Lecture 11

Adsorption (1st step)/Desorption (last step):

(1) Langmuir model (1918)

Assumptions: - Maximum one layer or monolayer
- Uniform surface activity
- No interaction between adsorbing molecules
- Constant activation energy and heat of adsorption, wrt surface
coverage, or ≠ 𝑓(𝜃))
𝑣𝑎𝑐𝑎𝑛𝑡 𝑠𝑖𝑡𝑒𝑠

sp ra = k a p(1 − θ)
rA = (adsorption rate)
(2πm𝐾T)1⁄2 (k a = k ao e−Ea ⁄RT )
s = α(1 − θ)e−Ea ⁄RT rd = k d θ(desorption rate)
0 ≤ θ ≤ V⁄V ≤ 1 ⇒ At equilibrium
m
ra = rd
p = Partial pressure of adsorbate
k a p(1 − θ) = k d (θ)
m = (Mw⁄N) k a ⁄k d p
θ=
𝐾 = Boltzman constant 1+ks ⁄kd p
α = sticking Coefficient
Kp
θ = fractional surface coverage θ=
1+Kp
Ea = activation energy of adsorption
V = present amount,
(𝑘𝑑 = 𝑘𝑑𝑜 𝑒 −𝐸𝑑 ⁄𝑅𝑇 )
Vm = full amount to cover the surface}

The model is good for chemisorption (one layer or monolayer)

𝑇
1.0
Linearized form:
Ө K𝑝
𝑇𝑦𝑝𝑒 − 1 𝑖𝑠𝑜𝑡ℎ𝑒𝑟𝑚 𝜃 = 𝑉⁄𝑉 =
𝑚 1 + K𝑝
𝑝 1 1
= + 𝑝
𝑉 K𝑉𝑚 𝑉𝑚
𝑝

(𝑓𝑢𝑙𝑙𝑦 𝑜𝑐𝑐𝑢𝑝𝑖𝑒𝑑 𝑠𝑢𝑟𝑓𝑎𝑐𝑒:

𝜃 = 1 ⇒ 𝑉 = 𝑉𝑚 )

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 𝑁𝑜 𝑖𝑛𝑡𝑒𝑟𝑎𝑐𝑡𝑖𝑜𝑛𝑠 between adjacent molecules:

𝐸, Δ𝐻 ≠ 𝑓(𝜃)

𝑝 1⁄
⁄𝑉 𝑉𝑚
1⁄
K𝑉𝑚

(2) Brunauer, Emmett and Teller (1938)

BET isotherm

Assumptions - Multilayer adsorption

- Energy of 1st layer ≠ that of 2nd layer; 2nd and the other layers have the
same energy level.
- We do not assume that 1st layer is saturated & then 2nd layer is formed
- Finite probability for sitting of one molecule on the vacant or occupied
sites.
𝑉 𝐶𝑃
Isotherm: 𝜃 = = 𝑝
𝑉𝑚 (𝑝𝑜 −𝑝)[1+(𝑐−1) ]
𝑝𝑜

𝑉 = 𝑉𝑜𝑙𝑢𝑚𝑒 𝑎𝑑𝑠𝑜𝑟𝑏𝑒𝑑; 𝑉𝑚 = 𝑉𝑜𝑙𝑢𝑚𝑒 𝑎𝑑𝑠𝑜𝑟𝑏𝑒𝑑 𝑓𝑜𝑟 𝑜𝑛𝑒 𝑙𝑎𝑦𝑒𝑟

𝐶 = 𝑝𝑎𝑟𝑎𝑚𝑒𝑡𝑒𝑟 𝑜𝑓 𝑚𝑜𝑑𝑒𝑙
(energy of the first layer)
= = 1 if the layers have the same energy.
(energy of the other layers)

If c ≫ 1 (very energetic surface)

T = constant and p ≪ po
𝑇𝑦𝑝𝑒 − C(p⁄po )
𝜃 θ=
1 + (p⁄po )
1𝑠𝑡 Kp
= (identical to Langmuir model)
𝑙𝑎𝑦𝑒𝑟 1 + Kp

𝑝 𝑝𝑜
Linearize: (𝑐𝑜𝑛𝑑𝑒𝑛𝑠𝑎𝑡𝑖𝑜𝑛) (𝐶−1)
𝑝 𝑆= 𝐶𝑉𝑚
𝑝 1 (𝐶−1)𝑝 𝑉(𝑝𝑜 −𝑝)
= +
𝑉(𝑝𝑜 −𝑝) 𝑉𝑚 𝐶 𝐶𝑉𝑚 𝑝 1
=𝐼 𝑝
𝐶𝑉𝑚 𝑝𝑜 2
 Data:

𝑉
𝑝

(3) Temkin Model:

𝑟𝑎 = 𝑘𝑎 𝑝 ∶ 𝑟𝑑 = 𝑘𝑑 𝜃 = (𝑘𝑑𝑜 𝑒 −𝐸𝑑 ⁄𝑅𝑇 )𝜃
{ (𝐸𝑑 = 𝐸𝑑𝑜 − 𝑏𝜃 ; 𝜃 ↑ 𝐸𝑑 ↓)
= 𝐴 exp(𝑏 ′ 𝜃)𝜃

At equilibrium, 𝑘𝑎 𝑝 = 𝐴 exp(𝑏 ′ 𝜃)𝜃

⇒ 𝜃 ∝ ln(𝑝)

Similarly, Δ𝐻(𝐸𝑑 − 𝐸𝑎 ) ∝ 𝑓(𝜃) = −Δ𝐻𝑚 𝑙𝑛𝜃 (1 > 𝜃 > 0)

(Heat of adsorption is dependent on surface coverage)
𝜃 ↑ ΔH ↓

(4) Freundlich (empirical)

𝜃 = 𝑎𝑝𝑎 𝑚
(For multi-component adsorption ⇒ use Toth, Sips isotherms ⇒ see the book by DO
,1998)
Different types of isotherms:

Physical adsorption (Physisorption) Chemical adsorption (Chemisorption)

- No bond formation - Bond formation

- Non-specific - Specific

- Forces between adsorbed & - Forces are strong

adsorbate molecules are weak (Covalent, valence forces)

(Vander Waals forces)

- Heat of adsorption is small -Heat of adsorption is large

3
 (0.5 - 5 kcal/mole) (>10 kcal/mole)

- Activation energy is low - Can be low or high

- T ↑ amount of adsorbed molecules ↓ - T ↑ amount ↓ 𝑜𝑟 ↑

- Coverage is multilayer - monolayer

- Characterizes the surface - Basic component of catalytic effect

Fundamental mechanism of heterogeneous reaction:

Rate equations:- Langmuir – Hinshelwood model/Eley-Rideal model:

(most common)
𝐴+𝐵 ⇌𝐶 +𝐷

(Reaction only in the presence of catalyst; non-elementary reaction)

: 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡 𝑠𝑢𝑟𝑓𝑎𝑐𝑒

𝑋 (𝑠𝑖𝑡𝑒𝑠)
Elementary steps: 𝐴 𝐵 𝐶 𝐷
↓↑ ↓↑ ↓↑ ↓↑
(1) Adsorption
(2) Surface-reaction 𝑋 𝑋 𝑋 𝑋
(3) Desorption
[𝐴𝑋] [𝐵𝑋] [𝐶𝑋] [𝐷𝑋]

L-H model assumes that the step (2) or surface reaction is the slowest or rate-determining step. Other
possibilities also exist. See the book by Froment - Bischoff for details.

𝑘1
𝐴 + 𝑋 ⇌ 𝐴𝑋
𝑘−1
1) 𝑎𝑑𝑠𝑜𝑟𝑝𝑡𝑖𝑜𝑛
𝑘2
𝐵 + 𝑋 ⇌ 𝐵𝑋
𝑘−2 }

𝑘3
𝐴𝑋 + 𝐵𝑋 ⇌ 𝐶𝑋 + 𝐷𝑋 ∶ Surface reaction/re − arrangement
𝑘−3 (slowest; other steps are at
equilibrium; they are fast
𝑘4 enough to reach equilibrium and r = 0)
𝐶𝑋 ⇌ 𝐶 + 𝑋
𝑘−4
𝑑𝑒𝑠𝑜𝑟𝑝𝑡𝑖𝑜𝑛
𝑘5
𝐷𝑋 ⇌ 𝐷 + 𝑋
𝑘−5 }

4
 (Note that there is ‘X’ balance in all steps;
𝑂2 + 2𝑋 ⇌ 2𝑂𝑋
)
𝑜𝑟 , 𝑂2 + 𝑋 ⇌ 𝑂2 𝑋

2) 𝑟 = 𝑘3 (𝐴𝑋)(𝐵𝑋) − 𝑘−3 (𝐶𝑋)(𝐷𝑋) (rate determining step)

(Replace all 𝐴𝑋, 𝐵𝑋, … 𝑒𝑡𝑐 in terms of major species A, B, C, D)

(AX) (BX) (CX) (DX)

3) K1 = (A)(X) ; K 2 = (B)(X) ; K 4 = (C)(X) ; K 5 = (D)(X)

(Note: 𝐾4 , 𝐾5 are defined in reverse manner to be consistent with reactions 1 & 2)

Substitute:

4) 𝑟 = 𝑘−3 [𝐾1 𝐾2 𝐾3 (𝐴)(𝐵) − 𝐾4 𝐾5 (𝐶)(𝐷)]𝑋 2

𝑋 is still unknown:

5) 𝑋 + 𝐴𝑋 + 𝐵𝑋 + 𝐶𝑋 + 𝐷𝑋 = 𝑋𝑜 (𝑝𝑟𝑜𝑝𝑒𝑟𝑡𝑦 𝑜𝑓 𝑎 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡)
(𝑡𝑜𝑡𝑎𝑙)
𝑓𝑟𝑒𝑒 𝑜𝑐𝑐𝑢𝑝𝑖𝑒𝑑

Xo
X=
1+∑i Ki Ci

k−3 Xo 2 [K1 K2 K3 (A)(B)−K4 K5 (C)(D)]

r= (1+∑i Ki Ci )2

Note: denominator term appears as the ‘inhibitor’ of the rate. It appears to decrease the rate.

Physically, 𝐴 & 𝐵 are adsorbed on the sites, occupying some of the sites, and therefore, inhibiting the
reaction. Adsorption is an essential part of the reaction, but at the same time it decreases the rate.

If equilibrium, 𝑟 = 0

(𝐶)(𝐷) 𝐾1 𝐾2
= 𝐾𝑒𝑞 = 𝐾3 𝐾1 … … 𝐾5 are the equilibirum constants of the elementary steps
(𝐴)(𝐵) 𝐾4 𝐾5

does not have physical or fundamental significance

(lumped parameter)

(Note: Any elementary reaction, even if it is not at equilibrium has an equilibrium constant. Therefore,
𝐾3 is well defined even if r in the step 2 is non-zero)

Note “r” can also be written as

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 𝐾𝑓 (𝐴)(𝐵)−𝐾𝑏 (𝐶)(𝐷)
𝑟= (1+∑ 𝐾𝑖 𝐶𝑖 )2

Suppose ∑ 𝐾𝑖 𝐶𝑖 ≪ 1

𝑟 ≈ 𝐾𝑓 (𝐴)(𝐵) − 𝐾𝑏 (𝐶)(𝐷)

It appears as an elementary reaction with K f & K b as the forward & reversible rate constants,
respectively! But K f & K b are lumped parameters. They cannot be written as K f = K fo exp(− E⁄RT), etc.

− These are the features of a catalytic reaction (non-elementary)