 NUCLEAR MAGNETIC

RESONANACE
 SPECTROSCOPY (NMR)

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 Introduction to NMR
 Types of NMR
 Source of NMR
 Theory of NMR
 Effect of magnetic field
 Principle of NMR
 Chemical shift
 Acquisition of spectra
 13
C NMR
 1
H NMR
 NMR set-up at IICPT
 Summary
 References
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 Nuclear magnetic resonance spectroscopy(NMR) is
a powerful analytical technique used to
characterize organic molecules by identifying
carbon-hydrogen frameworks within molecules.

 It is a research technique that exploits the magnetic

properties of certain atomic nuclei.

 It determines the physical and chemical properties

of atoms or the molecules in which they are
contained.
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 Two common types of NMR spectroscopy are
used to characterize organic structure:

 1
H NMR:- Used to determine the type and number of H
atoms in a molecule
 13
C NMR:- Used to determine the type of carbon atoms
in the molecule

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• The source of energy in NMR is radio waves which
have long wavelengths having more than 107nm,
and thus low energy and frequency.

• When low-energy radio waves interact with a

molecule, they can change the nuclear spins of
some elements, including 1H and 13C.

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 In a magnetic field, there are now two energy states for a proton:
a lower energy state with the nucleus aligned in the same
direction as Bo, and a higher energy state in which the nucleus
aligned against Bo.

 When an external energy source that matches the energy

difference between these two states is applied, energy is
absorbed, causing the nucleus to “spin flip” from one orientation
to another.

 The energy difference between these two nuclear spin states

corresponds to the low frequency RF region of the
electromagnetic spectrum.
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 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.

 Normally, these tiny bar magnets are randomly oriented in space. However,
in the presence of a magnetic field B0, they are oriented with or against this
applied field.

 More nuclei are oriented with the applied field because this arrangement is
lower in energy.

 The energy difference between these two states is very small (<0.1 cal).

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 A nucleus is in resonance when it absorbs RF radiation and
“spin flips” to a higher energy state.
 Thus, two variables characterize NMR: an applied magnetic
field B0, the strength of which is measured in tesla (T), and
the frequency n of radiation used for resonance, measured in
hertz (Hz), or megahertz (MHz).

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 The frequency needed for resonance and the
applied magnetic field strength are proportionally
related:
  BO

 The stronger the magnetic field, the larger energy

difference between two nuclear spin states and
higher the  needed for the resonance.

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 Both liquid and solid type of samples can be used in NMR
spectroscopy.

 For liquid sample, conventional solution-state NMR spectroscopy

is used for analysing where as for solid type sample, solid-state
spectroscopy NMR is used.

 In solid-phase media, samples like crystals, microcrystalline

powders, gels, anisotropic solutions, proteins, protein fibrils or all
kinds of polymers etc. can be used.

 In liquid phase, different types of liquid solutions, nucleic acid,

protein, carbohydrates etc. can be used.
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 Any proton or nucleus with odd mass number spins on its own
axis. By application of an electric field

 The sample is dissolved in a solvent, usually CDCl3(deutero-

chloroform), and placed in a magnetic field.

 A radiofrequency generator then irradiates the sample with a

short pulse of radiation, causing resonance.

 When the nuclei fall back to their lower energy state, the
detector measures the energy released and a spectrum is
recorded.

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Electromagnet

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 Protons in different environments absorb at slightly
different frequencies, so they are distinguishable by
NMR.

 The frequency at which a particular proton absorbs

is determined by its electronic environment.

 The size of the magnetic field generated by the

electrons around a proton determines where it
absorbs.
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 Modern NMR spectrometers use a constant magnetic field
strength B0, and then a narrow range of frequencies is applied to
achieve the resonance of all protons.

 Only nuclei that contain odd mass numbers (such as 1H, 13C, 19F
and 31P) or odd atomic numbers (such as 2H and 14N) give rise to
NMR signals.

The spin state of a nucleus is affected by an applied magnetic

field….
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 absorb E
-spin states -spin states
release E

Signals detected by NMR

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 The relative energy of resonance of a particular nucleus resulting
from its local environment is called chemical shift.

 NMR spectra show applied field strength increasing from left to

right.

 Left part is downfield, the right is upfield.

 Nuclei that absorb on upfield side are strongly shielded where

nuclei that absorb on downfield side is weakly shielded.

 Chart calibrated versus a reference point, set as 0, tetramethylsilane

[TMS].
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The electrons surrounding a nucleus affect the effective
magnetic field sensed by the nucleus.

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 Shielded nuclei do not ‘sense’ as large a magnetic field as
deshielded nuclei do. As a result, the energy difference
between the - and -spin states is much lower in energy for
shielded nuclei and resonate at a lower frequency.

Deshielded nuclei have a much higher energy difference between

the - and -spin states and these resonate at a much higher
frequency.
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 Numeric value of chemical shift: difference between
strength of magnetic field at which the observed
nucleus resonates and field strength for resonance of a
reference.

 Difference is very small but can be accurately

measured
 Taken as a ratio to the total field and multiplied by
106 so the shift is in parts per million (ppm)

 Absorptions normally occur downfield of TMS, to the

left on the chart.
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 The received nuclear magnetic resonance response is very weak in
signal and requires a sensitive radio receiver to pick up.

 A Fourier transform is done to extract the frequency-domain

spectrum from the raw time-domain spectrum.

 Good 1H NMR spectra can be acquired with 16 repeats, which

takes only minutes.

 However, for heavier elements than hydrogen, acquisition of

quantitative heavy-element spectra can be time-consuming, taking
tens of minutes to hours.

 Then a average of all the acquired spectrum will be generated and

displayed through the graph.

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 Carbon-13: only carbon isotope with a nuclear spin
 Natural abundance 1.1% of C’s in molecules
 Sample is thus very dilute in this isotope

 Sample is measured using repeated accumulation of data and averaging of

signals, incorporating pulse and the operation of Fourier transform (FT-
NMR).

 All signals are obtained simultaneously using a broad pulse of energy and
resonance recorded.

 Frequent repeated pulses give many sets of data that are averaged to
eliminate noise .

 Fourier-transform of averaged pulsed data gives spectrum shown in next

slide.
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Carbon-13 NMR spectra of 1-pentanol, CH3CH2CH2CH2CH2OH
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 Proton NMR is much more sensitive than 13
C and the active
nucleus (1H) is nearly 100 % of the natural abundance.

 Shows how many kinds of nonequivalent hydrogens are in a

compound.

 Theoretical equivalence can be predicted by seeing if replacing

each H with “X” gives the same or different outcome.

 Equivalent H’s have the same signal while nonequivalent are

“different” and as such may cause additional splitting
(diastereotopic effect).

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 Replacement of each H with “X” gives a different
constitutional isomer.

 Then the H’s are in constitutionally heterotopic

environments and will have different chemical shifts –
they are nonequivalent under all circumstances.

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 Type:- Bench top NMR spectrophotometer
 Frequency:- 60 MHz
 Magnet:- Permanent electromagnet
 Available nuclei:- 1H, 19F
 Sample:- Standard 5mm NMR glass tubes
 Field strength:- 1.41T
 Resolution:- 70 ppb
 Operating temperature:- 18-26C
 Power supply:- 100-240 VAC(50-60 Hz)
 Dimensions:- 242843 cm
 Weight:- 18kg
 Software:- Mnova software
 Cost:- 34,41,000

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 Nuclear magnetic resonance spectroscopy basically
provides the detailed information about the structure,
dynamics, reaction state, and chemical environment of
molecules.

 It has various applications in food industries, food

science, chemical analysis of different products,
pharmaceutical approach etc.

 To analyse the carbon-hydrogen framework in the

molecule is the basic work of NMR technique.

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 www.wikipedia.com
 "Background and Theory Page of Nuclear Magnetic Resonance
Facility". Mark Wainwright Analytical Centre - University of
Southern Wales Sydney. 9 December 2011. Retrieved9
February 2014.
 Schweiger A, Geschke G.  Principles of Pulse Paramagnetic
Resonance.  Oxford University Press. Oxford, 2001.
 Haner, R.L. and Keifer, P.A. (2009). "Flow Probes for NMR
Spectroscopy". Encyclopedia of Magnetic
Resonance. doi:10.1002/9780470034590.emrstm1085. ISBN 04
70034599.
 Chapter 13. Nuclear Magnetic Resonance Spectroscopy. Jo
Blackburn. Richland College, Dallas, TX. Dallas County
Community College District. ã 2003 
 http://orgchem.colorado.edu/Spectroscopy/nmrtheory/
THSNMR.ppt

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THANK YOU

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