1 Collision Theory and Transition State Theory

Theories hypothesize the nature of reaction/how it occurs, probability of reaction occurring and rate of reaction (why there is
concentration and temperature dependence).

1.1 Collsion Theory

Collision theory simplifies molecules to rigid spheres, where one remains stationary and the other is in motion. Reaction
occurs when one sphere collides with another. Assumptions:

 molecule “A” is moving at velocity UR,

1
8𝜅𝐵 𝑇 2
𝑈𝑅 = ( )
𝜋𝜇𝐴𝐵
Because the form of the relative velocity requires the reduced mass (which in some cases is difficult to determine
because of lack of information for the entire system), the alternative is to determine B/AB

𝜅𝐵 𝑅
=( )
𝜇𝐴𝐵 𝑀𝐴 𝑀𝐵
𝑀𝐴 + 𝑀𝐵

 Collision occurs through cross section Sr=π2AB, where

𝜎𝐴𝐵 = 𝑐𝑜𝑙𝑙𝑖𝑠𝑖𝑜𝑛 𝑟𝑎𝑑𝑖𝑢𝑠 = 𝜎𝐴 + 𝜎𝐵
when center of B is AB away from center of A
 The number of collsions for 1 molecule of A and all molecules of A are given as follows
2 ̂
𝑍̂1𝐴⋅𝐵 = 𝜋𝜎𝐴𝐵 𝐶𝐴𝐵 𝑈𝑅
1
8𝜅𝐵 𝑇 2
𝑍̂𝐴𝐵 = 2
𝜋𝜎𝐴𝐵 ( ) 𝐶̂𝐴 𝐶̂𝐵
𝜋𝜇𝐴𝐵

 The rate equation is obtained by combining the above.

1
2
8𝜅𝐵 𝑇 2
−𝑟𝐴 = [𝜋𝜎𝐴𝐵 ( ) 𝑁𝐴𝑣𝑜 ] 𝐶𝐴 𝐶𝐵 = 𝐴𝐶𝐴 𝐶𝐵
𝜋𝜇𝐴𝐵

A downside of collision theory is that the rigid sphere assumption is an oversimplification of the system. It tends to
overpredict the frequency factor. Moreover, it doesn’t account for the Arrhenius temperature dependence commonly found in
rate equations. Other downsides:

 Does not account for molecular orientation

 Does not account for activation barriers
 Assumes that the molecules all move at the average velocity
The collision theory can be improved by considering the probability of reaction, Pr. This parameter modifies the cross-
sectional area.
2
𝑆𝑟 = 𝑃𝑟 𝜋𝜎𝐴𝐵
Reaction will only occur if the kinetic energy is sufficiently large (i.e. large enough velocity). That is, collisions at a given
temperature only occur if they have an energy of EA or greater. The probability can be considered either strictly 0 or 1 OR as a
sliding scale between 0 and 1.
1.1.1 Binomial Probability
 If E < EA, Pr=0
 If E ≥ EA, Pr=1
 The predicted rate constant is
𝐸𝐴 𝐸𝐴
𝑘= 𝐴 ⋅ exp (− )
𝑅𝑇 𝑅𝑇
1.1.2 Line of Centers
 If E ≤ EA, Sr=0
 If E > EA,
𝐸 − 𝐸𝐴
𝑃𝑟 =
𝐸
2
(𝐸 − 𝐸𝐴 )
𝑆𝑟 = 𝜋𝜎𝐴𝐵
𝐸
 The predicted rate constant is

2
8𝜋𝜅𝐵 𝑇 1/2 𝐸𝐴
𝑘 = 𝜎𝐴𝐵 ( ) 𝑁𝐴𝑣𝑜 exp (− )
𝜇𝐴𝐵 𝑅𝑇
𝐸
−𝑟𝐴 = 𝐴𝑒𝑥𝑝 (− )𝐶 𝐶
𝑅𝑇 𝐴 𝐵

1.1.3 Activation Energy Estimation

The Polanyi equation relates the activation energy to the heat of reaction. It takes either the Morse or Lennard-Jones potentials
for each of the molecules participating in the reaction. Lines are then drawn from the minima of the potentials to the tangent
points of the curve to provide two overlapping lines.
The Polanyi equation is given as

𝐸𝐴 = 𝐸𝐴∗ + 𝛾𝑝 𝛥𝐻𝑟𝑥𝑛

1.2 Transition State Theory

The theory is best for small molecules and is in most cases, more accurate in predicting the reaction rate as compared to
collision theory. The premise of the theory is that an activated complex is formed provided that the required activation barrier
is overcome. This occurs because the reactant molecules momentarily become less stable as they approach each other. This
activated complex is an intermediate which is weakly bonded to the molecule from which it will release its bond and to the
molecule to which it will form the bond; it is assumed to be in equilibrium with its reactants (only valid if the reaction is not
extremely fast) and decomposes to form either products or reactants. For the following reaction,

𝐴+𝐵 →𝐶
𝑘 + 𝐶𝐶+ 𝐾𝐶 𝐶𝐶+ 𝑘 + 𝐾𝐶
𝑘= ; ° = ;𝑘 =
𝐶𝐴 𝐶𝐵 𝐶 𝐶𝐴 𝐶𝐵 𝐶°

Transition state theory uses statistical mechanics to determine the equilibrium constant activitiesCC+. The rate is then

𝑟 = (𝑠𝑒𝑡 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑡𝑖𝑜𝑛 𝑓𝑢𝑛𝑐𝑡𝑖𝑜𝑛𝑠 & 𝑇)𝐶𝐴 𝐶𝐵

2 Catalysis
2.1 Catalysts and Catalyst Selection
Catalysts are used to lower the reaction temperature (activation energy barrier) so that the reaction can proceed under design
specs. and control the reaction pathway. It can also increase the activity and improve the selectivity. They can be changed in
reaction, but are not consumed in reaction.
Homogeneous Catalyst Heterogenous Catalyst
Same phase as reactant Different phase than reactant
Usually liquid Usually solid
Single, Well-defined active site Multiple, ill-defined active sites
High activity and high selectivity Either high activity OR high selectivity, not both
Not easily recyclable Easy recyclable
Have to separate from products and recycled Can remain in reactor
e.g. enzymes, transition metals with ligands (Suzuki reaction), e.g. powders, monoliths, amorphous silica (support for many
acids (esterification using H2SO4) active catalysts), high-area aluminas (can be catalysts or
support metal deposits), zeolites (can have integrated metals),
high SA carbons (support or catalyst, activated carbons,
carbon blacks, nanostructures)

Note that the catalyst only makes the reaction more likely to occur (i.e. kinetics) but it doesn’t change the equilibrium
composition (i.e. thermodynamics). Mass transfer is also important in the process.

𝐴𝑑𝑠𝑜𝑟𝑝𝑡𝑖𝑜𝑛 → 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 → 𝐷𝑒𝑠𝑜𝑟𝑝𝑡𝑖𝑜𝑛

The above outlines the process for heterogenous catalysts. One of the steps is usually limiting.
Adsorption- T dependent process

 Physisorption
o Like condensation
o Small (-) Hads
o VdW forces dominate
 Chemisorption
o Chemically bonded to surface
o Large (-) Hads ~ O(Hrxn)
  Adsorption occurs on active sites, the type of which can determine what type of products will be formed
o Usually adsorbs preferentially on any irrefularities, defects, edge sites (areas where surface free energy is
reduced by adsorbing species)
A measure of catalyst “efficiency” is TOF or turnover frequency. It gives the amount of catalyst needed for a given rate of
production# of mol. reacting/active site/second
Examples: Alkylation & Dealkylation reactions, Isomerization reactions, Hydrogenation & Dehydrogenation reactions,
Oxidation, Hydration & Dehydration, Halogenation & Dehalogenation (catalyst lowers Top and controls selectivity).
Catalyst selection

 Product selectivity
 Stability
 Cost
 Volume
 Overall effective rate of reaction

2.2 Catalytic Reactors

Overarching assumption is that no reaction occurs in the fluid phase and that the reaction occurs at the surface (though
running an empty reactor without the catalyst would confirm if this is actually the case). Another assumption is that there is no
mass transfer limitation.

2.2.1 Packed Bed Reactor

 Fluid flows in void space around the pellets and the
reaction occurs on the pellet surface.
 Can be modeled as a PFTR, but the volume is
differentiated between the reactor, fluid, and catalyst
𝑉𝑅 = 𝑉𝐹 + 𝑉𝐶 = 𝜀𝑉𝑅 + (1 − 𝜀𝑉𝑅 )
For a single reaction system
𝑑𝐶𝑗
𝑢 = 𝑣𝑗 𝑟
𝑑𝑧
For a multiple reaction system
𝑑𝐶𝑗
𝑢 = ∑ 𝑣𝑖𝑗 𝑟𝑖
𝑑𝑧
𝑖

For a given reaction,

𝐶𝐴 𝐶𝐴 𝐶𝐴
𝜀𝑉𝑅 𝜀𝐿 𝑑𝐶𝐴 𝑑𝐶𝐴 𝑑𝐶𝐴
𝜏= = = −∫ = −∫ ′
= − ∫
𝑣 𝑢𝑜 𝐶𝐴0 𝑟𝐴 𝐶𝐴0 𝜌𝑐 𝑟 𝐶𝐴0 𝑆𝑔 𝜌𝑐 (1 − 𝜀)𝑟"

2.2.2 Slurry & Fluidized Bed Reactors

Assumptions

 Fluid and catalyst are stirred/well-mixed

 Stirred reactors are slurry reactors for liquids and solid catalyst or an emulsion reactor
 Fluidized bed reactors have gas flowing through the reactor which levitates the catalyst particles
 Can model as a CSTR
𝑉𝐹 𝜀𝑉𝑅
𝜏= =
𝑣 𝑣
2.2.2.1 Riser Reactors
Essentially a fluidized bed reactor but the velocity is significantly greater such that the particles flow in a streamline with the
fluid (e.g. FCC) and the catalyst is separated externally. Can be modeled as a PFTR.

2.2.3 Reactor Modeling/Calculations

2.2.3.1 Nomenclature
 Rate of reaction per unit volume
o –rA[=]mol/L-sec
 Rate of reaction per unit mass of catalyst
o –rA’[=]mol/g cat.-sec
 Rate of reaction per unit surface area of catalyst
o –rA”[=]mol/m2-sec
𝐴
𝑟 = 𝜌𝑐 𝑟 ′ = 𝑟"
𝑉
The mass balances still require r but we can write surface reactions in terms of r”

𝑟" = k"𝐶𝐴𝑆
where k”[=]L/t. A/V is given as
𝐴 𝑉𝐶
= 𝑆𝑔 𝜌𝑐 = 𝑆𝑔 𝜌𝐶 (1 − 𝜀)
𝑉 𝑉𝑅

2.3 Pore Diffusion

There is usually a mass transfer limitation associated with porous catalysts. This is accounted for by an effectiveness factor.

𝑟=k𝐶𝐴𝑆 𝜂
𝑎𝑐𝑡𝑢𝑎𝑙 𝑟𝑎𝑡𝑒
𝜂=
𝑖𝑑𝑒𝑎𝑙 𝑟𝑎𝑡𝑒
The effectiveness factor depends on the rate coefficient, the catalyst geometry, order of reaction, and the Thiele modulus. As
the Thiele modulus increases, the diffusion limitation increases. As it decreases, the surface reaction limitation increases.
𝑛−1 𝑛
𝑘𝑛 𝑅2 𝐶𝐴𝑆 𝑘𝑛 𝑅𝐶𝐴𝑆
𝜙𝑛2 = =
𝐷𝑒 𝐶 −0
𝐷𝑒 [ 𝐴𝑆𝑅 ]

The effective diffusivity is given as

𝐷𝐴𝐵 𝜙𝑃 𝜎𝐶
𝐷𝑒 =
𝜏̂
𝑎𝑐𝑡𝑢𝑎𝑙 𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 𝑡𝑤𝑜 𝑝𝑜𝑖𝑛𝑡𝑠
𝜏̂ = ~3
𝑠ℎ𝑜𝑟𝑡𝑒𝑠𝑡 𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 𝑡𝑤𝑜 𝑝𝑜𝑖𝑛𝑡𝑠
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑣𝑜𝑖𝑑 𝑠𝑝𝑎𝑐𝑒
𝜙𝑃 = ~ 0.4
𝑡𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒
𝜎𝑐 = 𝑐𝑜𝑛𝑠𝑡𝑟𝑖𝑐𝑡𝑖𝑜𝑛 𝑓𝑎𝑐𝑡𝑜𝑟 (𝑎𝑣𝑒𝑟𝑎𝑔𝑒𝑑 𝑐𝑟𝑜𝑠𝑠 − 𝑠𝑒𝑐𝑡𝑖𝑜𝑛𝑎𝑙 𝑎𝑟𝑒𝑎)~ 0.8
For a spherical pellet,

 0th order

𝜙0 = 𝑅√𝑘0 "𝑆𝑎 𝜌𝑐 /𝐷𝑒 𝐶𝐴𝑜 = 𝑅√𝑘0 /𝐷𝑒 𝐶𝐴0

 1st order

𝜙1 = 𝑅√𝑘1 "𝑆𝑎 𝜌𝑐 /𝐷𝑒 = 𝑅√𝑘1 /𝐷𝑒

  2nd order

𝜙2 = 𝑅√𝑘2 "𝑆𝑎 𝜌𝑐 𝐶𝐴𝑜 /𝐷𝑒 = 𝑅√𝑘2 𝐶𝐴0 /𝐷𝑒

In terms of geometry for a first order reaction,

 sphere
𝑅
𝜙1 = √𝑘1 "𝑆𝑎 𝜌𝑐 /𝐷𝑒 = 𝑅√𝑘1 /𝐷𝑒
3
 cylinder
𝑅 𝑅
𝜙1 = √𝑘1 "𝑆𝑎 𝜌𝑐 /𝐷𝑒 = √𝑘1 /𝐷𝑒
2 2
 slab
𝜙1 = 𝐿√𝑘1 "𝑆𝑎 𝜌𝑐 /𝐷𝑒 = 𝐿√𝑘1 /𝐷𝑒
If the Thiele modulus is large,
1 1
2 2 3 2 2 3 𝐷𝑒 (1−𝑛)/2
𝜂=( ) = ( ) √ 𝐶
𝑛 + 1 𝜙𝑛 𝑛 + 1 𝑅 𝑘𝑛 𝐴𝑠

As the reaction order increase, the effectiveness factor decreases as the surface concentration increases. If the Thiele modulus
<<1, the surface concentration is relatively constant, >>1, decreases significantly along the pore pathway.

2.3.1 Langmuir-Hinselwood Kinetics

Things to consider

 Available reactants
 Available/free active sites
The reaction can only occur if there are active sites on which the reactants can attach. The coverage of the active site/catalyst
surface is
𝑛𝑗 𝑚𝑜𝑙𝑒𝑠 𝑎𝑑𝑠𝑜𝑟𝑏𝑒𝑑 𝑜𝑛 𝑠𝑢𝑟𝑓𝑎𝑐𝑒/𝐴𝑟𝑒𝑎
𝜃𝑗 = =
𝑛𝑗0 𝑚𝑜𝑛𝑜𝑙𝑎𝑦𝑒𝑟 𝑐𝑜𝑣𝑒𝑟𝑎𝑔𝑒

When determining the effective rate laws, it is helpful to do active site balances

𝐶𝑡 = 𝐶𝑣 + 𝐶𝐴𝑆 + 𝐶𝐵𝑆
Again,

𝐴𝑑𝑠𝑜𝑟𝑝𝑡𝑖𝑜𝑛 → 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 → 𝐷𝑒𝑠𝑜𝑟𝑝𝑡𝑖𝑜𝑛

For the catalytic reaction cycle (gas phase reaction)

𝐴 + 𝑆𝐴𝑆 𝑟𝑎𝐴 " = 𝑘𝑎𝐴 𝑃𝐴 𝜃𝑠

𝐴𝑆𝐴 + 𝑆 𝑟𝑑 " = 𝑘𝑑𝐴 𝜃𝐴
𝐴𝑆𝐵𝑆 𝑟𝑅 " = 𝑘𝑅 𝜃𝐴
The mole balances are
𝑑𝜃𝐴
= 𝑘𝑎𝐴 𝑃𝐴 (1 − 𝜃𝐴 − 𝜃𝐵 ) − 𝑘𝑑𝐴 𝜃𝐴 − 𝑘𝑅 𝜃𝐴
𝑑𝑡
𝑑𝜃𝐵
= 𝑘𝑎𝐵 𝑃𝐵 (1 − 𝜃𝐴 − 𝜃𝐵 ) − 𝑘𝑑𝐵 𝜃𝐵 + 𝑘𝑅 𝜃𝐴
𝑑𝑡
If no species accumulate,
 𝑘𝑅 𝐾𝐴′ 𝑃𝐴
𝑟𝑅 " =
1 + 𝐾𝐴′ 𝑃𝐴 + 𝐾𝐵′ 𝑃𝐵
𝑘𝑎𝑗
𝐾𝑗′ =
𝑘𝑑𝑗 + 𝑘𝑗

For the reaction limiting case, the adsorption-desorption steps are comparitively large and ~ 0/
𝐾𝐴 𝑃𝐴
𝜃𝐴 =
1 + 𝐾𝐴 𝑃𝐴 + 𝐾𝐵 𝑃𝐵
Kj is the ratio of the rate constant for adsorption to desorption for species j. In the Langmuir isotherm case, KB or PB may be
zero.
𝐾𝐴 𝑃𝐴 𝐸𝐴
𝜃𝐴 = ; 𝐾𝐴 = 𝐾0𝐴 exp (− )
1 + 𝐾𝐴 𝑃𝐴 𝑅𝑇
𝐾𝐴 𝑃𝐴
𝑟𝑅 = 𝑘𝑅 𝜃𝐴 = 𝑘𝑅 𝑓𝑜𝑟 𝐴 → 𝐵
1 + 𝐾𝐴 𝑃𝐴
The difference between Langmuir-Hinshelwood and Eley-Rideal kinetics is that the former requires all reactant molecules to
firstly adsorb before they react while the latter only requires that one species adsorb before the other reacts with the adsorbed
species. Though not mentioned explicity before, the assumptions used were

 Equilibrium
 Pseudo steady state