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REACTION

KINETICS

Why Reaction
AB + C D Take place.
The chemical reaction take
place inorder the system
becomes:
1. More order . ?
2. More stable . ?
AB + C
---------


AC + B
---------------
E
e
n
e
r
g
y

L
e
v
e
l

Reaction Coordinate
AH
reaction
Why reaction between element occur
Atom at distance
Atom Bonded In Molecule
AEnergy
Lowest Energy
? Most stable
Non-Bonding
Stability of molecule system compared to atom
1. Sharing electron among the elements ( covalent )
2. Give/received the electron(s) ions
3. Attraction between different ions ( ionic )
4. Restructuring the electronic configuration in the
molecules, by:
Breaking down the bonds = (required energy)
Rearrangement the pair(s) of electron(s)/Bonding
Formation of new bonds (released energy)
A + A B (H + H H
2
)
AB + C AC + B (H
2
+ O
2
H
2
O)
How does the reaction occur?
Rate of reaction

E.g; aA + bB cC +
dD

Rate of consumption of reactant A =

Rate of consumption of reactant B =

Rate of formation of product C =

Rate of formation of product D =


dt
dA

dt
dB

dt
dC
dt
dD
The sign (+) and (-) the formation of
product and the consumption of
reactant.

A and
B
C and D
Time
C
o
n
c
e
n
t
r
a
t
i
o
n

The differential rate equation, u


Example:
A + 2B 3C + D




dt
] D [ d
d
1
dt
] C [ d
c
1
dt
] B [ d
b
1
dt
] A [ d
a
1
+ = + = = = u
dt
] D [ d
dt
] C [ d
3
1
dt
] B [ d
2
1
dt
] A [ d
+ = + = = = u
[
N
2
O
5
]
,
M


Time (t), hours
Can you explain how to determine the rate of reaction from the graph?
Example 1.
The radical of CH
3
reaction below occur
at certain condition. Find the rate of
reaction and the rate of formation of
CH
3
CH
3
where the rate of formation of
CH
3
radical is,
= - 1.2molL
-1
s
-1


2CH
3
(g) CH
3
CH
3


dt
CH d ]
3
[
Rate law and rate constant

Consider a general equation
aA + bB cC + dD
u = k[A]
x
[B]
y

Where : k = rate constant.
In mathematical function, the rate of
reaction;
u = f([A],[B],..)



For gases reaction concentration of
species replace by partial pressure
u = f(p
A
, p
B
, )
The rate law is determined by an
experiment not by chemical reaction
equation.
E.g: A reaction between hydrogen and
Bromine
H
2
(g) + Br
2
(g) 2HBr (g)
The rate law is given:
] [ ' ]
2
[
2
3
]
2
][
2
[
HBr k Br
Br H k
+
= u
Order of reaction

Consider a general reaction below;
aA + bB cC + dD
Rate law, u = k[A]
x
[B]
y

Where, x and y = partial order of reaction
x + y = overall order of reaction
Determination of rate law, order of
reaction and rate constant

1. Differential method
The rate of reaction can be determined by the gradient
of graph concentration vs times.




t
C
rate
A
A
=
C
C
1
C
2
C
3
time,t

AC
1

At
At
At
AC
2

AC
3

The rate law equation given by:-
u = kC
n

Where; k = rate constant
C = concentration of reactant
n = Order of reaction
u = rate of reaction
In logarithme,
ln u = ln k + n ln C
Plot of ln u vs ln C gives a straight line
ln u = n ln C + ln k

y = mx + c
ln u
ln C
Slope = A ln u = n
A ln C
the intercept of ln u = ln k
2. Integrated method

(a) Zero order
Consider the following reaction;

A Z




The rate of formation of Z,






time, t [A] [Z]
t = 0 a
0
0
t = t a
0
- x x
0
) (
] [
x a k
dt
dx
dt
Z d

= =
Rearrange;


And
Integrate the equation;



A plot of x against t will give a straight line graph




k
dt
dx
=
kdt dx =
} }
= dt k dx
kt x =
x = kt 0
y = mx + c
x
t
Slope, m = k
(b) 1
st
order
A Z
Rate of formation of Z :-



Rearrange:

And integrate the equation:



-ln (a
0
x) = kt + C

1
) (
] [
x a k
dt
dx
dt
Z d

= =
kdt
x a
dx
=

) (
} }
=

dt k
x a
dx
) (
At t = 0, value of x = 0 , therefore C = -ln a
0

So that equation become;
-ln (a
0
x) = kt + (-ln a
0
)

Simplified the equation where;
a
0
= A
0
and a
0
x = A
t



ln A
t
= -kt + ln A
0




Plot of graph ln A
t
vs t gives a straight line

Intercept = ln A
0


Slope = k

ln A
t


t

(c) 2
nd
order identical molecule
2A Z

+ =
A
kt
t
A
1 1
Slope=k

A
1
t
A
1
t
Intercept =
2
nd
order non identical molecules
A + B Z




Plot of against t gives a

straight line
kt
x b a
x a b
b a
=




) (
) (
ln
1
(
(




) (
) (
ln
) (
1
x b a
x a b
b a
The summary of order of reaction, integrated equation
and differential equation


Order of
reaction

Differential equation

Integrated equation
0
x = kt
1
ln
2
3
0
) ( x a k
dt
dx
=

1
) ( x a k
dt
dx
=

kt
x a
a
=

) (
2
) ( x a k
dt
dx
=

kt
a x a
=


1
) (
1
) )( ( x b x a k
dt
dx
=

kt
x b a
x a b
b a
=




) (
) (
ln
1
3
) ( x a k
dt
dx
=

kt
x a a
x x a
=

2 2
2
) ( 2
2
3. Half-life method, t
1/2


In logarithme,

ln t
1/2
= ln k (n-1) ln a
0


where; a
o
= initial concentration
n = overall order of reaction
k = rate constant

1
1
2 / 1

n
a
t o
1
2 / 1

=
n
a
k
t
plot of ln t
1/2
vs ln a
0


Slope = n - 1
Intercept = ln k
ln a
o

ln t
4. Isolation method
Requires that all the reactant except one are
arranged to be in large excess.
The dependence of the reaction rate on the one
reactant present in small concentration.
Consider the following reaction,
2I
-
+ S
2
O
8
2-
I
2
+ 2SO
4
2-

The rate of reaction;
u = k
2
[S
2
O
8
2-
][I
-
]

If [I
-
] is in excess and its concentration remain
essentially constant during the course of reaction, the
reaction will appear to follow first order and is said to
be pseudo-first order reaction.
u = k[S
2
O
8
2-
] where; k = k
2
[I
-
]

5. Method of Initial Rates

Experiments
Method of Initial Rates
If reaction is sufficiently slow
or have very fast technique
Can measure [A] vs. time at very beginning of
reaction
before it curves up very much, then




Set up series of experiments, where initial
concentrations vary
|
|
.
|

\
|

=
0 1
0 1
t t
] A [ ] A [
rate initial
Example 6
3A + 2 B products
Rate = k[A]
m
[B]
n

Expt. [A]
0
, M [B]
0
, M Initial Rate, M/s
1 0.10 0.10 1.2 10
4

2 0.20 0.10 4.8 10
4

3 0.20 0.20 4.8 10
4
Convenient to set up experiments so
[X] of one species is doubled or tripled
while [X] of all other species are held constant
Tells us effect of [varied species] on initial rate
Answer
Expt. # [A]
0
, M [B]
0
, M Initial Rate, M/s
1 0.10 0.10 1.2 10
4

2 0.20 0.10 4.8 10
4

3 0.20 0.20 4.8 10
4
30
Comparing 1 and 2
4
10 2 . 1
10 8 . 4
1 Rate
2 Rate
4
4
=

| | | |
| | | |
| | | |
| | | |
| |
| |
m
m
m
n m
n m
n
1
m
1
n
2
m
2
2
10 . 0
20 . 0
10 . 0 10 . 0 k
10 . 0 20 . 0 k
B A k
B A k
1 Rate
2 Rate
4 = = = = =
2
m
= 4 or m = 2
31
Comparing 2 and 3
1
10 8 . 4
10 8 . 4
2 Rate
3 Rate
4
4
=

| | | |
| | | |
| | | |
| | | |
| |
| |
n
n
n
n m
n m
n
2
m
2
n
3
m
3
2
10 . 0
20 . 0
10 . 0 20 . 0 k
20 . 0 20 . 0 k
B A k
B A k
2 Rate
3 Rate
1 = = = = =
2
n
= 1 or n = 0
Conclusion: rate = k[A]
2
Can use data from any experiment to determine k
Lets choose experiment 1
| | ( )
1 1 2
2
4
2
10 2 . 1
10 . 0
10 2 . 1
A
rate

= = s M
M
M/s
k
The relationship of order of
reaction and half life

From the integral equation for zero order,
x = kt
When t = t
1/2
and x =
therefore;


t
1/2
=

2

a
2 / 1
2
kt
a
=

k
a
2

The summary of order of reaction and half life



Order of reaction t
1/2

0 t
1/2
=
1 t
1/2
=
2 t
1/2
=
3 t
1/2
=
k
a
2

k
2 ln

ka
1
|
|
|
|
.
|

\
|

2
2
3 1
a
k
Examples
1. Cyclopropane isomerizes into propene when heated to
500C in the gas phase. The extent of conversion for
various initial pressures has been followed by gas
chromatography by allowing the reaction to proceed for
a time with various initial pressures. Where p
0
is the
initial pressure and p is the final pressure of
cyclopropane.




Find the order of reaction and rate constant for the
reaction under these conditions.

P
0
/Torr 200 200 400 400 600 600
t/s 100 200 100 200 100 200
P/Torr 186 173 373 347 559 520
2. The following reaction was studied at -10C and the
obtained data was tabulated in the table. The rate of
reaction was given as;
2NO (g) + Cl
2
(g) 2NOCl (g)






(a) Find the rate law
(b) Find the rate constant.
(c) Find the value of x

[NO] (mol L
-1
) [Cl
2
] (mol L
-1
) Initial rate (mol L
-1
min
-
1
)
0.10 0.10 0.18
0.10 0.20 0.35
0.20 0.20 1.45
0.10 0.30 x
3. The following graph was plot based on dimerization of
nitrile oxide (A) in ethanol solution at 313K. Find the
order of reaction by using half life method.

0
10
20
30
40
50
60
70
80
0 50 100 150 200 250 300 350 400 450
t/min
[
A
]
/

m
m
o
l
d
m
-
3

4. Sulfuryl Chloride, SO
2
Cl
2
is highly reactive gas. The
gas will decomposed when heated as follows,

SO
2
Cl
2
(g) SO
2
(g) + Cl
2
(g)



A sample of 6.75 g SO
2
Cl
2
was put into 5.00 x 10
-1
L of
container and the temperature was rise to 600 K.
Find the pressure in the container if decomposition
occurred.
The decomposition occurred in first order reaction and
the data was tabulated in following table. Determine
the rate constant, internal pressure after 20.0 hours
and the remaining sulfuryl chloride after 20.0 hours.

Time (Hours) 1.00 2.00 4.00 8.00 16.10
The container
pressure (atm)

5.60

6.34

7.33

8.56

9.52