Science (journal)/Volume 47 New Series/No. 1201/The Nomenclature Used in Colloid Chemistry. A Plea for Reform
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Science, Volume 47 New Series, No. 1201 (January 4, 1918)
|Address at the Funeral Services of Joseph Young Bergen→|
|DOI: 10.1126/science.47.1201.10, pages 10-14|
THE NOMENCLATURE USED IN COLLOID CHEMISTRY. A PLEA FOR REFORM
Colloid chemistry is no longer considered as a mere collection of mysterious substances and "abnormal" reactions. It is an important branch of chemical and physical science possessing a fairly well established working basis and is rapidly acquiring new students.
It suffers, however, like all virgin sciences, the affliction of superfluity of terms used to describe essentially the same things, careless and loose use of some expressions, and confusion of nomenclature in general. This condition results in a great handicap to new students. It is very difficult for them to acquire clear conceptions from their first readings of the various works on the subject.
It is time that this matter be taken in hand by some committee of our Chemical Society for the purpose of removing this needless handicap and confusion by defining the various terms used in colloid science, eliminating unnecessary ones and by standardization of the terminology in general, just as was done with the terminology of the proteins by the biological chemists some years ago.
The paragraphs which follow attempt to point out some of the cases of malusage of terms.
No objection can be raised against the word "colloid." It is distinctive, but the use of the expression "colloidal solution" is to be strongly condemned, since it is so evident that substances in the colloidal condition are not dissolved, in the strict sense of the term. Colloidal particles are in a condition midway between solution and mechanical suspension, and they are held in this peculiar state of dispersion by virtue of their surface energy, electrical charge, their kinetic energy as manifested by the Brownian movement, and the adsorbed ions of electrolytes which are essential to the stability of all colloids.
The general term "dispersion," as suggested by Wo. Ostwald, is to be preferred to the special term "solution." E,g., "Mechanical suspensions " are Coarse dispersions, "Colloidal solutions" are Colloidal dispersions, and "True solutions" are Molecular dispersions.
The particles, or "internal phase" of these systems are known as the "dispersed phase," and the liquid in which they are dispersed, the external phase, is known as the "dispersion medium."
The present usage of the word "sol" and of its modifications — "hydrosol," "alcosol," etc., to describe a colloidal dispersion, is the same as that of Graham, their originator. I have noticed, however, that the word "sol" has been used by a few writers in the sense of the dispersed phase, i. e., the particles in colloidal dispersion. Is this use of the term to be permitted? Graham invented it as a short and convenient substitute for colloidal "solution" and a perusal of the works by Bechhold, Cassuto, Freundlich, Hatchek, Ostwald, Taylor and Zsigmondy shows that the original sense of the expression has been retained by these writers.
The use of the term "gel," however, and of its modifications, "hydrogel," "alcogel," etc., is deplorably loose and confusing. This term was coined by Graham and first used by him in discussing the "pectization" or coagulation of the hydrosol of silicic acid. Therefore, if we are to limit the use of "gel" to its original sense, we should use it only when speaking of the definite coagula of sols. This is not the case, however. Any substance which resembles a jelly in appearance is called "gel," although in chemical and physical properties it may be entirely different from the kind of matter which Graham had in mind when he invented the term. This use of the expression is exceedingly popular and would be very difficult to overcome.
Let us take up a case or two to show how unscientific this latter usage of the term is. For example, consider the dissolution or dispersion of gelatine in hot water. It forms a very mobile "solution" or rather dispersion, and in this form is called a hydrosol or sol. If this hydrosol be allowed to cool, it becomes very viscous and "sets" to a jelly-like mass. In this stiffened form it is popularly known as a "hydrogel" or "gel." If it be warmed again, its viscosity decreases, it becomes mobile and is called a "sol." Now if this use of the term "gel" (which is not as Ghraham intended) is to be permitted, then what is the line of demarcation between the sol and gel states? A change in state has occurred, it is true, for in the sol condition the water was the external phase whereas in the so-called gel state the gelatine became the external phase and the water internal. The change is very gradual, however, and our change of terms to suit the change in appearance of the system is exceedingly arbitrary and unscientific. Furthermore no chemical change in the nature of the gelatine has taken place.
If some alum or a trace of mercuric chloride be added to the gelatine hydrosol, a coagulum is obtained which is correctly termed a gel according to Graham. This is a coagulated compound, however, a chemical reaction has taken place. It will not redissolve in water and is, therefore, entirely different from the case discussed above, which is also commonly called gel.
To further complicate matters, the dry pieces of gelatine (and in fact any other colloid which will "dissolve" readily) which were used to make the original sol are also quite commonly called "gel." Lottermoser called attention to this several years ago and suggested that such pieces of gelatine, or of any other dry "soluble" colloid be called "solid sol." This suggestion is obviously bad. Why apply any special term at all?
When a hydrous ferric oxide sol is allowed to evaporate spontaneously, it will go through a jelly-like stage and finally become a hard scaly residue when all or nearly all of the water has left it. The jelly-like form will redisperse when warmed with an excess of water, while the amorphous form will not. Yet both forms are called "gel"! Zsigmondy distinguishes between these two different forms by calling the first one "hydrogel" and the second, "gel." A review of the texts on colloidal chemistry shows the following conceptions of this term. Cassuto calls a gel the gelatinous precipitate obtained from a sol by means of an electrolyte, heat or evaporation. I. e., a gel is formed by coagulation of a sol. He calls stiffened sols (or jellies), "gelatines."
Bechhold remarks the loose use of the word "gel" and states that he restricts it to the description of the coagula from sols. To the stiffened sols or jellies he applies the term "Gallerte," which in English might be called "jelly."
Freundlich says that systems of solid dispersion media and liquid dispersed phase are gels as distinguished from the reverse which are suspensions or emulsions. In other words he applies the word "gel" to jellies.
Hatschek refers to the fact that Graham applied the name "gels" to the products obtained by the coagulation of sols, but later on in his book he calls jellies, gels also.
Ostwald in his "Handbook of Colloid Chemistry," considers all colloids as gels when the system becomes "microscopically heterogeneous." That is to say, he applies the term promiscuously.
Taylor uses "gel" in the same loose general manner as Ostwald, Hatschek and Freimdlich.
Zsigmondy in his " Kolloidchemie," limits the word "gel " to the dry residue which will not redisperse in a solvent, but he applies "hydrogel" to the jelly-like mass formed by removal of the dispersion medium or by salt coagulation.
Hardy recognized the difference in properties of substances called "gels" and he qualified the term — "gels by coagulation" and "gels by stiffening."
I feel confident that Graham did not apply this term as loosely as is popular at the present time. In his remarks on the properties of colloidal tungstic acid he says: "It is remarkable that the purified acid is not pectized by acids or salts even at the boiling temperature. Evaporated to dryness, it forms vitreous scales, like gum or gelatine." Note that he describes the dry residue as "scales, like gum or gelatine" and not as gel.
It is evident, then, that the original meaning of the term gel has not been adhered to and in fact is more often applied to the state best described as jellies. Shall we adhere to Graham's definition or shall we discard it, restricting the term gel and its modifications to jellies, as popularity favors, and do away with any special terms to describe coagula from sols by electrolytes, or residues formed by evaporation to dryness? Special terms to describe these last two cases are obviously unnecessary and serve only to encumber colloid chemistry.
Lately the word "peptization" or "peptinization," as originated by Graham, has shown tendencies of wider use than formerly. Graham used this expression to describe the formation of a sol from a gel by the influence of a small amount of foreign reagent as, for example, the formation of a hydrous ferric oxide sol from a coagulum of ferric hydroxide by treatment with a small amount of hydrochloric acid or ferric chloride. He named it "peptization" because it resembled the hydrolysis of egg white to peptone by acid.
Cassuto, Hatschek, von Weimam and Zsigmondy preserve the original sense of this term. Bancroft has recently proposed, however, that we use peptization to describe all cases of transformation of gel (using this term in the present popular sense) to sol and not restrict it merely to cases where a foreign electrolyte has been added to accomplish the change. E. g., when dry gelatine is "dissolved" in water Bancroft would call it a case of gelatine being peptized by water. This usage has its merits because it eliminates the word "dissolve" and the implication of "solution." Ostwald defines peptization as the phenomenon opposed to coagulation.
Taylor prefers a new term, "solation," which he applies to all cases of gel → sol transformations, and incidentally he urges the adoption of "gelation" to define all cases of sol → gel transformations instead of coagulation or pectization. "Pectization," another of Graham's terms, is rapidly dying out. The word "coagulation" covers all cases of pectization and therfore why preserve an unnecessary term? Furthermore, why adopt the new term "gelation" proposed by Taylor. "Coagulation" is adequate. Of course, if it is decided to name jellies (stiffened sols) "gels," then the word "gelation" would be a good one to describe the "setting" of the gel or the stiffening of the sol. Elimination of some synonymous terms is decidedly necessary from the list of names applied to the two more or less distinct classes or systems of colloid dispersions. For example, these two systems are variously named as follows:
|Noyes||Colloidal solutions||Colloidal suspensions|
|Hardy, Zsigmondy||Reversible colloids||Irreversible colloids|
|Billitzer||Baser colloids||Typical or genuine colloids|
|"||Hydrophilous colloids||Anhydrophilous colloids|
|Henri||Stable colloids||Unstable colloids|
|Perrin, Freundlich,Neumann||Lyophilic colloids||Lyophobic colloids|
|Bary||Dissolving colloids||Electrical colloids|
|Wo. OstwaldCite error: Closing
|Burton||Gelatinizing type||Non-gelatinizing type|
The terms "emulsoid" and "suspensoid" are very popular. "Lyophilic" and "lyophobic" are very expressive. The stable-unstable" and the "reversible-irreversible" terms should also be abolished, since they describe the conduct and changes in state of colloids when subjected to external conditions and are not always sharply defined. For example, hydrous ferric oxide sol is fairly stable in the presence of neutral electrolyte (much more so than colloidal gold or platinum), while it is irreversible when evaporated to dryness. Most writers classify it with the suspensoids, although Taylor calls it an emulsoid (since if it be evaporated not quite to dryness it is partially reversible). In reality it belongs to neither of these two generally accepted classes; its properties place it midway between the two, nearer the suspensoid than the emulsoid class. All the hydrous oxides of the basic or acidic elements act similar to hydrous ferric oxide.
On account of this confusion of classification Bancroft has suggested that the distinction between these two groups be done away with. He prefers to classify colloidal systems according as to whether water or the more mobile phase, is the internal or the external phase and states: "While we are reasonably sure that colloidal gold is a solid and that colloidal oil is a liquid, the two behave exactly alike when both are suspended electrically."
This suggestion is alone the proper lines, but it is too sweeping, since colloidal gold and colloidal oil do not behave alike.
After a condiseration of all the terms, it would seem that "lyophilic" and "lyophobic," or more special derivatives, "hydrophobic" are the least objectionable terms, since most colloids answer to one of these designations. When our knowledge of colloids becomes exact enough to sharply differentiate between these two classes then we may find names for those systems which now seem to have properties which place them in neither of the above.
Before concluding, attention is directed to the irritating, although not very serious, mistake in the translations of the German terms "disperse" and "dispersions Mittel" by some authors. The German adjective "disperse" is "dispersed" in English, not "disperse," and "disperse Phase" is "dispersed phase," while "dispersions Mittel" is "dispersion medium" and not "dispersion means." These mistakes are like the old one of translating "Wanderung der Ionen" "wandering of the ions" instead of "migration of ions."
Arthur W. Thomas
Department of Chemistry, Columbia University
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|This work is in the public domain in the United States because it was published before January 1, 1923.
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