WESTERN LEYTE COLLEGE

SENIOR HIGH SCHOOL- SCIENCE, TECHNOLOGY,

ENGINEERING AND MATHEMATICS (STEM)
K to 12 CURRICULUM

CHEMICAL
KINETICS

Instructor: Elton Jhon M. Meridor

Principal: Isabelita T. Peroso

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General Chemistry I
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CHEMICAL KINETICS

Objectives
Define chemical kinetics, and distinguish the factors affecting the rate and the different rate laws

Overview
In this lesson, learners are expected define chemical kinetics and conditions that are necessary
for a chemical reactions to occur, the various factors influence the rate of a reaction. In addition,
students are projected to differentiate the different types of laws of reaction.

Background
Chemical Kinetics
It is the study of the rates of chemical reactions and the steps or series of steps through which the
reaction occurs. The word “kinetic” suggests movement and thus, it refers to the rate of reaction which
is the change in the concentration of a reactant or a product with time (M/s). It is expressed as:
For the general reaction: aA + bB cC + dD
Where: small letters represent the coefficient, big letters are the reactants and products
∆R ∆P
rate = - =
∆t ∆t
−1 ∆ [ A] −1 ∆ [B] 1 ∆ [C ] 1 ∆ [D]
rate = = = =
a ∆t b ∆t c ∆t d ∆t
Example:
Write the rate expression for the following reactions in terms of the disappearance of the
reactants and the appearance of the products
1. I- (aq) + OCl- (aq) Cl- (aq) + OI- (aq)

rate = −¿ ∆ ¿ ¿ = −¿ ∆ ¿ ¿ = ∆ ¿ ¿ = ∆ ¿ ¿

2. 4NH3 (g) + 5O2 (g) 4NO (g) + 6H2O (g)

−1 ∆ [NH 3 ] −1 ∆ [O 2] 1 ∆ [NO ] 1 ∆ [H 2O]

rate = = = =
4 ∆t 5 ∆t 4 ∆t 6 ∆t

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Factors Affecting Rates of Reaction:

1. Nature of Reactants - The physical states of reacting substances are important in determining
their reactivities. Bonds are broken and other bonds are formed in reactions. The rate of reaction
depends on the particular reactants and bonds involved.
2. Concentration of the Reactants - Predicting the mathematical relationship between rate and
concentration is difficult because most chemical reactions occur in a series of steps, and only one
of these steps determines the rate of reaction. If the number of effective collisions increases, the
rate will also increase. An increase in rate is expected if the concentration of one or more of the
reactants is increased. In general, the higher is the concentration, the faster is the reaction.
3. Temperature - An increase in temperature increases the average kinetic energy of the particles.
This can result in a greater number of effective collisions when substance is allowed to react with
another substance. Thus, a rise in temperature produces an increase in collision energy as well as
in collision frequency. On the other hand, decreasing the temperature of a reaction system shows
the opposite effect.
4. Presence of Catalyst - A catalyst is a substance that changes the rate of reaction without itself
being consumed, a process called catalysis. It provides an alternative energy pathway or reaction
mechanism in which the potential-energy barrier between reactants and products is lowered. A
catalyst that is in the same phase as all the reactants and products in a reaction system is called a
homogeneous catalyst, and for the different phase, it is called heterogeneous catalyst.
5. Area of Contact of Reacting Phase (Surface Area) - In heterogeneous reactions, the reaction rate
depends on the area of contact of the reaction substances. The bigger is the surface area, the
faster is the rate of reaction.
Rate Law
The rate law is an equation wherein the rate of the reaction is given as a function of
concentration. It is an equation shows the relationship between the rate of the reaction and the
concentration of the reacting substances.
For the general reaction: aA + bB cC + dD
rate = k [A]x[B]y
where: k is the specific rate constant
x is the order of reaction with respect to A

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y is the order of reaction with respect to B

The exponents x and y specify the relationships between the concentrations of reactants A and B
and the reaction rate. These exponents will give the overall reaction order when added together.
Reaction order is the sum of the powers to which all reactant concentrations appearing in the rate law are
raised.
Example
The reaction of nitric oxide with hydrogen at 1280 ˚C is
2NO (g) + 2H2 (g) N2 (g) + 2H2O (g)
From the following data collected at this temperature, determine the rate law, the rate constant
and the rate of the reaction when [NO] = 12.0 x 10-3 M and [H2] = 6.0 x 10-3 M.
EXPERIMENT [NO] (M) [H2] (M) INITIAL RATE (M/S)
1 5.0 x 10-3 2.0 x 10-3 1.3 x 10-5
2 10.0 x 10-3 2.0 x 10-3 5.0 x 10-5
3 10.0 x 10-3 4.0 x 10-3 10.0 x 10-5

Strategies:
From the given set of concentration and reaction rate data:
 determine the values of x and y;
 calculate the value of k once the orders of the reactants are known;
 k can be calculated from any set of rate and concentrations; and
 calculate the rate at any concentrations of NO and H2.
Solution:
rate = k [NO]x[H2]y
Values of x and y:
For x with respect to NO, consider two experimental set-ups which the concentration of H 2 is constant.
With this, the ratio of the rates in experimental 1 and 2 will be taken.
x y
rate 2 k [ NO ] [ H 2 ]
=
rate 1 k [ NO ] x [ H 2 ] y
x y
5.0 x 10 M /s k [ 10.0 x 10 M ] [ 2.0 x 10 M ]
−5 −3 −3

−5 = x y
1.3 x 10 M /s k [ 5.0 x 10 M ] [ 2.0 x 10 M ]
−3 −3

3.846 = 2x

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2x = 3.846
2x ≈ 4
x=2
For y with respect to H2, consider two experimental set-ups which the concentration of NO is constant.
With this, the ratio of the rates in experimental 2 and 3 will be taken.
x y
rate 3 k [ NO ] [ H 2 ]
=
rate 2 k [ NO ] x [ H 2 ] y
x y
10.0 x 10 M /s k [ 10.0 x 10 M ] [ 4.0 x 10 M ]
−5 −3 −3

−5 = x y
5.0 x 10 M /s k [ 10.0 x 10 M ] [ 2.0 x 10 M ]
−3 −3

2 = 2y
y=1
Rate Law: rate = k [NO]2[H2]
Rate Constant, consider the data from experiment 2:
rate
k=
[ NO ] 2 [H 2]
−5
5.0 x 10 M / s
k= 2
[ 10.0 x 10−3 M ] −3
[2.0 x 10 M ]
k = 2.5 x 102 /M2 ۰ s
Rate of the Reaction:
rate = k [NO]2[H2]
rate = (2.5 x 102 /M2 ۰ s) (12.0 x 10-3 M)2(6.0 x 10-3 M)
rate = 2.2 x 10-4 M/s

The Relation between Reactant Concentration and Time

Integrated rate law expresses the concentrations of the reacting substances as a function of time.
It can be used to calculate the half-life, t 1/2, of a reactant. Half-life is defined as the time it takes for half
of that reactant to be converted into product. The integrated rate equation and the half-life are different
for reactions of different order. The different types of integrated rate laws are:
1. First-Order Reactions
2. Second-Order Reactions
3. Zero-Order Reactions

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First-Order Reactions
It is a reaction whose rate depends on the reactant concentration raised to the first power. First-
order reaction is mathematically expressed as:
[ A]t
ln = - kt or ln[A]t = - kt + ln[A]o
[ A]o

Example:
The conversion of cyclopropane to propene in the gas is a first-order reaction with a rate constant
of 6.7 x 10-4 s-1 at 500 ˚C.
a. If the initial concentration of cyclopropane was 0.25 M, what is the concentration after 8.8
minutes?
b. How long (in minutes) will it take for the concentration of cyclopropane to decrease from
0.25 M to 0.15 M?
c. How long (in minutes) will it take to convert 74% of the starting material?
Solution:
60 s
8.8 min x = 528 s
1min
a. ln[A]t = - kt + ln[A]o

= -[ (6.7 x 10-4 s-1) (528s) + ln (0.25)

= -1.74
= e -1.74
[A]t = 0.18 M
[ A]t
b. ln = - kt
[ A]o
[ 0.15 ]
ln = -(6.7 x 10-4 s-1)t
[ 0.25 ]
t = 7.6 x102 s
1min
t = 7.6 x102 s x
60 s
t = 12.67 min
[ A]t
c. ln = - kt
[ A]o
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[ 0.26 ]
ln = -(6.7 x 10-4 s-1)t
[ 1.00 ]
t = 2.0 x103 s
1min
t = 2.0 x103 s x
60 s
t = 33.33 min
Half-life for First-Order Reaction
1 0.693
It is expressed as: t1/2 = ln 2 =
k k
Example:
At 700 ˚C, the decomposition of ethane to methyl radicals is a first-order reaction with a rate
constant of 5.36 x 10-4 s-1. Calculate the half-life of the reaction in minutes.
Solution:
0.693
t1/2 =
k
0.693
= −4 −1
5.36 x 10 s
= 1.29 x 103 s
1min
= 1.29 x 103 s x
60 s
t1/2 = 21.5 min
Second-Order Reactions
It is a reaction whose rate depends on the concentration of one reactant raised to the second
power or on the concentration of two different reactants, each raised to the first power. Second-order
reaction is mathematically expressed as:
1 1 1 1
– = kt or = kt +
[ A]t [ A]o [ A]t [ A]o
Half-life for Second-Order Reaction
1
It is expressed as: t1/2 =
k [A]o
Example:
Iodine atoms combine to form molecular iodine in the gas phase. This reaction follows second-
order kinetics and has a rate constant 7.0 x 10 9 /M ۰ s at 23 ˚C. If the initial concentration of I was 0.086

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M, calculate the concentration after 2.0 minutes. Calculate the half-life of the reaction if the initial of
concentration is 0.60 M and if it is 0.42 M.
Solution:
a. Concentration After 20 Min:
60 s
2.0 min x = 120 s
1min
1 1
= kt +
[ A]t [ A]o
1 1
= (7.0 x 109 /M ۰ s) (120 s ¿ +
[ A]t 0.086
1 = 8.4 x 1011 [A]t
[A]t = 1.2 x 10-12 M
b. Half-life:
For 0.60 M:
1
t1/2 =
k [A]o
1
t1/2 = 9
(7.0 x 10 /M ۰ s)(0.60 M )
t1/2 = 2.4 x 10-10 s
For 0.42 M:
1
t1/2 =
k [A]o
1
t1/2 = 9
(7.0 x 10 /M ۰ s)(0.42 M )
t1/2 = 3.4 x 10-10 s
Zero-Order Reactions
It is a reaction whose rate is independent on the concentration of reactants. Zero-order reaction is
mathematically expressed as:
[A]t – [A]o = -kt or [A]t = -kt + [A]o
Half-life for Zero-Order Reaction
[ A]o
It is expressed as: t1/2 =
2k
Summary of Relationships for Various Orders of the Reaction (Silberg)

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Order
Zero First Second
Rate Law Rate = k Rate = k[A] Rate = k[A]2
Units for k mol/L ۰ s 1/s L/mol ۰ s
[A]t – [A]o = -kt [ A]t 1 1
ln = - kt – = kt
Integrated or [ A]o [ A]t [ A]o
Rate [A]t = -kt + [A]o or or

Law ln[A]t = - kt + ln[A]o 1 1

= kt +
[ A]t [ A]o

Half-life [ A]o 1 0.693 1

t1/2 = t1/2 = ln 2 = t1/2 =
2k k k k [A]o

Plot for Straight Line [A]t vs time ln[A]t vs time 1/[A]t vs time

REFERENCES

CALIBO, C., A. ACABAL, J. G. JANSALIN, A. ACABAL, O. CORALES, E. QUEVEDO, M. P.

LORETO, A. RAMAL, F. SALAS, E. LANDERITO, and D. A. VARRON. 2010. Laboratory
manual in Chemistry 11: General Chemistry. Revised Ed. Visayas State University, Visca,
Baybay City.

CHANG, R. 2010. Chemistry, 10th ed. McGraw-Hill Companies, Inc.

WHITTEN, K., DAVIS, R., PECK, M. L. and G. STANLEY. 2010. Chemistry, 9th ed.

SMITH, J. 2011. Organic Chemistry, 3rd ed.

USC Chemistry Review Center. 2016. Chemistry Review Manual.

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Name: ______________________________ Section: ________________________________

Date Received: _______________________ Date Submitted: _________________________
Score: ____________
Instructions: Answer the following problems by showing a step-wise solution and enclosed in a box the
final answer.
1. Pentane, C5H12, burns to give CO2 and H2O according to the equation:
2C5H12 + 16O2 10CO2 + 12H2O
If the pentane concentration is decreasing at the rate of 0.30 mol/L ۰ s, what is the rate at which
the oxygen concentration is decreasing? What are the rates at which the product concentrations are
increasing?

2. For the thermal decomposition of acetaldehyde, CH3CHO:

CH3CHO (g) CH4 (g) + CO (g)
The following data at 800 K are given:
[CH3CHO] mol/L Rate of decomposition of CH3CHO (mol/L ۰ s)
0.100 9.0 x 10-7
0.200 36.0 x 10-7
0.300 81.0 x 10-7
0.400 14.4 x 10-6
a. Write the rate law for the reaction.
b. What is the order of the reaction?
c. Calculate the rate constant for the reaction at 800 K.
d. Calculate the decomposition rate at 800 K at the instant when [CH 3CHO] is equal to 0.250
mol/L.

3. The reaction of peroxydisulfate ion (S2O8-2) with iodide ion (I-) is:
S2O8-2 (aq) + 3I- (aq) 2SO4-2 (aq) + I-3 (aq)
Experiment [S2O8-2] (M) [I-] (M) Initial Rate (M/s)
1 0.080 0.034 2.2 x 10-4
2 0.080 0.017 1.1 x 10-4
3 0.16 0.017 2.2 x 10-4
From the data collected at a certain temperature, determine the rate law and calculate the rate
constant.

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4. The reaction 2A forming B is a first order in A with a rate constant of 2.8 x 10 -2 /s at 80 ˚C.
How long will it take for A to decrease from 0.88 M to 0.14 M?

5. The reaction 2A producing B is a second order with a rate constant of 51 /M ۰ min at 24 ˚C.
a. Starting with [A]o = 0.0092 M, how long will it take for [A]t = 3.7 x 10-3 M?
b. Calculate the half-life of the reaction.

6. Given the following data, determine the rate-law expression and the value of the rate constant
for the reaction:
2A + B + C D + E

Experiment [A] (M) [B] (M) [C] (M) Rate (M/min)

1 0.20 0.20 0.20 2.4 x 10-6

2 0.40 0.30 0.20 9.6 x 10-6

3 0.20 0.30 0.20 2.4 x 10-6

4 0.20 0.40 0.60 7.2 x 10-6

7. Use the following initial rate data to determine the form of the rate-law expression for the
reaction:
3A + 2B 2C + D

Experiment [A] (M) [B] (M) Rate (M/min)

1 1.00 x 10-2 1.00 x 10-2 6.00 x 10-3

2 2.00 x 10-2 3.00 x 10-2 1.44 x 10-1

3 1.00 x 10-2 2.00 x 10-2 1.20 x 10-2

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8. The reaction:
2N2O5 (g) 2N2O4 (g) + O2 (g)

It obeys the rate law: rate = k[N2O5] in which the specific rate constant is 0.00840 /s at a certain
temperature. If 2.50 moles of N2O5 were placed in a 5-L container at that temperature, how many
moles of N2O5 would remain after 1.00 minute? How long would it take for 90% of the original
N2O5 to react?

9. Compounds A and B react to form C and D in a reaction that was found to be second-
order in A and second-order overall. The rate constant at 30 ˚C is 0.622 liter per mole per
minute. What is the half-life of A when 4.10 x 10-12 M A is mixed with excess B?

10. The gas-phase decomposition of NOBr is second-order in [NOBr], with k = 0.810 / M ۰ s-

1
at 10 ˚C. The starting amount of NOBr in a flask at the given temperature is 4.00 x 10 -3 M. How
many seconds will it take to use up 1.50 x 10-3 M of this NOBr?

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Assignment
Instructions:
 answer comprehensively the following items;
 do not simply copy and paste the information;
 provide references if the information is not yours; and
 attach your assignment together with exercise.

1. What is the effect of temperature on reaction rate? How it is mathematically expressed?

2. What is activation energy? What is the relationship of temperature and activation energy?
Provide an expression that shows the relation.
3. Discuss major models that could explain the effect of concentration and temperature on reaction
rates. Provide pictures to support your answer.
4. What is a reaction mechanism? Provide an example, discuss each step and label properly.
5. The rate constant of a first-order reaction is 3.46 x 10 -2 s-1 at 298 K. What is the rate constant at
350 K if the activation energy for the reaction is 50.2 kJ/mol?
6. The gas-phase decomposition of nitrous oxide (N2O) is believed to occur via elementary steps:
k1
Step 1: N2O N2 + O
k2
Step 2: N2O + O N2 + O2
Experimentally the rate law is found to be rate = k[N2O]. Write the equation for the overall
reaction. Identify the intermediates. What can you say about the relative rates of step 1 and 2?
7. Discuss the two diagrams below:
8.

Differentiate and discuss: Heterogeneous Catalysis, Homogeneous Catalysis, and Enzyme Catalysis.
Provide illustration to support your answer.

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General Chemistry I