CHEMICAL KINETICS

Chemical Kinetics
- the area of chemistry that deals
with rate of reactions.
Collision Theory – molecules must collide to react
•greater frequency of collisions the greater the
reaction rate
•for most reactions only a small fraction of
collisions leads to a reaction
•Molecules must have a minimum amount of energy
to react
•Energy comes from kinetic energy of collisions
•Kinetic energy used to break bonds
•Activation energy, Ea – minimum energy required to
initiate a chemical reaction
•Activated complex or transition state – atoms at the
top of the energy barrier
•Rate depends on temperature and Ea
•Lower Ea means faster reaction
•Reactions occur when collisions between molecules
occur with enough energy and proper orientation
Factors Affecting Rate of Reaction

1. Nature of reactants
2. concentrations of reactants
3. temperature at which reaction occurs
4. presence of a catalyst
5. surface area of solid or liquid reactants

*Pressure
Change in pressure has very little effect on the
liquids and solids.
For gaseous reactants, an increase in pressure
increases the rate of reaction. Consequently, a
decrease in pressure decreases the rate of
reaction.
 Chemical Kinetics
Reaction rate is the change in the
concentration of a reactant or a product with
time (M/s).
A→B
D[A] D[A] = change in concentration of
rate = - A over time period Dt
Dt

D[B] D[B] = change in concentration of B over

rate =
Dt time period Dt
Because [A] decreases with time, D[A] is
negative.
 A B

time

D[A]
rate = - Dt

D[B]
rate =
Dt
Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)

time
 Reaction Rates and Stoichiometry

2A → B
Two moles of A disappear for each mole of B that is formed.

1 D[A] D[B]
rate = - Dt rate =
2 Dt

aA + bB cC + dD

1 D[A] 1 D[B] 1 D[C] 1 D[D]

rate = - =- = =
a Dt b Dt c Dt d Dt
Write the rate expression for the following reaction:

CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (g)

D[CH4] 1 D[O2] D[CO2] 1 D[H2O]

rate = - =- = =
Dt 2 Dt Dt 2 Dt
Write the expressions for the following:
a) I-(aq) + OCl-(aq) → Cl-(aq) + OI-(aq)

b) 3O2(g) → 2O3(g)

c) 4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g)

 The Rate Law
The rate law expresses the relationship of the rate of a reaction to the
rate constant and the concentrations of the reactants raised to some
powers.
aA + bB cC + dD

Rate = k [A]x[B]y

reaction is xth order in A

reaction is yth order in B
reaction is (x +y)th order overall
Please go to the link below and watch the video.
https://www.youtube.com/watch?v=6Ng8ayarWHw

Continue reading and answer the practice

exercise that follows.
F2 (g) + 2ClO2 (g) 2FClO2 (g)
 F2 (g) + 2ClO2 (g) 2FClO2 (g)

rate = k [F2]x[ClO2]y
Double [F2] with [ClO2] constant Rate doubles x=1
Quadruple [ClO2] with [F2] constant Rate quadruples y=1
rate = k [F2][ClO2]

The reaction is 1st order in F2

The reaction is 1st order in ClO2
The reaction is 2nd order overall.
 Rate Laws

• Rate laws are always determined experimentally.

• Reaction order is always defined in terms of reactant

(not product) concentrations.

• The order of a reactant is not related to the

stoichiometric coefficient of the reactant in the balanced
chemical equation.

F2 (g) + 2ClO2 (g) 2FClO2 (g)

rate = k [F2][ClO2]
Determine the rate law and calculate the rate constant
for the following reaction from the following data:
S2O82- (aq) + 3I- (aq) 2SO42- (aq) + I3- (aq)

Initial Rate
Experiment [S2O82-] [I-]
(M/s)
1 0.08 0.034 2.2 x 10-4

2 0.08 0.017 1.1 x 10-4

3 0.16 0.017 2.2 x 10-4

Double [I-], rate doubles (experiment 2 & 1)

Double [S2O82-], rate doubles (experiment 2 & 3)
 Determine the rate law and calculate the rate constant
for the following reaction from the following data:
S2O82- (aq) + 3I- (aq) 2SO42- (aq) + I3- (aq)

Initial Rate
Experiment [S2O82-] [I-]
(M/s)
1 0.08 0.034 2.2 x 10-4

2 0.08 0.017 1.1 x 10-4

3 0.16 0.017 2.2 x 10-4

rate = k [S2O82-]x[I-]y

Double [I-], rate doubles (experiment 1 & 2) y=1

Double [S2O82-], rate doubles (experiment 2 & 3) x = 1
rate = k [S2O82-][I-]
Determine the rate law and calculate the rate constant
for the following reaction from the following data:
S2O82- (aq) + 3I- (aq) 2SO42- (aq) + I3- (aq)
Initial Rate
Experiment [S2O82-] [I-]
(M/s)
1 0.08 0.034 2.2 x 10-4

2 0.08 0.017 1.1 x 10-4

3 0.16 0.017 2.2 x 10-4

rate = k [S2O82-][I-]

rate 2.2 x 10 -4 M/s

k= = = 0.08/M•s
2- -
[S2O8 ][I ] (0.08 M)(0.034 M)
 NO(g)+O3(g)⟶NO2(g)+O2(g)

This reaction has been studied in the laboratory, and the following
rate data were determined at 25 °C.

Trial [NO] (mol/L) [O3] (mol/L) Rate

1 1.00 × 10−6 3.00 × 10−6 6.60 × 10−5

2 1.00 × 10−6 6.00 × 10−6 1.32 × 10−4
3 1.00 × 10−6 9.00 × 10−6 1.98 × 10−4
4 2.00 × 10−6 9.00 × 10−6 3.96 × 10−4
5 3.00 × 10−6 9.00 × 10−6 5.94 × 10−4
Table 3.
1. Determine the rate law and the rate constant for the
reaction at 25 °C.
2. Find the rate of the reaction if [NO] is
1.50 X 10-6 M and [O3] = 5.00 X 10-6 M.