University of California SOUTHERN REGIONAL LIBRARY FACILITY Return this material to the library from which it was borrowed. & Quarter Loan, B*e OUL 1 1995 fctjr,, to BM N BRAN -,ALIfl LIBRARY, 000 737 771 6 CALIF EFRACTIVE INDEX BSORPTION WAVE-LENGTH ftP [ROTATORY POWER in RELATION TO MOLECULAR STRUCTURE sg SECOND EDITION ADAM HILGER LIMITED | 75 A CAMDEN ROAD - LONDON N.W.i Telegraph SPHERICITY PHONE LONDON Telephone Ni6 77 & 1678 Cable Addreu SPHERICITY LONDON Cable Code WESTERN UNION 9650 I : PREFACE 7? OUR booklets have been issued similar in * form to this one, and describing respectively the Abbe Refractometer , the Hilger W^avelength Spectrometer and Nutting Photometer, the Hilger Wavelength Spectrometer and High Resolving Power Accessories, and the Polarimeter, as made by this firm. These instruments are widely and increasingly used by chemists for the identification and estimation of substances, in the control of industrial processes, and so forth. But measurements of refractive index, wave- length, absorption, and rotatory power have a deeper significance than appears in such practical applications, and it is the purpose of the present essay to remind the members of our staff and our clients how greatly the study of these pro- perties has already contributed towards our present knowledge of the structure of matter, and what a wide and promising field it offers for further investigations. The present, second edition of the essay, is a slightly amplified reproduction of its first edition published in May, 1919. ADAM HILGER LTD .\ ;:,.;;': ....... ... JUNE, 1920 REFRACTIVE INDEX ABSORPTION WAVELENGTH AND ROTATORY POWER in RELATION TO MOLECULAR STRUCTURE TTNTRODUCTION. Everybody is familiar with the fact of the simple behaviour of light in empty space, in such regions of space, that is, from J. which palpable, ponderable matter has been either artifici- ally removed or highly attenuated, or better still, in those immense interplanetary or interstellar regions where owing to some natural conditions there is, comparatively speaking, but very little left of it. In such empty regions or practical vacua luminous waves are propagated with constant, and for all directions the same, velocity, amounting very nearly to 300,000 kilometers, or 3-io 10 cm. per second, independent of intensity or amplitude, of wave-length or colour, and of the state of polarisation. The rays of light, which in this case are generated by the normals to a wave-surface in its successive positions, are, and remain throughout, straight lines. The energy stored in light, although spreading over greater and greater regions, remains invariable in its total amount. Nor does light in empty space show any tendency to change its .nature in any respect whatever, apart from the weakening of its intensity while it inundates ever-growing regions of space. These simple properties are all more or less profoundly modified when light encounters and has to fight its way through material bodies, those marvellously complicated assemblages of atoms and molecules, themselves highly com- plex systems of structural elements still more minute, elec- trons and what not, about which modern science has only just begun to give us some reliable information. This change of propagational and other properties of light due to the presence of matter manifests itself not only in the case of those very dense aggregates known as solid and liquid bodies, but also, to a well-observable degree, in gases under ordinary 5 ADAM HILGER LIMITED 75A Camdeu Road, London. N.'W.l conditions. Moreover, and this is a fact not only beautiful in itself, but of the greatest practical importance, the amount and the nature of the modification of light properties is pro- foundly characteristic for each kind of matter, placed under definite, controllable conditions (such as temperature and pressure or the intensity of an impressed magnetic field), in distinction from others. K1FRACTIVE INDEX. The most prominent, and longest known, among these changes is what is most familiar as refraction, at any oblique incidence', but what in its deeper aspect is best described as the change the velocity of propagation of light experiences in various kinds of matter, as compared with its velocity in empty space. In fact, what is called the refractive index of a substance is the ratio of the sines of the angles of incidence (from a vacuum or practically from air) and of refraction ; this ratio is, apart from some cases in which absorption plays a very strong part, constant i.e., independent of the incidence angle and its numerical value is equal to the ratio of the vacuum-velocity to the velocity of propagation within the substance (medium) in question. In a piece of glass, for example, of index n= 1*5, the light velocity is but two-thirds of its undisturbed value, i.e., 200,000 km. per second, and so on. And this is true either on the old-fashioned elastic theory or the now firmly established electromagnetic theory, according to which light differs from other electromagnetic waves (such as are used in wireless telegraphy) only by its considerably smaller wave-length. Thus we can say in the literal sense of the word that a Refractometer enables us to measure the velocity of propaga- tion of light in a substance, this velocity, being inversely proportional to what is called the index of refraction. Now, the propagation velocity being undoubtedly the result of a very delicate and intimate reaction upon light waves of the molecules and of their configuration within the lump of matter, its value, and therefore that of the refractive index, 6 ADAM HILGER LIMITED 75x Camdeu Road, London. N. W. 1 will stand for some very characteristic attributes of the substance in question. In fact, the refractive index, /u, especially as it can now easily be measured to four or five decimal figures,* offers one of the most reliable means of identifying a substance. It goes without saying that the value of this index depends not only upon the chemical nature of the substance, but to a considerable extent also on its temperature and pressure ; these, however, can easily be controlled, and it can be said without exaggeration that the value of the refractive index, even if accurate only to four decimals, together with the temperature and pressure under which it has been obtained, are much more characteristic for a substance than, say, its specific gravity, even when measured with very refined means. DISPERSION. We have hitherto spoken of the propagation velocity and of the refractive index of a substance only for the sake of shortness and in order to keep the various aspects of the action of matter upon light a little apart from one another. We should have spoken of a velocity and of an index M X corresponding to light of a given colour or of a definite wave-length. And this brings us to the second of the subtle changes wrought in light propagation by the presence of matter. In fact, the velocity of light within material media is not only in general different from (and as a rule, to which sodium, silver, gold and copper are an exception, smaller than) that in empty space, but its value, and therefore also that of the index /i, differs very considerably for different colours or wave-lengths. This beautiful phenomenon distinguishing material media from empty space is generally known by the name of Dis- persion. What is called the dispersion curve of a substance (under given physical conditions) is the graphic representa- tion of this property ; the abscissae of the curve giving, in * By some recent methods based upon the principles of interferometry variations of the refractive index can be detected which amount only to one- tenmillionth and less. ADAM HILGER LIMITED 75x Camden Road, London, N.W. 1 some conventional scale, the wave-lengths A, and the ordi- nates, the corresponding values p. of the refractive index, or of some particularly interesting function of p, such as /u 2 - 1, or perhaps ^ I //t 2 + 2 , and so on. Now if the refractive index for some chosen light quality, say the D of the sodium light, is already characteristic of a substance, its dispersion curve is still more so. Moreover, while n itself varies considerably with the physical conditions of the substance, the dispersion curve, although not independent of such agents, retains more permanently or more tenaciously its features, and especially those singularities associated with what are known as free or natural oscillation frequencies (manifesting themselves as absorption lines or bands), and there is but little doubt that it does not merely represent properties of the whole structure, the piece of solid or the drop of liquid, but reveals to us some very intimate secrets of the individual bricks, the molecules or atoms. As such the dispersion should attract the greatest attention of the chemist as well as of the mole- cular physicist. ^yrSbCJlvr 1 1UJN. Intimately connected with I ^ the dispersion is the Absorption of a substance / % which, when carefully investigated, always turns 1 JL-Out to be, in a more or less pronounced way, selec- tive i.f. t again dependent on the wave-length or the oscilla- tion frequency of the impingent light. Many substances, shortly called transparent, have their absorption regions, absorption lines or bands, in the ultra-violet or the infra- red. Other substances, visibly coloured, show absorption bands (mostly very broad and without sharp limits) in the more accessible, that is, in the visible part of the spectrum. At any rate there is scarcely a substance devoid altogether of absorption ; in more recent times even all such " transparent " gases as oxygen have been incontestably proved to possess well-defined absorption bands ; nor do such transparent crystals as is the diamond show an exception to the rule. But what is of prime importance is that the absorption, which in its dependence 8 ADAM HILGER LIMITED 75x Camden Road, London. N.W. 1 upon the wave-length can again be represented by a curve or (in pronouncedly selective cases) by a number of isolated peaks, is eminently characteristic for a substance or for a chemical group, and thus offers a most welcome supplement to the dispersion curve. Moreover, the absorption bands, and especially the finer and sharply defined lines, correspond directly to the free frequencies of a substance (attributable to a great extent to the molecules themselves, and only in part modified by the interactions within the aggregate) which mould, so to speak, the character of the whole dis- persion curve. Those constants in every modern dispersion formula (of the Ketteler-Helmholtz type) which are known by the name oifree wave-lengths^ and which, in conjunction with the remaining constants, serve for the actual numerical calculation of the refraction index for any desired wave-length, represent directly the free oscillation frequencies for which the absorption is strongest. A careful study of both the absorption and the dispersion curve of a substance will thus be seen to be a most important step towards the exploration of the intimate structure of the aggregate and, under favourable conditions, also of its mole- cules, and therefore of the physico-chemical aspect of a substance. It is true that some generalisations, made chiefly by organic chemists on the great road opened by Gladstone and Dale, and by Bruehl and Landolt, associated with the names and concepts of molecular and atomic refraction, were too rash and notably too naive. But there is undoubtedly a profound and intrinsic link or a correspondence between the dispersive and the absorptive properties on the one hand, and the structure of a molecule out of its atoms, and of these out of subatomic entities, on the other hand. The simple " additivity " of atomic refractions, those two- or three- figure numbers given in the practical chemist's tables, is certainly not the rule, but rather the exception ; although it cannot be denied that it has in many cases aided and will still be helpful to the organic chemist in selecting a constitution formula among two or more otherwise equally possible ones. ADAM HILGER LIMITED 75x Camden Road. London, N.W. 1 But let us look more deeply and in a less sanguine manner upon the whole question. Then we shall certainly have to confess that the supposed simple additivity of optical pro- perties is but a rough, and even very rough, first approxima- tion to the truth, that it is actually swept away by innumerable instances of evidence of a much more delicate and immensely more complicated constitutivity of optical properties, the manifestation of an intricate interaction of atoms. But this is exactly the reason why we are justified in asserting that in this direction an inexhaustible field of inquiry lies open for many generations of chemists and of physicists, theorists as well as experimentalists. And the practical, technical or industrial advantages of this as of any other kind of investi- gations, even if originally undertaken with the purest scien- tific aim in view, will not fail to follow of themselves. The more complicated a class of natural phenomena appears to be, the more reason there is to investigate it with increasingly powerful and accurate instruments, aided by careful methods and cautious criticism. W'AVE-LENGTHS OF EMIS- SION AND ABSORPTION ^* HI 4 microns.* They cover also the cases of anomalous rotatory dispersion observed in absorbing organic liquids. A further development of even this rough electrical theory and the comparison of its results with obser- * A micron is one-thousandth of a millimetre or 10,000 A.U. 16 ADAM HILGER LIMITED 75A Camden Road. London, N.W.I vations would not be without value for the exploration of the interior of molecules and of atoms, especially as it sheds some interesting light upon the " active " or " rotatory " electrons, which in general appear as distinct from those responsible for the ordinary dispersion and absorption phenomena. An important quantitatively additive property relating to compounds containing two or more asymmetric carbon atoms which was already announced by van't Hoff (1875) has more recently been verified experimentally in a very satisfactory manner. It asserts that the rotatory power of such a compound is equal to the algebraic sum of the powers due to the separate " asymmetric carbon atoms " together, of course, with their satellites. This so-called law of optical superposition seems to be the only notable consolation of the " additivity " hunter in this beautiful domain of optical phenomena. It is, no doubt, based upon a rather loose association of the two or more component parts of the whole compound. The intrinsic physics of each of them as a system is still awaiting its thorough investigation. If an ultimate reduction to atoms is aimed at, the phenomenon of natural rotation of the plane of polarisation is manifestly a constitutive one par excellence. But the more it is so, the more active attention of the physico-chemist does it deserve. Last, not least, the rotatory power of organic compounds seems also to open a very promising field for the biologist owing to the well-established selective attitude of certain living organisms or of their enzymes towards stereo-isomeres, a class of phenomena already discovered and utilised by Pasteur himself, and more recently studied by Emil Fischer and others. According to the latter's simile, in order that an enzyme may successfully attack one of two enantiomorph molecules, there must be between the aggressor and its victim some similarity of intramolecular configuration, some- what as between " lock and key." But the very appeal to this, no doubt, most happy comparison will serve to remind the modern bio-chemist how much remains still to be done in the rich field of this class of phenomena. May, 1920. L - SILBERSTEIN. 17 ADAM HILGER LIMITED 75A Camden Road. London. N.W.I 493 50 'DIVERSITY OF CALIFORNIA AT LOS ANGELES THE BRANCH, OF CALIFORNIA, LIBRARY, LOS ANGELES. CAL.K E19560 W. H. S. & S. 5/20