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Exercises · 6.6

Q.For the following equilibrium, Kc= 6.3 × 10¹⁴ at 1000 K NO

(g) + O3
(g) ⇌ NO2
(g) + O2
(g) Both the forward and reverse reactions in the equilibrium are elementary bimolecular reactions. What is Kc, for the reverse reaction?
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For an elementary reaction, the equilibrium constant of the reverse reaction is simply the reciprocal of the forward constant. Therefore, Kc(reverse)=1/(6.3×1014)≈1.6×10−15K_c(\text{reverse}) = 1 / (6.3 \times 10^{14}) \approx 1.6 \times 10^{-15}.

The key idea here is beautifully simple: when a reaction is elementary (meaning it occurs in a single step, exactly as written), the equilibrium constant for the reverse reaction is just the reciprocal of the forward constant. This isn't a guess — it follows directly from the law of mass action.

Let’s see why.

  1. Write the forward equilibrium expression. For the forward reaction

NO(g)+O3(g)⇌NO2(g)+O2(g)\text{NO}(g) + \text{O}_3(g) \rightleftharpoons \text{NO}_2(g) + \text{O}_2(g)

the equilibrium constant KcK_c is defined as

Kc(forward)=[NO2][O2][NO][O3]=6.3×1014.K_c(\text{forward}) = \frac{[\text{NO}_2][\text{O}_2]}{[\text{NO}][\text{O}_3]} = 6.3 \times 10^{14}.

  1. Now consider the reverse reaction. The reverse reaction is simply the forward equation read from right to left:

NO2(g)+O2(g)⇌NO(g)+O3(g).\text{NO}_2(g) + \text{O}_2(g) \rightleftharpoons \text{NO}(g) + \text{O}_3(g).

Its equilibrium constant is

Kc(reverse)=[NO][O3][NO2][O2].K_c(\text{reverse}) = \frac{[\text{NO}][\text{O}_3]}{[\text{NO}_2][\text{O}_2]}.

  1. Spot the relationship. Compare the two expressions. The reverse constant is exactly the reciprocal of the forward constant:

Kc(reverse)=1Kc(forward).K_c(\text{reverse}) = \frac{1}{K_c(\text{forward})}.

This is always true for any equilibrium, regardless of mechanism — but the problem explicitly tells us both directions are elementary, which confirms we don’t need to worry about rate laws or intermediates.

  1. Plug in the number. Kc(reverse)=16.3×1014≈1.587×10−15.K_c(\text{reverse}) = \frac{1}{6.3 \times 10^{14}} \approx 1.587 \times 10^{-15}. …

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