CHOH
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CHOH
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COONa
which is obtained by adding ammonia to the readily procurable salt hydrogen sodium racemate. Sodium ammonium racemate was found by Pasteur to be decomposable into the salts of dextro and lævo tartaric acids, on crystallisation of a solution saturated at 28° C. by inoculation with a crystal of either of those active salts. The solution on cooling being in the state of slight supersaturation, which we now know from the work of Ostwald and of Miers as the metastable condition, corresponding to the interval between the solubility and supersolubility curves (see Fig. 98), if a crystal say of sodium ammonium lævo-tartrate be introduced, this variety crystallises out first and can be separated from the residual dextro-salt, which can then be subsequently crystallised. Moreover, in certain direct crystallisations of sodium ammonium racemate without such specialised inoculation, Pasteur found all the crystals hemimorphic, some right-handed and some left-handed, and he was actually able to isolate from each other crystals of the two varieties. On separate recrystallisation of these two sets of crystals, he found them to retain permanently their right or left-handed character, indicating that the molecules themselves composing these crystals were enantiomorphous. Their solutions correspondingly rotated the plane of polarisation of light in opposite directions. Pasteur afterwards obtained from the dextro-salt pure ordinary (dextro) tartaric acid, and from the lævo-salt the lævo-acid, by converting them first into the lead salts and then precipitating the lead as sulphide by sulphuretted hydrogen.
In the case of lævo tartaric acid, this was its first isolation, as it had hitherto been unknown. Gernez afterwards independently found that a saturated solution of sodium ammonium racemate affords crystals of the lævo-salt just as readily as of the dextro-salt; if a crystal of either salt be introduced, crystals corresponding to that variety are produced.
Another most fruitful observation of Pasteur, the principle of which has since been the means of isolating one of the two constituents of many racemic compounds, was that when the spores of Penicillium glaucum are added to a solution of racemic acid containing traces of phosphates the ordinary dextro component is destroyed by the organism, while the lævo component is unattacked so long as any dextro remains; hence, if the fermentation operation be stopped in time the lævo-acid may be isolated and crystallised. Why a living organism thus eats up by preference one variety only, possessing a particular right or left-handed screw structure, of a compound containing the same elementary constituents chemically united in the same manner, remains a most interesting biological mystery.
The crystals of both dextro and lævo tartaric acids prove to be pyro-electric, that is, develop electric excitation when slightly heated. The end which exhibits the development of the clinodome develops positive electricity in each case, when the crystal is allowed to cool after warming, so that the two varieties are oppositely pyro-electric, just as they are oppositely optically active. The most convenient method of demonstrating the fact is to dust a little of Kundt’s powder, a mixture of finely powdered red lead and sulphur, through a fine muslin sieve on to the crystal as it cools. The sulphur becomes negatively electrified and the red lead positively by mutual friction of the particles in the sifting, and the sulphur thus attaches itself to the positively electrified part of the crystal and the red lead to the negatively electrified end. This phenomenon of the development by the two varieties of an optically active substance of opposite electrical polarity has since been shown to be a general one.
Finally, on mixing concentrated solutions containing equivalent weights of dextro and lævo tartaric acid Pasteur observed that heat was evolved, a sign of chemical combination, and the solution afterwards deposited on cooling crystals of racemic acid. Hence, the only conclusion possible is that racemic acid must be a molecular compound of the two oppositely optically active tartaric acids. It thus partakes of the character of a double salt, analogous to potassium magnesium sulphate for instance. Consequently the crystal structure is one in which alternating molecules of the two acids are uniformly distributed, and the case is actually presented of two oppositely enantiomorphous sets of molecules producing a homogeneous structure.