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Alcohols, Phenols and Ethers - Primary, secondary and tertiary alcohols

Grade 12ICSEChemistry

Review the key concepts, formulae, and examples before starting your quiz.

🔑Concepts

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Alcohols are classified as primary (1∘1^{\circ}), secondary (2∘2^{\circ}), and tertiary (3∘3^{\circ}) based on the number of carbon atoms directly attached to the carbon bearing the hydroxyl (−OH-OH) group.

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Primary (1∘1^{\circ}) Alcohols: The −OH-OH group is attached to a carbon atom which is further attached to only one alkyl group (or hydrogen in the case of methanol). General structure: R−CH2−OHR-CH_2-OH.

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Secondary (2∘2^{\circ}) Alcohols: The −OH-OH group is attached to a carbon atom which is further attached to two alkyl groups. General structure: R2CH−OHR_2CH-OH.

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Tertiary (3∘3^{\circ}) Alcohols: The −OH-OH group is attached to a carbon atom which is further attached to three alkyl groups. General structure: R3C−OHR_3C-OH.

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Lucas Test: Used to distinguish between the three types. It uses Lucas reagent (conc. HClHCl + anhydrous ZnCl2ZnCl_2). 3∘3^{\circ} alcohols give immediate turbidity, 2∘2^{\circ} give turbidity within 5 minutes, and 1∘1^{\circ} alcohols do not give turbidity at room temperature.

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Oxidation: Primary alcohols oxidize to aldehydes (RCHORCHO) and then to carboxylic acids (RCOOHRCOOH); secondary alcohols oxidize to ketones (R2C=OR_2C=O); tertiary alcohols are resistant to oxidation in neutral/alkaline conditions but undergo dehydration/oxidation in acidic conditions to give ketones/acids with fewer carbons.

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Catalytic Dehydrogenation: Passing vapors over heated CuCu at 573 K573 \, K. 1∘→1^{\circ} \rightarrow Aldehyde, 2∘→2^{\circ} \rightarrow Ketone, 3∘→3^{\circ} \rightarrow Alkene (dehydration occurs instead of dehydrogenation).

📐Formulae

CnH2n+1OHC_nH_{2n+1}OH

R−CH2OH→[O]R−CHO→[O]R−COOHR-CH_2OH \xrightarrow{[O]} R-CHO \xrightarrow{[O]} R-COOH

R2CHOH→[O]R2C=OR_2CHOH \xrightarrow{[O]} R_2C=O

R−OH+HCl→anhydrous ZnCl2R−Cl+H2OR-OH + HCl \xrightarrow{\text{anhydrous } ZnCl_2} R-Cl + H_2O

(CH3)3C−OH→Cu,573 K(CH3)2C=CH2+H2O(CH_3)_3C-OH \xrightarrow{Cu, 573\,K} (CH_3)_2C=CH_2 + H_2O

💡Examples

Problem 1:

Identify the type of alcohol and the product formed when CH3CH2CH(OH)CH3CH_3CH_2CH(OH)CH_3 is treated with K2Cr2O7/H2SO4K_2Cr_2O_7/H_2SO_4.

Solution:

The alcohol is Butan-2-ol, which is a secondary (2∘2^{\circ}) alcohol. Oxidation of a secondary alcohol yields a ketone. The product is Butan-2-one (CH3COCH2CH3CH_3COCH_2CH_3).

Explanation:

In Butan-2-ol, the −OH-OH group is attached to a carbon bonded to two other carbons (a CH3CH_3 group and a CH2CH3CH_2CH_3 group), making it 2∘2^{\circ}. Secondary alcohols are oxidized to ketones with the same number of carbon atoms.

Problem 2:

An unknown alcohol XX reacts with Lucas reagent and produces cloudiness/turbidity immediately. What is the classification of XX?

Solution:

XX is a tertiary (3∘3^{\circ}) alcohol.

Explanation:

Tertiary alcohols react fastest with the Lucas reagent because the intermediate formed is a stable tertiary carbocation (R3C+R_3C^+), leading to the immediate formation of insoluble alkyl chlorides.

Problem 3:

Predict the product when Ethanol (CH3CH2OHCH_3CH_2OH) is passed over heated Copper at 573 K573\,K.

Solution:

CH3CH2OH→Cu,573 KCH3CHO+H2CH_3CH_2OH \xrightarrow{Cu, 573\,K} CH_3CHO + H_2

Explanation:

Ethanol is a primary alcohol. Catalytic dehydrogenation of primary alcohols removes two hydrogen atoms to form an aldehyde (Ethanal).