Actinium

Template:Distinguish Template:Use dmy dates Template:Infobox actinium Actinium is a chemical element; it has symbol Ac and atomic number 89. It was discovered by Friedrich Oskar Giesel in 1902, who gave it the name emanium; the element got its name by being wrongly identified with a substance André-Louis Debierne found in 1899 and called actinium. The actinide series, a set of 15 elements between actinium and lawrencium in the periodic table, are named for actinium. Together with polonium, radium, and radon, actinium was one of the first non-primordial radioactive elements to be discovered.

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 compounds. Actinium is found only in traces in uranium and thorium ores as the isotope ²²⁷Ac, which decays with a half-life of 21.772 years, predominantly emitting beta and sometimes alpha particles, and ²²⁸Ac, which is beta active with a half-life of 6.15 hours. One tonne of natural uranium in ore contains about 0.2 milligrams of actinium-227, and one tonne of thorium contains about 5 nanograms of actinium-228. The close similarity of physical and chemical properties of actinium and lanthanum makes separation of actinium from the ore impractical. Instead, the element is prepared, in milligram amounts, by the neutron irradiation of Template:Chem2 in a nuclear reactor. Owing to its scarcity, high price and radioactivity, actinium has no significant industrial use. Its current applications include a neutron source and an agent for radiation therapy.

History

André-Louis Debierne, a French chemist, announced the discovery of a new element in 1899. He separated it from pitchblende residues left by Marie and Pierre Curie after they had extracted radium.<ref name="Adloff"/> In 1899, Debierne described the substance as similar to titanium<ref>Template:Cite journal</ref> and (in 1900) as similar to thorium.<ref>Template:Cite journal</ref> Friedrich Oskar Giesel found in 1902<ref>Template:Cite journal</ref> a substance similar to lanthanum and called it "emanium" in 1904.<ref>Template:Cite journal</ref> After a comparison of the substances' half-lives determined by Debierne,<ref>Template:Cite journal</ref> Harriet Brooks in 1904, and Otto Hahn and Otto Sackur in 1905, Debierne's chosen name for the new element was retained because it had seniority, despite the contradicting chemical properties he claimed for the element at different times.<ref>Template:Cite journal</ref><ref>Template:Cite journal</ref>

Articles published in the 1970s<ref name="discovery">Template:Cite journal</ref> and later<ref name="Adloff">Template:Cite journal</ref> suggest that 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 other than a minor constituent of Debierne's 1899 and 1900 results; in fact, the chemical properties he reported make it likely that he had, instead, accidentally identified protactinium, which would not be discovered for another fourteen years, only to have it disappear due to its hydrolysis and adsorption onto his laboratory equipment. This has led some authors to advocate that Giesel alone should be credited with the discovery.<ref name="Kirby" /> A less confrontational vision of scientific discovery is proposed by Adloff.<ref name="Adloff" /> He suggests that hindsight criticism of the early publications should be mitigated by the then nascent state of radiochemistry: highlighting the prudence of Debierne's claims in the original papers, he notes that nobody can contend that Debierne's substance did not contain actinium.<ref name="Adloff" /> Debierne, who is now considered by the vast majority of historians as the discoverer, lost interest in the element and left the topic. Giesel, on the other hand, can rightfully be credited with the first preparation of radiochemically pure actinium and with the identification of its atomic number 89.<ref name="discovery" />

The name actinium originates from the Ancient Greek aktis, aktinos (ακτίς, ακτίνος), meaning beam or ray.<ref name="CRC" /> Its symbol Ac is also used in abbreviations of other compounds that have nothing to do with actinium, such as acetyl, acetate<ref>Template:Cite book</ref> and sometimes acetaldehyde.<ref>Template:Cite book</ref>

Properties

Actinium is a soft, silvery-white,<ref name="blueglow" /><ref name="brit">Actinium, in Encyclopædia Britannica, 15th edition, 1995, p. 70</ref> radioactive, metallic element. Its estimated shear modulus is similar to that of lead.<ref>Seitz, Frederick and Turnbull, David (1964) Solid state physics: advances in research and applications. Academic Press. Template:ISBN pp. 289–291</ref> 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.<ref>Template:Cite book</ref> 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.<ref>Template:Cite journal</ref>

The first element of the actinides, actinium gave the set its name, much as lanthanum had done for the lanthanides. The actinides are much more diverse than the lanthanides<ref name="Jorgensen">Template:Cite journal</ref> 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<ref>Template:Cite journal</ref> (although it had been proposed as early as 1892 by British chemist Henry Bassett).<ref name="Thyssen">Template:Cite book</ref>

Actinium reacts rapidly with oxygen and moisture in air forming a white coating of actinium oxide that impedes further oxidation.<ref name="blueglow">Template:Cite journal</ref> As with most lanthanides and actinides, actinium exists in the oxidation state +3, and the Ac³⁺ ions are colorless in solutions.<ref name="bse" /> 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.<ref name="brit" /> Although the 5f orbitals are unoccupied in an actinium atom, it can be used as a valence orbital in actinium complexes and hence it is generally considered the first 5f element by authors working on it.<ref>Template:Cite journal</ref><ref>Template:Cite journal</ref><ref name="AcNatureChem"/> Ac³⁺ is the largest of all known tripositive ions and its first coordination sphere contains approximately 10.9 ± 0.5 water molecules.<ref>Template:Cite journal</ref>

Chemical compounds

Template:Main 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, AcPO₄ and Ac(NO₃)₃. They all contain actinium in the oxidation state +3.<ref name="bse" /><ref name="j2" /> In particular, the lattice constants of the analogous lanthanum and actinium compounds differ by only a few percent.<ref name="j2" />

Formula	color	symmetry	space group	No	Pearson symbol	a (pm)	b (pm)	c (pm)	Z	density, g/cm3
Ac	silvery	fcc<ref name="ach">Template:Cite journal</ref>	FmTemplate:Overlinem	225	cF4	531.1	531.1	531.1	4	10.07
AcH2	unknown	cubic<ref name="ach" />	FmTemplate:Overlinem	225	cF12	567	567	567	4	8.35
Ac2O3	white<ref name="blueglow" />	trigonal<ref name="aco">Template:Cite journal</ref>	PTemplate:Overlinem1	164	hP5	408	408	630	1	9.18
Ac2S3	black	cubic<ref name="acs">Template:Cite journal</ref>	ITemplate:Overline3d	220	cI28	778.56	778.56	778.56	4	6.71
AcF3	white<ref name="m71">Meyer, p. 71</ref>	hexagonal<ref name="j2" /><ref name="aco" />	PTemplate:Overlinec1	165	hP24	741	741	755	6	7.88
AcCl3	white	hexagonal<ref name="j2" /><ref name="accl">Template:Cite journal</ref>	P63/m	165	hP8	764	764	456	2	4.8
AcBr3	white<ref name="j2" />	hexagonal<ref name="accl" />	P63/m	165	hP8	764	764	456	2	5.85
AcOF	white<ref name="m87" />	cubic<ref name="j2" />	FmTemplate:Overlinem			593.1				8.28
AcOCl	white	tetragonal<ref name="j2" />				424	424	707		7.23
AcOBr	white	tetragonal<ref name="j2" />				427	427	740		7.89
AcPO4·0.5H2O	unknown	hexagonal<ref name="j2" />				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

Template:Main Actinium oxide (Ac₂O₃) can be obtained by heating the hydroxide at Template:Cvt or the oxalate at Template:Cvt, in vacuum. Its crystal lattice is isotypic with the oxides of most trivalent rare-earth metals.<ref name="j2" />

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 Template:Cvt in an all-platinum setup. Treating actinium trifluoride with ammonium hydroxide at Template:Cvt yields oxyfluoride AcOF. Whereas lanthanum oxyfluoride can be easily obtained by burning lanthanum trifluoride in air at Template:Cvt for an hour, similar treatment of actinium trifluoride yields no AcOF and only results in melting of the initial product.<ref name="j2" /><ref name="m87">Meyer, pp. 87–88</ref>

AcF₃ + 2 NH₃ + H₂O → AcOF + 2 NH₄F

Actinium trichloride is obtained by reacting actinium hydroxide or oxalate with carbon tetrachloride vapors at temperatures above Template:Cvt. Similarly to the oxyfluoride, actinium oxychloride can be prepared by hydrolyzing actinium trichloride with ammonium hydroxide at Template:Cvt. However, in contrast to the oxyfluoride, the oxychloride could well be synthesized by igniting a solution of actinium trichloride in hydrochloric acid with ammonia.<ref name="j2" />

Reaction of aluminium bromide and actinium oxide yields actinium tribromide:

Ac₂O₃ + 2 AlBr₃ → 2 AcBr₃ + Al₂O₃

and treating it with ammonium hydroxide at Template:Cvt results in the oxybromide AcOBr.<ref name="j2" />

Other compounds

Actinium hydride was obtained by reduction of actinium trichloride with potassium at Template:Cvt, and its structure was deduced by analogy with the corresponding LaH₂ hydride. The source of hydrogen in the reaction was uncertain.<ref>Meyer, p. 43</ref>

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 Template:Cvt 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 Template:Cvt.<ref name="j2">Template:Cite journal</ref>

Isotopes

Template:Main Naturally occurring actinium is principally composed of two radioactive isotopes; Template:Chem (from the radioactive family of Template:Chem) and Template:Chem (a granddaughter of Template:Chem). Template:Chem 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.<ref name="Kirby" /> Thirty-three radioisotopes have been identified, the most stable being Template:Chem with a half-life of 21.772 years, [[actinium-225|Template:Chem]] with a half-life of 10.0 days and Template:Chem 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 Template:Chem (half-life of 69 nanoseconds) which decays through alpha decay. Actinium also has two known meta states.Template:NUBASE2016 The most significant isotopes for chemistry are ²²⁵Ac, ²²⁷Ac, and ²²⁸Ac.<ref name="Kirby" />

Purified Template:Chem 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%);Template:NUBASE2016 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, Template:Chem is difficult to detect directly by its emission and it is therefore traced via its decay products.<ref name="bse">Actinium, Great Soviet Encyclopedia (in Russian)</ref> The isotopes of actinium range in atomic weight from 203 u (Template:Chem) to 236 u (Template:Chem).Template:NUBASE2016

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
226Ac	226Ra(d,2n)→226Ac	α, β− electron capture	29.37 hours
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

File:Uraninite-39029.jpg

Uraninite ores have elevated concentrations of actinium.

Actinium is found only in traces in uranium ores – one tonne of uranium in ore contains about 0.2 milligrams of ²²⁷Ac<ref name="Hagemann1950">Template:Cite journal</ref><ref name="g946">Template:Greenwood&Earnshaw2nd</ref> – 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 properties to those of lanthanum and other lanthanides, which are always abundant in actinium-bearing ores, render separation of actinium from the ore impractical. The most concentrated actinium sample prepared from raw material consisted of 7 micrograms of ²²⁷Ac in less than 0.1 milligrams of La₂O₃, and complete separation was never achieved.<ref name=KirbyReview>Template:Cite book</ref> Instead, actinium is prepared, in milligram amounts, by the neutron irradiation of Template:Chem2 in a nuclear reactor.<ref name="g946" /><ref>Template:Cite book</ref>

<chem>^{226}_{88}Ra + ^{1}_{0}n -> ^{227}_{88}Ra ->[\beta^-][42.2 \ \ce{min}] ^{227}_{89}Ac</chem>

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).<ref name="Hagemann1950" /> 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.<ref name="sep" />

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.<ref>Template:Cite journal</ref> 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.<ref>Template:Cite bookTemplate:Dead link</ref>

Actinium metal has been prepared by the reduction of actinium fluoride with lithium vapor in vacuum at a temperature between Template:Cvt. 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.<ref name="CRC">Hammond, C. R. The Elements in Template:RubberBible86th</ref><ref name="blueglow" />

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.<ref name="CRC" /><ref name="AcNatureChem">Template:Cite journal</ref> 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.<ref name="b1">Russell, Alan M. and Lee, Kok Loong (2005) Structure-property relations in nonferrous metals. Wiley. Template:ISBN, pp. 470–471</ref> 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:

<chem>^{9}_{4}Be + ^{4}_{2}He -> ^{12}_{6}C + ^{1}_{0}n + \gamma</chem>

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.<ref>Majumdar, D. K. (2004) Irrigation Water Management: Principles and Practice. Template:ISBN p. 108</ref><ref>Chandrasekharan, H. and Gupta, Navindu (2006) Fundamentals of Nuclear Science – Application in Agriculture. Template:ISBN pp. 202 ff</ref> Such probes are also used in well logging applications, in neutron radiography, tomography and other radiochemical investigations.<ref>Template:Cite journal</ref>

File:DOTA polyaminocarboxylic acid.png

Chemical structure of the DOTA carrier for ²²⁵Ac in radiation therapy

²²⁵Ac is applied in medicine to produce Template:Chem2 in a reusable generator<ref name="sep">Template:Cite journal</ref> 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).<ref name="AcNatureChem" /> Additionally, ²²⁵Ac decays to nontoxic ²⁰⁹Bi rather than toxic lead, which is the final product in the decay chains of several other candidate isotopes, namely ²²⁷Th, ²²⁸Th, and ²³⁰U.<ref name="AcNatureChem" /> Not only ²²⁵Ac itself, but also its daughters, emit alpha particles which 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 (Template:Nowrap)<ref>Template:Cite journal</ref> or DOTA (Template:Nowrap) 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.<ref>Template:Cite journal</ref><ref>Template:Cite journal</ref><ref>Template:Cite journal</ref>

The medium half-life of ²²⁷Ac (21.77 years) makes it a 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.<ref>Template:Cite journal</ref><ref>Template:Cite journal</ref>

There are theoretical predictions that AcH_x hydrides (in this case with very high pressure) are a candidate for a near room-temperature superconductor as they have T_c significantly higher than H₃S, possibly near 250 K.<ref>Template:Cite journal</ref>

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.<ref>Template:Cite journal</ref> 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.<ref>Template:Ullmann</ref>

See also

• Actinium series

Bibliography

• Template:Cite book

External links

• Actinium at The Periodic Table of Videos (University of Nottingham)
• NLM Hazardous Substances Databank – Actinium, Radioactive
• Actinium in Template:Cite book