Given
C(graphite) + O2(g) → CO2(g);
ΔrHº = – 393.5 kJ mol–1
H2(g) + O2(g) → H2O(l);
ΔrHº = –285.8 kJ mol–1;
CO2(g) + 2H2O(l) → CH4(g) + 2O2(g);
ΔrHº = +890.3 kJ mol–1
Based on the above thermochemical equations, the value of ΔrHº at 298 K for the reaction
C(graphite) + 2H2(g) → CH4(g) will be:
(1) C(graphite) + O2 (g) CO2(g), ΔrHº = – 393.5 kJ mol–1
(2) H2(g) +O2(g) H2O(l), ΔrHº = – 285.8 kJ mol–1
(3) CO2(g) + 2H2O(l) CH4(g) + 2O2 (g), ΔrHº = + 890.3 kJ mol–1
C(graphite) + 2H2(g) → CH4(g)
ΔrHº = – 393.5 – (2 × 285.8) + 890.3
= – 74.8 kJ/mol–1
To find the standard enthalpy change, ΔrH°, for the reaction C(graphite) + 2H2(g) → CH4(g), we can use Hess's Law. Hess's Law states that the total enthalpy change for a reaction is the same, regardless of the number of steps taken, as long as the initial and final conditions are identical. This means we can manipulate the given thermochemical equations algebraically to obtain the target reaction.
Step 1: List the given equations with their enthalpy changes:
(1) C(graphite) + O2(g) → CO2(g); ΔrH° = –393.5 kJ mol–1
(2) H2(g) + O2(g) → H2O(l); ΔrH° = –285.8 kJ mol–1
(3) CO2(g) + 2H2O(l) → CH4(g) + 2O2(g); ΔrH° = +890.3 kJ mol–1
Step 2: Identify the target reaction:
C(graphite) + 2H2(g) → CH4(g)
Step 3: Manipulate the given equations to match the target:
Notice that in the target, we have C(graphite) and 2H2(g) as reactants, and CH4(g) as the product. We need to eliminate CO2, O2, and H2O, which are not in the target.
2 × [H2(g) + O2(g) → H2O(l)] gives:
2H2(g) + O2(g) → 2H2O(l); ΔrH° = 2 × (–285.8) = –571.6 kJ mol–1
Reverse of (3): CH4(g) + 2O2(g) → CO2(g) + 2H2O(l); ΔrH° = –890.3 kJ mol–1 (since reversing changes the sign)
Step 4: Add the manipulated equations together:
(1) C(graphite) + O2(g) → CO2(g); ΔH = –393.5 kJ
(2 multiplied) 2H2(g) + O2(g) → 2H2O(l); ΔH = –571.6 kJ
(3 reversed) CH4(g) + 2O2(g) → CO2(g) + 2H2O(l); ΔH = –890.3 kJ
Now, add these three equations:
C(graphite) + O2(g) + 2H2(g) + O2(g) + CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) + CO2(g) + 2H2O(l)
Simplify by canceling species that appear on both sides:
Left: C(graphite) + 2H2(g) + CH4(g) + 4O2(g)
Right: 2CO2(g) + 4H2O(l)
Better Approach: Directly combine to cancel intermediates:
We want: C(graphite) + 2H2(g) → CH4(g)
From the equations, we see that if we take:
(1) C(graphite) + O2(g) → CO2(g); ΔH₁ = –393.5
(2 multiplied) 2H2(g) + O2(g) → 2H2O(l); ΔH₂ = –571.6
(3) CO2(g) + 2H2O(l) → CH4(g) + 2O2(g); ΔH₃ = +890.3
Now, add these three equations:
Left: C(graphite) + O2(g) + 2H2(g) + O2(g) + CO2(g) + 2H2O(l)
Right: CO2(g) + 2H2O(l) + CH4(g) + 2O2(g)
Cancel common terms on both sides:
- CO2(g) cancels.
- 2H2O(l) cancels.
- O2(g): on left, 2O2; on right, 2O2; they cancel.
We are left with: C(graphite) + 2H2(g) → CH4(g)
This is exactly our target reaction.
Step 5: Calculate the total enthalpy change:
ΔrH° = ΔH₁ + ΔH₂ + ΔH₃ = (–393.5) + (–571.6) + (+890.3) kJ
Compute step by step:
–393.5 – 571.6 = –965.1
–965.1 + 890.3 = –74.8 kJ mol–1
Final Answer: The value of ΔrH° for C(graphite) + 2H2(g) → CH4(g) is
Hess's Law: The total enthalpy change for a reaction is independent of the pathway, and can be calculated by the algebraic sum of enthalpy changes of individual steps that lead from reactants to products.
Standard Enthalpy of Formation (ΔfH°): The enthalpy change when one mole of a compound is formed from its elements in their standard states. The reaction we solved is actually the formation reaction for CH4(g), so ΔrH° = ΔfH°(CH4, g).
Manipulating Thermochemical Equations: When reversing an equation, the sign of ΔH is changed. When multiplying an equation by a factor, ΔH is multiplied by that factor.