Chapter 6.

Previous
Laws of electro-chemical decomposition.

In our conceptions and reasonings regarding the forces of nature, we perpetually make use of symbols which, when they possess a high representative value, we dignify with the name of theories. Thus, prompted by certain analogies, we ascribe electrical phenomena to the action of a peculiar fluid, sometimes flowing, sometimes at rest. Such conceptions have their advantages and their disadvantages; they afford peaceful lodging to the intellect for a time, but they also circumscribe it, and by-and-by, when the mind has grown too large for its lodging, it often finds difficulty in breaking down the walls of what has become its prison instead of its home. (1)

No man ever felt this tyranny of symbols more deeply than Faraday, and no man was ever more assiduous than he to liberate himself from them, and the terms which suggested them. Calling Dr. Whewell to his aid in 1833, he endeavoured to displace by others all terms tainted by a foregone conclusion. His paper on Electro-chemical Decomposition, received by the Royal Society on January 9, 1834, opens with the proposal of a new terminology. He would avoid the word 'current' if he could. (2) He does abandon the word 'poles' as applied to the ends of a decomposing cell, because it suggests the idea of attraction, substituting for it the perfectly natural term Electrodes. He applied the term Electrolyte to every substance which can be decomposed by the current, and the act of decomposition he called Electrolysis. All these terms have become current in science. He called the positive electrode the Anode, and the negative one the Cathode, but these terms, though frequently used, have not enjoyed the same currency as the others. The terms Anion and Cation, which he applied to the constituents of the decomposed electrolyte, and the term Ion, which included both anions and cations, are still less frequently employed.

Faraday now passes from terminology to research; he sees the necessity of quantitative determinations, and seeks to supply himself with a measure of voltaic electricity. This he finds in the quantity of water decomposed by the current. He tests this measure in all possible ways, to assure himself that no error can arise from its employment. He places in the course of one and the same current a series of cells with electrodes of different sizes, some of them plates of platinum, others merely platinum wires, and collects the gas liberated on each distinct pair of electrodes. He finds the quantity of gas to be the same for all. Thus he concludes that when the same quantity of electricity is caused to pass through a series of cells containing acidulated water, the electro-chemical action is independent of the size of the electrodes. (3) He next proves that variations in intensity do not interfere with this equality of action. Whether his battery is charged with strong acid or with weak; whether it consists of five pairs or of fifty pairs; in short, whatever be its source, when the same current is sent through his series of cells the same amount of decomposition takes place in all. He next assures himself that the strength or weakness of his dilute acid does not interfere with this law. Sending the same current through a series of cells containing mixtures of sulphuric acid and water of different strengths, he finds, however the proportion of acid to water might vary, the same amount of gas to be collected in all the cells. A crowd of facts of this character forced upon Faraday's mind the conclusion that the amount of electro-chemical decomposition depends, not upon the size of the electrodes, not upon the intensity of the current, not upon the strength of the solution, but solely upon the quantity of electricity which passes through the cell. The quantity of electricity he concludes is proportional to the amount of chemical action. On this law Faraday based the construction of his celebrated Voltameter, or Measure of Voltaic electricity.

But before he can apply this measure he must clear his ground of numerous possible sources of error. The decomposition of his acidulated water is certainly a direct result of the current; but as the varied and important researches of MM. Becquerel, De la Rive, and others had shown, there are also secondary actions which may materially interfere with and complicate the pure action of the current. These actions may occur in two ways: either the liberated ion may seize upon the electrode against which it is set free, forming a chemical compound with that electrode; or it may seize upon the substance of the electrolyte itself, and thus introduce into the circuit chemical actions over and above those due to the current. Faraday subjected these secondary actions to an exhaustive examination. Instructed by his experiments, and rendered competent by them to distinguish between primary and secondary results, he proceeds to establish the doctrine of 'Definite Electro-chemical Decomposition.'

Into the same circuit he introduced his voltameter, which consisted of a graduated tube filled with acidulated water and provided with platinum plates for the decomposition of the water, and also a cell containing chloride of tin. Experiments already referred to had taught him that this substance, though an insulator when solid, is a conductor when fused, the passage of the current being always accompanied by the decomposition of the chloride. He wished to ascertain what relation this decomposition bore to that of the water in his voltameter.

Completing his circuit, he permitted the current to continue until 'a reasonable quantity of gas' was collected in the voltameter. The circuit was then broken, and the quantity of tin liberated compared with the quantity of gas. The weight of the former was 3.2 grains, that of the latter 0.49742 of a grain. Oxygen, as you know, unites with hydrogen in the proportion of 8 to 1, to form water. Calling the equivalent, or as it is sometimes called, the atomic weight of hydrogen 1, that of oxygen is 8; that of water is consequently 8 + 1 or 9. Now if the quantity of water decomposed in Faraday's experiment be represented by the number 9, or in other words by the equivalent of water, then the quantity of tin liberated from the fused chloride is found by an easy calculation to be 57.9, which is almost exactly the chemical equivalent of tin. Thus both the water and the chloride were broken up in proportions expressed by their respective equivalents. The amount of electric force which wrenched asunder the constituents of the molecule of water was competent, and neither more nor less than competent, to wrench asunder the constituents of the molecules of the chloride of tin. The fact is typical. With the indications of his voltameter he compared the decompositions of other substances, both singly and in series. He submitted his conclusions to numberless tests. He purposely introduced secondary actions. He endeavoured to hamper the fulfilment of those laws which it was the intense desire of his mind to see established. But from all these difficulties emerged the golden truth, that under every variety of circumstances the decompositions of the voltaic current are as definite in their character as those chemical combinations which gave birth to the atomic theory. This law of Electro-chemical Decomposition ranks, in point of importance, with that of Definite Combining Proportions in chemistry.

                                                                                                                                                                                                                                                                                                           

Clyx.com


Top of Page
Top of Page