CHAPTER 9.

CHEMICAL KINETICS Example: Consider a hypothetical reaction:

A + B à C
Chemical kinetics. Deals with the rate of reaction and the Experiment [A] (mol/L) [B] (mol/L) Rate (mol·L 1 /s x 10 5 )
factors affecting them. 1 0.100 0.100 4.0
2 0.100 0.200 4.0
In a balanced chemical equation, the reaction rate can 3 0.200 0.100 16.0
be written as:
rate law = k[A]x[B]y
aA + bB à cC + dD
Step 1. In order to get the rate order with respect to A,
1 ∆[A] !    ∆[!] identify the set of data that has the constant
rate = - in terms of A rate = − in terms of B
a ∆t ! ∆! concentration of B but different concentrations of A.

1 ∆[C] !    ∆[!] 𝑟𝑎𝑡𝑒  3 𝑘[0.200]! [.100]!

rate = in terms of C rate = in terms of D =  
c ∆t ! ∆! 𝑟𝑎𝑡𝑒  1 𝑘  [.100]! [.100]!

where a,b,c,d are the number of moles of substance Step 2. Solve for x.
A,B,C,D. 16.0  𝑀/𝑠 𝑘[0.200𝑀]! [.100]!
=   =   2.00!
4.0  𝑀/𝑠 𝑘  [.100𝑀]! [.100]!
∆[A] change in concentration of A or [A] final – [A] initial
∆t
  means change in time or t final – t initial 4 =     2.00! ; x = 2

Rate Law. experimentally determined equation and can Step 3. In order to get the rate order with respect to B,
be used to predict the relationship between the rate of a identify the set of data that has the constant
reaction and the concentrations of the reactants. concentration of A but different concentrations of B.

In a chemical reaction: aA + bB à cC + dD 𝑟𝑎𝑡𝑒  2 𝑘[0.100]! [.200]!

=  
𝑟𝑎𝑡𝑒  1 𝑘  [.100]! [.100]!
The rate law can be written as: rate = k[A]x[B]y where k is
the rate constant, x is the reaction order with respect to A, Step 4. Solve for y.
and y is the rate order with respect to B. 4.0  𝑀/𝑠 𝑘[0.100𝑀]! [.200]!
=   =   2.00!
4.0  𝑀/𝑠 𝑘  [.100𝑀]! [.100]!
The sum of x and y is called he overall reaction order. 1 =     2.00! ; y = 0
Step 5. Write the complete rate law
rate = k[A]2[B]0 . rate = k[A]2. Therefore, reaction order is
second order with respect to A and zeroth order with
respect to B. The overall reaction order is second order.
Elementary Step. the overall progress of a chemical
reaction can be expressed at the molecular level by a
series of steps called elementary steps.
The sequence of elementary steps that leads to product
formation is called reaction mechanism.
Example: The actual reaction is the formation of NO2
through the following reaction:
NO2 (g) + CO (g) à CO2 (g) + NO(g)
This can be expressed in a series of elementary steps:
Step 1. NO2(g) + NO2(g) à NO3 (g) + NO(g) (slow)
Step 2. NO3 (g) + CO (g) à NO2 (g) + CO2(g) (fast)
Overall NO2 (g) + CO (g) à CO2 (g) + NO(g)
Step 1 and 2 are elementary steps.
Rate determining step. Slowest elementary step. The
stoichiometric coefficients will also serve as the reaction
order for the overall rate law of the overall reaction.
In this case, Step 1 is the rate determining step.
Therefore, rate law is: rate=k[NO2]2
Intermediate. A species involved in the elementary steps
but not shown in the overall reaction. Intermediates are
products on the first elementary step but also serve as the
reactants on the second elementary step.
In this case, NO3 (g) is the intermediate.
Consider the following reaction mechanism:
Step 1. H2O2 + I- à H2O + IO-
Step 2. H2O2 + IO- à H2O + I- + O2
Overall H2O2 + I- + H2O2 + IO- à H2O + IO- + H2O + I- + O2
Overall 2H2O2 à 2H2O + O2
The intermediate is IO-.
Catalyst. substance that increases the rate of a reaction
without itself being consumed. It increases the rate of
reaction by providing a reaction pathway with lower
activation energy.
In this particular example, the catalyst is I- since it is initially
one of the reactants in the first elementary step but it also
ended up as a product in the second elementary step.
Molecularity of a Reaction. Depends on the number of
mole of reactants present in a particular elementary step
or reaction.
1 mole of reactant = unimolecular/ molecularity of 1
2 moles of reactants = bimolecular/ molecularity of 2
3 moles of reactants = termolecular/ molecularit of 3
In the example above, both Steps 1 and 2 are
bimolecular. The overall reaction is also bimolecular.
Interpreting Reaction rates Graphs

The following graph shows an endothermic reaction. The following graph shows an exothermic reaction.
y- axis represents the energy involved in the reaction as
time increases (x). y- axis represents the energy involved in the reaction as
time increases (x).
Activation energy. Energy required for a reaction to
proceed. If the final energy of the product is lower than the initial
energy by the reactant, the reaction is exothermic. It
If the final energy of the product is greater than the initial means ∆𝐻 is negative. This represents the energy released
energy by the reactant, the reaction is endothermic. It by the reaction.
means ∆𝐻 is positive. (represented by the small arrow with Le Chatalier’s Principle
label energy) This represents the energy absorbed by the Change Effect on Equilibrium
reaction. Increase in concentration Shift to opposite side
Decrease in concentration Shift to same side
With the presence of catalyst. The activation energy will be Increase in pressure Shift to side with lesser mole
lower. Decrease in pressure Shift to side with greater mole
Increase in temperature Shift in endothermic direction
Activated Complex. High energy state that a reaction Decrease in temperature Shift in exothermic direction
goes through in order to change reactants to products. Addition of catalyst No change
Peak of the graph where reactant turns to products.