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12.17.     Explain the terms Inductive and Electromeric effects. Which electron displacement effect explains the following correct orders of acidity of the carboxylic acids?

                (a) Cl_{3}CCOOH> Cl_{2}C\! H\! \, COOH> ClC\! H_{2}COOH

                (b) CH_{3}CH_{2}COOH> (CH_{3})_{2}CHCOOH> (CH_{3})_{3}C.COOH

               

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Inductive effect- The permanent displacement of sigma (\sigma) electrons along the saturated chain, whenever an electron donating or withdrawing group is present, is known as the inductive effect. It could be +I/-I effect.

Electromeric effect- The complete transfer of the shared pair of \pi-electrons to one of the atoms linked by multiple bonds on the demand of attacking reagent. It is a temporary effect. It may be +E(electrons transferred towards attacking reagent) or -E effect(electron transferring away from the attacking reagent).

(a) The order of acidity can be explained by the negative inductive effect (-I). As the no. of chlorine atom increases, the -I effect also increases and so, the acidic strength also increases.
Cl_{3}CCOOH> Cl_{2}C\! H\! \, COOH> ClC\! H_{2}COOH

(b) This can be explained by the +I effect of the alkyl group. As the number of electron donor group increases, +I effect will also increase. With the increases in +I effect, the acidic character decreases accordingly.
CH_{3}CH_{2}COOH> (CH_{3})_{2}CHCOOH> (CH_{3})_{3}C.COOH

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