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NMR

The document provides an overview of spectroscopy, particularly focusing on Nuclear Magnetic Resonance (NMR) spectroscopy, which analyzes molecular structures by measuring nuclear spins in a magnetic field. It explains the principles of NMR, including the energy states of protons, resonance, and the factors affecting chemical shifts in NMR spectra. Additionally, it discusses the interpretation of 1H NMR spectra, including the significance of signal number, position, intensity, and spin-spin splitting.

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19 views

NMR

The document provides an overview of spectroscopy, particularly focusing on Nuclear Magnetic Resonance (NMR) spectroscopy, which analyzes molecular structures by measuring nuclear spins in a magnetic field. It explains the principles of NMR, including the energy states of protons, resonance, and the factors affecting chemical shifts in NMR spectra. Additionally, it discusses the interpretation of 1H NMR spectra, including the significance of signal number, position, intensity, and spin-spin splitting.

Uploaded by

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Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Dr.

Shahbaa Shafeeq
5th Stage
Spectroscopy is the study of the absorption and emission
of light and other radiation by matter, as related to the
dependence of these processes on the wavelength of the
radiation. More recently, the definition has been expanded to
include the study of the interactions between particles such
as electrons, protons and ions as well as their interaction with
other particles as a function of their collision energy.

2
Fluorimetry
Emission
Flame
photometer
Spectroscopy
NMR

Absorption IR

UV

3
An Introduction to NMR Spectroscopy
NMR is an abbreviation for Nuclear Magnetic Resonance. NMR is
spectroscopic technique allows the molecular structure of a material
to be analyzed by observing and measuring the interaction of nuclear
spins when placed in a powerful magnetic field.

Two common types of NMR spectroscopy are used to characterize


organic structure:

• 1H NMR (proton NMR) is used to determine the number and type of


hydrogen atoms in a molecule.

•13C NMR (carbon NMR) is used to determine the type of carbon


atoms in a molecule.
The Basis of NMR Spectroscopy
The source of energy in NMR is radio waves. Radiation in the
radiofrequency region of the electromagnetic spectrum (so-called RF
radiation) has very long wavelengths, so its corresponding frequency and
energy are both low. When these low-energy radio waves interact with a
molecule, they can change the nuclear spins of some elements, including
1H and 13C. When a charged particle such as a proton spins on its axis, it
creates a magnetic field. Therefore, a nucleus is a tiny bar magnet,
symbolized by . Normally these nuclear magnets are randomly oriented
in space, but in the presence of an external 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, but the
energy difference between these two states is very small.
In a magnetic field, there are now two different energy states for a proton:
• A lower energy state with the nucleus aligned in the same direction as B0
• A higher energy state with the nucleus aligned opposed to B0
When an external energy source (hν) that matches the energy difference (∆E)
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 lower frequency radiation in
the RF region of the electromagnetic spectrum.
o A nucleus is in resonance when it absorbs RF radiation and “spin flips” to a
higher energy state.
Strength of applied magnetic field B0
Proton spin flip
These spectrometers use very powerful magnetic fields to create
a small, but measurable energy difference between the two
possible spin states. If all protons absorbed at the same
frequency in a given magnetic field, the spectra of all
compounds would consist of a single absorption, rendering NMR
useless for structure determination. Fortunately, however, this is
not the case.
The frequency at which a particular proton absorbs is determined by
its electronic environment. Because electrons are moving charged
particles, they create a magnetic field opposed to the applied field B0,
and the size of the magnetic field generated by the electrons around a
proton determines where it absorbs. 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 1 H, 13C, 19F, and
31P) or odd atomic numbers (such as 2H and 14N) give rise to NMR
signals. Because both 1 H and 13C, the less abundant isotope of carbon,
are NMR active, NMR allows us to map the carbon and hydrogen
framework of an organic molecule.
A 1 H NMR Spectrum
An NMR spectrum plots the intensity of a signal against its chemical
shift measured in parts per million (ppm). NMR absorptions are
measured relative to the position of a reference signal at 0 ppm on the
δ scale due to tetramethylsilane (TMS). TMS is a volatile and inert
compound that gives a single peak upfield from other typical NMR
absorptions.
Four different features of a 1H NMR spectrum
provide information about a compound’s
structure:

[1] Number of signals


[2] Position of signals
[3] Intensity of signals
[4] Spin–spin splitting of signals
1HNMR: Number of Signals
Types of protons
1H NMR: Number of Signals
How many 1H NMR signals does a compound exhibit?
The number of NMR signals equals the number of different types
of protons in a compound.
Problem: How many different kinds of H atoms does CH3CH2CH2CH2CH3
contain?
What happens if the electron density around a nucleus is decreased, instead? For
example, how do the chemical shifts of the protons in CH4 and CH3Cl compare?
The less shielded the nucleus becomes, the more of the applied magnetic field
(B0) it feels. This deshielded nucleus experiences a higher magnetic field strength,
so it needs a higher frequency to achieve resonance. Higher frequency is to the
left in an NMR spectrum, toward higher chemical shift, so deshielding shifts an
absorption downfield, as shown in Figure for CH3Cl versus CH4. The
electronegative Cl atom withdraws electron density from the carbon and
hydrogen atoms in CH3Cl, thus deshielding them relative to those in in CH4.
The distance between peaks in a multiplet called coupling
constant and denoted J. Coupling constants are measured in
Hertz and generally fall in the range between 0 and 18 Hz. The
exact value of J between two neighbouring protons depends on
the geometry of the molecule (typically J value for open an chain
alkanes J= 6 to 8 Hz)
Overlapping protons
Practice
Deduce the chemical structure of a compound having the following NMR
spectrum

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