scholarly journals Second letter on the electrolysis of secondary compounds, addressed to Michael Faraday, Esq., D. C. L., F. R. S., &c. By J. Frederic Daniell. Esq., For. Sec. R. S., Professor of Chemistry in King's College, London

The author, in this letter, prosecutes the inquiry he had commenced in the former one, into the mode in which the chemical elements group themselves together to constitute radicles , or proximate principles. He considers his experiments as establishing the principle that, considered as electrolytes, the inorganic oxy-acid salts must be regarded as compounds of metals, or of that extraordinary compound of nitrogen and four equivalents of hydrogen to which Berzelius has given the name of ammonium , and compound anions, chlorine, iodine, &c., of the Haloide salts; and as showing that this evidence goes far to establish experimentally the hypothesis originally brought forward by Davy, of the general analogy in the constitution of all salts, whether derived from oxy-acids or hydro-acids. Some remarks are made on the subject of nomenclature, and the rest of the paper is occupied with the details of the experiments, all bearing on the important subject which he has undertaken to investigate.

1840 ◽  
Vol 130 ◽  
pp. 209-224

My dear Faraday, You will not, I think, be surprised or displeased at my addressing you again upon the Electrolysis of Secondary Compounds . The whole of my very limited leisure, since my last Letter which the Royal Society did me the honour to publish in the Philosophical Transactions for 1839, has been occupied with experiments upon the subject; and I have obtained some results which I trust will not be found unworthy of the continued attention of yourself and the Society. The mode of investigation which I have adopted seems to me calculated not only to throw light upon the nature of electrolytes, but upon the mode in which the chemical elements group themselves together to constitute Radicles or Proximate Principles , the question which now seems universally to occupy the attention of chemists. I feel more than ever satisfied that the laws of electrolysis will be found to lead to the solution of this great problem. Upon reflecting upon the constitution of the oxyacid salts, as developed in my last Letter, I conceived that it might be possible to obtain further evidence that the simple cathion travelled as a metal to the platinode, while the compound anion was passing in the opposite direction; and that means might be devised of stopping it, as it were, in transitu . Your beautiful experiment, which I have often repeated with success, of precipitating the magnesia from a solution of Epsom salt against a surface of pure water, in the course of a voltaic current, suggested the mode of proceeding. According to my view of that experiment, the first electrolyte was resolved into the compound anion, sulphuric acid + oxygen, which passed to the zincode; and the simple cathion, magnesium, which on its passage to the platinode was stopped at the surface of water, from not finding any ion , by temporarily combining with which it could be further transferred according to the laws of electrolysis. At this point, therefore, it gave up its charge to the hydrogen of the water, which passed in the usual manner to the platinode; and the circuit was completed by the decomposition of this second electrolyte. The corresponding oxygen, of course, met the magnesium at the point where it was arrested in its progress, and, combining with it, magnesia was precipitated.


The discovery of definite electrochemical action naturally suggests the inquiry into the relative proportion of that part of a voltaic current, which, in the case of its decomposing a saline solution, is carried by the elements of the water, and that part which is carried by the elements of the saline compound, and into the definite relations, if any such there be, subsisting between the two electrolytes so decomposed. This question was the origin of the investigation which forms the subject of the present letter. The power which the author employed in this experimental inquiry was that of a small constant battery of thirty cells, six inches in height, with tubes of earthenware, charged in the manner he has described in his former communications to the Society. The result of the first experiment evidently indicated that the decomposition of one equivalent of water was accompanied by the decomposition of an exact equivalent of sulphate of soda. The author then endeavours to ascertain whether the power of the current is equally divided between what had hitherto been regarded as the two equivalent electrolytes. The first experiments he made in order to determine this point seemed to lead to the extraordinary conclusion, that the same current which is just sufficient to separate an equivalent of oxygen from an equivalent of hydrogen in one vessel, will at the same time separate an equivalent of oxygen from one of hydrogen, and also an equivalent of sulphuric acid from one of soda in another vessel. The author then examines the remarkable phenomena relative to the transfer of matter from one electrode to the other without the decomposition of the transported compound; a phenomenon which was first observed by Mr. Porret in glass cells divided into two compartments by a diaphragm of bladder.


1839 ◽  
Vol 129 ◽  
pp. 97-112 ◽  

My dear Faraday, I Have no doubt that you will agree with me in thinking that the decomposition of secondary compounds by the voltaic current, particularly in connexion with water, has not yet received all the attention which it deserves, and that the subject is worthy of further experimental research. When water is present in an electrolyte, you have yourself remarked that it is probable that it is always resolved into its first principles; and, on the other hand, the early experiments of Sir H. Davy prove that when saline substances are present in water, even in the minutest quantities, they are also separated into their elements, or into their proximate principles. Whether these simultaneous decompositions bear any relation to each other, has never, that I am aware of, been made the object of inquiry.


1839 ◽  
Vol 129 ◽  
pp. 89-95 ◽  

My dear Faraday, In my last letter to you, which the Royal Society have done me the honour to publish in the Philosophical Transactions for 1838, I observed, that “the principal circumstance which might be supposed to limit the power of an active point within a conducting sphere, in any given electrolyte, is the resistance of that electrolyte, which increases in a certain ratio to its depth or thickness.” The superficial measure of the conducting sphere, and the distance of the generating metal, or the depth and resistance of the electrolyte, are, in fact, the variable conditions in a voltaic combination upon which its efficiency depends; and their relations require further investigation before we shall be able to determine what may be the proper proportions for the economical application of the power to useful purposes. I shall venture, therefore, to trouble you with the results of some further experiments upon the subject, and upon different combinations of the constant battery, before I proceed to communicate some observations upon Electrolysis, which I trust you will find not without interest, and to which, according to my plan, my attention has been lately exclusively directed. Looking, for a moment, upon the affinity which circulates in the battery as a radiant force, it seemed desirable to ascertain what would be the result of intercepting the rays by the conducting surface nearer to their centre than in the arrangements which have been previously described, as the relation of the generating and conducting metals to each other might be thereby more clearly ascertained.


In the course of an inquiry on the effects of changes of temperature upon voltaic action, the author was led to observe some curious disturbances and divisions of the electric current produced by the battery, arising from secondary combinations; the results of which observations form the subject of the present paper. He found that the resistance to the passage of the current was diminished by dissolving the sulphate of copper which was in contact with the copper in the standard sulphuric acid, instead of water. The increased effect of the current, as measured by the voltameter, was farther augmented by the heat evolved during the mixture; and wishing to study the influence of temperature in modifying these effects, the author placed the cells of the battery in a tub, filled with hot water. On charging the cells with a solution of muriate of ammonia in the interior, and aqueous solution of sulphate of copper in the exterior compartment, he observed that a portion of the current is discharged by the water in which the apparatus was immersed; its passage being indicated by the disengagement of gas betwixt the adjacent cells, in which case, one of the zinc rods is thrown out of action, and the copper of that cell acts merely as an electrode to the antecedent zinc. A saturated solution of common salt was next placed in contact with the zinc, while the exterior compartments of the cells were filled with a saturated aqueous solution of sulphate of copper; but the effects were much diminished. It thus appeared that the substitution of solutions of the muriates for dilute sulphuric acid was in every way disadvantageous; and it was moreover found that, when the circuit was broken, the copper became seriously injured by their action, and by the formation of a submuriate of that metal.


1842 ◽  
Vol 132 ◽  
pp. 137-155 ◽  

My dear Faraday, I Must beg permission to address you once more upon the subject of Voltaic Combinations. To this I am prompted by several considerations. In the first place, the beautiful law of Ohm, and the simple expression which he has given of the electromotive force and resistances of a voltaic circuit, enable me to review with advantage, and to correct, many of the conclusions which I had derived from former experiments; and have suggested additional experiments, the results of which will tend, I trust, to remove some obscurities and ambiguities which were left in my former communications.


Author(s):  
Peter P. Edwards ◽  
Russell G. Egdell ◽  
Dieter Fenske ◽  
Benzhen Yao

The historical roots, the discovery and the modern relevance of Dmitri Mendeleev's remarkable advance have been the subject of numerous scholarly works. Here, with a brief overview, we hope to provide a link into the contents of this special issue honouring the great scientist. Mendeleev's advance, announced in March 1869, as he put it in 1889, to the ‘… then youthful Russian Chemical Society… ’, first set out the very basis of the periodic law of the chemical elements, the natural relation between the properties of the elements and their atomic weights. This was, and still is, the centrepiece of a historical journey for chemistry to today's position as a pre-eminent science. This article is part of the theme issue ‘Mendeleev and the periodic table'.


1899 ◽  
Vol 6 (5) ◽  
pp. 220-222
Author(s):  
Alfred Harker

The subject of the average composition of collections of rocks has been dealt with in a paper published ten years ago by Mr. F. W. Clarke on “The Relative Abundance of the Chemical Elements.” The object of that paper was to arrive at an estimate of the mean chemical composition of the earth's crust, but incidentally the author shows a close correspondence between the mean compositions of groups of miscellaneous rocks from different regions. It appears from his figures that a moderate number of analyses—less than a hundred—if taken without any selection, is enough to give value to their mean. It may therefore be of interest to apply the method to our own country.


The purport of this letter is to follow the consequences of the law of Ohm, and the expressions which result from it, relative to the electromotive force, and to the resistances in the course of a voltaic circuit; to apply this theory to the verification of the conclusions which the author had formerly deduced from his experiments; and to suggest additional experiments tending to remove some obsculities and ambiguities which existed in his former communications. In following out these principles, the author is led to offer various practical remarks on the different forms of voltaic batteries which have been proposed with a view either to the advancement of our theoretical knowledge of the science, or to the service of the arts. The author enters more particularly into an explanation of the principles on which the cylindric arrangement of the battery he has introduced is founded, which appear to him to have been greatly misunderstood. The formulæ and the calculations which form the body of this paper are not of a nature to admit of being reported in the present abstract.


In a Rutherford Memorial Lecture there are two alternative courses that might be taken. One is to describe one or other of the great developments that have later followed out from the many things which Rutherford started; the other is to describe some aspect of his own work from a historical point of view. If, as we hope and intend, the institution of these lectures should survive for many years, the first policy will probably be more useful in later times, but there still remain a number of people who lived through the wonderful experiences of those days, and while we survive it may be more interesting perhaps for us to leave some small records of what we saw. But there seems little purpose in merely giving again and again a biography recounting all the things that Rutherford did, and so I have chosen one item from among his discoveries, and I propose to give an account of this. It is the discovery of Atomic Number. I am going to try and give a picture of this whole subject; in it Rutherford of course played the leading part, but others made very important contributions, and it will be the whole history of it that I shall try to describe, and not merely his part in it. In the history of science there has been every now and then what I may call an ‘easy’ discovery, by which I do not in the least mean that it was easy to discover, but that when discovered it is so easy to understand, that it is difficult afterwards to see how people had got on without it. One example of such an ‘easy’ discovery was the discovery by Copernicus that the earth goes round the sun. After his time it was possible for anyone almost to forget what astronomy had been like before his day, and yet we have to recognize that the subject had been studied for three or four thousand years by many exceedingly intelligent men. Atomic number is another such ‘easy’ discovery. Any recent book on chemistry or physics describes the chemical elements in terms of it, and now with the development of atomic energy, even the daily press discusses quite readily the differences between uranium 238 and 235, and possibly even recalls that uranium is element number 92. In all the doubts that we may have about how future scientific discoveries will reshape our outlook on the world, we can feel sure that this one thing will never be changed; that the isotopes of the atoms of chemical elements will always have known atomic numbers and atomic weights. It now seems so simple that it is hard to believe how recently it was all discovered, and I want to show you that this ‘easy’ discovery was not at all easy to make.


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