MAGNETIC
RESONANCE (NMR)
SPECTROSCOPY
Siti Nor Atika Baharin (Ph.D)
Syllabus
3.1 The NMR Phenomenon
3.2 Theory of NMR
3.3 Chemical Shift and its Measurement
3.4 Factors influencing Chemical Shift
3.5 Proton NMR Spectroscopy
3.5.1 Correlation Data
3.5.2 Solvents Used in NMR
3.5.3 Integrals in Proton NMR Spectra
3.5.4 Spin-Spin Coupling-Spin-Spin Splitting
3.5.5 Factors Influencing the Coupling Constant, J
3.5.6 Non-first-order Spectra
3.5.7 Simplification of Complex Proton NMR Spectra
3.5.8 Tables of Data for Proton NMR
Learning outcome
• Understand the NMR phenomenon
• Understand in how the chemical shift occurred
& its measurements
• Understand the factor that influence of chemical
shift in NMR spectra.
NMR?
Hydrogen nuclei
(1H-NMR)
NMR gives information
about the number of
magnetic distinct
atoms of the type of
being studied
Carbon nuclei
(13C-NMR)
NMR phenomenon
(nuclear spin)
The nuclei of some atoms have a property called “SPIN”.
Nuclear Spin
Quantum No 1/2 1 0 1/2 1 0 5/2 1/2
(I)
No. of Spin 2 3 0 2 3 0 6 2
States
+ +
Magnetic
Absorb energy
field
+hv
direction
• Energy absorption is quantized process
• Energy absorbed must equal with the energy
difference between the two states involved.
Eabsorbed ( E 1 / 2 state E 1 / 2 state) hv
The energy difference (∆E) is a function of the strength of the
applied magnetic field (B0)
Absorption of energy
N
-1/2
The stronger the unaligned
applied magnetic
field (Bo),
The greater energy DE
difference between
the possible
spin states
magnetogyric
ratio g
frequency of g
the incoming n Bo
radiation that
will cause a 2p
transition strength of the
magnetic field
w Nuclei precess at
frequency w when
RADIOFREQUENCY
placed in a strong
40 - 600 MHz magnetic field.
hn
NUCLEAR
MAGNETIC
If n = w then RESONANCE
energy will be
absorbed and NMR
the spin will
invert. S
POPULATION AND SIGNAL STRENGTH
The strength of the NMR signal depends on the
Population Difference of the two spin states
Radiation
induces both
upward and
downward resonance
induced
transitions. emission
RF (60 MHz) hn
Oscillator absorption RF
Recorder
signal Detector
Transmitter
Receiver
MAGNET MAGNET
~ 1.41 Tesla
N S (+/-) a few ppm
Probe
Fortunately, different types of protons precess at
different rates in the same magnetic field.
N Bo = 1.41 Tesla
hn
To cause absorption
60 MHz 59.999820 MHz of the incoming 60 MHz
the magnetic field strength,
Bo , must be increased to
S a different value for each
type of proton.
Differences are very small,
in the parts per million range.
IN THE CLASSICAL NMR EXPERIMENT THE INSTRUMENT
SCANS FROM “LOW FIELD” TO “HIGH FIELD”
LOW HIGH
FIELD FIELD
NMR CHART
DOWNFIELD UPFIELD
scan
NMR Spectrum of Phenylacetone
O
CH2 C CH3
n2
n1
O
BROADBAND
RF PULSE CH2 C CH3
contains a range
of frequencies n3
(n1 ..... nn)
S
All types of hydrogen are excited
simultaneously with the single RF pulse.
FREE INDUCTION DECAY
( relaxation )
n1
O
CH2 C CH3 n2
n3
n1 + n2 + n3 + ......
time
FOURIER TRANSFORM
A mathematical technique that resolves a complex
FID signal into the individual frequencies that add
together to make it. ( Details not given here. )
FT-NMR
computer
COMPLEX
SIGNAL n1 + n2 + n3 + ......
Fourier
Transform
individual
a mixture of frequencies
frequencies
decaying (with time)
converted to a spectrum
The Composite FID is Transformed into a
classical NMR Spectrum :
O
CH2 C CH3
signal enhanced
noise signal
1st pulse
2nd pulse
add many
pulses
noise is random
nth pulse etc. and cancels out
INTEGRATION
METHOD 1
integral line
integral
line
simplest ratio
55 : 22 : 33 = 5:2:3 of the heights
Benzyl Acetate (FT-NMR)
Actually : 5 2 3
O
CH2 O C CH3
METHOD 2
digital assume CH3
33.929 / 3 = 11.3
integration
Integrals are
good to about
10% accuracy.
magnetic field
lines
Bo applied B induced
(opposes Bo)
fields subtract at nucleus
PROTONS DIFFER IN THEIR SHIELDING
All different types of protons in a molecule
have a different amounts of shielding.
SPECTRUM
DOWNFIELD UPFIELD
Less shielded protons Highly shielded
appear here. protons appear here.
It takes a higher field
to cause resonance.
CHEMICAL SHIFT & ITS MEASUREMENT
Rather than measure the exact resonance position of a
peak, we measure how far downfield it is shifted from TMS.
g
n= B
2p o
NMR Field 1H Operating
Strength Frequency
constants
1.41 T 60 Mhz
2.35 T 100 MHz
hn = ( K) Bo 7.05 T 300 MHz
HIGHER FREQUENCIES GIVE LARGER SHIFTS
The shift observed for a given proton
in Hz also depends on the frequency
of the instrument used.
Higher frequencies
= larger shifts in Hz.
TMS
shift in Hz
downfield
n 0
THE 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:
parts per
million
chemical shift in Hz
shift
= d = = ppm
spectrometer frequency in MHz
7 6 5 4 3 2 1 0 ppm
TMS
12 11 10 9 8 7 6 5 4 3 2 1 0 d (ppm)
H
CH2F CH2Ar C-CH-C
RCOOH RCHO C=C CH2Cl CH2NR2
CH2S C
CH2Br
CH2I C C-H C-CH2-C
CH2O C=C-CH2 C-CH3
CH2NO2 CH2-C-
O
Ranges can be defined for different general types of protons.
This chart is general, the next slide is more definite.
APPROXIMATE CHEMICAL SHIFT RANGES (ppm) FOR SELECTED TYPES OF PROTONS
C-H where C is
CH on C
acid aldehyde benzene alkene attached to an aliphatic
next to
COOH CHO CH =C-H electronega- pi bonds C-H
tive atom
X=C-C-H
X-C-H
12 10 9 7 6 4 3 2 0
NMR CHART
most TMS
deshielded
deshielding increases with the
electronegativity of atom X
Substitution Effects on Chemical
Shift
most
deshielded -CH2-Br -CH2-CH2Br -CH2-CH2CH2Br
3.30 1.69 1.25 ppm
Circulating p electrons
Deshielded
H H fields add together
protons are
deshielded
H H
Deshielded
shifted
fields add downfield
C=C
H H
secondary
magnetic
(anisotropic)
field lines
Bo
ANISOTROPIC FIELD FOR AN ALKYNE
H
C
C
H secondary
magnetic
(anisotropic)
Shielded hydrogens field
Bo
are shielded
fields subtract
HYDROGEN BONDING DESHIELDS PROTONS