The Rate-determining Step

Most reactions take place in more than one step. These separate steps are known as the

reaction mechanism
For example
2NO + 2H2 N2 + 2H2O Actually has three steps
Step 1:
Step 2: Step 3:

Why?

2NO N2O2 N2O2 + H2 N2O + H2O N2O + H2 N2 + H2O

With so many molecules it is unlikely that they will all collide at the same time

The Rate-determining Step

As weve seen the steps normally follow one after the other The products of one step forming the reactants of the next step If one step is slower than the others we may get a

This slowest step is known as the

rate-determining step
(rate-limiting step)

The Rate-determining Step

Any steps after the rate-determining step have no bearing on the reaction rate and will therefore not appear in the overall equation
fast

Step 1

A + B

D
Step 2 slow

D
Overall reaction

E
Step 3 fast

E + C

Y +Z

A + B Y + Z

The Rate-determining Step

Only the molecules in the rate-determining step will appear in the rate expression For example
1 2 3 4 slow fast fast

CH3-CO-CH3 + H+ CH3-CHO-CH3+ CH3-CHO-CH3+ CH2-CHO-CH3 CH2-CHO-CH3 + I2 CH2I-CHOI-CH3 CH2I-CHOI-CH3 CH2I-CO-CH3 + H+ + IWhat is the rate expression?

fast

Question What is the rate-determining step?

rate = k[CH3-CO-CH3][H+]
(CH3-CO-CH3 + I2 CH2I-CO-CH3 + HI)

The Rate-determining Step

What can we work out if we are told the following 2 step reaction NO2 + CO NO + CO2 rate = k[NO2]2 Working rate = k[NO2]2 = [NO2] x [NO2]

Since this is the only species in the rate equation the slow step must be The fast step must look something like this

NO2 + NO2 ?
? + CO ?

The Rate-determining Step

Working NO2 + CO NO + CO2 Based on the overall equation there must be a CO2 as a product There must be a NO2 in the fast step to cancel out the 2 NO2 in the slow step Looking at the fast step, count the number of atoms to work out ? NO2 + NO2 ? ? + CO ? + CO2 NO2 + NO2 ? ? + CO NO2 + CO2 NO2 + NO2 ? NO3 + CO NO2 + CO2

Finally, NO3 can be placed in the slow NO2 + NO2 NO3 + NO NO3 + CO NO2 + CO2 step and the equation balanced

Using the order of a reaction

It is possible to use the order of a reaction to work out the ratedetermining step

C4H9Br + OH- C4H9OH + BrMechanism 1 Step 1 (slow) C4H9Br C4H9+ + Br Step 2 (fast) C4H9+ + OH- C4H9OH Mechanism 2 One step (slow) C4H9Br + OH- C4H9OH + Br-

The C-H bond breaks at the same time as the C-OH bond forms

Using the order of a reaction

1-bromobutane
Experiments show that the overall reaction order is 2, so the reaction rate expression is

C4H9Br has three isomers

rate = k[C4H9Br][OH-]

which means that the concentration of both the 1-bromobutane and the OH- ions have an equal say in the reaction rate (mechanism 2)

2-bromo-2-methylpropane
Experiments show that the overall reaction order is 1 based on the slow step, so the reaction rate expression is

rate = k[C4H9Br]

which means that the concentration of the 2-bromo-2-methylpropane is the only factor affecting the reaction rate (mechanism 1)

Looking at both these rate expression means that the breaking of the C-Br bond is the rate-determining step

Questions
The following reaction schemes show possible mechanisms for the overall reaction: A + E Scheme 1 A+B C F
fast slow

catalyst Scheme 2

G Scheme 3
fast

C F G

A+B C F
fast

fast

C F G

A+B C F
slow

C F G

D+B
fast

D+B
slow

D+B
fast

D+E

D+E

D+E

fast

slow

fast

In scheme 2 which species is the catalyst?

B
F and G

Which species cannot appear in the rate expression for scheme 1?

Which is the rate-determining step in scheme 3?

Second one