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Exercises · 6.31

Q.Dihydrogen gas used in Haber’s process is produced by reacting methane from natural gas with high temperature steam. The first stage of two stage reaction involves the formation of CO and H 2. In second stage, CO formed in first stage is reacted with more steam in water gas shift reaction, CO

(g) + H2O
(g) ⇌ CO2
(g) + H2
(g) If a reaction vessel at 400 °C is charged with an equimolar mixture of CO and steam such that pco = pH2O = 4.0 bar, what will be the partial pressure of H2 at equilibrium? Kp= 10.1 at 400°C
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The equilibrium partial pressure of H₂ is found by setting up an ICE table in terms of partial pressures, using the given Kp = 10.1 and initial pressures of 4.0 bar each for CO and steam. Solving the resulting quadratic gives pH2≈3.0p_{\text{H}_2} \approx 3.0 bar.

The key idea here is that the water gas shift reaction is a gas-phase equilibrium with a known Kp. Since the initial pressures of CO and steam are equal and the reaction has a 1:1:1:1 stoichiometry, the algebra simplifies nicely. The equilibrium constant tells us the reaction proceeds strongly to the right (Kp > 1), so we expect most of the CO and steam to convert into CO₂ and H₂.

Let’s work through it step by step.

  1. Write the balanced reaction and the expression for Kp. The reaction is:

CO(g)+H2O(g)⇌CO2(g)+H2(g)\text{CO}(g) + \text{H}_2\text{O}(g) \rightleftharpoons \text{CO}_2(g) + \text{H}_2(g)

Since the number of moles of gas does not change (2 moles on each side), Kp is simply the ratio of product partial pressures to reactant partial pressures:

Kp=pCO2⋅pH2pCO⋅pH2O=10.1K_p = \frac{p_{\text{CO}_2} \cdot p_{\text{H}_2}}{p_{\text{CO}} \cdot p_{\text{H}_2\text{O}}} = 10.1

  1. Set up an ICE table in terms of partial pressures.

    Initial: pCO=4.0p_{\text{CO}} = 4.0 bar, pH2O=4.0p_{\text{H}_2\text{O}} = 4.0 bar, pCO2=0p_{\text{CO}_2} = 0, pH2=0p_{\text{H}_2} = 0.

    Let xx be the partial pressure of H₂ formed at equilibrium (in bar). Because the stoichiometry is 1:1:1:1, the change in each species is:

    • CO decreases by xx: pCO=4.0−xp_{\text{CO}} = 4.0 - x
    • H₂O decreases by xx: pH2O=4.0−xp_{\text{H}_2\text{O}} = 4.0 - x
    • CO₂ increases by xx: pCO2=xp_{\text{CO}_2} = x
    • H₂ increases by xx: pH2=xp_{\text{H}_2} = x
    Watch out

    A common mistake is to forget that the total pressure changes if the mole count changes — but here it doesn’t, so partial pressures add up nicely. Also, never assume xx is small unless Kp is very small or very large; here Kp = 10.1, so xx will be significant.

  2. Substitute into the Kp expression.

Kp=(x)(x)(4.0−x)(4.0−x)=x2(4.0−x)2=10.1K_p = \frac{(x)(x)}{(4.0 - x)(4.0 - x)} = \frac{x^2}{(4.0 - x)^2} = 10.1

  1. Solve for xx. Take the square root of both sides (since both numerator and denominator are squares, and pressures are positive): x4.0−x=10.1\frac{x}{4.0 - x} = \sqrt{10.1} …

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