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Chemistry — Class 12 — L26: Alcohols, Phenols and Ethers

NIOS Code 313 · Module 7 · Chemistry of Organic Compounds

Notes extracted from NIOS Chemistry Course (313), Lesson 26 — Alcohols, Phenols and Ethers (313_Chemistry_Eng_Lesson26.pdf). Content covers sections 26.1–26.3.
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Overview — Alcohols, Phenols and Ethers

Compounds with C–O single bonds: alcohols (ROH), phenols (ArOH) and ethers (ROR′). They are central in industry (ethanol, phenol, bakelite) and synthesis. This lesson covers classification, IUPAC names, preparation, H-bonding, reactions (including Lucas test and dehydration), phenol acidity and electrophilic reactions, and ether synthesis (Williamson) and cleavage.

Section 1: Alcohols — Classification & Preparation (26.1.1–26.1.2)

1°: RCH₂OH · 2°: R₂CHOH · 3°: R₃COH. IUPAC: parent + -ol with lowest number for OH (propan-1-ol, propan-2-ol, 2-methylpropan-2-ol).

Preparation: (1) RX + aq KOH/NaOH. (2) Alkene hydration — acid-catalysed (Markovnikov); oxymercuration–demercuration; hydroboration–oxidation (anti-Markovnikov). (3) Reduction of carbonyls — aldehydes/acids/esters → 1° alcohols; ketones → 2° (NaBH₄, LiAlH₄, H₂/Pd).

Alcohol Classification 1° RCH₂OHethanol 2° R₂CHOHpropan-2-ol 3° R₃COHtert-butanol Count alkyl groups on the carbinol carbon
Primary, secondary and tertiary alcohols — structure decides reactivity.
RCH=CH₂ + H₂O/H⁺ → RCH(OH)CH₃  |  BH₃ then H₂O₂ → RCH₂CH₂OH
Markovnikov acid hydration · anti-Markovnikov hydroboration–oxidation

Section 2: Alcohols — Properties & Reactions (26.1.3–26.1.5)

Physical: O–H H-bonding raises b.p. and water solubility of lower alcohols. Methanol/ethanol fully miscible; higher homologues less so.

Acid–base: Weak acids (pKₐ ~15–16) — NaH or Na metal → alkoxide. Also weak bases — protonated by strong acids to ROH₂⁺.

→ Alkyl halides: HX, PBr₃, SOCl₂ (gases by-product). 3° react readily with HCl; 1°/2° prefer PBr₃/SOCl₂.

Lucas test: anhyd. ZnCl₂ + conc. HCl — turbidity: 3° immediate, 2° within minutes, 1° none (or very slow).

Dehydration: H₂SO₄/H₃PO₄ — ease 3°>2°>1°; E1 via carbocation. ~413 K intermolecular → ether; higher T → alkene.

Lucas Test Turbidity 1° alcoholno turbidity 2° alcohol~5 min 3° alcoholimmediate Turbidity = alkyl chloride (insoluble)
Lucas reagent classifies alcohols by how fast RCl forms.
2C₂H₅OH → C₂H₅OC₂H₅ (413 K)  |  → CH₂=CH₂ (higher T)
Same acid catalyst · temperature selects ether vs alkene

Oxidation: 1° → aldehyde → carboxylic acid (strong oxidant); 2° → ketone; 3° resistant (no H on carbinol C). Controlled oxidation of 1° with PCC etc. stops at aldehyde (higher level).

Uses: fuels, solvents, beverages (ethanol), antifreeze, synthesis of RX, alkenes, esters.

Section 3: Phenols (26.2)

OH attached to aromatic ring. Disinfectant; precursor to aspirin, bakelite, dyes. Names: phenol, o/m/p-cresol, nitrophenols, catechol, resorcinol, hydroquinone, naphthols.

Preparation: (1) ArN₂⁺ hydrolysis (mild, general). (2) Alkali fusion of sodium benzenesulphonate. (3) Dow: PhCl + aq NaOH, high T/P. (4) Cumene: benzene + propene → cumene → air oxidation → acid → phenol + acetone (main industrial route).

Cumene Process benzene + propene cumene O₂ H₂SO₄ PhOH + acetone Two valuable products from one process
Industrial phenol manufacture via cumene hydroperoxide.
Phenol pKₐ ≈ 10  |  Ethanol pKₐ ≈ 16
Phenoxide resonance delocalises charge · phenols dissolve in NaOH

Acidity: much stronger than alcohols — phenoxide resonance. e⁻-withdrawing groups (especially o/p–NO₂) increase acidity (picric acid very strong). e⁻-donating alkyls slightly decrease acidity.

Reactions: NaOH → sodium phenoxide; FeCl₃ violet complex (test); Br₂ water → 2,4,6-tribromophenol white ppt (ring highly activated); nitration; Kolbe–Schmitt (CO₂ → salicylic acid); Reimer–Tiemann (CHCl₃/NaOH → salicylaldehyde); azo coupling with ArN₂⁺ → dyes. Electrophilic substitution is o/p-directed and faster than benzene.

Phenol Acidity & Activation Phenoxideresonance stabilised Ring activatedo/p · Br₂, NO₂, azo FeCl₃ violet · Br₂ water white ppt — classic tests
Acidity and electrophilic reactivity both stem from oxygen–ring interaction.

Section 4: Ethers (26.3)

R–O–R′ (alkyl/aryl). Symmetrical (diethyl ether) or unsymmetrical (ethyl methyl ether). Cyclic ethers (THF) are solvents. IUPAC: larger group as parent alkane, smaller as alkoxy (methoxyethane).

Preparation: intermolecular dehydration of alcohols (lower T than alkene formation); Williamson: RONa + primary R′X → ROR′ (SN2; 3° R′X fails → elimination).

ROH + Na → RONa  |  RONa + R′X → ROR′ + NaX
Williamson synthesis · use 1° alkyl halide

Structure: bent like water; polar C–O; no H on O → no intermolecular H-bonds between ether molecules → lower b.p. than isomeric alcohols; good polar solvents.

Reactions: generally unreactive (hence solvents). Autoxidation → explosive peroxides (store carefully). Protonated by strong acids (oxonium). Cleavage with hot HI/HBr: ROR + HI → ROH + RI then further to 2 RI; Nu attacks less hindered alkyl group in unsymmetrical ethers.

Alcohol vs Ether Boiling Points ROH H-bonds ROR Same mass · alcohols boil higher (intermolecular H-bonding)
Hydrogen bonding elevates alcohol boiling points relative to ethers.
C₂H₅OC₂H₅ + 2HI → 2C₂H₅I + H₂O
Hot concentrated HI cleaves both C–O bonds

Uses: diethyl ether as solvent and (historically) anaesthetic; THF solvent; MTBE fuel additive (context-dependent).

Exam Connections and Chapter Summary

High-yield: 1°/2°/3° classification; hydration methods and anti-M hydroboration; Lucas; dehydration T control; oxidation products; phenol acidity reason; cumene process; Br₂/FeCl₃ tests; Williamson constraints; ether vs alcohol b.p.; HI cleavage.

Links L25 (ROH→RX, SN2) and L24 (alkene hydration). Next: aldehydes, ketones, carboxylic acids (L27) — oxidation of alcohols feeds those chapters.

MCQ Quiz — L26 Alcohols, Phenols and Ethers

0 / 10 correct

Flashcards — L26

1 / 18

Golden Rules — L26 Alcohols, Phenols and Ethers

Most exam-important points from this chapter:

Alcohols

1°/2°/3° by structure. Prep: RX, hydration (M/anti-M), carbonyl reduction. Lucas, dehydration T, oxidation products.

Physical ROH

H-bonding → high b.p. & water solubility. Weak acids; form alkoxides with Na.

Phenols

More acidic than alcohols (resonance). Cumene/Dow/diazonium prep. Br₂, FeCl₃, Kolbe, Reimer–Tiemann, azo dyes.

Ethers

Williamson with 1° R′X. Polar solvents; no intermolecular H-bonds. HI cleavage; peroxide hazard.

Links

ROH→RX (L25) · alkenes (L24) · oxidation → carbonyls (L27).

1° / 2° / 3° alcohols
R–X → ROH · hydration
Hydroboration anti-M
Lucas · turbidity order
Dehydration → alkene/ether
Phenol more acidic
Cumene → PhOH + acetone
Williamson R′OR
HI cleaves ethers

Section 1: Alcohols

NIOS Chemistry 313, Module 7 — Alcohols, Phenols and Ethers (sections 26.1–26.3).

Classification & Preparation

1°: RCH₂OH · 2°: R₂CHOH · 3°: R₃COH · IUPAC: -ol with lowest number

RX + aq KOH → ROH · alkene + H₂O/H⁺ (Markovnikov)

Oxymercuration–demercuration · hydroboration–oxidation (anti-Markovnikov)

RCHO/RCOOH → 1° ROH · R₂C=O → 2° ROH (NaBH₄, LiAlH₄, H₂/Pd)

Physical Properties & Reactions

H-bonding → high b.p., water solubility (lower members)

Weak acids (pKₐ ~15–16) · Na → alkoxide · protonated by strong acids

ROH → RX (HX, PBr₃, SOCl₂) · Lucas: 3° instant turbidity · 2° ~5 min · 1° none

Dehydration: 3°>2°>1° · E1 · low T intermolecular → ether · high T → alkene

Oxidation: 1° → aldehyde → acid · 2° → ketone · 3° resistant

Section 2: Phenols

Preparation & Acidity

ArN₂⁺ + H₂O → PhOH · alkali fusion of ArSO₃Na · Dow: PhCl + NaOH (pressure)

Cumene process: benzene + propene → cumene → O₂ → hydroperoxide → H₂SO₄ → phenol + acetone

More acidic than alcohols (pKₐ ~10) · phenoxide resonance · e⁻-withdrawing groups ↑ acidity (picric acid pKₐ 0.38)

Phenol Reactions

NaOH → PhONa · FeCl₃ violet · Br₂ water → 2,4,6-tribromophenol (white ppt)

Nitration · Kolbe (CO₂ → salicylic acid) · Reimer–Tiemann (CHCl₃/NaOH → salicylaldehyde)

EAS activated o/p · azo coupling with diazonium → dyes

Section 3: Ethers

Ethers

ROR′ · IUPAC: alkoxyalkane (methoxyethane) · common: alkyl alkyl ether

Williamson: RONa + R′X (1° R′X) → ROR′

Dehydration of ROH at lower T → ether

No H-bonding between ether molecules · lower b.p. than alcohols · polar solvents

HI/HBr heat: ROR + 2HI → 2RI + H₂O · Nu attacks less hindered alkyl

Peroxides form on storage (explosion hazard)

Section 2: Definitions

Primary alcohol: –OH on carbon attached to one alkyl group (RCH₂OH).

Lucas reagent: Conc. HCl + anhyd. ZnCl₂ — classifies 1°/2°/3° alcohols by turbidity time.

Williamson synthesis: Alkoxide + primary alkyl halide → ether (SN2).

Cumene process: Industrial phenol + acetone from isopropylbenzene.

Phenoxide ion: Resonance-stabilised conjugate base of phenol — explains high acidity.

Section 3: Visual Map

L26 Map — ROH · PhOH · ROR Alcohols 1°2°3° Phenols acidic Ethers solvent Lucas · dehydration · oxidation · cumene · Williamson · HI cleavage H-bonding alcohols/phenols · no intermolecular H-bond in ethers

Section 5: Q&A (12 Questions)

Q1: Classify CH₃CH(OH)CH₃.

Secondary alcohol (propan-2-ol).

Q2: Anti-Markovnikov hydration of alkene?

Hydroboration–oxidation (BH₃ then H₂O₂/OH⁻).

Q3: Lucas test for 3° alcohol?

Immediate turbidity with conc. HCl + anhyd. ZnCl₂.

Q4: Dehydration of ethanol products at 413 K vs 443 K?

Lower T → ethoxyethane (ether); higher T → ethene.

Q5: Why is phenol more acidic than ethanol?

Phenoxide ion resonance-stabilised; ethoxide is not.

Q6: Cumene process products?

Phenol and acetone.

Q7: Industrial phenol from chlorobenzene?

Dow process: PhCl + NaOH under pressure → PhONa → PhOH.

Q8: Br₂ water with phenol?

White ppt of 2,4,6-tribromophenol (activated ring).

Q9: Williamson synthesis requirements?

RONa + primary R′X (SN2); 3° R′X gives elimination.

Q10: IUPAC of CH₃OCH₂CH₃?

Methoxyethane.

Q11: Cleavage of diethyl ether with excess HI?

2CH₃CH₂I + H₂O.

Q12: Why are old ethers hazardous?

Autoxidation forms explosive peroxides.

Section 6: Tips & Exam Hacks

Memory Aids

  • Lucas: "3° now · 2° soon · 1° never"
  • Hydroboration: "Anti-M OH"
  • Phenol acid: "Resonance holds the O⁻"
  • Williamson: "1° halide only for S_N2"
  • Cumene: "Phenol + free acetone"

Exam Tips

  • Oxidation distinguishes 1°/2°/3° alcohols
  • Dehydration mechanism is E1 (carbocation)
  • Phenol + FeCl₃ is qualitative test
  • o/p–NO₂ increases phenol acidity
  • Ether + HI: Nu attacks less hindered R

Section 8: Quick Reference

• 1°/2°/3° ROH · prep from RX, alkenes, carbonyls

• H-bond · Lucas · ROH→RX · dehydrate · oxidise

• Phenol: cumene, Dow, diazonium · acidic · Br₂, Kolbe, Reimer–Tiemann

• Ether: Williamson · low b.p. · HI cleavage · peroxide hazard

PYQ — Previous Year Questions

Extracted from NIOS Chemistry (313) board exam papers in your PDF. Chapter L26 — Alcohols, Phenols and Ethers only. Use Model Answer for marking points; Explanation for concept clarity.

L26 — Alcohols, Phenols and Ethers

3 question(s) · Sources: 313/MAY/205C, 313/TUS/105A

Section A — MCQ / Objective (from papers)

PYQ1. Hemiacetals are chemically — (A) alkoxy alcohols   (B) alkyl alcohols   (C) gem-dialkoxy compounds   (D) ethylene glycol ho‘rEogrQ>¡b amgm¶{

1 mark · Q12 · 313/TUS/105A

Model Answer

Model approach (select the best option):

  • (A) alkoxy alcohols
  • (B) alkyl alcohols
  • (C) gem-dialkoxy compounds
  • (D) ethylene glycol ho‘rEogrQ>¡b amgm¶{

Eliminate options that contradict definitions/equations from the chapter notes. NIOS awards full mark for the single correct choice.

Explanation

This MCQ belongs to L26. Recall the core definition or formula from notes, then match it to one option. Paper: 313/TUS/105A · Q12.

Tip: For numerical MCQs, write the formula first, substitute values, then pick the option.

PYQ2. Read the passage given below and answer the following questions (out of four attempt any two) : Ethers are organic compounds in which an oxygen atom is bonded to two alkyl groups or aryl groups. Ethers have geometry similar to water and alcohols. Draw the geometry of an ether molecule. Illustrate the basic nature of ethers with the help of a suitable reaction. What is the IUPAC name of methyl propyl ether? How can ethers be prepared by Williamson’s synthesis? Illustrate with an example.

2 marks · Q25 · 313/TUS/105A

Model Answer

State the precise definition from the L26 notes in 1–2 sentences, include formula/example if marks ≥ 2, and avoid extra theory beyond the ask.

Explanation

Definition questions score for accuracy of wording + one supporting point/example. Do not write full chapter summaries.

How to write for NIOS: Use 30–50 words (VSA) or short objective. Open with definition/equation, then reason, end with conclusion. Paper 313/TUS/105A · Q25 · 2 mark(s) · L26.

Section B — Short / Long answer (from papers)

PYQ3. Why is the purification of final product not required when ethanol reacts with thionyl chloride? Also, give the chemical equation for the reaction. O~ EWoZm°b, Wm¶mo{Zb ³bmoamBS> Ho$ gmW A{^{H«$¶m

2 marks · Q36 · 313/MAY/205C

Model Answer

Give the chemical reason linked to structure/bonding/equilibrium. Start with the principle, then apply to the species named in the question.

Explanation

Reasoning marks require principle + application. Cite electron effects, stability, or Le Chatelier as relevant.

How to write for NIOS: Use 30–50 words (VSA) or short objective. Open with definition/equation, then reason, end with conclusion. Paper 313/MAY/205C · Q36 · 2 mark(s) · L26.

Problem Solving — L26 Alcohols, Phenols and Ethers

Six problems spanning this chapter’s NIOS syllabus. Every question is built from the notes and formula sheet: solve with equations first, then read the formal textbook-style write-up, the easy explanation, and the topic in depth (formulas, meaning, exam tips). If the question says draw, a labelled pencil sketch is provided. Explanations open by default.

Question 1 of 6Class

Classify alcohols as 1°, 2°, 3° with one example each.

Pencil sketch (labelled)

Key functional groups —OH alcohol / phenol —CHO aldehyde >C=O ketone —COOH carboxylic acid —NH₂ amine
Pencil sketch: common organic groups

Solution — step by step with formulas

  1. 1° RCH₂OH; 2° R₂CHOH; 3° R₃COH e.g. ethanol, propan-2-ol, 2-methylpropan-2-ol.

Final answer: 1°/2°/3° by C bearing OH

Textbook formal language

Based on number of carbons attached to carbinol carbon.

Working formulas: (see solution steps). State the definition or law first (NIOS style), use SI units, and box the final numerical answer with unit.

Easy language (same idea, plain words)

Count how many C stick to the C–OH carbon.

Read once for the idea, once for the numbers. Write the formula, substitute, then simplify. Check whether you used moles, grams, or litres correctly.

Topic in depth — Alcohol classification

Affects oxidation and Lucas test.

Linked to chapter notes (L26). Remember: (see solution steps). Most exam errors are unit mix-ups (g vs mol, mL vs L) or wrong mole ratios from the equation.

Exam tip

Write (see solution steps) before substituting. Keep three significant figures until the end when data allow.

Common mistakes

  • Confusing mass (g) with amount of substance (mol).
  • Forgetting Avogadro’s number unit mol⁻¹ or STP volume 22.7 L mol⁻¹ (1 bar).
  • Using wrong mole ratio from the balanced equation.
  • Mixing up empirical and molecular formulas.
Question 2 of 6Prep

How is ethanol manufactured from ethene industrially?

Solution — step by step with formulas

  1. Acid-catalysed hydration of ethene.

Final answer: Hydration of ethene

Textbook formal language

Electrophilic addition of water across C=C.

Working formulas: (see solution steps). State the definition or law first (NIOS style), use SI units, and box the final numerical answer with unit.

Easy language (same idea, plain words)

Add water across the double bond with acid catalyst.

Read once for the idea, once for the numbers. Write the formula, substitute, then simplify. Check whether you used moles, grams, or litres correctly.

Topic in depth — From alkenes

Fermentation is biological route to ethanol.

Linked to chapter notes (L26). Remember: (see solution steps). Most exam errors are unit mix-ups (g vs mol, mL vs L) or wrong mole ratios from the equation.

Exam tip

Write (see solution steps) before substituting. Keep three significant figures until the end when data allow.

Common mistakes

  • Confusing mass (g) with amount of substance (mol).
  • Forgetting Avogadro’s number unit mol⁻¹ or STP volume 22.7 L mol⁻¹ (1 bar).
  • Using wrong mole ratio from the balanced equation.
  • Mixing up empirical and molecular formulas.
Question 3 of 6Phenol

Why is phenol more acidic than ethanol?

Solution — step by step with formulas

  1. Phenoxide stabilised by resonance; ethoxide not.

Final answer: Resonance stabilisation of phenoxide

Textbook formal language

Delocalisation of negative charge on phenoxide ion.

Working formulas: (see solution steps). State the definition or law first (NIOS style), use SI units, and box the final numerical answer with unit.

Easy language (same idea, plain words)

After losing H⁺, charge spreads into the ring—more stable.

Read once for the idea, once for the numbers. Write the formula, substitute, then simplify. Check whether you used moles, grams, or litres correctly.

Topic in depth — Acidity of phenol

Electron-withdrawing groups increase phenol acidity.

Linked to chapter notes (L26). Remember: (see solution steps). Most exam errors are unit mix-ups (g vs mol, mL vs L) or wrong mole ratios from the equation.

Exam tip

Write (see solution steps) before substituting. Keep three significant figures until the end when data allow.

Common mistakes

  • Confusing mass (g) with amount of substance (mol).
  • Forgetting Avogadro’s number unit mol⁻¹ or STP volume 22.7 L mol⁻¹ (1 bar).
  • Using wrong mole ratio from the balanced equation.
  • Mixing up empirical and molecular formulas.
Question 4 of 6Ether

Outline Williamson ether synthesis.

Solution — step by step with formulas

  1. Alkoxide + alkyl halide (preferably 1°) → ether (SN2).

Final answer: RO⁻ + R′X → ROR′

Textbook formal language

Classic SN2 route to unsymmetrical ethers.

Working formulas: (see solution steps). State the definition or law first (NIOS style), use SI units, and box the final numerical answer with unit.

Easy language (same idea, plain words)

Salt of alcohol attacks alkyl halide to make ether.

Read once for the idea, once for the numbers. Write the formula, substitute, then simplify. Check whether you used moles, grams, or litres correctly.

Topic in depth — Williamson synthesis

Avoid 3° RX (elimination).

Linked to chapter notes (L26). Remember: (see solution steps). Most exam errors are unit mix-ups (g vs mol, mL vs L) or wrong mole ratios from the equation.

Exam tip

Write (see solution steps) before substituting. Keep three significant figures until the end when data allow.

Common mistakes

  • Confusing mass (g) with amount of substance (mol).
  • Forgetting Avogadro’s number unit mol⁻¹ or STP volume 22.7 L mol⁻¹ (1 bar).
  • Using wrong mole ratio from the balanced equation.
  • Mixing up empirical and molecular formulas.
Question 5 of 6Test

What does Lucas test distinguish?

Solution — step by step with formulas

  1. 1°, 2°, 3° alcohols by rate of turbidity with ZnCl₂/HCl.

Final answer: Alcohol class by turbidity rate

Textbook formal language

3° react fastest via SN1.

Working formulas: (see solution steps). State the definition or law first (NIOS style), use SI units, and box the final numerical answer with unit.

Easy language (same idea, plain words)

Cloudiness appears quickest for tertiary alcohols.

Read once for the idea, once for the numbers. Write the formula, substitute, then simplify. Check whether you used moles, grams, or litres correctly.

Topic in depth — Lucas test

Room temperature vs heat conditions matter.

Linked to chapter notes (L26). Remember: (see solution steps). Most exam errors are unit mix-ups (g vs mol, mL vs L) or wrong mole ratios from the equation.

Exam tip

Write (see solution steps) before substituting. Keep three significant figures until the end when data allow.

Common mistakes

  • Confusing mass (g) with amount of substance (mol).
  • Forgetting Avogadro’s number unit mol⁻¹ or STP volume 22.7 L mol⁻¹ (1 bar).
  • Using wrong mole ratio from the balanced equation.
  • Mixing up empirical and molecular formulas.
Question 6 of 6Oxidation

What does acidic KMnO₄ do to primary alcohol (complete)?

Solution — step by step with formulas

  1. Oxidises to carboxylic acid (via aldehyde).

Final answer: 1° → carboxylic acid

Textbook formal language

Strong oxidants convert 1° alcohols to acids.

Working formulas: (see solution steps). State the definition or law first (NIOS style), use SI units, and box the final numerical answer with unit.

Easy language (same idea, plain words)

Chop all the way to –COOH with strong oxidant.

Read once for the idea, once for the numbers. Write the formula, substitute, then simplify. Check whether you used moles, grams, or litres correctly.

Topic in depth — Oxidation of alcohols

PCC can stop at aldehyde.

Linked to chapter notes (L26). Remember: (see solution steps). Most exam errors are unit mix-ups (g vs mol, mL vs L) or wrong mole ratios from the equation.

Exam tip

Write (see solution steps) before substituting. Keep three significant figures until the end when data allow.

Common mistakes

  • Confusing mass (g) with amount of substance (mol).
  • Forgetting Avogadro’s number unit mol⁻¹ or STP volume 22.7 L mol⁻¹ (1 bar).
  • Using wrong mole ratio from the balanced equation.
  • Mixing up empirical and molecular formulas.