KEY

Name: ___________________________________________________________ Period: _________

Lecture 28
Reaction Mechanisms (AP Chemistry Topic 5.4, 5.7, 5.8, 5.9)
Student Notes

Enduring Understanding Learning Objective(s)

• There is a relationship between the speed of a • Represent an elementary reaction as a rate law
reaction and the collision frequency of particle expression using stoichiometry
collisions. • Identify the rate law for a reaction from a
• Many chemical reactions occur through a series of mechanism in which the first step is rate limiting.
elementary reactions. These elementary reactions • Identify the components of a reaction mechanism.
when combined form a chemical equation. • Identify the rate law for a reaction from a
mechanism in which the first step is not rate limiting.
Reaction Mechanisms
several
Most chemical reactions do not occur in a single step; they occur over the course of _______________ steps
___________.
When we write a chemical equation, we usually represent the overall reaction, not the series of individual steps by which
the reaction occurs.

reaction
The _________________ mechanism is the
_________________
series of individual chemical steps
_______________________________________________________________by which an overall chemical reaction
occurs.

molecular level
Reaction mechanisms provide a complete, detailed description of the reaction at the __________________ ___________
individual
by specifying the _____________________ collisions
_____________________ and reactions that result in the overall reaction.

elementary
Each step in a reaction mechanism is an ______________________
Step Elementary steps cannot be broken down into simpler
_________.
species that
exact _______________
steps and they represent the ___________
colliding
are ___________________ in the reaction.

individual
The _____________________ steps in the mechanism
___________
MUST _______
_________ overall
add _____ to the _______________
up
reaction
_________________.

Reaction Intermediates and Catalysts

reaction intermediate
A _________________ _______________________ is a catalyst speeds up a chemical reaction by
A _________________
species that forms in one elementary step and is lowering the activation energy for the reaction. A catalyst is
consumed in another. It does not show up in the overall consumed in one step and then reformed in another step so
chemical reaction. that overall, it remains unchanged. Catalysts also do not
show up in the overall chemical reaction
Given the following two step mechanism, determine the Given the following three step mechanism, determine the
following: following:

1. Overall chemical equation 1. Overall chemical equation

2. Identify any intermediates 2. Identify any intermediates

3. Identify any catalysts 3. Identify any catalysts

We can characterize elementary steps by their

_______________________ which is the _____________
_____ __________________ involved in the step.

The _________ ______________ molecularities are

________________________ and
________________________.

_________________________ ___________, elementary

steps in which three reactant particles collide, are
________ _________ because the probability of three
particles simultaneously colliding in the correct
orientation is small.

The _________ _______ for an ____________________ _________ can be inferred by the

__________________________ of the molecules participating in the collision

Consider this two-step mechanism for a reaction and determine the rate law for each elementary step:

Notice that we do not write the rate law for the overall reaction using stoichiometry, only for the elementary steps!!
 Elementary Steps and Reaction Rate Laws

In most chemical reactions, one of the elementary steps is

Consider this overall reaction:
_________ _____________ than the others. This step is called the
________-___________________ _________. AB + C → A + BC

The rate-determining step in a reaction limits the overall rate of the The following mechanism for the reaction:
reaction and therefore _____________________ _______ AB + AB → AB2 + A (slow)
_________ _______ for the _______________
_________________. AB2 + C → AB + BC (fast)

What is the rate law for this reaction overall?

When the _______________ _________ is the slow step, the
_______________ _________for the reaction will be based on the
_________ _______ of the ________-___________________
_________.

The following reaction occurs in a single elementary The decomposition of nitrous oxide, N2O, is believed to
reaction: occur by a two-step mechanism:

H2(g) + Br2(g) → 2 HBr(g) N2O(g) → N2(g) + O(g) (slow)

Predict the rate law for this reaction. N2O(g) + O(g) → N2(g) + O2(g) (fast)

1.What is the equation for the overall reaction?

Ozone reacts with nitrogen dioxide to produce 2. Write the rate law for the overall reaction
dinitrogen pentoxide and oxygen:

O3(g) + 2 NO2(g) → N2O5(g) + O2(g)

The reaction is believed to occur in two steps: The rate law for the reaction between NO2(g) and CO(g)
is experimentally determined to be rate =k[NO2]2. Two
O3(g) + NO2(g) → NO3(g) + O2(g) mechanisms are proposed for this reaction:

NO3(g) + NO2(g) → N2O5(g) Mechanism 1

The experimental rate law is rate = k[NO2][O3]. What can Step 1: NO2(g) + CO(g) → CO2(g) + NO(g)
you say about the relative rates of the two steps of the
mechanism? Mechanism 2
The first step is the slow step (rate-
determining step) since the overall rate Step 1: NO2(g) + NO2(g) → NO3(g) + NO(g) (slow)
law corresponds to the rate law of that
Step 2: NO3(g) + CO(g) → NO2(g) + CO2(g) (fast)
elementary step.
Based on the information above, does the reaction
between NO2(g) and CO(g) occur in one step or in two
steps? Justify your answer
The reaction occurs in two steps. The
experimentally determined rate law for the reaction
supports the mechanism where there are two steps.
The experimental rate law is the same as the rate
law predicted by the slow step in that mechanism.
 2 H2(g) + 2 NO(g) → N2(g) + 2 H2O(g)

If the rate law of the reaction shown above is experimentally

If the rate law of the overall reaction is determined to be rate =k[H2][NO]2 and the following mechanism
known, a mechanism can be is proposed
supported or rejected based on the
Step 1: H2(g) + NO(g)→ H2O(g) + N (g) (slow)
rate law of the slow step.
Step 2: N(g) + NO(g) → N2(g) + O(g) (fast)
The rate law of the slow step can be
examined and compared to the rate Step 3: O(g) + H2(g) → H2O(g) (fast)
law of the overall reaction to
determine the validity of the proposed Is this proposed mechanism a valid mechanism for this
mechanism reaction? Justify your answer.
This mechanism is not valid. The rate law
predicted by the slow step in this mechanism
does not match the experimentally determined
rate law.
Mechanisms with a Fast Initial Step (Steady-State Approximation)

When the proposed mechanism for a reaction has a _________

______________ _________, the rate law predicted by the
mechanism contains _________ _______ ___________________ in
the overall reaction.

In cases where with a _________ _______________ _________,

when we write the rate law that is predicted by this rate limiting Overall Reaction:
step it ____________________________
2 H2(g) + 2 NO(g) → 2 H2O(g) + N2(g)
___________________________________________.
Proposed Mechanism:
However, an ________________________ should not appear in
the overall reaction equation therefore it 2 NO(g) ⇆ N2O2(g) (Fast)
____________________________________________________
H2(g) + N2O2(g) → H2O(g) + N2O(g) (Slow)
_________for the reaction.
N2O(g) + H2(g) → N2(g) + H2O(g) (Fast)
To solve this problem, we can express the concentration of the
intermediates in terms of the reactants and substitute The rate law predicted by this mechanism is:
rate = k[H2][N2O2].
However we cannot have N2O2 in the rate law
for this reaction since it is not a reactant

When the first step is fast, the products of the first step build up. However,
the rate at which they are consumed is limited by a slower step down the
line.

The build up of products from the fast initial step leads to an

_______________________ (represented by double arrows) because some of
that products undergoes the reverse reaction and reforms reactants.

Since an equilibrium is reached, the rate of the forward reaction is equal to

the rate of the reverse reaction.
 How can we write an overall rate law for this reaction?

1. What is the rate law predicted for this reaction by the

proposed mechanism?
Rate = k,[H2] [N202]
↓
in the
No cannot remain .
bic it is not a reactant
rate law
2. We will need to express the concentration of the intermediate
in terms of the reactants of the overall equation by using the
first step.
from
3
Rate = K, [No]
for the forward rxn
rxn Rate =
k [N202] Step 1
for the reverse
Rate
= H2]ENO2]
_,

Rate (forward)
= Rate (reverse) eblc of
equilibrium ↓

↑
simplify

-
K, [NOL]" = K
_, [N202] 2

rearrange Rate = k[H][NOc]

[N2O2]=SNO
substitute
[N2O) where K =

12 [Hc] SN]
k 1
Rate [H2][N2O2]
-

= K -> Rate =
-

<

The two-step mechanism below has been proposed for a reaction between nitrogen monoxide and
molecular chlorine. Use this mechanism to derive the overall chemical equation and predicted rate law for
the overall reaction.
/
/
overall 2 NO(g) +
Cl2(g) -> 2 NOC rate=k[No] [Ck]
rate= Ky[NOCI][NO] Ka[NO][CI] Ka[NOCk] = simplify where
k
=
SNOJECI
X
-
[NOCI]= 1
& sub
- /
-
L
stitute
Kal

-SNO]SCI][NO
rate= ki

The mechanism shown here is proposed for the gas phase reaction, 2 N 2O5 → 2 NO2 + O2. What is the rate
law predicted by this mechanism?
rate= kz [NO < ][Nos]

K , [N205] = K ., [NOJ[NOs] 3 from 1

Step

[NO <][NOs]=1[N205]
k -
1

~ Rate = 12 1
:

[N205]
k -
1

Rate = k [N205] where k= 1

k -1
 Ozone naturally decomposes to oxygen by this reaction:
2 O3(g) → 3 O 2(g)
The experimentally observed rate law is:
Rate = k[O 3]2[O2]-1
Show that this proposed mechanism is consistent with the experimentally observed rate law
O3(g) ⇆ O2(g) + O(g) (fast)
O3(g) + O(g) → 2 O 2(g) (slow)

A Note on Valid Reaction Mechanisms

For a proposed reaction mechanism to be valid, two conditions must be met:

1.The elementary steps in the mechanism must sum to the overall reaction
2.The rate law predicted by the mechanism must be consistent with the experimentally observed rate law

Make sure you use these two conditions as justification when discussing whether a mechanism is valid or not!!