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NCERT Exemplar · Q54

Q.Write a relation between ΔG and Q and define the meaning of each term and answer the following :

(a) Why a reaction proceeds forward when Q < K and no net reaction occurs when Q = K.
(b) Explain the effect of increase in pressure in terms of reaction quotient Q. for the reaction : CO
(g) + 3H2
(g) ⇌ CH4
(g) + H2O (g)
Telangana TsbieLong· 3mImportance★★★★★est
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The relation ΔG=ΔG∘+RTln⁡Q\Delta G = \Delta G^\circ + RT \ln Q connects the free energy change to the reaction quotient; a reaction proceeds forward when Q<KQ < K because ΔG<0\Delta G < 0, and at equilibrium Q=KQ = K gives ΔG=0\Delta G = 0. Increasing pressure on the given reaction shifts it forward because QQ temporarily drops below KK.

The Fundamental Relation

The connection between spontaneity and composition is captured by

ΔG=ΔG∘+RTln⁡Q\Delta G = \Delta G^\circ + RT \ln Q

where:

  • ΔG\Delta G is the Gibbs free energy change under the current, non-standard conditions — it tells us whether the reaction will proceed forward (ΔG<0\Delta G < 0), backward (ΔG>0\Delta G > 0), or sit at equilibrium (ΔG=0\Delta G = 0).
  • ΔG∘\Delta G^\circ is the standard Gibbs free energy change, measured when all species are at unit activity (1 bar for gases, 1 M for solutions). It is a fixed number for a given reaction at a given temperature.
  • RR is the universal gas constant (8.314 J mol−1K−18.314 \, \text{J mol}^{-1} \text{K}^{-1}).
  • TT is the absolute temperature in kelvin.
  • QQ is the reaction quotient, the ratio of product activities to reactant activities raised to their stoichiometric coefficients, evaluated at any moment:

Q=[products][reactants]Q = \frac{[\text{products}]}{[\text{reactants}]}

At equilibrium, ΔG=0\Delta G = 0 and QQ becomes the equilibrium constant KK, so

0=ΔG∘+RTln⁡K⇒ΔG∘=−RTln⁡K0 = \Delta G^\circ + RT \ln K \quad \Rightarrow \quad \Delta G^\circ = -RT \ln K

Substituting this back into the first equation gives an alternative form:

ΔG=RTln⁡QK\Delta G = RT \ln \frac{Q}{K}

This version makes the role of QQ and KK transparent.


(a) Why Q<KQ < K drives the reaction forward, and Q=KQ = K means equilibrium

The sign of ΔG\Delta G determines direction. From ΔG=RTln⁡QK\Delta G = RT \ln \frac{Q}{K}:

  1. When Q<KQ < K: The ratio QK<1\frac{Q}{K} < 1, so ln⁡QK<0\ln \frac{Q}{K} < 0, which makes ΔG<0\Delta G < 0. A negative free energy change means the forward reaction is spontaneous — the system can lower its free energy by converting reactants into products. The reaction proceeds forward until QQ rises to equal KK.

  2. When Q=KQ = K: Now QK=1\frac{Q}{K} = 1, so ln⁡1=0\ln 1 = 0 and ΔG=0\Delta G = 0. The system is at equilibrium. The forward and reverse rates are equal, and there is no net change in composition. The free energy is at a minimum with respect to the reaction coordinate; any shift in either direction would increase GG.

  3. When Q>KQ > K: The ratio QK>1\frac{Q}{K} > 1, so ln⁡QK>0\ln \frac{Q}{K} > 0 and ΔG>0\Delta G > 0. The reverse reaction is spontaneous; the system will convert products back into reactants until QQ falls to KK.

Tip

Think of KK as the target and QQ as the current position. The reaction always moves to close the gap: if you have too few products (Q<KQ < K), make more; if you have too many (Q>KQ > K), decompose some.


(b) Effect of increasing pressure on the reaction CO (g)+3H2(g)⇌CH4(g)+H2O(g)\text{CO (g)} + 3\text{H}_2\text{(g)} \rightleftharpoons \text{CH}_4\text{(g)} + \text{H}_2\text{O(g)}

First, count moles of gas on each side:

  • Reactants: 1+3=41 + 3 = 4 moles of gas
  • Products: 1+1=21 + 1 = 2 moles of gas

The forward reaction reduces the total number of gas molecules.

What happens when we increase pressure?

For an ideal gas, partial pressure is proportional to molar concentration at constant temperature. The reaction quotient in terms of partial pressures is

Qp=PCH4⋅PH2OPCO⋅PH23Q_p = \frac{P_{\text{CH}_4} \cdot P_{\text{H}_2\text{O}}}{P_{\text{CO}} \cdot P_{\text{H}_2}^3}

When we suddenly compress the system (increase total pressure), every partial pressure scales up by the same factor, say α>1\alpha > 1. The new quotient becomes …

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