Scientific Culture, and Other Essays Part 5

In order to investigate the question thus presented, I placed the radiometer before a common kerosene lamp, and observed, with a stop-watch, the number of seconds that elapsed during ten revolutions of the little wheel. Finding that this number was absolutely constant, I next screened one half of the bulb, so that only the blackened faces were exposed to the light as the wheel turned them into the beam. Again, I several times observed the number of seconds during ten turns, which, although equally constant, was greater than before. Lastly, I screened the blackened surfaces so that, as the wheel turned, only the l.u.s.trous surfaces of mica were exposed to the light, when, to my surprise, the wheel continued to turn in the same direction as before, although much more slowly. It appeared as if the l.u.s.trous surfaces were attracted by the light. Again I observed the time of ten revolutions, and here I have collected my results, reducing them, in the last column, so as to show the corresponding number of revolutions in the same time:

----------------------+--------------------------+-------------------- CONDITIONS. Time of ten revolutions. No. of revolutions in same time.

---------------------- -------------------------- -------------------- Both faces exposed 8 seconds. 319 Blackened faces only 11 " 232 Mica faces only 29 " 88 ----------------------+--------------------------+--------------------

It will be noticed that 88 + 232 equals very nearly 319. Evidently the effect, so far from being differential, is concurrent. Hence, the action which causes the motion must take place between the parts of the instrument, and can not be a direct effect of impulses imparted by ether waves; or else we are driven to the most improbable alternative, that lampblack and mica should have such a remarkable selective power that the impulses imparted by the light should exert a repulsive force at one surface and an attractive force at the other. Were there, however, such an improbable effect, it must be independent of the thickness of the mica vanes; while, on the other hand, if, as seemed to us now most probable, the whole effect depended on the difference of temperature between the lampblack and the mica, and if the light produced an effect on the mica surface only because, the mica plate being diathermous to a very considerable extent, the lampblack became heated through the plate more than the plate itself, then it would follow that, if we used a thicker mica plate, which would absorb more of the heat, we ought to obtain a marked difference of effect. Accordingly, we repeated the experiment with an equally sensitive radiometer, which we made for the purpose, with comparatively thick vanes, and with this the effect of a beam of light on the mica surface was absolutely null, the wheel revolving in the same time, whether these faces were protected or not.

But one thing was now wanting to make the demonstration complete. A heat engine is reversible, and if the motion of the radiometer depended on the circ.u.mstance that the temperature of the blackened faces of the vanes was higher than that of the gla.s.s, then by reversing the conditions we ought to reverse the motion. Accordingly, I carefully heated the gla.s.s bulb over a lamp, until it was as hot as the hand would bear, and then placed the instrument in a cold room, trusting to the great radiating power of lampblack to maintain the temperature of the blackened surfaces of the vanes below that of the gla.s.s. Immediately the wheel began to turn in the opposite direction, and continued to turn until the temperature of the gla.s.s came into equilibrium with the surrounding objects.

These early experiments have since been confirmed to the fullest extent, and no physicist at the present day can reasonably doubt that the radiometer is a very beautiful example of a heat engine, and it is the first that has been made to work continuously by the heat of the sunbeam. But it is one thing to show that the instrument is a heat engine, and quite another thing to explain in detail the manner in which it acts. In regard to the last point, there is still room for much difference of opinion, although physicists are generally agreed in referring the action to the residual gas that is left in the bulb. As for myself, I became strongly persuaded--after experimenting with more than one hundred of these instruments, made under my own eye, with every variation of condition I could suggest--_that the effect was due to the same cause which determines gas pressure_, and, according to the dynamical theory of gases, this amounts to saying that the effect is due to molecular motion. I have not time, however, to describe either my own experiments on which this opinion was first based, or the far more thorough investigations since made by others, which have served to strengthen the first impression.[D] But, after our previous discussions, a few words will suffice to show how the molecular theory explains the new phenomena.

[D] See notice of these investigations by the author of this article, in "American Journal of Science and Arts,"

September, 1877 (3), xiv, 231.

Although the air in the bulb has been so nearly exhausted that less than the one-thousandth part remains, yet it must be borne in mind that the number of molecules left behind is by no means inconsiderable. As will be seen by referring to our table, there must still be no less than 311,000 million million in every cubic inch. Moreover, the absolute pressure which this residual gas exerts is a very appreciable quant.i.ty.

It is simply the one-thousandth of the normal pressure of the atmosphere, that is, of 14-7/10 pounds on a square inch, which is equivalent to a little over one hundred grains on the same area. Now, the area of the blackened surfaces of the vanes of an ordinary radiometer measures just about a square inch, and the wheel is mounted so delicately that a constant pressure of one-tenth of a grain would be sufficient to produce rapid motion. So that a difference of pressure on the opposite faces of the vanes, equal to one one-thousandth of the whole amount, is all that we need account for; and, as can easily be calculated, a difference of temperature of less than half a degree Fahrenheit would cause all this difference in the pressure of the rarefied air.

But you may ask, How can such a difference of pressure exist on different surfaces exposed to one and the same medium? and your question is a perfectly legitimate one; for it is just here that the new phenomena seem to belie all our previous experience. If, however, you followed me in my very partial exposition of the mechanical theory of gases, you will easily see that on this theory it is a more difficult question to explain why such a difference of pressure does not manifest itself in every gas medium and under all conditions between any two surfaces having different temperatures.

We saw that gas pressure is a double effect, caused both by the impact of molecules and by the recoil of the surface attending their rebound.

We also saw that when molecules strike a heated surface they rebound with increased velocity, and hence produce an increased pressure against the surface, the greater the higher the temperature. According to this theory, then, we should expect to find the same atmosphere pressing unequally on equal surfaces if at different temperatures; and the difference in the pressure on the lampblack and mica surfaces of the vanes, which the motion of the radiometer wheel necessarily implies, is therefore simply the normal effect of the mechanical condition of every gas medium. The real difficulty is, to explain why we must exhaust the air so perfectly before the effect manifests itself.

The new theory is equal to the emergency. As has been already pointed out, in the ordinary state of the air the amplitude of the molecular motion is exceedingly small, not over a few ten-millionths of an inch--a very small fraction, therefore, of the height of the inequalities on the lampblack surfaces of the vanes of a radiometer. Under such circ.u.mstances, evidently the molecules would not leave the heated surface, but simply bound back and forth between the vanes and the surrounding ma.s.s of dense air, which, being almost absolutely a non-conductor of heat, must act essentially like an elastic solid wall confining the vanes on either side. For the time being, and until replaced by convection currents, the oscillating molecules are as much a part of the vanes as our atmosphere is a part of the earth; and on this system, as a whole, the h.o.m.ogeneous dense air which surrounds it must press equally from all directions. In proportion, however, as the air is exhausted, the molecules find more room and the amplitude of the molecular motion is increased, and, when a very high degree of exhaustion is reached, the air particles no longer bound back and forth on the vanes without change of condition, but they either bound off entirely like a ball from a cannon, or else, having transferred a portion of their momentum, return with diminished velocity, and in either case the force of the reaction is felt.[E]

[E] The reader will, of course, distinguish between the differential action on the opposite faces of the vanes of the radiometer and the reaction between the vanes and the gla.s.s which are the heater and the cooler of the little engine. Nor will it be necessary to remind any student that a popular view of such a complex subject must be necessarily partial. In the present case we not only meet with the usual difficulties in this respect, but, moreover, the principles of molecular mechanics have not been so fully developed as to preclude important differences of opinion between equally competent authorities in regard to the details of the theory. To avoid misapprehension, we may here add that, in orderto obtain in the radiometer a reaction between the heater and the cooler, it is not necessary that the s.p.a.ce between them should actually be crossed by the moving molecules. It is only necessary that the momentum should be transferred across the s.p.a.ce, and tide may take place along lines consisting of many molecules each. The theory, however, shows that such a transfer can only take place in a highly rarefied medium. In an atmosphere of ordinary density, the accession of heat which the vanes of a radiometer might receive from a radiant source would be diffused through the ma.s.s of the inclosed air. This amounts to saying that the momentum would be so diffused, and hence, under such circ.u.mstances, the molecular motion would not determine any reaction between the vanes and the gla.s.s envelope. Indeed, a dense ma.s.s of gas presents to the conduction of heat, which represents momentum, a wall far more impenetrable than the surrounding gla.s.s, and the diffusion of heat is almost wholly brought about by convection currents which rise from the heated surfaces. It will thus be seen that the great non-conducting power of air comes into play to prevent not only the transfer of momentum from the vanes to the gla.s.s, but also, almost entirely, any direct transfer to the surrounding ma.s.s of gas. Hence, as stated above, the heated molecules bound back and forth on the vanes without change of condition, and the ma.s.s of the air retains its uniform tension in all parts of the bulb, except in so far as this is slowly altered by the convection currents just referred to. As the atmosphere, however, becomes less dense, the diffusion of heat by convection diminishes, and that by molecular motion (conduction) increases until the last greatly predominates. When, now, the exhaustion reaches so great a degree that the heat, or momentum, is rapidly transferred from the heater to the cooler by an exaggeration, or, possibly, a modification, of the mode of action we call conduction, then we have the reaction on which the motion of the radiometer wheel depends.

Thus it appears that we have been able to show by very definite experimental evidence that the radiometer is a heat engine. We have also been able to show that such a difference of temperature as the radiation must produce in the air in _direct_ contact with the opposite faces of the vanes of the radiometer would determine a difference of tension, which is sufficient to account for the motion of the wheel. Finally, we have shown, as fully as is possible in a popular lecture, that, according to the mechanical theory of gases, such a difference of tension would have its normal effect only in a highly rarefied atmosphere, and thus we have brought the new phenomena into harmony with the general principles of molecular mechanics previously established.

More than this can not be said of the steam-engine, although, of course, in the older engine the measurements on which the theory is based are vastly more accurate and complete. But the moment we attempt to go beyond the general principles of heat engines, of which the steam-engine is such a conspicuous ill.u.s.tration, and explain how the heat is transformed into motion, we have to resort to the molecular theory just as in the case of the radiometer; and the motion of the steam-engine seems to us less wonderful than that of the radiometer only because it is more familiar and more completely harmonized with the rest of our knowledge. Moreover, the very molecular theory which we call upon to explain the steam-engine involves consequences which, as we have seen, have been first realized in the radiometer; and thus it is that this new instrument, although disappointing the first expectations of its discoverer, has furnished a very striking confirmation of this wonderful theory. Indeed, the confirmation is so remote and yet so close, so unexpected and yet so strong, that the new phenomena almost seem to be a direct manifestation of the molecular motion which our theory a.s.sumes; and when a new discovery thus confirms the accuracy of a previous generalization, and gives us additional reason to believe that the glimpses we have gained into the order of Nature are trustworthy, it excites, with reason, among scientific scholars the warmest interest.

And when we consider the vast scope of the molecular theory, the order on order of existences which it opens to the imagination, how can we fail to be impressed with the position in which it places man midway between the molecular cosmos on the one side and the stellar cosmos on the other--a position in which he is able, in some measure at least, to study and interpret both?

Since the time to which we referred at the beginning of this lecture, when man's dwelling-place was looked at as the center of a creation which was solely subservient to his wants, there has been a reaction to the opposite extreme, and we have heard much of the utter insignificance of the earth in a universe among whose immensities all human belongings are but as a drop in the ocean. When now, however, we learn from Sir William Thomson that the drop of water in our comparison is itself a universe, consisting of units so small that, were the drop magnified to the size of the earth, these units would not exceed in magnitude a cricket-ball,[F] and when, on studying chemistry, we still further learn that these units are not single ma.s.ses but systems of atoms, we may leave the illusions of the imagination from the one side to correct those from the other, and all will teach us the great lesson that man's place in Nature is not to be estimated by relations of magnitude, but by the intelligence which makes the whole creation his own.

[F] "Nature," No. 22, March 31, 1870.

But, if it is man's privilege to follow both the atoms and the stars in their courses, he finds that, while thus exercising the highest attributes of his nature, he is ever in the presence of an immeasurably superior intelligence, before which he must bow and adore, and thus come to him both the a.s.surance and the pledge of a kins.h.i.+p in which his only real glory can be found.

V.

MEMOIR OF THOMAS GRAHAM.

_Reprinted from the "Proceedings of the American Academy of Arts and Sciences," Vol. VIII, May 24, 1870._

It would be difficult to find in the history of science a character more simple, more n.o.ble, or more symmetrical in all its parts than that of Thomas Graham, and he will always be remembered as one of the most eminent of those great students of nature who have rendered our Saxon race ill.u.s.trious. He was born of Scotch parents in Glasgow in the year 1805, and in that city, where he received his education, all his early life was pa.s.sed. In 1837 he went to London as Professor of Chemistry in the newly established London University, now called University College, and he occupied this chair until the year 1855, when he succeeded Sir John Herschel as Master of the Royal Mint, a post which he held to the close of his life. His death, on the 16th of September last (1869), at the age of sixty, was caused by no active disease, but was simply the wearing out of a const.i.tution enfeebled in youth by privations voluntarily and courageously encountered that he might devote his life to scientific study. As with all earnest students, that life was uneventful, if judged by ordinary standards; and the records of his discoveries form the only materials for his biography.

Although one of the most successful investigators of physical science, the late Master of the Mint had not that felicity of language or that copiousness of ill.u.s.tration which added so much to the popular reputation of his distinguished contemporary, Faraday; but his influence on the progress of science was not less marked or less important. Both of these eminent men were for a long period of years best known to the English public as teachers of chemistry, but their investigations were chiefly limited to physical problems; yet, although both cultivated the border ground between chemistry and physics, they followed wholly different lines of research. While Faraday was so successfully developing the principles of electrical action, Graham with equal success was investigating the laws of molecular motion. Each followed with wonderful constancy, as well as skill, a single line of study from first to last, and to this concentration of power their great discoveries are largely due.

One of the earliest and most important of Graham's investigations, and the one which gave the direction to his subsequent course of study, was that on the diffusion of gases. It had already been recognized that impenetrability in its ordinary sense is not, as was formerly supposed, a universal quality of matter. Dalton had not only recognized that aeriform bodies exhibit a positive tendency to mix, or to penetrate through each other, even in opposition to the force of gravity, but had made this quality of gases the subject of experimental investigation. He inferred, as the result of his inquiry, "that different gases afford no resistance to each other; but that one gas spreads or expands into the s.p.a.ce occupied by another gas, as it would rush into a vacuum; at least, that the resistance which the particles of one gas offer to those of another is of a very imperfect kind, to be compared to the resistance which stones in the channel of a stream oppose to the flow of running water." But, although this theory of Dalton was essentially correct and involved the whole truth, yet it was supported by no sufficient evidence, and he failed to perceive the simple law which underlies this whole cla.s.s of phenomena.

Graham, "on entering on this inquiry, found that gases diffuse into the atmosphere with different degrees of ease and rapidity." This was first observed by allowing each gas to diffuse from a bottle into the air through a narrow tube in opposition to the solicitation of gravity.

Afterward an observation of Doebereiner on the escape of hydrogen gas by a fissure or crack in a gla.s.s receiver caused him to vary the conditions of his experiments, and led to the invention of the well-known "diffusion tube." In this simple apparatus a thin septum of plaster of Paris is used to separate the diffusing gases, which, while it arrests in a great measure all direct currents between the two media, does not interfere with the molecular motion. Much later, Graham found in prepared graphite a material far better adapted to this purpose than the plaster, and he used septa of this mineral to confirm his early results, in answer to certain ill-considered criticisms in Bunsen's work on gasometry. These septa he was in the habit of calling his "atomic filters."

By means of the diffusion tube, Graham was able to measure accurately the relative times of diffusion of different gases, and he found that _equal volumes of any two gases interpenetrate each other in times which are inversely proportional to the square roots of their respective densities_; and this fundamental law was the greatest discovery of our late foreign a.s.sociate. It is now universally recognized as one of the few great cardinal principles which form the basis of physical science.

It can be shown, on the principles of pneumatics, that gases should rush into a vacuum with velocities corresponding to the numbers which have been found to express their diffusion times; and, in a series of experiments on what he calls the "_effusion_" of gases, Graham confirmed by trial this deduction of theory. In these experiments a measured volume of the gas was allowed to find its way into the vacuous jar through a minute aperture in a thin metallic plate, and he carefully distinguished between this cla.s.s of phenomena and the flowing of gases through capillary tubes into a vacuum, in which case, however short the tube, the effects of friction materially modify the result. This last cla.s.s of phenomena Graham likewise investigated, and designated by the term "transpiration."

While, however, it thus appears that the results of Graham's investigation were in strict accordance with Dalton's theory, it must also be evident that Graham was the first to observe the exact numerical relation which obtains in this cla.s.s of phenomena, and that all-important circ.u.mstance ent.i.tles him to be regarded as the discoverer of the law of diffusion. The law, however, at first enunciated, was purely empirical, and Graham himself says that something more must be a.s.sumed than that gases are vacua to each other, in order to explain all the phenomena observed; and according to his original view this representation of the process was only a convenient mode of expressing the final result. Such has proved to be the case.

Like other great men, Graham built better than he knew. In the progress of physical science during the last twenty-five years, two principles have become more and more conspicuous, until at last they have completely revolutionized the philosophy of chemistry. In the first place, it has appeared that a host of chemical as well as of physical facts are coordinated by the a.s.sumption that all substances in the state of gas have the same molecular volume, or, in other words, contain the same number of molecules in a given s.p.a.ce; and in the second place, it has become evident that the phenomena of heat are simply the manifestations of molecular motion. According to this view, the temperature of a body is the _vis viva_ of its molecules; and, since all molecules at a given temperature have the same _vis viva_, it follows that the molecules must move with velocities which are inversely proportional to the square roots of the molecular weights. Moreover, since the molecular volumes are equal, and the molecular weights therefore proportional to the densities of the aeriform bodies in which the molecules are the active units, it also follows that the velocities of the molecules in any two gases are inversely proportional to the square roots of their respective densities. Thus the simple numerical relations first observed in the phenomena of diffusion are the direct result of molecular motion; and it is now seen that Graham's empirical law is included under the fundamental laws of motion. Thus Graham's investigation has become the basis of the new science of molecular mechanics, and his measurements of the rates of diffusion prove to be the measures of molecular velocities.

From the study of diffusion Graham pa.s.sed by a natural transition to the investigation of a cla.s.s of phenomena which, although closely allied to the first as to the effects produced, differ wholly in their essential nature. Here also he followed in the footsteps of Dalton. This distinguished chemist had noticed that a bubble of air separated by a film of water from an atmosphere of carbonic anhydride gradually expanded until it burst. In like manner a moist bladder, half filled with air and tied, if suspended in an atmosphere of the same material, becomes in time greatly distended by the insinuation of this gas through its substance. This effect can not be the result of simple diffusion, for it is to be remembered that the thinnest film of water, or of any liquid, is absolutely impermeable to a gas as such, and, moreover, only the carbonic anhydride pa.s.ses through the film, very little or none of the air escaping outward. The result depends, first, upon the solution of the carbonic anhydride by the water on one surface of the film; secondly, on the evaporation into the air, from the other surface, of the gas thus absorbed. Similar experiments were made by Drs. Mitch.e.l.l and Faust, and others, in which gases pa.s.sed through a film of India-rubber, entering into a partial combination with the material on one surface, and escaping from it on the other.

Graham not only considerably extended our knowledge of this cla.s.s of phenomena, but also gave us a satisfactory explanation of the mode in which these remarkable results are produced. He recognized in these cases the action of a feeble chemical force, insufficient to produce a definite compound, but still capable of determining a more or less perfect union, as in the case of simple solution. He also distinguished the influence of ma.s.s in causing the formation or decomposition of such weak chemical compounds. The conditions of the phenomena under consideration are simply these:

First. A material for the septum capable of forming a feeble chemical union with the gas to be transferred.

Secondly. An excess of the gas on one side of the film and a deficiency on the other.

Thirdly. Such a temperature that the unstable compound may form at the surface, where the aeriform const.i.tuent is present in large ma.s.s, while it decomposes at the opposite surface, where the quant.i.ty is less abundant.

One of the most remarkable results of Graham's study of this peculiar mode of transfer of aeriform matter through the very substance of solid bodies was an ingenious method of separating the oxygen from the atmosphere. The apparatus consisted simply of a bag of India-rubber kept distended by an interior framework, while it was exhausted by a Sprengel pump. Under these circ.u.mstances the selective affinity of the caoutchouc determines such a difference in the rate of transfer of the two const.i.tuents of the atmosphere that the amount of oxygen in the transpired air rises to forty per cent., and by repeating the process nearly pure oxygen may be obtained. It was at first hoped that this method might find a valuable application in the arts, but in this Graham was disappointed; for the same result has since been effected by purely chemical methods, which are both cheaper and more rapid.

These experiments on India-rubber naturally led to the study of similar effects produced with metallic septa, which, although to some extent previously observed in pa.s.sing gases through heated metallic tubes, had been only imperfectly understood. Thus, when a stream of hydrogen or carbonic oxide is pa.s.sed through a red-hot iron tube, a no inconsiderable portion of the gas escapes through the walls. The same is true to a still greater degree when hydrogen is pa.s.sed through a red-hot tube of platinum, and Graham showed that, through the walls of a tube of palladium, hydrogen gas pa.s.ses, under the same conditions, almost as rapidly as water through a sieve. Moreover, our distinguished a.s.sociate proved that this rapid transfer of gas through these dense metallic septa was due, as in the case of the India-rubber, to an actual chemical combination of its material with the metal, formed at the surface, where the gas is in excess, and as rapidly decomposed on the opposite face of the septum. He not only recognized as belonging to this cla.s.s of phenomena the very great absorption of hydrogen by platinum plate and sponge in the familiar experiment of the Doebereiner lamp, but also showed that this gas is a definite const.i.tuent of meteoric iron--a fact of great interest from its bearing on the meteoric theory.

We are thus led to Graham's last important discovery, which was the justification of the theory we have been considering, and the crowning of this long line of investigation. As may be antic.i.p.ated from what has been said, the most marked example of that order of chemical compounds, to which the metallic transpiration of aeriform matter we have been considering is due, is the compound of palladium with hydrogen. Graham showed that, when a plate of this metal is made the negative pole in the electrolysis of water, it absorbs nearly one thousand times its volume of hydrogen gas--a quant.i.ty approximatively equivalent to one atom of hydrogen to each atom of palladium. He further showed that the metal thus becomes so profoundly altered as to indicate that the product of this union is a definite compound. Not only is the volume of the metal increased, but its tenacity and conducting power for electricity are diminished, and it acquires a slight susceptibility to magnetism, which the pure metal does not possess. The chemical qualities of this product are also remarkable. It precipitates mercury from a solution of its chloride, and in general acts as a strong reducing agent. Exposed to the action of chlorine, bromine, or iodine, the hydrogen leaves the palladium and enters into direct union with these elements. Moreover, although the compound is readily decomposed by heat, the gas can not be expelled from the metal by simple mechanical means.

These facts recall the similar relations frequently observed between the qualities of an alloy and those of the const.i.tuent metals, and suggest the inference made by Graham, that palladium charged with hydrogen is a compound of the same cla.s.s--a conclusion which harmonizes with the theory long held by many chemists, that hydrogen gas is the vapor of a very volatile metal. This element, however, when combined with palladium, is in a peculiarly active state, which sustains somewhat the same relation to the familiar gas that ozone bears to ordinary oxygen.

Hence Graham distinguished this condition of hydrogen by the term "hydrogenium." Shortly before his death a medal was struck at the Royal Mint from the hydrogen palladium alloy in honor of its discovery; but, although this discovery attracted public attention chiefly on account of the singular chemical relations of hydrogen, which it brought so prominently to notice, it will be remembered in the history of science rather as the beautiful termination of a life-long investigation, of which the medal was the appropriate seal.

Simultaneously with the experiments on _gases_, whose results we have endeavored to present in the preceding pages, Graham carried forward a parallel line of investigation of an allied cla.s.s of phenomena, which may be regarded as the manifestations of molecular motion in _liquid_ bodies. The phenomena of diffusion reappear in liquids, and Graham carefully observed the times in which equal weights of various salts dissolved in water diffused from an open-mouth bottle into a large volume of pure water, in which the bottle was immersed. He was not, however, able to correlate the results of these experiments by such a simple law as that which obtains with gases. It appeared, nevertheless, that the rate of diffusion differs very greatly for the different soluble salts, having some relation to the chemical composition of the salt which he was unable to discover. But he found it possible to divide the salts into groups of equi-diffusive substances, and he showed that the rate of diffusion of the several groups bear to one another simple numerical ratios.

More important results were obtained from the study of a cla.s.s of phenomena corresponding to the transpiration of gases through India-rubber or metallic septa. These phenomena, as manifested in the transfer of liquids and of salts in solution through bladder or a similar membrane, had previously been frequently studied under the names of exosmose and endosmose, but to Graham we owe the first satisfactory explanation. As in the case of gases, he referred these effects to the influence of chemical force, combination taking place on one surface of the membrane and the compound breaking up on the other, the difference depending, as in the previous instance, on the influence of ma.s.s. He also swept away the arbitrary distinctions made by previous experimenters, showed that this whole cla.s.s of phenomena are essentially similar, and called this manifestation of power simply "osmose."

While studying osmotic action, Graham was led to one of his most important generalizations--the recognition of the crystalline and amorphous states as fundamental distinctions in chemistry. Bodies in the first state he called crystalloids; those in the last state, colloids (resembling glue). That there is a difference in structure between crystalloids, like sugar or felspar, and colloids, like barley candy or gla.s.s, has of course always been evident to the most superficial observer; but Graham was the first to recognize in these external differences two fundamentally distinct conditions of matter not peculiar to certain substances, but underlying all chemical differences, and appearing to a greater or less degree in every substance. He showed that the power of diffusion through liquids depends very much on these fundamental differences of condition--sugar, one of the least diffusible of the crystalloids, diffusing fourteen times more rapidly than caromel, the corresponding colloid. He also showed that, in accordance with the general chemical rule, while colloids readily combine with crystalloids, bodies in the same condition manifest little or no tendency to chemical union. Hence, in osmose, where the membranes employed are invariably colloidal, the osmotic action is confined almost entirely to crystalloids, since they alone are capable of entering into that combination with the material of the septum on which the whole action depends.

On the above principles Graham based a simple method of separating crystalloids from colloids, which he calls "dialysis," and which was a most valuable addition to the means of chemical a.n.a.lysis. A shallow tray, prepared by stretching parchment paper (an insoluble colloid) over a gutta-percha hoop, is the only apparatus required. The solution to be "dialyzed" is poured into this tray, which is then floated on pure water, whose volume should be eight or ten times greater than that of the solution. Under these conditions the crystalloids will diffuse through the porus septum into the water, leaving the colloids on the tray, and in the course of a few days a more or less complete separation of the two cla.s.ses of bodies will have taken place. In this way a.r.s.enious acid and similar crystalloids may be separated from the colloidal materials with which, in the case of poisoning, they are usually found mixed in the animal juices or tissues.

But, besides having these practical applications, the method of dialysis in the hands of Graham yielded the most startling results, developing an almost entirely new cla.s.s of bodies, as the colloidal forms of our most familiar substances, and justifying the conclusion that the colloidal as well as the crystalline condition is an almost universal attribute of matter. Thus, he was able to obtain solutions in water of the colloidal states of aluminic, ferric, chromic, stannic, metastannic, t.i.tanic, molybdic, tungstic, and silicic hydrates, all of which gelatinize under definite conditions like a solution of glue. The wonderful nature of these facts can be thoroughly appreciated only by those familiar with the subject, but all may understand the surprise with which the chemist saw such hard, insoluble bodies as flint dissolved abundantly in water and converted into soft jellies. These facts are, without doubt, the most important contributions of Dr. Graham to pure chemistry.

In this sketch of the scientific career of our late a.s.sociate, we have followed the logical, rather than the chronological, order of events, hoping thus to render the relations of the different parts of his work more intelligible. It must be remembered, however, that the two lines of investigation we have distinguished were in fact inter-woven, and that the beautiful harmony which his completed life presents was the result, not of a preconceived plan, but of a constant devotion to truth, and a childlike faith, which unhesitatingly pressed forward whenever nature pointed out the way.

Although the investigations of the phenomena connected with the molecular motion in gases and liquids were by far the most important of Dr. Graham's labors, he also contributed to chemistry many researches which can not be included under this head. Of these, which we may regard as his detached efforts, the most important was his investigation of the hydrates and other salts of phosphorus. It is true that the interpretation he gave of the results has been materially modified by the modern chemical philosophy, yet the facts which he established form an important part of the basis on which that philosophy rests. Indeed, it seems as if he almost antic.i.p.ated the later doctrines of types and polybasic acids, and in none of his work did he show more discriminating observation or acute reasoning. A subsequent investigation on the condition of water in several crystalline salts and in the hydrates of sulphuric acid is equally remarkable. Lastly, Graham also made interesting observations on the combination of alcohol with salts, on the process of etherification, on the slow oxidation of phosphorus, and on the spontaneous inflammability of phosphureted hydrogen. It would not, however, be appropriate in this place to do more than enumerate the subjects of these less important studies; and we have therefore only aimed in this sketch to give a general view of the character of the field which this eminent student of nature chiefly cultivated, and to show how abundant was the harvest of truth which we owe to his faithful toil.

Graham was not a voluminous writer. His scientific papers were all very brief, but comprehensive, and his "Elements of Chemistry" was his only large work. This was an admirable exposition of chemical physics, as well as of pure chemistry, and gave a more philosophical account of the theory of the galvanic battery than had previously appeared. Our late a.s.sociate was fortunate in receiving during life a generous recognition of the value of his labors. His members.h.i.+p was sought by almost all the chief scientific societies of the world, and he enjoyed to a high degree the confidence and esteem of his a.s.sociates. Indeed, he was singularly elevated above the petty jealousies and belittling quarrels which so often mar the beauty of a student's life, while the great loveliness and kindliness of his nature closely endeared him to his friends.