Nuclear Magnetic

Resonance (NMR)
spectroscopy

Asal usul gejala NMR

Inti-inti atom dapat dikelompokkan sebagai
(1)mempunyai spin atau (2)tidak mempunyai
spin. Suatu inti berspin akan menimbulkan medan
magnet kecil, yang ditunjukkan oleh suatu
momen magnet nuklir, berupa suatu vektor.
Diantara inti-inti yang lebih umum yang memiliki
spin dan tidak memiliki spin antara lain :

Untuk setiap inti yang memiliki spin, jumlah kedudukan

spin adalah tertentu dan ditentukan oleh bilangan
kuantum spin inti I. Bilangan ini adalah tetap untuk
setiap inti.
Untuk inti dengan bilangan kuantum spin I, terdapat
kedudukan spin berjumlah 2I + 1 yang berkisar dengan
perbedaan dari + I hingga I. Kedudukan spin individu
sesuai dengan urutan I, (-I +1),.....(I-1), I.
Sebagai contoh (inti hidrogen) mempunyai bilangan
kuantum spin I = maka akan mempunyai kedudukan
spin ( 2 x (1/2) + 1 = 2) untuk intinya = -1/2 dan + .
Untuk klor, I = 3/2, maka terdapat kedudukan spin 2
(3/2) + 1 = 4, untuk intinya : -3/2, -1/2, + , dan + 3/2.

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.

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Chapter 13

Bila tidak ada medan magnet yang

diberikan, semua kedudukan/ tingkatan spin
dari suatu inti mempunyai tenaga yang
sama, dengan arah tidak beraturan.
Bila medan magnet digunakan, maka setiap
inti yang berputar menghasilkan medan
magnet, dengan arah momen magnet
menjadi searah ( atau + 1/2) atau
berlawanan arah ( atau -1/2) terhadap Bo
(medan magnet luar)

Absorption of energy

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.
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The mechanism of
absorption

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.
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Chapter 13

15

Shielded Protons
Magnetic field strength must be increased
for a shielded proton to flip at the same
frequency.

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Chapter 13

16

Protons in a Molecule
Depending on their chemical environment,
protons in a molecule are shielded by
different amounts.

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Chapter 13

17

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.
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Chapter 13

18

The NMR Spectrometer

Chapter 13

19

Schematic NMR Spectrometer

Fourier transformation and the NMR spectrum

RF Pulse

TheNMRspectrum

Fourier
transform

TheFouriertransform(FT)is
acomputationalmethodfor
analyzingthefrequencies
presentinanoscillatingsignal

The NMR Graph

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Chapter 13

23

Tetramethylsilane

CH3
H3C

Si CH3
CH3

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.
Solvent doesnt contain proton (CCl or
4
CDCl3)

Chapter 13

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24

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.
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Chapter 13

25

Delta Scale

Chapter 13

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26

Typical Values

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Chapter 13

27

Integral and integration

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.

Chapter 13

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30

Local diamagnetic
shielding
1. Electronegativity effect
2. Hybridization effect
3. Acidic and Exchangeble Protons; Hydrogen bonding

 sp3

 sp2

 sp2

and sp are influenced by

anisotropy effect

 Acidic

and Exchangeble Protons;

Hydrogen bonding

 Magnetic

anisotropy

Signal Splitting for 1H

Peak:
The units into which an NMR signal is split; doublet, triplet, quartet,
multiplet, etc.

Signal splitting:
Splitting of an NMR signal into a set of peaks by the influence of
neighboring nonequivalent hydrogens.

(n + 1) rule:
If a hydrogen has n hydrogens nonequivalent to it but equivalent
among themselves on the same or adjacent atom(s), its 1H-NMR
signal is split into (n + 1) peaks.

1,1,2-Tribromoethane

Nonequivalent protons on adjacent carbons.

Chapter 13

44

Doublet: 1 Adjacent
Proton

Chapter 13

Triplet: 2 Adjacent
Protons

Pascals triangle
The relative peak intensities for
multiplet peaks arising from Jcoupling of a 1H to N equivalent
1
H can be determined using Pascals
triangle:

Coupling Constants
Distance between the peaks of multiplet
Measured in Hz
Not dependent on strength of the external
field
Multiplets with the same coupling constants
may come from adjacent groups of protons
that split each other.

49

Values for
Coupling Constants

Chapter 13

52