CRE II Heterogeneous Catalysis

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Prof. K.K.Pant Department of Chemical Engineering IIT Delhi. kkpant@chemical.iitd.ac.in

Langmuir Adsorption Isotherm

Simple approach to quantitatively describe an adsorption process at the gas/solid interface

N = N +N number of vacant sites V S

Assumptions:

Solids surface is homogeneous and contain a number of equivalent sites,each of which is occupied by a single adsorbate molecule.
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 A dynamic equilibrium exist between gas phase reactant and adsorbed species. No interactions between adsorbed species. Adsorbed species localised,Hads is independent of coverage ..

Chemisorption rates:

Adsorption data is reported in the form of isotherms

Chemisorption may be considered as a reaction between a reactant molecule and an active site resulting in an adsorbed molecule A + A (or) A + S AS Turnover Frequency (N): defined as the number of molecules reacting per active site per second at the conditions of the experiment a measure for the activity of the catalyst
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Langmuir Isotherm - Assumptions:

Surface is uniformly active

All sites are identical

Amounts of adsorbed molecules will not interfere with further adsorption

Uniform layer of adsorption Site balance:
No. of vacant sites v v Fraction of vacant sites total sites t No. of occupied sites A A Fraction of sites occupied by A total sites t v A 1

Alternately:
Ct Molar conc. of activesites Cv Molar conc. of vacant sites C AS Molar conc. of sites by A
Cv C AS Ct

No. of active sites / unit mass Avogadro' s number No. of vacant sites / unit mass Avogadro' s number No. of sites by A / unit mass Avogadro' s number

Though other isotherms account for non-uniform surfaces, they have primarily been developed for single adsorbing components. Thus, the extensions to interactions in multi-component systems is not yet possible, as with the Langmuir isotherm. Langmuir isotherms are only used for developing kinetic rate expressions.
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Effect of increasing reactant concentration:

Increasing the reactant concentration increases both the driving force and adsorption inhibition terms.

rate

CA

Volcano shape results from a competition between kinetic driving force and adsorption inhibition terms.
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Remarks:
For a given mechanism, the driving force is unique, irrespective of RDS.
The product of equilibrium constant of all steps in the mechanism yield the overall eq. constant In the kinetic term, the rate constant of RDS will appear. If adsorption of A is not RDS, then KApA will appear in the adsorption term. If desorption of B is not rate limiting, then pB/KD will appear in the adsorption term.

If SR is RDS, then the adsorption term will be raised to the power equal to the number of sites involved in the SR step.
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Simplified rate laws: Over limited pressure range, the Langmuir isotherm = Kp/(1+Kp) can be replaced by an approximation = kpn

In such cases the rate law assumes the form:

r = k pAm pBn pCo Such rate laws may be reasonably accurate Example: CO + Cl2 COCl2 (Over charcoal)
rCOCl2 kKCO K Cl 2 pCO pCl 2 (1 K Cl 2 pCl 2 K COCl 2 pCOCl 2 ) 2

L-H approach

1/ 2 rCOCl2 kpCO pCl 2

Simplified equation
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