CBSE

Class 12 Chemistry
Important Questions
Aldehydes, Ketones and Carboxylic Acids

CONCEPTUAL QUESTIONS

1. Although phenoxide ion has more no. of resonating structures than carboxylate ion,
even though carboxylic acid is a stronger acid why?
Ans:- The phenoxide ion has non-equivalent resonance structures in which –ve charge is
at less electronegative C atom and +ve charge as at more electronegative O-atom.
In carboxylate ion –ve charge is delocalized on two electronegative O-atoms hence
resonance is more effective and a stronger acid.

2. Why Corboxylic acid have higher boiling point than alcohols as alcohol forms
strongest inter molecular hydrogen bonding?
Ans. As Corboxylic acid forms a dimer due to which their surface area increases and
forms strong intermolecular H-bonding- It having more boiling point than alcohols.
3. There are two-NH2 group in semicarbazide . However only one is involved in
formation of semicarbazones. Why?

Ans.

Due to resonance one NH2 group undergoes or involved in resonance and hence can’t
participate in the formation of semicarhazone.

Long pair of NH2 group is not involved in resonance and is available for nucleophillic

attack
4. Why does solubility decreases with increasing molecular mass in carboxytic acid?
Ans. Because of increase in alkyl chain length which is hydrophobic in nature. Hence

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 solubility decreases.
5. Why are aldehydes are more reactive than ketones when undergo nucleophillic
addition reaction?
Ans.
a. + I effect:- The alkyl group in Ketones due to their e-releasing character decrease the
+ve charge on C-Atom and thus reduce its reactivity.
b. Steric hinderance:- Due to steric hinderance in ketones they are less reactive.

6. Why PCC cannot oxidise methanol to methanoic acid and while KMNO4 can?

Ans. This is because PCC is a mild oxidising agent and can oxide methanol to methanal
only.
While KMNO4 being strong oxidising agent oxidises it to methanoic acid.

7. During preparation of esters from a carboxylic acid and an alcohol in the presence
of acid catalyst water or ester formed should be removed as soon as it is formed.
Ans. The formation of esters from a carboxylic acid and an alcohol in the presence of
acid catelyst in a reversible reaction.
R – COOH + R′OH H2SO4 R – COOR′ + H2O

To shift the equilibrium in forward direction, the water or ester formed should be
removed as fast as it is formed.
8. Why HCOOH does not give HVZ reaction while CH3COOH does?

Ans. CH3COOH contains α-hydrogens and hence give HVZ reaction but HCOOH does not

contain α-hydrogen and hence does not give HVZ reaction.

9. Suggest a reason for the large difference in the boling point of butanol and butanal
although they have same solubility in water.
Ans. Because Butanol has strong intermolacular H-bonding while butanal has weak
dipole-dipole interaction.
However both of them form H-bonds with water and hence are soluble.
10. Would you expect benzaldehyde to be more reactive or less reactive in
nuderophillic addition reaction than propanol. Explain.
Ans. C-atom of Carbonyl group of benzaldehyde is less electrophilic than Catom of

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 Carbonyl group in propanol. Polarity of Carbonyl group is in bonzaldehyde reduced due
to resonance making it less reactive in nucleophillic addition reactions.

11. Why does methanal not give aldol condensation while ethanol gives?
Ans. This is because only those compounds which have α-hydrogen atoms can undergo
aldol reaction ethanol pessess α-hydrogen and undergoes aldol condensation Methanal
has no alpha hydrogen atoms hence does not undergo aldol condensation.
12. Why does methanal undergo cannizaro’s reaction?
Ans. because it does not possesses α-hydrogen atom.
13. Which acid is stronger and why?
F3C-C6H4COOH and CH3C6H4COOH

Ans. has strong (-I) effect Whereas, has strong (+I)effect

Due to greater stability of F3CC6H4COO ion over CH3-C6H4COO ion

CF3 C6H4COOH is much stronger acis than CH3-C6H4COOH.

14. Explain why O-hydroxy benzaldehyde is a liquid at room temperature while p-

hydroxy benzaldehyde is a high melting solid.
Ans. Due to intramolecular H-bonding in O-hydroxy benzaldehyde exists as discrete
molecule whereas due to intermolecular H-bonding p-hydroxy benzaldehyde exist as
associated molecules. To break this intermolecular H-bonds a large amount of energy is
needed. Consequently P-isomer has a much higher m.p. and b.p. than that of O-isomer. As
a result O-hydroxy benzaldehyde is liquid.
15. Why is the boiling point of an acid anhydride higher than the acid from which it is
derived?
Ans. Acid anhydrides are bigger in size than corresponding acids have more surface area
more van der Waals. Force of attraction hence have higher boiling point.
16. Why do Carboxylic acids not give the characteristic reactions of a carbonyl group?
Ans. Due to resonance, It doesn’t give the characteristics reactions of carbonyl group. It
does not have free

17. Cyclohexanone forms cyanohydrin in good yield but 2,2,6 trimethyle cyclo-hexanone

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 does not. Why?
Ans. In 2,2,6 trimethyl cyclohexaunone there is strearic hinderance of 3 methyl groups, It
does not form cynohydrin in good yield.
18. Why is carboxyl group in benzoic acid meta directing?
Ans. In benzoic acid the Carboxyl group is meta directing because it is electron-
withdrawing
There is +ve charge on ortho acid para positions
Electrophillic substitution takes place at meta-position.
19. Treatment of Benzaldehyde with HCN gives a mixture of two isomers which cannot
be separated even by careful fractional distillation. Explain why?
Ans. It is because we get two optical isomers which have same physical Properties Cannot
be Separated by Fractional distillation.

20. Sodium Bisulphite is used for the purification of aldehydes and Ketones. Explain.
Ans. Aldehydes and Ketones form addition compounds with NaHSO3 whereas impurities

do not. On hydrolysis we get pure aldehydes and Ketones back.

21. Why pH of reaction should be carefully controlled while preparing ammonia

derivatives of carbonyl compound?
Ans. In strongly acidic medium ammonia derivatives being basic will react with acids
and will not react with carbonyl compound. In basic mesium, OH will attack carbonyl
group.pH of a reaction should be carefully controlled.

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22. Why formic acid is stronger acid than acetic acid?
Ans. Due to +I effect, CH3- group in acetic acid increases e- density on carbon atom which
makes it. Weak acid. While in formic acid no such pushing group is present, hence is
more stronger acid than acetic acid.
23. Why is oxidation of alcohols to get aldehydes carried out under controlled
conditions?
Ans. It is because aldehydes get further oxidised to acids, oxidation of alcohols to
aldehydes needs to be controlled.
24. Why the oxidation of toluene to benzaldehyde with CrO3 is carried out in the

presence of acetic anhydride.

Ans. If acetic anhydride is not used we will get benzoic acid. Acetic anhydride used to
prevent oxidation of benzaldehyde to benzoic acid.
25. Melting point of an acid with even no. of carbon atoms is higher than those of its
neighbour with odd no. of carbon atoms.
Ans. They fit into crystal lattice more readily than odd ones that is why they have higher
lattice energy and higher melting point.
26. Why do aldehydes have lower boiling point than corresponding alcohols?
Ans. alcohols have lower boiling point as they are not associated with intermolecular
whereas alcohols are associated with intermoleculer H-bonding Aldehydes have lower
B.p.
27. Why do aldehydes behave like polar compounds?
Ans.

28. Most aromatic acids are solids while acetic acid and others of this series are liquids.
Explain why?
Ans. Aromatic acids have higher molecular weight, More van-der waals force of
attracrtion as compared to aliphalic acids They are solids.
29. ethers possess a dipole moment ever if the alkyl radicals in the molecule are
identical. Why?
Ans. It is because ethers are bent molecles, dipole do not get cancelled.

30. Why does acyl chlorides have lower Boling point than corresponding acids?

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 Ans. Acyl chlorides are not associated with intermolecular H-bonding They have lower
boiling point.
31. Why ethers are stored in coloured bottles?
Ans. They are stored in coloured bottles. In presence of sunlight they react with oxygen
to form peroxides which may cause explosion.
32. Why formaldehyde cannot be prepared by Rosenmund’s reduction?
Ans. Because the formyl chloride thus formed is unstable at room temperature. Cannot
be prepared by Rosenmund reduction.

1. An organic compound (A) {C8H16O2} was hydrolysed with dilute sulphuric acid to

give a carboxylic acid (B)and an alcohol (C). Oxidation of (C)with chromic acid
produced (B).(C) on dehydration gives but-1-ene .Identity A,B,C
Ans-:

CH3CH2CH2CH2OH CH3CH2CH=CH2 (bute - 1 ene)

2. An organic compound with the molecular formula C9H10O forms 2,4 DNP derivative

reduces tollens reagent and undergoes cannizaro reaction. on vigorous oxidation ,it
gives 1,2 benzenecarboxylic acid . identify the compound.
Ans:-

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3. An organic compound (A) with molecular formula C8H8O forms an orange-red

precipitate with 2,4 DNP reagent and gives yellow precipitate on heating with iodine
in the presence of sodium hydroxide. It neither reduces tollen’s or fetiling’s reagent
, nor does it decolourise bromine water or baeyer’s reagents .On drastic oxidation
with chromic acid .it gives a carboxylic acid (B) having molecular formula C7H6O2.

Identify the compounds (A) and (B).

Ans.

4. Two moles of organic compound A on treatment with a strong base gives two
compounds B and C. Compound B on dehydration with cu gives A while acidification

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 of C yields carboxylic acid D having molecular formula of CH2O2. Identify the

compounds A, B, C, D
Ans:-

5. An aliphatic compound ​A ’with a molecular formula of C3H6O reacts with

phenylhydrazine to give compound ​B’ . Reaction of ​A’ with I2 in alkalene medium on

warming gives a yellow precipitate ​C’. Identify the component A,B,C

Ans:- CH3COCH3 + C6H5 NH - NH2 →

6. A component ‘​A’ with molecular formula C5H10O gave a positive 2, 4 DNP test but a

negative tollen’s reagents test . It was oxidised to carboboxylic acid ​B’ with
molecular formula C3H602 when treated with alkalines KMnO4 under vigrous

condition . sodium salt of ​B’ gave hydrocarbon ​C’ on kolbe electrolysis reduction.
Identify A , B, C and D.
Ans: -

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7. An organic compound ​A’ has the molecular formula C5H10O. It does not reduce

fehling’s solution but forms a bisulphite compound. It also gives positive Iodoform
test. What are possible structure of ​A’? Explain your reasoning.
Ans-: It does not reduce fehling’s solution but forms bisulpphite compound so it is a
ketone therefore it gives positive iodoform test therefore it is methyl ketone.
8. An organic compound ​‘A’ which has characteristic odour , on treatment with NaOH
forms two compounds ‘​B’ and ​C’. Compound ​B’ has the molecular formula C7H8O

which on oxidation gives back compound ​‘A’. Compound ‘C’ is the sodium salt of an
acid which when heated with soda lime yields an aromatic hydrocarbon ​D’. Deduce
A, B, C, D
Ans.

9. An organic compound ​‘A’ is resistant to oxidation forms an oxidation forms a

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 compound 'B​(C3H80) on reduction.​ ‘B'reacts with HBr to form a bromide ​C’ which on

treatment with alcoholic KOH forms an alkene ​‘D’ (C3H6). Deduce A,B,C,D.

Ans: -

10. Eherial solution of an organic compound 'A’ when heated with magnesium gave 'B’
on treatment with ethanal followed by acid hydrolysis gave 2-propanol .Identify the
compound 'A​. What is 'B' known as?

Ans: -

11. Identify A, B, C, D

Ans. A = CH3CH2CHO

B = CH3CH = CH - CH3

C =

D = CH3 - C = C - CH3

12. Primary alkyl halide C4H9Br (A) reacted with alcoholic KOH to give compound (B) is

reacted with HBr to give (C) which is an isomer of (A). When (A) is reacted with
sodium metal it gives compound (D) C8H18 that was different from the compound

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 formed when n-butyl bromide is reacted with sodium . Give the formula of (A) and
write equations.

Ans: -

C is the isomer of A

13. An organic compound 'A’ having molecular formula C4H8 on treatment with

dil.H2SO4 gives 'B​’. ​B​on treatment with conc. HCL and anhydrous ZnCl2 gives C and

on treatment with sodium ethoxide gives back A.Identify A, B, C.

Ans: - CH3CH = CH – CH3 + H20 (B)

(A) CH3 – CH – CH2 – CH3

14. An aromatic compound A on treatment with aqueous ammonia and heating forms
compound B which on heating with Br2 and KOH forms a compound C of molecular

formula C6H7N. Identify A, B, C.

Ans: -

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15. Two isomeric compound A and B having molecular formula C15H11N, both lose N2 on

treatment with HNO2 and gives compound C and D. C is resistant to oxidation but

immediately responds to oxidation to lucas reagent after 5 minutes and gives a

positive Iodoform test. Identify A and B.
Ans: -

But ‘D’ respond to lucas reagent in 5 minutes.

CH3 - CH(OH) - CH2 - CH + I2 + NaOH → CHL3 + CH3 - CH2 COONa

16. An organic compound ​A’ having molecular formula C2H5O2N reacts with HNO2 and

gives C2H4O3N2. On reduction ​A’ gives a compound ‘B’ with molecular formula

C2H7N.​C’ on treatment with HNO2 gives ​C’ which givespositive idoform test . Identify

A, B, C.

Ans :-

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17. An organic compound ​A’ having molecular formula C3H5N on reduction gave

another compound ​B’. The compound B on treatment with HNO2 gave propyl

alcohol. B on warming with CHCl3 and alcoholic caustic potash give the offensive

smelling C. Identify A,B,C HNO2

Ans:-

18. Idomethane reacts with KCN to form a major product A Compound ​A’ on reduction
in presence of LiAlH4 forms a higher amine 'B’. Compound B on treatment with

CuCl2 forms a blue colure complex C. Identify A, B, C

Ans.

19. An aliphatic compound A with molecular formula C2H3Cl on treatment with AgCN

gives two isomeric compounds of unequal amount with the molecular formula
C3H3N. The minor of these two products on complete reduction with H2 in the

presence of Ni gives a compound ‘B’ with molecular formula C3H9N.Identify the

compounds.
Ans:-

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20. A compound ‘X’ having molecular formula C3H7NO reacts with Br2 in presence of

KOH to give another compound Y. the compound Y reacts with HNO2 to form

ethanol N2 gas. Identify X,Y,

Ans:-

21. A compound ​A’ of molecular formula C3H7O2N reaction with Fe and conc, HCl gives

a compound ​B’ OF molecular formula C3H9N. Compound ​B’ on treatment with

NaNO2 and HCl gives another compound ​C’ of molecular formula C3H8O. The

compound C’gives effervescences with Na on oxidation with CrO3.The compound ​C’

gives a saturated aldehyde containing three carbon atom deduce A,B,C.

Ans: -

22. A Chloro compound ​A’ on reduction with Zn – Cu and alcohol gives the hydro carbon
(B) with five carbon atom.When ​A’ is dissolved in ether and treated with sodium
2,2,5,5 tetramethyl hexhane is formed structure of A and B?
Ans.

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 IDENTIFY A, B, C

1.

Ans. A= CH3CONH2, B = CH3NH2, C = CH3OH

2.

Ans. A = C6H5NH2, B =C6H5N2+Cl-,

3.

Ans. A = CH3CH2CN, B =CH3CH2-CH2NH2, C = CH3CH2CH2OH

4.

Ans. A= C6H5NH2, B= C6H5N2+Cl-, C= CH3CH2CH2OH

5.

Ans. A = C6H5CN, B = C6H5COOH, C= C6H5CONH2

6.

Ans. A= CH3CH2CN, B = CH3CH2CONH2, C = CH2CH2NH2

7.
Ans.

8.

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 Ans. C6H5NO2 = A

9.

Ans. A = CH3CONH2, B = CH3NH2, C = CH3OH

10.

Ans.

11.

Ans. A= CH3CH2COONH4, B= CH3CH2CONH2, C= CH3CH2NH2

12.
Ans. A = CH3Cl, B = CH3NC, C= CH3-CH2-NH-CH3

13.

Ans. A = CH3COOH, B = CH3CH2OH

14.

Ans.

15.

Ans.

16.

Ans.

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17.

Ans.

VERY SHORT ANSWER TYPE QUESTIONS 1 MARK QUESTIONS

1. Name the reaction and the reagent used for the conversion of acid chlorides to the
corresponding aldehydes.
Ans. Name : Rosenmund‘s reaction Reagent : H2 in the presence of Pd (supported over

BaSO4) and partially poisoned by addition of Sulphur or quinoline.

2. Suggest a reason for the large difference in the boiling points of butanol and
butanal, although they have same solubility in water.
Ans. The b.p. of butanol is higher than that of butanal because butanol has strong
intermolecular H-bonding while butanal has weak dipole-dipole interaction. However
both of them form H-bonds with water and hence are soluble.
3. What type of aldehydes undergo Cannizaro reaction?
Ans. Aromatic and aliphatic aldehydes which do not contain α- hydrogens.
4. Out of acetophenone and benzophenone, which gives iodoform test? Write the
reaction involved. (The compound should have CH3CO-group to show the iodoform

test.)

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 Ans. Acetophenone (C6H5COCH3) contains the grouping (CH3CO attached to carbon) and

hence given iodoform test while benzophenone does not contain this group and hence
does not give iodoform test.

5. Give Fehling solution test for identification of aldehyde gp (only equations). Name
the aldehyde which does not give Fehling‘s soln. test.

Ans. R — CHO — 2 Cu2+ + 5 OH– → RCOO– + Cu2O + 3 H2O Benzaldehyde does not give

Fehling soln. test. (Aromatic aldehydes do not give this test.)

6. What makes acetic acid a stronger acid than phenol?
Ans. Greater resonance stabilization of acetate ion over phenoxide ion.
7. Why HCOOH does not give HVZ (Hell Volhard Zelinsky) reaction but CH3COOH does?

Ans. CH3COOH contains α- hydrogens and hence give HVZ reaction but HCOOH does not

contain α-hydrogen and hence does not give HVZ reaction

8. During preparation of esters from a carboxylic acid and an alcohol in the presence
of an acid catalyst, water or the ester formed should be removed as soon as it is
formed.
Ans. The formation of esters from a carboxylic acid and an alcohol in the presence of
acid catalyst in a reversible reaction.

To shift the equilibrium in the forward direction, the water or ester formed should be
removed as fast as it is formed
9. Arrange the following compounds in increasing order of their acid strength. Benzoic
acid, 4-Nitrobenzoic acid, 3, 4-dinitrobenzoic acid, 4-methoxy benzoic acid.
Ans. 4-methoxybenzoic acid < benzoic acid < 4-nitrobenzoic acid <4, dinitrobenzoic acid.
10. How is tert-butyl alcohol obtained from acetone?
Ans.

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SHORT ANSWER TYPE QUESTIONS 2/3 MARKS QUESTIONS

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

Explain by giving reasons.
CH3CHO, CH3CH2OH, CH3OCH3, CH3CH2CH3.

Ans. The molecular masses of all these compounds are comparable:

CH3CHO (44), CH3CH2OH (46), CH3COCH3 (46), CH3CH2CH3 (44).

CH3CH2OH exists as associated molecule due to extensive intermolecular hydrogen

bonding and hence its boiling point is the highest (351 K). Since dipoledipole interaction
are stronger in CH3CHO than in CH3OCH3, hence boiling point of CH3CHO (293 K) is much

higher than that of CH3OCH3 (249 K). Further, molecules of CH3CH2CH3 have only weak

Vander Waals forces while the molecules of CH3OCH3 have little stronger dipole-dipole

interactions and hence the boiling point of CH3OCH3 is higher (249 K) than that of

CH3CH2CH3 (231 K).

Thus the overall increasing order of boiling points is :

CH3CH2CH3 < CH3OCH3 < CH3CHO < CH3CH2O

2. Which acid of each pair shown here would you expect to be stronger?
CH3CO2H or FCH2CO2H

Ans.

Thus 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.

3. Which acid is stronger and why?

Ans.

CH3 - C6H4 - COOH

F3C - C6H4 - COOH,
CH3 has a weak (+1) effect.
A. CF3 has a strong (-I) effect.
It stabilizes the carboxylate ion by
It stabilizes the carboxylate ion by
intensifying the -ve

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 dispersing the -ve charge.

4. Arrange the following compounds in increasing order of their reactivity towards

HCN. Explain it with proper reasoning. Acetaldehyde, Acetone, Di-tert-butyl ketone,
Methyl tert-butyl ketone.
Ans. Addition of HCN to the carboxyl compounds is a nucleophilic addition reaction.
The reactivity towards HCN addition decreases as the + I effect of the alkyl groups
increases and/or the steric hindrance to the nucleophilic attack by CN– at the carboxyl
carbon increases. Thus the reactivity decreases in the order.

——————— + I effect increases———————

——————— Steric hindrance increases———————
——————— Reactivity towards HCN addition decreases —————
In other words, reactivity increases in the reverse order, i. e.
Ditert-butyl Ketone < tert-Butyl methyl Ketone < Acetone < Acetaldehyde
5. Explain why o-hydroxybenzaldehyde is a liquid at room temperature while p-
hydroxybenzaldehyde is a high melting solid.
Ans. Due to interamolecular H-bonding ortho-hydroxy benzaldehyde exists as discrete
molecule whereas due to intermolecular H-bonding, p- hydroxybenzaldehyde exists as
associated molecules. To break these intermolecular H-bonds, a large amount of energy is
needed. Consequently, p-hydroxybenzaldehyde has a much higher m.p. and b.p. than
that of o-hydroxy benzaldehyde. As a result, o-hydroxy benzaldehyde is a liquid at room
temperature while p-hydroxy benzaldehyde is a high melting solid.

LONG ANSWER TYPE QUESTIONS 5 MARKS QUESTIONS

1. Arrange the following compounds in order ot their property as indicated.

Ans.
i. Acetaldehyde, Acetone, di-tert-butyl ketone, Methyl tert-butyl ketonereactivity
towards HCN
di-tert-butyl ketone < Methyl tert-butyl ketone <Acetone <Acetaldehyde

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 aldehydes are more reactive towards nucleophilic addition across the >C=O
due to steric and electronic reasons.
Sterically the presence of two relatively large substituents inketones hinders
the approach of nucleophile to carbonyl carbon than in aldehydes having only
one such substituent.
Electronically , the presence of two alkyl groups reduces the electrophilicity of
the carbonyl carbon in ketones.
ii. CH3CH2CHBrCOOH, CH3CHBrCH2COOH, (CH3)2CHCOOH, CH3CH2CH2COOH acid

strength
(CH3)2CHCOOH<CH3CH2CH2COOH<CH3CHBrCH2COOH< CH3CH2CHBrCOOH

Electron withdrawing groups like –Br increases the acidity of carboxylic aids
by stabilizing the conjugate base through delocalisation of negative charge by
negative inductive effect. The closer the electron withdrawing group to the –
COOH group, greater is the stabilising effect.
Electron donating groups decrease the acidity by destabilizing the conjugate
base.greater the number of –CH3 groups, greater the destabilizing effect and
lower the acidity.
iii. Benzoic acid, 4-Nitrobenzoic acid, 3,4-Dinitrobenzoic acid, 4- Methoxybenzoic acid (
acid strength)

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