Solution

ALDEHYDES KETONES AND CARBOXYLIC ACIDS

Class 12 - Chemistry
1. To distinguish between formic acid (HCOOH) and acetic acid (CH3COOH), use tollens test (silver mirror test,
tollens reagent = ammonical silver nitrate [Ag(NH3)2]OH solution) ) or fehling solution . Formic acid gives
positive test indicated by the formation of a silver mirror( Silver oxide precipitate on the walls of the test tube)
but acetic acid fails to form a silver mirror. This is because the formic acid behaves as an aldehyde as there is a
CHO group the other side of the OH group and it is easily oxidised to CO2.

HC OOH + 2 [Ag (N H3 )2 ] OH → 2Ag + 2H2 O + C O2 + 4N H3

C H3 C OOH + 2 [Ag (N H3 ) ] OH → N o reaction

2

2.

2-hydroxybenzoic acid
3. The IUPAC name of CH3-CH=CH-CHO is But-2-en-1-al.
4. The IUPAC name is 2-methylpropan-1-al.
5. 3,3,5-Trimethylhexan-2-one
4 3 2 1

6. C H3 − C H − C H2 − C OOH
|

OH

IUPAC Name: 3-hydroxybutanoic acid

7.

8. In Hoffmann bromamide reaction, an amide on reacting with bromine in alkali solution, gets converted into a
primary amine that has one carbon less than the starting amide. It is used to reduce the carbon numbers in an
organic molecule. For example: conversion of acetamide to methylamine;

9. Increasing order of acidic character is:

Cresol < Phenol < Benzoic Acid

10.

11. Gattermann-Koch reaction is formylation (introduction of -CHO group) to the benzene nucleus i.e benzaldehyde
by treating with anhydrous AlCl3.
Friedel-Crafts acylation reaction is the introduction of RCO- group in the benzene ring.

In Friedel-Crafts acylation reactions, the benzene is treated with an acid chloride in the presence of anhydrous
AlCl3. So, Gattermann-Koch reaction can be considered similar to Friedel-Crafts acylation reaction.

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12. i. 3-Methylpent-2-ene-1, 5-dioic acid
ii. 6-Bromo-3-hydroxy-5-nitrobenzoic acid
13. i. The increasing order of their reactivity towards nucleophilic addition reaction is

ii. The correct increasing order of their acidic character is:

O Cl O F O

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C H3 − C − OH < C H2 − C − OH < C H2 − C − OH

14. A carbonyl group is an organic functional group composed of a carbon atom double-bonded to an oxygen atom. It
is represented as > C = O. The simplest carbonyl groups are aldehydes and ketones. The carbonyl carbon is prone
to additions and nucleophilic attack because or carbon's positive charge and oxygen's negative charge, as shown
in its resonating structures:

15. i. Formula of Hexaamminecobalt (III) sulphate is [Co(NH3)6]2(SO4)3.

ii. Formula of Potassium trioxalatochromate (III) is K3[Cr(C2O4)3].
16. When C6H5CH2Br reacts with Mg in dry ether, it will forms Grignard reagent C6H5CH2MgBr. When this Grignard
reagent reacts with CO2 , it forms the salt of carboxylic acid which in turn give corresponding carboxylic acid
after acidification with mineral acid.
O

dry ether (i)CO2 ||

C6 H5 C H2 Br + M g −−−−−→ C6 H5 C H2 M gBr −−−−−→ C6 H5 C H2 − C − OH

+
(ii)H3 O

17. Only aldehydes are oxidized by Tollen's reagent.

18. Completed reaction are given below:

Zn

i. R-CHO −−→ R-CH3 + H2O (Clemmensen reduction)

HCl

ii.

+ HNO2 ⟶ H3C-COOH + NH3

19. i. 2-Phenylacetaldehyde
ii. 2-Bromobutanoic acid

20. i.

ii.

21. i. C6 H5 C OOH + SOC l2 → C6 H5 C OC l + S O2 + HC l

Benzoic acid T hionyl chloride

red P

ii. C H3 C OOH + 6HI −−−→ C H3 − C H3 + 3I2 + 2H2 O

Acetic acid Ethane

iii. 2C H3 C OOH + Zn → (C H3 C OO)2 Zn + H2

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22. a. Salicylic acid is treated with acetic anhydride in the presence of H+ to give aspirin.

b. Anisole is treated with CH3Cl/anhydrous AlCl3 to obtain ortho and para substitued methylated anisole.

c. Phenol in the presence of acidified sodium dichromate gives benzoquinone.

23. Compound 'A' has characteristic odour that means it can be benzaldehyde, which undergo cannizzaro reaction
with NaOH to give alcohol and sodium salt of acid. Compound 'B' can be alcohol as it contain only one oxygen
atom which on oxidation gives back compound 'A'. Compound 'C' can be sodium salt of benzoic acid which on
heating with sodalime yields aromatic compound 'D', which may be benzene. Reaction involved are given below

24. 1. C5 H5 N H + C rO3 C l− (P C C ) (PCC is pyridinium chlorochromate, is a better reagent for selective oxidation
of primary alcohols to aldehydes stage only and it gives good yield of aldehydes.)
2. K2 C r2 O7 in acidic medium (strong oxidizing agent)
3. C rO2 C l2 , H2 O (Etard Reaction: Chromyl chloride(CrO2Cl2) oxidizes methyl group to a chromium complex,
which on hydrolysis gives corresponding benzaldehyde)
4. DIBALH (Di-isobutyl aluminium hydride) (mild reducing agent) followed by hydrolysis.
25. The molecular formula of the compound is C8H8O. As A does not give Tollens or Fehling's test. It must be a ketone.
It gives a positive test with 2, 4-DNP, and iodoform test. It means it is methyl ketone. B is iodoform and C is
benzoic acid.

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26. This is cross aldol condensation reaction.
(i) dil NaOH

C H3 C HO + C H3 C H2 C HO −−−−−−−−→ C H3 C H = C HC HO + C H3 C H2 C H = C − C HO +
|
(ii) Heat

CH3

C H3 C H = C − C HO + C H3 C H2 C H = C HC HO
|

CH3

27. To begin with both ethanol and phenol react with PCl5 to give the corresponding chlorophosphate esters.

Since in ethanol, the newly formed bond has only single bond character, therefore, nucleophilic attack by Cl- ion
occurs easily on chlorophosphate ester (i) to give chloroethane.

However, in the case of phenol, bonds have some double bond character due to resonance and hence are difficult
to break. Here a subsequent nucleophilic attack by C6H5OH occurs on the chlorophosphate ester (II) to form
intermediate (III). Further nucleophilic attack by C6H5OH on (III) does not occur due to steric hindrance; instead
intermediate (III) undergoes hydrolysis by water to form triphenylphosphate.

28. i.

ii.

29.

30.

Since (D) is a carboxylic acid with one carbon only, it is HCOOH. As it is obtained from (C) acidification, (C) COONa
and (A) is HCHO which on treatment with strong base (NaOH) gives CH3OH & HCOONa. This is Cannizzaro
reaction in which formaldehyde undergoes self oxidation and reduction(disproportion) on treatment with

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 concentrated alkali. The reactions are as follows:-

31. i. IUPAC name: Heptan-2-one Common name: Methyl n-propyl ketone

ii. IUPAC name: 4-Bromo-2-methylhexanal Common name: γ − Bromo − α− methylcaproaldehyde
iii. IUPAC name: Heptanal Common name: heptanaldehyde
iv. IUPAC name: 3-phenylprop-2-enal Common name: β-Pheynolacrolein
v. IUPAC name: Cyclopentanecarbaldehyde Common name: Cyclopentanealdehyde
32. i.

The +I effect of the alkyl group increases in the order:

Ethanal < Propanal < Propanone < Butanone
The electron density at the carbonyl carbon increases with the increase in the +I effect. As a result, the
chances of attack by a nucleophile decrease. Hence, the increasing order of the reactivities of the given
carbonyl compounds in nucleophilic addition reactions is:
Butanone < Propanone < Propanal < Ethanal
ii.

The +I effect is more in ketone than in aldehyde. Hence, acetophenone is the least reactive in nucleophilic
addition reactions. Among aldehydes, the +I effect is the highest in p-tolualdehyde because of the presence of
the electron-donating -CH3 group and the lowest in p-nitrobezaldehyde because of the presence of the
electron-withdrawing -NO2 group. Hence, the increasing order of the reactivities of the given compounds are:
Acetophenone < p-tolualdehyde < Benzaldehyde < p-Nitrobenzaldehyde
33. As 'A' does not give Fehling's or Tollen's test so it does not have - CHO group but it gives positive iodo form test and
DNP test so it has C H3 − C − group.
||
O

So 'A' is

B is carboxylic acid obtained by the oxidation of 'A' with H2CrO4. So 'B' is

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