The 14th International Conference on

Miniaturized Systems for Chemistry and Life Sciences

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Group 4 element


Group 4 element

Group 4 is a group of elements in the periodic table. It contains the elements titanium (Ti), zirconium (Zr), hafnium (Hf) and rutherfordium (Rf). This group lies in the d-block of the periodic table. The group itself has not acquired a trivial name; it belongs to the broader grouping of the transition metals.

The three Group 4 elements that occur naturally are titanium, zirconium and hafnium. The first three members of the group share similar properties; all three are hard refractory metals under standard conditions. However, the fourth element rutherfordium (Rf), has been synthesized in the laboratory; none of its isotopes have been found occurring in nature. All isotopes of rutherfordium are radioactive. So far, no experiments in a supercollider have been conducted to synthesize the next member of the group, either unpenthexium (Uph, element 156) or unpentoctium (Upo, element 158), and it is unlikely that they will be synthesized in the near future.

British minerologist William Gregor first identified titanium in ilmenite sand beside a stream in Cornwall, Great Britain in the year 1791. After analyzing the sand, he determined the weakly magnetic sand to contain iron oxide and a metal oxide that he could not identify. During that same year, minerologist Franz Joseph Muller produced the same metal oxide and could not identify it. In 1795, chemist Martin Heinrich Klaproth independently rediscovered the metal oxide in rutile from the Hungarian village Boinik. He identified the oxide containing a new element and named it for the Titans of Greek mythology.

Martin Heinrich Klaproth discovered zirconium when analyzing the zircon containing mineral jargoon in 1789. He deduced that the mineral contained a new element and named it after the already known Zirkonerde (zirconia). However, he failed to isolate the newly discovered zirconium. Cornish chemist Humphry Davy also attempted to isolate this new element in 1808 through electrolysis, but failed. In 1824, Swedish chemist Jons Jakob Berzelius isolated an impure form of zirconium, obtained by heating a mixture of potassium and potassium zirconium fluoride in an iron tube.

Hafnium had been predicted by Dmitri Mendeleev in 1869 and Henry Moseley measured in 1914 the effective nuclear charge by X-ray spectroscopy to be 72, placing it between the already known elements lutetium and tantalum. Dirk Coster and Georg von Hevesy were the first to search for the new element in zirconium ores. Hafnium was discovered by the two in 1923 in Copenhagen, Denmark, validating the original 1869 prediction of Mendeleev. There has been some controversy surrounding the discovery of hafnium and the extent to which Coster and Hevesy were guided by Bohr's prediction that hafnium would be a transition metal rather than a rare earth element. While titanium and zirconium, as relatively abundant elements, were discovered in the late 18th century, it took until 1923 for hafnium to be identified. This was only partly due to hafnium's relative scarcity. The chemical similarity between zirconium and hafnium made a separation difficult and, without knowing what to look for, hafnium was left undiscovered, although all samples of zirconium, and all of its compounds, used by chemists for over two centuries contained significant amounts of hafnium.

If the abundance of elements in Earth's crust is compared for titanium, zirconium and hafnium, the abundance decreases with increase of atomic mass. Titanium is the seventh most abundant metal in Earth's crust and has an abundance of 6320 ppm, while zirconium has an abundance of 162 ppm and hafnium has only an abundance of 3 ppm.

All three stable elements occur in heavy mineral sands ore deposits, which are placer deposits formed, most usually in beach environments, by concentration due to the specific gravity of the mineral grains of erosion material from mafic and ultramafic rock. The titanium minerals are mostly anatase and rutile, and zirconium occurs in the mineral zircon. Because of the chemical similarity, up to 5% of the zirconium in zircon is replaced by hafnium. The largest producers of the group 4 elements are Australia, South Africa and Canada.

Titanium metal and its alloys have a wide range of applications, where the corrosion resistance, the heat stability and the low density (light weight) are of benefit. The foremost use of corrosion-resistant hafnium and zirconium has been in nuclear reactors. Zirconium has a very low and hafnium has a high thermal neutron-capture cross-section. Therefore, zirconium (mostly as zircaloy) is used as cladding of fuel rods in nuclear reactors, while hafnium is used in control rods for nuclear reactors, because each hafnium atom can absorb multiple neutrons.

The group 4 elements are not known to be involved in the biological chemistry of any living systems. They are hard refractory metals with low aqueous solubility and low availability to the biosphere. Titanium is one of the few first row d-block transition metals with no known biological role. Rutherfordium's radioactivity would make it toxic to living cells.


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