The 14th International Conference on
Miniaturized Systems for Chemistry and Life Sciences
Bulk francium has never been viewed. Because of the general appearance of the other elements in its periodic table column, it is assumed that francium would appear as a highly reactive metal, if enough could be collected together to be viewed as a bulk solid or liquid. Obtaining such a sample is highly improbable, since the extreme heat of decay caused by its short half-life would immediately vaporize any viewable quantity of the element.
Francium was discovered by Marguerite Perey in France (from which the element takes its name) in 1939. It was the last element first discovered in nature, rather than by synthesis. Outside the laboratory, francium is extremely rare, with trace amounts found in uranium and thorium ores, where the isotope francium-223 continually forms and decays. As little as 20–30 g (one ounce) exists at any given time throughout the Earth's crust; the other isotopes (except for francium-221) are entirely synthetic. The largest amount produced in the laboratory was a cluster of more than 300,000 atoms.
Francium is one of the most unstable of the naturally occurring elements: its longest-lived isotope, francium-223, has a half-life of only 22 minutes. The only comparable element is astatine, whose most stable natural isotope, astatine-219 (the alpha daughter of francium-223), has a half-life of 56 seconds, although synthetic astatine-210 is much longer-lived with a half-life of 8.1 hours. All isotopes of francium decay into astatine, radium, or radon. Francium-223 also has a shorter half-life than the longest-lived isotope of each synthetic element up to and including element 105, dubnium.
Francium coprecipitates with several caesium salts, such as caesium perchlorate, which results in small amounts of francium perchlorate. This coprecipitation can be used to isolate francium, by adapting the radiocaesium coprecipitation method of Lawrence E. Glendenin and Nelson. It will additionally coprecipitate with many other caesium salts, including the iodate, the picrate, the tartrate (also rubidium tartrate), the chloroplatinate, and the silicotungstate. It also coprecipitates with silicotungstic acid, and with perchloric acid, without another alkali metal as a carrier, which provides other methods of separation. Nearly all francium salts are water-soluble.
There are 34 known isotopes of francium ranging in atomic mass from 199 to 232. Francium has seven metastable nuclear isomers. Francium-223 and francium-221 are the only isotopes that occur in nature, though the former is far more common.
Francium-223 is the most stable isotope, with a half-life of 21.8 minutes, and it is highly unlikely that an isotope of francium with a longer half-life will ever be discovered or synthesized. Francium-223 is the fifth product of the actinium decay series as the daughter isotope of actinium-227. Francium-223 then decays into radium-223 by beta decay (1.149 MeV decay energy), with a minor (0.006%) alpha decay path to astatine-219 (5.4 MeV decay energy).
Francium-221 has a half-life of 4.8 minutes. It is the ninth product of the neptunium decay series as a daughter isotope of actinium-225. Francium-221 then decays into astatine-217 by alpha decay (6.457 MeV decay energy).
Francium's ability to be synthesized, trapped, and cooled, along with its relatively simple atomic structure, has made it the subject of specialized spectroscopy experiments. These experiments have led to more specific information regarding energy levels and the coupling constants between subatomic particles. Studies on the light emitted by laser-trapped francium-210 ions have provided accurate data on transitions between atomic energy levels which are fairly similar to those predicted by quantum theory.
As early as 1870, chemists thought that there should be an alkali metal beyond caesium, with an atomic number of 87. It was then referred to by the provisional name eka-caesium. Research teams attempted to locate and isolate this missing element, and at least four false claims were made that the element had been found before an authentic discovery was made.
Soviet chemist D. K. Dobroserdov was the first scientist to claim to have found eka-caesium, or francium. In 1925, he observed weak radioactivity in a sample of potassium, another alkali metal, and incorrectly concluded that eka-caesium was contaminating the sample (the radioactivity from the sample was from the naturally occurring potassium radioisotope, potassium-40). He then published a thesis on his predictions of the properties of eka-caesium, in which he named the element russium after his home country. Shortly thereafter, Dobroserdov began to focus on his teaching career at the Polytechnic Institute of Odessa, and he did not pursue the element further.
In 1930, Fred Allison of the Alabama Polytechnic Institute claimed to have discovered element 87 when analyzing pollucite and lepidolite using his magneto-optical machine. Allison requested that it be named virginium after his home state of Virginia, along with the symbols Vi and Vm. In 1934, H.G. MacPherson of UC Berkeley disproved the effectiveness of Allison's device and the validity of his discovery.