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Problems · Problem 5.14

Q.At 60 °C, dinitrogen tetroxide is 50 per cent dissociated. Calculate the standard free energy change at this temperature and at one atmosphere.

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Find KpK_p from the 50%50\% dissociation, then use ΔG⊖=−RTln⁡Kp\Delta G^\ominus = -RT\ln K_p. With Kp=4/3K_p = 4/3 at 333 K333\ \text{K}, ΔG⊖=−796.5 J mol−1\Delta G^\ominus = -796.5\ \text{J mol}^{-1} (≈−0.80 kJ mol−1\approx -0.80\ \text{kJ mol}^{-1}).

Set up the equilibrium

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

Start with 11 mol N2O4\text{N}_2\text{O}_4; degree of dissociation α=0.5\alpha = 0.5:

  • N2O4=1−0.5=0.5 mol\text{N}_2\text{O}_4 = 1 - 0.5 = 0.5\ \text{mol}
  • NO2=2×0.5=1.0 mol\text{NO}_2 = 2 \times 0.5 = 1.0\ \text{mol}
  • total =1.5 mol= 1.5\ \text{mol}

Partial pressures (total pressure =1 atm= 1\ \text{atm})

pN2O4=0.51.5×1=13 atm,pNO2=1.01.5×1=23 atm.p_{\text{N}_2\text{O}_4} = \frac{0.5}{1.5} \times 1 = \frac{1}{3}\ \text{atm},\qquad p_{\text{NO}_2} = \frac{1.0}{1.5} \times 1 = \frac{2}{3}\ \text{atm}.

Equilibrium constant

Kp=pNO2 2pN2O4=(2/3)21/3=4/91/3=43≈1.333.K_p = \frac{p_{\text{NO}_2}^{\,2}}{p_{\text{N}_2\text{O}_4}} = \frac{(2/3)^2}{1/3} = \frac{4/9}{1/3} = \frac{4}{3} \approx 1.333.

Standard free energy change …

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