Chapter 5

H H H/ \ /H——Cl; H——O——H; H——N ; C\ / \H H H

Instances of penta, hexa, and even hepta-valency are not wanting.

This was the key to unlock the structure of chemical compounds; and Frankland’s views, just stated, are still held by chemists. The determination of the constitution of compounds, chiefly those of carbon, occupiedthe attention of chemists, almost exclusively, until 1880. The plan of action is much the same as that of a mechanician who wishes to imitate a complicated mechanism. He must first dissect it into groups of mechanical contrivances; these are next constructed; and they are finally built together into the complete machine. In certain cases the atoms of carbon are arranged in “chains,” as, for example, in pentyl alcohol:

H3C——C——C——C——C——O——HH2H2H2H2

each atom being tetrad, and its “affinities,” or powers of combination, saturated either with hydrogen or with those of neighboring atoms of carbon; in others they are in the form of a “ring,” as in benzene, the formula of which was first suggested by Kekulé, viz.:

H HC——C/ \HC CH;\ /C==CH H

or in both, as in ethyl benzene,

H HC——C/ \ H HHC C——C——CH.\ / H HC==CH H

One or more atoms of nitrogen, or of oxygen, may form part of the circle, as in pyridine:

H H H HC——C C C/ \ /N CH and furfurane, O == ,\ / \C==C C CH H H H

and so on. By means of conceptions such as these many interesting compounds have been built up out of the elements which they contain;e.g., urea and uric acid, constituents of urine; theobromine and caffeine, the essential principles of cocoa and tea; alizarine and indigo, valuable dyestuffs; and several of the alkaloids, bitter principles contained in plants, of great medicinal value.

They have led, too, to the discovery of many brilliant colors, now almost universally employed, to the exclusion of those less brilliant, because less pure, derived from plants, and in one or two cases from animals; the manufacture of gun-cotton, dynamite, and similar high explosives; and to the development of the candle industry; the sugar manufacture; to improvement in tanning, in brewing, and in the preparation of gas and oils for illuminating purposes. In short, it may be said that the industrial progress of the latter half of the century has been due to the theoretical views of which a short sketch has just been given.

Such formulas, however, can evidently not represent the true constitution of matter, inasmuch as the atoms are imagined to lie on a plane, whereas it is evident that they must occupy space of three dimensions and possess the attributes of solidity. The conception which led to the formulation of such views was due first to Pasteur, in his later years director of the institute known by his name at Paris, and more directly to LeBel and Van’t Hoff, now professor at Berlin, independently of each other. In 1848 Pasteur discovered that it was possible to separate the two varieties of tartaric acid from each other; and that that one which rotated the plane of polarized light to the right gave crystals with an extra face, unsymmetrically disposed with regard to the other faces of the crystal. The variety, the solution of which in water was capable of producing left-handed rotation, also possessed a similar face, but so placed that its reflection in a mirror reproduced the right-handed variety. Pasteur also showed that a mixture of these acids gave crystals not characterized by an unsymmetrically placed face; and also that the solution was without action on polarized light. These observations remained unexplained, until LeBel and Van’t Hoff, in 1874, simultaneously and independentlydevised a theory which has, up till now, stood the test of research. It is briefly this: Imagine two regular tetrahedra, or three-sided pyramids, standing each on its triangular base. An idea can best be got by a model, easily made by laying on a table three lucifer matches so as to form an equilateral triangle, and erecting a tripod with three other matches, so that each leg of the tripod stands on one corner of the triangle. At the centre of such a tetrahedron, an atom of carbon is supposed to be placed. Marsh gas, CH4, is supposed to have such a structure, each corner, or solid angle of the structure (of which there are four), being occupied by an atom of hydrogen. This represents the solid orstereochemicalformula of methane or marsh gas. Now, suppose one of the atoms of hydrogen in each of these structures to be replaced by chlorine, the group (OH), or any other monovalent element or group. It is evident that if not exactly similar (owing to the replacement not having been made at similar corners in each), the two structures can be made similar by turning one of them round, until the position of the substituting atom or group (which we will term X) coincides in position with X in the stationary one. If two such replacements be made, say, with X and Y in each, coincidence can again be made to take place; but the same is not the case if X, Y, and Z replace three atoms of hydrogen in the structure; for there is one way of replacement which is the optical image of the other, and represents the other’s reflection in a mirror.

(Tetrahedron XYZ) and (Tetrahedron XZY)

Now, it is found that when the four corners of such a structure are occupied by four separate atoms or groups,or when (as the expression goes) the body contains an “asymmetrical carbon atom,” if the substance or one of its derivations can be obtained in a crystalline form, the crystals are also asymmetric,i.e., arc develops a face which is the mirror-reflection of a similar face developed on the other variety; and if a beam of polarized light be passed through the solution of the substance, its plane is rotated to the left if one variety be used, and, if the other, to the right. This hypothesis of LeBel’s and Van’t Hoff’s has had an enormous influence on the progress of organic chemistry. By its means Fischer, now professor at Berlin, has explained the reason of the existence of the enormous number of bodies analogous to grape and cane sugar, and has prepared many new varieties; and it appears likely that the terpenes, a class of bodies allied to turpentine, and comprising most of the substances to which the odor of flowers is due, may thereby find their explanation. It may be mentioned in passing that Pasteur, having found that ordinary mould destroyed one variety of tartaric acid rather than the other in a mixture of the two, and made use of this observation in order to prepare the unattached variety in a state of purity, was led to study the action of organisms more or less resembling mould; and that this has led to the development of the science of bacteriology, which has had an enormous influence on our views regarding fermentation in general, and guides the work of our physicians, our surgeons (witness Lister’s antiseptic treatment), our sanitary engineers in their estimate of the purity of drinking-water and of the disposal of sewage, of our manufacturers of beer and spirits, of wine-growers, and more recently of farmers. All these processes depend upon the action of organisms in producing chemical changes, whether in the tissues of the body, causing or curing disease, or in the production of flavored alcoholfrom sugar, or in the manufacture of butter and cheese, or in preparing the land for the reception of crops. We also owe to the genius of Van’t Hoff the most important advance of recent times in the region of physical chemistry. It has been observed by Raoult, professor at Grenoble, that the freezing-point of a solvent as a general rule is lowered to the same extent if there be dissolved in it quantities of substances proportional to their molecular weights. Thus, supposing 1.80 grams of grape-sugar be dissolved in 100 grams of water and the solution cooled below 0° with constant stirring, ice separates suddenly in thin spicules, and the temperature rises to −0.185°. If 3.42 grams of cane-sugar be similarly dissolved in 100 grams of water, the freezing-point of the solution is again −0.185°. Now, 1.80 and 3.42 are respectively the hundredth part of the molecular weights of grape-sugar (C6H12O6) and cane-sugar (C12H22O11). Similarly, Raoult found that quantities proportional to molecular weights dissolved in a solvent depress the vapor pressure of that solvent equally, or, what comes to the same thing, raise its boiling-point by an equal number of degrees. But ordinary salts, such as sodium chloride, potassium nitrate, etc., dissolved in water, give too great a depression of the freezing-point and too high a boiling-point. Next, it has been observed by botanists, Devries, Pfeffer, and others, who had examined the ascent of sap in plants, that if a vessel of unglazed porcelain, so treated as to cause a film of cupric ferrocyanide (a slimy red compound) to deposit in the pores of its walls, be filled with a weak (about 1 per cent.) solution of sugar or similar substance, and plunged in a vessel of pure water, water entered through the pores. By attaching a monometer to the porous vessel the pressure exerted by the entering water could be measured. Such pressure was termed “osmotic pressure,” referring to the “osmosis” or passage through the walls of the vessel.Such prepared walls are permeable freely to water, but not to sugar or similar bodies. Van’t Hoff pointed out that the total pressure registered is proportional to the amount of substance in solution, and that it is proportional to the absolute temperature, and he showed, besides, that the pressure exerted by the sugar molecules is the same as that which would be exerted at the same temperature were an equal number of molecules of hydrogen to occupy the same volume as the sugar solution. This may be expressed by stating that when in dilute solution sugar molecules behaveas ifthey were present in the gaseous state. Here again, however, it was noticed that salts tended to give a higher pressure; it was difficult to construct a semi-permeable diaphragm, however, which would resist the passage of salt molecules, while allowing those of water to pass freely. Lastly, Arrhenius, of Stockholm, had shown that the conductivity of salt solutions for electricity may be explained on the assumption that when a salt, such as KNO3is dissolved in water, it dissociates into portions similar in number and kind to those it would yield if electrolyzed (and if no secondary reactions were to take place). Such portions (K and NO3, for example) had been named ions by Faraday. The conductivity of such solutions becomes greater, per unit of dissolved salt, the weaker the solution, until finally a limit is reached, after which further dilution no longer increases conductivity. Now Van’t Hoff united all these isolated observations and showed their bearing on each other. Stated shortly, the hypothesis is as follows: When a substance is dissolved in a large quantity of a solvent, its molecules are separated from each other to a distance comparable with that which obtains in gases. They are, therefore, capable of independent action; and when placed in a vessel the walls of which are permeable to the solvent, but not to the dissolved substance (“semi-permeable membrane”), the imprisoned molecules of the latter exert pressure on the interior surface of these walls as if they were gaseous. Van’t Hoff showed the intimate connection between this phenomenon and the depression of freezing-point and the use of vapor pressure already alluded to. He pointed out further that the exceptions to this behavior, noticed in the case of dissolved salts, are due to their “electric dissociation,” or “ionization,” as it is now termed; and that in a sufficiently dilute solution of potassium nitrate, for example, the osmotic pressure, and the correlated depression of freezing-point and rise of boiling-point, are practically equal to what would be produced were the salt to be split into its ions, K and NO3. These views were vigorously advocated by Ostwald, professor at Leipzig, in hisZeitschrift für physikalische Chemie, and he and his pupils have done much to gather together facts in confirmation of this theory, and in extending its scope.

It must be understood that the ions K and NO3are not, strictly speaking, atoms; they arechargedatoms; the K retains a +, and the NO3a − charge. On immersing into the solution the poles of a battery, one charged + and the other −, the + K atoms are attracted to the − pole, and are there discharged; as soon as they lose their charge they are free to act on the water, when they liberate their equivalent of hydrogen. Similarly, the − NO3groups are discharged at the + pole, and abstract hydrogen from the water, liberating an equivalent quantity of oxygen. Thus the phenomenon of electrolysis, so long a mysterious process, finds a simple explanation. The course of ordinary chemical reactions is also readily realized when viewed in the light of this theory. Take, for example, the ordinary equation:

AgNO3.Aq + NaCl.Ag = AgCl + NaNO3.Aq;

i.e., solutions of silver nitrate and sodium chloride givea precipitate of silver chloride, leaving sodium nitrate in solution. By the new views, such an equation must be written:

+ − + − + −Ag.Aq + NO3.Aq + Na.Aq + Cl.Aq = AgCl + Na.Aq + NO3.Aq.

The compound, silver chloride, being insoluble in water, is formed by the union of the ions Ag and Cl, and their consequent discharge, forming an electrically neutral compound; while the sodium ions, charged positively together with the NO3ions, negatively charged, remain in solution.

One more application of the principle may be given. Many observers—Andrews, Favre, and Silbermann, but especially Julius Thomsen, of Copenhagen, and M. Berthelot, of Paris—have devoted much labor and time to the measurement of the heat evolved during chemical reactions. Now, while very different amounts of heat are evolved when chlorine, bromine, or iodine combine respectively with sodium or potassium, the number of heat units evolved on neutralizing sodium or potassium hydroxide with hydrochloric, hydrobromic, hydriodic, or nitric acids is always about 13,500. How can this fact be explained? It finds its explanation as follows: These acids and bases are ionized in solution as shown in the equation:

+ − + − + −H.Aq + Cl.Aq. + Na.Aq + OH.Aq = H.OH + Na.Aq + Cl.Aq.

Water is the only compound formed; and it is produced by the union of the hydrogen-ion originally belonging to the acid, and the OH or hydroxyl-ion originally belonging to the base. No further change has occurred; hence the uniform evolution of heat by the interaction of equivalent quantities of these acids and bases.

It now remains to give a short account of the greatest generalization which has as yet been made in chemistry.It has been termed the “Periodic Arrangement of the Elements.”

In 1864 Newlands, of London, and Lothar Meyer, late of Tübingen, found that by arranging the elements in the order of their atomic weights certain regularities were to be observed between each element, and in general the eighth in succession from it, in the order of their numerical value. Such similar elements formed groups or quantities; while the elements separating them belong to aperiod, hence the name “periodic arrangement.” Commencing with lithium, a light, lustrous metal found in silicate in certain minerals, we have the following series:

LithiumBerylliumBoronCarbonNitrogenOxygenFluorineNeon79.2111214161920SodiumMagnesiumAluminumSiliconPhosphorusSulphurChlorineArgon2324.32728313435.540

and so on. It is unnecessary to point out in detail the resemblances between the elements which stand in the vertical columns; but it may be stated that the resemblance extends also to the formulas and properties of their compounds. Thus the chlorides of lithium and sodium are each white soluble salts, of the formulas LiCl and NaCl; oxides of magnesium and of beryllium are both insoluble white earthy powders, MgO and BeO (GeO), and so on. Newlands, in his preliminary sketch, termed this order the “Law of Octaves,” and predicted the existence of certain undiscovered elements which should occupy unfilled positions in the table. Mendeléef, professor at St. Petersburg, in 1869 amplified and extended these relations; and he and Meyer pointed out that the volume occupied by equal numbers of atoms of such elements underwent a periodicvariation when the elements are classified as above. The prediction of undiscovered elements was made by Mendeléef in a more assured manner; and in several cases they have been realized. Thus what Mendeléef called “ekaboron” has since been discovered by Lecoq de Boisbandron and named, patriotically, “gallium”; Mendeléef’s “eka-silicon” is now known as “germanium,” discovered by Winkler; and “eka-aluminum” is now Cléve’s “scandium.” Moreover, the atomic weights of cæsium, beryllium, molybdenium, and mercury have been altered so that they fit the periodic table; and further research has justified the alteration.

The valency of these elements increases from right to left, as will be seen by inspection of the following series:

LiClBeCl3BCl3CCl4NH4ClNa2OMgOB2O3SiO2PCl3Monad.Dyad.Triad.Tetrad.Triad and Pentad.OH2FHNe——SO3Cl(OH)O3A——Dyad and Hexad.Monad and Heptad.No valency.

The elements of no valency are of recent discovery. In 1894 Lord Rayleigh had determined the density of the nitrogen of the atmosphere, having separated from it the oxygen and carbon dioxide which is mixed with nitrogen in air. He found it to be of somewhat higher density than that obtainable from ammonia and other compounds of nitrogen. In conjunction with Ramsay he investigated atmospheric nitrogen; it was absorbed either by a method devised by Cavendish, or by making it combine with magnesium at a red heat. They found that the unabsorbable residue possessed an unknown spectrum, and that its density was nearly 20. To this new gas they gave the name “argon,” or inactive, seeing that all attempts to cause it to enter into combinationhad failed. In 1895 Ramsay, searching for possible combinations of argon in minerals, experimented with one which had been previously examined by Hillebrand, of Baltimore, and obtained from it helium, a gas of density 2, possessing a spectrum which had been previously discovered in 1868 in the chromosphere of the sun, by Jannsen, of Paris, and named helium by Frankland and Lockyer. Subsequent liquefaction of crude argon by means of liquid air, prepared by a process invented simultaneously by Linde and Hampson, gave a residue which was named by its discoverers, Ramsay and Travers, “neon.” Liquid argon has yielded two other gases also, “krypon” and “xenon.” These elements form a separate group in the Periodic Table, commencing with helium, with atomic weight, 4; neon, 20; argon, 40; krypon, 82; and xenon, 128. They all agree in being mono-atomic,i.e., their molecules consist of single atoms; and they have no tendency to form compounds,i.e., they possess no valency.

In this sketch of the progress of chemistry during the century which has just passed, attention has been paid chiefly to the progress of thought. Allusions must, however, be made to the applications of chemistry to industrial purposes. The development of the soda industry, the preparation of carbonate of soda and caustic from common salt—initiated in France by LeBlanc (1742–1806)—has been developed by Tennant, in Scotland, and Muspeath and Gossage, and by Hargreaves, Weldon, and Maetea, in England; this process has at present a serious rival in the ammonia-soda process, developed by Solway, in Belgium, and by Brunner and Mond, in England. The main action of sulphuric acid, so long associated with the alkali process, has made enormous strides during the present century, but is still, in the main, the original process of causing sulphur dioxide in presence of water to absorb the oxygen of the air throughnitric oxide. But the saving of the oxides of nitrogen through the invention of a sulphuric acid power by Gay-Lussac, known by his name, and the re-utilization of these oxides in the “Glover” power, invented by John Glover, of Newcastle, have greatly lessened the cost of the acid. Concentration of the acid in iron vessels is now common, the cost of platinum or of fragile glass vessels being thereby saved. The desulphurization of iron and the removal of silicon, carbon, and phosphorus by Bessemer’s process, modified by Thomas and Gilchrist through the introduction of a “basic magnesia lining” for the convertors, has made it possible to obtain pure iron and steel from ores previously regarded as of little value.

The use of artificial manures, prepared by mixing refuse animal matters with tetra-hydrogen, calcium phosphate, and nitrate of soda, or sulphate of ammonia, first introduced by Liebig, has created a revolution in agricultural methods and in the weight of crops obtainable from a given area of soil. The influence of manures on crops has been fully studied by Lawes and Gilbert for more than fifty years in their experimental farm at Rothampstead. The most remarkable advances which have been made, however, are due to cheap electric current. The electrolysis of alumina, dissolved in fused cryolite to obtain aluminum, an operation carried out at Schaffhausen-on-the-Rhine, and at the Falls of Foyers, in Scotland; the electro-deposition of pure copper for electric wires and cables, electro-silvering, gilding, and nickelling, all these are instances where decomposition of a compound by the electric current has led to important industrial results. At present soda and chlorine are being manufactured by the electrolysis of salt solution contained in rocking trays, one of the electrodes being mercury, by the Castner-Kellner process. This manufacture is being carried on at Niagara, as well as in England. But electricity as a heating agent findsever-extending application. Louis Moisson, professor at Paris, led the way by utilizing the enormous heat of the ore in his electric furnace, thereby, among other interesting reactions, manufacturing diamonds, small, it is true, though none the less real. The use of electricity as a heating agent has received new applications. Phosphorus is now made by distilling a mixture of phosphates of lime and alumina with coke; a new polishing agent has been found in “carborundum,” a compound of carbon and silicon, produced by heating in an electric furnace a mixture of sand and coke; and cyanide of potassium, almost indispensable for the extraction of gold from ores poor in gold, is now manufactured by heating a mixture of carbon and carbonate of barium in an electric furnace in a current of carbon monoxide. These are but some of the instances in which electricity has been adopted as an agent in effecting chemical changes; and it may be confidently predicted that the earlier years of the twentieth century will witness a great development in this direction. It may be pointed out that the later developments of industrial chemistry owe their success entirely to the growth of chemical theory; and it is obvious that that nation which possesses the most competent chemists, theoretical and practical, is destined to succeed in the competition with other nations for commercial supremacy and all its concomitant advantages.

William Ramsay.

Back to Index Next