15 Chem Kinet

15 Chemical Kinetics
1
Chemical kinetics: the study of reaction rate, a quantity
conditions affecting it,
the molecular events during a chemical reaction (mechanism), and
presence of other components (catalysis).
Factors affecting reaction rate:
Concentrations of reactants
Catalyst
Temperature
Surface area of solid reactants or catalyst
What quantities do we study regarding chemical reactions?
2
Reaction Rate Defined
Reaction rate: changes in a concentration
of a product or a reactant per unit time.
[ ] concentration
Reaction rate =
t
[ ]
t
[ ]
t
change
Define reaction rate and explain
Average reaction rate
Instantaneous reaction rate
(2 tangents shown)
Initial reaction rate
3
Expressing reaction rates
For a chemical reaction, there are many ways to express the reaction
rate. The relationships among expressions depend on the equation.
Note the expression and reasons for their relations for the reaction
2 NO + O
2
(g) = 2 NO
2
(g)
[O
2
] 1 [NO] 1 [NO
2
]
Reaction rate = = =
t 2 t 2 t
Make sure you can write expressions for any reaction and figure out
the relationships. For example, give the reaction rate expressions for
2 N
2
O
5
= 4 NO
2
+ O
2
How can the rate expression be unique and universal?
4
Calculating reaction rate
The concentrations of N
2
O
5
are 1.24e-2 and 0.93e-2 M at 600 and
1200 s after the reactants are mixed at the appropriate temperature.
Evaluate the reaction rates for
2 N
2
O
5
= 4 NO
2
+ O
2
Solution:
(0.93 1.24)e-2 0.31e-2 M
Decomposition rate of N
2
O
5
= =
1200 600 600 s
= 5.2e-6 M s
-1
.
Note however,
rate of formation of NO
2
= 1.02e-5 M s
-1
.
rate of formation of O
2
= 2.6e-6 M s
-1
.
The reaction rates are
expressed in 3 forms
Be able to do this type problems
5
Determine Reaction Rates
To measure reaction rate, we measure the concentration
of either a reactant or product at several time intervals.
The concentrations are measured using spectroscopic
method or pressure (for a gas). For example, the total
pressure increases for the reaction:
2 N
2
O
5
(g) 4 NO
2
(g) + O
2
(g)
Because 5 moles of gas products are produced from 2
moles of gas reactants. For the reaction
CaCO
3
(s) CaO(s) + CO
2
(g)
The increase in gas pressure is entirely due to CO
2

formed.
barometer
6
Differential Rate Laws
Dependence of reaction rate on the concentrations of reactants is
called the rate law, which is unique for each reaction.
For a general reaction, a A + b B + c C products
the rate law has the general form
order wrt A, B, and C, determined experimentally
reaction rate = k [A]
X
[B]
Y
[C]
Z

the rate constant
For example, the rate law is
rate = k [Br
-
] [BrO
3
-
] [H
+
] for
5 Br- + BrO
3
-
+ 6 H
+
3Br
2
+ 3 H
2
O
The reaction is 1
st
order wrt all three reactants, total order 3.
Use differentials
to express rates
7
Variation of Reaction rates and Order
First order, rate = k [A]
k = rate, 0
th
order
[A]
rate
2nd order, rate = k [A]
2
The variation of reaction rates as functions of concentration for
various order is interesting.
Mathematical analysis is an important scientific tool, worth noticing.
[A] = ___?
8
Differential Rate Law determination
Estimate the orders and rate constant k from the results observed for the
reaction? What is the rate when [H
2
O
2
] = [I
-
] = [H
+
] = 1.0 M?
H
2
O
2
+ 3 I
-
+ 2 H
+
I
3
-
+ 2 H
2
O
Exprmt [H
2
O
2
] [I
-
] [H
+
] Initial rate M s
-1

1 0.010 0.010 0.0050 1.15e-6
2 0.020 0.010 0.0050 2.30e-6
3 0.010 0.020 0.0050 2.30e-6
4 0.010 0.010 0.0100 1.15e-6
Solution next
Learn the strategy to determine the rate law from this example.
Figure out the answer without writing down anything.
9
Differential Rate Law determination - continue
Estimate the orders from the results observed for the reaction
H
2
O
2
+ 3 I
-
+ 2 H
+
I
3
-
+ 2 H
2
O
Exprmt [H
2
O
2
] [I
-
] [H
+
] Initial rate M s
-1

1 0.010 0.010 0.0050 1.15e-6
2 0.020 0.010 0.0050 2.30e-6 1 for H
2
O
2

3 0.010 0.020 0.0050 2.30e-6 1 for I
-

4 0.010 0.010 0.0100 1.15e-6 0 for H
+
1.15e-6 = k [H
2
O
2
]
x
[I
-
]
y
[H
+
]
z

1.15e-6 k (0.010)
x
(0.010)
y
(0.0050)
z
exprmt 1 1 1
----------- = ------------------------------------- ---- = ---
2.30e-6 k (0.020)
x
(0.010)
y
(0.0050)
z
exprmt 2 2 2
x = 1
( )
x
10
Other orders are determined in a similar way as shown before.
Now, lets find k and the rate
Thurs, rate = 1.15e-6 = k (0.010)(0.010) from exprmt 1
k = 1.15e-6 M s
-1
/ (0.010)(0.010) M
3
= 0.0115 M
-1
s
-1
And the rate law is therefore,
d [H
2
O
2
] k
rate = = 0.0115 [H
2
O
2
] [I
-
] a differential rate law
d t total order 2
The rate when [H
2
O
2
] = [I
-
] = [H
+
] = 1.0 M:
The rate is the same as the rate constant k, when concentrations of
reactants are all unity (exactly 1), doesnt matter what the orders are.
11
Differential Rate Law determination continue
The reaction rate d[H
2
O
2
]/dt = 0.0115 [H
2
O
2
] [I
], for
H
2
O
2
+ 3 I
-
+ 2 H
+
I
3
-
+ 2 H
2
O
What is d[I
]/dt when [H
2
O
2
] = [I
] = 0.5?
Solution: Please note the stoichiometry of equation and how the rate changes.
d[I
]/dt = 3 d[H
2
O
2
]/dt = 3* 0.0115 [H
2
O
2
] [I
]
= 0.0345 * 0.5 * 0.5
= 0.0086 M s
-1

In order to get a unique rate constant k, we evaluate k for the
reaction
a A + b B product
this way
rate = -
1
/
a
d[A]/dt = -
1
/
b
d[B]/dt = k [A]
x
[B]
y

Note the reaction rate expression and the stoichiometry of equation.
12
From the following reaction rates observed in 4 experiments, derive the
rate law for the reaction
A + B + C products
where reaction rates are measured as soon as the reactants are mixed.
Expt 1 2 3 4
[A]
o
0.100 0.200 0.200 0.100
[B]
o
0.100 0.100 0.300 0.100
[C]
o
0.100 0.100 0.100 0.400
rate 0.100 0.800 7.200 0.400
Solution next
This example illustrates the strategy to determine, and a
reliable method to solve rate-law experimentally.
13
From the following reaction rates, derive the rate law for the reaction
A + B + C products
where reaction rates are measured as soon as the reactants are mixed.
Expt 1 2 3 4 order
[A]
o
0.100 0.200 0.200 0.100 3 from expt 1 & 2
[B]
o
0.100 0.100 0.300 0.100 2 expt 1, 2 & 3
[C]
o
0.100 0.100 0.100 0.400 1 expt 1 & 4
rate 0.100 0.800 7.200 0.400
0.800 k 0.2
x
0.1
y
0.1
z

----- = ----------------------
0.100 k 0.1
x
0.1
y
0.1
z
Therefore 8 = 2
x

log 8 = x log 2
x = log 8 / log 2
= 3
Assume rate = k [A]
x
[B]
y
[C]
z
14
Integrated Rate Laws
concentrations as functions of time
One reactant A decomposes in 1
st
or 2
nd
order rate law.
Differential rate law Integrated rate law
d[A] / dt = k [A] = [A]
o
k t
d[A]
= k [A] [A] = [A]
o
e
k t
or ln [A] = ln [A]
o
k t
d t
d[A] 1 1 [A] conc at t
= k [A]
2
= k t
d t [A] [A]
o
[A]
o
conc at t = 0
Describe, derive and apply the integrated rate laws
Learn the strategy to determine rate-law
15
Concentration and time of 1
st
order reaction
Describe the features of plot of [A] vs. t and ln[A] vs. t for 1
st
order
reactions. Apply the technique to evaluate k or [A] at various times.
[A]
t
ln[A]
t
[A] = [A]
o
e
k t
ln [A] = ln [A]
o
k t
t

16
Half life & k of First Order Decomposition
The time required for half of A to decompose is called half life t
1/2
.
Since [A] = [A]
o
e
k t
or ln [A]
= ln [A]
o
k t

When t = t
1/2
, [A] = [A]
o

Thus ln [A]
o
= ln [A]
o
k t
1/2

ln 2 = k t
1/2

k t
1/2
= ln 2 = 0.693 relationship between k
and t
1/2
Radioactive decay usually follow 1
st
order kinetics, and half life of an
isotope is used to indicate its stability.
Evaluate t
from k or k from t

17
1
st
order reaction calculation
N
2
O
5
decomposes according to 1
st
order kinetics, and 10% of it
decomposed in 30 s. Estimate k, t
and percent decomposed in 500 s.

Solution next
If the rate-law is known, what are the key parameters?
18
1
st
order reaction calculation
N
2
O
5
decomposes according to 1
st
order kinetics, and 10% of it decomposed
in 30 s. Estimate k, t
and percent decomposed in 500 s.

Solution: Assume [A]
o
= [N
2
O
5
]
o
= 1.0, then [A] = 0.9 at t = 30 s or
0.9 = 1.0 e
k t
apply [A]o = [A] e
k t

ln 0.9 = ln 1.0 k 30 s
0.1054 = 0 k * 30
k = 0.00351 s
1

t
=
0.693
/
k
= 197 s apply k t = ln 2
[A] = 1.0 e
0.00351*500
= 0.173
Percent decomposed: 1.0 0.173 = 0.827 or 82.7 %
After 2 t
(2*197=394 s), [A] = ()

2
=, 75% decomposed.
After 3 t
(3*197=591 s), [A] = ()

3
=1/8, 87.5% decomposed.
Apply integrated rate law to solve problems
19
Typical Problem wrt 1
st
Order Reaction
The decomposition of A is first order, and [A] is monitored. The following
data are recorded:
t / min 0 2 4 8
[A]/[M] 0.100 0.0905 0.0819 0.0670
Calculate k (What is the rate constant? k = 0.0499)
Calculate the half life (What is the half life? Half life = 13.89)
Calculate [A] when t = 5 min. (What is the concentration when t = 5 min?)
Calculate t when [A] = 0.0100. (Estimate the time required for 90% of A
to decompose.)
Work out all the answers
20
A 2
nd
Order Example
Dimerization of butadiene is second order:
2 C
4
H
6
(g) = C
8
H
12
(g).
The rate constant k at some temperature is 0.100 /min. The initial
concentration of butadiene [B] is 2.0 M.
Calculate the time required for [B] = 1.0 and 0.5 M
Calculate concentration of butadiene when t = 1, 5, 10, and 30.
Solution next
If the rate-law is known, what are the key parameters?
Apply the right model and work out all the parameters.
21
A 2
nd
Order Example
Dimerization of butadiene is second order:
2 C
4
H
6
(g) = C
8
H
12
(g).
The rate constant k at some temperature
is 0.100 /min. The initial concentration of
butadiene [B] is 2.0 M.
Calculate the time t required for [B] = 1.0
and 0.5 M
Calculate concentration of butadiene
when t = 1, 5, 10, and 30.
1 1
= k t
[B] [B]
o

1 1

[B] [B]
o
t =
k
[B]
o

[B] =
[B]
o
k t + 1

t = 1 5 10 15 30 35
[B] = 1.67 1.0 0.67 0.50 0.29 0.25
Work out the formulas and
then evaluate values
22
Half life of 2
nd
Order Chemical Kinetics
t = 1 5 10 15 30 35
[B] = 1.67 1.0 0.67 0.50 0.29 0.25
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
1/[B]
How does half life vary in 2
nd
order reactions?
23
Plot of [B] vs. t & 1/[B] vs. t for 2
nd
Order Reactions
t = 1 5 10 15 30 35
[B] = 1.67 1.0 0.67 0.50 0.29 0.25
[B]
1

[B]
t t
1 1
= k t
[B] [B]
o

[B]
o

[B] =
[B]
o
k t + 1

What kind of plot is linear for 1
st
and 2
nd
reactions?
24
Chemical Reaction and Molecular Collision
Molecular collisions lead to chemical reactions.
Thus, the reaction constant, k is determined by
several factors.
k = Z f p
Z: collision frequency
p, the fraction with proper orientation
f, fraction of collision having sufficient energy for reaction
f is related to the potential energy barrier called
activation energy, E
a
.
f e
Ea / RT
or exp ( E
a
/ R T)
Thus, k = A e
Ea / RT
constant
E
a
Potential
energy
reaction
constant
How does temperature affect reaction rates?
Explain energy aspect in a chemical reaction
25
Energy in chemical reactions
Potential
energy
Progress of reaction
R + A
P + D
H
exothermic
E
a
E
a
for reverse reaction

Endothermic rxn
RA-PD
activated
complex
Explain the various terms and energy changes in a chemical reaction
26
The Arrhenius Equation
1903 Nobel Prize citation in recognition of the extraordinary services he has
rendered to the advancement of chemistry by his electrolytic theory of dissociation
The temperature dependence of the rate constant k is best
described by the Arrhenius equation:
k = A e
Ea / R T

or ln k = ln A E
a
/ R T
If k
1
and k
2
are the rate constants at T
1
and T
2
respectively, then
k
1
E
a
1 1
ln =

k
2
R T
1
T
2

How does temperature affect reaction rates?
Derive and apply these relationship to solve problems,
and recall the Clausius-Clapeyron equation.
27
Application of Arrhenius Equation
From k = A e
Ea / R T
, calculate A, E
a
, k at a specific temperature and T.
The reaction:
2 NO
2
(g) -----> 2NO(g) + O
2
(g)
The rate constant k = 1.0e-10 s
-1
at 300 K and the activation energy
E
a
= 111 kJ mol
-1
. What are A, k at 273 K and T when k = 1e-11?
Method: derive various versions of the same formula
k = A e
Ea / R T

A = k e
Ea / R T

A / k = e
Ea / R T
ln (A / k) = E
a
/ R T
Make sure you know how to
transform the formula into
these forms.
28
Application of Arrhenius Equation (continue)
The reaction:
2 NO
2
(g) -----> 2NO(g) + O
2
(g)
The rate constant k = 1.0e-10 s
-1
at 300 K and the activation energy
E
a
= 111 kJ mol
-1
. What are A, k at 273 K and T when k = 1e-11?
Use the formula derived earlier:
A = k e
Ea / R T
= 1e-10 s
-1
exp (111000 J mol
-1
/ (8.314 J mol
-1
K
1
*300 K))
= 2.13e9 s
-1

k = 2.13e9 s
-1
exp ( 111000 J mol
-1
) / (8.314 J mol
-1
K
1
*273 K)
= 1.23e-12 s
-1
T = E
a
/ [R* ln (A/k)] = 111000 J mol
-1
/ (8.314*46.8) J mol
-1
K
-1

= 285 K
29
The Effect of Temperature on Reaction Rates
Reaction rate = k [A}
x
[B]
y
[C]
z
(Concentration effect at constant T)

k = A exp ( E
a
/ RT) (Temperature effect)
Use graphic method to discuss the
variation of k vs. T
variation of k vs 1 / T
variation of ln(k) vs T
variation of ln(k) vs 1 / T

See a potential multiple choice question in an exam?
30
Elementary Reactions and Mechanism
Elementary reactions are steps of molecular events showing how
reactions proceed. This type of description is a mechanism.
The mechanism for the reaction between CO and NO
2
is proposed to be
Step 1 NO
2
+ NO
2
NO
3
+ NO (an elementary reaction)
Step 2 NO
3
+ CO NO
2
+ CO
2
(an elementary reaction)
Add these two equations led to the overall reaction
NO
2
+ CO = NO + CO
2
(overall reaction)
A mechanism is a proposal to explain the rate law, and it has to satisfy
the rate law. A satisfactory explanation is not a proof.
Explain terms in red
31
Molecularity of Elementary Reactions
The total order of rate law in an elementary reaction is molecularity.
The rate law of elementary reaction is derived from the equation. The
order is the number of reacting molecules because they must collide to
react.
A molecule decomposes by itself is a unimolecular reaction (step);
two molecules collide and react is a bimolecular reaction (step); &
three molecules collide and react is a termolecular reaction (step).
O
3
O
2
+ O rate = k [O
3
]
NO
2
+ NO
2
NO
3
+ NO rate = k [NO
2
]
2
Br + Br + Ar Br
2
+ Ar* rate = k [Br]
2
[Ar]
Caution: Derive rate laws this way only for elementary reactions.
32
Molecularity of elementary reactions - Example
Some elementary reactions for the
reaction between CH
4
and Cl
2
are
Cl
2
2 Cl
2 Cl Cl
2
2Cl + CH
4
Cl
2
+ CH
4
*
Cl + CH
4
HCl + CH
3
CH
3
+ Cl CH
3
Cl
CH
3
+ CH
3
CH
3
-CH
3
CH
3
Cl + Cl HCl + CH
2
Cl
CH
2
Cl + Cl CH
2
Cl
2
* * * (more)
Write down the rate laws
and describe them as
uni- bi- or ter-molecular
steps yourself, please.
33
Elementary Reactions are Molecular Events
N
2
O
5
NO
2
+ NO
3

NO + O
2
+ NO
2
NO
2
+ NO
3
Explain differences between elementary and over reaction equations
34
Rate Laws and Mechanisms
A mechanism is a collection of elementary steps devise to explain the the
reaction in view of the observed rate law. You need the skill to derive a
rate law from a mechanism, but proposing a mechanism is task after you
have learned more chemistry
For the reaction, 2 NO
2
(g) + F
2
(g) 2 NO
2
F (g), the rate law is,
rate = k [NO
2
] [F
2
] .
Can the elementary reaction be the same as the overall reaction?
If they were the same the rate law would have been
rate = k [NO
2
]
2
[F
2
],
Therefore, they the overall reaction is not an elementary reaction. Its
mechanism is proposed next.
35
Rate-determining Step in a Mechanism
The rate determining step is the slowest elementary step in a mechanism,
and the rate law for this step is the rate law for the overall reaction.
The (determined) rate law is, rate = k [NO
2
] [F
2
],
for the reaction, 2 NO
2
(g) + F
2
(g) 2 NO
2
F (g),
and a two-step mechanism is proposed:
i NO
2
(g) + F
2
(g) NO
2
F (g) + F (g)
ii NO
2
(g) + F (g) NO
2
F (g)
Which is the rate determining step?
Answer:
The rate for step i is rate = k [NO
2
] [F
2
], which is the rate law, this
suggests that step i is the rate-determining or the s-l-o-w step.
Explain rate determining step in a mechanism
and use it to derive the rate law.
36
Deriving a Rate Law From a Mechanism - 0
The decomposition of H
2
O
2
in the presence of I

follow this
mechanism,
i H
2
O
2
+ I

k
1
H
2
O + IO

slow
ii H
2
O
2
+ IO

k
2
H
2
O + O
2
+ I

fast
What is the rate law? Energy
Solve the problem
E
ai
E
aii
reaction
37
Deriving a rate law from a mechanism - 1
The decomposition of H
2
O
2
in the presence of I

follow this mechanism,
i H
2
O
2
+ I

k
1
H
2
O + IO

slow
ii H
2
O
2
+ IO

k
2
H
2
O + O
2
+ I

fast
What is the rate law?
Solution
The slow step determines the rate, and the rate law is:
rate = k1 [H
2
O
2
] [I
]
Since both [H
2
O
2
] and [I
] are measurable in the system, this is the

rate law.
38
Derive the rate law for the reaction, H
2
+ Br
2
= 2 HBr,
from the proposed mechanism:
i Br
2
2 Br fast equilibrium (k
1
, k
-1
)

ii H
2
+ Br k
2
HBr + H slow
iii H + Br k
3
HBr fast
Solution:
The fast equilibrium condition simply says that
k
1
[Br
2
] = k
-1
[Br]
2

and [Br] = (k
1
/k
-1
[Br
2
])

The slow step determines the rate law,
rate = k
2
[H
2
] [Br] Br is an intermediate
= k
2
[H
2
] (k
1
/k
-1
[Br
2
])

= k [H
2
] [Br
2
]
;
k = k
2
(k
1
/k
-1
)

M
-
s
-1

total order 1.5
explain
39
The decomposition of N
2
O
5
follows the mechanism:
1 N
2
O
5
NO
2
+ NO
3
fast equilibrium
2 NO
2
+ NO
3
k
2
NO + O
2
+ NO
2
slow
3 NO
3
+ NO k
3
NO
2
+ NO
2
fast
Derive the rate law.
Solution:
The slow step determines the rate,
rate = k
2
[NO
2
] [NO
3
] NO
2
& NO
3
are intermediate
From 1, we have
[NO
2
] [NO
3
]
= K K, equilibrium constant
[N
2
O
5
] K differ from k
Thus, rate = K k
2
[N
2
O
5
]
40
Deriving rate laws from mechanisms steady-state approximation
The steady-state approximation
is a general method for deriving
rate laws when the relative
speed cannot be identified.
It is based on the assumption
that the concentration of the
intermediate is constant.
Rate of producing the
intermediate, R
prod
, is
the same as its rate of
consumption, R
cons
.
R
prod
= R
cons
[Intermediate]
time
R
prod
< R
cons

R
prod
> R
cons

Be able to apply the steady-
state approximation to derive
rate laws
41
Steady-state
approximation - 2
Lets assume the mechanism for the reaction.
H
2
+ I
2
2 HI
as follows.
Step (1) I
2
k
1
2 I
Step (1) 2 I k
-1
I
2

Step (2) H
2
+ 2 I k
2
2 HI
Derive the rate law.
Derivation:
rate = k
2
[H
2
] [I]
2
(cause this step gives products)
but I is an intermediate, this is not a rate law yet.
Since k
1
[I
2
] (= rate of producing I)
= k
-1
[I]
2
+ k
2
[H
2
] [I]
2
(= rate of consuming I)
Thus, k
1
[I
2
]
[I]
2
=
k
-1
+ k
2
[H
2
]
rate = k
1
k
2
[H
2
] [I
2
] / {k
-1
+ k
2
[H
2
] }
Steady state
42
Steady-state approximation - 3
From the previous result:
k
1
k
2
[H
2
] [I
2
]
rate =
{k
-1
+ k
2
[H
2
] }
Discussion:
(i) If k
-1
<< k
2
[H
2
] then {k
-1
+ k
2
[H
2
]} = k
2
[H
2
] ,
then rate = k
1
k
2
[H
2
] [I
2
] / {k
2
[H
2
] } = k
1
[I
2
] (pseudo 1st order wrt I
2
)
using large concentration of H
2
or step 2 is fast (will meet this condition).
(ii) If step (2) is slow, then k
2
<< k
1
,
and if [H
2
] is not large, we have {k
-1
+ k
2
[H
2
]} = k
-1

and rate = k
1
k
2
[H
2
] [I
2
] / k
1
= k
2
[H
2
] [I
2
]
43
Steady-state approximation - 4
In an alkaline solution, peroxydisulfate oxidizes sulfite to yield sulfate,
S
2
O
8
2-
+ SO
3
2-
+ 2 OH
-
3 SO
4
2-
+ H
2
O.
The following mechanism has been proposed:
i S
2
O
8
2-
+ SO
3
2-
k
1
S
2
O
7
2-
+ SO
4
2-

ii S
2
O
7
2-
+ H
2
O k
2
2 SO
4
2-
+ 2 H
+

iii H
+
+ OH
-
k
3
H
2
O (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
See page 607 PHH Text
44
Catalysis
A catalyst is a substance that changes the rate
of a reaction by lowing the activation energy, E
a
.
It participates a reaction in forming an
intermediate, but is regenerated.
Enzymes are marvelously selective catalysts.
A catalyzed reaction,
NO (catalyst)
2 SO
2
(g) + O
2
2 SO
3
(g)

via the mechanism
i 2 NO + O
2
2 NO
2
(3
rd
order)
ii NO
2
+ SO
2
SO
3
+ NO
Uncatalyzed rxn
Catalyzed rxn
rxn
Energy
45
Catalyzed decomposition of ozone
R.J. Plunkett in DuPont discovered carbon fluorine chlorine compounds.
The CFC decomposes in the atmosphere:
CFCl
3
CFCl
2
+ Cl
CF
2
Cl
3
CF
2
Cl + Cl.
The Cl catalyzes the reaction via the mechanism:
i O
3
+ h v O + O
2
,
ii ClO + O Cl + O
2

iii O + O
3
O
2
+ O
2
.
The net result or reaction is
2 O
3
3 O
2

Scientists sound the alarm, and the CFC is banned now.
46
Homogenous vs. heterogeneous catalysts
A catalyst in the same phase (gases and solutions) as the reactants is a
homogeneous catalyst. It effective, but recovery is difficult.
When the catalyst is in a different phase than reactants (and products),
the process involve heterogeneous catalysis. Chemisorption, absorption,
and adsorption cause reactions to take place via different pathways.
Platinum is often used to catalyze hydrogenation
Catalytic converters reduce CO and NO emission.
47
Heterogeneous catalysts
Ceryx's vision is to design, produce,
and commercialize advanced
systems that balance Cost,
Performance, Emissions Reduction,
and Fuel Penalty to make the
economics of pollution control
viable.

We explore new ways to look at the
air quality challenges faced by
industry and search for potential
solutions by combining proven
technologies with state-of-the-art
science.
Catalyzed reactions:
CO + O
2
CO
2

2 NO N
2
+ O
2
48
49
Enzymes selective catalysts
Enzymes are a long protein molecules that fold into balls. They often
have a metal coordinated to the O and N sites.
Molecules catalyzed by enzymes are called substrates. They are
held by various sites (together called the active site) of the enzyme
molecules and just before and during the reaction. After having
reacted, the products P
1
& P
2
are released.
E
nzyme
+ S
ubstrate
ES (activated complex)
ES P
1
+ P
2
+ E
Enzymes are biological catalysts for biological systems.
50

X-ray 3-D structure of
fumarate reductase. It
reduces fumerate, an
important role in the
metabolism of
anaerobic bacteria,
from Max Planck Inst.
51
Chemical Kinetics - Summary
Explain how the various factors affect reaction rates.
Define reaction rates, average rates, initial rates and rate constants.
Evaluate rate law from experiments
Properly apply 1
st
and 2
nd
differential rate laws and integrated rate laws.
Interpret elementary reactions and mechanisms. Derive rate laws from
a given mechanism. Apply the steady-state method to derive the rate
law of a given mechanism, and discuss the results.
Explain the action of catalysts in terms of chemistry and in terms of
energy of activation.

15 Chem Kinet

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15 Chemical Kinetics

and percent decomposed in 500 s.

and percent decomposed in 500 s.

(2*197=394 s), [A] = ()

(3*197=591 s), [A] = ()

] are measurable in the system, this is the

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