The thermal decomposition of nitryl chloride in the gas phase proceeds according to…

CHEMISTRY · Multi-part · AP · Chemistry · Kinetics · Kinetics

Problem

The thermal decomposition of nitryl chloride in the gas phase proceeds according to the stoichiometric equation NO2Cl(g) →\rightarrow NO2(g) + 12\frac{1}{2} Cl2(g) One mechanism consistent with several observations is Step 1 NO2Cl(g) ⇌\rightleftharpoons NO2(g) + Cl(g) fast equilibrium Kp=2.6×10−4K_p = 2.6\times10^{-4} (at 350 K350\,\text{K}) Step 2 Cl(g) + NO2Cl(g) →\rightarrow NO2(g) + Cl2(g) slow k2=1.8×105 L mol−1s−1k_2 = 1.8\times10^{5}\,\text{L mol}^{-1}\text{s}^{-1} At 350 K350\,\text{K} a sealed reaction vessel contains initial partial pressures of 0.300 atm0.300\,\text{atm} NO2Cl and 0.050 atm0.050\,\text{atm} NO2. Assume the ideal-gas law applies and that the volume of the vessel is 1.00 L1.00\,\text{L}. (a) Write the rate law for the slow elementary step in terms of the concentrations of Cl(g) and NO2Cl(g). (b) Derive an expression for the concentration of Cl(g) in terms of the equilibrium constant KpK_p and the concentrations of NO2Cl and NO2. (c) Obtain the overall rate law expressed only in terms of the measurable species NO2Cl and NO2. Identify the overall reaction orders with respect to each species. (d) Using the given numerical data, calculate the initial rate of disappearance of NO2Cl in mol L−1s−1\text{mol L}^{-1}\text{s}^{-1}.

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