NMR Spectroscopy

NMR spectroscopy
 It is used to determine relative location of atoms within a
molecule

 It is the most helpful spectroscopic technique in organic

chemistry

 It is related to Magnetic Resonance Imaging (MRI) in medicine

 It maps carbon-hydrogen framework of molecules

 It depends on very strong magnetic fields

 NMR Spectroscopy
NMR is a technique used to map the carbon-hydrogen framework

It detects the energy absorption accompanying the transition

between nuclear spin states that occurs when a molecule is
placed in a strong magnetic field and irradiated with
radiofrequency waves.

NMR is the most powerful tool available for organic structure

determination. It is used to study a wide variety of nuclei:
1H, 13C, 15N, 19F, 31P
About nuclear magnetic field
 All nuclei carry a charge. In some nuclei this charge “spins” on
the nuclear axis, and this circulation of nuclear charge generates
a magnetic dipole along the axis.
 A nucleus with an odd atomic number or an odd mass number
has a nuclear spin.
 The spinning charged nucleus generates a magnetic field.
About nuclear magnetic field
 The most important nuclei for organic structure determination are
1H (ordinary hydrogen) and 13C, a stable nonradioactive isotope of

ordinary carbon.
 When placed in an external field, spinning protons act like bar
magnets.
Principles of NMR Spectroscopy
Two Energy States

A photon with the right

amount of energy can be
absorbed and cause the
spinning proton to flip.

In the absence of an external

magnetic field(a), magnetic nuclear
spins are oriented randomly
The magnetic fields of the spinning
nuclei will align either with the
external field, or against the
field(b).
 Principles of NMR Spectroscopy

The parallel spin state (orientation) is slightly

lower in energy and therefore favored (more
populated).

When the oriented nuclei are irradiated with proper electromagnetic

radiation frequency, energy is absorbed and the nuclei “spin-flip” from
the lower-energy state (parallel) to the higher-energy state
(antiparallel)

 Magnetic nuclei are said to be in resonance with the applied

radiation (hence the name of nuclear magnetic resonance).

 The absorption of energy is detected, amplified and displayed as a

nuclear magnetic resonance spectrum
Principles of NMR Spectroscopy
The exact frequency necessary for resonance depends on:
i) strength of the external magnetic field ii) identity of the nuclei

In the absence of an applied magnetic field, spin states have equal

energies. In the presence of a magnetic field (Bo), spin states have
unequal energies
If a very strong magnetic field is applied, the energy difference between
the two spin states (DE) is larger, and higher-frequency (higher-energy)
radiation is required for a spin-flip
The Mechanism of Absorption
(a) A top precessing in the earth’s gravitational field; (b) the
precession of a spinning nucleus resulting from the influence of an
applied magnetic field.
The Mechanism of Absorption
The nuclear magnetic resonance process: absorption occurs when ν = ω.
Where ν is applied radio frequency and ω is the angular frequency of
precession.
Population densities of nuclear spin
states
 For a proton, if the applied magnetic
field strength is 1.41 Tesla,
resonance occurs at about 60 MHz

 The energy different between the

two spin states is about 6 x 10-6
kcal/mole in a 60 MHz instrument

 At room temperature both the states

are almost equally populated

 There is slight excess of nuclei in the

lower energy state
Problems
The amount of energy required to spin-flip a nucleus depends both
on the strength of the external magnetic field and on the nucleus. At
a field strength of 4.7 T, rf energy of 200 MHz is required to bring a
1H nucleus into resonance, but energy of only 187 MHz will bring a

19F nucleus into resonance. Use the equation below to calculate the

amount of energy required to spin-flip a 19F nucleus. Is this amount

greater or less than that required to spin-flip a 1H nucleus?

Calculate the amount of energy required to spin-flip a proton in a

spectrometer operating at 300 MHz. Does increasing the
spectrometer frequency from 200 to 300 MHz increase or decrease
the amount of energy necessary for resonance?
Measuring an NMR Spectrum
The magnetic field strength and the size of the energy gap between
nuclear spin states are directly related.

 In earlier NMR spectrometers, a constant radio frequency was

applied, the strength of the applied magnetic field was varied, and
different nuclei resonated at different magnetic field strengths.

 In modern Fourier transform (FT-NMR) spectrometer, the applied

magnetic field is held constant, and the radio frequency is varied.
The instrument computer uses a mathematical process called
Fourier transformation to sort the signal that is produced into the
resonance rfs of the different 1H nuclei.
The NMR spectrometer
Nature of NMR Absorptions
The absorption frequency is not the same for all 1H or 13C nuclei in a
molecule. All nuclei in molecules are surrounded by electrons with
their own magnetic fields Blocal

When an external field is applied to a molecule, the effective field

(Beffective) felt by the nucleus is a bit smaller than the applied field
(Bapplied) : Beffective = Bapplied – Blocal

Electrons setting up local magnetic fields shield nearby nuclei from

the full effect of the applied field

Since each specific nucleus in a molecule is shielded to a slightly

different extent, the effective magnetic field is not the same for each
nucleus:
A distinct NMR signal for each chemically distinct 1H or 13C nucleus in
a molecule can be detected.
 Magnetic Shielding

 If all protons absorbed the same amount of energy in a given

magnetic field, not much information could be obtained.

 But protons are surrounded by electrons that shield them from the
external field.

 Circulating electrons create an induced magnetic field that

opposes the external magnetic field.
Shielded Protons
Magnetic field strength must be increased for a shielded proton to
flip at the same frequency.
Protons in a Molecule
Depending on their chemical environment, protons in a molecule
are shielded by different amounts.

=>
NMR Spectrum

NMR spectrum – plots the effective field strength felt by the nuclei
(X-axis) versus the magnitude or intensity of NMR resonance signals
(corresponding to the intensity of rf energy) (Y-axis)

The intensity of NMR resonance signals is proportional to the molar

concentration of the sample.

Each peak in the NMR spectrum corresponds to a chemically distinct

1H or 13C nucleus in the molecule

1H or 13C spectra cannot be observed on the same spectrometer

because of the difference in energy required to spin-flip the nuclei
 NMR spectrum
A plot of the frequencies of the absorption peaks versus peak intensities
constitutes an NMR spectrum.
Measuring an NMR spectrum

 A 1H-NMR spectrum is usually obtained by dissolving the sample

in some inert solvent that does not contain 1H nuclei.

 Examples of such solvents are CCl4, or solvents with the

hydrogens replaced by deuterium, such as CDCl3, and CD3COCD3.

 A small amount of a reference compound is also added.

 The solution, in a thin glass tube, is placed in the center of a radio

frequency (rf) coil, between the pole faces of a powerful magnet.
Reference compound
 Tetramethylsilane (TMS) is added to the sample.

 All 12 nuclei of its hydrogens are equivalent, so it shows only one

sharp NMR signal, which serves as a reference point

 Silicon is less electronegative than carbon and hence its hydrogen

signals appear at higher field than do most 1H signals in other
organic compounds, thus making it easy to identify the TMS peak

 TMS protons signal is defined as zero in d scale

 Organic protons absorb downfield (to the left) of the TMS signal.

 TMS is inert, so it does not react with most organic compounds.

and
 TMS boiling point is low (26-28 °C)and can be removed easily at
the end of a measurement
Chemical Shift
 The relative energy of resonance of a particular nucleus resulting
from its local environment

 The position on the NMR chart where a nucleus absorbs

 Ratio of shift downfield from TMS (Hz) to total spectrometer

frequency (MHz). It is called the delta(d) scale and expressed as
parts per million(ppm)

 The chemical shift of an NMR absorption in d units is constant,

regardless of the operating frequency of the spectrometer
(independent of instrument’s field strength)
Example: A 1H nucleus at d = 2.0 ppm on a 60 MHz
instrument also absorbs at d = 2.0 ppm on a 300 MHz.
Chemical Shift
Interpretation of a spectrum is easier with higher operating
spectrometer frequency (less likelihood of signal overlap)

For 60 MHz instrument, 1d = 60 Hz

For 300 MHz instrument, 1d = 300 Hz

Absorptions normally occur downfield of TMS:

Almost all 1H NMR absorptions occur 0-10 ppm from TMS
Almost all 13C NMR absorptions occur 0-220 ppm from TMS.
Chemical Shift - Delta Scale(d)
Chemical Shift
NMR spectra show the applied field strength increasing from left to
right:
 Left part is downfield (or low-field); Nuclei that absorb on the
downfield side are weakly shielded

 Right part is upfield (or high-field); Nuclei that absorb on the

upfield side are strongly shielded
Problems
1. When the 1H NMR spectrum of acetone, CH3COCH3, is recorded on an
instrument operating at 200 MHz, a single sharp resonance at 2.1 d is
seen.

a) How many hertz downfield from TMS does the acetone

resonance correspond to?

b) If the 1H NMR spectrum of acetone were recorded at

500 MHz, what would be the position of the absorption
in d units?

c) How many hertz downfield from TMS does this 500 MHz
resonance correspond to?

2. The following 1H NMR peaks were recorded on a spectrometer

operating at 200 MHz. Convert each into d units.

a) CHCl3; 1454 Hz, b) CH3Cl; 610 Hz,

c) CH3OH; 693 Hz, d) CH2Cl2; 1060 Hz
NMR Signals

 The number of signals shows how many different kinds of protons

are present

 The location of the signals shows how the proton is shielded or

deshielded

 The intensity of the signal shows the number of protons of that

type

 Signal splitting shows the number of protons on adjacent atoms.

NMR Signals
Chemically equivalent nuclei are shielded to the same extent (i.e they
have the same electronic environment)
always show a single absorption

The 3H’s on –OCH3 The 3H’s on CH3C=O

are equivalent are equivalent
Integral of Signals
 The area under each peak is proportional to the number of protons

 Shown by integral trace.

Location of Signals

 More electronegative atoms deshield more

and give larger shift values.

 Effect decreases with distance.

 Additional electronegative atoms cause

increase in chemical shift.