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Monday 15 June 2015 – Afternoon

A2 GCE CHEMISTRY A
F325/01 Equilibria, Energetics and Elements
* 5 0 0 3 0 1 0 2 0 9 *

Candidates answer on the Question Paper.

OCR supplied materials: Duration: 2 hours

• Data Sheet for Chemistry A (inserted)

Other materials required:

• Scientific calculator

* F 3 2 5 0 1 *

INSTRUCTIONS TO CANDIDATES
• The Insert will be found inside this document.
• Write your name, centre number and candidate number in the boxes above. Please write
clearly and in capital letters.
• Use black ink. HB pencil may be used for graphs and diagrams only.
• Answer all the questions.
• Read each question carefully. Make sure you know what you have to do before starting your
answer.
• Write your answer to each question in the space provided. If additional space is required, you
should use the lined page at the end of this booklet. The question number(s) must be clearly
shown.
• Do not write in the bar codes.

INFORMATION FOR CANDIDATES

• The number of marks is given in brackets [ ] at the end of each question or part question.
• Where you see this icon you will be awarded marks for the quality of written
communication in your answer.
This means, for example, you should:
• ensure that text is legible and that spelling, punctuation and grammar are accurate so that
meaning is clear;
• organise information clearly and coherently, using specialist vocabulary when appropriate.
• You may use a scientific calculator.
• A copy of the Data Sheet for Chemistry A is provided as an insert with this question paper.
• You are advised to show all the steps in any calculations.
• The total number of marks for this paper is 100.
• This document consists of 24 pages. Any blank pages are indicated.
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Answer all the questions.

1 This question looks at properties of transition elements, ions and complexes.

(a) What is the oxidation number of Cr in the complex ion [CrOCl5]2–?

.............................................................................................................................................. [1]

(b) Write the equation for a reaction catalysed by a named transition element, compound or ion.

Equation: ...................................................................................................................................

Catalyst: ............................................................................................................................... [1]

(c) An octahedral complex ion A, C9H30N6Ni3+, exists as two optical isomers.

In complex ion A, Ni3+ is bonded to three molecules of a bidentate ligand B.

(i) State what is meant by a bidentate ligand.

...........................................................................................................................................

...........................................................................................................................................

...................................................................................................................................... [1]

(ii) What is the molecular formula of the bidentate ligand B?

...................................................................................................................................... [1]

(iii) Draw a possible structure for B and explain how B is able to act as a bidentate ligand.

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...........................................................................................................................................

...................................................................................................................................... [2]

(iv) What is the coordination number of complex ion A?

...................................................................................................................................... [1]

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(v) Complete the 3-D diagrams of the shapes of the optical isomers of complex ion A.

You can show the bidentate ligand simply as

3+ 3+

Ni Ni

[1]

(d) Describe the reactions of EITHER aqueous copper(II) ions OR aqueous cobalt(II) ions with:
• aqueous sodium hydroxide
• excess aqueous ammonia
• hydrochloric acid.

In your answer you should link observations with equations.

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[Total: 14]

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2 Hydrogen, H2, reacts with nitrogen monoxide, NO, as shown below:

2H2(g) + 2NO(g) N2(g) + 2H2O(g)

(a) The rate equation for this reaction is:

rate = k[H2(g)][NO(g)]2

The concentration of NO(g) is changed and a rate–concentration graph is plotted.

9.0

8.0

7.0

6.0

initial rate / 5.0

10–4 mol dm–3 s–1
4.0

3.0

2.0

1.0

0.0
0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0
[NO(g)] / 10 mol dm–3
–4

The chemist uses H2(g) of concentration 2.0 × 10–2 mol dm–3.

Using values from the graph, calculate the rate constant, k, for this reaction.

Give your answer to two significant figures and in standard form.

Show your working.

k = .................................... units ............................... [4]

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(b) A chemist investigates the effect of changing the concentration of H2(g) on the initial reaction
rate at two different temperatures.

The reaction is first order with respect to H2(g).

(i) Using the axes below, sketch two graphs of the results.

Label the graphs as follows:

• L for the lower temperature
• H for the higher temperature.

initial rate

0,0
[H2(g)]
[2]

(ii) State the effect of the higher temperature on the rate constant, k.

...................................................................................................................................... [1]

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(c) The reaction can also be shown as being first order with respect to H2(g) by continuous
monitoring of [H2(g)] during the course of the reaction.

• Using the axes below, sketch a graph to show the results.

• State how you would use the graph to show this first order relationship for H2(g).

[H2(g)]

time

...................................................................................................................................................

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.............................................................................................................................................. [2]

(d) The chemist proposes a three-step mechanism for the reaction:

2H2(g) + 2NO(g) N2(g) + 2H2O(g)

(i) On the dotted line below, write the equation for step 3.

step 1: 2NO N2O2 fast

step 2: H2 + N2O2 N2O + H2O slow

step 3: .......................................... fast [1]

(ii) Explain why this mechanism is consistent with the rate equation rate = k[H2(g)][NO(g)]2.

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[Total: 11]
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3 This question looks at two reactions involving sulfur compounds.

(a) Hydrogen reacts with carbon disulfide as shown below.

4H2(g) + CS2(g) CH4(g) + 2H2S(g)

For this reaction, ΔH = –234 kJ mol–1 and ΔS = –164 J K–1 mol–1.

(i) Why does the reaction have a negative entropy change?

...........................................................................................................................................

...................................................................................................................................... [1]

(ii) Standard entropies are shown in the table below.

substance CS2(g) CH4(g) H2S(g)

S o / J K–1 mol–1 238 186 206

Calculate the standard entropy for H2.

S o = ....................................... J K–1 mol–1 [2]

(iii) Explain, with a calculation, whether this reaction is feasible at 25 °C.

Show your working.

...........................................................................................................................................

...................................................................................................................................... [3]

(iv) Explain, with a calculation, the significance of temperatures above 1154 °C for this
reaction.

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(b) A chemist investigated methods to improve the synthesis of sulfur trioxide from sulfur dioxide
and oxygen.

2SO2(g) + O2(g) 2SO3(g)

The chemist:
• mixed together 1.00 mol SO2 and 0.500 mol O2 with a catalyst at room temperature
• compressed the gas mixture to a volume of 250 cm3
• allowed the mixture to reach equilibrium at constant temperature and without changing
the total gas volume.

At equilibrium, 82.0% of the SO2 had been converted into SO3.

(i) Determine the concentrations of SO2, O2 and SO3 present at equilibrium and calculate
Kc for this reaction.

Kc = .......................... units .......................... [6]

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(ii) Explain what would happen to the pressure as the system was allowed to reach
equilibrium.

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(iii) The value of Kc for this equilibrium decreases with increasing temperature.

Predict the sign of the enthalpy change for the forward reaction. State the effect on the
equilibrium yield of SO3 of increasing the temperature at constant pressure.

ΔH: .....................................................................................................................................

Effect on SO3 yield: ...................................................................................................... [1]

(iv) The chemist repeated the experiment at the same temperature with 1.00 mol SO2 and an
excess of O2.
The gas mixture was still compressed to a volume of 250 cm3.

State and explain, in terms of Kc, how the equilibrium yield of SO3 would be different
from the yield in the first experiment.

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[Total: 19]

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4 A student is supplied with 0.500 mol dm–3 potassium hydroxide, KOH, and 0.480 mol dm–3
propanoic acid, C2H5COOH.

The acid dissociation constant, Ka, for C2H5COOH is 1.35 × 10–5 mol dm–3.

(a) C2H5COOH is a weak Brønsted–Lowry acid.

What is meant by a weak acid and Brønsted–Lowry acid ?

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(b) Calculate the pH of 0.500 mol dm–3 potassium hydroxide.

pH = .......................................................... [2]

(c) The student dilutes 25.0 cm3 0.480 mol dm–3 C2H5COOH by adding water until the total
volume is 100.0 cm3.

(i) Write the expression for Ka for C2H5COOH.

[1]

(ii) Calculate the pH of the diluted solution.

pH = .......................................................... [3]

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(d) Aqueous propanoic acid, C2H5COOH, reacts with carbonates and alkalis.

(i) Write the full equation for the reaction of aqueous propanoic acid with sodium carbonate.

...................................................................................................................................... [1]

(ii) Write the ionic equation for the reaction of aqueous propanoic acid with aqueous
potassium hydroxide.

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(e) A student prepares a buffer solution containing propanoic acid C2H5COOH and propanoate
ions, C2H5COO–. The concentrations of C2H5COOH and C2H5COO– are both 1.00 mol dm–3.

The following equilibrium is set up.

C2H5COOH(aq) C2H5COO–(aq) + H+(aq)

The acid dissociation constant, Ka, for C2H5COOH is 1.35 × 10–5 mol dm–3.

(i) Calculate the pH of this buffer solution.

Give your answer to two decimal places.

pH = .......................................................... [1]

(ii) A small amount of aqueous ammonia, NH3(aq), is added to the buffer solution.

Explain, in terms of equilibrium, how the buffer solution would respond to the added
NH3(aq).

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(iii) The student adds 6.075 g Mg to 1.00 dm3 of this buffer solution.

Calculate the pH of the new buffer solution.

Give your answer to two decimal places

pH = .......................................................... [4]

[Total: 16]

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5 Iron(II) iodide, FeI2, is formed when iron metal reacts with iodine.

(a) The table below shows enthalpy changes involving iron, iodine and iron(II) iodide.

Enthalpy change /
kJ mol–1

Formation of iron(II) iodide –113

1st electron affinity of iodine –295

1st ionisation energy of iron +759

2nd ionisation energy of iron +1561

Atomisation of iodine +107

Atomisation of iron +416

(i) The incomplete Born–Haber cycle below can be used to determine the lattice enthalpy of
iron(II) iodide.

In the boxes, write the species present at each stage in the cycle.

Include state symbols for the species.

Fe2+(g) + 2I(g) + 2e–

Fe(s) + 2I(g)

FeI2(s)

[4]

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(ii) Define the term lattice enthalpy.

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...................................................................................................................................... [2]

(iii) Calculate the lattice enthalpy of iron(II) iodide.

lattice enthalpy = ........................................... kJ mol–1 [2]

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(b) Some electrode potentials for ions are shown below.

Fe2+(aq) + 2e– Fe(s) E o = –0.44 V

Fe3+(aq) + e– Fe2+(aq) E o = +0.77 V

½I2(aq) + e– I–(aq) E o = +0.54 V

½Br2(aq) + e– Br–(aq) E o = +1.09 V
½Cl 2(aq) + e– Cl –(aq) E o = +1.36 V

(i) Complete the electron configurations for Fe2+ and Br–.

Fe2+: 1s2 ...........................................................................................................................

Br–: 1s2 ...........................................................................................................................

[2]

(ii) Predict the products of reacting Fe(s) separately with I2(aq), Br2(aq) and Cl 2(aq).

Explain your predictions using the electrode potential data above.

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(c) Fe2+ ions can be used to test for NO3– ions.
In this test, aqueous iron(II) sulfate is added to a solution containing NO3– ions, followed by
slow addition of concentrated sulfuric acid. The sulfuric acid forms a layer below the aqueous
solution.
In the presence of NO3– ions, a brown ring forms between the two layers.

Two reactions take place.

Reaction 1: In the acid conditions Fe2+ ions reduce NO3– ions to NO.
Fe2+ ions are oxidised to Fe3+ ions.
Water also forms.
Reaction 2: A ligand substitution reaction of [Fe(H2O)6]2+ takes place in which one NO ligand
exchanges with one water ligand. A deep brown complex ion forms as the brown
ring.

Construct equations for these two reactions.

Reaction 1:

...................................................................................................................................................

Reaction 2:

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[Total: 16]

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6 Three redox systems, C, D and E are shown in Table 6.1.

C Ag(NH3)2+(aq) + e– Ag(s) + 2NH3(aq)

D Ag+(aq) + e– Ag(s)
E Ag(CN)2–(aq) + e– Ag(s) + 2CN–(aq)

Table 6.1

The two cells below were set up in an experiment to compare the standard electrode potentials of
redox systems C, D and E. The signs on each electrode are shown.

+ V – – V +

salt bridge salt bridge

Ag Ag Ag Ag

NH3(aq) CN–(aq) NH3(aq)

Ag(NH3)+2(aq) Ag(CN))2–(aq) Ag(NH3)+2(aq) Ag+(aq)

(a) List the three redox systems in order by adding the labels C, D and E to the table below.

o redox
E
system

Most
negative

Least
negative
[1]

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(b) A standard cell is set up between redox system D in Table 6.1 and a standard hydrogen half-
cell. The standard cell potential of redox system D is +0.34 V.

The cell delivers a current for a length of time.

The pH of the solution in the standard hydrogen half-cell decreases.

(i) What is the pH of the solution in a standard hydrogen half-cell?

pH = ......................................................... [1]

(ii) Explain, in terms of electrode potentials and equilibrium, why the pH of the solution in the
hydrogen half-cell decreases as this cell delivers current.

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(iii) Write the equation for the overall cell reaction that takes place in this cell.

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(c) The CN– ion is the conjugate base of a very toxic weak acid.

In aqueous solutions of CN– ions, an acid–base equilibrium is set up.

(i) Complete the equation for this equilibrium and label the conjugate acid–base pairs.

CN– + H2O ..................... + .....................

..................... ..................... ..................... .....................

[1]

(ii) Explain, in terms of equilibrium, why acidic conditions should not be used with cells
containing CN–(aq) ions.

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(d) Direct-ethanol fuel cells (DEFCs) are being developed in which the fuel is ethanol rather than
hydrogen.

The half-equation for the reaction at the ethanol electrode of the DEFC is shown below:

C2H5OH + 3H2O 2CO2 + 12H+ + 12e–

(i) State one important difference between a fuel cell and a modern storage cell.

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(ii) Suggest one advantage of using ethanol, rather than hydrogen, in a fuel cell for vehicles.

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(iii) The overall reaction in a DEFC is the same as for the complete combustion of ethanol.

Write the equation for the overall reaction in a DEFC.

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(iv) Deduce the half-equation for the reaction at the oxygen electrode in a DEFC.

...................................................................................................................................... [1]

(v) Using oxidation numbers, show that oxidation and reduction take place in a DEFC.

Oxidation: ..........................................................................................................................

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Reduction: .........................................................................................................................

...................................................................................................................................... [2]

[Total: 13]

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Turn over for the next question

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7 Chromite is the main ore of chromium. The chromium-containing compound in chromite is
Fe(CrO2)2. The percentage of chromium in a sample of chromite can be determined using the
method below.

Step 1
A 5.25 g sample of chromite ore is heated with sodium peroxide, Na2O2.

2Fe(CrO2)2 + 7Na2O2 2NaFeO2 + 4Na2CrO4 + 2Na2O

Water is added to the resulting mixture.

Na2CrO4 dissolves in the water forming a solution containing CrO42– ions.

Step 2
The mixture from Step 1 is filtered and the filtrate is made up to 1.00 dm3 in a volumetric
flask.
A 25.0 cm3 sample of this alkaline solution is pipetted into a conical flask and an excess
of aqueous potassium iodide is added.

• A redox reaction takes place between I– ions, CrO42– ions and H2O.
• In this reaction 1 mol CrO42– forms 1.5 mol I2.

Step 3
The resulting mixture is titrated with 0.100 mol dm–3 sodium thiosulfate, Na2S2O3(aq) to
estimate the I2 present:

I2(aq) + 2S2O32–(aq) 2I–(aq) + S4O62–(aq)

The average titre of Na2S2O3(aq) is 25.5 cm3.

(a) In Step 1 Na2O and NaFeO2 react with water forming an alkaline solution containing a brown
precipitate. This is not a redox reaction.

Write equations for:

• the reaction of Na2O with water
• the reaction of NaFeO2 with water.

...................................................................................................................................................

.............................................................................................................................................. [2]

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(b) Determine the percentage, by mass, of chromium in the ore.

Give your answer to one decimal place.

[6]

(c) This part refers to Step 2 of the method.

In the redox reaction between I– ions, CrO42– ions and H2O:

• CrO42– ions, are reduced to chromium(III) ions, Cr3+
• I– ions are oxidised to iodine, I2
• Construct an overall equation for the redox reaction and write half equations for the
oxidation and reduction.

Overall equation:

Half equations:

[3]
[Total: 11]
END OF QUESTION PAPER
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