CATALYTIC REACTIONS

ENZYME CATALYZED REACTIONS Enzymes are proteins of high molecular weight and possess exceptionally high catalytic properties. These are important to plant and animal life processes. An enzyme, E, is a protein or protein-like substance with catalytic properties. A substrate, S, is the substance that is chemically transformed at an accelerated rate because of the action of the enzyme on it. Most enzymes are normally named in terms of the reactions they catalyze. In practice, a suffice -ase is added to the substrate on which the enzyme acts. For example, the enzyme that catalyzes the decomposition of urea is urease, the enzyme that acts on uric acid is uricase, and the enzyme present in the micro-organism that converts glucose to gluconolactone is glucose oxidase. The three major types of enzyme reaction are: Soluble enzymeinsoluble substrate Insoluble enzymesoluble substrate Soluble enzymesoluble substrate The study of enzymes is important because every synthetic and degradation reaction in all living cells is controlled and catalyzed by specific enzymes. Many of these reactions are the soluble enzyme soluble substrate type and are homogeneous in the liquid phase. The simplest type of enzymatic reaction involves only a single reactant or substrate. The substrate forms an unstable complex with the enzyme that decomposes to give the product species or, alternatively, to generate the substrate. Using the Bodenstein steady state approximation for the intermediate enzyme substrate complexes derives reaction rate expressions for enzymatic reactions. A possible mechanism of a closed sequence reaction is:

Enzyme Substrate enzyme-substrate complex where E = enzyme S = substrate ES* = enzyme-substrate complex P = product of the reaction The stoichiometry of the reaction may be represented as:

The net rate of an enzymatic reaction is usually referred to as its velocity, V, represented by:

The concentration of the complex can be obtained from the net rate of disappearance:

Using the steady state approximation,

Or

Substituting Equation 1-99 into Equation 1-96 gives:

From the material balance, the total concentration of the enzyme in the system, CET, is constant and equal to the sum of the concentrations of the free or unbounded enzyme, CE, and the enzymesubstrate complex, CSE*, that is:

For the substrate CS, the total concentration of the substrate in the system, C ST, is equal to the sum of the concentration of the substrate and the enzyme substrate complex CSE*

In laboratory conditions, CST k CET, since CSE* cannot exceed CET. This shows that CST CS. Rearranging Equation 1-101 gives:

Using CST CS in Equation 1-102 and substituting Equation 1-103 into Equation 1-98 gives:

Or

Substituting Equation 1-105 into Equation 1-96 gives

Equation 1-106 predicts that the initial rate will be proportional to the initial enzyme concentration, if the initial substrate concentration is held constant. If the initial enzyme concentration is held constant, then the initial rate will be proportional to the substrate concentration at low substrate concentrations and independent of the substrate concentration at high substrate levels. The maximum reaction rate for a given total enzyme concentration is

Equation 1-106 can be rearranged to

Equation 1-108 can be considered as the Michaelis-Menten equation, where Km is the Michaelis constant and represented as

Equation 1-108 then becomes

Rearranging Equation 1-110 gives

Equation 1-111 is known as the Lineweaver-Burk or reciprocal plot. If the data fit this model, a plot of 1/Vo versus 1/CST will be linear with a slope Km/Vmax and the intercept 1/Vmax. At low substrate concentration, Equation 1-110 becomes

At high substrate concentration,

and Equation 1-110 becomes

Figure 1-5 shows a plot of

Figure 1-5. Lineweaver-Burk plot.

ACID-BASE CATALYSIS: HOMOGENEOUS LIQUID PHASE A catalyst is defined as a substance that influences the rate or the direction of a chemical reaction without being consumed. Homogeneous catalytic processes are where the catalyst is dissolved in a liquid reaction medium. The varieties of chemical species that may act as homogeneous catalysts include anions, cations, neutral species, enzymes, and association complexes. In acid-base catalysis, one step in the reaction mechanism consists of a proton transfer between the catalyst and the substrate. The protonated reactant species or intermediate further reacts with either another species in the solution or by a decomposition process. Table 1-1 shows typical reactions of an acidbase catalysis. An example of an acid-base catalysis in solution is hydrolysis of esters by acids.

Mechanism

AUTOCATALYTIC REACTIONS

There are many reactions in which the products formed often act as catalysts for the reaction. The reaction rate accelerates as the reaction continues, and this process is referred to as autocatalysis. The reaction rate is proportional to a product concentration raised to a positive exponent for an autocatalytic reaction. Examples of this type of reaction are the hydrolysis of several esters. This is because the acids formed by the reaction give rise to hydrogen ions that act as catalysts for subsequent reactions. The fermentation reaction that involves the action of a micro-organism on an organic feedstock is a significant autocatalytic reaction. Normally, when a material reacts, its initial rate of disappearance is high and the rate decreases continuously as the reactant is consumed. However, in autocatalytic reaction, the initial rate is relatively slow since little or no product is formed. The rate then increases to a maximum as the products are formed and then decreases to a low value as the reactants are consumed. Consider the following mechanism for an autocatalytic reaction:

where AB is an intermediate complex. The observed rate of reaction is the rate of formation of species:

Table 1-1 Examples of acid-base catalysis in aqueous solution

Types of catalysis Specific acid Brief title of rearction Inversion of cane sugar Hydrolysis of acetals Hydration Specific base Specific acid and base General acid of unsaturated aldehydes Cleavage diacetone-alcohol Hydrolysis of esters Decomposition of Equation of reaction

General base General acid and base

acetaldehyde hydrate Decomposition of nitramide Halogenation exchange racemization of ketones

The concentration of the reaction intermediate AB may be determined by using the steady state approximation for intermediates,

Therefore,

Substituting Equation 1-121 into Equation 1-119 gives

Therefore, the mechanism results in a rate expression in which species B is responsible for the autocatalytic behavior. GAS-SOLID CATALYTIC REACTIONS Consider a gaseous reactant flowing through a bed of solid catalyst pellets. The physical steps involved are the transfer of the component gases up to the catalyst surface, diffusion of reactants into the interior of the pellet, diffusion of the products back to the exterior surface, and finally the transfer of the products from the exterior surface to the main stream. Interpreting the experimental results requires minimizing the resistance offered by each of these physical processes and focusing on the chemical aspects of the reaction. The chemical procedures involve activated adsorption of reactants with or without dissociation, surface reactions on active sites, and activated desorption of the products. The uncatalyzed reaction also takes place in the main gas stream simultaneously with the surface reaction. In industrial applications of kinetics, an understanding of the mechanisms of chemical reactions is essential. This is helpful in establishing the optimum operating conditions in relation to parameters such as temperature, pressure, feed composition, space velocity, and the extent of recycling and conversion. Yang and Hougen [7] have established procedures in planning and correlating experimental data for gaseous reactions catalyzed by solids. They provided methods for eliminating, minimizing, or

evaluating the temperatures and concentration gradients in gas films and catalyst pellets. Hougen and Watson [8] have developed rate equations for various mechanisms that may occur in gaseous reactions when catalyzed by solid surfaces. The following illustrates a gas-solid catalytic reaction:

Adsorption Step:

Surface Reaction:

Desorption Step:

The rate equations are:

Assume: 1. (+rx2)net and (+rx3)net are zero 2. Number of active sites remains constant, CT. Thus,

Usually, one of the elementary steps is rate controlling (that is, it is very slow relative to all the other steps). Suppose that A + x1 x2 is the rate-controlling step and the reverse reaction is ignored, then

Under these conditions, the desorption process and surface reactions are in a pseudo-equilibrium state:

And

Rearranging Equations 1-132 and 1-133 in terms of Cx2 and Cx3 and substituting them in Equation 1-134 gives

Therefore,

Where

Substituting Equation 1-136 into Equation 1-131 to eliminate Cx1 , yields

Or

If the reverse step in adsorption is not ignored, then