At an advanced stage of the fractionation, when the quantity of material in each fraction is small, the separation by crystallisation is less efficacious, the cooling being too rapid and the volume of the solution to be decanted too small. It is then advisable to add water containing a known quantity of hydrochloric acid; this quantity may be increased as the fractionation proceeds.
The advantage gained thus consists in increasing the quantity of the solution, the solubility of the chlorides being less in water acidified with hydrochloric acid than in pure water. By using water containing much acid, excellent separations are effected, and it is only necessary to work with three or four fractions.
The crystals, which form in very acid solution, are elongated needles, those of barium chloride having exactly the same appearance as those of radium chloride. Both show double refraction. Crystals of barium chloride containing radium are colourless, but when the proportion of radium becomes greater, they have a yellow colouration after some hours, verging on orange, and sometimes a beautiful pink. This colour disappears in solution. Crystals of pure radium chloride are not coloured, so that the colouration appears to be due to the mixture of radium and barium. The maximum colouration is obtained for a certain degree of radium present, and this fact serves to check the progress of the fractionation.
I have sometimes noticed the formation of a deposit composed of crystals of which one part remained uncoloured, whilst the other was coloured, and it seems possible that the colourless crystals might be sorted out.
The fractional precipitation of an aqueous solution of barium chloride by alcohol also leads to the isolation of radium chloride, which is the first to precipitate. This method, which I first employed, was finally abandoned for the one just described, which proceeds with more regularity. I have, however, occasionally made use of precipitation by alcohol to purify radium chloride which contains traces of barium chloride. The latter remains in the slightly aqueous alcoholic solution, and can thus be removed.
M. Giesel, who, since the publication of our first researches, has been preparing radio-active bodies, recommends the separation of barium and radium by fractional crystallisation in water from a mixture of the bromides. I can testify that this method is advantageous, especially in the first stages of the fractionation.
Determination of the Atomic Weight of Radium.
In the course of my work I determined at intervals the atomic weight of the metal contained in specimens of barium chloride containing radium. With each newly obtained product I carried the concentration as far as possible, so as to have from 0·1 grm. to 0·5 grm. of material containing most of the activity of the mixture. From this small quantity I precipitated with alcohol or with hydrochloric acid some milligrams of chloride for spectral analysis. Thanks to his excellent method, Demarçay only required this small quantity of material to obtain the photograph of the spark spectrum. I made an atomic weight determination with the product remaining.
I employed the classic method of weighing as silver chloride the chlorine contained in a known weight of the anhydrous chloride. As control experiment, I determined the atomic weight of barium by the same method, under the same conditions, and with the same quantity of material, first 0·5 grm. and then 0·1 grm. The figures obtained were always between 137 and 138. I thus saw that the method gives satisfactory results, even with a very small quantity of material.
The first two determinations were made with chlorides, of which one was 230 times and the other 600 times as active as uranium. These two experiments gave the same figure as the experiment with the pure barium chloride. There was therefore no hope of finding a difference except by using a much more active product. The following experiment was made with a chloride, the activity of which was about 3500 times as great as that of uranium; and this experiment enabled me, for the first time, to observe a small but distinct difference; I found, as the mean atomic weight of the metal contained in this chloride, the number 140, which showed that the atomic weight of radium must be higher than that of barium. By using more and more active products, and obtaining spectra of radium of increasing intensity, I found that the figures obtained rose in proportion, as is seen in the following table (p. [28]).