SIR MICHELANGELO REFALO
SIXTH FORM
Annual Exam 2017
Subject: Chemistry ADV 1st Time: 3 hours
Answer 6 questions. All questions carry equal marks. You are reminded of the importance
of clear presentation in your answers, and the use of good English. A Periodic Table of
Elements is provided on the last page.
Important information: The ionic product of water, Kw, is 1.00 x 10-14 mol2 dm-6 at 298 K.
Molar Gas Constant R = 8.31 J K-1 mol-1
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1. This question is about acids and bases.
a) Phenol, C6H5OH, is a weak monoprotic acid having Ka value of 1.05 x 10-10 mol dm-3.
Consider an aqueous solution of phenol having a concentration of 0.010 mol dm-3.
Calculate the following properties of the solution:
(i) the pH (3 marks)
(ii) the concentration of hydroxide ion (1 mark)
b) Sketch a pH vs. volume of alkali titration curve for the titration of equimolar solutions
of phenol and sodium hydroxide. (1½ marks)
c) Give an estimate of the pH at the equivalence point of the titration described in (b),
and explain your answer. (1½ marks)
d) Name an indicator which would be suitable for the titration of a phenol solution with
aqueous sodium hydroxide, and give a reason for your choice. (1 mark)
e) Ethanoic acid is a weak acid having a pKa value of 4.76. Using the appropriate
calculation(s), state whether ethanoic acid or phenol is the weaker acid. (1½ marks)
f) Using your answer to (e), explain which of two equimolar aqueous solutions of
phenol and ethanoic acid would have the higher electrical conductivity. (1½ marks)
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g) Calculate the pH of a solution made up by mixing 100 cm3 of a 0.010 mol dm-3
hydrochloric acid solution and 50 cm3 of 0.050 mol dm-3 solution of sodium
hydroxide. (4 marks)
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2. This question is about reaction kinetics and catalysis.
a) The following reaction was carried out using different concentrations of reagents and
catalyst at a constant temperature of 35oC:
The results obtained are shown in the table below:
Initial [CH3COCH3] Initial [Br2] Initial [H+] (mol dm-3) Initial rate of reaction
(mol dm-3) (mol dm-3) (mol dm-3 s-1)
0.65 0.0050 0.040 0.020
0.65 0.0100 0.040 0.020
1.30 0.0050 0.040 0.040
0.65 0.0050 0.080 0.040
(i) Determine, giving reasons, the order of reaction with respect to CH3COCH3, Br2 and
H +. (3 marks)
(ii) Write the rate equation for the reaction. (1 mark)
(iii) Calculate the value of the rate constant of the reaction at 35oC. (1 mark)
b) With the aid of a Maxwell-Boltzmann distribution curve, explain the action of a catalyst
in increasing the reaction rate. (2 marks)
c) Ammonium ions react with nitrite ions in aqueous solution as follows:
NH4+ (aq) + NO2- (aq) N2 (g) + 2H2O (l)
Explain briefly an experimental method by which one could measure the rate of this reaction.
(2 marks)
d) Distinguish between a homogenous catalyst and a heterogenous catalyst. Give an
example of a reaction catalysed by a homogenous catalyst and a reaction catalysed by
a heterogenous catalyst, mentioning the catalyst in both cases. (2 marks)
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e) An increase in temperature causes an increase in reaction rates for TWO reasons.
State these two reasons, and mark with an asterisk (*) the most important of the two
reasons. (2 marks)
f) Draw energy profiles for (i) exothermic and (ii) endothermic reactions. Indicate on the
diagrams the activation energy and the enthalpy change of reaction in each case.
(2 marks)
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3. This question is about the chemistry of the s-block elements.
a) Explain what is meant by the term polarising power of an ion, and use it to explain
why the bonding in BeCl2 is different from that in MgCl2. (2 marks)
b) Write balanced chemical equations, including state symbols, for the reactions between:
(i) magnesium and steam;
(ii) barium oxide and oxygen (at 500oC);
(iii) sodium peroxide and water (3 marks)
c) Explain fully why magnesium sulfate is more soluble in water than barium sulfate, but
barium hydroxide is more soluble in water than magnesium hydroxide. (3 marks)
d) Compound L is a white inorganic solid which imparts a yellow-orange colour to a
Bunsen flame. On addition of aqueous barium chloride to an aqueous solution of L, a
white precipitate forms which dissolves on addition of HCl (aq) to produce a colourless
solution. Bubbling acidified dichromate(VI) into an aqueous solution of L results in the
formation of a green solution. Identify compound L, and explain the chemical changes
taking place, including equations. (4 marks)
e) Consider the decomposition of magnesium carbonate:
∆
MgCO3 (s) → MgO (s) + CO2 (g)
Explain whether you would expect the entropy change of this reaction to be positive,
negative or equal to zero. (1 mark)
f) Write balanced chemical equations for the thermal decomposition of lithium nitrate(V)
and potassium nitrate(V). Include all state symbols. (2 marks)
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4. This question is about redox chemistry and ionic equilibria.
a) Complete and balance the following equation for a redox reaction that takes place in
an acidic medium:
MnO4- + Fe2+ → Mn2+ + Fe3+ (1 mark)
b) Complete and balance the following equation for a redox reaction that takes place in
an alkaline medium:
Cr3+ + H2O2 → CrO42- + H2O (1 mark)
c) Define oxidising agent in terms of electron transfer. (½ mark)
d) Consider the following two half-equations for two redox systems and their associated
standard electrode potentials:
VO2+ (aq) + 2H+ (aq) + e- VO2+ (aq) + H2O (l) Eθ = + 1.00 V
Zn2+ (aq) + 2e- Zn (s) Eθ = - 0.76 V
(i) Draw a fully labelled diagram of a galvanic cell based on the above half-reactions,
labelling the anode and cathode and direction of electron flow when the cell is
operating. (3 marks)
(ii) Write the cell statement for the galvanic cell. (1 mark)
(iii) Write the complete equation, including state symbols, for the redox reaction which
occurs when the cell is in use. (1 mark)
e) Magnesium hydroxide, Mg(OH)2, is a sparingly soluble substance.
(i) Write an expression for the solubility product of magnesium hydroxide. (½ mark)
(ii) Explain the meaning of molar solubility of a sparingly soluble substance. (1 mark)
(iii) Write an expression that relates Ksp to the molar solubility of Mg(OH)2. (1 mark)
(iv) Explain what would happen to the solubility of magnesium hydroxide in a solution if
some sodium hydroxide were added to it, and name the phenomenon responsible for
this alteration in solubility. (1 mark)
f) Determine whether a precipitate of MgCO3 will form if 20.0 cm3 of 1.0 x 10-4 mol dm-3
aqueous Mg(NO3)2 is mixed with 30.0 cm3 of 1.0 x 10-5 mol dm-3 aqueous Na2CO3.
(The solubility product of MgCO3 is 3.5 x 10-8 mol2 dm-6). (4 marks)
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5. This question is about energetics.
a) Define the term enthalpy of solution of a solute. (1 mark)
b) Draw a labelled Hess cycle that relates the enthalpy of solution of LiCl (s) to its lattice
enthalpy and the enthalpies of solvation of the ions. (2 marks)
c) Define the term lattice enthalpy of an ionic lattice, and state, giving a reason, whether
lattice enthalpies are endothermic or exothermic. (2 marks)
d) Use the following information to draw the Born-Haber cycle for magnesium oxide, MgO,
including state symbols and the enthalpy values for each step. Hence calculate the lattice
enthalpy of MgO. (7 marks)
Process Enthalpy Change / kJ mol-1
Enthalpy of atomisation of magnesium +150
First ionisation enthalpy of magnesium +735
Second ionisation enthalpy of magnesium +1445
Enthalpy of atomisation of oxygen +247
First electron affinity of oxygen -141
Second electron affinity of oxygen +878
Enthalpy of formation of magnesium oxide -602
e) The lattice enthalpy of calcium oxide (CaO) is less exothermic than that of MgO. Explain
the reason for this. (1 mark)
f) The value of the lattice enthalpy of NaCl when calculated using a Born-Haber cycle was
found to be slightly different than the value of the lattice enthalpy of NaCl when calculated
by experiment. Suggest a reason for this difference. (2 marks)
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6. This question is about the chemistry of Group IV elements.
a) Explain, with the help of chemical equations, how these conversions can be achieved:
(i) NaHCO3 from CO2
(ii) PbCl2 from PbCl4
(iii) Na2Pb(OH)4 from PbO
(iv) SnO from Sn(COO)2 (4 marks)
b) Explain fully why CCl4, unlike SiCl4, is not hydrolysed at room temperature. (2 marks)
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c) Tin(II) compounds tend to be good reducing agents, while lead(IV) compounds tend
to be good oxidising agents. Explain why, and give examples of chemical reactions
where tin(II) and lead(IV) compounds exhibit these redox properties. (3 marks)
d) Explain the following observations with the help of chemical equations where
appropriate:
(i) Lead(II) hydroxide is insoluble in water, but dissolves in both aqueous nitric(V) acid
and aqueous sodium hydroxide.
(ii) On warming lead(IV) oxide with aqueous hydrochloric acid, a yellow-green gas is
evolved. No such reaction is observed with tin(IV) oxide. (4 marks)
e) What volume of gas is produced at 400oC and 1.01 x 105 Pa when 10.0g of lead(II)
nitrate(V) are decomposed by heating? (2 marks)
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7. This question is about volumetric analysis and chemical equilibria.
a) Describe in detail an experiment which can be used to determine the exact
concentration of a solution of potassium manganate(VII) in the laboratory. Include
chemical equations for all reactions mentioned. (4 marks)
b) Ammonium sulfate(VI), (NH4)2SO4, is a common fertiliser. The purity of a sample of
(NH4)2SO4 is determined by titrating a solution of the fertiliser with NaOH solution. The
volume of 0.1045 mol dm-3 NaOH solution required to neutralise 0.3144 g of (NH4)2SO4
was 24.42 cm3. The following is the equation for the reaction taking place in the
titration:
(NH4)2SO4 (aq) + 2NaOH (aq) → Na2SO4 (aq) + 2NH3 (aq) + 2H2O (l)
Calculate the percentage purity of the sample of (NH4)2SO4. (4 marks)
c) Explain the meaning of dynamic equilibrium. (1 mark)
d) When carbon dioxide is passed over hot graphite, carbon monoxide is formed according
to the reaction:
CO2 (g) + C (graphite) 2CO (g)
(i) State, giving a reason, what conditions of pressure favour the formation of CO (g).
(1 mark)
(ii) The forward reaction is favoured at high temperatures. State, giving a reason, whether
the forward reaction is exothermic or endothermic. (1 mark)
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e) A gas container of volume 3.50 dm3 was filled with 5.00 moles of NOCl and heated to
400oC. At equilibrium, 31.0% of the NOCl had dissociated according to the following
equation:
2NOCl (g) 2NO (g) + Cl2 (g)
Calculate the equilibrium constant Kc for the reaction. (4 marks)
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8. This question is about the chemistry of Group VII elements.
a) Describe and explain any changes that may be observed if a sample of chlorine gas is
bubbled into a test tube containing potassium iodide solution. Write the chemical
equation for the reaction that occurs when this procedure is carried out. (2 marks)
b) Use dot-and-cross diagrams to show the electronic arrangements in the following
compounds:
(i) NaClO (ii) NaClO4 (2 marks)
c) Sketch a graph to show the variation in the bond dissociation enthalpies of the
halogens in going down the group, and explain it fully. (2 marks)
d) Explain why anhydrous AlCl3 cannot be obtained by heating AlCl3.nH2O. (1 mark)
e) Distinguish between electron affinity and electronegativity, and explain how and why
the electronegativity of the halogens varies in going down the group. (3 marks)
f) A white crystalline solid A gives a lilac colour in a Bunsen flame. A is very soluble in
water and the solution forms a pale yellow precipitate B on addition of nitric(V) acid
and silver nitrate(V). Addition of hot, concentrated phosphoric(V) acid to solid A
produces white fumes of substance C. Identify substances A, B and C and explain,
with the aid of balanced chemical equations, all the reactions mentioned. (3½ marks)
g) Give the electronic configuration, in terms of orbitals, of the following species:
(i) F- (ii) Cl (iii) Cl+ (1½ marks)
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