Example 4 Reactive Liquid Mixture

This example considers distillation of a reacting ternary mixture in an open batch distillery with flowing sweep gas. From this example, one can see the determination of reactive azeotropes and reactive arheotropes . The considered hypothetical reaction is 

In the following, component A is numbered as 1, component B as 2, and component C as 3. At chemical equilibrium conditions, the following relationship holds  

Blotting paper soaked with iso-propanol after 16 min 

Blotting paper soaked with water after 16 min 

The relative volatilities are assumed to be an = 5 and ab = 3, and gas phase mass transfer coefficients are fcj.gas = 0.5 m s-1 and fc2,gas = 1.0 m s-1. The flow rate per unit interface area of the sweep gas is chosen between G = 0.001 to 0.4 m s-1, which results in either high or low gas phase NTl/i-values. Presupposing that the vapor mole fractions are low, i.e. y 1, one can say that  

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When the mixture of monomers is cast in an open mold, the air bubbles formed at the jet nozzle in the mold usually have enough time to leave the material due to the low viscosity of the reactive liquid. When more viscous oligomers and prepolymers are used, particularly in the case of low-lifetime reactive mixtures, it may be necessary to use some simple procedures, for example, filling through a pipe immersed into the mold, to prevent the formation of air bubbles in the product. 

Microencapsulated adhesive Reactive adhesive mixture, with the (liquid) components encapsulated by a protective skin in the form of finest drops, preventing a reaction during storage. Only after the destruction of the capsule wall, for example, by screwing a nut onto a suchlike coated screw, does a chemical reaction set in and an adhesive layer develop. 

Chloroaluminate ionic liquids (typically a mixture of a quaternary ammonium salt with aluminum chloride see Table 6.9) exhibit at room temperature variable Lewis acidity and have been successfully used as solvent/catalyst for Diels-Alder reactions [57]. The composition of chloroaluminate ionic liquids can vary from basic ([FMIM]C1 or [BP]C1 in excess) to acidic (AICI3 in excess) and this fact can be used to affect the reactivity and selectivity of the reaction. The reaction of cyclopentadiene with methyl acrylate is an example (Scheme 6.31). 

Intelligent engineering can drastically improve process selectivity (see Sharma, 1988, 1990) as illustrated in Chapter 4 of this book. A combination of reaction with an appropriate separation operation is the first option if the reaction is limited by chemical equilibrium. In such combinations one product is removed from the reaction zone continuously, allowing for a higher conversion of raw materials. Extractive reactions involve the addition of a second liquid phase, in which the product is better soluble than the reactants, to the reaction zone. Thus, the product is withdrawn from the reactive phase shifting the reaction mixture to product(s). The same principle can be realized if an additive is introduced into the reaction zone that causes precipitation of the desired product. A combination of reaction with distillation in a single column allows the removal of volatile products from the reaction zone that is then realized in the (fractional) distillation zone. Finally, reaction can be combined with filtration. A typical example of the latter system is the application of catalytic membranes. In all these cases, withdrawal of the product shifts the equilibrium mixture to the product. 

At present there are few examples of isolable, well-characterized sources of tellurolate anions (RTe-).1 Although insertion of elemental tellurium into reactive metal-carbon bonds has been known for many years, the resulting solutions contain a mixture of compounds in addition to the RTe- species of interest.2 Alkali metal phenyltellurolate salts, prepared via metal reduction of diphenyl ditelluride in liquid ammonia, were first isolated by Klar and co-workers.3 More recently Lange and Du Mont reported the synthesis of the bulky aryl tellurolate (THF)3Li[Te(2,4,6-f-Bu3C6H2)],4 and Sladky described the in situ formation of a bulky alkyl tellurolate via reaction of tellurium with LiC(SiMe3)3.5 Acidification of aryltellurolate anions affords thermally sensitive tellurols (RTeH) that are stable only below room temperature.6... 

A combination of different techniques can frequently improve yields of final compounds or synthetic conditions, for example a reunion of direct electrochemical synthesis and simultaneous ultrasonic treatment of the reaction system [715]. Reunion of microwave and ultrasonic treatment was an aim to construct an original microwave-ultrasound reactor suitable for organic synthesis (pyrolysis and esterification) (Fig. 3.7) [716], The US system is a cup horn type the emission of ultrasound waves occurs at the bottom of the reactor. The US probe is not in direct contact with the reactive mixture. It is placed a distance from the electromagnetic field in order to avoid interactions and short circuits. The propagation of the US waves into the reactor occurs by means of decalin introduced into the double jacket. This liquid was chosen by the authors of Ref. 716 because of its low viscosity that induces good propagation of ultrasonic waves and inertia towards microwaves. 

Figure A.2 (right) emphasizes a particular position where phase equilibrium and stoichiometric lines are collinear. In other words the liquid composition remains unchanged because the resulting vapor, after condensation, is converted into the original composition. This point is a potential reactive azeotrope, but when the composition satisfies chemical equilibrium too it becomes a true reactive azeotrope. Some examples of residue curve maps are presented below. Ideal mixtures are used to illustrate the basic features, which may be applied to some important industrial applications.

The lacking special description of the Gibbs phase rule in MEIS that should be met automatically in case of its validity is very important for solution of many problems on the analysis of multiphase, multicomponent systems. Indeed, without information (at least complete enough) on the process mechanism (for coal combustion, for example, it may consist of thousands of stages), it is impossible to specify the number of independent reactions and the number of phases. Prior to calculations it is difficult to evaluate, concentrations of what substances will turn out to be negligibly low, i.e., the dimensionality of the studied system. Besides, note that the MEIS application leads to departure from the Gibbs classical definition of the notion of a system component and its interpretation not as an individual substance, but only as part of this substance that is contained in any one phase. For example, if water in the reactive mixture is in gas and liquid phases, its corresponding phase contents represent different parameters of the considered system. Such an expansion of the space of variables in the problem solved facilitates its reduction to the CP problems. 

Measurement of conversions of various formulations at various EB doses can be used to rank the reactivity of the formulation. A particularly useful procedure has been to prepare a standard mixture of an acrylate resin with various reactive diluent monomers in order to compare the volatility and reactivity of new monomers. For these studies, a mixture of 40 weight % of a Bis-phenol A epoxy dlacrylate resin with 60% of the test liquid monomer has proved convenient. A viscosity measurement of the mixture also provides information on the relative viscosity reducing ability of the test monomer. Illustrative examples of these measurements are shown in Table I and Figure 1. Mote from these examples that a monofunctional monomer, Monomer B, can be used to provide the low volatility and high reactivity typical of the multifunctional monomers, while also serving to reduce the crosslinking. Many other available monofunctional monomers are found to be either more volatile or less reactive than Monomer B. 

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