scholarly journals I. Notes on supersaturated saline solutions

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.

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.


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.


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.


1975 ◽  
Vol 27 (2) ◽  
pp. 323-330 ◽  
Author(s):  
Michel Hupet ◽  
Brigitte Le Bouedec

In Experiment I, subjects were given active and passive sentences where the definiteness of nominals is varied and about which uncertainty was expressed, e.g. “I thought that the policeman had been injured by a gangster, but I was mistaken, in fact.”. Their task was to decide what was the target of the mistake by completing freely the sentence in such a way that the account would be corrected. When the nominals are differentially determined (a-the, the-a), the pattern of responses indicates that, for both active and passive, subjects were more likely to conclude that it was the non-definitely marked nominal that had been involved in the mistake rather than the definitely marked one. When both nominals are similarly determined (a-a, the-the), subjects were more likely to indicate the event itself as having been involved in the mistake. This supports the hypothesis that subjects are able to utilize definiteness to determine the relation between presupposed and assertional information. In Experiment II, subjects were given paired active and passive sentences with differentially determined nominals and were required to choose between the two syntactic forms of each pair the one they would prefer to use. The pattern of responses clearly shows that subjects were more likely to choose the voice allowing the hypothesized preferential order “Definitely marked grammatical subject-non-definitely marked grammatical object”. Passive transformational rule is thus interpreted as a particular case of a more general rule specifying the ways in which what is made known (comment) is nested on to what is already assumed to be the case (topic).


If we attempt to decipher the biological meaning of reciprocal innervation its various instances when marshalled together say plainly that one of the functional problems which it meets and solves is mechanical antagonism. Where two muscles have directly opposed effect on the same lever, “reciprocal innervation” is the general rule observed by the nervous system in dealing with them, and this holds whether the reciprocal innervation is peripheral as with the antagonists of the arthropod claw, or is central as with vertebrate skeletal muscles. Also where one and the same muscle is governed by two nerves influencing it oppositely, reciprocal innervation seems again the principle followed in the co-ordination of the two opponent centres, as has been shown by Bayliss in his observations on vasomotor reflexes. But the distribution and occurrence of reciprocal innervation extend beyond cases of mere mechanical antagonism. The reflex influence exerted by the limb-afferents on symmetrical muscle-pairs such as right knee-extensor and left is reciprocal. Thus right peroneal nerve excites the motoneurones of left vastocrureus, and concomitantly inhibits those of the right. The reflex inhibition of the one is concurrent with, increases with increase, and decreases with decrease of, the excitatory effect on the other. Here the muscles are not in any ordinary sense antagonistic; not only do they not operate on the same lever, but they are not even members of the same limb, nor do they belong even to the same half of the body. They are, however, actuated conversely in the most usual modes of progression—the walking and the running step—though not always in galloping.


2020 ◽  
Vol 2020 ◽  
pp. 1-13
Author(s):  
Long Tan ◽  
Penglin Zheng ◽  
Qingbing Liu

Bentonite, when used as buffer/backfill material in the deep disposal of high-level radioactive waste (HLW), could undergo desiccation shrinkage or even cracking due to the heat released from HLW, impairing the efficiency of the barrier system. Furthermore, in-service buffer materials are inevitably in contact with the groundwater, which sometimes contain high salt concentrations. The groundwater salinity may modify the properties of bentonite and hence affect the process of desiccation and its performance. To investigate this effect, in this study, a series of temperature-controlled desiccation tests was conducted on compacted specimens of Gaomiaozi (GMZ) bentonite preliminarily saturated with two different saline solutions (NaCl and CaCl2) at the concentration varying from 0.5 to 2.0 mol/L. The experimental results indicated that, as the concentration of saline solution increases, the initial saturated water content of bentonite decreases, whereas the residual water content at the completion of the desiccation test increases. The water evaporation rate is reduced for the specimens saturated with a high-concentration saline solution, and CaCl2 has a more significant influence on water evaporation than NaCl. The evolution of cracks on the sample surface during the desiccation process can be divided into four stages: crack growth, maintenance, closure, and stabilization; an increase in the salt concentration effectively inhibits crack development. It was shown that the infiltration of saline solutions alters the microstructure of bentonite by changing the arrangement of clay particles from a dispersed pattern to more aggregate state, which results in a decrease in shrinkage strain and shrinkage anisotropy.


2020 ◽  
Author(s):  
Lucius Caviola ◽  
Stefan Schubert ◽  
Andreas Mogensen

Across eight experiments (N = 2,310), we studied whether people would prioritize rescuing individuals who may be thought to contribute more to society. We found that participants were generally dismissive of general rules that prioritize more socially beneficial individuals, such as doctors instead of unemployed people. By contrast, participants were more supportive of one-off decisions to save the life of a more socially beneficial individual, even when such cases were the same as those covered by the rule. This generality effect occurred robustly even when controlling for various factors. It occurred when the decision-maker was the same in both cases, when the pairs of people differing in the extent of their indirect social utility was varied, when the scenarios were varied, when the participant samples came from different countries, and when the general rule only covered cases that are exactly the same as the situation described in the one-off condition. The effect occurred even when the general rule was introduced via a concrete precedent case. Participants’ tendency to be more supportive of the one-off proposal than the general rule was significantly reduced when they evaluated the two proposals jointly as opposed to separately. Finally, the effect also occurred in sacrificial moral dilemmas, suggesting it is a more general phenomenon in certain moral contexts. We discuss possible explanations of the effect, including concerns about negative consequences of the rule and a deontological aversion against making difficult trade-off decisions unless they are absolutelynecessary.


Author(s):  
Philip Coppens

The electron density in transition metal complexes is of unusual interest. The chemistry of transition metal compounds is of relevance for catalysis, for solid-state properties, and for a large number of key biological processes. The importance of transition-metal-based materials needs no further mention after the discovery of the high-Tc superconducting cuprates, the properties of which depend critically on the electronic structure in the CuO2 planes. The results of theoretical calculations of systems with a large number of electrons can be ambiguous because of the approximations involved and the frequent occurrence of low-lying excited states. The X-ray charge densities provide independent evidence from a technique with very different strengths and weaknesses, and thus can make significant contributions to our understanding of the properties of transition-metal-containing molecules and solids. In inorganic and organometallic solids, the average electron concentration tends to be high. This means that absorption and extinction effects can be severe, and that the use of hard radiation and very small crystals is frequently essential. Needless to say that the advent of synchrotron radiation has been most helpful in this respect. The weaker contribution of valence electrons compared with the scattering of first-row-atom-only solids implies that great care must be taken during data collection in order to obtain reliable information on the valence electron distribution. When the field exerted by the atomic environment is not spherically symmetric, as is the case in any crystal, the degeneracy of the d-electron orbitals is lifted. In the electrostatic crystal field theory, originally developed by Bethe (1929) and Van Vleck (1932), all interactions between the transition metal atom and its ligands are treated electrostatically, and covalent bonding is neglected. Since the ligands are almost always negatively charged, electrons in orbitals pointing towards the ligands are repelled more strongly, and the corresponding orbitals will be higher in energy. The discussion is the simplest for the one d-electron case, in which d-d electron repulsions are absent.


Sign in / Sign up

Export Citation Format

Share Document