Rate Determining Step (AQA A Level Chemistry) : Revision Note

Rate Determining Step

Rate-determining step & intermediates

• A chemical reaction can only go as fast as the slowest part of the reaction

  • So, the rate-determining step is the slowest step in the reaction

• If a reactant appears in the rate-determining step, then the concentration of that reactant will also appear in the rate equation

• For example, the rate equation for the reaction below is rate = k [CH₃Br] [OH^-]
  
  CH₃Br + OH^- → CH₃OH + Br^-
  

  • This suggests that both CH₃Br and OH^- take part in the slow rate-determining step

• This reaction is a bimolecular reaction

  • Unimolecular: one species involved in the rate-determining step

  • Bimolecular: two species involved in the rate-determining step

• The intermediate is derived from substances that react together to form it in the rate-determining step

  • For example, for the reaction above the intermediate would consist of CH₃Br and OH^-

The intermediate is formed from the species that are involved in the rate-determining step (and thus appear in the rate equation)

Predicting the reaction mechanism

• The overall reaction equation and rate equation can be used to predict a possible reaction mechanism of a reaction

  • This shows the individual reaction steps which are taking place

• For example, nitrogen dioxide (NO₂) and carbon monoxide (CO) react to form nitrogen monoxide (NO) and carbon dioxide (CO₂)

  • The overall reaction equation is:

NO₂ (g) + CO (g) → NO (g) + CO₂ (g)

• The rate equation is:

Rate = k [NO₂]²

• From the rate equation it can be concluded that the reaction is zero order with respect to CO (g) and second order with respect to NO₂ (g)

• This means that there are two molecules of NO₂ (g) involved in the rate-determining step and zero molecules of CO (g)

• A possible reaction mechanism could therefore be:

Step 1:

 2NO₂ (g) → NO (g) + NO₃ (g)                   slow (rate-determining step)

Step 2:

   NO₃ (g) + CO (g) → NO₂ (g) + CO₂ (g)     fast

Overall:

    2NO₂ (g) + NO₃ (g) + CO (g) → NO (g) + NO₃ (g) + NO₂ (g) + CO₂ (g)

    =     NO₂ (g) + CO (g) → NO (g) + CO₂ (g)

Predicting the reaction order & deducing the rate equation

• The order of a reactant and thus the rate equation can be deduced from a reaction mechanism if the rate-determining step is known

• For example, the reaction of nitrogen oxide (NO) with hydrogen (H₂) to form nitrogen (N₂) and water

2NO (g) + 2H₂ (g) → N₂ (g) + 2H₂O (l)

• The reaction mechanism for this reaction is:

Step 1:

   NO (g) + NO (g) → N₂O₂ (g)                      fast

Step 2:

   N₂O₂ (g) + H₂ (g) → H₂O (l) + N₂O (g)     slow (rate-determining step)

Step 3:

   N₂O (g) + H₂ (g) → N₂ (g) + H₂O (l)           fast

• The second step in this reaction mechanism is the rate-determining step

• The rate-determining step consists of:

  • N₂O₂ which is formed from the reaction of two NO molecules

  • One H₂ molecule

• The reaction is, therefore, second order with respect to NO and first order with respect to H₂

• So, the rate equation becomes:

Rate = k [NO]² [H₂]

• The reaction is, therefore, third order overall

Identifying the rate-determining step

• The rate-determining step can be identified from a rate equation given that the reaction mechanism is known

• For example, propane (CH₃CH₂CH₃) undergoes bromination under alkaline solutions

• The overall reaction is:

CH₃CH₂CH₃ + Br₂ + OH^- → CH₃CH₂CH₂Br + H₂O + Br^-

• The reaction mechanism is:

Reaction mechanism for the bromination of propane under alkaline conditions

• The rate equation is:

Rate = k [CH₃CH₂CH₃] [OH^-]

• From the rate equation, it can be deduced that only CH₃CH₂CH₃ and OH^- are involved in the rate-determining step and not bromine (Br₂)

• CH₃CH₂CH₃ and OH^- are only involved in the first step of the reaction mechanism, therefore the rate-determining step is:

  • CH₃CH₂CH₃ + OH^- → CH₃CH₂CH₂^- + H₂O

Identifying intermediates & catalyst

• When a rate equation includes a species that is not part of the chemical reaction equation then this species is a catalyst

• For example, the halogenation of butanone under acidic conditions

• The reaction mechanism is:

• The reaction mechanism is:

Reaction mechanism of the halogenation of butanone under acidic conditions

• The rate equation is:

Rate = k [CH₃CH₂COCH₃] [H⁺]

• The H⁺ is not a reactant in the chemical reaction equation but does appear in the rate equation

  • H⁺ must, therefore, be a catalyst

• Furthermore, the rate equation suggest that CH₃CH₂COCH₃ and H⁺ must be involved in the rate-determining (slowest) step

• The CH₃CH₂COCH₃ and H⁺ appear in the rate-determining step in the form of an intermediate (which is a combination of the two species)

Intermediate is formed in the rate-determining step from the reaction of CH₃CH₂COCH₃ and H⁺