Solubility of organic acids

The solubility of organic acids in water is due to the hydrophilic 0x0- and hydroxo-groups of the acid that form hydrogen bonds with water molecules. If the hydrogen ion of the acid is solvated by a donor organic base, B, in the... 

Figure 3. Solubility of organic acid (pKa = 4.5) and base (pKa = 10), illustrating the effect of solubility product, [M+] [X ], where M+ and X are the counterions of the acid and base respectively.

It is frequently advisable in the routine examination of an ester, and before any derivatives are considered, to determine the saponification equivalent of the ester. In order to ensure that complete hydrolysis takes place in a comparatively short time, the quantitative saponi fication is conducted with a standardised alcoholic solution of caustic alkali—preferably potassium hydroxide since the potassium salts of organic acids are usuaUy more soluble than the sodium salts. A knowledge of the b.p. and the saponification equivalent of the unknown ester would provide the basis for a fairly accurate approximation of the size of the ester molecule. It must, however, be borne in mind that certain structures may effect the values of the equivalent thus aliphatic halo genated esters may consume alkali because of hydrolysis of part of the halogen during the determination, nitro esters may be reduced by the alkaline hydrolysis medium, etc. 

Reaction with alcoholic silver nitrate. To carry out the test, treat 2 ml. of a 2 per cent, solution of silver nitrate in alcohol with 1 or 2 drops (or 0 05 g.) of the compound. If no appreciable precipitate appears at the laboratory temperature, heat on a boiling water bath for several minutes. Some organic acids give insoluble silver salts, hence it is advisable to add 1 drop of dilute (5 per cent.) nitric acid at the conclusion of the test most silver salts of organic acids are soluble in nitric acid. 

Polonium is readily dissolved in dilute acids, but is only slightly soluble in alkali. Polonium slats of organic acids char rapidly halide amines are reduced to the metal. 

TABLE 5.2 Solubilities of Inorganic Compounds and Metal Salts of Organic Acids in Water at Various Temperatures... 

Other simple nickel salts of organic acids include the oxalate [20543-06-0] oleate [68538-38-5], and stearate [2223-95-2]. The latter two have been used as oil-soluble nickel forms in the dyeing of synthetic polyolefin fibers (see Driers and metallic soaps). Nickel oxalate has been used as a catalyst intermediate (59). 

Table 7. Solubility of Boric Acid, Borax Decahydrate, and Borax Pentahydrate in Organic Solvents...

Salts of Organic Acids. Calcium salts of organic acids may be prepared by reaction of the carbonate hydroxide and the organic acid (9). Calcium lactate [814-80-2] is an iatermediate ia the purification of lactic acid from fermentation of molasses. Calcium soaps, soaps of fatty acids, ate soluble ia hydrocarbons, and are useful as waterproofing agents and constituents of greases (9). 

Table 8. Solubilities of Alkanoic Acids in Water and Organic Solvents...

The solubility of phosphoric acid esters in water and organic solvents is controlled by the chain length of the alkyl groups and the ethylene oxide con-... 

A carboxylic acid can be represented as R — CO2 H. Many different carboxylic acids participate in organic chemistry and biochemishy. Although carboxylic acids react in many different ways, breaking the C—OH bond is the only reaction that is important in polymer formation. A carboxylic acid is highly polar and can give up H to form a carboxylate anion, R — CO2. The carboxyl group (— CO2 H) also forms hydrogen bonds readily. These properties enhance the solubility of carboxylic acids in water, a particularly important property for biochemical macromolecules. 

Especially in dicotyledonous plant species such as tomato, chickpea, and white lupin (82,111), with a high cation/anion uptake ratio, PEPC-mediated biosynthesis of carboxylates may also be linked to excessive net uptake of cations due to inhibition of uptake and assimilation of nitrate under P-deficient conditions (Fig. 5) (17,111,115). Excess uptake of cations is balanced by enhanced net re-lea,se of protons (82,111,116), provided by increased bio.synthesis of organic acids via PEPC as a constituent of the intracellular pH-stat mechanism (117). In these plants, P deficiency-mediated proton extrusion leads to rhizosphere acidification, which can contribute to the. solubilization of acid soluble Ca phosphates in calcareous soils (Fig. 5) (34,118,119). In some species (e.g., chickpea, white lupin, oil-seed rape, buckwheat), the enhanced net release of protons is associated with increased exudation of carboxylates, whereas in tomato, carboxylate exudation was negligible despite intense proton extrusion (82,120). 

Aliphatic compounds Several water-soluble simple organic acids and alcohols are cannon plant and soil constituents. They include methanol, ethanol, n-propanol and butanol (40), and crotonic, oxalic, formic, butyric, lactic, acetic and succinic acids (41, 42), all of which inhibit seed germination or plant growth. Under aerobic conditions, however, aliphalic acids are metabolized in the soil and therefore, should not be considered a major source of allelopathic activity (40). 

Metal ions in aqueous solution exist as complexes with water. The solubility of organic compounds in water depends primarily on their polarity and their ability to form hydrogen bonds with water. Organic compounds with a large part of polar components such as acetic acid, dissolve in water without limit. In such cases, the polar part dominates. By contrast, soaps and detergents have a polar end attached to a relatively large nonpolar part of the molecule. They have limited solubility and the molecules tend to coalesce to form micelles. 

The complexity of wine composition is a central reason for the vast variety of wines in the marketplace. In addition to water and ethanol, the major components, a variety of organic acids as well as metal ions from minerals in the skin of the grape are present. Initially, all of these substances remain dissolved in the bottled grape juice. As the fermentation process occurs, the increasing alcohol concentration in the wine alters the solubility of particular combinations of acid and metal ions. Unable to remain in solution, the insoluble substances settle as crystals. Since the process of red-wine making involves extended contact of the grape juice with the skins of the grapes (where the minerals are concentrated), wine crystals are more common in red wines than in white wines. 

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