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Topic Scopes
TOPIC 6
Reaction Kinetics
Rate of reactions
Rate constant, half-life of a reaction
Zero,1st & 2nd order of reactions
Factors affecting rate of reactions:
concentration, temperature, catalyst and
surface area
Concept of activation energy
Arrhenius equation
2
Reaction Rate
Reaction Kinetics
D[A]
rate =
Dt
D[B]
Dt
rate =
1) Initial rate
rate of the reaction when the reactants are
pure (precisely known)
2) Instantaneous rate (tangent rate)
rate of change in concentration at any
particular instant during a reaction
3) Average reaction rate
A measure of the change in concentration
over a defined period
The differences in concentrations of a reactant
between 2 points in time are divided by the
time elapsed
6
1 D[A]
2 Dt
rate =
aA + bB
Slope of
tangent
rate = -
D[B]
Dt
cC + dD
1 D[C]
1 D[D]
1 D[A]
1 D[B]
=
=
=d Dt
c Dt
a Dt
b Dt
D[N2]
Dt
=-
1 D[H2]
3 Dt
Extra Question
Decomposition of nitrogen pentaoxide is shown as below:
N2O5(s) ->NO2(g) + O2(g)
1 D[NH3]
Dt
2
Rate Law
Expresses the relationship of the a reaction rate
to the rate constant and the concentrations of
the reactants raised to some powers.
aA + bB
cC + dD
Rate = k [A]x[B]y
10
can be 0, 1, 2 or fraction
must be determined by experiment
total reaction order = (x + y)
2FClO2 (g)
1
rate = k [F2][ClO2]
11
12
2 FClO2 (g)
Rate = k[F2]x[ClO2]y
13
No
change
x4
x4
14
No
change
x2
x2
Rate doubles
Rate quadruples
Rate Experiment 2 k 0.10 M 0.040 M
4.8 10 Ms
-3
-1
Rate 1 0.10 1.2 10 3
x
Rate 2 0.040
4.8 10 3
Rate 1 0.010
1.2 10 3
y
2 = (2)x, x = ____
4 = (4)y, y = ______
The reaction is ______ order in [ClO2]
15
x = ___ , y = ___
rate = ________
Zero-Order Reactions
A
D[A]
rate = - Dt
product
rate = k [A]0 = k
D[A]
Dt = k
Rate = k [F2][ClO2]
[A] = [A]0 - kt
Using Exp. 1:
Rate = 1.2 x 10-3 M s-1 = k [0.10 M][0.010 M]
k = ______ M-1 s-1 = ______ L mol-1 s-1
or
Using Exp. 2:
Rate = 4.8 x 10-3 M/s = k [0.10 M][0.040 M]
k = ______ M-1 s-1 = ______ L mol-1 s-1
17
18
First-Order Reactions
A
rate = -
D[A]
Dt
rate = k [A]
ln[A] = ln[A]0 - kt
The reaction 2A
B is first order in A
with a rate constant of 2.8 x 10-2 s-1 at
800C. How long will it take for A to
decrease from 0.88 M to 0.14 M ?
product
-
D[A]
= k [A]
Dt
19
20
Half-Life, t1/2
The time required
for a reactant to
decrease to half of
its initial
concentration /
amount
21
22
Problem :
At a given temperature, hydrogen peroxide
(H2O2) decomposes to water and oxygen with
the rate law as below:
Rate = k[peroxide], k = 1.06 x 10-3 min-1
24
Solution:
After 15% of the H2O2 has decomposed,
85% remains.
fraction remaining is 0.85
ln(
Problem:
Radioactive decay is a first order process.
Tritium electron + helium
3H
0 e
3He
-1
[H 2 O 2 ]t
) kt
[H 2 O 2 ]o
85
) (1.06 10 3 min 1 )(t )
100
ln0.85 (1.06 10 3 min 1 )(t )
t
ln(
min
25
Solution:
ln [A]/[A]0 = -kt
[A] = ?
[A]0 = 1.50 mg,
26
Second-Order Reactions
A
t = 49.2 years
rate = -
1
1
=
+ kt
[A]t [A]0
D[A]
= k [A]2
Dt
28
- D[A]/Dt = k [A]1
rate = k [A]2
27
- D[A]/Dt = k [A]0
D[A]
Dt
product
Concentrations
Temperature
Physical state of reactants
(surface area)
Catalysts
- D[A]/Dt = k [A]2
30
Rate Temperature
Reactions generally
occur slower at lower
T.
Rate concentration
31
32
34
Activation Energy, Ea
35
AB
+
+
C+D
Endothermic Reaction
36
Activation Energy, Ea
Collision Theory
37
Arrhenius Equation
38
ln k = -
Ea 1
+ lnA
R T
Ea = activation energy
T = temperature (K)
39
Example:
40
Solution:
41
42
Catalysis
Learning Outcomes
44