CONTENTS
The rate of a Chemical Reaction
Measuring Reaction Rates
The Effect of Concentrations on
Rates of reaction:The Rate Law
ZeroOrder Reactions
Firstorder Reactions
SecondOrder 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 zeroorder 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
ZeroOrder Reactions
A zeroorder 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 zeroorder, the rate
equation is
Rate of reaction= k [A]
0
=k=constant
Other features of the zeroorder reactions are
The concentrationtime 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
FirstOrder 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
FirstOrder 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.
FirstOrder 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 halflives
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 FIRSTORDER PROCESSES
PROCESS HALFLIFE,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
SecondOrder 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 peroxidisulfateiodide 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:
SecondOrder 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 ReactionThe 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 halflife, 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