Accelerating Change Catalysts

P- Speeding up chemical reactions with catalysis Producing materials from plastics to medicines faster and cheaper Using transition metal complexes as catalysts 

A catalyst helps change the speed of a chemical reaction. A catalyst can be either a positive catalyst that speeds up a reaction or a negative catalyst, commonly referred to as an inhibitor, which slows down a reaction. Positive 

A potential energy diagram showing how a catalyst works by giving alternative energy pathways in a reaction. 

Although there are a few different reaction schemes, most catalysts work in a cycle where they regenerate themselves. For example, assume you have a relatively slow reaction that forms a product (Z) from two reactants (X and Y)  

If you add catalyst (C), a possible reaction scheme could look like  

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Sulphuric acid catalysed nitration in concentrated nitric acid, but the effect was much weaker than that observed in nitration in organic solvents ( 3.2.3). The concentration of sulphuric acid required to double the rate of nitration of i-nitroanthraquinone was about 0-23 mol 1, whereas typically, a concentration of io mol 1 will effect the same change in nitration in mixtures of nitric acid and organic solvents. The acceleration in the rate was not linear in the concentration of catalyst, for the sensitivity to catalysis was small with low concentrations of sulphuric acid, but increased with the progressive addition of more catalyst and eventually approached a linear acceleration. 

FIGURE 14.1 Reaction profile showing large AG for glucose oxidation, free energy change of —2,870 kj/mol catalysts lower AG, thereby accelerating rate. 

Schneider and Busch have showed that tetraazafS 1 8 l paracyclophane catalyzes the nitration of alkyl bromides with sodiiun nitrite In dioxane-water d l at 30 C, the reaction of 2-bromomethylnaphthalene with sodiiun nitrite is accelerated by a factor of 20 in the presence of the catalyst Concomitantly, the product ratio of [R-ONO [RNO-, changes from 0 50 1 to 016 1 Thus, an acciuruiladon of nitrite ions at the positively charged cyclophanes or IRA-900-nitrite form provides a new method for selective nitration of alkyl halides... 

Ostwald first came to catalysis through his work on the acceleration of homogeneous reactions by acids. This work was popular at the time although ultimately it would be shown to be incorrect because he believed that the acid, acting as a catalyst, did not enter into the chemical change which it influenced but rather acted by its mere presence (contact catalysis). 

The second major discovery regarding the use of MTO as an epoxidation catalyst came in 1996, when Sharpless and coworkers reported on the use of substoichio-metric amounts of pyridine as a co-catalyst in the system [103]. A change of solvent from tert-butanol to dichloromethane and the introduction of 12 mol% of pyridine even allowed the synthesis of very sensitive epoxides with aqueous hydrogen peroxide as the terminal oxidant. A significant rate acceleration was also observed for the epoxidation reaction performed in the presence of pyridine. This discovery was the first example of an efficient MTO-based system for epoxidation under neutral to basic conditions. Under these conditions the detrimental acid-induced decomposition of the epoxide is effectively avoided. With this novel system, a variety of... 

Catalyst Basically a phenomenon in which a relatively small amount of substance augments the rate of a chemical reaction without itself being consumed recovered unaltered in form and amount at the end of the reaction. It generally accelerates the chemical change. The materials ordinarily used to aid the polymerization of most plastics are not catalysts in the strict sense of the word (they are consumed), but common usage during the past century has applied this name tathem. 

To see how the catalyst accelerates the reaction, we need to look at the potential energy diagram in Fig. 1.2, which compares the non-catalytic and the catalytic reaction. For the non-catalytic reaction, the figure is simply the familiar way to visualize the Arrhenius equation the reaction proceeds when A and B collide with sufficient energy to overcome the activation barrier in Fig. 1.2. The change in Gibbs free energy between the reactants, A -r B, and the product P is AG. 

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