It is well known that the paraffine obtained by the distillation of petroleum residues is crystalline, while that obtained directly (as in the filtration of residuum) is amorphous. Ozokerite or ceresine differs but slightly from paraffine, the principal distinction being want of crystalline structure in it as found. Other characteristics, such as the melting point, specific gravity, etc., vary in both, and so are not of importance in a comparison. Hence it has been asked, Is the paraffine occurring in petroleum and ozokerite identical with that which is produced by their distillation? As crystalline paraffine could be obtained from ozokerite by distillation alone, many persons have supposed that it was engendered in the process. Recently, however, crystalline paraffine has been obtained from ozokerite by dissolving the latter in warm amyl alcohol; on cooling the greater part separates out in crystals having the luster of mother-of-pearl. By repetition of this process, a substance is obtained that is scarcely to be distinguished from the paraffine obtained by distillation. Apparently there exists then in ozokerite, together with paraffine, other substances not capable of crystallization which keep the paraffine from crystallizing.

These colloids appear to be separated by amyl alcohol in virtue of their greater solubility in that menstruum. It is also reasonable to suppose that they undergo change or decomposition by distillation.

So as petroleum residues are amorphous, and the crystalline paraffine is first produced by distillation, it has been argued that the paraffine present in crude petroleum is approximately the same thing as ozokerite.

This, however, is not sufficient to establish the pyrogenic origin of all crystallized paraffine, as crystals can be obtained from the amorphous residues by distillation at normal or reduced pressure or in a current of steam. To explain these facts two assumptions are possible. Either the chemical and physical properties of all or some of the solid constituents are changed by the distillation, and the paraffine is changed from the amorphous into the crystalline variety, or the change produced by the distillation takes place in the medium (i.e., the mother liquid) in which the paraffine exists. The change effected in ozokerite and in petroleum residues when crystalline paraffine is obtained by distillation is to be regarded as a purification, and can be effected partially by treatment with amyl alcohol. In the same way, by repeated treatment of petroleum residuum with amyl alcohol, a substance of melting point 59° C. can be obtained, which cannot be distinguished from ordinary paraffine.

The treatment with amyl alcohol has therefore accomplished the same results as was obtained by distillation, and the action is probably the same, i.e., a partial separation of colloid substance. These facts point to the conclusion that crystallizable paraffine exists ready formed in both petroleum and in ozokerite, but in both cases other colloidal substances prevent its crystallization. By distillation, these colloids appear to be destroyed or changed so as to allow the paraffine to crystallize.

It is a generally known fact that liquids always appear among the products of the distillation of paraffine, no matter in what way the distillation be conducted. This shows that some paraffine is decomposed in the operation.

The name proto-paraffine has been given to ozokerite and to the paraffine of petroleum in contradistinction to pyro-paraffine, the name that has been applied to the paraffine obtained by distillation from any source.

According to Reichenbach, paraffine may crystallize in three forms: needles, angular grains, and leaflets having the luster of mother-of-pearl. Hofstadter, in an article on the identity of paraffine from different sources, confirmed this statement, and added further that at first needles, then the angular forms, and then the leaflets are formed. Fritsche found, by means of the microscope, in the ethereal solution of ozokerite, very fine and thin crystal leaflets concentrically grouped, and in the alcoholic solution fine irregular leaflets. Zaloziecki has recently developed these microscopic investigations to a much greater extent. According to this observer, the principal part of paraffine, as seen under the microscope, consists of shining stratified leaflets with a darker edge. The most characteristic and well developed crystals are formed by dissolving paraffine in a mixture of ethyl and amyl alcohols and chilling. The crystals are rhombic or hexagonal tablets or leaves, and are quite regularly formed. They are unequally developed in different varieties of paraffine. The best developed are those obtained from ceresine.

Their relative size and appearance give an indication as to the purity of the paraffine, and, as they are always present, they are to be counted among the characteristic tests for paraffine. Reichenbach observed that mere traces of empyreumatic oil prevented their formation.

The old method of determining the amount of paraffine in petroleum was to carry out the refining process on a small scale; that is, to distill the residue from the kerosene oils to coking, chill out the paraffine, press it thoroughly between filter paper, and weigh the residue. The sources of error in this procedure are manifold; the principal one is the solubility of paraffine in oils, which depends upon the character of both the paraffine and the oil, and also upon the temperature. The next greatest source of error is variation in the process of distillation and the difference between working on the small scale and on the large scale.

In most cases, where a paraffine determination is to be carried out, one has to deal with a mixture of paraffine with liquid oils. Now, paraffine is not a substance defined by characteristic physical properties which distinguish it from the liquid portions of petroleum. It consists of a mixture of homologous hydrocarbons, which form a solid under ordinary conditions. The hydrocarbons of this mixture show a gradation in their properties, and gradually approximate to those which are liquid at ordinary temperatures. It is a well known fact that a separation of these homologues is entirely impossible by distillation. It has also been ascertained that the liquid constituents of petroleum do not always possess boiling points that are lower than those of the solid constituents. This shows that we have to deal not merely with hydrocarbons of one, but of several series.

When determinations of the amount of paraffine are to be made, then it becomes necessary to specify with exactness what is to be called paraffine. The most definite property that can be made use of for this purpose is the melting point. For several reasons it is convenient to include under this name hydrocarbons of melting point as low as 35°-40° C.

The method proposed by Zaloziecki for the determination of paraffine is the following: The most volatile portions of the petroleum are separated by distillation, until the thermometer shows 200° C. These portions are separated, as they exert great solvent action upon paraffine. At the same time he finds that no pyro-paraffine is formed under this temperature. A weighed portion of the residue is taken and mixed with ten parts by weight of amyl alcohol and ten parts of seventy-five per cent. ethyl alcohol: the mixture is then chilled for twelve hours to 0° C. It is then filtered cold, washed first with a mixture of amyl and ethyl alcohols, and then with ethyl alcohol alone. The paraffine is transferred to a small porcelain evaporating dish and dried at 110° C. It is then heated with concentrated sulphuric acid to 150°-160° C. for fifteen to thirty minutes with constant stirring. The acid is then neutralized and the paraffine extracted by petroleum ether. On evaporation of the solvent, the paraffine is dried at 100° C. and weighed.

Zaloziecki found, according to this method, in three samples of Galician petroleums, 4.6, 5.8 and 6.5 per cent., respectively, of proto-paraffine. The method was carried out as above with four samples of American petroleums, Colorado oil from Florence, Col.; Warren County oil from Wing Well, Warren, Pa.; Washington oil from Washington County, Pa.; Middle District oil from Butler County, Pa., all furnished by Professor Sadtler.

They were very different in physical properties and in appearance, the Colorado oil being a much heavier oil than the others and the Washington oil being an amber oil, while the other two were of the ordinary dark green color and consistence. The losses on distillation to 200° C. were very different, being about one-tenth in the case of the Colorado oil and nearly one-half in the case of the others. The percentages of partially refined proto-paraffine in the four reduced oils (all below 200° C. off) were as follows: for the Colorado oil, 23.9 per cent.; for the Warren oil, 26.5 per cent.; for the Washington oil, 26.6 per cent.; and for the Middle District oil, 28.2 per cent.

The question now arises, What value has this determination of the proto-paraffine which may exist in an oil? As before said, a portion of the paraffine is always decomposed in distillation at temperatures sufficiently high to drive over the paraffine oils, so the yield of pyro-paraffine is always less than the proto-paraffine shown to be present originally. Zaloziecki found this in the case of the several Galician oils he examined. Corresponding to the 4.6, 5.8 and 6.5 per cent. of proto-paraffine in the several oils he obtained 2.18, 2.65 and 2.35 per cent., respectively, of pyro-paraffine.

For the present, however, the extraction of proto-paraffine on a large scale by means of such solvents as amyl and ethyl alcohols is out of the question on account of their cost. A distillation, under reduced pressure and with superheated steam, would, however, prevent much of the decomposition of the original proto-paraffine and increase the yield of pyro-paraffine.

This study of Zaloziecki's method and the examination of American oils was suggested by Professor Sadtler and carried out in his laboratory.


An abstract of thesis by E.A. Partridge, class of '89, Univ. of Pa. Read before the Chemical Section of the Franklin Institute by Prof. S.P. Sadtler.