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CHOH
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COOH
Tartaric acid was isolated by Scheele in 1769, and its discovery was described in the very first memoir of that distinguished chemist. Another very similar acid, as regards some of its more apparent properties, was afterwards, in 1819, described by John of Berlin, and investigated by Gay-Lussac in 1826; the latter obtained it from the grape juice deposits of the wine manufactory of Kestner at Thann in the Vosges. It was still more fully investigated by Gmelin in 1829, who called it racemic acid (Traubensäure). But it needed the genius of Berzelius to prove that it really had the same composition as tartaric acid, although so different to that acid in some of its properties.
We have here as a matter of fact, the first instance brought to light involving the principle of isomerism, the existence of two or more distinct compounds having the same chemical composition as regards the numbers of atoms of the same elements present, but differing in chemical or physical properties, or both, owing to the different arrangement of those atoms within the molecule. The “isomers” may be chemical or purely physical; the latter involves no alteration of the linking of the atoms, but merely of their disposition in space, and is the kind met with in the case of the tartaric acids.
Biot, so noted for his optical researches, showed afterwards that tartaric and racemic acids behave optically differently in solution, an aqueous solution of the former rotating the plane of polarisation to the right whilst that of racemic acid is optically inactive, not rotating the plane of polarisation at all. That is, if the dark field be produced in the polariscope, by crossing the polarising and analysing Nicol prisms at right angles, tartaric acid solution will restore the light again, and the analyser will have to be rotated to the right in order to reproduce darkness. In the case of tartaric acid, the crystals themselves also rotate the plane of polarisation, the amount being as much as 11°.4 in sodium fight for a plate of the crystal one millimetre thick. On the other hand, neither the solution nor the crystals of racemic acid rotate the plane of polarisation at all.
Pasteur’s discovery, made in the year 1848, consisted in finding that racemic acid is really a molecular compound of two physical “isomers,” namely, of ordinary tartaric acid, which, as we have seen, rotates the plane of polarisation to the right, and of another variety of tartaric acid which rotates the beam of polarised fight to the same extent to the left. The latter and ordinary tartaric acid he therefore distinguished as lævo tartaric acid and dextro-tartaric acid respectively. Pasteur went even further than this, in discovering yet a fourth variety of tartaric acid, which is optically inactive like racemic acid, but which cannot be split up into two optically active antipodes.
Indeed, it has since been shown that there are three varieties of this truly inactive tartaric acid; they are cases of isomerism of the chemical molecule itself, that is, the stereometric arrangement of the atoms in the molecule is different in the three cases. For the molecule of tartaric acid—in common with the molecules of all carbon compounds the solutions of which, or which themselves in the liquid state, rotate the plane of polarisation—possesses an asymmetric carbon atom, an atom of carbon which is linked by its four valency attachments to four different kinds of atoms or radicle groups; indeed, the molecule of tartaric acid contains two such asymmetric carbon atoms, namely, the two in the pair of CHOH groups. For each of these carbon atoms is linked by one attachment to the carbon atom of the outer COOH group, by another to an atom of hydrogen, by a third to the oxygen of the group OH, and by its fourth attachment to the carbon atom of the other group CHOH, which carries the rest of the molecule, that is, this attachment is to the other half-molecule CHOH.COOH. Hence, it is quite obvious that there can be two different dispositions of the atoms in space, one of which would be the mirror-image of the other, while leaving the arrangement of the atoms about the two asymmetric carbon atoms dissimilar and not symmetrical in mirror-image fashion. That is, the two dispositions would render the molecules in the two cases enantiomorphous with respect to each other, and these two would be the arrangements respectively in the two optically active varieties. That this is the correct explanation of the ordinary dextro variety and the lævo variety of tartaric acid can now admit of no doubt.
But if the groups round the two asymmetric carbon atoms are symmetrical in mirror-image fashion, there will be compensation within the molecule itself, and the substance will be optically inactive from internal reasons. This is the explanation of the optically inactive variety which is unresolvable into any components. The different varieties of this inactive form are doubtless due to the different possibilities of arrangement of the atoms in each half, while leaving the two halves round each asymmetric carbon atom symmetrical to each other.