5 nm
Calculated value = 235 nm

Example 7: Calculate the value of absorption maximum for the following compound:

Solution: It is a homodiene system. There are five ring residues on the double bonds, one
exocyclic bond and also two double bonds which extend conjugation.
Basic value = 253 nm
2-double bonds extending conjugation 2  30 = 60 nm
5-Ring residues 5  5 = 25 nm
1-Exocyclic double bond 1  5 = 5 nm
Calculated value = 343 nm
Woodward-Fieser Rules for Calculating Absorption Maximum in α,β-unsaturated
Carbonyl Compounds
 The basic value of α,β -unsaturated ketone is taken as 215 nm
 For a compound, = CH—COX, basic value is 215 nm, if X is an alkyl group.
 If X=H, basic value becomes 207 nm.
 The basic value is 193 nm if X is OH or OR.
 The structural increments for estimating λmax for a given α,β -unsaturated carbonyl
compound are as follows :
i. For each exocyclic double bond= + 5 nm
ii. For each double bond endocyclic in five or seven membered ring except cyclo-pent-2
enone= + 5 nm
iii. For each alkyl substituent or ring residue at the
i. α –position = +10 nm
ii. β –position = +12 nm
iii. γ and δ- position = +18 nm
iv. (vi) For each double bond extending conjugation= + 30 nm
v. (v) For a homoannular conjugated diene = +39 nm

Example 1: Calculate max for the given structure:

Solution: The basic value for acyclic , -unsaturated ketone is 215 mμ. In this structure, we
see two -alkyl substituents. The value of absorption maximum is thus calculated as:
Basic value = 215 nm
2–alkyl substituents (2  12) = 24 nm
Calculated value = 239 nm

Example 2: Calculate max for the given structure:

Solution:
Basic value = 215 nm
2-ring residues (2  12) = 24 nm
1 exocyclic double bond = 5 nm
Calculated value = 244 nm

Example 2: Calculate max for the given structure:

Solution:
Basic value = 215 nm
-ring residue = 10 nm
-ring residue = 18 nm
1 exocyclic double bond = 5 nm
Homoannular conjugated diene = 39 nm
1 double bond extending conjugation = 30 nm
Calculated value = 317 nm
 Infra-red Spectroscopy
Calculation of number of fundamental vibrations
Polyatomic molecules may exhibit more than one fundamental vibrational absorption bands.
The number of these fundamental bands is related to the degrees of freedom in a molecule.
The number of degrees of freedom is equal to the sum of the co-ordinates necessary to locate
all the atoms of a molecule in space. Each atom has three degrees of freedom corresponding to
the three cartesian co-ordinates (X, Y, Z) necessary to describe its position relative to other
atoms in a molecule. An isolated atom which is considered as a point mass has only
translational degrees of freedom. It cannot have vibrational and rotational degrees of freedom.
When atoms combine to form a molecule, no degrees of freedom are lost, i.e., the total number
of degrees of freedom of a molecule will be equal to 3n where n is the number of atoms in a
molecule. A molecule which is of finite dimensions will, thus, be made up of rotational,
vibrational and translational degrees of freedom. So,
3n degrees of freedom = Translational + Rotational + Vibrational.
Rotational degrees of freedom result from the rotation of a molecule about an axis through the
centre of gravity. Since we are concerned only with the number of fundamental vibrational
modes of a molecule, so we calculate only the number of vibrational degrees of freedom of a
molecule.
Since only three co-ordinates are necessary to locate a molecule in space, we say that a
molecule has always three translational degrees of freedom.
In case of linear molecule, there are only two degrees of rotation. It is due to the fact that the
rotation of such a molecule about its axis of linearity does not bring about any change in the
position of the atoms while rotation about the other two axes changes the position of the atoms.
Thus, for a linear molecule of n atoms.
Total degrees of freedom = 3n
Translational degrees of freedom = 3
Rotational degrees of freedom = 2
 Vibrational degrees of freedom = 3n – 3 – 2 = 3n – 5
Each vibrational degree of freedom corresponds to the fundamental mode of vibration and
each fundamental mode corresponds to a band.
Hence, theoretically there will be 3n – 5 possible fundamental bands for the linear
molecules.
In a linear molecule of carbon dioxide (CO2), the number of vibrational degrees of freedom
can be calculated as follows:

Number of atoms (n) = 3

Total degrees of freedom = 3n = 3 × 3 = 9

Translational = 3

Rotational = 2

 Vibrational degrees of freedom = 9 – 3 – 2 = 4

Hence, for carbon dioxide molecule, the theoretical number of fundamental bands should be
equal to four.

In the case of non-linear molecule, there are three degrees of rotation as the rotation about
all the three axes (X, Y, Z) will result in a change in the position of the atoms. So, for a non-
linear molecule of n atoms, the vibrational degrees of freedom can be calculated as follows:

Total degrees of freedom = 3n

Translational degrees of freedom = 3

Rotational degrees of freedom = 3

 Vibrational degrees of freedom = 3n – 3 – 3 = 3n – 6

Thus, in a non-linear molecule, C6H6, the number of vibrational degrees of freedom can be
calculated as follows:

Number of atoms (n) = 12

Total degrees of freedom = 3 × 12 = 36

Translational = 3

Rotational = 3

 Vibrational degrees of freedom = 36 – 3 – 3 = 30

So, theoretically there should be 30 fundamental bands in the Infra-red spectrum of benzene.

It has been observed that the theoretical number of fundamental vibrations are seldom obtained.
Examples
Predict the number of fundamental vibrational modes in the following molecules.
(i) H2 S
(ii) C2H2
(iii) H2O and
(iv) HCl

Solution:

(i) H2 S

This a non-linear molecule. Thus, the number of normal modes of vibration = (3n – 6).
Where n = Total number of atoms in the molecule. Here n = 3.
Number of normal modes of vibrations in H2S = 3 × 3 – 6 = 3
(ii) HC  CH. Acetylene is a linear molecule

Here n = 4
 Number of normal modes of vibrations = (3n – 5) = 3 × 4 – 5 = 7

(iii) H2O, This is non-linear molecule

n=3, Thus, the number of normal modes of vibration = (3n – 6) = 3 x 3-6= 3

(iv) HCl is a linear molecule

n=2,  Number of normal modes of vibrations = (3n – 5) = 3 × 2 – 5 = 1

 Nuclear Magnetic Resonance Spectroscopy

Number of Signals
Each signal corresponds to a set of equivalent protons. It may be noted that magnetically
equivalent protons are chemically equivalent protons.
Chemically equivalent protons must also be stereo-chemically equivalent
A particular set of protons are said to be chemically equivalent only if they remain in exactly
similar environment when the stereo-chemical formula of the molecule under consideration is
written

Examples:
Give no. of signals of NMR for the following compounds:

Ans.:
i) 4, ii) 2, iii) 2, iv) 3

Splitting of NMR Signals

Protons in a molecule. It is found that in certain molecules, a single peak (singlet) is not
observed, but instead, a multiplet (group of peaks) is observed. Consider a molecule of

, ethyl bromide. This molecule has two kinds of protons in it and thus, two signals
are expected in its nmr spectrum. It has been observed that for each kind of protons, we do not
get singlets but a group of peaks are observed.

For ‘a’ kind of protons (CH3), a triplet, i.e., a group of three peaks is observed and a quartet
(group of four peaks) is noticed for ‘b’ kind of protons (—CH2—).
Spin-spin coupling

The spin of two protons (—CH2—) can couple with the adjacent methyl group (— CH3) in
three different ways relative to the external field. The three different ways of alignment are:

Similarly, the spin of three protons (CH3—) can couple with the adjacent methylene group
(—CH2—) in four different ways relative to the external field
The splitting of a signal is due to the different environment of the absorbing proton not with
respect to electrons but with respect to the nearby protons.

There is a formula for predicating the number of peaks base on the neighboring hydrogens and
that is known as the n + 1 rule, where n is the number of neighboring protons.
Interpretation of some important NMR spectra
i) One proton singlet = 3.05 δ
ii) Five proton unsymmetrical multiplet 7.2–7.6 δ