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15 Chemical Kinetics
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?
15 Chemical Kinetics
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
15 Chemical Kinetics
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?
15 Chemical Kinetics
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
15 Chemical Kinetics
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
15 Chemical Kinetics
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
15 Chemical Kinetics
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] = ___?
15 Chemical Kinetics
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.
15 Chemical Kinetics
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
15 Chemical Kinetics
10
Differential Rate Law determination - continue
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.
15 Chemical Kinetics
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.
15 Chemical Kinetics
12
Differential Rate Law determination - continue
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.
15 Chemical Kinetics
13
Differential Rate Law determination - continue
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
15 Chemical Kinetics
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 Chemical Kinetics
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
15 Chemical Kinetics
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
15 Chemical Kinetics
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
=
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
]
Since both [H
2
O
2
] and [I
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
15 Chemical Kinetics
39
Deriving a rate law from a mechanism - 3
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
]
15 Chemical Kinetics
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
15 Chemical Kinetics
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
15 Chemical Kinetics
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
]
15 Chemical Kinetics
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
15 Chemical Kinetics
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
15 Chemical Kinetics
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.
15 Chemical Kinetics
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.
15 Chemical Kinetics
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
15 Chemical Kinetics
48
15 Chemical Kinetics
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.
15 Chemical Kinetics
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.
15 Chemical Kinetics
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.