Nuclear Magnetic

Resonance (1H-NMR)
Spectroscopy

Adapted from Donald Pavia: http://atom.chem.wwu.edu/pavia/c352ppt.html

 Exercise N.3
• Pre-lab Preparation
– Read Wade, Ch. 13
• Lab notebook
– No entries required
• Practice Problems
– Will get in lab
• Datasheet
– Spectra problem set (graded)
– Download from BB (after lab)
 TYPES OF INFORMATION
FROM THE 1H NMR SPECTRUM
1. Each different type of hydrogen gives a signal.

2. The chemical shift (d, in ppm) gives a clue as

to the type of hydrogen generating the signal
(alkane, alkene, benzene, aldehyde, etc.)

3. The integral gives the relative numbers of each

type of hydrogen in a particular signal.
4. Spin-spin splitting gives the number of hydrogens
on adjacent carbons.

5. The coupling constant J also gives information

about the arrangement of the atoms involved.
 # signals = # types of protons Integration = # protons
in each signal

3H

Splitting patterns tell number of

protons on adjacent carbons
3H

2H

Chemical shift tells electronic environment

 Nuclear “Spin” (angular momentum)
Spin
1. A fundamental property of nature like electrical charge or
mass
2. Comes in multiples of ½ and can be + or –
3. Protons, neutrons, and electrons all possess angular
momentum (spin)
4. + and – spins can pair up and eliminate the observed
manifestation of spin
5. When placed in a magnetic field, a nucleus with net spin can
absorb a photon
Nuclei Unpaired Protons Unpaired Neutrons Net Nuclear spin
1H 1 0 ½
2H 1 1 1
12C 0 0 0
13C 0 1 ½
19F 1 0 ½
31P 1 0 ½
 The “Resonance” Phenomenon

Resonance – a transition between two energy states by the

absorption of a photon

A particle (electron, nucleus, molecule, etc) in the lower

energy state absorbs a photon and ends up in the upper
energy state.

The energy of this photon must exactly match the energy

difference between the two states. E = hν

Infrared spectroscopy – two vibrational states

NMR – two nuclear spin states

Nuclear Spin States - Hydrogen Nucleus

The two states

are equivalent
in energy in the
absence of a
+½ -½ magnetic or an
electric field.
α β
 Zeeman Energy Diagram
The energy difference between the two proton spin states
increases as the applied magnetic field strength
increases.

β spin state
(anti-parallel)

E
degenerate
at Bo = 0
α spin state
(parallel to B0 )
Bo
increasing magnetic field strength
 Absorption of Energy
quantized

β β

DE
DE = hn

α α

Bo
 The
Theenergy
energydifference
differencebetween
betweenthe
the
h two
twospin
spinstates
statesneeded
neededfor
DE   B0 for
2 resonance.
resonance.

Where γ = the gyromagnetic ratio (the slope of the

Where γ = the gyromagnetic ratio (the slope of the
line
lineininthe
theprevious
Zeemanslide. γ is unique
diagram. for each
γ is unique for each
different
differentnucleus.
nucleus. hhisisPlanck’s
Planck’sconstant.
constant.BB0 0isisthe
the
strength
strengthofofthe
themagnetic
magneticfield.
field.
γγ==26,753 sec-1 gauss-1 for a proton
26,753 sec-1 gauss-1 for a proton

SinceΔE
Since ΔE==hν,
hν,ititfollows
followsthat
1
that n  B0
2
The
Thefrequency
frequencyneeded
neededfor
forresonance
resonanceatataagiven
given
magnetic
magneticfield
fieldstrength.
strength.
 If you do the math from the previous equation …
β spin state
(anti-parallel)

ν 60 MHz
100 MHz
200 MHz
300 MHz
400 MHz

α spin state
(parallel to B0 )
Bo

1.41T 2.35T 4.70T 7.05T 9.56T

(T = Tesla = 10,000 gauss)

 1H and 13C Frequencies Differ
For a given field strength 1H has its resonance at a
different (higher) frequency than 13C.

1H Divide the hydrogen

frequency by 4 (approximately)
for carbon-13
1.41 T 60 MHz
2.35 T 100 MHz
7.05 T 300 MHz 13C
1.41 T 15.1 MHz
2.35 T 25.0 MHz
7.05 T 75.0 MHz
 During an NMR Experiment
1. Apply an external magnetic field
2. This causes the protons (hydrogen nuclei) to
precess at an angular frequency 
3. Then apply a short pulse (~ 5 microseconds) of
radio frequency energy
4. If the frequency of photons in the pulse match the
precessional frequency of the spinning nuclei, the
photon is absorbed and the nucleus moves from
the low energy spin state to the high energy spin
state. (Resonance)
5. The spectrometer detects the energy absorption
and converts it to a graphical display
That’s really cool, but so what??

Won’t all the protons precess at the same

frequency?
(Which would lead to the same resonance frequency
for all the protons, which leads to one peak in the
spectrum)

In other words, isn’t it a nice experiment that

doesn’t tell us much?

NO!! It turns out the protons precess at

different frequencies in most molecules.
So they have different resonance frequencies.

Why is this the case???

 Magnetic Shielding
• The protons are surrounded by electrons which
have their own magnetic field and which oppose
the external, applied magnetic field.
• Electronegative atoms such as halogens or
oxygen pull electron density a way from the
protons, leaving them more “exposed”
– “Deshielding”
• Changes the electronic environment of the
protons
• Leads to different precessional frequencies in a
magnetic field
• Leads to different resonance frequencies
 More on Shielding
The result (of having protons surrounded by electrons which have
their own magnetic field and which oppose the external, applied
magnetic field) is that the effective field actually experienced by the
proton is always less than the applied field.

Beffective = Bapplied – Bshielding

So the greater the shielding, the smaller the effective field felt by the
nucleus. This shielding can be factored into the resonance equation
as 1-σ where σ is the shielding constant. As σ increases, 1-σ
decreases.
1
n resonance  Bo (1   )
2
If the effective field felt by the nucleus decreases, the frequency
required for resonance also decreases (at constant Βo).
Bottom line: the greater the shielding, the smaller the
effective field felt by the proton and the smaller the
frequency required for resonance.

10 NMR scale 0

• Less shielding • More shielding

• “deshielded” • “shielded”
• Large energy gap • Small energy gap
• Higher resonance • Lower resonance
frequency frequency
• Downfield (outdated) • Upfield (outdated)
 10 NMR scale 0

β spin state
(anti-parallel)

1
n Bo (1   ) E
2

α spin state
(parallel to B0 )

Low Shielding High Shielding

Large Effective Field Small Effective Field

High Resonance Frequency Low Resonance Frequency

 THE CHEMICAL SHIFT “d”
the shift observed
CH3 depends on the
tetramethylsilane frequency of the
CH3 Si CH3 TMS instrument used

CH3 reference cmpound TMS

(CH3)4Si
shift in Hz
parts per
n 0 million

d = Position of signal – position of TMS peak (Hz) = ppm

spectrometer frequency in MHz

this division gives a number independent of the instrument used

Electronegativity Dependence
of Chemical Shift

Deshielding increases
Substitution Effects on Chemical
Shift

CH3F CH3Cl CH3Br

4.3 3.1 2.7 ppm

CHCl3 CH2Cl2 CH3Cl

7.3 5.3 3.1 ppm

-CH2-Br -CH2-CH2Br -CH2-CH2CH2Br

3.3 1.7 1.3 ppm
 NMR Correlation Charts

Lab text:
p. 128 (chart),
p. 129 table,
inside back cover

Wade:
p 570 and Appendix 1-A
 Number of Signals

Number of signals = number of different

types of hydrogens in a molecule
 Types of Hydrogens

O
CH3
1 type = 1 signal CH3 C CH3
CH3

CH3 CH2 CH2 CH3

2 types = 2 signals
a b b a
CH3 CH2 CH2 CH3
 Types of Hydrogens

CH3 O CH2 CH2 O CH3 2 signals

2 signals
O

O
4 signals
 INTEGRATION

Integration = determination of the area

under a peak

The area under a peak is proportional

to the number of hydrogens that
generate the peak.
 Benzyl Acetate

55 : 22 : 33 = 5:2:3
 Benzyl Acetate (FT-NMR)
actually : 5 2 3

58.117 / 11.3 = 5.14 21.215 / 11.3 = 1.90 33.929 / 11.3 = 3.00

assume CH3
33.929 / 3 = 11.3
 Spin-Spin Splitting

NMR Spectrum of Bromoethane

a

b a
Br CH2CH3
b
 NMR Spectrum of Acetaldehyde

a O a
b
CH3 C
H

offset = 2.0 ppm

NMR Spectrum of 2-Nitropropane

a bH a a
CH3 C CH3
N +
O O-

b
 Spin-Spin Splitting
Protons that have the same chemical shift do not
split each other’s signal.

The basis for spin-spin splitting is spin-spin

coupling – the communication of nuclear spin
information via the electrons in the bonds between
the nuclei.

Coupling is greatest when the number of

intervening bonds is small.

Vicinal protons are separated by three bonds. So

the coupling is sometimes referred to as vicinal
coupling or three-bond coupling.
Some Common Splitting Patterns (n+1 rule)
X CH CH Y CH3 CH
(x=y)

CH2 CH CH3 CH2

CH3
X CH2 CH2 Y
CH
(x=y) CH3
 SPIN ARRANGEMENTS
one neighbor one neighbor
n+1 = 2 n+1 = 2
doublet doublet

H H H H
C C C C

The resonance pattern (splitting) of a given hydrogen is

affected by the possible spins of its neighbor.
 SPIN ARRANGEMENTS
two neighbors one neighbor
n+1 = 3 n+1 = 2
triplet doublet

H H H H
C C C C
H H

The methine proton sees The methylene protons

all the spin states of the see the two spin states of
methylene protons the methine proton
SPIN ARRANGEMENTS
three neighbors two neighbors
n+1 = 4 n+1 = 3
quartet triplet

H H H H
C C H C C H
H H H H
 triplet = 2 adjacent hydrogens

singlet = 0 adjacent hydrogens

quartet = 3 adjacent hydrogens

 PASCAL’S TRIANGLE
The interior
entries are 1 singlet
the sums of
the two 1 1 doublet

numbers
immediately 1 2 1 triplet

above.
1 3 3 1 quartet

1 4 6 4 1 quintet

1 5 10 10 5 1 sextet

1 6 15 20 15 6 1 septet

1 7 21 35 35 21 7 1 octet
 THE COUPLING CONSTANT
H H
J
C C H

J J H H
J J
J

The coupling constant is the distance J (measured in Hz)

between the peaks in a multiplet.
J is a measure of the amount of interaction between the
two sets of hydrogens creating the multiplet.
 Some Representative Coupling Constants
(Lab text, p. 134)
H H
6 to 8 Hz three bond 3J
C C
H
trans C C 12 to 23 Hz three bond 3J

H
H H
cis C C 5 to 12 Hz three bond 3J

H
geminal C 0 to 2Hz two bond 2J
H

Hax Hax,Hax = 8 to 14
Heq Hax,Heq = 0 to 7 three bond 3J

Heq Hax Heq,Heq = 0 to 5

 Protons on Heteroatoms
Oxygen and Nitrogen
•Chemical shift is temperature and concentration
dependent

•Usually don’t show splitting because of rapid

exchange with other molecules

Amines d = 1-3
Alcohols d = 0.5-5
Phenols d = 6-8
Carboxylic Acids d = 10-13
General Approach to NMR Problems

1. If the formula is known, calculate the degree of

unsaturation (p. 140 of lab text)
U = ((2C+2)-H)/2
2. Examine the spectrum and look for the number of signals
• Tells you the number of types of protons
3. Integrate the spectrum
4. Use the chemical shift of each group to get an idea of the
functional groups
• Needs to be consistent with formula!!
5. Look for characteristic splitting patterns
6. Put it all together – find a structure consistent with all the
data
 Sample Problem 1

1. Unsaturation
C4H9Cl
2. No. of kinds of H d 0.9, triplet (3H)
d 1.4, sextet (2H)
3. Integration d 1.7, pentet (2H)
d 3.4, triplet (2H)
4. Types of H (d)

5. Splitting (n+1)

6. Identity
 Sample Problem 2

1. Unsaturation
C8H8O
2. No. of kinds of H
d 2.5, singlet (3H)
3. Integration d 7.2-7.8, 2 doublets (4H)
d 10.0, singlet (1H)
4. Types of H (d)

5. Splitting (n+1)

6. Identity
 Sample Problem 3

1. Unsaturation
C8H10O
2. No. of kinds of H d1.4, triplet (3H)
d 3.96, quartet (2H)
3. Integration d 6.9, multiplet (2H)
d 7.2, multiplet (3H)
4. Types of H (d)

5. Splitting (n+1)

6. Identity
MODERN INSTRUMENTATION
typical today

PULSED FOURIER TRANSFORM

TECHNOLOGY

FT-NMR
 Pulse Sequence
(Typical 1-dimensional pulse)

Relaxation delay Preparation time Detection time

Waiting for all the Excite the molecules Detect the signal
molecules to come with an Rf pulse
to equilibrium
(~5µs)

Time

About 2 seconds total

The entire sequence is often repeated hundreds

of times to increase the signal to noise ratio.
 PULSED EXCITATION
N

n2
n1
O
RF PULSE
CH2 C CH3
n3

S
All types of hydrogen are excited
simultaneously with the single RF pulse.
FREE INDUCTION DECAY

n1

O
CH2 C CH3 n2

n3
COMPOSITE FID
(“time domain“ spectrum)

n1 + n2 + n3 + ......
time
 Signal amplitude as a function
of time (composite FID)

Fourier Transform
“mathemagic”

Signal amplitude as a function

of frequency.