CRE II Heterogeneous Catalysis L9

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

Physical Adsorption Vs. Chemisorption

Item Forces of attraction Specificity Quantity Heat Effects Physical Adsorption Weak VanderWaals forces Low Large Exothermic, 1-15 kCal/mol Chemisorption Strong valency forces High Small Exothermic, 10-100 kCal/mol

Activation energy
Effect of Temp.

Low
Rapid at low temperatures & reach equilibrium quickly. Beyond TC of the gas, no ads. Increases with increase in pressure Whole surface active Multi-layer adsorption

High
Slow at low temp., Rate increases with temp. Little effect Fraction of surface only Mono-layer adsorption
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Effect of Pressure Surface Layers

Chemisorption: There is some sort of interaction between the surface of the catalyst and the reactant molecules which makes them more reactive. This might involve an actual reaction with the surface, or some weakening of the bonds in the attached molecules.

Chemisorption: A chemical bond involving substantial rearrangement of electron density, is formed between the adsorbate and substrate. The Nature of this bond may lie anywhere between the extremes of virtually complete ionic or complete covalent character.
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Chemisorption
Metal Dispersion

Supported Metal Particles

Mechanism of Heterogeneous Catalysis: 1. Bulk Diffusion of reacting molecules to the surface of the catalyst 2. Pore Diffusion of reacting molecules into the interior pores of the catalyst 3. Adsorption of reactants (chemisorption) on the surface of the catalyst 4. Reaction on the surface of the catalyst between adsorbed molecules 5. Desorption of products 6. Pore Diffusion of product molecules to the surface of the catalyst 7. Bulk Diffusion of product molecules

Mechanism of Heterogeneous Catalysis:

Mechanism of Heterogeneous Catalysis:

Pore and film resistances in a catalyst particle

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Rate-Determining Step (rds) In a kinetics scheme involving more than one step, it may be that one change occurs much faster or much slower than the others (as determined by relative magnitudes of rate constants). In such a case, the overall rate, may be determined almost entirely by the slowest step, called the ratedetermining step (rds). The rate of the rds is infinitesimal when compared to the rates of other steps. Alternately the rates of other steps are infinite compared to the rate of rds.

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Chemisorption: Chemisorption controlled reactions are usually fast Rate increases rapidly with increase in temp. Permits the use of wide reactors Surface reaction: 70% of the reactions which are not controlled by diffusion falls under this case Rate increases rapidly with increase in temp. Permits the use of wide reactors
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Desorption: Desorption of a product could also be rate controlling in a few cases Complexities: Theoretically more than one step can be rate controlling Too many possible mechanisms Experimental data is normally fitted to any single rate controlling step, which is then called the most plausible mechanism
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Bonding strength between H2 & metal surface increases with increase in vacant d orbital.

Maximum catalytic activity will not be realized

if the bonding is too strong and the products

are not easily desorbed from the surface.

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Adsorption at gas/solid interface.

Adsorption: Term used to describe the process Whereby a molecule(the adsorbate) forms a Bond to a solid surface(an adsorbent). Fractional surface coverage Ns number of sites occupied by adsorbate = N total number of adsorption sites When =1,NS=N and an adsorbed monolayer is formed.The fractional coverage depends on pressure of adsorbing gas phase species. This =(P) relationship is called an adsorption isotherm.
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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 ..

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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

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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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