NMR Spectroscopy in Organic Chemistry

Course # CHM-745

Instructor: Dr. Habib-ur-Rehman

M U S T
WISOM & virtue
 Comparison
Comparison of Atomicof and
Atomic and Molecular
Molecular Theories
Theories
Theory Atomic Structure Molecular Structure
Localized Delocalized Coordinate Complexes
Planer 3-Dimensional
Democritus (400 BC) √??????? X X X X

Dalton (1800) √??????? X X X X

Quantum (1899) √?????? X X X X
Thomson (1903) √????? X X X X
Rutherford (1911) √???? X X X X

Bohr (1913) X X X X
√???
Werner (1925) X X X √ X
Valence Bond (1928) √ √ √ X X
With Resonance
Crystal Field (1929) X X X √ √
Molecular Orbital (1930) √ √ √ √ √
m/e = H2r2/ 2V Mass Equation

‘m/e’ is mass to charge ratio

‘H’ is magnetic field strength
‘R’ is radius of deflection
‘V’ is accelerating voltage
This equation governs the behavior of an ion in the mass analyzer portion of mass
spectrometer. The relation shows that for an ion of given m/e the radius of
deflection “r” can be increased either by increasing accelerating voltage “V” or
by decreasing magnetic field strength “H”.

Slight increase in “V’ will cause the radius of deflection of all the ions to
increase; thus the ions of correct m/e will no longer pass through the slit and into
the collector but ions of smaller m/e.
UV Equation log (Io / I) = A = ε.c.l.

where “A” is optical density (OD) or the absorbance (A).

“Io” is intensity of the light incident upon the sample cell or the
intensity of light after passing through the reference cell.

“I” is intensity of the light leaving the sample cell

“ε” is molar absorptivity. “c” is concentration in moles per liter.

“l” is cell length in decemeter.

The molar absorptivity (formerly known as molar extinction
coefficient) is a property of the molecule under going an electronic
transition and is not a function of the variables parameters involved in
preparing solution. The absorptivity is controlled by the size of the
absorbing system and by the probability that the electronic transition
will take place.

The absorptivity may range from 0 -106. Values above 104 are termed
high intensity absorption while values below 103 are termed low
intensity absorptions.

Forbidden transitions have absorptivities in the range from 100-1000.

The medium intensity = 103-104.
The vibrational frequencies of a bond may be related to the masses of the
vibrating atoms of the force constant “f” of the vibrating bond.
________________
υ = 1/2 π c √ f (m1 + m2) / m1m2 IR Equation

where ‘υ’ is frequency ‘c’ is velocity of light

‘m1’ is mass of atom 1in gram ‘m2’ is mass of atom 2 in gram
‘f’ is force constant
_____
υ = 1/2 π c √ f / μ
where ‘μ’ = m1m2 / m1 + m2 or M1M2 / (M1 + M2) (6.02 x 1023)
masses of atoms in amu
Removing Avogadro's number from the denominator of reduced masses;
_____ _____
we get υ = 7.76 x 1011 / 2 π c √ f / μ υ = 4.12√ f / μ

where ‘f’ is force constant in dynes/cm i.e. the force acting per centimeter

μ = M1M2 / (M1 + M2) where M1 and M2 are atomic weights.

This equation corresponds to a simple Hooks Law model of two units coupled by
a spring in which the force constant is the restoring force provided by the spring.

The larger the force constant, the higher the vibrational frequency and greater will
be the energy spacing between vibrational quantum levels. The force constant for
single, double and triple bonds are approximately.

5 x105, 10x105 and 15x105 dynes. cm-1

The most important spectroscopic tool, NMR gives information about the
number of each type of hydrogen. It also gives information regarding the
nature of the immediate environment of each of these types of hydrogen atoms.

NMR spectroscopy differs from other spectroscopic techniques in that, the

difference in energy states (spin states) being examined are created by
magnetic field. That, a molecule is placed between powerful magnetic field to
create different energy states (spin states), which are then detected by
absorption of light of appropriate energy. In the absence of magnetic field, the
different states all have nearly the same energy.
Nuclear Spin States: The motion involved in NMR spectroscopy is of
nuclear spin. Many atomic nuclei behave as if they were spinning. Since
they are positively charged; a moving charge +ve or –ve is associated with
magnetic field. The spinning nuclei behaves as they were tiny bar magnet,
i.e., such nuclei have magnetic moments. In fact, any atomic nucleus which
possesses either an odd mass number or odd atomic number or both, has a
quantized spin angular momentum and a magnetic moment.

(atomic number) 6

C
(mass number/ atomic mass/ weight) 12
Among the more common nuclei which possess spin: 1H1, 1H2, 6C13, 7N14, 8O17
and 9F19. Nuclei of the ordinary (most abundant) isotopes; 6C12 and 8O16 do not
possess spin property, as their individual pairs of protons and neutrons have
opposed spins so that net spin of the nucleus is zero (many nuclei have zero spin).

All even-even nuclei; those having an even number of protons and even number of
neutrons are in this important class). For each of the nuclei with spin, the number of
allowed spin states which it may adopt is quantized and is determined by its nuclear
spin quantum number, I, a physical constant for each nucleus.

For a nucleus of spin quantum number I, there are 2I+1 allowed spin states, which
range with integral difference from +I to -I;

-I, (-I+1), …………………, (I -1), I

In those nuclei where the magnitude of spin is not zero, the nuclear spin quantum
number I, may assume any of the values; 1/2, 1, 3/2, 2 etc. We will consider the
nuclei have spin +1/2 e.g. H, C & F.

A proton (hydrogen nucleus) has I = 1/2, has two allowed spin states, [2 (1/2) +1 = 2]
for its nucleus e.g. -1/2 and +1/2. For chlorine I = 3/2, there are four spin states
[2 (3/2) + 1 = 4] for its nucleus e.g. -3/2, -1/2, +1/2 and +3/2.

Elements: : H H C C N O O F P Cl

Nuclear spin quantum number: 1/2 1 0 1/2 1 0 5/2 1/2 1/2 3/2

Number of spin states : 2 3 0 2 3 0 6 2 2 4

All nuclei carry a charge, thus possess spin a angular momentum. The moment
of spin angular momentum is quantized, i.e., only those nuclei which have a
finite value of spin quantum number (I > 0) will precess along the excess of
rotation. The spin quantum number is associated with mass number and atomic
number of nuclei.

Mass number Atomic number Spin quantum number

Odd Odd or Even 1/2, 3/2, 5/2,….

Even Even 0 …………………….

Even Odd 1, 2, 3, …...

Rotational Spectra: Atomic nuclei spin about their axis. Nuclei are composed
of proton and neutrons, the protons have charge and neutrons are neutral
magnetic properties occur with those nuclei which have:

Odd atomic and odd mass number e.g., 1 H, 15 N, 19 F

1 7 9
Odd atomic number and even mass number 1 H(D), 14 N
2 7
Even atomic number and odd mass number 13 C
6

Nuclei which have no magnetic moment are those with even atomic and even
mass number; 126C, 168O, ---------- particle in such nuclei is paired. There is no
resultant spin and hence no magnetic moment in these nuclei where the I = 0,
the nuclear spin quantum number “I” may have the values 1/2, 1, 3/2, 2, etc.
In the absence of an applied magnetic field, the spin states of a given nucleus are
nucleus are of equivalent energy (degenerate) all of the spin states should be
almost equally populated, with equal number of atoms having each of the allowed
spin e.g., Nuclear spin can have only two alternative values associated with the
quantum numbers +1/2 (α) and -1/2 (β). Nuclear magnetic moment with no
magnetic field.
When these nuclei are placed in a magnetic field, their magnetic moments tend
either to align with the field (corresponding to “α”-spin) or against the field
(corresponding to “β”-spin);

If the system is irradiated with light of the proper frequency or wavelength, a

nucleus with “α”-spin can absorb a light quantum and converted to higher energy
“β”-spin states, the process called a “flipping of spin”.
Nuclear Magnetic Moment: Spin states are not of equivalent energy in an applied
magnetic field, the nucleus is a charged particle and any moving charge generates
a magnetic field of its own. Thus, the nucleus has a magnetic moment (µ)
generated by its charge and spin.

A hydrogen nucleus may have a clockwise (+1/2) or a counter clockwise (-1/2)

spin, and the nuclear magnetic moment (µ) in the two cases are in opposite
direction.

In an applied magnetic field, all protons have their magnetic moments either
aligned with the field or opposed to it.
The two Allowed Spin States for a Proton
Hence as an external field is applied, the degenerate spin states split into two
states of unequal energy.

The spin states of a proton both in the absence and in the presence of an applied magnetic field
In case of chlorine nucleus there will four energy levels, the +3/2 and -3/2 spin
states are aligned with the applied field and apposed to the applied field
respectively. The +1/2 and -1/2 spin states have intermediate orientation

Spin States of a Chlorine Atom both in the Presence and in the Absence of an Applied Magnetic Field
Absorption of Energy: The NMR phenomenon occurs when nuclei aligned with the
applied field are induced to absorb energy and change their spin orientation with respect
to the applied field.

The energy absorption is a quantized process and the energy absorbed must equal the
energy difference between the two states involved.

Eabsorbed = (E -1/2 state - E +1/2 state) = h υ

This energy difference is a function of the applied magnetic field, Ho e.g., the
energy difference involved is proportional to the magnetic field strength. The
stronger the applied magnetic field, the greater the energy difference between
the possible spin states.

∆E = f Ho

The NMR Absorption Process for a Proton

The magnitude of the energy level separation also depend on the particular nucleus involved.
Each nucleus (1H or 35Cl etc.) has a different ratio of its magnetic moment to its angular
momentum (since each has different charge and mass). This ratio, called the magnetogyric ratio,
γ, is constant for each nucleus and determines the energy dependence on the magnetic field
∆E= f (γHo) = h υ

Since the angular momentum of the nucleus is quantized in units of h/2π, the final
equation takes the form:

∆E = γ (h/2π) Ho = h υ

Solving the equation for the frequency of the absorbed light γHo = 2π υ

or υ = (γ /2π) Ho
To understand further: Consider a spinning top, spinning axis of the top
moves slowly around a vertical. This is precessional motion and the top is said
to be precessing around the vertical axis of earth’s gravitational field.

The precession arises from the interaction of spin with earth’s gravity acting
vertically downward. It is called gyroscopic motion.

It has been found that the proton (tiny magnet) precesses around the axis of the
external magnetic field in the same manner in which a spinning gyroscope
precesses under the influence of gravity. It has been found that;
 ω = γ Ho

where “ω” is the angular precessional velocity

“Ho” is applied field in gauss

“γ” is gyro magnetic ratio = 2π µ / hI

“µ” is magnetic moment of the spinning bar magnet.

“I” is spin-quantum number. of the spinning magnet.

“h” is Plank’s constant.

The magnetogyric ratio of the nucleus is the ratio of the angular momentum
(from the rotating nuclear mass) and the magnetic moment (from the rotating
nuclear charge) and is characteristic and different for each nucleus.

Fundamental NMR equation correlates electromagnetic frequency with

magnetic field:

γ Ho = 2π υ

Where “υ” is frequency of electromagnetic radiations, “υ” is called precessional

frequency.

Thus angular precessional velocity ω = 2π υ

 γ Ho = ω as ω = 2π υ

The frequency of the absorbed light = υ = (γ/ 2π) Ho:

The NMR Equation (The Felix Bloch Equation describe the behavior of
nuclear spin in a magnetic field under the influence of radiofrequency
pulses). The relationship between the frequency of the radiation υ and the
strength of the magnetic field Ho.
For the proton “γ” has the value 2.6752 x 104 radians. sec-1. tesla-1 when, Ho is
given in units of gauss,

“υ” in cycles per sec or Hertz (Hz)

As the energy difference involved is proportional to the magnetic field. The

energy difference between α and β-spin states for an isolated hydrogen atom in a
magnetic field of 14,092 gauss is given by;

υ = 26,752 x 14092/ 2π = 60 x 106 = 60 MHz

The precessional frequency may be defined as the number of revolutions per
second made by the magnetic moment vector of the nucleus around the external
field Ho, or the precessional frequency of the nucleus may be defined as equal
to the frequency of the electromagnetic radiations in megacycles per second
necessary to induce a transition from one spin state to another

The energy difference between “α” and “β” spin states in the magnetic field is
proportional to the magnetic field with proportionality constant that is
characteristic of the nucleus.

The frequency of 60 MHz corresponds to a wave length of 500 cm and is in the

radiowave region of the electromagnetic spectrum.
The 60 MHz NMR spectrometer was common and instrument with large
field strengths in which the proton “flip” corresponds to 100, 220, 300,
360, 400 and 500 MHz.

If the correct value of “γ” for the proton is substituted, one finds that
unshielded proton should absorb radiation of “υ” 42.6 MHz in a field
strength of 10,000 gauss or radiation of υ= 60.0 MHz in a field strength
of 14,100 gauss.
For a proton, if the Ho = 14,100 gauss, the ∆E will be 5.72 x 10-6 K.cal/mole.
Radiation with a frequency of υ~ 60MHz, corresponds to this ∆E. Other nuclei
have ∆E value between their spin states which are both larger and smaller then
those for hydrogen.

The most common NMR spectrometer apply a variable magnetic field ~ 14,100
gauss and supply a constant RF of 60 MHz, effectively able to induce transitions
only among proton spin states in a molecule and are not useful for other nuclei.

Usually, separate instruments are required to observe transitions in other nuclei.

Some of the modern instruments are equipped to observe several different nuclei.
The Mechanism of Absorption (Resonance): The NMR involves the
interaction between an oscillating magnetic field of electromagnetic radiation
and the magnetic energy of the hydrogen nucleus or some other type of nuclei
when these are placed in an external static field.

The sample absorbs electromagnetic radiation in radio-wave region at different

frequencies since the absorption depends upon the type of protons or certain
nuclei in the sample.
To understand the nature of the spin transition. Consider a “spinning top”. If a
proton is placed in a magnetic field. Energy is absorbed by protons because of
the fact that they begin precess in an applied magnetic field. As a spinning for
owing to the influence of the earth’s gravitational field, the top begins to
“wobble, or precess, about its axis
A spinning nucleus will behave similarly under the influence of an applied
magnetic field. When the magnetic field is switched on, the nucleus will begin to
precess about its own axis of spin with an angular frequency ω.

The frequency at which a proton will process is directly proportional to the

strength of the applied magnetic field. The stronger the field the faster the rates
(angular frequency ω) of precession.

For a proton, if Ho = 14100 gauss ω ~ 60MHz. e.g. in a field of 14,092 gauss the
energy required to cause “flipping” corresponds to 60 MHz.
If a proton is placed in a magnetic field, then it starts processing at a certain
frequency in the radiowave region and that take one of the two orientation.

Alignment with the field.

Alignment against the field.

If a proton is processing in the aligned orientation it can pass into the opposed
orientation by absorbing energy. From the high energy opposed orientation,
it comes back to the low energy aligned orientation by losing energy. The
transition from one energy state to the other is called “flipping” of proton.
The energy required to bring about the transition (∆E = hυ) or to flip the
proton depend upon the strength of the external field.
Stronger the field, greater will be the tendency of the nuclear magnet to remain
lined up with it and higher will be the frequency of the radiation needed to flip the
proton to higher energy state.

Since the nucleus has a charge, the precession generates an oscillating electric field
of the same frequency. If RF waves of this same frequency are supplied to the
precessing proton, the energy can be absorbed e.g. if we irradiate the precessing
nuclei with a beam of electromagnetic radiation of desired frequency, then the low
energy nuclei will absorb and move to high energy state.

The precessing proton will absorb energy from the RF source only if the precessing
frequency is the same as the frequency of the RF beam, i.e., when the quantum
energy (hυ) of electromagnetic radiation matches up the energy difference between
the two energy states.
When this occurs the nuclei and the RF beam are said to be “in resonance”. Hence the
term nuclear magnetic resonance (NMR); that is, when the frequency of the
oscillating electric field component of the incoming radiation just matches the
frequency of the electric field generated by the precessing nucleus, the two fields can
couple, and energy can be transformed from the incoming radiation to the nucleus,
thus causing spin change. This condition is called “resonance”, and the nucleus is
said to have resonance with the incoming electromagnetic wave.

The NMR Process; Absorption Occur Where υ=ω

This technique consists in exposing the protons to a powerful external field.
The different protons in a molecule will precess at different frequencies.

Now, we irradiative these precessing protons with steadily changing

frequencies and observe the frequencies at which the absorption occurs.

It is common to keep the RF constant and the strength of the magnetic field is
constantly varied. At some value of the field strength the energy required to
flip the protons matches the energy of the radiation.
NMR Spectrum: All protons do not absorb at the same applied field but the
absorption depends upon the magnetic field which a particular proton feels. Thus
the effective field strength is different for different sets of protons, as one set of
protons will have slightly different environment from any other set of protons.

Thus at different RF different protons will require slightly different applied field
strengths to produce the same effective field strength which causes absorption.
Absorption occurs and the signal is observed, such a spectrum called NMR
spectrum.

In the NMR spectrum we measure applied field strength for each set of protons
and the absorption peaks are plotted. The number of signals at different applied
field strength is equal to the different sets of protons.
A Schematic Representation of the NMR Process
The NMR Spectrum of an Ordinary Ethanol Sample
tThere are two types of protons in the organic molecule:
Chemically Equivalent: Protons are those which occupy chemically equivalent
positions i.e., are in identical chemical environments. Such protons have same
chemical shift. A simple test for chemically equivalence of two or more protons is
to replace each proton one at a time by a substituent “Z” and if by doing so the
same compound (or its mirror image) is obtained, then these protons are
chemically equivalent.
For example: CH3 – CH3

Replacement of one proton one at a time showed that the 3 protons on each carbon
are chemically equivalent, have same chemical shift and consequently there is no
splitting with in a CH3 group and none due to coupling between the groups.
Magnetically Equivalent: A group of 2 or more protons are said to be magnetically
equivalent when not only do they have the same chemical shift, i.e., are chemically
equivalent, but also the set of coupling constants to all other protons is identical for
each member of the group.

For example; 1-bromo-1-chloro-ethane

Ha and Hb are chemically equivalent also are Hc and Hd (for each
pair chemical environment are same).
Br

Hd Hc

Ha Hb
Cl

The Jad and Jbd however are not equal; hence Ha and Hb are not magnetically equivalent.
“J” decreases very rapidly with increase in the number of bonds connecting the protons.
 H H
H H
C
C C
Geminal protons Vicinal protons

A coupling between protons on adjacent carbon atom is called vicinal coupling

(vicinal meaning neighbor) while geminal (geminal, meaning twin) when they are on
the same carbon.

A HaHb or Hc Hd couple with splitting only if there environments are different. If

coupling occurs through 4 or more bonds, referred to as long range coupling, usually
negligible for saturated compounds but may be large in unsaturated compounds.
In addition to depending on the number of intervening bonds, “J” is also angular
dependent, e.g. its magnitude varies with the angle between the methylene
protons (when these are not chemically equivalent), and the dihedral angle for
vicinal hydrogen.

If we take the eclipsed conformation, the CH2Br kept stationary and then CH2Cl
group is rotated until the Cl and Br and consequently HaHc and HbHd are in line,
eclipsed conformation, the dihedral angle is zero (0º).
It has been found that the value of “J” for a given pair of vicinal hydrogens,
depends on the dihedral angle (angle of rotation), being largest when the
angle is 0º or 180º and very small (or zero) when the angle is 90º.

Thus, since the dihedral angle for Ha Hd is 60º and that for Hb, Hd is 180º,
“J” for the later is larger than that for the former.

Hence, the “Js” for Ha and Hb with Hd are different. Thus Ha and Hb are not
magnetically equivalent.
J = c Cos2 φ - 0.28 where “c” is a constant

(i) c = 8.5 Hz for 0º < φ <90º (ii) c = 9.5 Hz for 90º < φ < 180º

A better relationship was latter proposed by Karplus;

J = 4.22 - 0.5 Cos φ + 4.2 Cos2 φ

All magnetically equivalent protons are chemically equivalent but not all
chemically equivalent protons are magnetically equivalent.

The Karplus equation (1959) on the basis of valence bond calculation showed
that the “J” for a vicinal pair of “H” atoms is a function of the dihedral angle
φ between the 2C–H bonds
Theory for the Transmission of Coupling: A given proton because of its
magnetic moment (due to spin) attracts the spins of the e-s forming the
covalent C-H bond.

This affects the spins of the C-C electron pair and this in turn affects the spins
of the e- pair in the adjacent C-H bond.

Thus the spin effect of one 1H are transmitted through the covalent bonds to
the other spinning proton.

Since these effects depends only on the structure and geometry of the
molecule and not due to the applied field, they are independent of the strength
of the applied field.
Transferring Spin Information Between Two Adjacent C-H Bonds
Definition of the Dihedral Angle ‘α’
The Nuclear Magnetic Resonance Spectrometer: The basic elements of in NMR
spectrometer are shown in figure. The sample is dissolved in a solvent having no
protons (usually CCl4) and a small amount of TMS as internal reference.

The sample cell (small cylindrical glass tube) which is suspended in the gap between
the faces of the pole pieces of the magnet. The sample is spun around its axis to
ensure that all parts of the solution experience a relatively uniform magnetic field.
Also in the magnetic gap is a coil attached to a 60 MHz RF generator.

Perpendicular to the RF oscillator coil is a detector coil. When no absorption of

energy is taking place, the detector will picks up none of the energy given off by the
RF oscillator coil..
When the sample absorbs energy, however, the reorientation of the nuclear
spin induces a RF signal in the plane of the detector coil, and the instrument
responds by recording this as a resonance signal or peak

The Basic Elements of NMR Spectrometer

 TMS
Lower field; down field

Absorption deshielding
higher field; up field

shielding
0

milligauss
Ho

p. p. m.
δ TMS = 0

α TMS = 0

υ TMS = 0

The typical NMR spectrometer uses a constant frequency RF signal and varies the
MFS to bring each proton in turn into resonance. As each type of proton comes
into resonance, it is recorded as a peak on the chart. It is only a matter of
instrumental design that the “Ho” is changed instead of the RF frequency.
Since highly shielded protons precess at a slower rate than relatively unshielded
protons, it is necessary to increase the field to induce them to precess at 60 MHz.
Hence, highly shielded protons appear to the right of this chart, and less shielded
protons appear to the left.

The region of the chart to the left is sometimes said to be downfield, and that to
the right up field. Varying the MF as is done in the usual spectrometer is exactly
equivalent to varying the RF frequency, and a change of 1 ppm in the MF
strength (increase) has the same effect as a 1 ppm change (decrease) in the RF
frequency.

Hence, it is only a matter of instrumental deign that the field strength is changed
instead of the RF frequency.
Some workers favor the τ scale because over the “δ” scale because higher
values of “τ” parallel higher field strengths and higher shielding.

Measurement of NMR spectra are normally carried out in liquids or solution

(5-20%). The best solvents that do not contain protons, CDCl3, CCl4 etc.

However, because of solubility problems the solvents curtaining protons may

also be used.
 CH 3

CH 2

OH

CH 3 CH2 OH
TMS

10 9 8 7 6 5 4 3 2 1 0
LR-NMR

CH 3

CH 3CH2 OH

CH
2

OH

HR-N MR
Appearance of NMR Spectrum of a Pure Ethanol Sample
Chemical Equivalence-Integrals: All of the protons in a molecule which are in a
chemically identical environments will often exhibit the same chemical shift e.g. all
the protons in TMS, benzene, cyclopentane or acetone have their respective resonance
value and each compound gives rise to a single absorption peak in its NMR spectrum.

The protons are said to be chemically equivalent. On the other hand, molecules which
have sets of protons which are chemically distinct from one another may give rise to a
different absorption peak for each set.
The Nuclear Magnetic Resonance Spectrum of Phenylacetone (the absorption peak at the
far right is caused by the added reference substance, TMS)
Thus, the NMR spectrum furnished a valuable type of information e.g., it gives the
number of chemically distinct types of protons in a molecule. Besides, it can also
reveal how many of each different type are contained with in the molecule.

Relative Peak Area: In NMR spectrum the area under each peak is proportional to
the number of hydrogens generating that peak. The area ratio in above peaks 5 : 2 : 3
is the same as the number of the 3 types of hydrogens.

NMR spectrometer has the capability to electronically integrate the area under each
peak. The height of the peak gives the relative number of each type of hydrogen,
rather the ratio of the various types of protons.
Chemical Shift: A proton in a molecule is surrounded by a cloud of electronic
charge. In a magnetic field elements move in such a way that their motion induces
a magnetic field characterized by a magnetic moment that is opposed to the
applied field.

Consequently, the net magnetic field at the hydrogen atom is slightly less than the
applied field.

The magnetic field H experienced by the nucleus is therefore;

H = Ho-H/
Where Ho is the applied field and H’ is the induced field. Because the nucleus
experiences a smaller magnetic field than that applied externally, it is said to be
shielded. This particular type of shielding is called diamagnetic shielding. If we
are irradiating the proton with 60 MHz frequency the change of α → β states
of “spin flipping” requires a field of 14,092 gauss at the proton.

However, since the nucleus is shielded by electrons, the applied field has to be
made some what higher than 14,092 gauss in order for the field at the nucleus
to have the resonance value of 14,092 gauss. Protons in different electronic
environments experience different amounts of shedding and the resonance
absorption of light energy will occur at different values for the applied field or
irradiating light frequency. These changes are referred to as chemical shifts.
A sample in glass tube is put between the poles of the powerful magnet. The
magnetic field creates the two energy states for various hydrogen nuclei in the
sample.

The sample is irradiated with radio-waves from a simple coil.

In one mode of operation we fix the radio frequency at say 60 MHz. We then vary
the magnetic field and as the field at each kind of proton reaches the resonance
value, energy is absorbed from the radio waves as the nuclear spins ‘flip” and this
absorption is measured and recorded on a graph
For example, 1, 2, 2-trichloropropane CH3CCl2CH2Cl. The CH2 group is
attached to chlorine, an electronegative element which withdraws electrons
from C and H.

Since there is less electron density around the CH2 protons, the diamagnetic
shielding of these protons is less than it is for the methyl protons.

The induced magnetic field is therefore lower at CH2 than at CH3 and the
applied field must be increased less in order to achieve resonance.

Thus the CH2 protons appear to the left or downfield compared to CH3 protons.
Alternatively we can keep the magnetic field constant and very the frequency
of the radio electromagnetic irradiation.

The lowed the electronic shielding of the nucleus, the higher the effective
magnetic field at H and the higher the frequency required to reach the
resonance condition.

If we plot the frequency increasing from right to left. The CH2 hydrogens now
appear at higher frequency than the CH3 hydrogens.
The standard compound TMS is used for most NMR spectrum. When a spectrum
is run at 23,487 the resonance frequency of H is 100 MHz. The large magnetic
field induces a large electron current which causes a larger diamagnetic shielding
at the nucleus.
The difference in diamagnetic shielding proportionally larger and the peaks spread
apart. The chemical shift of the CH3 group is now 223 Hz downfield from TMS
instead of 134 Hz. Because different NMR instruments are in common use, it as
convenient to define a unit less measure that is independent of field strength.

The unit used “δ”. It is simply the ratio of the chemical shift of the resonance in
question in Hertz to the total light frequency used. Since the resulting number is
small, it is multiplied by 106, the δ has the units of parts per million (ppm) and
represents a chemical shift downfield (higher frequency) from TMS
 δi = (υi-υTMS/υ°) x 106 ppm

δi is the chemical shift of proton “i”

υi is the resonance frequency of that proton

υTMS is the resonance frequency of TMS

υ° is the accelerating frequency of the instrument.

The value of “δ” is expressed in ppm. Most chemical shifts have δ values between
0 and 10. In the τ scale signal for standard reference TMS is taken as 10 ppm.

τ = 10 - δ
Thus for CH3CCl2CH2Cl δ(CH3) = 134/ 60 = 2.23 ppm and

δ(CH2) = 240/ 60 = 4.00 ppm

NMR signal is usually plotted with magnetic field strength increasing to the right.
Thus the signal for TMS (highly shielded) appears at the extreme right of
spectrum with δ=0 ppm.

Greater the deshielding of protons, larger will be the value of δ. The extent of
shielding is represented in terms of shielding parameter α.

H=Ho (1-α)
Greater the value of α greater will be the value of applied field strength which has to be
applied to get the effective field required for absorption.

H0
Chemical Shift “δ”: The chemical shift may be reported in various ways. Since the
resonance frequency is dependent on the strength of the applied field, the shift may be
reported in field units (milliguass).

However, the field can be expressed in terms of Hertz. This separation in Hertz is also
proportional to the frequency of the oscillator, e.g. if the separation between a proton
signal and TMS is 60 Hz at 40 MHz, the separation at 60 MHz becomes 90 Hz;

60 x 60/ 40 = 90

Hence it is desirable to be able to report chemical shifts in units which are independent
of the operating conditions of the spectrometer.
Chemical Shift (δ) = Separation in Hz (observed shift from TMS in Hertz) x 60
Oscillator frequency (operating frequency of the instrument Hertz)

A separation of 60 Hz at an oscillator of 40 MHz

δ = 60x 106/40x106 = 1.5

Because 90 Hz at 60 MHz;

δ = 90 x 106/ 60 x 106 = 1.5 ppm

Shift of the Hs in CH3Br is 162 Hz in 60 MHz NMR spectrometer shift of the Hs in
CH3Br is 270 Hz in 100 MHz NMR spectrometer.

The number of Hz shift from TMS for a given proton will depend on the strength of the
applied magnetic field.

Resonance of a “H” 100 MHz/ 60 MHz = AF 23500 gauss/ AF 14,100 gauss = 5/3

Ratio of the resonance υ is the same as the applied field. Hence in the 100 MHz shift
from TMS will be 5/3 larger for a given H than it will be in the 60 MHz.
This could be confusing for workers trying to compare data if they have
spectrometers of different strength. The confusion is easily overcome if one
defines a new parameter that is independent of field strength.

This can be done by dividing the shift in H2 of a given H by the υ in MHz of

spectrometer with which the shift value was obtained.

δ = (shift in Hz)/ υ of spectrometer

υ = 162 Hz/ 60MHz = 270Hz/ 100 MHz = 2.7 ppm

where 162 Hz and 270 Hz are shifts of Hs of CH3Br in 60 MHz and 100 MHz
NMR spectrometer respectively.
The Chemical Shift and Shielding: Not every proton in a molecule has resonance
at the same frequency, as various protons are surrounded by electrons and exist in
a slightly different electronic environments from one another. The protons are
shielded by the electrons which surround them. In a magnetic field, the circulating
valence electrons of the protons generate counter magnetic fields which appose the
applied magnetic field.

Thus, each proton in a molecule is shielded from the applied magnetic field to an
extent that depends on the electron density that surrounds it. The greater the
electron density around a nucleus, the greater is the induced counter field which
opposes the applied field. The nucleus experiences a lower applied magnetic field;
it will precess at lower frequency.
This means it will also absorb RF radiation at this lower frequency. Each proton
in a molecule will be in a slightly different chemical environment and will have
a slightly different amount of electronic shielding which will result in a slightly
different resonance frequency.

The standard substance used is tetramethyl silane (CH3)4 Si or TMS, chosen

because the protons of its CH3 groups are more shielded than those of most
other known compounds. Tetramethyl silane (CH3)4 Hs are most shielded.

Thus, when another compound is measured, the resonances of its protons are
reported in terms of how far (in Hz) they are shifted from those TMS.
The differences are very small, as the difference between the resonance frequencies
of the protons in CH3Cl and CH3F is only 72 Hz when the Ho= 14,100 gauss. Since
the radiation used to induce proton spin transitions at that magnetic field strength is
of a υ ~ 60 MHz, this difference represents a change of υ of only slightly more than
one part in a million.

It is very difficult to measure exact υs to that precision; hence, no attempt is made

to measure the exact resonance frequency of any proton. Instead, a reference
compound is placed in the solution of the substance to be measured, and the
resonance frequency of each proton in the sample is measured relative to the
resonance frequency of the protons of the reference substance. In other words, the
∆υ is measured directly.
The number of Hz shift from TMS for a given proton will depend on the Ho,
when Ho= 14,100 gauss ~ 60 MHz and for Ho = 23,500 gauss ~ 100 MHz.

The ratio of the resonance frequencies is the same as the ratio of the two
field strength.
100 MHz/ 60 MHz = 23,500/ 14,100 = 5/3

Hence, in the 100 MHz range the shift from TMS will be 5/3 larger for a
given proton than it will be for the same proton in the 60 MHz range.
Nuclear Shielding and Chemical Shift:

+
bare proton H H C

proton in an organic molecule

/
H0 H 0 >H0
downfield upfield
In a molecule, the bonded electrons, affect the magnetic environment of the
proton. A bare proton undergoes its spin flip at some value of the Ho.

A field strength slightly greater than Ho is required to flip the spin of the
proton in an organic molecule.

The NMR signal of the bounded proton appears at higher field than the signal
of the bare proton and call this difference between the two a chemical shift.

A chemical shift is the change in the resonance position of a nucleus which is

brought about by its molecular environment
The reason that higher field strengths are required to achieve the same separation of
energy levels of bound Hs compared with bare Hs is that the electrons in molecules
shield the bound Hs from the external field. Under the influence of an external field
there is an induced magnetic field associated with the e-s that opposes the Ho. Thus
the magnetic field “felt” by a proton is less than the actual Ho.

C H

H0
The resultant magnetic field by the H is slightly less than Ho.
In order to achieve a separation between levels equal to the energy of the RF
radiation, the strength of the Ho must be increased by an amount equal to the
strength of the opposing induced magnetic fields of the electrons.

Increased shielding of a nucleus requires higher magnetic field strengths to

achieve resonance.
Factors Influencing Chemical Shift:

(i) Inductive Effect: CH3–CH2–Cl

(ii) Vander Waal’s Deshielding: In crowded molecules some Hs occupy the

sterically hindered position. The electron cloud of a bulky group will tend to
repel the e- cloud surrounding the proton, deshielding results.

Axial protons are comparatively shielded and absorb 0.5 ppm upfield as
compared to equatorial protons. The deshielding effect due to a particular group
decreases as its distance from the absorbing proton increases.
Diamagnetic Shielding: Consider the Molecule CH3–CCl2–CH2Cl2. Since there is less
electron density around the CH2 protons, the diamagnetic shielding of these Hs is less. The
induced magnetic field is therefore lower at CH2 than at CH3.
H = Ho – H/

CH 2

H0

Where H is the magnetic field experienced by the nucleus. H/ is induced magnetic field.
The net magnetic field at the Hs is slightly less than the applied field. Therefore, the
applied field has to be increased and made somewhat higher than 14,092 gauss in
order for the field at the nucleus to have the resonance value of 14,092 guess.

This could be confusing if different workers have different strength spectrometers.

So we need a new parameter independent of field strength. This can be done by
dividing the shift in Hz of a given proton by the υ in MHz of the spectrometer with
which the shift value was obtained.

In this manner a field independent measure called the chemical shift (δ) is obtained
position of signal-portion of TMS peak (observed shift form TMS in Hz).
Chemical shift (δ) = (Shift in Hz/ Spectrometer υ in MHz) x 106

Shift in Hz = Position of signal - position of TMS peak (observed shift from the
TMS in Hz).

‘δ’ of a H in CHCl3 = (437 Hz – 0 Hz/ 60 x 106 Hz) x 106 = 7.28 ppm

The chemical shift in “δ” units expresses the amount by which a proton
resonance is shifted from TMS in ppm of the spectrometer’s basic operating υ.

Values of δ for a given proton will always be same irrespective of the field
strength of the instrument.
 TMS
13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2 δ scale

-3 -2 -1 0 1 2 3 4 5 6 7 8 9 10 11 12 τ scale

The NMR Spectrometer Actually Scans from High “δ” Values to Low Ones
At 60 MHz the shift of the protons in CH3Br is 162 Hz from TMS, while at
100 MHz the shift is 270 Hz. However, both of these correspond to the same
value of δ = 2.70.

δ = 162 Hz/ 60 MHz = 270 Hz/ 100 MHz = 2.7 ppm (δ)

By agreement, most workers report chemical shifts in “δ” unit. In this scale
the resonance of the protons in TMS comes at exactly 0.00 (by definition).

Some used a related scale of chemical shift, “τ”, the resonance position of
TMS = 10.00.
Different protons have different chemical shifts, which is characteristic of the
proton. Every type of proton has only a limited range of δ values. Hence, the
numerical value (in δ or τ units) of the chemical shift for a proton gives a clue as
to the type of proton originating the signal, just as an IR “υ” gives a clue the type
of bond or functional group.

Being attached to the electronegative element “O” the protons are more
deshielded.

It is important to learn the ranges of chemical shifts (crudely) over which the
common type of protons have resonance. It is more important to get a feel for the
regions and the types of protons
Spin-Spin Coupling: Consider the spectrum of EtOH at 60 MHz (LR-NMR and
HR-NMR). This fine structure has been explained as being due to shielding of
protons by protons on adjacent carbon atoms.

First let us consider the influence of the methylene group CH2 on the methyl
group, CH3 each proton in the CH2 group may have its magnetic moment lined up
with or against the applied field, the following four combinations.

CH-CH
3 2
-OH (I) (II) (II I) (IV)
Thus the shielding effect will depend on the type of combination operating.
However, combination (II) and (III) will have the same shielding effect on the
adjacent CH3 group.

Hence there are three shielding combinations, and statistically it can be expected
that at any given moment 25% of CH2 protons will be in combination (I), 25% in
(IV) and 50% in (II) and (III).

The net result is that the CH3 protons signal is split into a triplet, the ratio of the
area being;

1:2:1
Similarly, the effect of the protons of the CH3 group on the CH2 protons,
there are 8 possible combinations.

(V) (VI) (VII) (VIII)

Each combination in (VI) give rise to the same shielding effect, this is also
the case for (VII). The net result is that there are 4 different shielding
combinations, resulting in the splitting of the methylene signal into a
quartet, the ratio of the area 1 : 3 : 3 : 1.
Each combination in (VI) give rise to the same shielding effect,
this is also the case for (VII).

The net result is that there are 4 different shielding

combinations, resulting in the splitting of the methylene signal
into a quartet, the ratio of the area 1 : 3 : 3 : 1
Chemical Shift Difference
This fine structure with in a particular signal is called spin-spin splitting, and the
magnitude of the separation between peaks in a multiplet is called the spin-spin
coupling constant (“J” in Hz). The magnitude of “J” is independent of the
oscillator frequency, but the spacing between signals is not. Hence, the change in
“υ” changes the signal separation, but not the spacing in a multiplet.

Thus, by measuring the NMR spectra of a given compound at two different

oscillator “υs”, if the spiting of a group of lines remain unchanged, the lines are
component of a multiplet. If the spacings changed, the group of lines arise from
non-equivalent protons.

No magnetic coupling between geminal hydrogen, are equivalent and having the
same chemical shift
The Relationship Between the Chemical Shift and the Coupling Constant
Spin-Spin Coupling: Protons which have similar chemical shifts are designated
by the letters A, B, C, ……… and the protons which have similar shifts that are
quite different from those of A, B, C,…….. are designated by the letters …….
X,Y, Z, when a proton has a chemical shift that lies between the above two sets
and is well separated by both is designated by M.

The earliest letters used to represent those protons which absorb at lower field
and choice of letters depends in which protons are different, how different they
are, and whether they are coupled or not. One practice is to designate Hs as A
and X if ∆v/J ≥ 6 and if less A and B.

CH3–CH2–OH CH3–NH–COH Cl–CH2–CH2Br

A3 M2 X A3 X Y AA’ BB’
The term spin system is used to describe groups of nuclei that are spin-spin coupled.
However, it is not necessary that all the nuclei in the spin-system are coupled.
In many cases the spin-system embraces the complete molecule: e.g.,

CH3–CH2=CH2 has a spin system

CH3–CH2–O–CH2–CH2–CH3 2-independents spin systems

5-spin ethyl group and the 7-spin n-propyl group.
Analysis of the Spectra: Consider the spectra of 1-brormo-3-chloropropane at 40
MHz. We shall indicate relative intensities by number. The A2, M2 and X2 represent
each group of equivalent protons and their spacing are proportional to the difference
in the chemical shifts.

Br–CH2–CH2–CH2–Cl Br–CH2–CH2–CH2–Cl Br–CH2–CH2–CH2–Cl

A2 M2 X2
 ν (~57 H z) ν (~51 H z)

JAM JMA JXM

JMX

6Hz 6Hz 6H z

1 1
1 1 1 1
1 2 1

1 2 1 1 2 1
1 3 3 1

1 4 6 4 1
If there is no coupling, then each CH2 group would have a singlet of equal
intensity. Since, however A2 and M2 are coupled as M2 and X2 splitting does
occur. Consider the signal of A2 group of protons coupled protons bear two
possible orientations. If we now consider the coupling with one proton in the
M2 group produce two lines of equal intensity (JAM). However, A2 is also
coupled with the other proton in M2.

Each component of the doublet is split into a second doublet, each pair being
separated by JAM. Hence, inner lines of 1 doublet overlaps with that of the other
doublet, thereby producing a triplet (1 : 2 : 1). In the same way, coupling of the
protons X2 with M2 gives triplet. In both cases, using the simple rule for
multiplicity with n = 2 the number of lines in the multiplet is 3 (n + 1), and
their relative intensities are 1 : 2 : 1 [The coefficient of expansion (1+x)2].
Consider the signal of M2, would be a multiplet of 9 lines [(2 + 1)(2 + 1) = 9].
However, the coupling between A2 and M2 shown as multiplet of 5 lines.
Because all “J” values are almost equal overlapping of “inner” components
occurs, and consequently the observed number of lines is smaller than that
calculated by the rule.

This happens when the “J” value between different groups of protons are all
same or nearly same. Also, in these cases, the total number of lines of the
multiplet is given by N= (nA + nx + 1). Here nA = nx = 2. Hence, N = 5,

Furthermore the relative intensities of the lines are given by the coefficient of
expression (1+x) (nA+ nB).
Spin-Spin Splitting (N+1) Rule: The chemical shift and integral (peak area) can
give information about the number and type of Hs contained in a molecule. A third
type of information that can be obtained from the NMR spectrum is that derived
from the spin-spin splitting phenomenon. Even in simple molecule, one finds that
each type of proton rarely gives a single resonance peak.

For example; 1, 1, 2-trichloroethane has two chemically distinct types of Hs.

C CH Cl
2

Cl
This phenomena is called spin-spin splitting, can be explained by the “N+1
Rule”. Each type of proton “senses” the number of equivalent proton(s) on
adjacent carbon atoms(s) and its resonance is split into (n+1) components.

equivalent Hs behave as a group

Ha Ha
Hb Hb

Cl C C Cl Cl C C Cl

Cl HC Cl HC

two neighbours give a triplet (n + 1 = 3) one neighbours givs a doublet (n + 1 = 2)

area = 1 area = 2

10 9 8 7 6 5 4 3 2 1 0
The spin-spin splitting gives a new type of structural information. It reveals
how many adjacent Hs there are to each type of H giving an absorption peak or
absorption multiplet.

When the protons attached to a single carbon are magnetically non-equivalent

(have different chemical shifts), the n + 1 rule value no longer applies.

That is, if one has geminal coupling that leads to spin-spin splitting the rule
begins to fail.
The Origin of Spin-Spin Splitting: Spin-Spin splitting arises because Hs on
adjacent carbon atoms “sense” one mother. The H on CA can sense the spin direction
of the H on CB. In some molecules of the solution the H on CB will have spin +1/2
(X-type molecules), while in other molecules in the solution the H on CB will have
spin -1/2 (y-type molecules).

Two different molecules in a solution with differing spin relationships between HA and HB.
Ethyl Iodide (CH3–CH2–I):

H H H H

H C C I H C C I

H H H H

three equivalent neighbours two equivalent neighbours

give a quartet (n + 1 = 4) give a triplet (n + 1 = 3)
area = 2 area = 3

integral = 3

integral = 2

10 9 8 7 6 5 4 3 2 1 0
2-Nitropropane [CH3–CH(NO2)–CH3]:

CH CH
3 3

H C NO H C NO
2 2

CH CH
3 3

si x equ iv alent neig hb ou rs

g iv e a sept et (n + 1 = 7 )
on e nei gh bo ur g i ves a d u b let (n + 1 = 2)
area = 6 area = 1

integral = 6

integ ral = 1

10 9 8 7 6 5 4 3 2 1 0
 Some Commonly Observed Splitting Pattern

X CH CH Y
(X Y)

CH CH H
2

X CH 2 CH 2 Y
(X Y)

CH CH
3

CH CH
3 2

CH
3
CH
CH 3
The chemical shift of HA will be influenced by the direction of the spin in HB. HA is
said to be coupled to HB. Its magnetic environment is affected by whether HB has a
+1/2 or a -1/2 spin state.

Thus, HA will absorb at a slightly different chemical shift value in the type X-
molecules than it will in type Y-molecules. In fact, in X type molecules, HA will be
slightly deshielded because the field of HB is aligned with the applied field, and its
magnetic moment will add to the Ho.

In Y-type molecules, HA will be slightly shielded with respect to what its chemical
shift would be in the absence of coupling.
The field of HB diminishes the Ho’s effect on HA. Since in a given solution there
will be approximately equal number of X and Y type molecules at any given
time, two absorptions will be observed for HA. HA’s resonance is said to have
been split by HB and the general phenomenon is called spin-spin splitting.
The Origin of Spin-Spin Splitting in Proton A’s NMR Spectrum

Of course, HB will be “split” by HA also, since HA can adopt two spin states as
well. The spectrum will consist of two doublets.

Two doublets will be observed for all such situations of this type, except for those in
which both HA and HB are identical by spectrometry
Except in unusual cases, coupling (spin-spin splitting) occurs only between Hs on
adjacent carbons. Hs on non-adjacent C atoms generally do not couple strongly
enough to produce observable splitting.

The splitting pattern of methyl protons due to presence of an adjacent methylene group
The splitting pattern of methylene protons due to the presence of an adjacent aethyl group.
Signal splitting arises from a phenomenon known as spin-spin coupling. Spin-
spin coupling effects are transferred primarily through the bonding e-s and are not
usually observed if the coupling protons are separated by more than 3 σ bonds.

Spin-spin splitting is not observed for Hs that are chemically equivalent or

enanatiotopic, i.e. spin-spin splitting do not occur between Hs that have exactly
the same chemical shift
 a b
CHCl2CH2Cl
a b

signa l splitting

a
CH
3

a b no signal split ting

CH C O CH
3 3

a CH
3

CH 3 CH 3 no signal split ting

 Failure of N + 1 Rule:

n + 1 = 5 (quintet)
H H
3 2

H H

H n + 1 = 3 (t ripl et)

4 O
H
n + 1 = 3 (triple t)

no s pin spi n spl itti ng due to gemi na l c oupl in g

(b) 3.12 (c) 3.83

H H

H
(b) 2.77
O

bec ause Ha and H b are non-equivalent , and bec ause Hc is c oupled dif ferent ly to Ha that to H b, t he n + 1 rule f ails
There is a subtle distinction between spin-spin coupling and spin-spin splitting.
Spin-spin coupling often occurs between sets of protons that have the same
chemical shift (and this coupling can be detected by different methods).

However, spin-spin coupling leads to signal splitting only when the sets of protons
have different chemical shifts.

Coupling does not always means splitting but splitting always comes from
coupling.
 Hb Ha Ha

A theoretical analysis is shown in A. A

signal in the absence of Hb

C C
(magnetic movement of Hb split
the signal of Ha into two peaks of
Jab equal intensity)
two magnetic orientations of Hb

applied field

The actual appearance of the protons

B
is shown in B. Jab
The separation of these peaks in frequency units is called the coupling constant
generally reported in Hertz (cycles per second), caused entirely by internal
forces, the magnitude of J are not dependent on the magnitude of the Ho.

Ha
Hb Ha
signal in the absence of Hb

C C
protons of Hb split the signal into
possible magnet orientations
a 1:2:1 triplet
of Hs protons of Hb
Hb

applied field
Relative Peak Area: The amount of energy absorbed at each resonance
frequency is proportional to the number of nuclei that are absorbing energy
at that frequency.

By measuring the areas of each of the resonance lines we may determine

the relative number of each different kind of H.

This is made by electronic integrator. After the NMR spectra have been
recorded the instrument is switched to an integrator mode of operation.

The integral line for each of the two peaks in spectrum of 1, 2, 2-

trichloropropane.
 10 9 8 7 6 5 4 3 2 1 0

The ratio of the heights of the two integral lines is equal to the ratio of the
number of Hs giving rise to the two peaks; 75/ 50 = 3/2.
Relaxation Processes: The NMR experiment does not measure all of the Hs
but just that have α-spin and absorb energy in flipping to β-spin. The
difference in α and β spins is rather small.

The energy different in α and β states in the magnetic field of a 60 MHz

NMR is only 0.006 cal. mole-1.

At equilibrium the population difference is given by the Boltzman’s

distribution Law;

N α / N β = e0.006/ RT = 1.00001
When we apply RF we excite the slight excess of α-nuclei to β. If there is not other
mechanism for converting β back to α, we will have equal population in both spin
states and could no longer observed any absorption of energy, there would be no
spectrum.

With a sufficient strong RF this can be done and the system is said to be saturated.

However, in normal operation, hydrogens in the “β” spin states continuously relax
back to the α-state because of local fields and equilibrium imbalance is maintained.

These local fields are associated with other spinning nuclei.

That is, even in the absence of applied RF field, individual Hs convert from
one state to another quite readily because in moving about the liquid, they
experience a magnetic field of other nearby nuclear magnetic moments.

Such moving and changing fields happen to have the resonance value, and
energy interchange can occur resulting in spin flipping.

In normal operation the distribution of α and β spins remains close to the

equilibrium value and the amount of energy absorbed is proportional to the
number of protons
Relaxation Processes: Relaxation processes involve some non-radiative transitions
by which a nucleus in an upper transition state returns to the lower spin state.
There are two kinds of relaxation processes are:

(i) Spin-Spin Relaxation

(ii) Spin-Lattice Relaxation

Spin-Spin Relaxation (Transverse Relaxation Diagonally Across): It is due to

the mutual exchange of spins by two precessing nuclei which are in close proximity
to each other. It involves the transfer of energy from one nucleus to the other but
there is no net loss of energy.
Spin-Lattice Relaxation (Longitudinal Relaxation): It involves the transfer
of energy from the nucleus in its higher energy state to the molecular lattice.
The energy is transferred to the components of the lattice as the additional
translational, vibrational, and rotational energy.

The total energy of the system remains same. An efficient relaxation involves a
short time and results in the broadening of absorption peaks.

Smaller the lines of the excited state, greater is the line width.

This process keeps the excess of nuclei in the lower energy state which is
necessary condition for NMR phenomenon
The number of signals in the NMR spectrum tells the number of different sets of
Hs in a molecule. Each signal corresponds to a set of equivalent protons. The
magnetically equivalent Hs are chemically equivalent Hs.

a
CH3
b a b a
C O C H3 OH CH3 CH NH
2 2
a
CH3

a b
CH3 H
C C

Cl H c
Rules for Determining Multiplicity: Some simple rules for determining the
multiplicity of signal have been developed, but those usually apply only when
∆V/J > 6 (where ∆υ in Hz is the separation of the signals of the interacting
groups). Spectra of this type are said to be First order spectra.

Equivalent protons when coupled do not cause splitting.

The spacing (J values) in a multiplet are equal and also equal to the spacing of a
multiplet arising from mutual coupling.
The multiplicity of a group of equivalent protons is equal to (n + 1) where n =
number of equivalent protons in the group which are coupled to the first group.

Furthermore, the relative intensities of the individual lines of a multiplet

corresponds to the numerical coefficient of term in the binomial expansion (1+x)n.

Thus the lines of the quartet (n = 3) have relative intensities 1 : 3 : 3 : 1 and those
of the triplet (n = 2), 1 : 2 : 1.

Also the lines of the multiplets are symmetrical about the midpoint of the multiplet.
When a group of equivalent protons is coupled to a group of equivalent
protons, na in one group and nb in another the multiplicity of the group is
equal to (na+1) (nb+1).

Consider the spectrum of EtOH. The -CH2 group coupled to both the CH3
group (na = 3) and O-H proton (nb = 1).

Hence, the multiplicity of CH2 signal is given by (3+1) 1 +1) = 8 i.e. an octet.
 Br Br

Br C C C(CH 3 )3
10 9 8 7 6 5 4 3 2 1 0

Ha Hb

Both the resonance of Ha and Hb appear as doublet. This splitting of peaks is common in
NMR spectra. This has its origin in the magnetic field associated with each individual
spinning proton.

The small magnetic fields affect the total magnetic field experienced by other protons.
The magnetic field associated with the spin of the nearby proton, Hb contributes to the
effective field experienced by Ha.
This is not through-space effect of the magnetic field associated with the
spinning nucleus Hb but results instead from interaction between each H nucleus
and electron spins e.g. the spin of Hb is relayed to Ha by way of shared electrons.

If Hb has α -spin, the effect is as if the total magnetic field at Ha were slightly
greater than that provided by the NMR instrument’s applied field. Thus less
applied field is required to achieve resonance than in the absence of Hb and we
find a slight downfield shift.

But only half of the nuclei have α-spin. The rest have β-spin in which the
opposite affect results and up-field shift occurs. Ha and Hb are said to be coupled.
 Jab Jab

Hb = α Hb = β

δ a δ b

The splitting of a signal is due to the different environment of the absorbing proton
not with respect to electrons but with respect to the nearby protons. The chemical
shift of a given proton depends on itself, but the nature of its splitting depends on its
proton neighbors.
Both lines in the lowfield doublet correspond to the transition of Ha. At these field
strength Hb, with its different chemical shift is not in resonance even though its
presence is felt by Ha and it produces two resonance positions instead of one.

As the field strength is increased the Hb comes into resonance. Now the effect of α
or β-spin of Ha affects the magnetic field experienced by Hb.

The effect of Ha on Hb is exactly the same as the effect of Hb on Ha. Thus the
splitting of Ha peaks has the same magnitude as that of the Hb peaks. Spacing
between the peaks is conventionally labeled by “J” in cycles per second or Hertz,
coupling constant between two protons.

Since “J” arises from the spin of the proton, its magnitude is not dependent on the
applied magnetic field. That is same “J” values applies for spectra at 6,100 or 250
MHz instruments.
 Hb Ha Hc

Ha
C C C

Hb Hc
Jab

Jac Jac
Jab Ja c 1 2 3 4

Jab > Jac

This means that the effect of Hb on Ha is greater than the effect of nucleus Hc on Ha.
TYPES OF PROTONS CHEMICAL SHIFT (δ)

0.2
R–CH3 0.9
C≡C–H 4.6-5.8
C=C–H 2.0-3.5
Ar–H 6.0-9.0
X–C–H 3.0-4.5
RO–C–H 3.3-4.0
ROOC–C–H 2.0-2.2
HOOC–C–H 2.0-2.5
R–CHO 9.0-10.0
R–OH 1.0-5.50
Ar–OH 4.0-12.0
C=C–OH 15.0-17.0
RCOOH 10.5-12.0
Pascal Triangle: The intensity ratio of multiplets derived from the n+1 rule follow
the entries in the mathematical mnemonic device call Pascal’s Triangle.

Each entry in the triangle is the sum of the two entries above it to the left and to the
right. Notice that the intensities of the outer peaks of a multiplet such as a septet
are so small compared to the inner peaks that they are often obscured in the back
line of the spectrum.
SIGNAL PEAK AREA RATIO
Singlet 1
Doublet 1 1
Triplet 1 2 1
Quartet 1 3 3 1
Quintet 1 4 6 4 1
Sextet 1 5 10 10 5 1
Septet 1 6 15 20 15 6
1
The Coupling Constant: Virtual Coupling: In the NMR spectrum of long
hydrocarbon chain, most of the protons in central portion of the chain appears as
a single broadened absorption peak.

These Hs all have similar chemical shifts and simple or Js to Hs on adjacent Cs.
However, the Hs on the carbon next to a functional group after have a different
chemical shift and are easily distinguished.

The terminal Me group of a chain is also easily distinguishable owing to the fact
that the methyl group protons typically appear upfield from methylene protons.
Spectrum of decanol illustrates this quite well. In addition, it can be seen
that the terminal methyl group is split by the methylene group next to it
into a crude triplet. This triplet is distorted and broadened by a coupling
phenomenon called virtual coupling.

virtual coupling
normal triplet
H H2 H3
1

C C C tripl et broade ned by

virt ual coupl ing
J2, 3 > (δ2 - δ3)
Normally Hs further than one C away do not couple. However, in a special case,
Hs on alternate Cs will appear to interact. They do not actually couple; but,
nevertheless, appear to do so.

The vicinal Hs (H1 and H2) clearly couple, but H1 appears to couple to H3 as
well, in spite of the fact that J1,3 = 0. This occurs because H2 and H3 have nearly
the same chemical shift value, and because the J between them is larger than
their “δ” difference.

In such a situation (H2 and H3 nearly equivalent), H2 and H3 behave as a unit and
somewhat distort the triplet.
Variation of “J” with the dihedral angle α
Magnetic Equivalence:

The Mechanism of Geminal Coupling:

Dependence of Magnitude of Geminal Coupling Constant on HCH Bond Angle ‘α’
The Coupling Constant: The quantitative amount by which the peaks split. The
distance between the peaks in a simple multiplet is called the coupling constant “J”.
This distance is measured on the same scale as the chemical shift and is expressed
either in cycles per second (cps) or in Hertz (Hz). In ethyl iodide “J” = 7.5 Hz.

J J J J

chemic a l s hift d iffernce

δa δb
1
H-NMR spectrum at 60 MHz, each ppm of chemical shift (“δ” unit) represent
60 Hz. Since there are 12 grid lines per ppm, each grid line represents 60 Hz/
12 = 5 Hz.

There are 20 chart divisions per 100 cps, one division equals

100 cps / 20 = 5 cps = 5 Hz.

If the spacing between the component peak is ~ 1.5 chart divisions,

J = 1.5 div x 5 Hz = 7.5 Hz

This is the coupling constant between the methyl and methylene Hs. The
magnitude of coupling in ethyl iodide is constant, hence “J” is called coupling
constant. The constant nature of “J” may be observed when NMR spectrum is
determined at both 600 MHz and 100 MHz.

J = 7.5 Hz J = 7.5 Hz

1 83 Hz
J = 7.5 Hz 110 H z
J = 7 .5 Hz

3 05 Hz
1 83 H z
A comparison of the two spectra will indicate that the 100 MHz spectrum is
greatly expanded over the 60 MHz spectrum.

The chemical shift in Hertz for the CH3 and CH2 hydrogens will be much
larger in 100 MHz spectrum, although the chemical sifts in “δ” or τ units for
these Hs will remain identical in both cases. Coupling constant “J”= 7.5 Hz in
both spectra.

The spacing of the lines of triplet and quartet does not expand when the
spectrum is determined at 100 MHz.

The extent of coupling between these two sets of Hs remains constant

irrespective of the spectrometer frequency
Interaction of most aliphatic Hs in acyclic system J = 7.5 Hz. In 1, 1, 2-
chloroethane, J = 6 Hz; 2-nitropropane J = 7Hz.

The coupling constants are typical for the interaction of two Hs on adjacent sp3
carbons. Different magnitude of “J” are found for different type of Hs.

For cis protons on double bond Jcis = 10 Hz and Jtrans = 17 Hz. In ordinary
compounds “J” may range from 0 to 18 Hz.

The magnitude of “J” will often provide structural clues. Cis olefin and trans olefin
can be distinguished on the basis of coupling constants for the vinyl Hs.
 Coupling Constants and Their Approximate Values in Hz

Note: The coupling constants of the groups of Hs which split one another must be
identical. This is extremely useful interpreting the spectrum that may have several
multiplets, each with a different coupling constant.
Double Nuclear Resonance (Spin Decoupling): Spin decoupling, some
times called double resonance, is another technique used to simplify NMR
spectra. It is useful to determine which spin-spin multiplets actually interact
with one another and also in locating absorptions that may be “hidden” or
buried under other group absorptions.

In spin decoupling, a second Rf is applied while the spectrum isbeing

scanned in the usual fashion. This second Rf can be set to irradiate a selected
group of Hs in the molecule.

Irradiation causes the selected group of Hs to undergo rapid transitions

among their nuclear spin states, these rapid nuclear transitions decouple the
Hs of this group from any spin-spin interactions, and the NMR spectrum is
simplified.
Consider the spectrum of propyl bromide at 60 MHz NMR Spectrum.
There are 3 triplets and 1 quartet. Which triplet is associate with the quartet?
It will, of course, be the one that has the same “J” values.

The Hs in each group interact to the same extent. It is obvious that quartet
(A) is associated with triplet (C) and not with triplet (B) or (D). Similarly,
the triplets “B” and “D” are related to each other in the interaction scheme.
Double Resonance (Spin Decoupling) Experiment

NMR Spectra of Propyl Bromide at 60 MHz

The Effect of Decoupling (Irradiating) the α CH2 Protons

The Effect of Decoupling (Irradiating) the β CH2 Protons

The effect of decoupling the γ CH3 Protons

Besides, decoupling by rapid exchange, decoupling is also done as follows;
Suppose 2 coupled protons A and B in different environment. Suppose
resonance “υ” of A is being measured. Then, at the same time as this is being
done, a strong RF field having the resonance “υ” of “B” is also applied. This
latter field produces both absorption and emission by “B” and consequently
“B” is decoupled, with respect to “A”, and the time average of coupling
between A and B is zero.

But it is not possible under the conditions of the experiment to record the
resonance of B. By applying double nuclear resonance to each type of proton,
each signal can be made to collapse into a singlet line. In this way, the DNR
method produces a much simpler system
NMR Spectra of Molecules Containing Double Bonds
H H H H

C C C C C C

H H
cis trans Jeminal
J (7-14 Hz) J (12-19 Hz) J (0-3 Hz)

The 2nd factor is different which produces different “J” values, so offer means of distinguishing
between cis and trans isomers.

H CH 2 CH 2

C C C C CH C C CH

H H

Vicinal Allylic Homo-allylic

J (4-10 Hz) J (0-2 Hz) J (0-2 Hz)
The spin-spin coupling constant depends on the number of covalent bonds
between the two interacting protons and on their geometry. The 1st factor is
same for the following:

“J” value for other groupings involving a double bond.

C2H4 (δ ~ 5) > C2H2 (δ ~ 2.5) > C2H6 (δ ~ 0.9)

Electronegativities of the carbon atom in the following compounds are in the
order C2H2 > C2H4 > C2H6. It therefore follows that the chemical shift
should also be in this order. However, the order is;

This can be explained on the basis that a shielding effect is operating in

acetylene and is very much smaller in ethylene.
If HC≡CH is placed in a magnetic field with its molecular axis parallel to the field.
The π e-s circulate in the annular π-molecular orbital, therefore producing an
induced field opposite to the Ho.

Thus protons in line with the triple bond are shielded, resulting in a decreased
chemical shift. Protons which lie above or below the bonding line, however, are
deshielded.

The over all result is that there are cones with in which shielding (being indicated
by +ve sign) is experienced and outside which deshielding (-ve sign) is
experienced. The cause of this shielding effect is believed to be as follows:
Anisotropy caused by the presence of π electrons in some common multiple bond
system
If the molecular axis of acetylene is perpendicular to the Ho, (C), no π-
electron circulation is produced and consequently no shielding or deshielding
occurs. The effect of these π -electron circulations, averaged out over all
possible orientations in the applied field, must therefore produce some
shielding (in line with the bond) of acetylenic protons, and this results in a
relatively high τ value (δ = 2.5).
In addition to this shielding effect in acetylene, long range coupling also exists.
In case of double bond the induced current is produced only when the molecular
axis lies perpendicular to Ho. Also, shielding and deshielding effects are worker
for a double bond than for a triple bond. In both type of multiple bonds, the
magnitude of the induced magnetic field depends on the angle of the molecular
axis with respect to the Ho. Because of this, compounds with multiple bonds are
said to be magnetically anisotropic.

doublet
CH3–C ≡C–H
quartet

This coupling extends over 4 bonds; coupling is absent or negligible over 4 single
bonds. This coupling also extends over 4 bonds when one is double bond. In both
cases “J” is small (1-2 Hz).
The NMR spectra of carbonyl compounds are effected by the strong inductive effect
(-I) of C=O group and also by magnetic anisotropy of the C=O double bond. Both
effects deshield an aldehydic proton protons in ketones are deshielded mainly by the
-I effect (the Hs are at the edge of the shielding cone) and thus the shift downfield is
much less (then for aldehydic proton).

Aromatic Compounds: Under the Ho perpendicular plane, the circulation takes place
in one direction, produces a ring current which induces a magnetic field
perpendicular to the molecular plane, which assists the Ho outside the ring and
oppose the Ho inside.

Thus there are volumes in which deshielding (-ve) and shielding (+ve) occurs. Thus
protons appear downfield.
Long Range Coupling: Normally, proton-proton coupling is observed between
Hs on adjacent atoms (if they are not equivalent) and only sometimes observed
between Hs on the same atom (if they are magnetically non-equivalent).

These are called vicinal and germinal couplings, respectively. Coupling between
Hs which lie further apart than those in these two types of coupling will occur
only under special circumstances. In addition, these couplings, which are made
possible through overlapping orbitals, usually have a stereochemical
requirement.

Couplings which occur over long distance than those of the vicinal or geminal
type are conveniently collected together under the heading “long range
coupling”.
 The Types of Coupling Present in Alkenes

The π electrons of the double bond apparently help to transmit the spin information
from one nucleus to the other.
 Allylic Coupling

When all the nuclei are co-planer, there is no interaction of the allylic C–H
bond orbital with the π-system and J = 0Hz. However, when the allylic CH
bond is perpendicular to the C=C plane, the interaction assume the
maximum value J = 3 Hz.
Allylic and Homoallylic Coupling in Acetylenes:

Coupling Between the meta Protons in an Aromatic

Long range coupling in compounds without π-system are less common but do
occur in special cases

Two Possible Overlap Mechanisms Explaining the Transfer of Spin

Information Between HA and HB When a Molecule is Arranged in a W Pattern.
Arrangement of atoms in the form of a “W” with Hs occupying the end positions. The
magnitude of “J” for W coupling is usually small except in highly strained ring systems.

O
H
H
H

Jab~1 Hz Jab~3Hz Jab~7Hz

NMR Spectrum: A graph of signal intensity (ordinate) against magnetic
field (abscissa); for a given field, the strength of the signal depends on the
magnetic moment of nucleus, (proton has one of the largest momentum);
In order that a PMR signal to be observed, the proton must be in a single state
for 10-2 to 10-1 second.

It has also been shown that the spectral lines width is inversely proportional the
average time the proton occupies the higher energy state.

Hence, the longer the time spent in this state, the sharper is the line; the shorter
the time, the broader is the line.

The resonance frequency for a given field depends on the nature of the atomic
nuclei concerned. This, however, is not the case.
The applied field causes e-s around a nucleus to circulate in a plane
perpendicular to the field, and these currents produce a field in opposition to
the applied field. Thus, the effective Ho experienced by the nucleus is smaller
than the Ho

H = Ho (1- σ)

where “σ” is the shielding or screening constant. It has a +ve value, but in
certain circumstances it may have -ve, e.g., the effective field is larger than
the applied field. In this case, the proton is said to be deshielded
Since the numerical value of “σ” depends on the chemical environment of a given
nucleus, the shielding or deshielding of a nucleus varies with its environment.
Shielding causes a shift of the resonance frequency to higher values of the applied
field, e.g., the shift is upfield.

On the other hand, deshielding causes a shift of the resonance “υ” to lower values of
the Ho, i.e., the shift is downfield.

The magnitude of this shift is known as chemical shift. Since the value of the field
experienced by the sample cannot be determined accurately, chemical shifts are
measured relative to some standard.
Various reference compounds (which are usually added to the sample) for
PMR have been used, but tetramethylsilane (TMS) is particularly useful
since it molecule (CH3)4Si contains 12 equivalent protons.

The PMR spectrum of this compounds shows a single sharp line which
occurs at a higher field than any protons in most of the common organic
compounds.

Halogens are electron- attracting (electronegative) and when joined to a

methyl group the e- density around each proton is decreased. Thus the
presence of “X” weakens the induced opposing field i.e., deshield the
protons.
Local Diamagnetic Shielding:

Electro-Negativity Effects: The trend of chemical shift involving

electronegative elements substituted at the same carbon to which the protons of
interest are also attached, simply increases as the electronegativity of the
attached element increases.

Compounds CH3 F CH3OH CH3Cl CH3Br CH3I CH4 (CH3)4Si

Electronegatvity 4.0 3.5 3.1 2.8 2.5 2.1 1.8
δ 4.26 3.40 3.05 2.68 2.16 0.23 0
Multiple substitutents have a stronger effects than a single substitutents.
The influence of the substituent drops off rapidly with distance

CHCl3 CH2Cl2 CH3Cl –CH2Br –CH2–CH2Br –CH2–(CH2)Br

7.27 5.30 3.05 3.30 1.69 1.25
Electronegative substituent reduces the valence electron density around the
protons attached to that carbon. These protons shield the proton from the applied
magnetic field. This effect is called local diamagnetic shielding

Local diamagnetic Shielding of a Proton Owing to its Valence electrons

Electronegative substitutents on carbon reduce the local diamagnetic
shielding in the vicinity of the attached protons because they reduce
the electron density around those protons e.g., the substitutents
deshield the proton.

The greater the electro-negativity of the substitutents, the more it

deshield protons, and, hence the greater is the chemical shift of those
protons.
Hybridization Effects: Off course, hydrogen on an sp3 carbon which is attached to a
heteroatom or an unsaturated carbon do not fall in this region but have greater shift

have resonance in the range δ 4.5-7.0

Sp2 vinyl-hydrogen ( H)
In an sp2 -1s, C–H bond of the carbon atom, having more s character,
behaves as if it were more electronegative than an sp3 Carbon (s orbital
holds electron closer to the nucleus than do the carbon p-orbital),
resulting in less shielding for the H.

Thus, vinyl Hs have a greater chemical shift than aliphatic hydrogens on

sp3 carbons.

Aldehyde protons (also attached on sp2 carbon) are further downfield (9-
10 ppm) since the I-effect of the O atom further decreases the electron
density on the attached proton.
SP-Hydrogen: Acetylenic Hs (C–H sp-1s) appear at δ 2-3 owing to
anisotropy. On the basis of hybridization one would expect these Hs to have a
chemical shift greater than that of the vinyl H.

An sp-carbon should behave as if it were more electronegative than an sp2

carbon.
Acidic and Exchangeable Protons; Hydrogen Bond: Least shielded
H is the one attached to the COOH group (~δ 10-12). Both resonances
and the electro-negativity effect of oxygen withdraw electrons from
the acid proton.

Hydrogen Bonding- Exchangeable Hydrogen: Protons which can

exhibit hydrogen bonding (OH or NH) exhibit extremely variable
position over a wide range.
The more hydrogen bonding that takes place the more deshielded a proton
becomes. The amount of hydrogen bonding is often a function of
concentration and temperature, at high dilution (no H-bonding), hydroxyl
protons absorb near (δ = 0.5-1.0) in concentrated solution (δ 4-5).

R H H
R O O O O
H
H R R
Free (dilute solution) hydrogen bonding (concentracted solution)
Diamagnetic Anisotropy: There are a number of types of protons whose
chemical sifts are not easily explained by simple consideration of the
electro-negativity of the attached groups.

Consider the protons of benzene or other aromatic systems, generally have

a chemical shift equivalent to the proton of CHCl3. alkenes, alkynes and
aldehydes also have protons whose resonance values are not in line with the
expected magnitude of any electron withdrawing or hybridization effect.

In each of these cases the effect is due to the presence of an unsaturated

system (π-electrons) in the vicinity of the proton in question.
For example benzene, which placed in a magnetic field, the π-electrons in
the aromatic ring system are induced to circulate around the ring. This
circulation is called “ring current”.

Moving electrons (the ring current) generate a magnetic field much like
that generated in a loop of wire through which a current is induced to flow.

The magnetic field which is generated covers a spatial volume large

enough that it influences the shielding of the benzene hydrogens.
Diamagnetic Anisotropy in Benzene
The benzene hydrogen are said to be deshielded by the diamagnetic anisotropy
(having the same value in all directions) of the ring. (An isotropic field is one of
uniform density everywhere or of spherically symmetrical distribution; anisotropic
field is not isotropic or non-uniform).

The applied field is anisotropic in the vicinity of the benzene molecule because the
labile e-s in the ring interact with the applied field. This creates a non-homogeneity
in the immediate vicinity of the molecule.

Thus, a proton attached to a benzene ring is influenced by three magnetic fields: the
strong magnetic field applied by the electromagnets of the NMR spectrometer; and
two weaker fields, one due to the unusual shielding by the valence electrons around
the proton, and other due to the anisotropy generated by the ring system electrons.
It is this anisotropic effect that gives the benzene protons a chemical shift
which is greater than expected. These protons just happen to lie in a
deshielding region of this anisotropic field. If a proton were placed in the
center of the ring rather than its periphery, it would be found to be shielded
since the field lines there would have the opposite direction.

Diamagnetic Anisotropy in Acetylene

All groups in a molecule which have π e-s generate secondary anisotropic field.
In acetylene the circulation of π e-s has a geometry such that the acetylenic Hs
are shielded.

Hence, acetylene hydrogen have resonance at higher field than expected. The
shielding and deshielding regions due to the various π e- functional groups have
characteristic shapes and directions.

Protons falling with in the cones (+areas) will be shielded and those falling
outside) will be deshielded. The magnitude of the anisotropic field decreases as
the distance increases.
Anisotropy Caused by the Presence of π-Electrons
The Effects of Anisotropy in Some Actual Molecules
Proton on Oxygen - Alcohols:

(i)Temperature
(ii) Purity of the sample
(iii) Solvent used

R-OHa + R'-OHb R-OHb + R'-OHb

For most alcohols, under usual conditions no coupling is observed between the
OH hydrogen and Hs on the C atom to which the OH group is attached. Contrast
to the geminal coupling where spin-spin splitting often is not observed, whether
or not spin-spin splitting involving the OH hydrogen is observed depends on
several factors:
The factors are all related to the rate at which OH protons exchange with one
another (or the solvent) in the solution.

Under the normal conditions, the rate of exchange of Hs between alcohol

molecules occurs at a rate faster than the NMR spectrometer can respond. It
requires ~ 10-2 to 10-3 second for an NMR transitional event to occur and be
recorded. At room temperature, an alcohol undergoes intermolecular proton
exchange at a rate of ~ 10-5 protons/sec.

This mean that the average residence time of a single proton on the oxygen atom
of a given alcohol is ~10-5 sec. before it exchanges. This is much shorter time,
than is required for a spin transition.
A proton just starting to have resonance may suddenly begin to exchange;
or one that is in between two molecules may begin to have resonance and
then suddenly affix itself to a molecule.

Since the NMR spectrometer cannot respond rapidly to these situations, the
net result, as far as it is concerned, is that the proton is unattached more
frequently then it is attached to oxygen, and the spin interaction between
the hydroxyl H and any other H in the molecule is effectively decoupled.

Rapid chemical exchange decouple spin infractions, and the NMR

spectrometer records only the average environment which it senses for the
exchange proton.
The hydroxyl proton often exchanges so rapidly that it “sees” all the possible
spin orientations of the Hs attached to the α-carbon as a single time-averaged
spin an configuration.

Similarly, the α Hs see so many different Hs on the hydroxyl oxygen (some

with spin +1/2 and some with -1/2), that the spin configuration they sense is an
average between +1/2 and -1/2 i.e. zero.

In fact, the NMR spectrometer behaves like a camera with a show shutter
speed in photographing a fast event. Events which are faster than the click of
the shutter mechanism are either blurred or averaged
NMR Spectra of MeOH at Various Temperatures
 HA HA

C2H5 HA + HB C2H5 O C2H5 O + C2H5OHB

HB H
C

It can be seen that the signal of the O-H proton which would be expected to be
triplet is not split. Thus absence of coupling has been explained on the basis of a
trace of acids. There is rapid exchange of proton between EtOH molecules.
Since a proton has 2 system orientations of almost same energy levels and the
population in these levels is practically equal, the exchanged protons have
about the same chance of having the same and opposite spin orientations.

The result is that the CH2 protons experience both spin-coupling the same
extent, the overall effect being a time average coupling effect that is zero.
Thus the CH2 signal not split by the OH proton and same does the OH signal.
Chemical exchange reaction is common for protons attached to O, N or S.

The rate of exchange is accelerated by a rise in temperature. Spin-decoupling

may some time be observed by rising or lowering the temperature at which
the NMR spectrum is measured.
The complications arising from a proton attached to O or N may be
removed by deuterium exchange, readily carried out by shaking a
solution of the compound in CDCl3 with a small amount of D2O.

The signal arising form OH or NH protons will no longer be observed. In

exchange reactions the shape of band depends on the rate of exchange.

We have seen that the rule for determining multiplicity usually

applies only when ∆υ/ J ≥ 6. We have also seen that ∆υ (the spacing
between the signals) is dependent on the oscillator “υ”, where as “J”
is independent of it.

Hence, by increasing the oscillator “υ”, ∆υ can be increased.

Shift Reagents: It has been known that the resonance peaks can be spread
over a wider range of magnetic field strength by the addition of a
paramagnetic substance called shift reagents, to the solution of the compound.
These are Lewis acids and form complexes with many Lewis bases (alcohols,
ketones, ethers, esters etc).

The europium chelate produces a downfield shift of the proton in the Lewis
base and the praseodymium chelate produces an up field shift. In this way the
shift reagents brings about resolution in a 60 MHz of 100 MHz (or greater)
spectrometer.
Protons on Nitrogen: In simple amines, as in alcohols, intermolecular proton
exchange is usually fast enough to decouple spin-spin interactions between Hs on N
and those on the α-carbon atom.

also unsplit

+
R CH NH + H R CH NH 3
2 2 excess (pH is less than 1) 2

seen as a sharp singlet (un-split)

The rate of exchange can be slowed down by making the solution strongly acidic
(pH < 1). The predominant species in solution is the protonated amine, and the rate
of intermolecular proton exchange is slowed down.
There is another factor that can complicate the splitting patterns of both
amines and amides: nitrogen itself has a nuclear spin (I = 1). It can therefore,
adopt spin states +1, 0, -1. We could predict the following possible types
interactions between H and N.

Direct coupling of course, not observed if the H on the N is undergoing rapid

exchange. The same conditions which decouple NH-CH or HO-CH proton-
proton interactions will also decouple N-H nitrogen-proton interactions.

In case where direct coupling is observed, the coupling constant is found to be

quite large J ~ 50 Hz. In amides, which are less basic than amines, the rate of
hydrogen exchange is slow.
The NMR Spectrum of CH3NH3+ in H2O
Analysis of the Protons on Nitrogen

Analysis of the Methyl Protons

The 3 methyl Hs split each peak into a quartet JNH–CH ~ 5 Hz, intensities 1 : 3 : 3 : 1.
Protons on Nitrogen: Quadrupole Broadening and Decoupling: Even Hs
which do not have rapidly exchanging amino Hs, the more usual case is the
N-H coupling in the NH resonance has either been decoupled or broadened
by the large electric quadrupole moment of N.

Nuclei which have either spin I = 0 or I = 1/2 have small electric quadrupole
moments, while those elements with I > 1/2 have relatively large electric
quadrupole moments.

Elements which have I = 0 or 1/2 have an approximately spherical

distribution of charge with in their nuclei. Those which have 1 > 1/2 have an
ellipsoidal distribution of charge.
Protons on Nitrogen: Quadrupole broadening and comparison of shapes
of nuclei with and without quadrupole moments
Because of the non-spherical distribution of charge in ellipsoidal nuclei, they
have a sort of “internal dipole moment” (the electric dipole moment) are much
more sensitive both to interaction with the magnetic field of the NMR and
valence electrons and or their environment.

This means that they undergo transitions at a faster rate and have very short
life time in their nuclear excited state. Thus bromine (I = 3/2) rapidly
undergoes transitions between all of the allowed state (+3/2, +1/2, -1/2, -3/2).

A hydrogen atom coupled to Br would require 10-2 to 10-3 sec. to undergo an

NMR transition (very slow than Br).
Therefore, doing its NMR transition from a +1/2 to a -1/2 state, H will “see” only
the average spin configuration of Br effectively a single spin state and will have
been decoupled from it even though the “J” might be quite large for HBr.

Nitrogen has only a moderately sized quadrupole moment. In many cases the
transitional rates of N in a particular molecule are very close to the rate at which
1H-NMR absorption is taking place, H is only partially decoupled from N. The H

is “less sure of what it sees”, results the absorption peak broadens. This
phenomenon is called nuclear quadrupole broadening of the NMR absorption
peak.

The three cases are summarized below:

Dependence of Quadrupole Broadening in an NH Absorption Peak on the Rate of Transitions
Among Nitrogen’s Nuclear Spin States
It should be carefully noted that not only must the rate of the spin transition in
nitrogen be rapid (compared to that in hydrogen), but the life time of +1 or 0 spin
state must also be short to give the averaging of spins or spin decoupling of JNH.

If the rate of the upward transition were instantaneous; and if the nucleus stayed
in the excited state for, say 20 second; and if it then made an instantaneous
transition downward, then all of the spin states of nitrogen would be represented
in one molecule or another during the proton transitions. Spin-spin splitting
would thus be observed.

There would be three distinct types of molecules in the solution, and three
absorptions would be seen since each proton in the three molecules represented
would have a slightly different chemical shift owing to the different spin states of
N in that molecule.
Of the three cases, the case 3 is the most common followed by the Case-2.
Case-1, discrete N–H spin-spin splitting, is not commonly observed. The
spectrum of the amide of propanoic acid clearly shows quadrupole
broadening of the –NH2 resonance.

In some compounds (for instance, pyrroles and other heterocycles), the NH

resonance can be subject to such a large broadening effect that it is difficult
to distinguish the absorption from the base line of the spectrum. The
spectrum of pyrrole provides a good example.
Carbon-13 NMR Spectra: Hydrogens (protons) are sensitive while carbons (C) are
selective 1H-NMR = 100MHz

C-NMR = 25 MHz as C is a 1/4 times poor magnetic as compare to hydrogen. The

13

magnet of 100 MHz feels by carbon as it was 25 MHz (1/4 x100 MHz).

Carbon-12, the most abundant isotope of carbon, does not possesses spin (I = 0); it
has both an even atomic number and an even atomic weight. However, C-13, does
have the nuclear spin property (I = 1/2). Unfortunately, 13C atomic resonances are not
easy to observe due to two factors.

The natural abundance of 13C is low; only 1.1%.

The magnetic moment (µ) of 13C is also low.
The Carbon-13 NMR some time referred as 13C-NMR or CMR spectroscopy
is the application of Nuclear Magnetic Resonance spectroscopy to carbon. It
is analogous to 1H-NMR.

In 1H-NMR Spectra it is easy to observe multiplets because of higher

isotopes abundance of 1H which is more than 99%, so coupling can occur.

Another difference is related to the chemical shift range of absorption

usually NMR goes from 1 to 10 ppm (in exceptional cases 1H signals appear
beyond 10 ppm and even appear above 20 ppm while 13C-NMR goes roughly
from 5 ppm to 200 ppm.
For these reasons, the resonances of 13C atoms are about 6000 times weaker
than those of H. Nevertheless, by special instrumental techniques, it is
possible to observe 13C NMR spectra.

The only useful parameter derived from 13C spectra is the “δ”. Integrals are
unreliable. Finally, although Hs which are attached to 13C atoms cause spin-
spin splitting, spin-spin interaction between adjacent carbon atoms is rare.

With its low natural abundance (0.01), the probability of finding a second
13C atom next to a first one is extremely low.
 The Normal Spectrum

Spectrum of Vinyl Protons of Allyl Bromide (CH2=CH-CH2-Br)

13C-NMR Spectra of Ethyl
While the chemical shifts of protons encompass a range of only about 20
ppm, 13C chemical shifts cover an extremely wide range of unto 200 ppm.
Carbons have their distinct resonance peaks clearly resolved.

Unusual to find any two Cs in a molecule having resonance at the same “δ”
unless these 2 Cs are equivalent by symmetry.
Coupled Spectrum: Although it cannot be seen on the spectrum, each of the
quartets (J = 6 Hz) lines are split into a closely spaced triplet (J ~ 1 Hz). This
additional fine splitting is caused by the adjacent –CH2 group; geminal coupling
(H-C-13C) of a type that commonly occurs in 13C-NMR spectra, with “J” generally
small (0 - 2 Hz).

The quartet is caused by direct coupling (13C-H); direct coupling constants are
larger, usually ~100-200 Hz. Each of the triplet peaks is finely split into a quartet
by the 3Hs on the adjacent CH3 group.

The carbonyl group carbon (δ171.1) appears as a singlet (no directly attached Hs),
but because of adjacent CH2 group, actually it is split finely into a triplet. The
aromatic ring Cs have resonance over the range from δ127-136.
Although, the splitting in a simple molecule yield interesting structural
information, the number of Hs attached to each C (as well as those adjacent if
spectrum is expanded). For large molecules the 13C spectrum becomes very
complex owing to the splitting and they often overlap.

It is customary, therefore, to decuple all the protons in the molecule by

irradiating them all simultaneously with a broad spectrum of frequencies
(“noise”) in the proper range. This type of spectrum is said to be noise
decoupled.

The noise decoupled spectrum (later) is much simpler, and for larger
molecules, much easier to interpret. Each peak represents a different C atom.
If two Cs are presented by single peak, they are then equivalent by symmetry.
Thus, the ortho carbons of the phenyl ring give a single peak and the meta
carbons also, just as for PMR spectra, the δ of each C indicates both its type
and its structural environment.

Electro-negativity, hybridization and anisotropy effects, all affect the 13C

chemical shifts just as they do for Hs, but in a more complex fashion.

–O–CH2– group carbon has a larger “δ” than the benzyl carbon.

Also note that the C=O carbon appears relatively far downfield, probably
owing to an anisotropy effect.
One of the most powerful features of 13C-spectra is that they allow one to
determine the number of different Cs in a molecule and thus allow a
recognition of equivalences or symmetry elements.

For instance, cyclo-octa-tetraene readily di-merizes to a solid.

On the basis of theory, two possible structures can be proposed for this dimmer:

The 1H decoupled 13C spectrum show only 4 sharp lines this effectively proves
structure 1, having two planes of symmetry.
The resonance frequencies of 13C-NMR are lower than those of protons in the
same applied field. In a 7.05 Tesla instrument, protons resonate at about 300 MHz
while carbons resonate at about 75 MHz, as carbon is 4 times poorer magnet as
compared to proton.

This is fortunate, as it allows us to look at 13C signals using a completely separate

‘window’ of radio frequency.

This means that signals of each carbon in a compound can almost always be seen
as a distinct peak without the overlapping that often plagues 1H-NMR spectra.
The chemical shift of a 13C-nucleus is influenced by essentially
the same factors that influence the proton chemical shift; bond to
electronegative atoms and diamagnetic anisotropy effects tends
to shift signals downfield (higher resonance frequency).

In addition, Sp2 hybridization results in a large downfield shift.

The 13C-NMR signals for carbonyl carbons are generally the far
downfield (170-270 ppm), due to both Sp2 hybridization and to
the double bond to oxygen.
Unlike the 1H-NMR signals, the area under 13C-NMR signals cannot be
used to determine the number of carbons to which it corresponds. This is
because the signals for some types of carbons are inherently weaker than
other types - peaks corresponding to carbonyl, for example, are much
weaker than those for methyl and methylene peaks.

Therefore, peak integration is generally not useful in 13C-NMR

spectroscopy, except when investigating molecules that have been
enriched with 13C isotopes.
Because of the low natural abundance of 13C- nuclei, it is very unlikely to
fine two 13C atoms adjacent to each other in the same molecule and thus
we do not see spin-spin coupling between neighboring carbons in a 13C-
NMR spectrum.

There is, however, hetero-nuclear coupling between 13C carbon and the
hydrogens to which they are bound. Carbon-proton coupling constants are
very large, in the order of 100-250 Hz.

For clarity, chemists generally use a technique called broadband

decoupling, which essentially ‘turns off’ C-H coupling, resulting in a
spectrum in which all carbon signals are singlets.
Carbon resonances from 0-220 ppm relative to TMS standard as appeared
to only 0-12 ppm for proton, 13C-signal rarely overlaps; and we can almost
always distinguish separate peaks for each carbon, even in relatively large
compound containing carbon in a very similar environment.

In the proton spectrum of 1-heptanol, for example, only the signals for the
alcohol (Ha) and the two protons on the adjacent carbon (Hb) are easily
analyzed. The other proton signals overlap, making analysis difficult.
In the 13C- spectrum of the small molecule, however, we can easily
distinguish each carbon signal and we know from this data that our
sample has seven non-equivalent carbons.

It may be noted that the chemical shifts of the carbons get progressively
smaller as they get farther away from the deshielded oxygen.

The 13C-chemicl shifts are greatly affected by the electronegative

effects. If a H atom in an alkane is replaced by the substitutents (O, N,
X), 13C-signals for nearby carbons shifted downfield. The effect will
diminish increasing distance from the electronegative atom.
Spin-Spin Coupling/ Splitting: The 13C-13C spin coupling does occur if
abundance of carbon-13 is sufficient at one and adjacent carbons but
splitting rarely exists between adjacent carbons because 13C is lower in
natural abundance (1.1%).

13C-1H Spin Coupling: 13C-1H spin coupling provides useful information

about the number of protons attached to a carbon atom. In case of one bond
coupling (1JCH), -CH, CH2 and CH3 would respectively appear as doublet,
triplet, quartet for the 13C-resonances in the spectrum. However, 13C-1H spin
coupling has disadvantage for 13C spectrum interpretation, as 13C-1H spin
coupling is hard to analyze due to overlapping peaks which results from
100% natural abundance of 1H.
Spin-Spin Decoupling: Spin-spin decoupling is the process of
removing 13C-1H coupling interactions to simplify a spectrum and
identify that which pair of nuclei is involved in the J-coupling.

The decoupling 13C- spectra show only one peak (singlet) for each
unique carbon in the molecule.

Decoupling is performed by irradiating at the frequency of one proton

with continuous low-power radio frequency.
Assignments of Carbon Signals in 13C-NMR Spectrum: Following 13C-
NMR experiments are used to identify different carbon signals in a
molecule.

The normal 13C-NMR Spectrum is called the Broadband Spectrum. The

following experiments are performed to assign each signal in a molecule.

1. Gated Spin Echo (GASPE) 13C-NMR Spectrum

2. Insensitive Nuclei Polarization Transfer (INEPT) Spectrum

3. Distortionless Enhancement Polarization Transfer (DEPT) Spectrum.

GASPE NMR Experiment: An improved method for assignment of
resonance multiplicity in 13C-NMR spectra. Assignment may be achieved
by direct observation of resonance intensity modulations resulted from
the Gated Spin Echo (GASPE) experiments or from the derivation of
‘selected multiplicity’ spectra containing only C, CH, CH2 or CH3 carbon
resonances.

The methods are time efficient and by comparison with the single
frequency off-resonance decoupling assignment technique show
improved spectral resolution
APT NMR Experiment: The Attached Proton Test NMR
experiment provides information about how many protons or
hydrogens are attached to a particular carbon and is a common way
to assign C-H multiplicities in the 13C-NMR spectra. It provides
information of all sorts of carbons within one experiment.

Depending on number of hydrogens bound to a carbon atom, n,

CHn spin vectors evolve differently after the initial pulse
The APT NMR Spectrum of Diethyl Phthalate.
INEPT NMR Experiment: Insensitive nuclei enhancement by polarization
transfer is a signal resolution enhancement method used to in NMR to
enhance the signal of a nucleus with low gyromagnetic ratio (13C or 15N) by
transfer of polarization from a nucleus with high gyromagnetic ratio (1H).

A carbon-13 nuclei is far less sensitive than a proton and nitrogen-15 is far
less sensitive than a proton. It involves the transfer of nuclear spin
polarization from spins with large Boltzmann polarization difference to
nuclear spins of interest with low Boltzmann population differences.
The INEPT uses J-coupling for the polarization transfer in contrast to
nuclear overhauser effect (NOE) which arises from dipolar cross-
relaxation. It is a useful method to measure the insensitive nuclei by
simultaneous polarization transfer from the proton to corresponding nuclei.

Due to its usefulness in signal enhancement, pulse sequences used in

heteronuclear NMR experiments often contain blocks of INEPT or INEPT
like sequences.
The INEPT 13C-NMR Spectrum of Isobutyl Bromide.
The doublets show one peak with positive phase and the other with negative
phase. Triplets show the outer two peaks with positive and negative amplitude
and central peak with weak positive amplitude.

Quartets have the first two peaks with positive amplitude and remaining two
peaks with negative amplitude.
DEPT NMR Experiment: Distortionless enhancement by polarization transfer
(DEPT) experiment is an NMR method for determining the presence if primary,
secondary and tertiary carbon atoms in a molecule.

With the development of more modern spectroscopic other structural features

 In a DEPT spectrum, a sequence of pulses with various delay times are used to
create the DEPT spectra where -CH3 and CH signals appear as normal
(upward) while CH2 peaks appear inverted. Quaternary carbons are not usually
seen.

 The DEPT experiments differentiates between CH, CH2 and CH3 groups by
variation of the selection angle parameter (the tip angle of the final 1H pulse);
the 135o angle gives all CH and CH3 in a phase opposite to CH2; 90o angle
gives only CH groups, the others being suppressed; 45o angle gives all carbons
with attached protons (regardless of numbers) in phase.
 Both DEPT and INEPT are polarization transfer experiments- uses population
difference for a nucleus with high magnetogyric ratio (1H) and transfer this to a
nucleus with low magnetogyric ratio (13C).

 The difference between DEPT and INEPT is that for INEPT the pulse angle is
dependent of the chemical shift while for DEPT it is not. So, DEPT is an easier
experiment to run and much more common.
Readings
R. M Silverstein and G. C. Bassler, Spectroscopic Identification of Organic Compounds, John
Wiley & Sons, New York (1967).

R. M. Silverstein, F. X. Webster, D. J. Kiemle and D. L. Bryce, Spectroscopic Identification of

Organic Compounds, John Wiley & Sons, New York (2014).

D. L. Pavia, G. M. Lampman and G. S. Kriz Jr, Introduction to Spectroscopy, Saunders College,

Philadelphia (1974).

J. M. Hollas, Modern SpecTroscopy, John Wiley and Sons, New York (1996).

James Keeler, Understanding NMR Spectroscopy, John Wiley and Sons, London (2005).

Atta-ur-Rahman, Magnetic Resonance: Basic Principles, Springer-Verlag, New York (1986).

Atta-ur-Rahman, One and Two Dimensional NMR Spectroscopy, Elsevier New York (1989).