Many atomic nuclei have a property called spin.

Any atomic nucleus that possesses either odd mass, odd atomic
number, or both has a quantized spin angular momentum and a magnetic moment.
For each nucleus with spin, the number of allowed spin states it may adopt is quantized and is determined by its
nuclear spin quantum number I (no simple formula to calculate I). For each nucleus, the number I is a physical
constant, and there are 2I + 1 allowed spin states:

Whereas infrared (IR) spectroscopy reveals the types of functional groups present in a molecule, NMR gives
information about the number of magnetically distinct atoms. One can determine the number of each of the
distinct types of hydrogen nuclei as well as obtain information regarding the nature of the immediate
environment…
A hydrogen nucleus may have a clockwise or counterclockwise spin, and the nuclear magnetic moments (μ) in the
two cases are pointed in opposite directions.
In an applied magnetic field, all protons have their magnetic moments either aligned with the field or opposed to it…

For H For Cl
 Leads to NMR signals (Relaxation is observed)

ΔE is the energy absorbed, ν is its frequency

γ is the magnetogyric ratio (a constant value for each nuclei)
The Mechanism for Absorption
(Resonance)

The precession of a spinning nucleus resulting

from the influence of an applied magnetic field.
For H nucleus, if the applied magnetic field (Bo) = 1.41 Tesla
→ Resonance is observed at 60 MHz, (2.39 x 10-5 kJ/mole) a small energy gap almost equally populated by
both spin states

There is, however, a slight excess of nuclei in the lower-energy spin state → source of the signal (!!!)

298 K, 60 MHz

Increasing Bo increases the

excess population and the
intensty of resulting NMR
signal (!!!)
! As Δ E increases so does the excess population
and the NMR signal
Electrons surrounding the
protons are also affected by
Bo, and respond by
generating an opposite
magnetic field

As a result the electron

density plays a crucial role
in the total magnetic field
protons are exposed to, in
their precession
frequencies and the
absorbed frequency at
resonance
If different Bo is used than a different frequency will result for the same nucleus, SO
AN INTERNAL SAMPLE IS ALWAYS PRESENT IN NMR ANALYSIS

Tetramethylsilane (TMS) (CH3)4Si is used since its nuclei are highly shielded:

All other absorbed frequencies coming from the analyte are reported as a distance in
PPM (parts per million), which is called ‘chemical shift’ (δ)

E.g. At 60 MHz the shift of the protons in CH3Br is 162 Hz from TMS, while at 100
MHz the shift is 270 Hz. Both are 2.70 ppm
INSTRUMENT

Modern sophisticated instruments use a powerful but short burst of energy, called a
pulse, that excites all of the magnetic nuclei in the molecule simultaneously

Old NMR spectrometers used variable magnetic field to subsequently excite all
different protons.
Many different frequencies of electromagnetic radiation are emitted simultaneously, to
result in free-induction decay (FID) signal
The FID is a superimposed combination of all the frequencies emitted and can be
quite complex. Individual frequencies of different nuclei are extracted by computer
through Fourier transform (FT) analysis.
Pulse technique and Fourier transform (FT) analysis can be performed fast allowing
for high number of scans (n).

As n increases so the signal to noise ratio

CHEMICAL EQUIVALENCE (and unequivalence…)

Single peak

Two peaks

Three peaks
INTEGRATION: Accurate quantification of relative numbers of distinct protons is
possible in NMR spectroscopy, a very important information in structural determination
CHEMICAL ENVIRONMENT determines the ‘Chemical Shift’
LOCAL DIAMAGNETIC SHIELDING and Electronegativity Effects
 sp2 Carbon is more
electronegative than sp3
Carbon deshielding its
protons

Aromatic protons have

resonance further downfield:
7-8 ppm, due to ‘anisotropy’

Hydrogens on an ‘sp’ ‘Anisotropy’ and inductive

hybridized Carbon appear at effects are combined in
an unexpectedly upfield aldehydes, bringing the shift
region between 2-3 ppm, due to 9 to 10 ppm
to ‘anisotropy’
Exchange of protons:
Number of C peaks,
and multiplicities on a
proton-coupled C13
NMR spectrum?