Chemical Kinetics
Learning goals and key skills:
C (diamond) → C (graphite)
∆G°rxn = -2.84 kJ spontaneous!
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Chemical Kinetics
Reaction Rates
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Collision model theory
Reaction rates
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Reaction Rates
C4H9Cl(aq) + H2O(l) → C4H9OH(aq) + HCl(aq)
• This is because as
the reaction goes
forward, there are
fewer collisions
between reactant
molecules.
Reaction Rates
• A plot of concentration
versus time for this
reaction yields a curve
like this.
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Reaction rates
rate = change in conc. / change in time
aA + bB → cC + dD
Example
Ammonia reacts with oxygen to form nitrogen
monoxide and steam. Relate the reactant and
product reaction rates.
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Rate laws
Rate laws show the relationship between the
reaction rate and the concentration of
reactants (and sometimes products).
aA + bB cC + dD
rate equation:
Rate = R = k [A]x [B]y
Rate laws
Rate = R = k [A]x [B]y
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Example
2 A + 3 B→ 2 C + D
Show that
rate = k [A]2[B]
where k = 2.0 M-2 s-1
Example
Prove that
rate = k [F2][ClO2]
where k = 1.2 M-1 s-1
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Integrated Rate Laws
∆A dA [ A ]tdA t
−
∆t
= −
dt
= kA x ∫[ A]0 A x = − ∫0kdt
If x = 0 [ A]0 − [ A]t = kt
[ A]t
If x = 1 ln = − kt
[ A]0
1 1
If x = 2 − = kt
[ A]t [ A]0
Using Graphs
Time
(min) H2O2 (M) ln (H2O2) 1/(H2O2)
0 0.02 -3.91202 50
200 0.016 -4.13517 62.5
400 0.0131 -4.33514 76.33588
600 0.0106 -4.5469 94.33962
800 0.0086 -4.75599 116.2791
1000 0.0069 -4.97623 144.9275
1200 0.0056 -5.18499 178.5714
1600 0.0037 -5.59942 270.2703
2000 0.0024 -6.03229 416.6667
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Zero Order Second Order
0.020
400
0.015
(M )
[H2O2] (M)
300
-1
0.010
-1
[H2O2]
200
0.005
100
0.000
0 500 1000 1500 2000
0 500 1000 1500 2000
Time / min
Time / min
First Order
-3
-4
ln([H2O2]) (ln[M])
-5
-6
-7
-8
0 500 1000 1500 2000
Time / min
Example
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Half-life, t1/2
The half-life, t1/2 is the time needed for the
concentration of a reactant to decrease to half
of its initial value.
[A]t1/2 = ½[A]0
[ A]t
For a 1st order ln = − kt
[ A]0
1
[ A]t 2 [ A] 0 1
ln ln ln
[ A]0 [ A]0 2 ln 2 0.693
t1/ 2 = − = − = − = =
k k k k k
Example
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Half-lives of radioactive elements
Radioactive decay follows first-order kinetics.
Rate of decay of radioactive isotopes are
given in terms of a half-life.
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Temperature and Rate
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Ea, Activation energy
• There is a minimum amount of energy required
for reaction: the activation energy, Ea.
• Just as a ball cannot get over a hill if it does not
roll up the hill with enough energy, a reaction
cannot occur unless the molecules possess
sufficient energy to get over the activation
energy barrier.
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Maxwell–Boltzmann Distributions
Arrhenius Equation
k = A e−Ea/RT
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Arrhenius Equation
1
ln k = -Ea/R ( ) + ln A
T
Example
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Reaction mechanisms:
A Microscopic View of Reactions
Molecularity
The molecularity of an
elementary step is equal to the
number of reactant molecules.
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Reaction mechanisms &
activation energy
Mechanisms
Cis Transition state Trans
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Mechanisms
Conversion of trans- to cis-butene
energy Activated
Complex
+262 kJ -266 kJ
cis 4 kJ/mol
trans
Activation energy
Reaction passes thru
a TRANSITION
STATE where there is
an activated complex
that has sufficient
energy to become a
product.
ACTIVATION ENERGY, Ea
= energy needed to form the activated complex.
Here Ea = 262 kJ/mol.
NOTE: Ea, reverse = 266 kJ/mol.
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Multistep Mechanisms
Mechanisms
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Mechanisms
Most rxns. involve a sequence of elementary
steps.
2 I- + H2O2 + 2 H+ → I2 + 2 H2O
Rate = k [I-] [H2O2]
NOTE
1. Rate law is determined from experiment.
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Slow Initial Step
• A proposed mechanism for this reaction is
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Fast Initial Step
A proposed mechanism is
k1
Step 1: NO + Br2 k-1
NOBr2 (fast)
k
Step 2: NOBr2 + NO →
2
2 NOBr (slow)
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Fast Initial Step
• Because Ratef = Rater ,
k1 [NO] [Br2] = k−1 [NOBr2]
• Solving for [NOBr2] gives us
k1
k−1
[NO] [Br2] = [NOBr2]
Substituting this expression for
[NOBr2] in the rate law for the
rate-determining step gives
k2k1
Rate = [NO] [Br2] [NO]
k−1
Rate = k [NO]2 [Br2]
Mechanisms
2 I - + H 2 O2 + 2 H + → I 2 + 2 H 2 O
Rate = k [I-] [H2O2]
Proposed Mechanism
Step 1 — slow H2O2 + I- → HOI + OH-
Step 2 — fast HOI + I- → I2 + OH-
Step 3 — fast 2 OH- + 2 H+ → 2 H2O
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Catalysts
• Catalysts increase the rate of a reaction by decreasing
the activation energy of the reaction.
• Catalysts change the mechanism by which the
process occurs.
Iodine-Catalyzed Isomerization
of cis-2-Butene
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Heterogeneous Catalysts
Enzymes
catalysts in biological systems
The substrate fits into the active site of the
enzyme much like a key fits into a lock.
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