Chapter IV Nuclear Magnetic

Resonance Spectroscopy

Chapter IV Nuclear Magnetic

Resonance Spectroscopy
What is nmr spectroscopy?
An instrumental technique based on the magnetic
properties of certain nuclei under the influence of a
magnetic field.
In 1946, Purcell (Harvard U) and Bloch (Stanford
Univ) invented techniques to detect the amount of
energy absorbed or emitted as the nuclei jump from
one energy level to another

Types of NMR
1. Proton-nmr (1H-nmr)
Takes into account the signals from protons
or H in a compound or molecule
2. 13C-nmr (CMR)
Takes into account the signals from carbon in
a compound or molecule

Theoretical framework
1. Like electrons, the nuclei of certain atoms
are considered to spin. Visualize the nuclear
charge is spinning around an axis.

Theoretical framework
2. Spinning charges in nucleus generates a magnetic
field with a magnetic moment () directed along
the axis of spin, so that the nuclei act like tiny bar
magnets

Theoretical framework
3. If a proton is placed in an external magnetic
field, its magnetic moment can be aligned
with or against the external field.
Alignment with the filed is more stable, and
energy must be absorbed to flip the tiny
proton magnet over to the less stable
alignment, against the field

Theoretical framework
4. The amount of energy needed to flip a
proton over depends on the strength of the
external field
The stronger the field, the greater the
tendency to remain lined up with it, and the
higher the frequency (v) of the radiation
needed to do the job)

E = h
v = Ho/2
Where v = frequency in Hertz (Hz)
Ho = strength of the magnetic field, in
gauss
= a nuclear constant
= the magnetogyric ratio
= 26750 for the proton

Resonance frequencies of 1H and

13C Nuclei in magnetic fields
v 1H (MHz)
60
90
100
200
400
500
600
750
800

v 13C (MHz)
15.087
22.629
25.144
50.288
100.577
125.720
150.864
188.580
201.154

Ho (Tesla)
1.4093
2.1139
2.3488
4.6975
9.3950
11.744
14.092
17.616
18.790

Theoretical framework
5. At a given radiofrequency, all protons
absorb at the same effective field strength,
but they absorb at different applied file
strengths
It is this applied field strength that is
measured, and against which the absorption
is plotted.

Schematic diagram of an nmr

1

2
8

6
3N

S4
9

7
5

Parts of nmr spectrometer

1. Sweep coils
2. Sample holder
3. Transmitter coil
4. Receiver coil
5. Magnet

6. R-F transmitter
7. Sweep generator
8. R-F receiver and
generator
9. Recorder

Parts of nmr spectrometer

Sample holder
Usually a glass tube spun by an air-driven
turbine to average the magnetic field over the
sample dimensions
Transmitter (Radio-Frequency oscillator)
Connected to a coil which transmits energy to
the sample in a direction perpendicular to the
magnetic filed

Parts of nmr spectrometer

R-F receiver
Connected to a coil encircling the sample
Two coils are perpendicular to each other and
to the magnetic field
Magnet
With a strong, stable, homogeneous field
Must be constant over the area of the sample
and over the period of time of the experiment

Characteristics of nmr magnets

1. The magnetic field must be strong
Sensitivity of nmr increases as the strength
of the magnet increases
Ensures adequate dispersion of signals
Simplification of the spectrum
2. The magnetic field must be extremely
homogeneous
So that all portions of the sample experience
exactly the same magnetic field

Characteristics of nmr magnets

2. Must be extremely homogeneous
Any inhomogenerity of the magnetic field
will result in broadening and distortion of
spectral bands
3. The magnetic field must be very stable
So that is does not drift during the
acquisition of the spectrum, w/c may take
from several seconds to several hours

Characteristics of nmr magnets

Parts of nmr spectrometer

Sweep generator
Supplies a variable d-c current to a secondary
magnet so that the total applied magnetic
field can be varied (swept) over a limited
range
Readout system
Consisting of an amplifier, recorder and
possible additional components for increased
sensitivity, accuracy, or convenience

Sample handling for nmr analysis

A. Liquid
1. Using a disposable pipet with a rubber
bulb, touch lightly to the side of the nmr
tube.
2. Let the sample go down the side of the
tube and fill to at least inch.
3. Then cap the tube with the nmr tube cap

Liquid sample handling

Nmr tube

disposable pipet

nmr cap

in

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Internal standards for nmr analysis

1. Tetramethylsilane (TMS)
Proton signals occur at lower frequency and give
sharp signals
Relatively inert bp at 26 28C
Easily removed after use

2. Hexamethyldisiloxane (HMDS)
Does not boil out of the nmr tube
B.p. is at 101C

Sample handling for nmr analysis

B. Solids
1. Dissolve in protonless solvents
Example: CCl4
- toxic and potentially carcinogenic (HWC)
2. Dissolve in deuterated solvents such as:
a. Deuterated chloroform, CDCl3
b. Deuterated benzene, C6D6
c. Deuterium oxide, deuterated water

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NMR Interpretation
A. The Zero Point
At the extreme right of the nmr, a sharp
peak from the protons is the internal
standard, TMS
This signal is defined as zero point and all
other values for the chemical shift are taken
from this point

The zero point

Low field end of
spectrum
Nuclei deshielded
Downfield
10

High field end of

spectrum
Nuclei shielded
Upfield
5

0 ppm
from
TMS

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NMR Interpretation
B. The Chemical Shift ()
Change in the position of the nmr signals
which depends on the chemistry of the
molecule
Shielded proton moves upfield (C2H2) and
resonate at lower delta values (toward
TMS)
Nuclei tend to be deshielded by groups with
withdrawn electron density

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