The Bromide method.
Huntington (Proc. Amer. Acad. 11.28) working under the direction of J. P. Cooke, determined the ratio of cadmium bromide to silver bromide and using the total quantities for the calculation the result for the atomic weight of cadmium is 112.239. He also determined the ratio of cadmium bromide to silver, obtaining 112.245 for the atomic weight of cadmium.
The work which will now be described was carried out very much like the work described under the chloride method. The ratio of cadmium bromide to silverbromide was investigated.
A large quantity of hydrobromic acid was prepared according to the method described by Dr. Edward R. Squibb (Trans. of Med. Soc. of the State of N. Y.). One part of water was added to seven parts of strong sulphuric acid (Sp. Gr. = 1.83) and the mixture cooled. Then six parts of potassium bromide were dissolved in six parts of hot water and the diluted sulphuric acid added to this hot solution. It was set aside untilcold in order to allow the sulphate of potassium to crystallize out. The crystals were drained on a filter-plate and quickly washed with two parts of water. The mother-liquor and washing were then distilled until no more acid was obtained on further heating. The acid thus obtained was distilled three times from potassium bromide, twice from cadmium bromide formed by adding a piece of pure cadmium to it, and twice without the addition of anything. It was tested and found to be free from sulphuric acid. Cadmium bromide was preparedfrom it, in exactly the same way that the cadmium chloride used in the chloride method was prepared from pure metal and hydrochloric acid. While the crystalline mass of cadmium bromide was still moist, it was transferred to a combination tube and dried at 300°C for several hours in a current of nitrogen. It was then sublimed in a vacuum as the chloride had been. This specimen served for the first three determinations. About nine grammes of it was placed in a platinum boat in a combustion tube, and part of it distilledin a current of nitrogen. The distillate, a portion of which had been tested with tropaeolin and found neutral, was used for determination I. The residue in the boat was used for determination II. Another portion of the main sample was resublimed in a vacuum and used in determination no. III. Cadmium bromide is not hygroscopic or at least only slightly, therefore the sublimed cadmium bromide can be transferred to a weighing-glass without taking up water. This cannot be done in the case of the chloride.It is probable that the hydrobromic acid as above prepared was perfectly free from hydrochloric acid. Chlorine in cadmium bromide would cause the atomic weight to be found lower than it really is. It was thought desirable, however, to prepare an acid which would certainly be free from chlorine. The method described by Stas (Aronstein’s German translation, p. 154.) was employed with the additional precaution that the above purified acid was used to start with and all reagents employed had been especially prepared so as to be free from chlorine. Pure silver was preparedaccording to Stas’ description (see Aronstein’s translation, page 34, also page 104) by the action of ammonium sulphite on an ammoniacal solution of silver nitrate and copper sulphate. The silver was dissolved in nitric acid free from chlorine, and then slowly added to a dilute solution of the above-described hydrobromic acid, and the precipitated silver bromide thoroughly washed. It was then digested for a long while in a strong solution of potassium bromide, first in the cold, then by heating. The potassium bromide had been made thus:Twice recrystallized potassium hydrogen tartrate was heated in a platinum dish in a muffle furnace until it was converted into carbonate, and the excess of carbon burned off. It was then dissolved in water, filtered and neutralized with some of the hydrobromic acid already described. The carbonate had been tested for both sulphuric acid and chlorine with negative results. After the silver bromide had been digested with the potassium bromide, it was washed very thoroughly, suspended in water, and a current of hydrogen sulphide passed into it. This converts it into sulphidehydrobromic acid being liberated. The acid was drained off on a porcelain plate, and then distilled a number of times. It was finally tested and found to be perfectly free from sulphates and also did not contain free bromine. Having started with an acid which was probably pure and subjected it to these operations with reagents free from chlorine, there can be no doubt as to the purity of the resulting acid. The hydrogen sulphide used was prepared from potassium hydrosulphide as in the sulphide method, and washed first with a solution of the hydrosulphide, then very thoroughlywith pure water. From the hydrobromic acid obtained, a specimen of cadmium bromide was prepared as before and sublimed twice in a vacuum. This specimen was used for determinations IV and V.
The first three determinations were made exactly like those in the chloride method. The last two were also made in the same manner, only the washing of the precipitate was varied. After the silver bromide had been contracted by warming on a water-bathit was washed by decantation and then agitated violently with cold water to remove occluded nitrates, but it was then so finely divided that it could not be filtered. The artifice used by Stas to contract it a second time was to pass a current of steam into the milky liquid. This was tried here, but for some reason or other did not work very well, and considerable difficulty was had in filtering it. The results of the five determinations are tabulated below. All weighings are reduced to the vacuum standard on the basis of Sp. Gr. of CdBr2= 4.6 and Sp. Gr. AgBr = 6.62.
The first three specimens were prepared under widely different conditions yet the results agree quite closely. The last two were prepared from the repurified hydrobromic acid. If chlorine had been removed during the second purification we should expect a higher resultbut the results are lower. There seems to be hardly any doubt that this is due to analytical errors rather than a change in the composition of the bromide. Whether this be true or not, the five determinations all fall within the limits obtained by the chloride method and confirms it as fully as can be expected.
The errors of the method are the same as those of the bromide method, only they are probably less in most cases. One filtrate was examined for bromium, but none was found showing the method to be more perfect in this respect.