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Instrumental Analysis

NUCLEAR MAGNETIC RESONANCE II

Dr. Nermin Salah


12th Lecture
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Objectives

Magnetic Shielding

Chemical Shift

Factors Affecting Chemical Shift


Inductive Effect by Electronegative Groups
s-character (Hybridization Effect)
Magnetic Anisotropic Effect
Hydrogen Bonding

Equivalent and Nonequivalent Protons

Integration of NMR Signal

Spin-Spin Splitting (Spin-Spin Coupling)


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MAGNETIC SHIELDING

NMR would not be very valuable if all protons absorbed at the


same frequency.

Different protons usually absorb different radiofrequencies ( ).

The electrons in a bond shield the nuclei from the magnetic field.
A moving charge (electron) creates a magnetic field, and the field
created by the moving electrons opposes the applied magnetic
field Bo.

The electrons in a bond shield the nuclei from the magnetic field.

The more electron density around a proton, the more the


shield, the lower magnetic field affecting the proton ,
The less electron density , the less the shield , the
higher magnetic field.

Z
C

This represents the electron density of a C-H bond. How much electron
density is on the proton depends on what else is attached to the carbon. If Z
is an elelctronegative atom, the carbon becomes electron deficient and pulls
some of the electron density away from the H. if Z is an electron donating
group, more electron density ends up on the H.

Shielded Protons
The effective magnetic field, therefore, what the hydrogen
nuclei actually sense through the surrounding electronic
environment is always less than the actual applied magnetic
field B0.
Beffective = Bapplied Blocal

In the classical NMR experiment, magnetic field strength must be5


increased for a shielded proton to flip at the same frequency.

Low external applied field

Higher external applied field


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Protons in a molecule

upfield
Lower frequency

downfield
higher frequency

The CHEMICAL SHIFT


The chemical shift is a field independent value.
Chemical shift is : the difference in frequency between the sample and
the standard over the operation frequency.

parts per
million

chemical
shift

shift in Hz
=
spectrometer frequency in MHz

= ppm

This division gives a number independent


of the instrument used.
A particular proton in a given molecule will always come at the same
chemical shift (constant value).
Of course, we dont do any of this, its all done automatically by the
NMR machine.

Tetramethylsilane (TMS)
CH3
H3C

Si CH3
CH3

TMS is added to the sample as internal standard.


TMS protons are all identical, highly shielded providing a single
sharp peak always isolated from peaks of interest. The TMS was
assigned .
Organic protons absorb downfield (to the left) of the TMS signal.
TMS is inert , highly soluble in organic liquids and easily removed
from samples by distillation.

FACTORS AFFECTING CHEMICAL SHIFT


Four major factors account for the resonance
positions (on the ppm scale) of most protons
1. Deshielding by electronegative elements
Inductive effect by electronegative groups
2. s-character (hybridization effect)
3. Magnetic Anisotropic effect (magnetic fields usually
due to -bonded electrons in the molecule(
4. Hydrogen bonding.
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1. DESHIELDING BY ELECTRONEGATIVE
ELEMENTS

Cl

electronegative
element

Chlorine deshields the proton,


that is, it takes valence electron
density away from carbon, which
in turn takes more density from
hydrogen deshielding the proton.

NMR CHART

deshielded
protons appear
at downfield
(higher )

highly shielded
protons appear
at upfield
(lower )

deshielding moves proton


resonance to lower field and higher

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ELECTRONEGATIVITY DEPENDENCE OF
CHEMICAL SHIFT

Dependence of the Chemical Shift of CH 3X on the Element X


Compound CH3X
Element X
Electronegativity of X
Chemical shift

most
deshielded

CH3F

CH3OH

CH3Cl

CH3Br

CH3I

CH4

(CH3)4Si

Cl

Br

Si

4.0

3.5

3.1

2.8

2.5

2.1

1.8

4.26

3.40

3.05

2.68

2.16

0.23

TMS
deshielding increases with the
electronegativity of atom X

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SUBSTITUTION EFFECTS ON CHEMICAL SHIFT

most
deshielded

most
deshielded

Cumulative Effect

CHCl3 CH2Cl2 CH3Cl


7.27
5.30
3.05

CH2Br
3.30

CH2CH2Br
1.69

The effect
increases with
greater numbers
ppmof electronegative
atoms.

CH2CH2CH2Br
1.25

The effect decreases with increasing


distance from the electronegative
atom. The effect completely vanished
at the fourth bond from the
electronegative atom.

13

pp

2. s-CHARACTER
(HYBRIDIZTION OF CARBON ATOM)

14

As s-character of carbon atom increases, the electronic cloud is


held more closer to the carbon and provides less electron density
for shielding of protons, and thus the chemical shift, , increases
(shifted downfield).
According to the above reasoning, the following trend for the
chemical shift is expected:

expected to be observed
at > 7
(down field - higher )

But in fact, we have the following order:

actually observed
at = 2-3

This suggested that other factors than the sp character of


carbon might affect the chemical shift in this case. The above
discrepancy can be explained by what is called Magnetic
Anisotropic Effect.

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3. MAGNETIC ANISOTROPIC FIELDS


DUE TO THE PRESENCE OF -BONDS

The presence of a nearby pi bond or pi system


greatly affects the chemical shift.

Induced magnetic fields due to the - electrons h


greatest effect.
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Aromatic protons
= 7-8 ppm

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Vinyl (Olefinic) protons,


= 5-6 ppm

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Acetylene protons
2.5 ppm

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Aldehyde proton
= 9-10 ppm

Electronegative
oxygen atom

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4. HYDROGEN BONDING
O-H and N-H Signals
HYDROGEN BONDING DESHIELDS PROTONS
R
O

H
O
R

H
H

O R

The chemical shift depends


on how much hydrogen bonding
is taking place (observed in high
concentrated solutions).
Hydrogen bonding lengthens the
O-H bond and reduces the valence
electron density around the proton
it is deshielded and shifted
downfield in the NMR spectrum.

Alcohols vary in chemical shift


from 0.5 ppm (free OH) to about
5.0 ppm (lots of H bonding).

D2O-exchangeable (peak for OH proton


in alcohol and NH in amines disappears
upon shaking with D2O)
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SOME MORE EXTREME EXAMPLES


-

+
-I

Carboxylic acids have strong


hydrogen bonding - they
form dimers.
-

Resonance, electronegativity of oxygen and the formation of


hydrogen bonding withdraw electron cloud from the acid
protons.
Thus, protons attached to carboxylic acids are the least
shielded protons and have a chemical shift of 10-12 ppm.

H3C O

H
O

In methyl salicylate, which has strong


internal hydrogen bonding, the NMR
absorption for O-H is at about 14 ppm,
(highly downfield(

Notice that a stable 6-membered ring is formed

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NMR CORRELATION CHART


Chemical shift gives the electronic environment of protons
(Shielding and Deshielding)
PROTON IN
ELECTRON-POOR
ENVIRONMENTS

disappears upon shaking


with D2O

-OH -NH

aromatic

DESHIELDED
DOWNFIELD
HIGHFREQUENCY
LARGE

SHIELDED
UPFIELD
LOWFREQUENCY
SMALL

0 - 5

CHCl3 , H
3 - 5
7-8

10-12

1.5 - 3
4.5 - 7

9-10
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PROTON IN
ELECTRON-RICH
ENVIRONMENTS

H
RCOOH

RCHO

C=C

acid

aldehyde

olefinic
sp2

TMS

0 2
4

CH2Ar
CH2F
C-CH-C
CH2NR2
CH2Cl
C
CH2S
CH2Br
C-CH2-C
C C-H
CH2I
C=C-CH2 C-CH3
CH2O
sp3
CH23NO2 CH23-Csp
sp sp O

(ppm)

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EQUIVALENT AND NONEQUIVALENT


PROTONS
All
of the protons in a molecule which are in
chemically identical environments will often
exhibits the same chemical shift i.e., shows
one signal in NMR spectrum at the same
value of .

The protons in this case are said to be


chemically equivalent

On the other hand, molecules which


have sets of protons which are
chemically distinct (have different
chemical environments) from one
another give rise to different
absorption signals from each other.

Chemically nonequivalent protons

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INTEGRATION OF A PEAK
Not only does each different type of hydrogen give a
distinct peak in the NMR spectrum, but we can also tell
the relative numbers of each type of hydrogen by a
process called integration.

Integration = determination of the area


under a peak
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In the NMR spectrum, the area under each peak is proportional to the
number of hydrogens generating that peak.
The NMR spectrometer has the capability to electronically integrate
the area under each peak.

The integrated area


measured by a ruler are
5 : 2.5 : 22

Divide by the smallest


number give us the
simplest ratio of 2 : 1 : 9

Note that the integration


gives only ratios, not
absolute values for the
number of the hydrogen
present in the sample

2,2-dimethyl-1-propanol (C4H12O)

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Modern spectrometers
automatically print out the
integrals as numbers on
the spectrum

NMR spectrum can reveal the number of protons assigned for each
signal
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Integral lines : no. of protons in each signal

SPIN-SPIN SPLITTING

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SPIN-SPIN SPLITTING
Often a group of hydrogens will appear as a multiplet
rather than as a single peak.
Multiplets are named as follows:
Singlet (s)
Doublet (d)
Triplet (t)
Quartet (q)

Quintet (quin)
Sixtet (six)
Septet (sept)
Multiplet (m)

This happens because of interaction with neighboring


hydrogens and is called
SPIN-SPIN SPLITTING
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Spin-spin coupling

1,1,2-Tribromoethane
Nonequivalent protons on adjacent carbons.

Chapter 13

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THE ORIGIN OF
SPIN-SPIN SPLITTING
HOW IT HAPPENS
Spin-spin splitting arises because hydrogen on
adjacent carbon atoms can sense one
another

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Doublet
1 adjacent proton

Chapter 13

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Triplet
2 Adjacent Protons

Chapter 13

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n+1
RULE peak
this hydrogens
is split by its two neighbors

these hydrogens are


split by their single
neighbor

H
two neighbors
n+1 = 3
triplet

MULTIPLETS

singlet
doublet
triplet
quartet
quintet
sixtet
septet

one neighbor
n+1 = 2
doublet

Where n is the number of EQUIVALENT protons on


Adjacent carbon atoms

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EXCEPTIONS TO THE n+1 RULE


IMPORTANT !
1)

Protons that are equivalent by symmetry usually do not split


one another
X CH2 CH2 Y
X CH CH Y
splitting if x y
two triplets

no splitting if x = y
2)

Protons in the same group usually do not split one another

H
C H
H

H
or

C
H

3) Splitting is not observed if the protons are separated by


more than three bonds

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INTENSITIES OF MULTIPLET PEAKS


PASCALS TRIANGLE
Intensities of
multiplet peaks

1
1 1
1 2
1
1 3 3 1

singlet

doublet

triplet
quartet
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NMR spectrum indicates the carbon skeleton


Spin-spin splitting gives the number of equivalent
protons on adjacent carbon atoms

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Summar
y
INFORMATION WE CAN GET FROM NMR SPECTRUM
Number of 1H-NMR signals = Number of kinds of
protons.

Chemical shift gives the electronic environment of


protons
(Shielding and Deshielding).
NMR spectrum can reveal the number of protons
assigned for each signal (integral lines : no. of protons in
each signal).
NMR spectrum indicates the carbon skeleton Spin-spin
splitting gives the number of equivalent protons on
adjacent carbon atoms.
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Typical Values

Note that these are typical values and that there


are lots of exceptions!

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Resources and references


Textbook: Principles of Instrumental Analysis,
Skoog, Holler, Nieman
Recommended further reading:
Principles of instrumental analysis, 5th ed. by
Skoog, Holler, Nieman Chapter 19.
Extra resources are available on the intranet.
Relevant web sites
http://www.chemguide.co.uk/analysismenu
.html

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