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Chemical Shift

based on ktu engineering chemistry

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89 views7 pages

Chemical Shift

based on ktu engineering chemistry

Uploaded by

Aliya Beegom
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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CHEMICAL SHIFT

➢ Dependence of the resonance frequency of a nucleus that results from its molecular
environment is called chemical shift
➢ Chemical shift is the separation between the peak of the reference standard (TMs) and
any other peak in an NMR spectrum
➢ The shift in the position of NMR absorption which arise due to shielding or dishielding
protons in the different structural environment are called chemical shifts
Note: Shift in the frequency depends upon the chemical environment.

Measurement of Chemical Shift


It is extremely difficult to measure the precessional frequency of group of nuclei in absolute
frequency units. The relative absorption frequency is measured using a suitable standard called
Tetramethyl Silane (TMS).

Advantages of TMS
➢ 12 equivalent protons and hence a sharp single signal is obtained.
➢ It appears lower frequency that most of the organic compounds due to lower
electronegativity.
➢ TMS is chosen as a reference because it is miscible with organic solvents and is volatile
hence can be easily removed from the system.

δ-scale and τ-scale


δ (delta) scale:
δ scale is an NMR scale in which the TMS peak is set at zero and peaks to the left of it (down
field) has increasingly positive values in ppm.
• Greater the deshielding, larger will be the δ-value.
T (tau) scale:
• In tau (τ) – scale, the TMS is arbitrarily assigned a value of 10ppm.
• At low τ – value represent low field absorption while high τ – value represent high field
absorption.
• The two scales are related as:

Equivalent Protons and Non-equivalent Protons


Equivalent Protons:
Protons that are identical and have the same magnetic environment which gives them the same
spin flip energy and give one signal.
Eg: CH3 – CH3 (ethane)
Non-equivalent Protons:
Protons that only have to differ in a single way and do not have same magnetic environment and
give different signals.

Eg:
No. of equivalent protons gives the no of peaks / signals.
CHEMICAL SHIFT (position of signal)
When a molecule placed in a magnetic field, the electrons rotating around it generate their own
secondary magnetic field. The induced magnetic field may align with the applied field or may
oppose it.
Shielding: If the induced magnetic field oppose the applied field, the proton experience a lesser
magnetic field than the applied field and the hydrogen nucleus is said to be shielded. Shielding
shifts the absorption up field i.e., at lower RF radiation frequency
Eg: Alkenes, Alkynes

Deshielding: the induced magnetic field reinforces or align with the applied field, the protons
fields higher strength and said to be deshielded. Deshielding shift absorption downfield. A more
deshielded protons absorps RF radiation at higher frequency.

Note:
➢ Greater the deshielding of protons larger will be the value of δ
➢ Upfield: Greater the value of δ and the signal for TMS appears at extreme right of the
spectrum with δ = 0 at high magnetic field strength.
➢ Downfield: Magnetic field decreases to the left.
Factors affecting Chemical Shift
1. Electronegativity:
As the electron density around proton decreases, shielding effect decreases and δ-value
increases.

2. Presence of electronegative atom / cumulative effect of electronegative atom:


When the electronegative substituents are attached to the protons, the electron density around
the proton decreases. As the shielding effect decreases and the chemical shift value increases.

3. Distance from the electronegative atom


As the proton gets closer towards the electronegative atom, the lectron density around the
proton decreases and thus shielding decreases i.e. δ-value decreases.

4. Deshielding
In deshielding, the induced magnetic field reinforces the applied magnetic field.
⸫ deshielding increases the δ -value

Interpretation of chemical shifts in a molecule


The following information are obtained from the NMR spectra.
➢ The no. of signals give the no. of sets equivalent protons
➢ The position of signals (δ- values) gives information about the nature of the proton
environment.
➢ Peak area gives the no. of protons in each equivalent set present in the compound.
➢ Larger the no. of equivalent protons, greater will be the energy absorbed and greater is
the area under the absorption peak.
Eg: Toluene

The spectrum has two signals, which indicates that the compound contains two sets of equivalent
protons. On measuring the no. of squares under the peak, the ratio of no. of squares under the
two peaks is 5:3. (5 protons of one kind and 2 of another)

Spin – Spin coupling. The splitting of signals


The protons on the neighboring carbons will generate magnetic fields whose magnetic moment
will interact with the magnetic moment of the external MF. This results in the splitting of the
NMR signal.
➢ The splitting of NMR signals due to the coupling interactions with the neighboring
protons is called spin-spin coupling or spin-spin splitting.
➢ The multiplicity of a given group is given by (nH) or (2nIH) ; where ‘n’ is the no. of
protons on adjacent atoms.
➢ The magnitude of the separation arising from spin-spin coupling under any given peak is
independent on the applied field.
Coupling Constant, J
The spacing between the peaks of multiplet is called coupling constant (J) and measured in
Hertz.
➢ Value of J decreases with the distance between the coupling group.

Pascals Triangle

Relative intensities of different signals can be obtained with the help of Pascals triangle.
Neighboring protons No. of Signals (n+1) Relative Intensity of signals
0 1 (a+1) 1
1 2 (1+1) 11
2 3 (2+1) 121
3 4 (3+1) 1331
4 5 (4+1) 14641
5 6 (5+1) 1 5 10 10 5 1
6 7 (6+1) 1 6 15 20 15 6 1

Applications of H1NMR
1. Keto enol Tautomerism
2. Determination of intermolecular and intra molecular H-bonding

Inter molecular H-bonding => low δ-value (upfielding)


Intra molecular H-bonding => No change in chemical shift.

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