Acids A2pp
Acids A2pp
(a) In this part of the question, write the appropriate letter in each box.
From the curves E, F, G and H, choose the curve produced by the addition of
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Page 1 of 141
(b) The table shows information about some acid-base indicators.
(i) Which indicator in the table could be used for the titration that produces curve E but
not for the titration that produces curve F?
pentamethoxy red
naphthyl red
4−nitrophenol
cresol purple
(1)
(ii) Give the colour change at the end point of the titration that produces curve H when
naphthyl red is used as the indicator.
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(Total 6 marks)
Page 2 of 141
Water dissociates slightly according to the equation:
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H2O(I) H+(aq) + OH−(aq)
Kw = [H+][OH−]
25 1.00 × 10−14
50 5.48 × 10−14
(a) Explain why the expression for Kw does not include the concentration of water.
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(c) Calculate the pH of pure water at 50 °C.
Give your answer to 2 decimal places.
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(Total 10 marks)
Page 4 of 141
The acid dissociation constant, Ka, for ethanoic acid is given by the expression
3
Ka =
The value of Ka for ethanoic acid is 1.74 × 10−5 mol dm−3 at 25 °C.
(a) A buffer solution is prepared using ethanoic acid and sodium ethanoate. In the buffer
solution, the concentration of ethanoic acid is 0.186 mol dm−3 and the concentration of
sodium ethanoate is 0.105 mol dm−3.
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(b) In a different buffer solution, the concentration of ethanoic acid is 0.251 mol dm−3 and the
concentration of sodium ethanoate is 0.140 mol dm−3.
A sample of hydrochloric acid containing 0.015 mol of HCl is added to 1000 cm3 of this
buffer solution.
Calculate the pH of the buffer solution after the hydrochloric acid has been added.
You should ignore any change in total volume.
Give your answer to 2 decimal places.
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(Total 8 marks)
A solution of chlorine in water is acidic. Swimming pool managers maintain pool water at a
4 constant pH by using a buffer. They do so by adding sodium hydrogencarbonate and sodium
carbonate.
(a) Hydrogen carbonate ions (HCO3−) act as a weak acid in aqueous solution. Write an
equation for this equilibrium.
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Page 6 of 141
(b) Use the equation in part (a) to explain how a solution containing sodium
hydrogencarbonate and sodium carbonate can act as a buffer when small amounts of acid
or small amounts of alkali are added.
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(Total 4 marks)
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(b) Suggest one other source of error in using the burette to carry out a titration.
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(c) During the titration, the inside of the conical flask is rinsed with distilled water.
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(d) Explain why adding this extra water does not change the volume of EDTA solution that is
required in the titration.
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(Total 4 marks)
Page 7 of 141
Ammonium chloride, when dissolved in water, can act as a weak acid as shown by the following
6 equation.
The following figure shows a graph of data obtained by a student when a solution of sodium
hydroxide was added to a solution of ammonium chloride. The pH of the reaction mixture was
measured initially and after each addition of the sodium hydroxide solution.
(a) Suggest a suitable piece of apparatus that could be used to measure out the sodium
hydroxide solution.
Explain why this apparatus is more suitable than a pipette for this purpose.
Apparatus ......................................................................................................
Explanation ....................................................................................................
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(b) Use information from the curve in the figure above to explain why the end point of this
reaction would be difficult to judge accurately using an indicator.
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Page 8 of 141
(c) The pH at the end point of this reaction is 11.8.
Use this pH value and the ionic product of water, Kw = 1.0 × 10−14 mol2 dm−6, to calculate
the concentration of hydroxide ions at the end point of the reaction.
(d) The expression for the acid dissociation constant for aqueous ammonium ions is
The initial concentration of the ammonium chloride solution was 2.00 mol dm−3.
Use the pH of this solution, before any sodium hydroxide had been added, to calculate a
value for Ka
Page 9 of 141
(e) A solution contains equal concentrations of ammonia and ammonium ions.
Use your value of Ka from part (d) to calculate the pH of this solution. Explain your working.
(If you were unable to calculate a value for Ka you may assume that it has the value 4.75 ×
10−9 mol dm−3. This is not the correct value.)
pH= ...............................
(2)
(Total 12 marks)
(a) Use the concept of electronegativity to justify why the acid strengths of ethanedioic acid
and ethanoic acid are different.
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Page 10 of 141
(b) A buffer solution is made by adding 6.00 × 10–2 mol of sodium hydroxide to a solution
containing 1.00 × 10–1 mol of ethanedioic acid (H2C2O4).
Assume that the sodium hydroxide reacts as shown in the following equation and that in
this buffer solution, the ethanedioic acid behaves as a monoprotic acid.
The dissociation constant Ka for ethanedioic acid is 5.89 × 10–2 mol dm–3.
pH = ....................................
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Page 11 of 141
(c) In a titration, the end point was reached when 25.0 cm3 of an acidified solution containing
ethanedioic acid reacted with 20.20 cm3 of 2.00 ×10–2 mol dm–3 potassium manganate(VII)
solution.
Deduce an equation for the reaction that occurs and use it to calculate the original
concentration of the ethanedioic acid solution.
Equation .........................................................................................................
Calculation
What is the pH of a 0.020 mol dm–3 solution of a diprotic acid which is completely dissociated?
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A 1.00
B 1.40
C 1.70
D 4.00
(Total 1 mark)
Page 12 of 141
The acid dissociation constant, Ka, of a weak acid HA has the value
9
2.56 × 10–4 mol dm–3.
A 5.96
B 3.59
C 2.98
D 2.37
(Total 1 mark)
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(b) Write an equation for the reaction of propanoic acid with sodium carbonate.
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Page 13 of 141
(c) Calculate the pH of a 0.0120 mol dm–3 solution of calcium hydroxide.
The ionic product of water Kw = 1.00 × 10–14 mol2 dm–6.
Give your answer to 2 decimal places.
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(3)
(d) The value of the acid dissociation constant Ka for benzenecarboxylic acid (C6H5COOH) is
6.31 × 10–5 mol dm–3.
(i) Write an expression for the acid dissociation constant Ka for benzenecarboxylic acid.
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Page 14 of 141
(ii) Calculate the pH of a 0.0120 mol dm–3 solution of benzenecarboxylic acid.
Give your answer to 2 decimal places.
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Page 15 of 141
(iii) A buffer solution with a pH of 4.00 is made using benzenecarboxylic acid and sodium
benzenecarboxylate.
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Page 16 of 141
(e) Two solutions, one with a pH of 4.00 and the other with a pH of 9.00, were left open to the
air.
The pH of the pH 9.00 solution changed more than that of the other solution.
Suggest what substance might be present in the air to cause the pH to change.
Explain how and why the pH of the pH 9.00 solution changes.
Explanation ....................................................................................................
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(3)
(Total 17 marks)
In an experiment to determine the acid dissociation constant (Ka) of a weak acid, 25.0 cm3 of an
11
approximately 0.1 mol dm–3 solution of this acid were titrated with a
0.10 mol dm–3 solution of sodium hydroxide.
The pH was measured at intervals and recorded. The table below shows the results.
Volume of NaOH / cm3 0.0 1.0 2.0 3.0 4.0 5.0 10.0 15.0
Volume of NaOH / cm3 20.0 22.0 23.0 24.0 25.0 26.0 27.0 28.0
Page 17 of 141
(a) On the grid below, plot the values from the table above on a graph of pH (y-axis) against
volume of NaOH.
You should start your y-axis at pH 4.0.
Draw a curve that represents the curve of best fit through these points. Ignore any
anomalous points.
Page 18 of 141
(4)
(b) Deduce the volume of the sodium hydroxide solution that would have been added at the
half-neutralisation point of this experiment. This is the point where half the amount of the
weak acid has been neutralised.
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(1)
(c) When half of the weak acid has been neutralised, the pH of the mixture at this point is
equal to the pKa of the weak acid.
Use your answer to part (b) and your graph to determine the pKa of the weak acid and,
hence, its Ka value.
pKa ...................................................................................................................
Ka .....................................................................................................................
(2)
(d) State the pH value for the anomalous point on your graph.
Suggest one reason for this anomaly. Assume that the reading on the pH meter is correct.
pH ..................................................................................................................
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(e) Suggest how the experimental procedure could be slightly modified in order to give a more
reliable value for the end-point.
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(Total 9 marks)
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Page 19 of 141
(b) (i) Write an expression for the acid dissociation constant Ka for ethanoic acid.
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(ii) The value of Ka for ethanoic acid is 1.75 × 10−5 mol dm−3 at 25 °C.
Calculate the concentration of ethanoic acid in a solution of the acid that has a pH of
2.69
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(4)
(c) The value of Ka for chloroethanoic acid (ClCH2COOH) is 1.38 × 10−3 mol dm−3 at 25 °C.
(i) Write an equation for the dissociation of chloroethanoic acid in aqueous solution.
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(ii) Suggest why chloroethanoic acid is a stronger acid than ethanoic acid.
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Page 20 of 141
(d) P and Q are acids. X and Y are bases. The table shows the strength of each acid and
base.
Acids Bases
P Q X Y
The two acids were titrated separately with the two bases using methyl orange as indicator.
The titrations were then repeated using phenolphthalein as indicator.
The pH range for methyl orange is 3.1 − 4.4
The pH range for phenolphthalein is 8.3 − 10.0
For each of the following titrations, select the letter, A, B, C, or D, for the correct statement
about the indicator(s) that would give a precise end-point.
Write your answer in the box provided.
(1)
(1)
(1)
Page 21 of 141
(e) Using a burette, 26.40 cm3 of 0.550 mol dm−3 sulfuric acid were added to a conical flask
containing 19.60 cm3 of 0.720 mol dm−3 aqueous sodium hydroxide.
Assume that the sulfuric acid is fully dissociated.
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(6)
(Total 18 marks)
In order to obtain a pH curve, you are provided with a conical flask containing 25.0 cm3 of a
13
0.100 mol dm–3 carboxylic acid solution and a burette filled with 0.100 mol dm–3 sodium
hydroxide solution. You are also provided with a calibrated pH meter.
(a) State why calibrating a pH meter just before it is used improves the accuracy of the pH
measurement.
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Page 22 of 141
(b) Describe how you would obtain the pH curve for the titration.
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(Total 6 marks)
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Page 23 of 141
(iii) At 75 °C, a 0.0470 mol dm–3 solution of sodium hydroxide has a pH of 11.36.
Calculate a value for Kw at this temperature.
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(ii) Write an expression for the acid dissociation constant Ka for methanoic acid.
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(iii) The value of Ka for methanoic acid is 1.78 × 10−4 mol dm−3 at 25 °C.
Calculate the pH of a 0.0560 mol dm−3 solution of methanoic acid.
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(3)
Page 24 of 141
(iv) The dissociation of methanoic acid in aqueous solution is endothermic.
Effect on pH .........................................................................................
Explanation ...........................................................................................
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(3)
(c) The value of Ka for methanoic acid is 1.78 × 10−4 mol dm−3 at 25°C.
A buffer solution is prepared containing 2.35 × 10−2 mol of methanoic acid and 1.84 × 10−2
mol of sodium methanoate in 1.00 dm3 of solution.
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(3)
Page 25 of 141
(ii) A 5.00 cm3 sample of 0.100 mol dm−3 hydrochloric acid is added to the buffer solution
in part (c)(i).
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(4)
(Total 20 marks)
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(1)
(b) Three equilibria are shown below. For each reaction, indicate whether the substance
immediately above the box is acting as a Brønsted–Lowry acid (A) or a Brønsted–Lowry
base (B) by writing A or B in each of the six boxes.
(1)
Page 26 of 141
(ii) CH3NH2 + H2O CH3NH3+ + OH–
(1)
(1)
(c) A 25.0 cm3 sample of 0.0850 mol dm–3 hydrochloric acid was placed in a beaker.
Distilled water was added until the pH of the solution was 1.25.
Calculate the total volume of the solution formed. State the units.
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(3)
(d) At 298 K, the value of the acid dissociation constant (Ka) for the weak acid HX in aqueous
solution is 3.01 × 10–5 mol dm–3.
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(1)
Page 27 of 141
(ii) Write an expression for the acid dissociation constant (Ka) for the weak acid HX.
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Page 28 of 141
(e) An acidic buffer solution is formed when 10.0 cm3 of 0.125 mol dm–3 aqueous sodium
hydroxide are added to 15.0 cm3 of 0.174 mol dm–3 aqueous HX.
The value of Ka for the weak acid HX is 3.01 × 10–5 mol dm–3.
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(6)
(Total 18 marks)
Page 29 of 141
When 1.00 mol dm–3 solutions of salicylic acid and sodium hydroxide are mixed a buffer solution
16
can be formed. Salicylic acid is a monoprotic acid that can be represented by the formula HA.
(a) Select a mixture from the table below that would produce a buffer solution. Give a reason
for your choice.
X 25 75
Y 50 50
Z 75 25
Mixture ...........................................................................................................
Reason ..........................................................................................................
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(2)
(b) Another mixture, formed by adding 50 cm3 of 1.00 mol dm–3 salicylic acid solution to 25
cm3 of 1.00 mol dm–3 sodium hydroxide solution, can be used to determine the pKa of
salicylic acid. State one measurement that must be made for this mixture and explain how
this measurement can be used to determine the pKa of salicylic acid.
Measurement .................................................................................................
Explanation ....................................................................................................
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(3)
(Total 5 marks)
Page 30 of 141
A student was given a task to determine the percentage purity of a sample of salicylic acid. The
17 method used by the student to prepare a solution of salicylic acid is described below.
(a) Give two additional instructions that would improve this method for making up the salicylic
acid solution.
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(2)
(b) The pH of this solution was measured and a value of 2.50 was obtained.
Calculate the concentration of salicylic acid in this solution.
Assume that salicylic acid is the only acid in this solution. The Ka for salicylic acid
is 1.07 × 10–3 mol dm–3. You may represent salicylic acid as HA.
Show your working.
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(3)
(c) Use your answer to part (b) to calculate the mass of salicylic acid (Mr = 138.0) present in
the original sample.
(If you were unable to complete the calculation in part (b), assume that the concentration of
salicylic acid is 8.50 × 10–3 mol dm–3. This is not the correct answer.)
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(2)
Page 31 of 141
(d) Use your answer to part (c) to calculate the percentage purity of the salicylic acid used to
make the solution.
(If you were unable to complete the calculation in part (c), assume that the mass of salicylic
acid is 0.347 g. This is not the correct answer.)
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(1)
(Total 8 marks)
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(1)
(b) (i) Write an equation for the reaction of ethylamine (CH3CH2NH2) with water to form a
weakly alkaline solution.
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(1)
(ii) In terms of this reaction, state why the solution formed is weakly alkaline.
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(1)
(c) State which is the stronger base, ammonia or ethylamine. Explain your answer.
Explanation ....................................................................................................
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(3)
Page 32 of 141
(d) Give the formula of an organic compound that forms an alkaline buffer solution when added
to a solution of ethylamine.
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(1)
(e) Explain qualitatively how the buffer solution in part (d) maintains an almost constant pH
when a small amount of hydrochloric acid is added to it.
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(2)
(Total 9 marks)
This question involves calculations about two strong acids and one weak acid.
19 All measurements were carried out at 25 °C.
(a) A 25.0 cm3 sample of 0.0850 mol dm–3 hydrochloric acid was placed in a beaker and
100 cm3 of distilled water were added.
Calculate the pH of the new solution formed.
Give your answer to 2 decimal places.
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Page 33 of 141
(b) HX is a weak monobasic acid.
(i) Write an expression for the acid dissociation constant, Ka, for HX.
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(3)
Page 34 of 141
(c) A 25.0 cm3 sample of 0.620 mol dm–3 nitric acid was placed in a beaker and 38.2 cm3 of
0.550 mol dm–3 aqueous sodium hydroxide were added.
Calculate the pH of the solution formed.
Give your answer to 2 decimal places.
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(6)
(Total 12 marks)
Page 35 of 141
Titration curves labelled A, B, C and D for combinations of different aqueous solutions of acids
20 and bases are shown below.
All solutions have a concentration of 0.1 mol dm–3.
(a) In this part of the question write the appropriate letter in each box.
From the curves A, B, C and D, choose the curve produced by the addition of
(3)
Page 36 of 141
(b) A table of acid.base indicators is shown below.
The pH ranges over which the indicators change colour and their colours in acid and alkali
are also shown.
(i) Select from the table an indicator that could be used in the titration that produces
curve B but not in the titration that produces curve A.
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(1)
(ii) Give the colour change at the end point of the titration that produces curve D when
cresol purple is used as the indicator.
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(1)
(Total 5 marks)
This question is about the pH of some solutions containing potassium hydroxide and ethanoic
21 acid.
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(1)
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(1)
Page 37 of 141
(iii) At 10 °C, a 0.154 mol dm–3 solution of potassium hydroxide has a pH of 13.72.
Calculate the value of Kw at 10 °C.
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(2)
(b) At 25 °C, the acid dissociation constant Ka for ethanoic acid has the value
1.75 × 10–5 mol dm–3.
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(1)
(ii) Calculate the pH of a 0.154 mol dm–3 solution of ethanoic acid at 25 °C.
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(3)
Page 38 of 141
(c) At 25 °C, the acid dissociation constant Ka for ethanoic acid has the value
1.75 × 10–5 mol dm–3.
(i) Calculate the pH of the solution formed when 10.0 cm3 of 0.154 mol dm–3 potassium
hydroxide are added to 20.0 cm3 of 0.154 mol dm–3 ethanoic
acid at 25 °C.
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(4)
Page 39 of 141
(ii) Calculate the pH of the solution formed when 40.0 cm3 of 0.154 mol dm–3 potassium
hydroxide are added to 20.0 cm3 of 0.154 mol dm–3 ethanoic acid at 25 °C.
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(4)
(Total 16 marks)
When iron(II) sulfate is used for killing weeds in lawns, it is often mixed with the fertiliser
22 ammonium sulfate. Ammonium sulfate also makes the soil acidic.
(a) Write an equation to show how the ammonium ion behaves as a Brønsted–Lowry acid in
water.
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(1)
Page 40 of 141
(b) Compounds such as ammonium sulfate react on warming with sodium hydroxide solution
as shown in the equation below.
Use this information to describe a simple test, other than smell, to show that ammonia is
evolved. State what you would observe.
Test ................................................................................................................
........................................................................................................................
Observation ...................................................................................................
(2)
(Total 3 marks)
Iron(II) sulfate is used to kill weeds in garden lawns. It is a by-product of the manufacture of steel.
23 When a lawn is treated with iron(II) sulfate, the iron(II) ions are oxidised to form iron(III) ions.
Iron(III) ions are acidic in aqueous solution as shown by the following equation.
........................................................................................................................
........................................................................................................................
(1)
(b) Write an expression for the equilibrium constant, Ka, for the dissociation of iron(III) ions in
aqueous solution.
........................................................................................................................
........................................................................................................................
(1)
Page 41 of 141
(c) Use your answer from part (b) to calculate the value of Ka for this reaction at 20 °C.
Give your answer to the appropriate precision. Show your working.
........................................................................................................................
........................................................................................................................
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........................................................................................................................
........................................................................................................................
........................................................................................................................
(4)
(d) Name the substance that is most likely to oxidise the iron(II) ions when iron(II) sulfate is
used as a weed killer.
........................................................................................................................
(1)
(e) Suggest a value for the pH of a 0.100 mol dm–3 solution of iron(II) sulfate.
........................................................................................................................
(1)
(Total 8 marks)
.............................................................................................................
(1)
.............................................................................................................
.............................................................................................................
(1)
(iii) Calculate the pH of the solution formed when 10.0 cm3 of 0.154 mol dm–3
hydrochloric acid are added to 990 cm3 of water.
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
(2)
Page 42 of 141
(b) The acid dissociation constant, Ka, for the weak acid HX has the value
4.83 × 10–5 mol dm–3 at 25 °C.
A solution of HX has a pH of 2.48
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(4)
(c) Explain why the pH of an acidic buffer solution remains almost constant despite the
addition of a small amount of sodium hydroxide.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
Page 43 of 141
(d) The acid dissociation constant, Ka, for the weak acid HY has the value
1.35 × 10–5 mol dm–3 at 25 °C.
A buffer solution was prepared by dissolving 0.0236 mol of the salt NaY in
50.0 cm3 of a 0.428 mol dm–3 solution of the weak acid HY
.............................................................................................................
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(4)
Page 44 of 141
(ii) A 5.00 × 10–4 mol sample of sodium hydroxide was added to this buffer solution.
Calculate the pH of the buffer solution after the sodium hydroxide was added.
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
(4)
(Total 18 marks)
Kw is the ionic product of water. The value of Kw is 5.48 × 10–14 mol2 dm–6 at 50 °C.
.............................................................................................................
(1)
.............................................................................................................
(1)
.............................................................................................................
.............................................................................................................
.............................................................................................................
(2)
Page 45 of 141
(ii) Suggest why this pure water is not acidic.
.............................................................................................................
.............................................................................................................
(1)
(iii) Calculate the pH of 0.140 mol dm–3 aqueous sodium hydroxide at 50 °C.
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
(3)
(c) Calculate the pH of the solution formed when 25.0 cm3 of 0.150 mol dm–3 aqueous sulfuric
acid are added to 30.0 cm3 of 0.200 mol dm–3 aqueous potassium hydroxide at 25 °C.
Assume that the sulfuric acid is fully dissociated.
......................................................................................................................
......................................................................................................................
......................................................................................................................
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......................................................................................................................
......................................................................................................................
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......................................................................................................................
(6)
(Total 14 marks)
Page 46 of 141
Ethanoic acid is manufactured in industry from methanol and carbon monoxide in a multi-step
26 process involving hydrogen iodide. Ethanoic acid is obtained from the reaction mixture by
fractional distillation. Methanoic acid is a useful by-product of this process.
The Ka value of an organic acid can be determined by using the pH curve obtained when the acid
is titrated against sodium hydroxide. The pH of the solution formed when exactly half of the acid
has been neutralised is equal to the pKa value of the acid. The Ka value of the acid can be used
to confirm its identity.
A chemist used a pH curve to determine the pKa value of acid Y, formed during the manufacture
of ethanoic acid. The chemist transferred 25.0 cm3 of a solution of acid Y into a beaker using a
pipette, and measured the pH of the acid solution using a pH meter which could be read to one
decimal place. A solution of sodium hydroxide of concentration 0.100 mol dm–3 was added from
a burette in small portions. The pH of the mixture was recorded after each addition of the sodium
hydroxide solution. The chemist’s results are given in the table below.
Page 47 of 141
(a) Use the results given in the table above to plot a graph of pH (y-axis) against volume of
sodium hydroxide solution added. Use the points to draw the pH curve, ignoring any
anomalous results.
(6)
Page 48 of 141
(b) Use your graph from part (a) to determine the
................... cm3
(ii) volume of sodium hydroxide solution needed to neutralise half the acid
................... cm3
(iii) pH of the half-neutralised mixture. Give your answer to one decimal place.
.........................
(3)
(c) Use the pH of the half-neutralised mixture from part (b) (iii) to calculate the value of the acid
dissociation constant, Ka, of the acid Y. Show your working.
........................................................................................................................
........................................................................................................................
........................................................................................................................
........................................................................................................................
(2)
(d) The table below shows the Ka values for some organic acids.
Use your answer from part (c) to identify acid Y from this table.
........................................................................................................................
(1)
Page 49 of 141
(e) For the pipette and the burette, the maximum total errors are shown below. These errors
take into account multiple measurements.
Estimate the percentage error in using each of these pieces of apparatus. You should use
your answer to part (b) (i) to estimate the percentage error in using the burette.
........................................................................................................................
........................................................................................................................
........................................................................................................................
(1)
(f) Calculate the difference between the Ka value from part (c) and the Ka value of the acid you
identified as the acid Y in the table in part (d).
Express this difference as a percentage of the value given in the table in part (d). (If you
could not complete the calculation in part (c), you should assume that the Ka value
determined from the graph is 1.9 × 10–4 mol dm–3. This is not the correct value.)
........................................................................................................................
........................................................................................................................
(1)
(g) Other than by using a different pH meter, state one way in which the accuracy of the pH
readings could be improved.
........................................................................................................................
........................................................................................................................
(1)
(h) State why there was little change in the pH value of the mixture when between 8 cm3 and
20 cm3 of alkali were added.
........................................................................................................................
(1)
(Total 16 marks)
Describe briefly how you would ensure that a reading from a pH meter is accurate.
27
.................................................................................................................................
.................................................................................................................................
.................................................................................................................................
(Total 2 marks)
Page 50 of 141
In this question, give all values of pH to 2 decimal places.
28
(a) (i) Write an expression for the term pH.
.............................................................................................................
(1)
(ii) Calculate the concentration, in mol dm–3, of an aqueous solution of sulfuric acid that
has a pH of 0.25
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
(2)
(b) A student carried out a titration by adding an aqueous solution of sodium hydroxide from a
burette to an aqueous solution of ethanoic acid. The end-point was reached when
22.60 cm3 of the sodium hydroxide solution had been added to 25.00 cm3 of
0.410 mol dm–3 ethanoic acid.
(i) Write an equation for the reaction between sodium hydroxide and ethanoic acid.
.............................................................................................................
(1)
(ii) Calculate the concentration, in mol dm–3, of the sodium hydroxide solution used.
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
(2)
Page 51 of 141
(iii) A list of indicators is shown below.
Indicator pH range
litmus 5.0–8.0
Select from the list the most suitable indicator for the end-point of this titration.
.............................................................................................................
(1)
(iv) Suggest why the concentration of sodium hydroxide in a solution slowly decreases
when left open to air.
.............................................................................................................
.............................................................................................................
(1)
(c) At 298 K, the value of the acid dissociation constant, Ka, for ethanoic acid in aqueous
solution is 1.74 × 10–5 mol dm–3
(i) Write an expression for the acid dissociation constant, Ka, for ethanoic acid.
.............................................................................................................
.............................................................................................................
(1)
(ii) Calculate the pH of 0.410 mol dm–3 ethanoic acid at this temperature.
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
(3)
Page 52 of 141
(iii) Calculate the pH of the buffer solution formed when 10.00 cm3 of 0.100 mol dm–3
potassium hydroxide are added to 25.00 cm3 of 0.410 mol dm–3 ethanoic acid.
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
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.............................................................................................................
.............................................................................................................
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.............................................................................................................
.............................................................................................................
.............................................................................................................
(6)
(Total 18 marks)
Page 53 of 141
Indicators and pH curves can be used to determine the end point in a titration.
29
(a) The pH curves labelled J, K, L and M for combinations of different acids and bases are
shown below. All solutions have a concentration of 0.1 mol dm–3.
Page 54 of 141
(ii) A table of acid–base indicators and the pH ranges over which they change colour is
shown below.
Indicator pH range
Select from the list above an indicator which could be used in the titration which
produces curve J but not in the titration which produces curve K.
.............................................................................................................
(4)
(b) The acid dissociation constant, Ka, for the weak acid, ethanoic acid, has a value of
1.74 × 10–5 mol dm–3 at 25 °C.
Ka =
.............................................................................................................
(ii) Calculate the pH of a 0.15 mol dm–3 solution of ethanoic acid. Give your answer to
2 decimal places.
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
(4)
(Total 8 marks)
Page 55 of 141
Buffer solutions are important in biological systems and in industry to maintain almost constant
30 pH values.
(a) In the human body, one important buffer system in blood involves the hydrogencarbonate
ion, , and carbonic acid, H2CO3, which is formed when carbon dioxide dissolves in
water.
(i) Use the following equation to explain how this buffer maintains a constant pH of 7.41
even if a small amount of acid enters the bloodstream.
.............................................................................................................
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.............................................................................................................
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.............................................................................................................
(5)
(b) In industry, the pH of a solution used to dye cloth must be controlled or else the colour
varies.
A solution of dye in a beaker is buffered by the presence of ethanoic acid and sodium
ethanoate. In the solution, the concentration of ethanoic acid is 0.15 mol dm–3 and the
concentration of sodium ethanoate is 0.10 mol dm–3. The value of Ka for ethanoic acid is
1.74 × 10–5 mol dm–3 at 298 K.
(i) A 10.0 cm3 portion of 1.00 mol dm–3 hydrochloric acid is added to 1000 cm3 of this
buffered solution.
.............................................................................................................
Page 56 of 141
(ii) Calculate the number of moles of ethanoic acid and the number of moles of sodium
ethanoate in the solution after addition of the hydrochloric acid.
.............................................................................................................
.............................................................................................................
(iii) Hence calculate the pH of this new solution. Give your answer to 2 decimal places.
.............................................................................................................
.............................................................................................................
.............................................................................................................
(6)
(Total 11 marks)
31
Summarised directions for recording responses to multiple completion questions
A B C D
(i), (ii) and (iii) (i) and (iii) correct (ii) and (iv) correct (iv) alone correct
correct only only only
(iii) KF + PF5 → K+ + PF
pH ................................................................................................................
Concentration ..............................................................................................
......................................................................................................................
(2)
Page 57 of 141
(b) A 0.150 mol dm–3 solution of a weak acid, HX, also has a pH of 2.34
(i) Write an expression for the acid dissociation constant, Ka, for the acid HX.
.............................................................................................................
.............................................................................................................
(ii) Calculate the value of Ka for this acid and state its units.
Calculation .........................................................................................
.............................................................................................................
.............................................................................................................
Units ....................................................................................................
(iii) Calculate the value of pKa for the acid HX. Give your answer to two decimal places.
.............................................................................................................
(5)
(c) A 30.0 cm3 sample of a 0.480 mol dm–3 solution of potassium hydroxide was partially
neutralised by the addition of 18.0 cm3 of a 0.350 mol dm–3 solution of sulphuric acid.
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
(iii) Calculate the number of moles of potassium hydroxide remaining in excess in the
solution formed.
.............................................................................................................
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Page 58 of 141
(v) Hence calculate the pH of the solution formed. Give your answer to two decimal
places.
.............................................................................................................
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(6)
(Total 13 marks)
The hydrolysis of methyl propanoate was studied in acidic conditions at 25°C and the rate
33 equation was found to be
rate = k[CH3CH2COOCH3][H+]
(a) Use the data below to calculate the value of the rate constant, k, at this temperature.
Deduce its units.
......................................................................................................................
......................................................................................................................
Units .............................................................................................................
......................................................................................................................
(3)
(b) The reaction in part (a) was repeated at the same temperature, but water was added so
that the volume of the reaction mixture was doubled. Calculate the initial rate of reaction
under these conditions.
......................................................................................................................
......................................................................................................................
(1)
Page 59 of 141
(c) A third experiment was carried out at a different temperature. Some data from this
experiment are shown in the table below.
Calculate the initial pH of the reaction mixture. Give your answer to two decimal places.
......................................................................................................................
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......................................................................................................................
......................................................................................................................
(3)
(Total 7 marks)
This question is based on the reactions and compounds shown in the scheme below.
34
A 0.100 mol dm−3 solution of X is found to have a pH of 2.50. The value of Ka in mol dm−3 is
A 3.16 × 10−2
B 3.16 × 10−3
C 1.00 × 10−4
D 1.00 × 10−5
(Total 1 mark)
KW = ….................................................................................................
pH = ....................................................................................................
Page 60 of 141
(ii) At 318 K, the value of Kw is 4.02 × 10–14 mol2 dm–6 and hence the pH of pure water
is 6.70
State why pure water is not acidic at 318 K.
.............................................................................................................
.............................................................................................................
(iii) Calculate the number of moles of sodium hydroxide in 2.00 cm3 of 0.500 mol dm–3
aqueous sodium hydroxide.
.............................................................................................................
.............................................................................................................
(iv) Use the value of Kw given above and your answer to part (a)(iii) to calculate the pH of
the solution formed when 2.00 cm3 of 0.500 mol dm–3 aqueous sodium hydroxide are
added to 998 cm3 of pure water at 318 K.
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
(6)
(b) At 298 K, the acid dissociation constant, Ka, for propanoic acid, CH3CH2COOH, has the
value 1.35 × 10–5mol dm–3.
.............................................................................................................
.............................................................................................................
(ii) Calculate the pH of 0.125 mol dm–3 aqueous propanoic acid at 298 K.
.............................................................................................................
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(4)
Page 61 of 141
(c) Sodium hydroxide reacts with propanoic acid as shown in the following equation.
(i) Calculate the number of moles of propanoic acid in 50.0 cm3 of 0.125 mol dm–3
aqueous propanoic acid.
.............................................................................................................
.............................................................................................................
(ii) Use your answers to part (a)(iii) and part (c)(i) to calculate the number of moles of
propanoic acid in the buffer solution formed when 2.00 cm3 of 0.500 mol dm–3
aqueous sodium hydroxide are added to 50.0 cm3 of 0.125 mol dm–3 aqueous
propanoic acid.
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(6)
(Total 16 marks)
Page 62 of 141
(a) Titration curves labelled A, B, C and D for combinations of different acids and bases are
36
shown below. All solutions have a concentration of 0.1 mol dm–3.
Page 63 of 141
(ii) A table of acid–base indicators and the pH ranges over which they change colour is
shown below.
Indicator pH range
Select from the table an indicator which could be used in the titration which produces
curve A but not in the titration which produces curve B.
.............................................................................................................
(4)
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
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(4)
Page 64 of 141
(c) The acid dissociation constant, Ka, for propanoic acid has the value of
1.35 × 10–5mol dm–3 at 25 °C.
(i) Calculate the pH of a 0.117 mol dm–3 aqueous solution of propanoic acid.
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
(ii) Calculate the pH of a mixture formed by adding 25 cm3 of a 0.117 mol dm–3 aqueous
solution of sodium propanoate to 25 cm3 of a 0.117 mol dm–3 aqueous solution of
propanoic acid.
.............................................................................................................
.............................................................................................................
.............................................................................................................
(5)
(Total 13 marks)
Page 65 of 141
The pH curve shown below was obtained when a 0.150 mol dm–3 solution of sodium hydroxide
37
was added to 25.0 cm3 of an aqueous solution of a weak monoprotic acid, HA.
(a) Use the information given to calculate the concentration of the acid.
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
(b) (i) Write an expression for the acid dissociation constant, Ka, for HA.
.............................................................................................................
.............................................................................................................
(iii) Using your answers to parts (b)(i) and (b)(ii), show that when sufficient sodium
hydroxide has been added to neutralise half of the acid,
.............................................................................................................
.............................................................................................................
.............................................................................................................
(4)
(c) Explain why dilution with a small volume of water does not affect the pH of a buffer solution.
......................................................................................................................
......................................................................................................................
(2)
Page 66 of 141
(d) (i) Calculate the change in pH when 0.250 mol dm–3 hydrochloric acid is diluted with
water to produce 0.150 mol dm–3 hydrochloric acid.
.............................................................................................................
.............................................................................................................
.............................................................................................................
(ii) Calculate the volume of water which must be added to 30.0 cm3 of 0.250 mol dm–3
hydrochloric acid in order to reduce its concentration to 0.150 mol dm–3.
.............................................................................................................
.............................................................................................................
.............................................................................................................
(4)
(Total 12 marks)
Use the information about the following solutions to answer the question below.
38
Solution F: This is a mixture of 1 mol of propanoic acid, 1 mol of methanol and 2 mol of water.
Solution G: This was originally the same mixture as solution F but it has been left to reach
equilibrium.
A considerably lower.
B slightly lower.
C slightly higher.
This question concerns the weak acid, ethanoic acid, for which the acid dissociation constant,
39
Ka, has a value of 1.74 × 10–5mol dm–3 at 25 °C.
(a) Write an expression for the term pH. Calculate the pH of a 0.150 mol dm–3 solution of
ethanoic acid.
(4)
Page 67 of 141
(b) A buffer solution is prepared by mixing a solution of ethanoic acid with a solution of
sodium ethanoate.
(ii) Write an equation for the reaction which occurs when a small amount of
hydrochloric acid is added to this buffer solution.
(3)
(c) In a buffer solution, the concentration of ethanoic acid is 0.150 mol dm–3 and the
concentration of sodium ethanoate is 0.100 mol dm–3.
(ii) A 10.0 cm3 portion of 1.00 mol dm–3 hydrochloric acid is added to 1000 cm3 of this
buffer solution.
Calculate the number of moles of ethanoic acid and the number of moles of sodium
ethanoate in the solution after addition of the hydrochloric acid. Hence, find the pH
of this new solution.
(8)
(Total 15 marks)
This question is about the following reaction scheme which shows the preparation of polymer P.
40
K is a weak acid with a pKa of 9.95. The pH of a 0.10 mol dm−3 solution of K is
A 4.48
B 4.98
C 5.48
D 5.98
(Total 1 mark)
Page 68 of 141
The value of the acid dissociation constant, Ka, for the weak acid HA, at 298 K, is
41
1.45 × 10–4 mol dm–3.
(a) Write an expression for the term Ka for the weak acid HA.
......................................................................................................................
......................................................................................................................
(1)
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(4)
(c) A mixture of the acid HA and the sodium salt of this acid, NaA, can be used to prepare a
buffer solution.
(i) State and explain the effect on the pH of this buffer solution when a small amount of
hydrochloric acid is added.
.............................................................................................................
.............................................................................................................
.............................................................................................................
(ii) The concentration of HA in a buffer solution is 0.250 mol dm–3. Calculate the
concentration of A– in this buffer solution when the pH is 3.59
.............................................................................................................
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.............................................................................................................
.............................................................................................................
(6)
(Total 11 marks)
Page 69 of 141
In which one of the following reactions is the role of the reagent stated correctly?
42
Reaction Role of reagent
For this question one or more of the options given may be correct. Select your answer by means
43 of the following code
C if 4 alone is correct
Directions summarised
A B C D
(a) By reference to the forces between molecules, explain why ammonia is very soluble in
44 water.
......................................................................................................................
......................................................................................................................
(2)
Page 70 of 141
(b) Aqueous solutions of ammonia have a pH greater than 7.
.............................................................................................................
(ii) Explain why the pH of a solution containing 1.0 mol dm–3 of ammonia is less than
14 at 298 K.
.............................................................................................................
.............................................................................................................
(3)
(c) An ammonium ion in aqueous solution can behave as a Brønsted–Lowry acid. State what
is meant by the term Brønsted–Lowry acid.
.....................................................................................................................................
(1)
(d) State what is meant by the term buffer solution. Identify a reagent which could be added to
a solution of ammonia in order to form a buffer solution.
......................................................................................................................
Reagent ........................................................................................................
(3)
(e) An acidic buffer solution is obtained when sodium ethanoate is dissolved in aqueous
ethanoic acid.
(i) Calculate the pH of the buffer solution formed at 298 K when 0.125 mol of sodium
ethanoate is dissolved in 250 cm3 of a 1.00 mol dm–3 solution of ethanoic acid.
The acid dissociation constant, Ka, for ethanoic acid is 1.70 × 10–5 mol dm–3 at 298 K.
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
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Page 71 of 141
(ii) Write an ionic equation for the reaction which occurs when a small volume of dilute
hydrochloric acid is added to this buffer solution.
.............................................................................................................
(5)
(Total 14 marks)
Which one of the following is the pH of a solution of magnesium hydroxide containing 4.0 × 10−5
mol dm−3 of hydroxide ions at 298 K?
(Kw = 1.0 × 10−14 mol2 dm−6 at 298 K)
A 9.6
B 9.5
C 8.6
D 8.3
(Total 1 mark)
HCN is a weak acid with a pKa value of 9.40. If a 0.010 mol dm−3 solution of HCN was used in
the first step, the concentration of cyanide ions, in mol dm−3, would be
A 2.0 × 10−6
B 6.4 × 10−5
C 2.0 × 10−5
D 3.1 × 10−1
(Total 1 mark)
Page 72 of 141
(a) At 50°C, the ionic product of water, Kw, has the value 5.48 × 10–14 mol2 dm–6.
47
(i) Define the term Kw
.............................................................................................................
.............................................................................................................
(iii) Calculate the pH of pure water at 50 °C. Explain why pure water at 50 °C is still
neutral even though its pH is not 7.
Calculation ..........................................................................................
.............................................................................................................
.............................................................................................................
Explanation ..........................................................................................
.............................................................................................................
(5)
(b) At 25°C, Kw has the value 1.00 × 10–14 mol2 dm–6. Calculate the pH at 25 °C of
.............................................................................................................
.............................................................................................................
.............................................................................................................
(ii) the solution formed when 35.0 cm3 of this solution of sodium hydroxide is mixed with
40.0 cm3 of a 0.120 mol dm–3 solution of hydrochloric acid.
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
(8)
Page 73 of 141
(c) In a 0.150 mol dm–3 solution of a weak acid HX at 25 °C, 1.80% of the acid molecules are
dissociated into ions.
.............................................................................................................
.............................................................................................................
(ii) Calculate the value of Ka for the acid HX at this temperature and state its units.
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
(5)
(Total 18 marks)
This question is about the reaction between propanone and an excess of ethane-1,2-diol, the
48 equation for which is given below.
If 0.100 g of the strong monoprotic acid, benzenesulphonic acid, was dissolved in 100 cm3 of
water, the pH of the solution would be
A 0.20
B 1.20
C 2.20
D 3.20
(Total 1 mark)
Page 74 of 141
The sketch below shows the change in pH when a 0.200 mol dm–3 solution of sodium hydroxide
49
is added from a burette to 25.0 cm3 of a 0.150 mol dm-3 solution of the weak acid HA at 25 °C.
(a) The volume of sodium hydroxide solution added at the equivalence point is x cm3.
Calculate the value of x.
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
.............................................................................................................
.............................................................................................................
(iii) Identify a suitable indicator for detecting the equivalence point of the titration.
.............................................................................................................
(3)
(c) The value of Kc for the weak acid HA at 25 °C is 2.75 × 10–5 mol dm–3.
.............................................................................................................
Page 75 of 141
(ii) Write an expression for Ka for the acid HA.
.............................................................................................................
(iii) Calculate the pH of the 0.150 mol dm–3 solution of acid HA before any sodium
hydroxide is added, i.e. the pH at point a.
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
(5)
(d) Calculate the pH of the solution formed when cm3 of the 0.200 mol dm–3 solution of
sodium hydroxide are added to 25.0 cm3 of the 0.150 mol dm–3 solution of HA, i.e. the pH
at point b.
......................................................................................................................
......................................................................................................................
......................................................................................................................
(3)
(Total 13 marks)
A 13.0
B 13.3
C 13.6
D 13.9
(Total 1 mark)
Page 76 of 141
Iodine and propanone react in acid solution according to the equation
51
I2 + CH3COCH3 → CH3COCH2I + HI
rate = k [CH3COCH3][H+]
(a) Deduce the order of reaction with respect to iodine and the overall order of reaction.
(b) At the start of the experiment, the rate of reaction was found to be 2.00 × 10–5 mol dm–3 s–1
when the concentrations of the reactants were as shown below.
CH3COCH3 1.50
I2 2.00 × 10–2
H+ 3.00 × 10–2
Use these data to calculate a value for the rate constant and deduce its units.
......................................................................................................................
......................................................................................................................
Units .............................................................................................................
(3)
(c) How can you tell that H+ acts as a catalyst in this reaction?
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
Page 77 of 141
(d) Calculate the initial rate of reaction if the experiment were to be repeated at the same
temperature and with the same concentrations of iodine and propanone as in part (b) but at
a pH of 1.25
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(3)
(Total 10 marks)
A 0.210 mol dm–3 solution of potassium hydroxide was added from a burette to 25.0 cm3 of a
52
0.160 mol dm–3 solution of ethanoic acid in a conical flask.
Given that the value of the acid dissociation constant, Ka, for ethanoic acid is
1.74 × 10–5 mol dm–3, calculate the pH at 25 °C of the solution in the conical flask at the following
three points:
The value of the acid dissociation constant, Ka, for ethanoic acid is 1.74 × 10–5 mol dm–3 at
53
298 K.
.............................................................................................................
Page 78 of 141
(ii) Calculate the pH at 298 K of a 0.220 mol dm–3 solution of ethanoic acid.
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
(5)
(b) A sample of the 0.220 mol dm–3 solution of ethanoic acid was titrated against sodium
hydroxide solution.
(i) Calculate the volume of a 0.150 mol dm–3 solution of sodium hydroxide required to
neutralise 25.0 cm3 of the ethanoic acid solution.
.............................................................................................................
.............................................................................................................
.............................................................................................................
.............................................................................................................
(ii) From the list below, select the best indicator for this titration and explain your choice.
Indicator ..............................................................................................
Explanation .........................................................................................
.............................................................................................................
.............................................................................................................
(5)
Page 79 of 141
(c) A buffer solution is formed when 2.00 g of sodium hydroxide are added to 1.00 dm3 of a
0.220 mol dm–3 solution of ethanoic acid.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(6)
(Total 16 marks)
The equation and rate law for the reaction of substance P with substance Q are given below.
54
2P + Q → R + S
rate = k[P]2[H+]
Under which one of the following conditions, all at the same temperature, would the rate of
reaction be slowest?
A 0.1 0
B 1 2
C 3 3
D 10 4
(Total 1 mark)
Page 80 of 141
Addition of which one of the following to 10 cm3 of 1.0 M NaOH would result in the pH being
55 halved?
A 10 cm3 of water
A solution of sodium ethanoate has a pH of 8.91 at 25 °C. The hydrogen ion and hydroxide ion
56 concentrations in this solution are
A [H+] = 1.00 × 10−9 mol dm−3 [OH−] = 1.00 × 10−5 mol dm−3
B [H+] = 1.00 × 10−9 mol dm−3 [OH−] = 8.13 × 10−6 mol dm−3
C [H+] = 1.23 × 10−9 mol dm−3 [OH−] = 1.00 × 10−5 mol dm−3
D [H+] = 1.23 × 10−9 mol dm−3 [OH−] = 8.13 × 10−6 mol dm−3
(Total 1 mark)
Which one of the following changes will result in a decrease in the pH of an aqueous solution of
the acid?
B 11
C 9
D 3
(Total 1 mark)
Page 81 of 141
Which one of the following could be true in an aqueous solution of sodium hydroxide?
59
A [H+] = (OH−]
B pH = −log10 [OH−]
C pH = 1.2
D pH = 12.8
(Total 1 mark)
Which one of the following is the change in units of pH which occurs when 10.0 cm3 of a 1.0 M
60
solution of a strong monoprotic acid are made up to 1.0 dm3 with water?
A 1
B 2
C 3
D 5
(Total 1 mark)
Page 82 of 141
Mark schemes
(a) (i) G
1 1
(ii) F
1
(iii) H
1
M1
1
M2
1
Page 83 of 141
(c) [H+] = √Kw (or = √5.48 × 10−14)
Correct pH answer scores 3
1
= 2.34 × 10−7
1
pH = 6.63
Final answer must have 2dp
1
= 4.566 × 10−13
1
pH = 12.34
If use alternative Kw (1.00 × 10−14) not as a repeat error, pH = 13.08
scores 1
If AE in Kw value made in part (c) is repeated here, do not penalise
again.
Final answer must have 2dp, but if dp penalised in (c) allow more
than 2dp here but not fewer.
1
[10]
Page 84 of 141
3
(a) [H+] = or = 1.74 × 10 −5 ×
Allow ( )
M1
1
= 3.08 × 10−5
If [HX] / [X-] or upside down, or any addition or subtraction lose M1 & M2.
M2
1
M3
1
Allow ( )
M1
M2
pH = = 4.51
so pH = 5.01
Must be to 2 dp
M3
M1
1
Page 85 of 141
mol X- after subtraction (= 0.140 − 0.015) = 0.125
For X− if no subtraction or error in subtraction (other than AE) (or subsequent extra add or
sub) MAX 3
M2
1
[H+] = ( )=
M3
1
M4
1
pH = 4.43
M5
1
Page 86 of 141
Alternative using Henderson−Hasselbach Equation
M1
M2
M3
pH = 4.76 − 0.328
M4
pH = = 4.43
If [HX] / [X−] upside down, lose M3 & M4 (or next two marks) but
can score M5 for correct pH conseq to their working, so if M1 & M2
correct, pH = 5.09 scores 3.
Allow more but not fewer than 2dp here.
M5
[8]
Page 87 of 141
(b) Acid: Increase in concentration of H+ ions, equilibrium moves to the left.
Allow H+ ions react with carbonate ions (to form HCO3-)
1
Alkali: OH- reacts with H+ ions, equilibrium moves to the right (to replace the H+ ions)
1
(a) As a droplet from the funnel could enter the burette / affect volume / readings / titre
5 1
(c) Ensures all reagents are able to react / mix / come into contact
Accept no reagent is left unreacted on sides of flask
Do not allow any reference to ‘removal’ of the solution unless it is
clear that it is added to the flask.
1
(d) The added water does not affect the mols / amount of reagents / reactants / solution
Z
Do not allow mols of solution or mols in the flask.
Allow water does not react with the reagents / water is not one of
the reactants
Do not allow ‘water is not involved’
1
[4]
(a) Burette
6 1
Page 88 of 141
Therefore, [OH–] = 1 × 10–14 / 1.58 × 10–12 = 6.33 × 10–3 (mol dm–3)
Allow 6.31–6.33 × 10–3 (mol dm–3)
1
Therefore Ka
1
(e) When [NH3] = [NH4+], Ka = [H+] therefore – log Ka= – log [H+]
Answer using alternative value
1
Page 89 of 141
(a) This question is marked using levels of response. Refer to the Mark Scheme Instructions
7 for Examiners for guidance on how to mark this question.
All stages are covered and the explanation of each stage is generally correct and
virtually complete.
All stages are covered but the explanation of each stage may be incomplete or may
contain inaccuracies OR two stages are covered and the explanations are generally
correct and virtually complete.
Answer is mainly coherent and shows a progression from stage 1 and stage 2 to
stage 3.
Level 2
3 – 4 marks
Two stages are covered but the explanation of each stage may be incomplete or may
contain inaccuracies, OR only one stage is covered but the explanation is generally
correct and virtually complete.
Answer includes some isolated statements, but these are not presented in a logical
order or show confused reasoning.
Level 1
1 – 2 marks
= 4.00 × 10–2
1
Ka = [H+][A–] / [HA]
B
8 [1]
C
9 [1]
Page 91 of 141
(b) 2CH3CH2COOH + Na2CO3 2CH3CH2COONa + H2O + CO2
OR
OR
OR
pH = 12.38 M3
Lose M3 if not 2 decimal places: 12.4 scores 2.
12.08 scores 1 (missing × 2) ; 12.1 scores 0.
11.78 scores 1 (dividing by 2) 11.8 scores 0.
1
(d) (i) Ka =
Page 92 of 141
(ii) M1 Ka = OR with numbers
M3 pH = 3.06
Must be 2 decimal places ie 3.1 loses M3.
1
M2 [X−] =
Ignore ( ) here.
If [HX] / [X−] upside down, can score M1 plus
M4 for 5.26 × 10−7.
1
M3 =
M4 = 7.572 × 10−3
1
Page 93 of 141
(e) M1 CO2
Allow NOx and SO2.
1
acidic (gas)
Scale – plotted points cover at least half the grid and y-axis should start at pH 4
1
Ka = 10−pKa M2
Ideally 1.0 × 10−9 to 7.9 × 10−10
Ignore precision of answer but lose M2 for 1 significant figure here.
1
Page 94 of 141
(d) pH 8.7
(e) Take more pH readings around the end-point / add smaller volumes of NaOH near
the end-point
Do not allow ‘use a more accurate / reliable pH meter / probe’.
Do not allow the use of a thermostatted mixture.
1
[9]
(b) (i)
M2
Ignore ( )
Mark for correctly rearranged expression incl [H+]2
1
M3
Page 95 of 141
(c) (i) ClCH2COOH ClCH2COO− + H+
OR ClCH2COOH + H2O ClCH2COO− + H3O+
Allow
Allow ClCH2CO2H and ClCH2CO 2−
1
(d) (i) A
1
(ii) C
1
(iii) D
1
(e) M1 Mol NaOH = mol OH− = (19.6 × 10–3) × 0.720 = 1.41(1) × 10−2
Mark for answer.
1
M4 XS mol H+ = 0.0149(3)
1
Page 96 of 141
M5 For dividing by volume
[H+ ] = 0.0149(3) × (1000 / 46.0) = 0.324 − 0.325 mol dm−3
If no use or wrong use of volume lose M5 and M6
ie can score 4 for pH = 1.83 (no use of vol)
Treat missing 1000 as AE (−1) & score 5 for pH = 3.49
1
M6 pH = 0.49
2dp (penalise more or less).
If × 2 missed & vol not used, pH = 3.39 scores M1 & M2 only.
1
[18]
(a) Over time / after storage meter does not give accurate readings
13
Do not allow ‘to get an accurate reading’ or ‘reading drifts’ on its
own.
Allow ‘temperature variations affect readings’.
1
pH = 6.73
Must be 2dp
1
Page 97 of 141
(iii) [H+] = 10−11.36 (= 4.365 × 10−12 OR 4.37 × 10−12)
Mark for working
1
(ii)
(iii) M1
Allow HA or HX etc.
Allow [H+] = (Ka × [HA]) for M1
1
Page 98 of 141
M2 Eqm shifts / moves to RHS OR more H+ OR Ka increases
OR more dissociation
1
(c) (i) M1
M2
(= 2.27 × 10−4)
1
M3
If [HX]/[X-] upside down here and is repeat error from (c)(i), max 3
(pH = 3.88 after 3.86 in (c)(i))
1
Page 99 of 141
M4 pH = 3.62 allow more than 2 dp but not fewer
pH calc NOT allowed from their wrong [H+] here
1
[20]
(b) (i) BB
Both need to be correct to score the mark
1
(ii) AA
Both need to be correct to score the mark
1
(iii) BA
Both need to be correct to score the mark
1
= OR
(= 3.27 × 10–5)
If either value of HX or X– used wrongly or expression upside down,
no further marks
1
(a) Z
16
Mark independently.
1
(b) pH
1
[HA] = [A−]
Accept solution half neutralised.
1
pH = pKa
Accept [H+] = Ka
1
[5]
= 0.322
Using 8.50 × 10–3 gives 0.293
Correct answer scores M1 and M2.
Do not penalise precision but must be to at least two significant
figures.
1
(c) M1 Ethylamine
If wrong no marks in (c)
1
OR increased availability of lp
(d) CH3CH2NH3Cl
Or any amine hydrochloride
OR H+ + OH– H2O
M2 pH = 1.77
2 dp
Allow M2 for correct pH calculation from their
wrong [H+] for this pH calculation only
1
M2 OR
Allow HA instead of HX
1
OR = 1.149 × 10−13
OR pOH = 1.06
If no use or wrong use of Kw or pOH no further marks
1
A
1
D
1
(ii) [H+][OH–]
Allow ( ) brackets, but must have charges
1
(b) (i) Ka =
Ka =
Allow HA
1
pH = 2.78 or 2.79
1
(c) (i) In pH values penalise fewer than 3 sig figs each time but
allow more than 2 dp
M1 Initially
M2 [H+] = Ka
or with numbers
Allow Henderson Hasselbach
pH = pKa + log
(ii) In pH values penalise fewer than 3 sig figs each time but
allow more than 2 dp
For values above 10, allow 3sfs - do not insist on 2 dp
or pOH = 1.29
Mark for Kw divided by their answer to M2
If pOH route, give one mark for 14 – pOH
1
M4 pH = 12.7(1)
Allow 3sf but not 12.70
1
(a) Idea that over time / after storage meter does not give accurate readings
23
Do not accept ‘to get an accurate reading’ without further
qualification.
Allow ‘temperature variations affect reading’.
1
[H+] = 0.0240
Do not penalise precision of [H+]
Correct answer scores M1 and M2.
1
(ii) 0.81
2dp required, no other answer allowed
1
M2 pH = 2.81
allow more than 2dp but not fewer
1
M2 Ka = or or using numbers
M3 [HX] =
M4 [HX] = 0.227
allow 0.225 – 0.23
1
OR
OR [Y] = .0236 ×
M4 pH = 4.91
allow more than 2dp but not fewer
allow M4 for correct pH calculation using their [H+] (this
applies in (d)(i) only)
1
OR [Y] = .0236 ×
M2 pKa = 4.87
1
log = –0.043
(ii) Can score full marks for correct consequential use of their
HY and Y– values from d(i)
if convert to concentrations
1
–
if HY/Y upside down, no further marks
M4 pH = 4.93
allow more than 2dp but not fewer
NOT allow M4 for correct pH calculation using their [H+] (this
allowance applies in (d)(i) only)
1
M3 log = –0.062
(ii) [H+][OH–]
1
pH = 6.63
Penalise fewer than 3 sig figs but allow more than 2 dp
1
M3 pH = 12.4(1)
not 12.40 (AE from 12.407)
1
Penalise fewer than 3 sig figs but allow more than 3 sfs
For values above 10, allow 3sfs - do not insist on 2 dp.
For values below 1, allow 2dp – do not insist on 3 sig figs
Not allow pH = 14 – pOH but can award M3 only for pH = 13.1(46)
Can award all three marks if pKw = 13.26 is used
(c) M1 mol NaOH = mol OH– = (30 × 10–3) × 0.20 = 6.0 × 10–3
mark for answer
1
M6 pH = 1.56
Penalise fewer than 3 sig figs but allow more than 3 sfs
For values above 10, allow 3sfs - do not insist on 2 dp.
For values below 1, allow 2dp – do not insist on 3 sig figs
1
[14]
Line through the points is smooth and has the correct profile
Ignore 0–5 cm3 section of the graph.
Lose this mark if graph is kinked or not a single line.
1
1.26 × 10–4
3.7 to 4.1 gives Ka = 7.9 × 10–5 to 2.0 × 10–4
Consequential marking from b(i).
Correct answer without working scores 1 mark only.
Do not penalise precision.
1
OR
(ii) mol acid = (25.0 × 10–3) × 0.41 = 1.025 × 10–2 or 1.03 × 10–2
1
OR
(c) (i) Ka =
1
allow HA etc here
This can be scored in part (c)(i) but doesn’t score there.
= 0.00925 or 0.0093
If A– is wrong, max 3 for M1, M2 and M3 or use of
pH = pKa – log [HA]/[A–]
M5 [H+] =
(a) (i) B 1
29
C
1
A
1
(b) pH = -log[H+]
1
Ka = or [H+] = [A–]
Ka =
(iii) [H+] =
= 1.74 × 10–5 ×
pH = 4.51
1
[11]
C
31 [1]
4.57 × 10–3
allow 4.6 × 10–3
ignore units
1
(ii) =
= 1.39 × 10–4
allow 1.39 – 1.41 × 10–4 mol dm–3
1
M4 is for answer
If vol is not 48 × 10–3 (unless AE) lose M4 and next mark gained
If multiply by 48 - this is AE - i.e. lose only M4
If multiply by 48 × 10–3 this is AE - i.e. lose only M4
1
pH = 12.57 (12.58) M6
Allow M6 conseq on AE in M5 if method OK
1
[13]
(a) k = rate/[CH3CH2COOCH3][H+]
33
1
or
= 0.415 (0.4146)
1
C
34 [1]
– log [H+]
1
pH = 10.40
1
= [H+]
[CH3CH2COOH]
1
pH = 2.89
1
[H+] = Ka × [CH3CH2COOH]
[CH3CH2COO–)
1
pH = 4.15
1
[16]
(a) (i) B;
36 1
C;
1
A;
1
(ii) cresolphthalein
OR
thymolphthalein;
1
OR
OH = 14 – pH;
1
OR
= 2.10;
1
= 7.9(4) × 10–3;
(if [H+] is wrong allow 1 for [OH] = KW/[H+] or as numbers)
1
OR
[H+]2/[HA]
OR
= 1.257 × l0–3
pH = 2.90;
1
OR
pKa = pH;
1
pH = 4.87;
(penalise 1dp once)
1
[13]
pH change = 0.22;
1
OR
C
38 [1]
(a) pH = –log[H+]
39
1
(= 2.61 × 10–5)
pH = 4.58
1
M4
(= 3.09 ×10–5)
M5 pH = 4.51
pKa = 4.76
1
1
alternative for penultimate mark of part (c)(ii)
C
40 [1]
[H+] =
H+ removed by A– forming HA
or acid reacts with salt
or more HA formed
1
[A–] =
3
= 0.141 (mol dm )
(Allow 0.139 to 0.141 and allow 0.14)
(If not used 3.59, to find [H+] can only score M2 for working)
(If 3.59 used but [H+] is wrong, can score M2 for correct method and
conseq M4)
If wrong method and wrong expression, can only score M1)
1
pH = pKa log
pKa = 3.84
1
1
[11]
D
42 [1]
B
43 [1]
A
45 [1]
A
46 [1]
= 2.34 × 10–7
or pOH = 0.82
pH = 13.18 (1)
or pH= 13.17
pH = 11.78 (1)f
or 11.77
8
or = 4.95 × 10–5
Notes
(c) If wrong Ka in (i) max 2 in part (ii) for [H+] (1) and conseq units (1)
but mark on fully from minor errors
eg no [ ] or charges missing
(2) Structures
C
48 [1]
or 18.75 cm3
2
(ii) Ka = (1)
NOT
Ka = (1)
[H+] =
pH = 2.69 (1)
pH should be given to 2 decimal places
penalise answer to 1 d.p. once in question
5
(d) moles OH– added = 1.875 × 10–3 = moles A– = moles HA left (1)
or [A–] = [HA]
pH = 4.56 (1)
3
[13]
C
50 [1]
(3.7 — 3.8)
Can score all 3 conseq on k from part (b)
3
[10]
Ka = (1)
pH = 2.78 (1)
4
[H+] = Ka × (1)
pH = 4.62 (1)
It forget subtraction : max 5
If Ka expression not used max 5
if moles of CH3COOH wrong but substitution used max 5
7
[H+] =
OR pOH =1.17
x = 25 × or 5.50 × 10–3 ×
for pH = 4.12 if upside down; answer 5.29 scores 3 for (1) (2)
(3)
6
[16]
C
54 [1]
D
55 [1]
D
56 [1]
B
57 [1]
B
58 [1]
D
59 [1]
B
60 [1]