Solid liquid reactions, examples

The various types of heterogeneous reactions are shown in Table 3.3. They are broadly grouped as solid-gas, solid-liquid, solid-solid, liquid-gas, and liquid-liquid reactions. The different types included in each group are also shown in the compilation. Some representative processes have been indicated as examples. It may be pointed out that in the group of solid-liquid reactions a specific mention of what is known as autocatalytic reactions has not been made. The autocatalytic processes occur when the liquid product reacts further with the solid undergoing reaction. The dissolution of copper in dilute sulfuric acid (or aqueous ammonia) in the presence of oxygen may be cited as an example ... 

It is noteworthy that Mossbauer spectroscopy applies not only to solid-gas reactions but also to solid-liquid reactions. It has been used, for example, to... 

SoHd-liguid phase-transfer catalysis. Crown ethers have commonly been used as catalysts for reactions between a solid-liquid interface, and quaternary ammonium and phosphonium salts have been used only as catalysts for reactions in two-phase liquid liquid reactions. However, several laboratories have reported that the latter catalysts are also satisfactory for two-phase solid liquid reactions. Thus dichlorocarbene can be generated from chloroform and solid sodium hydroxide under catalysis from benzyltriethylammonium chloride in yields comparable to those of the classical Makosza method. Another example of this type of catalysis is the oxidation of terminal and internal alkynes by solid potassium permanganate in CH2CI2 with Adogen 464 as catalyst. Aliquat 336 has been found to be as satisfactory as a crown ether for certain displacement reactions with NaOAc, KSCN, KNOa, and KF in CH3CN or CHaCla. ... 

The most pertinent effects of ultrasound in solid-liquid reactions are mechanical, which are attributed to symmetrical and/or asymmetrical cavitation. Symmetrical cavitation (the type encountered in homogeneous systems) leads to localized areas of high temperatures and pressures and also to shock waves that can create microscopic turbulence (Elder, 1959). As a result, mass transfer rates are considerably enhanced. For example, Hagenson and Doraiswamy (1998) observed a twofold increase in the intrinsic mass transfer coefficient in the reaction between benzyl chloride (liquid) and sodium sulfide (solid). In addition, a decrease in particle size and therefore an increase in the interfacial surface area appears to be a common feature of ultrasound-assisted solid-liquid reactions (Suslick et al., 1987 Ratoarinoro et al., 1992, 1995 Hagenson and Doraiswamy, 1998). 

The chemical activation of carbons is a complex solid-liquid reaction. The reaction takes place when the solid (carbon) reacts, at about 500°C, with a liquid (hydroxide), producing mainly H2, alkaline metal, and carbonate, if the heat treatment temperature is lower than 750°C. This reaction is a redox process in which carbon is oxidized to carbonate and hydroxide is rednced to alkali metal and hydrogen. This set of reaction products and the type of reactions taking place are not necessarily the same for all carbonaceous materials thus, for example, lignocellulosic... 

Fluid-fluid (gas-liquid and liquid-liquid) reactions are of great industrial importance and contribute to more than 70% of industrial applications. For gas-liquid, liquid-liquid, gas-liquid-solid (noncatalytic and catalytic), and solid-liquid systems, examples of industrial importance have been given by many authors. 

More complex in its kinetics is the reaction of a solid with a liquid or gas to give a second solid as, for example. 

Surface science studies of corrosion phenomena are excellent examples of in situ characterization of surface reactions. In particular, the investigation of corrosion reactions with STM is promising because not only can it be used to study solid-gas interfaces, but also solid-liquid interfaces. 

To date a number of reactions have been carried out in ionic liquids [for examples, see Dell Anna et al. J Chem Soc, Chem Commun 434 2002 Nara, Harjani and Salunkhe Tetrahedron Lett 43 1127 2002 Semeril et al. J Chem Soc Chem Commun 146 2002 Buijsman, van Vuuren and Sterrenburg Org Lett 3 3785 2007]. These include Diels-Alder reactions, transition-metal mediated catalysis, e.g. Heck and Suzuki coupling reactions, and olefin metathesis reactions. An example of ionic liquid acceleration of reactions carried out on solid phase is given by Revell and Ganesan [Org Lett 4 3071 2002]. 

The thermodynamic properties of a chemical substance are dependent upon its state and, therefore, it is important to indicate conditions when writing chemical reactions. For example, in the burning of methane to form carbon dioxide and water, it is important to specify whether each reactant and product are solid, liquid, or gaseous since different changes in the thermodynamic property will occur depending upon the state of each substance. Thus, different volume and energy changes occur in the reactions... 

The most common states of a pure substance are solid, liquid, or gas (vapor), state property See state function. state symbol A symbol (abbreviation) denoting the state of a species. Examples s (solid) I (liquid) g (gas) aq (aqueous solution), statistical entropy The entropy calculated from statistical thermodynamics S = k In W. statistical thermodynamics The interpretation of the laws of thermodynamics in terms of the behavior of large numbers of atoms and molecules, steady-state approximation The assumption that the net rate of formation of reaction intermediates is 0. Stefan-Boltzmann law The total intensity of radiation emitted by a heated black body is proportional to the fourth power of the absolute temperature, stereoisomers Isomers in which atoms have the same partners arranged differently in space, stereoregular polymer A polymer in which each unit or pair of repeating units has the same relative orientation, steric factor (P) An empirical factor that takes into account the steric requirement of a reaction, steric requirement A constraint on an elementary reaction in which the successful collision of two molecules depends on their relative orientation. 

Chemical engineers could also work to devise processes to improve the flow characteristics of powders after they are formed. Such research would help control agglomeration of particles in subsequent processing steps as well as facilitate the production of compacted ceramic preforms. For example, gas-solid chemical reactions might be used to tailor the chemical composition of powders. As another example, better methods of componnding powders with binders might be achieved by processes that mix powders with suitable binders in a liquid and then spray dry the resulting suspension. 

Chapter 11 treats reactors where mass and component balances are needed for at least two phases and where there is interphase mass transfer. Most examples have two fluid phases, typically gas-liquid. Reaction is usually confined to one phase, although the general formulation allows reaction in any phase. A third phase, when present, is usually solid and usually catalytic. The solid phase may be either mobile or stationary. Some example systems are shown in Table 11.1. 

The 0-silylation reaction of alcohols is important as a protection method of hydroxyl groups. 0-Silylations of liquid or crystalline alcohols with liquid or crystalline silyl chlorides were found to be possible in the solid state. For example, when a mixture of powdered L-menthol (26), ferf-butyldimethylsilyl chloride (27), and imidazole (28) was kept at 60 °C for 5 h, 0-tert-butyldi-methylsilyl L-menthol (29) was obtained in 97% yield [8] (Scheme 4). Similar treatments of 26 with the liquid silyl chlorides, trimethyl- (30a) and triethylsilyl chloride (30b), gave the corresponding 0-silylation products 31a (89%) and 31b (89%), respectively, in the yields indicated [8] (Scheme 4). However, 0-silylation of triisopropyl- (30c) and triphenylsilyl chloride (30d) proceeded with difficultly even at 120 °C and gave 31c (57%) and 31d (70%), respectively, in relatively low yields. Nevertheless, when the solvent-free silylation reactions at 120 °C were carried out using two equivalents of 30c and 30d, 31c (77%) and 31d (99%) were obtained, respectively, in relatively high yields. 

Since solid-state reactions can easily be monitored by continuous measurement of spectra, it is easy to study the mechanism of the reactions. For this purpose, IR spectroscopy is the most useful, because IR spectra can be measured simply as Nujol mulls or directly for any mixture of solid-solid, solid-liquid, or liquid-liquid by using the ATP (attenuated total reflection) method. Some such examples of the mechanistic study are described. 

As was stated above, the very strong acidity (and probably together with the organophilicity of the pore wall) makes these salts very active catalysts in liquid-solid organic reaction systems. We wish to emphasize that this is the first example for the shape selective catalysis of heteropolyacids at least to our knowledge. 

In phase transfer catalysis of the solid/liquid type, the organic phase (containing dissolved organic reactant and a small amount of the crown) is mixed directly with the solid inorganic salt. Such a procedure enables the reaction to proceed under anhydrous conditions this is a distinct advantage, for example, when hydrolysis is a possible competing reaction. Because of their open structure, crown ethers are readily able to abstract cations from a crystalline solid and are often the catalysts of choice for many solid/liquid phase transfer reactions. 

The interfacial barrier theory is illustrated in Fig. 15A. Since transport does not control the dissolution rate, the solute concentration falls precipitously from the surface value, cs, to the bulk value, cb, over an infinitesimal distance. The interfacial barrier model is probably applicable when the dissolution rate is limited by a condensed film absorbed at the solid-liquid interface this gives rise to a high activation energy barrier to the surface reaction, so that kR kj. Reaction-controlled dissolution is somewhat rare for organic compounds. Examples include the dissolution of gallstones, which consist mostly of cholesterol,... 

Diffusion of particles in the polymer matrix occurs much more slowly than in liquids. Since the rate constant of a diffusionally controlled bimolecular reaction depends on the viscosity, the rate constants of such reactions depend on the molecular mobility of a polymer matrix (see monographs [1-4]). These rapid reactions occur in the polymer matrix much more slowly than in the liquid. For example, recombination and disproportionation reactions of free radicals occur rapidly, and their rate is limited by the rate of the reactant encounter. The reaction with sufficient activation energy is not limited by diffusion. Hence, one can expect that the rate constant of such a reaction will be the same in the liquid and solid polymer matrix. Indeed, the process of a bimolecular reaction in the liquid or solid phase occurs in accordance with the following general scheme [4,5] ... 

Solid deposition from gas- or liquid-phase reactants Solid-deposition reactions are important in the formation of coatings and fdms from reactive vapors (called chemical vapor deposition or CVD) and of pure powders of various solids. Examples are ... 

We first present further examples of the types of reactions involved in two main classifications, and then a preliminary discussion of various types of reactors used. Following an examination of some factors affecting the choice of reactor, we develop design equations for some reactor types, and illustrate their use with examples. The chapter concludes with a brief introduction to trickle-bed reactors for three-phase gas-liquid-solid (catalyst) reactions. 

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