RATE LAW

11.1

Objectives:

5. calculate the value and determine the units of
rate constants
At the end of the lesson the students should be able
to:
1. define rate law and write the rate equation
2. define the order of reaction and the rate constant
3. calculate the order with respect to a certain reactant
from experimental data
4. determine the overall order of a reaction from
experimental data

The Rate Law
The rate law expresses the relationship of the rate of a
reaction to the rate constant and the concentrations of
the reactants raised to some powers.
aA + b c! + d"
#ate $ k %A&
x
%&
'
reaction order is x with respect to A
reaction order is ' with respect to
(verall reaction order is (x + y)
The exponents x, y, The exponents x, y, can be integers, can be integers,
fractions or decimal or negative values. fractions or decimal or negative values.
k k is called is called rate constant rate constant
Rate reactant!

Rate Law
"
The values of x and y can only be determined
experimentally.
"
Reaction order is usually defined in terms of
reactant concentrations.
)
*he order of a reactant is not related to the stoichiometric
coefficients of the reactants in the balanced chemical
equation.
+
2
,g- + 2!l(
2
,g- 2+!l(
2
,g-
rate $ k %+
2
&%!l(
2
&
1

The units of rate
constant, #
A $roducts
Rate, r % # A!
x
i& The reaction is 'ero order
Rate % # A!
0
Rate % #
unit # %unit rate
% mol L
()
s
()
or * s
()

ii& +irst order
Rate % # A!
)
,nit # %
* s
-1
*
% s
-1
iii& -econd order
Rate % # A!
2
A!
2
# %
rate
%
* s
-1
*
2
% *
-1
s
-1
.nit /
A!
# %
rate

Example .
S
2
O
8
2-
+ 3I
-
2SO
4
2-
+ I
3
-
The above reaction is first order with respect to iodide ions and
to thiosulphate ions.
a& Write the rate of e/uation for the reaction.
b& What is the unit of rate constant, #0
-olution .
a& Rate % # -
2
1
8
2-
!
1
2
-
!
1
b& Rate % # -
2
1
8
2-
!
1
2
-
!
1
# %
rate
-
2
1
8
2-
!
1
2
-
!
1
%
*s
-1
*
2
% *
-1
s
-1
.nit /

The order of
reaction
+or reaction
A $roducts
Rate % # A!
x
i& I x ! 0
Rate is not dependent on A!
Rate % # A!
0
Rate % #
Therefore this reaction is zero order with respect to A

ii" I x! 1
Rate % # A!
)
Assume A!
i
% ).3*
Rate % # 4).3*&
2f the A! is doubled from ).3* to 5.3*,
Rate % # 45.3*&
% 5#4).3*&
hence
Rate % 5#A!
6oubling the A! will double the rate of reaction.
Therefore this reaction is first order with respect to A

iii" I x ! 2
Rate % #A!
2
Assume A!
i
% ).3 *
Rate % # 4).3 *&
2
2f the A! is doubled from ).3 * to 5.3 *,
Rate % # 45.3 *&
2
% 7#4).3 *&
hence
Rate % 7#A!
6oubling A!, the rate will increase by a factor of 7.
Therefore the reaction is second order with respect to A

Example
#eter$inin% Reaction Order ro$ Rate Law
+or each of the followin0 reactions1 determine the
reaction order with respect to each reactant and the
overall order from the 0iven rate law.
(a) 2NO(g) + O
2
(g) 2NO
2
(g); rate = k[NO]
2
[O
2
]
overall reaction order $ 3
*he reaction order respect to 2( : 2
*he reaction order respect to (
2
: 1

-olution.
The reaction order with respect to 89
:
891 . :;5
The reaction order 4overall& . :;5
-olution.
The reaction of order with respect to 9
5
1
5
. )
The reaction of order with respect to 2
(
. )
and 'ero order in 9
<
, while overall order is 2.
,b- !3
3
!3( ,g- !3
4
,g- + !(,g-4
rate $ k%!3
3
!3(&
32
(c) !
2
O
2
(aq) + 3I
"
(aq) + 2!
+
(aq) I
3
"
(aq) + 2!
2
O(l);
rate = k[!
2
O
2
][I
"
]

Experiment
#nitial $eactant
%oncentrations (mol&
"'
)
#nitial $ate
(( s
"'
)
O
2
NO
'
2
3
)
*
'+',x',
"2
'+3,x',
"2
3+2'x',
"3
'+',x',
"2
3+-,x',
"2
2.+.x',
"3
2+2,x',
"2
'+',x',
"2
3+3,x',
"2
'+3,x',
"2
2+/,x',
"2
'+3,x',
"2
/+),x',
"3
'2+.x',
"3
-+/,x',
"3
6etermination of the orders of reaction rate=
O
2
(g) + 2NO(g) 2NO
2
(g)

O
2
(g) + 2NO(g) 2NO
2
(g)
rate $ k %(
2
&
m
%2(&
n
8ompare 5 experiments in which the concentration of one
reactant varies and the concentration of the other
reactant4s& remains constant.
rate
2
k %(
2
&
2
m
%2(&
2
n
k %(
2
&
1
m
%2(&
1
n
$
rate
1

=
%(
2
&
2
m
%(
2
&
1
m
$
%(
2
&
2
%(
2
&
1
m
5.46x16
73
8s
71
3.21x16
73
8s
71
$
1.16x16
72
mol9:
2.26x16
72
mol9: m
4
2 $ 2
m
1 m $ 1
"o a similar calculation for the other reactant,s-.
-olution.
*he reaction is first order with respect to (
2

To find the order with respect to >1, we
compare experiment : and ), in which 1
5
! is
held constant and >1! is doubled.
$
/ %(
2
&
3
m
%2(&
3
n
/ %(
2
&
1
m
%2(&
1
n
#ate 3
#ate 1
%2(&
3
$
%2(&
1
n
12.; x 16
73
8s
71
3.21 x 16
73
8s
71
$
2.56 x 16
72
mol9:
1.36 x 16
72
mol9:
n
4 $ 2
n
n $ 2 4
*he reaction is second order with respect to 2(
*hus the rate law is :
#ate $ /%(
2
&%2(&
2

*he results of the /inetic studies are 0iven below.
<xercise:
exp %!l(
2
&
8
%(3
7
&
8
=nitial rate1
8s
71
1 6.6421 6.61;5 ;.21 1 6
73
2 6.6522 6.61;5 1.25 1 6
72
3 6.6421 6.62;5 1.25 1 6
72
!l(
2
,aq- + 2(3
7
,aq- products
a- <xplain what is meant b' the order of reaction.
b- #efferin0 to the data determine
,i- rate law 9rate equation
,ii- rate constant1 /
,iii- the reaction rate if the concentration of both !l(
2

and (3
7
$ 6.65 8

i- >hen %A& is doubled1 rate also doubles. ut
doublin0 the %& has no effect on rate.
ii- >hen %A& is increased 3x1 rate increases 3x1
and increasin0 of %& 3x causes the rate to
increase ?x.
iii- #educin0 %A& b' half has no effect on the rate1
but reducin0 %& b' half causes the rate to be
half the value of the initial rate.
<xercise:
A + !
>rite rate law for this equation1

<xercise:
8an' 0aseous reactions occur in a car en0ine and exhaust
s'stem. (ne of the 0as reaction is 0iven below.
2(
2
,0- + !(,0- 2(,0- + !(
2
,0-
#ate $
/ %2(
2
&
m
%!(&
n
<xperiment =nitial #ate,8s
71
-
=nitial %2(
2
&,8- =nitial %!(&,8-
1
6.6656
6.16 6.16
2
6.6;6 6.46 6.16
3
6.6656 6.16
6.26
.se the followin0 data to determine the individual and overall reaction orders: