VII. On the action of nuclei in producing the sudden solidification of supersaturated solutions of Glauber's salt

1879 ◽  
Vol 29 (196-199) ◽  
pp. 326-331 ◽  

I propose now to state the general conclusions at which I have arrived since resuming the study of this subject two years ago. The remarks that will be made refer to solutions of the typical salt, sodic sulphate, in the proportions of 6 of salt to 3 of water. In my first two papers on supersaturated saline solutions, a nucleus is defined as a body that has a stronger adhesion for the salt, or for the liquid of a solution, than subsists between the salt and the liquid.

1872 ◽  
Vol 20 (130-138) ◽  
pp. 109-112

When a solution of the ordinary ten-atom hydrate of sodic sulphate, saturated at about 93° F., its maximum point of solubility, is boiled and filtered into a clean flask, which, being closed, is left to cool to 40° and under, a modified or seven-atom hydrate is formed at the bottom of the solution; this increases in quantity as the temperature falls, and passes into solution as the temperature rises; and, so far, the observation is supposed to be complete. But if a supersaturated solution of Glauber’s salt be reduced from ordinary atmospheric temperatures to low ones by means of a freezing-mixture of snow and salt, the results obtained are so remarkable that I venture to think a short statement of them may be worthy of a place in the 'Proceedings,’ by way of addenda to Section II. of my second paper “On Supersaturated Saline Solutions,” contained in the Philosophical Transactions for 1871, page 59.


1870 ◽  
Vol 18 (114-122) ◽  
pp. 533-537

The object of this paper is to develop more fully the principles attempted to be established in Part I., not only by clearer definitions of terms, but also by new facts and conclusions. The paper is divided into two sections; in the first of which are stated the conditions under which nuclei act in separating salt or gas or vapour from their supersaturated solutions, while in the second section is shown the action of low temperatures on supersaturated saline solutions. The first section opens with definitions of the terms used.


1877 ◽  
Vol 25 (171-178) ◽  
pp. 124-131

In making experiments on the sensitiveness of supersaturated solutions to air and greasy surfaces, I was much annoyed by the solutions so frequently crystallizing on the removal of the cotton-wool, as this necessitated boiling the flask again and waiting till it was cool. I noticed that frequently part of the cotton-wool adhered to the mouth of the flask; and it struck me that in removing this some fibres must get detached and fall in, carrying with them in all probability crystals of the salt. I soon convinced myself that this was the case, and that cottonwool is perhaps the worst material that could be chosen for covering these solutions. I now always use paper or tinfoil; and I find that these can be removed many times from the same solution without inducing crystallization. I then found that even the most sensitive solutions could be taken up in a clean glass tube and dropped on a clean glass plate without crystallizing; and that they will remain liquid exposed to the air for a very long time, often, in fact, till they dry up by evaporation in modified forms. Twenty drops on a plate give twenty experiments on the effect of air, clean and unclean surfaces, and evaporation; then the plate is cleaned, and more drops are taken from the original solution till this is used up. The trouble of boiling is thus reduced to a minimum, and the drops can be put upon all kinds of surfaces to test their activity. The slow growth of the modified salts can be watched for hours; and their forms are sometimes peculiar. Thus sulphate of soda often gives a single, square, flat pyramid, or a broad well-shaped prism, or occasionally small oetahedra round the edge of the drop. The pyramids and prisms change to opaque white when touched, and are apparently the 7-atom salt; the octahedra do not change, and are evidently the anhydrous salt. This fact is interesting, from its supporting the view that it is the anhydrous salt which is in solution. Or, again, a plate with drops may be dried over calcium chloride; and this sometimes modifies the results, as in the case of ammonia alum. This salt, when allowed to evaporate in air, generally forms a shining semitransparent film of greenish colour with a depression at the top, in which is often a circular opening, while inside small globular concretions of a dull, opaque, milky white colour are formed; these will remain moist inside for a couple of days or more. When touched with the normal salt, the whole drop becomes brilliant opaque white, quite dry, and apparently increases in volume, as the crust often breaks up and curls outwards.


1868 ◽  
Vol 158 ◽  
pp. 659-673 ◽  

The phenomena of supersaturation have been studied chiefly with reference to solutions of Glauber’s salt. In 1809, Ziz of Mayence showed that the sudden crystallization of these solutions is not due to agitation; that the vessels containing them need not be hermetically sealed, but if put under a bell-glass, or loosely covered as with a capsule, they can be preserved during a long time; that solids brought into con­tact with the solutions act as nuclei and produce instant crystallization, especially when dry; if wet or boiled up with the solution they become inactive . The best nucleus is a crystal of the salt itself. Air, if artificially dried, ceases to be a nucleus. Three varieties of the sodic sulphate are noticed, i. e . the anhydrous , the ordinary 10- atom hydrate , and also a modified salt formed when supersaturated solutions are left to cool down in closed vessels. This salt contains less water of crystallization than the ordinary salt, and is more soluble. If the vessel in which it is formed be suddenly opened, or a nucleus touch the mother-liquor, this instantly solidifies into the 10-atom hydrate, and the crystals of the more soluble salt become opaque, like the boiled white of egg. In 1819 Gay-Lussac referred the state of supersaturation to the inertia of the saline molecules, the molecular condition of the sides of the vessel, and other causes. He also showed that solutions of some other salts besides Glauber’s salt exhibit the phenomena of supersaturation. In 1832 the number of such salts was stated by Dr. Ogden § to be not less than 21.


1878 ◽  
Vol 26 (179-184) ◽  
pp. 523-534 ◽  

There is probably no subject in science that is more involved in contradiction than that of supersaturation. All the phenomena connected with it seem to behave differently in the hands of different inquirers, so that the facts affirmed by one writer are simply denied by another; and the same theory which seems to have been disproved by one is again and again brought forward by another. Take one point by way of example, namely, the nuclear action of bodies in producing the sudden crystallization of a supersaturated saline solution. Ziz, in 1809, stated that not only air, but solids, act best as nuclei when dry: if wet, or boiled with the solution, or thrown into it while hot and allowed to cool with it, they are inactive. Löwel (1850-57) denies that air, whether wet or dry, has any nuclear action; but he admits that solids exposed to the air become active, and that alcohol is always active. Selmi and Goskynski, in 1851, assert that dry air is nuclear, and acts by getting rid of water at the surface, and producing small crystals there which continue the action. This seems to be a revival of Gay Lussac’s theory, namely, that air is absorbed at the surface of the solution and precipitates a portion of the salt in the same way that one salt may precipitate another, and this precipitate continues the crystallization. Lieben, in 1854, states that soot is a nucleus, also platinum black whether ignited or not; that pounded glass heated in sulphuric acid produces sudden crystallization, but that platinum sponge and precipitated sulphate of baryta after being heated have no action. Schröder, in 1859, remarks that it is always a matter of chance whether such or such a substance produces crystallization. “Such facts,” he says, "singularly increase the difficulty of interpreting theoretically the phenomena of supersaturation.” He concludes that the only general rule that can be admitted in the presence of so many opposed and contradictory results is that bodies act on supersaturated solutions only after having been exposed to the air. In 1866 Gernez and Viollette and in 1868 Schiff are satisfied that there is only one nucleus for a supersaturated solution, and that is a salt of the same kind as the one in solution or one isomeric therewith. In 1866 Jeannel opposes this theory of pancrystallography, as he calls it, on the ground that it. cannot be supposed that crystals, often of rare salts, are to be found waiting in the atmosphere, ready to enter our flasks as soon as they are uncovered. Pellogio also, in 1875, “gives proofs that the phenomena of supersaturation are not so simple as the French physicists would imply, namely, that the only nucleus is a salt of the same kind,” seeing that some supersaturated solutions, such as those of hyposulphite of soda, acetate of lead, acetate of soda, &c., may be exposed to the air, in places where the air is any thing but still, for fifteen or twenty days without the formation of crystals. He states further that porous bodies are active, such as common sponge, platinum black, iron reduced by hydrogen, and carbon. For example, carbon was raised to a red heat, quenched under mercury, and introduced into a solution of 100 sodic sulphate to 102 of water: it fell to the bottom and disengaged gas for sometime; crystallization then set in and spread all through the mass. Viollette, on the contrary, finds that bodies greedy of water and capable of being hydrated, such as the fused sulphates of copper and of iron, and porous bodies recently calcined, such as carbon, have no action on supersaturated saline solutions.


1868 ◽  
Vol 16 ◽  
pp. 403-411 ◽  

This memoir is divided into six parts. The first part contains a definition of the subject; the second an historical sketch; the third is on the action of nuclei in inducing crystallization, and the effect of low temperatures on a number of supersaturated solutions contained in chemically clean vessels; the fourth is on the formation of a modified salt, as in the case of zinco-sulphate and sodic sulphate; the fifth contains an inquiry as to whether anhydrous salts form supersaturated solutions; and the sixth and last part is a summary with a classified list of the salts examined 1. Definition .—When water at a high temperature is saturated with a salt, and, on being left to cool in a closed vessel, retains in solution a larger quantity of the salt than it could take up at the reduced temperature, the solutionis said to be supersaturated.


1871 ◽  
Vol 161 ◽  
pp. 51-68 ◽  

I have already in former papers considered the conditions under which gas 1 or steam 2 or salt 3 is separated from its supersaturated solution, and have endeavoured to show that a body is active or inactive as a nucleus, according as it is chemically unclean or clean . An objection to these terms has been started, on the ground that a stick of tallow, for example, may be as chemically clean as a catharized glass rod. In the first Section of this paper an attempt is made to define with rigour the terms clean and unclean , and to settle the conditions on which nuclei really act. In the second place, an attempt is made to confirm the conclusion arrived at in Part I., that supersaturation depends mainly on the absence of a nucleus, by a number of examples in which highly supersaturated saline solutions, when reduced to temperatures at and below the zero of Fahrenheit’s scale, rather solidify than crystallize, and in melting reassume the condition of clear, bright, supersaturated solutions. Section I.— On the Functions Nuclei . I have already endeavoured to show that the obscure and often contradictory behaviour of solids as nuclei in separating gas or vapour or salt from their supersaturated solutions, becomes clear by considering whether the solids used as nuclei were or were not chemically clean as to surface at the moment of contact with the solution into which they were placed.


1879 ◽  
Vol 29 (196-199) ◽  
pp. 24-29

It is stated in my second paper on supersaturated saline solutions (“Phil. Trans.,” 1870, p. 53), that among nuclear bodies “are permanently porous substances, such as charcoal, coke, pumice, meerschaum,” also that “certain liquids act as nuclei by separating water instead of salt from supersaturated solutions. Absolute alcohol acts in this way.” Some eminent observers have denied the accuracy of these statements. Thus, M. Viollette concludes from his experiments that porous bodies, such as pumice, calcined baryta, lime, and gypsum, and bodies greedy of water, and capable of being hydrated, such as calcined sulphate of iron and of copper, have no influence on supersaturated solutions.


2000 ◽  
Vol 25 (4) ◽  
pp. 331-332
Author(s):  
W.M. Boek ◽  
N. Keles ◽  
K. Graamans ◽  
E.H. Huizing

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