NCERT Textbook Questions

NCERT Intext Questions

Q. 1. Write the structures of the following compounds:
(i) a-Methoxypropionaldehyde (ii) 3-Hydroxybutanal
(iii) 2-Hydroxycyclopentane carbaldehyde
(iv) 4-oxopentanal (v) Di-sec. butyl ketone
(vi) 4-Fluoroacetophenone
CH3 O O OH O
| || | ||
Ans. (i) H3 C—CH—C—H (ii) H3 C—CH—CH 2 —C—H
O
||
(iii) CHO (iv) CH3 —C—CH 2 —CH 2 —CHO

OH
CH3 O CH3 O
| || |
(v) CH3 CH 2 CH—C—CH—CH2 CH3 (vi) F C CH3

Q. 2. Write the structures of products of the following reactions:

O
anhyd. AlCl3
(i) + C
CS2
C2H5 Cl

(ii) (C 6 H 5 CH 2) 2 Cd + 2CH 3 COCl

CH3
2+
Hg , H 2 SO 4 1. CrO2Cl2
(iii) H 3 C—C / C—H   (iv)
2. H3O+

NO2
O

O C—C2H5
anhyd. AlCl 3
+ C + HCl
Ans. (i) CS 2
C 2H 5 Cl
Benzene Propanoyl chloride Propiophenone
O
O
CH2—C—CH3
Dry
(ii) (C6H5CH2)2Cd + 2CH3—C—Cl ether 2 + CdCl2
Dibenzyl cadmium Acetyl chloride
1-Phenylpropan-2-one

SRS OH WWW
V
O
SS | W ||
Hg2 ,
+ SS W Tautomerises
(iii) H3 C—C / C—H
dil. H2 SO 4
SSCH3 —C == CH 2 WWW CH3 —C—CH3
 Propyne SS WW Propanone
SS WW
T X
2CrO2Cl2 OCrCl2OH H3O
+
(iv) O2N CH3 O2N CH O2N CHO
CS2 OCrCl2OH
(Etard reaction)
p-Nitrotoluene p-Nitrobenzaldehyde

Aldehydes, Ketones and Carboxylic Acids 485

Q. 3. Arrange the following compounds in increasing order of their boiling points.
CH3CHO, CH3CH2OH, CH3OCH3, CH3CH2CH3
Ans. CH3CH2CH3 < CH3OCH3 < CH3CHO< CH3CH2OH
Q. 4. Arrange the following compounds in increasing order of their reactivity in nucleophilic addition
reactions.
(i) Ethanal, Propanal, Propanone, Butanone
(ii) Benzaldehyde, p-Tolualdehyde, p-Nitrobenzaldehyde, Acetophenone
Ans. (i) The reactivity in nucleophilic addition reactions increases in the order:
Butanone < Propanone < Propanal < Ethanal
(ii) Acetophenone is a ketone. All the other three compounds are aldehydes. Hence, acetophenone is least
reactive.
p-Tolualdehyde has an electron-donating methyl group at the para position of the benzene ring
whereas p-nitrobenzaldehyde has an electron-withdrawing nitro group at the para position. Thus,
p-tolualdehyde is less reactive and p-nitrobenzaldehyde is more reactive than benzaldehyde.
Therefore, the required order is as follows:
Acetophenone < p-Tolualdehyde < Benzaldehyde < p-Nitrobenzaldehyde
Q. 5. Predict the products of the following reactions:
O +
H
(i) + HO—NH2
O 2N
O
(ii) + NH2 NH NO2
O
|| +
H
(iii) R—CH == CH—CHO + NH 2 — C —NH—NH 2
O
C +
(iv) CH3 + CH CH NH H
3 2 2

O2N
N OH NNH NO2
Ans. (i) (ii)

O
||
(iii) R—CH == CH—CH == N—NH—C—NH 2
H3C
C N CH2CH3
(iv)

Q. 6. Give the IUPAC names of the following compounds:

(i) PhCH2CH2COOH (ii) (CH3)2C==CHCOOH
CH3 NO2

COOH COOH
(iii) (iv)
O2N NO2
Ans. (i) 3-Phenylpropanoic acid
(ii) 3-Methylbut-2-enoic acid
(iii) 2-Methylcyclopentanecarboxylic acid
(iv) 2, 4, 6-Trinitrobenzoic acid.

486 Xam idea Chemistry–XII

Q. 7. Show how each of the following compounds can be converted to benzoic acid:
(i) Ethylbenzene (ii) Acetophenone
(iii) Bromobenzene (iv) Phenylethene (Styrene)
CH2CH3 COOK COOH
KMnO4– KOH H3O +
Ans. (i) Heat

Ethylbenzene Benzoic acid

COCH3 COOK COOH
+
KMnO4/KOH H 3O
(ii)
Heat
Acetophenone Benzoic acid
O
COOH
Br Mg
MgBr C HOH
O—C—O OMgBr
(iii) Dry ether

Bromobenzene Phenylmagnesium Benzoic acid

bromide

COOH
CH—CH2 COOK
KMnO4 / KOH H3O+
(iv) + HCOOK + HCOOH
Methanoic
Phenylethene Benzoic acid acid

Q. 8. Which acid of each pair shown here would you expect to be stronger?
(i) CH3CO2H or CH2FCO2H (ii) CH2FCO2H or CH2ClCO2H
(iii) CH2FCH2CH2CO2H or CH3—CHF—CH2CO2H

(iv) F3C COOH or H3C COOH

O O
O O
Ans. (i) CH3 — C — O — H F — CH2 — C — O — H CH3 — C – F — CH2 — C –
The release of a proton is difficult The release of a proton is easier O O
because +I-effect of CH3 group because –I-effect of F decreases By intensifying the negative By dispersing the negative
increases the electron density in the electron density in the charge , +I-effect destabilises charge, –I-effect stabilises
the O—H bond. O—H bond. the carboxylate ion. the carboxylate ion.

Therefore, due to lesser electron density in the O—H bond and greater stability of FCH2COO– ion
over CH3COO– ion, FCH2COOH is a stronger acid than CH3COOH.
(ii) The FCH2COO– ion is much more stable than ClCH2COO– ion due to much stronger –I effect of
F than Cl and thus FCH2COOH is a stronger acid than ClCH2COOH.
O CH3 O
(iii) F — CH2 — CH2 — CH2 — C — O — H F — CH — CH2 — C — O — H
4-Fluorobutanoic acid 3-Fluorobutanoic acid

Inductive effect decreases with distance, therefore, –I effect of F is somewhat stronger in

3-fluorobutanoic acid than in 4-fluorobutanoic acid. Hence, CH3CHFCH2COOH is a stronger acid
than FCH2CH2CH2COOH.
O O
(iv) F3C C – CH3 C –
O O
CF3 has a strong –I-effect, CH3 has a weak +I-effect,
it stabilises the carboxylate it destabilises the carboxylate
ion by dispersing the –ve charge ion by intensifying the –ve charge

Hence, due to greater stability of F3C—C6H4—COO– (p) ion than CH3—C6H4COO– (p) ion,
F3C—C6H4—COOH (p) is a much stronger acid than CH3—C6H4—COOH (p).

Aldehydes, Ketones and Carboxylic Acids 487

NCERT Textbook Exercises
Q. 1. What is meant by the following terms? Give an example of the reaction in each case.
(i) Cyanohydrin (ii) Acetal (iii) Semicarbazone
(iv) Aldol (v) Hemiacetal (vi) Oxime
(vii) Ketal (viii) Imine (ix) 2, 4-DNP derivative
(x) Schiff’s base
Ans. (i) gem-Hydroxynitriles, i.e., compounds possessing hydroxyl and cyano groups on the same carbon
atom are called cyanohydrins. Aldehydes and ketones react with hydrogen cyanide (HCN) to
yield cyanohydrins. It is catalysed by a base and the generated cyanide ion (CN–) being a stronger
nucleophile readily adds to carbonyl compounds to yield corresponding cyanohydrin.
–
HCN + OH– CN + H2O

– O– H+ CN
C—O + CN C C
CN OH
Tetrahedral intermediate Cyanohydrin
(ii) gem-Dialkoxy compounds in which the two alkoxy groups are present on the terminal carbon atom are
called acetals. These are produced by the action of an aldehyde with two equivalents of a monohydric
alcohol in the presence of dry HCl gas.

CH3 H—OCH2CH3 Dry HCl gas CH3 OCH2CH3

C— O + C + H2O
H H—OCH2CH3 H OCH2CH3
Acetaldehyde Ethyl alcohol Acetaldehyde
diethyl acetal
These are easily hydrolysed by dilute mineral acids to regenerate the original aldehydes. Therefore,
these are used for the protection of aldehydic group in organic synthesis.
(iii) Semicarbazones are derivatives of aldehydes and ketones and are produced by the action of
semicarbazide on them in weak acidic medium.
O
CH3 pH 3.5 CH3
C—O + H2NNH—C—NH2 – H O C—NNHCONH2 + H2O
CH3 2 CH3
Acetone Semicarbazide Acetone semicarbazone
These are used for identification and characterisation of aldehydes and ketones.
(iv) Aldols are b-hydroxy aldehydes or ketones and are produced by the condensation two same or
different molecules of aldehyde or ketones.
dil. NaOH
2CH3 —CHO CH3 —CH—CH 2 —CHO
Ethanal |
OH
3 - Hydroxybu tan al
(Aldol)
  
CH3
Ba (OH) 2
|
2CH3 —CO—CH3 CH3 — C—CH 2 —CO—CH3
Propanone |
OH
4 - Hydroxy - 4 - methylpen tan - 2 - one
(v) gem-Alkoxyalcohols are called hemiacetals. These are produced by addition of one molecule of a
monohydric alcohol to an aldehyde in presence of dry HCl gas.
CH3 Dry HCl gas H3C OH
C—O + H—OCH3 C
H H OCH3
Ethanal Methyl alcohol 1-Hydroxy-1-methoxyethane
(A hemiacetal)

488 Xam idea Chemistry–XII

 (vi) Oximes are produced when aldehydes or ketones react with hydroxylamine in weak acidic medium.
CH3 CH3
pH 3.5
C—O + H2 NOH C—NOH + H2O
H H
   Acetaldehyde Hydroxylamine Acetaldoxime
(vii) gem-Dialkoxyalkanes are called ketals. In ketals, the two alkoxy groups are present on the same
carbon within the chain. These are produced when a ketone is heated with ethylene glycol in presence
of dry HCl gas or p-toluenesulphonic acid (PTS).
Dry HCl gas
CH3 H—O—CH2 or PTS ∆ H3C O—CH2
C— O + | C | + H2O
CH3 H—O—CH2 H3C O—CH2
Acetone Ethylene glycol Acetone ethylene ketal
These are easily hydrolysed by dilute mineral acids to regenerate the original ketones. Therefore,
ketals are used for protection of keto groups in organic synthesis.
(viii) Compounds containing C N— group are called imines. These are produced when aldehydes and
ketones react with ammonia derivatives.
C O + H2N—Z C N—Z + H 2O
Aldehyde/Ketone Ammonia Imines
   derivative
Z = H, Alkyl, aryl, —NH2 , —OH, —C6H5NH, —NHCONH2, etc.
(ix) 2, 4-Dinitrophenylhydrazones ( 2, 4-DNP derivatives) are produced when aldehydes or ketones react
with 2, 4-dinitrophenylhydrazine in weakly acidic medium.
NO2 NO2
CH3 pH 3.5 CH 3
C O + H2 NNH NO2 C NNH NO2
–H2O
CH3 CH3
2, 4-Dinitrophenyl Acetone 2, 4-dinitrophenylhydrazone
hydrazine
2, 4-DNP derivatives are used for identification and characterisation of aldehydes and ketones.
(x) Aldehydes and ketones react with primary aliphatic or aromatic amines to form azomethines or
Schiff’s bases.
+
Trace of H
 R—CH == O + H 2 N—Rl R—CH == N—Rl + H 2 O
Heat
Aldehyde 1° Amine Schiff’s base

Q. 2. Name the following compounds according to IUPAC system of nomenclature.

(i) CH3CH(CH3)CH2CH2CHO (ii) CH3CH2COCH(C2H5)CH2CH2Cl
(iii) CH3CH—CHCHO [CBSE 2019(56/5/2)]
(iv) CH3COCH2COCH3 (v) CH3CH(CH3)CH2C(CH3)2COCH3
(vi) (CH3)3CCH2COOH (vii) OHCC6H4CHO-p
Ans. (i) 4-Methylpentanal (ii) 6-Chloro-4-ethylhexan-3-one
(iii) But-2-en-1-al (iv) Pentane-2, 4-dione
(v) 3, 3, 5-Trimethylhexan-2-one (vi) 3, 3-Dimethylbutanoic acid
(vii) Benzene-1, 4-dicarbaldehyde
Q. 3. Draw the structures of the following compounds:
(i) 3-Methylbutanal (ii) p-Nitropropiophenone
(iii) p-Methylbenzaldehyde (iv) 4-Methylpent-3-en-2-one
(v) 4-Chloropentan-2-one (vi) 3-Bromo-4-phenylpentanoic acid
(vii) p-p'-Dihydroxybenzophenone (viii) Hex-2-en-4-ynoic acid
CH3 O
| ||
Ans. (i) CH3 —CH—CH 2 —C—H (ii) O2N COCH2CH3

Aldehydes, Ketones and Carboxylic Acids 489

 (iii) CH3 CHO (iv) CH3 —C—CH == C—CH3
|| |
O CH3
(v) CH3 —C—CH 2 —CH—CH3 (vi) CH3 —CH — CH —CH2 —COOH
|| | | |
O Cl C6 H5 Br
O
(vii) HO C OH (viii) CH3—C ≡ C—CH—CH—COOH

Q. 4. Write the IUPAC names of the following ketones and aldehydes. Wherever possible, give also
common names.
(i) CH3CO(CH2)4CH3 (ii) CH3CH2CHBrCH2CH(CH3)CHO
(iii) CH3(CH2)5CHO (iv) Ph—CH—CH—CHO
CHO
(v)       (vi) PhCOPh
Ans.
S.No. IUPAC Name Common Name
(i) Heptan-2-one Methyl n-pentyl ketone
(ii) 4-Bromo-2-methylhexanal g-Bromo-a-methylcaproaldehyde
(iii) Heptanal —
(iv) 3-Phenylprop-2-enal b-Phenylacrolein
(v) Cyclopentanecarbaldehyde Cyclopentanecarbaldehyde
(vi) Diphenylmethanone Benzophenone

Q. 5. Draw structures of the following derivatives:

(i) The 2, 4-dinitrophenylhydrazone of benzaldehyde
(ii) Cyclopropanone oxime
(iii) Acetaldehydedimethylacetal
(iv) The semicarbazone of cyclobutanone
(v) The ethylene ketal of hexan-3-one
(vi) The methyl hemiacetal of formaldehyde.
N OH
NO2
Ans. (i) CH—NNH NO2 (ii)
O
CH3 OCH3
(iii) C (iv) NNH C NH2
H OCH3

H2C CH2
O O
H OH
(v) CH3—CH2—C—CH2—CH2—CH3 (vi) C
H OCH3

Q. 6. Predict the products formed when cyclohexanecarbaldehyde reacts with following reagents:
(i) PhMgBr and then H3O+
(ii) Tollens’ reagent
(iii) Semicarbazide and weak acid
(iv) Excess ethanol and acid
(v) Zinc amalgam and dilute hydrochloric acid.

490 Xam idea Chemistry–XII

 OMgBr OH
CH—O Ph–MgBr C H 3O + C
Ans. (i) H H
Dry ether Ph Hydrolysis Ph
Cyclohexane Cyclohexylphenyl carbinol
carbaldehyde

CH—O + –
COO–
(ii) + 2[Ag(NH3)2] + 3OH + 2Ag + 4NH3 + 2H2O
Silver
Cyclohexane Tollens’s reagent Cyclohexane Mirror
carbaldehyde carboxylate ion

O
O
CHO CH—NNH C NH2 + H2O
(iii) + H2NNH C NH2 Weak acid
Cyclohexane Semicarbazide Cyclohexanecarbaldehyde
carbaldehyde semicarbazone

OC2H5
CH O H OC2H5 H+ C
(iv) OC2H5 + H2O
+ H
H OC2H5
Cyclohexane Cyclohexanecarbaldehyde
carbaldehyde Ethanol (excess) diethyl acetal

CHO Zn / Hg – HCl CH3

(v) (Clemmensen reduction)
Cyclohexane Methylcyclohexane
carbaldehyde

Q. 7. Which of the following compounds will undergo aldol condensation, which the Cannizzaro reaction
and which neither? Write the structures of the expected products of aldol condensation and
Cannizzaro reaction.
(i) Methanal (ii) 2-Methylpentanal
(iii) Benzaldehyde (iv) Benzophenone
(v) Cyclohexanone (vi) 1-Phenylpropanone
(vii) Phenylacetaldehyde (viii) Butan-1-ol
(ix) 2, 2-Dimethylbutanal.
Ans. (i) Methanal does not contain a-hydrogen and hence undergoes cannizzaro reaction.
conc. NaOH
2HCHO CH3 OH + HCOONa
Methanal Methanol Sodium methanoate

(ii) 2-Methylpentanal, contains a-hydrogens and hence undergo aldol condensation.

CH3
7 6 5 |4 3 2
dil. NaOH
2CH3 CH 2 CH2 —CH—CHO CH3 CH3 CH 2 CH —CH— C — CH 2 CH 2 CH3
| | | 1|
CH3 CH3 OH CHO
2-Methylpentanal
3-Hydroxy-2,4-dimethyl-2-propylheptanal

(iii) Benzaldehyde does not contain a-hydrogen and hence undergoes cannizzaro reaction.
conc. NaOH
2 CHO CH2OH + COONa
Benzaldehyde Benzyl alcohol Sodium benzoate
(iv) Benzophenone is a ketone having no a-hydrogen. It neither undergoes aldol condensation nor
Cannizzaro reaction.

Aldehydes, Ketones and Carboxylic Acids 491

 (v) Cyclohexanone contains a-hydrogens and hence undergo aldol condensation.
O
Dil. NaOH
2 O 1 2

Cyclohexanone OH
2-(1-Hydroxy-1-cyclohexyl)
cyclohexan-1-one
(vi) 1-Phenylpropanone contains a-hydrogens and hence undergo aldol condensation.
HO CH3
3 1
Dil. NaOH 2

2 COCH2CH3 C CH C
5 4
1-Phenylpropanone H3C—CH2 O
3-Hydroxy-2-methyl-1,3-diphenylpentan-1-one
(vii) Phenylacetaldehyde contains a-hydrogen and hence undergoes aldol condensation.
1
OH CHO
Dil. NaOH
2 CH2CHO CH2 CH CH
4 3 2
Phenylacetaldehyde
3-Hydroxy-2, 4-diphenylbutanal
(viii) Butan-1-ol is an alcohol, so it neither undergoes aldol condensation nor Cannizzaro reaction.
(ix) 2, 2-dimethylbutanal does not contain a-hydrogen and hence undergo Cannizzaro reaction.
CH3 CH3 CH3
| | |
conc. NaOH
CH3 CH 2 —CH—CHO CH3 CH 2 — C—CH 2 OH + CH3 CH 2 — C—COONa
| | |
CH3 CH3 CH3
2, 2-Dimethylbutanal 2, 2-Dimethylbutan-1-ol Sodium 2, 2-Dimethylbutanonate
Q. 8. How will you convert ethanal into the following compounds?
(i) Butane-1, 3-diol (ii) But-2-enal (iii) But-2-enoic acid.
Dil. NaOH 4 3 2 1 NaBH 4 4 3 2 1
Ans. (i) 2CH3 CHO CH3 CHOH—CH 2 —CHO CH3 —CHOH—CH 2 CH 2 OH
(Aldol condensation) (Reduction)
Ethanal 3 - Hydroxybu tan al Bu tan e - 1. 3 - diol

Dil. NaOH 4 3 2 1 +
H3 O /Heat
(ii) 2CH3 CHO CH3 —CHOH—CH 2 —CHO CH3 —CH == CH—CHO
(Aldol condensation) – H2 O
Ethanal 3 - Hydroxybu tan al But - 2 - enal
+
(i) dil. NaOH [Ag (NH3) 2] OH –
(iii) 2CH3 CHO +
CH3 CH == CHCHO CH3 CH == CHCO 2 H
(ii) H , D Tollens’ reagent
Ethanal But - 2 - enal But - 2 - enoic acid
Q. 9. Write structural formula and names of four possible aldol condensation products from propanal and
butanal. In each case indicate which aldehyde acts as nucleophile and which as electrophile.
Ans. (i) Propanal serves as nucleophile and also as electrophile.
OH CH3
5 4 3| 2| 1
CH3 CH 2 CHO + CH3 CH 2 CHO CH3 CH 2 CH— C— CHO
Propanal Propanal 3 - Hydroxy - 2 - methylpen tan al
(Nucleophile) (Electrophile)

(ii) Butanal serves both as nucleophile and an electrophile.

OH CH 2 —CH3
6 5 2| 41 3|
CH3 CH 2 CH 2 CHO + CH3 CH 2 CH 2 CHO CH3 CH 2 CH 2 —CH—CHCHO
Butanal Butanal 2 - Ethyl - 3 - hydroxyhexanal
(Electrophile) (Nucleophile)

(iii) Butanal as electrophile and propanal as nucleophile.

CH3 OH
6 5 | 14 3| 2
CH3 CH 2 CH 2 CHO + CH3 CH 2 CHO
CH3 CH 2 CH 2 —CH—CH—CHO
Butanal Propanal 3 - Hydroxy - 2 - methylhexanal
(Electrophile) (Nucleophile)

492 Xam idea Chemistry–XII

 (iv) Propanal as electrophile and butanal as nucleophile.
CH 2 CH3
OH
5 4 2| 3|
1
CH3 CH 2 CHO + CH3 CH 2 CH 2 CHO CH3 CH 2 —CH—CHCHO
Propanal Butanal 2 - Ethyl - 3 - hydroxypentanal
(Electrophile
  ) (Nucleophile)

Q. 10. An organic compound with molecular formula C9H10O forms 2, 4-DNP derivative, reduces Tollens’
reagent and undergoes Cannizzaro reaction. On vigorous oxidation, it gives 1, 2-benzenedicarboxylic
acid. Identify the compound. [HOTS]
Ans. (i) The given compound with molecular formula C9H10O forms a 2, 4-DNP derivative and reduces
Tollens’ reagent, it must be an aldehyde.
(ii) As it undergoes Cannizzaro reaction, therefore, CHO group is directly attached to the benzene ring.
(iii) On vigorous oxidation, it gives 1, 2-benzenedicarboxylic acid, therefore, it must be an
ortho-substituted benzaldehyde. The only o-substituted aromatic aldehyde having molecular formula
C9H10O is o-ethylbenzaldehyde. All the reactions can be explained on the basis of this structure.

COO– [Ag(NH3 )2]+ OH– CHO [O]

COOH
Ag +
Tollens’ reagent
Silver C2H5 C 2 H5 COOH
mirror
2-Ethylbenzoate o-Ethylbenzaldehyde 1, 2-Benzenedicarboxylic acid
(M.F. C9H10O)

2, 4-DNP

NO2
CH—NNH NO2 + H2O

C2H5
2, 4-DNP derivative

Q. 11. An organic compound (A) (molecular formula C8H16O2) was hydrolysed with dilute sulphuric acid
to a carboxylic acid (B) and an alcohol (C). Oxidation of (C) with chromic acid produced (B). (C) on
dehydration gives but-1-ene. Write equations for the reactions involved.
[CBSE Delhi 2010; (AI) 2009] [HOTS]
Ans. As the organic compound (A) with molecular formula C8H16O2 upon hydrolysis gives carboxylic acid (B)
and the alcohol (C) therefore (A) must be an ester and oxidation of (C) with chromic acid produces the acid
(B), therefore, both the carboxylic acid (B) and alcohol (C) must contain the same number of carbon atoms.
Now ester (A) contains eight carbon atoms, therefore, both the carboxylic acid (B) and the alcohol (C) must
contain four carbon atoms each.
As the alcohol (C) on dehydration gives but-1-ene, therefore, (C) must be a straight chain alcohol, i.e.,
butan-1-ol.
If C is butan-1-ol, then the acid (B) which it gives on oxidation must be butanoic acid and the ester (A) must
be butyl butanoate.
The relevant equations for all the reactions involved may be explained as follows:
O O
|| ||
Dil. H2 SO 4
CH3 CH 2 CH 2 —C— OCH 2 CH 2 CH 2 CH3 CH3 CH 2 CH 2 —C—OH + CH3 CH 2 CH 2 CH 2 OH
Hydrolysis
Butyl butanoate, (A) Butanoic acid, (B) Butan - 1 - ol, (C)
(M.F. = C8 H16 O2)
O
||
CrO3 /CH3 COOH Dehydration
CH3 CH 2 CH 2 —C—OH CH3 CH 2 CH 2 CH 2 OH CH3 CH 2 CH == CH 2
(Oxidation) (– H 2 O )
Butanoic acid, (B) Butan - 1 - ol, (C) But - 1 - ene

Aldehydes, Ketones and Carboxylic Acids 493

Q. 12. Arrange the following compounds in increasing order of their property as indicated:
(i) Acetaldehyde, Acetone, Di-tert-butyl ketone, Methyl tert-butyl ketone (reactivity towards HCN).
(ii) CH3CH2CH(Br)COOH, CH3CH(Br)CH2COOH, (CH3)2CHCOOH, CH3CH2CH2COOH (acid
strength).
(iii) Benzoic acid, 4-nitrobenzoic acid, 3, 4-dinitrobenzoic acid, 4-methoxy benzoic acid (acid strength).
Ans. (i) The reactivity towards HCN addition decreases as the +I-effect of the alkyl group/s increases and/or
the steric hindrance to the nucleophilic attack by CN– at the carbonyl carbon increases. Hence, the
reactivity decreases in the order:
CH3 O CH3 O CH3
CH3 CH3
C— O > C — O > CH3 — C — C — CH3 > CH3 — C — C — C — CH3
H CH3
CH3 CH3 CH3
Acetaldehyde Acetone
Methyl tert-butyl ketone Di-tert-butyl ketone
+ I-effect increases
Steric hindrance increases

Thus, di-tert-butyl ketone < methyl tert-butyl ketone < Acetone < Acetaldehyde.
(ii) As we know + I-effect decreases while – I-effect increases the acid strength of carboxylic acids. As
+I-effect of isopropyl group is more than that of n-propyl group, therefore, (CH3)2CHCOOH is a
weaker acid than CH3CH2CH2COOH.
Now –I-effect decreases with distance, therefore, CH3CH2CH(Br)COOH is a stronger acid than
CH3CH(Br)CH2COOH.
Therefore, the overall acid strength increases in the order:
CH3
|
CH3 —CH—COOH < CH3 CH 2 CH 2 —COOH < CH3 —CH—CH 2 —COOH
|
Br
< CH3 —CH 2 —CH—COOH
|
Br
(iii) As electron-donating groups decrease the acid strength, therefore 4-methoxybenzoic acid is a weaker
acid than benzoic acid.
Now electron-withdrawing groups increase the acid strength, therefore, both 4-nitrobenzoic acid and
3, 4-dinitrobenzoic acids are stronger acids than benzoic acid. Further due to the presence of an
additional NO2 groups at m-position w.r.t. COOH group, 3, 4-dinitrobenzoic acid is a little stronger
acid than 4-nitrobenzoic acid. Therefore, the overall acid strength increases in the following order:
4-methoxybenzoic acid < benzoic acid < 4-nitrobenzoic acid < 3, 4-dinitrobenzoic acid.
Q. 13. Give simple chemical tests to distinguish between the following pairs of compounds:
 [CBSE 2019(56/2/1)]
(i) Propanal and Propanone (ii) Acetophenone and Benzophenone
(iii) Phenol and Benzoic acid (iv) Benzoic acid and Ethyl benzoate
(v) Pentan-2-one and Pentan-3-one (vi) Benzaldehyde and Acetophenone
(vii) Ethanal and Propanal
Ans. (i) Propanal and propanone:
Iodoform test: This test is given by propanone and not by propanal. Propanone on reacting with hot
NaOH/I2 gives a yellow precipitate of CHI3 while propanal does not.
2NaOH + I 2 NaI + NaOI + H 2 O

CH3 —C—CH3 + 3NaOI CHI3 . + CH3 COONa + 2NaOH
|| Sodium Yellow Sodium acetate
hypo - iodite ppt.
O

494 Xam idea Chemistry–XII

 (ii) Acetophenone and benzophenone: Acetophenone responds to iodoform test, but benzophenone
does not.
COCH3 I2 /NaOH
COONa
+ 3NaOI + CHI3 + 2NaOH
Heat
Yellow ppt.
Sodium (Iodoform)
Benzoate

(iii) Phenol and benzoic acid: Benzoic acid reacts with NaHCO3 giving CO2 gas with effervescence,
whereas phenol does not.
COOH COONa

+ NaHCO3 + H2O + CO2

Benzoic acid Sodium benzoate
(iv) Benzoic acid and ethyl benzoate: Benzoic acid on reaction with sodium hydrogencarbonate gives
out CO2 gas with effervescence, while ethyl benzoate does not.
COOH COONa
+ NaHCO3 + H2O + CO2

(v) Pentan-2-one and Pentan-3-one: Pentan-2-one when treated with NaOI (I2/NaOH) gives yellow
precipitate of iodoform but pentan-3-one does not give this test.
CH3 —CH 2 —CH 2 —COCH3 + 3NaOI
CH3 CH 2 CH 2 COONa + CHI3 . + 2NaOH
Pen tan - 2 - one Sodium Iodoform
hypoiodite (Yellow ppt.)
(vi) Benzaldehyde and Acetophenone: Benzaldehyde being an aldehyde gives silver mirror with

Tollens’ reagent but acetophenone being a ketone does not give this test.
+
C6 H5 CHO + 2 [Ag (NH3) 2] + 3OH –
C6 H5 COO – + 2Ag . + 4NH3 + 2H 2 O
Benzaldehyde Tollens’ reagent Silver mirror

(vii) Ethanal (CH3CHO) and propanal (CH3CH2CHO): Ethanal responds to iodoform test, while
propanal does not.
NaOH/I2
CH3 CHO + 3NaOI
CHI3 . + HCOONa + 2NaOH
D
(Yellow ppt.)
Q. 14. How will you prepare the following compounds from benzene? You may use any inorganic reagent
and any organic reagent having not more than one carbon atom.
(i) Methyl benzoate (ii) m-nitrobenzoic acid
(iii) p-nitrobenzoic acid (iv) Phenylacetic acid
(v) p-nitrobenzaldehyde
Br MgBr COOH COOCH3
CH 3OH(excess);
Br2/FeBr3 Mg, dry ether CO 2 conc. H2SO 4,
Ans. (i) + (Esterification)
(Bromination) (Grignard H3 O
reaction)
Benzene Methyl
benzoate
COOH COOH
Conc. HNO3/
As in ( i ) above conc. H2SO4,
(ii)
Nitration NO2
Benzene Benzoic acid m-Nitrobenzoic acid

CH3 CH3 COOH

Conc. HNO3 /
CH 3 Cl/Anhyd. AlCl 3 conc. H2SO4, (i) KMnO4/KOH,
(iii) (F.C. alkylation) (Nitration) ( ii ) H2SO4
Benzene Toluene
NO2 NO2
p-Nitrotoluene p-Nitrobenzoic acid
(Major product)

Aldehydes, Ketones and Carboxylic Acids 495

 CH3 CH2Br
CH3Cl/Anhyd. AlCl3 NBS, hv or Br2, and hv Alc. KCN, ∆
(iv)
(Side chain, bromination) (Nucleophilic substitution)
Benzene Toluene Benzyl bromide

CH2CN CH2COOH
H+ / H2O
Hydrolysis
Benzyl cyanide Phenylacetic acid

CH3 CHO
As in (iii) (i) CrO3 /(CH3 CO)2 O
(v)
(above) (ii) H3 O +
Benzene
NO2 NO2
p-Nitrobenzaldehyde

Q. 15. How will you bring about the following conversions in not more than two steps?
(i) Propanone to Propene (ii) Benzoic acid to Benzaldehyde
(iii) Ethanol to 3-Hydroxybutanal (iv) Benzene to m-Nitroacetophenone
(v) Benzaldehyde to Benzophenone (vi) Bromobenzene to 1-Phenylethanol
(vii) Benzaldehyde to 3-Phenylpropan-1-ol
(viii) Benzaldehyde to a-Hydroxyphenylacetic acid
(ix) Benzoic acid to m-Nitrobenzyl alcohol
Ans. (i) Propanone to Propene
H2 /Ni conc. H2 SO 4
CH3 —C—CH3 CH3 —CH—CH3 CH3 —CH == CH 2
443 K
|| | Propene
O OH
Propanone 2 - propanol
(ii) Benzoic acid to Benzaldehyde
SOCl 2 H 2/Pd-BaSO4
COOH COCl CHO
–SO2 , –HCl boiling xylene
Benzoic acid Benzoyl chloride Benzaldehyde

(iii) Ethanol to 3-Hydroxybutanal

OH
– |
Mild Oxidation OH
—CH
CH3 2 —OH CH3 —CHO CH3 —CH—CH2 —CHO
KMnO 4 /dil. H2 SO 4 Dil. NaOH
Ethanol Acetaldehyde 3-hydroxybutanal
(Two molecules)
(iv) Benzene to m-Nitroacetophenone
COCH3 COCH3
(CH3CO2)2O/ conc. HNO3/
anhyd. AlCl3 conc. H2SO4
(Friedel Crafts Acylation) Nitration NO2
Acetophenone m-nitroacetophenone

(v) Benzaldehyde to Benzophenone

O
(i) K2Cr2O7/H2SO4 dry distil.
C O (C6H5 COO)2Ca –CaCO3
C
(ii) CaCO3
H Calcium benzoate
Benzaldehyde
Benzophenone

496 Xam idea Chemistry–XII

 (vi) Bromobenzene to 1-phenylethanol:
Mg ( i ) CH3—CHO
Br Mg Br CH CH3
Dry ether ( ii ) H 2O/H+
(Phenyl Magnesium OH
bromide) 1-Phenyl ethanol

(vii) Benzaldehyde to 3-phenylpropan-1-ol:

CH—CHCHO
H
OH – H2O
C O + HCH2CHO (Cross aldol
C CH2CHO
H Acetaldehyde condensation)
OH 3-phenyl-prop-2-enal
Benzaldehyde
H2 /Ni
CH2 CH2CH2OH
3-Phenylpropanol
(viii) Benzaldehyde to a-Hydroxyphenylacetic acid
CN H
HO—C—H HO—C—COOH
H2O/H+
C O + HCN
(Complete hydrolysis)
H Hydrogen α-Hydroxyphenyl
Benzaldehyde cyanide acetic acid

(ix) Benzoic acid to m-nitrobenzyl alcohol:
COOH COCl CH2 OH
(i) Conc. HNO 3 ( i ) NaBH4
Conc. H 2SO 4 NO2 ( ii ) H 3O + NO2
(ii) SOCl2
Benzoic acid m-nitrobenzoyl m-nitrobenzyl
chloride alcohol

Q. 16. Describe the following:

(i) Acetylation (ii) Cannizzaro reaction
(iii) Cross aldol condensation (iv) Decarboxylation
Ans. (i) Acetylation: The replacement of an active hydrogen of alcohols, phenols or amines with an acyl
(RCO) group to form the corresponding esters or amides is called acetylation. This replacement
is carried out by using acid chloride or an acid anhydride in the presence of a base like pyridine or
dimethylaniline.
Pyridine
CH3 COCl + C2 H5 OH CH3 COOC2 H5 + HCl
Ethyl acetate

Pyridine
(CH3CO)2 + OH CH3COC6H5 + CH3COOH
Phenyl acetate

CH3 COCl + C2 H5 NH 2
CH3 CONHC 2 H5 + HCl
N - Ethylacetamide

(ii) Cannizzaro reaction: Refer to Basic Concepts Point 17( j).

(iii) Cross aldol condensation: When aldol condensation is carried out between two different aldehydes
and/or ketones, it is called cross aldol condensation. If both of them contain a-hydrogen atoms, it gives
a mixture of four products. This is illustrated below by aldol reaction of a mixture of benzaldehyde
and acetophenone.
O
OH –
CHO + C CH3 CH CH C
293 K
O 1, 3-Diphenylprop-2-en-1-one
(Benzalacetophenone)
(Major product)

Aldehydes, Ketones and Carboxylic Acids 497

 (iv) Decarboxylation: Carboxylic acids lose carbon dioxide to form hydrocarbons when their sodium
salts are heated with sodalime (NaOH and CaO in the ratio of 3 : 1). The reaction is known as
decarboxylation.
NaOH & CaO
R—COONa R—H + Na 2 CO3
Heat

Q. 17. Complete each synthesis by giving missing starting material, reagent or products.
CH2CH3 KMnO4 COOH SOCl 2
(i) KOH, heat
(ii) Heat
COOH
O
C
H 2 NCONHNH 2
(iii) C 6 H 5 CHO (iv)

O [Ag(NH 3) 2]
+ CHO NaCN/HCl
(v) (vi)
CHO COOH
dil. NaOH
(vii) C 6 H 5 CHO + CH 3 CH 2 CHO
D
(i) NaBH 4 CrO3
(viii) CH 3 COCH 2 COOC 2 H 5 +
(ix) OH
(ii) H
(i) O3
(x) CH2 CHO (xi) 2 O
(ii) Zn–H2O

CH2CH3 KMnO4
COOK
Ans. (i) KOH, heat
Ethylbenzene Potassium benzoate

COOH SOCl 2
COCl
(ii) Heat
COOH COCl
Phthalic acid Phthaloyl chloride
(iii) C6 H5 CHO + H 2 NNHCONH 2 C6 H5 CH == NNHCONH2 + H 2 O
Benzaldehyde Semicarbazide Benzaldehyde semicarbazone
O
COCl C
Anhyd. AlCl3
(iv) + + HCl
F.C. acylation
Benzene Benzoyl chloride Benzophenone

(v) Only aldehydes are oxidised by Tollens’ reagent.

O [Ag(NH ) ] + O
32
Oxidation –
CHO COO
4-Oxocyclohexanecarbaldehyde 4-Oxocyclohexanecarboxylate anion
(vi) Cyanohydrin formation occurs at the aldehyde group
OH
CHO NaCN/HCl CH CN
COOH COOH
2-Formylbenzoic acid 2-[1-Hydroxycyanomethyl]
benzoic acid

CH3 CH3
dil. NaOH 3 2 1
(vii) C6H5CH O + H2 C—CHO Claisen-Schmidt condensation
C6H5CH—C—CHO
Benzaldehyde Propanal 2-Methyl-3-phenyl-prop-2-enal

498 Xam idea Chemistry–XII

 (viii) Only keto group is reduced by NaBH4.
O OH
|| |
(i) NaBH 4
CH3 —C—CH 2 COOC2 H5 +
CH3 —CH—CH 2 COOC2 H5
(ii) H
Ethyl - 3 - oxobutanoate Ethyl - 3 - hydroxybutanoate

CrO3
(ix) OH O
H2SO4
Cyclohexanol Cyclohexanone

B2H6/ H2O2 PCC

(x) CH2 CH2 B CH2OH CHO
THF NaOH
3 Cyclohexane
Methylenecyclohexane carbaldehyde
(i) O3
(xi) 2 O
(ii) Zn-H2O
Cyclohexylidenecyclohexane Cyclohexanone

Q. 18. Give plausible explanation for each of the following:

(i) Cyclohexanone forms cyanohydrin in good yield but 2,2,6-trimethylcyclohexanone does not.
(ii) There are two —NH2 groups in semicarbazide, only one is involved in the formation of semicarbazone.
(iii) During the preparation of esters from a carboxylic acid and an alcohol in the presence of an
acid catalyst, the water or the ester should be removed as soon as it is formed.
O HO CN
Ans. (i) HCN

Cyclohexanone Cyclohexanone cyanohydrin

O HO CN
H3 C 2 CH3 H3C CH3
6 CH3 HCN CH3
2,2,6-trimethylcyclohexanone
Due to the presence of three methyl groups at a-position with respect to the C—O group, the
nucleophilic attack by the CN– ion does not occur due to steric hindrance. As there is no such steric
hindrance in cyclohexanone, hence, nucleophilic attack by the CN– ion occurs readily and hence
cyclohexanone cyanohydrin is obtained in good yield.
– –
O O O
+ +
(ii) H2 N—C—NHNH2 H2 N — C—NH—NH2 H2 N— C NH—NH2
Semicarbazide
Semicarbazide has two –NH2 groups but one of them (i.e., directly attached to C—O) is involved in
resonance as shown above. Thus, electron density on this NH2 group decreases hence it does not act
as a nucleophile. In contrast, the lone pair of electrons on the other NH2 group (i.e., attached to —NH)
is not involved in resonance and hence is available for nucleophilic attack on the C—O group of
aldehydes and ketones.
(iii) The formation of esters from a carboxylic acid and an alcohol in presence of an acid catalyst is a
reversible reaction.
H2 SO 4
     RCOOH + Rl OH RCOORl + H 2 O
Carboxylic acid Alcohol Ester
To shift the equilibrium in the forward direction, the water or the ester formed should be removed as
fast as it is formed.
Q. 19. An organic compound contains 69.77% carbon, 11.63% hydrogen and rest oxygen. The molecular
mass of the compound is 86. It does not reduce Tollens’ reagent but forms an additional compound
with sodium hydrogensulphite and gives a positive iodoform test. On vigorous oxidation, it gives
ethanoic acid and propanoic acid. Write the possible structure of the compound.
[CBSE Delhi 2009; (AI) 2009] [HOTS]

Aldehydes, Ketones and Carboxylic Acids 499

 Ans.
Element Percentage Atomic mass No. of moles Simplest molar ratio
C 69.77 12 69.77 5.81
= 5.81 =5
12 1.16
11.63 11.63
H 11.63 1 = 11.63 = 10
1 1.16
O (100 – 81.4) = 18.60 16 18.60 1.16
= 1.16 =1
16 1.16

Empirical formula of the compound A = C5H10O

Molecular formula of the compound A = n (Empirical formula)
Molecular mass of compound A
            n =
Empirical formula mass of compound A
Molecular mass of compound A = 86
Empirical formula mass of compound A = 5 × 12 + 1 × 10 + 1 × 16 = 60 + 10 + 16 = 86
86
             n = =1
86
Molecular formula of the compound A = 1 (C5H10O) = C5H10O
As the compound A forms addition compound with NaHSO3 therefore it must be either an aldehyde or ketone.
As it does not reduce Tollens’ reagent and give positive iodoform test therefore it must be a methyl ketone.
As on oxidation the compound A gives a mixture of ethanoic acid and propanoic acid, therefore compound A is
O
||
CH3 —C—CH 2 —CH 2 —CH3
Pentan - 2 - one

The chemical reactions are:

O OH
|| |
CH3 —C—CH2 —CH2 —CH3 + NaHSO3
CH3 — C—CH2 —CH 2 —CH3
Pentan - 2 - one |
–+
SO3 Na
Sodium hydrogen sulphite _ addition product i
O
||
CH
3 — C —CH 2 —CH2 —CH3 + 3I 2 + 4NaOH
Pentan - 2 - qne
Iodoform – +
CHI3 . + CH3 —CH 2 —CH 2 —COONa + 3NaI + 3H 2 O
reaction
(Iodoform yellow ppt.)

O
||
K2 Cr2 O 7

CH3 —C—CH 2 —CH 2 —CH3 CH3 —COOH + CH3 —CH 2 —COOH
H2 SO 4
Pentan - 2 - qne Ethanoic acid Propanoic acid

Q. 20. Although phenoxide ion has more number of resonating structures than carboxylate ion, carboxylic
acid is stronger acid than phenol. Why?
Ans. Consider the resonating structures of carboxylate ion and phenoxide ion.
–
O O
R—C – R—C
O O

I II

500 Xam idea Chemistry–XII

 – –
O O O O O
– –

–
III IV V VI VII
In the resonating structures IV, V, VI of phenoxide ion carry a negative charge on the less electronegative
carbon atom. Therefore, their contribution towards the resonance stabilisation of phenoxide ion is very
small and hence can be rejected.
In structures I and II of carboxylate ion the negative charge on the carboxylate ion is delocalised over two
electronegative oxygen atoms while in structures III and VII of phenoxide ion, the negative charge on
electronegative oxygen atom remains localised while the electrons of the benzene ring only are delocalised.
As the delocalisation of benzene electrons contributes little towards the stability of phenoxide ion, therefore,
carboxylate ion is much more resonance stabilised than phenoxide ion. Thus, the release of proton from
carboxylic acid is much easier than from phenol. Hence, carboxylic acid is a stronger acid than phenol.

Multiple Choice Questions [1 mark]

Choose and write the correct option(s) in the following questions.
1. Which of the following compounds will give butanone on oxidation with alkaline KMnO4 solution?
[NCERT Exemplar]
(a) Butan-1-ol (b) Butan-2-ol (c) Both of these (d) None of these
2. Addition of water to alkynes occurs in acidic medium and in the presence of Hg2+ ions as a catalyst.
Which of the following products will be formed on addition of water to but-1-yne under these condition?
 O O [NCERT Exemplar]
|| ||
(a) CH3 —CH 2 —CH 2 —C—H (b) CH3 —CH 2 —C—CH3
O O O
|| || ||
(c) CH3 —CH 2 —C—OH + CO 2 (d) CH3 —C—OH + H—C—H
40%H 2 SO 4 Isomerisation
3. CH 3 —C // CH A
CH 3 —C —CH 3
1%HgSO 4
||
O
Structure of ‘A’ and type of isomerism in the above reaction are respectively. [NCERT Exemplar]
(a) Prop–1–en–2–ol, metamerism (b) Prop–1–en–1–ol, tautomerism
(c) Prop–2–en–2–ol, geometrical isomerism (d) Prop–1–en–2–ol, tautomerism
4. Which of the following compounds is most reactive towards nucleophilic addition reactions?
[NCERT Exemplar]
O O O
|| || O
(a) CH3 —C—H (b) CH3 —C—CH3 (c) (d)
—C—H —C—CH3

5. The formation of cyanohydrin from propanone is which type of reaction?

(a) Electrophilic substitution (b) Nucleophilic substitution
(c) Electrophilic addition (d) Nucleophilic addition
6. Compounds A and C in the following reaction are _____________. [NCERT Exemplar]
Hydroboration
(i) CH 3 MgBr H 2 SO 4, D oxidation

CH 3 CHO (A) (B) (C)
(ii) H 2 O
(a) identical (b) positional isomers (c) functional isomers (d) optical isomers
7. The reagent which does not react with both, acetone and benzaldehyde is [NCERT Exemplar]
(a) Sodium hydrogensulphite (b) Phenyl hydrazine
(c) Fehling’s solution (d) Grignard reagent

Aldehydes, Ketones and Carboxylic Acids 501

 8. Which is the most suitable reagent for the following conversion? [NCERT Exemplar]
O O
|| ||
CH 3 —CH— —CH—CH 2 —C —CH 3 CH 3 —CH— —CH—CH 2 —C —OH
(a) Tollens’ reagent (b) Benzoyl peroxide
(c) I2 and NaOH solution (d) Sn and NaOH solution
9. Which of the following compounds do not undergo aldol condensation?
O CH3
|| |
(a) CH3—CHO (b) —CHO (c) CH3 —C—CH3 (d) CH3 — C—CHO
|
CH 3
10. Cannizzaro’s reaction is not given by _____________. [NCERT Exemplar]
CHO

(a) (b) —CHO (c) HCHO (d) CH3CHO
CH3
11. Which product is formed when the compound —CHO is treated with concentrated aqueous
KOH solution? [NCERT Exemplar]
O
+ – + –

(a) KO— —CHO (b) —C—OK + —CH2OH

O O
+ – – + + – – + – + – +
(c) KO— —C—OK + KO— —OK (d) —C—OK + —OK

12. Which of the following reactions will not result in the formation of carbon-carbon bond?
(a) Friedel-Crafts acylation (b) Wurtz reaction
(c) Cannizzaro reaction (d) Reimer-Tiemann reaction
13. An aromatic compound ‘X’ with molecular formula C9H10O gives the following chemical tests.
(i) Forms 2, 4-DNP derivative
(ii) Reduces Tollens’ reagent
(iii) Undergoes Cannizzaro reaction
(iv) On vigorous oxidation, 1-2-benzenedicarboxylic acid is obtained.
X is:
CHO CHO CHO
COCH3 C2H5
(a) (b) (c) (d)
CH3 C2H5
C2H5
14. The acid formed when propyl magnesium bromide is treated with CO2 is :
(a) C3H7COOH (b) C2H5COOH (c) both (d) None of these
O
||
15. Treatment of compound Ph—O—C —Ph with NaOH solution yields [NCERT Exemplar]
(a) Phenol (b) Sodium phenoxide (c) Sodium benzoate (d) Benzophenone
16. Which of the following compounds will give brisk effervescence of CO2 on treatment with NaHCO3?
(a) Phenol (b) Acetic acid (c) both (d) None of these
17. The correct order of increasing acidic strength is _____________. [NCERT Exemplar]
(a) Phenol < Ethanol < Chloroacetic acid < Acetic acid
(b) Ethanol < Phenol < Chloroacetic acid < Acetic acid
(c) Ethanol < Phenol < Acetic acid < Chloroacetic acid
(d) Chloroacetic acid < Acetic acid < Phenol < Ethanol

502 Xam idea Chemistry–XII

 18. The weakest acid among the following is:
(a) CHCl2COOH (b) CH3COOH (c) CH2ClCOOH (d) CCl3COOH
19. Arrange the following acids in order of the increasing acidity.
COOH COOH COOH COOH
NO2
, , ,

NO2 OH
(A) (B) (C) (D)

(a) B < C < A < D (b) A < B < C < D (c) C < B < D < A (d) C < D < B < A
20. Which one of the following reagents is used for the conversion of ethanoic acid to ethanoic anhydride?
(a) P2O5, ∆ (b) SOCl2, ∆ (c) PCl3, ∆ (d) both (a) and (b)

Answers
1. (b) 2. (b) 3. (d) 4. (a) 5. (d) 6. (b) 7. (c) 8. (c) 9. (b, d) 10. (d)
11. (b) 12. (c) 13. (c) 14. (a) 15. (b, c) 16. (b) 17. (c) 18. (b) 19. (d) 20. (a)

Assertion-Reason Questions
In the following questions, two statements are given—one labeled Assertion (A) and the other labeled
Reason (R). Select the correct answer to these questions from the codes (a), (b), (c) and (d) as given below:
(a) Both Assertion (A) and Reason (R) are correct statements, and Reason (R) is the correct explanation of
the Assertion (A).
(b) Both Assertion (A) and Reason (R) are correct statements, but Reason (R) is not the correct explanation
of the Assertion (A).
(c) Assertion (A) is correct, but Reason (R) is incorrect statement.
(d) Assertion (A) is incorrect, but Reason (R) is correct statement.
1. Assertion (A) : Formaldehyde is a planar molecule.
Reason (R) : It contains sp2 hybridised carbon atom.
2. Assertion (A) : The solubility of aldehydes and ketones in water decreases with increase in the size of
alkyl group.
Reason (R) : Alkyl groups are electron-repelling groups.
3. Assertion (A) : Compounds containing —CHO group are easily oxidised to corresponding carboxylic
acids.
Reason (R) : Carboxylic acids can be reduced to alcohols by treatment with LiAlH4.
4. Assertion (A) : Aldehydes and ketones, both react with Tollens’ reagent to form silver mirror.
Reason (R) : Both, aldehydes and ketones contain a carbonyl group.
5. Assertion (A) : The a-hydrogen atom in carbonyl compounds is less acidic.
Reason (R) : The anion formed after the loss of a-hydrogen atom is resonance stabilised.
6. Assertion (A) : Acetaldehyde undergoes aldol condensation with dil. NaOH.
Reason (R) : Aldehydes which do not contain a-hydrogen undergoes aldol condensation.
7. Assertion (A) : Benzoic acid does not undergo Friedel-crafts reaction.
Reason (R) : The carboxyl group is activating and undergo electrophilic substitution reaction.
[CBSE 2020(56/4/2)]
–
8. Assertion (A) : A carboxylate ion (RCOO ) is stabilised by resonance to a greater extent as compared to
the acid (RCOOH).
Reason (R) : The contributing structures of RCOO– are equivalent while those of RCOOH are not.

Aldehydes, Ketones and Carboxylic Acids 503

 9. Assertion (A) : CH3– adds to >C = O group irrevesibly but CN– ion adds reversibly.
Reason (R) : CH3– ion is much stronger nucleophile than CN– ion.
10. Assertion (A) : Aromatic acids do not undergo Friedel-Crafts reaction.
Reason (R) : —COOH group is a m-directing group.

Answers
1. (a) 2. (b) 3. (b) 4. (d) 5. (d) 6. (c) 7. (c) 8. (a) 9. (b) 10. (b)

Passage-based/Case-based Questions
Read the given passages and answer the questions that follow.

PASSAGE–1
Aldehydes and ketones are highly reactive compounds. Since both these classes of organic compounds have
the same functional group, i.e., polarized carbonyl group, they show a number of common reactions. However,
the presence of a H-atom on the carbonyl group of aldehydes make them much more reactive than ketones. At the
same time, this H-atom is responsible for many reactions in which aldehydes differ from ketones. The carbonyl
group ) C—O — ) undergoes nucleophilic addition reactions due to electronegativity difference between carbon and
oxygen atoms. Aldehydes and ketones react with hydrogen cyanide (HCN) to yield cyanohydrins. Further aldehydes
and ketones having atleast one α-H atom in the presence of dilute alkali as a catalyst form β-hydroxy aldehyde
(aldol) or β-hydroxy ketones (ketol). This reaction is known as aldol condensation. Aldehydes which do not have an
α-hydrogen undergo disproportionation reaction in the presence of concentrated alkali giving a mixture of alcohol
and salt of carboxylic acid. This reaction is called Cannizzaro reaction. Cannizzaro reaction involves a hydride ion
shift from the carbonyl carbon that is attacked by the base to another carbonyl carbon. Since, there is no hydrogen
attached to the carbonyl carbon in a ketone therefore it does not undergo Cannizzaro reaction.

1. Propose the mechanism for the following reaction:

O OH
|| + |
H
CH3—CH2—C—H + HCN
CH—
3
CH 2
—CH—CN

Ans. The reaction proceeds through the nucleophilic attack of CN– ion as follows.
– CN CN
CN
H –
+ +
Step 1 Step 2, H
C O C – C
Slow H Fast H OH
O
H3CH2C
H3CH2C H3CH2C

2. Propanone is less reactive than ethanal towards nucleophilic addition reactions. Why?
Ans. The methyl group due to its +I effect reduces the magnitude of positive charge on carbonyl carbon atom.
Moreover, it also hinders the approach of the nucleophile. Since in propanone, there are two methyl groups
while in acetaldehyde there is one methyl group, therefore, propanone is less reactive than acetaldehyde
towards nucleophilic addition reactions.
3. How will you convert ethanal to 2-hydroxy propanoic acid?
O OH OH
|| | H2O/H+ ;
+HCN
Ans. CH3 —C —H H+
CH3 — CH —CN CH3 —CH—COOH
Ethanal 2 - Hydroxy Propanoic acid

504 Xam idea Chemistry–XII

 4. Which of the following compounds will undergo Cannizzaro reaction?
(i) (CH3)3—C—CHO (ii) CH 3 —CH 2 — CH —CHO
|
CH 3
Write the structures of expected product of the Cannizzaro reaction.
Ans. (i) will undergo Cannizzaro reaction as it does not contain α-hydrogen.
CH3 CH3 CH3
α conc. – +
2CH3—C—CHO NaOH
CH3—C—CH2—OH + CH3—C—COONa
CH3 CH3 CH3
2,2-Dimethyl 2, 2-Dimethyl Sodium-2,2-dimethylpropanoate
propanal propan-1-ol

5. What happens when acetone undergoes aldol condensation? Write the reaction and name of the
products.
O O OH O O
Ba(OH)2
Ans. CH3—C + H—CH2—C—CH3 CH3—C—CH2—C—CH3 –H2O
CH3—C—CH—C—CH3
Acetone
CH3 CH3 CH3
4-Hydroxy-4-methyl-pentan-2-one 4-Methyl pent-3-en-2-one
(Ketol)

PASSAGE–2
Carboxylic acids are the most acidic amongst all the organic compounds studied so far. However,carboxylic
acids are much weaker acids than the mineral acids.
Carboxylic acids are more acidic than alcohols and phenols due to the less electrophilic nature of carboxyl
carbon which puts a partial positive charge on the hydroxyl O-atom. The value of Ka is a measure of the acidic
strength of an acid. Greater the value of Ka, greater is the tendency of the acid to ionize and hence stronger is the
acid. The acidic strength of saturated aliphatic carboxylic acids depends mainly upon the inductive effect of the
substituent and its position with respect to —COOH group. Electron-donating substituents tend to decrease whereas
electron-withdrawing substituents tend to increase the acidic strength. The acidic strength of aromatic carboxylic
acids, on the other hand depends upon both the inductive and the resonance effect of the substituents.

1. What is meant by ‘acidity constant’ Ka? How is it expressed?

Ans. Acidity constant Ka is a measure of the strength of the acid. It is expressed as,
[ RCOO  ][ H 3 O  ]
Ka 
[ RCOOH]
2. What makes ethanoic acid a stronger acid than ethanol?
Ans. Ethanoate ion obtained by loss of a proton from ethanoic acid is stabilized by resonance but ethoxide ion
obtained by loss of a proton from ethanol does not.
3. Why is pKa of chloroacetic acid lower than pKa of acetic acid?
Ans. Due to –I effect of Cl atom and +I effect of CH3 group the electron density in the O—H bond in chloroacetic
acid is much weaker than in acetic acid and hence loses a proton more easily than acetic acid.
4. Arrange the following in the decreasing order of their acidic character:
CH3CH2OH, CH3COOH, ClCH2COOH, FCH2COOH, C6H5CH2COOH
Ans. FCH2COOH > ClCH2COOH > C6H5CH2COOH > CH3COOH > CH3CH2OH
5. Although phenoxide ion has more number of resonating structures than carboxylate ion, carboxylic
acid is a stronger acid than phenol. Give two reasons.
Ans. l Resonating structures of carboxylate ion are more stable than phenoxide ion.

l Negative charge is dispersing on two electronegative oxygens in carboxylate ion whereas it is on one

oxygen atom in phenoxide ion.

Aldehydes, Ketones and Carboxylic Acids 505

Very Short Answer Questions [1 mark]
Q. 1. Give IUPAC name of the following compound: [CBSE (F) 2010]
(CH3)2C==CHCOCH3
Ans. 4-Methyl-pent-3-en-2-one
Q. 2. Write the structure of the following compound : 3-oxopentanal. [CBSE (F) 2011]
O O
|| ||
Ans. CH3 —CH 2 —C—CH 2 —C—H
Q. 3. Write the IUPAC name of the following compound: [CBSE (F) 2014]
OH

CHO
Ans. 2-hydroxybenzaldehyde
Q. 4. Write the IUPAC name of the following compound: [CBSE 2019(56/3/2)]
O
||
CH 2 —
—CH—C —CH 3
Ans. But-3-en-2-one
Q. 5. Give the name of the reagent that bring the following transformation: But-2-ene to ethanal.
Ans. O3/H2O—Zn dust
Q. 6. Arrange the following in increasing order of their boiling point:
CH3CH2OH, CH3CHO, CH3—O—CH3 [CBSE 2019(56/3/2)]
Ans. CH3—O—CH3 < CH3CHO < CH3—CH2—OH
Q. 7. Arrange the following compounds in increasing order of their reactivity in nucleophilic addition
reactions: ethanal, propanal, propanone, butanone. [CBSE Delhi 2012]
Ans. Butanone < Propanone < Propanal < Ethanal
Q. 8. What is Tollens’ reagent? Write one usefulness of this reagent. [CBSE (AI) 2010]
Ans. Ammonical silver nitrate (AgNO3 + NH4OH) solution is known as Tollens’ reagent. It is used to detect the
presence of —CHO group in an organic compound.
Q. 9. What do you mean by Schiff’s base? Give an example.
Ans. Aldehydes and ketones react with primary aliphatic or aromatic amines to form azomethines or Schiff’s
bases.
+
Trace of H
R—CH == O + H 2 N—Rl R—CH == N—Rl + H 2 O
Heat
Aldehyde 1° Amine Schiff’s base

Q. 10. Propose the mechanism for the following reaction: [HOTS]

+
H
CH 3 CHO + HCN
CH 3 — CH —CN
|
OH
Ans. The reaction proceeds through the nucleophilic attack of CN– ion as follows:
O– OH
O CN– H+
CH3—C CH3—C—CN CH3—C—CN
H+
H H H
Acetaldehyde Intermediate Acetaldehyde cyanohydrin

506 Xam idea Chemistry–XII

Q. 11. Name the aldehyde which does not give Fehling’s solution test.
Ans. Benzaldehyde
Q. 12. How will you prepare benzyl alcohol from benzaldehyde without using a reducing agent? [HOTS]
CHO CH2 OH COONa
Cannizzaro reaction
Ans. 2 + NaOH +
(50%)
Benzaldehyde Benzyl alcohol Sodium benzoate

Here, a concentrated solution of NaOH is used which is not a reducing agent.

Q. 13. Write two important uses of formalin. [CBSE Sample Paper 2011]
Ans. Formalin is used in the
(i) preservation of biological specimens.
(ii) manufacture of bakelite.
Q. 14. Write the structural formula and IUPAC name of terephthalic acid.
O O
Ans. HO—C— —C—OH Benzene-1, 4-dicarboxylic acid

Short Answer Questions–I [2 marks]

Q. 1. Would you expect benzaldehyde to be more reactive or less reactive in nucleophilic addition reactions
than propanal? Explain your answer.
Ans. The carbon atom of the carbonyl group of benzaldehyde is less electrophilic than carbon atom of the
carbonyl group present in propanal. The polarity of the carbonyl group is reduced in benzaldehyde due to
resonance as shown below and hence it is less reactive than propanal.
–
O O
C C
H H
+

Q. 2. Complete the following reaction sequence: [NCERT Exemplar]
O
|| +CH 3 —Br
(i) CH 3 MgBr Na metal
CH 3 —C —CH 3 (A) (B) (C)
(ii) H 2 O Ether

CH3 CH3
| | –+
Ans. A = CH3 —C—OH , B = C H3 —C—ONa
| |
CH3 CH3
2-methyl propan-2-ol Sodium tert. butoxide

CH3
|
C = CH3 —C— OCH3
|
CH3
2-methoxy-2-methylpropane

Aldehydes, Ketones and Carboxylic Acids 507

Q. 3. Write the equations involved in the following reactions:
(i) Wolff-Kishner reduction
(ii) Etard reaction [CBSE Delhi 2017]
Ans. (i) Wolff–Kishner reduction:
+ NH2–NH2 KOH
C==O – H2O
C==NNH2 Ethylene glycol, ∆
CH2 + N2
Hydrazone
CH3 + NH2–NH2 CH3 KOH
C==O – H2O
C==NNH2 Ethylene glycol, ∆
CH3—CH2—CH3 + N2
CH3 CH3 Propane
Acetone
(ii) Etard reaction:
OCr(OH)Cl2
CH3 HC CHO
OCr(OH)Cl2 +
CrO2Cl2 H3O
CS2
Toluene Chromium complex Benzaldehyde
Q. 4. Write structures of main compounds A and B in each of the following reactions. [CBSE 2019(56/2/3)]
PCC CH 3 OH/dry HCl (g)
(i) CH 3 CH 2 OH A B
NaOI
(ii) C 6 H 5 COCH 3 A+B
O OCH3
|| |
Ans. (i) A = CH3 —C—H B = CH3 —C—H
Acetaldehyde |
OH
Hemiacetal

O
|| – +
(ii) A and B = CHI3 , C6 H5 —C—ONa
Iodoform Sodium
benzoate
Q. 5. Oxidation of ketones involves carbon–carbon bond cleavage. Name the products formed on oxidation
of 2, 5-dimethylhexan-3-one. [NCERT Exemplar]
CH3 O CH3
| || |
h C—
Ans. CH3 —CH— h CH —C—CH [ O]
h h 2 3

CH3 CH3 O
| | ||
CH3 — C—COOH + CH3 — C—CH 2 —COOH + CH3 —C—CH3
(2 - Methylpropanoic acid) (3 - Methylbu tan oic acid) (Propan - 2 - one)
O
||
[ O]

CH3 —C—CH3 CH3 COOH + HCOOH
(Acetone) (Ethanoic acid) (Methanoic acid)

Q. 6. An organic compound ‘A’ with molecular formula C5H8O2 is reduced to n-pentane on treatment
with Zn–Hg/HCl. ‘A’ forms a dioxime with hydroxylamine and gives a positive lodoform test and
Tollens’ test. Identify the compound A and deduce its structure. [HOTS]
Ans. As ‘A’ gives positive iodoform test, so it has CH3 —C— group.
||
O
As ‘A’ gives positive Tollens’ test, so it must have —CHO group.
So ‘A’ is CH3 — C—CH 2 CH 2 CHO
||
O
4 - oxopentanal

508 Xam idea Chemistry–XII

 Q. 7. What product will be formed on reaction of propanal with 2-methylpropanal in the presence of
NaOH? Write the name of the reaction also. [NCERT Exemplar] [HOTS]
Ans. The reaction taking place is cross aldol condensation.
CH3 OH CH3 CH3
Dil. NaOH ∆/H+
CH3CH2CHO + CH3CHCHO CH3CH2CH—CH—CHO (–H2O)
CH2—CH—C—CHO
Propanal 2-Methyl propanal
CH3 2-Methylpent-2-en-al
3-Hydroxy-2-methylpentanal
CH3 OH CH3 H 3C
∆
+ CH3CH—CH—C—CHO –CH3OH
CH—CH—C—CHO
CH3 H 3C CH3
3-Hydroxy-2,2,4-trimethylpentanal 2, 4-Dimethylpent-en-al

Q. 8. Name the reagents used in the following reactions: [CBSE Delhi 2015]
?
(i) CH 3 —CO—CH 3 CH 3 —CH—CH 3
|
OH
? +
(ii) C 6 H 5 —CH 2 —CH 3 C 6 H 5 —COO – K
Ans. (i) Sodium borohydride (NaBH4) or Lithium aluminium hydride (LiAlH4)
(ii) Alkaline potassium permanganate (KMnO4—KOH)
Q. 9. Name the electrophile produced in the reaction of benzene with benzoyl chloride in the presence of
anhydrous AlCl3. Name the reaction also. [NCERT Exemplar]
⊕
Ans. C6H5CO (Benzoylinium cation)
Friedel–Crafts acylation reaction
Q. 10. Do the following conversions in not more than two steps: [CBSE (F) 2017]
(i) Propene to Acetone
(ii) Propanoic acid to 2-hydroxypropanoic acid
OH O
| K2Cr2O7
||
H2 O
Ans. (i) CH3 —CH == CH 2 +
CH3 —CH—CH3 H2SO4
CH3 —C—CH3
Propene H Acetone

Cl OH
(i) Cl2 /red P
| |
NaOH (aq)
(ii) CH3 —CH 2 —COOH (ii) H2O
CH3 —CH—COOH CH3 — CH —COOH
Propanoic acid 2 - Hydroxy propanoic acid

Q. 11. An aromatic compound ‘A’ on treatment with CHCl3 and KOH gives two compounds, both of
which give same product ‘B’ when distilled with zinc dust. Oxidation of ‘B’ gives ‘C’ with molecular
formula C7H6O2. Sodium salt of ‘C’ on heating with soda lime gives ‘D’ which may also be obtained
by distilling ‘A’ with zinc dust. Identify ‘A’, ‘B’, ‘C’ and ‘D’. [CBSE 2019(56/5/2)]
OH
COOH
Ans. A= , B= CHO , C = , D=
Phenol Benzaldehyde Benzoic acid Benzene
Q. 12. Write the reagents used in the following reactions: [CBSE Ajmer 2015]
?
(i) C 6 H 5 —CO—CH 3 C 6 H 5 —CH 2 —CH 3
?
(ii) CH 3 COOH CH 3 —COCl
Ans. (i) Zn—Hg, conc. HCl or H2NNH2 and KOH/ethylene glycol, Heat
(ii) PCl5 or SOCl2

Aldehydes, Ketones and Carboxylic Acids 509

Q. 13. Identify the compounds A, B and C in the following reaction: [NCERT Exemplar]
+
Mg/Ether (i) CO 2 CH 3 OH/H

CH 3 —Br (A) (B) (C)
(ii) Water D

O O
|| ||
Ans. A = CH3 MgBr , B = CH3 —C—OH , C = CH3 —C—O—CH3
Methyl Ethanoic acid Methyl
magnesium bromide ethanoate

Q. 14. Arrange the following compounds in increasing order of their property as indicated:
(i) CH3COCH3, C6H5—CO—C6H5, CH3CHO (reactivity towards nucleophilic addition reaction)
(ii) Cl—CH—COOH , Cl—CH2—COOH, CCl3—COOH (acidic character)
|
Cl

[CBSE Bhubaneshwar 2015]
Ans. (i) C6H5COC6H5 < CH3COCH3 < CH3CHO
(ii) Cl—CH2 —COOH < Cl— CH —COOH < CCl3—COOH
|
Cl
Q. 15. Give reasons:
(i) Oxidation of aldehydes is easier than ketones. [CBSE 2019 (51/5/2)]
OR
Oxidation of propanal is easier than propanone. [CBSE 2020 (56/4/3)]
(ii) CH2—CH—COOH is more acidic than CH3CH2—COOH. [CBSE East 2016]
Ans. (i) As aldehydes contain H atom on the carbonyl group but ketones do not. Cleavage of C—H bond in
aldehydes is easier than cleavage of C—C bond in ketones.
(ii) This is because in CH2—CH—COOH, the carbonyl group attached to sp2 hybridised carbon atom
which is more electronegative and makes release of H+ ion easy.
Q. 16. (i) Give reason: [CBSE 2019(56/2/1)]
(a) Benzoic acid is a stronger acid than acetic acid.
(b) Methanal is more reactive towards nucleophilic addition reaction than ethanal.
(ii) Give a simple chemical test to distinguish between propanal and propanone.
Ans. (i) (a) This is because of greater electronegativity of sp2 hybridised carbonyl to which carboxyl carbon
is attached in benzoic acid.
sp2 sp3
C6H5—COOH CH3—COOH
Benzoic acid Acetic acid

(b) The methyl group due to its +ve I effect reduces the positive charge on carbonyl carbon atom.
Moreover it also hinders the approach of the nucleophile. Since in ethanal there is one methyl
group while in methanal there is no methyl group on carbonyl carbon atom therefore methanal is
more reactive towards nucleophilic addition reaction than ethanal.
(ii) Propanal being an aldehyde gives silver mirror with Tollens’ reagent while propanone being a ketone
does not give this test.
+
CH3 CH 2 CHO + 2 [Ag (NH3) 2] + 3OH –
CH3 CH 2 COO – + 2Ag . + 4NH3 + 2H 2 O
Propanal Tollens’ reagent Silver mirror

Q. 17. Arrange the following in the decreasing order of their acidic character.
(i) C6H5COOH, FCH2COOH, NO2CH2COOH
(ii) CH3CH2OH, CH3COOH, ClCH2COOH, FCH2COOH, C6H5CH2COOH
Ans. (i) NO2CH2COOH > FCH2COOH > C6H5COOH
(ii) FCH2COOH > ClCH2COOH > C6H5CH2COOH > CH3COOH > CH3CH2OH

510 Xam idea Chemistry–XII

Q. 18. Arrange the following in order of property indicated for each set.
(i) CH3CHO, CH3CH2OH, CH3OCH3, CH3CH2CH3 (increasing order of boiling points)
(ii) (CH3)2CHCOOH, CH3CH2CH(Br)COOH, CH3CH(Br)CH2COOH (increasing order of their
acid strengths)
Ans. (i) CH3CH2CH3 < CH3OCH3 < CH3CHO< CH3CH2OH
(ii) (CH3) 2 CHCOOH < CH3 —CH—CH 2 —COOH < CH3 —CH 2 —CH—COOH
| |
Br Br

Short Answer Questions–II [3 marks]

Q. 1. An alkene ‘A’ molecular formula (C5H10) on ozonolysis gives a mixture of two compounds ‘B’ and
‘C’. Compound ‘B’ gives positive Fehling’s test and also reacts with iodine and NaOH solution.
Compound ‘C’ does not give Fehling’s test but forms iodoforms. Identify the compounds ‘A’, ‘B’ and
‘C’ giving suitable explanation and write the reactions of ozonolysis and iodoform formation from
either ‘B’ or ‘C’. [NCERT Exemplar] [HOTS]
Ans. Compound ‘B’ gives both Fehling’s test and iodoform test and therefore it must be an aldehyde with
—COCH3 group. Moreover, compound ‘C’ doesn’t give Fehling’s test but give positive iodoform test and
therefore it must be a ketone with —COCH3 group. Thus, the compound A, B and C are as follows:
(i) O3
CH3 —CH == C —CH3 H3 C—CHO + O == C —CH3
(ii) Zn/H2 O
| |
CH3 (B) CH3
( A) Acetaldehyde (C)
2 - Methylbut - 2 - ene Acetone
Iodoform
CH3 —CHO + 3I 2 + 4NaOH
HCOONa + CHI3 . + 3NaI + 3H 2 O
reaction
Other isomers of ‘A’ will not give products corresponding to the given test.
Q. 2. Write down functional isomers of a carbonyl compound with molecular formula C3H6O. Which
isomer will react faster with HCN and why? Explain the mechanism of the reaction also. Will the
reaction lead to the completion with the conversion of whole reactant into product at reaction
conditions? If a strong acid is added to the reaction mixture what will be the effect on concentration
of the product and why? [NCERT Exemplar] [HOTS]
Ans. CH3CH2CHO   CH3COCH3
 (I)       (II)
(a) Compound I will react faster with HCN due to less steric hinderance and electronic reasons than II.
Mechanism: Nucleophilic addition reaction:
– CN CN
CN
H –
+ +
Step 1 Step 2, H
C O C – C
Slow H Fast H OH
O
H3CH2C
H3CH2C H3CH2C
(b) No, it is a reversible reaction. Hence, equilibrium is established.
(c) Addition of acid inhibits the reaction because the formation of CN– ions is prevented.
Q. 3. (A), (B) and (C) are three non-cyclic functional isomers of a carbonyl compound with molecular
formula C4H8O. Isomers (A) and (C) give positive Tollens’ test whereas isomer (B) does not give
Tollens’ test but gives positive Iodoform test. Isomers (A) and (B) on reduction with Zn(Hg)/conc.
HCl give the same product (D).
(i) Write the structures of (A), (B), (C) and (D).
(ii) Out of (A), (B) and (C) isomers, which one is least reactive towards addition of HCN?
[CBSE 2018]

Aldehydes, Ketones and Carboxylic Acids 511

 O O
|| ||
Ans. (i) A = CH3 —CH 2 —CH 2 —C—H, B = CH3 —CH 2 —C—CH3,
Bu tan al Bu tan one
Butanal Butanone
CH3 O
| ||
C = CH3 — CH —C—H, D = CH3 —CH 2 —CH 2 —CH3
2 - Methylpropanal Bu tan e
2-Methylpropanal Butane

O
||
(ii) CH3 —CH 2 —C—CH3
Bu tan one (B)

Q. 4. An organic compound (A) having molecular formula C4H8O gives orange red precipitate with
2, 4-DNP reagent. It does not reduce Tollens’ reagent but gives yellow precipitate of iodoform on
heating with NaOH and I2. Compound (A) on reduction with NaBH4 gives compound (B) which
undergoes dehydration reaction on heating with conc. H2SO4 to form compound (C). Compound (C)
on Ozonolysis gives two molecules of ethanal.
Identify (A), (B) and (C) and write their structures. Write the reactions of compound (A) with
(i) NaOH/I2 and (ii) NaBH4 and explain the reactions. [HOTS] [CBSE 2020 (56/4/3)]
O
Ans. A = Butan-2-one; CH3—CH2—C—CH3
B = Butan-2-ol ; CH3—CH2—CH—CH3
OH
C = But-2-ene ; CH3—CH—HC—CH3
Reactions involved:
CH3 NO2 CH3 NO2
CH3—CH2—C—O + H 2N—NH— —NO2 —
CH3—CH2—C—N—NH— —NO2

2,4-DNP Orange red ppt

O O
|| ||
CH3 —CH 2 —C—CH3 + 3NaOI
CHI3 . + CH3 —CH 2 —C—O – Na + + 2NaOH
Iodoform
(yellow ppt.)

O OH
|| |
CH 3  C H 2  C  CH3 
 CH 3  C H 2  CH  CH 3
LiAlH 4

Butan-2-ol

OH
|
conc. H2 SO 4
CH3 —CH2 —CH—CH3 CH3 —CH == CH—CH3 + O3
D
Butan-2-ol But-2-ene

O
CH3 —CH CH—CH3
Zn/HCl
2CH3CHO –H2O2
Ethanal
O O

512 Xam idea Chemistry–XII

Q. 5. An unknown aldehyde ‘A’ on reacting with alkali gives a b-hydroxy aldehyde, which loses water to form
an unsaturated aldehyde, But-2-enal. Another aldehyde ‘B’ undergoes disproportionation reaction in
the presence of conc. alkali to form products C and D. C is an arylalcohol with the formula, C7H8O.
(i) Identify A and B.
(ii) Write the sequence of reactions involved.
(iii) Name the product, when ‘B’ reacts with zinc amalgam and hydrochloric acid. [HOTS]
Ans. (i) A is CH3CHO (ethanal) and B is C6H5CHO (benzaldehyde).
OH
NaOH
|
– H2 O
(ii) 2CH3 CHO CH3 —CH—CH 2 CHO — —CHO
CH3 —CH—CH
[A] But - 2 - enal

CHO CH2OH COO–

Conc. alkali
2 +
[B] [C] [D]

(iii) Toluene.
Q. 6. (i) Account for the following:
(a) Cl—CH2COOH is a stronger acid than CH3COOH.
(b) Carboxylic acids do not give reactions of carbonyl group.
(ii) Out of CH3CH2—CO—CH2—CH3 and CH3CH2—CH2—CO—CH3, which gives iodoform
test? [CBSE (AI) 2014]
Ans. (i) (a) Because of –I effect of Cl atom in ClCH2COOH and +I effect of CH3 group in CH3COOH the
electron density in the O—H bond in ClCH2COOH is much lower than CH3COOH. As a result
O—H bond in ClCH2COOH is much weaker than in CH3COOH therefore loses a proton more
easily than CH3COOH. Hence ClCH2COOH acid is stronger acid than CH3COOH.
(b) Carboxylic acids are resonance hybrid of the following structures:
–
O O
R—C R—C +
O—H O—H
(I) (II)

Similarly, a carbonyl group of aldehydes and ketones may regarded as resonance hybrid of
following structures.
+ –
C O C O
(III) (IV)
Because of contribution of structure (IV), the carbonyl carbon in aldehydes and ketones is
electrophilic. On the other hand, electrophilic character of carboxyl carbon is reduced due to
contribution of structure (II). As carbonyl carbon of carboxyl group is less electropositive than
carbonyl carbon in aldehydes and ketones, therefore, carboxylic acids do not give nucleophilic
addition reactions of aldehydes and ketones.
(ii) CH3—CH2—CH2—COCH3
Q. 7. Arrange the following compounds in increasing order of their property as indicated:
(i) Acetaldehyde, Acetone, Methyl tert-butyl ketone (reactivity towards HCN)
(ii) Benzoic acid, 3,4-Dinitrobenzoic acid, 4-Methoxybenzoic acid (acid strength)
(iii) CH3CH2CH(Br)COOH, CH3CH(Br)CH2COOH, (CH3)2CHCOOH (acid strength)
 [CBSE (AI) 2012]
Ans. (i) Methyl tert-butyl ketone < Acetone < Acetaldehyde
(ii) 4-Methoxy benzoic acid < Benzoic acid < 3,4-Dinitrobenzoic acid
(iii) (CH3)2CHCOOH < CH3CH(Br)CH2COOH < CH3CH2CH(Br)COOH

Aldehydes, Ketones and Carboxylic Acids 513

 Q. 8. Complete each synthesis by giving missing reagents or products in the following:
COOH SOCl 2
(i)
heat
COOH
H 2 NCONHNH 2
(ii) C 6 H 5 CHO

(iii) CH2 —CHO [CBSE (AI) 2011]

COOH SOCl 2 COCl

Ans. (i) + SO2 + HCl
heat
COOH COCl
H2 NCONHNH 2
(ii) C6 H5 CHO C6 H5 CH == NNHCONH2 + H2 O
(i) B2H6, H2O2/OH
(iii) CH2 —CHO
(ii) PCC

Q. 9. Write structures of compounds A, B and C in each of the following reactions:

Mg/dryether (a) CO 2 (g) PCl 5
(i) C 6 H 5 Br A +
B C
( b) H 3 O

(a) SnCl 2 /HCl dil. NaOH D

(ii) CH 3 CN +
A B C [CBSE Delhi 2017]
( b) H 3 O

=
Ans. (i) A =
C 6 H 5 MgBr , B C 6 H 5 COOH, C = C 6 H 5 COCl
Phenyl magnesium Benzoic acid Benzoyl chloride
bromide
OH
|
(ii) A = CH3 CHO, B = CH3 —CH—CH 2 —CHO, C = CH3 —CH == CH—CHO
Benzaldehyde 3 - Hydroxybu tan al But - 2 - enal

Q. 10. Do the following conversions in not more than two steps: [CBSE Delhi 2017]
(i) Benzoic acid to Benzaldehyde
(ii) Ethyl benzene to Benzoic acid
(iii) Propanone to Propene
Ans. (i) Benzoic acid to Benzaldehyde
COOH COCl CHO
PCl 5 +H 2

Pd/BaSO4

Benzoic acid Benzaldehyde

(ii) Ethyl benzene to Benzoic acid

– +
CH2—CH3 COOK COOH
+
KMnO4/KOH H 3O

∆

Benzoic acid

(iii) Propanone to Propene

O OH
|| + NaBH 4
|
conc. H2 SO 4

CH3 —C—CH3 CH3 —CH—CH3 CH3 —CH == CH 2
D
Propanone Propene

514 Xam idea Chemistry–XII

Q. 11. Predict the products of the following reactions: [CBSE Delhi 2015]
(i) H 2 N–NH 2
(i) CH 3 —C == O ?
(ii) KOH/Glycol, D
|
CH 3
NaOH/I 2
(ii) C 6 H 5 —CO—CH 3 ? + ?
NaOH/CaO
(iii) CH 3 COONa ?
D
Ans. (i) CH3—CH2—CH3 (Propane)
(ii) C6H5COO–Na+ (Sodium benzoate) and CHI3 (Iodoform)
(iii) CH4 (Methane)
Q. 12. How do you convert the following?
(i) Benzoic acid to Benzaldehyde
(ii) Ethyne to Ethanal
(iii) Acetic acid to Methane [CBSE (F) 2015]
COOH COCl CHO

+ SOCl2 H2/Pd
Ans. (i)
BaSO4
Benzoic acid Benzaldehyde
RS V O
SS OHWW
+ H2 O SS | WWW ||
(ii) CH // CH SSCH == CHWW CH3 —C—H
HgSO 4 /H2 SO 4 SS 2 WW
Ethyne Ethanal
S W
T X
+ NaOH – + NaOH/CaO
(iii) CH3 COOH CH3 COONa CH 4
D
Acetic acid Methane

Q. 13. An organic compound (A) has characteristic odour. On treatment with NaOH, it forms compounds
(B) and (C). Compound (B) has molecular formula C7H8O which on oxidation gives back (A). The
compound (C) is a sodium salt of an acid. When (C) is treated with soda-lime, it yields an aromatic
compound (D). Deduce the structures of (A), (B), (C) and (D). Write the sequence of reactions
involved. [CBSE Sample Paper 2015]
– +
CHO CH2OH COONa

Ans. A= ; B= ; C= ; D=
Benzaldehyde Benzyl Sodium Benzene
alcohol benzoate
Reaction involved are:

– +
CHO CH2OH COONa
NaOH/Conc.
+

(A) (B) (C)

– +
COONa
NaOH/CaO
∆
+ Na2CO3

(C) (D)

Aldehydes, Ketones and Carboxylic Acids 515

Q. 14. How would you bring about the following conversions? Write the complete equation in each case.
(i) Ethanal to 3-hydroxybutanal
(ii) Benzoic acid to m-nitrobenzyl alcohol
(iii) Benzaldehyde to benzophenone [CBSE (AI) 2011]
OH
|
dil. NaOH
Ans. (i) CH3 CHO CH3 —CH—CH 2 —CHO
Ethanal 3 - Hydroxybutanal

COOH COOH CONH2

HNO3 (conc.) +NH3
(ii) H2SO4 (conc.),
NO2 NO2
Benzoic acid
LiAlH4

CH2OH CH2—NH2
HNO2

NO2 NO2
m-Nitro benzyl alcohol
O
CHO COOH COCl
+ C
K2Cr2O7/H2SO4 SOCl 2
(iii) (O) AlCl3 (anhyd.)
Benzaldehyde Benzoic Benzophenone
acid
Q. 15. Give reasons:
(i) The a-hydrogen of aldehydes and ketones are acidic in nature. [CBSE 2020 (56/4/3)]
(ii) Propanone is less reactive than ethanal towards addition of HCN.
(iii) Benzoic acid does not give Friedel-Crafts reaction. [CBSE (F) 2016]
Ans. (i) The acidity of a-hydrogen atom of carbonyl carbon is due to the strong withdrawing effect of the
carbonyl group and resonance stabilisation of the conjugate base.
–
O O O
—C—C— —C—C— —C—C—

H B
(ii) This is due to steric and electronic reasons. Sterically, the presence of two methyl groups in propanone
hinders more the approach of nucleophile to carbonyl carbon than in ethanal having one methyl
group. Electronically two methyl groups reduce the positivity of the carbonyl carbon more effectively
in propanone than in ethanal.
(iii) Benzoic acid does not give Friedel Craft reaction because:
(a) the carboxyl group is strongly deactivating.
(b)the catalyst AlCl3 which is a lewis acid gets bonded to the carboxyl group strongly.

Long Answer Questions [5 marks]

Q. 1. Give names of the reagents that bring about the following transformations:
(i) Hexan-1-ol to hexanal
(ii) p-Fluorotoluene to p-fluorobenzaldehyde
(iii) Ethanenitrile to ethanol
(iv) Allyl alcohol to propenal
(v) Ethanoic acid to ethanol

516 Xam idea Chemistry–XII

Ans. [C5H5NH]+[CrO3Cl]– (PCC)
(i)
(ii) CrO3 in the presence of acetic anhydride/1. CrO2Cl2 2. H3O+
(iii)Diisobutyl aluminium hydride (DIBAL-H)
(iv) PCC
(v) LiAlH4
Q. 2. (i)
A ketone A which undergoes haloform reaction gives compound B on reduction. B on heating
with sulphuric acid gives compound C, which forms mono-ozonide D. The compound D on
hydrolysis in presence of zinc dust gives only acetaldehyde. Write the structures and IUPAC
names of A, B and C. Write down the reactions involved.
(ii) Predict the products formed when cyclohexanecarbaldehyde reacts with following reagents.
(a) PhMgBr and then H3O+

(b) Tollens’ reagent. [CBSE Sample Paper 2017]
O OH
|| |
Ans. (i) A = CH3 —C—CH 2 —CH3 , B = CH3 —CH—CH 2 —CH3 , C = CH3 —CH == CH—CH3
Bu tan - 2 - one Bu tan - 2 - ol But - 2 - ene

The reactions are as follows:

O OH
LiAlH4 H2SO4 (conc.)
CH3—C—CH2—CH3 CH3—CH—CH 2—CH3 —
CH3—CH—CH—CH 3
(A) (B) (C)
+O3

O
O
H2O/Zn H3C—HC CH—CH3
2CH3—C—H
O O
Acetaldehyde
(D)

OMgBr OH
O
C + C
(ii) (a) H Ph-MgBr H H 3O H
Dry ether Ph Ph
Cyclohexane Cyclohexylphenyl
carbaldehyde carbinol
O O

H C –
(b) + 2[Ag(NH 3)2]+ + 3OH
– O + 2Ag + 4NH3 + 2H2O
Cyclohexane Tollens’ reagent Cyclohexane Silver
carbaldehyde carboxylate ion mirror
Q. 3. Write the structures of A, B, C, D and E in the following reactions: [CBSE Delhi 2016]
CH3COCl Zn-Hg/conc. HCl (i) KMnO4–KOH,
C6H6 Anhyd. AlCl3
A B (ii) H3O+
C
NaOI

D+E
O O O
– +
C—CH3 CH2—CH3 C—OH C—ONa

Ans. A= ; B= ; C= ; D or E = CHI3 ; E or D =
Acetophenone Ethyl Benzoic Iodoform Sodium
benzene acid benzoate

Aldehydes, Ketones and Carboxylic Acids 517

Q. 4. (i) Carry out the following conversions: [CBSE 2019 (56/4/1)]
(a) p-nitrotoluene to 2-bromobenzoic acid
(b) Propanoic acid to acetic acid
(ii) An alkene with molecular formula C5H10 on ozonolysis gives a mixture of two compounds,
B and C. Compound B gives positive Fehling test and also reacts with iodine and NaOH solution.
Compound C does not give Fehling solution test but forms iodoform. Identify the compounds
A, B and C.

CH3 CH3 CH3 CH3 CH3 COOH

Br2
Br Sn/HCl
Br NaNO2/HCl
Br H2O
BrKMnO Br
Ans. (i) (a) 4
273–278 K H3PO2 OH–

NO2 NO2 NH2 N2Cl

NH3 Br2 /KOH

(b) CH3 CH 2 COOH Heat
CH3CH2CONH2 CH3CH2NH2
+
HNO3 KMnO 4 /H or OH –
273 K
CH3 CH 2 OH CH3 COOH

(ii) A : 2-Methylbut-2-ene/CH3CH—C(CH3)2
B: Ethanal/Acetaldehyde /CH3CHO
C: Propanone/Acetone /CH3COCH3
Q. 5. (i) Write the structures of A, B, C and D in the following reactions:
H2/Pd – BaSO4 conc. NaOH
C6H5COCl A B+C
+
CH3MgBr/H3O

D
(ii) Distinguish between the following:
(a) C6H5 —COCH3 and C6H5 —COCH2CH3
(b) Propanal and butan-2-one [CBSE (F) 2014]
(iii) Write the structure of 2-hydroxybenzaldehyde. [CBSE Chennai 2015]

OH
CHO COONa CH2—OH CH—CH3

Ans. (i) A = , B or C = , C or B = , D=
Benzaldehyde Sodium Benzyl 1-Phenyl
benzoate alcohol ethanol

(ii) (a) C6H5COCH3 being a methyl ketone gives iodoform test while C6H5COCH2CH3 does not.
C6 H5 COCH3 + 3NaOI
C6 H5 COONa + CHI3 . + 2NaOH
Acetophenone Iodoform
(Yellow ppt.)

(b) Propanal being an aldehyde reduces Tollens’ reagent to silver mirror but propanone being a
ketone does not.
+
CH3 CH 2 CHO + 2 [Ag (NH3) 2] + 3OH – CH3 CH 2 COO – + 2Ag . + 4NH3 + 2H 2 O
Propanal Silver
mirror
Tollens’ reagent
CH3 COCH3 No silver mirror
Propanone

518 Xam idea Chemistry–XII

 O
C—H
OH
(iii)

Q. 6. (i) Carry out the following conversions:

(a) Benzoic acid to aniline
(b) Bromomethane to ethanol
(ii) Write the structure of major product(s) in the following:
(a) H 2 N – NH 2

(a) CH 3 —CH 2 — C —H
(b) KOH, Glycol/heat
||
O

CH 3 COOH
| conc. NaOH NaOH

(b) CH 3 — C— CHO   (c) [CBSE 2019 (56/4/1)]
|
CH3
COOH CONH2 NH2
NH3 Br2, KOH
Ans. (i) (a)
Heat

KCN (alc.) H2 O LiAlH 4 /Ether or B2 H6

(b) CH3 Br CH3 CN +
CH3 COOH +
CH3 CH 2 OH
H /OH – H3 O

2 (a) H N – NH
2
(ii) (a) CH3 —CH 2 —C—H (b) KOH, Glycol/heat
CH3 CH 2 CH3
||
O
CH3
| conc. NaOH
(b) CH3 —C— CHO (CH3) 3 CCH 2 OH + (CH3) 3 CCOONa
|
CH3

COOH COONa
NaOH

(c)

Q. 7. (i) Give a simple chemical test to distinguish between benzaldehyde and ethanal. [CBSE (F) 2013]
(ii) Bring out the following conversions:
(a) 4-Nitrotoluene to 2-bromobenzoic acid
(b) Ethylcyanide to 1-phenyl propanone
(iii) A and B are two functional isomers of compound C3H6O. On heating with NaOH and I2, isomer
B forms yellow precipitate of iodoform whereas isomer A does not form any precipitate. Write
the formulae of A and B.
Ans. (i) Benzaldehyde and Ethanal
Ethanal reacts with NaOI (I2/NaOH) to form yellow precipitate of iodoform while benzaldehyde does
not give this test.
– +
CH3 CHO + 3I 2 + 3NaOH HCOONa + CHI3 . + 3NaI + 3H 2 O
Iodoform
(Yellow ppt.)

Aldehydes, Ketones and Carboxylic Acids 519

 (ii) (a) 4-Nitrotoluene to 2-bromobenzoic acid
CH3 CH3 CH3 CH3
Br Br Br NaNO2/HCl
Br
2 Sn/HCl
273-278 K

NO2 NO2 NH2 N2Cl

H2O H3PO2

COOH CH3
Br KMnO4
Br
–
OH

(b) Ethylcyanide to 1-phenyl propanone
NMgBr O
+C6 H5 MgBr
|| + ||
H3 O

CH3 —CH 2 —CN CH3 CH 2 —C—C6 H5 CH3 CH 2 —C—C6 H5
Ether

O O
|| ||
(iii) A = CH3 —CH 2 —C—H B = CH3 —C—CH3
Propanal Propanone

Reaction involved:
O O
|| ||
D
CH3 —C—CH3 + 3I 2 + 4NaOH
CHI3 + CH3 —C—O – —Na+ + 3NaI + 3H 2 O
Propanone Iodoform
(Yellow ppt.)

Q. 8. An organic compound ‘A’ on treatment with ethyl alcohol gives carboxylic acid ‘B’ and compound ‘C’.
Hydrolysis of ‘C’ under acidic conditions gives ‘B’ and ‘D’. Oxidation of ‘D’ with KMnO4 also gives
‘B’. B on heating with Ca(OH)2 gives ‘E’ with molecular formula C3H6O. ‘E’ does not give Tollens’ test
or reduce Fehling solution but forms 2, 4-dinitrophenyl hydrazone. Identify A, B, C, D, E. [HOTS]
O
O O
CH3—C
Ans. A = O B = CH3—C—OH C = CH3—C—O—CH2—CH3
CH3—C
Acetic acid Ethyl acetate
O
Acetic anhydride

O
D = CH3—CH2—OH E = CH3—C—CH3
Ethyl alcohol Acetone

Reactions are:

O
O O
CH3—C
O + CH3—CH2—OH CH3—C—OH + CH3—C—OC2H5
CH3—C Ethyl alcohol Acetic acid Ethyl acetate
(B) (C)
O
Acetic anhydride
(A)

520 Xam idea Chemistry–XII

 O O
|| + ||
H2 O/H

CH3 —C—O—CH 2 —CH3 CH3 —C—OH + CH3 —CH 2 —OH
Ethyl acetate Acetic acid Ethyl alcohol
(C) (B) ( D)

O
||
KMnO 4

CH3 —CH 2 —OH CH3 —C—O—H
[ O]
Ethyl alcohol Acetic acid
( D) (B)

O O
|| ||
(i) Ca (OH) 2

CH3 —C—O—H CH3 —C—CH3
(ii) Distil
Acetic acid Acetone
(B) ( E)

Q. 9. Complete each synthesis by giving missing starting material, reagent or products:

O +
(i) H (ii) CH3 KMnO4
+ HO—NH2 KOH, heat

O O
CH2
(iii) OH SOCl2 (iv) H
O ∆

OH O

(v)  [CBSE Sample Paper 2017]

O H
+ N—OH
Ans. (i) + HO—NH 2 + H 2O

– +
CH2—CH3 KMnO4–KOH COOK H3O
+ COOH
(ii)
∆
Ethylbenzene Benzoic acid

O O
C—OH SOCl 2
C—Cl
(iii)
C—OH C—Cl
O O
Phthalic acid Phthaloyl chloride

B2 H6 H 2O 2 PCC
(iv) CH2 —CH2 B – —CH2—OH —CHO
OH
3
Methylenecyclohexane Cyclohexanecarbaldehyde

O O
C Anhyd. AlCl3 C
(v) + Cl + HCl
Benzene Benzoyl chloride Benzophenone

Aldehydes, Ketones and Carboxylic Acids 521

Q. 10. (i) Write the structures of A, B, C and D in the following reactions:
(i) SnCl2—HCl dil. NaOH Heat
CH3CN (ii) H2O
A B C
HCN

D
(ii) Distinguish between:
(a) C6H5—CH—CH—COCH3 and C6H5—CH—CH—COCH2CH3
(b) CH3CH2COOH and HCOOH
(iii) Arrange the following in the increasing order of their boiling points:
CH3CH2OH, CH3COCH3, CH3COOH [CBSE North 2016]
O OH O
|| | ||
Ans. (i) A = CH3 —C—H B = CH3 —CH—CH 2 —C—H
Ethanal 3 - Hydroxybu tan al
O OH
|| |
C = CH3 —CH == CH—C—H D = CH3 —CH—CN
But - 2 - enal 2 - Hydroxy propanenitrile

(ii) (a) C6H5CH—CH—COCH3 on warming with NaOI (I2/NaOH) gives yellow precipitate of iodoform
while C6H5CH—CH—CO—CH2—CH3 does not.
–
+
C6 H5 CH == CHCOCH3 + 3NaOI
CHI3 . + C6 H5 CH == CH—COONa + 2NaOH
Iodoform
(Yellow ppt.)

(b) Formic acid reduces Tollens’ reagent to metallic silver while propionic acid does not.
+
HCOOH + 2 [Ag (NH3) 2] + 2OH –
2Ag . + CO 2 + 2H 2 O + 4NH3
Formic acid Silver mirror

(iii) CH3—CO—CH3 < CH3—CH2—OH < CH3—COOH

Q. 11. (i) Write the product(s) in the following reactions:
O COONa

(a) CaO
+ HCN ? (b) + NaOH ∆
?
(a) DIBAL–H
(c) CH 3 —CH——CH—CN ?
(b) H 2 O
(ii) Give simple chemical tests to distinguish between the following pairs of compounds:
(a) Butanal and Butan-2-one (b) Benzoic acid and Phenol [CBSE (AI) 2017]
OH
Ans. (i) (a) CN (b) (c) CH3 —CH == CH—CHO
But - 2 - en - 1 - al
Cyclohexane Benzene
cyanohydrin

(ii)(a) Butanal being an aldehyde reduces Tollens’ reagent to give silver mirror but butan-2-one being
a ketone does not.
+
CH3 —CH 2 —CH 2 —CHO + 2 [Ag (NH3) 2] + 3OH –
Bu tan al Tollens’ reagent
CH3 —CH 2 —CH 2 —COO – + Ag . + 4NH3 + 2H 2 O
Butanoate ion Silver mirror

(b) Benzoic acid decomposes NaHCO3 to produce brisk effervescence due to evolution of CO2 while
phenol does not.
– +
C6 H5 COOH + NaHCO3 C6 H5 COONa + CO2 - + H 2 O
Benzoic acid Sodium benzoate

522 Xam idea Chemistry–XII

Self-Assessment Test
Time allowed: 1 hour Max. marks: 30
Choose and write the correct answer for each of the following. (3 × 1 = 3)
1. Toluene can be oxidised to benzoic acid by
(a) KMnO4(alk.) (b) K2Cr2O7
(c) Both (d) None
2. Carbonyl group undergoes
(a) Electrophilic addition reaction (b) Nucleophilic addition reactions
(c) Both (d) None
3. Ethyl alcohol on oxidation with K2Cr2O7 gives
(a) Acetic acid (b) Acetaldehyde
(c) Formaldehyde (d) Formic acid

In the following questions, two statements are given—one labeled Assertion (A) and the other labeled
Reason (R). Select the correct answer to these questions from the codes (a), (b), (c) and (d) as given below:
(a) Both Assertion (A) and Reason (R) are correct statements, and Reason (R) is the correct explanation of
the Assertion (A).
(b) Both Assertion (A) and Reason (R) are correct statements, but Reason (R) is not the correct explanation
of the Assertion (A).
(c) Assertion (A) is correct, but Reason (R) is incorrect statement.
(d) Assertion (A) is incorrect, but Reason (R) is correct statement. (3 × 1 = 3)

4. Assertion (A) : Acetic acid does not undergo haloform reaction.

Reason (R) : Acetic acid has no alpha hydrogen.
5. Assertion (A) : 2, 2-Dimethylpropanal undergoes Cannizzaro reaction with conc. NaOH.
Reason (R) : Cannizzaro reaction is a disproportionation reaction.
6. Assertion (A) : Nitration of benzoic acid gives m-nitrobenzoic acid.
Reason (R) : Carboxyl group increases the electron-density at meta-position.

Answer the following questions:

7. Write the IUPAC name of the following compound:

Cl COOC2H5 (1)

8. How will you distinguish between ethanol and ethanal? (1)

9. Complete the following reactions by identifying A, B and C.
Pd/BaSO4
(i) A + H2 (g) (CH3) 2 CH—CHO

CH3
|
(ii) CH3 —C — C —CH3 + NaOI B + C (2)
| ||
CH3 O

Aldehydes, Ketones and Carboxylic Acids 523

10. Give reasons for the following:
(i) Benzaldehyde reduces Tollens’ reagent but not the Fehling’s or Benedict’s solution.
(ii) (CH3)2CH—CHO undergoes aldol condensation whereas (CH3)3C—CHO does not.
[CBSE (F) 2017] (2)
11. Write the reagents required in the following reactions: [CBSE Allahabad 2015]
?
(i) CH2—CH—CH2OH 
 CH2—CH—CHO
?
(ii) CH3—COOH  CH3—CONH2 (2)
12. An organic compound ‘A’ with molecular formula C8H8O gives positive DNP and iodoform
tests. It does not reduce Tollens’ or Fehling’s reagent and does not decolourise bromine water
also. On oxidation with chromic acid (H2CrO4), it gives a carboxylic acid (B) with molecular
formula C7H6O2. Deduce the structures of A and B. (2)
13. Write the products formed when (CH3)3C—CHO reacts with the following:
(i) Zinc amalgam and dilute hydrochloric acid
(ii) Concentrated sodium hydroxide solution [CBSE 2020 (56/3/2)]
(iii) Semicarbazide and a weak acid [CBSE 2019 (56/5/2)] (3)
14. Write the chemical equations for the following conversions (not more than 2 steps):
(i) Ethyl benzene to benzene
(ii) Acetaldehyde to butane-1, 3-diol
(iii) Acetone to propene (3)
15. An organic compound ‘A’ (C3H4) on hydration in presence of H2SO4/HgSO4 gives compound
‘B’ (C3H6O). Compound ‘B’ gives white crystalline product (D) with sodium hydrogensulphite.
It gives negative Tollens’ test and positive iodoform’s test. On drastic oxidation ‘B’ gives
compound ‘C’ (C2H4O2) along with formic acid. Identify compounds ‘A’, ‘B’ and ‘C’ and explain
all the reactions. (3)
16. Identify the unknown organic compounds (A) to (E) in the following series of chemical reactions.

CHC6H5 1. O3
(i) (A) + (B)
2. Zn/H2O

dil. NaOH
(ii) (A) + (B) (C) + H2 O
1. O3
(iii) (C) (A) + (D)
2. Zn/H2 O

H2 /Ni
(iv) (D) (E) (5)
D

Answers
1. (c) 2. (b) 3. (a) 4. (c) 5. (b) 6. (c)
zzz

524 Xam idea Chemistry–XII