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Chemistry · Ch 8 — Physical and Chemical Equilibrium

Predicting the direction of a reaction

8.7.2

Predicting the direction of a reaction

Knowing KCK_C tells us where equilibrium lies, but a reaction mixture is not always sitting at equilibrium. To find out which direction a given (non-equilibrium) mixture still needs to move, define the reaction quotient, Q, for a general reaction xA+yB⇌lC+mDxA + yB \rightleftharpoons lC + mD as

Q=[C]l[D]m[A]x[B]yQ = \frac{[C]^l[D]^m}{[A]^x[B]^y}

Q has exactly the same algebraic form as KCK_C, evaluated with whatever concentrations of reactants and products happen to be present at that instant -- concentrations that need not be the equilibrium ones. As the reaction proceeds, the concentrations of reactants and products keep changing, so Q keeps changing too, right up until the reaction reaches equilibrium -- at which point Q becomes numerically equal to KCK_C and, once equilibrium is reached, stops changing any further. Comparing Q with KCK_C at any instant therefore predicts the direction in which the reaction will move:

  • If Q=KCQ = K_C, the reaction is already at equilibrium (no further net change).
  • If Q>KCQ > K_C, the reaction proceeds in the reverse direction, i.e. toward the formation of reactants.
  • If Q<KCQ < K_C, the reaction proceeds in the forward direction, i.e. toward the formation of products.

Example 1. For H2(g)+I2(g)⇌2HI(g)H_2(g)+I_2(g)\rightleftharpoons 2HI(g), KC=48K_C = 48 at 717 K. At a particular instant, [H2]=0.2[H_2]=0.2, [I2]=0.2[I_2]=0.2, [HI]=0.6[HI]=0.6 mol L−1^{-1}. Q=(0.6)2(0.2)(0.2)=9Q = \dfrac{(0.6)^2}{(0.2)(0.2)} = 9. Since Q(9)<KC(48)Q(9) < K_C(48), the reaction proceeds in the forward direction.

Example 2. For N2O4(g)⇌2NO2(g)N_2O_4(g)\rightleftharpoons 2NO_2(g), KC=0.21K_C = 0.21 at 373 K. At a given time, [N2O4]=0.125[N_2O_4]=0.125, [NO2]=0.5[NO_2]=0.5 mol dm−3^{-3}. Q=(0.5)20.125=2Q = \dfrac{(0.5)^2}{0.125} = 2. Since Q(2)>KC(0.21)Q(2) > K_C(0.21), the reaction proceeds in the reverse direction, until Q falls back to 0.21. …

Figure 8.4Predicting the direction of a reaction

What this figure shows. Three small panels, each plotting Qc against 'progress of reaction' with a horizontal dashed reference line at Kc. Left panel: Qc starts below Kc and rises toward it, labelled 'reactants to products' (forward). Middle panel: Qc starts above Kc and falls toward it, labelled 'products to reactants' (reverse). Right panel: Qc sits exactly on the Kc line throughout, labelled 'equilibrium' …

Misc 8.7.2-example-1Example 1: Q vs Kc for HI formation

Worked out. H2(g)+I2(g)⇌2HI(g)H_2(g) + I_2(g) \rightleftharpoons 2HI(g), KC=48K_C = 48 at 717 K. At a particular instant [H2]=0.2[H_2] = 0.2, [I2]=0.2[I_2] = 0.2, [HI]=0.6[HI] = 0.6 mol L−1^{-1}. Q=(0.6)2(0.2)(0.2)=9Q = \dfrac{(0.6)^2}{(0.2)(0.2)} = 9. Since Q(9)<KC(48)Q(9) < K_C(48), the reaction proceeds in the forward direction. …

Misc 8.7.2-example-2Example 2: Q vs Kc for N2O4/NO2

Worked out. N2O4(g)⇌2NO2(g)N_2O_4(g) \rightleftharpoons 2NO_2(g), KC=0.21K_C = 0.21 at 373 K. At a given time [N2O4]=0.125[N_2O_4] = 0.125, [NO2]=0.5[NO_2] = 0.5 mol dm−3^{-3}. Q=(0.5)20.125=2Q = \dfrac{(0.5)^2}{0.125} = 2. Since Q(2)>KC(0.21)Q(2) > K_C(0.21), the reaction proceeds in the reverse direction until Q falls back to 0.21. …

Misc 8.7.2-evaluate-yourselfEvaluate Yourself: water-gas shift direction

Worked out. CO(g)+H2O(g)⇌CO2(g)+H2(g)CO(g) + H_2O(g) \rightleftharpoons CO_2(g) + H_2(g), an important industrial route to hydrogen gas, KP=2.7K_P = 2.7 at a given temperature. If 0.13 mol CO, 0.56 mol H2_2O, 0.78 mol CO2_2 and 0.28 mol H2_2 are introduced into a 2 L flask, find in which direction the reaction must proceed to reach equilibrium. …