Reaction series reactions

As with parallel reactions, series reactions might not only lead to a loss of materials and useful products, but might also lead to byproducts being deposited on, or poisoning catalysts (see Chapters 6 and 7). 

A reaction or set of reactions that consists of several elementary reactions. See also Elementary Reaction Primitive Change Parallel Reactions Series Reactions... 

F,F ATPase COMPLEX REACTION ELEMENTARY REACTION PRIMITIVE CHANGE PARALLEL REACTIONS SERIES REACTIONS OOMPONENT... 

The stoichiometric chemical equation. Reactions may be divided in this manner into five major types simple reactions, parallel reactions, series reactions, complex series reactions, and reversible reactions. 

Series Reactions. Series reactions are those in which the product of the reaction goes on to react further. The simplest example is... 

The problem of reactions that do not go to completion is a frequently occurring one. We have shown here only the mechanics of deahng with a reversible system in which the reaction in each direction is first-order. Other cases that might arise are reversible second-order reactions, series reactions in which only one step is reversible, etc. These cases are quite complicated mathematically, and their treatment is beyond the scope of this book. However, many such systems have been elegantly described (see, for example, Schmid and Sapunov, 1982). The interested reader is directed to these worked-out exercises in applied mathematics for more details. 

The multiple reaction algorithm can be applied to parallel reactions, series reactions, complex reactions, and independent reactions. The availability of software packages (ODE solvers) makes it much easier to solve problems using moles or molar flow rates Fj rather than conversion. For liquid systems, concentration is usually the preferred variable used in the mole balance equations. 

An example of a series reaction system is the production of formaldehyde from methanol ... 

Mixed parallel and series reactions producing byproducts. In more complex reaction systems, both parallel and series reactions can occur together. Mixed parallel and series reactions are of the type... 

An example of mixed parallel and series reactions is the production of ethanolamines by reaction between ethylene oxide and ammonia ... 

Here the ethylene oxide undergoes parallel reactions, whereas the monoethanolamine undergoes a series reaction to diethanolamine and triethanolamine. 

Multiple reactions in series producing byproducts. Consider the system of series reactions from Eq. (2.7) ... 

Selectivity for series reactions of the types given in Eqs. (2.7) to (2.9) is increased by low concentrations of reactants involved in the secondary reactions. In the preceding example, this means reactor operation with a low concentration of PRODUCT—in other words, with low conversion. For series reactions, a significant reduction in selectivity is likely as the conversion increases. 

But what is the correct choice a byproduct reaction calls for a continuous well-mixed reactor. On the other hand, the byproduct series reaction calls for a plug-flow reactor. It would seem that, given this situation, some level of mixing between a plug-flow and a continuous well-mixed reactor will give the best... 

Figure 2.3 Choice of reactor type for mixed parallel and series reactions when the parallel reaction has a higher order than the primary reaction.

Multiple reactions in series producing byproducts. For the series reaction system in Eq. (2.18), the series reaction is inhibited by low concentrations of PRODUCT. It has been noted already that this can be achieved by operating with a low conversion. 

If the reaction involves more than one feed, it is not necessary to operate with the same low conversion on all the feeds. Using an excess of one of the feeds enables operation with a relatively high conversion of other feed material, and still inhibits series reactions. Consider again the series reaction system from Example 2.3 ... 

An example of where recycling can be effective in improving selectivity is in the production of benzene from toluene. The series reaction is reversible. Hence recycling diphenyl to the reactor can be used to suppress its formation at the source. 

Mixed parallel and series reactions producing byproducts. As with parallel and series reactions, use of an excess of one of the feeds can be effective in improving selectivity with mixed reactions. As an... 

Solution We wish to avoid as much as possible the production of di- and triethanolamine, which are formed by series reactions with respect to monoethanolamine. In a continuous well-mixed reactor, part of the monoethanolamine formed in the primary reaction could stay for extended periods, thus increasing its chances of being converted to di- and triethanolamine. The ideal batch or plug-flow arrangement is preferred, to carefully control the residence time in the reactor. 

Series reactions occur in which the tert-butyl hydrogen sulfate reacts to unwanted tert-butyl alcohol ... 

Other series reactions form unwanted polymeric material. 

In fact, it is often possible with stirred-tank reactors to come close to the idealized well-stirred model in practice, providing the fluid phase is not too viscous. Such reactors should be avoided for some types of parallel reaction systems (see Fig. 2.2) and for all systems in which byproduct formation is via series reactions. 

The next example shows how different search queries can be combined to shed more light onto a series of related reactions. A reaction substructure search for reactions that break a P-O bond provided 304 reactions as hits. Figure 10.3-27 shows one of the reactions in this hit list. 

The reaction parameter p depends upon the reaction series but not upon the substituents employed. Values of the reaction parameter for some aromatic and aliphatic systems are given in Tables 9.2 and 9.3. 

Intraparticle mass transport resistance can lead to disguises in selectivity. If a series reaction A — B — C takes place in a porous catalyst particle with a small effectiveness factor, the observed conversion to the intermediate B is less than what would be observed in the absence of a significant mass transport influence. This happens because as the resistance to transport of B in the pores increases, B is more likely to be converted to C rather than to be transported from the catalyst interior to the external surface. This result has important consequences in processes such as selective oxidations, in which the desired product is an intermediate and not the total oxidation product CO2. 

In the benzazole series, reactions of the type discussed for monocyclic derivatives in Section 4.02.3.1.9 are generalized by Scheme 45 and examples are given in Table 9. 

Reactions (7.2), (7.3) and (7.4) form a series of chain reactions, with reaction (7.3) the rate-determining stage. The chain reaction terminates by the reactions... 

Neither the principles of thermodynamics nor theories of reaction rates require that there should be such linear relationships. There are, in fact, numerous reaction series that fail to show such correlations. Some insight into the origin of die correlation can be gained by considering the relationship between the correlation equation and the free-energy changes involved in the two processes. The line in Fig 4.2 defines an equation in which m is the slope of the line ... 

Since AG and AG are combinations of enthalpy and entropy terms, a linear free-energy relationship between two reaction series can result from one of three circumstances (1) AH is constant and the AS terms are proportional for the series, (2) AS is constant and the AH terms are proportional, or (3) AH and AS are linearly related. Dissection of the free-energy changes into enthalpy and entropy components has often shown the third case to be true. °... 

The numerical values of the terms a and p are defined by specifying the ionization of benzoic acids as the standard reaction to which the reaction constant p = 1 is assigned. The substituent constant, a, can then be determined for a series of substituent groups by measurement of the acid dissociation constant of the substituted benzoic acids. The a values so defined are used in the correlation of other reaction series, and the p values of the reactions are thus determined. The relationship between Eqs. (4.12) and (4.14) is evident when the Hammett equation is expressed in terms of fiee energy. For the standard reaction, o%K/Kq = ap. Thus,... 

One underlying physical basis for the failure of Hammett reaction series is that substituent interactions are some mixture of resonance, field, and inductive effects. When direct resonance interaction is possible, the extent of the resonance increases, and the substituent constants appropriate to the normal mix of resonance and field effects then fail. There have been many attempts to develop sets of a values that take into account extra resonance interactions. 

In this equation, the substituent parameters and reflect the incremental resonance interaction with electron-demanding and electron-releasing reaction centers, respectively. The variables and r are established for a reaction series by regression analysis and are measures of the extent of the extra resonance contribution. The larger the value of r, the greater is the extra resonance contribution. Because both donor and acceptor capacity will not contribute in a single reaction process, either or r would be expected to be zero. 

In general, the dissection of substituertt effects need not be limited to resonance and polar components, vdiich are of special prominence in reactions of aromatic compounds.. ny type of substituent interaction with a reaction center could be characterized by a substituent constant characteristic of the particular type of interaction and a reaction parameter indicating the sensitivity of the reaction series to that particular type of interactioa For example, it has been suggested that electronegativity and polarizability can be treated as substituent effects separate from polar and resonance effects. This gives rise to the equation... 

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