CHE 490: Special Topics in CHE

Computational Catalysis
Lecture#4: Reaction Energies (1)

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General Information
• Homework#1 is due next Wednesday
• Today’s lecture is covered in Chapter 2 of the book “Fundamental
Concepts in Heterogeneous Catalysis”
• Quiz#1 is September 15

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Summary of the previous Lecture
• Overall chemical reaction is the summation of basic elementary steps
• Each elementary step described a maximum of one chemical bond
being created or broken
• Adsorption is typically the first step in a catalytic process
• Adsorption is classified into a physi-sorption and chemi-sorption

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Summary of the previous Lecture
• Ammonia synthesis Overall reaction
• N2 + 3H2 à 2NH3
• Elementary steps:
• N2(g) + * à N2* (adsorption)
• N2* + * à N*+N* (dissociation)
• H2(g) + * à H2* (adsorption) (repeated 3 times)
• H2* + * à H*+H* (dissociation) (repeated 3 times)
• N*+H* à NH* + * (association) (repeated 2 times)
• NH*+H* à NH2* + * (association) (repeated 2 times)
• NH2*+* à NH3* + * (association) (repeated 2 times)
• NH3*+* à NH3(g) + 2* (association) (repeated 2 times)

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Summary of the previous Lecture
• What are the elementary steps in the following two reactions?

• 2 NH3 + 5/2 O2 à 2 NO + 3 H2O

• CH3OH + 2 O2 à 2 H2O + CO2

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Lecture Outline
• Reaction energy
• Exothermic vs. Endothermic reactions
• Activation barrier

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Reaction Energy
• Reaction energy is the difference

Initial State (reactants)

in energy between the initial
state (IS) and final state (FS)

Final State (products)

ΔE = E!" − E#"

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Reaction Energy
• Reaction energy is the difference in energy between the initial state (IS) and final
state (FS)
ΔE = E!" − E#"

• Example:
• Assume the following chemical reaction: A + B à AB
• The initial state is (A+B)
• The final state is (AB)
ΔE = E!" − E! − E"

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Reaction Energy
• The sign of the reaction energy
(ΔE) determines the type of
reaction:

Initial State
• ΔE > 0 (endothermic reaction)
• ΔE < 0 (exothermic reaction)

Final State
• What is the difference between
an exothermic and an
endothermic reaction?

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Reaction Energy
• What is an example of an
exothermic reaction?

Initial State
• What is an example of an
endothermic reaction?

Final State
• Is it more desirable to have an
endothermic or an exothermic
reaction?

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Reaction Energy: Examples
• Exothermic reactions:
• CH4 + 2 O2 à CO2 + 2H2O (ΔE = -891 kJ/mol)
• C2H6 + 7/2 O2 à 2CO2 + 3H2O (ΔE = -1561 kJ/mol)

• Endothermic reactions:
• H2S à H2 + 1/2 S2

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Activation barrier
• Activation barrier (Ea): Transition State (TS)

• Ea = ETS – EIS

where ETS is the energy of the

transition state

• Example:
• N2* + * à N-N* + * à N* + N*
• Ea = EN-N* – EN2*

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Activation barrier
• Activation barrier (Ea): Transition State (TS)
• Ea = ETS – EIS

where ETS is the energy of the

transition state

• Example:
• N2* + * à N-N* + * à N* + N*
• Ea = EN-N* – EN2*

What is the energy of the reverse

reaction?
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Activation barrier
• What is a reasonable activation Transition State (TS)

barrier?
(!
Rate = v exp(− ) * ), where:
"
• v : rate constant
• kB: Boltzman constant
• T: Temperature

v is typically 1013 s-1

kBT is around 0.025 eV at 300 K

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Activation barrier
• What is a reasonable activation Transition State (TS)
barrier?
!
Rate = v exp(− " !#), where:
"

v is typically 1013 s-1

kBT is around 0.025 eV at 300 K

1. Which actiation energy gives k = 1

s-1 at 300K?
2. What temperature will a process
with Ea= 2 eV have k = 1 s-1?
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Summary
• Reaction energy is the energy difference between the final state and
the initial state
• Reaction can be either exothermic or endothermic
• Activation barrier is the energy difference between the transition
state and the initial state

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Next Lecture
• Role of entropy in the chemical reaction
• Gibbs free energy

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