CHEM-533

CHEM-533: Organic Spectroscopy

Jan 20, 2023
Dr. Rahman S. Z. Saleem

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Lecture 02
 CHEM-533:
Spectroscopic Organic Spectroscopy
methods

Use less amount of compound (generally few μ-milligrams for complete analysis)

Mostly non-destructive (the compound is not consumed in the testing process)

Cheap (no long list of reagents are needed other than solvents)

Fast (give the desired information mostly in few minutes)

Can be used for qualitative and quantitative analysis 2

 CHEM-533: Organic Spectroscopy

Electromagnetic spectrum
11.4 -1.9 kcal/mole
Bond Electronic Vibrational Rotational Nuclear spin
breaking transitions transitions transitions transitions
4000-667cm-1 1-5 m

Energy (E), frequency (ʋ), wave number (ṽ)

wavelength (λ)
hc
𝐸 = hʋ = λ = hcṽ
h=Plank’s constant=6.626x10-34m2kgs-1,
c= speed of light=299732458ms-1

in IR we use the wave numbers for electromagnetic radiations

3 -1
which is equal to the inverse of wavelength and tells the number of waves per unit length(cm ).
 CHEM-533: Organic Spectroscopy

Infra-Red Spectroscopy
Wave number is preferred because

it is directly proportional to energy and of course values are easy to speak

hc
𝐸 = hʋ = λ = hcṽ

So stronger a bond, more will be its bond energy and higher will be its wave number

So even before we start talking about the IR, we can predict about the wave numbers

~85KCal.mol-1 110KCal.mol-1
1000-1260cm-1 3300-3400cm-1

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 CHEM-533: Organic Spectroscopy

Infra-Red Spectroscopy
IR is a wonderful technique that can be use to tell the functional groups

and functional groups are all important when we are carrying out our reactions

3000-3400cm-1

1700-1740cm-1 3000-3400cm-1

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 CHEM-533: Organic Spectroscopy

Infra-Red Spectroscopy
In order to understand the IR spectroscopy, think of each bond to be like a spring:

All the atoms in a molecule are vibrating

Appropriate wavelength of IR radiations leads to increased amplitude of vibrations.

Energy of IR is about 8-40kJ/mol that is good to amplify vibrations in most covalent bonds
11.4 <------>1.9 kcal/mole

The absorptions are quantized and each functional group absorbs energy that
corresponds to its bond strength.

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 CHEM-533: Organic Spectroscopy

Infra-Red Spectroscopy: Modes of vibrations

There are two types of vibrations

Stretching vibrations and bending vibrations

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 CHEM-533: Organic Spectroscopy

Infra-Red Spectroscopy: Modes of stretching and bending

The stretching could be
Symmetric stretching Asymmetric stretching For a triatomic molecule there
would be only one bending more

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 CHEM-533: Organic Spectroscopy

Example of stretching vibrations in functional groups with two similar atoms

Symmetric stretching Asymmetric stretching

Methyl

Anhydride

Amine(1o)

Nitro
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 CHEM-533: Organic Spectroscopy

Infra-Red Spectroscopy: Modes of stretching and bending

But for a polyatomic molecules with more than 3 atoms bending could be

Scissoring Rocking

Wagging Twisting

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 CHEM-533: Organic Spectroscopy

Infra-Red Spectroscopy: Modes of stretching and bending

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 CHEM-533: Organic Spectroscopy

Infra-Red Spectroscopy: Change in dipole moment

Only the stretching that involves change in the dipole moment can be observed in IR.
Consider the example of CO2

O=C=O
Symmetric Assymmetric Bending

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 CHEM-533: Organic Spectroscopy

Infra-Red Spectroscopy: Change in dipole moment

(CH3)2C=C(CH3)2

Thus IR can also tell us about the shape of the molecule, however one has to be
careful about pseudo-symmetric compounds

C2H5(CH3)C=C(CH3)2
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 CHEM-533: Organic Spectroscopy

Overtones, combination & difference bands & Fermi Resonance

The peaks that we have seen so far arise from the excitation from ground state to
lowest-energy energy state.
But
generally the spectrum is complicated by presence of weak overtones, combination or
difference bands.

Overtones correspond to excitation to higher energy levels and appear as weak

integral multiple of the fundamental wave number (2ṽ, 3ṽ, …).

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 CHEM-533: Organic Spectroscopy

Overtones, combination & difference bands & Fermi Resonance

Combination band results for sum of the two interacting bands (ṽ=ṽ1+ṽ2)

Difference band results for sum of the two interacting bands (ṽ=ṽ1-ṽ2)

Fermi Resonance, when the fundamental vibration couples with an overtone or

combination band, the resulting couples vibration is called Fermi resonance

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Not all possible combinations of differences occur
 CHEM-533: Organic Spectroscopy

Bond properties and absorption trends

Consider stretching motion of a diatomic molecule:

Two vibrating masses connected by a spring

The bond distance is a average or equilibrium distance between the atoms.

During vibration, the kinetic and potential energies are continuously interconverting

Such that the total energy and frequency of vibration are proportional

E ∝ ʋosc

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 CHEM-533: Organic Spectroscopy

Bond properties and absorption trends

From Hooke’s Law

varies from one bond to another and
depends upon the strength

1 𝐾 (force constant of spring) As a rough approximation force constants

for triple bonds are three times the single
𝑣ҧ = bonds and those of double bonds are twice
2𝜋𝑐 𝜇 the single bonds
Stronger bonds –higher force constant – higher ṽ
Weaker bonds – smaller force constant – lower ṽ

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 CHEM-533: Organic Spectroscopy

Bond properties and absorption trends

𝑚1 𝑚2

From Hooke’s Law

1 𝐾
𝑣ҧ =
2𝜋𝑐 𝜇 (reduced mass) 𝜇=
𝑚1𝑚2
𝑚1 + 𝑚 2

Depends on the atoms making the bond (and their surrounding atoms)

Heavier the atoms –more will be reduced mass – lower ṽ

Lighter the atoms – lower will be reduced mass – higher ṽ

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 CHEM-533: Organic Spectroscopy

Bond properties and absorption trends

Bending motions require less energy – appear at lower ṽ
𝑚1 𝑚2

Hybridization affects the force constant

> >

Resonance affects the force constant

Normal ketone conjugated ketone

~1715cm-1 ~1675-1680cm-1
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 CHEM-533: Organic Spectroscopy

Bond properties and absorption trends

𝑚1 𝑚2

Hooke’s Law

Stronger bonds –higher force constant – higher ṽ

1 𝐾 (force constant of spring)
Weaker bonds – smaller force constant – lower ṽ
𝑣ҧ =
2𝜋𝑐 𝜇 (reduced mass)
Heavier the atoms –more will be reduced mass – lower ṽ
Lighter the atoms – lower will be reduced mass – higher ṽ

The equation can be simplified

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 CHEM-533: Organic Spectroscopy

Bond properties and absorption trends

𝑚1 𝑚2

𝜋 = 3.14
𝑐 = 𝑠𝑝𝑒𝑒𝑑 𝑜𝑓 𝑙𝑖𝑔ℎ𝑡 = 3𝑥1010 𝑐𝑚. 𝑠𝑒𝑐−1
𝑚1𝑚2 𝑀1𝑀2
1 𝐾 𝜇 = 𝑟𝑒𝑑𝑢𝑐𝑒 𝑚𝑎𝑠𝑠 =
𝑚1 + 𝑚2
=
𝑀1 + 𝑀2 6.02𝑥10
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𝑣ҧ = 4.12
2𝜋𝑐 𝜇 m=mass in g M=mass in amu

𝑀1𝑀2
where 𝜇 =
𝑀1+𝑀2
M1 and M2 are atomic masses and

K is force constant in dyne. sec−1

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This equation may be used to calculate the approximate position of a band in the IR spectrum
 CHEM-533: Organic Spectroscopy

Bond properties and absorption trends

−1)
𝐾
𝑣(cm
ҧ = 4.12 𝑚1 𝑚2
𝜇
C—C bond C—H bond C—D bond
𝐾 = 10𝑥105 𝑑𝑦𝑛𝑒𝑠. 𝑠𝑒𝑐−1 𝐾 = 5𝑥105 𝑑𝑦𝑛𝑒𝑠. 𝑠𝑒𝑐−1 𝐾 = 10𝑥105 𝑑𝑦𝑛𝑒𝑠. 𝑠𝑒𝑐−1
𝑀1𝑀2 12𝑥12 12𝑥1 12𝑥2
𝜇= = =6 𝜇= =0.923 𝜇= =1.71
𝑀1+𝑀2 12+12 12+1 12+2

10𝑥105 5𝑥105 10𝑥105

𝑣ҧ = 4.12 𝑣ҧ = 4.12 𝑣ҧ = 4.12
6 0.923 1.71
= 1682cm-1 = 3030cm-1 = 2228cm-1
Experimental~1650cm-1 Experimental~3000cm-1 Experimental~2206cm-1
The calculated value may differ significantly due to
resonance, hybridization and other effects
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