Carboxylic Acid and Derivatives Tutorial 2024 Semester 1

CATHOLIC JUNIOR COLLEGE

H2 CHEMISTRY (SYLLABUS 9729)
Carboxylic Acid and Derivatives Tutorial
Summary
Carboxylic acids can undergo a variety of reactions to produce new compounds. Complete the summary map and list out the type of reaction that
is occurring for each reaction.

+ H2(g)
Oxidation
K2Cr2O7(or KMnO4), + H2O
dil. H2SO4 (aq), + H2O
Oxidation Acid-base +CO2
heat under reflux Acid-base
NaOH (aq)
K2Cr2O7, Reduction Na2CO3
Redox
dil. H2SO4 (aq), LiAlH4 Na(s),
heat with immediate in dry ether r.t. Nucleophilic substitution
distillation Nucleophilic substitution
Oxidation PCls, rt or SOCl2, CH3NH2,
K2Cr2O7, heat under reflux r.t.
dil. H2SO4 (aq),
heat under reflux H2O, r.t.
Carboxylic acid Hydrolysis
Acyl chloride
Acid-catalysed
hydrolysis CH3CH2OH,
Condensation
dil. H2SO4 (aq), Acidification conc. H2SO4
heat under CH3CH2OH,
dil. H2SO4 heat under reflux
reflux dil. H2SO4(aq), Condensation
r.t.
heat under reflux
Acid-catalysed
NaOH (aq),
heat under hydrolysis
reflux
Base-catalysed
+ NH3 + H2O
hydrolysis

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Carboxylic Acid and Derivatives Tutorial 2024 Semester 1

Self-Practice Questions (may not be discussed in tutorials)

1 Arrange the following acids in order of increasing acid strength:

I. CH3CH2CH2CO2H
II. CH2ClCH2CH2CO2H
III. CH3CH2CHClCO2H
IV. CH3CH2CCl2CO2H

A I, II, III, IV B I, III, II, IV

C IV,III, II, I D IV, II, III, I

Answer: A
I does not contain any electron withdrawing atoms so it is the weakest acid.
Both II and III contain 1 electron withdrawing Cl atom but the Cl atom is nearer to the CO2H
group in III, thus making III a stronger acid as compared to II.
IV is the strongest acid as it has 2 electron withdrawing Cl atoms attached to C atom
adjacent to the CO2H group.

2 Which sequence shows the correct order of decreasing ease of hydrolysis?

A CH3CH2COCl > CH3CH2Cl > CH2=CHCl

B CH3CH2Cl > CH3CH2Br > CH3CH2I

[NJC / MCQ / Q29]

Answer: A
Ease of hydrolysis:
acyl chloride > chloroalkane > Cl attached to a C in a C=C / chlorobenzene
B is incorrect because C-X bond strength decreases down the group and thus
C-Cl > C-Br > C-I, therefore C-I bond is the easiest to hydrolyse.
C is incorrect because C6H5CH2Br is easier to hydrolyse than the other 2.
D is incorrect because C6H5CH2I is easier to hydrolyse than the other 2.

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Carboxylic Acid and Derivatives Tutorial 2024 Semester 1

3 The same carboxylic acid is obtained either by the hydrolysis of a nitrile P or by the oxidation of
alcohol Q. Which of the following pairs could be P and Q?

Nitrile P Alcohol Q
A CH3CH2CN CH3CH2OH
B (CH3)2CHCN (CH3)3COH
C C6H5CH2CN C6H5CH2CH2OH
D C6H5CH(CH3)CN C6H5CH2CH(OH)CH3
[SRJC / MCQ / Q29]
Answer: C
For option A, P and Q do not contain the same number of C atoms thus it is incorrect.
For option B, Q is a tertiary alcohol which cannot be oxidized thus it is incorrect.
For option C, after P undergoes hydrolysis, C6H5CH2CO2H will be formed. After Q undergoes
oxidation of the alcohol(not side chain oxidation), C6H5CH2CO2H will be formed.
For option D, Q is a secondary alcohol which will be oxidised to a ketone instead of a carboxylic
acid upon oxidation.

2) Discussion Questions

[1.2 Physical Properties]

4 The structure of maleic acid is as shown below.

Maleic acid and fumaric acid are stereoisomers with different physical properties.
Suggest a reason why maleic acid is less soluble in water in comparison with fumaric acid.
Intra-molecular hydrogen bonding occurs in maleic acid, which reduce the extent of
inter-molecular hydrogen bonding between maleic acid molecules with water molecules,
hence less soluble in water.

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Carboxylic Acid and Derivatives Tutorial 2024 Semester 1

[2. Acidity of Carboxylic Acids]

5 Arrange the following three compounds in order of increasing pH values of their aqueous solution.
Explain your answer.
(i) CH3CO2H
(ii) CH2ClCO2H
(iii) CH3COCl
pH of CH3COCl < pH of CH2ClCO2H < pH of CH3CO2H

CH2ClCO2H is more acidic than CH3CO2H.

CH3CO2H ⇌ CH3CO2– + H+
CH2ClCO2H ⇌ CH2ClCO2– + H+
The electron-withdrawing Cl atom in CH2ClCO2– (conjugate base) helps to disperse the
negative charge on the oxygen atom of the carboxylate ion better, thereby stabilising
CH2ClCO2– better than in CH3CO2– and thus, decreasing the tendency of CH2ClCO2– to
recombine with H+ to form the undissociated acid.
Hence position of equilibrium lies more to the right, thus the CH2ClCO2H dissociates to a
larger extent and is a stronger acid.

• CH3COCl is the most acidic because it undergoes hydrolysis readily to give HCl which is
a strong acid. Hence, it gives the smallest pH value.
(or show equation for hydrolysis and indicate HCl as strong acid)
CH3COCl + H2O → CH3CO2H + HCl (strong acid)

[3.2 Reactions of Carboxylic Acids involving OH group]

6 For each of the following, suggest a simple chemical test to distinguish one compound from the
other. You should state the reagents and conditions and describe clearly how each compound
behaves for each test.
(i) chloroethane and ethanoyl chloride
Test: Add AgNO3(aq) to each compound separately at room temperature.

Observation:
• With ethanoyl chloride, an immediate white precipitate of AgCl is obtained.
Ag+(aq) + Cl–(aq) → AgCl(s)
• With chloroethane, white precipitate of AgCl is only observed after some time. .

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Carboxylic Acid and Derivatives Tutorial 2024 Semester 1

(ii) CH3CH2CO2H and CH3COCH2OH

Test: Add I2(aq) + NaOH(aq) to each compound separately and heat. (CHI3 test)

Observation:
• With CH3COCH2OH (due to the presence of –CH3CO group), yellow precipitate of CHI3
is obtained.
• With CH3CH2CO2H, no such yellow precipitate is obtained.

(or 2,4-DNPH to test for C=O, carbonate to test for CO2H)

(iii)

and

Test: Add dilute HCl and then heat. Followed by add KMnO4, dilute H2SO4 and heat to
hydrolysed products.
Observations:
O

• With , purple KMnO4 is decolourised.

Note: The hydrolysed products will undergo the following oxidation reaction in KMnO4 and
dilute H2SO4
O CH3 O CH3

HO C CH2 C CH2CH2OH HO C CH2 C CH2COOH

CH3
+ 2 [O] → CH3
+ 2 H2O
O

• With , purple KMnO4 remains purple. (As the alcohol is a tertiary alcohol
and will not undergo oxidation)

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Carboxylic Acid and Derivatives Tutorial 2024 Semester 1

[4. Preparation of Carboxylic Acids]

7 Propose a series of synthesis steps to produce compound X from a suitable carbonyl compound
of your choice and suggest a possible by product.

I: HCN, trace of NaOH, 10 – 20 oC

II: dilute HCl or dilute H2SO4, heat under reflux
III: CH3CH2OH, conc. H2SO4, heat under reflux

Possible by-product: from reaction between themselves to form

Or

(Notice the product after step III can further react since it still has free carboxylic acid and
alcohol group)

[5.1.2 Reactions of Acyl Chlorides]

8 When ethanol reacts with carboxylic acids, it acts as a nucleophile.

Phenol does not react directly with carboxylic acids.
(i) Suggest and explain why phenol does not react with carboxylic acids. [2]
(ii) Phenol can be converted to phenylethanoate via a two-step process. [2]
Identify the reactant required for each step. [N19/P2/Q3(a)]
(i)
Phenol is a poor nucleophile as the lone pair of electrons on oxygen is delocalised into the
benzene ring and is less readily available. Hence, it cannot react with carboxylic acids.

(ii) Step 1: NaOH(aq)

Step 2: ethanoyl chloride

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Carboxylic Acid and Derivatives Tutorial 2024 Semester 1

[6.2.3 Reactions of esters]

9 Name the following esters and suggest the products formed when heated with NaOH(aq).

(a)

(b)

(a) ethyl benzoate Products:

(b) phenyl propanoate Products:

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Carboxylic Acid and Derivatives Tutorial 2024 Semester 1

3) Assignment Questions
10 State which compound, trichloroethanoic acid or ethanoic acid, is the stronger acid.
Explain your answer. [3]
[2016 A level P2 Q5(b)(i)]
CH3CO2H ⇌ CH3CO2– + H+
CCl3CO2H ⇌ CCl3CO2– + H+
Trichloroethanoic acid is the stronger acid compared to ethanoic acid due to the
presence of 3 electron-withdrawing Cl atoms help to disperse the negative charge on
the CCl3CO2– carboxylate ion. This stabilises the CCl3CO2– anion to larger extent and
thus decreasing the tendency for CCl3CO2– to recombine with H+.
Ethanoic acid has a electron-donating group that intensifies the negative charge on the
O atom on the carboxylate ion, destabilises the anion, increasing the tendency for the
ion to recombine with H+/ poe lies to the left, [H+] decrease.

Given both acids partially dissociate in the following manner to act as an acid to give

protons, RCO2H ⇌ RCO-2 + H+

The position of equilibrium for trichloroethanoic acid will lie much further to the right, due to
-
the higher stability of CCl3CO2 , thus CCl3CO2H dissociates to a larger extent to give more
H+ ions, given the same concentration of both acids.

11 Compound A has molecular formula C7H14O2 and can exhibit both cis-trans isomerism and
enantiomerism. When one mole of A is heated with acidified potassium manganate(VII), one
mole of B, C5H8O2, is produced together with two moles of carbon dioxide. Subsequently,
when one mole of B is warmed with an alkaline solution of iodine, one mole of C is produced
together with two moles of a yellow precipitate D. Upon treatment of C with dilute sulfuric acid,
compound E, C3H4O4, is produced which can undergo reaction with ethane-1,2-diol to form the
cyclic compound F shown below.

Compound F
(i) Identify the structures of A, B, C, D, and E using appropriate balanced equations to explain
the reactions they undergo.
(ii) Give the structure of the organic product formed when compound B reacts with excess 2,4-
dinitrophenylhydrazine. [12]
[CJC Prelim 2008/paper 3]

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Carboxylic Acid and Derivatives Tutorial 2024 Semester 1

(i)

Observation/data Type of Deduction Structure

reaction
Compound A has --- A contains C=C and has a --
molecular formula chiral carbon with no plane
C7H14O2 and can exhibit of internal symmetry.
both geometrical and
optical isomerism.
When one mole of A is Oxidative A is
heated with acidified cleavage
potassium
manganate(VII), one
mole of B, C5H8O2, is A contains 2 terminal [1]
produced together with alkenes or A produces
two moles of carbon ethane-dioic acid upon
dioxide. oxidative cleavage. [1]

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Carboxylic Acid and Derivatives Tutorial 2024 Semester 1

One mole of B is Oxidation B contains 2 –COCH3 B is

warmed with an alkaline group.
solution of iodine, one *B cannot contain –
mole of C is produced CH(OH)CH3 as it would
together with two moles been oxidized.* [1]
[1]
of a yellow precipitate D.
C contains 2 carboxylate
anions. C is

Upon treatment of C
with dilute sulfuric acid,
compound E, C3H4O4, is
produced which can
undergo reaction with
Condensation
ethane-1,2-diol to form
the cyclic compound F
D is CHI3 [1]
Acidification Upon acidification of C, E is E is
formed with 2 CO2H
functional groups
E reacts with ethane-1,2-
diol(2 carbons) to form F(5
[1 for C and E]
carbons) which is a diester.
Therefore E has (5-2 =3)
carbons. [1]

Equations:
1.

[1]

2.

[1]

3.

[1]

4.

[1]
(ii)

[1]
[Total: 12]

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Carboxylic Acid and Derivatives Tutorial 2024 Semester 1

4) Additional Practices (not discussed in tutorials)

12 There are few naturally occurring organic compounds that contain fluorine.

The South African plant Dichapetalum cymosum contains fluoroethanoic acid, FCH2CO2H. Data
about ethanoic, fluoroethanoic and chloroethanoic acids are given below.

CH3CO2H FCH2CO2H ClCH2CO2H

pKa 4.76 2.57 2.87

Suggest an explanation for the differences in acid strengths of the three acids in terms of their
structures and bonding.
[2006 A level P2 Q5(b)(ii)]

Decreasing acid strength: FCH2CO2H > ClCH2CO2H > CH3CO2H

FCH2CO2H is the most acidic as F atom is very electronegative and thus disperse the negative
charge on O of the carboxylate anion to a large extent. This results in greater stability of the
anion and reduce tendency to recombine with H+.

ClCH2CO2H is the less acidic than FCH2CO2H as Cl atom is less electronegative than F. Thus
the negative charge on O of the carboxylate anion is dispersed to a smaller extent.

CH3CO2H is the least acidic as it does not have any electron withdrawing groups attached.
Thus the negative charge on O of the carboxylate anion is dispersed to the smallest extent,
and the stability of the anion is the lowest.

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Carboxylic Acid and Derivatives Tutorial 2024 Semester 1

13 On warming compound A, HOCH2CH2CH(CH3)CO2H with concentrated sulfuric acid, a ester B,

C5H8O2 is formed. A reacts with PCl5 to give C, which rapidly reacts with water to give D,
C5H9ClO2. Treatment of D with alcoholic KCN, followed by acidic hydrolysis gives E, C6H10O4.

Deduce a possible identity of each substance B to E. Suggest, with a reason, how you would
expect E to undergo dehydration readily to the compound, C6H8O3.
A undergoes esterification; ester
linkage is formed within molecule O
A
Conc H2SO4 B
HOCH2CH2CH(CH3)CO2H
C5H8O2 O
heat

A undergoes
nucleophilic
substitution. PCl5
Both the Alkyl chloride in D
alcoholic OH undergoes nucleophilic
and acid OH substitution to form a nitrile
groups
reacted. Rapid reaction D Alcoholic hydrolysis
C E
with water C5H9ClO2 KCN
ClCH2CH2CH(CH3)COCl HO2CCH2CH2CH(CH3)CO2H
ClCH2CH2CH(CH3)CO2H
C is likely to The nitrile undergoes
The acyl chloride in C
contain hydrolysis to form a
undergoes hydrolysis.
alkyl chloride carboxylic acid, E
D is likely to be a carboxylic acid
and
acyl chloride

Observation/Data Type of Deduction Structure

reaction
HOCH2CH2CH(CH3)CO2H Esterification/ A has undergone A is
reacts in the presence of Condensation condensation as it has an OH
concentrated sulfuric acid, group and a CO2H function
to form a cyclic ester B, group.
C5H8O2 is formed
Ester B is

A reacts with PCl5 to give C, Nucleophilic Both OH functional group and C is

which rapidly reacts with
water to give D, C5H9ClO2.
substitution CO2H function group can
undergo nucleophilic
substitution with PCl5 to give
C. D is
Upon hydrolysis in water, only
acyl chloride is hydrolysed to
give CO2H, forming D

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Carboxylic Acid and Derivatives Tutorial 2024 Semester 1

Treatment of D with Nucleophilic Chloroalkane undergoes Intermediate:

alcoholic KCN, followed by substitution nucleophilic substitution to
hydrolysis gives E, C6H10O4 followed by give intermediate with nitrile
acid-catalysed functional group.
hydrolysis
E is
The nitrile group in the
intermediate undergoes acid-
catalysed hydrolysis to form
CO2H.

E is readily dehydrated due to close proximity of the –CO2H groups, to form a cyclic acid anhydride.
Note: A cyclic acid anhydride
is formed (not in syllabus, but
be familiar with this
dehydration process.)

14 An ester of molecular formula C9H10O2 was heated under reflux with aqueous sodium hydroxide.
On distilling the product, a colourless liquid was obtained which, on warming with iodine and
aqueous sodium hydroxide, gave a pale yellow precipitate. The residue in the distilling flask gave
a white precipitate on acidification with hydrochloric acid. Identify the ester, explaining your
reasoning, and write a balanced equation for its reaction with sodium hydroxide.
[5]

[1]

[1]
[1]

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Carboxylic Acid and Derivatives Tutorial
Observation /
information
An ester of molecular
formula C9H10O2
heated under reflux with
aqueous sodium
hydroxide
On distilling the product,
a colourless liquid was
obtained which, on
warming with iodine and
aqueous sodium
hydroxide, gave a pale
yellow precipitate.
The residue in the
distilling flask gave a
white precipitate on
acidification with
hydrochloric acid.
Therefore, ester is
Balanced equation:
Additional Question: why can’t the ester be
Hint: Consider the iodoform reaction.
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2024 Semester 1
Functional group
Type of reaction Structure
present
ratio of C:H is
almost 1:1 
-- --
benzene ring could
be present.
Base-catalysed
hydrolysis of ester [1]
The alcohol has at
least 2 C atoms.
Since benzoic acid is
present in the
ester(refer to point
below), the alcohol
Distillation product
has (9-7=2 ) carbon
undergoes iodoform
atoms, thus alcohol
reaction with I2/NaOH
is :
Present in the
alcohol group
[1]
Acidification of salt to
Benzene ring
give white precipitate
present in acid
of benzoic acid
White ppt [1]
[1]
[1]
?
Carboxylic Acid and Derivatives Tutorial 2024 Semester 1

15 Malic acid occurs in green apples and grapes. It is often added to beverages and confectionery
to confer a sour taste.

When malic acid is heated with acidified K2Cr2O7, compound N is formed. Heating N in an inert
solvent for several hours produces P, C3H4O3 and a gas Q. Both N and P react with 2,4-
dinitrophenylhydrazine. Compound P also gives a yellow precipitate with aqueous alkaline
iodine.
(a) Suggest structures for N and P, and use the information given to suggest the identity of
gas Q. [3]
Malic acid can be dehydrated to give a mixture of two isomeric alkenedioic acids, J and K, with
the formula C4H4O4. Gently heating the anhydrous crystals of one of the isomers produces a
neutral compound L, C4H2O3, which does not react with sodium metal or give a precipitate with
2,4-dinitrophenylhydrazine.
Compound L reacts with ammonia to give a compound M, C4H5NO3, which gives a salt on
reaction with NaOH but not HCl. Compound M decolourises Br2(aq).
(b) Suggest structures for J to M, and identify which isomer, J or K, produces L. Write
equations for all reactions, and explain the observations. [7]
[N12/P3/Q5, modified]
(a)

Since
2°alcohol in N undergoes C4H4O5 → C3H4O3 + CO2
oxidation to form ketone
Gas Q is CO2
acidified K2Cr2O7 Heat in P + gas
N inert solvent C3H4O3 Q
Reacts with Reacts with Forms yellow ppt
2,4-DNPH 2,4-DNPH with aq alkaline I2

• P contains • P contains
• N contains ketone carbonyl -COCH3
functional group functional
group.
• P is a ketone

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Carboxylic Acid and Derivatives Tutorial 2024 Semester 1

Observation/data Type of Deduction Structure

reaction
When malic acid is Oxidation The secondary alcohol in
heated with acidified malic acid is oxidized to
K2Cr2O7, compound N form ketone
is formed.

Heating N in an inert -- --
solvent for several
hours produces P,
C3H4O3 and a gas Q
By balancing the equation,
gas Q is CO2.
Both N and P react Condensation presence of carbonyl group --
with 2,4-DNPH in both N and P
P gives a yellow ppt Oxidation presence of CH3CO- group
with aqueous alkaline in P
iodine

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(b)

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