1

NMR SPECTROSCOPY
 Theory of NMR
2

 A spectroscopic technique that gives us information about the

number and types of atoms in a molecule.
 Nuclear magnetic resonance spectroscopy is a powerful
analytical technique used to characterize organic molecules by
identifying carbon-hydrogen frameworks within molecules.

Nuclear Magnetic Resonance

In the Nucleus Involves In the Nucleus

Magnets
3

 Two common types of NMR spectroscopy are used to

characterize organic structure: 1H NMR is used to determine the
type and number of H atoms in a molecule; 13C NMR is used to
determine the type and number of C atoms in the molecule.
 The source of energy in NMR is radio waves which have long
wavelengths, and thus low energy and frequency.
 When low-energy radio waves interact with a molecule, they
can change the nuclear spins of certain atoms in presence of
strong magnetic fields, including 1H and 13C.
 All the atoms contains nuclei and all nuclei contains protons (+ve)
charge in which some charge nuclei posses “Spin” on their own
axis.
4

 Spin nuclei are those which contains either Odd atomic number or
odd atomic mass number or both e.g. 1H, 2H, 13C, 14N, 17O,
35Cl etc are useful for NMR.
 Those nuclei contains Even number of atomic and mass number are
not useful for NMR e.g. 12C, 16O etc.
 The nuclei posses spin, they spin on their nuclear axis leads to
generate magnetic dipole ‘µ’ so the angular momentum of this
spinning charge is quantified and described by Quantum Spin
Number “ I ”.
1 2 12 13 14 15 16 19 31 32
Eleme nt H H C C N N O F P S

Nuclear spin
quantum 1/2 1 0 1/2 1 1/2 0 1/2 1/2 0
number ( I )

Number of 2 3 1 2 3 2 1 2 2 1
spin states
5

 The individual protons have spin quantum number +1/2 or -1/2.

 i.e. Hydrogen have spin quantum number (I) = +1/2 or -1/2.
+1/2 - 1/2

Fig. 1. Two spin states allowed for proton (H)

 These spin states have equal amount of energy (degenerated) in
the absence of magnetic field.
 When a charged particle such as a proton spins on its axis, it
creates a magnetic field. Thus, the nucleus can be considered to
be a tiny bar magnet.
6

 But when magnetic field is applied, the proton (H) posses spin &
their own magnetic field align themselves either or opposite to
magnetic field.
 For e.g. 1H has +1/2 & -1/2 spin state, the proton (H) have
+1/2 spin state align themselves with field (Lower energy) and
with -1/2 spin state align opposite to field (Higher energy).
7

Fig.2. Change in spin state energy separation with increase by applied magnetic
field, B0
8

 Stronger the applied magnetic field, greater will be the

difference between the spin state, ∆E = f(B0) eq. ------1
 As Eabsorbed (∆E) = difference in energy levels of two energy
states = hv.
 Each nucleus depending on its charge and mass has its own
magnetogyric ratio ‘Ý’ which is ratio of magnetic dipole moment
to angular momentum, and it constant for each nucleus,
therefore,
 ∆E = f(ÝB0) = hv ------------2
 ∆E = Ý(h/2πB0) = hv --------3
 v = (Ý/2π) B0 ----------------4
 Here, v is frequency of electromagnetic radiation.
9

 Precessional frequency:- May be defined as revolutions per

second made by the magnetic moment vector of the nucleus
around the external magnetic field Bo & Alternatively
precessional frequency of spinning bar magnet may be defined
as equal to the frequency of EMR in megacycles per second
necessary to induce a transition from one spin state to another
spin state.
 The energy required to bring transition in NMR (∆E = hv) or to
flip proton depends upon the strength of external magnetic field.
 So, stronger the field greater will be the tendency of nucleus
magnet to remain lined up with it and higher will be the
frequency of radiation needed to flip proton to higher energy
state.
 Nuclear Magnetic Resonance
10

 NMR is phenomenon which occurs when those nuclei which are

aligned with applied magnetic field are induce to absorb
energy and change their spin state to opposite state, it is called
as resonance.
 Fig. 3. shows
11

 The proton (Nucleus) +ve charge particle generates an

magnetic field on its axis with same frequency as that of
applied magnetic field, is called precessional frequency.
 The frequency of precession (proton) is directly proportional to
the strength of applied magnetic field.
 If the precessing nucleus is irradiated with electromagnetic
radiation of the same frequency as that frequency of
precession nucleus, then
 The two frequencies couple
 Energy is absorbed
 The nuclear spin is flipped from spin state +1/2 (with the
applied field) to -1/2 (against the applied field).
12

Fig.4. A nucleus is in resonance when it absorbs RF radiation

and spin flips to higher energy states.
 Instrumentation
13

 The NMR spectrophotometer consists of following components;

 A magnet
 Sample and sample holder
 Radiofrequency generator
 Detector
 Recorder
 In NMR spectrophotometer, the sample is dissolved in CDCl3 and
placed in magnetic field. Then radiofrequency generator irradiates
the sample with short pulse of radiation causing resonance. When
nuclei fall back to their low energy state, detector measures the
energy released and spectrum is recorded. The superconducting
magnet in modern NMR spectrometers have coils that are cooled in
liquid helium and conduct electricity with no resistance.
14

 A line diagram of NMR spectrophotometer along with its

components are as follows;
15

 Magnet:- A strong magnet provides stable and homogenous

field. The magnet size is 15 inches in diameter and capable of
producing strong fields up to 23,500 gauss for 100MHz.
 Sample and sample holder:- A 1 – 30 mg sample is used in the
form of dilute solution (2 – 10%) and solvent doesn’t contain
hydrogen of its own ions. The sample holder is glass tube about
5mm in diameter and 15 – 20 cm in length.
 Radiofrequency oscillator:- The RF oscillator is installed
perpendicular to magnetic field and transmits radio waves of
some mixed frequency such as 60, 100, 220, 300 MHz. a
sweep generator is installed to supply dc current to sec. magnet.
16

 RF detector or Receiver:- It is installed perpendicular to both

magnetic field and the oscillator coil and is tuned to the same
frequency as transmitter. When precession frequency is match
with RF the nuclei induces (emf) in detector coil and this signal
is amplified and sent to recorder.
 Recorder :- The recorder gives a spectrum as a plot of strength
resonance signal on Y axis & strength of magnetic field on X
axis. The strength of resonance signal is directly proportional
to number of nuclei resonating at that particular field strength.
 Working of instrument
17

 Sample placed in long cylindrical glass tube especially made

for NMR.
 Dissolved the sample in proton free solvent like CDCl3 or CCl4
and add small amount of TMS as internal reference.
 Placed the sample in gap between two magnetic poles where
coil is attached to a specific RF generator (e.g. 60 MHz).
 This coil supply EMR energy required to change spin orientation
of proton.
 Then detector coil detects radiofrequency signal when
resonance occurs.
 As magnetic field strength increase, the precessional frequency
of all protons increase and when this frequency proton reaches
18

60 MHz, the resonance occurs.

 So, as magnetic field increase linearly the recorder pen travels
from left to right, thus protons which achieve resonance faster
i.e. (Deshielded) appears on left side (downfield), where as
those protons (Shielded) appears on right side (upfield) of chart
in the form of peaks.
 TMS is shown at a peak value of δ = 0 ppm.
 Solvents
19

 The solvent used for dissolving sample should have following

properties;
 Should not contain proton,

 Inexpensive

 Low boiling point and non polar in nature.

 Generally deuterated chloroform CDCl3 is used as solvent.

 If sample is soluble in polar solvent, then deuterium oxide (D2O),
DMSO, CCl4, CS2, Cf3, COOH are used as solvent.
 CH3
CH3 Si CH3
Internal Standard CH3
Tetrameth yls ilane (TMS)
20

 But TMS (Tetra methyl silane) is most commonly used as IS for

measuring the position of 1H, 13C and 29Si in NMR spectroscopy.
Due to following reasons;
 It is chemically inert and miscible with a large range of
solvents.
 Its twelve protons are all magnetically equivalent.

 Its protons are highly shielded and gives a strong peak even

small quantity.
 It is less electronegative than carbon.

 It is highly volatile and can be easily removed to get back

sample.
 It does not take part in intermolecular associations with sample.
21

 Its resonance position is far away from absorptions due to

protons in most organic molecules, thus signals of TMS = 0.
 Chemical Shift (Position of Signals)
22

 The utility of NMR is that all protons do not show resonance at

same frequency boz, it is surrounded by particular no. of
valence electrons which vary from atom to atom so, they exist in
slightly different electronic environment from one another.
 Position of signals in spectrum help us to know nature of protons
i.e. aromatic, aliphatic, acetylinic, vinylic, adjacent to electron
releasing or withdrawing grp. Thus they absorb at different
field strength.
 When molecule placed in magnetic field, so its surrounding
electron circulate & generates counter field which opposes the
applied magnetic field on proton so that, field feels by proton is
reduced and that proton called as the Shielded proton.
23

 Rotation of electrons (π) to nearby nuclei generate field that can

either oppose or strong the field on proton.
 If magnetic field is oppose applied magnetic field on proton,
that proton said shielded proton and if field is strong the
applied field then, proton feels high magnetic field strength and
such proton called as Deshielded proton.
 So, shielded proton shifts absorption signal to right side
(upfield) and deshielded proton shifts absorption signal to left
side (down field) of spectrum.
 So, electric environment surrounding proton tells us where proton
shows absorption in spectrum.
24

 Such shifting in position of NMR absorption signals which arise

due to the shielding or deshielding of proton by surrounding
electrons are called as Chemical shift.
 Shielding or Deshielding Protons In Molecule
25

 As we have seen, depending on electronic environment protons

in molecules are shielded or deshielded by different amounts.
26

 So, shielded proton shows absorption of signals to right side

and deshielded protons at left side of spectrum.
27

 For measuring chemical shifts of various protons in a molecule,

the signal of TMS is taken as reference, due to low electro-
negativity of Si atom and shielding of equivalent protons gives
1 NMR signal is greater than most of organic compounds.
 The nmr signal for particular protons will appear at different
field strength compared to signal from TMS.
 This difference in the absorption position of the proton with
respect to TMS signal is called as chemical shift (δ – value).
 In majority of organic compound, protons resonate at lower
field than protons of TMS boz, its signals appears at the
extreme right side of spectrum, thus assigning delta (δ) value
for TMS equal to zero (0).
28

 Any proton or set of protons which absorb at lower field than

TMS is given a positive value for (δ).
 The value of δ for a substance w.r.p to TMS can be obtained by
Chemical shift, ppm δ = Shift downfield from TMS (in Hz)
Spectrometer frequency (in MHz)
 The value of chemical shift, δ expressed in ppm and their value
is between 0 to 10 in the δ scale.
 In the τ scale, signal for standard reference, TMS taken as 10
ppm.
 The two scales are related by the expression
 τ = 10 - δ
29

Chemical shift depends upon following parameters:

 Electro negativity of nearby atoms

 Hybridization of adjacent atoms

 Diamagnetic effects from adjacent pi bonds

30

 Electro negativity of nearby atoms

Electron eg- Chem ical
CH3 - X ativ ity of X Shif t ()
CH3 F 4.0 4.26
CH3 OH 3.5 3.47
CH3 Cl 3.1 3.05
CH3 Br 2.8 2.68
CH3 I 2.5 2.16
( CH3 ) 4 C 2.1 0.86
( CH3 ) 4 Si 1.8 0.00
31

 Hybridization of adjacent atoms

Type of Hydrogen Name of Chemical

(R = alkyl) Hydrogen Sh ift ()
RCH3 , R2 CH2 , R3 CH Alkyl 0.8 - 1.7
R2 C=C(R)CHR2 Allylic 1.6 - 2.6
RC CH Acetylen ic 2.0 - 3.0
R2 C=CHR, R2 C=CH2 Vinylic 4.6 - 5.7
RCHO Aldehydic 9.5-10.1
32

 Diamagnetic effects from adjacent pi bonds

A carbon-carbon triple bond shields an acetylenic
hydrogen and shifts its signal to lower frequency (to the
right) to a smaller  value.
 A carbon-carbon double bond deshields vinylic
hydrogens and shifts their signal to higher frequency (to
the left) to a larger  value.
Chemical
Type of H N ame Shift ()
RCH3 Alk yl 0.8- 1.0
RC CH Acetylenic 2.0 - 3.0
R2 C=CH2 Vin ylic 4.6 - 5.7
 Chemical Shift Values (Benzene)
33

 In a magnetic field, the six  electrons in benzene circulate around

the ring creating a ring current.
 The magnetic field induced by these moving electrons reinforces the

applied magnetic field in the vicinity of the protons.

 The protons thus feel a stronger magnetic field and a higher

frequency is needed for resonance. Thus they are deshielded and

absorb downfield.
34

 In a magnetic field, the loosely held  electrons of the double bond

create a magnetic field that reinforces the applied field in the
vicinity of the protons.
 The protons now feel a stronger magnetic field, and require a

higher frequency for resonance. Thus the protons are deshielded

and the absorption is downfield.
35

 In a magnetic field, the  electrons of a carbon-carbon triple

bond are induced to circulate, but in this case the induced
magnetic field opposes the applied magnetic field.
 Thus, the proton feels a weaker magnetic field, so a lower
frequency is needed for resonance. The nucleus is shielded and
the absorption is upfield.
36
 Factors affecting chemical shift
37

Following are the factors which influence the chemical

shift;
 Inductive effect
 Van der Waal’s deshielding
 Anisotropic effect
 Hydrogen bonding
 Spin-Spin Splitting in NMR Spectrum
38

 Peaks are often split into multiple peaks due to magnetic

interactions between nonequivalent protons on adjacent
carbons, The process is called Spin-spin Splitting/Coupling.
 Spin-spin splitting: It occurs only between nonequivalent protons
on the same carbon or adjacent carbons.
 Peak: The units into which an NMR signal is split; doublet, triplet,
quartet, multiplet, etc.
 Signal splitting: Splitting of an NMR signal into a set of peaks by
the influence of neighboring nonequivalent hydrogens.
 Signal coupling: An interaction in which the nuclear spins of
adjacent atoms influence each other and lead to the splitting of
NMR signals.
 Equivalent & Nonequivalent Protons
39

 Equivalent protons are like this;

 These equivalent protons do not split each other.

 Protons bonded to the same carbon will split each other only if
they are not equivalent.
 Equivalent protons have the same chemical shift.
40

 Equivalent protons have same chemical shift without splitting

occurs
41

 Nonequivalent protons are like this;

 If Ha and Hb are not equivalent, the splitting is observed.

 Nonequivalent protons on adjacent carbons have magnetic fields
that may align with or oppose the external field.
 This magnetic coupling causes the proton to absorb slightly
downfield when the external field is reinforced and slightly
upfield when the external field is opposed.
 All possibilities exist, so signal is split.
42

 Non equivalent protons have different chemical shift with

splitting occurs
43

 Splitting is not generally observed between protons separated

by more than three  bonds.
44

 Peak: The units into which an NMR signal is split; doublet, triplet,
quartet, multiplet, etc.
 So now, let us consider how the doublet signal due to the CH2
group on BrCH2CHBr2 occurs:
 When placed in an applied field, (B0), the adjacent proton

(CHBr2) can be aligned with () or against () B0.

 Thus, the absorbing CH2 protons feel two slightly different

magnetic fields—one slightly larger than B0, and one slightly

smaller than B0.
 Since the absorbing protons feel two different magnetic fields,

they absorb at two different frequencies in the NMR spectrum,

thus splitting a single absorption into a doublet, where the two
peaks of the doublet have equal intensity.
 How doublet signal arises
45

J
46

 Let us now consider how a triplet arises:

 When placed in an applied magnetic field (B0), the adjacent

protons Ha and Hb can each be aligned with () or against
() B0.
 Thus, the absorbing proton feels three slightly different
magnetic fields—one slightly larger than B0(ab). one
slightly smaller than B0(a b) and one the same strength as
B0(a b).
47

 Because the absorbing proton feels three different magnetic

fields, it absorbs at three different frequencies in the NMR
spectrum, thus splitting a single absorption into a triplet.
 Because there are two different ways to align one proton with
B0, and one proton against B0—that is, ab and ab—the
middle peak of the triplet is twice as intense as the two outer
peaks, making the ratio of the areas under the three peaks
1:2:1.
 Two adjacent protons split an NMR signal into a triplet.
 When two protons split each other, they are said to be coupled.
 The spacing between peaks in a split NMR signal, measured by
the J value, is equal for coupled protons.
 How triplet signal arises
48
 Doublet and triplet signals
49
 How quartet signal arises
50
 Signal Splitting: The (n + 1) Rule
51

 In a NMR spectrum all equivalent protons do not appear as a signal

peak, e.g. 1,1,2 - tribromoethane which has two types of
equivalent protons, thus it shows two peaks in NMR spectrum.
 But the actual spectrum consists of two peaks but subdivided into 3
and 2 sub peaks or splitting one for (CH) and two for (CH2Br)
protons respectively.
 This phenomenon of splitting of equivalent protons into (n + 1) rule,
where n is the no. of equivalent protons attached to the adjacent
carbon to which the protons under consideration is attached.
 So as per the (n + 1) rule in 1,1,2- tribromoethane, the (C1) has
two equivalent protons of Methylene on the carbon next to it,
therefore, n = 2 and hence it will split into (2+1) = 3 peaks
(Triplet).
52

 The Methylene protons are having n = 1 therefore, it will split

(1+1) = 2 peaks (Doublet).
 Another example
53

For these hydrogens, n = 1; For this hydrogen, n = 3;

their signal is split into CH3 - CH- Cl its signal is split into
(1 + 1) = 2 peaks; a doublet Cl (3 + 1) = 4 peaks; a quartet
 1H NMR—Structure Determination
54
55
56
57
 Applications of NMR Spectrum
58

 Identification of structural isomers

 Detection of hydrogen bonding
 Detection of aromaticity
 Distinction between Cis-trans isomers and conformers
 Detection of electronegative atoms or group
 Detection of some double bond character due to
resonance
59

References:-
 Elementary Organic Chemistry, Principles and Chemical
Applications; by Y.R. Sharma, Pg.no: 180 – 237.

 Basics Concepts in Pharmaceutical Research, by Bijiya

Ghosh and Sonal Dubey; Pg. no: 160 – 175.
60