Francium

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Francium, 87Fr
General properties
Name, symbol francium, Fr
Pronunciation /frnsim/
fran-see-m
Francium in the periodic table
Hydrogen (diatomic nonmetal)
Helium (noble gas)
Lithium (alkali metal)
Beryllium (alkaline earth metal)
Boron (metalloid)
Carbon (polyatomic nonmetal)
Nitrogen (diatomic nonmetal)
Oxygen (diatomic nonmetal)
Fluorine (diatomic nonmetal)
Neon (noble gas)
Sodium (alkali metal)
Magnesium (alkaline earth metal)
Aluminium (post-transition metal)
Silicon (metalloid)
Phosphorus (polyatomic nonmetal)
Sulfur (polyatomic nonmetal)
Chlorine (diatomic nonmetal)
Argon (noble gas)
Potassium (alkali metal)
Calcium (alkaline earth metal)
Scandium (transition metal)
Titanium (transition metal)
Vanadium (transition metal)
Chromium (transition metal)
Manganese (transition metal)
Iron (transition metal)
Cobalt (transition metal)
Nickel (transition metal)
Copper (transition metal)
Zinc (transition metal)
Gallium (post-transition metal)
Germanium (metalloid)
Arsenic (metalloid)
Selenium (polyatomic nonmetal)
Bromine (diatomic nonmetal)
Krypton (noble gas)
Rubidium (alkali metal)
Strontium (alkaline earth metal)
Yttrium (transition metal)
Zirconium (transition metal)
Niobium (transition metal)
Molybdenum (transition metal)
Technetium (transition metal)
Ruthenium (transition metal)
Rhodium (transition metal)
Palladium (transition metal)
Silver (transition metal)
Cadmium (transition metal)
Indium (post-transition metal)
Tin (post-transition metal)
Antimony (metalloid)
Tellurium (metalloid)
Iodine (diatomic nonmetal)
Xenon (noble gas)
Caesium (alkali metal)
Barium (alkaline earth metal)
Lanthanum (lanthanide)
Cerium (lanthanide)
Praseodymium (lanthanide)
Neodymium (lanthanide)
Promethium (lanthanide)
Samarium (lanthanide)
Europium (lanthanide)
Gadolinium (lanthanide)
Terbium (lanthanide)
Dysprosium (lanthanide)
Holmium (lanthanide)
Erbium (lanthanide)
Thulium (lanthanide)
Ytterbium (lanthanide)
Lutetium (lanthanide)
Hafnium (transition metal)
Tantalum (transition metal)
Tungsten (transition metal)
Rhenium (transition metal)
Osmium (transition metal)
Iridium (transition metal)
Platinum (transition metal)
Gold (transition metal)
Mercury (transition metal)
Thallium (post-transition metal)
Lead (post-transition metal)
Bismuth (post-transition metal)
Polonium (post-transition metal)
Astatine (metalloid)
Radon (noble gas)
Francium (alkali metal)
Radium (alkaline earth metal)
Actinium (actinide)
Thorium (actinide)
Protactinium (actinide)
Uranium (actinide)
Neptunium (actinide)
Plutonium (actinide)
Americium (actinide)
Curium (actinide)
Berkelium (actinide)
Californium (actinide)
Einsteinium (actinide)
Fermium (actinide)
Mendelevium (actinide)
Nobelium (actinide)
Lawrencium (actinide)
Rutherfordium (transition metal)
Dubnium (transition metal)
Seaborgium (transition metal)
Bohrium (transition metal)
Hassium (transition metal)
Meitnerium (unknown chemical properties)
Darmstadtium (unknown chemical properties)
Roentgenium (unknown chemical properties)
Copernicium (transition metal)
Nihonium (unknown chemical properties)
Flerovium (post-transition metal)
Moscovium (unknown chemical properties)
Livermorium (unknown chemical properties)
Tennessine (unknown chemical properties)
Oganesson (unknown chemical properties)
Cs

Fr

(Uue)
radon francium radium
Atomic number (Z) 87
Group, block group 1 (alkali metals), s-block
Period period 7
Element category alkali metal
Standard atomic weight (Ar) (223)
Electron configuration [Rn] 7s1
Electrons per shell
2, 8, 18, 32, 18, 8, 1
Physical properties
Phase solid presumably
Melting point ? 300 K (30 C, 80 F)
Boiling point ? 950 K (680 C, 1300 F)
Density near r.t. 2.83.0 g/cm3 (extrapolated)[1]
Vapor pressure (extrapolated)
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 404 454 519 608 738 946
Atomic properties
Oxidation states +1 (a strongly basic oxide)
Electronegativity Pauling scale: >0.79
Ionization energies 1st: 393[2] kJ/mol
Covalent radius 260 pm (extrapolated)
Van der Waals radius 348 pm (extrapolated)
Miscellanea
Crystal structure body-centered cubic (bcc) Body-centered cubic crystal str
ucture for francium
(extrapolated)
Thermal conductivity 15 W/(mK) (extrapolated)
Electrical resistivity 3 m (calculated)
Magnetic ordering Paramagnetic
CAS Number 7440-73-5
History
Naming after France, homeland of the discoverer
Discovery and first isolation Marguerite Perey (1939)
Most stable isotopes of francium
iso NA half-life DM DE (MeV) DP
221Fr trace 4.8 min 6.457 217At
222Fr syn 14.2 min 2.033 222R
223Fr tr ce 22.00 min 1.149 223R
5.430 219At
view talk edit | references | in Wikidata
Francium is a chemical element with symbol Fr and atomic number 87. It used to b
e known as eka-caesium and actinium K.[note 1] It is the second-least electroneg
ative element, behind only caesium, and is the second rarest naturally occurring
element (after astatine). Francium is a highly radioactive metal that decays in
to astatine, radium, and radon. As an alkali metal, it has one valence electron.
Bulk francium has never been viewed. Because of the general appearance of the ot
her elements in its periodic table column, it is assumed that francium would app
ear as a highly reactive metal, if enough could be collected together to be view
ed as a bulk solid or liquid. Obtaining such a sample is highly improbable, sinc
e the extreme heat of decay (the half-life of its longest-lived isotope is only
22 minutes) would immediately vaporize any viewable quantity of the element.
Francium was discovered by Marguerite Perey in France (from which the element ta
kes its name) in 1939. It was the last element first discovered in nature, rathe
r than by synthesis.[note 2] Outside the laboratory, francium is extremely rare,
with trace amounts found in uranium and thorium ores, where the isotope franciu
m-223 continually forms and decays. As little as 2030 g (one ounce) exists at any
given time throughout the Earth's crust; the other isotopes (except for franciu
m-221) are entirely synthetic. The largest amount produced in the laboratory was
a cluster of more than 300,000 atoms.[3]
Contents [hide]
1 Characteristics
2 Isotopes
3 Applications
4 History
4.1 Erroneous and incomplete discoveries
4.2 Perey's analysis
5 Occurrence
5.1 Natural
5.2 Synthesis
6 See also
7 Footnotes
8 References
9 External links
Characteristics[edit]
Francium is one of the most unstable of the naturally occurring elements: its lo
ngest-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 sy
nthetic astatine-210 is much longer-lived with a half-life of 8.1 hours.[4] All
isotopes of francium decay into astatine, radium, or radon.[4] Francium-223 also
has a shorter half-life than the longest-lived isotope of each synthetic elemen
t up to and including element 105, dubnium.[5]
Francium is an alkali metal whose chemical properties mostly resemble those of c
aesium.[5] A heavy element with a single valence electron,[6] it has the highest
equivalent weight of any element.[5] Liquid franciumif createdshould have a surfa
ce tension of 0.05092 N/m at its melting point.[7] Francium's melting point was
calculated to be around 27 C (80 F, 300 K).[8] The melting point is uncertain beca
use of the element's extreme rarity and radioactivity. Thus, the estimated boili
ng point value of 677 C (1250 F, 950 K) is also uncertain.
Linus Pauling estimated the electronegativity of francium at 0.7 on the Pauling
scale, the same as caesium;[9] the value for caesium has since been refined to 0
.79, but there are no experimental data to allow a refinement of the value for f
rancium.[10] Francium has a slightly higher ionization energy than caesium,[11]
392.811(4) kJ/mol as opposed to 375.7041(2) kJ/mol for caesium, as would be expe
cted from relativistic effects, and this would imply that caesium is the less el
ectronegative of the two. Francium should also have a higher electron affinity t
han caesium and the Fr ion should be more polarizable than the Cs ion.[12] The CsF
r molecule is predicted to have francium at the negative end of the dipole, unli
ke all known heterodiatomic alkali metal molecules. Francium superoxide (FrO2) i
s expected to have a more covalent character than its lighter congeners; this is
attributed to the 6p electrons in francium being more involved in the franciumox
ygen bonding.[12]
Francium coprecipitates with several caesium salts, such as caesium perchlorate,
which results in small amounts of francium perchlorate. This coprecipitation ca
n be used to isolate francium, by adapting the radiocaesium coprecipitation meth
od of Glendenin and Nelson. It will additionally coprecipitate with many other c
aesium salts, including the iodate, the picrate, the tartrate (also rubidium tar
trate), the chloroplatinate, and the silicotungstate. It also coprecipitates wit
h silicotungstic acid, and with perchloric acid, without another alkali metal as
a carrier, which provides other methods of separation.[13][14] Nearly all franc
ium salts are water-soluble.[15]
Isotopes[edit]
Main article: Isotopes of francium
There are 34 known isotopes of francium ranging in atomic mass from 199 to 232.[
16] Francium has seven metastable nuclear isomers.[5] Francium-223 and francium-
221 are the only isotopes that occur in nature, though the former is far more co
mmon.[17]
Francium-223 is the most stable isotope, with a half-life of 21.8 minutes,[5] an
d it is highly unlikely that an isotope of francium with a longer half-life will
ever be discovered or synthesized.[18] Francium-223 is the fifth product of the
actinium decay series as the daughter isotope of actinium-227.[19] Francium-223
then decays into radium-223 by beta decay (1149 keV decay energy), with a minor
(0.006%) alpha decay path to astatine-219 (5.4 MeV decay energy).[20]
Francium-221 has a half-life of 4.8 minutes.[5] It is the ninth product of the n
eptunium decay series as a daughter isotope of actinium-225.[19] Francium-221 th
en decays into astatine-217 by alpha decay (6.457 MeV decay energy).[5]
The least stable ground state isotope is francium-215, with a half-life of 0.12 s
. (9.54 MeV alpha decay to astatine-211):[5] Its metastable isomer, francium-215
m, is less stable still, with a half-life of only 3.5 ns.[21]
Applications[edit]
Due to its instability and rarity, there are no commercial applications for fran
cium.[22][23][24][19] It has been used for research purposes in the fields of ch
emistry[25] and of atomic structure. Its use as a potential diagnostic aid for v
arious cancers has also been explored,[4] but this application has been deemed i
mpractical.[23]
Francium's ability to be synthesized, trapped, and cooled, along with its relati
vely simple atomic structure, has made it the subject of specialized spectroscop
y experiments. These experiments have led to more specific information regarding
energy levels and the coupling constants between subatomic particles.[26] Studi
es on the light emitted by laser-trapped francium-210 ions have provided accurat
e data on transitions between atomic energy levels which are fairly similar to t
hose predicted by quantum theory.[27]
History[edit]
As early as 1870, chemists thought that there should be an alkali metal beyond c
aesium, with an atomic number of 87.[4] It was then referred to by the provision
al name eka-caesium.[28] Research teams attempted to locate and isolate this mis
sing element, and at least four false claims were made that the element had been
found before an authentic discovery was made.
Erroneous and incomplete discoveries[edit]
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 natura
lly occurring potassium radioisotope, potassium-40).[29] He then published a the
sis on his predictions of the properties of eka-caesium, in which he named the e
lement russium after his home country.[30] Shortly thereafter, Dobroserdov began
to focus on his teaching career at the Polytechnic Institute of Odessa, and he
did not pursue the element further.[29]
The following year, English chemists Gerald J. F. Druce and Frederick H. Loring
analyzed X-ray photographs of manganese(II) sulfate.[30] They observed spectral
lines which they presumed to be of eka-caesium. They announced their discovery o
f element 87 and proposed the name alkalinium, as it would be the heaviest alkal
i metal.[29]
In 1930, Fred Allison of the Alabama Polytechnic Institute claimed to have disco
vered element 87 when analyzing pollucite and lepidolite using his magneto-optic
al machine. Allison requested that it be named virginium after his home state of
Virginia, along with the symbols Vi and Vm.[30][31] In 1934, H.G. MacPherson of
UC Berkeley disproved the effectiveness of Allison's device and the validity of
this false discovery.[32]
In 1936, Romanian physicist Horia Hulubei and his French colleague Yvette Caucho
is also analyzed pollucite, this time using their high-resolution X-ray apparatu
s.[29] They observed several weak emission lines, which they presumed to be thos
e of element 87. Hulubei and Cauchois reported their discovery and proposed the
name moldavium, along with the symbol Ml, after Moldavia, the Romanian province
where Hulubei was born.[30] In 1937, Hulubei's work was criticized by American p
hysicist F. H. Hirsh Jr., who rejected Hulubei's research methods. Hirsh was cer
tain that eka-caesium would not be found in nature, and that Hulubei had instead
observed mercury or bismuth X-ray lines. Hulubei insisted that his X-ray appara
tus and methods were too accurate to make such a mistake. Because of this, Jean
Baptiste Perrin, Nobel Prize winner and Hulubei's mentor, endorsed moldavium as
the true eka-caesium over Marguerite Perey's recently discovered francium. Perey
took pains to be accurate and detailed in her criticism of Hulubei's work, and
finally she was credited as the sole discoverer of element 87.[29] All other pre
vious purported discoveries of element 87 were ruled out due to francium's very
limited half-life.[30]
Perey's analysis[edit]
Eka-caesium was discovered in 1939 by Marguerite Perey of the Curie Institute in
Paris, when she purified a sample of actinium-227 which had been reported to ha
ve a decay energy of 220 keV. Perey noticed decay particles with an energy level
below 80 keV. Perey thought this decay activity might have been caused by a pre
viously unidentified decay product, one which was separated during purification,
but emerged again out of the pure actinium-227. Various tests eliminated the po
ssibility of the unknown element being thorium, radium, lead, bismuth, or thalli
um. The new product exhibited chemical properties of an alkali metal (such as co
precipitating with caesium salts), which led Perey to believe that it was elemen
t 87, produced by the alpha decay of actinium-227.[28] Perey then attempted to d
etermine the proportion of beta decay to alpha decay in actinium-227. Her first
test put the alpha branching at 0.6%, a figure which she later revised to 1%.[18
]
Perey named the new isotope actinium-K (it is now referred to as francium-223)[2
8] and in 1946, she proposed the name catium for her newly discovered element, a
s she believed it to be the most electropositive cation of the elements. Irne Jol
iot-Curie, one of Perey's supervisors, opposed the name due to its connotation o
f cat rather than cation.[28] Perey then suggested francium, after France. This
name was officially adopted by the International Union of Pure and Applied Chemi
stry in 1949,[4] becoming the second element after gallium to be named after Fra
nce. It was assigned the symbol Fa, but this abbreviation was revised to the cur
rent Fr shortly thereafter.[33] Francium was the last element discovered in natu
re, rather than synthesized, following rhenium in 1925.[28] Further research int
o francium's structure was carried out by, among others, Sylvain Lieberman and h
is team at CERN in the 1970s and 1980s.[34]
Occurrence[edit]
A shiny gray 5-centimeter piece of matter with a rough surface.
This sample of uraninite contains about 100,000 atoms (3.31020 g) of francium-223
at any given time.[23]
Natural[edit]
223Fr is the result of the alpha decay of 227Ac and can be found in trace amount
s in uranium minerals.[5] In a given sample of uranium, there is estimated to be
only one francium atom for every 1 1018 uranium atoms.[23] It is also calculate
d that there is at most 30 g of francium in the Earth's crust at any given time.
[35]
Synthesis[edit]
A complex experimental setup featuring a horizontal glass tube placed between tw
o copper coils.
Neutral francium atoms can be trapped in the MOT using a magnetic field and lase
r beams.[36]
A round ball of red light surrounded by a green glow
Image of light emitted by a sample of 200,000 francium atoms in a magneto-optica
l trap
A small white spot in the middle surrounded by a red circle. There is a yellow r
ing outside the red circle, a green circle beyond the yellow ring and a blue cir
cle surrounding all the other circles.
Heat image of 300,000 francium atoms in a magneto-optical trap
Francium can be synthesized in the nuclear reaction:
197Au + 18O 210Fr + 5 n
This process, developed by Stony Brook Physics, yields francium isotopes with ma
sses of 209, 210, and 211,[37] which are then isolated by the magneto-optical tr
ap (MOT).[36] The production rate of a particular isotope depends on the energy
of the oxygen beam. An 18O beam from the Stony Brook LINAC creates 210Fr in the
gold target with the nuclear reaction 197Au + 18O 210Fr + 5n. The production req
uired some time to develop and understand. It was critical to operate the gold t
arget very close to its melting point and to make sure that its surface was very
clean. The nuclear reaction embeds the francium atoms deep in the gold target,
and they must be removed efficiently. The atoms quickly diffuse to the surface o
f the gold target and are released as ions, but this does not happen every time.
The francium ions are guided by electrostatic lenses until they land in a surfa
ce of hot yttrium and become neutral again. The francium is then injected into a
glass bulb. A magnetic field and laser beams cool and confine the atoms. Althou
gh the atoms remain in the trap for only about 20 seconds before escaping (or de
caying), a steady stream of fresh atoms replaces those lost, keeping the number
of trapped atoms roughly constant for minutes or longer. Initially, about 1000 f
rancium atoms were trapped in the experiment. This was gradually improved and th
e setup is capable of trapping over 300,000 neutral atoms of francium a time.[3]
These are neutral metallic atoms in a gaseous unconsolidated state. Enough fran
cium is trapped that a video camera can capture the light given off by the atoms
as they fluoresce. The atoms appear as a glowing sphere about 1 millimeter in d
iameter. This was the first time that anyone had ever seen francium. The researc
hers can now make extremely sensitive measurements of the light emitted and abso
rbed by the trapped atoms, providing the first experimental results on various t
ransitions between atomic energy levels in francium. Initial measurements show v
ery good agreement between experimental values and calculations based on quantum
theory. Other synthesis methods include bombarding radium with neutrons, and bo
mbarding thorium with protons, deuterons, or helium ions.[18] Francium has not b
een synthesized in amounts large enough to weigh.[4][8][23]
See also[edit]