ALDEHYDES,KETONES AND CARBOXYLIC ACIDS

A.GIVE REASONS:
1.Why cyclohexanone forms cyanohydrin in good yield but 2,2,6-trimethyl cyclohexanone does
not?
ANS-In 2,2,6 tri -methyl cyclohexanone the presence of three bulky alkyl groups creates steric
hindrance which makes the attack of CN - nucleophile difficult.
2.There are two –NH2 groups in semicarbazide .However only one is involved in the formation
of semicarbazones. Justify.
ANS-The -NH2 group nearer to the carbonyl group undergoes or is involved in
resonance . Hence can't participate in the formation of semicarhazone.
3.Why the water or the ester should be removed as soon as it is formed during the preparation of
esters from a carboxylic acid and an alcohol in the presence of an acid catalyst?
ANS- The formation of esters from a carboxylic acid and an alcohol in the presence of acid
catalyst is a reversible reaction. To shift the equilibrium in forward direction ,the water or ester
formed should be removed as fast as it is formed.
4.Although phenoxide ion has more number of resonating structures than carboxylate ion,
carboxylic acid is a stronger acid than phenol. Why?
ANS- The resonating structures of the carboxylate ion contributes more towards its stability than
those of phenoxide ion .As a result, carboxylate ion is more resonance-stabilized than phenoxide
ion because in the carboxylate ion the –ve charge is delocalized on the electronegative O-atom .
Hence, carboxylic acid is a stronger acid than phenol.
5.Why aldehydes are more reactive than ketones towards nucleophilic reagents?
ANS-Aldehydes are usually more reactive toward nucleophilic substitutions than
ketones because of both steric and electronic effects.
i)In ketones the carbonyl Carbon is surrounded by two alkyl groups on both sides which
produces steric hinderance and makes the attack of the nucleophile difficult.
ii)In ketones the presence of the two +I effect producing alkyl group decreases the positive
charge density(electrophilicity) on the carbonyl C which makes the attack of the nucleophile
difficult.
6.Why electrophilic substitution in benzoic acid takes place at meta position?
ANS-Carboxylic group is a deactivating group. The presence of electron withdrawing carboxylic
group decreases the electron density at ortho and para position. Hence the electrophile attacks
the meta position.
7.Why Carboxylic acids do not give the characterstic reactions of carbonyl group?
ANS- Because the lone pairs on oxygen atom attached to hydrogen atom in the −COOH group
are involved in resonance thereby making the carbon atom less electrophilic. Hence, carboxylic
acids do not give characteristic reaction of carbonyl group.
8.Why Chloroacetic acid is stronger than acetic acid?
ANS- Due to the –I effect of the chlorine atom the polarity of O-H bond increases and the
release of H+ becomes easier. Hence Chloroacetic acid is more acidic.
9.Why pKa of F-CH2-COOH is lower than that of Cl-CH2-COOH?
ANS-Because of F is more electronegative than Cl. Thus the acidic strength of F-CH2-COOH is
more and its pKa value is lower.
10.Why benzaldehyde is less reactive than propanal in nucleophilic addition reactions?
ANS-The carbon atom of the carbonyl group of benzaldehyde is less electrophilic due to
resonance . Hence less reactive.
11.Why is ethanoic acid more soluble than benzoic acid?
ANS- Ethanoic acid is capable of forming hydrogen bonds with water but benzoic acid is not
capable of the forming hydrogen bonding and is not soluble.
12.Why the solubility of aliphatic carboxylic acids decreases with increase in number of carbon
atoms?
ANS-The increase in number of Carbon atoms creates steric hinderance towards H-bonding
with water molecules , hence solubility decreases.
13.Why are lower members of aldehyde and ketones are miscible in water whereas higher
member are almost insoluble?
ANS-The increase in number of Carbon atoms in aldehydes and ketones creates steric
hinderance towards H-bonding with water molecules , hence solubility decreases.
14.Why are aldehydes and ketones have lower boiling point than corresponding alcohol?
ANS-Because of lesser degree of H-bonding amongst the molecules of aldehydes and no
H-bonding amongst the molecules of ketones they have lesser boiling point.
15.Why are alpha hydrogen in carbonyl compounds are acidic in nature?
ANS- i)Due to strong electron -withdrawing effect of the carbonyl group.
ii)The conjugate base is resonance stbilised.
16.Why benzoic acid does not give Friedel Craft’s Reaction?
ANS-Because the carboxylic group is deactivating and the Lewis acid catalyst and carboxylic
group are bonded which hinders the reaction.
17.Why formic acid does not show HVZ reaction?
ANS-Formic acid does not have α-hydrogen atom hence formic acid cannot be halogenated.
18.The HVZ reaction fails to accomplish the fluorination and iodination of carboxylic acids.
Justify.
ANS-Iodine is large, therefore, it can't undergo substitution in the presence of COOH group.
Fluorine is reactive enough to replace multiple hydrogen, thus doesn't undergo HVZ reaction.
19.Why is nitro acetic acid stronger than acetic acid?
ANS-Nitroacetic acid is stronger acid than acetic acid because −I effect of −NO2 group weakens
O−H bond in nitroacetic acid and facilitate the release of H + ions. Since nitroacetic acid is
stronger acid than acetic acid, therefore, it has lower pKa value than acetic acid.
20.Why aldehydes and ketones undergo nucleophilic addition reactions?
ANS-Due to polarity of the carbonyl group aldehydes and ketones undergo nucleophilic addition
reactions.
21.Why benzaldehyde do not reduce Fehling’s solution?
ANS-Benzaldehyde, lacks alpha hydrogen and cannot form an enolate and thus do not give a
positive test with Fehling's solution which is comparatively a weaker oxidizing agent than
Tollen's reagent, under usual conditions. Therefore, it tests negative.
22.Formaldehyde does not take part in Aldol condensation. Why ?
ANS:Formaldehyde does not contain a-hydrogen atom. Therefore it does not take part in aldol
condensation.
22)Why are carboxylic acids more acidic than alcohols or phenols, although they all have
hydrogen atoms attached to an oxygen atom (-0-H)?
ANS- Because the conjugate base of carboxylic acids or the carboxylate ion is stabilised by
resonance. Due to the resonance in carboxylic acids, the negative charge is at the more
electronegative atom (oxygen atom). In alcohols or phenols, the negative charge is on the less
electronegative atoms. Thus, carboxylic acids can release protons easier than alcohols or
phenols.
B.GIVE SUITABLE CHEMICAL TEST TO DISTINGUISH BETWEEN THE
FOLLOWING PAIRS OF COMPOUNDS:-
1.Propanal and Propanone
Ans- Tollen’s Test
Propanal +Tollen’s Reagent (Freshly prepared ammonical silver nitrate solution) → Bright
Silver Mirror is produced.
Propanone doesn’t respond to the above test.

2.Phenol and benzoic acid

Ans- Sodium Bicarbonate Test
When benzoic acid was treated with sodium bicarbonate brisk effervescence of carbondioxide
was observed.
Phenol doesn’t respond to the above test.
OR
Bromine water Test
Phenol when treated with bromine water gives white ppt of 2,4,6 –Tribromophenol.
Benzoic acid doesn’t respond to the above test.

3.Acetophenone and Benzophenone

Iodoform Test
Acetophenone when treated with NaOH/I2 gives yellow ppt of Iodoform.
Benzophenone doesn’t respond to the above test.

4.Benzoic acid and ethylbenzoate

Ans- Sodium Bicarbonate Test
When benzoic acid was treated with sodium bicarbonate brisk effervescence of carbondioxide
was observed.
Ethyl benzoate doesn’t respond to the above test.

5.Pentan-2-one and pentan-3-one

Ans- Iodoform Test
Pentan-2-one when treated with NaOH/I2 gives yellow ppt of Iodoform.
Pentan-3-one doesn’t respond to the above test.

6.Benzaldehyde and acetophenone

Ans- Tollen’s Test
Benzaldehyde +Tollen’s Reagent (Freshly prepared ammonical silver nitrate solution)→ Bright
Silver Mirror is produced.
Acetophenone doesn’t respond to the above test.
7.Ethanal and Propanal
Ans- Iodoform Test
Ethanal when treated with NaOH/I2 gives yellow ppt of Iodoform. (CHI3)
Propanal doesn’t respond to the above test.

8.Acetaldehyde and Benzaldehyde

Ans- Iodoform Test

Acetaldehyde when treated with NaOH/I2 gives yellow ppt of Iodoform. (CHI3)
Benzaldehyde doesn’t respond to the above test.

9.Benzoic acid and Benzaldehyde

Ans-Sodium Bicarbonate Test
When benzoic acid was treated with sodium bicarbonate brisk effervescence of carbondioxide
was observed.
Benzaldehyde doesn’t respond to the above test.
OR
Tollen’s Test
Benzaldehyde +Tollen’s Reagent (Freshly prepared ammonical silver nitrate solution)→ Bright
Silver Mirror is produced.
Benzoic acid doesn’t respond to the above test.
10.Benzaldehyde and Propanal

Ans- Fehling’s Test

Propanal + Fehling’s solution( alkaline solution of CuSO4 containing some Rochelle salt) →
reddish ppt. of cuprous oxide is formed.

Benzaldehyde doesn’t respond to the above test.

C.REACTIVITY ORDER AND ACIDIC STRENGTH:

1..Arrange the following compounds in the increasing order of their boiling points:

a)CH3CH2CH2CHO, CH3CH2CH2CH2OH, H5C2-O-C2H5, CH3CH2CH2CH2CH3.

ANS-CH3CH2CH2CH2CH3 < H5C2-O-C2H5 < CH3CH2CH2CHO < CH3CH2CH2CH2OH

b)CH3-CHO,CH3CH2OH,CH3OCH3,CH3CH2CH3

ANS-CH3CH2CH3 < CH3OCH3 < CH3CHO < CH3CH2OH

2.Arrange the following compounds in increasing order of their reactivity in nucleophilic

addition reactions:

a)Ethanal, Propanal, Propanone, Butanone

ANS- Butanone < Propanone < Propanal < Ethanal

b)Benzaldehyde, p-Tolualdehyde, p-Nitrobenzaldehyde, Acetophenone.

ANS- Acetophenone < p-Tolualdehyde < Benzaldehyde < p-Nitrobenzaldehyde

3.Which acid of each pair shown here would you expect to be stronger?

a)CH3CO2H and CH2FCO2H

ANS- CH2FCO2H

b)CH2FCO2H or CH2ClCO2H

ANS- CH2FCO2H

c)CH2FCH2CH2CO2H or CH3CHFCH2CO2H

ANS- CH3CHFCH2CO2H

d) F3C-------- ------COOH or H3C ------ -------COOH

ANS- i) is more acidic

4.Arrange the following compounds in increasing order of their property as indicated:

a)Acetaldehyde, Acetone, Di-tert-butyl ketone, Methyl tert-butyl ketone(reactivity towards

HCN)

ANS- Di-tert-butyl ketone < Methyl tert-butyl ketone < Acetone < Acetaldehyde

b)CH3CH2CH(Br)COOH,CH3CH(Br)CH2COOH,(CH3)2CHCOOH,CH3CH2CH2COOH (acid
strength)

ANS-(CH3)2CHCOOH < CH3CH2CH2COOH < CH3CH(Br)CH2COOH

< CH3CH2CH(Br)COOH

c)Benzoic acid,4-Nitro benzoic acid ,3,4-Dinitrobenzoic acid,4-Methoxybenzoic acid(acid

strength)

ANS- 4-Methoxybenzoic acid < Benzoic acid < 4-Nitro benzoic acid < 3,4-Dinitrobenzoic acid

5. Arrange the following compounds in increasing order of their acidic strength and Ka value:

a)NO2-CH2-COOH , F-CH2-COOH , Cl-CH2-COOH , CN-CH2-COOH

ANS- Cl-CH2-COOH < F-CH2-COOH < CN-CH2-COOH < NO2-CH2-COOH

b) F-CH2-COOH , Cl-CH2-COOH, Br-CH2-COOH , I-CH2-COOH

ANS- I-CH2-COOH < Br-CH2-COOH < Cl-CH2-COOH < F-CH2-COOH

c) NO2-CH2-COOH , CF3-COOH, CN-CH2-COOH

ANS- CN-CH2-COOH < NO2-CH2-COOH < CF3-COOH

d)CH(Cl)-CH2-CH2-COOH , CH3-CH2-CH(Cl)-COOH , CH3-CH(Cl)-CH2-COOH

ANS- CH(Cl)-CH2-CH2-COOH < CH3-CH(Cl)-CH2-COOH < CH3-CH2-CH(Cl)-COOH

e)(CH3)3CCOOH,CH3CH2COOH,(CH3)2CHCOOH,CH3COOH

ANS- (CH3)3CCOOH < (CH3)2CHCOOH < CH3CH2COOH < CH3COOH

f) CH2=CHCOOH , HC≡C-COOH , C6H5COOH,CH3COOH

ANS- CH3COOH < CH2=CHCOOH < C6H5COOH < HC≡C-COOH

g) Benzoic acid , Acetic acid , Formic acid

ANS- Acetic acid < Benzoic acid < Formic acid

h) p-Nitrobenzoic acid , p-Toluic acid(p-methyl benzoic acid) ,Benzoic acid

ANS- p-Toluic acid < Benzoic acid < p-Nitrobenzoic acid

i) o-Nitrobenzoic acid , m-Nitrobenzoic acid , p-Nitrobenzoic acid

ANS- m-Nitrobenzoic acid < p-Nitrobenzoic acid < o-Nitrobenzoic acid

j) m-Toluic acid , p-Toluic acid , o-Toluic acid

ANS- p-Toluic acid < m-Toluic acid < o-Toluic acid

NOTE :
Decreasing order of Ka value-
CF3COOH > CCl3COOH > Cl2CHCOOH > O2NCH2COOH
> NCCH2COOH > FCH2COOH > ClCH2COOH > BrCH2COOH > ICH2COOH
> HCOOH > ClCH2CH2COOH > C6H5COOH > CH3COOH > CH3CH2COOH

Higher is the Ka value lower is the pKa value

Increasing order of pKa value-

CF3COOH < CCl3COOH < Cl2CHCOOH < O2NCH2COOH
< NCCH2COOH < FCH2COOH < ClCH2COOH < BrCH2COOH < ICH2COOH
< HCOOH < ClCH2CH2COOH < C6H5COOH < CH3COOH < CH3CH2COOH

Structure of Toluic acid:-

Structure of Tolualdehyde:-

D.NAME REACTIONS:

1)Rosenmund’s reduction

2)Stephen reaction

3)Etard reaction
4)Gatterman-Koch reaction

4)Clemmenson’s reduction

5)Wolf-Kishner reduction

6) Tollen’s test

7)Fehling’s test
8)Haloform
)Haloform reaction(Iodoform reaction)

9)Aldol Condensation

10)Cannizarro’s reaction

11)HVZ reaction
E.WORD PROBLEMS:

1) 5.An organic compound A has molecular formula C8H16O2.It gets hydrolysed with dilute
sulphuric acid and gives carboxylic acid B and an alcohol C. Oxidation of C with chromic acid
also produced B. C on dehydration reaction gives but-1-ene.Identify A,B and C and write the
reactions involved.
SOLUTION

2.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 Tollen’s reagent but forms an addition
compound with sodium hydrogen sulphite and gives positive iodoform test. On vigorous
addition, it gives ethanoic acid and propanoic acids. Derive the structure of the compound.
SOLUTION
3.An organic compound with the molecular formula,C 9H10O forms 2,4-DNP derivative, reduces
Tollen’s reagent and undergoes Cannizzaro reaction. On vigorous oxidation , it gives 1,2-
benzene dicarboxylic acid. Identify the compound.
SOLUTION

4.An organic compound A having molecular formula C8H8O forms an orange red precipitate
with 2,4-DNP reagent .Compound “A” gives a yellow precipitate when heated in presence of
Iodine and NaOH along with a colourless compound . ‘A’ does not reduce Tollen’s reagent or
Fehling’s solution nor does it decolourise bromine water. On drastic oxidation of “A” with
chromic acid, a carboxylic acid B of molecular formula C7H6O2 is formed. Identify the
compounds (A) and (B) and explain the reactions involved.
SOLUTION
5.An organic compound ‘A’ with molecular formula C5H8O2 is reduced to n-pentane with
hydrazine followed by heating with NaOH and Glycol. ‘A’ forms a dioxime with hydroxylamine
and gives positive iodoform and Tollen’s test. Identify ‘A’ and give its reaction for Iodoform and
Tollen’s test.

SOLUTION
6.An organic compound ‘A’ with molecular formula C4H8O2 undergoes acid hydrolysis to form
compounds ‘B’ and ‘C’. Oxidation of ‘C’ with acidified potassium permanganate also produces
‘B’.Sodium salt of ‘B’ on heating with sodalime gives methane.
i) Identify ‘A’ , ‘B’ and ‘C’.
ii) Out of ‘B’ and ‘C’ which will have higher boiling point? Give reason.
SOLUTION

ii) B has higher boiling point than C because of its greater degree of intermolecular
H-bonding.

7.An organic compound ‘X’ with molecular formula C5H10O forms 2,4-DNP derivative , does
not reduce Tollen’s reagent but gives positive iodoform test on heating with I2 in the presence of
NaOH. Compound ‘X’ gives ethanoic acid and propanoic acid on vigorous oxidation .Write the
i) structure of the compound X
ii) structure of the product obtained when compound X reacts with 2,4 –DNP reagent.
iii) structures of the products obtained when compound X is heated with I2 in the presence of
NaOH.
SOLUTION
i) X = CH3-C0-CH2-CH2-CH3(pentan-2-one)
ii)

iii)
8.You are given four organic compounds ‘A’ ,’B’ , ‘C’ and ‘D’. The compounds ‘A’ . ‘B’ and
‘C’ forms an orange –red precipitate with 2,4-DNP reagent, Compounds ‘A’ and ‘B’ reduce
Tollen’s reagent while compounds ‘C’ and ‘D’ do not. Both ‘B’ and ‘C’ gives a yellow
precipitate when heated with iodine in the presence of NaOH . Compound ‘D’ gives brisk
effervescence with sodium bicarbonate solution . Identify ‘A’ , ‘B’ and ‘C’ and ‘D’ given the
number of carbon atoms in three of these carbon carbon compounds is three while one has two
carbon atoms.Give an explanation for your answer.

SOLUTION

9.An organic compound X having molecular formula C 4H8O gives orange red precipitate with
2,4-DNP reagent . It does not reduce Tollen’s reagent but gives yellow ppt of iodoform on
heating with NaOH . Compound X on reduction with LiAlH 4 gives compound Y which
undergoes dehydration reaction on heating with conc.H2SO4 to form But-2-ene . Identify the
compound X and Y.

SOLUTION
X= Butan-2-one and Y =Butan-2-ol

10. An aliphatic compound (A) with a molecular formula C3H6O reacts with phenylhydrazine to
give compound (B) . Reaction of (A) with I2 in alkaline solution on warming gives a yellow
precipitate (C) . Identify the compounds A,B and C.
SOLUTION
F.CONVERSIONS:- (Practice only two step conversion)
1)Ethylbenzene to Benzoic acid 2)Acetophenone to Benzoic acid
3)Bromobenzene to Benzoic acid 4)Phenylethene (styrene) to Benzoic acid

5)Ethanal to Butane-1,3-diol 6)Ethanal to But-2-enal

7)Ethanal to But-2-enoic acid 8)Benzene to p-nitrobenzaldehyde
9)Propanone toPropene 10)Benzoic acid to Benzaldehyde
11)Ethanol to 3-Hydroxybutanal 12)Benzene to m-Nitroacetophenon
Nitroacetophenone
13)Benzaldehyde
Benzaldehyde to Benzophenone `14)Bromobenzene to 1-Phenylethano
Phenylethanol
15)Benzaldehyde to 3-Phenylpropan
Phenylpropan-1-ol. `16)Benzaldehyde to α- Hydroxy phenylacetic acid
17)Benzoic acid to m-Nitrobenzyl
Nitrobenzyl alcohol

G.FILL IN THE BLANKS:-

1)
2)

3)