In this brief communication, I shall confine myself to presenting some initial propositions and the principal conclusions of my work (see the article). When considering the thermal state of a piece of solid substance (e.g., a piece of gold), it is therefore necessary to take into account three surfaces: 1. The external surface, which delimits the piece of solid substance from the surrounding space. 2. The internal surface of contact between the crystalline grains constituting the piece. 3. The total internal dynamic (pulsating) surface of the crystalline grains.
It has long been obsered that certain physical and chemical processes involving sulfur-containing substances produce colors of violet, indigo-blue, blue and green, some of which are remarkable in their beauty. These color reactions are historically closely linked to hypothetical modifications of elemental sulfur; black sulfur, which is translucent blue in thin layers, Magnus's sulfur and Wöhler's blue sulfur. The presence of these modifications in ultramarine was explained by a number of scientists as the reason for its diverse colors.
Working in 1902 with concentrated solutions of Mn(CNS)₃ and Ba(CNS)₂, and in 1905-1906 with a series of concentrated solutions of particularly readily soluble salts for the purpose of obtaining jellies of crystalline substances, I noticed that under the influence of these salts, filters swell and become so slimy that they slip through the narrow tube of the funnel in the form of a more or less gelatinous lump. According to my theory of peptization (1907-1908), cellulose is peptized because, at a certain high concentration of salt and a certain high temperature, it must transform into some truly soluble compound. The theory given above (see the article) can be generalized to any dispersoid that hydrolyzes into a soluble compound.
The article examines the vectorial nature of molecular forces of attraction and clarifies the question of changes in the character and degree of molecular orientation. The author draws the following conclusions: 1. Matter is vectorial in all its aggregate states. 2. By increasing the degree of dispersion of any solid crystalline substance, one can change the degree of its overall orientation; moreover, at extremely high degrees of dispersion, the resulting crystalline systems become practically indistinguishable from liquids in terms of orientation. The work further covers: the gaseous-liquid crystalline state of matter and its universality; the systematics and nomenclature of various kinds of the vectorial state of matter; the fundamental law of dispersoidology and its application.
Scientific research carried out jointly by several individuals always gives rise to rumors about the degree of participation of individual researchers in the overall work, and these rumors often take on a highly unpleasant character. To avoid the latter, I consider it necessary to note that in works published jointly on behalf of myself and the names of my students, both the topic and the plan of its elaboration belong to me. Preparatory work, such as preparation of solutions, determination and calculation of their concentration, analysis, etc., is carried out entirely by my employees.
In this study, the conditions formation and certain properties of the following disperse systems were studied: No.1. Disperse systems with a liquid disperse phase xH₂O+ yHCl. No.2. Dispersed systems with a solid disperse phase of CuCl₂ composition. No.3. Disperse system with a solid disperse phase of the composition xH₂O + yHCl·H₂O. No.4. Disperse systems with solid disperse phase CuCl₂ · 2H₂O. No.5. Disperse systems with solid disperse phase CuCl₂·2H₂O and a complex liquid disperse phase of the composition (see the article). No.6. Disperse systems with a liquid disperse phase of the composition (see the article). No.7. Disperse systems with a solid disperse phase of composition (xH₂2O + y.cupric oleate). No.8. Disperse systems with a solid disperse phase of the composition (see the article).
The article examines the following issues: obtaining, for any substance, a dispersoid solution of low concentration and of significant concentration, as well as the problems of the crystallizability of colloids, obtaining crystalline substances in the colloidal state; dynamic processes within the dispersion medium as factors of stability, theorems on the stability of dispersoid solutions; dynamic and static chemical compounds, etc.
One of the fundamental principles of dispersoid chemistry is the assertion that all properties, both physical and chemical, are functions of the degree of dispersion of a given dispersed system. The author considers the following issues: 1) The effect of increasing the degree of dispersion on the electrical conductivity of chemically pure metals; 2) The influence of the degree of dispersion on the electrical conductivity of alloys representing a mechanical combination of component crystals; 3) The electrical conductivity of coarse-dispersed alloys representing solid solutions; 4) Alloys representing solid solutions and electronic theory; 5) The electrical conductivity of coarse-dispersed metals at very low temperatures; 6) The electric ultramicroscope.
In this article, only the following dispersed systems will be considered: Liquid + Solid. Liquid + Liquid, moreover, in view of the identity of the characteristics of the three types into which classes a and b are divided, I will limit myself to a more detailed analysis of the class a types. Any dispersed system can be characterized by: 1. The magnitude and sign of the dispersing (or aggregating) force, 2. The degree of dispersion at a given moment, 3. The aggregate state of the dispersed phase. 4. The degree of contamination (adsorption) of the surface of the dispersed phase.
In this article I wish to share with readers some of the results of my experiments on the gelation of solutions, which, although obtained back in 1908, have not been published in sufficient detail. In my work on the gelation of solutions, I came to the following four conclusions (see the article and tables). In conclusion, I would like to draw attention to the fact that during the so-called “salting out” of organic colloids, the hydration capacity of the added salt plays a certain role, because, at least at a sufficiently high concentrations, there must be a struggle between the salt and colloid molecules for possession of hydration water.
I wish to point out the importance of knowledge of thefundamental principles of colloidal chemistry for other branches of natural science. Knowledge of them is necessary for a physicist, because a deep understanding of the doctrine of states of aggregation is impossible without a clear assimilation of the properties of dispersed systems. For a crystallographer and a mineral chemist, these foundational principles of the study of colloids are no less important, because, when obtaining highly dispersed systems through the method of crystallization, we are present at the birth of a crystal and monitor all its embryonic forms. The study of colloidal chemistry is even more important for representatives of the biological sciences, since the true cradle of nascent life is a typical complex disperse system — plasma.
In my report of April 6, 1906, I wrote that two factors play the most important role in the process of melting dispersed systems: the degree of disruption of the continuity of the body and the associated change in the conditions of heat transfer, both before the melting process and during this process The degree of discontinuity affects, firstly, the latent heat of fusion, and, secondly, together with the altered conditions of heat transfer, the softening of the solid system even before the start of melting. The surface layer of a crystal is chemically inhomogeneous, which affects the physical and physicochemical properties of the substance especially strongly at a high degree of dispersion.
Suppose wehave a unit volume of a solution of substance X in some solvent Y; add to the solution of another solvent Z, which dissolves solvent Y well, but practically does not dissolve substance X, even if solvent Z is mixed a little with solvent Y. Then solvent Z will begin to extract solvent Y out of the solution and substance X should precipitate as crystals.
Our experiments with alcohol solutions of Na Br, KCl and NaCl gave exactly the same results as for sulfur and phosphorus. To avoid the absorption of water by alcohol, these experiments must be carried out in hermetically sealed test tubes, inside of which, above the surface of the alcohol, a cup (of a special design) with phosphorus anhydride is suspended. Such an arrangement is essential because the solubility of the mentioned salts increases (for S and P, on the contrary, it decreases) upon the absorption of water by alcohol, and the increase in solubility during the experiment greatly affects the course of the condensation and dispersion processes during the heating of solid suspensoid solutions.
The author describes in detail the gaseous and dissolved states; the osmotic pressure of colloidal solutions, as well as the differences between suspensoid (colloidal) and suspensied (true) solutions. Highly dispersed colloidal solutions have quite a measurable osmotic pressure, and this pressure cannot be less than the gaseous pressure under the same conditions.
When a thin stream of molten sulfur, superheated above 400°, is poured into liquid air, the sulfur is obtained in the form of very thin threads, 0.5-1 mm in diameter. The threads taken out of liquid air are at first quite solid and brittle, but then, as soon as the temperature rises somewhat, they acquire an extraordinary elasticity, similar to the elasticity of rubber. The more easily it is to obtained a substance in a gelatinous or glassy state, the more capable it is of forming various modifications. Sulfur is the most typical example of such substances.
In my previous works, I provided a formula for obtaining sodium chloride in a colloidal state. At room temperature, as is known, one cannot expect the formation of any significant quantities of complex esters, therefore, the mechanism of the above mentioned reaction is very simple. In view of the decrease in the solubility of NaCl with a reduction in temperature, it is very useful, especially for obtaining stable NaCl salts, to carry out reactions at low temperatures (see the report).
As I have previously demonstrated, when mixing sufficiently concentrated reacting solutions, any substance that is poorly soluble in the selected dispersion medium is obtained in the form of a coarse-meshed jelly. The general principle is as follows: by altering the rate of molecular condensation W, any substance, regardless of its chemical and physical properties (such as chemical composition, solubility, etc.) can be obtained in crystals of any degree of dispersity, from very large to negligible.
I have repeated the experiments described in my report “Colloidal Ice”, now with liquid air, strongly enriched with oxygen (boiling point at approx. -185°C) and with the same success. See in the note: 1. On the solidification of water upon mixing it with liquid air. 2. On the production of dispersed systems such as: Ice - liquid air.
I tried to implement the conditions of dispersoid condensation to obtain colloidal ice; my efforts were crowned with success. See in the note: 1. Solid suspensoid solutions of ice. 2. Liquid suspensoid solutions of ice. The example provided in the report of obtaining ice in a colloidal state can most clearly confirm my proposition on the generality of the colloidal state (1906) and my opinion that this state is the result of the corresponding directions of the condensation process.
In my previous studies, published in 1905-1908 in Russian and German, I showed that any substance, both of simple and complex chemical composition, can be obtained: in well-formed clear crystals; in an “irreversible” colloidal state (in the form of sols and “irreversible” colloidal-amorphous sediments); in a “reversible” colloidal state (by rapid cooling and increasing the association of dissolved particles into the solution).
In my numerous reports and articles published in Russian and German from 1905 to 1908, I experimentally proved that the appearance and structure of a sediment of any substance can be changed at the discretion of the researcher.
This work, although it represents only one of the most important links in my extensive work on the states of matter, which I publish, for certain reasons, in German, is a completely accomplished independent whole. This work treats the question of the influence of the concentration of reacting solutions on the appearance and structure of sediments - a question that has not yet been completely undeveloped in science, except for a few fragmentary observations.