OF ELECTRO-CHEMISTRY. Electricity, like chemistry, is a modern science; for it can scarcely claim an older origin than the termination of the first quarter of the preceding century; and during the last half of that century, and a small portion of the present, it participated with chemistry in the zeal and activity with which it was cultivated by the philosophers of Europe and America. For many years it was not suspected that any connexion existed between chemistry and electricity; though some of the meteorological phenomena, especially the production of clouds and the formation of rain, which are obviously connected with chemistry, seem likewise to claim some connexion with the agency of electricity. The discovery of the intimate relation between chemistry and electricity was one of the consequences of a controversy carried on about the year 1790 between Galvani and Volta, two Italian philosophers, whose discoveries will render their names immortal. Galvani, who was a professor of anatomy, was engaged in speculations respecting muscular motion. He was of opinion that a peculiar fluid was secreted in the brain, which was sent along the nerves to all the different parts of the body. This nervous fluid possessed many characters analogous Volta, who repeated these experiments, explained them in a different manner. According to him, the convulsions were produced by the passage of a current of common electricity through the limb of the frog, which was thrown into a state of convulsion merely in consequence of its irritability. This irritability vanishes after the death of the muscle; accordingly it is only while the principle of life remains that the convulsions can be produced. Every metallic conductor, according to him, possesses a certain electricity which is peculiar to it, either positive or negative, though the quantity is so small, as to be imperceptible, in the common state of the metal. But if a metal, naturally positive, be placed in contact, while insulated, with a metal naturally negative, the charge of electricity in both is increased by induction, and becomes perceptible when the two metals are separated and presented to a sufficiently delicate electrometer. Thus zinc is naturally positive, and copper and silver naturally negative. If we take two discs of copper and zinc, to the centre Such was Volta's simple explanation of the convulsions produced in galvanic experiments in the limb of a frog. Galvani was far from allowing the accuracy of it; and, in order to obviate the objection to his reasoning advanced by Volta from the necessity of employing two metals, he showed that the convulsions might, in certain cases, be produced by one metal. Volta showed that a very small quantity of one metal, either alloyed with, or merely in contact with another, were capable of inducing the two electricities. But in order to prove in the most unanswerable manner that the two electricities were induced when two different metals were placed in contact, he contrived the following piece of apparatus: He procured a number (say 50) of pieces of zinc, about the size of a crown-piece, and as many pieces of copper, and thirdly, the same number of pieces of card of the same size. The cards were steeped in a solution of salt, so as to be moist. He lays upon the table a piece of zinc, places over it a piece of copper, and then a piece of moist card. Over the card is placed a second piece of zinc, then a piece of copper, then a piece of wet card. In this way Messrs. Nicholson and Carlisle were the first persons who repeated Volta's experiments with this apparatus, which speedily drew the attention of all Europe. They ascertained that the zinc end of the pile was positive and the copper end negative. Happening to put a drop of water on the uppermost plate, and to put into it the extremity of a gold wire connected with the undermost plate, they observed an extrication of air-bubbles from the wire. This led them to suspect that the water was decomposed. To determine the point, they collected a little of the gas extricated and found it hydrogen. They then attached a gold wire to the zinc end of the pile, and another gold wire to the copper end, and plunged the two wires into a glass of water, taking care not to allow them to touch each other. Gas was extricated from both wires. On collecting that from the wire attached to the zinc end, it was found to be oxygen gas, while that from the copper end was hydrogen gas. The volume of hydrogen gas extricated was just double that of the oxygen gas; and the two gases being mixed, and an electric spark passed through them, they burnt with an explosion, and were completely converted into water. Thus it was demonstrated that water was decomposed by the action of the pile, and that the oxygen was extricated from the positive pile and the hydrogen from the negative. This held when the communicating wires were gold or platinum; but if they were of copper, silver, iron, lead, tin, or zinc, then only hydrogen gas was extricated from the negative wire. The positive wire extricated little or no gas; but it was rapidly oxidized. Thus the connexion between chemical decompositions and electrical currents was first established. It was soon after observed by Henry, Haldane, Davy, and other experimenters, that other chemical But it was Davy that first completely elucidated the chemical decompositions produced by galvanic electricity, who first explained the laws by which these decompositions were regulated, and who employed galvanism as an instrument for decomposing various compounds, which had hitherto resisted all the efforts of chemists to reduce them to their elements. These discoveries threw a blaze of light upon the obscurest parts of chemistry, and secured for the author of them an immortal reputation. Humphry Davy, to whom these splendid discoveries were owing, was born at Penzance, in Cornwall, in the year 1778. He displayed from his very infancy a spirit of research, and a brilliancy of fancy, which augured, even at that early period, what he was one day to be. When very young, he was bound apprentice to an apothecary in his native town. Even at that time, his scientific acquirements were so great, that they drew the attention of Mr. Davis Gilbert, the late distinguished president of the Royal Society. It was by his advice that he resolved to devote himself to chemistry, as the pur After the discovery of the different gases, and the investigation of their properties by Dr. Priestley, it occurred to various individuals, nearly about the same time, that the employment of certain gases, or at least of mixtures of certain gases, with common air in respiration, instead of common air, might be powerful means of curing diseases. Dr. Beddoes, at that time professor of chemistry at Oxford, was one of the keenest supporters of these opinions. Mr. Watt, of Birmingham, and Mr. Wedgewood, entertained similar sentiments. About the beginning of the present century, a sum of money was raised by subscription, to put these opinions to the test of experiment; and, as Dr. Beddoes had settled as a physician in Bristol, it was agreed upon that the experimental investigation should take place at Bristol. But Dr. Beddoes was not qualified to superintend an institution of the kind: it was necessary to procure a young man of zeal and genius, who would take such an interest in the investigation as would compensate for the badness of the apparatus and the defects of the arrangements. The greatest part of the money had been subscribed by Mr. Wedgewood and Mr. Watt: their influence of course would A few years before, a philosophical institution had been established in London, under the auspices of Count Rumford, which had received the name of the Royal Institution. Lectures on chemistry and natural philosophy were delivered in this institution; a laboratory was provided, and a library established. In 1811 he was knighted, and soon after married Mrs. Apreece, a widow lady, daughter of Mr. Ker, who had been secretary to Lord Rodney, and had made a fortune in the West Indies. He was soon after created a baronet. About this time he resigned his situation as professor of chemistry in the Royal Institution, and went to the continent. He remained for some years in France and Italy. In the year 1821, when Sir Joseph Banks died, a very considerable number of the fellows offered their votes to Dr. Wollaston; but he declined standing as a candidate for the president's chair. Sir Humphry Davy, on the other hand, was anxious to obtain that honourable situation, and was accordingly elected president by a very great majority of votes on the 30th of November, 1821. This honourable situa It was his celebrated paper "On some chemical Agencies of Electricity," inserted in the Philosophical Transactions for 1807, that laid the foundation of the high reputation which he so deservedly acquired. I consider this paper not merely as the best of all his own productions, but as the finest and completest specimen of inductive reasoning which appeared during the age in which he lived. It had been already observed, that when two platinum wires from the two poles of a galvanic pile are plunged each into a vessel of water, and the two vessels united by means of wet asbestos, or any other conducting substance, an acid appeared round the positive wire and an alkali round the negative wire. The alkali was said by some to be soda, by others to be ammonia. The acid was variously stated to be nitric acid, muriatic acid, or even chlorine. Davy demonstrated, by decisive experiments, that in all cases the acid and alkali are derived from the decomposition of some salt contained either in the water or in the vessel containing the water. Most commonly the salt decomposed is common salt, because it exists in water and in agate, basalt, and various other stony bodies, which he employed as vessels. When the same agate cup was used in successive experiments, the quantity of acid and alkali evolved diminished each time, and at last no appreciable quantity could be perceived. When glass vessels When a salt was put into the vessel in which the positive wire dipped, the vessel into which the negative wire dipped being filled with pure water, and the two vessels being united by means of a slip of moistened asbestos, the acid of the salt made its appearance round the positive wire, and the alkali round the negative wire, before it could be detected in the intermediate space; but if an intermediate vessel, containing a substance for which the alkali has a strong affinity, be placed between these two vessels, the whole being united by means of slips of asbestos, then great part, or even the whole of the alkali, was stopped in this intermediate vessel. Thus, if the salt was nitrate of barytes, and sulphuric acid was placed in the intermediate vessel, much sulphate of barytes was deposited in the intermediate vessel, and very little or even no barytes made its appearance round the negative wire. Upon this subject a most minute, extensive, and satisfactory series of experiments was made by Davy, leaving no doubt whatever of the accuracy of the fact. The conclusions which he drew from these experiments are, that all substances which have a chemical affinity for each other, are in different states of electricity, and that the degree of affinity is proportional to the intensity of these opposite states. According to this view of the subject, chemical affinity is merely a case of the attractions exerted by bodies in different states of electricity. Volta first broached the idea, that every body possesses naturally a certain state of electricity. Davy went a step further, and concluded, that the attractions which exist between the atoms of different bodies are merely the consequence of these different states of electricity. The proof of this opinion is founded on the fact, that if we present to a compound, sufficiently strong electrical poles, it will be separated into its constituents, and one of these constituents will invariably make its way to the positive and the other to the negative pole. Now bodies in a state of electrical excitement always attract those that are in the opposite state. If electricity be considered as consisting of two distinct fluids, which attract each other with a force Such is a very imperfect outline of the electrical theory of affinity first proposed by Davy to account for the decompositions produced by electricity. It has been universally adopted by chemists; and some progress has been made in explaining and accounting for the different phenomena. It would be improper, in a work of this kind, to enter further into the subject. Those who are interested in such discussions will find a good deal of information in the first volume of Berzelius's Treatise on Chemistry, in the introduction to the TraitÉ de Chimie appliquÉ aux Arts, by Dumas, or in the introduction to my System of Chemistry, at present in the press. Davy having thus got possession of an engine, by means of which the compounds, whose constituents adhered to each other might be separated, immediately applied it to the decomposition of potash and soda; bodies which were admitted to be compounds, though all attempts to analyze them had hitherto failed. His attempt was successful. When a platinum wire from the negative pole of a strong battery in full action was applied to a lump of potash, slightly moistened, and lying on a platinum tray attached to the positive pole of the battery, small globules of a white metal soon appeared at its extremity. This white metal he speedily proved to be the basis of potash. He gave it the name of potassium, and very soon proved, that potash is a compound of five parts by weight of this metal and one part of oxygen. Potash, then, is a metallic oxide. He proved soon after that soda is a compound of oxygen and another white metal, to which he gave the name of sodium. Lime is a compound of calcium and oxygen, magnesia of magnesium and oxygen, barytes of barium and oxygen, and strontian of strontium and oxygen. In short, the fixed alkalies and alkaline earths, are metallic oxides. When lithia was afterwards discovered Davy did not succeed so well in decomposing alumina, glucina, yttria, and zirconia, by the galvanic battery: they were not sufficiently good conductors of electricity; but nobody entertained any doubt that they also were metallic oxides. They have been all at length decomposed, and their bases obtained by the joint action of chlorine and potassium, and it has been demonstrated, that they also are metallic oxides. Thus it has been ascertained, in consequence of Davy's original discovery of the powers of the galvanic battery, that all the bases formerly distinguished into the four classes of alkalies, alkaline earths, earths proper, and metallic oxides, belong in fact only to one class, and are all metallic oxides. Important as these discoveries are, and sufficient as they would have been to immortalize the author of them, they are not the only ones for which we are indebted to Sir Humphry Davy. His experiments on chlorine are not less interesting or less important in their consequences. I have already mentioned in a former chapter, that Berthollet made a set of experiments on chlorine, from which he had drawn as a conclusion, that it is a compound of oxygen and muriatic acid, in consequence of which it got the name of oxymuriatic acid. This opinion of Berthollet had been universally adopted by chemists, and admitted by them as a fundamental principle, till Gay-Lussac and Thenard endeavoured, unsuccessfully, to decompose this gas, or to resolve it into muriatic acid and chlorine. They showed, in the clearest manner, that such a resolution was impossible, and that no direct evidence could be ad The very curious and important facts respecting chlorine and muriatic acid gas which they had ascertained, were made known by Gay-Lussac and Thenard to the Institute, on the 27th of February, 1809, and an abstract of them was published in the second volume of the MÉmoires d'Arcueil. There can be little doubt that it was in consequence of these curious and important experiments of the French chemists that Davy's attention was again turned to muriatic acid gas. He had already, in 1808, shown that when potassium is heated in muriatic acid gas, muriate of potash is formed, and a quantity of hydrogen gas evolved, amounting to more than one-third of the muriatic acid gas employed, and he had shown, that in no case can muriatic acid be obtained This was introducing an alteration in chemical theory of the same kind, and nearly as important, as was introduced by Lavoisier, with respect to the action of oxygen in the processes of combustion and calcination. It had been previously supposed that sulphur, phosphorus, charcoal, and metals, were compounds; one of the constituents of which was phlogiston, and the other the acids or oxides which remained after the combustion or calcination had taken place. Lavoisier showed that the sulphur, phosphorus, charcoal, and metals, were simple substances; and that the acids or calces formed were compounds of these simple bodies and oxygen. In like manner, Davy showed that chlorine, instead of being a compound of muriatic acid and oxygen, was, in fact, a simple substance, and muriatic acid a compound of chlorine and hydrogen. This new doctrine immediately overturned the Lavoisierian hypothesis respecting oxygen as the acidifying principle, and altered all the previously received notions respecting the muriates. What had been called muriates were, in fact, combinations of chlorine with the combustible or metal, and were analogous to oxides. Thus, when muriatic acid gas was made to act upon hot litharge, a double decomposition took place, the chlorine united to the lead, while the hydrogen of the muriatic acid united with the oxygen of the litharge, and formed water. Hence the reason of the appearance of water in this case; and hence It was not likely that this new opinion of Davy should be adopted by chemists in general, without a struggle to support the old opinions. But the feebleness of the controversy which ensued, affords a striking proof how much chemistry had advanced since the days of Lavoisier, and how free from prejudices chemists had become. One would have expected that the French chemists would have made the greatest resistance to the admission of these new opinions; because they had a direct tendency to diminish the reputation of two of their most eminent chemists, Lavoisier and Berthollet. But the fact was not so: the French chemists showed a degree of candour and liberality which redounds highly to their credit. Berthollet did not enter at all into the controversy. Gay-Lussac and Thenard, in their Recherches Physico-chimiques, published in 1811, state their reasons for preferring the old hypothesis to the new, but with great modesty and fairness; and, within less than a year after, they both adopted the opinion of Davy, that chlorine is a simple substance, and muriatic acid a compound of hydrogen and chlorine. The only opponents to the new doctrine who appeared against it, were Dr. John Murray, of Edinburgh, and Professor Berzelius, of Stockholm. Dr. Murray was a man of excellent abilities, and a very zealous cultivator of chemistry; but his health had been always very delicate, which had prevented him from dedicating so much of his time to experimenting as he otherwise would have been inclined to do. The only experimental investigations into which he entered was the analysis of some mineral waters. Dr. John Davy was the brother of Sir Humphry, and had shown, by his paper on fluoric acid and on the chlorides, that he possessed the same dexterity and the same powers of inductive reasoning, which had given so much celebrity to his brother. The controversy between him and Dr. Murray was carried on for some time with much spirit and ingenuity on both sides, and was productive of some advantage to the science of chemistry, by the discovery of phosgene gas or chlorocarbonic acid, which was made by Dr. Davy. It is needless to say to what side the victory fell. The whole chemical world has for several years unanimously adopted the theory of Davy; showing sufficiently the opinion entertained respecting the arguments advanced by either party. Berzelius supported the old opinion respecting the compound nature of chlorine, in a paper which he published in the Annals of Philosophy. No person thought it worth while to answer his arguments, though Sir Humphry Davy made a few animadversions upon one or two of his experiments. The discovery of iodine, which took place almost immediately after, afforded so close an analogy with chlorine, and the nature of the compounds which it forms was so obvious and so well made out, that chemists were immediately satisfied; and they furnished so satisfactory an answer to all the objections of Berzelius, that I am not aware of any person, either in Great Britain or in France, who adopted his opinions. I have not the same means of knowing the impression which his paper made upon the chemists of Germany and Sweden. Berzelius con The recent discovery of bromine, by Balard, has added another strong analogy in favour of Davy's theory; as has likewise the discovery by Gay-Lussac respecting prussic acid. At present, then, (not reckoning sulphuretted and telluretted hydrogen gas), we are acquainted with four acids which contain no oxygen, but are compounds of hydrogen with another negative body. These are
So that even if we were to leave out of view the chlorine acids, the sulphur acids, &c., no doubt can be entertained that many acids exist which contain no oxygen. Acids are compounds of electro-negative bodies and a base, and in them all the electro-negative electricity continues to predominate. Next to Sir Humphry Davy, the two chemists who have most advanced electro-chemistry are Gay-Lussac and Thenard. About the year 1808, when the attention of men of science was particularly drawn towards the galvanic battery, in consequence The first part contains a very minute and interesting examination of the galvanic battery, and upon what circumstances its energy depends. They tried the effect of various liquid conductors, varied the strength of the acids and of the saline solutions. This division of their labours contains much valuable information for the practical electro-chemist, though it would be inconsistent with the plan of this work to enter into details. The next division of the work relates to potassium. Davy had hitherto produced that metal only in minute quantities by the action of the galvanic battery upon potash. But Gay-Lussac and Thenard contrived a process by which it can be prepared on a large scale by chemical decomposition. Their Being thus in possession, both of potassium and sodium in considerable quantities, they were enabled to examine its properties more in detail than Davy had done: but such was the care and industry with which Davy's experiments had been made that very little remained to be done. The specific gravity of the two metals was determined with more precision than it was possible for Davy to do. They determined the action of these metals on water, and measured the quantity of hydrogen gas given out with more precision than Davy could. They discovered also, by heating these metals in oxygen gas, that they were capable of uniting with an additional dose of oxygen, and of forming peroxides of potassium and sodium. These oxides have a yellow colour, and give out the surplus oxygen, and are brought back to the state of potash and soda when they are plunged into water. They exposed a great variety of substances to the action By heating together anhydrous boracic acid and potassium in a copper tube, they succeeded in decomposing the acid, and in showing it to be a compound of oxygen, and a black matter like charcoal, to which the name of boron has been given. They examined the properties of boron in detail, but did not succeed in determining with exactness the proportions of the constituents of boracic acid. The subsequent experiments of Davy, though not exact, come a good deal nearer the truth. Their experiments on fluoric acid are exceedingly valuable. They first obtained that acid in a state of purity, and ascertained its properties. Their attempts to decompose it as well as those of Davy, ended in disappointment. But Ampere conceived the idea that this acid, like muriatic acid, is a compound of hydrogen with an unknown supporter of combustion, to which the name fluorine was given. This opinion was adopted by Davy, and his experiments, though they do not absolutely prove the truth of the opinion, give it at least considerable probability, and have disposed chemists in general to adopt it. The subsequent researches of Berzelius, while they have added a great deal to our former knowledge respecting fluoric acid and its compounds, have all tended to confirm and establish the doctrine that it is a hydracid, and similar in its nature to the other hydracids. But such is the tendency of fluorine to combine with every substance, that hitherto it has been impossible to obtain it in an insulated state. We want therefore, still, a decisive proof of the accuracy of the opinion. To the experiments of Gay-Lussac and Thenard I pass over a vast number of other new and important facts and observations contained in this admirable work, which ought to be studied with minute attention by every person who aspires at becoming a chemist. Besides the numerous discoveries contained in the Recherches Physico-chimique, Gay-Lussac is the author of two of so much importance that it would be wrong to omit them. He showed that cyanogen is one of the constituents of prussic acid; succeeded in determining the composition of cyanogen, and showing it to be a compound of two atoms of carbon and one atom of azote. Prussic acid is a compound of one atom of hydrogen and one atom of cyanogen. Sulpho-cyanic acid, discovered by Mr. Porrett, is a compound of one atom sulphuric, and one atom cyanogen; chloro-cyanic acid, discovered by Berthollet, is a compound of one atom chlorine and one atom cyanogen; while cyanic acid, discovered by WÖhler, is a compound of one atom oxygen and one atom cyanogen. I take no notice of the fulminic acid; because, although Gay-Lussac's experiments are exceedingly ingenious, and his reasoning very plausible, it is not quite convincing; especially as the results obtained by Mr. Edmund Davy, and detailed by him in his late interesting memoir on this subject, are somewhat different. The other discovery of Gay-Lussac is his demonstration of the peculiar nature of iodine, his account of iodic and hydriodic acids, and of many To M. Thenard we are indebted for the discovery of the important fact, that hydrogen is capable of combining with twice as much oxygen as exists in water, and determining the properties of this curious liquid which has been called deutoxide of hydrogen. It possesses bleaching properties in perfection, and I think it likely that chlorine owes its bleaching powers to the formation of a little deutoxide of hydrogen in consequence of its action on water. The mantle of Davy seems in some measure to have descended on Mr. Faraday, who occupies his old place at the Royal Institution. He has shown equal industry, much sagacity, and great powers of invention. The most important discovery connected with electro-magnetism, next to the great fact, for which we are indebted to Professor Œrstedt of Copenhagen, is due to Mr. Faraday; I mean the rotation of the electric wires round the magnet. To him we owe the knowledge of the fact, that several of the gases can be condensed into liquids by the united action of pressure and cold, which has removed the barrier that separated gaseous bodies from vapours, and shown us that all owe their elasticity to the same cause. To him also we owe the knowledge of the important fact, that chlorine is capable of combining with carbon. This has considerably improved the history of chlorine and served still further to throw new light on the analogy which exists between all the supporters of combustion. They are doubtless all of them capable of combining with every one of the other simple bodies, and of |