S_N1 Reaction: Kinetics

Tertiary alkyl halides have bulky alkyl groups that create significant steric hindrance around the carbon bearing the leaving group. This steric obstruction prevents the nucleophile from accessing the substrate for the backside attack required in SN2 mechanisms, making them practically inert to SN2 substitution despite the presence of strong nucleophiles.

A first-order dependence on substrate concentration means the reaction rate increases linearly with substrate concentration. When researchers doubled the substrate concentration, the reaction rate doubled proportionally. This indicates that only one substrate molecule participates in the rate-determining step, making the overall reaction first-order.

They performed substitution reactions with tertiary halides under two conditions: one with low hydroxide concentration (10⁻7 M) and another with high hydroxide concentration (0.05 M). The product formation rate remained constant regardless of nucleophile concentration or strength, proving the nucleophile was not involved in the rate-determining step.

The molecularity of the SN1 rate-determining step is unimolecular because only one chemical entity—the substrate—participates in this step. Since only the alkyl halide is involved, the reaction is zeroth-order for the nucleophile and first-order overall, classifying it as an SN1 (Substitution, Nucleophilic, 1st order) reaction.

SN2 reactions depend on both nucleophile and substrate concentrations, making them second-order overall. SN1 reactions depend only on substrate concentration, making them first-order overall. Additionally, SN1 reactions are zeroth-order for the nucleophile, meaning nucleophile concentration and strength do not affect the reaction rate.

Tertiary halides cannot use the SN2 mechanism due to steric hindrance, but they can undergo SN1 substitution because this mechanism does not require nucleophilic attack on the substrate. Instead, the substrate spontaneously ionizes in the rate-determining step, forming a carbocation intermediate that is subsequently attacked by the nucleophile.

When researchers varied the hydroxide ion concentration from 10⁻7 M to 0.05 M while keeping substrate concentration constant, the rate of tert-butyl alcohol formation remained unchanged. This independence of product formation rate from nucleophile concentration and reactivity directly demonstrated that the nucleophile does not participate in the rate-determining step.