11.1. Classify the following as primary, secondary and ter ary alcohols.

Ans: Primary alcohols: (i), (ii), (iii)

Secondary alcohols: (iv), (v)
Ter ary alcohols: (vi)

11.2. Iden fy aliylic alcohols in the above examples.

Ans: (ii) and (iv) i.e. H2C=CH – CH2OH and
11.3. Name the following compounds according to IUPAC system.

Ans:
11.4. Show how are the following alcohols prepared by the reac on of a suitable Grignard reagent on
methanal ?
Ans:
11.5. Write structures of the products of the following reac ons:
Ans:

11.6. Give structures of the products you would expect when each of the following alcohol reacts with
(a)HCl-ZnCl2 (b)HBrand (c) SOCl2
(i)Butan-1-ol
(ii)2-Methylbutan-2-ol
Ans:
11.7. Predict the major product of acid catalysed dehydra on of
(i) 1-nicthylcyclohcxanoland
(ii) butan-1-ol
Ans:

11.8. Ortho and para nitrophenols are more acidic than phenol. Draw the resonance structures of the
corresponding phenoxide ions.
Ans:
The resonance structures of o-and p- nitrophenoxide ions and phenoxide ion are given below:

11.9; Write the equa ons involved in the following reac ons:
(i) Reimer-Tiemann reac on
(ii) Kolbe’s reac on
Ans: (i) Reimer-Tiemann reac on

11.10. Write the reac ons of Williamson synthesis of 2-ethoxy-3-methylpentane star ng from ethanol
and 3-methylpentan-2-ol.
Ans: In Williamsons’s synthesis, the alkyl halide should be primary. Thus, the alkyl halide should be
derived from ethanol and the alkoxide ion from 3-methylpentan-2-ol. The synthesis is as follows
11.11. Which of the following is an appropriate set of reactants for the prepara on of l-methoxy-4-
nitrobenzene and why?

Ans:

11.12. Predict the products of the following reac ons:

Ans:

NCERT EXERCISES

11.1. Write IUPAC names of the following compounds:

Ans: (i) 2,2,4-Trimethylpentan-3-ol
(ii) 5-Ethylheptane-2,4-dioI
(iii) Butane-2,3-diol
(iv) Propane-1,2,3-triol
(v) 2-Methylphenol
(vi) 4-Methylphenol
(vii) 2,5-DimethylphenoI
(viii) 2,6-Dimethylphenol
(ix) 1-Methoxy-2-methylpropane
(x) Ethoxybenzene
(xi) 1-Phenoxyheptane
(xii) 2-Ethoxybutane

11.2. Write structures of the compounds whose IUPAC names are as follows:
(i)2-Methylbutan-2-ol
(ii)l-Phcnylpropan-2-ol
(iii)3,5-DimethyIhexane-l,3,5-triol
(iv)2,3-Dicthylphenol
(v)1-Ethoxypropane
(vi)2-Ethoxy-3-methylpentane
(vii) Cyclohexylmethanol
(viii) 3-Cyclohexylpcntan-3-ol
(ix)Cyclopcnt-3-en-l-ol
(x)4-ChIoro-3-ethylbutan-l-ol
Ans:
11. 3. (a) Draw the structural formulas and write IUPAC names of all the isomeric alkanols with the
molecular formula CsH12O
(b) Classify the isomers of alcohols given in part (a) as primary, secondary and ter ary alcohols.
Ans:
(a) The molecular formula C5H120 represents eight isomeric alkanols. These are :

(b) Praimary: (i), (ii), (iii), (iv) ; Secondary :(v), (vi), (viii) ; Ter ary : (vii)

11.4. Explain why propanol has higher boiling point than that of the hydrocarbon, butane?
Ans: The molecules of butane are held together by weak van der Waal’s forces of a rac on while those
of propanol are held together by stronger intermolecular hydrogen bonding.

11.5. Alcohols are compara vely more soluble in water than hydrocarbons of comparable molecular
masses. Explain this fact.
Ans: Alcohols can form hydrogen bonds with water and by breaking the hydrogen bonds already exis ng
between water molecules. Therefore, they are soluble in water.

On die other hand, hydrocarbons cannot from hydrogen bonds with water and hence are insoluble in
water.

11.6. What is meant by hydrobora on-oxida on reac on? Illustrate it with an example.
Ans: The addi on of diborane to alkenes to form trialkyl boranes followed by their oxida on with
alkaline hydrogen peroxide to form alcohols is called hydrobora on-oxida on. For example,

11.7. Give the structures and IUPAC names of monohydric phenols of molecular formula, C 7H8O.
Ans: The three isomers are:

11.8. While separa ng a mixture of ortho and para nitrophenols by steam dis lla on, name the
isomer which will be steam vola le. Give reason.
Ans: 0-N itrophenol is steam vola le due to chela on (intramolecular H – bonding) and hence can be
separated by steam dis lla on from/Miitrophenol which is hot steam vola le because of intermolecular
H-bonding.

11.9. Give the equa ons of the reac on for the prepara on of phenol from cumene.
Ans: This process has a great industrial importance because it gives the prepara on of two very useful
compounds i.e. phenol and acetone. The raw materials are benzene and propene and it ini ally proceeds
by Friedel Cra s alkyla on of benzene.

Oxygen is bubbled through the above solu on to form cumene hydroperoxide which is decomposed with
aqueous acid
solu on to form phenol and acetone as follows:

11.10. Write chemical reac on for the prepara on of phenol from chlorobenzene.
Ans:
11.11. Write the mechanism of hydra on of ethene to yield ethanol.
Ans: Direct addi on of H20 to ethene in presence of an acid does not occur. Indirectly, ethene is first
passed through concentrated H2S04, when ethyl hydrogen sulphate is formed.

11.12. You are given benzene, cone. H2S04and NaOH. Write the equa ons for the prepara on of
phenol using these reagents.
Ans:

11.13. Show how will you synthesise

(i) 1 -phenylethanol from a suitable alkene.
(ii) cyclohexylmethanol using an alkyl halide by an SN2 reac on.
(iii) Pentan-l-ol using a suitable alkyl halide?
Ans:

11.14. Give two reac ons that show the acidic nature of phenol. Compare its acidity with that of
ethanol.
Ans: The reac ons showing acidic nature of phenol are:
(a) Reac on with sodium: Phenol reacts with ac ve metals like sodium to liberate H, gas.

(b) Reac on with NaOH: Phenol dissolves in NaOH to form sodium phenoxide and water.

Phenol is more acidic than ethanol. This is due to the reason that phenoxide ion le a er the loss of a
proton from phenol is stabilized by resonance, while ethoxide ion le a er less of a proton from ethanol,
is not.

11.15. Explain why is orthonitrophenol more acidic than orthomethoxyphenol?

Ans: Nitro (NO2) group is an electron withdrawing group while methoxy (OCH3) group is electron
releasing in nature. The release of H+ ion is therefore, easier from o-nitrophenol while it is quite difficult
from o-methoxyphenol. Apart form that, o-nitrophenoxide ion is stabilised due to resonance o-
nitrophenol is steam vola le while p-nitrophenol is not. This is on account of intramolecular hydrogen
bonding in the molecules of o-nitrophenol. As a result, its boiling point is less than that of p-nitrophenol
in which the molecules are linked by intermolecular hydrogen bonding.
It is interes ng to note that in the subs tuted phenols, the nature and posi on of the subs tuent
influences the boiling point of phenol.
For example: .o-nitrophenol is steam vola le while p-nitrophenol is not. This is supported by the fact
that the boiling point temperature of o-nitrophenol (100°C) is less than that of p-nitrophenol, (279°C). In
o-nitrophenol, there is intramolecular hydrogen bonding in OH and NO2 groups placed in a adjacent
posi ons. However, these are linked by intermolecular hydrogen bonding in the p-isomers. It is quite
obvious that extra energy is needed to the cleave the hydrogen bonds in the p-isomer. Consequently, its
boiling point is more.

o-nnrophenol with lower boiling point is steam vola le while p-nitrophenol is not. This helps in the
separa on of the two isomers present in the liquid mixture. On passing steam, o-nitropbenol vola lises
and its vapours rise alongwith steam and a er condensa on, collect in the receiver p-nitrophenol is le
behind in the dis lla on flask. e-nkrophenol p-nnrophenol.
On the contrary, o-methoxyphenoxide is destabilised since the electron density on the nega vely
charged oxygen tends to increase due to the electron releasing tendency of the methoxy(OCH 3) group.

In the light of the above discussion, we may conclude that o-nitrophenol is a stronger acid (pKa = 7-23)
than o-methoxyphenl (pKa = 9.98)

11.16. Explain how does the – OH group a ached to a carbon of benzene ring ac vate it towards
electrophilic subs tu on?
Ans: Phenol may be regarded as a resonance hybrid of structures I-V, shown below.

As a result of +R effect of the -OH group, the electron density in the benzene ring increases thereby
facilita ng the a ack of an electrophile. In other words, presence of -OH group, ac vates the benzene
ring towards electrophilic subs tu on reac ons. Further, since the electron density is rela vely higher at
the two o-and one p-posi on, therefore electrophilic subs tu on occurs mainly at o-and p-posi ons.

11.17. Give equa ons of the following reac ons:

(i) Oxida on of propan-l-ol with alkaline KMnO4 solu on.
(ii) Bromine in CS2 with phenol.
(iii) Dilute HNO3 acid with phenol
(iv) Trea ng phenol with chloroform in presence of aqueous NaOH.
Ans:

11.18. Explain the following with an example

(i) Kolbe’s reac on
(ii) Reimer – Tiemann reac on –
(iii) Williamson ether synthesis
(iv) Unsymmetrical ether
Ans: (i) Kolbe’s reac on: Sodium phenoxide when heated with C02 at 400K under a pressure of 4-7
atmospheres followed by acidifica on gives 2-hydroxybenzoic acid (salicylic acid) as the major product
along with a small amount of 4-hydroxybenzoic acid.This reac on is called Kolbe’s reac on.

(ii) Reimer-Tiemann reac on: Treatment of phenol with CHC13 in presence of aqueous sodium or
potassium hydroxide at 340 K followed by hydrolysis of the resul ng product gives 2-
hydroxybenzaldehyde (salicyialdehyde) as the major product. This reac on is called Reimer-Tiemann
reac on.
(iii) Williamson’s ether synthesis: It involves the treatment of an alkyl halide with a suitable sodium
alkoxide to obtain ethers. The sodium alkoxide needed for the purpose is prepared by the ac on of
sodium on a suitable alcohol. In this reac on alkyl halide should primary. Secondary and ter ary halides
will predominantly give an alkene.

(iv) Unsymmetrical ether: If the alkyl or aryl groups a ached to the oxygen atom are different, ethers are
called unsymmetrical ethers. For example, ethyl methyl ether, methyl phenyl ether, 4-chlorophenyl- 4-
nitrophenyl ether, etc.

11.19. Write the mechanism of acid dehydra on of ethanol to yield ethene.

Ans: The mechanism of dehydra on of alcohols to form alkenes occur by the following three steps:

11.20. How are the following conversions carried out?

(i) Propane → Propan-2-ol
(ii) Benzyl chloride → Benzyl alcohol
(iii) Ethyl mag. chloride → Propan-1-ol
(iv) Methyl mag. bromide → 2-Methylpropan-2-ol.
Ans:

11.21. Name the reagents used in the following reac ons:

(i) Oxida on of a primary alcohol to carboxylic acid.
(ii) Oxida on of a primary alcohol to aldehyde.
(iii) Bromina onofphenolto2,4,6-tribromophenol
(iv) Benzyl alcohol to benzoic acid.
(v) Dehydra on of propan-2-oI to propene.
(vi) Butan-2-one to butan-2-oL .
Ans: (i) Acidified potassium dichromate or neutral/ acidic/ alkaline potassium permanganate.
(ii) Pyridinium chlorochromate (PCC), (C5H5NH)+ ClCrO3– in CH2Cl2
or Pyridinium dichromate (PDC),[(C5H5NH)2]2+Cr2O72-in CH2Cl2
(iii) Aqueous bromine, i.e., Br2/H2O.
(iv) Acidified or alkaline potassium permanganate.
(v) 85% H2S04 at 440 K.
(vi) Ni/H2 or NaBH4 or LiAlH4.

11.22. Give reason for the higher boiling point of ethanol in comparison to methoxymethane.
Ans: Ethanol undergoes intermolecular H-bonding due to the presence of a hydrogen atom a ached to
the electronega ve oxygen atom. As a result, ethanol exists as associated molecules.
Consequently, a large amount of energy is required to break these hydrogen bonds. Therefore, the
boiling point of ethanol is higher than that of methoxymethane which does not form H-bonds.

11.23. Give IUPAC names of the following ethers.

Ans: (i)1-Ethoxy-2-methylpropane
(ii) 2-Chlorlo-l-methoxy ethane
(iii) 4-Nitroanisole
(iv) 1-Methoxypropane
(v) 1 -Ethoxy-4 -4 – dimethyl cyclohexane
(vi)Ethoxybenzene

11,24. Write the names of the reagents and equa ons for the prepara on of the following ethers by
Williamson’s synthesis :
(i) 1-Propoxypropane
(ii) 2-Methoxy-2-methylpropane
(iii) Ethoxybenzene
(iv) Methoxyethane.
Ans:

11.25. Illustrate with examples the limita ons of Willamson synthesis for the prepara on of certain
types of ethers.
Ans: Williamson’s synthesis is a versa le method for the synthesis of both symmetrical and
unsymmetrical ethers. However, for the synthesis of unsymmetrical ethers, a proper choice of reactants
is necessary. Since Williamson’s synthesis occurs by SN2 mechanism and primary alkyl halides are most
reac ve in Sn2 reac on, therefore, best yields of unsymmetrical ethers are obtained when the alkyl
halides are primary and the alkoxide may be primary, secondary or ter ary. For example, tert-butylethyl
ether is prepared by trea ng ethyl bromide with sodium tert-butoxide.

11.26. How is 1-propoxypropane synthesised from propane-1-ol? Write mechanism of the

reac on. (C.B.S.E. Sarnie Paper 2015)
Ans: Two methods can be used for the synthesis of 1-propoxypropane from propan-1-ol
By Williamson’s synthesis
The halogen deriva ve such as bromoderiva ve and sodium salt of the alcohol take part in the
Williamson’s synthesis

11.27. Prepara on of ethers by acid dehydra on of secondary or ter ary alcohols is not a suitable
method. Give reason.
Ans: Acid catalysed dehydra on of primary alcohols to ethers occurs by SN2 reac on involving
nucleophilic a ack by the alcohol molecule on the protonated alcohol molecule.

Under these condi ons, 2° and 3° alcohols, however, give alkenes rather than ethers. The reason being
that due to steric hindrance, nucleophilic a ack by the alcohol molecule on the protonated alcohol
molecule does not occur. Instead protonated 2° and 3° alcohols lose a molecule of water to form stable
2° and 3° carboca on. These carboca ons prefer to lose a proton to form alkenes rather than undergoing
nucleophilic a ack by alcohol molecules to form ethers.

11.28. Write the equa on of the reac on of hydrogen iodide with (i)1-propoxypropane
(ii)methoxybenzene, and (iii)benzyl ethyl ether
Ans:

11.29. Explain the fact that in alkyl aryl ethers, alkoxy group :
(i) ac vates the benzene ring towards electrophilic subs tu on.
(ii) directs the incoming subs tuents towards ortho and para posi ons in the ring.
Ans:
(i) The alkoxy group (RO -) with lone electron pairs on the oxygen atom ac vates the ortho and para
posi ons in the ring by + M (or + R) effect as shown below :
As the ortho and para posi ons in the ring become points of high electron density, the electrophiles
prefer to a ack these posi ons.

(ii) The alkoxy group directs the incoming group which is an electrophile towards the ortho and para
posi ons in the ring. As a result, a mixture of isomeric products is formed.

11.30. Write the mechanism of the reac on of HI with methoxymethane.

Ans: When equimolar amounts of HI and methoxy methane are reacted, a mixture of methyl alcohol and
methyl iodide is formed by the following mechanism:

11.31. Write equa ons of the following reac ons:

(i) Friedel-Cra s reac on -alkyla on of anisole
(ii) Nitra on of anisole.
(iii) Bromina on of anisole in ethanoic acid medium
(iv) Friedel-Cra ’s acetyla on of anisole.
Ans:
11.32. Show how will you synthesise the following from appropriate alkenes.

Ans: All the alcohols are formed by the hydra on of alkenes in the acidic medium. The addi on follows
Markownikov’s rule. 1-Methylcyclohexene can be used in the reac on.

(ii) 4-Methylpent-3-ene upon hydra on in the acidic medium will give the desired alcohol.
(iii) Pent-2-ene gives the desired alcohol upon hydra on in the presence of acid.

(iv) The cyclic alkene used in this reac on is 2-cyclohexylbut-2-ene.

11.33. When 3-methylbutant 2-ol is treated with HBr, the following reac on takes place:

Give a mechanism for this reac on.

(Hint: The secondary carboca on formed in step II rearranges to a more stable ter ary carboca on by
a hydride ion shi from 3rd carbon atom.)
Ans:

Protona on of the given alcohol followed by loss of water gives a 2° carboca on(I), which being unstable
rearranges by 1,2-hydride shi to form the more stable 3° carboca on (II). Nucleophilic a ack by Br ion
on this carboca on (II) gives the final product.
Multiple Choice Questions

Single Correct Answer Type

Question 1. Monochlorination of toluene in sunlight followed by hydrolysis with aq.

NaOH yields.
(a) o-Cresol (b) w-Cresol
(c) 2, 4-Dihydroxytoluene (d) Benzyl alcohol
Solution: (d) Monochlorination of toluene in sunlight gives benzyl chloride. On
hydrolysis with aq. NaOH, benzyl chloride shows nucleophilic substitution reaction to
give benzyl alcohol.

Question 2. How many alcohols with molecular formula C4H10O are chiral in nature?
(a) 1 (b) 2 (c) 3 (d) 4
Solution: (a) Only one alcohol contains chiral carbon atom.

Question 3. What is the correct order of reactivity of alcohols in the following reaction?

Solution: (c) The given reaction is nucleophilic substitution reaction in which -OH group
is replaced by -Cl. Tertiary alcohols, when react with HCl in presence of ZnCl 2, form
tertiary carbocation.
This intermediate 3° carbocation is more stable than 2° carbocation as well as 1°
carbocation. The higher the stability of intermediate, the higher will be the reactivity of
reactant molecule.
So, the order of reactivity of alcohols in the given reaction is 3° > 2° > 1°.

Question 4. CH3CH2OH can be converted into CH3CHO by .

(a) catalytic hydrogenation
(b) treatment with LiAlH4
(c) treatment with pyridinium chlorochromate
(d) treatment with KMnO4
Solution: (c) Alcohols are oxidized to aldehydes and finally to acids.

Question 5. The process of converting alkyl halides into alcohols involves .

(a) addition reaction (b) substitution reaction
(c) dehydrohalogenation reaction (d) rearrangement reaction
Solution: (b) Conversion of alkyl halides into alcohols involves substitution reaction.

Question 6. Which of the following compounds are/is aromatic alcohol?

Solution: (c) Compound (A) i.e., phenol and compound (D) i.e., a derivative of phenol
cannot be considered as aromatic alcohol. As phenol is also known as, carbolic acid
cannot be considered as aromatic alcohol.
Compound (B) and (C), -OH group is bonded to sp3 hybridised carbon which in turn is
bonded to benzene ring.
Question 7. Give IUPAC name of the compound given below.

Solution: (c)

Question 8. IUPAC name of m-cresol is .

(a) 3-methylphenol (b) 3-chlorophenol
(c) 3-methoxyphenol (d) benzene- 1,3-diol
Solution:

Question 9. IUPAC name of the compound

Solution:

Question 10. Which of the following species can act as the strongest base?

Solution: (b) Weakest acid has the strongest conjugate base. Since R-OH is the weakest
acid, therefore, RO is the strongest base.

Question 11. Which of the following compounds will react with sodium hydroxide
solution in water?
(a) C6H5OH (b) C6H5CH2OH (C) (CH3)3COH (d) C2H5OH
Solution: (a) Phenol being more acidic reacts with sodium hydroxide solution in water
to give sodium phenoxide which is resonance stabilized.
Alcohols are very weak acids.
C6H5OH + NaOH -> C6H5ONa + H2O

Question 12. Phenol is less acidic than .

(a) ethanol (b) o-nitrophenol
(c) o-methylphenol (d) o-methoxyphenol
Solution: (b) In o-nitrophenol, nitro group is present at ortho position. Presence of
electron withdrawing group at ortho position increases the acidic strength. On the other
hand, in o-methylphenol and in o-methoxyphenol and in o-methoxyphenol, electron
releasing group (-CH3-OCH3)
Presence of these groups at ortho or para positions of phenol decreases the acidic strength of phenols.
So, phenol is less acidic than o-nitrophenol.

Question 13. Which of the following is most acidic?

(a) Benzyl alcohol (b) Cyclohexanol
(c) Phenol (d) m-Chlorophenol
Solution: (d) Alcohols are less acidic than phenol. Further electron withdrawing group
(like – Cl) increases the acidity of phenol, therefore, m-chlorophenol is most

Question 14. Mark the correct order of decreasing acid strength of the following

Solution:

-NO2 is an electron withdrawing group which increases the acidity of phenol and the
effect is more pronounced at ortho and para positions. Similarly methoxy group is an
electron releasing group which decreases the acidity of phenol and the effect is more
pronounced at ortho and para positions.

Question 15. Mark the correct increasing order of reactivity of the following
compounds with HBr/HCl.
Solution: (c) All three benzyl alcohols react with HBr/HCl through the formation of
intermediate carbocation. The more stable the carbocation, the more reactive is the
alcohol. The electron releasing groups i.e. NO 2, Cl decrease the stability of the
carbocation. Since -NO2 group is stronger electron withdrawing than -Cl group, therefore,
stability of carbocation increases in the order:

Therefore, the reactivity of benzyl alcohols increases in the order: (II) < (III)<(I)

Question 16. Arrange the following compounds in increasing order of boiling point.
Propan-l-ol, butan-2-ol, pentan-l-ol
(a) Propan-1 -ol, butan-2-ol, butan-1 -ol, pentan-l-ol
(b) Propan-1 -ol, butan-1 -ol, butan-2-ol, pentan-1 -ol
(c) Pentan-1 -ol, butan-2-ol, butan-1 -ol, propan-1 -ol
(d) Pentan-1 -ol, butan-1 -ol, butan-2-ol, propan-1 -ol
Solution: (a) Boiling point increases with increase in molecular mass of the alcohols.
Among isomeric alcohols 1° alcohols have higher boiling points than 2° alcohols. Thus,
correct order is:
Propan-l-ol < butan-2-ol < butan-l-ol < pentan-l-ol.

More than One Correct Answer Type

Question 17. Which of the following are used to convert RCHO into RCH 2OH?
(a) H2/Pd
(b) LiAlH4
(c) NaBH4
(d) Reaction with RMgX followed by hydrolysis
Solution: (a, b, c) Conversion of aldehyde into alcohol is a reduction reaction. This
reduction can be carried out by adding hydrogen in presence of finely divided metal
catalyst such as platinum, palladium or nickel.

Question 18. Which of the following reaction will yield phenol?

Solution:

Haloarene requires extreme conditions for nucleophilic substitution reaction.

Chlorobenzene does not undergo hydrolysis on treatment with aqueous NaOH at 298 K
and 1 atm.

Question 19. Which of the following reagents can be used to oxidize primary alcohols
to aldehydes?
(a) CrO3 in anhydrous medium
(b) KMnO4 in acidic medium
(c) Pyridinium chlorochromate
(d) Heat in the presence of Cu at 573 K
Solution: (a, c, d) CrO3 in anhydrous medium, PCC and heating in presence of Cu
(dehydrogenation) will oxidize primary alcohols to aldehydes. KMnO 4 will further oxidize
it to acid.
Question 20. Phenol can be distinguished from ethanol by the reactions with ………….
(a) Br2/water (b) Na
(c) Neutral FeCl3 (d) All of these
Solution: (a, c) Phenol reacts with bromine water to give a colourless tribromo
derivative and gives a violet coloured complex with FeCl3. Ethanol does not give these
reactions.

Question 21. Which of the following are benzylic alcohols?

Solution: (b, c) In benzylic alcohols, the -OH group is attached to a sp3 hybridised
carbon atom next to an aromatic ring. In compounds (a) and (d), the -OH group is
attached to a sp3 hybridised carbon atom but this carbon is not attached to the
benzene ring.
On the other hand, in compounds (a) and (c), the -OH group is attached to a sp3
hybridised carbon atom next to an aromatic ring.

Short Answer Type Questions

Question 22. What is the structure and IUPAC name of glycerol?

Solution:

Question 23. Write the IUPAC name of the following compounds,

Solution:

Question 24. Write the IUPAC name of the compound given below.

Solution:

Question 25. Name the factors responsible for the solubility of alcohols in water.
Solution: Alcohols are soluble in water because of hydrogen bonding with water
molecules.

The solubility decreases with increase in size of alkyl or aryl group.

Question 26. What is denatured alcohol?

Solution: Alcohol is made unfit for drinking by mixing some copper sulphate and
pyridine to it. This process is called denaturation of alcohol and alcohol mixed with
copper sulphate and pyridine is called denatured alcohol.

Question 27. Suggest a reagent for the following conversion.

Solution: Cr03, pyridine and HC1 (Pyridinium chlorochromate) C3H5 N HCr03Cl .

Question 28. Out of 2-chloroethanol and ethanol which is more acidic and why?
Solution: 2-Chloroethanol is more acidic, due to -I effect of chlorine atom.

Question 29. Suggest a reagent for conversion of ethanol to ethanal.

Solution: CrO3, pyridine and HCl (Pyridinium chlorochromate, PCC) in CH 2C12.

Question 30. Suggest a reagent for conversion of ethanol to ethanoic acid.

Solution: Any strong oxidising agent e.g., acidified K2Cr2O7 or KMnO4.

Question 31. Out of o-nitrophenol and p-nitrophenol, which is more volatile? Explain.
Solution: Ortho nitrophenol is much more volatile in steam due to chelation.
Intramolecular hydrogen bonding is present in o-nitrophenol and intermolecular
hydrogen bonding in p-nitrophenol.

Question 32. Out of o-nitrophenol and o-cresol which is more acidic?

Solution:

Question 33. When phenol is treated with bromine water, white precipitate is obtained.
Give the structure and the name of the compound formed.
Solution:

Question 34. Arrange the following compounds in increasing order of acidity and give
a suitable explanation:
Phenol, o-Nitrophenol, o-Cresol
Solution:

Question 35. Alcohols react with active metals, e.g., Na, K, etc., to give corresponding
alkoxides. Write down the decreasing order or reactivity of sodium metal towards
primary, secondary and tertiary alcohols.
Solution: Decreasing order of reactivity of sodium metal is: 1° > 2° > 3°
Alcohols react with sodium metal to form alkoxides and hydrogen is liberated:

The order of reactivity of alcohols is primary > secondary > tertiary. This can be
explained on the basis of cleavage of O – H bond. The alkyl groups are electron
releasing groups (+1 effect) and they increase the electron density around the oxygen.
As a result, the electrons of O – H bond cannot be withdrawn strongly towards oxygen
and O – H remains strong. Therefore, greater is the number, of alkyl groups present,
smaller will be reactivity of alcohol.
Question 36. What happens when benzene diazonium chloride is heated with water?
Solution:

Question 37. Arrange the following compounds in decreasing order of acidity:

H2O, R-OH, HC = CH
Solution: Decreasing order of acidify is:
H2O>R-OH>HC = CH

Question 38. Name the enzymes and write the reactions involved in the preparation of
ethanol from sucrose by fermentation.
Solution:

Question 39. How can propan-2-one be converted into tert-butyl alcohol?

Solution:

Question 40. Write the structures of the isomers of alcohols with molecular formula
C4H10O. Which one of these isomers exhibits optical activity?
Solution: Isomers of alcohols (C4H10O) are:

Question 41. Explain why is OH group in phenols more strongly held as compared to
OH group in alcohols.
Solution: In phenol, oxygen atom is attached to sp 2-hybridised carbon atom while in
alcohol, it is attached to sp3-hybridised carbon atom. The bond formed between oxygen
and .sp2-hybridised carbon is more strongly held then that formed between oxygen and
sp3-hybridised carbon.

Question 42. Explain why nucleophilic substitution reactions are not very common in
phenols.
Solution: The C – O bond in phenols has some double bond character due to resonance
and hence cannot be easily cleaved by nucleophiles. So, nucleophilic substitution
reactions are not very common in phenols and they give many electrophilic substitution
reactions.

Question 43. Preparation of alcohols from alkenes involves the electrophilic attack on
alkene carbon atom. Explain its mechanism.
Solution: The mechanism of acid catalysed addition of water (hydration) to alkenes
involves the following three steps:
Step 1: Electrophilic attack by hydronium ion (H3O+) on alkene gives an intermediate,
carbocation.

Question 44. Explain why is O = C = O nonpolar while R – O – R is polar.

Solution: O = C = O molecule is linear so that the polarities of two C – O bonds get
cancelled and the molecule is linear.
Ethers have structures similar to water and have angular or bent structure. Therefore,
the polarity of two R – O groups does not get cancelled and these have net dipole
moment. Thus, R – O – R is polar.

Question 45. Why is the reactivity of all three classes of alcohols with cone. HCl and
ZnCl2 (Lucas reagent) different?
Solution: The alcohol combine with HCl to form protonated alcohol. The positive charge
on oxygen weakens the C – O bond leading to its cleavage.

The rate determining step in the above mechanism is (ii), which is a slow step reaction.
The stability of carbocation will determine the reactivity of the reaction. Since the order
of stability of carbocation is: Pri. < sec. < tert. Hence the order of formation of alkyl
halide in the above reaction is pri. < sec. < tert.

Question 46. Write steps to carry out the conversion of phenol to aspirin.
Solution:
Question 47. Nitration is an example of aromatic electrophilic substitution and its rate
depends upon the group already present in the benzene ring. Out of benzene and
phenol, which one is more easily nitrated and why?
Solution: Phenol is more easily nitrated than benzene because the —OH group in phenol
increases the electron density at o- and p-positions in benzene ring by +R effect.
Nitration which is an electrophilic substitution reaction takes place more readily where
the electron density is more.

Question 48. In Kolbe’s reaction, instead of phenol, phenoxide ion is treated with
carbon dioxide. Why?
Solution: Phenoxide ion is more reactive than phenol towards electrophilic substitution.
The negative charge on oxygen is transferred to benzene through resonance. This helps
in the attachment of Co2 which is a weak electrophile to the benzene ring finally giving
salicylic acid. .

Question 49. Dipole moment of phenol is smaller than that of methanol. Why?
Solution: In phendl, C – O bond is less polar due to electron withdrawing effect of
benzene ring, whereas in methanol C – O bond is more polar due to electron releasing
effect of—CH3 group. Hence, the dipole moment of phenol (1.54 D) is smaller than that
of methanol (1.71 D).

Question 50. Ethers can be prepared by Williamson’s synthesis in which an alkyl halide
is reacted with sodium alkoxide. Di-tert-butyl ether cannot be prepared by this
method. Explain.
Solution: In tert-butyl halides, the elimination reaction is favoured over substitution. So,
alkene is the only reaction product formed and not the ether.

Question 51. Why is the C – O – H bond angle‘in alcohols slightly less than the
tetrahedral angle whereas the C – O – C bond angle in ether is slightly greater?
Solution: The C – O – H bond angle in alcohols is slightly less than the tetrahedral angle
(109.5°) because of larger repulsions between the lone pairs of electrons. For example
in methanol C – O – H bond angle is 108.9°.
In ethers, the C – O – C bond angle is slightly greater than tetrahedral angle. For
example in dimethyl ether C – O – C bond angle is 111.7°. The larger bond angle in
ethers may be because of greater repulsions between bulkier alkyl groups as compared
to one H in alcohols.
Question 52. Explain why are low molecular mass alcohols soluble in water?
Solution:

Question 53. Explain why is p-nitrophenol more acidic than phenol?

Solution: The electron withdrawing group (-NO2), withdraws electrons and disperses the
negative charge. Therefore, -NO2 group stabilizes the phenoxide ion. Hence p-
nitrophenol is more acidic than phenol.

Question 54. Explain why alcohols and ethers of comparable molecular mass have
different boiling points.
Solution:

Question 55. The carbon-oxygen bond in phenol is slightly stronger than that in
methanol. Why?
Solution: This can be explained as under:
(i)In phenol, the conjugation of unshared electron pairs over oxygen with aromatic ring
results in partial double bond character in C – O bond.

In methanol, no such conjugation (resonance) is possible.

(ii) In phenol, oxygen is attached to sp 2 hybridised carbon while in methanol, oxygen
attached to sp2 hybridised carbon. An sp2 hybridised carbon is more electronegative
(because of greater 5-character) than sp3 hybridised carbon atom. Therefore, the bond
between oxygen and sp2 hybridised carbon is more stable than the bond between
oxygen and sp2, hybridised orbital.

Question 56. Arrange water, ethanol and, phenol in increasing order of acidity and give
reason for your answer.
Solution: Increasing order of acidity is: ethanol < water < phenol.
This is because the phenoxide ion obtained after the removal of H + is resonance
stabilised, while the ethoxide ion obtained after the removal of H + is destabilised by +1
effect of ethyl group. Thus phenol is a stronger acid than ethanol.
Now, ethanol is a weaker acid than water because the electron releasing ethyl group
increases the ethanol density on oxygen and consequently the proton will not be
released easily. There is no such effect is water.

Matching Column Type Questions

Question 57. Match the structures of the compounds given in Column I with the name
of the compounds given in Column II.
Solution: (i —» d), (ii —» c), (iii —> f), (iv —> a), (v —» g), (vi —» b)
(i) Cresols are organic compounds which are methyl phenols. There are three forms of
cresol: o-cresol, p-cresol and w-cresol.
(ii) Catechol is also known as pyrocatechol. Its IUPAC name is 1, 2-dihydrobenzene. It is
used in the production of pesticides, perfumes and pharmaceuticals.
(iii) Its IUPAC name is 1, 3-dihydroxybenzene. Resorcinol is used to treat acne,
seborrheic dermatitis and other skin disorder.
(iv) Hydroquinone is also known as quinol. Its IUPAC name is 1, 4-dihydroxybenzene.
Itisawhite granularsolid.lt isagoodreducing agent.
(v) Anisole or methoxy benzene, is a colourless liquid with a smell reminiscent of anise
seed.
(vi) Phenetole is an organic compound. It is also known as ethylphenyl ether. It is
volatile in nature and its vapour are explosive in nature.

Question 58. Match the starting materials given in Column I with the products formed
by these (Column II) in the reaction with HI.
Solution: (i —> d), (ii —» e), (iii —> b), (iv —» a)
(i) CH3 – O – CH3 is a symmetrical ether so the products are CH3I and CH2OH.
(ii) In (CH3)2CH – O – CH3 unsymmetrical ether, one alkyl group is primary while another
is secondary. So, it follows SN 2mechanism. Thus, the halide ion attacks the smaller alkyl
group and the products are

(iii) In this case, one of the alkyl group is tertiary and the other is primary. It
follows SN 1 mechanism and halide ion attacks the tertiary alkyl group and the products
are (CH3)3 C-I and CH3OH.
(iv) Here, the unsymmetrical ether is alkyl aryl ether. In this ether 0-CH 3 bond is weaker
than 0-C6H5bond which has partial double bond character due to resonance. So, the
halide ion attacks on alkyl group and the products are C 6H5-OH and CH3I.

Question 59. Match the items of Column I with items of Column II.

Solution: (i e), (ii —> f), (iii —> d), (iv —» c), (v —> a), (vi —» b)
(i) IUPAC name of ethylene glycol is ethane-1, 2-diol. It is primarily used as raw material
in the manufacturing of polyester fibers and fabric industry. A small percentage of it is
used in antifreeze formulations.
(ii) Ethanol is a good solvent for fatty and waxy substances. Fats and waxes provide
odour to the perfumes. Apart from being a good solvent, it is less irritating to the skin.
So, it is used in perfumes.
(iii) Phenol is converted into picric acid (2, 4, 6-trinitro-phenol) by the reaction of phenol
with cone. HNO3.

(iv) Methanol, CH3OH is also known as ‘wood spirit’ as it was produced by the
destructive distillation of wood.
(v) Neutral ferric chloride give purple/red colour when treated with phenols. It is the
reagent used for detection of phenolic group.
(vi) Soaps are prepared by the reactions of fatty acid with NaOH.
Question 60. Match the items of Column I with items of Column II.

Solution: (i —» d), (ii -» a), (iii -> f), (iv -> e), (v -> c), (vi -> b) .
(i) Methanol is also known as ‘wood spirit’ as it was produced by the destructive
distillation of wood.
(ii) In Kolbe’s reaction, 2-hydroxy benzoic acid (salicylic acid) is prepared by the reaction
of phenol with CO2 gas.

Assertion and Reason Type Questions

In the following questions, a statement of Assertion (A) followed by a statement of

Reason (R) is given. Choose the correct answer out of the following choices:
(a) Assertion and Reason both are correct and Reason is the correct explanation of
Assertion.
(b) Both Assertion and Reason are wrong.
(c) Assertion is correct but Reason is wrong.
(d) Assertion is wrong but Reason is correct.
(e) Both Assertion and Reason are correct but Reason is not the correct explanation of
Assertion. .

Question 61. Assertion (A): Addition reaction of water to but-l-ene in acidic medium
yields-butan-l-ol.
Reason (R): Addition of water in acidic medium proceeds through the formation of
primary carbocation.
Solution: (b) Addition of water to but-l-ene in acidic medium yields butan-2-ol.
Addition of water proceeds through formation of secondary carbocation.

Question 62. Assertion (A): p-Nitrophcnol is more acidic than phenol.

Reason (R): Nitro group helps in the stabilization of the phenoxide ion by dispersal of
negative charge due to resonance.
Solution: (a) p-Nitrophenol is more acidic than phenol because nitro group stabilizes
phenoxide ion by dispersal of negative charge.

Question 63. Assertion (A): IUPAC name of the compound

Reason (R): In IUPAC nomenclature, ether is regarded as hydrocarbon derivative in

which a hydrogen atom is replaced by -OR or -OAr group [where R = alkyl group and Ar
= aryl group]
Solution: (d) IUPAC name of the compound is 2-propoxypropane.

Question 64. Assertion (A): Bond angle in ethers is slightly less than the tetrahedral
angle. Reason (R): There is a repulsion between the two bulky (-R) groups.
Solution: (d) Bond angle in ethers is slightly more than the tetrahedral angle due to
repulsion between two bulky alkyl group.

Question 65. Assertion (A): Boiling points of alcohols and ethers are high.
Reason (R): They can form intermolecular hydrogen bonding.
Solution: (b) Boiling points of alcohols are higher than ethers. Alcohols can form
intermolecular hydrogen bonding whereas ethers cannot.

Question 66. Assertion (A): Like bromination of benzene, bromination of phenol is also
carried out in the presence of Lewis acid.
Reason (R): Lewis acid polarizes the bromine molecule.
Solution: (d) Bromination of phenol can be carried out in absence of Lewis acid.
Question 67. Assertion (A): o-Nitrophenol is less soluble in water than the m- and p-
isomers.
Reason (R): m-Nitrophenol and p-Nitrophenol exists as associated molecules.
Solution: (e) In o-nitrophenol there is intramolecular H-bonding.

Thus, o-nitrophenol does not form H-bond with H2O but m-nitrophenol and p-nitrophenol
form H-bonds with H2O. Also, due to intermolecular H-bonding m-nitrophenol and p-
nitrophenol exist as associated molecules.

Question 68. Assertion (A): Ethanol is a weaker acid than phenol.

Reason (R): Sodium ethoxide may be prepared by the reaction of ethanol with aqueous
NaOH.
Solution: (c) Phenol is stronger acid than ethanol as phenoxide ion is stabilized by
resonance whereas no such stabilization occurs in ethoxide ion. Sodium ethoxide can
be prepared by reaction of ethanol with sodium.

Question 69. Assertion (A): Phenol forms 2,4, 6-tribromophenol on treatment with
Br2 in carbon disulphide at 273 K.
Reason (R): Bromine polarizes in carbon disulphide.
Solution: (b) Phenol forms 2, 4, 6-tribromophenol on treatment with bromine in water. In
phenols, the polarization of bromine takes place even in the absence of Lewis acid.

Question 70. Assertion (A): Phenols give o-nitrophenol and p-nitrophenol on nitration
with cone. HNO3 and H2SO4 mixture.
Reason (R): -OH group in phenol is o-,p-directing.
Solution: (d) Phenols give o, p-nitrophenol on nitration with dil. HNO 3 and with cone.
• HNO3, 2,4, 6-trinitrophenol is formed.

Long Answer Type Questions

Question 71. Write the mechanism of the reaction of HI with methoxybenzene.

Solution: In case of alkyl aryl ethers, the products are always phenol and an alkyl halide
because due to resonance C6H5 – O bond has partial double bond character.

Question 72. (a) Name the starting material used in the industrial preparation of
phenol.
(b) Write complete reaction for the bromination of phenol in aqueous and non-aqueous
medium.
(c) Explain why Lewis acid is not required in bromination of pheflol?
Solution: (a) Cumene (Isopropyl benzene) is the starting material used in industrial
preparation of phenol.
(c) Usual halogenation is carried out in the presence of Lewis acid, FeBr3 which
polarises the halogen molecule. In case of phenol, the polarisation of bromine occurs
even in the absence of Lewis acid. This is because of highly activating effect of -OH
group on the benzene ring. The reaction follows:

Note: In aqueous solution, phenol ionizes to give phenoxide ion. Due to the presence of
the negative charge, the oxygen atom of the phenoxide ion donates electrons to the
benzene ring to a large extent. As a result, the ring gets highly activated leading to the
formation of trisubstituted product. On the other hand, in the non-polar solvents, the
ionization of phenol does not occurs to a large extent. As a result, the -OH group
donates electrons to the benzene ring only to a small extent. Consequently, the ring is
activated slightly and, therefore, only monosubstitution occurs.

Question 73. How can phenol be converted to aspirin?

Solution: Phenol is converted into salicylic acid.
The reaction is usually carried out by allowing sodium phenoxide to absorb carbon
dioxide and then heating the product to 400 K and 4-7 atm pressure. First unstable
intermediate is formed which undergoes a proton shift to form sodium salicylate. The
subsequent acidification of sodium salicylate gives

Question 74. Explain a process in which a biocatalyst is used in industrial preparation

of a compound known to you.
Solution: Biocatalysts are complex organic compounds which act as catalysts in
reaction taking place in living organism. These biocatalysts (enzymes) are used in the
manufacture of ethanol.
Ethanol from sugar solution (molasses):
Molasses is a non-crystalline form of sugar obtained as the mother liquor after
crystallisation of sugar from sugar solution. This contains about 50% sugar. It is diluted
to about 10% solution and yeast is added and kept for about 2-3 days. Yeast supplies
the enzymes invertase and zymase. The enzyme invertase hydrolyses sucrose to
glucose and fructose. The enzyme zymase (found in yeast) converts glucose and
fructose to ethanol.

In wine making, grapes are the source of sugars and yeast. As grapes ripen, the quantity
of sugar increases and the yeast grows on the skin of the grapes. When the grapes are
crushed, sugar and enzyme come in contact and fermentation starts. Fermentation
takes place under anaerobic conditions (i.e., in the absence of air). During fermentation
CO2 is released.
The action of enzyme is inhibited when the concentration of alcohol exceeds 14%. If air
enters the fermentation mixture, the O2 of the air oxidised ethanol to ethanoic acid
which spoils the taste of alcoholic drinks and makes it sour.