1911 Encyclopædia Britannica/Acid
|←Achromatism||1911 Encyclopædia Britannica, Volume 1
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ACID (from the Lat. root ac-, sharp; acere, to be sour), the name loosely applied to any sour substance; in chemistry it has a more precise meaning, denoting a substance containing hydrogen which may be replaced by metals with the formation of salts. An acid may therefore be regarded as a salt of hydrogen. Of the general characters of acids we may here notice that they dissolve alkaline substances, certain metals, &c., neutralize alkalies and redden many blue and violet vegetable colouring matters.
The ancients probably possessed little knowledge indeed of acids. Vinegar (or impure acetic acid), which is produced when wine is allowed to stand, was known to both the Greeks and Romans, who considered it to be typical of acid substances; this is philologically illustrated by the words oxus, acidus, sour, and oxos, acetus, vinegar. Other acids became known during the alchemistic period; and the first attempt at a generalized conception of these substances was made by Paracelsus, who supposed them to contain a principle which conferred the properties of sourness and solubility. Somewhat similar views were promoted by Becher, who named the principle acidum primogenium, and held that it was composed of the Paracelsian elements ``earth and ``water. At about the same time Boyle investigated several acids; he established their general reddening of litmus, their solvent power of metals and basic substances, and the production of neutral bodies, or salts, with alkalies. Theoretical conceptions were revived by Stahl, who held that acids were the fundamentals of all salts, and the erroneous idea that sulphuric acid was the principle of all acids.
The phlogistic theory of the processes of calcination and combustion necessitated the view that many acids, such as those produced by combustion, e.g. sulphurous, phosphoric, carbonic, &c., should be regarded as elementary substances. This principle more or less prevailed until it was overthrown by Lavoisier's doctrine that oxygen was the acid-producing element; Lavoisier being led to this conclusion by the almost general observation that acids were produced when non-metallic elements were burnt. The existence of acids not containing oxygen was, in itself, sufficient to overthrow this idea, but, although Berthollet had shown, in 1789, that sulphuretted hydrogen (or hydrosulphuric acid) contained no oxygen, Lavoisier's theory held its own until the researches of Davy, Gay-Lussac and Thenard on hydrochloric acid and chlorine, and of Gay-Lussac on hydrocyanic acid, established beyond all cavil that oxygen was not essential to acidic properties.
In the Lavoisierian nomenclature acids were regarded as binary oxygenated compounds, the associated water being relegated to the position of a mere solvent. Somewhat similar views were held by Berzelius, when developing his dualistic conception of the composition of substances. In later years Berzelius renounced the ``oxygen acid theory, but not before Davy, and, almost simultaneously, Dulong, had submitted that hydrogen and not oxygen was the acidifying principle. Opposition to the ``hydrogen-acid theory centred mainly about the hypothetical radicals which it postulated; moreover, the electrochemical theory of Berzelius exerted a stultifying influence on the correct views of Davy and Dulong. In Berzelius' system potassium sulphate is to be regarded as K2O+.SO3-; electrolysis should simply effect the disruption of the positive and negative components, potash passing with the current, and sulphuric acid against the current. Experiment showed, however, that instead of only potash appearing at the negative electrode, hydrogen is also liberated; this is inexplicable by Berzelius's theory, but readily explained by the ``hydrogen-acid theory. By this theory potassium is liberated at the negative electrode and combines immediately with water to form potash and hydrogen.
Further and stronger support was given when J. Liebig promoted his doctrine of polybasic acids. Dalton's idea that elements preferentially combined in equiatomic proportions had as an immediate inference that metallic oxides contained one atom of the metal to one atom of oxygen, and a simple expansion of this conception was that one atom of oxide combined with one atom of acid to form one atom of a neutral salt. This view, which was specially supported by Gay-Lussac and Leopold Gmelin and accepted by Berzelius, necessitated that all acids were monobasic. The untenability of this theory was proved by Thomas Graham's investigation of the phosphoric acids; for he then showed that the ortho- (ordinary), pyro- and metaphosphoric acids contained respectively 3, 2 and 1 molecules of ``basic water (which were replaceable by metallic oxides) and one molecule of phosphoric oxide, P2 O5. Graham's work was developed by Liebig, who called into service many organic acids—citric, tartaric, cyanuric, comenic and meconic—and showed that these resembled phosphoric acid; and he established as the criterion of polybasicity the existence of compound salts with different metallic oxides. In formulating these facts Liebig at first retained the dualistic conception of the structure of acids; but he shortly afterwards perceived that this view lacked generality since the halogen acids, which contained no oxygen but yet formed salts exactly similar in properties to those containing oxygen, could not be so regarded. This and other reasons led to his rejection of the dualistic hypothesis and the adoption, on the ground of probability, and much more from convenience, of the tenet that ``acids are particular compounds of hydrogen, in which the latter can be replaced by metals; while, on the constitution of salts, he held that ``neutral salts are those compounds of the same class in which the hydrogen is replaced by its equivalent in metal. The substances which we at present term anhydrous acids (acid oxides) only become, for the most part, capable of forming salts with metallic oxides after the addition of water, or they are compounds which decompose these oxides at somewhat high temperatures.
The hydrogen theory and the doctrine of polybasicity as enunciated by Liebig is the fundamental characteristic of the modern theory. A polybasic acid contains more than one atom of hydrogen which is replaceable by metals; moreover, in such an acid the replacement may be entire with the formation of normal salts, partial with the formation of acid salts, or by two or more different metals with the formation of compound salts (see SALTS). These facts may be illustrated with the aid of orthophosphoric acid, which is tribasic:—
Acid. Normal salt. Acid salts. H3PO4 Ag3PO4 Na2HPO4; NaH2PO4 Phosphoric Silver phosphate. Acid sodium acid. phosphates. Compound salts. Mg(NH4)PO4; Na(NH4)HPO4. Magnesium ammonium Microcosmic phosphate; salt. Reference should be made to the articles CHEMICAL ACTION, THERMOCHEMISTRY and SOLUTIONS, for the theory of the strength or avidity of acids.
Organic Acids.—Organic acids are characterized by the presence of the monovalent group—CO.OH, termed the carboxyl group, in which the hydrogen atom is replaceable by metals with the formation of salts, and by alkyl radicals with the formation of esters. The basicity of an organic acid, as above defined, is determined by the number of carboxyl groups present. Oxy-acids are carboxyllc acids which also contain a hydroxyl group; similarly we may have aldehyde-acids, ketone-acids, &c. Since the more important acids are treated under their own headings, or under substances closely allied to them, we shall here confine ourselves to general relations.
Classification.—It is convenient to distinguish between aliphatic and aromatic acids; the first named being derived from open-chain hydrocarbons, the second from ringed hydrocarbon nuclei. Aliphatic monobasic acids are further divided according to the nature of the parent hydrocarbon. Methane and its homologues give origin to the ``paraffin or ``fatty series of the general formula Cn H2n+1COOH, ethylene gives origin to the acrylic acid series, CnH2n-1COOH, and soon. Dibasic acids of the paraffin series of hydrocarbons have the general formula CnH2(COOH)2n; malonic and succinic acids are important members. The isomerism which occurs as soon as the molecule contains a few carbon atoms renders any classification based on empirical molecular formulae somewhat ineffective; on the other hand, a scheme based on molecular structure would involve more detail than it is here possible to give. For further information, the reader is referred to any standard work on organic chemistry. A list of the acids present in fats and oils is given in the article OILS.
Syntheses of Organic Acids.—The simplest syntheses are undoubtedly those in which a carboxyl group is obtained directly from the oxides of carbon, carbon dioxide and carbon monoxide. The simplest of all include: (1) the synthesis of sodium oxalate by passing carbon dioxide over metallic sodium heated to 350 deg. -360 deg. ; (2) the synthesis of potassium formate from moist carbon dioxide and potassium, potassium carbonate being obtained simultaneously; (3) the synthesis of potassium acetate and propionate from carbon dioxide and sodium methide and sodium ethide; (4) the synthesis of aromatic acids by the interaction of carbon dioxide, sodium and a bromine substitution derivative; and (5) the synthesis of aromatic oxy-acids by the interaction of carbon dioxide and sodium phenolates (see SALICYLIC ACID). (Carbon monoxide takes part in the syntheses of sodium formate from sodium hydrate, or soda lime (at 200 deg. -220 deg. ), and of sodium acetate and propionate from sodium methylate and sodium ethylate at 160 deg. —200 deg. . Other reactions which introduce carboxyl groups into aromatic groups ave: the action of carbonyl chloride on aromatic hydrocarbons in the presence of aluminium chloride, acid-chlorides being formed which are readily decomposed by water to give the acid; the action of urea chloride Cl.CO.NH2, cyanuric acid (CONH)3, nascent cyanic acid, or carbanile on hydrocarbons in the presence of aluminium chloride, acid-amides being obtained which are readily decomposed to give the acid. An important nucleus-synthetic reaction is the saponification of nitriles, which may be obtained by the interaction of potassium cyanide with a halogen substitution derivative or a sulphonic acid.
Acids frequently result as oxidation products, being almost invariably formed in all cases of energetic oxidation. There are certain reactions, however, in which oxidation can be successfully applied to the synthesis of acids. Thus primary alcohols and aldehydes, both of the aliphatic and aromatic series, readily yield on oxidation acids containing the same number of carbon atoms. These reactions may be shown thus:-
R.CH2OH -> R.CHO -> R.CO.OH. In the case of aromatic aldehydes, acids are also obtained by means of ``Cannizzaro's reaction (see BENZALDEHYDE). An important oxidation synthesis of aromatic acids is from hydrocarbons with aliphatic side chains; thus toluene, or methylbenzene, yields benzoic acid, the xylenes, or dimethyl-benzene, yield methyl-benzoic acids and phthalic acids. Ketones, secondary alcohols and tertiary alcohols yield a mixture of acids on oxidation. We may also notice the disruption of unsaturated acids at the double linkage into a mixture of two acids, when fused with potash.
In the preceding instances the carboxyl group has been synthesized or introduced into a molecule; we have now to consider syntheses from substances already containing carboxyl groups. Of foremost importance are the reactions termed the malonic acid and the aceto-acetic ester syntheses; these are discussed under their own headings. The electrosyntheses call for mention here. It is apparent that metallic salts of organic acids would, in aqueous solution, be ionized, the positive ion being the metal, and the negative ion the acid residue. Esters, however, are not ionized. It is therefore apparent that a mixed salt and ester, for example KO2C.CH2.CH2.CO2C2H5, would give only two ions, viz. potassium and the rest of the molecule. If a solution of potassium acetate be electrolysed the products are ethane, carbon dioxide, potash and hydrogen; in a similar manner, normal potassium succinate gives ethylene, carbon dioxide, potash and hydrogen; these reactions may be represented:-
CH3.CO2 K CH3 CO2 K* CH2.CO K CH2 CO2 K. | -> | + + | | ->|| + + CH3.CO2 K CH3 CO2 K* CH2.CO K CH2 CO2 K. By electrolysing a solution of potassium ethyl succinate, KO2C.(CH2)2CO2C2H5, the KO2C. groups are split off and the two residues .(CH2)2CO2C2H5 combine to form the ester (CH2)4(CO2C2H5)2. In the same way, by electrolysing a mixture of a metallic salt and an ester, other nuclei may be condensed; thus potassium acetate and potassium ethyl succinate yield CH3.CH2.CH2.CO2C2H5.
Reactions.—Organic acids yield metallic salts with bases, and ethereal salts or esters (q.v.), R.CO.OR', with alcohols. Phosphorus chlorides give acid chlorides, R.CO.Cl, the hydroxyl group being replaced by chlorine, and acid anhydrides, (R.CO)2O, a molecule of water being split off between two carboxyl groups. The ammonium salts when heated lose one mobecule of water and are converted into acid-amides, R.CO.NH2, which by further dehydration yield nitriles, R.CN. The calcium salts distilled with calcium formate yield aldehydes (q.v.); distilled with soda-lime, ketones (q.v.) result.