Single-phase Reaction Systems

The behaviour of the hydrodynamic mode of single-phase reaction systems in tubular turbulent devices will help to select the optimal conditions for fast liquid-phase 

A two-phase mixture flow in the turbulent mode leads to the deformation of the interphase boundary surface, which should change the hydrodynamic mode and 

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Significantly, these reactions were not homogeneous single-phase reaction systems as neither reactant was soluble in the aqueous alkaline reaction medium. The workers postulated that selective absorption of microwaves by polar molecules and intermediates in a multi-phase system could substitute as a phase transfer catalyst without using any phase transfer reagent, thereby providing the observed acceleration similar to ultrasound irradiation [92],... 

The hydrodynamic mode of a liquid-gas reaction system is influenced by the position of a tubular turbulent diffuser-confusor device in space. In the case of a single-phase reaction system, the device position in space does not influence the rate of longitndinal mixing (Figure 2.53). Therefore, industrial turbulent diffnser-confnsor devices for fast chemical reactions in a single-phase reaction mixtnre can be positioned vertically, horizontally, and even in the inclined position. 

Consider a single-phase closed system in which there are no chemical reactions. Under these restric tious the composition is fixed. If such a system undergoes a differential, reversible process, then by Eq. (4-1)... 

This chapter is restricted to homogeneous, single-phase reactions, but the restriction can sometimes be relaxed. The formation of a second phase as a consequence of an irreversible reaction will not affect the kinetics, except for a possible density change. If the second phase is solid or liquid, the density change will be moderate. If the new phase is a gas, its formation can have a major effect. Specialized models are needed. Two-phase ffows of air-water and steam-water have been extensively studied, but few data are available for chemically reactive systems. 

In general, a multitude of different phenomena of flow, heat and mass transfer occur during a liquid/liquid or gas/liquid reaction. Rather than discussing all relevant effects, which would be a tremendous task, the focus of this section is solely on flow phenomena in either single-phase aqueous systems or air/water systems. 

Higher selectivity, easier processing, use of inexpensive solvents, use of cheaper chemicals, and ease of heat removal have been realized through phase-transfer catalysis (PTC). It appears that no catalytic method has made such an impact as PTC on the manufacture of fine chemicals (Sharma, 1996). Many times we benefit by deliberately converting a single-phase reaction to a two-phase reaction. Consider catalysis by. sodium methoxide in a dry organic. solvent. This can invariably be made cheaper and safer by using a two-pha.se. system with a PT catalyst. 

Steefel, C. I. and A.C. Lasaga, 1994, A coupled model for transport of multiple chemical species and kinetic precipitation/dissolution reactions with application to reactive flow in single phase hydrothermal systems. American Journal of Science 294, 529-592. 

The primary use of chemical kinetics in CRE is the development of a rate law (for a simple system), or a set of rate laws (for a kinetics scheme in a complex system). This requires experimental measurement of rate of reaction and its dependence on concentration, temperature, etc. In this chapter, we focus on experimental methods themselves, including various strategies for obtaining appropriate data by means of both batch and flow reactors, and on methods to determine values of rate parameters. (For the most part, we defer to Chapter 4 the use of experimental data to obtain values of parameters in particular forms of rate laws.) We restrict attention to single-phase, simple systems, and the dependence of rate on concentration and temperature. It is useful at this stage, however, to consider some features of a rate law and introduce some terminology to illustrate the experimental methods. 

Our treatment of chemical kinetics in Chapters 2-10 is such that no previous knowledge on the part of the student is assumed. Following the introduction of simple reactor models, mass-balance equations and interpretation of rate of reaction in Chapter 2, and measurement of rate in Chapter 3, we consider the development of rate laws for single-phase simple systems in Chapter 4, and for complex systems in Chapter 5. This is... 

The results of this analysis of the product and catalyst distribution show that only a limited range of systems may be apphcable for the telomeriza-tion of butadiene and carbon dioxide. The reaction was performed in the biphasic systems EC/2-octanol, EC/cyclohexane and EC/p-xylene. The yield of 5-lactone reached only 3% after a reaction time of 4 hours at 80 °C. hi the solvent system EC/2-octanol triphenylphosphine was used as the hgand. With the ligand bisadamantyl-n-butyl-phosphine even lower yields were achieved in a single-phase reaction in EC or in the biphasic system EC/cyclohexane. The use of tricyclohexylphosphine led to a similar result, only 1% of the desired product was obtained in the solvent system EC/p-xylene, which forms one homogeneous phase at the reaction temperature of 80 °C. Even at a higher temperature of 100 °C and a longer reaction time of 20 hours no improvement could be observed. Therefore, we turned our interest to another telomerization-type process. 

Upon variation of the stirring velocity between 500 and 1500 rpm the conversion of the olefin remained at the same high level and the selectivity to the linear aldehyde also remained constant. Obviously there is no mass transfer limitation in this two-phase reaction system. In comparison to the single-phase reaction in propylene carbonate as the only solvent [23], the selectivity decreases from 95% to 70%, which can be explained by the high concentration of the non-electron-donating solvent dodecane in the propylene carbonate phase. The presence of the dodecane leads to a decrease of the isomerization velocity, which results in a lower hnearity of the formed aldehydes. 

In the case of a single-phase, multicomponent system undergoing just a single reaction, the total Gibbs energy is as follows ... 

These considerations can be extended to reversible processes. They also apply to single phase, liquid systems. For the case, rather common in heterogeneous catalysts, in which one reactant is in a gas phase and the others and the products are in a liquid phase, application of the principles given above is straightforward provided that there is mass transfer equilibrium between gas phase and liquid phase, i.e., the fugacity of the reactant in the gas phase is identical with its fugacity in the liquid phase. In such case, a power rate law for an irreversible reaction of the form... 

In general, the active ester method gives the better yield because the coupling reaction can be run in a single-phase solvent system such as DMF/H20. In such a solvent system, the active ester and salt of 1-aminoalkylphosphonic acids (sodium or triethylamine) are soluble. 

Ideally, biphasic catalysis is performed in such a way that mass-transfer from one phase to the other does not restrict the rate of the reaction. An elegant solution to overcome this potential limitation is reversible two phase-single phase reaction conditions. An example of a temperature-controlled reversible ionic liquid-water partitioning system has been demonstrated for the hydrogenation of 2-butyne-l,4-diol, see Figure 3.2.1251... 

For the case of equilibrium with respect to chemical reaction within a single-phase closed system, combination of Eqs. (4-16) and (4-271) leads immediately to... 

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