KALINGA INSTITUTE OF INDUSTRIAL TECHNOLOGY (KIIT)

(Deemed to be University)

School of Applied Sciences (Chemistry)

Course Handout

Subject Code-CH1007
 Chapter-3: Organic Spectroscopy

Lecture-1: Introduction, UV-Vis spectroscopy: Beer Lambert’s law, Types of transition

Introduction: Spectroscopy may be defined as the study of the quantized interaction of
electromagnetic radiations with matter. Electromagnetic radiations are produced by the oscillation
of electric charge and magnetic field residing on the atom.

Electromagnetic spectrum

Frequency (ν) is defined as the number of waves which can pass through a point in one second,
measured in cycles per second (cps) or hertz (Hz) (1Hz= 1 cps).

Wavelength (λ) is defined as the distance between two consecutive crests or troughs measured in
micrometer (µm) or micron (µ) (1 µm = 1 µ =10-6 m), nanometer (nm) or millimicron (mµ) (1 nm
= 1 mµ =10-9 m) and angstrom (Å) (l Å = 10 -10 m).

Wavenumber (𝝂 ̅ ) is defined as the number of waves which can pass through per unit length usually
1cm. lt is the reciprocal of wavelength expressed in centimeter (cm-1)

Absorption of Electromagnetic radiation by organic molecules:

Organic molecules absorb radiation in discrete “packets” of ∆E = hν, which are also called quanta
of energy. Spectroscopy is essentially a technical procedure by which the energy differences
between the allowed states of a system are measured by determining the frequencies of the
corresponding light absorbed.

E2
En
er ∆E = E2– E =1 hc/λ = hν
gy

E1

V3
E1
Vibrational energy levels

V2
Electronic energy levels

V1
Rotational energy levels

V0
E0

Ultraviolet- Visible Spectroscopy:

Ultraviolet-Visible Spectroscopy (Electronic Spectroscopy) is primarily used to measure the
multiple bond or, aromatic conjugation within the molecule.

UV-VIS region extends from 100-800nm. It can be divided into three regions:

Ultraviolet- Visible Region Wavelength(λ)

Vacuum UV region 100-190nm
Ultraviolet region 190-400nm
Visible region 400-800nm

Note: Vacuum UV region: The molecules of air absorb radiation in this region and thus this region
is accessible only with special vacuum equipment.
Beer Lambert’s law:
This law states that, “When a beam of monochromatic radiation is passed through a solution of an
absorbing substance, the rate of decrease of intensity of radiation with thickness of the absorbing
solution is proportional to the intensity of incident radiation as well as the concentration of the
solution.”
It can be formulated as follows:

A = log (I0/I ) = ϵcl for a given wavelength

A = absorbance
I0 = intensity of light incident upon sample cell
I = intensity of light leaving sample cell
c = molar concentration of solute
l = length of sample cell (cm) ϵ
= molar absorptivity

Types of electronic transitions in Ultraviolet-Visible spectroscopy:

UV-visible absorption spectra originate from electronic transitions within a molecule. These
transitions involving promotion of valence electrons from the ground state to the higher-energy
state (excited state) are called electronic excitations and are caused by the absorption of radiation
energy in the UV-Visible regions of the electromagnetic spectrum.

According to molecular orbital theory, the excitation of a molecule by the absorption of radiation
in the UV visible regions involves promotion of its electrons from a bonding, or non-bonding (n)
orbital to an anti-bonding orbital.

σ, π: Bonding orbitals
n: Nonbonding orbitals
σ*, π*: Anti-Bonding orbitals
Various Allowed Electronic Transitions:

σ→ σ*, n→σ*, π→ π*, n→ π*

Energy required for various transitions: σ→ σ*˃ n→σ*˃ π→ π*˃ n→ π*

*
σ

*
π

E
n
er
n
*
*
nπ π
n σ
*
π σ
*
σ σ

Electronic Energy levels and relative energies of electronic transitions

σ→ σ* transitions: It is a high energy process and thus absorptions mostly take place below 200
nm. This transition is studied under vacuum UV region. Ex: Alkanes
n→σ* transitions: Compounds containing non-bonding electrons on a heteroatom can show
absorption due to n→σ* transitions. Ex: Alkyl halides, alcohols, ethers, aldehydes, ketones etc.
π→ π* transitions: These types of transitions occur in compounds containing one or more
covalently unsaturated groups like C=C, C=O, NO2 etc. Ex: Alkenes, Aromatics, Carbonyl
compounds, Cyanides, Azo Compounds etc.
n→ π* transitions: This transition requires lowest energy among all the transitions and in this
transition promotion of an electron from a non-bonding orbital to an antibonding orbital takes
place. Ex: Saturated aldehydes, ketones etc.

Note: This transition is a symmetry forbidden transition and thus the peak intensity is extremely
low.

Lecture-2: Concept of auxochrome and chromophore, factors affecting 𝝀𝒎𝒂𝒙 Concept of

Chromophore:

“It is defined as any isolated covalently bonded group that shows a characteristic absorption in
UV-VIS region.” For example, C =C, C =C, C =O, C =N, N =N, NO2 etc.

A chromophore may or may not impart colour to a compound depending on whether the
chromophore absorbs radiation in the visible or UV region. Mostly the chromophoric group shows
their effect through π→ π* or n→ π* transitions.
Examples:

Nitro group acts as a chromophore and imparts yellow colour

to the compound.

Auxochrome Concept:
“An auxochrome can be defined as any group which does not act as a chromophore but when
attached to a chromophore, changes both the wavelength and the intensity of the absorption
maximum.” Auxochromes generally increase the value of λmax as well as ϵmax by extending the
conjugation through resonance. These are also called colour enhancing groups.
Examples: -OH, -OR, -NH2, -NHR, -NR2, -SH etc.
Effect of Substitution on the chromophore: Absorption (λmax) and Intensity (ϵmax) shift:
Hyperchromic
Depending upon the λmax value and ϵmax value, four types of shift or effect is observed,

Hypsochromic Bathochromic

(Blue shift) (Red shift)

ϵ Hypochromic
max

λ
max

Bathochromic Shift or Effect: The shift of an absorption maximum to a longer wavelength region
due to the presence of an auxochrome, or solvent effect is called a bathochromic shift or Red shift.
Hypsochromic Shift or Effect: The shift of an absorption maximum to a shorter wavelength region
is called hypsochromic or blue shift.
Hyperchromic Effect: An effect which leads to an increase in absorption intensity (ϵmax) is called
hyperchromic effect.
Hypochromic Effect: An effect which leads to a decrease in absorption intensity (ϵmax) is called
hypochromic effect.

Effect of conjugation on Absorption (λmax):

The conjugation of any double and triple bonds shifts the absorption maximum towards longer
wavelength region. Each additional double bond in the conjugated π-electron system shifts the
absorption maximum about 30 nm in the same direction. Increased conjugation brings the HOMO
and LUMO orbitals closer together. The energy (∆E) required for the excitation of an electron is
therefore less (∆E1 ˃ ∆E2 in the fig) and the wavelength that provides this energy is increased
correspondingly. Thus, the more highly conjugated the system, the smaller the HOMO-LUMO
gap and therefore the lower the frequency and longer the wavelength.

*
*
σ
(LUMO) π4
*
En π
er * (LUMO)
π3
gy
∆E1 ∆E2
n
π2 (HOMO)
π
(HOMO) π1
σ

Effect of Solvent on Absorption (λmax):

Polarity of the solvent plays a vital role and the position, and the intensity of absorption maxima
may be shifted by changing solvent polarity.

π→ π* transitions: Polar solvents lower the energy of the excited state more than the ground state,
so red shift is observed from non-polar to polar solvent.
n→ π* transitions: It has been found that an increase in solvent polarity usually shifts n→ π*
transitions to shorter wavelengths (higher energy). The dipole-dipole interaction or hydrogen
bonding with a polar solvent lowers the energy of the ground state more than that of the excited
state resulting in the hypsochromic shift.

Effect of pH on Absorption (λmax):

The UV-Visible spectra of some of the compounds, especially certain substituted aromatic
compounds, show the dramatic changes with a change in the pH of the solvent. Phenols and
substituted phenols are acidic and display striking changes to their absorptions upon the addition
to base. Similarly Aniline shows a blue shift upon addition of acid. Increase and decrease in
conjugation is the reason behind the red or blue shift.

Lecture-3: Woodward-Fieser rules for calculation of 𝝀𝒎𝒂𝒙 in diene systems Woodward and
Fieser formulated
a set of empirical rules for calculating or predicting λmax in conjugated acyclic and six-membered
ring dienes.

Following terms used in Woodward-Fieser rules:

Base value for acyclic or heteroannular diene: 214nm

Base value for homoannular diene: 253 nm
Increment for each:
Alkyl substituent or ring residue: 5 nm
Double bond extending conjugation: 30 nm
-OR (alkoxy): 6 nm
-Cl,-Br: 6 nm
-OCOR (acyloxy): 0 nm
-SR (alkylthio): 30 nm
-NR2 (dialkylamino): 60 nm
Bicyclic strain corrections: 15nm
If one double bond is exocyclic to one ring: 5 nm
If one double bond is exocyclic to two rings simultaneously: 10 nm
Examples:
1.

Base value: 214 nm

Two alkyl substituents (2 x 5): 10 nm
Calculated λmax: 224 nm
Observed λmax: 227 nm

2.
Myrcene

Base value: 214 nm

One alkyl substituent: 5 nm
Calculated λmax: 219 nm
Observed λmax: 224 nm

3.
 β-Phellandrene

Base value: 214 nm

Two alkyl substituents (2 x 5): 10 nm
One exocyclic double bond: 5 nm
Calculated λmax: 229 nm
Observed λmax: 232 nm

4.
Base value: 253 nm
Three ring residues (3 x 5): 15 nm
One exocyclic double bond: 5 nm
Calculated λmax: 273 nm
Observed λmax: 275 nm

5.
Base value: 253 nm
Two ring residues (2 x 5): 10 nm
One extended conjugation: 30 nm
Calculated λmax: 293 nm

Questions for practice:

1. To increase the λmax of absorption in the electronic spectrum which of the following can be used as
substituent in benzene? a. –CH=CH2, b. –CH2CH3, c. –OH, d. –N=NCH3

2. A ketone of molecular mass 110 has an absorption band with λmax at 215 nm and ε at 10000. A solution of it showed
absorbance= 2.0 with a 1cm cell. Calculate the concentration of the ketone in g/L

3. Calculate λmax for the following compounds.

4. Why does an ester show lower λmax value for n-π* transition than that of a ketone?

5. The signal for n-π* transition found in aniline vanishes when it comes in contact with an acid. Give reason.

Lecture-4: IR spectroscopy: Introduction, types of vibration, selection rules Introduction:

IR spectroscopy is
most widely used for the detection of functional groups and identification of organic
compounds.The position of an infrared absorbtion band is specified in
frequency units by its wavenumber (𝝂
̅ ) measured in reciprocal of centimeters (cm-1) or, by its
wavelength λ measured in micrometers (µm; old name micron, µ). 𝜈̅ = 1/λ (with λ in cm) or, 𝜈̅ =
10,000/λ (with λ in µm)
Infrared spectrum is the graph of % transmittance versus either increasing wavelength or
decreasing frequency.

T = I/I0,
T% (percent transmittance) =( I/I0) X 100
A = log (1/T )

The ordinary infrared region 4000-667 cm-1 (2.5-15 µm) is of greatest practical use to organic
chemists. This particular region can be divided into two parts, Functional group region (4000-1500
cm-1) and fingerprint region (1500-667 cm-1). In the region 1500-667 cm-1, a unique pattern of
absorptions are observed and it is impossible for any two different compounds to have precisely
the same infrared spectrum, thus it is known as finger print region.

Infrared radiation does not have sufficient energy to cause excitation of electrons, however it
causes atoms and groups of the organic compounds to vibrate faster about the covalent bonds
which connect them. IR spectra are often called vibrational-rotational spectra.

Types of vibration:
Various atoms in a molecule may be regarded as balls of different masses and the covalent bonds
between them as weightless tiny springs holding such balls together. Atoms in a molecule are not
still but they vibrate.

The two types (modes) of fundamental molecular vibrations known are:

(I) Stretching and
(II) Bending vibrations
(I) Stretching Vibrations: In stretching vibrations, the distance between two atoms increases
or decreases, but the atoms remain in the same bond axis. Stretching vibrations are of two
types:
(a) Symmetrical stretching. In this mode of vibration, the movement of atoms with respect
to the common (or central) atom is simultaneously in the same direction along the same
bond axis.
 (b) Asymmetrical Stretching. In this vibration, one atom approaches the common atom while
the other departs from it.
(II)

Bending Vibrations: In such vibrations, the positions of the atoms change with respect to
their original bond axes. Bending vibrations are of four types:

a) Scissoring b) Rocking c) Wagging d) Twisting

In-plane bending vibrations Out-of-plane bending vibrations

Selection rules: The selection rule says, that vibrations are only IR active (or allowed), if the
molecular dipole moment changes during the vibration. A diatomic molecule with the same atoms
cannot be excited to vibrate because no dipole moment is present. In contrast, molecules with
various types of atoms can interact with incident radiation, and even if a dipole moment is not
present in the beginning it can be induced due to antisymmetric displacement of the center of
charge (e.g., CO2).

Examples:

HCl, CO: Polar (IR Active)

H2, N2: Nonpolar (IR inactive)

CO2: Nonpolar (IR Active: Asymmetrical stretching vibration is IR active)

Fundamental Bands and Overtones

 Vibrational energy level (Ev) = (ν+1/2)hν

E2 = 5/2 hν

E1 = 3/2 hν

Eo = ½ hν

Transition from ν = 0 to ν = n (n>1) is responsible for overtone

For first overtone ΔE = hν

For second overtone ΔE = 2hν

Number of Fundamental Vibrations:

Each atom has three degrees of freedom corresponding to the three Cartesian Coordinates (x, y and
z) necessary to describe its position relative to other atoms in the molecule. Therefore, a molecule
having n atoms will have 3n degrees of freedom.

In case of a nonlinear molecule, three of the degrees of freedom describe rotation and three
describe translation. Thus, the remaining (3n - 3 - 3) = 3n - 6 degrees of freedom are its vibrational
degrees of freedom or fundamental vibrations, because, Total degrees of freedom (3n) =
Translational + Rotational + Vibrational degrees of freedom
In case of a linear molecule, only two degrees of freedom describe rotation (because rotation
about its axis of linearity does not change the positions of the atom) and three describe translation.
Thus, the remaining (3n - 2 - 3) = 3n – 5 degrees of freedom are vibrational degrees of freedom or
fundamental vibrations.

Examples:
1. Carbon dioxide (CO2): 3 atoms, linear molecule
vibrational degress of freedom: 3n-5 = (3x 3-5) = 4
2. Ethane (C2H6): 8 atoms, non linear molecule
Total degrees of freedom: 3x 8 = 24
vibrational degress of freedom: 3n-6 = (24-6) = 18

Lecture-5: Hooke’s law, problems, identification of functional groups like C-C, C=C, -OH, -
NH2 and -C=O
Calculation of Vibrational Frequencies: Hooke’s law:
The stretching vibrations of two bonded atoms may be regarded as the vibration of two balls
connected by a spring, a situation for which Hooke's law applies. Thus, an approximate value for
the Stretching vibrational frequency, i.e., the stretching absorption frequency of a bond, can be
ca!culated by Hooke's law,
1 ᶄ
ῡ = 2ch√ μ

μ= m1m2 , reduced mass and m1 and m2 are the masses of the atoms. k is the force
m1+m2

constant, c is the velocity of light.

Problem: Calculate the wave number of the stretching vibration of a carbon-carbon double bond.
The force constant given is, 106 dynes/cm.

Solution: µ = (m1m2) /(m1+m2) = (12 x12)/ (12+12) = 6amu

6amu = 6 x (1.66 x 10-24) g = 9.97 x 10-24g

1 √ = 1680 cm-1
ῡ= 106

(2x 3.14x 3x 1010) 9.97 x 10−24

Factors Affecting Vibrational Frequencies:

Coupled Vibrations: Sometimes more than one Stretching vibrational frequency are observed for
one bond. This is due to the mechanical coupling or interaction between the two vibrations.
Example: carboxylic acid anhydrides show two peaks in which symmetrical and asymmetrical
stretching vibrations appear in the region 1720-1825 cm-1. This is due to the coupling of the
vibrations and it is also considered as a characteristic peak for the acid anhydrides.

Hydrogen Bonding: Hydrogen bonding remarkably lowers the Stretching frequencies of both the
groups involved in it, and also changes the shape and intensity of the absorption bands. The
stronger the hydrogen bond, lower is the O-H Stretching frequency.
Distinction between inter- and intramolecular hydrogen bondings: Thus, intermolecular
hydrogen bonding is concentration dependent. On dilution with non-polar solvents, intermolecular
hydrogen bonds are broken. Hence, there is decrease in intensity or disappearance of the hydrogen-
bonded O-H stretching band and increase in intensity or appearance of free O-H
stretching absorption.
However intramolecular hydrogen bonds are unaffected by dilution, and so the absorption band
is also unaffected.
lnductive and Mesomerie (Resonance) Effects: Absorption frequencies of a particular group are
affected by electronic effects, especially inductive and mesomeric (resonance) effects of the nearby
groups. Strength (force constants) of a particular bond is changed by these effects and hence its
Stretching frequency is also changed with respect to the normal values.

Conjugation:
Conjugation lowers the stretching frequency,

Identification of functional groups:

1. Identification of Alkane residues (C-C system): Most organic compounds contain alkane
residues and their general appearance may be seen in the IR spectrum. The most
characteristic absorptions in alkanes is C-Hstr and it can be the stretching of both methyl
and methylene group.
Characteristic IR frequencies of Alkanes:
C-H stretching vibrations: 2850-3000 cm-1
 CH2 and CH3 Bending vibrations: 1450-1470 cm-1, 1370-1380 cm-1, 720-725 cm-1

2. Identification of C=C system in an organic molecule: Mostly C=C bond is observed in

alkenes, aromatics etc. Introduction of C=C system in any compound gives rise to the
formation a new band due to C=C stretching and along with that it also affects the normal
C-H stretching vibrations.

Characteristics IR frequencies:
C=C stretching vibrations in Alkene: 1600-1680 cm-1
Aromatics: 1600 and 1475 cm-1

C-H stretching vibrations in Alkene: 3100–3000 cm-1

Aromatics: 3150–3050cm-1

Out of plane bending vibrations in Alkene: 1000–650cm-1

Aromatics: 900–690 cm-1

3. Identification of O-H group in an organic molecule:

OH-group is generally observed in alcohols and phenols. Alcohols and phenols will show
strong and broad hydrogen-bonded O-H stretching bands centered between 3400 and 3200
cm−1. In solution, it will also be possible to observe a “free” O-H (non H-bonded) stretching
band at about 3600 cm−1 (sharp and weaker) to the left of the hydrogen-bonded O-H peak.
In addition, a C-O stretching band will also appear in the spectrum at 1300–1000 cm−1.
Characteristics IR frequencies:

O-H stretching in alcohols and phenols (Free): 3650–3600 cm-1

O-H stretching in alcohols and phenols (H-Bonded): 3400–3200 cm-1

C-O stretching in alcohols and phenols: 1300–1000 cm−1

4. Identification of NH2 group in an organic molecule:

Primary amines, R-NH2, show two N-H stretching bands in the range 3500–3300 cm−1,
whereas secondary amines, R2NH, show only one band in that region. Tertiary amines will
not show an N-H stretch. Because of these features, it is easy to differentiate among
primary, secondary, and tertiary amines by inspection of the N-H stretch region.
Characteristics IR frequencies:

N-H stretching frequencies in Primary and secondary amines and amides: 3500–3100cm-1

N-H bending vibrations in Primary and secondary amines and amides: 1640–1550 cm-1

stretching frequencies in Primary and secondary amines: 1350–1000 cm-1

C=N stretching frequencies in imines and oximes: 1690–1640 cm-1

5. Identification of C=O group in an organic molecule:

 The carbonyl group is present in aldehydes, ketones, acids, esters, amides, acid chlorides,
and anhydrides. This group absorbs strongly in the range from 1850 to 1650 cm−1 because
of its large change in dipole moment. Since the C=O stretching frequency is sensitive to
attached atoms, the common functional groups already mentioned absorb at characteristic
values. Factors like conjugation, ring size, α-substitution and hydrogen bonding affects the
C=O stretching frequency.

Normal base values for the CJO stretching vibrations for carbonyl groups

Characteristics IR frequencies:

C=O stretching frequencies in,

Aldehyde: 1740–1720 cm-1

Ketone: 1725–1705 cm-1
Carboxylic acid: 1725–1700 cm-1
Ester: 1750–1730 cm-1
Amide: 1680–1630 cm-1
Anhydride: 1810 and 1760 cm-1
Acid chloride: 1800 cm-1
stretching frequencies in Alcohols, ethers, esters, carboxylic acids and
anhydrides:1300–1000 cm-1

Questions for practice:

1. What is fingerprinting zone? Explain it’s significance.

2. CO2 is IR active although it is non-polar- explain.
3. How will you distinguish between propanaldehyde and propanone in terms of IR spectroscopy?
4. How can you distinguish between ortho-nitrophenol and para-nitrophenol by IR spectroscopy?
5. Define fundamental band and overtone.
6. Calculate the wave number (cm-1) of the fundamental peak due to the stretching vibration of a CO group.
(K= 106 dyne cm-1).
7. For the following set of reactions some characteristic picks (IR absorption) will appear and some will
disappear. Which will appear and which will disappear?
a. PhCOPh PHCH(OH)Ph
b. CH3CH2CN CH3CH2COOH
8. Deduce the structure of the isomeric compounds A and B having molecular formula C3H6O and the
following spectral data:
A: 1710 cm-1
B: 3300 and 1640 cm-1
Lecture-6: Basics of NMR spectroscopy, chemical shift, Shielding and de-shielding effect,
Factors affecting chemical shift
Introduction
Spectroscopy is the study of the interaction of electromagnetic radiation with matter. Nuclear
magnetic resonance spectroscopy is the use of the NMR phenomenon to study physical, chemical,
and biological properties of matter. As a consequence, NMR spectroscopy finds applications in
several areas of science. NMR spectroscopy is routinely used by chemists to study chemical
structure using simple one-dimensional techniques. Two-dimensional techniques are used to
determine the structure of more complicated molecules.

What happens in NMR:

Nuclear magnetic resonance or NMR is a phenomenon which occurs when the nuclei of certain
atoms are immersed in a static magnetic field and exposed to a second oscillating magnetic field.
Some nuclei experience this phenomenon, and others do not, dependent upon whether they possess a
property called spin.

Not all nuclei possess the property called spin. A list of these nuclei has been presented in the
following part.

Table 1: Some atoms with spin quantum numbers

NMR Active Nuclei: nuclear spin

quantum number (I) ≠ 0

Even mass nuclei that have even

number of neutron have I = 0 (NMR
inactive)
Even mass nuclei that have odd
number of neutrons have an integer
spin quantum number (I = 1, 2, 3, etc)
Odd mass nuclei have half-integer spin
quantum number
(I = 1/2, 3/2, 5/2,
etc) I= 1/2: 1H,
How to get a signal in NMR (particularly in 1H NMR)?

For a proton (hydrogen atom), nucleus contains only positive charge. This spinning involves the
movement of a positive charge, and, according to the laws of physics, the movement of charged
particles creates a magnetic field with a magnetic moment. The magnetic moments that come from
the nuclear spins have direction.

+
The distribution of nuclear spins is random in the absence of an external magnetic field as shown
below.

+
+ +
+ +
Random orientation of nuclear spin in the absence of External Magnetic field

But, under the influence of an external magnetic field, nuclear spins have a certain orientations.

Orientation of nuclear spin in the presence of External Magnetic field

The allowed nuclear spin states are determined by the spin quantum number, I, of the nucleus
given by the formula 2I+1. The value of the spin states will vary from –I to +I. As for example I
value of H is ½. So, under the external magnetic field (Bo), the spin states of nucleus of H will be
oriented in (2×1/2 +1 =) 2 ways. One is parallel (+1/2) to the external field and other is antiparallel
(-1/2) to the external field (Bo) as shown in the diagram below. The first one is called  spin state
and second one is designated as -spin state. There is a certain energy gap (E) between these two
spin states.

How much lower in energy these nuclei are depends on the strength of external magnetic field
(Bo). As the strength of the magnet increases, the difference in energy (ΔE) between the spins
aligning with the magnetic field (α) and those going against the magnetic field (β) also increases.
This energy gap between the two kinds of spins α and β is what an NMR experiment measures.

• Energy difference is proportional to the magnetic field strength.

∆𝐸 = ℎ = The Larmor Equation

• γhB0
2


• Gyromagnetic ratio () is a constant for each nucleus (26,753 s-1gauss-1 for H).
In an NMR experiment, a radio wave (which indicates light of radio frequencies) effects a
transition between the α and the β spin energy levels. When the frequency of the radio
wave that hits the sample has the exact energy of the energy gap between the α and β spins
(ΔE), the light is absorbed by the nuclei.

The energy from the light absorption is used as a kind of nuclear spatula to flip the α spins
into β spins, a process called spin flipping. When a nucleus absorbs light and flips its spin,
the nucleus is said to be in resonance (which is where the term nuclear magnetic
resonance comes from; this resonance is not to be confused with resonance structures). A
detector can measure the frequency of this absorption and plot it on a spectrum (which is
the plot of an NMR experiment, which shows the intensity of the light absorption versus
the frequency of the light absorbed). A high-frequency light absorption indicates a large
energy gap between the α and β states; a low-frequency light absorption indicates a small
energy gap.

A schematic presentation of NMR Spectrometer

 The sample is placed inside a huge magnet (called the external magnetic field, or B

The direction of the magnetic moments of the nuclei line up either with the external
magnetic field (an α spin) or against it (a β spin).

The energy difference between an α spin and a β spin is the ΔE. Upon absorption of light
that has energy equal to the energy gap (ΔE), the nuclei come into resonance, and α spins
are flipped into β spins.

A detector measures the frequency of the absorbed light (which is proportional to the
energy gap between the α and β spins) and then plots the frequency of the light absorbed
on the NMR spectrum versus the intensity of light absorption.

Secondary Magnetic field: important for nmr signals

So, that’s how an NMR spectrometer determines the energy gap. But if all the hydrogen nuclei
would have the same energy gap (as the external magnetic field remains same) between α and β
spins, the NMR spectrum would show only a single peak (or single light absorption), representing
all the hydrogens in the molecule. And that wouldn’t be particularly helpful. But discussion so far
has omitted one key ingredient — electrons! So far, this discussion has been limited to bare nuclei
that have no electrons surrounding them.

A moving charge (electron) creates a magnetic field is secondary magnetic field, and the field
created by the moving electrons opposes the applied external magnetic field Bo
1
H nuclei are shielded by the magnetic field produced by the surrounding electrons. The higher
the electron density around the nucleus, the higher the magnetic field required to cause resonance.
The effective/resultant magnetic field, therefore, what the hydrogen nuclei actually “sense”
through the surrounding electronic environment is always less than the actual applied magnetic
field B0. This can be understood from the following diagram.

Beffective = Bapplied  Blocal

Standardizing chemical shifts

One potential problem for NMR is that if the nuclei are placed into a large magnet, their resonance
frequency will be larger than when they are placed into a little magnet, because the energy gap
increases as the external magnetic field increases (refer to Figure below).

This means that a proton will show up at a different frequency for the poor person who can only
afford a small magnet than it will for a rich person who can afford a big magnet. To make the
NMR spectrum the same for a given molecule regardless of how large the magnet is, the resonance
frequency is plotted relative to a reference compound, called internal standard and usually
tetramethylsilane (TMS) is used for that purpose. This way, regardless of how big the external
magnetic field is, the peaks in the NMR spectrum will always occur at the same location relative
to TMS. The signal of TMS appeared at a position (of the energy axis) which is considered as
zero.
Internal Standard: TMS (Tetramethyl silane)

TMS has following advantages as the reference compound:

1. It is chemically inert and non-toxic.

2. It is volatile (b.pt 270C) and soluble in most organic solvents.

3. It gives a single sharp peak as it has 12 equivalent hydrogens.

4. Since silicon is less electronegative than carbon, TMS protons are highly shielded. Signal
defined as zero.

5. Organic protons absorb downfield (to the left) of the TMS signal.

Chemical Shift

The shifts from TMS in Hz are bigger in higher field instruments (300 MHz, 500 MHz) than they
are in the lower field instruments (100 MHz, 60 MHz). We can adjust the shift to a field-
independent value, the “chemical shift” in the following way:

Factors affecting e-Density of H: Shielding/Deshielding

• Four major factors:

 Deshielding by electronegative elements : Inductive effect by electronegative

groups
Electron density of hydrogen can be controlled by the electron withdrawing or
donating group attached with the carbon atom. More electron density around the H
 shields the nucleus and comparatively less electron density around the H nucleus
have less shielding effect. This phenomenon affects the chemical shift of H.

 s-character (hybridization effect): proton attached with a carbon having different

hybridization character affects on the electron density of the proton, thus affects
the chemical shifts.

 Magnetic Anisotropic effect (magnetic fields usually due to -bonded electrons in

the molecule(
Sometimes, we cannot explain the chemical shieft of particular type of proton by simple
electronic induction theory. It can be explained by using the Magnetic Anisotropic effect.
Whereas the local circulation of electrons around a proton is a shielding effect (i.e., to
the right in the NMR spectrum, -δ), there can be both shielding and deshielding effects
from electron motion in other parts of the molecule. We refer to such interactions
as magnetic anisotropy effects, since they are caused by anisotropic electron circulation
(i.e., the electron circulation is stronger in some orientations of the molecule in the
magnetic field than in others).

These chemical shift effects occur because electron circulation is stronger when the plane
of the benzene ring is perpendicular to the magnetic field than when it is parallel to it. Few
examples are provided in the below diagram.

Nature and Intensity of Signals

Lecturer-7: Structural elucidation of simple compounds
Some of the individual absorptions split further into smaller peaks. This is called coupling.
Coupling is a phenomenon that’s useful in determining how each piece of the molecule is
connected to the others, coupling tells you how many hydrogens live next door to that
hydrogen. Coupling comes from the interaction of the magnetic moments of the hydrogens
with the magnetic moments of the neighboring hydrogens. In most cases, hydrogens only
couple the hydrogens that are on adjacent carbons. Chemically equivalent hydrogens don’t
couple, which is why hydrogens on the same carbon don’t couple most of the time and why
the six hydrogens in benzene don’t couple.

The “n + 1 rule” and the coupling constant

Coupling follows what is called the n + 1 rule. This rule says that a peak will be split n +
1 times, where n is the number of equivalent neighboring hydrogens. A peak that does not
couple and just shows a single line is called a singlet. The alcohol hydrogen in ethanol does
not couple so it gives a singlet. A peak that’s split into two is called a doublet, three
a triplet, four a quartet, and so on.

The coupling constant, or J value, is proportional to the distance between the lines (or the
tops of the peaks) in a signal. This value is given in frequency units (hertz, or Hz), rather
than in ppm, to make the coupling constant independent of the size of the external magnetic
field.

Intensity of Signals

The peak intensity — or the area underneath a peak on a spectrum — is related to the
number of hydrogens that the peak represents. A computer uses the mathematical process
of integration to find the areas underneath each peak. Traditionally, integration is shown
on the spectrum by the addition of an integration curve (see below fig.), although modern
computing has made digital integration common that doesn’t require you to do any
measuring. The height of this integration curve is proportional to the area underneath a
peak, so this height is proportional to the number of hydrogens the peak represents.
 Splitting of the Signals follw Pascal’s triangle rule.

Few Important Points in NMR Spectrum

Chemical shift: Refers to where a peak appears on a spectrum, relative to the reference molecule
TMS (also called the δ value). The chemical shift is given in units of parts per million (ppm). It
gives you an idea of what kinds of functional groups a hydrogen or carbon is surrounded by.

Integration: Tells you the area underneath a peak, which in turn gives you information about how
many hydrogens a peak represents, relative to the other peaks in the spectrum. Carbon NMR
usually does not have integration on the peaks.

Coupling: Tells you how many hydrogen neighbors a hydrogen sees, following the n + 1 rule.
The n + 1 rule can be applied all at once if a hydrogen is surrounded only by chemically equivalent
 hydrogens. It must be done individually when it’s surrounded by two or more chemically
nonequivalent hydrogens. NMR tree-splitting diagrams are used to predict how many peaks will
be found in the spectrum of a given hydrogen that’s surrounded by two or more nonequivalent
hydrogens. Hydrogens on either nitrogen or oxygen generally don’t couple because of fast
exchange processes — these hydrogens generally show up as fat singlets (which go away when
the sample is shaken with D2O).

Coupling constant: Is proportional to the distance between the tops of the peaks in a multiplet.
The coupling constant is referred to as the J value (given in units of Hz). This value can tell you
which hydrogens are coupled to each other because coupled hydrogens have the same coupling
constant

Application of NMR

1. Structure Determination of Organic Compounds: By using this technique, one can able to
determine the C-C, C-H bond connectivity in a molecule: Based on the signal, you have to
predict the structure of simple organic compounds.
2. Reaction monitoring: Signal of 1H NMR can be utilized to predict the progress of a
reaction.

References:

 Sharma, Y.R., Elementary Organic Spectroscopy, S. Chand

 Silverstein, R.M., Webster, F.X., Kiemle, D. Spectrometric identification of organic compounds, 7th
Edition, Wiley
 Kalsi, P.S., Spetroscopy of Organic Compounds, 5th Edition, New Age International Publishers
 Pavia, D. L.; Lampman, G. M.; Kriz,G. S.; Vyvyan, J. R., Introduction to spectroscopy, 4th Edition
BOOKS/COLE Cenage Learning.

Questions for practice:

1. What is chemical shift? Mention it’s unit. How do shielding and de-shielding influence chemical
shift values of protons in proton-NMR spectroscopy?

2. What is magneto anisotropic effect? Explain the role of it for identification of olefinic and
acetylinic protons through NMR spectroscopy. How does the effect influence chemical shifts of
aromatic protons?

3. Arrange the following compounds in terms of δ values, found in their 1H-NMR spectroscopic data,
with logic.

a. CH3F, CH3Cl and CH3Br , b. CHF3, CH2F2 and CH3F

4. For assignment of each carbon and oxygen environment in a molecule we use 13C and 17O – NMR
spectroscopic technique, instead of 12C and 16O. Why?
5. Why do OH, NH and SH protons appear at higher δ value at high concentrations than in dilute
solutions?

6. Predict the multiplicities of the signals in the proton-NMR spectra of 1,3-dichloropropane and
1,1,2,3-tetrachloropropane.

7. Why is CDCl3 chosen as a solvent instead of CHCl3 for recording of proton-NMR spectra of a
compound?

8. An organic compound having molecular formula C4H10O was subjected to proton-NMR

spectrometer. The two signals found in NMR spectroscopic data were listed as:
a. q, δ= 3.472 ppm
b. t, δ= 1.206 ppm
Predict the structure of the compound.

9. Predict the nature of the proton-NMR spectra of the following compounds:

a. PhCHO,

b. CH3CH2OH,
OCH3
c.

NO2

H
d.
COOH