CHEMICAL SHIFT

 When an organic molecule is in a magnetic field, circulating electrons create secondary magnetic fields,
that is induced magnetic field
 Electron rotation around the proton diminishes the field felt by the proton, shielding it.
 Rotation of electrons around neighbouring nuclei can either reinforce or oppose the applied magnetic
field at the proton.
 If the induced field opposes the applied field, the proton is shielded.
 Electron-releasing substituents like alkyl groups can shield the proton.
 If the induced field reinforces the applied field, the proton is deshielded, increasing the field felt by the
proton.
 Electron-withdrawing substituents like halogens on the carbon bearing the proton deshield the proton.
 Compared to a naked proton, a shielded proton needs a stronger magnetic field, while a deshielded
proton requires a weaker magnetic field for effective absorption.
 Shielding shifts absorption upfield, while deshielding shifts absorption downfield.
 Chemical shifts result from the shielding or deshielding of protons by electrons, altering the position of
NMR signals.
 Chemical shifts are measured relative to a standard, typically tetramethylsilane (TMS), in proton
magnetic resonance spectroscopy.
 TMS is chosen because its equivalent protons are highly shielded due to the low electronegativity of
silicon.
 NMR signals for different types of protons are measured relative to TMS, resulting in varied field
strengths.
 The difference in absorption position of the proton compared to the TMS signal is called chemical shift
(δ Value).
 Chemical shift is measured in equivalent frequency units, divided by the spectrometer frequency.
 Protons with the same chemical shift are equivalent, while those with different shifts are nonequivalent.
 Two commonly used scales, δ (Delta) and τ (tau), describe chemical shifts.
 In most organic compounds, protons resonate at a lower field than TMS protons.
 Assigning a δ value of zero to TMS establishes a scale where most proton resonances have the same
sign.
 Protons absorbing at a field lower than TMS are given a positive δ value.
 TMS is the most convenient reference and the reasons why TMS is used as a reference compound are:
(1) It is miscible with almost all organic substances
(2) It is highly volatile and hence can be readily removed from the system.
(3) It does not take part in intermolecular associations with the sample
(4) It has 12 equivalent protons which give an intense single signal. Therefore even a small quantity of it
gives a measurable signal
(5) Silicon less electronegative than carbon, protons of TMS are therefore highly shielded.
 TMS's silicon-based protons are highly shielded, reducing interference with other proton signals.