Chemical industry, importance reactions rates

We deal with many reactions that are not elementary. Most industrially important reactions go through a complex kinetic mechanism before the final products are reached. The mechanism may give a rate expression far different than Equation (1.14), even though it involves only short-lived intermediates that never appear in conventional chemical analyses. Elementary reactions are generally limited to the following types. 

The tasks of chemical engineers are the design and operation of chemical reactors for converting specific feed material or reactants into marketable products. They must have knowledge of the rates of chemical reactions involved, the nature of the physical processes interacting with the chemical reactions, and conditions which affect the process. The rates of the physical processes (mass and heat transfer) involved in commonly used chemical reactors can often be estimated adequately from the properties of the reactants, the flow characteristics, and the configuration of the reaction vessel. Chemical process rate data for most industrially important reactions cannot, however, be estimated reliably from theory and must be determined experimentally. 

Friedrich Wilhelm Ostwald, 1853-1932, was bom in Riga, Latvia, in a German family. He was professor of chemistry in Riga and at the University of Leipzig. Ostwald was primarily responsible for the founding of the Zeitschrift fur physikalische Chemie (1887), the first journal in the field of physical chemistry. His process jfor the conversion of ammonia to nitric acid became of great industrial importance. Ostwald won the Nobel Prize for chemistry in 1909 for his work on catalysis, chemical equilibria, and reaction rates. 

Generalized charts are appHcable to a wide range of industrially important chemicals. Properties for which charts are available include all thermodynamic properties, eg, enthalpy, entropy, Gibbs energy and PVT data, compressibiUty factors, Hquid densities, fugacity coefficients, surface tensions, diffusivities, transport properties, and rate constants for chemical reactions. Charts and tables of compressibiHty factors vs reduced pressure and reduced temperature have been produced. Data is available in both tabular and graphical form (61—72). 

Chapter 10 begins a more detailed treatment of heterogeneous reactors. This chapter continues the use of pseudohomogeneous models for steady-state, packed-bed reactors, but derives expressions for the reaction rate that reflect the underlying kinetics of surface-catalyzed reactions. The kinetic models are site-competition models that apply to a variety of catalytic systems, including the enzymatic reactions treated in Chapter 12. Here in Chapter 10, the example system is a solid-catalyzed gas reaction that is typical of the traditional chemical industry. A few important examples are listed here ... 

As an indispensable source of fertilizer, the Haber process is one of the most important reactions in industrial chemistry. Nevertheless, even under optimal conditions the yield of the ammonia synthesis in industrial reactors is only about 13%. This Is because the Haber process does not go to completion the net rate of producing ammonia reaches zero when substantial amounts of N2 and H2 are still present. At balance, the concentrations no longer change even though some of each starting material is still present. This balance point represents dynamic chemical equilibrium. 

Multiphase catalytic reactions, such as catalytic hydrogenations and oxidations are important in academic research laboratories and chemical and pharmaceutical industries alike. The reaction times are often long because of poor mixing and interactions between the different phases. The use of gaseous reagents itself may cause various additional problems (see above). As mentioned previously, continuous-flow microreactors ensure higher reaction rates due to an increased surface-to-volume ratio and allow for the careful control of temperature and residence time. 

The mechanisms considered above are all composed of steps in which chemical transformation occurs. In many important industrial reactions, chemical rate processes and physical rate processes occur simultaneously. The most important physical rate processes are concerned with heat and mass transfer. The effects of these processes are discussed in detail elsewhere within this book. However, the occurrence of a diffusion process in a reaction mechanism will be mentioned briefly because it can lead to kinetic complexities, particularly when a two-phase system is involved. Consider a reaction scheme in which a reactant A migrates through a non-reacting fluid to reach the interface between two phases. At the interface, where the concentration of A is Caj, species A is consumed in a first-order chemical rate process. In effect, consecutive rate processes are occurring. If a steady state is achieved, then... 

The man-made catalysts, mostly solids, usually aim to cause the high-temperature rupture or synthesis of materials. These reactions play an important role in many industrial processes, such as the production of methanol, sulfuric acid, ammonia, and various petrochemicals, polymers, paints, and plastics. It is estimated that well over 50% of all the chemical products produced today are made with the use of catalysts. These materials, their reaction rates, and the reactors that use them are the concern of this chapter and Chapters 19-22. 

The Diels-Alder reaction is an important and widely used reaction in organic synthesis (Sauer and Sustmann, 1980), and in the chemical industry (Griffiths and Previdoli, 1993). Rate enhancement of this reaction has been achieved by the use of solvents such as water, surfactants, very high pressure, lithium amides, alkylammonium nitrate salts, and macrocyclic hosts (Sherman et ak, 1998). Diels-Alder reactions can be ran in neutral ionic liquids (such as 1-butyl-3-methylimidazolium trifluoromethanesulfo-nate, l-butyl-3-methylimidazolium hexafluorophophate, l-butyl-3-methylimidazolium tetrafluoroborate, and l-butyl-3-methylimidazolium lactate). Rate enhancements and selectivities are similar to those of reactions performed in lithium perchlorate-diethyl ether mixtures. 

Many industrially important chemical processes are high pressure processes. Examples are the production of ammonia and the production of low density polyethylene. Basically, the pressure affects both the equilibrium yield of a chemical reaction and the reaction rate. Here, only the influence on the equilibrium yield is discussed. 

Initially, we will be concerned with the physical properties of alkanes and how these properties can be correlated by the important concept of homology. This will be followed by a brief survey of the occurrence and uses of hydrocarbons, with special reference to the petroleum industry. Chemical reactions of alkanes then will be discussed, with special emphasis on combustion and substitution reactions. These reactions are employed to illustrate how we can predict and use energy changes — particularly AH, the heat evolved or absorbed by a reacting system, which often can be estimated from bond energies. Then we consider some of the problems involved in predicting reaction rates in the context of a specific reaction, the chlorination of methane. The example is complex, but it has the virtue that we are able to break the overall reaction into quite simple steps. 

Chemical kinetics is a subject of crucial environmental and economic importance. In the upper atmosphere, for example, maintenance or depletion of the ozone layer, which protects us from the sun s harmful ultraviolet radiation, depends on the relative rates of reactions that produce and destroy O3 molecules. In the chemical industry, the profitability of the process for the synthesis of ammonia, which is used as a fertilizer, depends on the rate at which gaseous N2 and H2 can be converted to NH3. 

Most chemical reactions give off heat and are classified as exothermic reactions. The rate of a reaction may be calculated by the Arrhenius equation, which contains absolute temperature, K, equal to the Celsius temperature plus 273, in an exponential term. As a general rule, the speed of a reaction doubles for each 10°C increase in temperature. Reaction rates are important in fires or explosions involving hazardous chemicals. A remarkable aspect of biochemical reactions is that they occur rapidly at very mild conditions, typically at body temperature in humans (see Chapter 3). For example, industrial fixation of atmospheric elemental nitrogen to produce chemically bound nitrogen in ammonia requires very high temperatures and pressures, whereas Rhizobium bacteria accomplish the same thing under ambient conditions. 

Heterogeneous catalytic reactions, by their nature, involve a separate phase of catalyst, embedded in a phase of reacting species Therefore, the chemical transformation relies on a number of physical transport processes which may have a strong influence on the rate of the overall process and which may introduce an additional dependence on the operating conditions In the industrially important situation that the catalyst is a porous solid and the reactants form either a gaseous or a liquid phase, the following seven steps can be observed (Fig 1)... 

---