The Rates of Phase Transfer Reactions

If the rate of phase transfer is much slower than the rate of reaction, then the reaction will be mass transport limited-typically pseudo-zeroth order, unless the availability of the nucleophile becomes significantly depleted over the course 

1 The Influence of Catalyst Structure on Phase Transfer Reactions 

The choice of the catalyst is an important factor in PTC. Very hydrophilic onium salts such as tetramethylammonium chloride are not particularly active phase transfer agents for nonpolar solvents, as they do not effectively partition themselves into the organic phase. Table 5.2 shows relative reaction rates for anion displacement reactions for a number of common phase transfer agents. From the table it is clear that the activities of phase transfer catalysts are reaction dependent. It is important to pick the best catalyst for the job in hand. The use of onium salts containing both long and very short alkyl chains, such as hexade-cyltrimethylammonium bromide, will promote stable emulsions in some reaction systems, and thus these are poor catalysts. 

Catalyst Relative rates for PhS (aq) + 1-bromooctane Relative rates for QSf-(aq) + 1-chlorooctane 

Source (a) Herriott A. W. and Picker D. J. Am. Chem. Soc. 1975, 97, 2345 (b) Starks C. M. and Liotta C. Phase Transfer Catalysis Principles and Techniques, Academic Press, New York, 1978. 

For a single, homogeneous liquid phase the equation is rate = / [snbstrate][nucleophile] 

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Figure 5.22 The effect of water concentration on the rate of phase transfer reactions.

The rate of phase transfer catalyzed reaction depends on the following ... 

In contrast, a fast reaction rate will result in steep concentration gradients for the reactants and a higher reaction rate near the solvent interface. This concept is represented diagrammatically in Figure 2.13b, where the concentration of reactant A is almost as high as that in phase 1 at the solvent interface, but plummets as it is rapidly consumed by the reaction. Thus, for a fast reaction, the majority of reactant is converted to product near the phase boundary layer and the rate of the reaction is limited by the rate of phase transfer and diffusion. 

Many quaternary ammonium salts containing one or two large alkyl groups, such as cetyltrimethylammonium bromide, C16H33N (CH3)3Br, produce micelles as well as being phase transfer agents. Indeed, there are borderline cases where a particular quaternary ammonium salt may behave as both a surfactant and a phase transfer catalyst or as either one, depending on the particular reaction conditions. Starks (6) discusses further similarities and essential differences of the two phenomena. The most important difference is that whereas the rate of phase transfer catalysed reactions are directly... 

Reaction rates of phase transfer reactions are sensitive to a number of factors, including the organic substrate and the inorganic salt, the catalyst itself, the organic solvent, and the amount of water used. 

Pha.se-Tra.nsfer Ca.ta.lysts, Many quaternaries have been used as phase-transfer catalysts. A phase-transfer catalyst (PTC) increases the rate of reaction between reactants in different solvent phases. Usually, water is one phase and a water-iminiscible organic solvent is the other. An extensive amount has been pubHshed on the subject of phase-transfer catalysts (233). Both the industrial appHcations in commercial manufacturing processes (243) and their synthesis (244) have been reviewed. Common quaternaries employed as phase-transfer agents include benzyltriethylammonium chloride [56-37-17, tetrabutylammonium bromide [1643-19-2] tributylmethylammonium chloride [56375-79-2] and hexadecylpyridinium chloride [123-03-5]. 

Reactions of the Side Chain. Benzyl chloride is hydrolyzed slowly by boiling water and more rapidly at elevated temperature and pressure in the presence of alkaHes (11). Reaction with aqueous sodium cyanide, preferably in the presence of a quaternary ammonium chloride, produces phenylacetonitrile [140-29-4] in high yield (12). The presence of a lower molecular-weight alcohol gives faster rates and higher yields. In the presence of suitable catalysts benzyl chloride reacts with carbon monoxide to produce phenylacetic acid [103-82-2] (13—15). With different catalyst systems in the presence of calcium hydroxide, double carbonylation to phenylpymvic acid [156-06-9] occurs (16). Benzyl esters are formed by heating benzyl chloride with the sodium salts of acids benzyl ethers by reaction with sodium alkoxides. The ease of ether formation is improved by the use of phase-transfer catalysts (17) (see Catalysis, phase-thansfer). 

When reactants are distributed between several phases, migration between phases ordinarily will occur with gas/liquid, from the gas to the liquid] with fluid/sohd, from the fluid to the solid between hquids, possibly both ways because reactions can occur in either or both phases. The case of interest is at steady state, where the rate of mass transfer equals the rate of reaction in the destined phase. Take a hyperbohc rate equation for the reaction on a surface. Then,... 

Chemical reaction always enhances the rate of mass transfer between phases. The possible magnitudes of such enhancements are indicated in Tables 23-6 and 23-7. They are no more predictable than are specific rates of chemical reactions and must be found experimentally for each case, or in the relatively sparse literature on the subject. 

More often than not the rate at which residual absorbed gas can be driven from the liqmd in a stripping tower is limited by the rate of a chemical reaction, in which case the liquid-phase residence time (and hence, the tower liquid holdup) becomes the most important design factor. Thus, many stripper-regenerators are designed on the basis of liquid holdup rather than on the basis of mass transfer rate. 

For many laboratoiy studies, a suitable reactor is a cell with independent agitation of each phase and an undisturbed interface of known area, like the item shown in Fig. 23-29d, Whether a rate process is controlled by a mass-transfer rate or a chemical reaction rate sometimes can be identified by simple parameters. When agitation is sufficient to produce a homogeneous dispersion and the rate varies with further increases of agitation, mass-transfer rates are likely to be significant. The effect of change in temperature is a major criterion-, a rise of 10°C (18°F) normally raises the rate of a chemical reaction by a factor of 2 to 3, but the mass-transfer rate by much less. There may be instances, however, where the combined effect on chemical equilibrium, diffusivity, viscosity, and surface tension also may give a comparable enhancement. 

Phase-transfer catalysis (Section 22.5) Method for increasing the rate of a chemical reaction by transporting an ionic reactant from an aqueous phase where it is solvated and less reactive to an organic phase where it is not solvated and is more reactive. Typically, the reactant is an anion that is carried to the organic phase as its quaternary ammonium salt. 

These studies have indicated that the independent parameters controlling the postulated solid-phase reactions significantly affect the resulting acoustic admittance of the combustion zone, even though these reactions were assumed to be independent of the pressure in the combustion zone. In this combustion model, the pressure oscillations cause the flame zone to move with respect to the solid surface. This effect, in turn, causes oscillations in the rate of heat transfer from the gaseous-combustion zone back to the solid surface, and hence produces oscillations in the temperature of the solid surface. The solid-phase reactions respond to these temperature oscillations, producing significant contributions to the acoustical response of the combustion zone. 

The concentration of gas over the active catalyst surface at location / in a pore is ai [). The pore diffusion model of Section 10.4.1 linked concentrations within the pore to the concentration at the pore mouth, a. The film resistance between the external surface of the catalyst (i.e., at the mouths of the pore) and the concentration in the bulk gas phase is frequently small. Thus, a, and the effectiveness factor depends only on diffusion within the particle. However, situations exist where the film resistance also makes a contribution to rj so that Steps 2 and 8 must be considered. This contribution can be determined using the principle of equal rates i.e., the overall reaction rate equals the rate of mass transfer across the stagnant film at the external surface of the particle. Assume A is consumed by a first-order reaction. The results of the previous section give the overall reaction rate as a function of the concentration at the external surface, a. ... 

Although the use of phase-transfer catalysis (PTC) for manufacturing esters has the merits of a mild reaction condition and a relatively low cost [1], PTC has its limitations, such as the low reactivity of carboxylic ion by liquid-liquid PTC [2], a slow reaction rate by solid-liquid PTC, and the difflculty of reusing the catalyst by both techniques. 

Both reactions are slow compared to the film diffusion in the liquid phase13-15. Hence, the reactions can be assumed to take place predominantly in the bulk phase of the liquid. The rate of mass transfer can be calculated using Equation 7.2. The interfacial concentration can be calculated using Henry Law. Mass transfer coefficients, interfacial area and gas hold-up data are required. Gas hold-up is defined as ... 

In heterogeneous liquid/liquid reactions, cavitational collapse at or near the interface will cause disruption and mixing, resulting in the formation of very fine emulsions. When very fine emulsions are formed, the surface area available for the reaction between the two phases is significantly increased, thus increasing the rates of reaction. The emulsions formed using cavitation, are usually smaller in size and more stable, than those obtained using conventional techniques and often require little or no surfactant to maintain the stability [8]. This is very beneficial particularly in the case of phase-transfer catalyzed reactions or biphasic systems. 

Ordinary or bulk diffusion is primarily responsible for molecular transport when the mean free path of a molecule is small compared with the diameter of the pore. At 1 atm the mean free path of typical gaseous species is of the order of 10 5 cm or 103 A. In pores larger than 1CT4 cm the mean free path is much smaller than the pore dimension, and collisions with other gas phase molecules will occur much more often than collisions with the pore walls. Under these circumstances the effective diffusivity will be independent of the pore diameter and, within a given catalyst pore, ordinary bulk diffusion coefficients may be used in Fick s first law to evaluate the rate of mass transfer and the concentration profile in the pore. In industrial practice there are three general classes of reaction conditions for which the bulk value of the diffusion coefficient is appropriate. For all catalysts these include liquid phase reactions... 

Energy transfer Because the species are continually in collision, the rate of energy transfer is never considered to be the rate-limiting step, unlike in unimolec-ular gas-phase reactions. 

The rate expressions developed in this section for gas-liquid systems, represented by reaction 9.2-1, are all based on the two-film model. Since liquid-phase reactant B is assumed to be nonvolatile, for reaction to occur, the gas-phase reactant A must enter the liquid phase by mass transfer (see Figure 9.4). Reaction between A and B then takes place at some location within the liquid phase. At a given point, as represented in Figure 9.4, there are two possible locations the liquid film and the bulk liquid. If the rate of mass transfer of A is relatively fast compared with the rate of reaction, then A reaches the bulk liquid before reacting with B. Conversely, for a relatively fast rate of reaction ( instantaneous in the extreme), A reacts with B in the liquid film before it reaches the bulk liquid. Since the intermediate situation is also possible, we may initially classify the kinetics into three regimes ... 

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