Part-02 Reaction Kinetics (KINETIKA KIMIA, 15 DES 2020)

part-02: Reaction Kinetics
The rate of a reaction or the reaction rate is the change

in concentration of a reactant or a product with time
(M/s).
3
5
Zero Order Rate Equation
❑ Differential rate equation d [A]
= k[A]a [B]b [C]l [D]d
−
dt
zero order, i.e. a=b=l=d=0, so that d [A]
− = k or d [A] = -kdt
dt
integration with boundary conditions at t=0 [A]=[A]0, and t=t [A]=[A]
[A] t

[A]0
d [A] =  - kdt  [A]- [A]0 = -kt
t0
or [A] = [A]0 - kt
100
[A], k=10 Graph produced by setting

80 [A], k=20 [A]0=100 mol, k=10,20 mol/s & t in s.
60
✓Concentration of reactant decreases
[A]
40
linearly with time from initial value, with
the slope=k
20
✓The larger k value is, the faster the

0
0 1 2 3 4 5 6
decrease of the reactant concentration
t
8
First Order Rate Equation d [A]
❑ Differential rate equation − = k[A]a [B]b [C]l [D]d
dt
d [A] d [A]
1st order, i.e. a+b+l+d=1, assume a=1 so that − = k[A] or = -kdt
dt [A]

[A] d [A] t
[A]0 [A] = t0 - kdt  ln[A]- ln[A]0 = -kt or [A] = [A]0 exp(-kt)
100
100
Graph produced by setting
[ A ] , k=1
80
[ A ] , k=1
[A]0=100 mol, k=1, 2 mol/s & t in s.
10 [ A ] , k=2
[ A ] , k=2
60 ✓Concentration of reactant decreases

1
[A] = [A]0 exp(−𝑘𝑡) exponentially with time from initial value

0. 1
40
✓When using semi-ln graph, a straight line

20
is obtained
0. 01
with
ln[A] = the slope=k
ln[A] − 𝑘𝑡 0
0 ✓The larger k value is the faster the
0. 001
0 1 2 3 4 5 6
0 1 2 3 4 5 6
t
t
9
Second Order Rate Equation
d [A]
❑ Differential rate equation − = k[A]a [B]b [C]l [D]d
dt
d [A] d [A]
2ndt order, i.e. a+b+l+d=2, assume a=2 so that − = k[A]2 or 2
= -kdt
dt [A]
[A] d [A] t 1 1 [A]0
[A]0 [A]2 = t0 - kdt  [A] - [A]0 = kt or [A] =
1 + kt[A]0
0. 12 Graph produced by setting
100
[ A ] , k=1
0. 1
[ A ] , k=2 [A]0=100 mol, k=1, 2 mol/s & t in s. [ A ] , k=1
1 1 80
[A]0 [ A ] , k=2
0. 08 = + 𝑘𝑡 [A] of
✓Concentration = reactant decreases
[A] [A]0 60
1 + 𝑘𝑡[A]0 from
0. 06 with time in a complicated way
initial value
40
0. 04
✓When plotting 1/[A] with time, a straight

20
0. 02
line is obtained with the slope=k
0
0
0 0. 01 0. 02 0. 03 0. 04 0. 05 0. 06 ✓The larger k value is the faster the
0 0. 01 0. 02 0. 03 0. 04 0. 05 0. 06
13
t
Summary of Rate Equations
14
❑ The Arrhenius Equation  − Ea  (1)

k = A exp  
 RT 
where: A pre-exponential factor
Ea is the reaction activation energy
R is the gas constant
T is the reaction temperature in Kelvin
Eqn.1 was initially found from fitting experimental results. After molecular
kinetic theory was established, the relation can be derived directly from the
theory.
energy
Ea
reactant
➢Usually A is related to the molecule collision
frequency or thermodynamically to the entropy product
➢Ea is an energy term which related to
the energy barrier for a reaction has to overcome reaction process
Exp. Determination of Arrhenius Parameters
 − Ea 
❑ From the Arrhenius Equation k = A exp   (1)
 RT 
To determine A and Ea
− Ea
Take log: ln k = lnA +
RT
Compare with linear equation: y=a+bx, where y=lnk, a= lnA, b=-Ea/R and x=1/T
If when can measure k at various temperature T’s slope=-Ea/R

intersect=ln A
lnk
Note: As k is a function of temperature, the k value measured
at each T as mentioned above should be different.
Therefore, the above method, strictly speaking, gives
1/T
average values of Ea and A within the T’s applied.
16
The molecularity of a reaction is the
number of molecules reacting in an
elementary step. These molecules
may be of the same or different
types.
Each of the elementary steps just

discussed is called a bimolecular
reaction, an elementary step that
involves two molecules.
An example of a unimolecular
reaction, an elementary step in
which only one reacting molecule
participates.
A catalyst is a substance that increases the rate of a reaction by lowering

the activation energy.
In heterogeneous catalysis, the reactants and the catalyst are in different

phases.
In homogeneous catalysis the reactants and catalyst are dispersed in a

single phase, usually liquid.
What is a “Catalyst”
❑A catalyst (Greek: καταλύτης, catalytēs) is a substance that
accelerates the rate of a chemical reaction without itself being
transformed or consumed by the reaction. (thank you Wikipedia)
k(T) = k0e-Ea/RT
Ea ′ < Ea
k0′ > k0
Ea k′ > k Ea′
ΔG = ΔG
A+B A+B+
ΔG catalyst ΔG
C C + catalyst
uncatalyzed catalyzed
W.
Types of Catalysts – Homogeneous vs.
Heterogeneous
Zeolite catalyst Catalyst powders

Homogeneous catalysis Heterogeneous catalysis
Single phase Multiphase
(Typically liquid) (Mostly solid-liquid and solid-gas)
Low temperature High temperature
Separations are tricky Design and optimization tricky
CBE
Types of Catalysts - Enzymes
❑ The “Gold Standard”
of catalysts
❑ Highly specific
❑ Highly selective
❑ Highly efficient
❑ Catalyze very difficult
reactions
 N2 → NH3
 CO2 + H2O → C6H12O6
Triosephosphateisomerase ❑ Works better in a cell

“TIM”
than in a 100000 l
reactor
Cytochrome C Oxidase
Highly tailored “active sites”

Often contain metal atoms

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part-02: Reaction Kinetics

part-02: Reaction Kinetics

The rate of a reaction or the reaction rate is the change

[A], k=10 Graph produced by setting

✓The larger k value is, the faster the

integration with boundary conditions at t=0 [A]=[A]0, and t=t [A]=[A]

60 ✓Concentration of reactant decreases

[A] = [A]0 exp(−𝑘𝑡) exponentially with time from initial value

✓When using semi-ln graph, a straight line

✓When plotting 1/[A] with time, a straight

❑ The Arrhenius Equation  − Ea  (1)

If when can measure k at various temperature T’s slope=-Ea/R

Each of the elementary steps just

A catalyst is a substance that increases the rate of a reaction by lowering

In heterogeneous catalysis, the reactants and the catalyst are in different

In homogeneous catalysis the reactants and catalyst are dispersed in a

Zeolite catalyst Catalyst powders

Triosephosphateisomerase ❑ Works better in a cell

Highly tailored “active sites”

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