Solution

ID: past-exam-of-the-chemistry-a-course-of-the-university-of-cambridge/2025/paper-2/a8/c/i/solution

Write and . An atom has no rotational or vibrational internal factor under the stated electronic assumption. The transition-state moment of inertia is , so the high-temperature rigid rotor result is
The translational factors therefore give
Substituting into the transition state theory expression and simplifying,
For distinct atoms, . This is a number-density rate coefficient, with units of volume per time. A rate law in molar concentrations uses . The derivation assumes a classical high-temperature rotor at the dividing surface and a transmission coefficient of one.

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