Inductive effect

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The inductive effect in Chemistry and Physics is an experimentally observable effect of the
transmission of charge through a chain of atoms in a molecule by electrostatic induction.[1]
The net polar effect exerted by a substituent is a combination of this inductive effect and the
mesomeric effect.

The electron cloud in a σ-bond between two unlike atoms is not uniform and is slightly
displaced towards the more electronegative of the two atoms. This causes a permanent state
of bond polarization, where the more electronegative atom has a slight negative charge(δ-)
and the other atom has a slight positive charge(δ+).

If the electronegative atom is then joined to a chain of atoms, usually carbon, the positive
charge is relayed to the other atoms in the chain. This is the electron-withdrawing inductive
effect, also known as the -I effect.

Some groups, such as the alkyl group are less electron-withdrawing than hydrogen and are
therefore considered as electron-releasing. This is electron releasing character and is
indicated by the +I effect.

As the induced change in polarity is less than the original polarity, the inductive effect rapidly
dies out, and is significant only over a short distance. The inductive effect is permanent but
feeble, as it involves the shift of strongly held σ-bond electrons, and other stronger factors
may overshadow this effect.

The inductive effect may be caused by some molecules also. Relative inductive effects have
been experimentally measured with reference to hydrogen.

Inductive effects can be measured through the Hammett equation.

Inductive Effect can also be used to determine whether a molecule is stable or unstable
depending on the charge present on the atom under consideration and the type of groups
bonded to it. For example, if an atom has a positive charge and is attached to a -I group its
charge becomes 'amplified' and the molecule becomes more unstable than if I-effect was not
taken into consideration. Similarly, if an atom has a negative charge and is attached to a +I
group its charge becomes 'amplified' and the molecule becomes more unstable than if I-effect
was not taken into consideration. But, contrary to the above two cases, if an atom has a
negative charge and is attached to a -I group its charge becomes 'de-amplified' and the
molecule becomes more stable than if I-effect was not taken into consideration. Similarly, if
an atom has a positive charge and is attached to a +I group its charge becomes 'de-amplified'
and the molecule becomes more stable than if I-effect was not taken into consideration. The
explanation for the above is given by the fact that more charge on an atom decreases stability
and less charge on an atom increases stability.

Definition
Polarity induced in a covalent bond due to the difference in electronegativities of the bonded
atoms is called Inductive Effect.

Applications
 Aliphatic carboxylic acids. The strength of a carboxylic acid depends on the extent
of its ionization: the more ionized it is, the stronger it is. As an acid becomes stronger,
the numerical value of its pKa drops. In aliphatic acids, the electron-releasing inductive
effect of the methyl group increases the electron density on oxygen and thus hinders
the breaking of the O-H bond, which consequently reduces the ionization. Greater
ionization in formic acid when compared to acetic acid makes formic acid (pKa=3.75)
stronger than acetic acid (pKa=4.76). Monochloroacetic acid (pKa=2.82), though, is
stronger than formic acid, since the electron-withdrawing effect of chlorine promotes
ionization.
 Aromatic carboxylic acids. In benzoic acid, the carbon atoms which are present in the
ring are sp2 hybridised.As a result, benzoic acid(pKa=4.20) is a stronger acid than
cyclohexane carboxylic acid(pKa=4.87). Also, electron-withdrawing groups
substituted at the ortho and para positions, enhance the acid strength.
 Dioic acids. Since the carboxyl group is itself an electron-withdrawing group, the
dioic acids are, in general, stronger than their monocarboxyl analogues.
 In the so-called Baker-Nathan effect the observed order in electron-releasing alkyl
substituents is apparently reversed.
Mesomeric effect
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See also: Resonance (chemistry)

+M effect of a methoxy group in an ether

–M effect of a carbonyl group in acroleine

The mesomeric effect or resonance effect in chemistry is a property of substituents or

functional groups in a chemical compound. The effect is used in a qualitative way and
describes the electron withdrawing or releasing properties of substituents based on relevant
resonance structures and is symbolized by the letter M. The mesomeric effect is negative (-
M) when the substituent is an electron-withdrawing group and the effect is positive (+M)
when based on resonance the substituent is an electron releasing group.

 Examples of -M substituents: acetyl (IUPAC ethanoyl) - nitrile - nitro

 Examples of +M substituents: alcohol - amine

The net electron flow from or to the substituent is determined also by the inductive effect.
The mesomeric effect as a result of p-orbital overlap (resonance) has absolutely no effect on
this inductive effect, as the inductive effect is purely to do with the electronegativity of the
atoms and their topology in the molecule (which atoms are connected to which).

The concepts of mesomeric effect, mesomerism and mesomer were introduced by Ingold in
1938 as an alternative to the Pauling's synonymous concept of resonance.[1] "Mesomerism" in
this context is often encountered in German and French literature but in English literature the
term "resonance" dominates.

Mesomerism in conjugated systems

Mesomeric effect can be transmitted along any number of carbon atoms in a conjugated
system. This accounts for the resonance stabilization of the molecule due to delocalization of
charge.