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TOPIC 10-CHEMICAL KINETICS

CONTENTS
The rate of a Chemical Reaction
Measuring Reaction Rates
The Effect of Concentrations on
Rates of reaction:The Rate Law
Zero-Order Reactions
First-order Reactions
Second-Order Reactions
Reaction Kinetics:Summary
The Rate of a Chemical Reaction
The Rate of a Chemical Reaction
The Rate of a Chemical Reaction
The Rate of a Chemical Reaction
Measuring Reaction Rates
In the decomposition of H
2
O
2
, O
2
(g) escapes from the
reaction mixture and the reaction goes to completion
2 H
2
O
2
(aq) 2 H
2
O + O
2
(g)
We can follow the progress of reaction by focusing either on
the formation of O
2
(g) or the disappearance of H
2
O
2
(aq).
That is, we can
Measure the volumes of O
2
(g) and relate these volumes to
decrease in concentration of H
2
O
2
Remove small samples of the reaction mixture from time
to time and analyze these samples of H
2
O
2
content. This
can be done, for example, by titration of KMnO
4
in acidic
solution. The net ionic equation for the oxidation-
reduction reaction is
2 MnO
4
-
+ 5 H
2
O
2
+ 6 H
+
2 Mn
2+
+ 8 H
2
O + 5 O
2
(g)
Measuring Reaction Rates
Table 1. Decomposition of H
2
O
2
Measurement of the rate of reaction
I II
t(s)


400

400

400

400

400


III IV
[H
2
O
2
], M




V
REACTION RATE= -
[H
2
O
2
]/t, Ms
-1

TIME(s) [H
2
O
2
], M
0 2,32
400 1,72
800 1,30
1200 0,98
1600 0,73
2000 0,54
2400 0,39
2800 0,28
-0,42
- 0,32
- 0,25
- 0,60
-0,19
-0,15
-0,11
15,0X 10
-4

10,5X10
-4

8,0X10
-4

6,3X10
-4

4,8X10
-4

3,8X10
-4

2,8X10
-4

Measuring Reaction Rates
The rate of this reaction is not
constant. In order to calculate
the instantaneous rate of
reaction a tangent line must be
drawn. Reaction rate is
determined from the slopes of
the tangent lines. The slope of
the first tangent line is given
below:
s M v
s
M
v
/ 10 7 , 5
2850
) 63 , 1 (
4
=

=
Graphical Representation of kinetic data for the
reaction 2 H
2
O
2
(aq) 2 H
2
O

+ O
2
(g)
Measuring Reaction Rates
=
11
11
Example
From the data in the previous Table and Figure for the decomposition
of H
2
O
2
a) determine the initial rate of decomposition of H
2
O
2
and b)
[H
2
O
2
]
t
at t=100 s.
initial rate
1,74x10
-3
Ms
-1

Measuring Reaction Rates
An alternate method is to use data from the table given : [H
2
O
2
]=2,32
M at t=0 and [H
2
O
2
]=2,01 M at t=200 s
The agreement between two methods is fairly good, although it
would probably better if the time interval were less than 200 s. Of
the two results, that based on the tangent line is presumably more
reliable because it is expressed with more significant figures. On the
other hand, the reliability of the tangent line depends on how
carefully the line is constructed.
Measuring Reaction Rates
The Effect of Concentrations on Rates of
Reactions: The Rate Law
One of the goals in chemical kinetics study is to derive an equation that can be
used to predict how a rate of reaction depends on the concentrations of
reactants. Such an experimentally determine equation is called a rate law or
rate equation.
Consider the hypothetical reaction
a A + b B + g G + h H +
Where a,b. Stand for coefficients in the balanced equation. We can express
the rate of reaction as
rate of reaction = k [A]
m
[B]
n

The terms [A] and [B] represent molarities. The exponents,m,n are generally
small whole numbers, although in some cases they may be zero, fractional
and/or negative.
The Effect of Concentrations on Rates of
Reactions: The Rate Law
The Effect of Concentrations on Rates of
Reactions: The Rate Law
Establishing the Order of a Reaction by the Method of Initial Rates

INITIAL CONCENTRATIONS, M INITIAL RATE OF REACTION,Ms
-1
, R
EXPT [S
2
O
8
-2
] [I
-
] R
1 0,038 0,060 R
1
= 1,4 x 10
-5

2 0,076 0,060 R
2
= 2,8 x 10
-5

3 0,060 0,120 R
3
= 4,4 x 10
-5

Use data from the table above to establish the order of reaction
S
2
O
8
2-
+ 3 I
-
2 SO
4
2-
+ I
3
-

with respect to S
2
O
8
2-
and I
-
and also the overall order of the reaction
The Effect of Concentrations on Rates of
Reactions: The Rate Law
rnek
The Effect of Concentrations on Rates of
Reactions: The Rate Law

This is not a problem because we now know the value m=1 and we can
substitute actual concentrations for [S
2
O
8
2-
].
R
3
= k x (0,060 M)
1
x (2 x [I
-
]
2
)
n


R
2
= k x (0,076 M)
1
x [I
-
]
2
n

R
3
/ R
2
= 4,4 x 10
-5
/ 2,8 x 10
-5
= 0,060 x 2
n
/ 0,076
2
n
= 2 n=1 .
The reaction is first order in S
2
O
8
2-
(m=1), first order in I
-
(n=1) and
second order overall ( m + n= 2)
The Effect of Concentrations on Rates of
Reactions: The Rate Law

In general, the effect of the initial rate caused by doubling of the
concentration of a reactant is related to the reaction order in the following
way:
For a zero-order reaction the initial rate is unaffected(2
0
=1);
For a first order reaction the initial rate doubles(2
1
=2)
With a second order reaction the initial rate increases fourfold(2
2
=4)
With a third order reaction,eightfold(2
3
=8)
The Effect of Concentrations on Rates of
Reactions: The Rate Law
Practice: Use the results in the previous example and data from the table to
establish the value of k in the rate equation
1 1 3
10 1 , 6

= s M k
Zero-Order Reactions
A zero-order reaction has a rate equation in which the
sum of the exponents(m+n+.) is equal to 0. In a
reaction in which a single reactant A decomposes to
products
A Products, if the reaction is zero-order, the rate
equation is
Rate of reaction= k [A]
0
=k=constant
Other features of the zero-order reactions are
The concentration-time graph(plotted above) is a
straight line with negative slope
The rate of reaction, which remains constant
throughout the reaction, is the negative of the slope
of this line
The units of k are the same as as the units of the rate
of reaction: molL
-1
s
-1
or Ms
-1


First-Order Reactions
A first order reaction has a rate
equation in which the sum of the
exponents (m+n+) is equal to 1. A
particularly common type of first order
reaction and the only type we will
consider, is that in which a single
reactant decomposes into products.
First Order Reactions
| |
( )
| | A A
t k
t 0
ln ln + =
Equation of straight line y= mx + b
First-Order Reactions
Example:
H
2
O
2
(aq), initially at a concentration of 2,32 M, is allowed to decompose.
What will [H
2
O
2
] be at t=1200 s? Use k= 7,30x10
-4
s
-1
for the first order
decomposition.
First-Order Reactions
Reactions Involving Gases
For gaseous reactions, rates are often measured in terms of gas
pressures. For the hypothetical reaction, A(g) products, the
initial partial pressure (P
A
)
0
, and the partial pressure at time t, (P
A
)
t,

are related to the expression:
To see how this equation is derived, start with the ideal gas equation
written for reactant A: P
A
V= n
A
RT. Note that the ratio n
A
/V is the same
as [A]
.
So, [A]
0
= (P
A
)
0
/RT and [A]
t
= (P
A
)
t
/RT. Substitute these terms in
the equation of the first order rate of reaction ,then you will get the
equation above.
Reactions Involving Gases
From the figure we see that t
1/2
= 8,0 x 10
1
min. For a first order
reaction :
1 3
min 10 7 , 8
min 80
693 , 0 693 , 0
2
1

= = =
t
k
a.
b.
mmHg P
mmHg P
s DTBP
DTBP
50 ] [
800 ] [
0
=
=
0
] [
16
1
] [
DTBP s DTBP
P P =
min 320 min 80 4 4
2
1
= = = t t
The reaction must go through four half-lives
C
8
H
12
O
2
(g) 2 C
3
H
6
O(g) + C
2
H
6
(g)
DTBP Aceton Ethane
Reaction is started with pure DTBP at 147C and 800,0 mm Hg pressure in
a flask of constant volume.a) What is the value of the rate constant k? b ) At
what time will the partial pressure of DTBP be 50,0 mm Hg?
First Order Reactions
SOME TYPICAL FIRST-ORDER PROCESSES

PROCESS HALF-LIFE,t
1/2
RATE CONSTANT k,s
-1

Radioactive decay of uranium isotope(M
A
=238) 4,51 x 10
9
years 4,87 x 10
-18

Radioactive decay of carbon isotope(M
A
=14) 5,73 x 10
3
years 3,83 x 10
-12

Radioactive decay of phosphorus(M
A
=32) 14,3 days 5,61 x 10
-7

C
12
H
22
O
11
(aq) + H
2
O C
6
H
12
O
6
(aq) + C
6
H
12
O
6
(aq)
sucrose fructose glucose
8,4 h 2,3 x 10
-5

(CH
2
)
2
O (g) CH
4
(g) +CO(g)
Ethylene oxide
56,3 min 2,05 x 10
-4

2 N
2
O
5
2 N
2
O
4
+ O
2
(g) 18,6 min 6,21 x 10
-4

HC
2
H
3
O
2
(aq) H
+
(aq) + C
2
H
3
O
2
(aq) 8,9 x 10
-7
s 7,8 x 10
5

15C
415C
in
CCl
4

45C
Second-Order Reactions
} }
=
] [
] [ 0
2
0
] [
] [
A
A
t
dt k
A
A d
A second order reaction has a rate equation in which the sum of
exponents(m+n+.) is equal to 2. The reaction of peroxidisulfate-iodide is
second order overall:
rate of reaction= k [S
2
O
8
2-
] [I
-
]
Some reactions involving a single reactant, that is of the type A products, are
also second order and their rate equations are
rate of reaction= -(rate of change of [A] = k [A]
2

To convert the rate law into an integrated equation, a
calculus derivation is required:


Second-Order Reactions
The straight line plot is obtained for1/[A] vs. t,(graph on the right hand) ,so the reaction is second order
Testing for the order of a reaction
Second- Order Reactions
Graphing Data to determine the Order of a Reaction-The data
listed in the table below refers to the decomposition of A
products. a) Establish the order of the reaction b) What is the rate
constant k? c) What is the half-life, t
1/2
, if [A]
0
=1,00 M.
KINETIC DATA
TIME,min [A], M ln [A] 1/[A]
0 1,00 0,00 1,00
5 0,63 -0,46 1,6
10 0,46 -0,78 2,2
15 0,36 -1,02 2,8
25 0,25 -1,39 4,0
Establishing the Order of a Reaction

Reaction Kinetics (Summary)


1. To calculate a rate of reaction when the rate law is known, use the
expression: rate of reaction= k [A]
m
[B]
n

2. To determine a rate of reaction when the rate law is not given, use
The slope of an appropriate tangent line to the graph of [A] vs. t.
The expression [A]/t, with a short time interval t
3. To determine the reaction order, depending on the data given,
Use the method of initial rates;
Find the graph of rate data that yields a straight line;
Test for the constancy of the half-life(good only for first-order)
Substitute data into integrated rate equations to find the equation that gives
a constant k,
4. To relate reactant concentrations and times, use the appropriated integrated
rate equation after first determining k


Theoretical Models For Chemical Kinetics
COLLISION THEORY: With the kinetic molecular theory it is possible to calculate
the number of molecular collisions per unit time (
c
= COLLISION FREQUENCY). In
a typical reaction involving gases
c
= 10
30
collisions per second. If each collision
yielded product molecules, the rate of reaction would be about
rxn
10
6
M/s ,an
extremely rapid rate. Gas phase reactions generally proceed at much slower rate,
rxn

10
-4
M/s . This means that only a fraction of the collisions among the gaseous
molecules lead to a chemical reaction. The minimum total kinetic energy that molecules
must bring to their collisions for a chemical reaction to occur is called Activation
Energy=E
a
. The rate of a reaction depends on the product of the collision frequency
and the fraction of these activated molecules. Moreover the higher the E
a
of a reaction,
the smaller the fraction of energetic collisions and the slower the reaction.
Theoretical Models for Chemical Kinetics
Theoretical Models for Chemical Kinetics
Another factor that affects the rate of reaction is the orientation of
the molecules at time of the collision. A particular orientation of the
molecules may be required if a collision is to be effective in
producing a chemical reaction. The number of unfavourable collisions
often exceeds the number of favorable ones. (The collision of two
slow moving automobiles bumper to bumper may produce no damage
at all, whereas if the bumper of one car strikes the fender of the other,
the damage may be considerable.
TRANSITION STATE THEORY: A hypothetical species with
properties intermediate to those of the reactants and products, called
transition state or activated complex.
The enthalpy change of a reaction is equal to the difference in
activation energies of the forward and reverse reactions
rxn
=
E
a
(forward)- E
a
(reverse)
For an endothermic reaction the activation energy must be equal to
or greater than the enthalpy of reaction
The Effect of Temperature on Reaction Rates
To speed up the biochemical reactions involved in cooking we raise the
temperature. To slow down other reaction we lower the temperature, as
in refrigerating milk to prevent it from souring.
In 1889 Svante Arrhenius demonstrated the rate constants of many
chemical reactions vary with temperature in accordance with the
expression:
The Effect of Temperature on Reaction Rates
Data are plotted as follows for the
representative point in black
To evaluate E
a,

Slope of line =
The Effect of Temperature on Reaction Rates
Exercise: Determine the temperature (T
2
) at which the decompositon
constant of N
2
O
5
k
2
was found 9,63x10
-5
considering the first condition
T
1
= 298 K and k
1
= 3,46x10
-5
s
-1
; (E
a
= 106 kJ/mol)?
CATALYSIS
A reaction can generally be made to go faster by raising the temperature.
Another way to speed up a reaction is to use a catalyst. A catalyst provides
an alternate reaction pathway of lower activation energy. It participates in a
chemical reaction without undergoing permanent change. As a result the
formula of a catalyst does not appear in the net chemical equation(Its
formula is placed over the reaction arrow.)
Some examples for the catalysts can be given as follows:
1-) Pt-Rh catalyst speed up the oxidation of NH
3
(g)
2-) Iodide ion (I
-
) is a good catalyst for the decomposition of H
2
O
2
(aq)
There are also some important biological enzymes such as lactase which
helps to convert milk sugar( lactose) into glucose and galactose