Heroes of Science Part 12

"In Nature," says Wordsworth, "everything is distinct, but nothing defined into absolute independent singleness."

At this stage of advance, then, an earth is regarded as differing from an alkali in being insoluble, or nearly insoluble in water; in not being soapy to the touch, and not turning vegetable reds to blue: but as resembling an alkali, in that it combines with and neutralizes an acid; and the product of this neutralization, whether accomplished by an alkali or by an earth, is called a salt. To the earth or alkali, as being the foundation on which the salt is built, by the addition of acid, the name of _base_ was given by Rouelle in 1744.

But running through every conception which was formed of these substances--acid, alkali, earth, salt--we find a tendency, sometimes forcibly marked, sometimes feebly indicated, but always present, to consider salt as a term of much wider acceptation than any of the others.

An acid and an alkali, or an acid and an earth, combine to form a salt; but the salt could not have been thus produced unless the acid, the alkali and the earth had contained in themselves some properties which, when combined, form the properties of the salt.

The acid, the alkali, the earth, each is, in a sense, a salt. The perfect salt is produced by the coalescence of the saltness of the acid with the saltness of the alkali. This conception finds full utterance in the names, once in common use, of _sal acidum_ for acid, _sal alkali_ for alkali, and _sal salsum_ or _sal neutrum_ for salt. All are salts; at one extreme comes that salt which is marked by properties called acid properties, at the other extreme comes the salt distinguished by alkaline properties, and between these, and formed by the union of these, comes the middle or neutral salt.

It is thus that the nomenclature of chemistry marks the advances made in the science. "What's in a name?" To the historical student of science, almost everything.

We shall find how different is the meaning attached in modern chemistry to these terms, _acid salt_, _alkaline salt_, _neutral salt_, from that which our predecessors gave to their _sal acidum_, _sal alkali_, and _sal neutrum_.

We must note the appearance of the term _vitriol_, applied to the solid salt-like bodies obtained from acids and characterized by a gla.s.sy l.u.s.tre.

By the middle of last century the vitriols were recognized as all derived from, or compounded of, sulphuric acid (oil of vitriol) and metals; this led to a subdivision of the large cla.s.s of neutral salts into (1) metallic salts produced by the action of sulphuric acid on metals, and (2) neutral salts produced by the action of earths or alkalis on acids generally.

To Rouelle, a predecessor of Lavoisier, who died four years before the discovery of oxygen, we owe many accurate and suggestive remarks and experiments bearing on the term "salt." I have already mentioned that it was he who applied the word "base" to the alkali or earth, or it might be metal, from which, by the action of acid, a salt is built up. He also ceased to speak of an acid as _sal acidum_, or of an alkali as _sal alkali_, and applied the term "salt" exclusively to those substances which are produced by the action of acids on bases. When the product of such an action was neutral--that is, had no sour taste, no soapy feeling to the touch, no action on vegetable colours, and no action on acids or bases--he called that product _a neutral salt_; when the product still exhibited some of the properties of acid, _e.g._ sourness of taste, he called it _an acid salt_; and when the product continued to exhibit some of the properties of alkali, _e.g._ turned vegetable reds to blue, he called it _an alkaline salt_.

Rouelle also proved experimentally that an acid salt contains more acid--relatively to the same amount of base--than a neutral salt, and that an alkaline salt contains more base--relatively to the same amount of acid--than a neutral salt; and he proved that this excess of acid, or of base, is chemically united to the rest of the salt--is, in other words, an essential part of the salt, from which it cannot be removed without changing the properties of the whole.

But we have not as yet got to know why certain qualities connoted by the term "acid" can be affirmed to belong to a group of bodies, why certain other, "alkaline," properties belong to another group, nor why a third group can be distinguished from both of these by the possession of properties which we sum up in the term "earthy." Surely there must be some peculiarity in the composition of these substances, common to all, by virtue of which all are acid. The atom of an acid is surely composed of certain elements which are never found in the atom of an alkali or an earth; or perhaps the difference lies in the number, rather than in the nature of the elements in the acid atoms, or even in the arrangement of the elementary atoms in the compound atom of acid, of alkali, and of earth.

I think that our knowledge of salt is now more complete than our knowledge of either acid, alkali, or earth. We know that a salt is formed by the union of an acid and an alkali or earth; if, then, we get to know the composition of acids and bases (_i.e._ alkalis and earths), we shall be well on the way towards knowing the composition of salts.

And now we must resume our story where we left it at p. 176. Lavoisier had recognized oxygen as the acidifier; Black had proved that a caustic alkali does not contain carbonic acid.

Up to this time metallic calces, and for the most part alkalis and earths also, had been regarded as elementary substances. Lavoisier however proved calces to be compounds of metals and oxygen; but as some of those calces had all the properties which characterized earths, it seemed probable that all earths are metallic oxides, and if all earths, most likely all alkalis also. Many attempts were made to decompose earths and alkalis, and to obtain the metal, the oxide of which the earth or the alkali was supposed to be. One chemist thought he had obtained a metal by heating the earth baryta with charcoal, but from the properties of his metal we know that he had not worked with a pure specimen of baryta, and that his supposed metallic base of baryta was simply a little iron or other metal, previously present in the baryta, or charcoal, or crucible which he employed.

But if Lavoisier's view were correct--if all bases contained oxygen--it followed that all salts are oxygen compounds. Acids all contain oxygen, said Lavoisier; this was soon regarded as one of the fundamental facts of chemistry. Earths and alkalis are probably oxides of metals; this before long became an article of faith with all orthodox chemists. Salts are produced by the union of acids and bases, therefore all salts contain oxygen: the conclusion was readily adopted by almost every one.

When the controversy between Lavoisier and the phlogistic chemists was at its height, the followers of Stahl had taunted Lavoisier with being unable to explain the production of hydrogen (or phlogiston as they thought) during the solution of metals in acids; but when Lavoisier learned the composition of water, he had an answer sufficient to quell these taunts.

The metal, said Lavoisier, decomposes the water which is always present along with the acid, hydrogen is thus evolved, and the metallic calx or oxide so produced dissolves in the acid and forms a salt. If this explanation were correct--and there was an immense ma.s.s of evidence in its favour and apparently none against it--then all the salts produced by the action of acids on metals necessarily contained oxygen.

The Lavoisierian view of a salt, as a compound of a metallic oxide--or base--with a non-metallic oxide--or acid--seemed the only explanation which could be accepted by any reasonable chemist: in the early years of this century it reigned supreme.

But even during the lifetime of its founder this theory was opposed and opposed by the logic of facts. In 1787 Berthollet published an account of experiments on prussic acid,--the existence and preparation (from Prussian blue) of which acid had been demonstrated three or four years before by the Swedish chemist Scheele--which led him to conclude this compound to be a true acid, but free from oxygen. In 1796 the same chemist studied the composition and properties of sulphuretted hydrogen, and p.r.o.nounced this body to be an acid containing no oxygen.

But the experiments and reasoning of Berthollet were hidden by the ma.s.ses of facts and the cogency of argument of the Lavoisierian chemists.

The prevalent views regarding acids and bases were greatly strengthened by the earlier researches of Sir Humphry Davy, in which he employed the voltaic battery as an instrument in chemical investigation. Let us now consider some of the electro-chemical work of this brilliant chemist.

In the spring of the year 1800 the electrical battery, which had recently been discovered by Volta, was applied by Nicholson and Carlisle to effect the decomposition of water. The experiments of these naturalists were repeated and confirmed by Davy, then resident at Bristol, who followed up this application of electricity to effect chemical changes by a series of experiments extending from 1800 to 1806, and culminating in the Bakerian Lecture delivered before the Royal Society in the latter year.

The history of Davy's life during these years, years rich in results of the utmost importance to chemical science, will be traced in the sequel; meanwhile we are concerned only with the results of his chemical work.

The first Bakerian Lecture of Humphry Davy, "On some Chemical Agencies of Electricity," deserves the careful study of all who are interested in the methods of natural science; it is a brilliant example of the disentanglement of a complex natural problem.

Volta and others had subjected water to the action of a current of electricity, and had noticed the appearance of acid and alkali at the oppositely electrified metallic surfaces. According to some experimenters, the acid was nitrous, according to others, muriatic acid. One chemist a.s.serted the production of a new and peculiar body which he called _the electric acid_. The alkali was generally said to be ammonia.

When Davy pa.s.sed an electric current through distilled water contained in gla.s.s vessels, connected by pieces of moist bladder, cotton fibre, or other vegetable matters, he found that nitric and hydrochloric acids were formed in the water surrounding the positively electrified plate or pole, and soda around the negatively electrified pole, of the battery.

When the same piece of cotton fibre was repeatedly used for making connection between the gla.s.s vessels, and was washed each time in dilute nitric acid, Davy found that the production of muriatic acid gradually ceased; hence he traced the formation of this acid to the presence of the animal or vegetable substance used in the experiments.

Finding that the gla.s.s vessels were somewhat corroded, and that the greater the amount of corrosion the greater was the amount of soda making its appearance around the negative pole, he concluded that the soda was probably a product of the decomposition of the gla.s.s by the electric current; he therefore modified the experiment. He pa.s.sed an electric current through distilled water contained in small cups of agate, previously cleaned by boiling in distilled water for several hours, and connected by threads of the mineral asbestos, chosen as being quite free from vegetable matter; alkali and acid were still produced. The experiment was repeated several times with the same apparatus; acid and alkali were still produced, but the alkali decreased each time. The only conclusion to be drawn was that the alkali came from the water employed. Two small cups of gold were now used to contain the water; a very small amount of alkali appeared at the negative pole, and a little nitric acid at the positive pole. The quant.i.ty of acid slowly increased as the experiment continued, whereas the quant.i.ty of alkali remained the same as after a few minutes'

action of the electric current. The production of alkali is probably due, said Davy, to the presence in the water of some substance which is not removed by distillation in a gla.s.s retort. By boiling down in a silver dish a quant.i.ty of the water he had used, a very small amount of solid matter was obtained, which after being heated was distinctly alkaline. Moreover when a little of this solid matter was added to the water contained in the two golden cups, there was a sudden and marked increase in the amount of alkali formed around the negative pole. Another quant.i.ty of the water which he had used was again distilled in a silver retort, and a little of the distillate was subjected to electrolysis as before. No alkali appeared. A little piece of gla.s.s was placed in the water; alkali quickly began to form. Davy thus conclusively proved that the alkali produced during the electrolysis (_i.e._ decomposition by the electric current) of water is not derived from the water itself, but from mineral impurities contained in the water, or in the vessel in which the water is placed during the experiment.

But the production of nitric acid around the positive pole was yet to be accounted for.

Before further experiments could be made it was necessary that Davy should form an hypothesis--that he should mentally connect the appearance of the nitric acid with some other phenomenon sufficient to produce this appearance; he could then devise experiments which would determine whether the connection supposed to exist between the two phenomena really did exist or not.

Now, of the const.i.tuents of nitric acid--nitrogen, hydrogen and oxygen--all except the first named are present in pure water; nitrogen is present in large quant.i.ty in the ordinary atmosphere. It was only necessary to a.s.sume that some of the hydrogen and oxygen produced during the electrolysis of water seized on and combined with some of the nitrogen in the air which surrounded that water, and the continual production of nitric acid during the whole process of electrolysis was explained.

But how was this a.s.sumption to be proved or disproved? Davy adopted a method frequently made use of in scientific investigations:--remove the a.s.sumed cause of a phenomenon; if the phenomenon ceases to be produced, the a.s.sumed cause is probably the real cause. Davy surrounded the little gold cups containing the water to be electrolysed with a gla.s.s jar which he connected with an air-pump; he exhausted most of the air from the jar and then pa.s.sed the electric current through the water. Very little nitric acid appeared. He now again took out most of the air from the gla.s.s jar, admitted some hydrogen to supply its place, and again pumped this out. This process he repeated two or three times and then pa.s.sed the electric current. _No_ acid appeared in the water. He admitted air into the gla.s.s vessel; nitric acid began to be produced. Thus he proved that whenever air was present in contact with the water being electrolysed, nitric acid made its appearance, and when the air was wholly removed the acid ceased to be produced. As he had previously shown that the production of this acid was not to be traced to impurities in the water, to the nature of the vessel used to contain the water, or to the nature of the material of which the poles of the battery were composed, the conclusion was forced upon him that the production of nitric acid in the water, and the presence of ordinary air around the water invariably existed together; that if one of these conditions was present, the other was also present--in other words, that one was the cause of the other.

The result of this exhaustive and brilliant piece of work is summed up by Davy in these words: "It seems evident then that water, chemically pure, is decomposed by electricity into gaseous matter alone, into oxygen and hydrogen."

From the effects of the electric current on gla.s.s, Davy argued that other earthy compounds would probably undergo change under similar conditions. He therefore had little cups of gypsum made, in which he placed pure water, and pa.s.sed an electric current through the liquid. Lime was formed around the negative, and sulphuric acid around the positive pole. Using similar apparatus, he proved that the electric current decomposes very many minerals into an earthy or alkaline base and an acid.

Picturing to himself the little particles of a salt as being split by the electric current each into two smaller particles, one possessed of acid and the other of alkaline properties, Davy thought it might be possible to intercept the progress of these smaller particles, which he saw ever travelling towards the positive and negative poles of the battery. He accordingly connected these small gla.s.s vessels by threads of washed asbestos; in one of the outer vessels he placed pure water, in the other an aqueous solution of sulphate of potash, and in the central vessel he placed ammonia. The negative pole of the battery being immersed in the sulphate of potash, and the positive pole in the water, it was necessary for the particles of sulphuric acid--produced by the decomposition of the sulphate of potash--to travel through the ammonia in the central vessel before they could find their way to the positive pole. Now, ammonia and sulphuric acid cannot exist in contact--they instantly combine to form sulphate of ammonia; the sulphuric acid particles ought therefore to be arrested by the ammonia. But the sulphuric acid made its appearance at the positive pole just as if the central vessel had contained water. It seemed that the mutual attraction ordinarily exerted between sulphuric acid and ammonia was overcome by the action of the electric current. Ammonia would generally present an insuperable barrier to the progress of sulphuric acid, but the electrical energy appeared to force the acid particles over this barrier; they pa.s.sed towards their goal as if nothing stood in their way.

Experiments are now multiplied by Davy, and the general conclusion drawn is that "Hydrogen, the alkaline substances, the metals and certain metallic oxides are attracted by negatively electrified metallic surfaces, and repelled by positively electrified metallic surfaces; and contrariwise, that oxygen and acid substances are attracted by positively electrified metallic surfaces, and repelled by negatively electrified metallic surfaces; and these attractive and repulsive forces are sufficiently energetic to destroy or suspend the usual operation of chemical affinity."[10]

To account for this apparent suspension of the ordinary chemical laws, Davy supposes that chemical compounds are continually decomposed and re-formed throughout the liquid which is subjected to the electrical action. Thus, in the experiment with water, ammonia and sulphate of potash, he supposes that the sulphuric acid and ammonia do combine in the central vessel to form sulphate of ammonia, but that this compound is again decomposed, by the electrical energy, into sulphuric acid--which pa.s.ses on towards the positive pole--and ammonia--which remains in the central vessel--ready to combine with more sulphuric acid as that comes travelling onwards from its source in the vessel containing sulphate of potash to its goal in the vessel containing water.

The eye of the philosopher had pierced beneath the apparent stability of the chemical systems which he studied. To his vision there appeared in those few drops of water and ammonia and sulphate of potash a never-ceasing conflict of contending forces; there appeared a continual shattering and rebuilding of the particles of which the ma.s.ses were composed. The whole was at rest, the parts were in motion; the whole was constant in chemical composition, the composition of each particle was changed a thousand times in the minutest portion of every second. To the mind of Davy, the electrolysis of every chemical compound was a new application of the great law established by Newton--"To every action there is an equal and opposite reaction."

Each step made in chemical science since Davy's time has but served to emphasize the universality of this principle of action and reaction, a principle which has been too much overlooked in the chemical text-books, but the importance of which recent researches are beginning to impress on the minds of chemists.

It is the privilege of the philosophic student of Nature to penetrate the veil with which she conceals her secrets from the vulgar gaze. To him are shown sights which "eye hath not seen," and by him are perceived sounds which "ear hath not heard." Each drop of water is seen by him not only to be built up of myriads of small parts, but each particle is seen to be in motion; many particles are being decomposed into still smaller particles of matter, different in properties from the original particles, but as the original particles are at the same time being reproduced, the continued existence of the drop of water with the properties of water is to him the result of the mutual action and reaction of contending forces. He knows that rest and permanence are gained, not by the cessation of action, but by the continuance of conflict; he knows that in the realm of natural phenomena, stable equilibrium is the resultant of the action of opposite forces, and that complete decomposition occurs only when one force becomes too powerful or another becomes too weak.

Pursuing the train of thought initiated by the experiments which I have described, Davy entered upon a series of researches which led him to consider every chemical substance as possessing definite electrical relations towards every other substance. "As chemical attraction between two bodies seems to be destroyed by giving one of them an electrical state different from that which it naturally possessed--that is, by bringing it into a state similar to the other--so it may be increased by exalting its natural energy." Thus zinc, a metal easily oxidized, does not combine with oxygen when negatively electrified, whereas silver, a metal oxidized with difficulty, readily combines with oxygen when positively electrified.

Substances in opposite electrical states appear to combine chemically, and the greater the electrical difference the greater the readiness with which chemical combination is effected. Electrical energy and chemical attraction or _affinity_ are evidently closely connected; perhaps, said Davy, they are both results of the same cause.

Thus Davy arrived at the conception of a system of bodies as maintained in equilibrium by the mutual actions and reactions of both chemical and electrical forces; by increasing either of these a change is necessarily produced in the other. Under certain electrical conditions the bodies will exert no chemical action on one another, but such action may be started by changing these electrical conditions, or, on the other hand, by changes in the chemical relations of the bodies a change in the electrical relations may be induced. Thus Davy found that if plates of copper and sulphur are heated, the copper exhibits a positive and the sulphur a negative electrical condition; that these electrical states become more marked as temperature rises, until the melting point of sulphur is reached, when the copper and sulphur combine together chemically and produce sulphide of copper.

When water is electrolysed, Davy looked on the oppositely electrified metallic plates in the battery as striving to attain a state of equilibrium; the negatively electrified zinc strives to gain positive electricity from the copper, which strives to gain negative electricity from the zinc. The water he regarded as the carrier of these electricities, the one in this direction, the other in that. In thus acting as a carrier, the water is itself chemically decomposed, with production of hydrogen and oxygen; but this chemical rearrangement of some of the substances which composed the original system (of battery and water) involves a fresh disturbance of electrical energy, and so the process proceeds until the whole of the water is decomposed or the whole of the copper or zinc plate is dissolved in the battery. If the water were not chemically decomposed, Davy thought that the zinc and copper in the battery would quickly attain the state of electrical equilibrium towards which they continually strive, and that the current would therefore quickly cease.

Davy thought that "however strong the natural electrical energies of the elements of bodies may be, yet there is every probability of a limit to their strength; whereas the powers of our artificial instruments seem capable of indefinite increase." By making use of a very powerful battery, he hoped to be able to decompose substances generally regarded as simple bodies.

Taking a wide survey of natural phenomena, he sees these two forces, which we call chemical and electrical, everywhere at work, and by their mutual actions upholding the material universe in equilibrium. In the outbreaks of volcanoes he sees the disturbance of this equilibrium by the undue preponderance of electrical force; and in the formation of complex minerals beneath the surface of the earth, he traces the action of those chemical attractions which are ever ready to bring about the combination of elements, if they are not held in check by the opposing influence of electrical energy.

We shall see how the great and philosophical conception of Davy was used by Berzelius, and how, while undoubtedly gaining in precision, it lost much in breadth in being made the basis of a rigid system of chemical cla.s.sification.

Davy's hope that the new instrument of research placed in the hands of chemists by Volta would be used in the decomposition of supposed simple substances was soon to be realized. A year after the lecture "On some Chemical Agencies of Electricity," Davy was again the reader of the Bakerian Lecture; this year (1807) it was ent.i.tled, "On some New Phenomena of Chemical Change produced by Electricity, particularly the Decomposition of the Fixed Alkalis; and the Exhibition of the New Substances which const.i.tute their Bases; and on the General Nature of Alkaline Bodies."

In his first experiments on the effect of the electrical current on potash and soda, Davy used strong aqueous solutions of these alkalis, with the result that hydrogen and oxygen only were evolved. He then pa.s.sed the current through melted potash kept liquid during the operation by the use of a spirit-lamp, the flame of which was fed with oxygen. Much light was evolved, and a great flame appeared at the negative pole; on changing the direction of the current, "aeriform globules, which inflamed in the air, rose through the potash."

On the 6th of October 1807, a piece of potash was placed on a disc of platinum, which was made the negative pole of a very powerful battery; a platinum wire brought into contact with the upper surface of the potash served as the positive pole. When the current was pa.s.sed, the potash became hot and soon melted; gas was evolved at the upper surface, and at the lower (negative) side "there was no liberation of elastic fluid, but small globules, having a high metallic l.u.s.tre, and being precisely similar in visible characters to quicksilver appeared, some of which burst with explosion and bright flame as soon as they were formed, and others remained, and were merely tarnished, and finally covered by a white film which formed on their surfaces."