Solubility of carboxylic acids

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. 

Solubility in water Carboxylic acids with low molecular masses are very soluble in water. The first four simple carboxylic acids (methanoic acid, ethanoic acid, propanoic acid, and butanoic acid) are miscible with water. Like alcohols, ketones, and aldehydes, the solubility of carboxylic acids in water decreases as the number of carbon atoms increases. 

The solubility of carboxylic acid extractants in aqueous solution is a function of temperature, pH, and salt concentration. Most of the information on the solubility of these reagents is limited to their solubility in water, and not much practical information is available on actual leach liquors and similar solutions. 

Compare the water solubilities of carboxylic acids with their sodium carboxylate salts. 

A consequence of the water solubility of carboxylic acid salts is that we can convert water-insoluble carboxylic acids to water soluble alkali metal or ammonium salts and then extract them into aqueous solution. In turn, we can transform the salt into the free carboxylic acid by adding HCl, H2SO4, or some other strong acid. These reactions allow us to separate water-insoluble carboxylic acids from water-insoluble neutral compounds. 

In aqueous solution intermolecular association between carboxylic acid molecules IS replaced by hydrogen bonding to water The solubility properties of carboxylic acids are similar to those of alcohols Carboxylic acids of four carbon atoms or fewer are mis cible with water m all proportions... 

Metal carboxylates are ionic and when the molecular weight isn t too high the sodium and potassium salts of carboxylic acids are soluble m water Carboxylic acids therefore may be extracted from ether solutions into aqueous sodium or potassium hydroxide... 

The solubility behavior of salts of carboxylic acids having 12—18 carbons is unusual and can be illustrated by considering sodium stearate (sodium octadecanoate) As seen by the structural formula of its sodium salt... 

Salt Formation. Salt-forming reactions of adipic acid are those typical of carboxylic acids. Alkali metal salts and ammonium salts are water soluble alkaline earth metal salts have limited solubiUty (see Table 5). Salt formation with amines and diamines is discussed in the next section. 

The transformation of the hydrophobic periphery composed of bromo substituents into a hydrophilic wrapping of carboxylic acid functions was achieved by reacting 31 with (i) n-butyllithium and (ii) carbon dioxide. The polymer-analogous transformation provides water soluble, amphiphilic derivatives of 31 which constitute useful covalently bonded unimolecular models for micellar structures. 

FIGURE 15.1 Scheme showing PLC group fractionation of soluble organic matter into fractions of aliphatic hydrocarbons, aromatic compounds with application of urea clathra-tion, and methylation of carboxylic acids in polar fractions based on experimental data given in Reference 36 to Reference 52, Reference 77 to Reference 81, and Reference 88 to Reference 89. 

FIGURE 15.3 PLC separation of carboxylic acids from soluble organic matter with the use of carboxylic acids esterification based on experimental data given in Reference 36, Reference 67 to Reference 69, and Reference 102 to Reference 104. 

An enantiotropically related pair of polymorphs was obtained for p-aminoben-zoic acid, with the system being characterized by a transition temperature of 25 °C [31]. The a-form was obtained as fibrous needles, while the /M orm was obtained in the form of prisms. The solubilities of the two forms are almost the same, indicating the existence of comparable values for AG, which in turn explained the slow transformation of the a-form into the [>-form. Nucleation of the a-form was found to be favored, which is reasonable considering that the structural motif of the a-form consists of carboxylic acid dimmers that would be expected to be stable association species in solution. 

In this paper we disclose the syngas homologation of carboxylic acids via ruthenium homogeneous catalysis. This novel homologation reaction involves treatment of lower MW carboxylic acids with synthesis gas (C0/H2) in the presence of soluble ruthenium species, e.g., Ru02, Ru3(C0)12, H4Ru4(C0)12, coupled with iodide-containing promoters such as HI or an alkyl iodide (1). 

The workhorse of the VLSI industry today is a composite novolac-diazonaphthoquinone photoresist that evolved from similar materials developed for the manufacture of photoplates used in the printing industry in the early 1900 s (23). The novolac matrix resin is a condensation polymer of a substituted phenol and formaldehyde that is rendered insoluble in aqueous base through addition of 10-20 wt% of a diazonaphthoquinone photoactive dissolution inhibitor (PAC). Upon irradiation, the PAC undergoes a Wolff rearrangement followed by hydrolysis to afford a base-soluble indene carboxylic acid. This reaction renders the exposed regions of the composite films soluble in aqueous base, and allows image formation. A schematic representation of the chemistry of this solution inhibition resist is shown in Figure 6. 

As with fullerenes, carbon nanotubes are also hydrophobic and must be made soluble for suspension in aqueous media. Nanotubes are commonly functionalized to make them water soluble although they can also be non-covalently wrapped with polymers, polysaccharides, surfactants, and DNA to aid in solubilization (Casey et al., 2005 Kam et al., 2005 Sinani et al., 2005 Torti et al., 2007). Functionalization usually begins by formation of carboxylic acid groups on the exterior of the nanotubes by oxidative treatments such as sonication in acids, followed by secondary chemical reactions to attach functional molecules to the carboxyl groups. For example, polyethylene glycol has been attached to SWNT to aid in solubility (Zhao et al., 2005). DNA has also been added onto SWNT for efficient delivery into cells (Kam et al., 2005). 

Ruthenium complexes B are stable in the presence of alcohols, amines, or water, even at 60 °C. Olefin metathesis can be realized even in water as solvent, either using ruthenium carbene complexes with water-soluble phosphine ligands [815], or in emulsions. These complexes are also stable in air [584]. No olefination of aldehydes, ketones, or derivatives of carboxylic acids has been observed [582]. During catalysis of olefin metathesis replacement of one phosphine ligand by an olefin can occur [598,809]. 

Khan, L, Brimblecombe, P., and Clegg, S.L. Solubilities of p3mrvic acid and the lower (Ci-Cg) carboxylic acids. Experimental determination of equilibrium vapour pressures above pure aqueous and salt solutions, J. Atmos. Chem., 22(3) 285-302,1995. 

Th effect of pH on the rate of hydrogenation of water-soluble unsaturated carboxylic acids and alcohols catalyzed by rhodium complexes with PNS [24], PTA [29], or MePTA r [32] phosphine ligands can be similarly explained by the formation of monohydride complexes, [RhHPJ, facilitated with increasing basicity ofthe solvent. 

Soluble loss of a reagent (extractant, modifier, or diluent) from the solvent phase is an inherent part of the solvent extraction process, since all organic compounds are soluble, to some extent, in water. The conditions prevailing in the system can also promote solubility, which can be a particular problem if the composition and properties of the aqueous phase are inflexible. For example, the solubility of alkylphosphoric acid and carboxylic acid extractants is dependent on temperature, pH, and salt concentration in the aqueous phase. 

Under conditions of low salt concentration in the aqueous phase, and above a pH 6, the solubility of these acids is economically prohibitive. Even at lower pH values, the solubility could be considered high from the point of view of pollution. For a C7-C9 fraction of aliphatic mono-carboxylic acids, the solubility in water as a function of concentration in the solvent phase is shown in Fig. 7.9 [14]. Here again, complete information is unavailable, since no reference is made to pH or salt concentration. Presumably, the pH is in the range 4-6. However, it is interesting to note the rapid increase in solubility in the aqueous phase as the extractant concentration is increased. This effect also applies to other extractants. 

Physical properties of carboxylic acids and derivatives include solubility, melting point, boiling point, and a few other characteristics. In this section we examine each class and discuss the most important physical properties. (In the upcoming section Considering the Acidity of Carboxylic Acids, we discuss the most important chemical property of Ccirboxylic acids — acidity.)... 

Copolymer particles can also be prepared from HIPEs [159]. Thus, a HIPE dispersed phase consisting of styrene and methacrylic acid was polymerised to give copolymers. The surface concentration of carboxylic acid groups increased linearly with concentration of methacrylic acid in the feed. The small amount of water present in the concentrated emulsion, relative to conventional emulsion polymerisation, reduces the loss of methacrylic acid, which is highly water-soluble. 

Problem 16.3 Account for the following physical properties of carboxylic acids, (a) Only RCOOH s with five or fewer C s are soluble in water, but many with six or more C s dissolve in alcohols. (f>) Acetic acid in the vapor state has a molecular weight of 120 not 60. (c) Their boiling and melting points are higher than those of corresponding alcohols. M... 

Carboxylic acids are more acidic than alcohols and acetylene. Strong aqueous bases can completely deprotonate carboxylic acids, and salts of carboxylic acids are formed. Strong aqueous mineral acids readily convert the salt back to the carboxylic acids. Saits are soluble in water but insoluble in nonpolar solvents, e.g. hexane or dichloromethane. 

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