The Curies announced the discovery of radium in 1898. Studying the radioactivity of pitchblende, they used chemical separation to find the substances responsible for its extra radioactivity.
Discovering an element and obtaining a pure sample are different stages. Processing large quantities of ore and repeatedly separating materials made early radioactivity research arduous.
The Curies and a new element
Radium was discovered by Marie Skłodowska-Curie and her husband Pierre Curie on 21 December 1898 in a uraninite (pitchblende) sample from Jáchymov. While studying the mineral earlier, the Curies removed uranium from it and found that the remaining material was still radioactive. In July 1898, while studying pitchblende, they isolated an element similar to bismuth which turned out to be polonium. They then isolated a radioactive mixture consisting of two components: compounds of barium, which gave a brilliant green flame color, and unknown radioactive compounds which gave carmine spectral lines that had never been documented before. The Curies found the radioactive compounds to be very similar to the barium compounds, except they were less soluble. This discovery made it possible for the Curies to isolate the radioactive compounds and discover a new element in them.
The Curies announced their discovery to the French Academy of Sciences on 26 December 1898. The naming of radium dates to about 1899, from the French word radium, formed in Modern Latin from radius (ray): this was in recognition of radium's emission of energy in the form of rays. The gaseous emissions of radium, radon, were recognized and studied extensively by Friedrich Ernst Dorn in the early 1900s, though at the time they were characterized as "radium emanations".
In September 1910, Marie Curie and André-Louis Debierne announced that they had isolated radium as a pure metal through the electrolysis of pure radium chloride (RaCl2) solution using a mercury cathode, producing radium–mercury amalgam. This amalgam was then heated in an atmosphere of hydrogen gas to remove the mercury, leaving pure radium metal. Later that same year, E. Ebler isolated radium metal by thermal decomposition of its azide, Ra(N3)2. Radium metal was first industrially produced at the beginning of the 20th century by Biraco, a subsidiary company of Union Minière du Haut Katanga (UMHK) in its Olen plant in Belgium. The metal became an important export of Belgium from 1922 up until World War II.
The general historical unit for radioactivity, the curie, is based on the radioactivity of Ra. It was originally defined as the radioactivity of one gram of radium-226, but the definition was later refined to be 3.7×10 disintegrations per second.
Production
Uranium had no large scale application in the late 19th century and therefore no large uranium mines existed. In the beginning, the silver mines in Jáchymov, Austria-Hungary (now Czech Republic) were the only large sources for uranium ore. The uranium ore was only a byproduct of the mining activities.
In the first extraction of radium, Curie used the residues after extraction of uranium from pitchblende. The uranium had been extracted by dissolution in sulfuric acid leaving radium sulfate, which is similar to barium sulfate but even less soluble in the residues. The residues also contained rather substantial amounts of barium sulfate which thus acted as a carrier for the radium sulfate. The first steps of the radium extraction process involved boiling with sodium hydroxide, followed by hydrochloric acid treatment to minimize impurities of other compounds. The remaining residue was then treated with sodium carbonate to convert the barium sulfate into barium carbonate (carrying the radium), thus making it soluble in hydrochloric acid. After dissolution, the barium and radium were reprecipitated as sulfates; this was then repeated to further purify the mixed sulfate.
Some impurities that form insoluble sulfides were removed by treating the chloride solution with hydrogen sulfide, followed by filtering. When the mixed sulfates were pure enough, they were once more converted to mixed chlorides; barium and radium thereafter were separated by fractional crystallisation while monitoring the progress using a spectroscope (radium gives characteristic red lines in contrast to the green barium lines), and the electroscope.