The Rate of a Reaction

The rate or speed of a reaction gives us an idea of the

Section Objective:
nature of a substance. This is important in the choice of the
At the end of this material used to produce certain products. For example, how
section, you should be able to; would you know how much copper metal need to be used in the
1. State the meaning of minting of a coin? Why are bronze statues used instead of iron
rate of a chemical statues2 What makes bronze different from iron?
reaction.
2. Calculate the rate of a The rate of a chemical reaction is a measure of the
chemical reaction from
a given set of data; and quantity of products produced per unit time or the amount of
3. Describe how reactant reacted/consumed per unit time.
observable properties
of a system can be used Consider the hypothetical reaction: 𝐴(𝑔) + 2𝐵(𝑔) → 𝑃(𝑔)
to determine the rate of
a chemical reaction.

Let us say that before the reaction starts, the

concentrations of A and B are [A]0 and [B]0 respectively, while the concentration of P is [P]0. After
the reaction has been allowed to take place tor a certain time, t, the concentration of the reactants
and products are designated as [A]t, [B]t and [P]t. The rate of the reaction if expressed in terms of
change in concentration or the product, P, is given by the equation:
𝐶ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
𝑅𝑎𝑡𝑒 =
𝑡𝑖𝑚𝑒
𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑎𝑡 𝑡𝑖𝑚𝑒 𝑡 − 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
=
𝑡𝑖𝑚𝑒
[𝑃]𝑡 − ∆[𝑃]𝑜 ∆[𝑃]
= =
𝑡𝑖𝑚𝑒 𝑡𝑖𝑚𝑒
We can see that the value, ∆[𝑃]is the change in amount, usually in terms of concentration
of the product.
Therefore, if after 5 min, the concentration of the product changed from 0 (because no
product is present yet at the start of the reaction) to 1.5 M, the rate becomes:
1.5𝑀 − 0 1.5 𝑀
𝑟𝑎𝑡𝑒 = = = 0.3 𝑀/𝑚𝑖𝑛
5 𝑚𝑖𝑛 5 𝑚𝑖𝑛
On the other hand, if the rate is expressed in terms of a reactant, the equation becomes:
𝐶ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
𝑅𝑎𝑡𝑒 =
𝑡𝑖𝑚𝑒
𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑎𝑡 𝑡𝑖𝑚𝑒 𝑡 − 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
=
𝑡𝑖𝑚𝑒
 [𝐴]𝑡 − [𝐴]𝑜 ∆[𝐴]
= =
𝑡𝑖𝑚𝑒 𝑡𝑖𝑚𝑒
where ∆[𝐴] denotes change in amount of the reactant A in concentration. So, if for the given
example, an initial concentration of the reactant of 3.0 M is observed to decrease to 1.5 M after 5
minutes, the rate of the reaction obtained will be:
1.5 𝑀−3.0 𝑀 −1.5 𝑚
𝑅𝑎𝑡𝑒 = = = −0.3M/min
5 𝑚𝑖𝑛 5 𝑚𝑖𝑛

Note that the rate computed from change in concentration of products is positive (+), while
that from the reactants is negative (-). The (+) and (-) signs indicate the increase in concentration
of the product and the decrease in concentration of the reactant, respectively, that results from the
appearance of products and the disappearance of reactants during a chemical change.
If the rate is expressed in terms of reactant B, do you think you would obtain the same
value as that obtained when the rate is expressed in terms of reactant A?
Note that the stoichiometry of A and B to the product is different. While 1 mole of P needs
1 mole of A, the same amount of P needs 2 moles of B to be formed. So if 3 moles of A and 6
moles of B are used based on stoichiometry, and 1.5 moles of A react after 5 minutes, then 3 moles
of B will also react. The rate of the reaction will be determined as follows:
[𝐵]𝑡 − [𝐵]𝑜 ∆[𝐵] 3 𝑀 − 6𝑀
𝑅𝑎𝑡𝑒 = = = = −0.6 𝑚/𝑚𝑖𝑛
𝑡𝑖𝑚𝑒 𝑡𝑖𝑚𝑒 5𝑚𝑖𝑛
Take note that the rate expressed in terms of B is twice the rate in terms of A.
Using the same sample reaction given in the above discussion, how would you compare
the rate of appearance of the product and the rate of disappearance of reactant A? How do you
think the rate of a reaction is measured in a given system?
One way by which the rate of a reaction can be determined is by comparison of observable
properties of a system that may be correlated to the amount of a reactant consumed or a product.
Examples of such properties are: (1) color change during a reaction, (2) change in intensity of color
of the reactant, (3) formation of an insoluble solid or dissolution of a solid, (4) change in pressure
(in the case of gaseous species reacting in a confined vessel), (5) rate of evolution of a gaseous
product, (6) change in volume, (7) change in ionic property which may be measured in terms of
the conductivity of the solution, (8) change in acidity/basicity of solution by monitoring the change
in pH, and (9) many other properties which could be directly or indirectly related to the quantity
of the substance being measured.
The intensity of the deep blue violet color can be used to monitor the amount or
concentration of the product.
 Factors that Affect Reaction Rates

Nowadays, roofing materials are usually of the repainted type. These roofing materials
have been found to be more resistant to corrosion compared with unpainted roof. Mussel growth
is observed to be faster during the summer season than during the cold season. Metal kettles
corrode more rapidly when used with highly acidic solutions than nonacidic solutions.
How would you explain the above observations? Rates of reactions differ from one another
because they are affected by several factors.
Nature of Reactants
Nowadays, we often commonly find cooking pans that are coated with Teflon 9a polymer)
or porcelain. Why do you think are they used to prepare cooking utensils?
Some reactions occur at a very slow rate that the change cannot be perceived by the naked
eye. On the other hand, some reactions occur at a very fast rate that change is perceived to be
explosive or almost explosive.
Can you imagine how long it took for organic matter to decay and form the fossil fuels that
we use nowadays?
For a reaction to occur, the reactants must absorb a certain amount of energy called the
activation energy, Ea. The activation energy serves as an energy barrier that reactant molecules
must overcome to be converted to the products. The product. The lower the energy barrier, the
easier it is to form the products. Therefore, reactions that involve absorption of small amounts of
energy or have low Ea are fast while reactions that involve absorption of large amounts of energy
or have large Ea are slow.
 The reaction between Mg(s) and water is relatively slow compared with the reaction
between Mg(s) and dilute acid. What does this say about the relative activation energies of the two
reactions?
Effect of Temperature
If the temperature of the reacting system is increased, the reaction can be observed to
proceed faster. In general, if the reaction temperature is increased by 10°C, the reaction becomes
2 or 3 times faster. This observation can be explained by considering the effect of temperature on
the reacting species. According to the kinetic molecular theory, “as the temperature increases, the
average kinetic energy of molecules also increases. “This means that the average molecular
velocities increase which increases the frequency of collisions. Based on the molecular collision
theory, an increase in the frequency of collisions will mean an increase in the probability of
producing effective collisions and result in a faster reaction.
The activation energy, E, which has a constant value for a given set of reactants, is based
on the average energy of the reacting substances. It means that by increasing the temperature, more
reacting molecules attain energies equal to or even higher than the required minimum energy
barrier (E) and cross over the energy barrier. Hence, increasing the temperature of the system
increases the rate of the reaction.
How would you use the principles of chemical kinetics to explain eutrophication?

Figure 9.2 Eutrophication promotes depletion of dissolved oxygen

Effect of Concentration of Reactants
In general, increasing the concentration of reactants increases the reaction rate. The specific
effect of the change in reactant concentration on reaction rate can best be described by the rate
law. A rate law is an equation that expresses the instantaneous rate in terms of the reactant
concentration at that instant.

The Rate Law

Section Objectives From the previous section, you learned that reaction
rate is affected by the nature of reactants and the temperature at
At the end of this
which the reaction occurs. However, aside from these, the
section, you should be able to
reaction rate is also affected by the concentration of the
1. write the mathematical reactants.
relationship between the rate of
a reaction, the rate constant, and At the end of this section, you will learn how to describe
the concentration of the the effect of concentration on reaction rate in terms of a
reactants;
mathematical expression and the symbols associated with it.
2. differentiate zero, first, and You will also learn about the significance of half-life, the term
second-order reactions; used to describe the stability of radionuclides.
3. write the rate law for first
Consider the hypothetical reaction:
order reactions; and

4. discuss the effect of 𝑥 𝐴(𝑔) + 𝑦 𝐵(𝑔) → 𝑑 𝐷(𝑔) + 𝑓 𝐹(𝑔)

concentration on the half-life of
a first-order reaction.
The general rate law expression for the above reaction
is given by:
where
Rate = rate of chemical reaction, based on formation of the products or one of the products,
or rate of disappearance of the reactants or one of the reactants.
k= Specific reaction rate constant, dependent on the kind of reaction and dependent on
temperature.
[A], [B] = molar concentrations of reactants A and B.
x, y= exponents showing the magnitude of the effect of the reactant on the rate of reaction.
The values give the order of the reaction with respect to each reactant and are
determined experimentally.

Sample Problem:
Determine the rate law expression for the hypothetical reaction:
 𝐴(𝑔)+ 3𝐵(𝑔) → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠

From the following data:

Experiment No [A]0’ [M]0, M Initial Rate, M/min
1 0.002 0.002 0.020
2 0.004 0.002 0.080
3 0.002 0.006 0.060

Solution:
First, write a general rate law expression for the reaction:
𝑅𝑎𝑡𝑒 = 𝑘[𝐴]𝑥 [𝐵]𝑦
Where the objective is to get the values of the exponents x and y, and the rate constant, k.

If we compare the results obtained in experiments 1 and 2, the concentration of B is held

constant therefore, the effect of changing the concentration of A can be evaluated. It can be
observed that the rate of the reaction changed from 0.020 to 0.080 or by a factor of 4 when the
concentration of A was doubled. We can thus write:
𝑅𝑎𝑡𝑒 = 𝑘[𝐴]𝑥 [𝐵]𝑦
0.080 0.004 𝑥
=( )
0.020 0.002
4 = (2)𝑥
2 = 𝑥 𝑜𝑟 𝑥 = 2
Thus, the reaction is second order with respect to reactant A.
Comparing the results obtained in experiments 1 and 3 where the concentration of A is held
constant, the rate is observed to be 3 times faster when the concentration of B ss tripled. Therefore:
(0.006/0.002)Y =0.060/0.020
(3)y = 1
Y=1
The reaction is first order with respect to reactant B.
The overall order of the reaction is the sum of the exponents of the reactants, A and B, and
is therefore equal to 3. It means that overall, the reaction is third order.
 Take note that in most instances, the coefficient of a reactant in the balanced chemical
reaction (molecularity) is not equal to the experimentally determined value of the exponents x or
y in the rate law.
We can now solve for the value of the rate constant by substituting the values of x and y
and any set of experimental data in the rate expression. if we substitute the values from experiment
1, we get:
Rate = k [A]x [B]y
0.020 M/min = k (0.002 M)2 (0.002 M)
k = 2.5 x 106 M-2/min
Kinetic Equations
From the rate law, a general expression can be written for the effect or the reactant
concentration on the rate of a one-reactant reaction represented as
.A→Products,
by the equation:
Rate= kn [A]n
where n is the order of the reaction with respect to the reactant. For each type of reaction,
the kinetic equation takes a form that is specific for the order of the reaction.
Zero-Order Reactions, n = 0. A reaction is said to be zero order when the rate of the
reaction is independent of the concentration of the reactants. For this type of reaction, the reaction,
the kinetic equation takes a form that is specific for the order or the reaction. rate law can be written
as:
Rate=ko [A]o
which gives:
Rate =ko
The equation shows that the rate of a zero-order reaction is fixed and has a value equal to
the rate constant. An example of a zero-order reaction is photosynthesis. In photosynthesis, the
amount of biomass produced by a chlorophyll-bearing organism is dependent on the intensity of
light and not on the amount of CO, and HO to which the plant is exposed. In fact, in the absence
of light, photosynthesis does not occur and the photosynthetic plant dies.
First-Order Reaction, n = 1. A reaction is first order if the rate of the reaction varies
directly with the concentration of the reactant. The rate law takes the form:
Rate= k1 [A]
 The equation states that the rate of the reaction increases by the same factor by which the
concentration of the reactant is changed. This is shown by the positive slope of the straight line
that corresponds to the first-order plot in Figure 9.3. This means that if the reactant concentration
is doubled, the rate of the reaction is also doubled.
Second-Order Reactions. Some one-reactant reactions are second order in nature. For this
type of reaction, A Product, the rate law can be written as:
Rate = k2 [A]2
The equation states that the rate of a reaction increases by a factor equal to the square of
the factor concentration is cl n is on rate of reaction is described graphically in Figure 9.3.

Kinetic Equation or a First-Order Reaction

The kinetic equation for the first-order reaction is given by:
[𝐴]𝑜 𝑘1 𝑘1 𝑡
log = 𝑡 𝑜𝑟 log[𝐴]𝑡 = + log[𝐴]0
[𝐴]𝑡 2.303 2.3
where [A]0,is the initial reactant concentration; [A]t is the concentration at time t; k, is the specific
rate constant of first-order reaction with unit 2/time (Example: 1/sec)and t is the time at which [A]t
is measured.
Radioactive disintegrations and decomposition reactions of some plastics are first-order
reactions.
Sample Problem:
A first-order decomposition reaction is observed to be 30.0% complete after 10.0 minutes.
Calculate the rate constant and the time needed for the decomposition reaction to be 75.0%
complete.
Solution:
The reaction is first order, therefore, we use the kinetic equation:
[𝐴]𝑜 𝑘1
log = 𝑡
[𝐴]𝑡 2.303
There is no given initial concentration but the % completion of the reaction is given which
is 30.0%. This means that 70.0%% of the reactant is still unreacted after 10.0 minutes. Ifwe
represent the initial reactant concentration as [A]0, it means that the reactant concentration after
10.0 minutes of reaction is 0.700 [A]0. Substituting the values in the kinetic equation:
[𝐴 ] 𝑜 𝑘1
log = 10.0𝑚𝑖𝑛𝑢𝑡𝑒𝑠
0.7𝑥 [𝐴]0 2.303
 k, = 0.0357 min-1
We now substitute the value of k, in the kinetic equation to solve for the time needed tor
the reaction to be 75.0% complete, at which time the remaining concentration of the reactant is
25% of the initial.
[𝐴]0 0.0357 𝑚𝑖𝑛−1
log = 𝑡
0.25𝑥 [𝐴]0 2.303
Exercise:
If it takes 8.0 minutes for a first-order reaction to go to 25.0% completion, what degree of
completion of reaction will be attained after 15.0 minutes?
Half-life of a Reaction
By definition, the half-life, t1/2, of a reaction is the time required to convert 2 of the reactant
to the product. This means that t = t1/2, when [A]t=1/2 [A]0
Consider a one -reactant, first-order reaction for which the kinetic equation is given by the
equation:
[𝐴]0 𝑘1
log = 𝑡
[𝐴]𝑡 2.303
By definition of half-life:
[𝐴]0 𝑘1
log = 𝑡
1/2[𝐴]𝑡 2.303 1/2
(2.303)(log 2) = (𝑘1 )(𝑘1 )
2
0.693
Therefore, t1/2= 𝑘1

The equation tells us that the concentration of the reactant will not affect the half-life of
one reactant first-order reaction or that the half-life will not be affected by the initial reactant
concentration. This means that the half-life of a first-order reaction is constant. For this reason,
radioactive disintegrations which are first-order reactions are characterized by their half-lives. For
a one-reactant, first-order reaction with a half-lite of 10 seconds, if the initial reactant concentration
is 1 M, the concentration will be reduced to 0.5 M after 10 seconds, and after another 10 seconds,
the concentration will be reduced to 0.25 M. This means that it will take the reaction 20 seconds
for the reactant concentration to be reduced to 4 the initial value.
Reference:

General Chemistry 2 (First Edition)

Authors:
Luciana V. Ilao
Betty M. Lontoc
Edwehna Ellinore S. Paderna-Gayon
Coordinator:
Josefina Gironella-Belen