INTRODUCTION TO SK 026

• PHYSICAL CHEMISTRY
CHAPTER 8 : REACTION KINETICS
CHAPTER 9 : THERMOCHEMISTRY
CHAPTER 10 : ELECTROCHMISTRY

• ORGANIC CHEMISTRY
CHAPTER 11 : INTRODUCTION TO ORGANIC
CHEMISTRY
CHAPTER 12 : HYDROCARBONS
CHAPTER 13 : BENZENE AND ITS DERIVATIVES
INTRODUCTION TO SK 026
CHAPTER 14 : HALOALKANES (ALKYL HALIDES)
CHAPTER 15 : HYDROXY COMPOUNDS
CHAPTER 16 : CARBONYL COMPOUNDS
CHAPTER 17 : CARBOXYLIC ACIDS AND ITS
DERIVATIVES
CHAPTER 18 : AMINES
CHAPTER 19 : AMINO ACIDS
CHAPTER 20 : POLYMERS
 8.1 8.0 8.3
REACTION KINETICS
Reaction Factors
Rate Affecting
Reaction
Rate

8.2
Collision
Theory &
Transition
State Theory
REACTION KINETICS

8.1 Reaction Rate

4
 Average reaction rate
Reaction Rate Instantaneous reaction rate
Initial reaction rate

Differential rate equation

Rate Law
Reaction
Rate Rate Constant
First Order
Reaction Orders
Second Order
Zero Order
Initial Rate Method
Overall reaction order from unit k

5
 First Order
Integrated Rate Law Second Order
Zero Order
Reaction Linear Graph Method
Rate Half Life First Order
Second Order
Zero Order

Overall reaction order from half life

6
 REACTION RATE
 Changes in concentrations of reactants
(or products) as a function of time
 Consider a reaction : A  B

When reaction occur, the concentration of

A is decreased while the concentration of
B increased with time.
As reaction proceed: [ reactant ]  and [ product ] 
9
 UNIT OF REACTION RATE

A B
D[A] D[B]
rate = – Dt rate =+
Dt

The negative sign indicates concentration of A decreases with time.

The positive sign indicates concentration of B increases with time.
Unit : molL–1s–1 or mol dm−3 s−1 or Ms–1
Unit of time: s (seconds), min, hr, day, year
Example: mol dm–3 min–1
10
CONCENTRATION OF REACTANT
AGAINST TIME
A(g)  B(g)
Concentration

[A]

Time

12
CONCENTRATION OF PRODUCT
AGAINST TIME
A(g)  B(g)

[B]
Concentration

Time

13
 CONCENTRATION OF REACTANT
AND PRODUCT AGAINST TIME
A(g)  B(g)

[B]
Concentration

[A]

Time

14
 INSTANTANEOUS RATE
& INITIAL RATE
 Instantaneous rate
• Rate at a particular instant during
reaction.
• Determined by slope of a line tangent to
the curve at a particular point.
 Initial rate
• Instantaneous rate at the moment
reactants are mixed.
• Determined by slope of a line tangent to
the curve at t = 0 15
 Fig. 16.5

instantaneous
rate at 35s

initial rate

16
 DIFFERENTIAL RATE EQUATION

 shows the relationship between the rate of

disappearance of reactants and formation of products.

Two moles of A disappear for

2A B each mole of B that formed

1 d[A] d[B]
rate = – rate =
2 dt dt

18
 aA + bB cC + dD

1 d[A] 1 d[B] 1 d[C] 1 d[D]

rate = – = – = =
a dt b dt c dt d dt

EXAMPLE:

H2(g) + I2(g)  2HI(g)

d[H2] d[I2] 1 d[HI]

rate = – =– =
dt dt 2 dt 19
 CHAPTER 8.1

EXAMPLE: 1

Write the rate expression (differential rate

equation) for the following reaction:

CH4(g) + 2O2(g)  CO2(g) + 2H2O(g)

20
 EXAMPLE: 1

CH4(g) + 2O2(g)  CO2(g) + 2H2O(g)

d[CH4] 1 d[O2] d[CO2] 1 d[H2O]

rate = – =– = =
dt 2 dt dt 2 dt

21
 CHAPTER 8.1

EXAMPLE: 2

Hydrogen sulfide burns in oxygen to form sulfur

dioxide and water.

2H2S(g) + 3O2(g)  2SO2(g) + 2H2O(g)

If sulfur dioxide (SO2) is being formed at a rate

of 0.30 molL–1s–1, what are the rates of
disappearance of hydrogen sulfide (H2S)
and oxygen (O2)?
23
 EXAMPLE: 2

2H2S(g) + 3O2(g)  2SO2(g) + 2H2O(g)

1 d[H2S] 1 d[O2] 1 d[SO2] 1 d[H2O]

rate = – =– = =
2 dt 3 dt 2 dt 2 dt
1 d[H2S] 1 d[SO2]
– =
2 dt 2 dt
d[H2S] = 1 0.30 molL–1s–1 X (2)
– 2
dt
= 0.30 molL–1s–1

So, rate of disappearance of H2S = 0.30 molL–1s–1 24

 EXAMPLE: 2

2H2S(g) + 3O2(g)  2SO2(g) + 2H2O(g)

1 d[H2S] 1 d[O2] 1 d[SO2] 1 d[H2O]

rate = – =– = =
2 dt 3 dt 2 dt 2 dt

1 d[O2] 1 d[SO2]
– =
3 dt 2 dt
d[O2] 3 (0.30 molL–1s)
– =
dt 2
= 0.45 molL–1s–1
So, rate of disappearance of O2 = 0.45 molL–1s–1 25
 RATE LAW
An equation that relates the rate of a reaction to the
rate constant and the concentrations of the reactants
raised to some powers.
Example: aA + bB  cC + dD
The rate equation or the rate law :

Rate = k [A]m [B]n

27
 RATE
RATE
CONSTANT
CONSTANT
(k) (k)

aA + bB cC + dD
Rate = k [A]x [B]y

 Proportionality constant for a given

reaction and temperature

 Does not change as reaction proceeds

28
 REACTION ORDERS

aA + bB cC + dD
Rate = k [A]x [B]y

 Exponent of x (0, 1, 2, etc) and y (0, 1, 2,etc)

 Define how the rate affected by reactant
concentration
The reaction orders cannot be predicted from
the stoichiometry of the balanced equation;
it must be determined experimentally.
29
 Order of a reactant is not related to
stoichiometric coefficient of reactant
in the balanced chemical equation

EXAMPLE:

F2 (g) + 2ClO2 (g) 2FClO2 (g)

1
rate = k [F2][ClO2]

30
 EXAMPLE:
2NO(g) + 2H2(g)  N2(g) + 2H2O(g)

Rate = k[NO]2[H2]

The reaction is:

 Second order with respect to NO,
 First order with respect to H2
 Overall reaction = third order reaction

31
 HALF–LIFE (t½ )

 Time required for the concentration

of a reactant to decrease to half of its
initial concentration

32
 ZERO ORDER

Rate Law: Rate = k[A]o = k

 Rate is not dependent on [A] at all

• Zero order in A

• Zero order overall

• Quite common in metal–catalyzed

and biochemical processes 34
 FIRST ORDER

Rate Law: Rate = k[A] 1

 If [A] double  rate double

• First order in A

• First order overall

• EXAMPLE: radioactive reaction

35
 SECOND ORDER

Rate Law: Rate = k[A]2

 If [A] double  rate quadruples

• Second order in A

• Second order overall

36
 CHAPTER 8.1

EXAMPLE: 3

For each of the following reactions, determine

the reaction order with respect to each reactant
and the overall order from the given rate law:

(a) 2NO(g) + O2(g)  2NO2(g); rate = k[NO]2[O2]

(b) CH3CHO(g)  CH4(g) + CO(g); rate = k[CH3CHO] 3

(c) H2O2(aq) + 3I–(aq) + H+(aq)  I3–(aq) + 2H2O(l);

rate = k[H2O2][I–] 37
RATE LAW:

Tell us the rate or concentration at a given instant

(time)

But, do not include time as variable

41
 INTEGRATED RATE LAW

 Consider time factor

 Answer questions such as:

“ How long will it take for x moles

per liter of A to be used up? ”

“ What is the concentration of A

after y minutes of reaction? ”
42
 ZERO ORDER REACTION

 In a zero-order reaction, the rate is independent

of the concentration of the reactant.

43
 If the reaction : A  products
is a zero-order reaction, therefore;
Rate = k[A]o -d[A]
Rate =
Combining both equation: dt
-d[A]
=k
dt

The integrated rate equation for zero order reaction is:

Where:
[A]o = the initial concentration
[A] = concentration at particular time
t = time of reaction
k = rate constant
 Graph Analysis
(a) From rate law of zero order : Rate = k[A]0
Rate
k

[A]
(b) From the integrated rate law:
(i) [A] = [A]o – kt (ii) [A]o – [A] = kt
[A] [A]o – [A]
[A]o
grad = k

t t
 FIRST ORDER REACTION

In a first-order reaction, the rate depends

on the concentration of a single reactant
raised to the first power.
If the reaction : A  products
is a first-order reaction, therefore;

Rate = k[A]1 Rate =-d[A]

dt
Combining both equation:

-d[A] = k[A]
dt
The integrated rate equation for first-order reaction is:

ln[A]o – ln[A] = kt

OR

OR
 Graph Analysis [A]
(a)
[A]o

t
(b) From rate law of first order : Rate = k[A]1

Rate

grad = k

[A]
(c) From the integrated rate law:

i) ln [A]o  kt ln[A]o
[A] [A]
grad = k

t
(ii) ln[A] = ln[A]o - kt ln[A]
ln[A]o

t
 CHAPTER 8.1

EXAMPLE: 4

The reaction 2A B is first order in A with a

rate constant of 2.8 x 10–2 s–1 at 80oC. How long will it
take for A to decrease from 0.88 M to 0.14 M ?
 EXAMPLE: 4

2A  B  first order reaction

[A]o = 0.88 M
ln
[A]o ln[A]o – ln[A] = kt
[A] = 0.14 M = kt
[A]
k = 2.8 x 10–2 s-1
ln[A] = ln[A]o - kt

[A]o 0.88 M
ln ln
[A] 0.14 M
t = =
k 2.8 x 10–2 s-1

= 66 s
 SECOND ORDER REACTION

 In a second-order reaction, the rate depends

on the concentration of two reactants or
to the square of the concentration of a single
reactant
If the reaction : A  products
is a second-order reaction, therefore;

Rate = k[A]2
The integrated rate law for second-order reaction is:

Graph Analysis

Rate Rate

[A] [A]2
 1 = kt + 1
1 [A] [A]o
[A]

time,t
 Zero order 1st order 2nd order
A  product A  product A  product
rate = k [A]0 rate = k [A]1 rate = k [A]2
Unit k = M s-1 Unit k = s-1 Unit k = M-1 s-1
rate rate rate
rate

[A] [A]
[A] [A]2
Integrated rate law Integrated rate law Integrated rate law
[A]0 – [A] = kt ln([A]0 / [A]) = kt 1/[A] – 1/[A]0 = kt

[A] t1/2 = [A]0/2k [A] ln[A] [A] 1/[A]

[A]0 ln[A]0
1/[A]0
t t t t t
[A]0 - [A]
ln([A]0 / [A]) 1/[A] – 1/[A]0

t1/2 = ln2/k t1/2 = 1/k[A]0

t t t
 CHAPTER 8.1

EXAMPLE: 5

Iodine atoms combine to form molecular iodine

in the gas phase
I(g) + I(g)  I2(g)
The rate constant of the reaction is
7.0 x 109/M•s at 23oC.
If the initial concentration of I was 0.086 M,
calculate the concentration after 2.0 min.
 EXAMPLE: 5
I(g) + I(g)  I2(g)
The reaction is second–order overall.

1 1
= + kt
[I] [I]o

k = 7.0 x 109 M–1s–1 t = 2.0 min x 60 s/min

= 120 s
[I]o = 0.086 M
[I] = ?
 EXAMPLE: 5
1 1
= + kt
[I] [I]o

1 1 + (7.0 x 109 M–1s–1) x 120s

=
[I] 0.086 M

= 8.4 x 1011 M–1

[ I ] = 1.190 x 10–12 M
 CHAPTER 8.1

EXAMPLE: 6

N2O5 decomposes into N2O4 and O2.

2N2O5(g)  2N2O4(g) + O2(g)
At 45oC, k = 6.22 x 10–4 s–1.
If the initial concentration of N2O5 in a carbon
tetrachloride solution at 45oC is 0.500 M, what
will the concentration be after exactly one hour?

ANS:
0.053 M
 INITIAL RATE METHOD

1. Use concentration measurement

to find initial rate

2. Use initial rates from several

experiments to find reaction orders

3. Use these values to calculate

rate constant
 CHAPTER 8.1

EXAMPLE: 7

Determine the rate law and calculate the rate

constant for the following reaction from the following
data:
F2 (g) + 2ClO2 (g) 2FClO2 (g)

Initial Rate
Experiment [F2] [ClO2]
(M/s)
1 0.10 0.010 1.2 x 10-3
2 0.10 0.040 4.8 x 10-3
3 0.20 0.010 2.4 x 10-3
 EXAMPLE: 7
Initial Rate
Experiment [F2] [ClO2]
(M/s)
1 0.10 0.010 1.2 x 10-3
2 0.10 0.040 4.8 x 10-3
3 0.20 0.010 2.4 x 10-3

Rate = k[F2]x[ClO2]y
 Find order in F2 with [ClO2] constant:
Rate 3 k[F2]x[ClO2]y 2.4 x 10-3 k[0.2]x[0.01]y
= =
Rate 1 k[F2]x[ClO2]y 1.2 x 10 -3 k[0.1]x[0.01]y
2.4 x 10-3 = (0.2)x
1.2 x 10-3 (0.1)x
(2.0)1 = (2.0)x x = 1  first order in F2
 EXAMPLE: 7
Initial Rate
Experiment [F2] [ClO2]
(M/s)
1 0.10 0.010 1.2 x 10-3
2 0.10 0.040 4.8 x 10-3
3 0.20 0.010 2.4 x 10-3

Rate = k[F2]x[ClO2]y
 Find order in ClO2 with [F2] constant:
Rate 2 k[F2]x[ClO2]y 4.8 x 10-3 k[0.1]x[0.04]y
= =-3
Rate 1 k[F2]x[ClO2]y 1.2 x 10 k[0.1]x[0.01]y
4.8 x 10-3 (0.04)y
-3
=
1.2 x 10 (0.01)y
(4.0)1 = (4.0)y y = 1  first order in ClO2
 EXAMPLE: 7

Rate = k[F2]x[ClO2]y

x = 1, y = 1 rate = k[F2][ClO2]

 Use any experiment data (example Exp. 1) to find k

1.2 x 10-3 M s–1 = k(0.1 M)(0.01 M)

k = 1.2 M–1s–1
 OVERALL REACTION ORDER
FROM THE UNIT OF k
Rate = k[A]x

Overall Reaction Units of k

Order (t in seconds)
molL–1s–1 or Ms–1
0
s–1
1

Lmol–1s–1 or M–1s–1
2
 You can always determine
the unit of k mathematically

EXAMPLE:

What is the unit of k for a third order reaction?

Rate = k[A]3
M = k (M)3
s
k = M–2s–1

= L2mol–2s–1
 CHAPTER 8.1

EXAMPLE: 8

Without consulting textbooks, give the units

of the rate constants for reactions with the
following orders: (Time: in s)
(a) First order
(b) Second order
(c) Third order
5
(d) order
2
 HALF–LIFE (t½ ) BASED ON
THE GRAPH CONCENTRATION
AGAINST TIME

ZERO ORDER REACTION

FIRST ORDER REACTION

SECOND ORDER REACTION

 ZERO ORDER REACTION

[A]o – [A] = kt

t = t½ when [A] = [A]o/2

[A]o
t½ =
2k

 t½ directly proportional to [A]o

 Zero-order reaction

[A]
[A]o

½ [A]o

¼[A]o

t½ (I) t½ (I) time,t

 FIRST ORDER REACTION
[A]o
ln = kt
[A]

t½ = t when [A] = [A]o/2

[A]o For first order,

ln
[A]o/2 t1/2 does not
t½ = depend on [A]o
k
ln 2 0.693
= =
k k

t½ = 0.693
k
 First-order reaction
[A]

[A]o

½[A]o

¼[A]o x x

t½ (I) t½ (II) time,t

First order-reaction :
First half life = Second half life
Thus, t½ (I) = t½ (II)
 CHAPTER 8.1

EXAMPLE: 9

What is the half–life (in min) of N2O5 if it decomposes

with a rate constant of
5.7 x 10–4 s–1?
 EXAMPLE: 9

The unit of k = s–1

 First order reaction

ln2 0.693
t½ = =
k 5.7 x 10–4 s–1

= 1216 s

= 20.27 min
 SECOND ORDER REACTION
1 1
– = kt
[A] [A]o

t½ = t when [A] = [A]o/2

1
t½ =
k[A]o

 t½ inversely proportional to [A]o

 As reaction proceeds, t½ increases

 Second-order reaction
[A]

[A]o

½[A]o

¼[A]o
x 2x

t½ (I) t½ (II) time,t

Second-order reaction :
t½ (II) = 2 t½ (I)
 CHAPTER 8.1

EXAMPLE: 10

The rate constant of the reaction 2A  B

is 51/M•min at 24oC.
(a) Starting with [A] = 0.0092 M, how long will it
take for [A] = 3.7 x 10–3 M?
(b) Calculate the half–life of the reaction.
 EXAMPLE: 10

2A  B
(a)
k = 51 M–1 min–1

The reaction is second–order overall.

1 1 [A]o = 0.0092 M
= + kt
[A] [A]o [A] = 3.7 x 10–3 M t =?

1 1
= + ( 51 M–1min–1 ) x t
3.7 x 10–3 M 0.0092 M

t = 3.168 min
 EXAMPLE: 10

(b) 2A  B
k = 51 M–1 min–1
The reaction is second–order overall.

1
t½ = [A]o = 0.0092 M
k[A]o

1
=
(51 M–1 min–1 )(0.0092 M)

= 2.131 min
 Concentration-Time Equation
(Integrated Rate Law)

Order Rate Law Half-Life

[A]o
0 rate = k [A] = [A]o – kt t½ =
2k
[A]o
1 rate = k [A] ln = kt t½ = ln2
[A] k
1 1 1
2 rate = k [A]2 = + kt t½ =
[A] [A]o k[A]o
How do scientists determine the ages of artifacts
from archaeological excavations?
The answers to these and other similar questions
can be found by applying chemical kinetics and
the radiocarbon dating technique
 [N]o
ln = kt
[N]

1 [N]o
t = ln
k [N]

1 decay rate at t = 0
t = ln
1.21 x 10–4yr–1 decay rate at t = t

1 decay rate of fresh sample

t = ln
1.21 x 10–4yr–1 decay rate at old sample
 LINEAR GRAPH METHOD
The reaction order also can be determined by
the integrated rate law !

How ?

By plotting the graph !

 look for the linear graph

Which graph ?
Which one ???

I don’t know. Just

try-and-error!
Order Rate Law Integrated Rate Law

0 rate = k [A] = [A]o – kt

[A]o
1 rate = k [A] ln = kt
[A]
ln [A] = ln [A]o – kt
1 1
2 rate = k [A]2 = + kt
[A] [A]o
Plot ln[reactant] vs. time:
linear graph  first order

Plot 1/[reactant] vs. time:

linear graph  second order

Plot [reactant] vs. time:

linear graph  zero order
EXAMPLE:

 The reaction is first order in N2O5

 CHAPTER 8.1

EXAMPLE: 11
Ethyl iodide (C2H5I) decomposes at a certain
temperature in the gas phase as follows:
C2H5I(g)  C2H4(g) + HI(g)
From the following data determine the order
of the reaction and the rate constant.
TIME (min) [ C2H5I ] (M)
0 0.36
15 0.30
30 0.25
48 0.19
75 0.13
 EXAMPLE: 11

TIME (min) [ C2H5I ] (M) ln[C2H5I] 1/[C2H5I]

0 0.36 – 1.02 2.78

15 0.30 – 1.20 3.33

30 0.25 – 1.39 4.00

48 0.19 – 1.66 5.26

75 0.13 – 2.04 7.69

101
 END OF
SLIDE SHOW