2019 H2 Chemistry

CARBOXYLIC ACIDS AND DERIVATIVES SOLUTIONS

SECTION A (MULTIPLE CHOICE)

1 Strength of an acid depends on the stability of its conjugate base. The more stable the D
conjugate base is, the more likely the acid ionises (Position of equilibrium lies to the
right.)
The acid strength of the 2 carboxylic acids in this question will be the greater than that of
phenol (narrow to options B and D) due to the greater dispersal of the negative charge
between the highly electronegative two O atoms of the carboxylate anion as compared
to that of the phenoxide ion.
Chloroethanoic acid is a stronger acid than ethanoic acid due to the electron withdrawing
Cl atom which disperses the negative charge on its conjugate base and stabilising it to
a greater extent, favouring the dissociation of O–H bond to form H+.

2 Chloroethanoic acid is a stronger acid than ethanoic acid due to the electron withdrawing D
Cl atom which disperses the negative charge on its conjugate base and stabilising it to
a greater extent, favouring the dissociation of O–H bond to form H+.

3 CH3CH2COBr hydrolyses in water to form CH3CH2COOH and HBr (a strong acid). A

Hence, an aqueous solution of CH3CH2COBr is the most acidic, and hence, has lowest
pH among the three compounds shown.

H2NCH(CH3)CO2H is an amino acid which exists as zwitterions, +H3NCH(CH3)COO. Its

acidity is lower than that of CH3CH2CO2H since its acidity is due to a NH3+ group, which
is less acidic than the COOH group in CH3CH2CO2H. Thus, an aqueous solution of
H2NCH(CH3)CO2H is the least acidic among the three compounds.

Hence, the compounds, arranged in order of increasing pH (decreasing acidity) are:

CH3CH2COBr, CH3CH2CO2H, H2NCH(CH3)CO2H.

4 Ester can be synthesised either using carboxylic acid and alcohol or acyl halide and C
alcohol / phenol. Hence all the options except D and E will give an ester, though only one
of them will give CH3CO2CH2CH(CH3)CH2CH3.

A CH3CH2CH(CH3)CH2CO2CH3 will be formed.

B CH3CH2CH(CH3)CH2CO2CH3 will be formed.
C CH3CO2CH2CH(CH3)CH2CH3 will be formed.
O CH3
CH3 C Cl HO CH2 CH CH2CH3

D CH3CO2– is not nucleohpilic enough to substitute the Cl atom due to the

delocalisation of charge between the two O atoms.

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5 OH- carboxylate salt distill alcohol with lower b.p. C

ester than the ionic salt will
+
Q alcohol / phenoxide be distilled off 1st.
heat

I2/OH- (for this qn)

residue

yellow solid formed

H+
alcohol with CH3CH(OH)- structure

white ppt (insoluble in aq. medium)

carboxylic acid
+
phenol (if alcohol is not present)

Hence, ester Q hydrolyses to give an alcohol and a carboxylic acid.

The alcohol has a CH3CH(OH)– structure as it gives positive iodoform test.
Since the carboxylic acid gives a white ppt, it is likely to contain a hydrophobic group and
hence remains insoluble in aqueous medium.

6 Hydrolysed products (assume acid–catalysed) C

A CH3CH2CO2H CH3CO2H + CH3OH
B CH3CH2CO2H CH3CO2H + CH3CH2OH
C CH3CH2CO2H CH3CH2CO2H + CH3OH
D C6H5CO2H + NH4+ C6H5NH3+ + CH3CO2H

7 Ease of hydrolysis depends on how electrophilic the electron deficient carbon is (for A
same X) and the bond strength of the C–X bond (for different X).

In general, rate of hydrolysis decreases in this order:

RCOX > RCH2X > RCH=CHX or Ar–X (where Ar = aryl / phenyl group)

A CH3CH2COCl will hydolyse the fastest due to the highly electron deficient
carbonyl carbon (bonded to 2 electronegative atoms).
CH2=CHCl will hydrolyse the slowest due to the partial double bond between C
and Cl formed from the delocalisation of lone pair of electrons on Cl into the 
bond of C=C.
B CH3CH2I will hydrolyse the fastest due the C–I bond being the weakest.
C C6H5CH2Br will hydrolyse the fastest due to absence of partial C–X double bond.
D C6H5CH2l will hydrolyse the fastest due to absence of partial C–X double bond.

8 A It is the opposite. If indeed the lone pair of electrons (lp) on the Cl atom is more C
readily delocalised, the carbonyl carbon will be less electron deficient and less
susceptible to nucleophilic attack (lower ease of hydrolysis).
The lp on Cl resides in the 3p orbital while the  bond of C=O is formed from
side–on overlap of the 2p orbitals of C and O. Hence the delocalisation of lp on
Cl into >C=O is less effective.

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B Similarly, it contradicts the observation. Otherwise, the carbonyl carbon will be

less electron deficient and less reactive.
C The carbonyl carbon of RCOCl is more electron deficient (greater positive
charge) and more susceptible to nucleophilic attack (greater ease of hydrolysis).

9 V has a more electron deficient C and reacts with water, phenol and ethanol (all are D
nucleophiles) more readily than U.
Both do not react with 2,4–DNPH (not aldehyde nor ketone).

10 Ethanoyl chloride will react with the alcohol group in glucose. D

OH OH OH
CH2 CH2 CH2 CH2 CH2 CHO
OH OH

11 A CH3CH2COCO2H likely to be formed. C

B CH3COCOCHO likely to be formed
D CH3COCH2OH and CH3CO2– likely to be formed.
O O O O
OH
CH3 C CH2 O C CH3 CH3 C CH2 OH O C CH3

12 The 1st step is nucleophilic (acyl) substitution while the 2nd step follows the nucleophilic A
addition mechanism. The 3rd step can be an acid–base reaction or hydrolysis reaction.

OH
H C H
O
H C H + OH- hydrolysis
O
H H

O H
H C H

+ OH- acid–base

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13 Hot NaOH(aq) will result in hydrolysis of ester and nitrile as shown. A

ether is not
ester O CN nitrile hydrolysed
H 3C O
O
H3 C
H 3 C CH 3
Cyphenothr in
NaOH (aq)
ref lux
O [+ NH3 (g)]
CO2 Na
H 3C
O Na + HO O
H3 C
H 3C CH 3

14 A is incorrect. CH3CH2CO2CH3, on alkaline hydrolysis and followed by acidification, D

forms CH3CH2CO2H and CH3OH. CH3OH does not give a positive triiodomethane test.

B is incorrect. CH3CH2OCOCH3, on alkaline hydrolysis and followed by acidification,

forms CH3CO2H and CH3CH2OH. No compound of formula C3H6O2 is formed.

C is incorrect since CH2(OH)CH2CH2COCH3 does not undergo hydrolysis.

D is correct since CH3CH2CO2CH2CH3, on alkaline hydrolysis and followed by

acidification, forms CH3CH2CO2H (with molecular formula C3H6O2) and CH3CH2OH.
CH3CH2OH gives a positive triiodomethane test.

15 Refer to Q4. C

16 “reacts with hot, NaOH”  reacts with phenol and/or carboxylic acid (circled). C
 hydrolyse ester and/or amide (boxed).

17 “contains four 1o alcohol”  four –CH2OH groups (accounted for C4H12O4, left with 1 C) A

CH2OH
HOCH2 C CH2OH
CH2OH
Structure of pentaerythritol is .

Upon oxidation, all four 1o alcohol will be oxidised to carboxylic acid with the structural
formula C(CO2H)4 i.e. molecular formula is C5H4O8.

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18 Absence of aldehyde / ketone in –valerolactone suggests that there will be no D

observable change with 2,4–DNPH.

19 Compound that will produce the largest mass of AgCl depends on amount of reactants B
used and how electrophilic is the electron deficient C atom.

Since 1 gram of each of the compounds is used, the compound with the smallest Mr will
form the largest mass of ppt.
Though options A and D are acid chlorides and they hydrolyse most readily, the reaction
mixture was heated before addition of AgNO3(aq) so both C–Cl bonds in option B will
also hydrolyse to give Cl–. Hence, B will give a larger amount of AgCl ppt and produce
the largest mass of AgCl(s).

20 A Both alcohol and carboxylic acid react with PCl5(s), hence 1 mol of citric acid will C
react with 4 mol of PCl5(s).
B Only alcohol will react with HCl(g) in the presence of ZnCl2, hence 1 mol of citric
acid will react with 1 mol of HCl(g).
C Both alcohol and carboxylic acid react with Na(s), hence 1 mol of citric acid will
react with 4 mol of Na(s).
D Only carboxylic acid react with NaOH(aq), hence 1 mol of citric acid will react with
3 mol of NaOH(aq).

21 Given that the unknown is dibasic [2 x –CO2H], you can deduce the molecular mass of C
the alkyl chain = 146 – 2(45) = 56.

Hence, the no. of C atoms = 4 [56  14 (each >CH2)] + 2 (from –CO2H) = 6.

22 A nucleophilic (acyl) substitution occurs readily and an immediate white precipitate D

would be observed.
B nucleophilic substitution does not occur due to the delocalisation of the lone pair
of electrons on the Cl atom into the benzene ring, creating a partial double bond
character in the C–Cl bond.
C same as A
D nucleophilic substitution occurs upon boiling with NaOH(aq) and the resulting
mixture contains Cl– ions. Upon cooling, acidification and addition of AgNO3(aq),
white precipitate would be observed.

23 PCl5 A
CH3CHBrCH(OH)CO2H M

The alcohol and carboxylic acid functional groups undergo nucleophilic substitution
with PCl5, to produce M (CH3CHBrCH(Cl)COCl).

24 From the functional groups in citric acid and structures of all four options, and the use of A
concentrated sulfuric acid, the question is based on ‘esterification’ reaction.

In order to determine if the alcohol or carboxylic acid groups of citric acid is involved in
the reaction, we need to see the change in molecular formula after esterification.
From C6H8O7 C9H12O8, there is an increase in 3 C, 1 O and 4 H atoms. To have a
gain in 1 O atom, it must be the alcohol group that has reacted to have an additional C=O
group from another acid. To gain 3 C atoms, the reacting acid must have 3 C atoms.

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25 1 Dexon contains ester linkages and so can be hydrolysed in the body. A

2 Dexon is a polyester and hence it takes time for the ester linkages to be
completely hydrolysed.
3 Upon hydrolysis, it forms 2–hydroxyethanoic acid, which can form intermolecular
hydrogen bonding with the water molecules and hence is water soluble.

26 1 CH2CN CH2CO2H D
product

2 CO2H CO2CH2CH3
COCl

3 CO2H CH2OH CH2OCOCH2CH3

27 For 1, ester group in X undergoes acid hydrolysis to form 3o alcohol which cannot be A
oxidised by K2Cr2O7. There is no change in the colour of solution. However, the acid
hydrolysis of Y formed 2o alcohol which can be oxidised by K2Cr2O7. The colour of
solution changes from orange to green.

For 2, both the ester groups in X and Y undergo base hydrolysis. However, only Y shows
a positive iodoform test due to presence of CH3CH(OH)– group after hydrolysis.
For 3, base hydrolysis of R–Br in X followed by excess HNO3(aq) and AgNO3(aq) results
in a cream ppt of AgBr. No cream ppt is observed for Y as the Br atom is bonded to C=C
bond where the p orbital of Br interacts with the p orbital of C in C=C, resulting in partial
double bond character in the C–Br bond.

28 1 After hydrolysis of the ester group, Br2 adds across the C=C bond (electrophilic B
addition) and substitutes onto the phenol (electrophilic substitution). With Br2(aq),
substitution occurs on the phenol at the 2– and 4–positions (the 6–position is blocked
by the alkyl side–chain). Hence the reaction is with 3 moles of Br2.

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2 Cold acidified KMnO4 will result in oxidative addition (mild oxidation), where –OH is
‘added’ across the C=C double bond to give the following product, which has 2 chiral
centres (marked with *):

3 The reactions are not nucleophilic, but electrophilic addition and electrophilic
substitution as the alkene and benzene rings are both electron–rich.

29 Option 1 (Correct) D
CH3CO2H + NaOH  CH3CO2–Na+ + H2O
CH3CO2– is the conjugate base (pH > 7 at 25 oC) of the weak acid, CH3CO2H.

Option 2 (Incorrect)
CH3CO2H reacts with ethylamine (CH3CH2NH2) to form a salt, [CH3CO2–][CH3CH2NH3+],
instead (via acid–base reaction).

Option 3 (Incorrect)
Cannot work. Phenol will undergo oxidation by conc H2SO4. To form ester in this case,
use CH3COCl, and react with phenol in the presence of NaOH(aq).

30 Option 1 (Correct) A
Cannot work. Bromobenzene cannot undergo nucleophilic substitution with the
carboxylate ion readily due to the partial double bond character of C–Br.

Option 2 (Correct)
Cannot work. Phenol will undergo oxidation by conc H2SO4. To form ester in this case,
use an appropriate acyl chloride, and react with phenol in the presence of NaOH(aq).

Option 3 (Correct)
Cannot work. Carboxylic acid cannot react with an acyl chloride.

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SECTION B (STRUCTURED/FREE RESPONSE QUESTIONS)

1 (a) (i)
HO COOH
R is

(ii) step 1: KMnO4, dilute H2SO4, heat under reflux

step 2: CH3OH, concentrated H2SO4, heat under reflux

(b)
+
Na-O COO-Na+
CH3OH and

(c) (i)
CH3COO CO2CH3

(ii) Ester

2 (a) I: CH3COCl, room temperature

II: CH3OH, concentrated H2SO4, heat under reflux

(b) (i) COO-Na+

OH
(ii) COO-Na+

O-Na+

(iii) COOH
O2N COOH
OH
OH NO2
or

(c) nNaOH required = 13.9 x 10–3 x 0.10 = 1.39 x 10–3 mol

naspirin present = 1.39 x 10–3 mol
molar mass of aspirin = 9(12.0) + 8(1.0) + 4(16.0) = 180.0 g mol–1
mass of aspirin = 1.39 x 10–3 x 180.0
= 0.250 g

(d) (i) Ca(OH)2 or Ca

(ii) Its calcium salt is an ionic compound and hence forms ion–dipole interactions with
the water molecules while aspirin, a simple molecular compound, is insoluble
because of the formation of intramolecular hydrogen bonding present within the
molecule.

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3 (a) (i) O H
C O C

L is H and
O
CH3 O C
P is

(ii)
CH3 OH NaOH
CH3 O-Na+

CO2H + anhydrous PCl5

N
P

(iii) KMnO4 in dilute H2SO4, heat under reflux.

(b) (i)
CH2OH < CH3 OH < CO2H

M Q N

Weakest acid Strongest acid

Relative acid strength: M < Q < N

Compare M and Q

C6H5CH2OH C6H5CH2O– + H+
In phenylmethanol, the alkyl group is electron–donating. This intensifies the
negative charge on the oxygen and makes the alkoxide ion less stable. Hence,
alcohols are less likely to dissociate into ions.

CH3 OH CH3 O- + H
+

In methylphenol, the lone pair of electrons on oxygen in the methylphenoxide

anion is delocalised into the  electron cloud of the benzene ring, thus,
dispersing the negative charge. Hence the methylphenoxide ion is resonance
stablised. Dissociation of the O–H bond in methylphenol to release H+ is thus
favoured. Therefore Q is a stronger acid than M.

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Compare Q and N

O O
C OH C O- + H+

For benzoic acid, the p–orbital on the C atom overlaps with the p–orbitals of
the 2 neighbouring O as well as the π orbitals of the benzene ring. Hence the
negative charge on the benzoate ion can be dispersed into the ring as well as
between the two O atoms resulting in a most stable conjugate base. Therefore
N is a stronger acid than Q.

(ii) I
CH3 OH + NaOH CH3 O-Na+ + H2O

CO2H + NaOH COO-Na+ + H2O

II
2 CO2H + Na2CO3 2 COO-Na+

N + CO2 + H2O

M will not react with NaOH and Na2CO3.

Q will not react with Na2CO3.

4 (a) room temperature

CH3CH2OH + CH3CH2CH2COCl CH3CH2CH2COOCH2CH3 + HCl

(b) dilute H2SO4, K2Cr2O7 H

CH3CH2OH CH3 C O
(1) warm and distil

H HCN, H
trace amt of NaOH
CH3 C O CH3 C OH

(2) CN

H
dilute HCl CH3CH(OH)
CH3 C OH
heat COOH
(3) CN

(c) dilute H2SO4, K2Cr2O7

CH3CH2CH2OH CH3CH2COOH
(1) heat
anhydrous PCl5 O
CH3CH2COOH CH3CH2 C Cl
(2) room temperature

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(d) CH3Cl, anhydrous AlCl3

CH3 CH3
(1) room temperature

dilute H2SO4, KMnO4

CH3 CH3 HOOC COOH
(2) heat

(e) anhydrous PCl5

CH2OH CH2Cl
(1) room temperature

KCN in ethanol
CH2Cl CH2CN
(2) heat

dilute HCl
CH 2CN CH2COOH
(3) heat

LiAlH4 in dry ether

CH2COOH CH2CH2OH
(4)

5 (a) Reaction I: CH3OH, concentrated H2SO4, heat under reflux

Reaction II: CH3COCl, with trace of NaOH added to gallic acid, followed by CH3COCl
at room temperature

(b) (i) COO-Na+

+
Na-O O-Na+
O-Na+

(ii) COO-Na+

HO OH

OH

(iii) COOH
O2N NO2

HO OH
OH

6 (a)
O 2N CH CH2 O 2N CH CH2 H 2N CH CH3
OH Br Br
A B C

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7 (a) Reaction I: concentrated HNO3, concentrated H2SO4, 30 °C / room temp

Reaction II: PCl5(s), room temperature OR SOCl2(l), heat
Reaction III: CH2(OH)CH2N(C2H5)2, room temperature
Reaction IV: Sn, concentrated HCl, heat; followed by NaOH(aq)

(b)

(c) Compound Q (or 4–nitrobenzoic acid) is more acidic than benzoic acid.

Compound Q has an electron–withdrawing –NO2 group

that disperses the negative charge on (O atom of) (OR 4–

nitrobenzoate ion) to a greater extent.

4–nitrobenzoate ion is more stable (than benzoate ion)

(d) No. of moles of methylbenzene used = 15.4 / 92.0 = 0.167 = no. of moles of procaine

Assuming 75% yield, no. of moles of procaine = 0.167/100 x 75 = 0.125

Mass of procaine collected = 0.125 x 236 = 29.6 g

(e) (i) Aqueous solutions of S and T turn blue litmus red => carboxylic acid present
Both S and T decolourise bromine => alkene present
Both S and T decolourise bromine => electrophilic addition

Since S and T undergo dehydration at different temperatures, they exist as a pair

of cis–trans isomers.

S (is trans isomer:)

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T (is cis–isomer:)

(ii) cis–trans isomerism

(iii) Dehydration of T (or cis–isomer) occurs at lower temperature because the two
carboxyl groups are cis to each other / nearer to each other.

(iv)

(f) (i) Amphiprotic means amphoteric / can react with acid and base / have both acidic
and basic properties / behave as acid and base.

(ii) HO2CCH2CO2– + H+  HO2CCH2CO2H

HO2CCH2CO2– + OH–  –O2CCH2CO2– + H2O

8 O

ClCH2 C N CH2CH2NH2

The COCl carbon is attached to two highly electronegative atoms, Cl and O, as compared to
only one electronegative Cl in the case for the CH2Cl carbon. Hence, the COCl carbon has a
higher partial positive charge than the CH2Cl carbon.

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9 Given that Type of reaction Deduction about structure

symmetrical hydrocarbon A Presence of plane of symmetry
in A

C10H16 reacts with 2 equivalent Electrophilic Presence of 2 C=C bonds in A.

of Br2 in the dark. addition

A reacts with KMnO4 to give B Oxidation A is likely is be a cyclic

(C5H8O3) as the only product. (Oxidative compound and B may contain a
cleavage) ketone functional group and a
carboxylic acid functional
group.
B reacts with Na2CO3 to give a Acid–base reaction CO2 is produced.
colourless gas.
B contains carboxylic acid
functional group.

B gives C, C4H6O4, with oxidation CH3

alkaline aqueous iodine
followed by acidification B contains C O.

C contains carboxylic acid

functional group.

C reacts with excess PCl 5 to Nucleophilic (acyl) HCl fumes are produced.
form D, C4H4O2Cl2 with the Substitution C contains 2 carboxylic acid
evolution of white fumes. functional groups.
D contains an acyl chloride
group.

D reacts rapidly with an Nucleophilic (acyl) HCl fumes are produced.

equimolar amounts of 1,2– substitution
cyclohexanediol to give a E is an ester.
sweet smelling compound E

CH3 CH3
O O O O
CH3 C CH2 CH2 C OH HO C CH2 CH2 C OH

B C
A

O
O C
O O
Cl C CH2 CH2 C Cl
O C
D E
O

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alternatively,

CH3
CH3
O CH3O O CH3O
CH3 C C C OH HO C C C OH
CH3 H C H
CH3
A B

CH3O O
O O C
Cl C C C Cl CH3
H
D E O C
O

10 (a) Given that Type of Deduction about structure

C:H ratio is about 1:1.
V and W reacts with
Na2CO3(aq) to form
CO2(g).
Both X and Y react with
2,4–DNPH to form
orange ppt.
Only Y, but not X, gives
silver mirror with Tollens’
reagent.
X is formed by oxidising
V.
V and X react separately oxidation
with alkaline aq I2 to form
CHI3.
Benzene–1,2–
dicarboxylic acid is the
only organic product upon
vigorous oxidation of V
and W.
reaction
Both V and W contain benzene
ring.
acid–base Both V and W contain –CO2H
group.
condensation X and Y contain aldehyde or
ketone.
oxidation Y contains aldehyde group.
X contains ketone group.
(Reason: X contains three O atoms.
Since two O atoms are already in ‒
CO2H group, and we know that X
contains carbonyl group but does not
contain aldehyde group, the third O
atom must belong to ketone.)
Since X contains ketone, V contains
2o alcohol.
X contains the CH3CO– group.
V contains the CH3CH(OH)– group.
V and W are 1,2–disubstituted
aromatic compounds.

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O CH3
CH(OH)CH3 CH2CH2OH CH2CHO
C
COOH COOH
COOH COOH

V W X Y

(b) K2Cr2O7, dilute H2SO4, warm with distillation.

(c) I O CH3
COO-Na+
C
COO-Na+
COOH 3I2 5OH-
CHI3 3I- 4H2O

II CH2CHO CH2COO-

COOH 2[Ag(NH3)2]+ 4OH- COO- 2Ag 4NH3 3H2O

(d) CH3

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