Separating acids and bases

A possibility that was proposed quite early for the glucose mutarotation, and that could conceivably be of importance for other reactions, is simultaneous catalysis by an acid and a base. It will be recalled from Section 8.1 that hydration requires addition of a proton at one site and removal of a proton from another. If both these processes were to occur in one step, either by means of separate acid and base molecules acting together or by action of a single molecule containing both an acidic and a basic center, we would designate the process as a concerted acid and base catalysis (Equation 8.39).60 Swain found that the rate of... 

In addition to the processes discussed so far there are two more electromembrane separation processes in which the driving force is not an externally applied electrical potential but a concentration gradient. The processes are referred to as diffusion dialysis and Donnan dialysis. Diffusion dialysis is utilizing anion- or cation-exchange membranes only to separate acids and bases from mixtures with salts. Donnan dialysis can be used to exchange ions between to solutions separated by an ion-exchange membrane. Both processes have so far gained only limited practical relevance [4] and will not be discussed in this chapter. 

Trommsdorff was the first German chemist (1789) to separate acids and bases from the class of salts. He called hydrogen sulphide Hydrothion-saure. The supposed new earth, Agust-Erde (from dycuoro , since its salts were tasteless) was extracted by Trommsdorff from Saxon beryl. Richter thought he had confirmed its individuality, but it was shown independently by Vaiiquelin, Klaproth, Bucholz and Trommsdorff himself in 1803 to be basic calcium phosphate. 

Three examples of simple multivariable control problems are shown in Fig. 8-40. The in-line blending system blends pure components A and B to produce a product stream with flow rate w and mass fraction of A, x. Adjusting either inlet flow rate or Wg affects both of the controlled variables andi. For the pH neutrahzation process in Figure 8-40(Z ), liquid level h and the pH of the exit stream are to be controlled by adjusting the acid and base flow rates and w>b. Each of the manipulated variables affects both of the controlled variables. Thus, both the blending system and the pH neutralization process are said to exhibit strong process interacHons. In contrast, the process interactions for the gas-liquid separator in Fig. 8-40(c) are not as strong because one manipulated variable, liquid flow rate L, has only a small and indirec t effect on one controlled variable, pressure P. 

An example of the effect of acid and base concentration on the separation of propranolol is shown in Fig. 2-13. In this case, the baseline separation is achieved by adjusting the concentration without changing the acid/base ratio. 

Another point is related to the high acidity level of the final solution, which leads to certain limitations in the subsequent technological steps. Specifically, the high acidity of the initial solution eliminates any possibility for selective extraction, i.e. sequential separation of tantalum and then of niobium. Due to the high concentration of acids, only collective extraction (of tantalum and niobium together) can be performed, at least at the first step. In addition, extraction from a highly acidic solution might cause additional contamination of the final products with antimony and other related impurities. In order to reduce the level of contaminants in the initial solution, some special additives are applied prior to the liquid-liquid extraction. For instance, some mineral acids and base metals are added to the solution at certain temperatures to cause the precipitation of antimony [455 - 457]. 

Solutions which prevent the hydrolysis of salts of weak acids and bases. If the precipitate is a salt of weak acid and is slightly soluble it may exhibit a tendency to hydrolyse, and the soluble product of hydrolysis will be a base the wash liquid must therefore be basic. Thus Mg(NH4)P04 may hydrolyse appreciably to give the hydrogenphosphate ion HPO and hydroxide ion, and should accordingly be washed with dilute aqueous ammonia. If salts of weak bases, such as hydrated iron(III), chromium(III), or aluminium ion, are to be separated from a precipitate, e.g. silica, by washing with water, the salts may be hydrolysed and their insoluble basic salts or hydroxides may be produced together with an acid ... 

The most widely used homogeneous catalysts are simple acids and bases which catalyse well-known reactions such as ester and amide hydrolysis, and esterification. Such catalysts are inexpensive enough that they can be neutralized, easily separated fi om organic materials, and disposed of. This, of course, is not a good example of green chemistry and contributes to the huge quantity of aqueous salt waste generated by industry. 

Catalytic transformations can be divided on the basis of the catalyst-type - homogeneous, heterogeneous or enzymatic - or the type of conversion. We have opted for a compromise a division based partly on type of conversion (reduction, oxidation and C-C bond formation, and partly on catalyst type (solid acids and bases, and biocatalysts). Finally, enantioselective catalysis is a recurring theme in fine chemicals manufacture, e.g. in the production of pharmaceutical intermediates, and a separate section is devoted to this topic. 

It is often customary to describe acids and bases together instead of considering them separately as individuals. 

Ion-pairing techniques are also used to separate weak acids and bases but additionally they find application in the separation of other ionic compounds. The methods originated in the field of solvent extraction. An ionised compound (A+q) that is water soluble can be extracted into an organic solvent by using a suitable counter ion (B q) to form an ion-pair, according to the equation ... 

Fig. 3.3f(/) shows the use of a combination of ion-pairing and ion-suppression to separate a mixture of acids and bases. The pH of the mobile phase is about 2.5, as at this pH the maleic acid is unionised and elutes quickly as a very polar molecule on the reverse phase column. The other solutes are all weak bases which at pH 2.5 are fully protonated and pair with the pentane sulphonic acid anion. 

Separation of a mixture of acids and bases by ion-pairinglion-suppression... 

Ease of separation of tritiated products from a reaction medium is an important feature in the choice of labeling procedure. Sometime ago we used polymer-sup-ported acid and base catalysts [12, 13] to good effect and with the current interest in Green Chemistry one can expect to see more studies where the rate accelerations observed under microwave-enhanced conditions are combined with the use of solid catalysts such as Nafion, or zeolites. 

When an acid in solution is exactly neutralized with a base the resulting solution corresponds to a solution of the salt of the acid-base pair. This is a situation which frequently arises in analytical procedures and the calculation of the exact pH of such a solution may be of considerable importance. The neutralization point or end point in an acid-base titration is a particular example (Chapter 5). Salts may in all cases be regarded as strong electrolytes so that a salt AB derived from acid AH and base B will dissociate completely in solution. If the acid and base are strong, no further reaction is likely and the solution pH remains unaffected by the salt. However if either or both acid and base are weak a more complex situation will develop. It is convenient to consider three separate cases, (a) weak acid-strong base, (b) strong acid-weak base and (c) weak acid-weak base. 

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