Vidyamandir Classes

Supplementary Booklet - 9/Chemistry [CBSE]

Aldehydes & Ketones Questions Based on CBSE Pattern

Type - 1
1. Draw the structural formula of 1-phenyl propan-1-one molecule.

2. Write the structure of 3-oxopentanal.

3. Write IUPAC name of following compound.
(i) CH3COCH2COCH3 (ii)

4. What is Tollen’s reagent? Write one usefulness of this reagent.

5. Identify A, B and C in the following reaction

dil H 2SO4 dil NaOH 
CH  CH 
HgSO
 A   B  C
4
6. Illustrate the following reactions giving a chemical equation for each.
(a) Cannizzaro’s reaction (b) Clemmenson reduction (c) Reimer-Tiemann reaction.

7. Complete the following reactions by giving the missing starting material, reagent or product as required.

(i) (ii)

(iii)

8. Arrange as directed.
(a) Acetaldehyde, Acetone, Ditertbutyl ketone, Methyl tert butyl ketone – Reactivity towards HCN
(b) Benzaldehyde, p-tolulaldehyde, p-nitrobenzaldehyde, Acetophenone – Reactivity towards nucleophilic
addition.
9. How are the following conversions carried out?
(i) Propanone to propene
(ii) Benzaldehyde from toluene
(iii) Benzoic acid to benzaldehyde
(iv) Benzene to Benzyl alcohol

10. How you will convert

(i) propane nitrile to 1-phenyl propanone
(ii) Bromobenzene to 1-phenyl ethanol.
Supplementary Booklet – 9 1 Chemistry
 Vidyamandir Classes

11. Explain why.

(i) Acetone is highly soluble in water but benzophenone is not.
(ii) Reaction of aldehyde/Ketone with NaHSO3 can be used for their separation and purification.
(iii)  -hydrogen of aldehyde/ketone is acidic in nature.
12. How would you account for the following.
(i) Aldehydes are more reactive than ketones towards nucleophiles.
(ii) The aldehyde and ketones undergoes a number of addition reactions.
13. An organic compound (A) which has characteristic odour, on treatment with NaOH it forms two 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 heated with sodalime it yields an aromatic hydrocarbon (D). Deduce the structures of A, B,
C and D. Write the sequence of reactions involved.
14. How are the following conversions carried out?
(i) Ethanol to Acetone
(ii) Benzene to Acetophenone
(iii) Benzaldehyde to benzophenone
15. An organic compound 'A' contain 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 oxidation it gives ethanoic and propanoic acids. Derive the possible
structure of compound 'A'.
16. Write the mechanism of the addition of Grignard reagent to the carbonyl group of a compound forming an adduct
followed by hydrolysis.

SOLUTIONS - QUESTIONS BASED ON CBSE PATTERN

Type - 1
O
||
1. Ph  CO  CH 2  CH 3 2. CH 3  CH 2  C  CH 2  CHO

3. (i) Pentane-2, 4-dione (ii) Cyclopentane carbaldehyde

4. Ammonical solution of silver nitrate is called Tollen’s reagent. It is used as an oxidizing agent/test for – CHO group.
B  CH 3  C H  CH 2  CHO
5. A  CH3CHO ; | ; C  CH3 CH  CH  CHO
OH
Conc. KOH
6. (a) 2HCHO 
 CH 3OH  HCOOK
formal dehyde Methanol Potassium formate

Zn  Hg
(b)  C  O 
HCl
  CH 2  H 2 O

(c)

Supplementary Booklet – 9 2 Chemistry

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7. (i)

(ii) BH 3 , H 2 O 2 / OH, PCC

(iii) A  ArCOONa , B  CHI3 , C  ArCOOH
8. (a) Ditert butyl ketone < methyl tert-butyl ketone < Acetone < Acetaldehyde
(b) Acetophenone < p-tolulaldehyde < benzaldehyde < p-nitrobenzaldehyde.

OH
9. (i) |
LiAlH 4 conc. H 2 SO 4
CH 3COCH 3 
 CH 3  C H  CH 3  
 CH 3CH  CH 2

(ii) Etard reaction,

(iii)

(iv)

10. (i) H O
CH 3CH 2 CN  C6 H5 MgBr 
 CH 3CH 2  C  NMgBr 
2  CH CH  C  O
3 2
| |
C6 H 5 C6 H 5

(ii)

11. (i) Acetone can make hydrogen bonds with water but benzophenone can not make hydrogen bonds due to
steric hindrance of two phenyl groups.
(ii) Because the bisulphite compounds formed can again be converted back into parent aldehyde or ketone by
reacting with acid or Alkali
(iii) Because the carbanion formed is resonance stabilised.

12. (i) Because two alkyl groups in ketones reduces the positive charge on carbon of the carbonyl group more
effectively than in aldehydes/or sterically, the presence of two relatively large substituents in ketones hinders
the approach of nucleophile to carbonyl carbon than in aldehydes having only one such substituent.
(ii) Because of the presence of the sp2 hybridised orbitals (or   bond ) of carbonyl carbon.

13.

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Cu (i) CH MgBr
14. (i) CH 3CH 2 OH 
573K
 CH 3CHO 
3


 CH3COCH 3
(ii) H 2O / H
(iii) Cu,573K

(ii)

(iii)

15. C 69.77/12 5.81 5.81/1.16 5

H 11.63/1 11.63 11.63/1.16 10
O 18.60/16 1.16 1.16/1.16 1
Empirical formula C5H10O
Empirical formula mass 60 + 10 + 16 = 86. Hence molecular formula C5H10O. It is a ketone as it appears from its
reactions as upon oxidation gives ethanoic acid and propanoic acids, hence the compound is CH 3COCH2CH2CH3.

16.

Adduct

Type - 2
1. Arrange the following compounds in increasing order of their boiling points.
CH3CHO, CH3CH2OH, CH3OCH3, CH3CH2CH3
2. Arrange the following compounds in an increasing order of their reactivity of nucleophilic addition reactions, Ethanal,
propanal, propanone, butanone.
3. Write the mechanism of the given reaction:
4. How will you distinguish between acetone and acetaldehyde?
5. Write Gatterman-Koch reaction. 6. Write Stephen reaction.
7. Arrange the following compounds in increasing order of their reactivity in nucleophilic addition reactions.
Benzaldehyde, p-tolualbenzaldehyde, p-nitrobenzaldehyde, acetophenone
8. Predict the products of the following reactions

(i) (ii)

O
||
H
(iii) RCH  CH  CHO  NH 2  C  NH  NH 2   (iv)

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9. Write structural formulae and names of the four possible aldol condensation products from propanal and butanal. In
each case indicate which aldehyde served as electrophile and which as nucleophile, (self aldol condensation).
O
||
(i)CH3MgBr Na metal CH3  Br
10. Complete the following reaction sequence : CH 3  C  CH 3  (ii)H O
 (A) 
Ether
 (B)  (C)
2

11. How will you convert ethanal into the following compounds?
(i) Butan-1, 3-diol (ii) But-2-enal (iii) But-2-enoic acid

12. An organic compound with molecular formula C9H10O 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.

13.

Identify (A), (B), (C), (D)

14. Write reactions and conditions for the following conversions.

(i) Benzaldehyde to benzophenone (ii) Acetaldehyde to crotonaldehyde
(iii) Propanal to butanone

15. Write down functional isomers of a carbonyl compounds 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? What will be the effect on the concentration of the
product on adding H+ & why.
16. Give reasons:
(i) Hydrazones of aldehydes are prepared in light acidic medium and not in high acidic medium.
(ii) Tollen’s reagent is reduced by benzaldehyde while Fehling’s or Benedict’s solution are not reduced by it.

17. How will you bring about the following conversion in not more than two steps?
(i) Propanone to propene (ii) Ethanol to 3-hydroxy butanal
(iii) Benzene to m-nitroacetophenone (iv) Benzaldehyde to benzophenone
(v) Bromobenzene to 1-pehnyl ethanol (vi) Benzaldehyde to 3-phenyl propan-1-ol

18. Complete each synthesis by giving missing starting material, reagent or products.

H 2 NCONHNH 2
(i) C6 H 5 CHO   (ii)
Benzaldehyde

C6 H5 CHO
Dil. NaOH
(iii) (iv)   

CH 3CH 2 CHO

(v) (vi)

(vii)

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19. Predict the product formed when cyclohexane-carbaldehyde reacts with following reagents.
(i) PhMgBr and then H3O+ (ii) Tollen’s reagent
(iii) Semicarbazide and weak acid (iv) Excess ethanol and acid
(v) Zinc amalgam and dilute hydrochloric acid.

20. (i) Give the chemical tests to distinguish between:

(a) propanol and propanone (b) benzaldehyde and acetophenone
(ii) Arrange the following compound in an increasing order of their property as indicated :
acetaldehyde, acetone, methyl tert-butyl ketone (reactivity towards HCN)
21. (i) Identify A , B and C is the following sequence of the reactions
(i) C H MgCl(i) Conc. H 2SO4 HBr / Peroxide
CH 3CHO 
2 5
(ii) H O
 A   B   C
2
(ii) Predict the structures of products formed when benzaldehyde is treated with
(a) conc. NaOH (b) HNO3/H2SO4 (at 273-383 K)
22. A ketone A (C4H8O) which undergoes a haloform reaction gives compound B on reduction. B on heating with sulphuric
acid gives a compound C which forms mono-ozonide D. D on hydrolysis with zinc dust gives only E. Identify A, B, C,
D and E. write the reactions involved.
Cl NaOH
2  CHCl  6 5 C H COCl
6 6 C H / AlCl
3 D  E .
23. Identify A, B, C, D and E in the given sequence : A  3  B  C 
excess
24. An organic compound A (C3H6O) is resistant to oxidation but forms compound B (C3H8O) on reduction. B reacts with
HBr to form the compound C. C with Mg forms Grignard reagent D which reacts with A to from a product on
hydrolysis gives E. Identify A to E.
25. Give simple chemical tests to distinguish between the following pairs of compounds.
(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

SOLUTIONS - QUESTIONS BASED ON CBSE PATTERN

Type - 2
1. CH3CH2CH3 < CH3OCH3 < CH3CHO < CH3CH2OH
Stronger the attractive forces, higher is the boiling point. Hydrocarbon are nonpolar having weakest attractive forces;
ethers are polar and aldehydes have strong dipolar interaction. Alcohol have maximum intermolecular forces due to H-
bonding.
2, Butanone < propanone < propanal < ethanal (as size of alkyl group increases, the reactivity decreases as electrophilic
character of carbonyl carbon decreases).

3.  : CN   H 2 O
HCN   OH 

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4. CH 3CHO  2[Ag(NH 3 ) 2 ]  3OH   CH 3COO   2H 2O  2Ag   4NH3

Acetaldehyde Tollen 's reagent Silver mirror

Tollen 's reagent

CH 3COCH3  No reaction
Acetone

H O
5. 6. RCN  SnCl2  HCl 
 RCH  NH 
3 RCHO

7. Acetophenone < p-tolualdehyde < benzaldehyde < p-nitrobenzaldehyde

Benzaldehyde & derivatives are more reactive than aromatic ketones. Nitro group, being electron withdrawing
(–R effect) increases reactivity.

8. (i) (ii)

O
||
(iii) R  HC  CH  CH  N  NH  C  NH 2 (iv)

9. (i) Propanal forms a nucleophile (carbanian/enolate ion) and also acts as electrophilic substrate.
OH CH 3
| |
CH 3 CH 2 CHO  CH 3CH 2 CHO 
 CH 3 CH 2 CH  CH  CHO
3 hydroxy  2  methyl pentanal

(ii) Butanal forms a nucleophile (carbanian/enolate ion) and also acts as electrophilic substrate.
OH CH 2 CH 3
| |
OH 
CH 3CH 2 CH 2 CHO  CH3CH 2CH 2CHO 
 CH 3CH 2CH 2 C H  C HCHO

(iii) Propanal acts as electrophilic substrate, whereas butanal forms enolate ion (as nucleophile).
OH CH 2 CH 3
| |
CH 3CH 2 CHO  CH 3CH 2 CH 2 CHO 
 CH 3CH 2  CH  CHCHO
Pr opanal Butanal 2  ethyl 3 hydroxy  pentanal

(iv) Butanal acts as electrophilic substrate, whereas propanal forms enolate ion (as nucleophile).
OH CH 3
| |
CH 3CH 2 CH 2 CHO  CH3 CH 2 CHO 
 CH 3CH 2 CH 2  CH  CH  CHO
Butanal Propanal 2  methyl 3 hydroxy  hexanal

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 
O OH ONa O  CH 3
|| | | |
(i) CH3 MgBr Na metal CH 3  Br
10. CH3  C  CH3   CH3  C CH3 (A)   CH3  C CH3  CH3  C  CH3
(ii) H 2 O Ether SN 2
| | |
CH3 CH3 CH3
(A) (B) (C)
2  methy  2  methoxy propane

4 3 2 1
Dil. NaOH NaBH
11. (i) 2CH 3CHO  
(Aldol condensation)
 CH 3  CHOH  CH 2  CHO  4  CH  CHOH  CH  CH OH
(Reduction) 3 2 2
 aldol  Butan 1,3diol

Dil. NaOH Heat

(ii) 2CH 3CHO  
(Aldol condensation)
 CH 3  CHOH  CH 2  CHO 
H O
CH 3  CH  CH  CHO
3 hydroxy butanol 2 But  2  en 1 al

(i) Dil. NaOH [Ag(NH ) ] OH 

(iii) 2CH 3CHO 
(ii)  H O, 
 CH3CH  CHCHO 
3 2

 CH 3CH  CHCOOH  Ag 
2 Tollen 's reagent, H But  2 enoicacid

12. (i) As the given compound with molecular formula C9H10O forms a 2, 4-DNP derivative and reduces Tollen’s
reagent, it must be an aldehyde.
(ii) As it undergoes cannizzaro reaction, hence CHO group is directly attached to the benzene ring.
(iii) On vigorous oxidation, it gives 1, 2-benzene-dicarboxilic acid, therefore, it must be an ortho-substituted
benzaldehyde. And, the only o-substituted aromatic aldehyde which have C9H10O molecular formula is o-
ethylbenzaldehyde.
Reactions:

13.

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14. (i) Benzaldehyde to benzophenone

(ii) Acetaldehyde to crotonaldehyde

Dil. NaOH heat
2CH 3  C  H   CH 3  CH  CH 2  C  H   CH 3  CH  CH  C  H
|| | || ||
O OH O O
Acetaldehyde 3-hydroxybutanl Crotonaldehyde

(iii) Propanal to butanone

[O] PCl (CH ) Cd
CH 3CH 2 CHO  CH 3CH 2 COOH 
5  CH CH COCl 
3 2
3 2  CH CH COCH
3 2 3
Propanal Butanone

15. (a) Functional isomers of C3H6O are: CH 3CH 2 CHO and CH3 COCH 3
Propanal Propanone

Propanal, CH3CH2CHO will react faster with HCN because there is less steric hindrance and favourable
electronic factors. (More electrophilic than CH3COCH3 due to greater to + I effect of CH3-group).

(b)  CN   H 2 O
The reaction mechanism is as follows: HCN  OH  

The reaction does not lead to completion because it is a reversible reaction. Equilibrium is established.
(c) If a strong acid is added to the reaction mixture, the reaction is inhibited because production of CN– ions is
prevented.
16. (i) In highly acidic medium the –NH2 group of hydrazine gets protonated.
 
NH 2  NH 2  H  
 NH 2  NH3
Hydrazine Pr otonated hydrazine


Due to electron-withdrawing effect of NH 3 group, the lone pair of electrons on the –NH2 group of protonated
hydrazine is not available for nucleophilic attack on the C = O and hence hydrazone formation does not occur.
(iii) Due to + R effect of benzene ring, the electron density in the carbonyl group of benzaldehyde increase. This is
turn, increases the electron density in the C–H bond of aldehyde group. As a result , the C – H bond becomes
stronger and hence only oxidising agent like Tollen’s agents;
Ag (NH3 )2 (E   0.8 V) can oxidise C  H to C  OH to form carboxylic acids but weaker oxidising
Ag / Ag

agents like Fehling’s solution or Benedict’s solution (E  0.18 V) fail to oxidise benzaldehyde to
Cu 2  / Cu 

benzoic acid. In general all three reagents oxidise aliphatic aldehydes but only Tollen’s reagent oxidizes
aromatic aldehydes.

Supplementary Booklet – 9 9 Chemistry

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LiAlH 4 H 2 SO 4 (Conc.)
17. (i) Propanone to propene : CH3COCH 3 2[H]
 CH 3 C HCH3  Heat
 CH 3CH  CH 2
(Propanone) | Propene
OH
Oxidation Aldol
(ii) Ethanol to 3-hydroxybutnal: CH3CH 2 OH 
CrO in anhy. medium
 CH 3CHO  CH 3CH(OH)CH 2 CHO
3 Ethanal 3  hydroxy butanal

(iii) Benzene to m-nitroacetophenone :

Oxidation Ca(OH)2
(iv) Benzaldehyde to benzophenone : C6 H 5 CHO 
KMnO
 C6 H5 COOH 
Heat
 C6 H5 COC6 H 5
Benzaldehyde 4 Benzoic acid Benzopheone

(v) Bromobenzene to 1-phenylethanol :

(vi) Benzaldehyde to 3-phenyl propan-1-ol

O
||
18. (i) C6 H 5 CHO  H 2 NNHCONH 2 
 C 6 H 5 CH  N  NH  C  NH 2  H 2 O
Benzaldehyde semicarbazone Benzaldehyde semicarbazone

(ii)

(iii)

CH 3
(iv) |
Dil. NaOH
C6 H 5 CHO  CH3 CH 2 CHO  
 C6 H 5  CH  C CHO
2  methyl  3 phenyl prop  2  en l al

(v)

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(vi)

(viii)

19. (i)

(ii)

(iii)

(iv)

(v)

20. (a) Propanone, because of the presence of COCH 3 group when treated with NaOH and I2, gives yellow

crystals of iodoform. CH 3COCH 3  4NaOH  3I 2 

 CHI3   CH 3COONa  3NaI  3H 2 O
Propanol (CH3CH2CH2OH) does not contain CH3  CH  group, so it does not give iodoform test.
|
OH
(b) Benzaldehyde contains –CHO group which reduces the Tollen’s reagent into silver mirror.
This test is not given by ketones (acetophenone).

(ii) Methyl t-butyl ketone < acetone < acetaldehyde

i.e., [CH3COC (CH3)3] < (CH3COCH3) < (CH3CHO) (Reactivity towards HCN)
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(i) C2 H5 MgCl
 OMgCl  (ii) H O Conc.H 2SO4
21.(i) CH 3CHO   |   2  CH  CH  C H 
3 2 5 
CH 3  CH  C 2 H 5  |
OH
(A)
HBr / peroxide
CH 3CH  CHCH 3 
 H3C  CH  CH  CH 3
But  2  ene | |
(B)
H Br
2  bromobutane
(C)

(ii) (a)

(b)

22. Since, A give haloform test, it must contains –COCH3 group. Thus, its possible formula is C2H5COCH3. On reduction
its gives 2-butanol which on dehydration give 2-butene (C). Ozonolysis of 2-butene gives only acetaldehyde. The
equation involved are:
[H] Conc. H 2SO 4
CH 3COCH 2 CH 3 
LiAlH 4
 CH 3  CH  CH 2 CH 3   CH 3  CH  CH  CH 3
(A) | (C)
Butan-2-one
OH
(B)

(A) gives iodoform reaction as:

CH 3COCH 2 CH 3  3I 2  4NaOH 
 CHI3   C 2 H 5 COONa  3NaI  3H 2 O

23.

24. The possible structures of the molecular formula C3H6O are CH3COCH3 (acetone) and CH3CH2CHO (propanal), the
former one is resistant to the oxidation. Thus, A is ketone, i.e., acetone.
(i) A on reduction gives B, thus B is a 2 alcohol, i.e., 2-propanol.
LiAlH
CH 3COCH3 
4  CH CH(OH)CH
3 3
(A) 2  propanol (B)

(ii) 2-propanol reacts with HBr to give 2-bromopropane.

OH
|
HBr
CH 3CHCH 3   CH 3CHCH 3
2  propanol |
(B)
Br
2  bromopropane
(C)

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(iii) C (2-bromopropane) gives D (Grignard reagent) with Mg.

Ether
CH 3CHCH 3  Mg   CH 3  CH  CH3
| |
Br MgBr
(D)

(iv) D reacts with acetone (A) to give on adduct which on hydrolysis gives a 3 alcohol (E)

25. (i) Propanal and propanone : Propanone responds to iodoform test whererase propanal (CH3CH2CHO) due to
absence of CH3CO– group does not.
CH 3COCH 3  3NaOI 
 CHI3   CH 3COONa  2NaOH
Sodium (Yellow ppt. Sodium
hypoiodite iodoform) acetate

(ii) Acetophenone and benzophenone : Acetophenone gives positive iodoform test whereas benzophenone
(C6H5COC6H5) does not.

(iii) Phenol and benzoic acid: Benzoic acid reacts with sodium bicarbonate to produce effervescences of carbon
dioxide whereas phenol (C6H5OH) does not.

(iv) Benzoic acid and ethyl benzoate : Benzoic acid reacts with sodium bicarbonate to produce effervescences of
carbon dioxide whereas ethyl benzoate (C6H5COOC2H5) does not.

(v) Pentan-2-one and pentan-3-one : Pentan-2-one responds positively towards iodoform test whereas
pentan-3-one (C2H5COC2H5) does not.

CH 3  CO  CH 2  CH 2  CH3  3NaOI 
 CHI3   CH 3CH 2 CH 2COONa  2NaOH
Pentan-2-one Yellow ppt.

Supplementary Booklet – 9 13 Chemistry

 Vidyamandir Classes

(vi) Benzaldehyde and acetophenone Acetophenone responds towards iodoform test positively wherease
benzaldehyde (C6H5CHO) does not.

(vii) Ethanal and propanal : Ethanal responds positively towards iodoform test whereas propanal (CH3CH2CHO)
does not.

CH 3CHO  3NaOI 
 CHI3   HCOONa  2NaOH
Ethanal Iodoform
(Yellow ppt.)

Supplementary Booklet – 9 14 Chemistry