Kinetika Reaksi Week 5:

Pseudo Steady State Hypothesis

Semester Genap 2020/2021

Dr. Hary Sulistyo

([email protected])

Program Magister Teknik Kimia

Departemen Teknik Kimia,
Fakultas Teknik,
Universitas Gadjah Mada
Learning Outcome
Level of Bloom Taxonomy
No Learning Outcome 1 2 3 4 5 6
M1 Mengembangkan persamaan kinetika reaksi berdasarkan √
mekanisme reaksi homogen.
M2 Mengembangkan bentuk umum dari kecepatan reaksi 
kimia berdasarkan pada mekanisme reaksi untuk sistem
heterogen dengan katalis dan tanpa katalis.
M3 Mengembangkan bentuk umum dari persamaan 
kecepatan reaksi kimia berdasarkan tahapan yang
mengontrol pada sistem heterogen dengan katalis dan
tanpa katalis.
M4 Mengembangkan kinetika reaksi gas-cair dan gas-padat 
dengan katalis dan tanpa katalitis.
M5 Menganalisis data eksperimen untuk menentukan √
kinetika reaksi.
M6 Memformulasikan model pada reaktor bio: batch dan 
kontinyu (chemostat).
M7 Memformulasikan model pada reaktor fixed bed satu 
dimensi pada berbagai kondisi.
Agenda:
• Konsep PSSH (Pseudo Steadt State Hypothesis)
• Example 1 Gas Phase Decomposition of Azomethane
• Example 2 NO oxidation to NO2

Learning Outcome:
• M1 Mengembangkan persamaan kinetika berdasarkan
mekanisme reaksi homogen

Referensi:
Chapter 9, Fogler, H. S., 2016, “Elements of Chemical Reaction
Engineering”, 5th ed. Pearson Education, Inc. Boston.
Active Intermediates and PSSH
From Chapter 3, a number of simple power-law models, such as:
−𝑟𝐴 = 𝑘𝐶𝐴𝑛
were presented, where n was an integer 0,1, or 2 corresponding to a zero-, first-, or
second-order reaction. However, for a large number of reactions, the orders are non
integer, such as the decomposition of acetaldehyde at 500oC
CH3CHO → 𝐶𝐻4 + 𝐶𝑂
where the rate law:
3/2
−rCH3CHO = 𝑘. 𝐶CH3CHO

Or, the rate law could also have concentration terms in both the numerator and
denominator such as the formation of HBr from H2 and Br2
H2 + Br2 → 2𝐻𝐵𝑟
where the rate law: 3/2
𝑘1𝐶𝐻2𝐶𝐵𝑟2
𝑟𝐻𝐵𝑟 =
𝐶𝐻𝐵𝑟 + 𝑘2𝐶𝐵𝑟2

Rate laws of this form usually involve a number of elementary reactions and at least one
active intermediate.
 Active Intermediates and PSSH
An active intermediate is a molecule that is in a highly
energetic and reactive state. It is short lived as it disappears
virtually as fast as it is formed. That is, the net rate of
reaction of an active intermediate, A*, is zero.

The assumption that the net rate of reaction is zero is called

the Pseudo Steady State Hypothesis (PSSH)

Active intermediate is a Ahmed Hassan Zewail (February 26, 1946 –

short lived molecule, which August 2, 2016) was an Egyptian-American chemist,
known as the "father of femtochemistry". He was
present for only ca. 10-15 awarded the 1999 Nobel Prize in Chemistry for
second (femtosecond) his work on femtochemistry. (WIKIPEDIA)
Active Intermediates and PSSH
Active Intermediates and PSSH

Chapter 9, Fogler, H. S., 2016, “Elements of Chemical Reaction Engineering”, 5th

ed. Pearson Education, Inc. Boston.
Example 1 Decomposition of
Azomethane
The rate law for the reaction
CH3 2N2 → 𝐶2𝐻6 + 𝑁2
Azomethane Ethane
A → B+C
is found from experiment to be
2
kC
− rA = A
1 + k C A
How did this rate law come about? Suggest a
mechanism consistent with the rate law.
Example 1 Decomposition of
Azomethane
For reactions with active intermediates, the reaction
coordinated now has trough in it and the active
intermediate, A*, sits in this trough
Example - Solution

(1) A + A ⎯⎯→ A * + A
k1
r1 A* = k1C 2
A

(2) A * + A ⎯⎯→ A + A
k2
r2 A* = −k 2C A*C A

(3) A * ⎯⎯→ B + C
k3
r3 A* = − k3C A*
Example 1 Decomposition of
Azomethane
Rate Laws:
k3 is defined w.r.t. A*

Reaction (1) r1 A* = k1C A2 (1)

Reaction (2) r2 A* = −k 2C AC A* (2)

Reaction (3) r3 A* = −k3C A* (3)

But C*A cannot be measured since it is so small

Relative Rates: r1 A = − r1 A* , r3 B = −r3 A*

Example 1 Decomposition of
Azomethane
Net Rates: Rate of Formation of Product
rB = r3 B = − r3 A* = k3C A* (4)

Pseudo Steady State Hypothesis r*A = 0

rA* =  rA* = r1 A* + r2 A*  r3 A* (5)

= k1C A2 − k2C AC A* − k3C A* = 0 (6)

Solving for C A*
k1C A2
C A* =
k3 + k 2C A
Example 1 Decomposition of
Azomethane
Substituting for C A* in Equation (4) the rate of
formation of B is
k1k3C A2
rB = (8)
 k3 + k 2C A
Relative rates overall
A → B+C
rA rB
=
−1 1
k1k3C A2
rA = −rB = − (9)
k3 + k 2C A
Example 1 Decomposition of
Azomethane
For high concentrations of A, we can neglect k 3 in
the denominator with respect to k 2C A
k 2C A  k3
and the rate law becomes
k1k3
rA = − C A = −kC A (10)
k2
(apparent first order)
Example 1 Decomposition of
Azomethane
For low concentrations of A, we can neglect k 2C A in
the denominator with respect to k3.
k3  k 2C A
and the rate law becomes
k3k1 2
rA = − C A = −k1C A2 (11)
k3
(apparent second order)
Dividing by k3 and letting k’=k2/k3 and k=k1 we have
the rate law we were asked to derive
kC A2
− rA = − (12)
1 + k C A
Active Intermediates
Why do so many reactions follow elementary rate laws?

What about − rA = kC A
kC A
−rA = ( I = Inert )
1 + k ' CI
(1) A + I ⎯⎯→
k1
A* +I
(2) A * + I ⎯⎯→ A + I
k2

(3) A ⎯⎯→
k3
B+C
k1k3C A
- rA =
k 2 + k 2C I
Active Intermediates/Free Radicals
and PSSH
Example 2: NO Oxidation to NO2 (Hall Of Fame Reaction)

The reaction: 2NO +O2→ 2NO2

has an elementary rate law
rNO2 = kC CO2
2
NO

However… Look what happens to the rate as the

temperature increases:

-rNO2

T
Example 2: NO Oxidation to NO2

Why does the rate law decrease with increasing

temperature?

Mechanism:
NO + O2 ⎯⎯→ NO
k1 *
3
(1)

NO ⎯⎯→ NO + O2
*
3
k2
(2)

NO + NO ⎯⎯→ 2 NO2
*
3
k3 (3)

Write rate of formation of product rNO2

Note: k3 is defined w.r.t. NO3*
Example 2: NO Oxidation to NO2
Define k with respect to NO3*
Assume that all reactions are elementary
reactions, such that:

r1NO3 = k1CNOCO2 = k1 [ NO][O2 ]

r2 NO* = -k2CNO* = k2 éë NO ùû
*
3
3 3

r3NO* = -k3CNO* CNO = k3 éë NO3* ùû [ NO]

3 3

rNO = 2 é -r3NO* ù
2 ë 3 û

19
Example 2: NO Oxidation to NO2
The net reaction rate for NO3* is the sum of the
individual reaction rates for NO3*:
r1NO* = r1 Þ r1NO* = k1[ NO] [O2 ]
3 3

-r2NO* = r2 Þ r2NO * = -k2 [ NO *

3 ]
3 3

−r3 NO* = r3  r3 NO* = −k3  NO   NO 

*
3
3 3

rNO* = r1NO * + r2NO* + r3NO*

3 3 3 3

rNO* = k1  NO  O2  − k2  NO  − k3  NO   NO 
*
3
*
3
3
Example 2: NO Oxidation to NO2

Pseudo Steady State Hypothesis (PSSH)

The PSSH assumes that the net rate of species A*
(in this case NO3*) is zero.
rNO *  0
3

0 = k1  NO  O2  − k2  NO3*  − k3  NO3*   NO 

0 = k1 [ NO] [O2 ] - éë NO3* ùû ( k2 + [ NO])

k1 [ NO ][O2 ]
éë NO ùû =
*

k2 + k3 [ NO ]
3
Example 2: NO Oxidation to NO2

Pseudo Steady State Hypothesis (PSSH)

𝑘1 𝑁𝑂 𝑂2
[𝑁𝑂3∗ ] =
𝑘2 + 𝑘3 𝑁𝑂

3

rNO2 = −2r3 NO* = 2 NO NO 
*
3 
k1 k 3 NO 2 O2
𝑟𝑁𝑂2 =2
k 2 + k 3 NO
Example 2: NO Oxidation to NO2

Pseudo Steady State Hypothesis (PSSH)

k2 >> k3 [ NO]
E2 − ( E1 + E3 )
rNO2 =2
k1k3
NO  O2  = 2
2 A1 A3
e RT
NO  O2 
2

k2 A2
E2  (E1 + E3 )

This result shows why the -rNO2

rate decreases as
temperature increases.
T
TERIMA KASIH

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