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concentration
change
[ ]
t
t
15 Chemical
barometer
for
Use differentials
to express rates
The reaction is 1st order wrt all three reactants, total order 3.
15 Chemical
[A] = ___?
[A]
[H2O2]
0.010
0.020
0.010
0.010
[I-]
0.010
0.010
0.020
0.010
[H+]
0.0050
0.0050
0.0050
0.0100
Learn the strategy to determine the rate law from this example.
Figure out the answer without writing down anything.
Solution next
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[H2O2]
0.010
0.020
0.010
0.010
[I-]
0.010
0.010
0.020
0.010
[H+]
0.0050
0.0050
0.0050
0.0100
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1
1
x
---- = --2
2
( )
11
1
0.100
0.100
0.100
0.100
2
0.200
0.100
0.100
0.800
3
0.200
0.300
0.100
7.200
4
0.100
0.100
0.400
0.400
Solution next
12
3
0.200
0.300
0.100
7.200
4
0.100
0.100
0.400
0.400
order
3 from expt 1 & 2
2 expt 1, 2 & 3
1 expt 1 & 4
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d[A] / dt = k
[A] = [A]o k t
d[A]
= k [A]
dt
d[A]
= k [A]2
dt
1
1
= k t
[A]
[A]o
[A] conc at t
[A]o conc at t = 0
14
ln[A]
ln [A] = ln [A]o k t
[A] = [A]o e k t
t
t
t
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[A] = [A]o e k t
or
When
Thus
ln [A] = ln [A]o k t
ln 2 = k t1/2
k t1/2 = ln 2 = 0.693 relationship between k and t1/2
Radioactive decay usually follow 1st order kinetics, and half life of an
isotope is used to indicate its stability.
Evaluate t from k or k from t
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16
Solution next
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17
18
2
0.0905
4
0.0819
8
0.0670
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Solution next
20
1
1
[B]
[B]o
1
1
[B]
[B]o
t =
k
t=
10
15
30
35
0.50
0.29
0.25
=kt
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[B]o
[B] =
[B]o k t + 1
21
1/[B]
2.5
2
1.5
1
0.5
0
t=
10
15
30
35
0.29
0.25
22
Plot of [B] vs. t & 1/[B] vs. t for 2nd Order Reactions
t=
10
15
30
35
0.50
0.29
0.25
[B]
[B]o
[B] =
[B]o k t + 1
[B]
t
What kind of plot is linear for 1st and 2nd15reactions?
Chemical
1
= k t
[B]o
t
23
k = A e Ea / RT
constant
Potential
energy
Ea
reaction
RA-PD
activated
complex
P+D
Endothermic rxn
Progress of reaction
k = A e Ea / R T
ln k = ln A Ea / R T
26
Ea / R T
Ea / R T
ln (A / k) = Ea / R T
27
28
k = A exp ( Ea / RT)
(Temperature effect)
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30
rate = k [O3]
rate = k [NO2]2
Br + Br + Ar Br2 + Ar*
rate = k [Br]2[Ar]
Caution: Derive rate laws this way only for elementary reactions.
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32
33
35
H2O2 + I
k1 H2O + IO
H2O2 + IO
k2 H2O + O2 + I
slow
fast
Energy
Eai
Eaii
reaction
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36
H2O2 + I
k1 H2O + IO
slow
H2O2 + IO
k2 H2O + O2 + I fast
Solution
The slow step determines the rate, and the rate law is:
rate = k1 [H2O2] [I ]
Since both [H2O2] and [I ] are measurable in the system, this is the
rate law.
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37
H 2 + Br2 = 2 HBr,
fast equilibrium (k1, k-1)
slow explain
fast
Solution:
The fast equilibrium condition simply says that
k1 [Br2] = k-1 [Br]2
and
[Br] = (k1/k-1 [Br2])
The slow step determines the rate law,
rate = k2 [H2] [Br]
Br is an intermediate
= k2 [H2] (k1/k-1 [Br2])
= k [H2] [Br2] ;
k = k2 (k1/k-1) M- s -1
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total order 1.5
38
K, equilibrium constant
K differ from k
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39
steady-state approximation
[Intermediate]
Rate of producing the
intermediate, Rprod, is
the same as its rate of
consumption, Rcons.
Rprod = Rcons
time
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40
k1 [I2]
[I]2 =
k-1 + k2 [H2]
rate = k k [H ] [I ] / {k + k15[HChemical
]}
41
Steady-state approximation - 3
From the previous result:
k1 k2 [H2] [I2]
rate =
{k-1 + k2 [H2] }
Discussion:
(i) If k-1 << k2 [H2] then {k-1 + k2 [H2]} = k2 [H2] ,
then rate = k1 k2 [H2] [I2] / {k2 [H2] } = k1 [I2] (pseudo 1st order wrt I2)
using large concentration of H2 or step 2 is fast (will meet this condition).
(ii) If step (2) is slow, then k2 << k1,
and if [H2] is not large, we have {k-1 + k2 [H2]} = k-1
and rate = k1 k2 [H2] [I2] / k1 = k2 [H2] [I2]
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42
Steady-state approximation - 4
In an alkaline solution, peroxydisulfate oxidizes sulfite to yield sulfate,
S2O82- + SO32- + 2 OH- 3 SO42- + H2O.
The following mechanism has been proposed:
i
S2O82- + SO32- k1 S2O72- + SO42ii
S2O72- + H2O k2 2 SO42- + 2 H+
iii
H+ + OH- k3 H2O (fast equilibrium to be discussed)
Steady-state approximation follows these steps:
What is or are the intermediates I?
Use which step to give the rate law that may involve [I]?
Express the rates of producing and consuming intermediate(s)
Express [I] of intermediate(s) in terms of [Reactants]
Derive the rate law in terms of [Reactants]
Discuss
43
Catalysis
Energy
A catalyst is a substance that changes the rate
Uncatalyzed rxn
of a reaction by lowing the activation energy, Ea.
It participates a reaction in forming an
intermediate, but is regenerated.
Enzymes are marvelously selective catalysts.
A catalyzed reaction,
NO (catalyst)
2 SO2 (g) + O2 2 SO3 (g)
via the mechanism
i
2 NO + O2 2 NO2 (3rd order)
ii
NO2 + SO2 SO3 + NO
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Catalyzed rxn
rxn
44
45
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46
Heterogeneous catalysts
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Catalyzed reactions:
CO + O2 CO2
2 NO N2 + O2
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