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CRE II Heterogeneous Catalysis L8

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

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.

Reactions / processes based on acid catalysis


Name of reaction Description Solid-acid catalyst used Silica-alumina; ZeoliteY ZSM-5 Cracking / Crack large molecules in hydrocrac petroleum oils king FCC additives for more C3 and octane Dewaxing Crak n-paraffins (waxes) in petroleum oils IsodeIsomerization of waxy waxing molecules. Xylene p- and o-xylenes from misomerixylene. sation

ZSM-5 SAPO-11 ZSM-5; Mordenite

Pore Size and Shape


Pore Diameter micropores (< 2 nm) mesopores (2 50 nm) macropores (> 50 nm) Pore Shape cylinder slit ink-bottle wedge

How do molecules bond to surfaces?


Two principle modes of adsorption of molecules to surfaces.

-Physical

Adsorption:

The only bonding is by weak van der waals-type


forces. There is no significant redistribution of electron density in either the molecule or at the substrate surfaces.
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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

Material on which gas adsorbs


Adsorbed gas Pore width 2 nm Pore width 250 nm Pore width 50 nm

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).

Physical Adsorption Vs. Chemisorption


Item Forces of attraction Specificity Quantity Heat Effects Activation energy Effect of Temp. Physical Adsorption Weak VanderWaals forces Low Large Exothermic, 1-15 kCal/mol Low Rapid at low temperatures & reach equilibrium quickly. Beyond TC of the gas, no ads. Increases with increase in pressure Chemisorption Strong valency forces High Small Exothermic, 10-100 kCal/mol High Slow at low temp., Rate increases with temp.

Effect of Pressure

Little effect

Surface Layers

Whole surface active Multi-layer adsorption

Fraction of surface only Mono-layer adsorption


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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

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

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Mechanism of Heterogeneous Catalysis:

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Mechanism of Heterogeneous Catalysis:

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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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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: 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.

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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