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CRE II Solid Catalysis Rate Limiting Step

The document discusses the concept of rate-limiting steps in heterogeneous reactions, emphasizing that one step in a series of reactions (adsorption, surface reaction, desorption) typically controls the overall reaction rate. It introduces the Langmuir-Hinshelwood approach for determining catalytic mechanisms and provides examples of reactions where either adsorption or surface reaction is rate-limiting. Additionally, it outlines the process of synthesizing rate laws and mechanisms to identify the rate-limiting step in catalytic reactions.

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Gautam Verma
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16 views23 pages

CRE II Solid Catalysis Rate Limiting Step

The document discusses the concept of rate-limiting steps in heterogeneous reactions, emphasizing that one step in a series of reactions (adsorption, surface reaction, desorption) typically controls the overall reaction rate. It introduces the Langmuir-Hinshelwood approach for determining catalytic mechanisms and provides examples of reactions where either adsorption or surface reaction is rate-limiting. Additionally, it outlines the process of synthesizing rate laws and mechanisms to identify the rate-limiting step in catalytic reactions.

Uploaded by

Gautam Verma
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PPTX, PDF, TXT or read online on Scribd
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CH3008D

CHEMICAL REACTION ENGINEERING II


Solid Catalyzed Reactions
The Rate Limiting Step
Which step is the Rate Limiting Step?
• When heterogeneous reactions are carried out at steady state, the
rates of each of the three steps in series (adsorption, surface
reaction, and desorption) are equal to one another:

• One particular step in the series is usually found to be rate-limiting


or rate-controlling.
• If we could make the rate limiting step go faster, the entire reaction
would proceed at an accelerated rate.
Electrical Analog to Heterogeneous
Reactions
• The Rate Limiting Step
• Which step has the largest
resistance?

• A given concentration of reactants is analogous to a given driving


force or electromotive force (EMF).

• Current I (Coulombs/s) is analogous to the rate of reaction, -rA’

(mol/s. gcat), and a resistance Ri is associated with each step in the


series.
Langmuir-Hinshelwood Approach
• The approach in determining catalytic and heterogeneous
mechanisms is usually termed as the Langmuir-Hinshelwood
approach.
• Uniform catalyst surface is assumed.
• First assume a sequence of steps in the reaction.
– Choose among such mechanisms as molecular or atomic adsorption, and
single- or dual-site reaction.

• Next, rate laws are written, assuming that all steps are reversible.
• Finally, a rate-limiting step is postulated.
Example of an Adsorption-Limited
Reaction
• The synthesis of ammonia (NH3) from hydrogen (H2) and nitrogen

(N2), over an iron (Fe) catalyst.

• The rate-limiting
step is believed to
be the adsorption
of the N2
molecule as a N
atom.
Example of an Surface Reaction-Limited
Reaction
• The reaction of two noxious automobile exhaust products, CO and
NO, carried out over copper (Cu) catalyst to form environmentally
acceptable products, N2 and CO2.
Synthesizing a Rate Law, Mechanism, and Rate-
Limiting Step
• Example: Catalytic (Pt-catalyzed) decomposition of cumene to form
benzene and propylene.
Synthesizing a Rate Law, Mechanism, and Rate-
Limiting Step (Contd.)
• Cumene adsorption –
Formation of a complex of
the π-orbitals of benzene
with the catalytic surface.

• The reaction sequence for decomposition of Cumene, as per


Langmuir-Hinshelwood kinetic mechanism:

C = cumene
B = benzene
P = propylene
Synthesizing a Rate Law, Mechanism, and Rate-
Limiting Step (Contd.)
• While writing rate laws for the three
steps, each step is considered as (1)
elementary reaction.
• For species concentration in gas phase, (2)

partial pressure term is used.


• Partial pressure can be calculated (3)

directly using, Ideal Gas law, PC = CCRT


Synthesizing a Rate Law, Mechanism, and Rate-
Limiting Step (Contd.)
• The rate expression for the adsorption
(1)
of cumene,

(2)

(3)
Units:
rAD – mol/(g cat.s)
CC.S – mol cumene
adsorbed/g cat
Cv – mol/g cat
PC – atm or Pa
Synthesizing a Rate Law, Mechanism, and Rate-
Limiting Step (Contd.)
• The rate law for the surface reaction
(1)
step producing adsorbed benzene and
propylene in the gas phase, (2)

(3)

• Propylene is not adsorbed on the


surface.
• So, CP.S = 0.
Synthesizing a Rate Law, Mechanism, and Rate-
Limiting Step (Contd.)
• The rate of benzene desorption,
(1)

(2)

• Benzene adsorption equilibrium (3)


constant, KB is just the reciprocal of
the benzene desorption constant, KDB
• KB = 1/KDB
Determination of The Rate-Limiting Step

• Since, there is no accumulation of reacting species on the


surface, the rates of each step in the sequence are all equal:

• For the mechanism postulated, it is intended to determine


which step is rate-limiting.
• So, first assume one of the steps to be rate-limiting (rate-
controlling) and then formulate the reaction rate law in terms
of the partial pressures of the species present.
Case 1: Adsorption of Cumene Rate-Limiting

• By assuming that this step is rate-limiting, we are


considering that the reaction rate constant of this step (in
this case kA) is small with respect to the specific rates of the

other steps (in this case kS and kD).

• The rate of adsorption is,

• For steady-state operation, we have


Case 1: Adsorption of Cumene Rate-Limiting
(Contd.)
• The surface reaction rate law is,

• For adsorption-limited reactions, kA is small and kS and kD


are large.

•  The ratios rS/kS and rD/kD are very small (approximately

zero), whereas the ratio rAD/kA is relatively large.


Case 1: Adsorption of Cumene Rate-Limiting
(Contd.)
• The rate of desorption of benzene is

• We have the rate of adsorption,

• Observe that by setting rAD = 0, the term (KsKc/KB) is simply the

overall partial pressure equilibrium constant “KP” for the


reaction,
Case 1: Adsorption of Cumene Rate-Limiting
(Contd.)

• Site balance:
• Ct = Cv + CC.S + CB.S

• The equilibrium constant can be determined from


thermodynamic data and is related to the change in the Gibbs
free energy, ΔG°,
Case 1: Adsorption of Cumene Rate-Limiting
(Contd.)
• How to verify the postulated rate-limiting step?
• We have the rate,
• The initial rate: Initially, no
products are present;
consequently, PP = PB = 0.

• Initial rate will be linear with


the initial partial pressure of
cumene.
Case 2: The Surface Reaction Rate-Limiting

• By assuming that this step is rate-limiting, we are


considering that the reaction rate constant of this step (in
this case kS) is small with respect to the specific rates of the

other steps (in this case kA and kD).

• The rate of surface reaction is,

• We must utilize the adsorption and desorption steps to


eliminate CC.S, and CB.S from this equation.
Case 2: The Surface Reaction Rate-Limiting
(Contd.)
Case 2: The Surface Reaction Rate-Limiting
(Contd.)
• How to verify the postulated rate-limiting step?
• We have the rate,

• The initial rate: Initially, no products are present;


consequently, PP = PB = 0.
Case 2: The Surface Reaction Rate-Limiting
(Contd.)
• The initial rate: Initially, no products are present;
consequently, PP = PB = 0.

• At low partial pressures of cumene

• At high partial pressures of cumene,


Case 2: The Surface Reaction Rate-Limiting
(Contd.)

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