Protactinium isolation

However, the quantity of Pa produced in this manner is much less than the amount (more than 100 g) that has been isolated from the natural source. The methods for the recovery of protactinium include coprecipitation, solvent extraction, ion exchange, and volatility procedures. AH of these, however, are rendered difficult by the extreme tendency of protactinium(V) to form polymeric coUoidal particles composed of ionic species. These caimot be removed from aqueous media by solvent extraction losses may occur by adsorption to containers and protactinium may be adsorbed by any precipitate present. 

The isolation and identification of 4 radioactive elements in minute amounts took place at the turn of the century, and in each case the insight provided by the periodic classification into the predicted chemical properties of these elements proved invaluable. Marie Curie identified polonium in 1898 and, later in the same year working with Pierre Curie, isolated radium. Actinium followed in 1899 (A. Debierne) and the heaviest noble gas, radon, in 1900 (F. E. Dorn). Details will be found in later chapters which also recount the discoveries made in the present century of protactinium (O. Hahn and Lise Meitner, 1917), hafnium (D. Coster and G. von Hevesey, 1923), rhenium (W. Noddack, Ida Tacke and O. Berg, 1925), technetium (C. Perrier and E. Segre, 1937), francium (Marguerite Percy, 1939) and promethium (J. A. Marinsky, L. E. Glendenin and C. D. Coryell, 1945). 

Radioactive, silvery metal of which only about 125 g exists worldwide, isolated from reactor material. Protactinium occurs in the decay series of 238U (K. Fajans) as 234Pa. It also occurs in that of 235U this isotope, 231Pa, was discovered by L. Meitner and 0. Hahn. The element is only of scientific interest. 

In every piece of uranium ore, such as pitchblende, there are 0.1-0.3 ppm of protactinium as an intermediate in the decay series. The isolation is not... 

As mentioned, protactinium is one of the rarest elements in existence. Although protactinium was isolated, studied, and identified in 1934, little is known about its chemical and physical properties since only a small amount of the metal was produced. Its major source is the fission by-product of uranium found in the ore pitchblende, and only about 350 milligrams can be extracted from each ton of high-grade uranium ore. Protactinium can also be produced by the submission of samples of throrium-230 (g Th) to radiation in nuclear reactors or particle accelerators, where one proton and one or more neutrons are added to each thorium atom, thus changing element 90 to element 91. 

The most common isotope of protactinium is Pa (tj/2 = 3.3 x 10 years), which occurs in pitchblende in the amount of 300 mg/ton, about the same as radium. The heroic efforts of British researchers resulted in the isolation of some hundred grams of Pa from the sludge left over from uranium processing without this supply, little or nothing would... 

Pa, protactinium, was first identified in 1913 in the decay products of U-238 as the Pa-234 isotope (6.7 h) by Kasimir Fajans and Otto H. Gohring. In 1916, two groups, Otto Hahn and Lisa Meitner, and Frederick Soddy and John A. Cranston, found Pa-231 (10 years) as a decay product of U-235. This isotope is the parent of Ac-227 in the U-235 decay series, hence it was named protactinium (before actinium). Isolation from U extraction sludges yielded over 100 g in 1960. 

Uranium-238 emits an alpha particle to become an isotope of thorium. This unstable element emits a beta particle to become the element now known as Protactinium (Pa), which then emits another beta particle to become an isotope of uranium. This chain proceeds through another isotope of thorium, through radium, radon, polonium, bismuth, thallium and lead. The final product is lead-206. The series that starts with thorium-232 ends with lead-208. Soddy was able to isolate the different lead isotopes in high enough purity to demonstrate using chemical techniques that the atomic weights of two samples of lead with identical chemical and spectroscopic properties had different atomic weights. The final picture of these elements reveals that there are several isotopes for each of them. 

The probable existence of protactinium was predicted as early as 1871 by Mendeleev to fill up the space on his peiiodic table between thorium (at, no. 90) and uranium (at. no, 92). He termed the unconfirmed element ekatantalum. In 1926, O. Hahn predicted the properties of the element in considerable detail, including descriptions of its compounds. In 1930, Aristid v. Grosse isolated 2 milligrams of what then was termed ekatantalum pentoxide and showed that element 91 differed m all reactions with comparable amounts of tantalum compounds with exception of precipitation by NH3. However, credit for the discovery of protactinium generally is attributed to Lise Meitner and Otto Hahn in 1917,... 

While protactinium is present at less than the parts per million level in uranium ores, this is still the major source because it can be extracted from the residues accumulated in large-scale production of uranium. There are extreme technical difficulties because of colloid formation but more than 100 g have been isolated. 

First identified in 1913 (the first compound, Pa20s, was isolated in 1927 by von Grosse, who isolated the element in 1931), protactinium is not generally extracted. Most of what is known about the chemistry of protactinium ultimately results from the extraction in 1960 by the UK Atomic Energy Authority of some 125 grams of Pa, from 60 tons of waste material left over from the extraction of uranium, at a cost of about 500,000 (very roughly, 1,250,000 at today s exchange rate). 

It is convenient to discuss protactinium(IV) and (V) bromo and iodo complexes together since they have only been prepared by reacting together the component halides in anhydrous methyl cyanide (40, 46, 48). Thus NMe4PaBrg, NEtiPaBrg, and PhgMeAsPala are isolated (40,46) by removal of solvent in vacuo at room temperature. Hexabromo-niobates(V) and tantalates(V) have been prepared in a similar manner (46). Attempts to obtain octabromo complexes for these three elements have been unsuccessful. The orange hexabromoprotactinates(V) are... 

Fig. 2. The structure of protactinium pentachloride (67). (a) Portion of the infinite chains in Pads. Coordination of Cl around each Pa is pentagonal bipyra-midal. (b) Bond distances and angles within an isolated PaCl7 group. The four Cl(3) atoms are bridging.

The terrestrial occurrence of Ac, Pa, U, and Th is due to the half-lives of the isotopes 235U, 238U and 232Th which are sufficiently long to have enabled the species to persist since genesis. They are the sources of actinium and protactinium formed in the decay series and found in uranium and thorium ores. The half-lives of the most stable isotopes of the trans-uranium elements are such that any primordial amounts of these elements appear to have disappeared long ago. However, neptunium and plutonium have been isolated in traces from uranium13 minerals in which they are formed continuously by neutron reactions such as... 

Protactinium as 231Pa occurs in pitchblende, but even the-richest-ores contain only about 1 part of Pa in 107. The isolation of protactinium from residues in the extraction of uranium from its minerals is difficult, as indeed is the study of protactinium chemistry generally, owing to the" extreme tendency of the compounds to hydrolyze. In aqueous solution, polymeric ionic species and colloidal particles are formed, and these are carried on precipitates and adsorbed on vessels in solutions other than those containing appreciable amounts of mineral acids or complexing agents or ions such as F , the difficulties are almost insuperable. 

The actinium decay series consists of a group of nuclides whose mass number divided by 4 leaves a remainder of 3 (the 4n + 3 series). This series begins with the uranium isotope which has a half-life of 7.04 X 10 y and a specific activity of 8 X 10 MBq/kg. The stable end product of the series is ° Pb, which is formed after 7 a- and 4 /3-decays. The actinium series includes the most important isotopes of the elements protactinium, actinium, ftancium, and astatine. Inasmuch as U is a conqx>nmt of natural uranium, these elem ts can be isolated in the processing of uranium minerals. The longest-lived protactinium isotope, Pa (ti 3.28 X 10 y) has been isolated on the 100 g scale, and is the main isotope for the study of protactinium chemistry. Ac (t 21.8 y) is the longest-lived actinium isotope. 

The seven remaining gaps in the periodic table were gradually filled, although not without further controversy in spite of the conclusive nature of Moseley s atomic number method. The first of these was element 91, discovered by Otto Hahn and Lise Meitner in 1917. The element behaved in the manner described by Mendeleev, who had given it the provisional name eka-tantalum. It now became known as protactinium but was not isolated until the year 1934 by Aristide Grosse in Germany. 

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