The Basics of NMR Spectroscopy: Theory,

Instrumentation, Chemical Shift and Coupling

Irishi N. N. Namboothiri
Department of Chemistry, Indian Institute of Technology
Bombay, Mumbai 400 076, E-Mail: irishi@iitb.ac.in

Faculty Development Workshop on Teaching and Learning Chemical

Spectroscopy through Hands-on Experience
Department of Chemistry and Teaching-Learning Centre
NIT Warangal
11 September 2017
SPECTROSCOPIC TECHNIQUES
IN ORGANIC CHEMISTRY
Radiation Effect on molecule and the information
absorbed obtained
UV –Vis Changes in electronic energy levels within
λ 190-400 nm the molecules
400-800 nm Extent of conjugation

IR Changes in the vibrational and rotational

λ 2.5-25 μm movements of the molecules
- -1 Detection of certain functional groups
 400-4000 cm
MW ESR or EPR: changes in the magnetic
ν 9.5x109 Hz properties of unpaired electrons
Detection of free radicals
RF Changes in the magnetic properties of
certain atomic nuclei
Detection of nuclei in different
ν 60-900 MHz environments
EI Ionization and fragmentation of the
molecule
70 ev Detection of molecular structures
 NMR
Nuclear Magnetic Resonance

Detects

changes in the magnetic properties

of certain atomic nuclei

nuclei in different environments

 RF range
~ 60-900 MHz
E2

E1
ΔE = h (Planck 1900)
 Magnetic Nuclei
u

Each nucleus possesses a spin angular momentum P and a

magnetic moment m
(PAULI 1924)
 P = Ih/2p
Where I = spin quantum number

When I = 0 NMR inactive

e.g. 4 He, 12 C, 16 O ….etc

2 6 8

I = 1/2, 3/2, 5/2 ……etc NMR active

I = 1/2 e.g. 1 H, 13 C, 19 F, 31 P…… etc

1 6 9 15

Odd or even atomic number, odd mass number

i.e. odd number of protons or neutrons
 I = 1,2,3,…etc NMR active

I = 1 e.g. 2 D, 14 N……etc
1 7
Odd atomic number
Even mass number
i.e.
odd number of protons
+
odd number of neutrons
 The Larmor Equation

ω =  Bo ……… (1)

where ω is the precessional

frequency of the nucleus

 - gyromagnetic ratio
ω =  Bo ……… (1)

(7) in
Number of Possible Orientations
in an Applied Magnetic Field

2I + 1
m = Magnetic moment of the nucleus

Bo = Applied field
Frequency and Field Strength
Frequency (MHz) and Field Strength (T)

Nucleus 1.4 2.3 4.7 7.1

1H 60 100 200 300

13C 15.1 25.1 50.3 75.5

19F 56.5 94.1 188.2 288.2

31P 24.3 40.5 81.0 121.3

e 3.9x104
 Magnetic Properties of Some
Nuclei
Isotope Spin Natural Sensitivity ν (MHz)
Abundance Rela Absb at T = 2.3
%
1H 1/2 99.98 1 1 100.00
2D 1 1.5 x 10-2 9.65 x 10-3 1.45 x 10-6 15.35
13C 1/2 1.108 1.59 x 10-2 1.76 x 10-4 25.14
14N 1 99.63 1.01 x 10-3 1.01 x 10-3 7.22
15N 1/2 0.37 1.04 x 10-3 3.85 x 10-6 10.13
19F 1/2 100 0.83 0.83 94.08
31P 1/2 100 6.63 x 10-2 6.63 x 10-2 40.48
a At constant field for equal number of nuclei, b product of rel sensitivity & NA
 The Boltzmann Distribution

At thermal equilibrium
Nb < Na Δ E << kT
At 1.4 T, a state is only 0.001% more populated
than b state
Even at 11.7 T, (500 MHz) Δ E ~ 10-4 kJ
 Relaxation Processes
Saturation of signal Nb = Na

Spin-Lattice relaxation T1

Spin-Spin relaxation T2

Line width Δ

Δ Δt ~ 1/2p ....where Δt is lifetime

of nucleus at b state
 EARLY NMR
The first observation
1930 I.I. RABI Nobel Prize 1944

Molecules passed through a

magnetic field absorbed energy
and caused measurable deflection
of the beam. RF used 3.518 MHz!
NMR of Bulk Materials and
the First Spectrometer

E. Purcell 1945 (paraffin oil)

F. Bloch 1946 (Liquid H2O)
Nobel Prize 1952

Varian Associates, CA
Introduced NMR (1955)
Improved version A-60 (1961)
• Richard Earnst (Varian), Nobel Prize 1991

• FT-NMR: faster, improved S/N ratio

• 2D-NMR (1975): Spectral information

spread out into two spacial co-ordinates

• High Field Magnets

Permanent magnets
Electromagnets
Superconducting magnets
 NMR in Solids
Catalysts, Zeolites, Semi-conductors,
glasses, polymers, macromolecules

Medical Applications (MRI)

Paul Lauterbur (1973): NMR image of two tubes of

liquid water

Peter Mansfield (1974): image of human finger

2003 Nobel Prize

 INSTRUMENTATION
The Magnet
Permanent Magnet

Electromagnet

Superconducting Magnet
Nb alloy solenoid, dipped in liquid He (-259oC)
Special dewars: He inner chamber, N2 outer chamber
 The Probe
Dedicated: 1H or 1H-13C Multinuclear (broad band)

Sample Tube Diameter: 5 mm, 10 mm, 15 mm

Sample Insertion
Sample Spinning
Probe Tuning (Frequency adjustment)

Coiled wire transmits RF pulses to the

sample and receives signals from the sample
Shimming (Magnetic Field Adjustment)

Main Magnet

Static field along Z axis

Superconducting gradient
coils-factory set

RT coils- Field along x, y, z axes adjusted on sample change

Sample spinning along z axis

 Gradient Adjustments
Adjustment of z & z2 necessary for
high resolution and correct line shape

Deuterium Lock
Constant ratio between the magnetic field and
RF maintained by making adjustments to the
field such that D always absorbs at the same
frequency
 Resonance

ω of nuclei in different environments differ

transition occurs when ω matches with ν

 CW (Continuous Wave) Vs
FT (Fourier Transform) NMR
CW (Continuous Wave)
I
N
At a time only a narrow T
E
region is scanned N
e.g. 400 MHz, d 0-10 0-4000 Hz
S
I
T
Y
v
Slow scanning
Poor resolution
Absorption spectrum
FT (Fourier Transform) NMR

I
N
T
E
N
S FID
I
T
Y

T time
Delay Delay
FID – Free Induction Decay
A range of frequencies
 Signal to Noise Ratio (S/N)

Signal - grows in one direction

S = k1A….. where A is # of scans

Noise - random, partly cancels out

doesn’t grow at the rate of signal
N = k2 A1/2
S/N = (k1/k2) A1/2 = KA1/2 a √A