SERANGOON JUNIOR COLLEGE

9647 H2 CHEMISTRY
2015 JC2
Carboxylic Acids and Derivatives (Part 1)
Tutorial
1.
J97/I/8
One of the products from the vigorous hydrolysis of oil of bitter almonds is mandelic acid,
H. It can be synthesised from benzaldehyde in two steps:
step I
step II
C6H5CHO
J
C6H5CH(OH)CO2H
H
(a) Suggest reagents and conditions for steps I and II, and draw the structural formula of the
intermediate J.
step I: HCN in trace amt of NaOH(aq) / HCN in trace amt of NaCN (aq), 10 20 C
step II: HCl (aq) / H2SO4(aq), heat
CN
C

OH

(b)

Suggest structural formulae for the products of the reaction of mandelic acid

C C
OH
(i)
(ii)
(iii)
(iv)
(v)

OH

with the following reagents.

HBr
PCl5
CH3COCl
C2H5OH/H+
NaOH(aq)

(i)

Br

H
COCl
C

(ii)

2. Regents & conditions given.

3. Identify type of reaction undergone.

No reaction with COOH

unless PBr3 added.

COOH
C

Thinking process
1. Identify all functional groups in structure.

Cl

COOH
C

O C
CH3

(iii)

CH 2CH 3

C
C

(iv)

H
-

COO Na
C

(v)

Reversible reaction.
Lower yield of esters
compared with (iii)

OH

OH

MONOBASIC acid! How

do you tell??
(c) A sample of mandelic acid isolated from bitter almonds was contaminated with a
neutral impurity. A 0.100 g sample of the impure acid required 6.00 cm3 of 0.100
mol dm-3 NaOH to neutralise it. Calculate the percentage purity of the mandelic
acid.
nNaOH nmandelic acid = (6/1000) x 0.100 = 6 x 10-4 mol
mmandelic acid = 6 x 10-4 [8(12) + 8(1) + 3(16)] = 0.0912 g
% purity = (0.0912/0.100) x 100 = 91.2 %

2.
(a)

J92/I/10(a)
Explain the following observations:
(i) ethanoic acid is more acidic than ethanol
CH3COOH

CH3COO + H+

C2H5OH
C2H5O + H+
The carboxylate ion is stabilised by charge delocalization or (resonance
stabilized)

O-

O
R C

(ii)

(iii)

O-

R C

This disperses the negative charge over the C atom and the 2 oxygen atoms on
the carboxylate ion.
Greater stabilisation of the carboxylate ion, promoting greatest loss of H+.
CH3CO2H is more acidic than CH3CH2OH
Alkoxide ion is not stabilised by charge delocalisation.
Presence of electron-donating alkyl group intensifies the negative charge on the
alkoxide ion.
This destabilises the alkoxide ion, least H+ released
Hence CH3CH2OH is a weaker acid.
chloroethanoic acid is stronger than ethanoic acid.
CH2ClCOOH
CH2ClCOO + H+
In chloroethanoic acid, the electron withdrawing group (Cl) disperse the negative
charge on the carboxylate ion hence stabilise the conjugate base and
increasing the stability of the carboxylate ions.
Acidity:

CH2ClCOOH > CH3COOH

Ethanoic acid (b.p 118C) has a higher boiling point than ethyl ethanoate (77C)
Ethanoic acid exists as polar molecules held together by stronger hydrogen
bonds while ethyl ethanoate exists as polar molecules held together by weaker
permanent dipole-permanent dipole interactions

(iv) Ethanoic acid and sodium ethanoate are soluble in water but ethyl ethanoate is
insoluble in water
Ethanoic acid is a simple molecular compound which can form hydrogen bonds with
water. Favourable hydrogen bonds between (Ethanoic acid) solute and water
molecules are formed via hydration.
Sodium ethanoate, an ionic compound, formation of favourable ion-dipole
interactions which results in the release of energy that overcome giant ionic
structure for hydration.
Ethyl ethanoate is a simple molecular compound that has weaker van der Waals
forces between solute molecules which are not strong enough to displace the
stronger hydrogen bonding between water molecules for hydration to occur.
(b)

How would you expect the acidity of 3-chloropropanoic acid

2-fluoropropanoic acid to compare with that of 2-chloropropanoic acid?

and

of

Comparing 2-chloropropanoic acid and 3-chloropropanoic acid

CH3CHClCOOH
CH2ClCH2COOH

CH3CHClCOO + H+
CH2ClCH2COO + H+

General effect :
The electron-withdrawing chloro group disperses the negative charge on the
carboxylate anion hence stabilises the carboxylate anion relative to the acid
Specfic effect:

Distance of electron withdrawing group from COOH group:

CH3CHClCOOH < CH2ClCH2COOH

Extent of electron-withdrawing effect:

CH3CHClCOOH > CH2ClCH2COOH

Extent of stability of carboxylate ion relative to acid::

CH3CHClCOOH > CH2ClCH2COOH

Acidity: CH3CHClCOOH > CH2ClCH2COOH

Comparing 2-chloropropanoic acid and 2-fluoropropanoic acid

CH3CHClCOOH
CH3CHFCOOH

CH3CHClCOO + H+
CH3CHFCOO + H+

General effect:
The electron-withdrawing chloro and fluoro groups disperses the negative
charge on the carboxylate anion hence stabilises the carboxylate anion relative to
the acid

Specfic effect:
F in CH3CHFCOOH is more electronegative than compared to Cl in
CH3CHClCOOH
Extent of electron-withdrawing effect from COOH group:
CH3CHFCOOH > CH3CHClCOOH

Extent of stability of carboxylate ion relative to acid::

CH3CHFCOOH > CH3CHClCOOH

Acidity: CH3CHFCOOH > CH3CHClCOOH

3.

N08/III/3(f)
2-hydroxyphenylethanoic acid, N, can be prepared from compound M by the following
route.
O
H
H
OH
OH
H+(aq)
C
C
KOH(aq)
C CHO
CO2H
CO2K
M
N
Suggest two tests (stating reagent and observations) that would enable the
compounds M and N to be distinguished from each other.
Test 1:
Add Na2CO3(aq) to test tubes containing M & N respectively. Pass any gas produced via
a delivery tube to a test tube containing Ca(OH)2 (aq)
Observation for test 1
M: No gas produced, no white ppt observed in test tube containing Ca(OH)2 (aq)
N: Gas produced formed white ppt in Ca(OH)2 (aq)
Test 2:
Add 2, 4-DNPH, warm to the test tubes containing M & N respectively
(Comment: accept Tollens or Fehlings as well as PCl5)
Observation for test 2
M: orange ppt is seen
N: no orange ppt

Presence of 2 carboxylic acids

group in the same structure

4.

(a)

J92/I/11
Compound B, a diacid that occurs in apples and fruits has the following composition by
mass:
C, 35.8%
H, 4.5%
O, 59.7%
B reacts with ethanol, in the presence of concentrated sulfuric acid under reflux
to give C, C8H14O5. Compound C evolves hydrogen gas when treated with sodium
metal and reacts with acidified potassium dichromate (VI) to give compound D.
Compound D produces an orange precipitate with
2,4dinitrophenylhydrazine but has no reaction with Fehlings or Tollens reagent.
Calculate the empirical formula of B.
C
% mass
35.8
moles
2.98
1
x 4 to get whole no.
4
Empirical formula of B: C4H6O5

(b)

H
4.5
4.5
1.5
6

O
59.7
3.73
1.25
5

Deduce structures for compounds B, C and D, explain the reactions described.

B undergoes nucleophilic substitution/esterification with CH3CH2OH in the
presence of conc.H2SO4 under reflux to form compound C (C8H14O5)
Since B gained 4 carbon atoms (4C 8C)
C may be a diester
C undergoes redox reaction with Na to form H2
C can be an alcohol or carboxylic acid
C undergoes oxidation with hot acidified K2Cr2O7 to form D
C is a primary or secondary alcohol
D is a carboxylic acid or ketone
D undergoes condensation with 2,4-DNPH to give orange ppt, but is not oxidised by
Fehlings or Tollens reagent.
D is a ketone
C is a secondary alcohol

Structures

O H H O

B:

HO C C C C OH
H OH

O H H O
C:

CH3CH2O C C C C O CH2CH3
H OH

D:

O O

HO C C C C OH

CH3CHOOH

5.

J2000/I/8
The limescale that collects in kettles in hard water areas is mostly calcium carbonate. It
can be removed fairly harmlessly by a warm solution of vinegar, which contains ethanoic
acid. The limescale dissolves with fizzing and a solution of calcium ethanoate
remains.

(a)

Write a balanced equation for the reaction between ethanoic acid and calcium
carbonate.
2CH3COOH + CaCO3 Ca(CH3COO)2 + CO2 + H2O

When the resulting solution produced in part (a) is evaporated, and the solid residue
calcium ethanoate heated strongly in a test tube, an organic compound G is formed.
Compound G condenses to a colourless liquid and the residue in the test tube consists
of calcium carbonate.
(b) When 0.10 g of G was injected into a gas syringe at a temperature of 383 K and a
pressure of 1.0 x 105 Pa (1 atm), 55 cm3 of vapour were produced.
Calculate the relative molecular mass of G.
PV = mRT/M
M = mRT/PV
= 0.1(8.31)(383)/(105 x 55 x 10-6) = 57.9 g mol-1
Mr of G = 57.9

(c)

Compound G is neutral and water-soluble. G does not react with sodium metal nor
with Fehlings solution but it does react with alkaline aqueous iodine. Suggest a
structural formula for G. Justify your answer by reference to these properties of G.
G is neutral and so is not carboxylic acid.
G is water-soluble, showing that it forms hydrogen bond with water molecules.
G does not undergo redox reaction with sodium metal and so is neither alcohol nor
carboxylic acid.
G is not aldehyde since it does not undergo oxidation reaction with Fehlings
solution.
G reacts with alkaline aqueous iodine via oxidation giving yellow precipitate of CHI3

O
showing that it contains the

C CH3

group.

O
C
=> Hence G is propanone
(d)

CH3

Construct a balanced equation for the formation of G by the action of heat on calcium
ethanoate.
heat

Ca(CH3COO)2
(e)

CH3

CH3COCH3

+ CaCO3

Suggest a simple one-step chemical test that you could carry out to confirm the identity
of the functional group present in G. State the reagents and the observations you
would make.
Add 2,4-DNPH to G and warm.
An orange ppt is obtained showing that G is a carbonyl compound.

(f)

Suggest the structural formula of the organic product you might expect when calcium
propanoate, (CH3CH2CO2)2Ca, is heated strongly.
Inferring from above:
Ca(CH3COO)2

(CH3CH2CO2)2Ca

O
C
CH3CH2

CH2CH3

Recognising patterns
in Organic Reactions
CH3COCH3 + CaCO3
CH3CH2COCH2CH3 + CaCO3

6.

Oxalic acid is an organic compound with the formula H2C2O4. This colourless solid is a
dicarboxylic acid. In terms of acid strength, it is about 3,000 times stronger than acetic
acid. Its conjugate base, known as oxalate (C2O42), is a reducing agent as well as a
chelating agent for metal cations.
Oxalic acid dissociates in water according to the following equations
HOOC-COOH + H2O
HOOC-COO- + H3O+ I
Ka1= 5.6 x 10-2 mol dm-3
HOOC-COO- + H2O
OOC-COO- + H3O+
II
Ka2 = 5.4 x 10-5 mol dm-3

(a)

(i) Explain why oxalic acid is more acidic than acetic acid.
The conjugate base of oxalic acid is more stable than that of acetic acid.
Stabilisation of the HOOC-COO- via intramolecular hydrogen bonding with the
unionised COOH group will result in favouring the dissociation of the first acid
proton in oxalic acid.
(ii) Explain why the value of Ka1 is larger than Ka2.

After the first dissociation, the second acid proton in the remaining COOH group
is held more tightly by the monoanion via intramolecular hydrogen bonding,
resulting in a very stable monoanion. i.e the second acid proton does not
dissociate easily.

Also, the removal of the second H+ from a species that already contain a negative
charge is electrostatically unfavourable.

(iii) Write expressions for acid dissociation constants for equation I and II above.

Ka1=

[H 3 O ][HOOC COO ]
[HOOC COOH]

Ka2 =

[H 3 O ][ OOC COO ]
[HOOC COO ]

(b)

(i)

The neutralisation between oxalic acid and sodium hydroxide corresponds to the two
equations given
HOOC-COOH + NaOH HOOC-COONa + H2O
step 1
+
HOOC-COONa + NaOH NaOOC-COONa + H2O step 2
A 25 cm3 sample of oxalic acid of concentration 0.100 mol dm-3 was titrated with
sodium hydroxide of concentration 0.100 mol dm-3.
The titration curve for the above titration was given below.
pH

25

50

Vol of NaOH/cm3

At the first equivalent point, X, the species formed is HOOC-COO-(aq), which is both an
acid and a base where the relevant equilibriums are:
HOOC-COO-(aq) + H2O(l)
H3O+(aq) +
(COO)22-(aq)
HOOC-COO-(aq) + H2O(l)
OH-(aq) +
(COOH)2 (aq)
It can be shown that in such an instance that the [H+] at the first equivalent point, X, can
be given by expression,
[H3O+] =

K a1 K a 2

Using the expression, determine the pH value at point X.

[H3O+] = 5.6x102 x5.4x105 = 1.74 x 10-3
pH =2.76

Calculate the pH value at the second equivalent point, Y, given that the [OH-] can be
assumed to be entirely due to the hydrolysis:

(ii)

OOC-COO- + H2O

Kb2 =

HOOC-COO- + OH-

[OH ][HOOC COO ]

[ OOC COO ]

K w [OH ][HOOC COO ]

=
K a2
[ OOC COO ]

Since [OH-] = [HOOC-COO-],

Kw
[OH ] 2
=
K a 2 [ OOC COO ]

[-OOC-COO-] = 25/1000 x 0.1 (25+50)/1000

= 0.0333 mol dm-3
[OH ] 2
0.0333
[OH ] = 2.48 x 10-6 mol dm-3

Hence, 1.85 x 10-10 =

pOH =5.61
pH = 8.39
(c)

The concentration of oxalic acid in a solution can be determined by an acid-base titration.

State another way by which its concentration can be determined volumetrically.
Another method will be to titrate an acidified solution of the oxalic acid with
potassium manganate (VII) through redox titration.

(d)

Oxalic acid was one of the products formed when an aromatic organic compound, A, with
molecular formula C10H10O2 undergoes oxidation with acidified manganate(VII) to form
another organic product, B, with the molecular formula C8H8O2. No other organic
compound was formed in the oxidation. Compound B reacts readily with 2 mole of Br2(aq)
to form compound E, C8H6O2Br2. Compounds A and B are both soluble in NaOH and
both A and B reacts with 2,4 - DNPH. Compound A reacts with acidified dichromate to
give an acid, C, C10H10O3. Compound C reacts with SOCl2 to form a sweet-smelling
compound D, C10H8O2.
Deduce the structures of A,B,C,D and E. Explain your deductions
-

A and B have comparable no. of C and H atoms and no. of C 6,

=> A and B contains a benzene ring

B undergoes easy electrophilic substitution with 1 mole of Br2(aq)

B contains phenol.

A and B are soluble in NaOH

A and B consists of carboxylic acids or phenol

A and B undergoes condensation with 2,4-DNPH

A and B contains the carbonyl functional group.

A undergoes oxidation with acidified dichromate to form an acid, C

A contains aldehyde.

C undergoes nucleophilic substitution with SOCl2 to form acyl chloride which will
then undergo nucleophilic substitution with the phenol to form a cyclic ester.

HO

HO

C C C
O

CH3

CH3

Compound A

Compound B

HO

O
H
C
O

O C

CH3

CH3

Compound C

Br

HO
HO

Compound D

CH3
Br
Compound E

7.

J90/I/28
The same carboxylic acid is obtained either by the hydrolysis of a nitrile P or by the
oxidation of an alcohol Q.
Which of the following pairs could be P and Q? Explain your choice.
P
Q
A
CH3CH2CN
CH3CH2OH
B
(CH3)2CHCN
(CH3)3COH
C
C6H5CH(CH3)CN
C6H5CH2CH(OH)CH3
Note: Use mild
D
C6H5CH2CN
C6H5CH2CH2OH
E
C6H5CN
C6H5OH
oxidation agent like
Answer: D
Acidic hydrolysis of P:
C6H5CH2CN + HCl + 2H2O C6H5CH2COOH + NH4Cl

K2Cr2O7 . Cannot use

KMnO4 otherwise
benzoic acid will be
formed.

Oxidation of Q:
C6H5CH2CH2OH + 2[O] C6H5CH2COOH + H2O

8.

Lower pKa stronger

acid

J96/III/28
In which sequence is it correctly stated that the value of pKa decreases continuously?
Explain your choice.
CH3CO2H > CCl3CO2H > C2H5OH > C6H5OH
A
CCl3CO2H > CH3CO2H > C2H5OH > C6H5OH
B
Make sure you can identify
C2H5OH > C6H5OH > CH3CO2H > CCl3CO2H
C
relative acidity of
C6H5OH > C2H5OH > CH3CO2H > CCl3CO2H
D
respective organic

compounds given to you

Answer: C
CCl3COOH

CCl3COO + H+

CH3COOH

CH3COO + H+

C6H5OH

C6H5O + H+

C2H5OH
C2H5O + H+
Both CCl3CO2H and CH3CO2H are more acidic than C6H5OH as carboxylate ion is
stabilised by charge delocalisation.
Lone pair of electrons on oxygen interacts with the carbonyl group.
This disperses the negative charge on the two oxygen on the carboxylate ion and
stabilises it to a greater extent. The loss of H+ is greatly promoted.

CCl3CO2H is the most acidic due to the presence of electron-withdrawing Cl

groups which disperses the negative charge on the carboxylate ion to an even
greater extent and stabilises it more.
C2H5OH is the least acidic due to the presence of electron-donating alkyl group
which intensifies the negative charge on the ethoxide ion and destabilizes it.
Therefore, least H+ is released.

Assignment
1.
N93/I/10
2-hydroxybenzoic acid, A, is a useful intermediate for making aspirin (an analgesic) and
oil of wintergreen (used in ointments).
COOH

COOH

II

OH

OCOCH 3

CO 2CH 3

OH

(a)

aspirin
A
oil of wintergreen
Suggest suitable reagents and conditions for reactions I and II.

[2]

(b)
(i)
(ii)
(iii)

Draw the structural formulae of the organic molecules produced when A reacts with
Na2CO3(aq),
NaOH(aq),
dilute HNO3

[3]

(c)

(d)
(i)
(ii)

When an aspirin tablet was crushed up in water and titrated with 0.1 mol dm-3 sodium
hydroxide, 13.9 cm3 of alkali were required to neutralize its acidity.
What was the mass of aspirin in the tablet?
[2]
A soluble aspirin contains the calcium salt of aspirin.
What reagent could you use to convert aspirin into its calcium salt?
Suggest why aspirin is insoluble in water whereas its calcium salt is soluble.
(a) reaction I : reagents and conditions: CH3COCl, r.t.p [1]
reaction II: reagents and conditions: CH3OH, conc. H2SO4, heat [1]
-

COO Na

(b) (i)

OH

[1]
-

COO Na

(ii)

[3]

O Na

[1]

COOH
O 2N

COOH

OH
NO 2
OH
(iii)
or
[1]
-3
(c) naspirin = (13.9/1000) x 0.1 = 1.39 x 10 mol [1]
Maspirin = 1.39 x 10-3 x [9(12) + 8(1) + 4(16)] = 0.250 g [1]
(d) (i) Ca(OH)2 [1]
(ii) Aspirin has more extensive intramolecular hydrogen bond.This reduces the
extent of hydrogen bond with water molecules. [1] Its calcium salt is ionic and
forms favourable ion-dipole interactions with the water molecules, thus easily
solvated. [1]

2.

Compound B has the structure as shown below:

OH
CHC

OH

O
(a)

Show how compound B can be synthesized starting from benzoic acid. Your answer
should include the intermediate compound(s) formed and the reagents and conditions
required for each of the step(s).
[4]

(b)

Compound B reacts with concentrated sulphuric acid under reflux to produce cyclic
compound C with molecular formula C16H12O4. C is neutral to litmus and has no reaction
with 2,4-DNPH. Draw the structure of compound C.
[1]
Solutions:
(a) Step 1
Reagents and conditions: LiAlH4 in dry ether, r.t.p

COOH + 4[H]

LiAlH4 in dry ether

CH2OH

rtp

+ H 2O
[1]

Step 2
Reagents and conditions: K2Cr2O7 in H2SO4 (aq), distillation
O
K2Cr2O7/H+
+ [O]
C +
CH2OH
distillation

H2O

[1]

Step 3
Reagents and conditions: HCN in NaOH (aq), 10 20 oC
[1]

CN
CHO + HCN

NaOH (aq)
o

10-20 C

CH
OH

Step 4
Reagents and Conditions: HCl (aq), heat

CN
+

CH + 2H2O + H
OH

reflux

CHCOOH

+ NH4+

OH
Compound B

[1]

(b)
O
C
O
CH

Self Esterification
CH
O

O
Compound C

3.

[1]

Values of the acid dissociation constants, Ka, for some weak acids are shown below:
acid
Formula
Ka / mol dm-3
Benzoic acid
C6H5COOH
6.5 x 10-5
Carbonic acid
H2CO3
4.5 x 10-7
Ethanoic acid
CH3COOH
1.8 x 10-5
Methanol
CH3OH
3.0 x 10-16
Phenol
C6H5OH
1.3 x 10-10
(a) Which of these weak acids are stronger than carbonic acids?

[1]

(b) Calculate the pH of 0.10 mol dm-3 of phenol

[1]

(c) Explain in terms of their molecular structures why methanol and phenol have
significantly different Ka values.
[2]
(d) Methyl benzoate, C6H5CO2CH3 and phenyl ethanoate, CH3CO2C6H5 are isomers.
(i)
Outline how methyl benzoate may be formed from benzoic acid.
(ii)
Outline how phenyl ethanoate may be produced from ethanoic acid.

[2]

[Total: 6]

(a) Ethanoic acid and benzoic acid (The larger the Ka, the stronger the acid and both of these
acids have a Ka > 4.5 x 10-7) [1]
(b) pH = 5.44 [1]

(c)
For Phenol: [1] for phenol explanation
Phenoxide ion is resonance stabilised, when the p-orbitals of oxygen overlaps with
the electron cloud of the benzene ring.

The negative charge is dispersed over six C atoms which have lower
electronegativity than the O atom.

Stabilises the phenoxide ion, promoting the loss of H+ resulting in a higher Ka value
as compared to methanol.

For methanol: [1] for methanol explanation

Alkoxide ion is not stabilised by charge delocalisation. Presence of electron-donating

alkyl group.

This intensifies the negative charge on the alkoxide ion.

Destabilises the alkoxide ion, least H+ released.

(d)
(i) Reagents and Conditions: CH3OH, concentrated H2SO4, heat [1]
(ii) Step 1: PCl3 (s) or PCl5 (s), rtp
[1]
Step 2: Phenol, r.t.p.

END