Protactinium is a chemical element; it has symbol Pa and atomic number 91.

It is a
dense, radioactive, silvery-gray actinide metal which readily reacts with oxygen,
water vapor, and inorganic acids. It forms various chemical compounds, in which
protactinium is usually present in the oxidation state +5, but it can also assume
+4 and even +3 or +2 states. Concentrations of protactinium in the Earth's crust
are typically a few parts per trillion, but may reach up to a few parts per million
in some uraninite ore deposits. Because of its scarcity, high radioactivity, and
high toxicity, there are currently no uses for protactinium outside scientific
research, and for this purpose, protactinium is mostly extracted from spent nuclear
fuel.

The element was first identified in 1913 by Kazimierz Fajans and Oswald Helmuth
Göhring and named "brevium" because of the short half-life of the specific isotope
studied, protactinium-234m. A more stable isotope of protactinium, 231Pa, was
discovered in 1917/18 by Lise Meitner in collaboration with Otto Hahn, and they
named the element protactinium.[8] In 1949, the IUPAC chose the name "protactinium"
and confirmed Hahn and Meitner as its discoverers. The new name meant "(nuclear)
precursor of actinium,"[9] suggesting that actinium is a product of radioactive
decay of protactinium. John Arnold Cranston (working with Frederick Soddy and Ada
Hitchins) is also credited with discovering the most stable isotope in 1915, but he
delayed his announcement due to being called for service in the First World War.
[10]

The longest-lived and most abundant (nearly 100%) naturally occurring isotope of
protactinium, protactinium-231, has a half-life of 32,760 years and is a decay
product of uranium-235. Much smaller trace amounts of the short-lived protactinium-
234 and its nuclear isomer protactinium-234m occur in the decay chain of uranium-
238. Protactinium-233 occurs as a result of the decay of thorium-233 as part of the
chain of events necessary to produce uranium-233 by neutron irradiation of thorium-
232. It is an undesired intermediate product in thorium-based nuclear reactors, and
is therefore removed from the active zone of the reactor during the breeding
process. Ocean science utilizes the element to understand the ancient ocean's
geography. Analysis of the relative concentrations of various uranium, thorium, and
protactinium isotopes in water and minerals is used in radiometric dating of
sediments up to 175,000 years old, and in modeling of various geological processes.
[11]

History

Dmitri Mendeleev's 1871 periodic table with a gap for protactinium on the bottom
row of the chart, between thorium and uranium
In 1871, Dmitri Mendeleev predicted the existence of an element between thorium and
uranium.[12] The actinide series was unknown at the time, so Mendeleev positioned
uranium below tungsten in group VI, and thorium below zirconium in group IV,
leaving the space below tantalum in group V empty. Until the general acceptance of
the actinide concept in the late 1940s, periodic tables were published with this
structure.[13] For a long time, chemists searched for eka-tantalum[note 1] as an
element with similar chemical properties to tantalum, making a discovery of
protactinium nearly impossible. Tantalum's heavier analogue was later found to be
the transuranic element dubnium – although dubnium is more chemically similar to
protactinium, not tantalum.[14]

In 1900, William Crookes isolated protactinium as an intensely radioactive material

from uranium; however, he could not characterize it as a new chemical element and
thus named it uranium X (UX).[12][15][16] Crookes dissolved uranium nitrate in
ether, and the residual aqueous phase contained most of the 234
90Th
and 234
91Pa
. His method was used into the 1950s to isolate 234
90Th
and 234
91Pa
from uranium compounds.[17] Protactinium was first identified in 1913, when
Kasimir Fajans and Oswald Helmuth Göhring encountered the isotope 234mPa during
their studies of the decay chains of uranium-238: 238
92U
→ 234
90Th
→ 234m
91Pa
→ 234
92U
. They named the new element "brevium" (from the Latin word brevis, meaning brief
or short) because of the short half-life of 1.16 minutes for 234m
91Pa
(uranium X2).[18][19][20][21][22][23] In 1917–18, two groups of scientists, Lise
Meitner in collaboration with Otto Hahn of Germany and Frederick Soddy and John
Cranston of Great Britain, independently discovered another isotope, 231Pa, having
a much longer half-life of 32,760 years.[8][22][24] Meitner changed the name
"brevium" to protactinium as the new element was part of the decay chain of
uranium-235 as the parent of actinium (from the Greek: πρῶτος prôtos, meaning
"first, before").[25] The IUPAC confirmed this naming in 1949.[26][27] The
discovery of protactinium completed one of the last gaps in early versions of the
periodic table, and brought fame to the involved scientists.[28]

Aristid von Grosse produced 2 milligrams of Pa2O5 in 1927,[29] and in 1934 first
isolated elemental protactinium from 0.1 milligrams of Pa2O5.[30] He used two
different procedures: in the first, protactinium oxide was irradiated by 35 keV
electrons in vacuum. In the other, called the van Arkel–de Boer process, the oxide
was chemically converted to a halide (chloride, bromide or iodide) and then reduced
in a vacuum with an electrically heated metallic filament:[26][31]

2 PaI5 → 2 Pa + 5 I2
In 1961, the United Kingdom Atomic Energy Authority (UKAEA) produced 127 grams of
99.9% pure protactinium-231 by processing 60 tonnes of waste material in a 12-stage
process, at a cost of about US$500,000.[26][32] For many years, this was the
world's only significant supply of protactinium, which was provided to various
laboratories for scientific studies.[12] The Oak Ridge National Laboratory in the
US provided protactinium at a cost of about US$280/gram.[33]

Isotopes
Main article: Isotopes of protactinium
Twenty-nine radioisotopes of protactinium have been discovered. The most stable are
231Pa with a half-life of 32,760 years,[34] 233Pa with a half-life of 27 days, and
230Pa with a half-life of 17.4 days. All other isotopes have half-lives shorter
than 1.6 days, and the majority of these have half-lives less than 1.8 seconds.
Protactinium also has two nuclear isomers, 217mPa (half-life 1.2 milliseconds) and
234mPa (half-life 1.16 minutes).[35]

The primary decay mode for the most stable isotope 231Pa and lighter (211Pa to
231Pa) is alpha decay, producing isotopes of actinium. The primary mode for the
heavier isotopes (232Pa to 239Pa) is beta decay, producing isotopes of uranium.[35]

Nuclear fission
The longest-lived and most abundant isotope, 231Pa, can fission from fast neutrons
exceeding ~1 MeV.[36] 233Pa, the other isotope of protactinium produced in nuclear
reactors, also has a fission threshold of 1 MeV.[37]
Occurrence
Protactinium is one of the rarest and most expensive naturally occurring elements.
It is found in the form of two isotopes – 231Pa and 234Pa, with the isotope 234Pa
occurring in two different energy states. Nearly all natural protactinium is
protactinium-231. It is an alpha emitter and is formed by the decay of uranium-235,
whereas the beta radiating protactinium-234 is produced as a result of uranium-238
decay. Nearly all uranium-238 (99.8%) decays first to the shorter-lived 234mPa
isomer.[38]

Protactinium occurs in uraninite (pitchblende) at concentrations of about 0.3-3

parts 231Pa per million parts (ppm) of ore.[12] Whereas the usual content is closer
to 0.3 ppm[39] (e.g. in Jáchymov, Czech Republic[40]), some ores from the
Democratic Republic of the Congo have about 3 ppm.[26] Protactinium is
homogeneously dispersed in most natural materials and in water, but at much lower
concentrations on the order of one part per trillion, corresponding to a
radioactivity of 0.1 picocuries (pCi)/g. There is about 500 times more protactinium
in sandy soil particles than in water, even when compared to water present in the
same sample of soil. Much higher ratios of 2,000 and above are measured in loam
soils and clays, such as bentonite.[38][41]

In nuclear reactors
Two major protactinium isotopes, 231Pa and 233Pa, are produced from thorium in
nuclear reactors; both are undesirable and are usually removed, thereby adding
complexity to the reactor design and operation. In particular, 232Th, via (n, 2n)
reactions, produces 231Th, which quickly decays to 231Pa (half-life 25.5 hours).
The last isotope, while not a transuranic waste, has a long half-life of 32,760
years, and is a major contributor to the long-term radiotoxicity of spent nuclear
fuel.[42]

Protactinium-233 is formed upon neutron capture by 232Th. It either further decays

to uranium-233, or captures another neutron and converts into the non-fissile
uranium-234.[43] 233Pa has a relatively long half-life of 27 days and high cross
section for neutron capture (the so-called "neutron poison"). Thus, instead of
rapidly decaying to the useful 233U, a significant fraction of 233Pa converts to
non-fissile isotopes and consumes neutrons, degrading reactor efficiency. To limit
the loss of neutrons, 233Pa is extracted from the active zone of thorium molten
salt reactors during their operation, so that it can only decay into 233U.
Extraction of 233Pa is achieved using columns of molten bismuth with lithium
dissolved in it. In short, lithium selectively reduces protactinium salts to
protactinium metal, which is then extracted from the molten-salt cycle, while the
molten bismuth is merely a carrier, selected due to its low melting point of 271
°C, low vapor pressure, good solubility for lithium and actinides, and
immiscibility with molten halides.[42]

Preparation

Protactinium occurs in uraninite ores.

Before the advent of nuclear reactors, protactinium was separated for scientific
experiments from uranium ores. Since reactors have become more common, it is mostly
produced as an intermediate product of nuclear fission in thorium fuel cycle
reactors as an intermediate in the production of the fissile uranium-233:

Th
90
232
+
n
0
1
⟶
Th
90
233
→
22.3

min
β
−
Pa
91
233
→
26.967

d
β
−
U
92
233
⋅
{\displaystyle {\ce {^{232}_{90}Th + ^{1}_{0}n -> ^{233}_{90}Th ->[\beta^-][22.3\
{\ce {min}}] ^{233}_{91}Pa ->[\beta^-][26.967\ {\ce {d}}] ^{233}_{92}U.}}}
The isotope 231Pa can be prepared by irradiating thorium-230 with slow neutrons,
converting it to the beta-decaying thorium-231; or, by irradiating thorium-232 with
fast neutrons, generating thorium-231 and 2 neutrons.

Protactinium metal can be prepared by reduction of its fluoride with calcium,[44]

lithium, or barium at a temperature of 1300–1400 °C.[45][46]

Properties
Protactinium is an actinide positioned in the periodic table to the left of uranium
and to the right of thorium, and many of its physical properties are intermediate
between its neighboring actinides. Protactinium is denser and more rigid than
thorium, but is lighter than uranium; its melting point is lower than that of
thorium, but higher than that of uranium. The thermal expansion, electrical, and
thermal conductivities of these three elements are comparable and are typical of
post-transition metals. The estimated shear modulus of protactinium is similar to
that of titanium.[47] Protactinium is a metal with silvery-gray luster that is
preserved for some time in air.[26][32] Protactinium easily reacts with oxygen,
water vapor, and acids, but not with alkalis.[12]

At room temperature, protactinium crystallizes in the body-centered tetragonal

structure, which can be regarded as distorted body-centered cubic lattice; this
structure does not change upon compression up to 53 GPa. The structure changes to
face-centered cubic (fcc) upon cooling from high temperature, at about 1200 °C.[44]
[48] The thermal expansion coefficient of the tetragonal phase between room
temperature and 700 °C is 9.9×10−6/°C.[44]

Protactinium is paramagnetic and no magnetic transitions are known for it at any

temperature.[49] It becomes superconductive at temperatures below 1.4 K.[12][45]
Protactinium tetrachloride is paramagnetic at room temperature, but becomes
ferromagnetic when cooled to 182 K.[50]

Protactinium exists in two major oxidation states: +4 and +5, both in solids and
solutions; and the +3 and +2 states, which have been observed in some solids. As
the electron configuration of the neutral atom is [Rn]5f26d17s2, the +5 oxidation
state corresponds to the low-energy (and thus favored) 5f0 configuration. Both +4
and +5 states easily form hydroxides in water, with the predominant ions being
Pa(OH)3+, Pa(OH)
2+
2
, Pa(OH)
+
3
, and Pa(OH)4, all of which are colorless.[51] Other known protactinium ions
include PaCl
2+
2
, PaSO
2+
4
, PaF3+, PaF
2+
2
, PaF
−
6
, PaF
2−
7
, and PaF
3−
8
.[52][53]