Extraction is one of the most frequently used separation techniques in organic chemistry.

An extraction essentially separates water-insoluble organic compounds from water-soluble organic and inorganic compounds. The isolated material is a crude product that usually requires further purification by recrystallization or another method. One almost always performs an extraction at the end of a chemical reaction as a way to separate the organic product(s) formed in the reaction from everything else in the reaction mixture. The typical extraction is also known as a liquid-liquid extraction, and as such involves a mixture of two immiscible liquidstwo solvents that do not dissolve in one another. The physical principle operating here is one we have seen before: "like dissolves like." In other words, a substance will dissolve best in the solvent with the most similar polarity characteristics to its own. As a general rule, water will dissolve salts, including organic ions, and substances with strong hydrogen bonding characteristics and very little hydrocarbon structure; whereas, organic solvents will dissolve neutral organic substances with weak intermolecular forces, i.e. compounds containing significant hydrocarbon structure and few hydrogen bonding interactions relative to hydrocarbon character. In acid base extraction, the most important difference is that the aqueous solvent- water, is not neutral; it is either acidic or basic. Most carboxylic acids are insoluble in water (the exceptions are low molecular weight carboxylic acids), because they are neutral and contain a fair amount of hydrocarbon character relative to hydrogen bonding of the carboxylic acid functional group. However, when base (hydroxide, carbonate, or bicarbonate) removes a proton from the carboxylic acid, a carboxylate salt is produced, which is an organic ion, and like any salt it will dissolve more readily in aqueous solvent than organic solvent. So, now when the two layers are separated in the usual fashion, the aqueous layer, not the organic layer, contains one of the compounds of interest. The carboxylate ion is then restored to its original carboxylic acid form by another acid base reaction as shown below. RCOO- Na+ (aq) + HC1 (aq) -> RCOOH + NaCl (aq) water-soluble water-insoluble Since the carboxylic acid becomes neutral again, it also becomes insoluble in water and precipitates from solution. Suction filtration can then be used to recover the pure carboxylic acid crystals. A similar reaction occurs with phenols, except that since they are less acidic than carboxylic acids, they can only be deprotonated with the stronger hydroxide bases and not the carbonate and bicarbonate bases. This can be advantageous when separating phenols from carboxylic acids. Note that an acid/base reaction does not occur with ordinary alcohols; they are not sufficiently acidic. ArOH + NaOH (aq) - ArO Na+ (aq) + H2O Compounds with an amine functional group can be converted into the amine hydrochloride by treatment with aqueous HC1, and in an analogous manner to the carboxylic acids, are converted from an organic soluble substance to an organic insoluble salt that becomes soluble in water as shown in the acid/base reaction below: RNH2 + HC1 (aq) -> RNH3+ Cl- (aq) water insoluble water soluble

Obviously, the difference from the carboxylic acid case is that addition of acid not base achieves salt formation and the salt is a cation instead of an anion. Either way it is a charge that causes it to be soluble in water. The aqueous extract containing the amine hydrochloride is drained into an Erlenmeyer flask, and is returned to the neutral amine form by treatment with sodium hydroxide. Since this acid/base reaction causes the organic substance to go from the water-soluble salt form into the water-insoluble neutral form, it precipitates from solution. The reaction is shown below. Once again, isolation is accomplished by a suction filtration. In summary, in a standard extraction carboxylic acids, amines, phenols and other organic compounds would all dissolve in the organic extract; however, when an acid/base extraction is performed, one can selectively remove the phenol with sodium hydroxide, the carboxylic acid with bicarbonate or sodium hydroxide, and the amine with HC1. All other organic substances remain in the organic extract. Incidentally, all inorganic substances are removed in the aqueous extract. This powerful and simple technique for isolating certain organic compounds.

BACKGROUND INFORMATION Extraction is a process that selectively dissolves one or more of the mixture compounds into an appropriate solvent. The solution of these dissolved compounds is often referred to as the extract. A compound can be separated from impurities in a solution by extracting the compound from the original or first solvent into a second solvent. The compound must be more soluble in the second solvent than in the first solvent, and the impurities must be insoluble in the second solvent. Also, to effect the extraction, the two solvents selected must be immiscible, or not soluble in one another, so that they produce two separate solvent layers. After dissolving the mixture in the first solvent, the solution is added to the second solvent. The two layers are vigorously mixed to maximize the surface area between them. The fundamental theory behind this technique is that salts, which are ionic, tend to be water-soluble while neutral molecules tend not to be. The addition of an acid to a mixture of an organic base and acid will result in the acid remaining uncharged, while the base will be protonated. If the organic acid, such as a carboxylic acid, is sufficiently strong, its self-ionization can be suppressed by the added acid. Conversely, the addition of a base to a mixture of an organic acid and base will result in the base remaining uncharged, while the acid is deprotonated to give the corresponding salt. Once again, the self-ionization of a strong base is suppressed by the added base. The acid-base extraction procedure can also be used to separate very weak acids from stronger acids and very weak bases from stronger bases as long as the difference of theirpKa (or pKb) constants is large enough. Examples are:

Very weak acids with phenolic OH groups Very weak bases from stronger