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CH 1001 - Chemical Kinetics l4

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13 views12 pages

CH 1001 - Chemical Kinetics l4

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Collin mirisi
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© © All Rights Reserved
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INTRODUCTORY CHEMISTRY I

CH 1001

LECTURE 4: CH E MI CAL KIN ET IC S


➢ Reaction Mechanisms
Reaction Mechanisms
Reaction Mechanism
The sequence of events that describes the actual process by
which reactants become products is called the reaction
mechanism.
• Reactions may occur all at once or through several
steps.

• Each of these processes is known as an elementary


reaction or elementary process.
Elementary Steps
For example, the overall reaction:

2A + B → C + D

may involve the following elementary steps in its mechanism:

Step-1: A + B → X;

Step-2: X + A → Y;

Step-3: Y→C+ D

Overall reaction: 2A + B → C + D;
Reaction Intermediates
Intermediates are species that appear in a reaction mechanism
but not in the overall balanced equation.

An intermediate is always formed in an early elementary step


and consumed in a later elementary step.

Elementary step: NO + NO N2O2


+ Elementary step: N2O2 + O2 2NO2
Overall reaction: 2NO + O2 2NO2
Molecularity in Elementary Steps

Molecularity is the number of molecular species that


react in an elementary process.
Rate Law for Elementary Processes:
Elementary Reactions Molecularity Rate Law
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯
A → product Unimolecular Rate = k[A]
2A → product Bimolecular Rate = k[A]2
A + B → product Bimolecular Rate = k[A][B]
2A + B → product Termolecular Rate = k[A]2[B]
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯
⎯
Requirements for Reaction Mechanism
• The sum of the elementary steps must give
the overall balanced equation for the
reaction.
• The rate-determining step should predict
the same rate law that is determined
experimentally.
The rate-determining step is the slowest step in
the sequence of steps leading to product formation.
Example: Decomposition of N2O5

2N2O5(g) → 4NO2(g) + O2(g)

Step 1: N2O5 ⇌ NO2 + NO3 (fast)

Step 2: NO2 + NO3 → NO + O2 + NO2 (slow)

Step 3: NO3 + NO → 2NO2 (fast)


Example: Slow Initial Step
A proposed mechanism for this reaction is

Step 1: NO2 + NO2 ⎯⎯→ NO3 + NO (slow)

Step 2: NO3 + CO ⎯⎯→ NO2 + CO2 (fast)

The NO3 intermediate is consumed in the second step.

As CO is not involved in the slow, rate-determining


step, it does not appear in the rate law.
Example: Slow Initial Step

NO2(g) + CO(g) ⎯⎯→ NO(g) + CO2(g)

The rate law for this reaction is found experimentally to


be

Rate = k[CO]

NO2 is necessary for this reaction to occur, but it is an


intermediate, so its not part of the rate law of the
reaction .

This suggests that the reaction occurs in two steps.


Activation Energy and Temperature
effects on Reaction Rate

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