Actinium

Actinium is a chemical element with the symbol Ac and

atomic number 89. It was first isolated by French chemist Actinium, 89Ac
André-Louis Debierne in 1899. Friedrich Oskar Giesel later
independently isolated it in 1902 and, unaware that it was
already known, gave it the name emanium.[3] Actinium
gave the name to the actinide series, a group of 15 similar
elements between actinium and lawrencium in the periodic
table. It is also sometimes considered the first of the 7th-
period transition metals, although lawrencium is less
commonly given that position. Together with polonium,
radium, and radon, actinium was one of the first non-
primordial radioactive elements to be isolated.

A soft, silvery-white radioactive metal, actinium reacts

rapidly with oxygen and moisture in air forming a white
coating of actinium oxide that prevents further oxidation.
As with most lanthanides and many actinides, actinium
assumes oxidation state +3 in nearly all its chemical Actinium
compounds. Actinium is found only in traces in uranium Pronunciation /ækˈtɪniəm/
and thorium ores as the isotope 227Ac, which decays with a (ak-TIN-ee-əm)
half-life of 21.772 years, predominantly emitting beta and
sometimes alpha particles, and 228Ac, which is beta active Appearance silvery-white, glowing with
with a half-life of 6.15 hours. One tonne of natural uranium an eerie blue light;[1]
in ore contains about 0.2 milligrams of actinium-227, and sometimes with a golden
one tonne of thorium contains about 5 nanograms of cast[2]
actinium-228. The close similarity of physical and chemical Mass number [227]
properties of actinium and lanthanum makes separation of
actinium from the ore impractical. Instead, the element is Actinium in the periodic table
prepared, in milligram amounts, by the neutron irradiation
La
of 226Ra in a nuclear reactor. Owing to its scarcity, high ↑
price and radioactivity, actinium has no significant Ac
↓
industrial use. Its current applications include a neutron (Ubu)
source and an agent for radiation therapy. radium ← actinium → thorium

Atomic number (Z) 89

Group group 3
Contents Period period 7
History Block d-block
Properties Element category Actinide, sometimes
Chemical compounds considered a transition
Oxides metal
Halides Electron [Rn] 6d1 7s2
Other compounds configuration
Isotopes Electrons per 2, 8, 18, 32, 18, 9, 2
Occurrence and synthesis shell
Applications Physical properties
Precautions Phase at STP solid
See also Melting point 1500 K (1227 °C, 2240 °F)
References (estimated)[2]

Bibliography Boiling point 3500±300 K

(3200±300 °C,
External links
5800±500 °F)
(extrapolated)[2]

History Density (near r.t.) 10 g/cm3

Heat of fusion 14 kJ/mol
André-Louis Debierne, a French chemist, announced the Heat of 400 kJ/mol
discovery of a new element in 1899. He separated it from
vaporization
pitchblende residues left by Marie and Pierre Curie after
they had extracted radium. In 1899, Debierne described the Molar heat 27.2 J/(mol·K)
substance as similar to titanium[4] and (in 1900) as similar capacity
to thorium.[5] Friedrich Oskar Giesel independently Atomic properties
discovered actinium in 1902[6] as a substance being similar
Oxidation states +3 (a strongly basic oxide)
to lanthanum and called it "emanium" in 1904.[7] After a
comparison of the substances half-lives determined by Electronegativity Pauling scale: 1.1
Debierne,[8] Harriet Brooks in 1904, and Otto Hahn and Ionization 1st: 499 kJ/mol
Otto Sackur in 1905, Debierne's chosen name for the new energies
element was retained because it had seniority, despite the 2nd: 1170 kJ/mol
contradicting chemical properties he claimed for the 3rd: 1900 kJ/mol
element at different times.[9][10] (more)

Articles published in the 1970s[11] and later[12] suggest that Covalent radius 215 pm
Debierne's results published in 1904 conflict with those
reported in 1899 and 1900. Furthermore, the now-known
chemistry of actinium precludes its presence as anything Spectral lines of actinium
other than a minor constituent of Debierne's 1899 and 1900
results; in fact, the chemical properties he reported make it Other properties
likely that he had, instead, accidentally identified Natural from decay
protactinium, which would not be discovered for another occurrence
fourteen years, only to have it disappear due to its
Crystal structure face-centered cubic (fcc)
hydrolysis and adsorption onto his laboratory equipment.
This has led some authors to advocate that Giesel alone
should be credited with the discovery.[2] A less
confrontational vision of scientific discovery is proposed
by Adloff.[12] He suggests that hindsight criticism of the Thermal 12 W/(m·K)
early publications should be mitigated by the then nascent conductivity
state of radiochemistry: highlighting the prudence of CAS Number 7440-34-8
Debierne's claims in the original papers, he notes that
nobody can contend that Debierne's substance did not History
contain actinium.[12] Debierne, who is now considered by Discovery and Friedrich Oskar Giesel
the vast majority of historians as the discoverer, lost first isolation (1902)
interest in the element and left the topic. Giesel, on the
Named by André-Louis Debierne
other hand, can rightfully be credited with the first
preparation of radiochemically pure actinium and with the (1899)
identification of its atomic number 89.[11] Main isotopes of actinium

Iso‐ Abun‐ Half-life Decay Pro‐

The name actinium originates from the Ancient Greek tope dance (t1/2) mode duct
aktis, aktinos (ακτίς, ακτίνος), meaning beam or ray.[13] Its 225Ac 221Fr
trace 10 d α
symbol Ac is also used in abbreviations of other
compounds that have nothing to do with actinium, such as β− 226Th
acetyl, acetate[14] and sometimes acetaldehyde.[15]
226Ac syn 29.37 h ε 226Ra

Properties α 222Fr

β − Th 227
Actinium is a soft, silvery-white,[16][17] radioactive, 227Ac trace 21.772 y
metallic element. Its estimated shear modulus is similar to α 223Fr
that of lead. [18] Owing to its strong radioactivity, actinium
glows in the dark with a pale blue light, which originates
from the surrounding air ionized by the emitted energetic particles.[19] Actinium has similar chemical
properties to lanthanum and other lanthanides, and therefore these elements are difficult to separate when
extracting from uranium ores. Solvent extraction and ion chromatography are commonly used for the
separation.[20]

The first element of the actinides, actinium gave the group its name, much as lanthanum had done for the
lanthanides. The group of elements is more diverse than the lanthanides and therefore it was not until 1945 that
the most significant change to Dmitri Mendeleev's periodic table since the recognition of the lanthanides, the
introduction of the actinides, was generally accepted after Glenn T. Seaborg's research on the transuranium
elements (although it had been proposed as early as 1892 by British chemist Henry Bassett).[21]

Actinium reacts rapidly with oxygen and moisture in air forming a white coating of actinium oxide that
impedes further oxidation.[16] As with most lanthanides and actinides, actinium exists in the oxidation state +3,
and the Ac3+ ions are colorless in solutions.[22] The oxidation state +3 originates from the [Rn]6d17s2
electronic configuration of actinium, with three valence electrons that are easily donated to give the stable
closed-shell structure of the noble gas radon.[17] The rare oxidation state +2 is only known for actinium
dihydride (AcH2); even this may in reality be an electride compound like its lighter congener LaH2 and thus
have actinium(III).[23] Ac3+ is the largest of all known tripositive ions and its first coordination sphere contains
approximately 10.9 ± 0.5 water molecules.[24]

Chemical compounds
Due to actinium's intense radioactivity, only a limited number of actinium compounds are known. These
include: AcF3, AcCl3, AcBr3, AcOF, AcOCl, AcOBr, Ac2S3, Ac2O3 and AcPO4. Except for AcPO4, they are
all similar to the corresponding lanthanum compounds. They all contain actinium in the oxidation state
+3.[22][25] In particular, the lattice constants of the analogous lanthanum and actinium compounds differ by
only a few percent.[25]
 space Pearson density,
Formula color symmetry No a (pm) b (pm) c (pm) Z
group symbol g/cm3

Ac silvery fcc[23] Fm3m 225 cF4 531.1 531.1 531.1 4 10.07

AcH2 unknown cubic[23] Fm3m 225 cF12 567 567 567 4 8.35

Ac2O3 white[16] trigonal[26] P3m1 164 hP5 408 408 630 1 9.18

Ac2S3 black cubic[27] I43d 220 cI28 778.56 778.56 778.56 4 6.71

AcF3 white[28] hexagonal[25][26] P3c1 165 hP24 741 741 755 6 7.88

AcCl3 white hexagonal[25][29] P63/m 165 hP8 764 764 456 2 4.8

AcBr3 white[25] hexagonal[29] P63/m 165 hP8 764 764 456 2 5.85

AcOF white[30] cubic[25] Fm3m 593.1 8.28

AcOCl white tetragonal[25] 424 424 707 7.23

AcOBr white tetragonal[25] 427 427 740 7.89

AcPO4·0.5H2O unknown hexagonal[25] 721 721 664 5.48

Here a, b and c are lattice constants, No is space group number and Z is the number of formula units per unit
cell. Density was not measured directly but calculated from the lattice parameters.

Oxides

Actinium oxide (Ac2O3) can be obtained by heating the hydroxide at 500 °C or the oxalate at 1100 °C, in
vacuum. Its crystal lattice is isotypic with the oxides of most trivalent rare-earth metals.[25]

Halides

Actinium trifluoride can be produced either in solution or in solid reaction. The former reaction is carried out at
room temperature, by adding hydrofluoric acid to a solution containing actinium ions. In the latter method,
actinium metal is treated with hydrogen fluoride vapors at 700 °C in an all-platinum setup. Treating actinium
trifluoride with ammonium hydroxide at 900–1000 °C yields oxyfluoride AcOF. Whereas lanthanum
oxyfluoride can be easily obtained by burning lanthanum trifluoride in air at 800 °C for an hour, similar
treatment of actinium trifluoride yields no AcOF and only results in melting of the initial product.[25][30]

AcF3 + 2 NH3 + H2O → AcOF + 2 NH4F

Actinium trichloride is obtained by reacting actinium hydroxide or oxalate with carbon tetrachloride vapors at
temperatures above 960 °C. Similar to oxyfluoride, actinium oxychloride can be prepared by hydrolyzing
actinium trichloride with ammonium hydroxide at 1000 °C. However, in contrast to the oxyfluoride, the
oxychloride could well be synthesized by igniting a solution of actinium trichloride in hydrochloric acid with
ammonia.[25]

Reaction of aluminium bromide and actinium oxide yields actinium tribromide:

Ac2O3 + 2 AlBr3 → 2 AcBr3 + Al2O3

and treating it with ammonium hydroxide at 500 °C results in the oxybromide AcOBr.[25]

Other compounds
Actinium hydride was obtained by reduction of actinium trichloride with potassium at 300 °C, and its structure
was deduced by analogy with the corresponding LaH2 hydride. The source of hydrogen in the reaction was
uncertain.[31]

Mixing monosodium phosphate (NaH2PO4) with a solution of actinium in hydrochloric acid yields white-
colored actinium phosphate hemihydrate (AcPO4·0.5H2O), and heating actinium oxalate with hydrogen sulfide
vapors at 1400 °C for a few minutes results in a black actinium sulfide Ac2S3. It may possibly be produced by
acting with a mixture of hydrogen sulfide and carbon disulfide on actinium oxide at 1000 °C.[25]

Isotopes
Naturally occurring actinium is composed of two radioactive isotopes; 227Ac (from the radioactive family of
235
U) and 228Ac (a granddaughter of 232Th). 227Ac decays mainly as a beta emitter with a very small energy,
but in 1.38% of cases it emits an alpha particle, so it can readily be identified through alpha spectrometry.[2]
Thirty-six radioisotopes have been identified, the most stable being 227Ac with a half-life of 21.772 years,
225Ac with a half-life of 10.0 days and 226Ac with a half-life of 29.37 hours. All remaining radioactive isotopes
have half-lives that are less than 10 hours and the majority of them have half-lives shorter than one minute.
The shortest-lived known isotope of actinium is 217Ac (half-life of 69 nanoseconds) which decays through
alpha decay. Actinium also has two known meta states.[32] The most significant isotopes for chemistry are
225Ac, 227Ac, and 228Ac.[2]

Purified 227Ac comes into equilibrium with its decay products after about a half of year. It decays according to
its 21.772-year half-life emitting mostly beta (98.62%) and some alpha particles (1.38%);[32] the successive
decay products are part of the actinium series. Owing to the low available amounts, low energy of its beta
particles (maximum 44.8 keV) and low intensity of alpha radiation, 227Ac is difficult to detect directly by its
emission and it is therefore traced via its decay products.[22] The isotopes of actinium range in atomic weight
from 205 u (205Ac) to 236 u (236Ac).[32]

Isotope Production Decay Half-life

221Ac 232Th(d,9n)→225Pa(α)→221Ac α 52 ms
222Ac 232Th(d,8n)→226Pa(α)→222Ac α 5.0 s
223Ac 232Th(d,7n)→227Pa(α)→223Ac α 2.1 min
224Ac 232Th(d,6n)→228Pa(α)→224Ac α 2.78 hours
225Ac 232Th(n,γ)→233Th(β−)→233Pa(β−)→233U(α)→229Th(α)→225Ra(β−)→225Ac α 10 days

α, β−
226Ac 226Ra(d,2n)→226Ac electron 29.37 hours
capture
227Ac 235U(α)→231Th(β−)→231Pa(α)→227Ac α, β− 21.77 years
228Ac 232Th(α)→228Ra(β−)→228Ac β− 6.15 hours
229Ac 228Ra(n,γ)→229Ra(β−)→229Ac β− 62.7 min
230Ac 232Th(d,α)→230Ac β− 122 s
231Ac 232Th(γ,p)→231Ac β− 7.5 min
232Ac 232Th(n,p)→232Ac β− 119 s

Occurrence and synthesis

Actinium is found only in traces in uranium ores – one tonne of uranium in ore
contains about 0.2 milligrams of 227Ac[33][34] – and in thorium ores, which
contain about 5 nanograms of 228Ac per one tonne of thorium. The actinium
isotope 227Ac is a transient member of the uranium-actinium series decay chain,
which begins with the parent isotope 235U (or 239Pu) and ends with the stable lead
isotope 207Pb. The isotope 228Ac is a transient member of the thorium series
decay chain, which begins with the parent isotope 232Th and ends with the stable
lead isotope 208Pb. Another actinium isotope (225Ac) is transiently present in the
neptunium series decay chain, beginning with 237Np (or 233U) and ending with
thallium (205Tl) and near-stable bismuth (209Bi); even though all primordial 237Np
has decayed away, it is continuously produced by neutron knock-out reactions on
natural 238U.

The low natural concentration, and the close similarity of physical and chemical Uraninite ores have
properties to those of lanthanum and other lanthanides, which are always abundant elevated concentrations
in actinium-bearing ores, render separation of actinium from the ore impractical, of actinium.
and complete separation was never achieved.[25] Instead, actinium is prepared, in
milligram amounts, by the neutron irradiation of 226Ra in a nuclear reactor.[34][35]

The reaction yield is about 2% of the radium weight. 227Ac can further capture neutrons resulting in small
amounts of 228Ac. After the synthesis, actinium is separated from radium and from the products of decay and
nuclear fusion, such as thorium, polonium, lead and bismuth. The extraction can be performed with
thenoyltrifluoroacetone-benzene solution from an aqueous solution of the radiation products, and the
selectivity to a certain element is achieved by adjusting the pH (to about 6.0 for actinium).[33] An alternative
procedure is anion exchange with an appropriate resin in nitric acid, which can result in a separation factor of
1,000,000 for radium and actinium vs. thorium in a two-stage process. Actinium can then be separated from
radium, with a ratio of about 100, using a low cross-linking cation exchange resin and nitric acid as eluant.[36]
225Ac was first produced artificially at the Institute for Transuranium Elements (ITU) in Germany using a
cyclotron and at St George Hospital in Sydney using a linac in 2000.[37] This rare isotope has potential
applications in radiation therapy and is most efficiently produced by bombarding a radium-226 target with 20–
30 MeV deuterium ions. This reaction also yields 226Ac which however decays with a half-life of 29 hours and
thus does not contaminate 225Ac.[38]

Actinium metal has been prepared by the reduction of actinium fluoride with lithium vapor in vacuum at a
temperature between 1100 and 1300 °C. Higher temperatures resulted in evaporation of the product and lower
ones lead to an incomplete transformation. Lithium was chosen among other alkali metals because its fluoride
is most volatile.[13][16]

Applications
Owing to its scarcity, high price and radioactivity, 227Ac currently has no significant industrial use, but 225Ac
is currently being studied for use in cancer treatments such as targeted alpha therapies.[13][39] 227Ac is highly
radioactive and was therefore studied for use as an active element of radioisotope thermoelectric generators,
for example in spacecraft. The oxide of 227Ac pressed with beryllium is also an efficient neutron source with
the activity exceeding that of the standard americium-beryllium and radium-beryllium pairs.[40] In all those
applications, 227Ac (a beta source) is merely a progenitor which generates alpha-emitting isotopes upon its
decay. Beryllium captures alpha particles and emits neutrons owing to its large cross-section for the (α,n)
nuclear reaction:
The 227AcBe neutron sources can be applied in a neutron probe – a standard device for measuring the quantity
of water present in soil, as well as moisture/density for quality control in highway construction.[41][42] Such
probes are also used in well logging applications, in neutron radiography, tomography and other radiochemical
investigations.[43]
225Ac is applied in medicine to produce 213Bi in a reusable generator[36] or can be
used alone as an agent for radiation therapy, in particular targeted alpha therapy
(TAT). This isotope has a half-life of 10 days, making it much more suitable for
radiation therapy than 213Bi (half-life 46 minutes).[39] Additionally, 225Ac decays
to nontoxic 209Bi rather than stable but toxic lead, which is the final product in the Chemical structure of the
decay chains of several other candidate isotopes, namely 227 Th, 228 Th, and DOTA carrier for 225Ac in
230U.[39] Not only 225Ac itself, but also its daughters, emit alpha particles which radiation therapy.
kill cancer cells in the body. The major difficulty with application of 225Ac was
that intravenous injection of simple actinium complexes resulted in their
accumulation in the bones and liver for a period of tens of years. As a result, after the cancer cells were quickly
killed by alpha particles from 225Ac, the radiation from the actinium and its daughters might induce new
mutations. To solve this problem, 225Ac was bound to a chelating agent, such as citrate,
ethylenediaminetetraacetic acid (EDTA) or diethylene triamine pentaacetic acid (DTPA). This reduced
actinium accumulation in the bones, but the excretion from the body remained slow. Much better results were
obtained with such chelating agents as HEHA
(1,4,7,10,13,16-hexaazacyclohexadecane-N,N′,N″,N‴,N‴′,N‴″-hexaacetic acid) [44] or DOTA
(1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) coupled to trastuzumab, a monoclonal antibody that
interferes with the HER2/neu receptor. The latter delivery combination was tested on mice and proved to be
effective against leukemia, lymphoma, breast, ovarian, neuroblastoma and prostate cancers.[45][46][47]

The medium half-life of 227Ac (21.77 years) makes it very convenient radioactive isotope in modeling the slow
vertical mixing of oceanic waters. The associated processes cannot be studied with the required accuracy by
direct measurements of current velocities (of the order 50 meters per year). However, evaluation of the
concentration depth-profiles for different isotopes allows estimating the mixing rates. The physics behind this
method is as follows: oceanic waters contain homogeneously dispersed 235U. Its decay product, 231Pa,
gradually precipitates to the bottom, so that its concentration first increases with depth and then stays nearly
constant. 231Pa decays to 227Ac; however, the concentration of the latter isotope does not follow the 231Pa
depth profile, but instead increases toward the sea bottom. This occurs because of the mixing processes which
raise some additional 227Ac from the sea bottom. Thus analysis of both 231Pa and 227Ac depth profiles allows
researchers to model the mixing behavior.[48][49]

There are theoretical predictions that AcHx hydrides (in this case with very high pressure) are a candidate for a
near room-temperature superconductor as they have Tc significantly higher than H3S, possibly near 250 K.[50]

Precautions
227Ac is highly radioactive and experiments with it are carried out in a specially designed laboratory equipped
with a tight glove box. When actinium trichloride is administered intravenously to rats, about 33% of actinium
is deposited into the bones and 50% into the liver. Its toxicity is comparable to, but slightly lower than that of
americium and plutonium.[51] For trace quantities, fume hoods with good aeration suffice; for gram amounts,
hot cells with shielding from the intense gamma radiation emitted by 227Ac are necessary.[52]

See also
 Actinium series

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Bibliography
Meyer, Gerd and Morss, Lester R. (1991) Synthesis of lanthanide and actinide compounds (http
s://books.google.com/books?id=bnS5elHL2w8C&pg=PA87), Springer. ISBN 0-7923-1018-7

External links
Actinium (http://www.periodicvideos.com/videos/089.htm) at The Periodic Table of Videos
(University of Nottingham)
NLM Hazardous Substances Databank – Actinium, Radioactive (http://toxnet.nlm.nih.gov/cgi-bin/
sis/search/r?dbs+hsdb:@term+@na+@rel+actinium,+radioactive)
Actinium (https://web.archive.org/web/20110825123745/http://radchem.nevada.edu/classes/rdch
710/files/actinium.pdf) in Kirby, H. W.; Morss, L. R. (2006). Morss; Edelstein, Norman M.; Fuger,
Jean (eds.). The Chemistry of the Actinide and Transactinide Elements (3rd ed.). Dordrecht, The
Netherlands: Springer. ISBN 978-1-4020-3555-5.

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