NMR Spectroscopy

Nuclear Magnetic Resonance

Mrinal Gosain
2k15/EP/37
Mridul Joshi
2k15/EP/36
 What is Spectroscopy?
● Spectroscopy is the study of the way light (electromagnetic
radiation) and matter interact.
● There are a number of different types of spectroscopic
technique and the basic principle shared by all is to shine
a beam of a particular electromagnetic radiation onto a
sample and observe how it responds to such a stimulus:
This allows scientists to obtain information about the
structure of the molecules.
Brief Recap:
 NMR
1. When some atoms are placed in a strong magnetic
field, their nuclei behave like tiny bar magnets aligning
themselves with the field. Electrons behave like this too,
and for this reason both electrons and nuclei are said
to possess ‘spin’, i.e. any spinning electric charge has
an
associated magnetic field.
2. Just as electrons with opposite spin pair up with each
other in bonding orbitals, a similar thing happens with
protons and neutrons in the nucleus.
 3.If a nucleus has an even number of protons and neutrons (e.g. 12C), their
magnetic fields cancel each other out and there is no overall magnetic field;
however, if the number of protons and neutrons is odd (e.g. 13C and 1H), the
nucleus has a
magnetic field.

4.If the substance is placed in an external magnetic field, the nuclear magnet lines
up with the field, in the same way as a compass needle lines up with a magnetic
field. The nuclear magnet can have two alignments, of low energy and high
energy.

5.To make the nucleus change to the higher energy alignment, energy must be
supplied. The energy absorbed corresponds to radio frequencies. The precise
frequency
of energy depends on the environment of the nucleus, that is, on the other nuclei
and electrons in its neighbourhood.
Splitting of Energy Bands:
1. Not all nuclei are suitable for NMR.
1
2. H and
13
C are the most important NMR active nuclei in organic chemistry
How NMR spectrometer looks like?
Schematic Diagram of Spectrometer
 Sample Handling:

1) Use the Correct Quantity of Material

At very low concentrations, the peaks from common contaminants such as water and grease tend to dominate
the spectrum. If we make up a sample at high concentration, it may result in a spectrum that has broader lines
than we would get from a more dilute solution.

2) Remove All Solid Particles

Solid particles distort the magnetic field homogeneity because the magnetic susceptibility of a particle is different
from that of the solution. A sample containing suspended particles thus has a field homogeneity distortion around
every single particle. This causes broad lines and indistinct spectra that cannot be corrected.

3) Make Samples to the Correct Depth

In the magnet, the main field direction is vertical, along the length of the sample.Each end of the sample causes
a major distortion of the field homogeneity which is corrected using the spectrometer's shim controls.Shorter
samples are very difficult to shim, and cause considerable delay in recording the spectrum. Samples that are too
long are also difficult to shim and are a waste of costly solvent.
4) Use Deuterated Solvents
Samples must be prepared using solvents that contain deuterium in place of hydrogen.
The NMR signal from the deuterium nuclei is called the NMR lock and is used by the
spectrometer for stabilization.

5) Use Clean Tubes and Caps and label the Samples

6) Degassing Samples
Some samples need to be degassed or have oxygen removed. The only effective way of
doing this is by using the Freeze-Pump-Thaw technique, at least three cycles. It is
sometimes sufficient to flush the space above the sample surface with nitrogen. This
should be done with great care to avoid blowing the solution out of the tube.
H-NMR spectrum looks like:
 Before Understanding the Graph we need to
look at these 4 aspects:
1. Number of peaks in the NMR spectrum equals to the
number/ type of hydrogen present in the molecule.
2. Proximity to an electronegative atom or multiple bonds
causes a peak to be shifted.
3. There is relation b/w the area under peak & the number of
hydrogens responsible for the peak.
4. Peak can be split due to neighbouring/different hydrogen
Before Moving onto Aspects some basic
terminologies:
Shielding:
Shielded and Deshielded state:
Shielded & DeShielded by Example
Upfield & Downfield:
How will you distinguish between these two
compounds?
 For this we need aspect 1:
Recall,
Number of peaks in the NMR spectrum equals the number
of different hydrogen in the molecule.
Learning about Beffective
Still learning…. :(
So far…..
Let the Fun begin :))
Interesting..? Pretty much!
Still up for it?
Aspect @2 : Shifting of Peaks
 Why ppm scale?

● To standardized the plots as different machines

have different operating frequencies.
What is TMS? TATA MotorS???
Let’s see Shifting causes in Action!

Concept- electronegative atoms or multiple bonds

causes peaks to shift
Some more...
Benzene : special case study!
Standard reference table:
 Aspect @3: Integration
Rel’ b/w area under a peak and number of hydrogen responsible for
the peak.

H-NMR can calculate area under peak while plotting the graph.
 Surprisingly :

It’s a fact not a coincidence!!

 In Actual H-NMR plot:

These vertical lines are proportional to the area of that

peak so that you can easily calculate the ratio.
Aspect @4 Multiplicity!
 N+1 Rule:
N is Number of neighbouring different Hydrogen!
Let’s solve & get more accurate Peaks
Igniting the Engine!!

Very Important case!

Containing Benzene Ring one!
Para- Substituded:
Doublet of doublet vs quartet
In quartet lower peak : taller peak = 1:3 this is due to number of orientations
possible of dipoles in magnetic field.

In doublet peak heights are in ratio 1:1

Gap between peaks : J-coupling

● Coupling: This coupling arises from the interaction of different spin

states through the chemical bonds of a molecule and results in the
splitting of NMR signals
● It is measured in hertz.
● It’s value is constant for particular bonds
Q- How to distinguish between Cis & trans?
- They have same molecular formula -
Mass spectroscopy fails
- They have same bonds- IR fails as
vibration,wagging would be the same
- Here multiplicity is also same means
peaks splitting number is same.
- Then How can we distinguish them??
J-coupling constant comes to Rescue
:))
Where N+1 rules fails : We need to follow
splitting diagrams!
 Take away points:
1. Splitting diagrams can be generated for complex splitting
in an NMR spectrum.
2. Generating splitting diagrams involves using N+1 rule
separately for left and right i.e each neighbouring
hydrogen along with J value
Now let’s Tackle this :’)
 Few application of NMR:
1. MRI : Magnetic Resonance Imaging
2. Chemical research and development: organic,
inorganic and physical chemistry
3. Finding out the structure of molecule
4. Sample purity determination.
5. Polymer industry
6. Biological and biochemical research
Detection using MRI:
Most Awaited Slide! :”)

THANK
YOU!