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Problems · Problem 6.8

Q.13.8 g of N2O4 was placed in a 1 L reaction vessel at 400 K and allowed to attain equilibrium: N2O4

(g) ⇌ 2NO2 (g). The total pressure at equilibrium was found to be 9.15 bar. Calculate Kc, Kp and partial pressures at equilibrium.
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From n0=0.15n_0 = 0.15 mol of N2_2O4_4 and the observed total pressure, a direct pressure-based ICE table gives PN2O4=0.81P_{N_2O_4}=0.81 bar, PNO2=8.34P_{NO_2}=8.34 bar, Kp=85.87K_p = 85.87 bar and Kc=2.6K_c = 2.6 mol L−1^{-1}.

N2O4(g)⇌2 NO2(g)\text{N}_2\text{O}_4(g) \rightleftharpoons 2\,\text{NO}_2(g)

1. Initial partial pressure. M(N2O4)=92M(\text{N}_2\text{O}_4) = 92 g mol−1^{-1}, so n0=13.892=0.15n_0 = \frac{13.8}{92} = 0.15 mol. In a 1 L vessel at 400 K:

p0=n0RTV=0.15×0.083×400=4.98 barp_0 = \frac{n_0 RT}{V} = 0.15 \times 0.083 \times 400 = 4.98\ \text{bar}

2. Work directly in pressures, not moles. Since p∝np \propto n at fixed V,TV,T, an ICE table can be written straight in bar -- this avoids the extra rounding a mole-based detour introduces. Let xx be the pressure of N2_2O4_4 that has dissociated:

N2_2O4_4(g)2NO2_2(g)
Initial4.98 bar0
Equilibrium4.98−x4.98-x2x2x

3. Use the measured total equilibrium pressure (9.15 bar).

ptotal=(4.98−x)+2x=4.98+xp_{total} = (4.98-x) + 2x = 4.98 + x

9.15=4.98+x  ⟹  x=4.17 bar9.15 = 4.98 + x \implies x = 4.17\ \text{bar}

4. Equilibrium partial pressures.

pN2O4=4.98−4.17=0.81 barp_{\text{N}_2\text{O}_4} = 4.98 - 4.17 = 0.81\ \text{bar}

pNO2=2x=2(4.17)=8.34 barp_{\text{NO}_2} = 2x = 2(4.17) = 8.34\ \text{bar}

5. KpK_p.

Kp=(pNO2)2pN2O4=(8.34)20.81=69.560.81=85.87 barK_p = \frac{(p_{\text{NO}_2})^2}{p_{\text{N}_2\text{O}_4}} = \frac{(8.34)^2}{0.81} = \frac{69.56}{0.81} = 85.87\ \text{bar}

6. Convert to KcK_c. For this reaction Δn=2−1=1\Delta n = 2-1 = 1:

Kp=Kc(RT)Δn  ⟹  Kc=KpRT=85.870.083×400=85.8733.2=2.586≈2.6 mol L−1K_p = K_c(RT)^{\Delta n} \implies K_c = \frac{K_p}{RT} = \frac{85.87}{0.083\times400} = \frac{85.87}{33.2} = 2.586 \approx 2.6\ \text{mol L}^{-1}

Watch out

A tempting but noisier route is to first convert everything to moles (via n=pV/RTn=pV/RT), solve for the moles reacted, and only then convert back to partial pressures using mole fractions. That path is mathematically equivalent in exact arithmetic, but rounding the intermediate mole values compounds and can shift KpK_p by a percent or two. Working directly in pressures throughout (as above) is both simpler and matches the textbook's own printed answer exactly.

✓Final answer

PN2O4=0.81P_{\text{N}_2\text{O}_4} = 0.81 bar, PNO2=8.34P_{\text{NO}_2} = 8.34 bar; Kp=85.87 barK_p = \boxed{85.87\ \text{bar}} and Kc=2.6 mol L−1K_c = \boxed{2.6\ \text{mol L}^{-1}}.

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