COLLISION THEORY

Learning Objectives
By the end of this section, you will be able to:
• Use the postulates of collision theory to explain the effects of physical state,
temperature, and concentration on reaction rates
• Define the concepts of activation energy and transition state
• Use the Arrhenius equation in calculations relating rate constants to temperature
We should not be surprised that atoms, molecules, or ions must collide before they can react with
each other. Atoms must be close together to form chemical bonds. This simple premise is the
basis for a very powerful theory that explains many observations regarding chemical kinetics,
including factors affecting reaction rates.
Collision theory is based on the following postulates:
1. The rate of a reaction is proportional to the rate of reactant collisions: Reaction rate ∝
rate of reactants collisions
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑐𝑜𝑙𝑙𝑖𝑠𝑖𝑜𝑛 Equation 1
𝑟𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 ∝
𝑡𝑖𝑚𝑒

2. The reacting species must collide in an orientation that allows contact between the atoms
that will become bonded
3. The collision must occur with adequate energy to permit mutual penetration of the
reacting species’ valence shells so that the electrons can rearrange and form new bonds
(and new chemical species).
We can see the importance of the two physical factors noted in postulates 2 and 3, the
orientation and energy of collisions, when we consider the reaction of carbon monoxide with
oxygen:
2CO(g)+O2(g) ⟶ 2CO2(g)
Carbon monoxide is a pollutant produced by the combustion of hydrocarbon fuels. To reduce this
pollutant, automobiles have catalytic converters that use a catalyst to carry out this reaction. It
is also a side reaction of the combustion of gunpowder that results in muzzle flash for many
firearms. If carbon monoxide and oxygen are present in sufficient quantity, the reaction is
spontaneous at high temperature and pressure.
The first step in the gas-phase reaction between carbon monoxide and oxygen is a collision
between the two molecules:
CO(g)+O2(g) ⟶ CO2(g)+O(g)

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Although there are many different possible orientations the two molecules can have relative to
each other, consider the two presented in Figure 1–1. In the first case, the oxygen side of the
carbon monoxide molecule collides with the oxygen molecule. In the second case, the carbon side
of the carbon monoxide molecule collides with the oxygen molecule. The second case is clearly
more likely to result in the formation of carbon dioxide, which has a central carbon atom bonded
to two oxygen atoms (O=C=O). This is a rather simple example of how important the orientation
of the collision is in terms of creating the desired product of the reaction.
Figure 1–1: Illustrated are two collisions that might take
place between carbon monoxide and oxygen molecules.
The orientation of the colliding molecules partially
determines whether a reaction between the two
molecules will occur.

If the collision does take place with the correct orientation, there is still no guarantee that the
reaction will proceed to form carbon dioxide. Every reaction requires a certain amount of
activation energy for it to proceed in the forward direction, yielding an appropriate activated
complex along the way. As Figure 1–2 demonstrates, even a collision with the correct orientation
can fail to form the reaction product. In the study of reaction mechanisms, each of these three
arrangements of atoms is called a proposed activated complex or transition state.

Figure 1–2: Possible transition states (activated complexes) for carbon monoxide reacting with
oxygen to form carbon dioxide. Solid lines represent covalent
bonds, while dotted lines represent unstable orbital overlaps that
may, or may not; become covalent bonds as product is formed. In
the first two examples in this figure, the O=O double bond is not
impacted; therefore, carbon dioxide cannot form. The third
proposed transition state will result in the formation of carbon
dioxide if the third “extra” oxygen atom separates from the rest
of the molecule.

In most circumstances, it is impossible to isolate or identify a transition state or activated

complex. In the reaction between carbon monoxide and oxygen to form carbon dioxide, activated
complexes have only been observed spectroscopically in systems that utilize a heterogeneous
catalyst. The gas-phase reaction occurs too rapidly to isolate any such chemical compound.
Collision theory explains why most reaction rates increase as concentrations increase. With an
increase in the concentration of any reacting substance, the chances for collisions between
molecules are increased because there are more molecules per unit of volume. More collisions
mean a faster reaction rate, assuming the energy of the collisions is adequate.

ACTIVATION ENERGY AND THE ARRHENIUS EQUATION

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The minimum energy necessary to form a product during a collision between reactants is called
the activation energy (Ea). The kinetic energy of reactant molecules plays an important role in a
reaction because the energy necessary to form a product is provided by a collision of a reactant
molecule with another reactant molecule. (In single-reactant reactions, activation energy may be
provided by a collision of the reactant molecule with the wall of the reaction vessel or with
molecules of an inert contaminant.) If the activation energy is much larger than the average
kinetic energy of the molecules, the reaction will occur slowly: Only a few fast-moving molecules
will have enough energy to react. If the activation energy is much smaller than the average
kinetic energy of the molecules, the fraction of molecules possessing the necessary kinetic
energy will be large; most collisions between molecules will result in reaction, and the reaction will
occur rapidly.
Figure 1–3 shows the energy relationships for the general reaction of a molecule of A with a
molecule of B to form molecules of C and D:
A+B⟶C+D
The figure shows that the energy of the transition state is higher than that of the
reactants A and B by an amount equal to Ea, the activation energy. Thus, the sum of the kinetic
energies of A and B must be equal to or greater than Ea to reach the transition state. After the
transition state has been reached, and as C and D begin to form, the system loses energy until its
total energy is lower than that of the initial mixture. This lost energy is transferred to other
molecules, giving them enough energy to reach the transition state. The forward reaction (that
between molecules A and B) therefore tends to take place readily once the reaction has started.
In Figure 1–3, ΔH represents the difference in enthalpy between the reactants (A and B) and the
products (C and D). The sum of Ea and ΔH represents the activation energy for the reverse
reaction:
C+D⟶A+B

Figure 1–3: This graph shows the potential energy

relationships for the reaction A + B⟶C + D. The
dashed portion of the curve represents the energy of
the system with a molecule of A and a molecule
of B present, and the solid portion the energy of the
system with a molecule of C and a molecule
of D present. The activation energy for the forward
reaction is represented by Ea. The activation energy
for the reverse reaction is greater than that for the
forward reaction by an amount equal to ΔH. The
curve’s peak is represented the transition state

We can use the Arrhenius equation to relate the activation energy and the rate constant, k, of
a given reaction:
𝐾 = 𝐴𝑒 𝐸𝑎⁄𝑅𝑇 Equation 2

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In this equation, R is the ideal gas constant, which has a value 8.314 J/mol/K, T is temperature on
the Kelvin scale, Ea is the activation energy in joules per mole, e is the constant 2.7183, and A is a
constant called the frequency factor, which is related to the frequency of collisions and the
orientation of the reacting molecules.
Both postulates of the collision theory of reaction rates are accommodated in the Arrhenius
equation. The frequency factor A is related to the rate at which collisions having the
correct orientation occur. The exponential term, e−Ea/RT, is related to the fraction of collisions
providing adequate energy to overcome the activation barrier of the reaction.
At one extreme, the system does not contain enough energy for collisions to overcome the
activation barrier. In such cases, no reaction occurs. At the other extreme, the system has so
much energy that every collision with the correct orientation can overcome the activation
barrier, causing the reaction to proceed. In such cases, the reaction is nearly instantaneous.
The Arrhenius equation describes quantitatively much of what we have already discussed about
reaction rates. For two reactions at the same temperature, the reaction with the higher
activation energy has the lower rate constant and the slower rate. The larger value of Ea results
in a smaller value for e−Ea/RT, reflecting the smaller fraction of molecules with enough energy to
react. Alternatively, the reaction with the smaller Ea has a larger fraction of molecules with
enough energy to react. This will be reflected as a larger value of e−Ea/RT, a larger rate constant,
and a faster rate for the reaction. An increase in temperature has the same effect as a decrease
in activation energy. A larger fraction of molecules has the necessary energy to react (Figure 1–
4), as indicated by an increase in the value of e−Ea/RT. The rate constant is also directly
proportional to the frequency factor, A. Hence a change in conditions or reactants that increases
the number of collisions with a favorable orientation for reaction results in an increase in A and,
consequently, an increase in k.

Figure 1–4. (a) As the activation energy of a reaction decreases, the number of molecules with at
least this much energy increases, as shown by the shaded areas. (b) At a higher temperature, T2,
more molecules have kinetic energies greater than Ea, as shown by the yellow shaded area.

A convenient approach to determining Ea for a reaction involves the measurement of k at

different temperatures and using of an alternate version of the Arrhenius equation that takes
the form of linear equation:
−𝐸𝑎 1 Equation 3
𝑙𝑛𝑘 = ( ) ( ) + ln 𝐴
𝑅 𝑇

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Thus, a plot of ln k versus 1/T gives a straight line with the slope −Ea/R, from which Ea may be
determined. The intercept gives the value of ln A.
Example 1
Determination of Ea
The variation of the rate constant with temperature for the decomposition of HI(g) to H2(g) and
I2(g) is given here. What is the activation energy for the reaction?
2HI(g)⟶H2(g)+I2(g)
Table 1-1
T (K) k (L/mol/s)
555 3.52 × 10−7
575 1.22 × 10−6
645 8.59 × 10−5
700 1.16 × 10−3
781 3.95 × 10−2
Solution
Values of 1/T and ln k are:
Table 1-2
1/T(K−1) ln k
1.80 × 10−3 −14.860
1.74 × 10−3 −13.617
1.55 × 10−3 −9.362
1.43 × 10−3 −6.759
1.28 × 10−3 −3.231

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Figure 1–5 is a graph of ln k versus 1T1T. To determine the slope of the line, we need two values
of ln k, which are determined from the line at two values of 1/T (one near each end of the line is
preferable). For example, the value of ln k determined from the line when 1/T=1.25×10−3 is −2.593;
the value when 1/T=1.78×10−3 is −14.447.

Figure 1–5. This graph shows the

linear relationship between
ln k and 1/T for the reaction 2H
I⟶ H2 + I2 according to the
Arrhenius equation.

The slope of this line is given by the following expression:

𝛥(𝑙𝑛𝑘) Equation 4
𝑆𝑙𝑜𝑝𝑒 =
1
𝛥(𝑇)

(−14.447) − (−2.593) Equation 5

=
(1.78𝑥 20−3 𝐾 −1 ) − (1.25𝑥 20−3 𝐾 −1 )

=
−11.854
= 2.2 𝑥 104 Equation 6
0.53 𝑥 10−3 𝐾−1

𝐸𝑎 = −𝑆𝑙𝑜𝑝𝑒 𝑥 𝑅 = −2.2𝑥 204 𝐾 −1 𝑥 8.314 𝐽 𝑚𝑜𝑙 −1 𝐾 −1 Equation 7

𝐸𝑎 = 1.8 𝐽 𝑚𝑜𝑙 −1 Equation 8

In many situations, it is possible to obtain a reasonable estimate of the activation energy without
going through the entire process of constructing the Arrhenius plot. The Arrhenius equation
(Equation 1):
can be rearranged as shown to give:
Equation 9
𝐸𝑎 𝛥𝑙𝑛𝑘
− = ( )
𝑅 1
𝛥(𝑇)
Or
𝑘1 𝐸𝑎 1 1 Equation 10
𝑙𝑛
= ( )( − )
𝑘2 𝑅 𝑇2 𝑇1
This equation can be rearranged to give a one-step calculation to obtain an estimate for the
activation energy:
Equation 11
𝑙𝑛𝑘2 − 𝑙𝑛𝑘2
𝐸𝑎 = −𝑅 ( )
1 1
−
𝑇2 𝑇1

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Using the experimental data presented here, we can simply select two data entries. For this
example, we select the first entry and the last entry:

Table 1-3

T (K) k (L/mol/s) 1/T(K−1) ln k

555 3.52 × 10−7 1.80 × 10−3 −14.860

781 3.95 × 10−2 1.28 × 10−3 −3.231

Calculate 1/T and ln k, the substitute into the Equation 11:

8.314𝐽 −3.231 − (−14.866) Equation 12
𝐸𝑎 = − ( )
𝑚𝑜𝑙 𝐾 1.28 𝑥 10−3 𝐾 −1 − 1.8 𝑥 10−3 𝐾 −1
Which gives Ea = 185,900 J/mol.
This method is very effective, especially when a limited number of temperature-dependent rate
constants are available for the reaction of interest.
Solve: The rate constant for the rate of decomposition of N2O5 to NO and O2 in the gas phase is
1.66 L/mol/s at 650 K and 7.39 L/mol/s at 700 K:
2N2O5(g) ⟶ 4NO(g)+3O2(g)
Assuming the kinetics of this reaction are consistent with the Arrhenius equation, calculate the
activation energy for this decomposition.
Answer: 113,000 J/mol

SUMMARY
Chemical reactions require collisions between reactant species. These reactant collisions must be
of proper orientation and sufficient energy in order to result in product formation. Collision
theory provides a simple but effective explanation for the effect of many experimental
parameters on reaction rates. The Arrhenius equation describes the relation between a reaction’s
rate constant and its activation energy, temperature, and dependence on collision orientation.

KEY EQUATIONS
𝐾 = 𝐴𝑒 𝐸𝑎⁄𝑅𝑇

−𝐸𝑎 1
𝑙𝑛𝑘 = ( ) ( ) + ln 𝐴
𝑅 𝑇
𝑘1 𝐸𝑎 1 1
𝑙𝑛 = ( )( − )
𝑘2 𝑅 𝑇2 𝑇1

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Definitions
activated complex
(also, transition state) unstable combination of reactant species representing the highest
energy state of a reaction system
activation energy (Ea)
energy necessary in order for a reaction to take place
Arrhenius equation
mathematical relationship between the rate constant and the activation energy of a
reaction
collision theory
model that emphasizes the energy and orientation of molecular collisions to explain and
predict reaction kinetics
frequency factor (A)
proportionality constant in the Arrhenius equation, related to the relative number of
collisions having an orientation capable of leading to product formation

Exercises
1. Chemical reactions occur when reactants collide. What are two factors that may prevent a
collision from producing a chemical reaction?
2. When every collision between reactants leads to a reaction, what determines the rate at
which the reaction occurs?
3. What is the activation energy of a reaction, and how is this energy related to the
activated complex of the reaction?
4. Account for the relationship between the rate of a reaction and its activation energy.
5. Describe how graphical methods can be used to determine the activation energy of a
reaction from a series of data that includes the rate of reaction at varying temperatures.
6. How does an increase in temperature affect rate of reaction? Explain this effect in terms
of the collision theory of the reaction rate.
7. The rate of a certain reaction doubles for every 10 °C rise in temperature.
(a) How much faster does the reaction proceed at 45 °C than at 25 °C?
(b) How much faster does the reaction proceed at 95 °C than at 25 °C?
8. In an experiment, a sample of NaClO3 was 90% decomposed in 48 min. Approximately how
long would this decomposition have taken if the sample had been heated 20 °C higher?
9. The rate constant at 325 °C for the decomposition reaction C4H8⟶2C2H4C4H8⟶2C2H4 is
6.1 × 10−8 s−1, and the activation energy is 261 kJ per mole of C4H8. Determine the frequency
factor for the reaction.
10. The rate constant for the decomposition of acetaldehyde, CH3CHO, to methane, CH4, and
carbon monoxide, CO, in the gas phase is 1.1 × 10−2 L/mol/s at 703 K and 4.95 L/mol/s at
865 K. Determine the activation energy for this decomposition.
11. An elevated level of the enzyme alkaline phosphatase (ALP) in the serum is an indication
of possible liver or bone disorder. The level of serum ALP is so low that it is very difficult
to measure directly. However, ALP catalyzes a number of reactions, and its relative
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 concentration can be determined by measuring the rate of one of these reactions under
controlled conditions. One such reaction is the conversion of p-nitrophenyl phosphate
(PNPP) to p-nitrophenoxide ion (PNP) and phosphate ion. Control of temperature during
the test is very important; the rate of the reaction increases 1.47 times if the
temperature changes from 30 °C to 37 °C. What is the activation energy for the ALP–
catalyzed conversion of PNPP to PNP and phosphate?
12. In terms of collision theory, to which of the following is the rate of a chemical reaction
proportional?
(a) the change in free energy per second
(b) the change in temperature per second
(c) the number of collisions per second
(d) the number of product molecules
13. Hydrogen iodide, HI, decomposes in the gas phase to produce hydrogen, H2, and iodine, I2.
The value of the rate constant, k, for the reaction was measured at several different
temperatures and the data are shown here:
Table 1-4
Temperature (K) k (M−1 s−1)
555 6.23 × 10−7
575 2.42 × 10−6
645 1.44 × 10−4
700 2.01 × 10−3

14. What is the value of the activation energy (in kJ/mol) for this reaction?
15. The element Co exists in two oxidation states, Co(II) and Co(III), and the ions form many
complexes. The rate at which one of the complexes of Co(III) was reduced by Fe(II) in
water was measured. Determine the activation energy of the reaction from the following
data:

Table 1-5

T (K) k (s−1)

293 0.054

298 0.100

16. The hydrolysis of the sugar sucrose to the sugars glucose and fructose,
C12H22O11 + H2O ⟶ C6H12O6 + C6H12O6

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follows a first-order rate equation for the disappearance of sucrose: Rate = k[C12H22O11] (The
products of the reaction, glucose and fructose, have the same molecular formulas but differ in
the arrangement of the atoms in their molecules.)
(a) In neutral solution, k = 2.1 × 10−11 s−1 at 27 °C and 8.5 × 10−11 s−1 at 37 °C. Determine the activation
energy, the frequency factor, and the rate constant for this equation at 47 °C (assuming the
kinetics remain consistent with the Arrhenius equation at this temperature).
(b) When a solution of sucrose with an initial concentration of 0.150 M reaches equilibrium, the
concentration of sucrose is 1.65 × 10−7M. How long will it take the solution to reach equilibrium at
27 °C in the absence of a catalyst? Because the concentration of sucrose at equilibrium is so low,
assume that the reaction is irreversible.
(c) Why does assuming that the reaction is irreversible simplify the calculation in part (b)?

Solutions to Exercises
1. The reactants either may be moving too slowly to have enough kinetic energy to exceed the
activation energy for the reaction, or the orientation of the molecules when they collide may
prevent the reaction from occurring.
3. The activation energy is the minimum amount of energy necessary to form the activated
complex in a reaction. It is usually expressed as the energy necessary to form one mole of
activated complex.
5. After finding k at several different temperatures, a plot of ln k versus 1/T, gives a straight line
with the slope −EaR from which Ea may be determined.
7. (a) 4-times faster (b) 128-times faster
9. 3.9×1015s−1
11. 43.0 kJ/mol
13. 177 kJ/mol
15. Ea = 108 kJ
A = 2.0 × 108 s−1
k = 3.2 × 10−10 s−1
(b) 1.81 × 108 h or 7.6 × 106 day. (c) Assuming that the reaction is irreversible simplifies the
calculation because we do not have to account for any reactant that, having been converted to
product, returns to the original state.

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