Solution

ID: past-exam-of-the-chemistry-course-of-the-year-1-of-the-natural-sciences-course-of-the-university-of-cambridge/2023/paper-1/5/c/v/solution

Using bonds broken minus bonds formed, the enthalpies per mole of elementary events are
Under the steady-state approximation in chemical kinetics, initiation and termination have equal event rates, so their enthalpy contributions cancel. The two propagation steps also have equal flux, and their combined enthalpy is per overall reaction producing two moles of HCl. Step 3 dominates the heat release; the small endothermic contribution of step 2 only slightly offsets it.
An insulated vessel cannot remove this released energy as heat, so its temperature rises as reaction proceeds. In a rigid vessel the precise energy balance uses reaction internal energy and constant-volume heat capacities, whereas a constant-pressure adiabatic balance uses enthalpy; the strong exothermic conclusion is the same. Warming changes the rate constants, and activated initiation and propagation can accelerate, producing positive thermal feedback and potentially a rapid temperature rise. A numerical final temperature or a claim of an inevitable explosion is not justified without composition, heat capacities and heat-loss information. The initially assumed 298-K rate constants cannot remain fixed throughout an appreciable adiabatic temperature rise.

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