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ALCOHOLS, PHENOLS AND ETHERS

IMPORTANT QUESTIONS

1. Alcohols are comparatively more soluble in water than the hydrocarbons of

comparable molecular masses? Explain?
Alcohols can form hydrogen bonds with water and therefore these are soluble
whereas hydrocarbon cannot form H-bonding and therefore are insoluble in water.

2. Explain why is orthonitrophenol more acidic than orthomethoxy phenol?

The nitro- is an electron withdrawing group .the presence of this group in the ortho
position decreases the electron density .As a result, it is easier to lose a proton.
Also the
orthonitrophenoxide ion formed is stabilized by the resonance. Hence, ortho
nitrophenol is a stronger acid
On the other hand, methoxy group is an
electron-releasing group. Thus, it increases the electron density. Therefore proton
cannot be given out easily.
So, ortho nitrophenol more acidic than orthomethoxy phenol.

3. Why lower alcohols soluble in water but higher alcohol not?

Due to the formation H-Bonds lower alcohol are soluble in water. Higher alcohol are
less soluble due to the presence of higher alcohols.

4. Why phenols have higher boiling point than arenes?

Due to H-Bonding.

5. Prepare phenol from Diazonium salts?

N2 Cl- H O
2 OH + N2 + HCl

6. How will you distinguish between primary, secondary and tertiary alcohols?
When primary, secondary, tertiary alcohols are treated with Lucas reagent at room
temperature, then
(i) If turbidity appears immediately, alcohols is tertiary
(ii) If turbidity appears in 5 minutes, alcohols is secondary
(iii) If no reaction, alcohols are primary.
(Lucas reagent is conc.HCl +anhydrous zinc chloride)

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7. Phenol is acidic in nature.

Phenol is acidic in nature because:
a) phenol , due to resonance, the positive charge rests on oxygen making the shared
pair of electrons more towards oxygen and hydrogen as H+
b) The carbon attached to OH is SP2 hybridize and is more electronegative, this
decreases the electron density on oxygen, increasing the polarity of O-H bond and
ionization of phenol.
c) The phenoxide ion formed by loss of H+ is more resonance stabilized than
phenol itself.

8. Diethyl ether does not react with sodium. Explain.

Diethyl ether does not contain any active hydrogen.

9. Write the reaction showing formation of aspirin?

10. What is the main product obtained when vapors of t-butyl alcohol are passed over Copper
at 300°C ?

Ans. It undergoes dehydration to form 2- Methylpropene.

11. Phenol has smaller dipole moment than methanol. Why?

Ans. Due to the electron withdrawing effect of phenyl group present in contrast to the
electron releasing group present in alcohols.

12. Why are Grignard reagents soluble in ether but not in benzene?

Ans. Because being polar nature of both ether as well as of Grignard reagents ,but benzene is
non polar solvent .

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13. (A) Write the mechanism of acid-catalysed dehydration of ethanol to yield ethene.

The mechanism of acid dehydration of ethanol to yield ethene involves the following
three steps:
Step 1:
Protonation of ethanol to form ethyl oxonium ion:

Step 2:
Formation of carbocation (rate determining step):

Step 3:
Elimination of a proton to form ethene:

(B)Write the mechanism of hydration of ethene to yield ethanol.

Answer
The mechanism of hydration of ethene to form ethanol involves three steps.
Step 1:
Protonation of ethene to form carbocation by electrophilic attack of H 3 O + :

Step 2:
Nucleophilic attack of water on carbocation:

Step 3:

Deprotonation to form ethanol:

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14. Arrange the following compounds in the increasing order of acid strength.

Propan-1-ol, 2, 4, 6-trinitrophenol, 3-nitrophenol, 3,5-dinitrophenol

Ans. 2, 4, 6-trinitrophenol> 3,5-dinitrophenol>3-nitrophenol>propan-1-ol

15. Arrange the following alcohols in the order of increasing reactivity towards Lucas reagent

2-butanol, 1-butanol, 2-methyl-2-propanol

Ans . 1-butanol< 2-butanol< 2-methyl-2-propanol.

16. Alcohols acts as weak bases. Why?

Ans. Due to the presence of lone pair of electron on oxygen, alcohol can accept a proton and hence act as a
weak Bronsted base.

17. Phenols are more acidic than alcohols. Why?

Ans. Due to formation of more stable phenolate ion phenols tend to loose proton easily while in case of
alcohols alkoxide ions are not stable.

18. How many ether metamers are represented by C4H10O ?

Ans. 3 metamers: diethyl ether, methyl n-propyl ether, methyl isopropyl ether

19. Arrange the following in increasing order of basicity:C6H4 (NO2)OH

, CH3OH,C6H5OH

Ans. CH3OH < C6H5OH < C6H4 (NO2) OH

20. Predict the product when sodium ethoxide and ethyl bromide are heated?

Ans. Diethyl ether

21. Name the products obtain when anisole is treated with HI?

Ans. C6H5OCH3+ HI ----C6H5OH + CH3I

22. Suggest a reason for the large difference in the boiling points of butanol and

Butanal, although they have same solubility in water.

Ans. This is due to presence of intermolecular hydrogen bonding in butanol which is absent in butanal.

23. Which is stronger acid –Phenol or cresol? Why?

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Ans. Phenol is stronger acid because in cresol, due to the presence of one –CH3 group having +I effect
increases electron density on O of –OH group and thus decreasing its acidic strength.

24. Explain the following

(a) Cyclohexanol is more soluble in water than 1-Hexanol.

(b) Propane 1,3-diol is more soluble in the water than propan-1-ol.

Ans. (a) this is due to the reason that in Cyclohexanol, due to compact size of hydrocarbon part, it readily
forms H-bond with water but in 1-hexanol, this is slightly hindered by the bulky alkyl group

(b) because in propane-1,3-diol, extent of H- bonding is more than in propane-1-ol due to the presence of
two –OH groups.

25. Arrange the following in order of increasing boiling points. State reason.

CH3CH2CH2CH2OH, CH3CH2CH2CH3, CH3CH2OCH2CH3, CH3CH2CH2CHO2

(i) (ii) (iii) (iv)

Ans. (ii) < (ii) < (iv) < (i)

Reason : This is due to the reason that there is increase in the magnitude of intermolecular forces in this
order, as polarity of C-O bond is increasing ,it’s tendency to form H-bond also increases and hence boiling
point which depend on the intermolecular forces also increases.

26. Ethers are cleaved by acids not by bases. Why?

Ans. The C-O-C bond in ethers is very strong .The addition of acid shall protonate the oxygen atom as a
result , the attack by nucleophiles as Br- /I- on the less hindered alkyl group makes the process facile.

27. How will you prepare:

I. 1-bromobutane
II. Phenol

Ans I. CH3CH2CH2CH2Br (aq KOH) CH3CH2CH2CH2OH

II C6H5Cl + NaOH(623K, 300atm)  C6H5OH

28. Give chemical test to distinguish b/w ?

I. Phenol and benzyl alcohol

II. Butan-2-ol and 2-methylpropan-2-ol

Ans.I. phenol decolorizes bromine water giving a white ppt but benzyl alcohol does not

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ii. Luas test: butan-2-ol react with Lucas reagent and milkiness appears with in 5 min. but second one
react with the same to give milkiness immediately.

29. Give IUPAC names of product formed in the following reactions:

i. catalytic reduction of butanal

ii. Hydration of propene in the presence of dil. Sulphuric acid

Ans i. butan-1-ol

ii. 2-methylpropan-2-ol

30.Explain
i) Riemer-Tieman Reaction.
ii) Kolbe’s Reaction.
Ans. i) Reimer Tiemann Reaction: In this reaction, salicyaldehyde(2-Hydroxy benzaldehyde) is prepared on
reaction of phenols with chloroform while salicylic acid(2-Hydroxy benzoic acid) is formed when phenols
are treated with carbon tetrachloride.

ii) Kolbe’s Reaction: In this reaction , salicylic acid is prepared by the reaction of sodium phenoxide with
carbon dioxide followed by acidification.

31. Explain :
i) Dow’s Process
ii) Williamson synthesis
Ans i) Dow’s Process: This process is used for the formation of phenols from chlorobenzene.

ii) Williamson synthesis: This reaction is used for the synthesis of symmetrical and
unsymmetrical ethers.

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32.(a) How can we produce nitro benzene from phenol ?

(b)Why are reactions of alcohol/phenol and with acid chloride in the presence of pyridine?

(c) How is tert-butyl alcohol obtained from acetone?

Ans (a) by nitration of phenol:

C6H6 + dil.HNO3 o-nitrobenzene + p- C6H4 (NO3)

C6H6+ 3HNO3 (conc.)  2, 4, 6- C6H3 (NO3)3

(b) Pyridine is used in acylation of alcohol/phenol to remove the acid produced (HCl or CH3COOH) during
the reaction

( c) This is obtained by treating acetone with Grignard’s reagent

CH3COCH3+ CH3MgBr  [(CH3)3-C-OMgBr] (CH3)3-C-OH + Mg (OH) Br

33. Predict the products of the following reactions

i. Tetrahydrofurane + HI (2 mol) →

ii. Tertiary butylbromide + KOH(alc)→

iii. C6H5OCH3 + CH3Cl →

Ans i. Tetrahydrofurane + HI (2 mol) →ICH2 CH2 CH2 CH2I + H2O

ii. Tertiary butylbromide + KOH (alc) →2-methylbromide +KBr +H2O

iii. C6H5OCH3 + CH3Cl  2-methylanisol +4-methylanisol

34.(a)Why is preparation of ethers by acid catalyzed dehydration of 2° and 3°

Alcohols not a suitable method?

(b)phenol has much less pka than alcohol, explain.

( c) Ethers possess a net dipole moment even if they are symmetrical in structure .explain

Ans. (a) Because it is accompanied by the formation of alkenes and is not a suitable method for the
preparation of ether from acid catalyzed dehydration of 2° and 3° alcohol, as this reaction involve SN2
mechanism, but dehydration of 2° and 3° alcohol, it follows SN1 due to steric hindrance and tend to form
alkenes preferably.

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(b) Due to resonance in phenol, O acquires +ve charge , there is decrease in the electron density on –OH
,increasing acidic nature ,hence has less pka value than alcohol

( c) because of greater electro negativity of O ,C-O bond is polar in nature ,there is a net dipole moment of
the molecule and in spite of having symmetrical structure ,it has net moment.

35. Account for the following:

(a) Propanol has higher boiling point than butane

(b) Phenol does not give protonation reaction readily

Ans. (a) both are of comparable masses but because of intermolecular H-bonding in propanol which is not
present in butane due to absence of –OH group. There are only weak VanDer Waals forces in butane and
hence has lower boiling point.

(b ) C-OH in phenol is stabilized due to resonance and electron pair at oxygen atom in phenol is not readily
available to proton ,thus protonation not occurs readily

HIGH ORDER THINKING SKILL QUESTIONS

36. Convert (i) toluene into benzyl alcohol

(ii) Benzyl alcohol into 2-phenylethanoic acid

Ans: (i)

(ii)

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37. The compound C4H10O is produced on reaction of an alkane with H2SO4/H2O which is not resolvable
into optical isomers. Identify the compound.

ANS: The formula suggests that the compound is an alcohol. Since it is not resolvable, it is symmetrical and
is tertiary butyl alcohol. The corresponding alkane is isobutane. The alcohol has been formed as follows:

(CH3)3C-H + H2SO4/heat →(CH3)3C-SO3H + H2O → (CH3)3C-OH

Iso butane Tert butyl alcohol

38 .Name the reagents which can be used for the following conversions:

(a) A primary alcohol to an aldehyde

(b) Butan -2-ol butan-2-ol
(c) Phenol to picric acid.
Ans: (a) Pyridinum chlorochromate

(b)Lithium aluminium hydride

(c) Nitrating mixture of conc.H2SO4 and conc.HNO3

39. Give chemical test to distinguish between

(a)C6H5OH and C6H11OH

(b) H3C-CHOH-CH3 and C6H5CH2OH

Ans: . (a) Add a few drops of blue litmus separately to the solutions of both the compounds taken I two test
tubes. The solution which changes the colour of blue litmus to red is that of phenol. The solution which doe
not bring about any colour change is that of cyclohexanol.

(b) Treat both the solutions separately with Lucas reagent which is a mixture of HCl(g) and anhydrous
ZnCl2. The compound that gives white fumes after sometime is propan-2-ol while the other is benzyl
alcohol.

40. A compound [A] with molecular formula C4H10O reacts rapidly with metallic sodium but very slowly
with Lucas reagent. When [A] is treated with hot concentrated H2SO4, it gives a compound [B] C4H8 which
upon hydration with aqueous H2SO4 forms a compound [C] with molecular formula C4H10O. The compound
[C] is almost inert to metallic sodium but reacts rapidly with Lucas reagent. What are the compounds [A],
[B] and [C]? Explain the reactions involved.

Ans: (a) As the compound [C] is almost inert towards sodium metal but reacts rapidly with Lucas reagent, it
is a tertiary alcohol.

b) The molecular formula C4H10O suggest alcohol to be tertiary butyl alcohol i.e. (CH3)3COH.

Since [C] has been formed by the hydration of compound [B] which is an alkene, the compound [B] is
therefore, (CH3)3C=CH2.

C) The compound [B] has formed from [A]. as a result of dehydration with concentrated H2SO4. Since
compound [A] reacts rapidly with metallic sodium but very slowly with Lucas reagent, it is primary alcohol
with the formula (CH3)2CHCH2OH.

The series of reactions involved are as follows:

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(CH3)2CHCH2OH + H2SO4 (conc.) → (CH3)2C=CH2 +H2O/H+→ (CH3)3COH

Isobutyl alcohol[A] Isobutylene[B] Tert butyl alcohol [C]

41. Give chemical tests to distinguish between

a) Isopropyl alcohol and n-propyl alcohol

b) Phenol and alcohol
c) Methyl ethanoate and ethyl ethanoate
Ans: . a) Isopropyl alcohol gives yellow precipitate of iodoform on heating with I2 and NaOH solution
while n-propyl does not.

b) Phenol gives a characteristic violet/red coloration with neutral FeCl3 while alcohol (e.g., ethyl alcohol)
does not respond to this test.

c) Both are esters and upon hydrolysis in the acidic medium, they form methanol and ethanol respectively,

CH3COOCH3 + H2O(acidic) → CH3COOH + CH3OH

Methyl ethanoate Methanol

CH3COOC2H5 + H2O (acidic) → CH3COOH + C2H5OH

Ethyl ethanoate Ethanol

Ethanol and methanol can be further distinguished by iodoform test given by ethanol and not by
methanol.

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