Monobasic

Hypophosphorous acid, H3PO2, H2P(0)0H. A monobasic acid. Ba(H2P02)2 is formed when white phosphorus is dissolved in Ba(OH)2 solution. H3PO2 and its salts are strong reducing agents. 

By oxidation with permanganate it forms pinonic acid, C,oH,<503, a monobasic acid derived from cyclobutane. With strong sulphuric acid it forms a mixture of limonene, dipentene, terpinolene, terpinene, camphene and p-cymene. Hydrogen chloride reacts with turpentine oil to give CioHijCl, bomyl chloride, artificial camphor . 

Ionisations 2, 3 and 5 are complete ionisations so that in water HCI and HNO3 are completely ionised and H2SO4 is completely ionised as a monobasic acid. Since this is so, all these acids in water really exist as the solvated proton known as the hydrogen ion, and as far as their acid properties are concerned they are the same conjugate acid species (with different conjugate bases). Such acids are termed strong acids or more correctly strong acids in water. (In ethanol as solvent, equilibria such as 1 would be the result for all the acids quoted above.) Ionisations 4 and 6 do not proceed to completion... 

Boron trioxide is not particularly soluble in water but it slowly dissolves to form both dioxo(HB02)(meta) and trioxo(H3B03) (ortho) boric acids. It is a dimorphous oxide and exists as either a glassy or a crystalline solid. Boron trioxide is an acidic oxide and combines with metal oxides and hydroxides to form borates, some of which have characteristic colours—a fact utilised in analysis as the "borax bead test , cf alumina p. 150. Boric acid. H3BO3. properly called trioxoboric acid, may be prepared by adding excess hydrochloric or sulphuric acid to a hot saturated solution of borax, sodium heptaoxotetraborate, Na2B407, when the only moderately soluble boric acid separates as white flaky crystals on cooling. Boric acid is a very weak monobasic acid it is, in fact, a Lewis acid since its acidity is due to an initial acceptance of a lone pair of electrons from water rather than direct proton donation as in the case of Lowry-Bronsted acids, i.e. 

In each case the P—O bonds have some multiple character. Phosphinic acid is a moderately strong monobasic acid. On heating the acid and its salts they disproportionate evolving phosphine ... 

Hydrochloric acid is a strong monobasic acid, dissolving metals to form salt and evolving hydrogen. The reaction may be slow if the chloride formed is insoluble (for example lead and silver are attacked very slowly). The rate of attack on a metal also depends on concentration thus aluminium is attacked most rapidly by 9 M hydrochloric acid, while with other metals such as zinc or iron, more dilute acid is best. 

Although some dibasic acids, e.g, succinic acid and phthalic acid, readily lose water on heating with the formation of cyclic anhydrides, most monobasic... 

Reduction of esters of monobasic acids with sodium and absolute ethyl alcohol (method of Bouveault and Blanc), for example ... 

By passing the vapour of a monobasic acid through a tube containing manganous oxide deposited on pumice and heated to 300-350°, the metallic ... 

If a mixture of monobasic acids is employed, the mixed ketone may be pre- ... 

SATURATED ALIPHATIC MONOBASIC ACIDS Saturated aliphatic acids may be prepared —... 

Place 1 0 g. of the monobasic acid and 2 g. of aniline or p-toluidine in a dry test-tube, attach a short air condenser and heat the mixture in an oil bath at 140-160° for 2 hours do not reflux too vigorously an acid that boils below this temperature range and only allow steam to escape from the top of the condenser. For a sodium salt, use the proportions of 1 g. of salt to 1 5 g. of the base. If the acid is dibasic, employ double the quantity of amine and a reaction temperature of 180-200° incidentally, the procedure is recommended for dibasic acids since the latter frequently give anhydrides with thionyl chloride. Powder the cold reaction mixture, triturate it with 20-30 ml. of 10 per cent, hydrochloric acid, and recrystallise from dilute alcohol. 

It is important that the solution of the sodium salt be faintly acid in order that the formation of coloured by-products in the subsequent reaction may be prevented. If the molecular weight of the monobasic acid is known, it is desirable to employ a slight excess of the sodium salt, since excess of the latter is more easily removed than the unchanged reagent. 

The benzene - alcohol method is useful for the esterification of valuable monobasic acids, but the b.p. of the ester must be at least 50° higher than that of benzene, for example ... 

The acid, if monobasic, can usually be distilled directly from the reaction mixture. If this procedure is not possible, the reaction mixture is poured into excess of crushed ice, and the acid is isolated by ether extraction or by other suitable means. The acid is then characterised (Section 111,85). The addition of hydrochloric acid (as sodium chloride say 5 per cent, of the weight of sulphuric acid) increases the rate of the reaction. 

This reaction is due to the combination of two da hydroxyl groups of the compound with the boric acid to form a much stronger monobasic acid ... 

With aeetie acid, 2 methylbenzimidazole, m.p. 173-174°, is formed indeed the conversion of aliphatie aeids into 2-alkylbenzimidazoles has been proposed as a method for preparing solid derivatives for the identification of monobasic aliphatic acids. 

The catalyst, which may be regarded as complementary to Raney nickel (Section VI,5) is largely used for the hydrogenation of esters (esters of monobasic and of dibasic acids to alcohols and glycols respectively) ... 

When the corresponding monobasic acid has a trivial name, the name of the aldehyde may be formed by changing the ending -ic acid or -oic acid to -aldehyde. Examples are... 

Mass 66 = Monobasic carboxylic acid Masses 77 and 91 = Benzene ring... 

AH the common monobasic (107) and dibasic esters (108) of tetrahydrofurfuryl alcohol have been prepared by conventional techniques the dibasic esters and some of the mono esters are effective as primary or secondary plasticizers for vinyl polymers. Tetrahydrofurfuryl acrylate [2399-48-6] and methacrjiate [2455-24-5] specialty monomers, have been produced by carbonylation (nickel carbonyl and acetylene) of the alcohol (109) as weU as by direct esterification (110—112) and ester interchange (111). 

Other by-products formed are relatively easy to separate, including esters of higher unsaturated monobasic acids (alkyl 3-pentenoate and 3,5-heptadienoate) (5) and esters of multiply-unsaturated dibasic acids, eg, suberates. 

Quality Specifications. Because of the extreme sensitivity of polyamide synthesis to impurities ia the iagredients (eg, for molecular-weight control, dye receptivity), adipic acid is one of the purest materials produced on a large scale. In addition to food-additive and polyamide specifications, other special requirements arise from the variety of other appHcations. Table 8 summarizes the more important specifications. Typical impurities iaclude monobasic acids arising from the air oxidation step ia synthesis, and lower dibasic acids and nitrogenous materials from the nitric acid oxidation step. Trace metals, water, color, and oils round out the usual specification Hsts. 

Monobasic acids are determined by gas chromatographic analysis of the free acids dibasic acids usually are derivatized by one of several methods prior to chromatographing (176,177). Methyl esters are prepared by treatment of the sample with BF.—methanol, H2SO4—methanol, or tetramethylammonium hydroxide. Gas chromatographic analysis of silylation products also has been used extensively. Liquid chromatographic analysis of free acids or of derivatives also has been used (178). More sophisticated hplc methods have been developed recentiy to meet the needs for trace analyses ia the environment, ia biological fluids, and other sources (179,180). Mass spectral identification of both dibasic and monobasic acids usually is done on gas chromatographicaHy resolved derivatives. 

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