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Question of 135

Q.State reasons :

(a) Relative ease of dehydration of alcohols is 3°>2°>1°.
(b) Cresols are less acidic than phenol.
(c) Boiling point of ethanol is higher than methoxymethane.
(OR)
What is Lucas test for distinguishing primary, secondary and tertiary alcohols? Explain.
Uttarakhand UbseUttarakhand Board Intermediate (Class 12) 2025Subjective· 3mImportance★★★★★
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Carbocation stability governs dehydration ease; electron donation by CH3 makes cresol a weaker acid than phenol; hydrogen bonding raises ethanol's boiling point above its ether isomer.

  1. Dehydration ease 3° > 2° > 1°: Acid-catalysed dehydration of alcohols proceeds via an E1 mechanism, whose rate-determining step is formation of a carbocation. The stability order of carbocations is 3°>2°>1°3° > 2° > 1° (due to increasing +I effect/hyperconjugation from more alkyl groups). Since a more stable carbocation forms faster, tertiary alcohols dehydrate fastest and primary alcohols dehydrate slowest.
  2. Cresols less acidic than phenol: Cresols (methylphenols, CH3−C6H4−OHCH_3-C_6H_4-OH) carry an electron-donating methyl group (+I+I effect / hyperconjugation) on the ring. This pushes electron density onto the ring/oxygen, which destabilises the phenoxide (conjugate base) ion formed on deprotonation (destabilising negative charge is bad for acidity) relative to the unsubstituted phenoxide ion. A less stable conjugate base means a weaker acid, so cresols are less acidic than phenol.
  3. Ethanol has higher bp than methoxymethane: Ethanol (C2H5OHC_2H_5OH) and methoxymethane/dimethyl ether (CH3OCH3CH_3OCH_3) are functional isomers (C2H6OC_2H_6O). Ethanol has an −OH-OH group with a hydrogen directly bonded to the electronegative oxygen, allowing extensive intermolecular hydrogen bonding between ethanol molecules. Dimethyl ether has no H atom bonded to O, so it cannot form hydrogen bonds — it experiences only weaker dipole-dipole and van der Waals forces. Breaking the hydrogen bonds in ethanol requires much more energy, so ethanol boils at a much higher temperature (78°C) than dimethyl ether (−24°C).

OR — Lucas test:

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