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Chemistry · Ch 6 — Chemical Kinetics

Pseudo-first order reactions

6.5.9

Pseudo-first order reactions

Certain reactions which are expected to be of higher order follow first order kinetics. Consider the hydrolysis of methyl acetate:

CH3COOCH3(aq)+H2O(l)⟶CH3COOH(aq)+CH3OH(aq)\mathrm{CH_3COOCH_3(aq) + H_2O({\it l}) \longrightarrow CH_3COOH(aq) + CH_3OH(aq)}

The rate law is

rate=k′ [CH3COOCH3] [H2O]\text{rate} = k'\,\mathrm{[CH_3COOCH_3]}\,\mathrm{[H_2O]}

The reaction is expected to follow second order kinetics; however, it obeys first order.

The reason is that the solvent water is present in such large excess that the change in its concentration is negligible compared to the initial one — its concentration remains constant. Thus [H2O]=constant=k′′\mathrm{[H_2O]} = \text{constant} = k''. The rate law becomes

rate=k′ [CH3COOCH3] k′′=k [CH3COOCH3]\text{rate} = k'\,\mathrm{[CH_3COOCH_3]}\,k'' = k\,\mathrm{[CH_3COOCH_3]} …