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Chemical Kinetics
NURUL AIN BINTI JAMION
1
CHAPTER 2
Rates of Reaction
Factors affecting rates of
reaction
Rates law and order of
reaction
Methods to determine order
of reaction
Relation between rate and
temperature
Reaction Mechanism
Catalytic kinetics
INTRODUCTION
Chemical
INTRODUCTION
RATEs of REACTION
Definition:
A measure of the change in the concentration of
a reactant or product in a given time.
[ x]
rate
t
Unit
= mole / liter =
mol / L
second
s
= Mol L-1 s-1
Reaction Rates(cont.)
depending on the experimental conditions :
average rate: rate measured between long time
interval
instantaneous rate: rate measured between
very short interval
initial rate: instantaneous rate at the beginning
of an experiment
12
RATEs of REACTION
Reactant
Product
the
with time.
[A]
rate = t
[B]
rate =
t
13
1 [A]
rate = 2
t
aA + bB
rate =
[B]
t
cC + dD
1 [A]
1 [B]
1 [C]
1 [D]
rate = ==
=
a t
b t
c t
d t
[CH4]
1 [O2]
rate = =
=t
2 t
[CO2]
1 [H2O]
=
t
t
2
16
17
TRY
2N2O 5(g) 4NO2(g) O 2(g)
Write the Differential rate equation for
above equation.
Solution
1 d[N 2 O 5 ]
1 d[NO 2 ]
d[O 2 ]
Rate
2
dt
4
dt
dt
18
TRY
2O3 ( g ) 3O2 ( g )
1 d [O3 ]
1 d [O2 ]
rate
2 dt
3 dt
TRY
TRY
Consider the reaction for the combustion
of methane, CH4 ,
CH4(g) + 2O2(g) CO2(g)+ 2H2O(g)
If the methane is burning at a rate of 0.16 molL-1s1 , at what rates are CO and H O being formed?
2
2
Solution
CH4(g) + 2O2(g) CO2(g)+ 2H2O(g)
Given d[CH4] = - 0.16 molL-1s-1
dt
so; -d[CH4] = d[CO2] = d[H2O]
dt
dt
2 dt
Solution
To calculate rate of N2;
d[CO2] = - d[CH4]
dt
dt
= -(-0.16 molL-1s-1 )
= 0.16 molL-1s-1
Solution
To calculate rate of H2O;
d[H2O] = 2x -d[CH4]
dt
dt
= 2 x (-0.16 molL-1s-1 )
= 0.32 molL-1s-1
24
2C2H4 (g)
C4H8(g)
Time(s)
10
20
40
60
[C2H4]/mol L-1
0.884
0.621
0.479
0.328
0.169
Answer :
At t = 0s, [C2H4] = 0.884 M
At t = 40s, [C2H4] = 0.328 M
Rate = (0.884 0.328)M
40s
= 0.0139 Ms-1
= 0.014 Ms-1 so, the rate of reactions at 40s is 0.014 Ms-1
aA + bB
cC + dD
Rate = k [A]a[B]b
k
= rate constant
a & b = reaction order with
respect to A & B
a + b = overall reaction
order
13.2
2FClO2 (g)
rate = k [F2][ClO2] 1
13.2
27
28
rate= k[A]
Second order reaction:
- Rate is directly proportional to the square of [A]
rate= k[A]2
Zero order reaction:
- the rate is not dependent on [A]
29
33
DETERMINING REACTION
ORDER
Initial
rate
Integrated Rate
Law
Half
life
34
35
Example 1
The results shown below are obtained for
the reaction between A and B. Determine
the rate equation for the reaction between
A and B.
Experiment
1
2
3
Concentration
(mol L-1)
[A]
[B]
0.0575
0.0713
0.0575
0.0216
0.0216
0.0333
Initial rate
(mol L-1 s-1)
8.21x10-3
1.26x10-2
1.26x10-2
36
8.2110
0.0575
2
1.2610
0.0713
37
Calculating n in [B]n; we
take the ratio of the
rate laws for two experiment 1 and 3, in
which [B] varies but [A] is constant
8.21 10
0.0216
2
1.26 10
0.0333
That is,
0.652 = 0.649n
log 0.652 = n x log 0.649
n 1
Hence, the reaction is first order with respect
to B.
The rate equation is
rate k[A]2[B]
38
Example 2
The reaction between C and D is represented as
follows :
C D E
1
2
Initial concentration
(M)
[C]
[D]
0.05
0.05
1.0
2.0
Time
interval
(minutes)
The change in
concentration
of C (M)
30
30
2.5 x 10-3
1.0 x 10-2
-3
39
2.5 10
1.0
2
1.0 10
2.0
Example :
Derive the rate law for the reaction
A + B + C products
from the following data :
[A]0
1
0.100
2
0.200
3
0.200
4
0.100
[B]0
0.100
0.100
0.300
0.100
[C]0
0.100
0.100
0.100
0.400
rate
0.100
0.800
7.200
0.400
Expriment
solution
Assume:
rate = k [A]x [B]y [C]z
From experiment 1 and 2, we have:
0.800 k [0.2]x [0.1]y [ 0.1]z
----- = -----------------------0.100 k [0.1]x [0.1]y [0.1]z
Thus, 8 = 2x; and x = ln8 / ln2 = 3
By similar procedures, we get y = 2 and z = 1.
Thus, the rate law is: rate = k [A]3 [B]2 [C]
overall order = 3+2+1 = 6
42
2.510
0.05
3
5.010
0.1
rate k [C][D]2
TRY
The following data refers to the following
reaction:
CH3COCH3 + I2 + H+ CH3COCH2I + HI
Expt.
[CH3COCH3],
3.0
M [H+],
M
Initial rate,
Ms-1
0.2
[I2],
M
0.02
3.0
0.4
0.02
12.0 x 10-6
4.0
0.4
0.02
16.0 x 10-6
4.0
0.2
0.04
8.0 x 10-6
6.0 x 10-6
rate
k
independent to [reactant]
[A]
45
rate
[A]
46
Rate
[A]
47
Unit
Integrated rate
law
[A] = [A]0 - kt
rate = k
Ms
rate = k [A]
s-1
ln[A] = ln[A]0 - kt
rate = k [A]
M s
1
1
=
+ kt
[A]
[A]0
-1
-1 -1
Half-Life
[A]0
t =
2k
t = ln 2
k
1
t =
k[A]0
2NO(g) + 2H2(g)
N2(g)
2H2O(g)
[NO] (M)
[H2] (M)
Initial
rate(M/s)
5.0 x 10-3
2.0 x 10-3
1.3 x 10-5
10.0 x 10-3
2.0 x 10-3
5.0 x 10-5
10.0 x 10-3
4.0 x 10-3
10.0 x 10-5
ln[A] = ln[A]0 - kt
[A] = 0.14 M
kt = ln[A]0 ln[A]f
ln[A]0 ln[A]t
=
t=
k
ln
[A]0
[A]t
k
ln
=
0.88 M
0.14 M
2.8 x 10 s
-2
-1
= 66 s
TRY
1. The rate constant for the decomposition of
N2O5 to NO2 and O2 at 70C is 6.82 x 10-3 s-1.
Suppose we start with 0.300 mol of N2O5(g) in
a 0.500 L container.
How many moles of N2O5 will remain after 1.5
min?
How many minutes will it take for the quantity
of N2O5 to drop to 0.030 mol?
What is the half-life of N2O5 at 70C ?
Ineffective
collision
Activation energy(cont.)
The height of the activation barrier influences the
rate:
If
If
lower concentration
higher concentration
0%
25%
reactants
product
50%
75%
100%
lower pressure
higher pressure
energy (kJ)
Ea with
catalyst
reaction (time)
Type of catalysis
a) Homogeneous
Temperature in K
Activation
energy
Gas constant
8.314 J/mol K
70
Example:
A plot of ln(k) vs. 1/T(K)
Rate vs. Temperature
2
y = -7330.4x + 25.417
ln rate
1.6
1.2
0.8
0.4
0
3.1E-03
3.2E-03
3.3E-03
3.4E-03
3.5E-03
3.6E-03
1/T, Kelvin
71
Example: (cont.)
Q1Calculate the activation energy for this
reaction?
Q2 Calculate rate would be expected for this
reaction at 30C?
Q3 Determine temperature is needed to
double this rate?
73
Ea
Ea = - (Slope) x (R)
Ea = - (-7330.4 K) x (8.314 J/molK)
Ea = 60.9 kJ/mol
So the activation energy for this reaction
is 60.9 kJ/mol
74
75
76
1
T2
Where T1 < T2
Example
The rate constant for the formation of HI at 600K and 650K
are measured and found to be 2.7x10-4 M-1s-1 and 3.5x10-3
M-1s-1, respectively. Determine the activation energy and
the rate constant at 800 K.
H2+I2 2HI
Solution
ln k2 = Ea 1
k1 R T1
ln (3.5x10-3 ) = Ea
(2.7x10-4 ) 8.314 Jmol-1
ln (13.0 )
Ea
= Ea
8.314 Jmol-1
=
1
T2
1
1
600K
650K
(1.28x10-4)
Example
Solution
To determine rate constant at 800K.
ln k2
= Ea
(3.5x10-3 )
R
1 650
1
800
81
TRY
The
ln k2 = Ea 1
k1 R T1
Answer:
1
T2
Reaction Mechanism
Elementary reactions
+
Elementary reactions
Elementary reactions
Unimolecular
Bimolecular
Trimolecular
REACTION
MECHANISM
Reaction
intermediate
Fast
Slow
Reaction Mechanisms
The overall progress of a chemical reaction can be represented
at the molecular level by a series of simple elementary steps
or elementary reactions.
The sequence of elementary steps that leads to product
formation is the reaction mechanism.
2NO (g) + O2 (g)
2NO2 (g)
Elementary step:
NO + NO
N 2 O2
+ Elementary step:
N2O2 + O2
2NO2
Overall reaction:
2NO + O2
2NO2
84
Intermediates are species that appear
in a reaction
mechanism but not in the overall balanced equation.
NO + NO
N 2 O2
+ Elementary step:
N2O2 + O2
2NO2
Overall reaction:
2NO + O2
2NO2
NO3 + CO
NO2 + CO2
NO + CO2
Thank you!