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Actinides

The 5f series elements

The group also known as Heavier


elements or inner series transition
elements following actinium from Ac to Lr.
Actinides series elements of which
uranium( U, 92) and plutonium( Pu, 94)
are best known are built up by completion
of the 5f orbitals.

Trans-uranium elements
For a very long time U (92) continued to
be the last heavy element known
After 1940 a series of 11 elements with Z
93-103 were identified and synthesized by
transformation of naturally occurring
elements by nuclear reactions.
These man made elements are called
trans-uranium elements

Actinium
A soft, silvery metal, which is reported to
glow blue. This is due to its radioactivity.
Actinium starts the series of actinoids
(elements 90-103), which are named after
this element. It naturally occurs from
uranium decay, the half-life of its most
stable isotope is less than 22 years. It has
very few applications, because it is difficult
to handle and very dangerous.

Chemically, it is similar to lanthanum. Most


actinium decays to thorium, about 1.4% to
francium.

Thorium
Thorium by far is the most stable and frequent
actinoid, the half-life of 232Th is 14 billion years.
The soft, in pure form silvery metal is chemically
very reactive and only light toxic.
However, its weak radioactivity can become
dangerous, if it is inhaled. Therefore it is not
longer much used for mantles in gas lights,
unlike years ago. It is still common for some
special alloys and in good camera lenses (as
ThO2). Thorium decays to radium.

Thorium

Protactinium
A compact chunk of the radioactive heavy
metal produces so much heat that it glows
red.
no stable isotopes
Protactinium primarly is generated from
the decay of the rare isotope uranium 235
(via the very unstable thorium 231).
Therefore it only exists in small amounts,
most of it is found in nuclear waste.

The half-life of the most stable isotope is


32,760 years, which makes the highly
toxic element even in tiny amounts very
dangerous for a long time.
Outside of science, no reasonable
applications for protactinium exist.
Nearly all protactinium decays further to
actinium.

Uranium

Uranium is a chemically very reactive,


grey heavy metal. Like all actinoids it is
radioactive, after thorium it is the second
most stable of those. The most abundant
natural isotope is 238U with a half-life of 4.5
billion years. The basis for nuclear power
plants is the fissile isotope 235U. The
fission products often are highly
radioactive isotopes of lower elements,
like Cs137 and Sr 90.

Uranium 235 is used for atomic bombs,


too, like the one in Hiroshima.
It has a natural abundance of only 0.7 %
and has to be enriched in an extensive
process.
For power plants, at least 3 % are needed,
for weapons much more.

The waste material of this process,


depleted uranium, sometimes is used in
ammunition, sometimes is turned into
plutonium in a breeder reactor, but most of
it is just thrown away.
Natural uranium decays to thorium.

Neptunium
Los Alamos National Laboratory, 2002
6 kg heavy neptunium 237 sphere.

Neptunium, a radioactive, silver heavy


metal, is quite stable for an element with a
high and odd atomic number, 237Np has a
half-life of 2 million years.
On Earth, it naturally occurs in tiny traces
in uranium ore, but it is found in much
bigger amounts in nuclear waste.

So far it is scarcely used, although it is


fissionable.
Like with every nuclear waste, there is no
method of a reasonable disposal. Most of
it decays to protactinium.

Plutonium

Plutonium, a silvery, very heavy and hard


metal, is perhaps the most dangerous of
all elements and the one that, relative to
its amount, did the worst damages to
humanity and environment.
It was in the bomb of Nagasaki and,
together with uranium, involved in the
Chernobyl disaster. In multiple nuclear
tests it devastated huge areas.

It is still used in nuclear power plants,


where it produces waste that cannot be
depolluted, can be made weapons-grade
and is a constant threat for the entire
world.
In nature, plutonium only occurs in very
small amounts, all that is in use is
artificially made from uranium.

Apart from its radioactivity, it is very toxic.


As fissile material, commonly 239Pu is
used.
When hit by a neutron, this decays and
releases more neutrons and radioactive
waste.
If not fissioned, most plutonium decays to
uranium.

Americium
1944: the first produced americium (as
hydroxide) on the bottom of a glass vial.

Americium is the first synthetic element,


from here onwards all elements have to be
produced in laboratories.
These are very radioactive.
The most stable isotope of americium,
243Am, has a half-life of just under 7400
years.

Due to its strong alpha radiation,


americium is very dangerous.
In some countries americium 241 (432
years half life) is used in tiny amounts in
smoke detectors for ionizing air.
Americium emerges in small amounts in
nuclear reactors from plutonium and
mostly decays to neptunium.

Curium
Chemically similar to gadolinium, but
highly radioactive, the metal produces
much heat.
The synthetic element curium is usually
made from plutonium and mostly decays
to this again. The most stable isotope,
247Cm, has a quite long half-life of 15.6
million years. However, this is scarcely
produced.

Much more frequent are the significantly more


unstable isotopes 242 and 244, which emit very
intense radiation. Therefore, the enormously
dangerous curium is used only rarely and in safe
environments, like in space missions.
The Mars rovers had it with them in their X-ray
spectrometers. Long and short lived curium
isotopes are also produced unintentionally in
atomic reactors and then end up in nuclear
waste.

Berkelium
The highly reactive, silvery metal is a
strong -emitter.
Berkelium is made from americium or
curium, mostly unintentional, because
outside of basic research it hasn't any
application. The most stable isotope,
247Bk, has a half-life of 1380 years, but this
is hardly produced.

The most commonly accrued 249Bk has a


half-life of only 330 days. Of this, each
year about 1 gram emerges worldwide as
waste in nuclear reactors, most of it
decays to californium.

Californium
The strong and neutron emitter produces
a considerable heat.
Californium emerges in tiny amounts
rather randomly from plutonium via the
elements between these two.
With Californium, it is a bother to
laboriously extract it, because for 252Cf,
which has a half-life of 2.6 years.
About 3% of this isotope spontaneously
fissions into large chunks and hot
neutrons.

Therefore it is used as a strong neutron


source, for example in detectors for metal
fatigue and in medicine for very intense
irradiation. The enrichment of californium
252 is very expensive, each year only
about 0.1 grams are made. When used,
strict safety regulations have to be
complied, although in each case only
some micrograms of it are involved. The
isotope 251Cf has a half-life of 900 years.
Most californium decays to curium.

Einsteinium and Fermium


Einsteinium and fermium are produced in
small amounts in the biggest man-made
explosions, those of hydrogen bombs,
from the igniter plutonium and neutrons
that are flying around. Einsteinium also
can be made in labs, however the highly
radioactive metal has no use outside of
basic research.

The most stable isotope has a half-life of


472 days. Einsteinium of course was
named after Albert Einstein, who himself
had no connection to the element.
Einsteinium decays to berkelium or
californium.

Mendelevium
Chemically similar to Thulium, the highly
radioactive heavy metal emits very
energetic -radiation.
Mendelevium is the first synthetic element,
which can't be produced any more by
neutron capture. To make mendelevium,
einsteinium is bombarded with helium
nuclei. Most of it decays to einsteinium
again.

The most stable mendelevium isotope has


a half-life of 52 days.
The element is named to honor Dmitri
Mendeleev, the developer of the periodic
table of elements.

Nobelium
Nobelium can only be made in very small
amounts and emits strong radiation of
various kinds.
Nobelium is produced for example by
bombarding californium with carbon or
uranium with neon. The most stable
isotope has a half-life of 58 minutes. Most
of it decays to fermium or by spontaneous
fission. Of its physical properties not much
is known, but they are probably similar to
those of the other actinoids.

Lawrencium
Lawrencium can only be made in very
small amoun
Lawrencium is produced for example by
bombarding californium with boron or
americium with oxygen.
The most stable isotope has a half-life of
3.6 hours.
This decays to nobelium, most other
isotopes to mendelevium.

Of its physical properties not much is


known, but they are probably similar to
those of the other actinoids.
Lawrencium could be the hardest and
heaviest of them.
It emits strong radiation.

Separation of Plutonium (Pu) from Uranium (U)


(Redox Process using Hexone)
UO22+ + Pu4+ + Fission Products (FPs)
Oxidize by K2Cr2O7

UO22+ + PuO22+ + FPsAdd Al(NO )


3 3
Extract with hexone

aq. Phase
FPs

org phase
UO22+ + PuO22+
Was with SO2

Org.phase
UO22+
Dil. HNO3

aq. Phase
Pu4+

Org.phase
recycle

Repeat oxidation
and extraction cycle

aq. Phase

Separation of Plutonium (Pu) from Uranium (U)


(Co-precipitation method using BiPO4)
UO22+ + Pu6+ + Fission Products (FPs)
NO2-

UO22+ + Pu4+ + FPs

(i) Add H2SO4 to prevent ppt of U6+


(ii) Add BiPO4

Residue
BiPO4 carrying Pu4+

Filtrate
UO22+

Dissolve in HNO3 and oxidize Pu4+ to


Pu6+ with KMnO4, K2Cr2O7

PuO22- + Bi3+ + FPs


PO4-3

Residue
BiPO4 carrying FPs

Filtrate
Pu6+

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