Lecture on

Fluid-solid Catalytic Reaction Mechanism &

Rate-Limiting Step

Instructor

Prof. Bishnupada Mandal

Room No. 102, Block - K
Department of Chemical Engineering
Indian Institute of Technology Guwahati

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Lecture 4: Fluid-solid Catalytic Reaction Mechanism &
Rate-Limiting Step

Lecture Outline
• Recap on previous lecture
• Dissociative Adsorption
• Surface Reaction
• Desorption
• Rate-Limiting Step
• Synthesizing rate law, mechanism and rate limiting step
 Molecular Adsorption
 Using Equation to give Cv in terms of CCO·S and the total number
of sites Ct we can solve for the equilibrium value of CCO·S in terms
of constants and the pressure of carbon monoxide:

 Rearranging gives us

 This equation thus gives the equilibrium concentration of CO adsorbed on the

surface, CCO·S, as a function of the partial pressure of CO, and is an equation
for the adsorption isotherm.

 This particular type of isotherm equation is called a Langmuir isotherm.

 Molecular Adsorption
 Below Figure shows the Langmuir isotherm for the amount of CO
adsorbed per unit mass of catalyst as a function of the partial
pressure of CO.

Langmuir isotherms for (a) molecular adsorption (b) dissociative adsorption of CO

 Molecular Adsorption
 One method of checking whether a model (e.g., molecular adsorption
versus dissociative adsorption) predicts the behavior of the
experimental data is to linearize the model's equation and then
plot the indicated variables against one another.
 For example, below Equation may be arranged in the form

 The linearity of a plot of PCO/CCO·S

as a function of PCO will determine
if the data conform to a Langmuir
single-site isotherm.
 Dissociative Adsorption
 Next, we derive the isotherm for carbon monoxide disassociating into
separate atoms as it adsorbs on the surface, i.e.

 When the carbon monoxide molecule dissociates upon adsorption, it

is referred to as the dissociative adsorption of carbon monoxide.
 As in the case of molecular adsorption, the rate of adsorption is
proportional to the pressure of carbon monoxide in the system
because this rate is governed by the number of gaseous
collisions with the surface.
 For a molecule to dissociate as it adsorbs, however, two adjacent
vacant active sites are required, rather than the single site needed
when a substance adsorbs in its molecular form.
 Dissociative Adsorption
 The probability of two vacant sites occurring adjacent to one another
is proportional to the square of the concentration of vacant sites.
 These two observations mean that the rate of adsorption is
proportional to the product of the carbon monoxide partial
pressure and the square of the vacant-site concentration, PCOCv2.
 For desorption to occur, two occupied sites must be adjacent,
meaning that the rate of desorption is proportional to the product
of the occupied-site concentration, (C·S)×(O·S).
 The net rate of adsorption can then be expressed as


 Dissociative Adsorption
 Factoring out kA, the equation for dissociative adsorption is

 For dissociative adsorption, both kA and k_A increase exponentially

with increasing temperature, while KA decreases with increasing
temperature.
 At equilibrium, rAD = 0:



 Dissociative Adsorption
 Substituting for CC.S and CO.S in a site balance Equation

 This value may be substituted into below Equation to give an

expression that can be solved for the equilibrium value of CCO·S.


 Taking the inverse of both sides of the equation, then multiplying
through by (PCO)1/2, yields
 Dissociative Adsorption
 Taking the inverse of both sides of the equation, then multiplying
through by (PCO)1/2, yields

 If dissociative adsorption is the correct model, a plot of (PCO1/2/CO.S)

versus (PCO)1/2 should be linear with slope (2/Ct).
 Adsorption of Multiple Substance
 When more than one substance is present, the adsorption
isotherm equations are somewhat more complex.
 The principles are the same, though, and the isotherm equations are
easily derived.
 It is left as an exercise to show that the adsorption isotherm of A in
the presence of another adsorbate B is given by the relationship:

 When the adsorption of both A and B are first-order processes, the

desorption are also first order, and both A and B are adsorbed as
molecules.
Fractional Coverage and Langmuir Adsorption Isotherm
 Instead of using the surface concentrations (CA-S) as the concentration
variable, it is often preferable to use the fractional coverage, defined
by θA = CA-S/Ct.
 In terms of the fractional coverage of A, the Langmuir isotherm is


K A PA
A 
1  K A PA  K B PB
 Assumptions of Langmuir Adsorption Isotherm
 The derivations of other Langmuir isotherms are relatively
easy. The Langmuir isotherm is based on 3 primary
assumptions:
(1) The solid surface is made up of a uniform array of energetically
identical adsorption sites.

(2) A maximum of one monolayer (one adsorbate molecule per site)

can be adsorbed.

(3) There are no interactions between the adsorbed molecules.

 The Rate-Limiting Step
 When heterogeneous reactions are carried out at steady state, the
rates of each of the three reaction steps in series (adsorption,
surface reaction, and desorption) are equal to one another:

 However, one particular step in the series is usually found to

be rate-limiting or rate-controlling.

 That is, if we could make this particular step go faster, the

entire reaction would proceed at an accelerated rate.
 The Rate-Limiting Step
 Consider the analogy to the electrical circuit shown in Figure

 A given concentration of reactants is analogous to a given

driving force or electromotive force (EMF).

 The current I (with units of Coulombs/s) is analogous to the

rate of reaction, -r’A (mol/s·g cat), and a resistance Ri is
associated with each step in the series.
 The Rate-Limiting Step
 Because the resistances are in series, the total resistance is
just the sum of the individual resistances, for adsorption (RAD ),
surface reaction (RS), and desorption (RD ). The current, I, for a
given voltage, E, is

 Since we observe only the total resistance, Rtot, it is our task to

find which resistance is much larger (say, 100 Ω) than the other
two resistances (say, 0.1 Ω).

 Thus, if we could lower the largest resistance, the current I (i.e.

-r’A) , would be larger for a given voltage, E.

 Analogously, we want to know which step in the adsorption-

reaction-desorption series is limiting the overall rate of reaction.
 The Rate-Limiting Step
 The approach in determining catalytic and heterogeneous mechanisms
is usually termed the Langmuir-Hinshelwood approach, since it is
derived from ideas proposed by Hinshelwood based on Langmuir's
principles for adsorption.

 The Langmuir-Hinshelwood approach was popularized by Hougen and

Watson and occasionally includes their names.

 It consists of first assuming a sequence of steps in the reaction. In writing

this sequence, one must choose among such mechanisms as molecular
or atomic adsorption, and single- or dual-site reaction.

 Next, rate laws are written for the individual steps assuming that all
steps are reversible.

 Finally, a rate-limiting step is postulated, and steps that are not rate-
limiting are used to eliminate all coverage-dependent terms.
 Where Are We Heading?

Collecting information for catalytic reactor design

Synthesizing Rate Law, Mechanism and Rate Limiting Step
 We now wish to develop rate laws for catalytic reactions that are not
diffusion-limited.

 To obtain a mechanism, a rate-limiting step, and a rate law consistent

with experimental observation, we shall discuss a particular catalytic
reaction: decomposition of cumene to form benzene and propylene. The
overall reaction is

 A conceptual model depicting the sequence of steps in this platinum-

catalyzed reaction of the adsorption of cumene is shown in Figure.
Synthesizing Rate Law, Mechanism and Rate Limiting Step

 A more realistic model is the

formation of a complex of the 
orbitals of benzene with the catalytic
surface, as shown in Figure:

 The nomenclature will be used to

denote the various species in this
reaction is: C = cumene, B =
benzene, and P = propylene. The
reaction sequence for this
decomposition is:
Synthesizing Rate Law, Mechanism and Rate Limiting Step
 When writing rate laws for these
steps, we treat each step as an
elementary reaction; the only
difference is that the species
concentrations in the gas phase
are replaced by their respective
partial pressures: CC → PC

 There is no theoretical reason for this replacement of the

concentration, CC, with the partial pressure, Pc; it is just the convention
initiated in the 1930s and used ever since. Fortunately, Pc can be
calculated directly from CC using the ideal gas law (i.e., PC = CCRT).

 The rate expression for the adsorption of cumene as given in Equation

is
Synthesizing Rate Law, Mechanism and Rate Limiting Step

 Rearranging,

 If rAD has units of (mol/g cat·s) and

Cc·s has units of (mol cumene
adsorbed/g cat), then typical units of
kA, k-A, and KC would be
Synthesizing Rate Law, Mechanism and Rate Limiting Step
 The rate law for the surface
reaction step producing adsorbed
benzene and propylene in the gas
phase

 Typical units for ks and Ks are s-1 and kPa, respectively.

 Propylene is not adsorbed on the surface. Consequently, its

concentration on the surface is zero.

 The rate of benzene desorption

Synthesizing Rate Law, Mechanism and Rate Limiting Step
 By viewing the desorption of benzene:

 from right to left, we see that desorption is just the reverse of the
adsorption of benzene.

 Consequently, as mentioned earlier, it is easily shown that the benzene

adsorption equilibrium constant KB is just the reciprocal of the benzene
desorption constant KDB:

 Therefore the below can be written as:

Synthesizing Rate Law, Mechanism and Rate Limiting Step
 Because 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 in the sequence, we wish to determine

which step is rate-limiting.
 We 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.
 From this expression we can determine the variation of the initial
reaction rate with the initial total pressure.
 If the predicted rate varies with pressure in the same manner as the rate
observed experimentally, the implication is that the assumed mechanism
and rate-limiting step are correct.
 Is the Adsorption of Cumene Rate-Limiting?
 To answer this question we shall assume that the adsorption of
cumene is indeed rate-limiting, derive the corresponding rate law, and
then check to see if it is consistent with experimental observation.
 By postulating that this (or any other) step is rate-limiting, we are
assuming 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

 Because we can measure neither Cv or CC·S, we must replace these

variables in the rate law with measurable quantities for the equation to
be meaningful.
 Is the Adsorption of Cumene Rate-Limiting?
 The rate of adsorption is

 Because we can measure neither Cv or CC·S, we must replace these

variables in the rate law with measurable quantities for the equation to
be meaningful.
 For steady-state operation we have
 For adsorption-limited reactions, kA is very small and kS and kD are
very large. Consequently, the ratios rs/kS and rD/kD are very small
(approximately zero), whereas the ratio rAD/kA is relatively large.
 The surface reaction rate law is
 Is the Adsorption of Cumene Rate-Limiting?
 The surface reaction rate law is

 Again, for adsorption-limited reactions, the surface-specific reaction rate kS

is large by comparison, and we can set

 and solve for CC·S:


 To be able to express CC·S solely in terms of the partial pressures of
the species present, we must evaluate CB·S. The rate of desorption of
benzene is
 Is the Adsorption of Cumene Rate-Limiting?
 To be able to express CC·S solely in terms of the partial pressures of
the species present, we must evaluate CB·S. The rate of desorption of
benzene is

 However, for adsorption-limited reactions, kD is large by comparison, and

we can set

 and then solve for CB·S 

 After combining, we have


 Is the Adsorption of Cumene Rate-Limiting?
 After combining, we have

 Replacing CC·S in the rate equation and then factoring Cv, we obtain

 We observe that at equilibrium rAD = 0 and this equation rearranges to

 Is the Adsorption of Cumene Rate-Limiting?
 We observe that at equilibrium rAD = 0 and this equation
rearranges to

 We also know from thermodynamics that for the reaction

 also at equilibrium (-r’C = 0) we have the following

relationship for partial pressure equilibrium constant
KP:

 Consequently, the following relationship must hold

 The equilibrium constant can be determined from

thermodynamics data and is related to the change in
the Gibbs free energy, Go, by the equation:
 Is the Adsorption of Cumene Rate-Limiting?
 The concentration of vacant sites, Cv, can now be eliminated from the
below Equation by utilizing the site balance to give the total
concentration of sites, Ct which is assumed constant:
 Total sites = Vacant sites+ Occupied sites

 Because cumene and benzene are adsorbed on the surface, the

concentration of occupied sites is (CC·S + CB·S), and the total concentration
of sites is

 Substituting below Equations into the above Equation, Solving for Cv, we
have

 Is the Adsorption of Cumene Rate-Limiting?
 Combining the below Equations, we find that the rate law for the
catalytic decomposition of cumene, assuming that the adsorption of
cumene is the rate-limiting step, is

 We now wish to sketch a plot of the initial rate of reaction as a

function of the partial pressure of cumene, PC0· Initially, no products
are present; consequently, Pp = PB = 0. The initial rate is given by