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Chemistry H2 9746
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Revision Exercise 6: Thermochemistry

1 Construct a Born-Haber, and use it to find the standard lattice enthalpy of cadmium(II)
iodide.
θ
Equation ∆ H / kJ mol-1
Cd (s) → Cd (g) + 113
Cd (g) → Cd2+ (g) + 2e- + 2490
I2 (s) → I2 (g) + 19.4
I2 (g) → 2I (g) + 151
I (g) + e- → I- (g) - 314
Cd (s) + I2 (s) → CdI2 (s) - 201

2 The table below shows the different lattice enthalpies and hydration enthalpies of lithium
chloride, lithium fluoride, sodium chloride and sodium fluoride.
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Enthalpies / kJ
LiCl LiF NaCl NaF
mol-1
Lattice -843 -1029 -775 -968
Hydration -883 -1023 -778 -965

(a) Describe the dissolution of an ionic solid in water, discussing the energetic of the process.

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(b) Suggest why, in general, A2+B2- compounds are less soluble than A+B+ compounds.

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(c) Suggest why

(i) LiF is less soluble than NaF

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(ii) LiCl is more soluble than NaCl

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(iii) NaF is less soluble than NaCl

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3 Calcium chloride, CaCl2, is a stable compound. Neither CaCl nor CaCl3 exists.
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According to calculations,

(a) CaCl3 would have a large positive standard enthalpy of formation.


(b) CaCl will have a small negative value

Explain (a) and (b) in terms of the Born-Haber cycle.

4(a) Define

(i) Standard enthalpy of formation

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(ii) Standard enthalpy of combustion

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(b) The standard enthalpy changes, in kJ mol-1, of the following reaction refer to a temperature
of 298 K.
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θ
C (s) + O2 (g) → CO2 (g) ∆ H = - 394
θ
H2 (g) + 0.5 O2 (g) → H2O (l) ∆ H = -286
θ
C2H4 (g) + 3O2 (g) → 2CO2 (g) + 2H2O (l) ∆ H = -1411

Using the information provided, calculate the standard enthalpy of formation of C2H4.

(c) If, at 298 K, the enthalpy of sublimation of graphite is 713 kJ mol -1 and the bond energy
terms H – H and C – H are 436 and 415 kJ mol -1 respectively, calculate the C = C bond
energy term.

(d) When ethene is burnt in oxygen, does the entropy increase, decrease or remain the same?
Explain your answer. Assume that the reactants and products are at 298 K.

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5 Some bond energy terms are listed below.


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Bond H–H C–H C – Br C–C C=C Br – Br


Bond
energy 435 415 284 356 598 193
/ kJ mol-1

(a) Explain what is meant by the term bond energy.

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(b) Using the given data, calculate the enthalpies of formation, from gaseous atoms, of

(i) Gaseous propene (propylene)

H H
| |
C=C–C–H
| | |
H H H

(ii) Gaseous 1,2-dibromopropane

H Br H
| | |
H–C–C–C–H
| | |
Br H H

θ
(c) Calculate the enthalpy change, ∆ H , for the reaction:

CH2 = CH – CH3 (g) + Br2 (g) → CH2BrCHBrCH3 (g)

6(a) Construct Born-Haber cycles for MgCl, MgCl2 and MgCl3, inserting all the values except
θ
∆ Hf . Since experimentally determined lattice energies for MgCl and MgCl 3 are not
available, use the theoretically calculated values:
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θ
∆ HLE [MgCl] = -753 kJ mol-1
θ
∆ HLE [MgCl3] = -5440 kJ mol-1

(b) Use the cycles to obtain values for


θ
(i) ∆ Hf [MgCl]

θ
(ii) ∆ Hf [MgCl2]

θ
(iii) ∆ Hf [MgCl3]
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(c) Which of the three compounds MgCl, MgCl2, MgCl3, is/are energetically stable with respect
to the elements? Explain your answer.

MgCl and MgCl2 are both energetically stable with respect to their elements, but
MgCl2 is more stable than MgCl.
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θ
(d) Using the ∆ Hf values calculated in (b), calculate the enthalpy change for the hypothetical
reaction

2MgCl (s) → MgCl2 (s) + Mg (s)

(e) Discuss briefly the relative stability of MgCl and MgCl2 in the light of your answer to (d).
Does this explain why MgCl is not known?

MgCl is unstable relative to MgCl2 and Mg. This explains why MgCl is unknown; as
soon as it forms, it would be converted to MgCl2 and Mg.
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7 Enthalpy, H, is a thermodynamic quantity. H is the chemical energy or heat content of a


system at constant temperature and pressure. What is important about enthalpy is its
change, ΔH, when a chemical process occurs.

Provided the process occurs at constant pressure (usually one atmosphere) and the only
work done by the system is possibly the production of gas, then ΔH is equal to the heat
energy produced or absorbed by the process.

The chart below shows the enthalpy changes produced by evaporation, melting and
dissolving.
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(a) From the chart, would you expect KBr or LiBr to dissolve more readily in water?

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(b) Which of the processes shown in the chart are exothermic?

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(c) The graph below shows the enthalpy change of formation for different compounds.
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Given its large negative enthalpy of formation, explain why rusting iron usually does not
feel warm to the touch (unless it has been left in the sun).

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(d) The graph below shows the enthalpies of formation for several atomic gases
from their more stable diatomic state.

Discuss what effect the bond structures of N2 and O2 have in determining the enthalpies of
formation of N and O.

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End of Paper