Question 16.6: CALCULATING ΔG° FOR A REACTION FROM ΔH° AND ΔS° Iron metal i...
CALCULATING ΔG° FOR A REACTION FROM ΔH° AND ΔS°
Iron metal is produced commercially by reducing iron(III) oxide in iron ore with carbon monoxide:
Fe_{2}O_{3}(s) + 3 CO(g) → 2 Fe(s) + 3 CO_{2}(g)
(a) Calculate the standard free-energy change for this reaction at 25 °C.
(b) Is the reaction spontaneous under standard-state conditions at 25 °C?
(c) Does the reverse reaction become spontaneous at higher temperatures? Explain.
STRATEGY
(a) We can calculate the standard free-energy change from the relation ΔG° = ΔH° – TΔS°, but first we must find ΔH° and ΔS° from standard enthalpies of formation ( ΔH°_{f}) and standard molar entropies (S°).
(b) The reaction is spontaneous under standard-state conditions if ΔG° is negative.
(c) The spontaneity of the reaction at higher temperatures depends on the signs and magnitudes of ΔH° and ΔS°.
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(a) The following values of ΔH°_{f} and S° are found in Appendix B:
So we have
ΔH° = [2 ΔH°_{f}(Fe) + 3 ΔH°_{f}(CO_{2})] – [ΔH°_{f}(Fe_{2}O_{3}) + 3 ΔH°_{f}(CO)]
= [(2 mol)(0 kJ/mol) + (3 mol)(-393.5 kJ/mol)]
– [(1 mol)(-824.2 kJ/mol) + (3 mol)(-110.5 kJ/mol)]
ΔH° = -24.8 kJ
and
ΔS° = [2 S°(Fe) + 3 S°(CO_{2})] – [S°(Fe_{2}O_{3}) + 3 S°(CO)]
= \left[(2 mol)\left(27.3 \frac{J}{K · mol}\right) + (3 mol)\left(213.6 \frac{J}{K · mol}\right)\right]
– \left[(1 mol)\left(87.4 \frac{J}{K · mol}\right) + (3 mol)\left(197.6 \frac{J}{K · mol}\right)\right]
ΔS° = +15.2 J/K or 0.0152 kJ/K
Therefore,
ΔG° = ΔH° – TΔS°
= (-24.8 kJ) – (298 K)(0.0152 kJ/K)
ΔG° = -29.3 kJ
(b) Because ΔG° is negative, the reaction is spontaneous at 25 °C. This means that a mixture of Fe_2O_{3}(s), CO(g), Fe(s), and CO_{2}(g), with each gas at a partial pressure of 1 atm, will react at 25 °C to produce more iron metal.
(c) Because ΔH° is negative and ΔS° is positive, ΔG° will be negative at all temperatures. The forward reaction is therefore spontaneous at all temperatures, and the reverse reaction does not become spontaneous at higher temperatures.
Fe_{2}O_{3}(s) CO(g) Fe(s) CO_{2}(g) |
ΔH°_{f} (kJ/mol) -824.2 -110.5 0 -393.5
S° [J/(K · mol)] 87.4 197.6 27.3 213.6 |