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(Part II)
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. forms new products.
Effective Collision
• If the reactant molecules collide with
sufficient energy and in the correct
orientation, the repulsion between
valence electrons will break the
existing bonds, allowing new bonds to
form. This is called an “effective
collision”
Effective Collision: Correct Orientation
Rate
constant
Temperature
ARRHENIUS EQUATION
No. of colliding molecules
Ea
-
rate P Z e RT
[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
-
rate P Z e RT
[A] [B] ...
• Compare with rate law:
rate k [A] [B] ...
• We see that:
Ea
- (PZ is often replaced
k P Ze RT
by the term A, known
as the pre-
• Thus exponential factor
Ea or frequency factor)
-
kA e RT
(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
-
kA e RT
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
−𝐸𝑎 1
• 𝐼𝑛 𝑘 = × + 𝐼𝑛 𝐴
𝑅 𝑇
• 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:
−𝑬𝒂
𝑺𝒍𝒐𝒑𝒆 =
𝑹
where R is the gas constant = 8.314 J/ mol.K.
−𝑬𝒂
−𝟏. 𝟒𝟕 =
𝟖.𝟑𝟏𝟒
𝑬𝑎 = 1222𝐽
(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.
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
k2 1.0356 0.236
k2 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 ?
Ea without
Energy
catalyst
Ea with
Reactant
catalyst
H= -ve
Product
Reaction coordinate
Maxwell-Boltzmann Curve
Uncatalysed Reaction:
H2 Haber Process
NH3
N2
Fe
Iron
N2 (g) + 3H2 (g) 2NH3 (g)
catalyst
Heterogeneous catalytic ethylene hydrogenation:
C2H4 + H2 → C2H6
Catalytic Converters
Activation Energy
𝐸𝑎 1
Temperature 𝐼𝑛 𝑘 = − + 𝐼𝑛𝐴
𝑅 𝑇
Energy of Collision
Catalyst
Increase Rate
50
Reference
• http://www.wwnorton.com/college/chemistry/gilbert/over
view/ch14.htm
(All flash videos are in Collision Theory and Arrhenius
Equation tutorials in above url)