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Chemical Kinetics
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Reaction Rates
Rate of a reaction - how fast the concentration of
a reactant or a product changes per unit time.
Rate = concentration/time
a. increase in the concentration of a product per unit time
b. decrease in the concentration of a reactant per unit time
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Reaction Rates
Relative rates of product formation and
reactant consumption depend on the
coefficients in the balanced equation.
Specify the reactant or product when quoting a
rate.
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Reaction Rates
Plot concentration (y axis) versus time (x axis).
(concentration) and (time) represent vertical and
horizontal sides of a right triangle.
Slope of hypotenuse of triangle is the average rate
during that time period.
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Reaction Rates
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Reaction Rates
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Reaction Rates
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Reaction Rates
EXAMPLE:
It was found that the rate of formation of N2 (g) in the following reaction
4 NH3 (g)
3 O2 (g)
2 N2 (g)
6 H2 O (g)
of
NH3.
SOLUTION: Knowing that the rate of appearance is 0.52 , we can use the
stoichiometry of the balanced equation to determine the rate of
disappearance of NH3.
mol N 2 4 mol NH 3
mol NH 3
0.52
= 1.04
Ls
2 mol N2
Ls
This rate should be reported as 1.04 Ms-1 because we are reporting the
rate of disappearance of NH3.
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[A]
= k[A]m [B ]n
t
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Experimental
Determination of a
Rate Law
To determine the reaction order (values of the
exponents in a rate law) - measure the initial
rate of a reaction as a function of different
sets of initial concentrations.
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Experimental
Determination of a
Rate Law
Experimental
Determination of a
Rate Law
To determine the reaction order (values of the
exponents in a rate law) - measure the initial
rate of a reaction as a function of different
sets of initial concentrations.
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Experimental
Determination of a
Rate Law
Can determine the value of k from the rate
law.
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Experimental
Determination of a
Rate Law
EXAMPLE:
The reaction
2 NO (g) + 2 H2 (g) N2 (g) + 2 H2O (g)
is first order in H2 and second order in NO.
1. Write the rate law.
2. What is the overall order of the reaction?
3. How does the reaction rate change if the concentration
of H2 is doubled and the concentration of NO is held
constant?
4. How does the reaction rate change if the concentration
of NO is cut in half and the concentration of H2 is held
constant?
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Experimental
Determination of a
Rate Law
SOLUTION:
1. Rate = [H2][NO]2
2. Overall order = 1 + 2 = 3
3. If the concentration of H2 is doubled while the
concentration of NO is held constant, the rate
will double, (2)1 = 2.
4. If the concentation of NO is cut half while the
concentration of H2 is held constant, the rate will
be cut by 1/2, (1/2)2 = 1/4
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Can
rearrange
[A ]t
ln
= kt
[A]0
the
equation
to
give
ln[A]t = kt + ln[A]0
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EXAMPLE:
When sucrose reacts with water, glucose is formed
according to the reaction:
C12H22O11 + H2O 2 C6H12O6
This reaction follows first order kinetics with respect to the
sucrose.
Calculate the value of k, if it takes 9.70 hours for the
concentration of sucrose to decrease from 0.00375 M to
0.00252 M.
Determine the amount of time required for the reaction to go to
80% completion.
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k = 4.10 10
-1
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We can now calculate the amount of time required for the reaction to be
80% complete. To determine the concentration at this time, we multiply
the initial concentration by 0.80.
0.80 0.00375 = 0.00300
This value represents the amount of sucrose that has reacted.
The amount of sucrose remaining after the reaction is 80% complete is
0.00375 0.00300 = 0.00075.
We now have the initial concentration and the concentration at time t,
which can be substituted into the first-order integrated rate law, along
with the value of k we calculated in the first part of the problem.
ln
0.00075
2 -1
= (4.10 10 h )t;
0.00375
t = 39.3 h
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only
on
the
rate
constant
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EXAMPLE:
Determine the half-life for the reaction of sucrose with
water.
SOLUTION: We can calculate the half-life by substituting
the rate constant determined in the previous example into
the equation for the first-order half-life.
t1/ 2
0.693
=
= 16.9 h
4.10 10 2 h -1
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Second-order
Reactions
Plot of
versus time gives a straight line if the
reaction is second-order.
1
[A ]0
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Second-order
Reactions
1
k[A]0
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Second-order
Reactions
EXAMPLE:
The reaction 2 NOBr (g) 2 NO (g) + Br2 (g)
is a second order reaction with respect to NOBr.
The rate constant for this reaction is k = 0.810 M-1s-1
when the reaction is carried out at a temperature of
10o C.
If the initial concentration of NOBr = 7.5 10-3 M, how
much NOBr will be left after a reaction time of 10
minutes?
Determine
the
half-life
of
this
reaction.
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Second-order
Reactions
[NOBr ]t = 1.6 10 3 M
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Second-order
Reactions
t1/ 2 =
1
=
k[A]0
1
= 160 s
-1 1
3
0.810 M s (7.5 10 M)
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Second-order
Reactions
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Reaction
Mechanisms
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Reaction
Mechanisms
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Reaction
Mechanisms
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Reaction
Mechanisms
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Elementary
Steps
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Unimolecular
Reactions
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Bimolecular
Reaction
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Bimolecular
Reaction
Bimolecular Reaction
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Termolecular
Reaction
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Reaction
Mechanisms
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SOLUTION:
To determine the overall reaction, we simply
cross out the species common on both the
reactant and product sides of the reactions.
Z2 2 Z
1 H2 O
2 Z + 3 H2O 2 ZH3 + 3/2 O2
2 ZH3 + 5/2 O2 2HZO3 + 2H2O
2/2 O2
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f =e
Ea / RT
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Arrhenius equation.
k = Ae
Ea
RT
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k 2 Ea 1
1
ln =
k1 R T2 T1
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EXAMPLE:
The activation energy for the reaction
ClO2F (g) ClOF (g) + O (g)
is 186 kJ/mol.
If the value of k is 6.76 10-4 s-1 at 322o C,
what is the value of k at 50o C?
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ln =
k1
R T2
T1
k2
1
1.86 10 5 J/mol 1
ln
=
4 -1
k2
ln
4 1 = 31.7
6.76 10 s
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k 2 Ea 1
1
ln =
k1 R T2 T1
k2
1
1.86 10 5 J/mol 1
ln
=
4 -1
6.76 10
k2
ln
= 31.7
6.76 10 4 s 1
k2
14
=
1.71
10
;
6.76 10 4 s -1
k 2 = 1.16 10 17 s -1
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Catalysis
Catalyst - a substance that increases the rate
of a reaction without being consumed in the
reaction.
Important in chemical industry and in living
organisms.
Chemical industry - favor formation of specific
products and lower reaction temperatures.
Living organisms - enzymes (catalysts) facilitate
specific reactions of crucial biological importance.
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Catalysis
Accelerates the rate of a reaction by making a
new and more efficient pathway available for
the conversion of reactants to products.
Speeds up reaction in two ways:
increases the frequency factor A
decreases the activation energy
rate constant is more sensitive to the Ea and a catalyst usually
functions
by
lowering
the
activation
energy
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Homogeneous and
Heterogeneous
Catalysts
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Homogeneous and
Heterogeneous
Catalysts
Industrial
chemical
processes
use
mostly
heterogeneous catalysts due to the ease of separation
of the catalyst from the reaction products.
Used in automobile catalytic converters.
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Terima Kasih