Learning Activity Sheet

GENERAL CHEMISTRY 2 Week 7A: Introduction to Reaction Kinetics

EXPLORE
The rusting of iron and burning candle are both chemical reactions, however, burning occurs almost
simultaneously unlike rusting that takes a significantly longer. What factors affect chemical reaction rates?

LEARN
Reaction Kinetics

Reaction kinetics is the study of the rate of chemical reactions. Kinetic studies are important in understanding
reactions, and they also have practical implications. For example, in industry, reactions are conducted in reactors in
which compounds are mixed together, possibly heated and stirred for a while, and then moved to the next phase of
the process. It is important to know how long to hold the reaction at one stage before moving on, to make sure that
reaction has finished before starting the next one. By understanding how a reaction takes place, many processes can
be improved. For example, if it is known that a particular intermediate is involved in a reaction, the use of conditions
(such as certain solvents) that are incompatible with that intermediate might be avoided. In addition, reagents might
be added that would make certain steps in the reaction happen more easily. Not only are kinetic studies important in
industry, but they are also used to understand biological processes, especially enzyme-catalyzed reactions. They also
play a role in environmental and atmospheric chemistry, as part of an effort to understand a variety of issues ranging
from the fate of prescription pharmaceuticals in wastewater to the cascade of reactions involved in the ozone cycle.

Collision Theory

Collision theory explains why different reactions occur at different rates, and suggests ways to change the rate
of a reaction. Collision theory states that for a chemical reaction to occur, the reacting particles must collide with one
another. The rate of the reaction depends on the frequency of collisions. The theory also tells us that reacting particles
often collide without reacting. For collisions to be successful, the following conditions must be met:

1) the reactants must collide

This rule is fundamental to any analysis of an ordinary reaction mechanism. It explains why termolecular
(simultaneous collision of three atoms, molecules or ions) processes are so uncommon. The kinetic theory of gases
states that for every 1000 binary collisions, there will be only one event in which three molecules simultaneously come
together. Four-way collisions are so improbable that this process has never been demonstrated in an elementary
reaction. Consider a simple bimolecular step:
A + B  Products
If the two molecules A and B are to react, they must approach closely enough to disrupt some of their existing
bonds and to permit the creation of any new ones that are needed in the products. Such an encounter is called a
collision.
The frequency of collisions between A and B in a gas is proportional to the concentration of each; if [A] is
doubled, the frequency of A-B collisions will double, and doubling [B] will have the same effect. If all collisions lead to
products, then the rate of a bimolecular process is first-order in A and in B, or second-order overall:
rate = k [A][B]
Note: [A], [B] –concentration of A, B; k – rate constant

2) the collision must be energetic enough

For a gas at room temperature and normal atmospheric pressure, there are about 10 33 collisions in each cubic
centimeter of space every second. If every collision between two reactant molecules yielded products, all reactions
would be complete in a fraction of a second. For example, when two billiard balls collide, they simply bounce off of
each other. This is the most likely outcome if the reaction between A and B requires a significant disruption or
rearrangement of the bonds between their atoms. In order to effectively initiate a reaction, collisions must be
sufficiently energetic (or have sufficient kinetic energy) to bring about this bond disruption.
3) the collision must occur at correct orientation
There is often one additional requirement. In many reactions, especially those involving more complex
molecules, the reacting species must be oriented in a manner that is appropriate for the particular process. For
example, in the gas-phase reaction of dinitrogen oxide with nitric oxide, the oxygen end of N2O must hit the nitrogen
end of NO; altering the orientation of either molecule prevents the reaction. Owing to the extensive randomization of
molecular motions in a gas or liquid, there are always enough correctly-oriented molecules for some of the molecules
to react. However, the more critical this orientational requirement is, the fewer collisions will be effective.

Factors that Affect Reaction Rate

1. Reactant concentration - Increasing the concentration of one or more reactants will often increase the rate
of reaction. This occurs because a higher concentration of a reactant will lead to more collisions of that reactant in a
specific time period.
2. Physical state of the reactants and surface area - If reactant molecules exist in different phases, as in a
heterogeneous mixture, the rate of reaction will be limited by the surface area of the phases that are in contact. For
example, if a solid metal reactant and gas reactant are mixed, only the molecules present on the surface of the metal
are able to collide with the gas molecules. Therefore, increasing the surface area of the metal by pounding it flat or
cutting it into many pieces will increase its reaction rate.
3. Temperature - An increase in temperature typically increases the rate of reaction. An increase in
temperature will raise the average kinetic energy of the reactant molecules. Therefore, a greater proportion of
molecules will have the minimum energy necessary for an effective collision
4. Presence of catalysts - A catalyst is a substance that accelerates a reaction by participating in it without
being consumed. Catalysts provide an alternate reaction pathway to obtain products. They are critical to many
biochemical reactions.

Defining Reaction Rate

The Reaction Rate for a given chemical reaction is the measure of the change in concentration of the reactants
or the change in concentration of the products per unit time. The speed of a chemical reaction may be defined as the
change in concentration of a substance divided by the time interval during which this change is observed:
𝛥[𝑋]
rate =
𝑑𝑡
For a reaction of the form A+B→C , the rate can be expressed in terms of the change in concentration of any
of its components
𝛥[𝐴]
rate = −
𝛥𝑡
𝛥[𝐵]
rate = −
𝛥𝑡
𝛥[𝐶]
rate =
𝛥𝑡

in which 𝛥[𝐴] is the difference between the concentration of A over the time interval t2–t1.
𝛥[𝐴] = [A2]-[A1]
Calculating Reaction Rates

For the stoichiometrically complicated reaction:

aA + bB  cC + dD
The reaction rate is:

−1 𝛥[𝐴] −1 𝛥[𝐵] 1 𝛥[𝐶] 1 𝛥[𝐷]

R= = = =
𝑎 𝛥𝑡 𝑏 𝛥𝑡 𝑐 𝛥𝑡 𝑑 𝛥𝑡

where a, b, c, d = coefficients of A, B, C, D, respectively

𝛥[𝐴] 𝛥[𝐵] 𝛥[𝐶] 𝛥[𝐷]
, , , = the rate at which the reaction/product is being consumed/formed
𝛥𝑡 𝛥𝑡 𝛥𝑡 𝛥𝑡

Notice that the equation will reduce to

𝛥[𝐴] 𝛥[𝐵] 𝛥[𝐶] 𝛥[𝐷]
R=− =− = =
𝛥𝑡 𝛥𝑡 𝛥𝑡 𝛥𝑡

If the coefficients are equal (that is, if a=b=c=d=1). This is the form of the equation that was presented in the definition
of reaction rate. However, the more general expression for reaction rate is

−1 𝛥[𝐴] −1 𝛥[𝐵] 1 𝛥[𝐶] 1 𝛥[𝐷]

R= = = =
𝑎 𝛥𝑡 𝑏 𝛥𝑡 𝑐 𝛥𝑡 𝑑 𝛥𝑡
Consider the reaction below:
A + 2B  2 D

We can from the equation that B is consumed twice as fast as A:

−1 𝛥[𝐴] −1 𝛥[𝐵]
=
𝑎 𝛥𝑡 𝑏 𝛥𝑡

1 𝛥[𝐴] 1 𝛥[𝐵]
=
1 𝛥𝑡 2 𝛥𝑡

𝛥[𝐴] 𝛥[𝐵]
2 =
𝛥𝑡 𝛥𝑡

On the other hand, B is consumed at the same rate as D is formed:

−1 𝛥[𝐵] 1 𝛥[𝐷]
=
𝑏 𝛥𝑡 𝑑 𝛥𝑡

−1 𝛥[𝐵] 1 𝛥[𝐷]
=
2 𝛥𝑡 2 𝛥𝑡

𝛥[𝐵] 𝛥[𝐷]
− =
𝛥𝑡 𝛥𝑡

Notice that rate can be measured in terms of either reactant (A or B) or either product (C or D). Not all variables
are needed to solve for the rate. Therefore, if you have the value for "A" as well as the value for "a" you can solve for
the reaction rate. Moreover, since [A] and [B] decrease over time (they are consumed since they are the reactants),
they are both negative rates. The minus sign for A and B ensures that we always get a positive reaction rate. Finally,
chemical reactions vary greatly in the speed at which they occur. Some are ultrafast, while others may take millions of
years to reach equilibrium (at this point, reactant consumption rate = product formation rate = constant).
Example:
For the oxidation of ammonia
4NH3 + 3O2  2N2 + 6H2O

it was found that the rate of formation of N 2 was 0.27 mol/L-s or Molar/s (or M/s).

a. At what rate was water being formed?

b. At what rate was ammonia being consumed?

Solution:
a. Since we know the rate of formation of N2, we will use this as our reference:
1 𝛥[N2 ] 1 𝛥[𝐻2 𝑂]
=
2 𝛥𝑡 6 𝛥𝑡

1 1 𝛥[𝐻2 𝑂]
(0.27 M/s) =
2 6 𝛥𝑡

6 𝛥[𝐻2 𝑂]
(0.27 M/s) =
2 𝛥𝑡

𝛥[𝐻2 𝑂]
= 𝟎. 𝟖𝟏 𝑴/𝒔
𝛥𝑡
𝛥[𝐻2 𝑂]
b. For the rate of consumption of ammonia, we can use either of the known rates, we’ll use
𝛥𝑡

1 𝛥[NH3 ] 1 𝛥[𝐻2 𝑂]
− =
4 𝛥𝑡 6 𝛥𝑡

𝛥[NH3 ] 4 𝛥[𝐻2 𝑂]
=−
𝛥𝑡 6 𝛥𝑡
𝛥[NH3 ] 4 0.81𝑀
= ( ) = − 𝟎. 𝟓𝟒 𝐌/𝐬
𝛥𝑡 6 𝑠

Observe how the reaction rate becomes positive using the rate of disappearance of [NH3 ]:

1 𝛥[NH3 ] 1 𝑀
R=− = − (−0.54 ) = 0.135 𝑀/𝑠
4 𝛥𝑡 4 𝑠

Observe also that we will arrive at the same reaction rate if I use the formation rate of H 2O:4

1 𝛥[𝐻2 𝑂] 1 𝑀
R= = (0.81 ) = 0.135 𝑀/𝑠
6 𝛥𝑡 6 𝑠

Application
Answer the following practice questions. Compare and discuss your answers with your classmates’.

For the reaction: 2A + B  2C + D

1. Write the equation for the reaction rate showing all the variables involved.

2. Find the rate of formation of A and the reaction rate given ∆[𝑨]= -𝟎.𝟎𝟎𝟐 𝑴 𝒂𝒏𝒅 ∆𝒕=𝟕𝟕𝒔