Faraday as a Discoverer - John Tyndall (children's ebooks online txt) 📗

into the heart of the decomposing body itself; he sees, and rightly sees, active within it the forces which produce the decomposition, and he rejects, and rightly rejects, the notion of external attraction; but beyond the hypothesis of decompositions and recompositions, enunciated and developed by Grothuss and Davy, he does not, I think, help us to any definite conception as to how the force reaches the decomposing mass and acts within it. Nor, indeed, can this be done, until we know the true physical process which underlies what we call an electric current.

 

Faraday conceives of that current as ‘an axis of power having contrary forces exactly equal in amount in opposite directions’; but this definition, though much quoted and circulated, teaches us nothing regarding the current. An ‘axis’ here can only mean a direction; and what we want to be able to conceive of is, not the axis along which the power acts, but the nature and mode of action of the power itself. He objects to the vagueness of De la Rive; but the fact is, that both he and De la Rive labour under the same difficulty. Neither wishes to commit himself to the notion of a current compounded of two electricities flowing in two opposite directions: but the time had not come, nor is it yet come, for the displacement of this provisional fiction by the true mechanical conception. Still, however indistinct the theoretic notions of Faraday at this time may be, the facts which are rising before him and around him are leading him gradually, but surely, to results of incalculable importance in relation to the philosophy of the voltaic pile.

 

He had always some great object of research in view, but in the pursuit of it he frequently alighted on facts of collateral interest, to examine which he sometimes turned aside from his direct course.

Thus we find the series of his researches on electrochemical decomposition interrupted by an inquiry into ‘the power of metals and other solids, to induce the combination of gaseous bodies.’ This inquiry, which was received by the Royal Society on Nov. 30, 1833, though not so important as those which precede and follow it, illustrates throughout his strength as an experimenter. The power of spongy platinum to cause the combination of oxygen and hydrogen had been discovered by Dobereiner in 1823, and had been applied by him in the construction of his well-known philosophic lamp. It was shown subsequently by Dulong and Thenard that even a platinum wire, when perfectly cleansed, may be raised to incandescence by its action on a jet of cold hydrogen.

 

In his experiments on the decomposition of water, Faraday found that the positive platinum plate of the decomposing cell possessed in an extraordinary degree the power of causing oxygen and hydrogen to combine. He traced the cause of this to the perfect cleanness of the positive plate. Against it was liberated oxygen, which, with the powerful affinity of the ‘nascent state,’ swept away all impurity from the surface against which it was liberated. The bubbles of gas liberated on one of the platinum plates or wires of a decomposing cell are always much smaller, and they rise in much more rapid succession than those from the other. Knowing that oxygen is sixteen times heavier than hydrogen, I have more than once concluded, and, I fear, led others into the error of concluding, that the smaller and more quickly rising bubbles must belong to the lighter gas.

The thing appeared so obvious that I did not give myself the trouble of looking at the battery, which would at once have told me the nature of the gas. But Faraday would never have been satisfied with a deduction if he could have reduced it to a fact. And he has taught me that the fact here is the direct reverse of what I supposed it to be. The small bubbles are oxygen, and their smallness is due to the perfect cleanness of the surface on which they are liberated.

The hydrogen adhering to the other electrode swells into large bubbles, which rise in much slower succession; but when the current is reversed, the hydrogen is liberated upon the cleansed wire, and then its bubbles also become small.

 

Footnotes to Chapter 5

 

[1] Buff finds the quantity of electricity associated with one milligramme of hydrogen in water to be equal to 45,480 charges of a Leyden jar, with a height of 480 millimetres, and a diameter of 160

millimetres. Weber and Kohlrausch have calculated that, if the quantity of electricity associated with one milligramme of hydrogen in water were diffused over a cloud at a height of 1000 metres above the earth, it would exert upon an equal quantity of the opposite electricity at the earth’s surface an attractive force of 2,268,000

kilogrammes. (Electrolytische Maasbestimmungen, 1856, p. 262.) [2] Faraday, sa Vie et ses Travaux, p. 20.

 

Chapter 6.

 

Laws of electrochemical 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 Electrochemical 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 electrochemical 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 electrochemical 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 Electrochemical 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