Paddington Academy

A LEVEL CHEMISTRY
TOPIC 10 –THERMODYNAMICS

ASSESSED HOMEWORK

Answer all questions

Max 80 marks

Name ……………………………………………………………..

Mark ……../80 ……....% Grade ………

1.

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2. Some thermodynamic data for fluorine and chlorine are shown in the table.
In the table, X represents the halogen F or Cl.

Fluorine Chlorine

Electronegativity 4.0 3.0

Electron affinity / kJ mol –1

–348 –364

Enthalpy of atomisation / kJ mol –1

+79 +121

Enthalpy of hydration of X (g) / kJ mol

– –1
–506 –364

(a) Explain the meaning of the term electron affinity.

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(b) Explain why the electronegativity of fluorine is greater than the electronegativity of
chlorine.

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(c) Explain why the hydration enthalpy of the fluoride ion is more negative than the
hydration enthalpy of the chloride ion.

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(d) The enthalpy of solution for silver fluoride in water is –20 kJ mol . –1

The hydration enthalpy for silver ions is –464 kJ mol . –1

(i) Use these data and data from the table to calculate a value for the lattice
enthalpy of dissociation of silver fluoride.

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(ii) Suggest why the entropy change for dissolving silver fluoride in water has a
positive value.

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(iii) Explain why the dissolving of silver fluoride in water is always a spontaneous
process.

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(2)
(Total 12 marks)

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2. The balance between enthalpy change and entropy change determines the feasibility of a
reaction. The table below contains enthalpy of formation and entropy data for some
elements and compounds.

N (g)
2 O (g)
2 NO(g) C(graphite) C(diamond)
ΔH ο/kJ mol
f
–1
0 0 +90.4 0 +1.9
Sο/J K mol
–1 –1
192.2 205.3 211.1 5.7 2.4

(a) Explain why the entropy value for the element nitrogen is much greater than the
entropy value for the element carbon (graphite).

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(b) Suggest the condition under which the element carbon (diamond) would have an
entropy value of zero.

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(c) Write the equation that shows the relationship between ΔG, ΔH and ΔS for a
reaction.

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(d) State the requirement for a reaction to be feasible.

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(e) Consider the following reaction that can lead to the release of the pollutant NO into
the atmosphere.

N (g) +
2 O (g)
2 NO(g)

Use data from the table above to calculate the minimum temperature above which
this reaction is feasible.

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(f) At temperatures below the value calculated in part (e), decomposition of NO into its
elements should be spontaneous. However, in car exhausts this decomposition
reaction does not take place in the absence of a catalyst.
Suggest why this spontaneous decomposition does not take place.

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(1)

(g) A student had an idea to earn money by carrying out the following reaction.

C(graphite) C(diamond)

Use data from the table above to calculate values for ΔH and ΔSο for this reaction.
Use these values to explain why this reaction is not feasible under standard
pressure at any temperature.

ΔHο ...............................................................................................................

ΔSο ...............................................................................................................

Explanation ..................................................................................................

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(3)
(Total 14 marks)

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3. Comparison of lattice enthalpies from Born-Haber cycles with lattice enthalpies from
calculations based on a perfect ionic model are used to provide information about bonding
in crystals.

(a) Define the terms enthalpy of atomisation and lattice dissociation enthalpy.

Enthalpy of atomisation ...............................................................................

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Lattice dissociation enthalpy ........................................................................

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(b) Use the following data to calculate a value for the lattice dissociation enthalpy of
sodium chloride.

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(c) Consider the following lattice dissociation enthalpy (ΔH ο) data. L

NaBr AgBr
ΔH ο(experimental)/kJ mol
L
–1
+733 +890
ΔH ο(theoretical)/kJ mol
L
–1
+732 +758

The values of ΔH ο (experimental) have been determined from Born–Haber cycles.

L

The values of ΔH ο (theoretical) have been determined by calculation using a perfect

L

ionic model.

(i) Explain the meaning of the term perfect ionic model.

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(ii) State what you can deduce about the bonding in NaBr from the data in the
table.

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(iii) State what you can deduce about the bonding in AgBr from the data in the
table.

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(1)
(Total 11 marks)

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4. Thermodynamics can be used to investigate the changes that occur when substances
such as calcium fluoride dissolve in water.

(a) Give the meaning of each of the following terms.

(i) enthalpy of lattice formation for calcium fluoride

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(ii) enthalpy of hydration for fluoride ions

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(b) Explain the interactions between water molecules and fluoride ions when the
fluoride ions become hydrated.

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(c) Consider the following data.

Use these data to calculate a value for the enthalpy of solution for CaF 2

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(2)
(Total 7 marks)

5. Ethyl ethanoate can be prepared by the reactions shown below.

Reaction 1
CH COOH(l) + C H OH(l)
3 2 5 CH COOC H (l) + H O(l)
3 2 5 2 ∆H = –2.0 kJ mol –1

Reaction 2
CH COCl(l) + C H OH(l) → CH COOC H (l) + HCl(g)
3 2 5 3 ∆H = –21.6 kJ mol
2 5
–1

Use the information given above and the data below to calculate values for the
standard entropy change, ∆S , and the standard free-energy change, ∆G , for
Reaction 2 at 298 K.

CH COCl(l)
3 C H OH(l)
2 5 CH COOC H (l)
3 2 5 HCl(g)

S /JK mol 1 1 201 161 259 187

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(Total 6 marks)

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6. The feasibility of a physical or a chemical change depends on the balance between

the thermodynamic quantities of enthalpy change (ΔH), entropy change (ΔS) and
temperature (T).

(a) Suggest how these quantities can be used to predict whether a change is feasible.

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(b) Explain why the evaporation of water is spontaneous even though this change is
endothermic.
In your answer, refer to the change in the arrangement of water molecules and the
entropy change.

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(c) This table contains some thermodynamic data for hydrogen, oxygen and water.

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

H (g) 2 131 0

O (g) 2 205 0

H O(g)
2 189 −242

H O(I)
2 70

(i) Calculate the temperature above which the reaction between hydrogen and
oxygen to form gaseous water is not feasible.

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(ii) State what would happen to a sample of gaseous water that was heated to a
temperature higher than that of your answer to part (c)(i).
Give a reason for your answer.

What would happen to gaseous water .................................................

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Reason ..................................................................................................

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(d) When hydrogen is used as a fuel, more heat energy can be obtained if the gaseous
water formed is condensed into liquid water.

Use entropy data from the table in part (c) to calculate the enthalpy change when
one mole of gaseous water is condensed at 373 K.
Assume that the free-energy change for this condensation is zero.

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(Total 15 marks)

7. Chlorine is formed in a reversible reaction as shown by the equation

4HCl(g) + O (g) 2 2Cl (g) + 2H O(g)

2 2

(a) Use the data below to calculate the standard enthalpy change, ΔH , and the
standard entropy change, ΔS , for this reaction.

Substance HCl(g) O (g)

2 Cl (g)
2 H O(g)
2

ΔH /kJ mol
f
–1 –92 0 0 –242

S / J K mol –1 –1 187 205 223 189

Standard enthalpy change, ΔH ................................................................

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Standard entropy change, ΔS ..................................................................

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(6)

(b) The data below apply to a different gas phase reversible reaction.

Standard enthalpy change, ΔH = +208 kJ mol –1

Standard entropy change, ΔS = +253 J K mol –1 –1

(i) Deduce the effect of an increase in temperature on the position of the

equilibrium in this reaction. Use Le Chatelier’s principle to explain your
answer.

Effect ..................................................................................................

Explanation .........................................................................................

(ii) Calculate the minimum temperature at which this reaction is feasible.

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(7)
(Total 13 marks)

8. Which one of the equations below represents a reaction that is feasible at all
temperatures?

A P(s) → Q(s) + R(g) endothermic

B 2L(g) + M(g) → 2N(g) exothermic

C S(g) → 2T(g) exothermic

D A(g) + B(g) → C(g) endothermic

(Total 1 mark)

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9. Using the information below, answer this question.

Fe2O3(s) + 3H2(g) → 2Fe(s) + 3H2O(g) ΔH = +96 kJ mol−1, ΔS = +138 J K−1 mol−1

Fe2O3(s) H2(g) Fe(s)

ΔH / kJ mol−1 −822.0 0 0

ΔS / J K−1 mol−1 90.0 131.0 27.0

The standard enthalpy of formation of steam is

A +286 kJ mol−1

B +242 kJ mol−1

C −242 KJ mol−1

D −286 kJ mol−1
(Total 1 mark)

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