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Diffusion

DIFFUSION (from the Lat. diffundere; dis-, asunder, and fundere, to pour out), in general, a spreading out, scattering or circulation; in physics the term is applied to a special phenomenon, treated below.

1. General Description. - When two different substances are placed in contact with each other they sometimes remain separate, but in many cases a gradual mixing takes place. In the case where both the substances are gases the process of mixing continues until the result is a uniform mixture. In other cases the proportions in which two different substances can mix lie between certain fixed limits, but the mixture is distinguished from a chemical compound by the fact that between these limits the composition of the mixture is capable of continuous variation, while in chemical compounds, the proportions of the different constituents can only have a discrete series of numerical values, each different ratio representing a different compound. If we take, for example, air and water in the presence of each other, air will become dissolved in the water, and water will evaporate into the air, and the proportions of either constituent absorbed by the other will vary continuously. But a limit will come when the air will absorb no more water, and the water will absorb no more air, and throughout the change a definite surface of separation will exist between the liquid and the gaseous parts. When no surface of separation ever exists between two substances they must necessarily be capable of mixing in all proportions. If they are not capable of mixing in all proportions a discontinuous change must occur somewhere between the regions where the substances are still unmixed, thus giving rise to a surface of separation.

The phenomena of mixing thus involves the following processes: - (1) A motion of the substances relative to one another throughout a definite region of space in which mixing is taking place. This relative motion is called "diffusion." (2) The passage of portions of the mixing substances across the surface of separation when such a surface exists. These surface actions are described under various terms such as solution, evaporation, condensation and so forth. For example, when a soluble salt is placed in a liquid, the process which occurs at the surface of the salt is called "solution," but the salt which enters the liquid by solution is transported from the surface into the interior of the liquid by "diffusion."

Diffusion may take place in solids, that is, in regions occupied by matter which continues to exhibit the properties of the solid state. Thus if two liquids which can mix are separated by a membrane or partition, the mixing may take place through the membrane. If a solution of salt is separated from pure water by a sheet of parchment, part of the salt will pass through the parchment into the water. If water and glycerin are separated in this way most of the water will pass into the glycerin and a little glycerin will pass through in the opposite direction, a property frequently used by microscopists for the purpose of gradually transferring minute algae from water into glycerin. A still more interesting series of examples is afforded by the passage of gases through partitions of metal, notably the passage of hydrogen through platinum and palladium at high temperatures. When the process is considered with reference to a membrane or partition taken as a whole, the passage of a substance from one side to the other is commonly known as "osmosis" or "transpiration" (see Solution), but what occurs in the material of the membrane itself is correctly described as diffusion.

Simple cases of diffusion are easily observed qualitatively. If a solution of a coloured salt is carefully introduced by a funnel into the bottom of a jar containing water, the two portions will at first be fairly well defined, but if the mixture can exist in all proportions, the surface of separation will gradually disappear; and the rise of the colour into the upper part and its gradual weakening in the lower part, may be watched for days, weeks or even longer intervals. The diffusion of a strong aniline colouring matter into the interior of gelatine is easily observed, and is commonly seen in copying apparatus. Diffusion of gases may be shown to exist by taking glass jars containing vapours of hydrochloric acid and ammonia, and placing them in communication with the heavier gas downmost. The precipitation of ammonium chloride shows that diffusion exists, though the chemical action prevents this example from forming a typical case of diffusion. Again, when a film of Canada balsam is enclosed between glass plates, the disappearance during a few weeks of small air bubbles enclosed in the balsam can be watched under the microscope.

In fluid media, whether liquids or gases, the process of mixing is greatly accelerated by stirring or agitating the fluids, and liquids which might take years to mix if left to themselves can thus be mixed in a few seconds. It is necessary to carefully distinguish the effects of agitation from those of diffusion proper. By shaking up two liquids which do not mix we split them up into a large number of different portions, and so greatly increase the area of the surface of separation, besides decreasing the thicknesses of the various portions. But even when we produce the appearance of a uniform turbid mixture, the small portions remain quite distinct. If however the fluids can really mix, the final process must in every case depend on diffusion, and all we do by shaking is to increase the sectional area, and decrease the thickness of the diffusing portions, thus rendering the completion of the operation more rapid. If a gas is shaken up in a liquid the process of absorption of the bubbles is also accelerated by capillary action, as occurs in an ordinary sparklet bottle. To state the matter precisely, however finely two fluids have been subdivided by agitation, the molecular constitution of the different portions remains unchanged. The ultimate process by which the individual molecules of two different substances become mixed, producing finally a homogeneous mixture, is in every case diffusion. In other words, diffusion is that relative motion of the molecules of two different substances by which the proportions of the molecules in any region containing a finite number of molecules are changed.

In order, therefore, to make accurate observations of diffusion in fluids it is necessary to guard against any cause which may set up currents; and in some cases this is exceedingly difficult. Thus, if gas is absorbed at the upper surface of a liquid, and if the gaseous solution is heavier than the pure liquid, currents may be set up, and a steady state of diffusion may cease to exist. This has been tested experimentally by C. G. von Hüfner and W. E. Adney. The same thing may happen when a gas is evolved into a liquid at the surface of a solid even if no bubbles are formed; thus if pieces of aluminium are placed in caustic soda, the currents set up by the evolution of hydrogen are sufficient to set the aluminium pieces in motion, and it is probable that the motions of the Diatomaceae are similarly caused by the evolution of oxygen. In some pairs of substances diffusion may take place more rapidly than in others. Of course the progress of events in any experiment necessarily depends on various causes, such as the size of the containing vessels, but it is easy to see that when experiments with different substances are carried out under similar conditions, however these "similar conditions" be defined, the rates of diffusion must be capable of numerical comparison, and the results must be expressible in terms of at least one physical quantity, which for any two substances can be called their coefficient of diffusion. How to select this quantity we shall see later.

2 Quantitative Methods of observing Diffusion. - The simplest plan of determining the progress of diffusion between two liquids would be to draw off and examine portions from different strata at some stage in the process; the disturbance produced would, however, interfere with the subsequent process of diffusion, and the observations could not be continued. By placing in the liquid column hollow glass beads of different average densities, and observing at what height they remain suspended, it is possible to trace the variations of density of the liquid column at different depths, and different times. In this method, which was originally introduced by Lord Kelvin, difficulties were caused by the adherence of small air bubbles to the beads.

In general, optical methods are the most capable of giving exact results, and the following may be distinguished, (a) By refraction in a horizontal plane. If the containing vessel is in the form of a prism, the deviation of a horizontal ray of light in passing through the prism determines the index of refraction, and consequently the density of the stratum through which the ray passes, (b) By refraction in a vertical plane. Owing to the density varying with the depth, a horizontal ray entering the liquid also undergoes a small vertical deviation, being bent downwards towards the layers of greater density. The observation of this vertical deviation determines not the actual density, but its rate of variation with the depth, i.e. the "density gradient" at any point, (c) By the saccharimeter. In the cases of solutions of sugar, which cause rotation of the plane of polarized light, the density of the sugar at any depth may be determined by observing the corresponding angle of rotation, this was done originally by W. Voigt.

3. Elementary Definitions of Coefficient of Diffusion. - The simplest case of diffusion is that of a substance, say a gas, diffusing in the interior of a homogeneous solid medium, which remains at rest, when no external forces act on the system. We may regard it as the result of experience that: (1) if the density of the diffusing substance is everywhere the same no diffusion takes place, and (2) if the density of the diffusing substance is different at different points, diffusion will take place from places of greater to those of lesser density, and will not cease until the density is everywhere the same. It follows that the rate of flow of the diffusing substance at any point in any direction must depend on the density gradient at that point in that direction, i.e. on the rate at which the density of the diffusing substance decreases as we move in that direction. We may define the coefficient of diffusion as the ratio of the total mass per unit area which flows across any small section, to the rate of decrease of the density per unit distance in a direction perpendicular to that section.

Note - this article incorporates content from Encyclopaedia Britannica, Eleventh Edition, (1910-1911)

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