5.6 Reaction Energy Profile

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College Board AP Chemistry Your notes
5.6 Reaction Energy Profile

Contents
Reaction Energy Profiles
The Arrhenius Equation
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Reaction Energy Profiles

Your notes
Elementary Reactions & Bonds
Collision theory explains some important features of an elementary reaction but does not explain the
role of activation energy
In elementary reactions, the energy from the collision of reactant molecules is used to break bonds
before products are formed
Bond breaking and bond making, in relation to activation energy, are described by the transition state
theory of reaction rate
Transition State Theory
Transition-state theory explains the reaction resulting from the collision of two molecules in terms of an
activated complex
An activated complex is an unstable, high-energy species that must be formed before the
reaction can occur
The transition state describes an intermediate where bonds in the reacting molecules have not been
completely broken and new bonds in products have not completely formed
For example in the reaction between carbon monoxide, CO, and nitrogen dioxide, NO2, the activated
complex is made up of CO and NO2 molecules in close contact
In this activated complex, the N—O bond in the NO2 molecule has been partially broken and a new
bond between carbon and oxygen has started to form
The dotted lines stand for “partial bonds” in the activated complex
Activated Complex
A diagram showing the reaction path involving the formation of activated complex
One advantage of the transition state theory is that it explains why the activation energy of reactions is
much smaller than the energy required to break the bonds in reacting molecules
This is because the formation of an activated complex requires the absorption of relatively little
energy needed to weaken the bonds rather than breaking them
In the reaction above, the activation energy is 134 kJ/mol
This is considerably smaller than the amount of energy required to break the bonds in the
reactants:
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CO ≡ 1075 kJ
N = O 607 kJ
N – O 222 kJ
Your notes
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Energy Profiles
The changes in the energies of the reactants during collision can be described by an energy profile Your notes
This can also be known as a potential energy diagram
Based on the transition state theory, the collision of reactant molecules results in a change in their
kinetic and potential energies
As molecules collide, their kinetic energy is converted to potential energy
After collision, the products formed recoil and the potential energy is reconverted to kinetic
energy
An energy profile plots the changes in potential energy as the reaction proceeds
Energy Profile Diagram
A diagram showing the changes in the energy for the reaction between CO and NO2. During the
reaction initiation, the activation energy (Ea) of 134 kJ must be given to the reactants for every mole of
CO that reacts
From the energy profile diagram for the reaction between CO and NO2 shown above:
The reactants are at a higher energy level than the products, which means the reaction is
exothermic
The overall difference in this potential energy is known as the enthalpy change, ΔH, of the
reaction
When reactants have less energy than products, the reaction is said to be endothermic
The difference between the maximum energy and the energy of the reactant indicates the
activation energy, Ea of the forward reaction
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The top of the activation energy barrier represents the transition state
The chemical species that exists at this transition point is called the activated complex
Your notes
Activation Energy and Reaction Rate
The rate of a reaction is dependent on the magnitude of Ea and not on the enthalpy change
Slow reactions have high activation energy
Fast reactions have low activation energy
This is because, for a slow reaction, relatively few reactants have sufficient kinetic energy for a
successful reaction
There is no way to predict the activation energy of a reaction from its enthalpy change
A highly exothermic reaction may be very slow because it has a high activation energy
On the other hand, an endothermic reaction may be very fast because it has a low activation
energy
The activation energy for the reverse reaction is simply the difference between the potential energy of
products and the maximum energy of the curve
For example, for the reaction between CO and NO2:
Ea (forward) = +134 kJ
ΔH = -226 kJ
Ea (reverse) = 134 -(-226)

Ea (reverse) = 360 kJ
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Your notes
The effect of temperature on reaction rate can be explained in terms of kinetic theory
Increasing temperature greatly increases the fraction of molecules with very high velocity and high
kinetic energies
These molecules are more likely to react on collision and produce enough energy equal to or
greater than the activation energy
Hence, the higher the temperature, the larger the fraction of molecules that can provide the
activation energy required for reaction
Based on the collision model, the rate constant for an elementary reaction was given as
k = p × Z × f (equation 1)
Where:
Z, the collision frequency
f, the fraction of collisions p, the steric factor
The steric factor, p, is presumably temperature-independent
The collision frequency, Z, is relatively insensitive to temperature
For example, when the temperature increases from 500 to 600 K, Z increases by less than 10%
On the other hand, the relationship between the fraction of collisions with energy greater than the
activation energy and temperature has been shown as:
f = e-Ea/RT (equation 2)
Where:
e is a mathematical constant (can be found on your calculator - it has the approximate value of
2.718
Ea is activation energy measured in J/mol
R is the gas constant (8.314 Jmol-1K-1)
T is the absolute temperature in K
A combination of equations 1 and 2 gives the Arrhenius equation, which shows how the rate constant is
dependent on temperature
k = Ae-Ea/RT
Where A is a constant and called the frequency factor
This factor is related to the frequency of collisions, Z and the steric factor, p
In general, as the value of Ea increases, k decreases
This is because the fraction of molecules that possess the required energy is smaller
On taking the natural log of both sides of the Arrhenius equation, the equation becomes:
ln k = ln A - Ea/RT
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A plot of ln k against 1/T gives a straight line with a negative slope:

Arrhenius’s Plot
Your notes
Graph showing the relationship between absolute temperature and the rate constant of a reaction
Exam Tip
Although calculations involving Arrhenius’s equation will not be assessed this year (2024), it is
important to take note of the relationship between rate constant, activation energy and
temperature of a reaction
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5.6 Reaction Energy Profile

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College Board AP Chemistry Your notes

5.6 Reaction Energy Profile

Reaction Energy Profiles

Ea (reverse) = 134 -(-226)

The Arrhenius Equation

A plot of ln k against 1/T gives a straight line with a negative slope:

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