University11 min

Complex mechanisms: from elementary steps to the rate law

Spot the intermediate and the slow step, handle a fast pre-equilibrium, and turn a mechanism into a rate law that can be tested against experiment.

The essentials

1

Elementary step and molecularity

An elementary step happens in a single event at the molecular scale. For it — and for it alone — each reactant's partial order is its coefficient: unimolecular v=k[A]v = k[\ce{A}], bimolecular v=k[A][B]v = k[\ce{A}][\ce{B}]. Molecularity 33 is rare: recombination A+B+MAB+M\ce{A + B + M -> AB + M}, where the third body M carries away the excess energy.
2

Intermediate and transition state

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3

Rate-determining step

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4

Fast pre-equilibrium

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5

Consistent, never proven

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ƒWrite my own sheetOr start from a blank page: rewriting a concept in your own words is how it sticks.