Ngo & Sons Chemistry

Module 6: Acid/Base Reactions

Marking Guidelines

Section I

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Multiple-choice Answer Key

Question Answer

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1 B
2 B
3
4
5
C
D
A
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6 B
7 A
8 D
9 C
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10 B
a

Rationale
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1 Lavoisier stated that acidic properties were due to the presence of oxygen while Davy
stated that they were due to the presence of hydrogen. Hydrochloric acid (HCl) only
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contains hydrogen and hence is classified as an acid by Davy.

2 The initial dip indicates that the solution is a weak base due to the formation of a buffer
solution. The pH after the equivalence point is very low, indicating that the acid used
was strong. Therefore, HCl (aq) and NH3 (aq) may have been the reactants.
3 As the initial pH was above 7.0, the solution was basic. The weakness of the base causes
the concentration of conductive OH – to be low, leading to a low initial conductivity.
After the equivalence point, H+ ions are added in excess from the strong acid, increasing
conductivity drastically.

4 a
pH = − log10 [H3 O+ ] =⇒ [H3 O+ ] = 10−pH

[H3 O+ ]initial = 10−2 mol L−1

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[H3 O+ ]final = 10−6 mol L−1

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c1 v1 = c2 v2

10−2 × 0.01 = 10−6 × v2

O v2 = 100 L

water added = 100 − 0.01 = 99.99 L

&S
5 Hydrobromic acid is a strong acid and hence has a low pH (pH = − log10 [H3 O+ ]). The
ammonium ion is the conjugate acid of the weak base ammonia and hence hydroly-
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ses preferentially to reform ammonia molecules by donating a hydrogen ion to water,

forming H3 O+ . Hence, ammonium nitrate is acidic. The fluoride ion is the conjugate
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base of the weak acid hydrofluoric acid and hence hydrolyses preferentially to reform
hydrofluoric acid molecules by accepting a hydrogen ion from water, forming OH – .
Hence, sodium fluoride is basic.
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6 Methyl orange is red in a solution with pH < 3.1 and yellow in a solution with pH > 4.4.

−−* − +
CH3 COOH (aq) + H2 O (l) )−− CH3 COO (aq) + H3 O (aq)

pKa = − log10 Ka = 4.74 (from Question 7)

[H3 O+ ][CH3 COO− ]

Ka = = 10−4.74
[CH3 COOH]

[CH3 COO− ] = [H3 O+ ] (1:1 molar ratio)

[CH3 COOH]initial = [CH3 COOH]eq = 0.10 mol L−1

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(small Ka )

[H3 O+ ]2
= 10−4.74
0.10

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p
[H3 O+ ] = 10−4.74 × 0.10 = 1.35 × 10−3 mol L−1

pH = − log10 [H3 O+ ] = − log10 (1.35 × 10−3 ) = 2.87 < 3.1

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&S
7 The larger the value of pKa , the weaker the acid. Hence, the weakest acid is methylam-
monium. Denote methylammonium using HA.

−−* + −
HA (aq) + H2 O (l) )−− H3 O (aq) + A (aq)
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pKa = − log10 [H3 O+ ] = 10.64

[H3 O+ ][A− ]
Ka = = 10−10.64
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[HA]

[A− ] = [H3 O+ ] (1:1 molar ratio)

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[HA]initial = [HA]eq = 0.10 mol L−1 (small Ka )

[H3 O+ ]2
= 10−10.64
0.10
p
[H3 O+ ] = 10−10.64 × 0.10 = 1.51 × 10−6 mol L−1

pH = − log10 [H3 O+ ] = − log10 (1.51 × 10−6 ) = 5.82

pOH = 14 − pH = 14 − 5.82 = 8.18

8 a
n(NaOH) = cv = 0.05 × 0.25 = 0.0125 mol

n(HNO2 ) = cv = 0.075 × 0.3 = 0.0225 mol

NaOH (aq) + HNO2 (aq) −−→ NaNO2 (aq) + H2 O (l)

n(NaOH)reacted = n(HNO2 )reacted (1:1 molar ratio)

n(HNO2 )excess = n(HNO2 )initial = n(NaOH) = 0.0225 − 0.0125 = 0.01 mol

n 0.01
[HNO2 ] = = = 0.08 mol L−1

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v 0.05 + 0.075

n(NaOH)reacted = n(NaNO2 ) = 0.0125 mol (1:1 molar ratio)

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n 0.0125
[NaNO2 ] = [NO2 − ] = = = 0.1 mol L−1
v 0.05 + 0.075
+ −
HNO2 (aq) + H2 O (l) −
)−
−*
− H3 O (aq) + NO2 (aq)

Ka = O
[H3 O+ ][NO2 − ]
[HNO2 ]
= 4.6 × 10−4
&S
[HNO2 ]initial = [HNO2 ]eq = 0.08 mol L−1 (small Ka )

[NO2 − ]initial = [NO2 − ]eq = 0.1 mol L−1 (small Ka )

[H3 O+ ] = 4.6 × 10−4 × 0.08 ÷ 0.1 = 3.68 × 10−4 mol L−1

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pH = − log10 [H3 O+ ] = − log10 (3.68 × 10−4 ) = 3.43

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 9 a
pOH = − log10 [OH− ] = 14 − pH = 14 − 7.40 = 6.60

[OH− ] = 10−6.60 mol L−1

HCO3 − (aq) + H2 O (l) )

−−
−* −
− H2 CO3 (aq) + OH (aq)

[OH− ][H2 CO3 ]

Kb = − = 2.3 × 10−8
[HCO3 ]
[H2 CO3 ] 2.3 × 10−8
= = 0.0916
[HCO3 − ] 10−6.60

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n(H2 CO3 )  n
= 0.0916 c=
n(HCO3 − ) v

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n(H2 CO3 ) = cv = 0.1 × 0.1 = 0.01 mol
1 × 0.01
n(HCO3 − ) = n(NaHCO3 ) = = 0.109 mol (1:1 molar ratio)
0.0916

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m(NaHCO3 ) = n × MM = 0.109 × (22.99 + 1.008 + 12.01 + 16 × 3) = 9.17 g
&S
10 Denote the metal hydroxide by XOH where X is the metal.

m 5.00 5.00
n(XOH) = = = mol
MM MM(X) + 16 + 1.008 MM(X) + 17.008
q 5.00 × 44.5 222.5
∆Hsol = − =⇒ qsol = = kJ
ndissolved MM(X) + 17.008 MM(X) + 17.008
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XOH (aq) + HNO3 (aq) −−→ XNO3 (aq) + H2 O (l)

5.00
n(H2 O)formed = n(XOH)reacted = mol L−1 (1:1 molar ratio)
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MM(X) + 17.008
q 5.00 × 58.3 291.5
∆Hneut = − =⇒ qneut = = kJ
n(H2 O) MM(X) + 17.008 MM(X) + 17.008
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qtotal = mc∆T = (100 + 5) × 4.18 × (54.2 − 25) = 12816 J = 12.8 kJ

qtotal = qsol + qneut

514
12.8 =
MM(X) + 17.008
514
MM(X) = − 17.008 = 23.10 g mol−1
12.8

This molar mass corresponds to sodium.

Section II

Question 11

An Arrhenius base ionises/dissociates in water to release hydroxide ions. Sodium hydroxide

releases hydroxide ions into water via the dissolution equation

NaOH (s) −−→ Na+ (aq) + OH− (aq).

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A Brønsted-Lowry base accepts protons from another species. The hydroxide ion in sodium
hydroxide accepts a proton from water and hence satisfies the definition.

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OH− (aq) + H2 O (l) −
)−
−* −
− H2 O (l) + OH (aq)

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1 mark − explains why NaOH is an Arrhenius base
1 mark − explains why NaOH is a Brønsted-Lowry base
&S
Question 12

+ −
C2 H5 NH2 (aq) + H2 O (l) −
)−
−*
− C2 H5 NH3 (aq) + OH (aq)
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pKb = − log10 Kb = 3.19

[C2 H5 NH3 + ][OH− ]

Kb = = 1.0 × 10−3.19
[C2 H5 NH2 ]
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[C2 H5 NH3 + ] = [OH− ] (1:1 molar ratio)

[C2 H5 NH2 ] ≈ 0.10 mol L−1 (assuming negligible ionisation due to small Kb )
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[OH− ]2
= 1.0 × 10−3.19
0.10
p
[OH− ] = 1.0 × 10−4.19 = 8.04 × 10−3 mol L−1

[OH− ] 8.04 × 10−3

% ionisation = × 100% = × 100% = 8.0%
[C2 H5 NH2 ] 0.10

1 mark − writes down the expression for Kb AND finds its value
1 mark − correctly calculates the percentage ionisation of the ethylamine solution
Question 13

An acid-base indicator suitable for a titration must change colour in accordance to the pH at
the equivalence point.

Hydrofluoric acid is a weak acid (ionises incompletely in water) while hydroiodic acid is a
strong acid (ionises completely in water). Hence, titrating hydrofluoric acid with potassium
hydroxide will produce a basic salt due to the conjugate base’s (F – (aq)) tendency to reform

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HF (aq) molecules.

F− (aq) + H2 O (l) −−
−* −
− HF (aq) + OH (aq)

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)

Hence, a basic indicator such as phenolphthalein should be used. However, the titration with

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hydroiodic acid will produce a neutral salt as I – (aq) will not reform HI (aq) molecules. Hence,
a neutral indicator such as bromothymol blue should be used.
&S
1 mark − identifies AND explains why phenolphthalein should be used for hydrofluoric acid
1 mark − identifies AND explains why bromothymol blue should be used for hydroiodic acid
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Question 14

Ammonia is a weak base and hence ionises partially in water.

+ −
NH3 (aq) + H2 O (l) −
)−
−*
− NH4 (aq) + OH (aq)

Adding hydrochloric acid introduces H+ (aq) ions that react with the OH – (aq) ions to produce
water.

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H+ (aq) + OH− (aq) −−→ H2 O (l)

Hence, adding HCl (aq) removes OH – ions from the solution, favouring the forward reaction

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to counteract the removal of product by Le Chatelier’s principle. The continuous removal of
OH – (aq) causes the reaction to assume completion much like sodium hydroxide, a strong base.
Therefore, the volume required is the same.
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1 mark − explains why the reaction with NH3 goes to completion
&S
1 mark − correctly identifies that the same volume of hydrochloric acid is required

Question 15
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Validity refers to how well the procedure addresses the aim of the experiment. As such, known
variables must be controlled and appropriate equipment must be used to. Rinsing the bulb
pipette with distilled water causes the standard solution to be transferred to be diluted. Hence,
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its actual concentration will differ from the one predetermined, thereby failing to control a
variable. Further, blowing through the pipette adds CO2 (g) which reacts with water to form
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H2 CO3 (aq). This reacts with the basic standard solution, reducing its concentration. Moreover,
the salt produced from the titration will be acidic due to the dissolution of the produced CO2 (g)
to form H2 CO3 (aq). However, phenolphthalein changes colour in a basic pH region and hence a
smaller volume of HCl (aq) is needed to achieve the end point compared to the volume required
for complete neutralisation. These errors cause the calculated concentration of the HCl (aq)
solution to be too high. Therefore, this procedure is invalid due to the failure to control these
variables as well as the lack of accuracy in the results.

1 mark each − identifies AND explains ONE error that affects the validity of the experiment
Question 16

6.6

5.4

4.8

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Temperature increase (◦ C)

4.2

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3.6

2.4

1.8
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1.2

0.6
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0
0 5 10 15 20 25 30 35 40 45 50
Time elapsed (s)
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Please turn over

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From the graph, the increase in temperature at the equivalence point is 6.15◦ C, achieved after
25 seconds.

n(HCl) = cv = 2 × 0.025 = 0.05 mol

n(NH4 OH) = cv = 2 × 0.05 = 0.1 mol

HCl (aq) + NH4 OH (aq) −−→ NH4 Cl (aq) + H2 O (l)

n(HCl)reacted
=1 (1:1 molar ratio)
n(NH4 OH)reacted

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n(HCl) 0.05
= <1
n(NH4 OH) 0.1

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∴ HCl is the limiting reagent

n(H2 O)formed = n(HCl)reacted = 0.05 mol (1:1 molar ratio)

∆Hneut = −
q
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q = mc∆T = (25 + 50) × 4.18 × 6.15 = 1928 J = 1.928 kJ

=−
1.928
= −38.6 kJ mol−1
&S
n(H2 O) 0.05

1 mark − correctly labels the axes of the graph including units

1 mark − accurately plots all points AND sketches TWO correct lines of best fit
1 mark − finds the amount of energy released from the neutralisation reaction
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1 mark − correctly calculates the enthalpy of neutralisation

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Question 17

Ammonia is a weak base and hence only partially ionises in water.

+ −
NH3 (aq) + H2 O (l) −
)−
−*
− NH4 (aq) + OH (aq)

During the titration, adding HCl introduces H+ ions to the equilibrium which react with OH –
ions to form water.

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H+ (aq) + OH− (aq) −−→ H2 O (l)

Hence, adding HCl removes OH – ions from the equilibrium. By Le Chatelier’s principle, the

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forward reaction will be favoured to counteract this change, causing further ionisation. As HCl
is continually added, the reaction essentially goes to completion and therefore all OH – ions are
released.
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However, the pH probe only measures the concentration of OH – at equilibrium, and hence the
&S
concentration will be less than the titration. As pH = − log10 [H+ ] and [OH – ] is higher in the
titration, the pH from the titration will consequently be higher than the pH probe.

1 mark − explains that the pH probe only measures [OH – ] from partial ionisation
1 mark − explains why the titration finds [OH – ] such that all ammonia is ionised
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1 mark − correctly identifies that the pH probe produces a lower pH than the titration
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Question 18

Neutralisation reactions are applied readily in the pharmaceutical, agricultural, and chemical
industry.

In the pharmaceutical industry, antacids are a class of medication used to relieve acid reflux
caused by excess stomach acid. This relief is achieved via a neutralisation reaction with the
basic active ingredient in antacids, typically milk of magnesia (Mg(OH)2 ).

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In the agricultural industry, plants grow better when the pH of its soil is within a certain range.
Hence, neutralisation reactions are used to make the soil more acidic or basic. Soil is made more

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acidic by adding compost which decomposes to form carbon dioxide gas, reacting with water to
form carbonic acid. This neutralises basic substances in the soil, decreasing its pH. Conversely,
soil is made more basic by adding lime (solid CaCO3 ) to neutralise acidic substances in soil.

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In the chemical industry, sodium bicarbonate is used to neutralise spills of acidic and basic
substances due to the ability of the bicarbonate ion to react with both types (amphoteric). It is
&S
also a weak base, minimising the heat produced from the neutralisation reaction.

1 mark each − describes ONE industrial application of neutralisation reactions

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Question 19

Before the titration,

[NaOH] = [OH− ] = 0.200 mol L−1 (1:1 molar ratio)

pH + pOH = 14

pH = 14 − pOH = 14 + log10 [OH− ] = 14 + log10 0.200 = 13.301

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At the equivalence point,

NaOH (aq) + HCN (aq) −−→ NaCN (aq) + H2 O (l)

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n(NaCN)formed = n(NaOH)reacted

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= cv = 0.025 × 0.2 = 0.005 mol

n(NaCN) = n(CN− ) = 0.005 mol

(1:1 molar ratio)

(1:1 molar ratio)

&S
n 0.005
[CN− ] = = = 0.0859 mol L−1
v 0.025 + 0.0332

pKa = − log10 Ka = 9.200

Ka × Kb = Kw
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Kw 10−14
Kb = = −9.2 = 10−4.8
Ka 10

CN− (aq) + H2 O (l) )

−−
−* −
− HCN (aq) + OH (aq)
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[HCN][OH− ]
Kb = = 10−4.8
[CN− ]
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Please turn over

a

[OH− ] = [HCN] (1:1 molar ratio)

[CN− ] ≈ 0.0859 mol L−1 (assume negligible ionisation due to small Kb )

[OH− ]2
= 10−4.8
0.0859
p
[OH− ] = 10−4.8 × 0.0859 = 1.17 × 10−3 mol L−1

pOH = − log10 [OH− ] = − log10 (1.17 × 10−3 ) = 2.933

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pH = 14 − pOH = 14 − 2.933 = 11.067

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1 mark − finds the initial pH
1 mark − finds the concentration of cyanide ions at the equivalence point

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1 mark − writes down the Kb expression for cyanide AND finds its value
1 mark − correctly calculates the pH at the equivalence point
&S
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Question 20

A primary standard is a substance that is used to prepare a standard solution (accurately known
concentration). This standard solution is used to determine the concentration of a strong
acid/base solution before titrating the latter against the analyte. Accuracy refers to how well the
actual measurement compares to a theoretical measurement − as the concentration of the stan-
dard solution is accurately known, the subsequent calculations involving the strong acid/base
and analyte will be accurate provided that there are no further errors.

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The accuracy of the concentration of the standard solution stems from the high purity and
non-reactivity to atmospheric substances of the primary standard, and its relatively high mo-

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lar mass which allows an accurate measurement of its mass, minimising weighing errors.
An example of a basic primary standard is sodium carbonate which satisfies these criteria −
MM = 22.99 × 2 + 12.01 + 16 × 3 = 105.99 g mol−1 .

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1 mark − explains the process from primary standard to the titration of the analyte
1 mark − explains why the calculations following the use of the primary standard will be ac-
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curate
1 mark − explains why primary standards produce a solution with an accurately known con-
centration
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Question 21

PV 100 × 0.335
PV = nRT =⇒ n = = = 0.0135 mol
RT 8.314 × (273.15 + 25)

HCl (g) + NaHCO3 (aq) −−→ NaCl (aq) + H2 O (l) + CO2 (g)

n(HCl)reacted = n(CO2 )formed = 0.0135 mol (1:1 molar ratio)

−−
CO2 (g) + H2 O (l) )−*
− H2 CO3 (aq)

n(H2 CO3 )formed = n(CO2 )dissolved = 0.0135 mol (complete dissolution, 1:1 molar ratio)

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n 0.0135
[H2 CO3 ] = = = 0.541 mol L−1
v 0.025

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+ −
H2 CO3 (aq) + H2 O (l) −
)−
−*
− H3 O (aq) + HCO3 (aq)

[H3 O+ ][HCO3 − ]
Ka =
[H2 CO3 ]
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pH = − log10 [H3 O+ ] = 4.118
&S
[H3 O+ ] = 1.000 × 10−4.118 mol L−1

[HCO3 − ] = [H3 O+ ] = 1.000 × 10−4.118 mol L−1 (1:1 molar ratio)

(1.000 × 10−4.118 )2
Ka = = 1.074 × 10−8
0.541
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Ka × Kb = Kw = 1.000 × 10−14

1.000 × 10−14
Kb = −8
= 9.309 × 10−7
1.074 × 10
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∴ pKb = − log10 Kb = − log10 (9.309 × 10−7 ) = 6.031

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1 mark − finds the amount of carbonic acid formed

1 mark − writes down the Ka expression for carbonic acid
1 mark − finds the value of Ka for carbonic acid
1 mark − correctly calculates the pKb of the bicarbonate ion
Question 22 (a)

The nitric acid reacts with ammonia to produce ammonium ions:

NH3 (aq) + HNO3 (aq) −−→ NH4 + (aq) + NO3 − (aq).

The ammonia molecules and ammonium ions form a buffer solution according to the equations

NH3 (aq) + H2 O (l) −−→ NH4 + (aq) + OH− (aq)

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NH4 + (aq) + H2 O (l) −−→ NH3 (aq) + H3 O+ (aq).

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Adding hydrochloric acid introduces H3 O+ ions to the solution. This increases [H3 O+ ] in the
second equation. By Le Chatelier’s principle, the reverse reaction is favoured to counteract this
change. Adding sodium hydroxide introduces OH – ions to the solution. This increases [OH – ]

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in the first equation. By Le Chatelier’s principle, the reverse reaction is favoured to counteract
this change.
&S
Either way, the change in [H3 O+ ] and [OH – ] is minimised due to the shift of equilibrium,
thereby resisting changes in pH (− log10 [H3 O+ ]).

1 mark − identifies that the ammonia molecules and ammonium ions establish equilibrium
1 mark − explains how the change in pH in minimised
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Question 22 (b)

n(NH3 ) = cv = 0.075 × 1.00 = 0.075 mol

n(HNO3 ) = 0.05 × 0.5 = 0.025 mol

n(NH3 )reacted = n(HNO3 )reacted (1:1 molar ratio)

n(NH3 ) > n(HNO3 )

∴ nitric acid is limiting

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n(NH4 + )formed = n(HNO3 )reacted = 0.025 mol (1:1 molar ratio)

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n(NH3 )excess = 0.075 − n(NH3 )reacted = 0.075 − 0.025 = 0.05 mol

n(NH3 ) = 2n(NH4 + )

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Therefore, twice the volume of hydrochloric acid can be added compared to sodium hydroxide
without significantly changing the pH of the solution.
&S
1 mark − shows that the amount of ammonia is twice the amount of ammonium
1 mark − correctly identifies that twice the volume of hydrochloric acid can be added
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Question 23

Find the concentration of the oxalic acid solution.

m 1.55
n((COOH)2 ) = = = 0.0172 mol
MM 2 × (12.01 + 16 × 2 + 1.008)
n 0.0172
[(COOH)2 ] = = = 0.0689 mol L−1
v 0.25

The titre volumes of the standardisation of sodium hydroxide are 21.45 mL, 21.30 mL, 21.30

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mL, and 21.35 mL. The last three volumes are concordant, so find the concentration of sodium
hydroxide.

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2 NaOH (aq) + (COOH)2 (aq) −−→ 2 NaCOO (aq) + 2 H2 O (l)

n(NaOH)reacted = 2n((COOH)2 )reacted (2:1 molar ratio)

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cNaOH vNaOH = 2c(COOH)2 v(COOH)2
2c(COOH)2 v(COOH)2 2 × 0.0689 × 0.025
&S
cNaOH = = 1 = 0.162 mol L−1
vNaOH 3 (0.0213 × 2 + 0.02135)

Find the amount of hydrochloric acid reacted with the metal.

HCl (aq) + NaOH (aq) −−→ NaCl (aq) + H2 O (l)

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n(HCl)reacted = n(NaOH)reacted (1:1 molar ratio)

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The titre volumes are 34.10 mL, 31.55 mL, 30.60 mL, 31.50 mL, and 31.60 mL. The 2nd, 4th,
and 5th titres are concordant.
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1
n(HCl) = cv = 0.162 × (0.03155 + 0.03160 + 0.03150) = 5.10 × 10−3 mol
3

n(HCl)remaining = 10 × 5.10 × 10−3 = 5.10 × 10−2 mol (25 mL aliquot from 250 mL)

n(HCl)initial = cv = 1.35 × 0.05 = 0.0675 mol

n(HCl)reacted = 0.0675 − 5.10 × 10−2 = 0.0165 mol

Please turn over

As the second ionisation energy of the metal is significantly higher than the first, it has a valency
of 2 as the second electron is being removed from a non-valence shell. Let the metal be X.

2 HCl (aq) + XCO3 (aq) −−→ H2 O (l) + CO2 (g) + XCl2 (aq)
1
n(XCO3 )reacted = n(HCl)reacted (1:2 molar ratio)
2
1
= × 0.0165 = 8.27 × 10−3 mol
2
m 1.63
MM(XCO3 ) = = = 197.1 g mol−1

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n 8.27 × 10−3

MM(X) + 12.01 + 16 × 3 = 197.1

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MM(X) = 137.1 g mol−1

Therefore, the identity is barium carbonate.

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1 mark − finds the concentration of the oxalic acid solution
1 mark − finds the concentration of the sodium hydroxide solution
&S
1 mark − finds the amount of hydrochloric acid reacted with the metal carbonate
1 mark − correctly deduces the identity of the metal carbonate
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G
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