The Titanium group

Lecture 4
 Titanium group of elements
Property 22Ti 40Zr 72Hf

No of Natural 5 5 6
isotopes
Electron [Ar]3d24s2 [Kr]4d25s2 [Xe]4f145d26s2
configuration
Electronegativity 1.5 1.4 1.3
Atomic radius (pm) 147 160 159
Density (25o C)/g 4.5 6.51 13.28
cm3
MP/oC 1667 1857 2222
BP/oC 3285 4200 4450
Common ores Ilmenite FeTiO3 Zircon ZrSiO4 MSiO4.xH2O (M =
Rutile TiO2 Baddeleyite, ZrO2 Hf, Th, Zr)
Terrestrial 0.63% (6320 ppm) 0.016% (162 ppm) 0.00028 % (2.8)
abundance ppm)

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 These elements are classified as type a metals
(hard acids)
They are found as silicates and oxides in many
silicaceous materials.
Because of the lanthanide contraction the ionic
radii of Zr and Hf the same and as a result they are
virtually identical chemically.
They have similar ores and usually occur together.

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 Titanium
Extracted by the Kroll process of 1932
(a) From Rutile
TiO2 + 3C + 4Cl2 2TiCl4(g) + CO2 + 2CO (at 950o C)
TiCl4(g) + 2Mg Ti(s) + 2MgCl2(s)
Solid MgCl2 removed at 1000 C
(b) From ilmenite
Heat the ore with a reducing agent in a stream of chlorine
FeTiO3 + 7Cl2 + 6C 2TiCl4 + FeCl3 + 6CO (at 900o C)

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 The TiCl4 is fractionally distilled from the FeCl3 and
other impurities
TiCl4 reduced with molten magnesium in a sealed
furnace under Ar.
Molten MgCl2 is tapped off periodically and after
cooling, residual MgCl2 and any excess Mg are
removed by leaching with dilute HCl and water or
by distillation leaving titanium sponge.
This is ground and washed with aqua regia and
melted under argon or vacuum and cast into ingots.
Reduction with Na gives a more readily leached
product.

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 Zirconium and hafnium
Also produced by the Kroll process
Silicate ores are extracted as follows:
fused NaOH Na2SiO3 boiling water
ZrSiO4 ZrO2.xH2O + SiO2.H2O
Na2ZrO3
Sodium silicate
and zirconate HCl

ZrOCl2 + SiO2.H2O
Zirconyl chloride

NH3

Mg metal C +Cl2
Zr/Hf ZrCl4 ZrO2.xH2O (pure)
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 Separation of the metals
This is achieved by solvent extraction taking
advantage of the difference in solubilities of the
nitrates in tri-n-butyl phosphate or the
thiocyanates in hexone (methyl isobutyl ketone
or MIBK).
MIBK has quite low solubility in water, making it useful for
liquid-liquid extraction. It has a similar polarity to ethyl
acetate, but greater stability towards aqueous acid and
base.
MIBK is used as a solvent for CS in the preparation of the CS
spray used currently as teargas

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 Purification of metals
When metal with low O and N2 content is required.
The van Arkel-de Boer method is used.
Crude metal is heated in an evacuated vessel with
a little iodine at about 200o C when ZrI4 volatilizes.
A W or Zr filament is simultaneously heated to
1300o C which decomposes the ZrI4 to give pure Zr
which is deposited on the filament.

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 Chemistry
The most important oxidation state is +4.
Most compounds in this oxidation state are
covalent though Zr and Hf have oxides which are
more basic than Ti and give more extensive and
less hydrolysed aqueous chemistry- ionic sizes.
They react directly at high temperature with most
non-metals, particularly, O2, H2 reversibly) and in
the case of titanium, nitrogen (Ti burns in N2).

SCH 400 9
 Chemistry

Metals are pyrophoric when finely divided - care

should be taken when machining these
elements.
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 Uses of the metals
Titanium - a light ( density 57% that of steel) ,
strong, lustrous, corrosion-resistant (including
resistance to sea water and chlorine) metal with a greyish
colour.
Ti can be alloyed with other elements such as
Fe, Al, V, Mo etc, to produce strong lightweight
alloys for
aerospace (jet engines, missiles, and spacecraft),
military,
industrial process (chemicals and petro-chemicals,
desalination plants, pulp and paper), etc.
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 Uses of the metals
When alloyed with small quantities of metals such
as Al and Sn, it has the highest strength to density
ratio of any of the engineering metals.
About 95% of titanium ore extracted goes to
titanium dioxide (TiO2), an intensely white
permanent pigment used in paints, paper,
toothpaste, and plastics.
It is also used in cement, in gemstones, as an
optical opacifier in paper, and a strengthening
agent in graphite composite fishing rods and golf
clubs.
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 Uses of the metals
(b) Zirconium
Has a high corrosion resistance and in certain chemical
plants it is preferred to stainless steel, titanium and
tantalum.
Used in alloying in a variety of steels.
Cladding for uranium dioxide fuel rods in water cooled
nuclear reactors-for this it is alloyed with 1.5% tin.
due to its corrosion resistance, stability under irradiation,
and extremely low absorption of thermal neutrons.
Any Hf present has to be removed because it has very
high absorption of thermal neutrons (600 times more
so than Zr).
Production of bullet-proof steels
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 Uses of the metals

(c) Hafnium (Hf)

Due to high neutron absorption ability it is
used for reactor control rods in nuclear
submarines.

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Binary compounds
Tetrahalides are most important
TiF4, is white solid mp 284o C. It forms a polymer
in the solid state consisting of corner sharing
TiF6 octahedra.
TiCl4 is colourless liquid mp -24o C while TiBr4 is
an orange solid with mp 38o C and TiI4 is a dark
brown solid with mp 155o C.
The tetrahalides of Zr and Hf, MX4 are all white
solids.

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 The tetrafluorides are white solids prepared by the action
of anhydrous hydrogen fluoride on the tetrachlorides.
TiCl4 + 4HF TiF4 + 4HCl
They are not attacked by water.
Excess fluoride gives complexes such as TiF62-, ZrF62-
(octahedral), and ZrF73- (pentagonal bipyramidal).

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 MX4 (X = Cl, Br) are prepared by passing the
halogen over heated dioxide in the presence
of a reducing agent such as C.
MO2 + C + 2Cl2 MCl4 + CO2
All tetrachlorides are hydrolysed by water.
TiCl4 + 2H2O TiO2.2H2O + 4HCl
MCl4 + 2H2O MOCl2 + HCl (M = Zr or Hf)

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TiCl4
Colourless liquid (mp -36C, bp 136 C,
purngent odour)
Fumes in moist air (Why?)
Vigorously and completely hydrolyzed by
water
TiCl4 + 2H2O TiO2 + 4HCl
Used to produce Ziegler - Natta catalysts for
the polymerization of ethene and other
terminal alkenes.
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Alkene polymerization with TiCl4/AlEt3

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 Key steps: reduction of Ti(IV) to Ti(III) by AlEt3
and then substitution of Cl by Et ion on
surface of the fibrous, heterogeneous catalyst
system.
Instead of TiCl4, TiCl3 can be used as the
starting molecule for the complex.
The polymer so obtained has regular
arrangement of the monomers i.e is
isotactic.
Stronger
Higher densities than those produced by heat
alone (the atactic ones)
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 Limited to ethylene and other -
olefins like propylene.
Produces linear polymer, with very
few branches (e.g., high density
polyethylene, HDPE).
Capable of producing homo-/iso-
tactic polymers.
Most commercial initiators are
insoluble complexes or supported
on insoluble carriers.
Very complex mechanism, still
poorly understood for the
heterogeneous systems.
Termination is almost exclusively by
chain transfer.
Modern "high mileage" initiators
produce up to 1000's of kg per g
initiator.

Cossee-Arlman mechanism
Oxides
The most important TiO2, ZrO2 and HfO2.
3 crystalline forms of TiO2 (rutile, anatase, brookite; all
naturally occurring) are known.
TiO2 mainly used as a white pigment base in paints. It
has replaced 2PbCO3.Pb(OH)2 due to the fact that:
White lead forms PbS (black) in industrial
atmospheres during the production or weathering
of paint.
Pb is toxic
TiO2 has exceptionally high refractive index in the
visible region of the spectrum and is chemically
inert.
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Pigment grade TiO2

Rutile

o
Coke and chlorine at 950 C

Cannot operate with

Crude TiCl4
Treat with H2S or boil to reduce
the volatile impurity VOCl3
Pure TiCl4
Heat in oxygen above 1000oC
lower grade ores. It
will produce chloride
wastes from which
chlorine cannot be
recovered.

Base pigment
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 1. Cannot use rutile due
to its insolubility in
H2SO4
2. Can operate on lower
grade ores .
3. Accounts for 56% of
all the TiO2 produced.

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Compounds with oxoanions
Normal salts of Ti4+ cannot be prepared from
aqueous solutions because they yield basic
hydrolyzed species instead.
Even for Zr4+ and Hf4+, normal salts like
Zr(NO3)4.5H2O and Zr(SO4)2.4H2O can only be
isolated from sufficiently acidic solutions.
Basic salts and anionic complexes are readily
isolated (recall high oxidation states are
favoured by basic conditions)

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Compounds with oxoanions
Anhydrous nitrates can be prepared by the
action of N2O5 on MCl4.
Ti(NO3)4 forms as a white sublimable highly
reactive 8-coordinate compound (mp = 58o C),
Zr(NO3)4 is isostructural but Hf(NO3)4 sublimes
at 100o C as the adduct Hf(NO3)4.N2O5

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 Complexes of Ti group metals
A large number of coordination compounds of
the MIV metals have been studied and complexes
such as [MF6]2- and those with O- or N- donor
ligands are especially stable.
The MIV TM ions, though much smaller than their
M3+ predecessors in Group 3, are, nonetheless,
sufficiently large, bearing in mind their high
charge, to attain a coordination number of 8 or
more, which is certainly higher than is usually
found for most transition elements.
SCH 400 27
 Complexes of Ti group metals
Eight is not a common coordination number for
Ti, but is very well known for Zr and Hf.
The spherical symmetry of the d0 configuration
allows a variety of stereochemistries.
Examples of 8-coordinate Zr(IV) complexes are
the carboxylate, Zr(O2CR)4,
the acetylacetonate, Zr(acac)4,
the oxalate, Na4[Zr(ox)4], and
the nitrate, Zr(NO3)4.

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 Complexes of Ti group metals
Lower oxidation states are rather sparsely
represented for Zr and Hf.
Even for Ti they are readily oxidized to +4 but
they are undoubtedly well defined.
In aqueous solution Ti3+ can be prepared by
reduction of Ti4+, either with Zn and dilute
acid or electrolytically, and it exists in dilute
acids as the violet, octahedral [Ti(H2O)6]3+ ion.

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 Complexes of Ti group metals

Ti3+ is subject to a certain amount of hydrolysis,

normal salts such as halides and sulfates can be
separated.
Zr3+ and Hf3+ are known mainly as the trihalides
or their derivatives and have no aqueous
chemistry since they reduce water.

SCH 400 30
Complexes of Ti group metals

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