Nicholson and Carlisle

I It must be noted that already a decade earlier the Dutchmen R van Troostwijk and J.R. Deim [7. Phys. 2,130 (1790)] showed that during spark discharge a (short-time) process of water electrolysis is achieved. These results were known by Nicholson and Carlisle when (using the then new Volta pile) they reported on long-time water electrolysis, but in their publication these results were not mentioned [R. de Levie, 7. Electroanal. Chem., 476, 92 (1999)]. 

Electrolytic water splitting was the first electrochemical process to be performed. Historically, the first experiment on water electrolysis was attributed to Nicholson and Carlisle, who in 1800, using the newly invented Volta s pile, observed the formation of gaseous products in the laboratory [1]. In reality, there are documents proving that Volta himself noted the phenomenon a few years earlier, although he never reported the observation in a publication [2]. 

Water was thought to be an elenient until about the end of the eighteenth century. At that time its composition was shown by the efforts of Cavendish, Priestley, and Lavoh sier, and, later, by Humboldt, Gay-Lussac, Nicholson and Carlisle, Dumas, and Davy. Their labors were so intermingled it will be impossible to follow their experiments chronologically. We shall, therefore, consider only the main facts which contributed to the discovery of the composition of water, together with some later work. 

Water was first decomposed by electricity in 1800 by Nicholson and Carlisle, and confirmed by Davy by a series of brilliant experiments extending through a period of six years. The decomposition of water by electricity is called Electrolysis. 

Shortly after the discovery of the voltaic pile Nicholson and Carlisle demonstrated, in 1800, the electrolytic decomposition of water. These investigators found that hydrogen and oxygen were evolved at the surface of gold and platinum wires if they were connected with the terminals of a pile and dipped in water. 

Nicholson and Carlisle in 1800 split water into oxygen and hydrogen by passing an electric current through it. Water was the first substance to be electrolyzed . 

In effect, Nicholson and Carlisle had decomposed water into hydrogen and oxygen, such decomposition by an electric current being called electrolysis. They had achieved the reverse of Cavendish s experiment (see page 62), in which hydrogen and oxygen had been combined to form water. 

The findings of Nicholson and Carlisle were strengthened by the work of a French chemist, Joseph Louis Gay-Lussac (1778-1850), who reversed matters. He discovered that 2 volumes of hydrogen combined with 1 volume of oxygen to form water. He went on to find, in fact, that when gases combined to form compounds, they always did so in small whole number ratios. Gay-Lussac announced this law of combining volumes in 1808. 

Meanwhile, the electric current, which had been used to such good effect by Nicholson and Carlisle, produced even more startling effects in the isolation of certain new elements. 

Nicholson and Carlisle achieved the first electrolysis of water by means of a battery and observed gas evolution, revealing the production of dIhydrogen. It can be noted that Volta had also achieved similar findings but he did not come to any conclusion. 

For his doctoral dissertation Berzelius built a voltaic pile and studied the effects of galvanic current on patients. He found no effects (and gained no new patients), but this started a chain of thought that culminated 11 years later in a dualistic theory of chemical affinity. Berzelius followed up the experiments of Nicholson and Carlisle to find that not only did electricity split water, but it also split salts. Simultaneously with Davy, who we encounter shortly, he used electrolysis to isolate such alkaline earth metals as calcium and barium. He then proposed a dualistic theory of chemical affinity based on electrical attraction ... 

Volta s letter to Sir Joseph Banks was in two parts and publication was delayed till the second part was received. In the meantime the discovery of the pile was made known in London and experiments with it were begun. The first of these were published by Nicholson and Carlisle, and Cruickshank, whose experiments Davy" said were the true origin of all that has been done in electrochemical science . 

William Cruickshank obtained similar results to those of Nicholson and Carlisle with water and also decomposed solutions of salts. With muriates (chlorides) of soda, ammonia, and magnesia, acid separated at the wire con-... 

Volta had focussed in his work on the source of the electricity in his devices, and had concluded that it emanated from the simple contact of two dissimilar metals he took no note of the chemical changes that accompanied current flow. It was William Nicholson who first established the chemical phenomena associated with galv2uiism, and his work with Carlisle set off the explosion of interest in the chemical aspects of galvanism in the spring of 1800 (6). Although publication of Nicholson and Carlisle s results was withheld until after Volta s paper was read to the Royal Society, word of their discoveries spread rapidly and the assembly of voltaic piles became the rage of scientific inquiry. The natural tendency was to increase the power of the pile by increasing the size and number of... 

Wollaston appeared to take great delight in showing by What small meams he could produce great results (11) Wollaston regularly attended the meetings of the Royal Society amd was fully acquainted with Nicholson and Carlisle s discoveries In a letter dated June 6, 1800 to his close friend Henry Hasted, Wollamton reported... 

The first battery was a pile of discs alternating between silver and zinc interleafed with a separator soaked in an electrolyte. Soon Volta had improved the system with a multicell battery called couronne de tasses, whereby it was possible to draw electric current from that multicell battery at a controlled rate (. After Volta s discovery in 1800, Nicholson and Carlisle in the same year (1800) decomposed water into hydrogen and oxygen by an electric current, and Cruickshank also in 1800 deposited metals from solutions. In 1803, Hisinger and Berzelius showed that when solutions are decomposed by electric current, acids, oxygen and chlorine are deposited at the positive pole, and alkalis, metals and hydrogen at the negative pole. All this within three years of Volta s discovery. 

The science of electrochemistry was born at the end of the eighteenth century following intense interest in the production of electricity by animals such as the torpedo and the electric eel. The key phenomena were observed just at the turn of the century. Volta invented his pile in which chemical species were consumed with the production of electricity and a few months afterwards Nicholson and Carlisle used this electricity to decompose water into hydrogen and oxygen. It is this two-way process which lies at the heart of electrochemistry it may be represented by a very simple diagram... 

Just a few months after the appearance of the Volta pile it was found that the electric current can exert a chemical action. As early as May of 1800, Nicholson and Carlisle carried out water electrolysis. In 1803 the processes of metal electrodeposition were discovered. In 1807 Davy for the first time isolated alkali metals by electrolysis of salt melts. Thus almost simultaneously with the creation of the first electrochemical power source - the "galvanic cell" or "galvanic battery" - many electrochemical processes were discovered and the foundations were laid of the science which to-day we call electrochemistry. 

Galvani — Volta — The Voltaic Pile — Voltaic Batteries — The Contact and Chemical Theories — Nicholson and Carlisle — Cruickshank — Fourcroy — Brugnatelli — Berzelim and Hisinger — Grotthuss. 

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