Reaction rate

Learning objective
Explore the rate of chemical reaction
Topics:
Definition of reaction rate
Outline the techniques for its measurement
Variables control
Definition of reaction rate
The reaction rate is the increase in
molar concentration of a product of
a reaction per unit time
It can also be expressed as the decrease
in molar concentration of a reactant
per unit time.
Why do we study the reaction rate?
Video of reaction
Halloween reaction
Nurdrage
Why do we study the reaction rate?
To predict how quickly a reaction mixture
approaches equilibrium
To optimise the rate by the appropiate
choice of condition
To an understanding of the mechanisme of
reactions, their analysis into a sequence of
elementary steps
A B
13.1
rate = -
A[A]
At
rate =
A[B]
At
time
Reaction rate is the change in the concentration of a
reactant or a product with time (M/s).
A B
rate = -
A[A]
At
rate =
A[B]
At
A[A] = change in concentration of A over
time period At
A[B] = change in concentration of B over
time period At
Because [A] decreases with time, A[A] is negative.
Br
2
(aq) + HCOOH (aq) 2Br
-
(aq) + 2H
+
(aq) + CO
2
(g)
time
393 nm
light
Detector
A[Br
2
] o AAbsorption
Br
2
(aq) + HCOOH (aq) 2Br
-
(aq) + 2H
+
(aq) + CO
2
(g)
average rate = -
A[Br
2
]
At
= -
[Br
2
]
final
[Br
2
]
initial
t
final
- t
initial
slope of
tangent
slope of
tangent
slope of
tangent
instantaneous rate = rate for specific instance in time
Br
2
(aq) + HCOOH (aq) 2Br
-
(aq) + 2H
+
(aq) + CO
2
(g)
rate o [Br
2
]
rate = k [Br
2
]
k =
rate
[Br
2
]
= rate constant
= 3.50 x 10
-3
s
-1
2H
2
O
2
(aq) 2H
2
O (l) + O
2
(g)
PV = nRT
P = RT = [O
2
]RT
n
V
[O
2
] = P
RT
1
rate =
A[O
2
]
At RT
1
AP
At
=
measure AP over time
Video of reaction
Hydrogen peroxide reaction
Nurdrage
Definition of Reaction Rates
Consider the gas-phase decomposition of
dinitrogen pentoxide.
) g ( O ) g ( NO 4 ) g ( O N 2
2 2 5 2
+
If we denote molar concentrations using
brackets, then the change in the molarity of
O
2
would be represented as
where
the symbol, A (capital Greek delta), means
the change in.
] O [
2
A
Figure 1:
The instantaneous
rate of reaction.
Figure 2 shows the increase in concentration
of O
2
during the decomposition of N
2
O
5
.
Definition of Reaction Rates
Note that the rate decreases as the
reaction proceeds.
Figure 2:
Calculation
of the
average rate.
Then, in a given time interval, At , the molar
concentration of O
2
would increase by A[O
2
].
This equation gives the average rate over the
time interval, At.
If At is short, you obtain an instantaneous
rate, that is, the rate at a particular instant.
(Figure 1)
Definition of Reaction Rates
The rate of the reaction is given by:
t
] [O
oxygen of formation of Rate
2
A
A
=
Because the amounts of products and
reactants are related by stoichiometry, any
substance in the reaction can be used to
express the rate.
Definition of Reaction Rates
t
] O [N
O N of ion decomposit of Rate
5 2
5 2
-
A
A
=
Note the negative sign. This results in a
positive rate as reactant concentrations
decrease.
The rate of decomposition of N
2
O
5
and the
formation of O
2
are easily related.
Definition of Reaction Rates
) (
t
] O [N
2
1
t
] [O
5 2 2
-
A
A
=
A
A
Since two moles of N
2
O
5
decompose for
each mole of O
2
formed, the rate of the
decomposition of N
2
O
5
is twice the rate of
the formation of O
2
.
Experimental Determination of
Reaction Rates
To obtain the rate of a reaction you must
determine the concentration of a reactant or
product during the course of the reaction.
One method for slow reactions is to withdraw
samples from the reaction vessel at various
times and analyze them.
More convenient are techniques that
continuously monitor the progress of a reaction
based on some physical property of the
system.
Figure 3: An experiment to follow the concentration
of N
2
O
5
as the decomposition proceeds.
Experimental Determination of
Reaction Rates
Gas-phase partial pressures.
Manometer readings provide the concentration
of N
2
O
5
during the course of the reaction based
on partial pressures.
When dinitrogen pentoxide crystals are sealed
in a vessel equipped with a manometer (see
Figure 3) and heated to 45
o
C, the crystals
vaporize and the N
2
O5(g) decomposes.
) g ( O ) g ( NO 4 ) g ( O N 2
2 2 5 2
+
Reaction Rates and Stoichiometry
2A B
Two moles of A disappear for each mole of B that is formed.
rate =
A[B]
At
rate = -
A[A]
At
1
2
aA + bB cC + dD
rate = -
A[A]
At
1
a
= -
A[B]
At
1
b
=
A[C]
At
1
c
=
A[D]
At
1
d
Write the rate expression for the following reaction:
CH
4
(g) + 2O
2
(g) CO
2
(g) + 2H
2
O (g)
rate = -
A[CH
4
]
At
= -
A[O
2
]
At
1
2
=
A[H
2
O]
At
1
2
=
A[CO
2
]
At
The Rate Law
13.2
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 + bB cC + dD
Rate = k [A]
x
[B]
y
reaction is xth order in A
reaction is yth order in B
reaction is (x +y)th order overall
F
2
(g) + 2ClO
2
(g) 2FClO
2
(g)
rate = k [F
2
]
x
[ClO
2
]
y
Double [F
2
] with [ClO
2
] constant
Rate doubles
x = 1
Quadruple [ClO
2
] with [F
2
] constant
Rate quadruples
y = 1
rate = k [F
2
][ClO
2
]
13.2
F
2
(g) + 2ClO
2
(g) 2FClO
2
(g)
rate = k [F
2
][ClO
2
]
Rate Laws
Rate laws are always determined experimentally.
Reaction order is always defined in terms of reactant
(not product) concentrations.
The order of a reactant is not related to the
stoichiometric coefficient of the reactant in the balanced
chemical equation.
1
13.2
Determine the rate law and calculate the rate constant for
the following reaction from the following data:
S
2
O
8
2-
(aq) + 3I
-
(aq) 2SO
4
2-
(aq) + I
3
-
(aq)
Experiment [S
2
O
8
2-
] [I
-
]
Initial Rate
(M/s)
1 0.08 0.034 2.2 x 10
-4
2 0.08 0.017 1.1 x 10
-4
3 0.16 0.017 2.2 x 10
-4
13.2
Determine the rate law and calculate the rate constant for
the following reaction from the following data:
S
2
O
8
2-
(aq) + 3I
-
(aq) 2SO
4
2-
(aq) + I
3
-
(aq)
Experiment [S
2
O
8
2-
] [I
-
]
Initial Rate
(M/s)
1 0.08 0.034 2.2 x 10
-4
2 0.08 0.017 1.1 x 10
-4
3 0.16 0.017 2.2 x 10
-4
rate = k [S
2
O
8
2-
]
x
[I
-
]
y
Double [I
-
], rate doubles (experiment 1 & 2)
y = 1
Double [S
2
O
8
2-
], rate doubles (experiment 2 & 3)
x = 1
k =
rate
[S
2
O
8
2-
][I
-
]
=
2.2 x 10
-4
M/s
(0.08 M)(0.034 M)
= 0.08/Ms
13.2
rate = k [S
2
O
8
2-
][I
-
]
First-Order Reactions
A product
rate = -
A[A]
At
rate = k [A]
A[A]
At
= k [A]
-
(1)
(2)
(3)
kdt dA
A
=
1
} }
=
A
A
t
o
dt k dA
A
0
1
kt
A
A
kt A A
=
|
|
.
|

\
|
=
0
0
ln
ln ln
kt
e A A

=
0
[A] is the concentration of A at any time t
[A]
0
is the concentration of A at time t=0
First-Order Reactions
A product
rate = -
A[A]
At
rate = k [A]
k =
rate
[A]
= 1/s or s
-1
M/s
M
=
A[A]
At
= k [A]
-
[A] is the concentration of A at any time t
[A]
0
is the concentration of A at time t=0
[A] = [A]
0
exp(-kt) ln[A] = ln[A]
0
- kt
2N
2
O
5
4NO
2
(g) + O
2
(g)
The reaction 2A B is first order in A with a rate
constant of 2.8 x 10
-2
s
-1
at 80
0
C. How long will it take for A
to decrease from 0.88 M to 0.14 M ?
ln[A] = ln[A]
0
- kt
kt = ln[A]
0
ln[A]
t =
ln[A]
0
ln[A]
k
= 66 s
[A]
0
= 0.88 M
[A] = 0.14 M
ln
[A]
0
[A]
k
=
ln
0.88 M
0.14 M
2.8 x 10
-2
s
-1
=
First-Order Reactions
The half-life, t

, is the time required for the concentration of a

reactant to decrease to half of its initial concentration.
t

= t when [A] = [A]

0
/2
ln
[A]
0
[A]
0
/2
k
= t

ln2
k
=
0.693
k
=
What is the half-life of N
2
O
5
if it decomposes with a rate
constant of 5.7 x 10
-4
s
-1
?
t

ln2
k
=
0.693
5.7 x 10
-4
s
-1
= = 1200 s = 20 minutes
How do you know decomposition is first order?
units of k (s
-1
)
A product
First-order reaction
# of
half-lives [A] = [A]
0
/n
1
2
3
4
2
4
8
16
Second-Order Reactions
A product
rate = -
A[A]
At
rate = k [A]
2
A[A]
At
= k [A]
2
-
[A] is the concentration of A at any time t
[A]
0
is the concentration of A at time t=0
1
[A]
=
1
[A]
0
+ kt
kdt dA
A
=
2
1
} }
=
A
A
t
dt k dA
A
0
0
2
1
kt
A A
o
= +
1 1
Second-Order Reactions
13.3
A product rate = -
A[A]
At
rate = k [A]
2
k =
rate
[A]
2
= 1/Ms
M/s
M
2
=
A[A]
At
= k [A]
2
-
[A] is the concentration of A at any time t
[A]
0
is the concentration of A at time t=0
1
[A]
=
1
[A]
0
+ kt
t

= t when [A] = [A]

0
/2
t

=
1
k[A]
0
Zero-Order Reactions
13.3
A product rate = -
A[A]
At
rate = k [A]
0
= k
k =
rate
[A]
0
= M/s
A[A]
At
= k
-
[A] is the concentration of A at any time t
[A]
0
is the concentration of A at time t=0
t

= t when [A] = [A]

0
/2
t

=
[A]
0
2k
[A] = [A]
0
- kt
Summary of the Kinetics of Zero-Order, First-Order
and Second-Order Reactions
Order Rate Law
Concentration-Time
Equation Half-Life
0
1
2
rate = k
rate = k [A]
rate = k [A]
2
ln[A] = ln[A]
0
- kt
1
[A]
=
1
[A]
0
+ kt
[A] = [A]
0
- kt
t

ln2
k
=
t

=
[A]
0
2k
t

=
1
k[A]
0
13.3
Exothermic Reaction
Endothermic Reaction
The activation energy (E
a
) is the minimum amount of
energy required to initiate a chemical reaction.
A + B AB C + D
+
+
NO
2
(g) + CO(g) NO(g) + CO
2
(g)
Temperature Dependence of the Rate Constant
k = A exp( -E
a
/ RT )
E
a
is the activation energy (J/mol)
R is the gas constant (8.314 J/Kmol)
T is the absolute temperature
A is the frequency factor
lnk = -
E
a
R
1
T
+ lnA
(Arrhenius equation)
13.4
lnk = -
E
a
R
1
T
+ lnA
c
2
) A + B products
( ) ( )
( )( )
( )( ) ( )( ) ( )( )
( )
( )
( )
kt
B A
B A
B A
b ax
a b ax
x A B A
dx
x B B A
dx
x B x A
dx
x B x A k
dt
dx
B B A A x
B A K
dt
A d
R
t
t
t t
=
|
|
.
|

\
|

+ =
+

=

=
= =
= =
}
} } }
] [ ] [
] [ ] [
ln
] [ ] [
1
) ln(
1 1
] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [
] [ ] [
] [ ] [ ] [ ] [
] [ ] [
] [
0
0
0 0
0 0 0 0 0 0 0 0
0 0
0 0
1 1
H
2
+ O OH + H
b
a
b
a
d) Third-Order reaction:
d
1
) A + A + A products
Kt
A A
dt K
A
A d
Kt
A A
x
n
x
dx
Kdt
A
A d
A K
dt
A d
R
t
t
A
A
t
n
b
a
n
t
6
] [
1
] [
1
3
] [
] [
3
] [
1
] [
1
2
1
1
) 1 (
1
3
] [
] [
] [
] [
3
1
2
0
2
0
] [
] [
3 2
0
2
1
3
3
0
+ =
= =
|
|
.
|

\
|

+
=
= = =
} }
}
t
[A]
t
-2
[A]
0
-2
m = 6K
b
a
I + I + M I
2
+ M
d
2
) A + A + B products
( ) ( )
( ) ( )
( )
Kt
B A
B A
B A
A A B A
Kdt
y B y A
dy
y B y A K
dt
dy
B A
y B B
y A A
B A K
dt
A d
R
t
t
t
t
t
=
|
|
.
|

\
|

+
|
|
.
|

\
|

=

=
=
=
= =
] [ ] [
] [ ] [
ln
] [ 2 ] [
1
] [
1
] [
1
] [ 2 ] [
1
] [ 2 ] [
] [ 2 ] [
] [ , ] [
] [ ] [
2 ] [ ] [
] [ ] [
] [
2
1
0
0
2
0 0
0 0 0
0
2
0
0
2
0
0 0
0
0
2
Partial fractions!
t K
A A
order pseudo B K K
A K
dt
A d
R
t
nd
' 2
] [
1
] [
1
2 ], [ '
] [ '
] [
2
1
0
2
+ =
=
~ =
[B]>>[A]
[B] = const.
O + O
2
+ M O
3
+ M
d
3
) A + B + C products
] ][ ][ [
] [
C B A K
dt
A d
R = =
Reaction rate for n order respect with only one reactant
| |
Kt n n
A A
nKt
A A
n
dt nk
A
A d
A K
dt
A d
n
R
n n
t
n n
t
A
A
t
n
n
t
) 1 (
] [
1
] [
1
] [
1
] [
1
) 1 (
1
] [
] [
] [
) (
1
) 1 (
0
) 1 ( ) 1 (
0
) 1 (
] [
] [ 0
0
=
|
|
.
|

\
|
=
|
|
.
|

\
|

=
= =

} }
e) Reaction half-lives:
Alternative method to
determine the reaction order
2
] [
] [
0
2
1
2
1
A
A t =
2 ln
1
] [
2 / ] [
ln
2 / ] [ ] [
] [
] [
ln
2 / 1
2 / 1
0
0
0
0
K
t
Kt
A
A
A A
Kt
A
A
t
t
=
=
=
=
First-order reaction
For a reaction of order n>1 in a
single reactant
Independent of [A]
0
( )
1
0
1
2
1
] )[ 1 (
1 2

=
n
n
A n K
t
This is function of [A]
0
1
st
order reaction half-lives:
0 10 20 30 40 50
0
0.2
0.4
0.6
0.8
1
1
6.738 10
3

A t ( )
50 0 t
T dependence of the rate constant, K
The Arhenius equation:
K
(T)
:
[i]
t
pH (only in solution)
T! (Strongly)
(

=
kT
E
T
Act
Ae K
) (
T
ln[K
(T)
]
lnA
m = -E
Act
/k
Chemical coordinates
E
E
Act
(F)
E
Act
(R)
Reac
Prod.
AH
0
Rxn
A :Frequency factor
0
Re
0
Pr
0
0
) ( ) (
ac od Rxn
Act Act Rxn
H H H
R E F E H
A A = A
= A
Ineffective Effective
Determinant Parameters
Catalysis
Task for next week:
Video animation or experiment
on factors affect the reaction rate
Work in group
Each group must collect at least
four video