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Chemical Kinetics
1
2
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 kinetics - is the study of chemical
rxns/processes with respect to reaction rates, effect
of various variables
INTRODUCTION
6
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
When the reactants change into products
the concentration of reactants decreases
the concentration of products increases
with time.
A B
[A]
rate = -
t
[B]
rate =
t
13
Measuring Reaction Rate
To measure a reaction rate, we usually monitor
either a product or a reactant for its change.
Some of the characteristics to be monitored are:
-changes in pressure
-changes in color (use spectrofotometer )
-temperature for exothermic or
endothermic reaction, and
-presence of certain key substance
Reaction Rates and Stoichiometry
2A B
1 [A] rate =
[B]
rate = -
2 t t
aA + bB cC + dD
16
17
TRY
2N2O5(g) 4NO2(g) O2(g)
Write the Differential rate equation for
above equation.
Solution
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)
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
Answer :
At t = 0s, [C2H4] = 0.884 M
At t = 40s, [C2H4] = 0.328 M
THE RATE LAW Expresses the relationship of the rate of a reaction to the rate
constant and the concentration of the reactants raised to some powers.
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
• Rate laws are always determined experimentally unless
you have been told a rate-limiting or slow step.
rate = k [F2][ClO2] 1
13.2
27
rate= k[A]
rate= k[A]2
Rate = k [ A ]m [ B ]n
a A + b B + products
Rate = k[A]x[B]y
If concentrations of B is kept
constant, you can measure the reaction
rate of A at various concentrations.
33
Initial rate
Half life
34
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.
m n
rate2 k [A] [B] 1.26 10 2
0.0713
That is, 0.652 = 0.806m
log 0.652 = m x log 0.806
m = 1.98 2
Thus, the reaction is
second order with respect to A
Calculating n in [B]n; we37take the ratio of the
rate laws for two experiment 1 and 3, in which
[B] varies but [A] is constant
m n
rate1 k [A] [B]
n
3
8.2110 0.0216
m n
rate 3 k [A] [B] 1.26 10 2
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 :
CD E
The experiment results are shown in the table below.
Determine the rate equation for the reaction
between C and D.
Initial concentration Time The change in
Experiment (M) interval concentration
(minutes) of C (M)
[C] [D]
1 0.05 1.0 30 2.5 x 10-3
2 0.05 2.0 30 1.0 x 10-2
3 0.1 1.0 120 5.0 x 10-3
39
m n
rate1 k [C] [D] 2.5 10 3
1.0
n
m n
rate 2 k [C] [D] 1.0 10 2
2.0
Expriment 1 2 3 4
[A]0 0.100 0.200 0.200 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
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
m
rate1 k [C]m [D]n 2.5 10 3
0.05
rate 3 k [C]m [D]n 5.0 10 3
0.1
rate k [C][D]2
TRY
The following data refers to the following
reaction:
CH3COCH3 + I2 + H+ CH3COCH2I + HI
independent to [reactant]
[A]
45
first order reaction
For first order, rate = k[A]
rate
[A]
46
second order reaction
the plot is a branch of a prabola, because
rate = k [A]2
Rate
[A]
47
The Rate Law &
Order Of Reaction
Summary of the Kinetics of Zero-Order, First-Order
and Second-Order Reactions
Integrated rate
Order Rate Law Unit law Half-Life
[A]0
0 rate = k Ms-1 [A] = [A]0 - kt t½ =
2k
[A]0 = 0.88 M
ln[A] = ln[A]0 - kt
[A] = 0.14 M
kt = ln[A]0 – ln[A]f
[A]0 0.88 M
ln ln
ln[A]0 – ln[A]t [A]t 0.14 M
t= = = = 66 s
k k 2.8 x 10-2 s-1
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 ?
The Collision Theory
In a chemical reaction, bonds are broken and
new bonds are formed.
Molecules can only react if they collide with
each other.
Furthermore, molecules must collide with the
correct orientation and with enough energy to
cause bond breakage and formation.
The Collision Theory
Effective
collision
Ineffective
collision
If
Ea is small, then many molecules possess
enough energy to get over the barrier; more
products are formed and the rate is faster.
What factors affect the rate of
reactions?
increased concentration of
dissolved reactants
increased pressure of gaseous
reactants
increased temperature
use of a catalyst
Ea with
catalyst
reaction (time)
Type of catalysis
a) Homogeneous
The catalyst is in the same phase as
the reactants.
b) Heterogeneous
The catalyst is in a different phase
than the reactants – often a solid
catalyst and liquid or gaseous
reactants.
67
How temperature and Catalysts Affect Reaction Rates
70
Example:
A plot of ln(k) vs. 1/T(K)
Rate vs. Temperature
y = -7330.4x + 25.417
2
1.6
ln rate
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.)
ln k = - Ea/R(1/T) + ln A
y = mx + c
y = -7330.4x + 25.417
73
Solution for Q1:
Slope = Ea
R
Ea = - (Slope) x (R)
Ea = - (-7330.4 K) x (8.314 J/molK)
Ea = 60.9 kJ/mol
74
Solution for Q2:
The rate at 30°C is …
( 30 + 273 = 303K)
75
Solution for Q3:
The temperature needed to double this
rate….( 3.4 x 2 = 6.8)
76
If we have two different k values at different
temperatures, you can combine the two
reactions to give:
ln k2 = Ea 1 1
k1 R T1 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 1
k1 R T1 T2
ln (3.5x10-3 ) = Ea 1 - 1
(2.7x10-4 ) 8.314 Jmol-1 600K 650K
ln (13.0 ) = Ea (1.28x10-4)
8.314 Jmol-1
ln k2 = Ea 1 - 1
(3.5x10-3 ) R 650 800
= 5.75
Taking the anti ln:
k2 = 314
3.5x10-3
TRY
Therate constant of a reaction is 1.2 x 10-3 sec-1 at
300 C and 2.1 x 10-3 sec-1 at 400 C. Calculate the
energy of activation of the reaction.
ln k2 = Ea 1 1
k1 R T1 T2
REACTION
MECHANISM
Reaction
intermediate
Fast
Slow
What can you say about the relative rates of steps 1 and 2?
rate = k[NO2]2 is the rate law for step 1 so
step 1 must be slower than step 2
13.5
Thank you!