NUCLEAR MAGNETIC RESONANCE ( NMR)

- Spectroscopic method that is more important to

organic chemist than IR.
NMR gives information about the number of
magnetically distinct atoms of the type being studied
It also on the nature of the immediate environment of
each type
Nuclei studied : hydrogen , carbon etc


Spectroscopy of the Electromagnetic
Spectrum
Radiant energy is proportional to its frequency (cycles/s = Hz)
as a wave (Amplitude is its height)
Different types are classified by frequency or wavelength ranges
Introduction
NMR is the most powerful tool available for organic
structure determination.
It is used to study a wide variety of nuclei:

1
H

13
C

15
N

19
F

31
P
=>
Nuclear Magnetic Resonance

NMR : Condition of the neighboring group.
: Difference between the characteristic of the nucleus.
: The location of the nucleus in the molecule.
: Propose the structure of the molecule.
E.g.
1
H,
13
C (for organic compound).

Started since 1960.

Nowadays : involve complicated instrumentation.
: CW instrument (60 MHz).
: FT NMR instrument.
: High Frequency (HF) NMR instrument (300MHz).

Complex structure = Stereochemistry.


Basic Principle
Nucleus can be split into several quantized level due to the strong magnetic
field. This is the magnetic characteristic from the particle. The transition
between the magnetic energy level occurred with the absorption of
electromagnet which has certain frequency.

The difference between the quantized levels of the magnetic nucleus atom
is in the region of radio frequency, 0.1-100 MHz ( 3000-3m).

1924: Pauli suggested that several nucleus of atoms could have spin
characteristic and magnetic moment:
- Magnetic field will split the energy level through the
absorption of the electromagnet light.
: This theory has been proven by Bloch and Purcell (1946).


Nuclear Spin States
To study the characteristic of the particle. It spins at one axis.
Therefore, it has spin characteristic.

Nucleus atom that has odd mass, odd number of atom or both will has
spin angular momentum and magnetic moment. e.g.
1
H,
3
H,
13
C,
14
N,
17O,
19
F.

For each nucleus that has spin; the allowed spin state will be
determined by nuclear spin quantum number, I.

For each nucleus, the number I is a physical constant, and there are 2I+1
allowed spin states with integral differences ranging from +I to I. The
individual spin states fit into the sequence
+I, (I-1),.., (-1+1),-I

e.g. - Proton;
1
H: I=1/2
spin state =2I + 1
=2(1/2) + 1 = 2
(-1/2 and +1/2)

- Chlorine;
35
Cl: I=3/2
spin state =2(3/2) +1=4
(-3/2, -1/2, +1/2, +3/2)


Number of
Proton
Number of
Neutron
I Total of Spin
State
Examples
Even Even 0 1
12
C,
16
O,
32
S
Odd Even 1/2
3/2
2
4
1
H.
19
F,
31
P
11
B,
78
Br
Even Odd 1/2
3/2
2
4
13
C
127
I
Odd Odd 1 3
2
H,
14
N
Table: Spin Quantum Number
In the absence of an applied magnetic field, all the spin states of a given
nucleus are of equivalent energy.
Magnetic Moment of Nucleus
Spin state will have different energy in the magnetic field.

Nucleus that has charge and spin will generate a magnetic field of its own.

The magnetic moment for the nucleus will align (e.g. proton):
- Align with applied field (+1/2).
- Oppose applied field (-1/2).

Particle that has spin quantum number, I and magnetic quantum number,
m (m=I, I-1, I-2, , -I) will possess quantized energy level:

E = - m H
0

I

H
0
= density of the applied field
= magneton nucleus constant, 5.049 x 10
24
erg-gaus
-1
= magnetic moment of particle
Example: Proton
I = ; Spin state (2)
Magnetic quantum number: +1/2, -1/2

When m = +1/2, E = -1/2 H
0

E = - H
0


When m = -1/2, E =-( -1/2 H
0
)

E = + H
0
The difference between quantum energy level is:
E = 2 H
0

e.g.
14
N has three quantum number (m=1, 0,-1)

In general, difference between energy:
E = H
0

I
Excitation of He to a higher magnetic quantum level occurs when there is
absorption of photon h.
E = h = H
0
I
I = spin number
m = spin quantum number
In NMR, Ho = 10
4
gauss
= 2.79 x 5.05 x 10-24 x 104
6.6 x 10
-27
x
= 4 x 10
7
Hz (Radio frequency)

m= -1/2 (higher energy)
m= +1/2
No field
0
E
Orientation of magnetic moment and energy level for
particle in magnetic field, H
0
.
Absorption of Energy
The nuclear magnetic resonance phenomenon occurs when nuclei
aligned with an applied field are induced to absorb energy and change
their spin orientation with respect to the applied field.

e.g. Hydrogen nucleus,


m=-1/2
m=+1/2
H
0
hv
Energy absorbed = (E-1/2-E+1/2) = h
The difference of the energy depends on the strength of magnetic field, H
0
.

E = f (H
0
)

E also depends on the nucleus involved (each nucleus has different ratio
of magnetic moment to angular momentum).

: gyromagnetic ratio

=
I(h/2) (for spinning particle)

E = f ( H
0
) = h
Since the angular momentum of the nucleus is quantized in units of h/2,
the final equation takes in the form:
E = (h/2) H
0
= h
= (/2) H
0

: Lamor frequency

If the correct value of for the proton is substituted in the equation, proton
will absorb radiation of frequency 42.6 MHz in a field of strength 10,000
G.
Table: Frequencies And Field Strengths At Which
Selected Nuclei Have Their
Nuclear Resonances.
Isotope H
0
(Gauss) (MHz)
1H 10000
14100
23500
51480
42.6
60
100
220
2H 10000 6.5
13C 10000 10.7
35Cl 10000 4.2
To understand the nature of a nuclear spin transition, the analogy of a
spinning is useful.

With the magnetic field, the nucleus starts to precess about its axis.

H
0
Spinning particle
The nucleus begins to precess on its own axis of spin with
angular frequency, .
H
0
The stronger the applied field, the higher the rate of precession.

Since the nucleus has a charge, the precession generates an oscillating
electric field of the same frequency. If the radiofrequency waves of this
frequency are applied to the precessing proton, the energy can be absorbed.
This condition is called resonance. Thus, it causes spin change.
= = 60 MHz
+1/2
H
0
, 14100G
H
0
hv
v = 60 MHz
- 1/2
Nuclear Spin
A nucleus with an odd atomic number or an odd
mass number has a nuclear spin.
The spinning charged nucleus generates a
magnetic field.
=>
External Magnetic Field
When placed in an external field, spinning protons act
like bar magnets.
=>
Two Energy States
The magnetic fields of the
spinning nuclei will align
either with the external
field, or against the
field.
A photon with the right
amount of energy can
be absorbed and cause
the spinning proton to
flip. =>
E and Magnet Strength
Energy difference is proportional to the
magnetic field strength.
E = h = h B
0

2
Gyromagnetic ratio, , is a constant for each
nucleus (26,753 s
-1
gauss
-1
for H).
In a 14,092 gauss field, a 60 MHz photon is
required to flip a proton.
Low energy, radio frequency. =>
Magnetic Shielding
If all protons absorbed the same amount of
energy in a given magnetic field, not much
information could be obtained.
But protons are surrounded by electrons that
shield them from the external field.
Circulating electrons create an induced
magnetic field that opposes the external
magnetic field. =>
Shielded Protons
Magnetic field strength must be increased for a
shielded proton to flip at the same frequency.
=>
Protons in a Molecule
Depending on their chemical environment,
protons in a molecule are shielded by
different amounts.
=>
NMR Signals
The number of signals shows how many
different kinds of protons are present.
The location of the signals shows how shielded
or deshielded the proton is.
The intensity of the signal shows the number of
protons of that type.
Signal splitting shows the number of protons
on adjacent atoms. =>
The NMR Spectrometer
=>
The NMR Graph
=>
Tetramethylsilane
TMS is added to the sample.
Since silicon is less electronegative than
carbon, TMS protons are highly shielded.
Signal defined as zero.
Organic protons absorb downfield (to the left)
of the TMS signal.

=>
Si
CH
3
CH
3
CH
3
H
3
C
Chemical Shift
Measured in parts per million.
Ratio of shift downfield from TMS (Hz) to total
spectrometer frequency (Hz).
Same value for 60, 100, or 300 MHz
machine.
Called the delta scale.
=>
Chemical Shift
Theoretically, the radiofrequency is applied to the sample and it will give
signal that can be measured. However, it is most unlikely because it is
difficult to build oscillator that can adjust the frequency.
In an applied magnetic field, the valence electrons are caused to circulate.
Each molecule has different shielding environment. It generates magnetic
field which is oppose to H
0
.
Proton precesses in different and it depends on the surrounding of the
nucleus.
These differences in resonance frequency are very small. Thus, it is
measured in ppm (part in million).
Fixed frequency is used; the shift from TMS for a given proton depends on
the strength of applied magnetic field. H
0
can be adjusted to ppm value
when the current of the magnet is changed. For most of the organic
compound, resonance:

: 0 10 ppm

As for proton which is highly shielded, precession occurs in lower
frequency. Therefore, higher field is required.

As for proton which is deshielded, lower difference of changing of field is
required.
10 ppm 0 ppm
- Deshielded.
- Low H
0
.
- Low shielding.
- High frequency
- Shielded.
- High H
0
.
- High shielding.
- Low frequency.
For sp
3
bonding (CH
3
, CH
2
, CH protons), nucleus will be shielded
by the electron.

The more effective the electron shielding, the bigger the outer field
is required to overcome the effect. For the deshielded protons, the
opposite is in effect.
Delta Scale
=>
Location of Signals
More electronegative atoms
deshield more and give larger
shift values.
Effect decreases with distance.
Additional electronegative
atoms cause increase in
chemical shift.
=>
Typical Values
=>
Aromatic Protons, 7-8
=>
Vinyl Protons, 5-6
=>
Acetylenic Protons, 2.5
=>
Aldehyde Proton, 9-10
=>
Electronegative
oxygen atom
O-H and N-H Signals
Chemical shift depends on concentration.
Hydrogen bonding in concentrated solutions
deshield the protons, so signal is around 3.5
for N-H and 4.5 for O-H.
Proton exchanges between the molecules
broaden the peak.
=>
Carboxylic Acid
Proton, 10+
=>
Number of Signals
Equivalent hydrogens have the same chemical
shift.
=>
Intensity of Signals
The area under each peak is proportional to
the number of protons.
Shown by integral trace.
=>