Scale reaction, homogeneous

Few mechanisms of liquid/liquid reactions have been established, although some related work such as on droplet sizes and power input has been done. Small contents of surface-ac tive and other impurities in reactants of commercial quality can distort a reac tor s predicted performance. Diffusivities in liquids are comparatively low, a factor of 10 less than in gases, so it is probable in most industrial examples that they are diffusion controllech One consequence is that L/L reactions may not be as temperature sensitive as ordinary chemical reactions, although the effec t of temperature rise on viscosity and droplet size can result in substantial rate increases. L/L reac tions will exhibit behavior of homogeneous reactions only when they are very slow, nonionic reactions being the most likely ones. On the whole, in the present state of the art, the design of L/L reactors must depend on scale-up from laboratoiy or pilot plant work. 

Equilibrium Compositions for Single Reactions. We turn now to the problem of calculating the equilibrium composition for a single, homogeneous reaction. The most direct way of estimating equilibrium compositions is by simulating the reaction. Set the desired initial conditions and simulate an isothermal, constant-pressure, batch reaction. If the simulation is accurate, a real reaction could follow the same trajectory of composition versus time to approach equilibrium, but an accurate simulation is unnecessary. The solution can use the method of false transients. The rate equation must have a functional form consistent with the functional form of K,i,ermo> e.g., Equation (7.38). The time scale is unimportant and even the functional forms for the forward and reverse reactions have some latitude, as will be illustrated in the following example. 

In order to exemplify the potential of micro-channel reactors for thermal control, consider the oxidation of citraconic anhydride, which, for a specific catalyst material, has a pseudo-homogeneous reaction rate of 1.62 s at a temperature of 300 °C, corresponding to a reaction time-scale of 0.61 s. In a micro channel of 300 pm diameter filled with a mixture composed of N2/02/anhydride (79.9 20 0.1), the characteristic time-scale for heat exchange is 1.4 lO" s. In spite of an adiabatic temperature rise of 60 K related to such a reaction, the temperature increases by less than 0.5 K in the micro channel. Examples such as this show that micro reactors allow one to define temperature conditions very precisely due to fast removal and, in the case of endothermic reactions, addition of heat. On the one hand, this results in an increase in process safety, as discussed above. On the other hand, it allows a better definition of reaction conditions than with macroscopic equipment, thus allowing for a higher selectivity in chemical processes. 

In cases where the operation time-scale is independent of the channel diameter, as for a homogeneous reaction, it is necessary to keep the residence time fixed when downscaling a reactor in order keep the efficiency constant. When the flow-rate Qtot of the process gas is given, this means that a reduction in the channel diameter has to be accompanied by an increase in the channel length L or the number of channels N, according to... 

Time-scale of homogeneous reaction (1st order) Time-scale of heterogeneous reaction (1st order) Time-scale for reactor heat-up... 

S.4. Guidelines for scale-up of semibatch reactors for fast homogeneous reactions in the absence of data on chemical kinetics and on the distribution of energy dissipation in the reaction zone... 

Although palladium or platinum on charcoal are widely used, there is a preference for homogeneous reactions on both the laboratory and the industrial scale. Complexes of ruthenium (II) and rhodium (I), particularly with phosphine ligands, do have some importance in special applications [4], but... 

Reaction scale-up using the Voyager system in genuine continuous-flow format is achieved by the use of special coiled flow-through cells. The reaction coils are made of glass or Teflon (Fig. 3.24) with a maximum flow rate of 20 mL min-1 and operational limits of 250 °C or 17 bar. The continuous-flow format should only be used for homogeneous solution-phase chemistry, as slurried mixtures may cause prob-... 

More complicated reactions that combine competition between first- and second-order reactions with ECE-DISP processes are treated in detail in Section 6.2.8. The results of these theoretical treatments are used to analyze the mechanism of carbon dioxide reduction (Section 2.5.4) and the question of Fl-atom transfer vs. electron + proton transfer (Section 2.5.5). A treatment very similar to the latter case has also been used to treat the preparative-scale results in electrochemically triggered SrnI substitution reactions (Section 2.5.6). From this large range of treated reaction schemes and experimental illustrations, one may address with little adaptation any type of reaction scheme that associates electrode electron transfers and homogeneous reactions. 

Many chemical reactions are performed on a batch basis, in which a reactor is filled with solvents, substrates, catalysts and anything else required to make the reaction proceed, the reaction is then performed and finally the reactor is emptied and the resultant mixture separated (Figure 11.2). Conceptually, a batch reactor is similar to a scaled up version of a reaction in a round-bottomed flask, although obviously the engineering required to realize a large scale reaction is much more complicated. Batch reactors are suitable for homogeneous reactions, and also for multiphasic reactions provided that efficient mixing between the phases may be achieved so that the reaction occurs at a useful rate. 

Figure 6.21 Computed plot of the ratio of peak currents, /p(back//p(focwani), against log (kx) for an EC reaction, where t is the time-scale of the CV and k is the rate constant of the first-order homogeneous reaction. Notice how the plot has a similar shape to that shown in Figure 6.20, but the jc-axis is offset by the amount log k.

The Ruhrchemie/Rhone-Poulenc process is performed annually on a 600,000 metric ton scale (18). In this process, propylene is hydroformylated to form butyraldehyde. While the solubility of propylene in water (200 ppm) is sufficient for catalysis, the technique cannot be extended to longer-chain olefins, such as 1-octene (<3 ppm solubility) (20). Since the reaction occurs in the aqueous phase (21), the hydrophobicity of the substrate is a paramount concern. We overcame these limitations via the addition of a polar organic co-solvent coupled with subsequent phase splitting induced by dissolution of gaseous CO2. This creates the opportunity to run homogeneous reactions with extremely hydrophobic substrates in an organic/aqueous mixture with a water-soluble catalyst. After C02-induced phase separation, the catalyst-rich aqueous phase and the product-rich organic phase can be easily decanted and the aqueous catalyst recycled. 

Thus there is an essential difference between classical homogeneous reactions in organic chemistry and reactions such as those in which catenanes and knots are formed. In the latter, there are heterogeneities on the micro scale. Thus supramolecular chemistry lies also in the border area between classical organic chemistry and surface chemistry. 

K. They noted a decay over timescales 95 and < 35 ns, respectively, which was attributed to geminate ion-pair recombination (see Fig. 33). The decay of the optical absorption is independent of the dose of radiation received and continues for about lps. Rather than displaying a dependence on time as eqn. (153), i.e. at f 3/2, the experimental results are more nearly represented by either at f 1 decay to an optical density about one tenth of the maximum or by a decay as t 1/2 to zero absorption. These effects may be the recombination of ions within a spur (or cluster of ion-pairs), which is more nearly like a homogeneous reaction. The range of electrons in propane at 100 K is 10 nm [334] and the extrapolated diffusion coefficient is 10 11 m2 s 1 [320]. The timescale of recombination is 10 ps. The locally greater concentration of ions within a spur probably leads to a faster rate of reaction and is consistent with the time-scale of the reaction observed. Baxendale et al. [395] observed the decay of the infrared optical absorption of the solvated electron in methylcyclo-hexane at 160 K. They noted that the faster decay occurring over < 50 ns was independent of dose and depended on time as t 1/2, i.e. the reaction rate decays as t 3/2, see eqn. (153). It was attributed to recombination of... 

It is probably the complexity of these theories that prohibited this particular aspect of electrode kinetics from being attractive for application in the study of homogeneous reaction kinetics per se. Yet it must be clear that the electrochemical techniques, together providing an extremely wide range of time scales, should be preeminently suited for investigations of both slow and (very) fast homogeneous reactions. This is the more true since, nowadays, the problem of the non-availability of a closed-form expression for the response—perturbation or response—time relation has been overcome by numerical analysis procedures conducted with the aid of computers. 

In more than one respect, the small-amplitude sinuosoidal a.c. method can be superior to the large-amplitude step methods for the study of coupled homogeneous reactions. First, the wide range of frequencies at which meaningful data can be obtained will correspond to an equally wide range of rate constants on which, in principle, information can be obtained. Second, the a.c. perturbation can be superimposed on a large-amplitude d.c. or step perturbation so that information in the time scale of the latter is incorporated as well. Moreover, this affords an internal check on the reliability of data interpretations. Finally, it is important... 

The small area of a microelectrode, with its proportionately low capacitance, allows its use at very short time scales compared to the time scale used with a classical voltammetric electrode. As we have seen earlier in this chapter, when microelectrodes are used at short time scales, the current follows the behavior expected for diffusion in one dimension. Thus, the development of high-speed voltammetric methods with microelectrodes was a logical step, and has greatly expanded the scope and capabilities of electrochemical techniques [41]. Rapid electrochemical methods allow evaluation of the larger rate constants of rapid heterogeneous and/or homogeneous reactions. For example, theories of hetero-... 

The mean residence time for a continuous stirred-tank reactor of volume Vc may be defined as Vc/v in just the same way as for a tubular reactor. However, in a homogeneous reaction mixture, it is not possible to identify particular elements of fluid as having any particular residence time, because there is complete mixing on a molecular scale. If the feed consists of a suspension of particles, it may be shown that, although there is a distribution of residence times among the individual particles, the mean residence time does correspond to Vc v if the system is ideally mixed. 

In another oudine, cellulose was complexed with cuprammonium ions (Nicoll and Conaway, 1943). Lately, laboratory-scale isolation has relied on polar aprotic solvents and solvent systems, e.g., dimethylsulfoxide, pyridine, Af,7V-dimethylacetamide-lithium chloride, and l-methyl-2-pyrrolidinone-lithium chloride (Baker et al., 1978 McCormick and Shen, 1982 Seymour et al., 1982 Arnold et al., 1994). These solvents have enabled such homogeneous17 reactions as O- and N-derivatization of cellulose and chitin (Williamson and McCormick, 1994) and selective site chlorination (Ball et al., 1994). Dimethylsulfoxide was the solvent in a homogeneous reaction of cellulose and paraformaldehyde, prior to isolation of purified cellulose (Johnson et al., 1975). In yet another outline, paraformaldehyde enabled superior quality extracts when the parent tissues were presoaked in this solution (Fasihuddin et al., 1988). 

Reagent-grade tetrahydrofuran was freshly distilled from sodium and benzophenone and maintained under nitrogen. In small-scale experiments (1 mmol of tungsten hexachloride in 10 mL of solvent) anhydrous ether was equally effective, but did not give a homogeneous reaction solution. 

In this section, we present spatially averaged multi-scale models for different types of homogeneous reactors. We consider a single homogeneous reaction involving M species, which is given by... 

Da reactor scale Damkohler number (homogeneous reaction)... 

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