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72
[PHYSICAL
CHEMISTRY

salt-formation, the production of colour may be explained as a particular form of ionization (Baeyer), or by a molecular rearrangement (Hantzsch). A dynamical theory due to E. C. C. Baly regards colour as due to “isorropesis” or an oscillation between the residual affinities of adjacent atoms composing the molecule.

Fluorescence and Constitution.—The physical investigation of the phenomenon named fluorescence—the property of transforming incident light into light of different refrangibility—is treated in the article Fluorescence. Researches in synthetical organic chemistry have shown that this property of fluorescence is common to an immense number of substances, and theories have been proposed whose purpose is to connect the property with constitution.

In 1897 Richard Meyer (Zeit. physik. Chemie, 24, p. 468) submitted the view that fluorescence was due to the presence of certain “fluorophore” groups; such groupings are the pyrone ring and its congeners, the central rings in anthracene and acridine derivatives, and the paradiazine ring in safranines. A novel theory, proposed by J. T. Hewitt in 1900 (Zeit. f. physik. Chemie, 34, p. 1; B.A. Report, 1903, p. 628, and later papers in the Journ. Chem. Soc.), regards the property as occasioned by internal vibrations within the molecule conditioned by a symmetrical double tautomerism, light of one wave-length being absorbed by one form, and emitted with a different wave-length by the other. This oscillation may be represented in the case of acridine and fluorescein as

EB1911 Chemistry - acridine and fluorescein.jpg

This theory brings the property of fluorescence into relation with that of colour; the forms which cause fluorescence being the coloured modifications: ortho-quinonoid in the case of acridine, para-quinonoid in the case of fluorescein. H. Kauffmann (Ber., 1900, 33, p. 1731; 1904, 35, p. 294; 1905, 38, p. 789; Ann., 1906, 344, p. 30) suggested that the property is due to the presence of at least two groups. The first group, named the “luminophore,” is such that when excited by suitable aetherial vibrations emits radiant energy; the other, named the “fluorogen,” acts with the luminophore in some way or other to cause the fluorescence. This theory explains the fluorescence of anthranilic acid (o-aminobenzoic acid), by regarding the aniline residue as the luminophore, and the carboxyl group as the fluorogen, since, apparently, the introduction of the latter into the non-fluorescent aniline molecule involves the production of a fluorescent substance. Although the theories of Meyer and Hewitt do not explain (in their present form) the behaviour of anthranilic acid, yet Hewitt has shown that his theory goes far to explain the fluorescence of substances in which a double symmetrical tautomerism is possible. This tautomerism may be of a twofold nature:—(1) it may involve the mere oscillation of linkages, as in acridine; or (2) it may involve the oscillation of atoms, as in fluorescein. A theory of a physical nature, based primarily upon Sir J. J. Thomson’s theory of corpuscles, has been proposed by J. de Kowalski (Compt. rend. 1907, 144, p. 266). We may notice that ethyl oxalosuccinonitrile is the first case of a fluorescent aliphatic compound (see W. Wislicenus and P. Berg, Ber., 1908, 41, p. 3757).

Capillarity and Surface Tension.—Reference should be made to the article Capillary Action for the general discussion of this phenomenon of liquids. It is there shown that the surface tension of a liquid may be calculated from its rise in a capillary tube by the formula γ = 1/2rhs, where γ is the surface tension per square centimetre, r the radius of the tube, h the height of the liquid column, and s the difference between the densities of the liquid and its vapour. At the critical point liquid and vapour become identical, and, consequently, as was pointed out by Frankenheim in 1841, the surface tension is zero at the critical temperature.

Mendeléeff endeavoured to obtain a connexion between surface energy and constitution; more successful were the investigations of Schiff, who found that the “molecular surface tension,” which he defined as the surface tension Relation to molecular weight.divided by the molecular weight, is constant for isomers, and that two atoms of hydrogen were equal to one of carbon, three to one of oxygen, and seven to one of chlorine; but these ratios were by no means constant, and afforded practically no criteria as to the molecular weight of any substance.

In 1886 R. Eötvös (Wied. Ann. 27, p. 452), assuming that two liquids may be compared when the ratios of the volumes of the liquids to the volumes of the saturated vapours are the same, deduced that γV2/3 (where γ is the surface tension, and V the molecular volume of the liquid) causes all liquids to have the same temperature coefficients. This theorem was investigated by Sir W. Ramsay and J. Shields (Journ. Chem. Soc. 63, p. 1089; 65, p. 167), whose results have thrown considerable light on the subject of the molecular complexity of liquids. Ramsay and Shields suggested that there exists an equation for the surface energy of liquids, analogous to the volume-energy equation of gases, PV = RT. The relation they suspected to be of the form γS = KT, where K is a constant analogous to R, and S the surface containing one gramme-molecule, γ and T being the surface tension and temperature respectively. Obviously equimolecular surfaces are given by (Mv)2/3, where M is the molecular weight of the substance, for equimolecular volumes are Mv, and corresponding surfaces the two-thirds power of this. Hence S may be replaced by (Mv)2/3. Ramsay and Shields found from investigations of the temperature coefficient of the surface energy that T in the equation γ(Mv)2/3 = KT must be counted downwards from the critical temperature T less about 6°. Their surface energy equation therefore assumes the form γ(Mv)2/3 = K(τ–6°). Now the value of K, γ being measured in dynes and M being the molecular weight of the substance as a gas, is in general 2.121; this value is never exceeded, but in many cases it is less. This diminution implies an association of molecules, the surface containing fewer molecules than it is supposed to. Suppose the coefficient of association be n, i.e. n is the mean number of molecules which associate to form one molecule, then by the normal equation we have γ(Mnv)2/3 = 2.121(τ–6°); if the calculated constant be K1, then we have also γ(Mv)2/3 = K1(τ–6°). By division we obtain n2/3 = 2.121/K1, or n = (2.121/K1)3/2 the coefficient of association being thus determined.

The apparatus devised by Ramsay and Shields consisted of a capillary tube, on one end of which was blown a bulb provided with a minute hole. Attached to the bulb was a glass rod and then a tube containing iron wire. This tube was placed in an outer tube containing the liquid to be experimented with; the liquid is raised to its boiling-point, and then hermetically sealed. The whole is enclosed in a jacket connected with a boiler containing a liquid, the vapour of which serves to keep the inner tube at any desired temperature. The capillary tube can be raised or lowered at will by running a magnet outside the tube, and the heights of the columns are measured by a cathetometer or micrometer microscope.

Normal values of K were given by nitrogen peroxide, N2O4, sulphur chloride, S2Cl2, silicon tetrachloride, SiCl4, phosphorus chloride, PCl3, phosphoryl chloride, POCl3, nickel carbonyl, Ni(CO)4, carbon disulphide, benzene, pyridine, ether, methyl propyl ketone; association characterized many hydroxylic compounds: for ethyl alcohol the factor of association was 2.74–2-43, for n-propyl alcohol 2.86–2.72, acetic acid 3.62–2.77, acetone 1.26, water 3.81–2.32; phenol, nitric acid, sulphuric acid, nitroethane, and propionitril, also exhibit association.

Crystalline Form and Composition.

The development of the theory of crystal structure, and the fundamental principles on which is based the classification of crystal forms, are treated in the article Crystallography; in the same place will be found an account of the doctrine of isomorphism, polymorphism and morphotropy. Here we shall treat the latter subjects in more detail, viewed from the standpoint of the chemist. Isomorphism may be defined as the existence of two or more different substances in the same crystal form and structure, polymorphism as the existence of the same substance in two or more crystal modifications, and morphotropy (after P. von Groth) as the change in crystal form due to alterations in the molecule of closely (chemically) related substances. In order to permit a comparison of crystal forms, from which we hope to gain an insight into the prevailing molecular conditions, it is necessary that some unit of crystal dimensions must be chosen. A crystal may be regarded as built up of primitive parallelepipeda, the edges of which are in the ratio of the crystallographic axes, and the angles the axial angles of the crystals. To reduce these figures to a common standard, so that the volumes shall contain equal numbers of molecules, the notion of molecular volumes is introduced, the arbitrary values of the crystallographic axes (a, b, c) being replaced by the topic parameters[1] (χ, ψ, ω), which are such that, combined with the axial angles, they enclose volumes which contain equal numbers of molecules. The actual values of the topic parameters can then readily be expressed in terms of the elements of the crystals (the axial ratios and angles), the density, and the molecular weight (see Groth, Physikalische Krystallographie, or Chemical Crystallography).

  1. This was done simultaneously in 1894 by W. Muthmann and A. E. H. Tutton, the latter receiving the idea from F. Becke (see Journ. Chem. Soc., 1896, 69, p. 507; 1905, 87, p. 1183).