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Titanium

1st Series Transition Element

zge ULAMILI EMMEZ


222010017

Its symbol Ti and atomic number 22


Titanium has the electronic
structure 3d4s
The energy of removal of four
electrons is so high that the Ti4+
ion.Compounds are covalent

The Lower Oxidation States

The +4 oxidation state dominates titanium chemistry with tetrahedral


geometry.
But compounds in the +3 oxidation state are also common.
Commonly, titanium adopts an octahedral coordination geometry in
its complexes, representative octahedral complexes are [TiF6]3
But tetrahedral TiCl4 is a notable exception. Because of its high
oxidation state, titanium(IV) compounds exhibit a high degree
of covalent bonding. Chlorides, bromides, and iodides , sulfides and
similar compounds have considerable covalent character.
The elements Ti form octahedral ions, [M(H2O)6]3 +
Ti3+ ions are oxidized by air.
In aqueous solution high acidities are required to prevent hydrolysis

Titanium tetrachloride, like SnCI4 is a distillable


liquid readily hydrolyzed by water behaving as a
Lewis acid
The bromide and iodide,form crystalline
molecular lattices are isomorphous with the
corresponding Group IVB halides
TiO2(rutile) is isomorphouswith SnO2(cassiterite)
and is similarly yellow when hot

Titanium tetrachloride, a colorless liquid


(bp136C),has a pungent odor,fumes
strongly in moist air,and is vigorously,
though not violently, hydrolyzed by water.
TiCl4 + H2O = TiO2 + 4 HCl
Partially hydrolyzed species are formed
with a deficit of water or on addition of
TiCl4 to aqueous HC.

Titanium oxide has three crystal forms


rutile,
anatase,
Brookite
all occur in nature.

The dioxide that is used in large quantities as a white pigment in


paints is made by vapor phase oxidation of TiCl4 with oxygen.
The precipitates obtained by addition of OHto TiN solutions are best
regarded as hydrous TiO2, not a true hydroxide.
This material is amphotericand dissolves in concentrated NaOH.

Compounds
Oxides
-Rutile is a titanium dioxide
body-centred tetragonal unit cell
Sulfides
-Titanium disulfide is an inorganic compound with
the formula TiS2 hexagonal close packed (hcp )
crystal structure and octahedral coordination
geometry

Nitrides -Titanium nitride (TiN) has Cubic, cF8, crystal


structure and coordination geometry is an Octahedral

Carbides
-Titanium carbide, TiC has Cubic, cF8, crystal structure
and coordination geometry is an Octahedral

Halides
Titanium tetrachloride
is the inorganic compound
with the formula TiCl4 .
TiCl4 is an unusual
example of a metal halide
that is highly volatile.

Organometallic complexes
Dicarbonylbis(cyclopentadienyl)titanium is the chemical
compound with the formula (5-C5H5)2Ti(CO)2, abbreviated
Cp2Ti(CO)2.

Hexaaquatitanium(III) or
(Titanium III hexahyrate)

hexaaquotitanium(III), Ti(H2O)63+.
The ligands (H2O in this example which is monodentate ligand)
are bound to the central ion by electron pairs contributed by
each ligand. Because the six ligands are located at the corners
of an octahedron centered around the metal ion, these electron
pairs are equivalent to clouds of negative charge that are
directed from near the central ion out toward the corners of the
octahedron. We will call this an octahedral electric field, or
the ligand field.

Ti has the electronic configuration [Ar] 3d2. In this complex


it is present as Ti3+ which has one unpaired electron in 3d
orbital. It undergoes d2sp3 (octahedral) hybridization to
accomodate 6 pairs of water according to valence bond
theory and III oxidation state.
So the complex is octahedral in shape, will be coloured
(violet) and paramagnetic due to presence of d1 one
unpaired electron.Monomeric and high symmetry.
Ti(III): d1 electronic configuration: (t2g)1 (eg)0
-> electronic ground state is degenerate => distortion
-> compression of the octahedron will likely occur (the
additional stabilization
energy is -2/3 2 as opposed to only -1/3 2 for the
elongated octahedron.
Ground state 2Tg, Oh point group.

Valence bond theory

UV-vis spectroscopy

Ti in [Ti(H2O)6] 3+ is a d1 ion, and an electron occupies


the t2g orbital produced by the
Octahedral ligand field splitting.

The absorption spectrum for [Ti(H2O)6]3+ has a


maximum absorption occurs at 520 nm (green and
yellow). So, the complex transmits all light except green
and yellow. Therefore, the complex is purple.

t2g1eg0 > t2g0eg1


The UV-Vis absorption spectrum reveals that this transition
occurs with a maximum at 20300 cm-1 which corresponds to
delta zero 243 kJ/mol.

Figure shows
Visible absorption
spectrum of [Ti(H2O)6] .

Colourless oxotitanium(IV) ion is reduced to the


purple hexaaquatitanium(III) ion colourless
Ti(IV) as [TiO]2+ ==> Ti(III) in acid solution giving
the purple [Ti(H2O)6)]3+(aq).But it is readily
oxidised back to Ti(IV) by dissolved oxygen from
the atmosphere (electrode potential chart
TiO2+/Ti3+ +0.10V is less positive than
O2+H+/H2O +1.23V in acid solution).
Titanium alloys are amongst the strongest
lightest of metal alloys and used in aircraft
production and use in bicycle