The subject of chemical reaction engineering initiated and evolved primarily to accomplish the task of describing how to choose, size, and determine the optimal operating conditions for a reactor whose purpose is to produce a given set of chemicals in a petrochemical application. However, the principles developed for chemical reactors can be applied to most if not all chemically reacting systems (e.g., atmospheric chemistry, metabolic processes in living organisms, etc.). In this text, the principles of chemical reaction engineering are presented in such rigor to make possible a comprehensive understanding of the subject. Mastery of these concepts will allow for generalizations to reacting systems independent of their origin and will furnish strategies for attacking such problems. The two questions that must be answered for a chemically reacting system are: (1) what changes are expected to occur and (2) how fast will they occur? The initial task in approaching the description of a chemically reacting system is to understand the answer to the first question by elucidating the thermodynamics of the process. For example, dinitrogen (N2) and dihydrogen (H2) are reacted over an iron catalyst to produce ammonia (NH3):
where b.H, is the enthalpy of the reaction (normally referred to as the heat of reaction). This reaction proceeds in an industrial ammonia synthesis reactor such that at the reactor exit approximately 50 percent of the dinitrogen is converted to ammonia. At first glance, one might expect to make dramatic improvements on the production of ammonia if, for example, a new catalyst (a substance that increases the rate of reaction without being consumed) could be developed. However, a quick inspection of the thermodynamics of this process reveals that significant enhancements in the production of ammonia are not possible unless the temperature and pressure of the reaction are altered. Thus, the constraints placed on a reacting system by thermodynamics should always be identified first.
In order to obtain a reasonable level of conversion at a commercially acceptable rate, ammonia synthesis reactors operate at pressures of 150 to 300 atm and temperatures of 700 to 750 K. Calculate the equilibrium mole fraction of dinitrogen at 300 atm and 723 K starting from an initial composition of XN2 = 0.25, XHz = 0.75 (Xi is the mole fraction of species i). At 300 atm and 723 K, the equilibrium constant, Ka , is 6.6 X 10- 3. (K. Denbigh, The Principles ofChemical Equilibrium, Cambridge Press, 1971, p. 153).
The next task in describing a chemically reacting system is the identification of the reactions and their arrangement in a network. The kinetic analysis of the network is then necessary for obtaining information on the rates of individual reactions and answering the question of how fast the chemical conversions occur. Each reaction of the network is stoichiometrically simple in the sense that it can be described by the single parameter called the extent ofreaction (see Section 1.2). Here, a stoichiometrically simple reaction will just be called a reaction for short. The expression “simple reaction” should be avoided since a stoichiometrically simple reaction does not occur in a simple manner. In fact, most chemical reactions proceed through complicated sequences of steps involving reactive intermediates that do not appear in the stoichiometries of the reactions. The identification of these intermediates and the sequence of steps are the core problems of the kinetic analysis. If a step of the sequence can be written as it proceeds at the molecular level, it is denoted as an elementary step (or an elementary reaction), and it represents an irreducible molecular event. Here, elementary steps will be called steps for short. The hydrogenation of dibromine is an example of a stoichiometrically simple reaction:
