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CRE II Heterogeneous Catalysis L3

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

The fundamental equations of thermodynamics

Study of the rates of chemical reactions and the factors that influence the rates.
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Three key aspects of catalyst action


taking part in the reaction it will change itself during the process by interacting with other reactant/product molecules. altering the rates of reactions in most cases the rates of reactions are increased by the action of catalysts; however, in some situations the rates of undesired reactions are selectively suppressed.
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Returning to its original form


After reaction cycles a catalyst with exactly the same nature is reborn.

In practice a catalyst has its lifespan


it deactivates gradually during use. A catalyst accelerates a chemical reaction without affecting the position of the equilibrium. Ostwald recognized catalysis as a ubiquitous phenomenon that was to be explained in terms

of the laws of physical chemistry.


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Schematic representation of the energetic in a catalytic cycle. The uncatalyzed reaction(a)has a higher Gibbs energy of activation G than any step in the catalyzed reaction (b). The gibbs energy of reaction rG for the overall reaction is unchanged from (a) to (b).
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Potential energy diagram of a heterogeneous catalytic reaction

Action of Catalysts
The reaction activation energy is altered The intermediates formed are different from those formed in non-catalytic reaction

The rates of reactions are altered (both


desired and undesired ones)

-Reactions proceed under less demanding conditions


Allow reactions occur under a milder conditions, e.g. at lower temperatures for those heat sensitive materials

It is important to remember that the use of catalyst DOES NOT vary DG & Keq values of the reaction concerned, it merely change the PACE of the process.

Mode of Action of Catalysts


The suitability of a catalyst for an industrial process depends mainly on the following three properties: Activity Selectivity Stability (deactivation behavior) The question which of these functions is the most important is generally difficult to answer because the demands made on the catalyst are different for each process.
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Catalysts are investigated in continuously operated test reactors, in which the conversions attained at constant space velocity/space time are compared . Space Velocity: is the volume flow rate V0, relative to the catalyst mass mcat : (V0/mcat) (made under constant conditions of starting material ratio, temperature, and pressure).
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Space time (mcat/V0)

Comparison of catalyst activities


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Activity
Activity is a measure of how fast one or more reactions proceed in the presence of the catalyst. Activity can be defined in terms of kinetics. In kinetic treatment, it is appropriate to measure reaction rates in the temperature and concentration

ranges present in the reactor.

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Chemical Kinetics
Collision Theory Collisions between reacting molecules are necessary before a reaction can occur.

Only those collisions having sufficient energy


are effective in bringing about a reaction activation energy. Colliding molecules must be properly oriented with respect to one another for the reaction to take place.
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Steps of Catalytic Reactions

Every catalytic reaction is a sequence of elementary steps, in which reactant molecules bind to the catalyst, where they react, after which the product detaches from the catalyst, liberating the latter for the next cycle.
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