Topic 2: Chemical Kinetics

(Part II)
 Summary of the Kinetics for Reactions of:
aA Products
that are zero, first or second order with respect to [A]
Zero order First order Second order

Rate law/ Differential Rate = k[A]0 Rate = k[A]1 Rate = k[A]2

Rate = k Rate = k[A] If double [A], reaction
equation
[A] does not affects If double [A], rate rate quadrupled.
reaction rate. doubled as well.

Integrated rate [A] = -kt + [A]0 ln[A] = -kt + ln[A]0 1 1

  
equation  

[A] Slope = -k ln[A]

Slope = -k 1 Slope = k


Time Time Time

Half life equation 

/ 


/ 
0.693

/ 
1
2  

Reaction mechanism A doesnt take part in the 1 A appears in the RDS. 2 A appears in the RDS.
RDS.
Learning Outcomes:
Use collision theory as model, explain how the following
factors affect the rate of reaction.
Concentration of reactants.
Increase in temperature
Addition of catalyst.
Draw energy profile to represent potential energy change
as function of reaction pathway.
Determine activation energy, rate constant and
temperature using Arrhenius Equation.
Collision Theory
In order for a chemical reaction to occur,
the reactant atoms or molecules must
collide with each other.
However, not all collisions are effective,
i.e. form new products.
 Sufficient
Energy
Break the
bonds in
Collision reactants Effective
between Collision
reactants (Products)
Correct
Orientation
Effective Collision: Correct Orientation

Ineffective Collision: Incorrect Orientation

Activation Energy: Ea

Minimum amount of energy

required to break chemical
bonds in a successful
collision.
Energy Profile
Transition state theory
Energy profile
The energy changes during a chemical reaction can be
graphed as a function of reaction pathway.

Reactants Activated complex Products

/ transition state
Potential Energy Changes During Chemical
Reaction
Activated complex
Also known as transition state.
Theoretical high energy particle that exists
for a fraction of a second at the instant the
particles collide.
The activated complex can break down
into either the reactants in an ineffective
collision or the products in an effective
collision.
Ea and rate of reaction

Ea Lower rate

Ea
Higher rate
Example 1:
Example 2:
How to increase rate?
By controlling the collision of reactants.
Faster rate of reaction if

Increase the number of collisions per unit

time (frequency of collision).
Increase the proportion of molecules that
can overcome the activation energy
(energy of collision).
Frequency of Collision
Number of collision per unit time.
Frequency of collision will be increased if:
Increase concentration of reactants. (More
amount of solute in a solution)
Increase pressure of gas (increase number of
gas particles in given volume)
Increase surface area.(more exposed surface
that is available for a collision.)
Explanation:
The more concentrated the particles are, the more
crowded they are and they will collide more
frequently.
If there are more collisions, the proportion of
effective collision will probably increase.
Hence when concentration of the reactants
increases, the rate will usually increase.
Energy of Collision
Energy possessed by molecules during collision.
If the energy of collision is lower than Ea, there is
no reaction.
Rate of reaction is governed by the proportion of
molecules that possess enough energy to
overcome the activation energy.
The more number of molecules have energy > Ea,
the higher is the rate of reaction.
Temperature
A measure of the average kinetic energy of
the particles in a substance (how fast the
particles in a substance, on average, are
moving).
Higher temperature, molecules have higher
average kinetic energy.
Maxwell-Boltzmann Distribution

Colored area = total number

of molecules with enough
energy to react
How temperature affects rate?
If temperature is increased, the particles will move
faster on average (higher kinetic energy).
Molecules will collide more frequently (higher
frequency of collision) and collide with higher
energy (higher energy of collision).
Proportion of collisions that can overcome the
activation energy for the reaction (% effective
collision) increases with temperature increase.
Therefore the rate of reaction increases.
 Increase frequency of
Increase collision,
concentration Increase rate most of the
time.

Increase Increase frequency of collision &

tempature Increase energy of collision,
Increase rate all the time.
Temperature and Rate constant
Increase in temperature will increase the rate constant
Usually every increase of 100C, the rate will be
doubled.

Rate
constant

Temperature
 ARRHENIUS EQUATION
No. of colliding molecules

Collision frequency Concentration

Ea
-
RT
rate = P Z e [A] [B] ...
Steric factor
(fraction of collisions Maxwell-Boltzmann statistics
with effective (fraction of collisions with
orientations) activation energy Ea or greater,
at T)
 Ea
-
RT
rate = P Z e [A] [B] ...
Compare with rate law:

rate = k [A] [B] ...
We see that:
Ea
- (PZ is often replaced
RT
k =P Ze by the term A, known
as the pre-
Thus exponential factor
Ea or frequency factor)
-
RT
k=Ae (Arrhenius equation)
 Arrhenius equation
The Arrhenius equation expresses this relationship
between rate (k) and temperature:

Gas constant =
8.134 J/K.mol Ea Activation
energy

Rate constant
k = Ae RT Temperature
in Kelvin

2.71828
Frequency factor, A= zp
z = collision frequency
P = steric factor
 Ea
-
RT
k=Ae
Taking the natural logarithm
of the Arrhenius equation
gives:
Ea
ln (k) = ln (A) -
RT
Rearrange

Ea 1
ln (k) = - + ln (A)
R T
y = m x + c
Example 1: Determine Ea
Calculate the activation energy, Ea, for a reaction with the
following temperature and rate constant data.
Temperature (K) Rate constant (s-1)
200 0.236
300 0.301
400 0.340
500 0.366
600 0.385
700 0.399
800 0.409
 From Arrhenius Equation
%&'

#$   )  #$ 
( *
Therefore a line would be a graph of In k versus 1/T
So find In k and 1/T :
Temperature, Rate constant, k 1/T In k
T(K) (s-1)
200 0.236 0.00500 -1.445
300 0.301 0.00333 -1.200
400 0.340 0.00250 -1.078
500 0.366 0.00200 -1.004
600 0.385 0.00167 -0.955
700 0.399 0.00143 -0.920
800 0.409 0.00125 -0.894
Plot graph In k vs 1/T
Solution:
The activation energy, Ea, is determined from the slope of
this line, 1.47.
The relationship between slope and activation energy is:
012
+,-./ 
3
where R is the gas constant = 8.314 J/ mol.K.
012
04. 56 
7. 845
19  1222:
(The activation energy unit is in joules.)
Example 2:
Use the information and answer from
Example 1, calculate the rate constant, k2 at
210 K.

From data given, k1 at 200K = 0.236

Ea found = 1222 J
Solution:
T1 = 200 K k1 = 0.236
T2 = 210 K k2 = ?
Step 1:
Substitute what we know into the equation:

k2 Ea 1 1
In( ) = ( )
k1 R T1 T2
k2 1222 1 1
In( )= ( )
0.236 8.314 200 210
Step 2:
Simplified the right hand side of the equation:

k2 1222 1 1
In( )= ( )
0.236 8.314 200 210
k2
In = 0.034995
0.236
 Step 3:
Then take antilog on both side of the equation:

k2
In = 0 . 034995
0 . 236
k2
= 1 . 0356
0 . 236
k 2 = 1 . 0356 0 . 236
k 2 = 0 . 2444
Catalyst
A substance that increases rate of reaction
without being consumed itself.
Often a catalyst works by holding reactant
molecules in a certain orientation that puts
stress on the bonds and make the collision
with the other reactants more effective.
How catalyst affects rate ?

Catalyst provides an alternative pathway for a

reaction (a different activated complex is formed).
The activation energy of new pathway is lower
than the original one,
So more proportion of molecules have E new Ea.
Hence, rate of reaction increases.
 Temporary,
Activated complex unstable
arrangement of
atoms that may
form products.

Ea without
Energy

catalyst

Ea with
Reactant
catalyst

H= -ve
Product

Reaction coordinate
Maxwell-Boltzmann Curve
Uncatalysed Reaction:

O3 (g) + O (g)
2O2(g) High Ea

Catalysed reaction
Catalyst and Rate constant

Addition of catalyst will alter the rate

constant.
Rate constant increases when right
catalyst is added.
Action of Heteregeneous Catalyst

H2 Haber Process
NH3
N2

Fe

Iron
N2 (g) + 3H2 (g) 2NH3 (g)
catalyst
Heterogeneous catalytic ethylene hydrogenation:
C2H4 + H2 C2H6
 Catalytic Converters

CO + Unburned Hydrocarbons + O2 CO2 + H2O

2NO + 2NO2 2N2 + 3O2

 Orientation
Effective Collision
Collision Theory

Activation Energy

;9 1
Temperature #$   0  #$
< =

Energy of Collision

Catalyst
Increase Rate

Frequency of Collision Concentration

50
Reference

http://www.wwnorton.com/college/chemistry/gilbert2/con
tents/ch14/studyplan.asp
(All flash videos are in Collision Theory and Arrhenius
Equation tutorials in above url)