Liebig's Chemical Letters

LETTER V

My dear Sir,
Until very recently it was supposed that the physical qualities of bodies, i.e. hardness, colour, density, transparency, &c., and still more their chemical properties, must depend upon the nature of their elements, or upon their composition. It was tacitly received as a principle, that two bodies containing the same elements in the same proportion, must of necessity possess the same properties. We could not imagine an exact identity of composition giving rise to two bodies entirely different in their sensible appearance and chemical relations. The most ingenious philosophers entertained the opinion that chemical combination is an inter-penetration of the particles of different kinds of matter, and that all matter is susceptible of infinite division. This has proved to be altogether a mistake. If matter were infinitely divisible in this sense, its particles must be imponderable, and a million of such molecules could not weigh more than an infinitely small one. But the particles of that imponderable matter, which, striking upon the retina, give us the sensation of light, are not in a mathematical sense infinitely small.
Inter-penetration of elements in the production of a chemical compound, supposes two distinct bodies, A and B, to occupy one and the same space at the same time. If this were so, different properties could not consist with an equal and identical composition.
That hypothesis, however, has shared the fate of innumerable imaginative explanations of natural phenomena, in which our predecessors indulged. They have now no advocate. The force of truth, dependent upon observation, is irresistible. A great many substances have been discovered amongst organic bodies, composed of the same elements in the same relative proportions, and yet exhibiting physical and chemical properties perfectly distinct one from another. To such substances the term Isomeric (from
åo
equal and æî
o
part) is applied. A great class of bodies, known as the volatile oils, oil of turpentine, essence of lemons, oil of balsam of copaiba, oil of rosemary, oil of juniper, and many others, differing widely from each other in their odour, in their medicinal effects, in their boiling point, in their specific gravity, &c., are exactly identical in composition, - they contain the same elements, carbon and hydrogen, in the same proportions.
How admirably simple does the chemistry of organic nature present itself to us from this point of view! An extraordinary variety of compound bodies produced with equal weights of two elements! and how wide their dissimilarity! The crystallised part of the oil of roses, the delicious fragrance of which is so well known, a solid at ordinary temperatures, although readily volatile, is a compound body containing exactly the same elements, and in the same proportions, as the gas we employ for lighting our streets; and, in short, the same elements, in the same relative quantities, are found in a dozen other compounds, all differing essentially in their physical and chemical properties.
These remarkable truths, so highly important in their applications, were not received and admitted as sufficiently established, without abundant proofs. Many examples have long been known where the analysis of two different bodies gave the same composition; but such cases were regarded as doubtful: at any rate, they were isolated observations, homeless in the realms of science: until, at length, examples were discovered of two or more bodies whose absolute identity of composition, with totally distinct properties, could be demonstrated in a more obvious and conclusive manner than by mere analysis; that is, they can be converted and reconverted into each other without addition and without subtraction.
In cyanuric acid, hydrated cyanic acid, and cyamelide, we have three such isomeric compounds.
Cyanuric acid is crystalline, soluble in water, and capable of forming salts with metallic oxides.
Hydrated cyanic acid is a volatile and highly blistering fluid, which cannot be brought into contact with water without being instantaneously decomposed.
Cyamelide is a white substance very like porcelain, absolutely insoluble in water.
Now if we place the first, - cyanuric acid, - in a vessel hermetically sealed, and apply a high degree of heat, it is converted by its influence into hydrated cyanic acid; and, then, if this is kept for some time at the common temperature, it passes into cyamelide, no other element being present. And, again inversely, cyamelide can be converted into cyanuric acid and hydrated cyanic acid.
We have three other bodies which pass through similar changes, in aldehyde, metaldehyde, and etaldehyde; and, again two, in urea and cyanuret of ammonia. Further, 100 parts of aldehyde hydrated butyric acid and acetic ether contain the same elements in the same proportion. Thus one substance may be converted into another without addition or subtraction, and without the participation of any foreign bodies in the change.
The doctrine that matter is not infinitely divisible, but on the contrary, consists of atoms incapable of further division, alone furnishes us with a satisfactory explanation of these phenomena. In chemical combinations, the ultimate atoms of bodies do not penetrate each other, they are only arranged side by side in a certain order, and the properties of the compound depend entirely upon this order. If they are made to change their place - their mode of arrangement - by an impulse from without, they combine again in a different manner, and another compound is formed with totally different properties. We may suppose that one atom combines with one atom of another element to form a compound atom, while in other bodies two and two, four and four, eight and eight, are united; so that in all such compounds the amount per cent. of the elements is absolutely equal; and yet their physical and chemical properties must be totally different, the constitution of each atom being peculiar, in one body consisting of two, in another of four, in a third of eight, and in a fourth of sixteen simple atoms.
The discovery of these facts immediately led to many most beautiful and interesting results; they furnished us with a satisfactory explanation of observations which were before veiled in mystery, - a key to many of Nature's most curious recesses.
Again; solid bodies, whether simple or compound, are capable of existing in two states, which are known by the terms amorphous and crystalline.
When matter is passing from a gaseous or liquid state slowly into a solid, an incessant motion is observed, as if the molecules were minute magnets; they are seen to repel each other in one direction, and to attract and cohere together in another, and in the end become arranged into a regular form, which under equal circumstances is always the same for any given kind of matter; that is, crystals are formed.
Time and freedom of motion for the particles of bodies are necessary to the formation of crystals. If we force a fluid or a gas to become suddenly solid, leaving no time for its particles to arrange themselves, and cohere in that direction in which the cohesive attraction is strongest, no crystals will be formed, but the resulting solid will have a different colour, a different degree of hardness and cohesion, and will refract light differently; in one word, will be amorphous. Thus we have cinnabar as a red and a jet-black substance; sulphur a fixed and brittle body, and soft, semitransparent, and ductile; glass as a milk-white opaque substance, so hard that it strikes fire with steel, and in its ordinary and well-known state. These dissimilar states and properties of the same body are occasioned in one case by a regular, in the other by an irregular, arrangement of its atoms; one is crystalline, the other amorphous.
Applying these facts to natural productions, we have reason to believe that clay-slate, and many kinds of greywacke, are amorphous feldspar, as transition limestone is amorphous marble, basalt and lava mixtures of amorphous zeolite and augite. Anything that influences the cohesion, must also in a certain degree alter the properties of bodies. Carbonate of lime, if crystallised at ordinary temperatures, possesses the crystalline form, hardness, and refracting power of common spar; if crystallised at a higher temperature, it has the form and properties of arragonite.
Finally, Isomorphism, or the equality of form of many chemical compounds having a different composition, tends to prove that matter consists of atoms the mere arrangement of which produces all the properties of bodies. But when we find that a different arrangement of the same elements gives rise to various physical and chemical properties, and a similar arrangement of different elements produces properties very much the same, may we not inquire whether some of those bodies which we regard as elements may not be merely modifications of the same substance? - whether they are not the same matter in a different state of arrangement? We know in fact the existence of iron in two states, so dissimilar, that in the one, it is to the electric chain like platinum, and in the other it is like zinc; so that powerful galvanic machines have been constructed of this one metal.
Among the elements are several instances of remarkable similarity of properties. Thus there is a strong resemblance between platinum and iridium; bromine and iodine; iron, manganese, and magnesium; cobalt and nickel; phosphorus and arsenic; but this resemblance consists mainly in their forming isomorphous compounds in which these elements exist in the same relative proportion. These compounds are similar, because the atoms of which they are composed are arranged in the same manner. The converse of this is also true: nitrate of strontia becomes quite dissimilar to its common state if a certain proportion of water is taken into its composition.
If we suppose selenium to be merely modified sulphur, and phosphorus modified arsenic, how does it happen, we must inquire, that sulphuric acid and selenic acid, phosphoric and arsenic acid, respectively form compounds which it is impossible to distinguish by their form and solubility? Were these merely isomeric, they ought to exhibit properties quite dissimilar!
We have not, I believe, at present the remotest ground to suppose that any one of those substances which chemists regard as elements can be converted into another. Such a conversion, indeed, would presuppose that the element was composed of two or more ingredients, and was in fact not an element; and until the decomposition of these bodies is accomplished, and their constituents discovered, all pretensions to such conversions deserve no notice.
Dr. Brown of Edinburgh thought he had converted iron into rhodium, and carbon or paracyanogen into silicon. His paper upon this subject was published in the Transactions of the Royal Society of Edinburgh, and contained internal evidence, without a repetition of his experiments, that he was totally unacquainted with the principles of chemical analysis. But his experiments have been carefully repeated by qualified persons, and they have completely proved his ignorance: his rhodium is iron, and his silicon an impure incombustible coal