Proton Magnetic Resonance

Spectroscopy

Group Members
Mohammad Osama Bashir
Shafqat Ali
Kashaf Khaliq
Marukh Ameer
HNMR

Shafqat Ali
 Introduction

 PROTON MAGNETIC RESONANCE SPECTROSCOPY concerns with
nucleus of hydrogen whose spin quantum number is ½ giving rise to two spin
states in an applied magnetic field.
 Proton absorbs EMR from radio waves to undergo spin flipping and produce
an NMR
 It is a technique which is based on the absorption of electromagnetic radiation
in the radio frequency region 4-900 MHz by nuclei of the atoms
 The most common form of NMR is based on the hydrogen-1 (1H), nucleus or
proton.
  It can give information about the structure of any molecule containing
hydrogen atoms
 Introduction

 When a charged particle such as a proton spins on its axis, it creates a magnetic
field. Thus, the nucleus can be considered to be a tiny bar magnet.
  Normally, these tiny bar magnets are randomly oriented in space. However, in
the presence of a magnetic field B0, they are oriented with or against this
applied field.
 The energy difference between these two states is very small (<0.1 cal).
 The angular momentum of the spinning charge can be described in terms of
quantum number I,I/2,1,3/2,5/2….
 If the spin I=0,no spin and hence no HNMR phenomenon.
 Introduction

 The distribution of nuclear spins is random in the absence of an external
magnetic field. •An external magnetic field causes nuclear magnetic moments
to align parallel and antiparallel to applied field.
 Transition between spin states gives NMR line
 Hydrogen has spin quantum number I=1/2,
possible orientation is ,(2I+1) is two
,{+1/2 and -1/2}
 Chemical Shift

 Chemical Shift: Chemical shift is the difference between the absorption
position of the sample proton and the absorption position of reference standard.
 Variations of the positions of NMR absorptions due to the electronic shielding
and deshielding.
 Spin-spin coupling (splitting): It is the interaction between the spins of
neighbouring nuclei in a molecule may cause the splitting of NMR spectrum.
 
 3.1 Chemical Shifting Chemical Environments

Chemical… …Shifting
Chemical shift is the position of signals in NMR
spectra due to various chemical influences

…Environments
Chemical environment is the molecular arrangement
(environments) within the molecule.

existing around a given proton. The magnitude of a chemical

shift is determined by the
chemical environment of a
given proton.

The specific
arrangement of atoms H H H
within a given
molecule creates
unique chemical
Br
C C C Br

environments for
protons experiencing
an applied field. H H H
 3.1 Chemical Shifting

These specialized environments are a creation

of the influences of several factors:
Understanding the
chemical environment
is important in NMR
spectroscopy because
hybridization the chemical
environment influences
Electronegativity the positioning of the
proton signals in the 1H
Hydrogen-bonding NMR spectrum.

Induced magnetic fields

These factors affect chemical

environments by either interacting
Applied magnetic field with the electron density
surrounding the proton or the
Electron Density magnitude of the applied
magnetic field felt by the proton.
 3.1 Chemical Shifting

 
Induced Magnetic . . .
When nuclei are excited by an external applied field, the electrons surrounding the
nuclei produce individual magnetic fields that can oppose the applied field.

𝑒  −

The opposing field created is called an induced magnetic field.

. . . Fields
 3.1 Chemical Shifting

The presence of an induced magnetic field slightly diminishes the influence

The Shielding Effect

of the applied external field on a proton because of its anti-parallel magnetic
field.

  Induced magnetic field

𝑒  −

This interaction is known as the Shielding Effect.

What effect do induced magnetic fields have on the

interaction between the nucleus and the applied external
field?
 3.1 Chemical Shifting
When a circulating electron produces a magnetic field aligned with the external field, it
enhances the external field’s affect on the proton.
This is known as deshielding.

Anti-parallel

Enhanced
induced magnetic
field

𝑒  − 𝑒  −

𝐻𝑒𝑓𝑓
 

Shielding Deshielding

  The effective field, is the amount of the external field a proton feels in the presence of an anti-
parallel induced magnetic field.
 3.1 Chemical Shifting

The importance of the shielding effect causes This is due to absorption of hibher radio
protons to appear in a different location on the frequencies by strongly shielded protons
NMR spectrum in comparison to deshielded compared to lower radio frequencies
and unaffected protons. absorbed by deshielded protons. (chem.)

Shielded protons will appear upfield and deshielded protons will appear downfield.

Deshielded Shielded Unaffected

   
𝑒 −
𝑒− 𝑒−
     

5.0 4.0 3.0 2.0 1.0

Down field Up field

 3.1 Chemical Shifting

E Another aspect affecting the location of protons is electron density.

L
Electron density is monumental to NMR spectroscopy because it behaves like a
E barrier between the nuclei of protons and the applied external field.
C
T
R
O  
N
H H
D
E
N
S
I
T The more dense a molecule’s electron cloud is, the greater the applied external
field required to bring a proton into resonance .
Y
 3.1 Chemical Shifting

A greater density of the electron cloud will cause a proton to appear upfield in the
NMR spectrum.

Likewise, an electron cloud which is minimal will cause protons to appear

downfield on the NMR spectrum.

In addition to the affects of shielding, the extent of which a proton will appear
down field on the spectrum is also dependent on the magnitude of distortion in
the electron cloud.

H
H
H

5.0 4.0 3.0 2.0 1.0

Down field Up field

 3.1 Chemical Shifting

Electronegativity
H The magnitude of
influence bonded atoms
O have on a proton will be
H H
dependent on the extent
of the electronegativity
C C of the atom, or groups of
atoms, and the atom(s)
C C O
bonding position is in
respect to the proton.
H H

H C N O F
Increasing
 3.1 Chemical Shifting

The closer electronegative atom(s) are to a proton, the

greater the downfield shift of the proton.

O
H H
A proton located more than
three sigma bonds is too far
C C away to interact and therefore
H will not cause any downfield
3 1 O shift.
C C

H 4 H H 2 H

Therefore, protons on carbon 2 will feel a larger decrease in their electron density
than protons on carbon 3. Carbon 4 protons will not be affected.
THE REFERENCE STANDARD

Mohammad Osama Bashir
 The Reference Standard

Why there is need for reference standard?

 The absolute position of absorption' cannot be obtained directly from

the Spectrophotometer.
 Incapability of
Spectrophotometer

 The difference in the absorption frequencies of various Protons is very
small (up to a few hundred hertz) as compared to the absolute value of
the frequency (around 108 hertz).
 The NMR spectrophotometer therefore must be able to discriminate
frequencies of the order of one part in 108 for an accurate measurement
of the absorption position of protons in various environments. Because
the strength of the applied magnetic field cannot be determined to the
desired degree of accuracy. Thus, Spectrophotometer FAILS to do so.
 ‫گھبرانا نہیں ہے‬

 However, the position of absorption of various protons can be
determined with the desired accuracy, relative to some arbitrarily
chosen reference standard.
 Internal Reference
 External Reference
 Internal & External Reference
Standards

The internal reference compound is dissolved in the same
solution as the sample to be studied.
The external reference compound is usually placed in a small
concentric capillary contained within the sample tube.

 More reliable chemical shift values are

obtained with the internal reference standard,
as in this case the sample and the Reference
standard both experience the same magnetic field.
 Criteria of a Good Reference
Standard

 It should be chemically inert to most organic compounds.
 It should be miscible with most organic liquids so it can be added to the
sample solutions as an internal reference standard.
 It should have low boiling point so it can be easily removed to recover
the precious sample materials.
 All the protons should be magnetically equivalent, so it would give rise
to an intense single sharp signal even at low concentration.
 Trimethylsilane TMS
(CH3)4,Si

 Chemically Inert
 Miscible with most organic compound
 Boiling Point 27 C
 All protons are magnetically equivalent.
 Silicon is electropositive relative to carbon (electronegativity of silicon is 1.8 and
that of carbon is 2.5) and tends to donate electron density to the methyl groups,
increasing thereby the shielding of the methyl protons and causing them to absorb
upfield from most other protons commonly encountered in organic compounds.
Most protons will therefore absorb at downfield from the TMS signal arbitrarily
set at zero, and their chemical shift values will have the same sign (+ve for
convenience).
 TMS

 Silicon is electropositive relative to carbon (electronegativity of silicon is
1.8 and that of carbon is 2.5) and tends to donate electron density to the
methyl groups, increasing thereby the shielding of the methyl protons
and causing them to absorb upfield from most other protons commonly
encountered in organic compounds. Most protons will therefore absorb
at downfield from the TMS signal arbitrarily set at zero, and their
chemical shift values will have the same sign (+ve for convenience).
 Therefore, The standard reference compound used for most PMR
spectra is tetramethylsilane (TMS), (CH3)4,Si.
 DSS
2,2-dimethyl-2silapentane-5sulfonic acid

 TMS is not soluble in water thus in aqueous solutions it is used as
external reference.
 DSS is water soluble therefore it is used as an internal reference in
aqueous solutions.
GAMMA VALUE

Kashaf Khaliq
 Definition


“The
  value of chemical shift in parts per million (ppm are called gamma
value”
(ppm) =

 = The resonance frequency of the proton.

 = The resonance frequency of the TMS.
 = The operational frequency of the spectrophotometer.
The gamma value of a proton in a molecule will be the same regardless of
the operational frequency of the spectrophotometer.


For example : PMR spectra of 1,2,2-trichloropropane taken on 60 MHz and
100 MHz spectrophotometers.


 There are two types of protons:

 The methylene protons.
 The methyl protons.
Since the electron withdrawing chlorine atom withdraws the electron
density from the methylene protons. These protons are shielded less than
the methyl protons. The induced magnetic field is less at methylene proton
than at methyl protons. Therefore, the applied magnetic field must be
increased less for the methylene protons to achieve resonance than for the
methyl protons.
 
When the spectrum is run on 60 MHz spectrophotometer. The difference in
applied magnetic field for the two kinds of protons to be at resonance is
only about 0.0249 G which is equivalent to 106 Hz. The methylene protons
absorb at 240 Hz downfield whereas the methyl protons absorb at 134 Hz
downfield from TMS.
 
 Alternatively, we can keep magnetic field fix and vary the frequency of
the electromagnetic radiations. In this case the less the electronic
shielding of a proton, the higher the effective magnetic field at the
proton and the higher the frequency required to reach the resonance
condition. Thus, the spectrum obtain by increasing the frequency from
right to left will look exactly the same as obtained by the filed-sweep
operation. The methylene protons will appear at higher frequency than
the methyl protons the difference will be 106 Hz.

 
When the spectrum is run on 100 MHz spectrophotometer both kind of
protons absorb at different positions.
The larger magnetic field (23500 G) induces a larger electronic current
which in turn produce a larger induced magnetic field, causing a larger
shielding of a proton. The difference in shielding of two types of proton is
also proportionately larger. Resulting in a larger separation of the two
absorption peaks. The methylene protons in this case appear at 400 Hz
downfield. Whereas the methyl protons appear at 223 Hz downfield from
TMS.

 Conclusion

  The chemical shift values in Hz of both kind of protons are different
when determined with different spectrophotometer. However, the
gamma values come out to be the same.

 at 60 MHz = or 4.00 ppm

 at 100 MHz = or 4.00 ppm
 
 

 at 60 MHz = or 2.23 ppm

 at 100 MHz = or 2.23 ppm
 Drawback

 One drawback in the gamma scale is that the higher number of gamma
value implies resonance at lower field.
Spin-Spin Splitting & Coupling

Marukh Ameer
 Introduction

• The simplest atom HYDROGEN is found in almost all organic
compounds that is composed of single proton and single electron.
• For the purpose of NMR ,the key aspect of hydrogen atom is its
ANGULAR MOMENTUM PROPERTIES that resemble classical
spinning particles.
• Spinning hydrogen nucleus generates magnetic field and possesses a
magnetic moment µ, just as charge moving in a circle.
• The NMR experiment exploits the magnetic properties of nuclei to
provide information on molecular structure.
 Multiplicity Of Absorption
Signal

 MULTIPLICITY;
• The number of peaks into which the absorption signal of a particular proton splits , is
called multiplicity.
• It depends on number of neighboring protons.

 PEAKS;
• SINGLET; each single peak is referred as singlet
• DUPLET; spectra may be split into two peaks called duplets
• TRIPLET; three peaks
• QUARTRET
• And so on …
 By examining the structure of 1,1,2-tribromoethane, we might expect
only two single peaks that corresponds to two different types of
hydrogen. However, what we see is slightly different. Instead of two
singlet peaks, each peak consists of multiple lines.


 
 The signals for Hb consists of a doublet and that for Ha consists of a
triplet. The splitting of the peaks into multiple peaks is called spin-spin
coupling which is the direct interaction between the neighboring
hydrogen nuclei.
 The chemical shift of Ha is affected both by it’s own density and also by
neighboring hydrogen.
 Each one of nuclei can spin either one of two ways: spin up (+1/2) or
spin down (-1/2). Since there are two Hb nuclei, there are 4 possible spin
combination around Ha atom. ( ), ( ), ( ) or ( ).
 Net magnetic field of Ha hydrogen can be modified by each one of the
different combination . Two identical combination sums up to give
higher intensity.
 Pascal Triangle And N+1 Rule

 PASCAL TRIANGLE;
 Graphical device used to predict the ratio of heights of lines in a
split NMR peaks
n+1 RULE;
 Used to predict the multiplicity
 ‘ n’ shows no. of H-atoms in surroundings


Hence 1,1,2-tribromoethane will give a TRIPLET

 Coupling Constant

 The spacing between the peaks in multiplet is called the coupling constant.
 Represented by; J
 Unit; Hertz (Hz)
 It shows;
How strongly the nuclear spins influence each other .
 J value is same regardless of the applied magnetic field strength of NMR
magnet . This is because the strength of magnetic moment of a neighboring
proton, which is the cause of spin-spin phenomena does not depend on the
applied field.
 FOR 1,1,2-tribromomethane spectrum, two sub peaks are separated by 6.1Hz