Removal of Water

Removal of water from gases may be by physical or chemical means, and is commonly by adsorption on to a drying agent in a low-temperature trap. The effectiveness of drying agents depends on the vapour pressure of the hydrated compound - the lower the vapour pressure the less the remaining moisture in the gas. 

Where large amounts of water are to be removed, a preliminary drying of liquids is often possible by shaking with concentrated solutions of calcium chloride or potassium carbonate, or by adding sodium chloride to salt out the organic phase (for example, in the drying of lower alcohols). 

Drying agents that combine irreversibly with water include the alkali metals, the metal hydrides (discussed in Chapter 2), and calcium carbide. 

Alumina. (Preheated to 175 for about 7h). Mainly as a drying agent in a desiccator or as a column through which liquid is percolated. 

Aluminium amalgam. Mainly used for removing traces of water from alcohols, which are distilled from it after refluxing. 

Methods for removing water from solids depend on the thermal stability of the solids or the time available. The safest way is to dry in a vacuum desiccator over concentrated sulfuric acid, phosphorus pentoxide, silica gel, calcium chloride, or some other desiccant. Where substances are stable in air and melt above 100°, drying in an air oven may be adequate. In other cases, use of an Abderhalden pistol may be satisfactoiy. 

in drying inorganic salts, the final material that is required is a hydrate. In such cases, the purified substance is left in a desiccator to equilibrate above an aqueous solution having a suitable water-vapour pressure. A convenient range of solutions used in this way is given in Table 17. 

The choice of desiccants for drying liqirids is more restricted because of the need to avoid all substances likely to react with the liquids themselves. In some cases, direct distillation of an organic liquid is a suitable method 

Cartridges for the removal not only water from solvents or solutions but other specific impurities, e.g. acids, amines, aldehydes, are now commercially available [see supplies listed at the end of the HPLC section together with their respective websites]. 

For further useful information on mineral adsorbents and drying agents, go to the SigmaAldrich website, under technical library (Aldrich) for technical bulletin AL-143. 

Barium oxide. Suitable for drying organic bases. 

Barium perchlorate. Expensive. Used in desiccators (covered with a metal guard). Unsuitable for drying solvents or organic material where contact is necessary, because of the danger of EXPLOSION 

Boric anhydride. (Prepared by melting boric acid in an air oven at a high temperature, cooling in a desiccator, and powdering.) Mainly used for drying formic acid. 

Calcium oxide. (Preheated to 700-900° before use.) Suitable for alcohols and amines (but does not dry them completely). Need not be removed before distillation, but in that case the head of the distillation column should be packed with glass wool to trap any calcium oxide powder that might be carried over. Unsuitable for acidic compounds and esters. Suitable for drying gaseous amines and ammonia. 

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Drying refers to the removal of water from a substance through a whole range of processes, including distillation, evaporation, and even physical separations such as with centrifuges. Here, consideration is restricted to the removal of moisture from solids and liquids into a gas stream (usually air) by heat, namely, thermal drying. Some of the types of equipment for removal of water also can be used for removal of organic liquids from solids. 

Chemical methods may be employed if the reagent attacks only one of the components. Thus quicklime may be employed for the removal of water in the preparation of absolute ethyl alcohol. Also aromatic and unsaturated hydrocarbons may be removed from mixtures with saturated hydrocarbons by sulphonation. 

We may now understand the nature of the change which occurs when an anhydrous salt, say copper sulphate, is shaken with a wet organic solvent, such as benzene, at about 25°. The water will first combine to form the monohydrate in accordance with equation (i), and, provided suflScient anhydrous copper sulphate is employed, the effective concentration of water in the solvent is reduced to a value equivalent to about 1 mm. of ordinary water vapour. The complete removal of water is impossible indeed, the equilibrium vapour pressures of the least hydrated tem may be taken as a rough measure of the relative efficiencies of such drying agents. If the water present is more than sufficient to convert the anhydrous copper sulphate into the monohydrate, then reaction (i) will be followed by reaction (ii), i.e., the trihydrate will be formed the water vapour then remaining will be equivalent to about 6 mm. of ordinary water vapour. Thus the monohydrate is far less effective than the anhydrous compound for the removal of water. 

The theory of the action of drying agents has been considered in Section 1,20. We are now concerned with the practical methods for the removal of water from organic solids and liquids and from solutions of... 

Method 2 (E. L. Smith, 1927). Sodium alone cannot be used for the complete removal of water in ethyl alcohol owing to the equilibrium between the resulting sodium hydroxide and ethyl alcohol ... 

Sometimes a large proportion of sulphuric acid is employed (see below under esters of dibasic acids). The good yields thus obtained are partially due to the removal of water by the acid as well as to the catalytic effect. 

Note 2. Prepared by azeotropic removal of water from the commercial, water-containing product by means of benzene. This solvent was removed in a water--pump vacuum and the remaining mass was powdered. The water-containing acid appeared to work much less efficiently as catalyst. 

Direct, acid catalyzed esterification of acryhc acid is the main route for the manufacture of higher alkyl esters. The most important higher alkyl acrylate is 2-ethyIhexyi acrylate prepared from the available 0x0 alcohol 2-ethyl-1-hexanol (see Alcohols, higher aliphatic). The most common catalysts are sulfuric or toluenesulfonic acid and sulfonic acid functional cation-exchange resins. Solvents are used as entraining agents for the removal of water of reaction. The product is washed with base to remove unreacted acryhc acid and catalyst and then purified by distillation. The esters are obtained in 80—90% yield and in exceUent purity. 

Protein-Based Adhesives. Proteia-based adhesives are aormaHy used as stmctural adhesives they are all polyamino acids that are derived from blood, fish skin, caseia [9000-71 -9] soybeans, or animal hides, bones, and connective tissue (coUagen). Setting or cross-linking methods typically used are iasolubilization by means of hydrated lime and denaturation. Denaturation methods require energy which can come from heat, pressure, or radiation, as well as chemical denaturants such as carbon disulfide [75-15-0] or thiourea [62-56-6]. Complexiag salts such as those based upon cobalt, copper, or chromium have also been used. Formaldehyde and formaldehyde donors such as h exam ethyl en etetra am in e can be used to form cross-links. Removal of water from a proteia will also often denature the material. 

Amidation. Heating of the diammonium salt or reaction of the dimethyl ester with concentrated ammonium hydroxide gives adipamide [628-94-4] mp 228°C, which is relatively insoluble in cold water. Substituted amides are readily formed when amines are used. The most industrially significant reaction of adipic acid is its reaction with diamines, specifically 1,6-hexanediamine. A water-soluble polymeric salt is formed initially upon mixing solutions of the two materials then hea ting with removal of water produces the polyamide, nylon-6,6. This reaction has been studied extensively, and the hterature contains hundreds of references to it and to polyamide product properties (31). 

Because lactic acid has both hydroxyl and carboxyl functional groups, it undergoes iatramolecular or self-esterificatioa and forms linear polyesters, lactoyUactic acid (4) and higher poly(lactic acid)s, or the cycUc dimer 3,6-dimethyl-/)-dioxane-2,5-dione [95-96-5] (dilactide) (5). Whereas the linear polyesters, lactoyUactic acid and poly(lactic acid)s, are produced under typical condensation conditions such as by removal of water ia the preseace of acidic catalysts, the formation of dilactide with high yield and selectivity requires the use of special catalysts which are primarily weakly basic. The use of tin and ziac oxides and organostaimates and -titanates has been reported (6,21,22). 

Lithium Iodide. Lithium iodide [10377-51 -2/, Lil, is the most difficult lithium halide to prepare and has few appHcations. Aqueous solutions of the salt can be prepared by carehil neutralization of hydroiodic acid with lithium carbonate or lithium hydroxide. Concentration of the aqueous solution leads successively to the trihydrate [7790-22-9] dihydrate [17023-25-5] and monohydrate [17023-24 ] which melt congmendy at 75, 79, and 130°C, respectively. The anhydrous salt can be obtained by carehil removal of water under vacuum, but because of the strong tendency to oxidize and eliminate iodine which occurs on heating the salt ia air, it is often prepared from reactions of lithium metal or lithium hydride with iodine ia organic solvents. The salt is extremely soluble ia water (62.6 wt % at 25°C) (59) and the solutions have extremely low vapor pressures (60). Lithium iodide is used as an electrolyte ia selected lithium battery appHcations, where it is formed in situ from reaction of lithium metal with iodine. It can also be a component of low melting molten salts and as a catalyst ia aldol condensations. 

Evaporated milk is a Hquid product obtained by the partial removal of water only from milk. It has a minimum milk-fat content of 7.5 mol % and a minimum milk-solids content of 25.0 mol %. Evaporated skimmed milk is a Hquid product obtained by the partial removal of water only from skimmed milk. It has a minimum milk-solids content of 20.0 mol %. Sweetened condensed milk is a product obtained by the partial removal of water only from milk with the addition of sugars. It has a minimum milk-fat content of 8.0 mol % and a minimum milk-solids content of 28.0 mol %. Skimmed sweetened condensed milk is a product obtained by the partial removal of water only from skimmed milk with the addition of sugars. It has a minimum milk-solids content of 24.0 mol %. AH may contain food additives (qv) as stabilizers, in maximum amounts, including sodium, potassium, and calcium salts of hydrochloric acid at 2000 mg/kg singly citric acid, carbonic acid, orthophosphoric acid, and polyphosphoric acid at 3000 mg/kg in combination, expressed as anhydrous substances and in the evaporated milk carrageenin may be added at 150 mg/kg. 

The large value for the hemiformal formation constant of methanol and its low molecular weight explains the high efficiency of methanol in stabilizing formalin solutions. Phenol, on the other hand, is inefficient, and phenol hemiformals are only formed by careful removal of water (17). 

Nylon-6,6 is made by the polycondensation of hexamethylene diamonium adipate salt with removal of water. 

Nylon-11. This nylon is produced from 11-aminoundecanoic acid, which is derived from castor oil. The acid is polymerized by heating to 200°C with continuous removal of water. Catalysts such as phosphoric acid are frequentiy used. There is no appreciable amount of unreacted monomer left in the product. 

The polyestetification reaction is reversible because it is induenced by the presence of condensate water in equiUbrium with the reactants and the polymer. The removal of water in the latter part of the reaction process is essential for the development of optimum molecular weight, on which the ultimate stmctural performance depends. 

The polyestetification reaction is carried out in the presence of an inert gas, such as nitrogen or carbon dioxide, to prevent discoloration. Usually, the sparge rate of the inert gas is increased in the final stages of polyestetification to assist the removal of residual water. Although the removal of water can be facihtated by processing under vacuum, this is rarely used on a commercial scale. 

When low boiling ingredients such as ethylene glycol are used, a special provision in the form of a partial condenser is needed to return them to the reactor. Otherwise, not only is the balance of the reactants upset and the raw material cost of the resin increased, but also they become part of the pollutant in the waste water and incur additional water treatment costs. Usually, a vertical reflux condenser or a packed column is used as the partial condenser, which is installed between the reactor and the overhead total condenser, as shown in Figure 3. The temperature in the partial condenser is monitored and maintained to effect a fractionation between water, which is to pass through, and the glycol or other materials, which are to be condensed and returned to the reactor. If the fractionation is poor, and water vapor is also condensed and returned, the reaction is retarded and there is a loss of productivity. As the reaction proceeds toward completion, water evolution slows down, and most of the glycol has combined into the resin stmcture. The temperature in the partial condenser may then be raised to faciUtate the removal of water vapor. 

Adsorbent Applications. One of the earliest uses for activated alumina was removal of water vapor from gases and this remains an... 

Nitrile Process. Fatty nitriles are readily prepared via batch, Hquid-phase, or continuous gas-phase processes from fatty acids and ammonia. Nitrile formation is carried out at an elevated temperature (usually >250° C) with catalyst. An ammonia soap which initially forms, readily dehydrates at temperatures above 150°C to form an amide. In the presence of catalyst, zinc (ZnO) for batch and bauxite for continuous processes, and temperatures >250° C, dehydration of the amide occurs to produce nitrile. Removal of water drives the reaction to completion. 

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