Ionic Equilibria

CIE A Level Chemistry Topical Paper 4 Topic 7: Ionic Equilibria
7 Equilibria
This topic illustrates that many chemical reactions are reversible and involve an equilibrium process.
The consideration of the many factors that can affect an equilibrium is an important aspect of physical
chemistry.
Learning outcomes
Candidates should be able to:
7.2 Ionic equilibria c) explain the terms pH, Ka, pKa and Kw and use them in calculations
d) calculate [H+(aq)] and pH values for strong and weak acids and
strong bases
e) explain the choice of suitable indicators for acid-base titrations,
given appropriate data
f) describe the changes in pH during acid-base titrations and explain
these changes in terms of the strengths of the acids and bases
g) (i) explain how buffer solutions control pH
(ii) describe and explain the uses of buffer solutions, including the
role of HCO3 – in controlling pH in blood
h) calculate the pH of buffer solutions, given appropriate data
i) show understanding of, and use, the concept of solubility product,
Ksp
j) calculate Ksp from concentrations and vice versa
k) show understanding of the common ion effect
7.3 Partition coefficients a) state what is meant by partition coefficient; calculate and use a
partition coefficient for a system in which the solute is in the same
molecular state in the two solvents
NIAZ AHMED AWAN (niaz.awan564@gmail.com +923004255956)

1 (a) Write an expression for Kw.

For
Examiner's
.................................................................................................................................... [1] Use
(b) Use your expression to help you calculate the pH of 0.200 mol dm–3 NaOH(aq).
..........................................................................................................................................
.................................................................................................................................... [2]
(c) The pH of 0.200 mol dm–3 NH3(aq) is 11.3. Explain why this answer differs from your
answer in (b).
..........................................................................................................................................
.................................................................................................................................... [1]
(d) A 20.0 cm3 sample of 0.200 mol dm–3 NH3(aq) was titrated with 0.100 mol dm–3 HC
On the following axes, sketch how the pH changes during this titration. Mark clearly
where the end point occurs.
l.
14
pH 7
0
0 10 20 30 40 50 60
volume of added acid / cm3
[3]
9701/4/S02
For
(e) From the following list of indicators, put a tick in the box by the side of the indicator you Examiner's
Use
consider most suitable for this titration.
pH at which colour place one tick only

indicator
changes in this column
methyl violet 0.0 - 1.6
methyl orange 3.1 - 4.4
bromothymol blue 6.0 - 7.6
phenolphthalein 8.3 - 10.0

[1]
(f) A solution containing NH3(aq) and NH4Cl(aq) acts as a buffer solution, resisting
changes in pH when acids or alkalis are added.
Explain with the help of equations how this mixture acts as a buffer.
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..................................................................................................................................... [2]
[Total: 10]
9701/4/S02
For
Examiner’s
2 (a) Barium ions are poisonous. Patients with digestive tract problems are sometimes given Use
an X-ray after they have swallowed a ‘barium meal’, consisting of a suspension of
BaSO4 in water. The [Ba2+(aq)] in a saturated solution of BaSO4 is too low to cause
problems of toxicity.
(i) Write an expression for the solubility product, Ksp, for BaSO4, including its units.
...................................................................................................................................
(ii) The numerical value of Ksp is 1.30 × 10–10. Calculate [Ba2+(aq)] in a saturated
solution of BaSO4.
...................................................................................................................................
...................................................................................................................................
(iii) The numerical value of Ksp for BaCO3 (5 × 10–10) is not significantly higher than
that for BaSO4, but barium carbonate is very poisonous if ingested. Suggest a
reason why this might be so.
...................................................................................................................................
...................................................................................................................................
[3]
(b) A useful commercial source of magnesium is sea water, where [Mg2+(aq)] is

0.054 mol dm–3. The magnesium is precipitated from solution by adding calcium
hydroxide.
Mg2+(aq) + Ca(OH)2(s) → Ca2+(aq) + Mg(OH)2(s)
(i) Write an expression for the Ksp of Mg(OH)2, including its units.
...................................................................................................................................
(ii) The numerical value for Ksp is 2.00 x 10–11. Calculate [Mg2+(aq)] in a saturated
solution of Mg(OH)2.
...................................................................................................................................
...................................................................................................................................
(iii) Hence calculate the maximum percentage of the original magnesium in the
seawater that this method can extract.
...................................................................................................................................
...................................................................................................................................
[5]
9701/04/M/J/03
For
3 (a) Methanoic acid, HCO2H, is a weak acid, with Ka = 1.77 x 10–4 mol dm–3. Examiner’s
Use
(i) Write an expression for the Ka of methanoic acid.
...................................................................................................................................
–3
(ii) Use your expression to calculate the [H+] in a 0.0500 mol dm solution of
methanoic acid.
...................................................................................................................................
(iii) Calculate the percentage of HCO2H molecules that are ionised in this solution.
(iv) Calculate the pH of this solution.
...................................................................................................................................
[4]
(b) Calculate the pH of a 0.0500 mol dm–3 solution of the strong acid HCl.
......................................................................................................................................[1]
(c) Both HCO2H and HCl react with powdered magnesium metal, giving off hydrogen gas.
For a fixed amount of magnesium, the rate equation for the reaction is as follows.
rate = k [H+(aq)]
(i) Write an equation for the reaction between HCO2H and Mg.
...................................................................................................................................
When 20.0 cm3 of a 0.0500 mol dm–3 solution of either acid is reacted with an excess of
powdered magnesium, the same volume of hydrogen is given off, but the methanoic
acid solution reacts much more slowly than the hydrochloric acid.
(ii) Calculate the volume of hydrogen given off.

9701/4/O/N/03
................................................................................................................................... For
Examiner’s
Use
(iii) Explain why the hydrogen is evolved more slowly from the methanoic acid solution.
...................................................................................................................................
...................................................................................................................................
(iv) Explain why, eventually, the methanoic acid solution produces just as much
hydrogen as the hydrochloric acid solution.
...................................................................................................................................
...................................................................................................................................
...............................................................................................................................[5]
[Total : 10]

9701/4/O/N/03
For
4
Examiner’s
Sulphuric acid is a strong dibasic acid, which ionises in solution as follows. Use
H2SO4(aq) 2H+(aq) + SO42–(aq)
(a) The organic base guanidine contains carbon, nitrogen and hydrogen. Its reaction with
acids can be represented as follows.
B(aq) + H+ (aq) BH+(aq)
where B represents the molecule of guanidine.
When a 25.0 cm3 sample of dilute sulphuric acid was titrated against a solution of
guanidine, the following titration curve was obtained.
14
pH
0
0 10 20 30 40 50 60 70
Volume of guanidine added / cm3
Use this curve to answer the following questions.
(i) Is guanidine a strong or a weak base? Explain your answer.
...................................................................................................................................
...................................................................................................................................
(ii) The pH at the start of the titration was 0.70. Calculate the [H+], and hence the
concentration of sulphuric acid, at the start of the titration.
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
© UCLES 2004 9701/04/O/N04

For
(iii) Calculate the concentration of guanidine in the solution in mol dm–3. Examiner’s
Use
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
(iv) The guanidine solution contained 8.68 g of the base per dm3. Use your answer to
(iii) calculate the Mr of guanidine.
.............................................................................................................................. [6]
(b) One of the major industrial uses of sulphuric acid is to convert phosphate rock (calcium
fluorophosphate(V)) into ‘superphosphate’ for use as a fertiliser. The process can be
represented by the following partially balanced equation.
2 Ca5(PO4)3F + 7H2SO4 → ....... CaSO4 + ....... Ca(H2PO4)2 + ....... HF

‘superphosphate’
(i) Balance the above equation.
(ii) Use your balanced equation to calculate the mass of H2SO4 required to
manufacture 1.0 kg of superphosphate fertiliser.
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
.............................................................................................................................. [4]
(c) Solutions of hydrogenphosphates make useful buffers for biochemical experiments.
H2PO4– HPO42– + H+
(i) Explain what is meant by the term buffer solution.
...................................................................................................................................
...................................................................................................................................
(ii) Calculate the pH of a buffer solution that contains 0.20 mol dm–3 NaH2PO4 and
0.10 mol dm–3 Na2HPO4. [Ka (H2PO4–) = 6.3 x 10–8 mol dm–3]
...................................................................................................................................
...................................................................................................................................
.............................................................................................................................. [3]
[Total: 13]
© UCLES 2004 9701/04/O/N04 [Turn over

For
Examiner's
5 (a) Give an expression for Ka as applied to the weak acid RCO2H. Use
..........................................................................................................................................
.................................................................................................................................... [1]
(b) The Ka values for three carboxylic acids are listed in the table below.
acid Ka / mol dm–3
CH3CO2H 1.8 × 10–5
ClCH2CO2H 1.4 × 10–3
Cl2CHCO2H 5.5 × 10–2
(i) Describe and explain the trend in acid strength illustrated by these values.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
(ii) Calculate the pH of a 0.100 mol dm–3 solution of ClCH2CO2H.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
(iii) Calculate the pKa value for Cl 2CHCO2H.
..................................................................................................................................
..................................................................................................................................
[5]
© UCLES 2005 9701/04/M/J/05

(c) The acid ClCH2CO2H features in the industrial synthesis of the important weedkiller For
Examiner's
2,4-D. Use
OH OH OCH2CO2H
Cl Cl
I II
+ NaOH
+ ClCH2CO2H
phenol
Cl Cl
2,4-D
(i) Suggest a possible reagent for reaction I.
..................................................................................................................................
(ii) What type of reaction is
reaction I, .................................................................................................................
reaction II? ...............................................................................................................

(iii) Describe a test (reagents and observations) that would distinguish phenol from
compound A.
CH2OH
compound A
reagents ...................................................................................................................
observation with phenol ...........................................................................................
observation with compound A ..................................................................................

[5]
[Total: 11]
© UCLES 2005 9701/04/M/J/05

6 Monuments made of marble or limestone, such as the Taj Mahal in India and the Mayan
For
Examiner’s
temples in Mexico, are suffering erosion by acid rain. The carbonate stone is converted by Use
the acid rain into the relatively more soluble sulphate.
CaCO3(s) + H2SO4(aq) → CaSO4(s) + H2O(l) + CO2(g)

acid rain
(a) (i) Write an expression for the solubility product, Ksp, of CaSO4, stating its units.
...................................................................................................................................
(ii) The Ksp of CaSO4 has a numerical value of 3 x 10–5. Use your expression in (i) to
calculate [CaSO4] in a saturated solution.
...................................................................................................................................
(iii) Hence calculate the maximum loss in mass of a small statue if 100 dm3 of acid rain
falls on it. Assume the statue is made of pure calcium carbonate, and that the acid
rain becomes saturated with CaSO4.
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
[5]
(b) The life of such monuments is now being extended by treating them with a mixture of
urea and barium hydroxide solutions. After soaking into the pores of the carbonate rock,
the urea gradually decomposes to ammonia and carbon dioxide. The carbon dioxide
then reacts with the barium hydroxide to form barium carbonate.
(NH2)2CO(aq) + H2O(l) ⎯→ 2NH3(g) + CO2(g)
Ba(OH)2(aq) + CO2(g) ⎯→ BaCO3(s) + H2O(l)
Acid rain then converts the barium carbonate to its sulphate.
BaCO3(s) + H2SO4(aq) ⎯→ BaSO4(s) + H2O(l) + CO2(g)
Barium sulphate is much less soluble than calcium sulphate. A saturated solution
contains [Ba2+] = 9.0 x 10–6 mol dm–3.
(i) Explain why barium sulphate is less soluble than calcium sulphate.
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................

© UCLES 2006 9701/04/M/J/06
For
(ii) Write an expression for the Ksp of barium sulphate and use the data to calculate its Examiner’s
value. Use
...................................................................................................................................
...................................................................................................................................
[4]
(c) (i) Explain what is meant by the term lattice energy.
...................................................................................................................................
...................................................................................................................................
(ii) Predict, with a reason, how the lattice energy of BaSO4 might compare with that of
MgSO4.
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
[3]
[Total: 12]
© UCLES 2006 9701/04/M/J/06 [Turn over

For
Examiner’s
7 Ibuprofen is one of the most commonly used non-steroidal anti-inflammatory drugs, used to Use
treat chronic arthritic pain caused by inflammation of the joints.
CH3
CH3 CH O
C
CH
CH3 CH2 OH
ibuprofen
(a) (i) Draw a circle around any chiral centre(s) in the above structure.
(ii) Write down the molecular formula of ibuprofen.
...................................................................................................................................
(iii) Calculate the Mr of ibuprofen and use it to calculate how many grams are
needed to make 100 cm3 of a 0.15 mol dm–3 solution.
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
(iv) Vigorous oxidation of ibuprofen produces a dibasic acid A. A solution containing

0.10 g of A required 12.0 cm3 of 0.10 mol dm–3 NaOH for neutralisation.
Suggest a structure for A, showing your working.
...................................................................................................................................
[7]
(b) The Ka value for ibuprofen is 6.3 × 10–6 mol dm–3.
(i) Write an expression for Ka.
...................................................................................................................................
(ii) Use the Ka value to calculate the pH of a 0.15 mol dm–3 solution of ibuprofen.
...................................................................................................................................
...................................................................................................................................
[3]
© UCLES 2006 9701/04/O/N/06

For
Examiner’s
(c) To avoid problems with digestive irritation over a long period of use, research is being Use
carried out into ways of administering ibuprofen using skin patches. For this use the
compound is dissolved in a hydrophilic gel which acts as a buffer.
(i) What do you understand by the term buffer ?
...................................................................................................................................
...................................................................................................................................
The buffer used in the pharmaceutical preparation is a solution containing Na2HPO4

and NaH2PO4. These salts contain the HPO2– –
4 and H2PO 4 ions respectively.
(ii) Write equations to show how this buffer reacts with
H+ ions, ....................................................................................................................
OH– ions. .................................................................................................................
(iii) A buffer solution containing equal concentrations of the two sodium phosphate
salts has a pH of 7.20.
Calculate the pH of a pharmaceutical preparation containing 0.002 mol dm–3 of
Na2HPO4 and 0.005 mol dm–3 of NaH2PO4.
[5]
[Total: 15]
© UCLES 2006 9701/04/O/N/06 [Turn over

For
8 (a) Use the general formula of a carboxylic acid, RCO2H, to write equations to explain the Examiner’s
following terms. Use
(i) Ka .............................................................................................................................
(ii) pKa ...........................................................................................................................

[2]
(b) The pKa values of four carboxylic acids are listed in the table below.
acid formula of acid pKa
1 CH3CH2CO2H 4.9
2 CH3CHCl CO2H 2.8
3 CH3CCl2CO2H 1.4
4 CH2Cl CH2CO2H 4.1
(i) Describe and explain the trend in acid strength shown by acids 1, 2 and 3.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
(ii) Suggest an explanation for the difference in the pKa values for acids 2 and 4.
..................................................................................................................................
..................................................................................................................................
(iii) Calculate the pH of a 0.010 mol dm–3 solution of propanoic acid (acid 1).
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
[6]
© UCLES 2007 9701/04/O/N/07

9 (c) The solubility product, Ksp, of magnesium hydroxide has a numerical value of For
Examiner’s
2.0 × 10–11. Use
(i) Write an expression for the Ksp of magnesium hydroxide, stating its units.
..................................................................................................................................
(ii) Use the value of Ksp given to calculate the concentration of Mg(OH)2 in a saturated
solution.
..................................................................................................................................
..................................................................................................................................
(iii) Explain whether magnesium hydroxide would be more or less soluble in

0.1 mol dm–3 MgSO4(aq) than in water.
..................................................................................................................................
..................................................................................................................................
[5]
[Total: 12]
10 (a) Explain what is meant by the Bronsted-Lowry theory of acids and bases.
..........................................................................................................................................
..........................................................................................................................................
..................................................................................................................................... [2]
(b) The Ka values for some organic acids are listed below.
acid Ka /mol dm−3
CH3CO2H 1.7 10−5
Cl CH2CO2H 1.3 10−3
Cl 2CHCO2H 5.0 10−2
(i) Explain the trend in Ka values in terms of the structures of these acids.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
(ii) Calculate the pH of a 0.10 mol dm−3 solution of Cl CH2CO2H.
pH = ...........................................
© UCLES 2007 9701/04/O/N/07
For
(iii) Use the following axes to sketch the titration curve you would obtain when 20 cm3 of Examiner’s
0.10 mol dm−3 NaOH is added gradually to 10 cm3 of 0.10 mol dm−3 Cl CH2CO2H. Use
14
pH 7
0
0 5 10 15 20
volume of NaOH added / cm3
[8]
(c) (i) Write suitable equations to show how a mixture of ethanoic acid, CH3CO2H, and
sodium ethanoate acts as a buffer solution to control the pH when either an acid or
an alkali is added.
..................................................................................................................................
..................................................................................................................................
(ii) Calculate the pH of a buffer solution containing 0.10 mol dm−3 ethanoic acid and
0.20 mol dm−3 sodium ethanoate.
pH = ...........................................
[4]
[Total: 14]

11 (c) Calcium hydroxide, Ca(OH)2, is slightly soluble in water. For

Examiner’s
(i) Write an expression for Ksp for calcium hydroxide, and state its units. Use
Ksp = units ............................................
(ii) 25.0 cm3 of a saturated solution of Ca(OH)2 required 21.0 cm3 of 0.0500 mol dm–3
HCl for complete neutralisation.
Calculate the [OH–(aq)] and the [Ca2+(aq)] in the saturated solution, and hence
calculate a value for Ksp.
[OH–(aq)] = .................................
[Ca2+(aq)] = ................................
Ksp = .........................................................................................
(iii) How would the solubility of Ca(OH)2 in 0.1 mol dm–3 NaOH compare with that in
water?
Explain your answer.
..................................................................................................................................
..................................................................................................................................
[6]
[Total: 14]

12 When an aqueous solution of compound G, NH2CH2CH2CH2NH2, is titrated with HCl(aq), For

Examiner’s
two successive acid-base reactions take place. Use
(a) Write equations for these two acid-base reactions.
..........................................................................................................................................
...................................................................................................................................... [2]
(b) A 0.10 mol dm–3 solution of G has a pH of 11.3. When 30 cm3 of 0.10 mol dm–3 HCl is
added to 10 cm3 of a 0.10 mol dm–3 solution of G, the final pH is 1.6.
Using the following axes, sketch the pH changes that occur during this addition of
HCl(aq).
12
pH 7
0
0 10 20 30
volume of HCl(aq) added / cm3
[2]
[Total: 4]
© UCLES 2010 9701/43/O/N/10

13 (a) State briefly what is meant by the following terms. For

Examiner’s
Use
(i) reversible reaction
..................................................................................................................................
(ii) dynamic equilibrium
..................................................................................................................................
..................................................................................................................................
[2]
(b) Water ionises to a small extent as follows.
H2O(l) H+(aq) + OH–(aq) ΔH = +58 kJ mol–1
(i) Write an expression for Kc for this reaction.
..................................................................................................................................
(ii) Write down the expression for Kw, the ionic product of water, and explain how this
can be derived from your Kc expression in (i).
..................................................................................................................................
..................................................................................................................................
(iii) State and explain how the value of Kw for hot water will differ from its value for cold
water.
..................................................................................................................................
..................................................................................................................................
[3]
(c) Kw can be used to calculate the pH of solutions of strong and weak bases.
(i) Use the value of Kw in the Data Booklet to calculate the pH of 0.050 mol dm–3
NaOH.
pH = ...........................................
Ammonia ionises slightly in water as follows.
NH3(aq) + H2O(l) NH4+(aq) + OH–(aq)
The following expression applies to this equilibrium.
[H2O] × Kc= [NH4+][OH–] / [NH3] = 1.8 × 10–5 mol dm–3
© UCLES 2011 NIAZ AHMED AWAN (niaz.awan564@gmail.com

9701/41/M/J/11 +923004255956)
For
(ii) Calculate [OH–(aq)] in a 0.050 mol dm–3 solution of NH3. You may assume that only Examiner’s
a small fraction of the NH3 ionises, so that [NH3] at equilibrium remains at Use
0.050 mol dm–3.
[OH–(aq)] = .................................
(iii) Use the value of Kw in the Data Booklet, and your answer in (ii), to calculate [H+(aq)]
in 0.050 mol dm–3 NH3(aq).
[H+(aq)] = ...................................
(iv) Calculate the pH of this solution.
pH = ...........................................
[6]
[Total: 11]
© UCLES 2011 9701/41/M/J/11

14 (a) Hydrogen fluoride, HF, behaves as a weak acid in water, with Ka = 5.6 × 10–4 mol dm–3. For
Examiner’s
Use
Calculate the pH of a 0.050 mol dm–3 solution of HF.
pH = ....................................... [2]
(b) Gaseous ammonia and hydrogen fluoride react together to give solid ionic ammonium
fluoride.
NH3(g) + HF(g) NH4F(s) ΔH = –147 kJ mol–1
(i) What type of reaction is this?
..................................................................................................................................
(ii) Draw dot-and-cross diagrams (outer shells only) describing the bonding in the three
compounds involved in this reaction.
NH3 HF NH4F
(iii) There are three types of bonding in NH4F.

Give the names of each of the three types, and state where in the compound each
type occurs.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
(iv) The reaction between NH3 and HF is reversible. What conditions of temperature
and pressure would favour the reverse reaction, i.e. the dissociation of NH4F?
Explain your answer.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
[9]
© UCLES 2011 NIAZ AHMED AWAN (niaz.awan564@gmail.com

9701/42/M/J/11 +923004255956)
16 (e) Solutions of amino acids are good buffers. For

Examiner’s
Use
(i) What is meant by the term buffer?
..................................................................................................................................
(ii) Write an equation to show how a solution of alanine, CH3CH(NH2)CO2H, behaves

as a buffer in the presence of an acid such as HCl(aq).
..................................................................................................................................
(iii) Briefly describe how the pH of blood is controlled.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
(iv) Calculate the pH of the buffer formed when 10.0 cm3 of 0.100 mol dm–3 NaOH is
added to 10.0 cm3 of 0.250 mol dm–3 CH3CO2H, whose pKa = 4.76.
pH = ......................................................
[7]
[Total: 19]
© UCLES 2011 9701/43/O/N/11

For
17 (c) (i) Write an expression for Ksp of silver sulfate, Ag2SO4, including units. Examiner’s
Use
Ksp = .................................................. units ..................................................
Using a similar experimental set-up to that illustrated opposite, it is found that [Ag+] in a
saturated solution of Ag2SO4 is 1.6 × 10–2 mol dm–3.
(ii) Calculate the value of Ksp of silver sulfate.
Ksp = ...................................
[3]
(d) Describe how the colours of the silver halides, and their relative solubilities in NH3(aq),
can be used to distinguish between solutions of the halide ions Cl –, Br – and I –.
...........................................................................................................................................
...........................................................................................................................................
...........................................................................................................................................
...........................................................................................................................................
...........................................................................................................................................
...........................................................................................................................................
..................................................................................................................................... [4]
(e) Describe and explain the trend in the solubilities of the sulfates of the elements in Group II.
...........................................................................................................................................
...........................................................................................................................................
...........................................................................................................................................
...........................................................................................................................................
...........................................................................................................................................
...........................................................................................................................................
..................................................................................................................................... [4]
[Total: 18]

For
18 (c) The reaction between Fe3+ ions and I– ions is an equilibrium reaction. Examiner’s
Use
2Fe3+(aq) + 2I–(aq) 2Fe2+(aq) + I2(aq)
(i) Use the Data Booklet to calculate the for this reaction.
....................................................................................................................................
(ii) Hence state, with a reason, whether there will be more products or more reactants
at equilibrium.
....................................................................................................................................
....................................................................................................................................
(iii) Write the expression for Kc for this reaction, and state its units.
Kc =
units .................................................
An experiment was carried out using solutions of Fe3+(aq) and I–(aq) of equal
concentrations. 100 cm3 of each solution were mixed together, and allowed to reach
equilibrium.
The concentrations at equilibrium of Fe3+(aq) and I2(aq) were as follows.
[Fe3+(aq)] = 2.0 × 10–4 mol dm–3

[I2(aq)] = 1.0 × 10–2 mol dm–3
(iv) Use these data, together with the equation given in (c), to calculate the concentrations
of Fe2+(aq) and I–(aq) at equilibrium.
[Fe2+(aq)] = ............................... mol dm–3
[I–(aq)] = ............................... mol dm–3
(v) Calculate the Kc for this reaction.
Kc = ......................................................
[8]
[Total: 15]
© UCLES 2013 9701/41/M/J/13

19 (b) A buffer solution is to be made using 1.00 mol dm–3 ethanoic acid, CH3CO2H, and For
Examiner’s
1.00 mol dm–3 sodium ethanoate, CH3CO2Na. Use
Calculate to the nearest 1 cm3 the volumes of each solution that would be required to
make 100 cm3 of a buffer solution with pH 5.50.
Clearly show all steps in your working.
Ka (CH3CO2H) = 1.79 × 10–5 mol dm–3
volume of 1.00 mol dm–3 CH3CO2H = ......................... cm3
volume of 1.00 mol dm–3 CH3CO2Na = ......................... cm3

[4]
(c) Write an equation to show the reaction of this buffer solution with each of the following.
(i) added HCl .................................................................................................................
(ii) added NaOH ..............................................................................................................

[2]

For
20 (a) (i) Using the symbol HZ to represent a Brønsted-Lowry acid, write equations which Examiner’s
show the following substances acting as Brønsted-Lowry bases. Use
NH3 + →
CH3OH + →
(ii) Using the symbol B– to represent a Brønsted-Lowry base, write equations which
show the following substances acting as Brønsted-Lowry acids.
NH3 + →
CH3OH + →
[4]
(b) State briefly what is meant by the following terms.
(i) reversible reaction
....................................................................................................................................
(ii) dynamic equilibrium
....................................................................................................................................
....................................................................................................................................
[2]
(c) (i) Explain what is meant by a buffer solution.
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(ii) Explain how the working of a buffer solution relies on a reversible reaction involving
a Brønsted-Lowry acid such as HZ and a Brønsted-Lowry base such as Z–.
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
[4]
© UCLES 2013 9701/42/O/N/13

For
(d) Propanoic acid, CH3CH2CO2H, is a weak acid with Ka = 1.34 × 10–5 mol dm–3. Examiner’s
Use
(i) Calculate the pH of a 0.500 mol dm–3 solution of propanoic acid.
Buffer solution F was prepared by adding 0.0300 mol of sodium hydroxide to 100 cm3 of
a 0.500 mol dm–3 solution of propanoic acid.
(ii) Write an equation for the reaction between sodium hydroxide and propanoic acid.
....................................................................................................................................
(iii) Calculate the concentrations of propanoic acid and sodium propanoate in buffer
solution F.
[propanoic acid] = ................................ mol dm–3
[sodium propanoate] = ................................ mol dm–3
(iv) Calculate the pH of buffer solution F.
pH = ................................
[6]

21 (c) (i) Write the expression for Kw. For

Examiner’s
Use
.............................................................................................................................................
(ii) Use your expression and the value of Kw in the Data Booklet to calculate the pH of
0.150 mol dm–3 NaOH(aq).
(iii) The pH of a 0.150 mol dm–3 solution of piperidine is 11.9.
HN
piperidine
Suggest why this answer differs from your answer in (c)(ii).
.............................................................................................................................................
.............................................................................................................................................
(iv) How would you expect the basicity of piperidine to compare to that of ammonia?
Explain your reasoning.
.............................................................................................................................................
.............................................................................................................................................
[5]
© UCLES 2014 9701/41/M/J/14

For
(d) 20.0 cm3 of 0.100 mol dm–3 HCl was slowly added to a 10.0 cm3 sample of 0.150 mol dm–3 Examiner’s
Use
piperidine. The pH was measured throughout the addition.
(i) Calculate the number of moles of HCl remaining at the end of the addition.
moles of HCl = .....................
(ii) Hence calculate the [H+] and the pH at the end of the addition.
pH = .....................
(iii) On the following axes, sketch how the pH will change during the addition of a total of
20.0 cm3 of 0.100 mol dm–3 HCl. Mark clearly where the end point occurs.
14
pH
7
0
0 5 10 15 20
volume HCl added / cm3
(iv) From the following list of indicators, put a tick in the box by the side of the indicator most
suitable for this titration.
pH at which place one tick only

indicator
colour changes in this column
A 0-1
B 3-4
C 11 - 12
D 13 - 14
[6]
[Total: 16]
© UCLES 2014
NIAZ AHMED AWAN (niaz.awan564@gmail.com
9701/41/M/J/14
+923004255956) [Turn over
For
22 (c) The acid dissociation constant, Ka, of ethanoic acid is 1.75  10–5 mol dm–3. Examiner’s
Use
(i) Explain why this value of Ka is
● much larger than that of ethanol, CH3CH2OH,
.............................................................................................................................................
.............................................................................................................................................
● smaller than that of chloroethanoic acid, Cl CH2CO2H.
.............................................................................................................................................
.............................................................................................................................................
(ii) Calculate the pH of a 0.100 mol dm–3 solution of ethanoic acid.
[4]
(d) 20.0 cm3 of 0.100 mol dm–3 NaOH were slowly added to a 10.0 cm3 sample of 0.100 mol dm–3
ethanoic acid, and the pH was measured throughout the addition.
(i) Calculate the number of moles of NaOH remaining at the end of the addition.
(ii) Calculate the [OH–] at the end of the addition.
(iii) Using the expression Kw = [H+][OH–] and your value in (ii), calculate [H+] and the pH of the
solution at the end of the addition.
© UCLES 2014 9701/42/M/J/14

(iv) On the following axes, sketch how the pH will change during the addition of a total of For
20.0 cm3 of 0.100 mol dm–3 NaOH. Mark clearly where the end point occurs. Examiner’s
Use
14
pH
7
0
0 5 10 15 20
volume NaOH added / cm3
(v) From the following list of indicators, put a tick in the box by the side of the indicator you
consider most suitable for this titration.

indicator
malachite green 0-1

thymol blue 1-2
bromophenol blue 3-4
thymolphthalein 9 - 10
[7]
[Total: 15]
23 (d) Phosphate ions in water can be removed by adding a solution containing Ca2+(aq) ions, which
form a precipitate of calcium phosphate, Ca3(PO4)2.
(i) Write an expression for the Ksp of Ca3(PO4)2.
Ksp =
(ii) The solubility of Ca3(PO4)2 is 2.50 × 10–6 mol dm–3 at 298 K.
Calculate the solubility product, Ksp, of Ca3(PO4)2 at this temperature. Include the units.
Ksp = .................................................................. units ....................................................

[4]

For
Examiner’s
24 (a) The following circuits were set up using aqueous hydrochloric and aqueous ethanoic acids as Use
electrolytes. Assume that the two circuits were identical apart from the electrolyte.
bulb switch bulb switch

1 2
graphite graphite
1 mol dm–3 1 mol dm–3
electrodes electrodes
HCl (aq) CH3CO2H(aq)
When the switches were closed, bulb 1 was brighter than bulb 2. Explain why.
....................................................................................................................................................
....................................................................................................................................................
....................................................................................................................................................
.............................................................................................................................................. [2]
(b) (i) State what is meant by a buffer solution.
.............................................................................................................................................
.............................................................................................................................................
(ii) Outline how a buffer solution can be prepared from ethanoic acid and a named base.
.............................................................................................................................................
.............................................................................................................................................
[4]
(c) Amino acids such as alanine, CH3CH(NH2)CO2H, can act as a buffer solution.
Construct two equations to illustrate this.
equation 1
equation 2
[2]
© UCLES 2014 9701/43/O/N/14

For
Examiner’s
(d) Tartaric acid is present in many plants. Use
OH O
HO
OH
O OH
tartaric acid
(i) Tartaric acid has two dissociation constants, K1 and K2, for which the pKa values are 2.99
and 4.40.
Suggest equations showing the two dissociations that give rise to these pKa values.
pKa 2.99
pKa 4.40
(ii) One stereoisomer of tartaric acid is shown.
HO
H
CO2H
HO2C
H
OH
Complete the diagrams showing two other stereoisomers of tartaric acid.
CO2H CO2H
[4]
[Total: 12]

25 (a) (i) What is meant by the term buffer solution? For

Examiner’s
Use
.............................................................................................................................................
.............................................................................................................................................
....................................................................................................................................... [2]
(ii) Write equations to show how the hydrogencarbonate ion, HCO3–, controls the pH of blood.
.............................................................................................................................................
....................................................................................................................................... [2]
(iii) A solution containing both Na2HPO4 and NaH2PO4 is commonly used as a buffer solution.
The following equilibrium is present in the solution.
H2PO4–(aq) HPO42–(aq) + H+(aq) Ka = 6.2 × 10–8 mol dm–3
Calculate the pH of a buffer solution made by mixing 100 cm3 of 0.5 mol dm–3 Na2HPO4 and
100 cm3 of 0.3 mol dm–3 NaH2PO4.
pH = ........................ [2]
(b) Silver phosphate, Ag3PO4, is sparingly soluble in water.
(i) Write an expression for the solubility product, Ksp, of Ag3PO4, and state its units.
Ksp = units: .............................. [1]
(ii) The numerical value of Ksp is 1.25 × 10–20 at 298 K. Use this value to calculate [Ag+(aq)] in
a saturated solution of Ag3PO4.
[Ag+(aq)] = ............................................... mol dm–3 [3]
NIAZ AHMED AWAN (niaz.awan564@gmail.com

9701/42/M/J/15 +923004255956)
(c) The half-equation for the redox reaction between phosphoric(III) acid and phosphoric(V) acid is For
Examiner’s
shown. Use
H3PO4(aq) + 2H+(aq) + 2e– H3PO3(aq) + H2O(l) E o = –0.28 V
Find suitable data from the Data Booklet to write an equation for the reaction between H3PO
and Fe3+(aq) ions, and calculate the for the reaction. 3
equation: ....................................................................................................................................
= ..................... V [2]
[Total: 12]
26 (a) Silver sulfate, Ag2SO4, is sparingly soluble in water. The concentration of its saturated solution
is 2.5 × 10–2 mol dm–3 at 298 K.
(i) Write an expression for the solubility product, Ksp, of Ag2SO4, and state its units.
Ksp = units: .............................. [1]
(ii) Calculate the value for Ksp(Ag2SO4) at 298 K.
Ksp = ............................................... [1]

Ϯϳ (c) (i) Write the expression for Kw. For

Examiner’s
Use
.............................................................................................................................................
(ii) Use your expression and the value of Kw in the Data Booklet to calculate the pH of
0.150 mol dm–3 NaOH(aq).
(iii) The pH of a 0.150 mol dm–3 solution of piperidine is 11.9.
HN
piperidine
Suggest why this answer differs from your answer in (c)(ii).
.............................................................................................................................................
.............................................................................................................................................
(iv) How would you expect the basicity of piperidine to compare to that of ammonia?
Explain your reasoning.
.............................................................................................................................................
.............................................................................................................................................
[5]
9701/41/M/J/14
For
(d) 20.0 cm3 of 0.100 mol dm–3 HCl was slowly added to a 10.0 cm3 sample of 0.150 mol dm–3 Examiner’s
Use
piperidine. The pH was measured throughout the addition.
(i) Calculate the number of moles of HCl remaining at the end of the addition.
moles of HCl = .....................
(ii) Hence calculate the [H+] and the pH at the end of the addition.
pH = .....................
(iii) On the following axes, sketch how the pH will change during the addition of a total of
20.0 cm3 of 0.100 mol dm–3 HCl. Mark clearly where the end point occurs.
14
pH
7
0
0 5 10 15 20
volume HCl added / cm3
(iv) From the following list of indicators, put a tick in the box by the side of the indicator most
suitable for this titration.

indicator
A 0-1
B 3-4
C 11 - 12
D 13 - 14
[6]
[Total: 16]
9701/41/M/J/14


Page 2 Mark Scheme Syllabus Paper
A/AS LEVEL EXAMINATIONS – JUNE 2003 9701 4
2 (a) (i) Ksp = [Ba2+][SO42-] [1] units: mol2dm-6 [1] ecf
(ii) [Ba2+] = √(1.3 x 10-10) = 1.14 x 10-5 (mol dm-3) [1]
(iii) BaCO3 can react with/dissolve in the acid/HCl in the stomach [1]
(or unbalanced equation showing, e.g. BaCO3 + HCl →) 4
(b) (i) Ksp = [Mg2+][OH-]2 [1] units: mol3dm-9 [1] ecf
(ii) calling [Mg2+] = x, then Ksp = x(2x)2 = 4x3 è x = 3 (Ksp/4) [1]
¡ [Mg2+] = 3 (2 x 10-11/4) = 1.7 x 10-4 (mol dm-3) [1]

allow ecf for use of 3
(iii) % left = 100 x (1.7 x 10-4)/(0.054) = 0.32%
¡ % extracted = 99.7 (%) [1]

A/AS LEVEL EXAMINATIONS – NOVEMBER 2003 9701 4
3 (a) (i) Ka = [HCO2–][H+]/HCO2H] (1)
(ii) √Ka[HCO2H] = √1.77 X 10–4 x 0.05 = 2.97 x 10–3 (1)

(3.0 x 10–3)
(iii) 100 x 2.97 x 10–3/ 0.05 = 5.94% (6%) (1)
(iv) pH = –log10(2.97 x 10–3) = 2.5(2) (1) [4]
(b) pH = –log10(0.05) = 1.30 (1) [1]
(c) (i) 2HCO2H + Mg → (HCO2)2Mg + H2 (1)

(or 2H+ + Mg → Mg2+ + H2)
(ii) moles of H+ = 0.05 x 20/1000 = 1 x 10–3 (1)
moles of H2 = 1 x 10–3/2 = 0.5 x 10–3
volume of H2 = 0.5 x 10–3 x 24, 000 = 12 cm3 (1)

(or = 0.5 x 10–3 x 22400 = 12 cm3
(iii) (rate α [H+]) lower [H+] in methanoic acid or HCO2H dissociates

slowly/partially (1)
(iv) the equilibrium (HCO2H ¾ HCO2– + H+) continually shifts to the

right as H+ is used up (1) [5]

A LEVEL – NOVEMBER 2004 9701 4
4 (a) (i) strong, because final pH is about 14 [1]
(ii) (pH = 0.70) ⇒ [H+] = 10-0.7 = 0.20 (mol dm-3) [1]
∴ [H2SO4] = (0.10 mol dm-3) ecf [1]
(iii) (end point is at 34.0 cm3 ( ± 0.5 cm3), so)
amount of H+ used = 0.2 x 25/1000 = 0.0050 mol ecf from (ii) [1]
moles of guanidine = moles of H+ = 0.0050 mol
[guanidine] = 0.005 x 1000/34.0 = 0.147 (mol dm-3) [1]
allow range: 0.145 – 0.149 ecf in 0.005 or 34.0 [1]
(iv) Mr = 8.68/0.147 = 59 (allow range 58 – 60) ecf from (iii) [1] 6
(b) (i) 7 CaSO4 + 3 Ca(H2PO4)2 + 2 HF [1]
(ii) Mr values: Ca(H2PO4)2 = 234.1, H2SO4 = 98.0 [1]
234.1 x 3 = 702.3 98 x 7 = 686 both [1]
ecf from ratios in equation, and from Mr values
∴ mass of H2SO4 needed = 1.0 x 686/702.3 = 0.98 kg [1]
(correct answer = [3] marks. accurate value is: 0.977 kg.

Allow ecf from incorrect Mr or incorrect multipliers) 4
(c) (i) A solution that resists changes in pH [NOT: results in no pH change] [1]
when small amounts of H+ or OH- are added [1]
(ii) pH = -log10(6.3 x 10-8) + log10(0.1/0.2) = 6.9 [1]
or [H+] = (6.3 x 10-8) x 0.2/0.1 = 1.26 x 10-7
∴ pH = -log10(1.26 x 10-7) = 6.9 3
Total 13


A LEVEL – JUNE 2005 9701 4
5 (a) Ka = [RCO2-][H+]/[RCO2H] [1]
Part (a): [1]
(b) (i) The more chlorine atoms in the molecule, the stronger the acid, [1]
due to the electron-withdrawing (inductive) effect of Cl... [1]

either...stabilising the anion, or spreading (-) charge more,
or...weakening the O-H bond in the acid, or...increasing ionisation,
or…facilitates H+ donation
or…causing the equilibrium RCO2H RCO2- + H+ to lie further to
the right.
Mark is conditional on reference to the effect of presence of
chlorine. [1]
(ii) [H+] = √(0.1 x 1.4 x 10-3) = 0.0118 (mol dm-3) allow 0.012 [1]
∴ pH = -log10(0.0118) = 1.93 Allow 1.9 or 1.92 e.c.f. [1]
(iii) pKa = -log10(5.5 x 10-2) = 1.26 Allow 1.3 [1]
Part (b): [6]
(c) (i) Cl2(aq) AlCl3 or UV negates [1]
(ii) Electrophilic substitution or addition-elimination [1]
Nucleophilic substitution or electrophilic substitution on OH group

If neither mark is awarded, could give “salvage” mark for
substitution x2 [1]
(iii) Either: add Br2(aq) phenol decolourises it, or gives a white ppt.
or: add FeCl3(aq) phenol give a purple colour
or: add NaOH(aq) phenol dissolves
or: add UI solution phenol goes yellow/orange (A stays green)
or: add “diazonium”to solution in OH-
phenol gives orange/red colour
(in each case, A give no reaction)
or: add Cr2O72-/H+/warm A changes colour from orange to green

or: add MnO4-/H+/warm A changes from purple to colourless
or: add PCl5/POCl3/PCl3/SOCl2 A gives fumes
or: add CH3CO2H + conc. H2SO4 A gives fruity smell
(in each case, no change with phenol)
Test + reagents [1] Both observations [1]
Part (c): [5]
Total: [12]


GCE A/AS Level – May/June 2006 9701 04
6 (a) (i) Ksp = [Ca

2+ 2-
][SO 4 ] [1]
units are: mol2dm-6 ecf [1]
(ii) [CaSO4] = √Ksp = 5.5 x 10-3 (5.477 x 10-3)(mol dm-3) ecf [1]
(iii) n(CaSO4) in 100 dm3 = 5.5 x 10-3 x 100 = 0.55 moles ecf from (ii) [1]
Mr(CaSO4) = 136.1
Thus mass(CaSO4) = 0.55 x 136.1 = 74.8g (0.55 x Mr) [1]
(if the accurate [CaSO4] is held throughout the calculation, ans = 74.5g) [5]
(b) (i) down the group: the ∆Hsolution becomes more endothermic;
both lattice energy and ∆Hhydration become less (exothermic);
due to ionic radius (of M2+) increasing;
but ∆Hhydration changes more than lattice energy any three points [3]
(ii) Ksp = [Ba2+][SO42-] = (9 x 10-6)2 = 8.1 x 10-11 NO ecf [1]

[4]
(c) (i) LE is the energy change when 1 mole of (ionic) solid [1]
is formed from its gaseous ions [1]
(ii) LE(BaSO4) < LE(MgSO4), due to larger radius of Ba2+ both points [1] [3]
[Total: 12]

GCE A/AS LEVEL - OCT/NOV 2006 9701 4
7 (a) (i) [one chiral centre only] (1)

(ii) C13H18O2 (1)
(iii) Mr = 206 ecf (1)
mass = 0.15 x (100/1000) x 206 = 3.1 g ecf (1)
(correct ans = (2) marks)
(iv) n(NaOH) = 0.1 x 12/100 = 1.2 x 10-3 moles (1)
n(A) = 0.6 x 10-3, so Mr = 0.1/(0.6 x 10-3) = 167 (allow 166-170) (1)

(correct ans = (2) marks)
This fits with HO2C-C6H4-CO2H (which has Mr = 166) (1) [7]
(b) (i) (Ka =) [H+][A-]/[HA] (1)
(ii) [H+] = √Ka.c = √6.3 x 10-6 x 0.15 = 9.72 x 10-4 (1)
pH = 3.0 (1) (correct ans = (2) marks) [3]

(c) (i) one that resists/control/maintains changes in pH (NOT no change in pH) (1)
when small amounts of acid/H+ (or base/OH-) are added. (1)
(ii) HPO42- + H+ → H2PO4- (1)

H2PO4- + OH- → HPO42- + H2O (1)
(iii) pH = pKa + log ([base]/[acid])

= 7.2 + log (.002/.005) = 6.8 (2)
(correct ans = (2) marks: deduct (1) for each error,
e.g. if ratio is upside down, hence pH = 7.6, answer is worth (1)) [6]
[Total: 16 max 15]


GCE A/AS LEVEL – October/November 2007 9701 04
8 (a) (i) Ka = [H+][RCO2–]/[RCO2H] [1]
(ii) pKa = –log10Ka or –logKa or log [H+]2/[RCO2H] NOT ln; [1]

[2]
(b) (i) acid strength increases from no. 1 to no. 3 or down the table or as Cls increase [1]
due to the electron-withdrawing effect/electronegativity of chlorine (atoms) [1]
stabilising the anion or weakening the O-H bond NOT H+ more available [1]
(ii) chlorine atom is further away (from O-H) in no. 4, so has less influence [1]
(iii) either: pH = ½ (pKa – log10[acid]) or Ka = 10–pKa = 1.259 x 10–3

= ½ (4.9 + 2) [H+] = √(Ka. c) = 3.55 x 10–4 [1]
= 3.4 (allow 3.5) pH = 3.4 ecf [1]
([1] for correct expression & values; [1] for correct working)
[6]

GCE A/AS LEVEL – October/November 2007 9701 04
9 (c) (i) (Ksp =) [Mg2+][OH–]2 [1]

units are mol3dm–9 ecf from Ksp [1]
(ii) (call [Mg(OH)2(aq)] = [Mg2+] = x) ∴ Ksp = 2 x 10–11 = 4x3 [1]
∴ x = 1.71 x 10–4 mol dm–3 ecf [1]
(iii) less soluble because of the common ion effect

or the equilibrium Mg(OH)2(s) Mg2+(aq) + 2OH–(aq) is moved to the left [1]
[5]
[Total: 12]

Page 2 Mark Scheme: Teachers’ version Syllabus Paper

GCE A/AS LEVEL – May/June 2009 9701 04
10 (a) acids are proton/H+ donors [1]

bases are proton/H+ acceptors [1] [2]
(b) (i) more Cl atoms produce a stronger acid or the larger the Ka the stronger the acid
(NOT just “the more Cl atoms, the larger the Ka” – must refer to acid strength) [1]
because the anion/RCO2– is more stable or the O-H bond is weaker/polarised [1]
due to the electronegativity/electron-withdrawing effect of Cl [1]
(ii) [H+] = √(Ka.c) = 0.0114 (mol dm–3) [1]

pH = 1.94 (allow 1.9) ecf from [H+] [1]
(correct answer = [2])
(iii)
start at pH = 1.94 (ecf from (ii) and goes up > 2 pH units before steep portion) [1]
steep portion (over at least 3 pH units) at V = 10 cm3 [1]
flattens off at pH 12–13 [1] [8]
(c) (i) CH3CO2H + OH– → CH3CO2– + H2O [1]
CH3CO2– + H+ → CH3CO2H [1]
(ii) pKa = –log10(1.7 x 10–5) = 4.77 or [H+] = 8.5 x 10–6 (mol dm–3) [1]
pH = pKa + log10(0.2/0.1) = 5.07 (allow 5.1) [1]
(correct answer = [2]) [4]
[Total: 14]

GCE AS/A LEVEL – May/June 2010 9701 42
11 (c) (i) Ksp = [Ca2+][OH– ]2 (needs the charges) units: mol3dm–9 (1) + (1)
(ii) n(H+) = n(OH–) = 0.05 × 21/1000 = 1.05 × 10–3 mol in 25 cm3
[OH– ] = 1.05 × 1000/25 = 4.2 × 10–2 (mol dm–3) (1)
[Ca2+] = 2.1 × 10–2 (mol dm–3) (1)
Ksp = 2.1 × 10–2 × (4.2 × 10–2)2 = 3.7 × 10–5 (1)
(iii) less soluble in NaOH due to the common ion effect or equilibrium is shifted
to the l.h.s. by high [OH– ] (NOT just a mention of Le Chatr on its own) (1) [6]
[Total: 15]

GCE AS/A LEVEL – May/June 2010 9701 43
12 (a) The amino acid is uncharged / neutral / a zwitterion or charges balance / are
equal (NOT “is non-polar”)
It is equally attracted by the anode / + and the cathode / – or attracted by neither
The pH of the buffer is at the isoelectric point/IEP of the amino acid any two (2) [2]
(b) (at pH 10), H2NCH2CO2– or NH2CH2COO– (1) [1]

GCE A LEVEL – May/June 2011 9701 41
13 (a) (i) One that can go in either direction. [1]
(ii) both forward & reverse reactions are going on at the same time, but the concentrations
of all species do not change (owtte)
or rate of forward = rate of backward reaction [1]
(b) (i) Kc = [H+][OH–]/[H2O] [1]
(ii) Kw = [H+][OH–] [1]

rearrangement of equation in (i) gives Kc[H2O] = [H+][OH–] & Kw = Kc[H2O] (owtte)
or the [H2O] is contained within Kw [1]
(iii) Kw will be higher in hot water because reaction is endothermic [1]
(c) (i) [OH–] = 5 × 10–2; [H+] = (1 × 10–14)/ 5 × 10–2 = 2 × 10–13 [1]

pH = –log10[H+] = 12.7 (correct ans = [2]) ecf [1]
(ii) [NH4+] = [OH–] (= x) [1]

x2 = 1.8 × 10–5 × 0.05 ⇒ x (= [OH–]) = 9.49 × 10–4 (mol dm–3) (correct ans = [2]) [1]
(iii) [H+] = Kw/[OH–] = (1 × 10–14)/ 9.49 × 10–4 = 1.05 × 10–11(mol dm–3) ecf [1]
(iv) pH = 11.0 ecf [1]

[Total: 12 max 11]


14 (a) [H+] = √(0.05 × 5.6 × 10–4) = 5.29 × 10–3 mol dm–3 [1]
pH = –log10(5.29 × 10–3) = 2.3 [1]
[2]
(b) (i) (Brønsted-Lowry) acid-base/proton transfer/neutralisation/exothermic/reversible/

equilibrium [1]
(ii)
H N H H F H N H F
H
H
[1] [1] [1] 3 x [1]
(iii) (in NH4F):

covalent: between N & H [1]
dative: between N & H [1]
ionic: between NH4+ & F– or N+ & F– or ammonium and fluoride (i.e. in words)
or between (oppositely charge) ions [1]
(iv) (reverse reaction, remember)

high temperature, because reverse reaction is endothermic [1]
low pressure, because reverse reaction causes an increase in no. of gaseous molecules
or an increase in partial pressure/volume. [1]
[9]

+ GCE A LEVEL
– – October/November 2011 9701 43
16 (e) (i) A buffer is a solution whose pH stays fairly constant or which maintains roughly the
same pH or which resists/minimises changes in pH [1]
when small/moderate amounts of acid/H+ or alkali/OH– are added [1]
(ii) NH2CH(CH3)CO2H + H(Cl) → +NH3CH(CH3)CO2H (+ Cl –) [1]
(iii) blood contain HCO3– (or in an equation) [1]

which absorbs H+ or equn H+ + HCO3– → H2CO3 (H2O + CO2)
–
or absorbs OH or equn OH– + HCO3– → CO32– + H2O [1]
(iv) [CH3CO2Na] = 0.05 [CH3CO2H] = 0.075 [1]

pH = 4.76 + log (0.05/0.075) = 4.58 or 4.6 [1]
[7]
[Total: 19]

GCE A LEVEL – October/November 2012 9701 42
17 (c) (i) Ksp = [Ag+]2[SO42–] [1]

units = mol3 dm–9 ecf on Ksp [1]
(ii) [SO42–] = [Ag+]/2 Ksp = (1.6 × 10–2)2 × 0.8 × 10–2 = 2.05 × 10–6 (mol3 dm–9) [1]
[3]
(d) AgCl white [1]
AgBr cream [1]
AgI yellow [1]
Solubility decreases down the group [1] [4]

(e) solubility decreases down the group [1]
as M2+/ionic radius increases [1]
both lattice energy and hydration(solvation) energy to decrease [1]
enthalpy change of solution becomes more endothermic [1]
[4]
[Total: 18]
9701 42
18 (c) (i) E = 0.77 – 0.54 = 0.23 (V)
⦵
[1]
⦵ ⦵
(ii) Since E is positive/ E >0
So more products / the equilibrium will be over to the right / forward reaction is favoured
ecf from (c)(i) [1]
(iii) Kc = [Fe2+]2[I2] / [Fe3+]2[I–]2 [1]
units are mol–1 dm3 ecf on expression [1]
2+ 2+ –3
(iv) ([Fe ] must always be twice [I2], so) [Fe ] = 0.02 (mol dm ) [1]
– 3+ – –4 –3
([I ] must always be equal to [Fe ], so) [I ] = 2 × 10 (mol dm ) [1]
(v) Kc = {(0.02)2 × 0.01} / {(2 x 10–4)2 × (2 × 10–4)2} correct expression [1]
(allow ecf from incorrect expression in (c)(iii))
(allow ecf from (c)(iv))
= (4 × 10–6) / (1.6 × 10–1.5) = 2.5 × 109 (mol–1 dm3) [1] [8]
[Total: 15]
19 (b) there are two ways of calculating the ratio:
pKa = –log10(Ka) = –log10(1.79 x 10 ) = 4.747 (4.75) or [H+] = 10-5.5 = 3.16 x 10-6
–5
[1]
log10([B] / [A]) = pH – pKa = 0.753 (0.75) or [salt] / [acid] = Ka / [H+] [1]
∴ [B] / [A] = 100.753 = 5.66

or = 1.79 x 10–5 / 3.16 x 10–6 = 5.66
(or [A] / [B] = 0.177) [1]
(correct ratio = [3] marks)
since B + A = 100,∴ (100–A) / A = 5.66 ⇒ vol of acid = 15 cm3
vol of salt = 85 cm3 [1]
[4]
(c) (i) CH3CO2Na + HCl → CH3CO2H + NaCl [1]
(ii) CH3CO2H + NaOH → CH3CO2Na + H2O [1]
[2]


GCE A LEVEL – October/November 2013 9701 42
20 (a) (i) NH3 + HZ → NH4+ + Z- [1]

CH3OH + HZ → CH3OH2+ + Z- [1]
(ii) NH3 + B- → NH2- + BH [1]

CH3OH + B- → CH3O- + BH [1]
[4]
(b) (i) a reaction that can go in either direction [1]
(ii) rate of forward = rate of backward reaction

or forward/back reactions occurring but concentrations of all species do not change [1]
[2]
(c) (i) a solution that resists changes in pH [1]
when small quantities of acid or base/alkali are added [1]
(ii) in the equilibrium system HZ + H2O Z- + H3O+ [1]
addition of acid: reaction moves to the left

or H+ combines with Z- and forms HZ [1]
addition of base: the reaction moves to the right

or H+ combines with OH- and more Z- formed [1]
[5 max 4]
(d) (i) [H+] = √(0.5 × 1.34 × 10-5) = 2.59 × 10-3 (mol dm-3) [1]
pH = 2.59/2.6 (min 1 d.p) ecf [1]
(ii) CH3CH2CO2H + NaOH → CH3CH2CO2Na + H2O [1]
(iii) n(acid) in 100 cm3 = 0.5 × 100/1000 = 0.05 mol

n(acid) remaining = 0.05 – 0.03 = 0.02 mol
[acid remaining] = 0.2 (mol dm-3) [1]
likewise, n(salt) = 0.03 mol

[salt] + 0.3 (mol dm-3) [1]
(iv) pH = 4.87 + log(0.3/0.2) = 5.04–5.05 ecf [1]
[6]

9701 42
21 (c) (i) Kw = [H+][OH–] [1]
(ii) In 0.15 mol dm–3 NaOH, [OH-] = 0.15 mol dm–3
[H+] = Kw / [OH–], so [H+] = 1 × 10–14 / 0.15 = 6.67 × 10–14 mol dm–3 [1]
pH = -log10[H+] = 13.18 (13.2) ecf from [H+] [1]
(iii) piperidine is a poorer proton acceptor
or piperidine is partially ionised [1]
(iv) piperidine should be a stronger base/more basic than ammonia
because of the electron-donating (alkyl/CH2) groups [1]
–3
(d) (i) n(HCl) at start = 0.1 × 20/1000 = 2.0 × 10 mol
n(HCl) at finish = 2 × 10–3 – 1.5 × 10–3 = 0.0005/5 × 10–4 mol [1]
(ii) this is in 30 cm3 of solution, so [HCl] at finish = 0.5 × 10–3/0.030 = 1.67 × 10–2 mol dm–3
pH = –log10(1.67 × 10–2) = 1.78 ecf from (d)(i) [1]
(iii) pH / vol curve: start at pH 11.9 [1]
vertical portion at V = 15 cm3 [1]
levels off at pH 1.8 [1]
(iv) indicator is B [1]
[Total: 16]

9701 42
22 (c) (i) Ka larger than that for ethanol because

the ethanoate ion / CH3CO2– is stabilised by charge delocalisation
or the O–H bond is weakened due to its proximity to C=O / carbonyl group or
the second electronegative / oxygen atom [1]
Ka smaller than that for chloroethanoic acid because
electron-withdrawing / electronegative chlorine (atom) makes the anion more
stable or O–H bond weaker or H more easily lost [1]
(ii) [H+] = √([CH3CO2H] × Ka) = √(0.1 × 1.75 × 10–5) = 1.32(3) × 10–3 (mol dm–3) [1]
pH = –log10[H+] = 2.88 (2.9) [1]

4
(d) (i) n(NaOH) at start = 0.1 × 20/1000 = 2.0 × 10–3 mol
n(NaOH) at finish = 1.0 × 10–3 mol [1]
(ii) this is in 30 cm3 of solution,
so [NaOH] at finish = 1.0 × 10–3 / 0.030 = 3.3(3) × 10–2 mol dm–3 ([2 s.f.) ecf
from (i) [1]
(iii) [H+] = Kw / [OH–] = 1 × 10–14 / 3.33 × 10–2 = 3.0 × 10–13 mol dm–3
pH = –log10[H+] = 12.5(2) [1]
or pOH = –log10(3.33 × 10–2) = 1.48

pH = pKw – pOH = 14 – 1.48 = 12.5(2) [1]
(iv) pH / vol curve: start at pH 2.88 (2.9) ecf [1]

vertical (over at least 2 pH units) portion at V = 10 cm3 [1]
levels off at pH 12.5 ± 0.3 ecf [1]
(v) indicator is thymolphthalein [1]
7
[Total: 15]


Cambridge International A Level – October/November 2014 9701 42
23 (d) (i) Ksp =[Ca2+]3[PO43–]2 1

(ii) [Ca2+] = 3 × 2.50 × 10–6 = 7.50 × 10–6 mol dm–3
[PO43–] = 2 × 2.50 × 10–6 = 5.00 × 10–6 mol dm–3 1
= (7.50 × 10–6)3(5.00 × 10–6)2

= 1.05(1.1) × 10–26 1
mol5dm–15 1 [4]

9701 42
24 (a) (HCl) stronger acid / more dissociated / ionised in solution 1

(HCl has) more ions / higher concentration of ions 1 [2]
(b) (i) A solution that resists changes in the pH / keeps pH fairly constant 1
when small quantities / amounts / vols of acid / H+ or base / OH– are added 1
(ii) add (ethanoic acid) to NaOH OR an equation 1

excess (ethanoic acid) 1 [4]
OR mix with sodium ethanoate
(c) CH3CH(NH2)COOH + H+ CH3CH(NH3+)COOH 1

CH3CH(NH2)COOH + OH– CH3CH(NH2)COO– + H2O 1 [2]
(d) (i) OH O OH O 1
pKa 2.99 HO HO
OH O + H+
O OH O OH
OH O OH O
HO -O
1
pKa 4.40 O O + H+
O OH O OH
HO H
(ii) 2 [4]
H COOH HO COOH
HOOC HOOC
OH H
H OH
(S,R) (R,S)
H
HO COOH
HOOC
OH
H
(R,R)
any two of the above


Cambridge International A Level – May/June 2015 9701 42
25 (a) (i) a solution that resists / minimises a change in its pH or helps maintain its pH..... [2]
(NOT any of: "maintains pH"; "keeps pH constant"; "no change in pH")
.....when small amounts of acid / H+ or base / OH– are added (both acid and
base are needed)
(ii) HCO3– reacts with H+ ions as follows: [2]

HCO3– + H+ → H2CO3 (or H2O + CO2)
–
and with OH ions thus:
HCO3– + OH– → CO32– + H2O
(the equation arrows can be equilibrium arrows, as long as HCO3– is on the left)
(iii) (pKa = –log(Ka) = 7.21) [2]
pH = pKa + log([base] / [acid] = 7.21 + log(0.5 / 0.3)

= 7.43 (7.4)
(b) (i) Ksp = [Ag+]3[PO43–] and units: mol4dm–12 [1]
(ii) call [PO43–] = x, then [Ag+] = 3x, and Ksp = 27x4 [3]
x = (Ksp / 27)1/4 = (1.25 × 10–20 / 27)1/4 = 4.64 × 10–6 mol dm–3
[Ag+] = 3x = 1.39 × 10–5 (mol dm–3) (allow 1.4 × 10–5)
(c) H3PO3 + 2Fe3+ + H2O → H3PO4 + 2Fe2+ + 2H+ [2]
Eocell = 0.77 –(–0.28) = (+)1.05 V
or 3H3PO3 + 3H2O + 2Fe3+ → 3H3PO4 + 6H+ + 2Fe
Eocell = –0.04 –(–0.28) = (+)0.24 V

[Total: 12]

9701 42
26 (a) (i) Ksp = [Ag+(aq)]2[SO42–(aq)] and units: mol3dm–9 1
(ii) Ksp = (2 x 0.025)2 x (0.025) = 6.25 x 10–5 1


Ϯϳ (c) (i) Kw = [H+][OH–] [1]
(ii) In 0.15 mol dm–3 NaOH, [OH-] = 0.15 mol dm–3

[H+] = Kw / [OH–], so [H+] = 1 × 10–14 / 0.15 = 6.67 × 10–14 mol dm–3 [1]
pH = -log10[H+] = 13.18 (13.2) ecf from [H+] [1]
(iii) piperidine is a poorer proton acceptor

or piperidine is partially ionised [1]
(iv) piperidine should be a stronger base/more basic than ammonia

because of the electron-donating (alkyl/CH2) groups [1]
(d) (i) n(HCl) at start = 0.1 × 20/1000 = 2.0 × 10–3 mol

n(HCl) at finish = 2 × 10–3 – 1.5 × 10–3 = 0.0005/5 × 10–4 mol [1]
(ii) this is in 30 cm3 of solution, so [HCl] at finish = 0.5 × 10–3/0.030 = 1.67 × 10–2 mol dm–3
pH = –log10(1.67 × 10–2) = 1.78 ecf from (d)(i) [1]
(iii) pH / vol curve: start at pH 11.9 [1]

vertical portion at V = 15 cm3 [1]
levels off at pH 1.8 [1]
(iv) indicator is B [1]
[Total: 16]

Ionic Equilibria

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Ionic Equilibria

Uploaded by

Copyright:

Available Formats

CIE A Level Chemistry Topical Paper 4 Topic 7: Ionic Equilibria

NIAZ AHMED AWAN (niaz.awan564@gmail.com +923004255956)

1 (a) Write an expression for Kw.

pH at which colour place one tick only

methyl orange 3.1 - 4.4

bromothymol blue 6.0 - 7.6

phenolphthalein 8.3 - 10.0

(b) A useful commercial source of magnesium is sea water, where [Mg2+(aq)] is

Mg2+(aq) + Ca(OH)2(s) → Ca2+(aq) + Mg(OH)2(s)

(i) Write an expression for the Ka of methanoic acid.

(iv) Calculate the pH of this solution.

(ii) Calculate the volume of hydrogen given off.

NIAZ AHMED AWAN (niaz.awan564@gmail.com +923004255956)

NIAZ AHMED AWAN (niaz.awan564@gmail.com +923004255956)

H2SO4(aq) 2H+(aq) + SO42–(aq)

B(aq) + H+ (aq) BH+(aq)

where B represents the molecule of guanidine.

Use this curve to answer the following questions.

(i) Is guanidine a strong or a weak base? Explain your answer.

© UCLES 2004 9701/04/O/N04

2 Ca5(PO4)3F + 7H2SO4 → ....... CaSO4 + ....... Ca(H2PO4)2 + ....... HF

(i) Balance the above equation.

(c) Solutions of hydrogenphosphates make useful buffers for biochemical experiments.

(i) Explain what is meant by the term buffer solution.

© UCLES 2004 9701/04/O/N04 [Turn over

acid Ka / mol dm–3

CH3CO2H 1.8 × 10–5

ClCH2CO2H 1.4 × 10–3

Cl2CHCO2H 5.5 × 10–2

© UCLES 2005 9701/04/M/J/05

(i) Suggest a possible reagent for reaction I.

reaction II? ...............................................................................................................

observation with phenol ...........................................................................................

observation with compound A ..................................................................................

© UCLES 2005 9701/04/M/J/05

CaCO3(s) + H2SO4(aq) → CaSO4(s) + H2O(l) + CO2(g)

(NH2)2CO(aq) + H2O(l) ⎯→ 2NH3(g) + CO2(g)

Ba(OH)2(aq) + CO2(g) ⎯→ BaCO3(s) + H2O(l)

Acid rain then converts the barium carbonate to its sulphate.

BaCO3(s) + H2SO4(aq) ⎯→ BaSO4(s) + H2O(l) + CO2(g)

NIAZ AHMED AWAN (niaz.awan564@gmail.com +923004255956)

(c) (i) Explain what is meant by the term lattice energy.

© UCLES 2006 9701/04/M/J/06 [Turn over

(ii) Write down the molecular formula of ibuprofen.

(iv) Vigorous oxidation of ibuprofen produces a dibasic acid A. A solution containing

(i) Write an expression for Ka.

© UCLES 2006 9701/04/O/N/06

(i) What do you understand by the term buffer ?

The buffer used in the pharmaceutical preparation is a solution containing Na2HPO4

(ii) Write equations to show how this buffer reacts with

OH– ions. .................................................................................................................

© UCLES 2006 9701/04/O/N/06 [Turn over

(ii) pKa ...........................................................................................................................

acid formula of acid pKa

2 CH3CHCl CO2H 2.8

4 CH2Cl CH2CO2H 4.1

© UCLES 2007 9701/04/O/N/07

(iii) Explain whether magnesium hydroxide would be more or less soluble in

acid Ka /mol dm−3

CH3CO2H 1.7 10−5

Cl CH2CO2H 1.3 10−3

Cl 2CHCO2H 5.0 10−2