CHEMICAL KINETICS

Aga Khan Higher Secondary School Hunza/Gakuch.

By: Rosedar SALEEM ULLAH:

Grade 11(Pre-Eng. and Pre- Medical).

1. Chemical kinetic deals with the speed of reactions and speed of reaction is defined as change in
concentration of reactants or products with time.
The study of chemical kinetics includes
a. The rate of reaction and rate law
b. Factors that influences the rate of reaction(factors are temperature.pressure,concentration
and catalyst)
c. The mechanism of reaction.
2. Suppose you are given a chemical reaction in which ’’ A’’ is reactant and ‘’B’’ is product.
A→ B
Rate of reaction for the above reaction will be expressed as (Hint .write expression)
a. Rate of disappearance of A=_________________________
b. Rate of appearance of B=___________________________
3. The unit of rate of reaction is
change∈concentration of reactant∨ products
Rate of reaction =
change on time
Unit of reaction rate= mole/L sec also moledm−3 s−1
Or = mole/L minutes also mole dm−3 min−1
= mole/L hours also moledm−3 h−1
Instead of liter dm 3 can also be written
4. Consider the reaction between CO and NO 2 .
CO + NO 2 → CO 2 + NO
The concentration of CO was found after every 10 second as

[CO] in mole dm−3 Time in sec

0.100 0
0.067 10
0.050 20
0.040 30

Find
a. The rate of disappearance of CO over the first 10 second
b. What is the rate of reaction in the interval 10 and 20 second
c. Compare the rate of reaction in the above two intervals

5. Rate law is experimental determined quantity .It shows the relation between concentration and
rate of reaction.
  The exact relation between concentration and rate of reaction is determined by
measuring the reaction rate with different initial reactant concentration.
Generally
A + B → product
Rate law
rate ∝ [ A ]x [ B] y
rate =k[ A ] x [ B]y
x=order of reaction w.r.t A
y= order of reaction w.r.t B
a. x and y is order of reaction which is determined experimentally and is not written by
looking at the balance chemical equation .
b. Power of concentration in the rate law are different from co-efficient of balance reaction,
for some elementary reactions the power in the rate law may corresponds to co-efficient in
balance chemical equation.
c. Power of concentration in the rate law is called order.
6. Consider the following reaction.
A + B → product
The reaction is first order in A and second order in B find
a. Rate law for the above reaction
b. The overall order of the reaction
7. Consider the following reaction
X + Y → product
The reaction is half order in X and second order in Y Find
a. Rate law of reaction
b. The overall order of reaction
8. Consider the following reaction.
X + Y → product
Suppose the reaction is zero order in Y and first order in X Find
a. The rate law
b. The overall order of reaction.
9. Suppose a reaction is second order in X and first order in Y if you increase the concentration of
r2
reactant X two time(double ) what will be the rate of reaction(Hint )
r1
10. Order of reaction
Order of reaction is defined in the following way
a. Sum of exponent in the rate law
b. The number of molecules participating in the rate determining step (if a reaction is
completed in more than one step).
c. Order of reaction w.r.t each reactant is defined as the exponent to which the concentration
term in the rate law is raised.
Solved problem
Consider the following reaction.
2NO + 2 H2 → N2 + 2 H2O
rate law
 Rate =k [ H 2][NO ]2
The reaction is first order in H 2
The reaction is second order in NO
Overall order = sum of exponent in rate law
Over all order = 1+2=3
0ver all reaction is third order.
11. Practice problem.
a. You are given a reaction with its rate law
NO 2 + CO → NO + CO 2..
rate=k [ NO 2] 2
a. order of reaction∈CO ___________________
b. order of reaction∈NO 2 ¿

c. overall order of reaction ________________

12. Find order for the following reactions from given rate law
a. NO + O 3 ¿ → NO 2 + O 2
¿

rate = k [NO] [O 3 ¿]
¿
b. NO 2 + CO → NO + CO 2
2
Rate = k[NO 2 ]
13. Rate Determining step.
a. When a reaction is completed in more than one step than there is one step which is the
slowest step and this slowest step is called the rate Determing step.
b. The slowest step is rate determining step because s reaction can proceed no faster than the
slowest step.
c. Number of molecules participating in the slowest step will be the order of reaction
d. We can write rate law for the slowest step
Example..
Consider the following reaction
NO 2 + CO → NO + CO 2
the above reaction iscompleted ∈two step which are following
NO 2 + NO 2 → NO 3 + NO (slow step)
NO + CO → NO + CO 2¿
3 2 (fast step)
¿
______________________
NO 2 + CO → NO + CO 2 overall reaction

a. rate law
2
rate=[ NO2 ]
b. . Overall order of reaction
second order
c. Order w.r.t CO
Zero order w.r.t CO
14. Chemical equation. Answer the questions given at the end
 2NO + 2 H 2 → N 2 + 2 H 2O

The above reaction is completed in two step.

Step 1

NO + H 2 → N 2 + H 2 O 2. (Slow step)

Step 2.

H 2 O 2 + H 2 → 2 H 2O (fast step)

Write

a. The complete reaction.

b. Write the rate equation/rate law
c. The order of reaction w.r.t each reactant.
d. The overall order of reaction.

Rate equation and order of reaction by initial rate method.

a. Effect of change in concentration of reactant on reaction rate cannot be predicted from

chemical equation

b. It is determined experimentally by determing the order of reaction.

c. Initial rate method is used to find the rate equation and order of reaction (experimental).During
performing experiment the concentration of one reactant is changed while other is kept
constant and the initial rate is determined.

15. Consider the following reaction in which rate law and order is found experimentally
NO + O3 → NO 2 + O 2
Experimentally obtained results are.

Exp No [] in mole/liter [] in mole/literinitial rate in mole

/liter sec
−6 −6
1 1.0×10 9.0×10 1.98×10−4
−6 −6
2 2.0×10 9.0×10 3.96×10−4
3 1.0×10−6 3.0×10−6 6.60×10−5
 . In the first and second experiment the concentration of ozone is kept constant and the
concentration of NO is doubled. The rate will be.
r1 : r2
1.98 ×10 : 3.96 ×10−4 
−4

Change in rate.
−4 − 4 
1.98 × 10 3.96  ×10
−4 : −4
1.98 × 10 1.98 × 10
1 : 2
Therefore
 rate ∝[NO].
 In the first and third experiment the concentration of nitric oxide is kept constant and
the concentration of ozone is decreased to 1/3.
r1 : r2
1.98 ×10 : 6.60 ×10−5
−4

Change in rate of reaction is

1.98 × 10− 4 6.60  ×10−5
:
1.98 × 10− 4 1.98 × 10− 4
1 : 1/3
Thus
rate ∝[O3]
Rate equation
rate ∝[NO][O3 ].
• rate =k[NO][O 3 ]
Order of reaction
n= x +y
n= 1+ 1 =2
Second order reaction.

PRACTICE QUESTIONS.
16. For the following reaction, using the experimentally determined rate, use initial rate method to
find rate law and order of reaction.
CO + Cl 2 → COCl 2
Experimentally determined data for the above reaction is.

Exp [CO] in mole/L [Cl 2] in mole/L Initial rate(mole/L

No sec)
1 1.00 0.100 1.29×10−29
2 0.100 0.100 1.30×10−30
3 0.100 1.00 1.30×10−30

17. Nitric oxide reacts with hydrogen gas (at 1100 K) and produces nitrogen gas and water vapors,
using the experimentally determined rate and concentration used .Find rate law and order of
reaction.
2NO + 2 H 2 → N 2 + 2 H 2 O
Experimentally determined data is.

Exp [NO] in mole dm−3 [ H 2] in mole dm−3 Rate(mole dm−3 s−1 ¿

No
1 5 ×10−3 2.5 ×10−3 3×10−5
2 1.0 ×10−2 2.5 ×10−3 1.2 ×10−4
3 1.0 ×10−2 5 ×10−3 2.4 ×10−4
18. Ammonia is an important industrial chemical, it is manufactured by Haber’s Process which is
used in the manufacture of fertilizer, and ammonia decomposes according to the following
reaction.
2 NH 3 → N 2 + 3 H 2
Experimentally determined data is

Experiment No [ NH 3]in mole dm−3 Rate(mole dm−3 s−1 ¿

1 0.400 2.0×10−3
2 0.200 2.0×10−3
3 0.100 2.0×10−3
Find
a. The rate law
b. The order of reaction.
19. Nitrogen dioxide is an important chemical which is used in the manufacture of nitric acid.it
decomposes according to the following reaction
2 NO2 → 2NO + O2
Experimentally determined data is

Experiment No [ NO 2] in mole dm−3 Rate(mole dm−3 s−1 ¿

1 0.400 16.0×10−3
2 0.200 4.0×10−3
3 0.100 2.0×10−3
Find (Hint.inital rate method)
a. The rate law
b. Overall order of reaction

Collision theory. Transition state theory and Activation energy

20. Two theories explain how reaction occurs.

a. Collision theory
b. Transition state theory.

Collision Theory

• According to collision theory a chemical reaction takes place only by collision between recanting
molecule.

• Not all collisions are effective only a small fraction of collision produce product

• Conditions for effective collision.

1. The colliding molecule must contain sufficient kinetic energy to cause a reaction

2. The reacting molecule must collide with proper orientation.

Effective and ineffective collision

Effective collision cause chemical reaction while in ineffective collision the reactant molecule bounce
as reactant molecule without converting into products.

Transition State Theory

According to transition state theory during collision the reacting molecule form activated complex or
transition state which decomposes to product

Thus during collision the reacting molecules are not directly converted into product as a result of
effective collision instead they are first converted into activated complex/transition state and this
activated complex is highly unstable which decomposes into products.
a. In transition state old bonds in reactant molecules are partially broken and new bond in the
products are partially formed, in the activated complex it is shown by a doted lines.
21. What are conditions for a reaction to take place according to collision theory
a. __________________________________
b. __________________________________
22. According to transition state theory effective collision results into a species which is than
decomposed into product the specie is
a. ________________________
b. Energy of species is ______________ as compare to reactant and products
Activation Energy ( Ea )
• The minimum amount of energy required to convert reactants into products is called activation
energy or
• The minimum amount of energy required for effective collision
• Consider a hypothetical reaction
A2 + B2 → 2 AB ¿ → AB + AB
Reactants transition state products
Graphically
For an exothermic reaction.
The energy level diagram is.

23. Combustion of methane is exothermic reaction when methane burns it produces carbon
dioxide water vapor and 891KJ/mole. The reaction has an activation energy equal to 172KJ/mole
sketch the reaction energy diagram.

CH 4 + O2 → CO 2 + H 2O + 891KJ/mole

Important points ¿ be noted

a. Energy of activation for exothermic reaction is small as compared to the energy released during
the reaction as a result once exothermic reaction is started it proceed own its own because the
energy released during the reaction is more than the activation energy and a part of this energy
released is utilized in activating the reactant molecule.
b. The product formed in exothermic reaction cannot be converted back to reactants because the
energy of activation for the products to convert back to reactants is high.
c. There is inverse relation between the rate reaction and energy of activation.
 1
Rate of reaction ∝
Ea
• If the energy of activation is less than the rate of reaction is fast
• If the activation energy is high than rate of reaction is slow.
• If activation energy is zero than rate of reaction is spontaneous

Endo thermic reaction.

Energy level diagram for endothermic reactions
a. Energy of activation in case of endothermic reaction is greater than the energy released
during the reaction.
b. We need to provide a continues energy during the reaction to provide the energy required
for the activation energy of the reactant molecule, because the energy release during the
reaction is less than the activation energy

c. The products can easily be converted back into reactants molecule in case of endothermic
reaction because the energy of activation for the products to convert them to reactants is
small.
d. Usually reversible reaction undergo endothermic reaction
24. Generally if we compare endothermic reaction and exothermic reactions which will take place at
a faster rate and why?(Answer in term of activation energy)

25. In the atmosphere there is mixture of air like nitrogen, oxygen etc. but they do not react to form
any particular compound at ordinary conditions why?

26. The reaction between hydrogen gas and carbon dioxide is an endothermic reaction

H 2O + CO 2 → H 2O + CO

The energy of activation for the above reaction is 248KJ/mole and the energy released when the
activated complex is 41KJ/mole
 a. Draw energy level diagram for the above reaction showing the energy of activation and the
energy which is released
27. Solved example.
Consider the reaction between hydrogen gas and carbon dioxide to form water and carbon
monoxide.
H 2O + CO 2 → H 2O + CO
Energy level diagram.

a. Compare the energy of activation and energy released.

b. The energy level diagram shows which particular type of reaction
c. What will happen if you will stop giving energy to the above reaction
28. The following reaction is completed in two steps, which are.
NO 2 + F 2 → NO 2F + F (slowest step)
NO 2 + F → NO 2F (fast step.)
Find
a. The overall reaction
b. The rate determining step
c. Rate law/rate equation
d. Order of reaction.
e. Order w.r.t each reactant.

INITIAL RATE OF REACTION.

29. The initial rate of a reaction is the instantaneous rate at the start of the reaction (i.e., when t =
0). The initial rate is equal to the negative of the slope of the curve of reactant concentration
versus time at t = 0.
Explanation
Consider the following reaction for which we determine initial rate
C 4 H 9Cl + H 2O → C 4 H 9 OH + HCl.
change ∈concentration with time is given
Time in sec ¿ ¿Cl ] in mole/L

0 0.100
 50 0.900
100 0.082
150 0.075
200 0.068
300 0.055
400 0.046
800 0.022
Steps to find the initial rate

a. Draw tangent to the concentration time cure at time t=0

b. Find the slope of this tangent will give initial rate
Thus negative slope of the tangent at time t=0 will give the initial rate of reaction

Graph of the above given data is

Initial rate = - slope

Slope =rise /run
(0.060−0.1)
Rate of reaction = -slope = -
(200−0)
(−0.04 )
Rate of reaction = -
(200)
Rate of reaction = 0.0002mole/L sec or 2 ×10−4mole/L sec
Keep in mind
Don’t worry about the length of tangent which is drawn to the curve at time ‘’t’’=0 you can draw
a small or large or any length of tangent ,it will not affect the value of rate of reaction, the rate
will always come out of same value.
Thus initial rate of reaction is equal to negative slope of tangent of curve at time t=0.
a. Instantaneous rate
The rate of reaction at any particular time is called is instantaneous rate.
Example
If I want to find rate of reaction at time t= 100 sec it is instantaneous rate
We will find instantaneous rate by drawing tangent to the curve at the given time and then
we will find the slope of that tangent it is give us instantaneous rate.
Example
 In the above graph the instantaneous rate at 600sec is to be founded the tangent is drawn
just find the slope of the tangent
Instantaneous rate at 600 sec____________________
Average rate.
The rate of reaction between two time intervals is called average rate.
Example
Find the rate of reaction between 300 sec and 400 sec, it will be average rate
(0.046−0.055)
Average reaction = -
(400−3000)
Average rate = 0.009/100 = 9×10−5mole/L sec
Remember
Initial rate is founded by
1. Drawing tangent to the curve at time ‘’t’’=0
2. Finding slope of that tangent will give initial rate.

Practice question.
30. Consider the reaction between CO and NO 2 .
CO + NO 2 → CO 2 + NO
Change in concentration with time is given

[CO] in mole dm−3 Time in sec

0.100 0
0.067 10
0.050 20
0.040 30
Find
a. The initial rate
b. Instantaneous rate at time t=20sec.
c. Average rate between 10 and 20 sec.
Practice Question.
31. A graph for any particular reaction is given.

a. Find the initial rate

b. Instantaneous rate at time ‘’t’’ =25 sec
c. Average rate between 50 and 90 sec.
32. If you are given the concentration of products and asked for finding the initial rate the graph will
be like this.

a. In this case the rate will be equal to positive slope of tangent.

Activation Energy and Catalyst.

a. For a chemical reaction to occur the reactant molecules must possess the activation energy ¿)
b. Smaller the activation energy the rate of reaction will be faster.
c. Catalyst provides another pathway with lower activation energy ¿), this mean that catalyst
lowers the energy of activation and increases the rate of reaction.

d. Although catalyst lowers the energy of activation, but the energy difference ∆ E between the
reactants and products remain same.
e. Also the rate constant remain the same(catalyst will not change the rate constant)
f. Positive catalyst increases the rate of reaction by increasing the activation energy
g. Negative catalyst decreases the rate of reaction by increasing the activation energy.
33. Two reactions with different activation energy, first reaction has small activation energy and the
second has high activation energy which one will occur at faster rate and why?
______________________________________________________________________________
______________________________________________________________________________
______________________________________________________________________________
______________________________________________________________________________.
34. Describe the following graph in two to three lines.
______________________________________________________________________________
______________________________________________________________________________
______________________________________________________________________________
______________________________________________________________________________.
Factors Affecting The Rate Of Reaction
a. Nature of reactant
b. Concentration of reactants
c. Surface area
d. Temperature.
Make sure we will discuss the role of temperature consedring the Arrhenius equation.
MOLECULARITY OF A REACTION
We two types of reaction
a. Elementary reaction
b. Complex reaction

Elementary reaction occurs in single step

Complex reaction occurs in two or more step.

Molecularity of elementary reaction

Number of reactant molecule involved in a reaction

The molecularity may be 1, 2, 3 etc.

Example.

H2 → 2H ( unimolecular )

2NO + O2 → 2 NO2 termolecular (three reactant molecules)

Make sure it is a theoretically determined not experimentally.

Molecularity of complex reaction.

For complex reaction the number of molecule involved in the rate determining step (slow
step) will be the molecularity of complex reaction.
 Example

2 N 2 O5 → 4 NO2 + O2
the above reaction iscompleted ∈three steps which are
2 N 2 O5 → 2 NO2 + 2 NO3 Slow step
NO 2 + NO 3 → NO + NO 2 + O2 Slowest step
NO + NO 3 → 2 NO2 Fast step
Overall reaction 2 N 2 O 5 → 4 NO2 + O2

Molecularity = Bimolecular

Because two molecules are participating in the slowest step.

Practice Question

Rate Determining step.

a. When a reaction is completed in more than one step than there is one step which is the
slowest step and this slowest step is called the rate Determing step.
b. The slowest step is rate determining step because s reaction can proceed no faster than the
slowest step.
c. Number of molecules participating in the slowest step will be the order of reaction
d. We can write rate law for the slowest step.
Example,
2 N 2 O5 → 4 NO2 + O2
the above reaction iscompleted ∈three steps which are
2 N 2 O5 → 2 NO2 + 2 NO3 Slow step
NO 2 + NO 3 → NO + NO 2 + O2 Slowest step
NO + NO 3 → 2 NO2 Fast step
Overalls reaction 2 N 2 O5 → 4 NO2 + O2

Find

a. Rate law
b. Order
c. Molecularity.

………………………………………………………………………………………………………………………………………….
a. Students try and search for the factors that control the rate of reactions and the
temperature factor we will discuss in class room.
b. Students we have already learned (in class) to find the unit of rate constant for zero,
first ,second and third order, if still confusion exists please consult .
c. Try to solve the practices question if you feel difficulty somewhere do ask.
d. I will share the work sheets of acid base and salt and solids after 15 January.
……………………Have a Nice Time………………………………….