Section VI.—A Review of the Fundamental Principles of the Mechanical Theory of Heat; with Remarks on the Thermic Phenomena of Currents of Elastic Fluids, as illustrating those Principles.

(Article 46.) I have been induced to write this Section, in continuation of a paper on the Mechanical Action of Heat, by the publication (in the Philosophical Magazine for December 1852, Supplementary Number) of a series of experiments by Mr Joule and Professor William Thomson, on the Thermal Effects experienced by Air in rushing through small Apertures. Although those authors express an intention to continue the experiments on a large scale, so as to obtain more precise results; yet the results already obtained are sufficient to constitute the first step towards the experimental determination of that most important function in the theory of the mechanical action of heat, which has received the name of Carnot's Function.

While the physical appearances of comets have ever excited such intense curiosity and interest, all the theories concerning them are generally confessed to be insufficient to explain them; and, certainly, if we may judge from the various views advocated by different writers, and the anomalous forces gratuitously brought in to support the different hypotheses—it is so.

This unsatisfactory state of things, so different from that in which is the theory of the motions of comets,—seems to be owing partly to the difficulty of making the necessary observations by reason of the undefinable nature of the bodies themselves, and partly from the untoward circumstances under which the observations must be made, as well as the rareness of any opportunities offering. Hence, theories are built upon accounts handed down from old astrological times when men's prejudices would have prevented them, even if their means had been ample, which they were not, from giving any satisfactory and trustworthy accounts of the phenomena displayed by the heavens of their day.

The study of the organic acids appears scarcely to have advanced of late years pari passu with the other branches of organic chemistry. It seems, indeed, as if the development of each of the different departments of the science had been, to a certain extent, periodical; each engrossing the labours of investigators to the temporary exclusion of the others, themselves to be renewed when some new experiments should reawaken an interest in them.

However this may be, the subject of the natural and artificial bases has proved so productive of interesting results as to have recently become the chosen and almost exclusive field of inquiry, notwithstanding several investigations which have thrown much light on one class of organic acids, namely, that represented by the general formula Cn Hn O4. With the exception of this section, the history of the organic acids remains very imperfect, and in many cases we have but a meagre account of a few of their salts.

Having expressed a decided opinion that there are, in all living bodies, chemical as well as mechanical phenomena, which, in the present state of our knowledge, ought to be designated as Vital, and referred to the operation of laws, distinct from those that regulate the chemical changes of inanimate matter, and observing that this opinion is controverted, and that the view of the chemical phenomena of life which I have maintained, is rejected as unphilosophical and delusive by two authors of high scientific reputation—Baron Humboldt and Dr Daubeny,—and that the judgment of other authors of acknowledged character on this subject is not clearly expressed, and seems to me to involve it in unnecessary obscurity, I am led to hope that some farther explanations may be of some use in establishing the first principles of a Science which, as it appears to me, has suffered, in several instances, not so much from want of facts, as from hypothetical and erroneous inferences, drawn from facts that are already known.

The ensuing paper forms part of a series of researches respecting the consequences of an hypothesis called that of Molecular Vortices, the object of which is to deduce the laws of elasticity, and of heat as connected with elasticity, by means of the principles of mechanics, from a physical supposition consistent and connected with the theory which deduces the laws of radiant light and heat from the hypothesis of undulations. Those researches were commenced in 1842, and after having been laid aside for nearly seven years, from the want of experimental data, were resumed in consequence of the appearance of the experiments of M. Regnault on gases and vapours.

The investigation which I have now to describe, relates to the mutual conversion of heat and mechanical power by means of the expansion and contraction of gases and vapours.

In a paper on Comenic Acid, read before this Society in April of last year, and since honoured with a place in its Transactions, I mentioned my being engaged in an investigation on Meconic Acid; the details of the experiments referred to form the matter of the present communication.

My object in undertaking this subject was to ascertain if products corresponding to those described as derived from comenic acid were formed under similar circumstances in the case of meconic acid. I also thought it probable, that as the former is itself a derivative of the latter, the changes undergone by meconic acid in some reactions, would be found to result in substances apparently the immediate derivatives of comenic acid. This remark refers to the action of heat on meconate of ammonia; and it will be seen that the expectation was realised. A similar result was found in other instances, where it had not been anticipated.

I propose in the following pages to communicate to the Society the progress of my investigation of the products of the destructive distillation of animal substances, the first part of which was published in the 16th volume of the Transactions. Since that period, partly owing to my numerous avocations, and partly to the inherent difficulties of the subject, less progress has been made than I had hoped or expected, but still I have accumulated some facts of considerable interest, which I think deserving of the attention of the Society.

It may be remembered that, in the paper just referred to, I announced the discovery, among those products, of picoline, which I formerly obtained from coaltar, and of a new base, to which I gave the name of Petinine; and I entered pretty fully into the method adopted for the preparation of these substances, and of certain other bases, the existence of which I merely indicated, without at the time attempting to characterize them. On proceeding to the more minute investigation of these bases, I soon found that the quantity of material at my disposal was much too small to admit of satisfactory or complete results, although I had employed for their preparation above 300 pounds of bone-oil. I found it necessary, therefore, to begin ab initio with the preparation of the bases from another equally large quantity of the oil; and after going through the whole of the tedious processes described in my previous paper, with the expenditure of the labour of some months, I found my object again defeated by deficiency of material. After various experiments, which, though they led to no definite or conclusive results, served to familiarize me with the nature and relations of the products obtained, I made up my mind once more to begin again; and being resolved on this occasion not to be foiled in the same way as before, I used for my new preparation no less than 250 gallons of crude bone-oil, the weight of which was somewhat above a ton. The result of this process, though involving an immense amount of labour, has been satisfactory, not only in supplying me with a large amount of material, but has also enabled me to obtain many substances, some of them possessed of very remarkable properties, which had escaped my observation when operating on a smaller scale.

The source from which plants obtain nitrogen, which is now recognised as one of their most important elements, has, from the first recognition of its importance, been matter of dispute. Latterly, however, chemists and physiologists have pretty unanimously come to the conclusion, that a large (perhaps the largest) part of the nitrogen of vegetables is derived from ammonia; whilst much discussion has been carried on as to the question, Is any part of their nitrogen yielded by nitric acid?

The most able advocate in this country of the claims of ammonia is Dr Gregory. The most able advocate of the claims of nitric acid is Professor Johnston of Durham, and the opposite conclusions to which accomplished chemists like these have come in reference to the point in dispute, have perplexed botanists, who know not which view to prefer. The extent to which they are pressed by this dilemma, has been so strongly represented to me by Dr Balfour, that I have engaged to bring the subject, as I now do, before this Society. I shall sedulously avoid discussing the question in a polemical spirit; and, as the shortest and most satisfactory way of doing justice to the rival views, I shall select Dr Gregory's clear and concise statement, as representing the opinions of those who deny that nitric acid is part of the food of plants; and then proceed to state what appear to me conclusive proofs that nitric acid does supply plants with nitrogen.

Having had the good fortune last autumn to get an antique marble bust of extreme beauty, the question naturally arose, of whom it might be the portrait, if, indeed, it was a portrait at all, and not an ideal head. I had proceeded some way in this inquiry, when it was suggested to me one day that it might interest the Society to know something of it, and that, though a little foreign no doubt to its usual topics, the change would be agreeable, and that ancient art was not without its charms. So urged I yielded,—perhaps too easily; but of this you will judge when I have done.

Sir Humphrey Davy, by his experiment of melting two pieces of ice by rubbing them together, established the following proposition:—“The phenomena of repulsion are not dependent on a peculiar elastic fluid for their existence, or caloric does not exist.” And he concludes that heat consists of a motion excited among the particles of bodies. “To distinguish this motion from others, and to signify the cause of our sensation of heat,” and of the expansion or expansive pressure produced in matter by heat, “the name repulsive motion has been adopted.”

What are the nutritive qualities of fish, compared with other kinds of animal food? Do different species of fish differ materially in degree in nutritive power? Have fish, as food, any peculiar or special properties? These are questions, amongst many others, which may be asked, but which, in the present state of our knowledge, I apprehend it would be difficult to answer in a manner at all satisfactory.

On the present occasion, I shall attempt little more than an opening of the inquiry, and that directed to a few points,—chiefly those alluded to in the foregoing queries.

1. The important researches of Joule on the thermal circumstances connected with the expansion and compression of air, and the admirable reasoning upon them, expressed in his paper “On the Changes of Temperature produced by the Rarefaction and Condensation of Air,” especially the way in which he takes into account any mechanical effect that may be externally produced, or internally lost, in fluid friction, have introduced an entirely new method of treating questions regarding the physical properties of fluids. The object of the present paper is to show how, by the use of this new method, in connection with the principles explained in my preceding paper, a complete theoretical view may be obtained of the phenomena experimented on by Joule; and to point out some of the objects to be attained by a continuation and extension of his experimental researches.

(1.) In February 1850, I laid before the Royal Society of Edinburgh a paper, in which the laws of the pressure and expansion of gases and vapours were deduced from the supposition, that that part of the elasticity of bodies which depends upon heat, arises from the centrifugal force of the revolutions of the particles of elastic atmospheres surrounding nuclei, or atomic centres. A summary of the results of this supposition, which I called the Hypothesis of Molecular Vortices, was printed in the Transactions of this Society, volume xx., as an introduction to a series of papers on the Mechanical Action of Heat; and the original paper has since appeared in detail in the Philosophical Magazine.

In 1836, Mr Fox Talbot communicated to the Royal Society a paper “On the Optical Phenomena of certain Crystals” which he obtained by dissolving a crystal of Borax in a drop of somewhat diluted Phosphoric acid. When the acid and the salt are in proper proportions, “the field of view of the microscope is seen covered with minute circular spots, each of which is like a tuft of silk radiating from a centre, and is composed of a close assemblage of delicate acicular crystals forming a star.” Among these crystals are seen interspersed “a number of circular transparent bodies, which are tufts or stars of acicular crystals, in such close assemblage as to be in optical contact with each other, and to produce the appearance of a single individual.”

In the accompanying tables are contained the results of some experiments respecting the rate at which aqueous vapour condenses on a cold surface.

These results are not so consistent as could be desired, but having been obtained by a definite and carefully-conducted process, they may claim at least to be received as approximately true.

In planning the experiments, it was assumed that c = m (f“ − f“ʹ), where c is the weight of moisture which is condensed on a surface of given area in a given time; f“ the tension of vapour at the dew-point; f“ʹ its tension at the temperature of the condensing surface; m a coefficient varying with the velocity of the current of air.

Correction of M. Regnault's Experiments for the Effect of Agitation.

The discovery by Mr Joule of the fact, that mechanical power expended in the agitation of liquids is converted into heat as the visible agitation subsides, renders a certain correction necessary in calculating the results of experiments on specific heat in which such agitation has occurred.

Of this kind are the experiments of M. Regnault on the apparent specific heat of liquid water at different temperatures. Water at a high temperature, T3, was emitted from a boiler into a calorimeter containing water at a low temperature, Tl, and the resulting intermediate temperature of the whole mass, T2, was used as the means of calculating the ratio of the mean specific heat of water between T3 and T2, to its mean specific heat between T2 and T1. Now, the upper part of the boiler contained steam at a high pressure, so that the hot water was expelled with great force.

The red prominences seen during total solar eclipses, are conspicuous rose-coloured objects which appear round the dark edge of the moon, as soon as the last rays of the sun have disappeared. In preparing my account of the total eclipse of the 28th July 1851, it was at first my intention to have stated some hypothetical views which I had formed regarding those remarkable objects, and other appearances I had observed during the total phase of the eclipse. I found, however, that the mere description of phenomena extended to so great a length, as to render such a course inexpedient; and I have since delayed resuming the subject, in order that by comparing a number of other observations with my own, I might be enabled, either to confirm or to modify my views.