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 This question is about thermodynamics.
1. Consider the reaction shown.

2 Al2O3(s) + 3 C(s) → 4 Al(s) + 3 CO2(g)

The table below shows some thermodynamic data.

Substance Al2O3(s) Al(s) C(s) CO2(g)

ΔfHϴ/ kJ mol–1 –1669 0 0 –394

Sϴ/ J K–1 mol–1 51 28 6 214

(a) Explain why the standard entropy value for carbon dioxide is greater than that for carbon.

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(b) State the temperature at which the standard entropy of aluminium is 0 J K–1 mol–1

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(c) Use the equation and the data in the table above to calculate the minimum temperature, in
K, at which this reaction becomes feasible.

Minimum temperature _______________ K

(7)
(Total 9 marks)

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 Methanol is formed when carbon dioxide and hydrogen react.
2.

CO2(g) + 3 H2(g) ⇌ CH3OH(g) + H2O(g)

The table contains enthalpy of formation and entropy data for these substances.

CO2(g) H2(g) CH3OH(g) H2O(g)

Δ fH / kJ mol–1 –394 0 –201 –242

S / J K–1 mol–1 214 131 238 189

(a) Use the equation and the data in the table above to calculate the Gibbs free-energy change
(ΔG), in kJ mol–1, for this reaction at 890 K

ΔG _______________ kJ mol–1
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The graph below shows how the Gibbs free-energy change varies with temperature in a different
gas phase reaction.

The straight line graph for this gas phase reaction has been extrapolated to zero Kelvin.

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(b) Use the values of the intercept and gradient from the graph to calculate the enthalpy
change (ΔH), in kJ mol–1, and the entropy change (ΔS), in J K–1 mol–1, for this reaction.

ΔH _______________ kJ mol–1
ΔS _______________ J K–1 mol–1
(4)

(c) State what the graph above shows about the feasibility of the reaction.

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(1)
(Total 11 marks)

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 The diagram shows an incomplete Born−Haber cycle for the formation of caesium iodide. The
3. diagram is not to scale.

Table 1 gives values of some standard enthalpy changes.

Table 1

Name of enthalpy change ∆H⦵ / kJ mol−1

Enthalpy of atomisation of caesium +79

First ionisation energy of caesium +376

Electron affinity of iodine −314

Enthalpy of lattice formation of caesium iodide −585

Enthalpy of formation of caesium iodide −337

(a) Complete the diagram above by writing the formulas, including state symbols, of the
appropriate species on each of the two blank lines.
(2)

(b) Use the diagram above and the data in Table 1 to calculate the standard enthalpy of
atomisation of iodine.

Standard enthalpy of atomisation of iodine _________________________ kJ mol−1

(2)

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 (c) The enthalpy of lattice formation for caesium iodide in Table 1 is a value obtained by
experiment.
The value obtained by calculation using the perfect ionic model is −582 kJ mol−1

Deduce what these values indicate about the bonding in caesium iodide.

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(d) Use data from Table 2 to show that this reaction is not feasible at 298 K

Table 2

CsI(s) Cs(s) I2(s)

S⦵ / J K−1 mol−1 130 82.8 117

(4)
(Total 9 marks)

The equation for the reaction between ammonia and oxygen is shown.
4.
4NH3(g) + 5O2(g) ⇌ 4NO(g) + 6H2O(g) ∆H = –905 kJ mol–1

Some standard entropies are given in the table.

Gas So / J K–1 mol–1

NH3(g) 193

O2(g) 205

NO(g) 211

H2O(g) 189

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(a) Calculate the entropy change for the reaction between ammonia and oxygen.

Entropy change ____________________ J K–1 mol–1

(2)

(b) Calculate a value for the Gibbs free-energy change (∆G), in kJ mol–1, for the reaction
between ammonia and oxygen at 600 °C

(If you were unable to obtain an answer to part (a), you should assume that the entropy
change is 211 J K–1 mol–1. This is not the correct answer.)

∆G ____________________ kJ mol–1
(2)

(c) The reaction between ammonia and oxygen was carried out at a higher temperature.

Explain how this change affects the value of ∆G for the reaction.

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(d) Platinum acts as a heterogeneous catalyst in the reaction between ammonia and oxygen. It
provides an alternative reaction route with a lower activation energy.

Describe the stages of this alternative route.

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(e) Deduce the change in oxidation state of nitrogen, when NH3 is oxidised to NO

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(f) When ammonia reacts with oxygen, nitrous oxide (N2O) can be produced instead of NO

Give an equation for this reaction.

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(1)
(Total 11 marks)

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 Titanium(IV) chloride can be made from titanium(IV) oxide as shown in the equation.
5.
TiO2(s) + 2C(s) + 2Cl2 (g) → 2CO(g) + TiCl4(l) ΔHo = −60.0 kJ mol−1

Some entropy data are shown in the table.

Substance TiO2(s) C(s) Cl2(g) CO(g) TiCl4(l)

So / J K−1 mol−1 50.2 5.70 223 198 253

Use the equation and the data in the table to calculate the Gibbs free-energy change for
this reaction at 989 °C

Give your answer to the appropriate number of significant figures.

Use your answer to explain whether this reaction is feasible.

Gibbs free-energy change ____________________ kJ mol−1

Explanation _________________________________________________________

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(Total 6 marks)

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 Hydrogen can be manufactured from the reaction of steam with methane.
6.
CH4(g) + H2O(g) CO(g) + 3H2(g)

(a) The table contains some enthalpy of formation and entropy data.

Substance ΔH f / kJ mol−1 S / J K−1 mol−1

CH4(g) −75 186

H2O(g) −242 189

CO(g) −111 198

H2(g) 0 131

CO2(g) −394 214

(i) Use data from the table to calculate the enthalpy change, ΔH, for the reaction of
steam with methane.

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(ii) Use data from the table to calculate the entropy change, ΔS, for the reaction of steam
with methane.

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(b) Use your values of ΔH and ΔS from parts (a)(i) and (a)(ii) to calculate the temperature
above which this reaction is feasible.

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(4)

(c) The temperature used for this manufacture of hydrogen is usually about 1300 K.

Suggest one reason, other than changing the position of equilibrium, why this temperature
is used rather than the value that you calculated in part (b).

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(1)

(d) Hydrogen can also be obtained by reaction of carbon monoxide with steam.

CO(g) + H2O(g) CO2(g) + H2(g) ΔH = −41 kJ mol−1, ΔS = −42 J K−1 mol−1

(i) Explain, using a calculation, why this reaction should not occur at 1300 K.

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(ii) Explain how the conditions for the reaction could be changed to allow this reaction to
take place.

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(2)
(Total 15 marks)

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