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Exercises · 6.28

Q.Dihydrogen gas is obtained from natural gas by partial oxidation with steam as per following endothermic reaction: CH4

(g) + H2O
(g) ⇌ CO
(g) + 3H2
(g)
(a) Write as expression for Kp for the above reaction.
(b) How will the values of Kp and composition of equilibrium mixture be affected by
(i) increasing the pressure
(ii) increasing the temperature
(iii) using a catalyst?
Uttarakhand UbseTextbookSubjective· 3mImportance★★★★★est
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The equilibrium constant KpK_p is expressed in terms of partial pressures. Changes in pressure, temperature, and catalyst affect KpK_p and the equilibrium composition according to Le Chatelier’s principle — pressure favours fewer moles, temperature favours the endothermic direction, and a catalyst does not change equilibrium.


Understanding the Reaction

We have the reaction:

CH4(g)+H2O(g)⇌CO(g)+3H2(g)\text{CH}_4(g) + \text{H}_2\text{O}(g) \rightleftharpoons \text{CO}(g) + 3\text{H}_2(g)

It is endothermic (absorbs heat) and involves 4 moles of gas on the right vs. 2 moles on the left. This imbalance in moles and the heat effect are the keys to predicting how changes affect equilibrium.


(a) Expression for KpK_p

KpK_p is the equilibrium constant expressed in terms of partial pressures of gases. For a general reaction:

aA(g)+bB(g)⇌cC(g)+dD(g)aA(g) + bB(g) \rightleftharpoons cC(g) + dD(g)

the expression is:

Kp=(PC)c(PD)d(PA)a(PB)bK_p = \frac{(P_C)^c (P_D)^d}{(P_A)^a (P_B)^b}

Here, PXP_X is the partial pressure of gas XX at equilibrium.

For our reaction:

Kp=PCO⋅(PH2)3PCH4⋅PH2OK_p = \frac{P_{\text{CO}} \cdot (P_{\text{H}_2})^3}{P_{\text{CH}_4} \cdot P_{\text{H}_2\text{O}}}

Kp=PCO⋅PH23PCH4⋅PH2OK_p = \frac{P_{\text{CO}} \cdot P_{\text{H}_2}^3}{P_{\text{CH}_4} \cdot P_{\text{H}_2\text{O}}}


(b) Effect of Changes on KpK_p and Composition

We now analyse three changes. Remember: KpK_p changes only with temperature, not with pressure or catalyst. The composition (position of equilibrium) shifts according to Le Chatelier’s principle.

1. Increasing the pressure
Tip

Le Chatelier’s principle: a system at equilibrium, when subjected to a change in pressure, shifts to the side with fewer moles of gas to relieve the stress.

  • Left side: 2 moles of gas (1 CH₄ + 1 H₂O)
  • Right side: 4 moles of gas (1 CO + 3 H₂)

Increasing pressure favours the side with fewer moles, i.e., the left (reactants). So the equilibrium shifts backward, producing more CH₄ and H₂O, and less CO and H₂.

Effect on KpK_p: No change — KpK_p is constant at a given temperature.

Effect on composition: The equilibrium mixture contains more reactants and less products than before.

2. Increasing the temperature

The reaction is endothermic (absorbs heat). Think of heat as a reactant:

CH4+H2O+heat⇌CO+3H2\text{CH}_4 + \text{H}_2\text{O} + \text{heat} \rightleftharpoons \text{CO} + 3\text{H}_2 …

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