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CHARACTERISTIC OF Tc

A. History
Technetium, as element 43, was discovered in 1937 by Perrier and Segr in a
sample of molybdenum which was irradiated by deuterons.1 The new element
received its name from the Greek word technetos, meaning artificial, because
technetium was the first element previously unknown on earth to be made
artificially.2 In 1939 Seaborg and Segr observed that molybdenum-98 irradiated
with slow neutrons gave rise to 99Tc through decay of the metastable isomer,
99mTc.3 Eventually 21 isotopes of technetium were discovered ranging from 90Tc to
110Tc, with technetium-110 having the shortest half-life (0.86 sec) and 97Tc the
longest (2.6 x 106 y). All technetium isotopes are radioactive.

B. Basic Chemical Properties of Tc


Technetium is the 43rd element in the periodic table, belongs to the group of
transient metals. Owing to its electron configuration of 4d5 5s2, technetium provides
several opportunities for complex formation with a large number of different ligands,
and its oxidation state (OS) can change from +1 up to +7. The OS is considered to be
a main parameter determining the chemical nature of the complexes. Technetium can
form chemical bonds consisting of both sigma and pi electrons, and the sigma bonds
can be colligative and coordinative types when spin compensation and electron pair
donation occur, respectively.
The structure of technetium complexes can also be characterized by the
coordination number (N), which can vary from 4 to 7, allowing tetrahedral (N=4),
tetragonal pyramidal (N=5), octahedral (N=6), capped octahedral (N=7) or
pentagonal bipyramidal (N=7) geometry. The third parameter for characterization of
technetium complexes is the electric charge (Z) of the whole molecule, which may
provide an anionic (Z=-1), neutral (Z=0) or cationic (Z=+1) character.
The high variability of the complexing centres results in different stabilities
for the various complexes. Partechnetate (N=4, OS=+7, Z=-1) is the most stable form
of technetium compound is possible, especially after long periods of post-labelling
storage. At lower oxidation states, the Tc-S, Tc-P(III) and Tc-C(II) chemical bonds are
quite stable in the appropriate geometry. At the same time, phosphonates, in which six
oxygen atoms are bound to technetium, are of a lower stability and are liable to form
oligomers, that is, polynuclear complexes. The hexacoordinated N2O4 and N3O3
complexes such as DPTA, EDTA, or HIDA derivates are also of a relatively low
stability and partially transform to heptacoordinated pentagonal bypiramidal
geometry, which might be an alternative structure provided by these complexing
centres and additional oxo-oxygen.
In many respects, the analytical behavior of Tc is similar to that of Re. Both
form stable XO4- anions that give insoluble salts with large cations; both form volatile
heptoxldes; and both form acid-insoluble heptasulfldes. However, there are subtle
differences between the two elements that can cause them to behave very differently
under certain conditions. The vapor pressure of Tc2O7 is much higher than that of
Re2O7 at low temperatures (e.g. 10-lMM at 100 C, compared to N 3 x 10 -5 mm for
Re2O7). In contrast to rhenium, technetium (VII) is therefore easily lost upon
evaporation of acid solutions unless a reducing agent is present or the evaporation is
conducted at a low temperature. Ignorance of these factors has led to a multitude of
conflicting statements concerning the volatility of technetium.
Another Important property of Tc (VII) is its relatively greater ease of
reduction, and the slowness of some of the intermediate steps in the reduction
process. Pertechnetate ion is reduced to a lower oxidation state by hydrochloric acid,
thiocyanate ionz, organic impurities present in tetraphenylarsonium chloride, anion
exchange resin, and some organic solvents. Yet the complete reduction to Tc (IV) is
slow and by analogy with rhenium, a multiplicity of reaction products may be
expected. Unless precautions are taken to maintain technetium in the appropriate
oxidation state, erratic results will be obtained.
C. Metallic Technetium
Technetium metal can be prepared by reduction of the sulfide with hydrogen
at 1100 C. A purer product is obtained by hydrogen reduction of ammonium
pertechnetate at 500-600 C, or by electrodeposltlon from 2~ H 2SO4 in the presence
of trace~ of fluoride . The metal has a density of 11.49 and melts at 214020 C
under atmospheric pressure.
Technetium metal dissolves in nitric acid, aqua regia, and hot, concentrated
sulfur acid. It is insoluble in hydrochloric acid and, In contrast to rhenium, In neutral
or alkaline hydrogen peroxide . It tarnishes slowly in moist air.

D. Solution Chemistry of Technetium


By analogy with rhenium, all oxidation states between -1 and +7 may be
expected for technetium. Of these, the +7 is the most important, though the +4, +5
and +6 states may also be of Interest In some analytical applications.
1. Oxidation State +7
Ammonium pertechnetate. The most common compound of Tc(VII) Is
ammonium pertechnetate, NH4TcO4, a white, water soluble salt. It Is usually
obtained by dissolving technetium heptasulfide in armnonlaand hydrogen
peroxide. When prepared In this manner, it Is often heavily contaminated with
(NH4)2SO4 and NH4NO2, and decomposes to TcO2 on heating but a somewhat
purer product has apparently been sublimed nn vacuo without decomposition.
Technetium heptoxlde and pertechnetlc acid. The yellow, crystalline oxide
has been prepared by burning the metal in oxygen at 400-600 oC 13. It melts at
119.5 C and boils at 311 c. Technetium heptoxlde colorless solution of HTcO4.
dissolves In water to give a the vapor pressures both the acid and the heptoxlde are
rather high even at low temperatures, and while this is a handicap in some
respects, it also makes possible a number of chemical separations. The
coprecipltatlon behavior of pertechnetate ion has been investigated in some detail.
It forms slightly soluble salts with large cations, e.g., T1; Ag+, Cs+, nitron, and
(C6H5)4 As+. At 0 C, precipitation with the last-mentioned reagent Is feasible at
concentrations as low as 5 mg Tc At lower concentrations, any of the XY4- anions
may be used as carriers: e.g., ReO4-, ClO4-, I04- and BF4- 15,16,17
. In acid solutions,
molybdenum also precipitates, but in basic solutions, it does not interfere.
Decontamination from other fission products is excellent: a single-step @
decontamination factor of 105 has been reported. The principal remaining
contaminants are Zr, Nb, and Ru. CO- Precipitation with (C6H5)4AsReO4 Is
probably the fastest known separation method for Tc; when milklng 5 sec. Tc102
from 11.5 min. Mo102, Flegenhelmer et al were able to precipitate and filter the
sample In 5-6 seconds. Removal of the technetlgm from the organic precipitate
may be accomplished by wet combustion, by electrolysis in concentrated H 2SO4,
or by passing an alcohol solution of the precipitate through a strong-base anion
exchanger.In the chloride form. The organic cation passes through the exchanger,
while the pertechnetate IS adsorbed and may be subsequently eluted by HClO4.
Pertechnetate does not coprecipltate with manganese and
ruthenium dioxides, zlrconlum hydroxide, tantallc and nioblc
acids, the 8-hydroxyqulnolate and benzidinate of molybdenum
(VI)20,21, 22
silver molybdate , lead molybdate, ferric hydrox-
ide, and &-benzoin oxime molybdate23 .

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