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ACID CATALYSIS
SOLID ACID CATALYSTS Examples: Zeolites SAPOs Clays; pillared clays Ion-exchange resins Oxides; X, SO4-oxides Mixed oxides; amorphous Heteropoly acids Two types of acid sites are recognized - Brnsted - Lewis
Most active Metals: Co, Ni, Rh, Ru, Pd, Ir, Pt, Approximately one vacant d orbital per atom. Whereas, V, Cr, Mo, W etc. each metal has a large number of vacant d orbital and are less active as a result of strong adsorption for the reactants or products or both.
However oxides of Mo (MoO2) and Cr (Cr2O3) are quite active for most rexns involving H2.
-Physical
Adsorption:
Terminology
Substrate- Frequently used to describe the solid surface onto which adsorption can occur; the substrate is also occasionally (although not here) referred to as the adsorbent. Adsorbate- The general term for the atomic or Molecular species which are adsorbed (or are capable of being adsorbed) onto the substrate. Adsorption- The process in which a molecule becomes adsorbed onto a surface of another Phase. (different from Absorption which is used when describing uptake into the bulk of a solid 7 or liquid phase )
Adsorptive
Gas to be adsorbed
Adsorbent
Adsorbate Micropore Mesopore Macropore
Coverage- A measure of the extent of adsorption of a species onto a surface. Exposure- A measure of the amount of gas which as surface has seen; more specifically it is the product of the pressure and time of
exposure.
(normal unit is the langmuir ,where 1 L=10-6 Torr *s).
Effect of Pressure
Little effect
Surface Layers
Physical Adsorption
Texture and morphology specific surface area of catalyst pore size pore shape pore-size distribution (same size or various sizes?) pore volume
Chemisorption
Surface Characterization Specific surface area of phases Types of active sites Number of active sites Reactivity of active sites Stability of active sites
Chemisorption
Metal Dispersion
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
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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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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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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: 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.
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Bonding strength between H2 & metal surface increases with increase in vacant d orbital.
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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:
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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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