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The vanadium group

Lecture 5
Physical properties
Property 23V 41Nb 73Ta

No of Natural 2 1 2
isotopes
Electron config. [Ar]3d34s2 [Kr]4d35s2 [Xe]4f145d36s2
Electronegativity 1.6 1.6 1.5
Atomic radius (pm) 134 146 146
Density (25 oC) g/ 6.11 8.57 16.65
cm3
MP/oC 1915 2468 2980
BP/oC 3350 4758 5534
Patronite VS4, Columbite or Columbite or
Common ores vanadite tantalite (Fe, tantalite
PbCl2.3Pb3(VO4)2 Mn)M2O6 M = Nb, (Fe,Mn)M2O6 (M =
carnotite Ta. Pyroclore, Nb, Ta)
K(UO2)(VO4).1.5H2O NaCaNb2O6F
Terrestrial 0.0136% (136 ppm) 0.0020% (20 ppm) 0.00017% (1.7
abundance ppm)
Extraction of vanadium
Crushed ore or vanadium residue

roast with NaCl or Na2CO3


o
at 850 C
2K(UO)VO4+7Na2CO3 2Na2(UO2)(CO3)3 + 2Na3VO4 + 2K2CO3
NaVO3 (sodium vanadate)

Leach with water and acidify with


H2SO4 to pH 2-3

Red cake (a polyvanadate)

fuse at 700oC

V2O5 (Black technical grade)


Ferrisilicon or Al or Fe or Fe ore
reduction with Ca
in an electric furnace in the presence
of line to remove SiO2 as a slag or Ca silicate

V Ferrovanadium (V/Fe alloy) (80% of all V produced)


Uses of vanadium
80% of the vanadium is used as an additive to
steel.
Reason
It forms V4C3 with any carbon present and this
disperses to produce fine grained steel with
increased resistance to wear and is stronger at high
temperatures. Such steels are used in the
manufacture of springs and high-speed tools.
Niobium and tantalum
The ore is fused with alkali or digested with
acids to solubilize the metals.
According to Marignac, dissolution in HF acid
yields the sparingly soluble K2TaF7 and the
soluble K2NbOF5.2H2O.
Filtration affords separation.
Niobium and tantalum
Presently, solvent extraction is used to separate
the metals. For example, Ta can be extracted
from dilute aqueous HF solutions by methyl
isobutyl ketone (MIBK). Increasing the acidity of
the aqueous phase allows Nb to be extracted into
a fresh batch of MIBK.
The metal complexes are then obtained from the
organic phases by stripping with water salts. After
drying and conversion to M2O5, the metals are
obtained by reduction of the pentoxides with Na,
carbon or the metal carbide.
Uses of the metals
Nb is used in the production of numerous stainless
steels for use at high temperatures and Nb/Zr wires
used in superconducting magnets.
Ta is used in construction of chemical plants,
especially where it can be used as a liner inside
cheaper metals.
This is because it has extreme corrosion resistance due to
the formation of an exceptionally tenacious film of oxide.
Ta is also used in bone repair and internal suturing due
to its complete inertness to body fluids.
Ta is also used in manufacture of capacitors where the
oxide film is an efficient insulator.
Physical properties
They have high mp, bp and enthalpies of
atomization due to stronger metallic bonds.
These quantities reach their maximum in this
and the next group.
Element Ti V Cr Mn
M.P./oC 1667 1915 1900 1244
B.P/oC 3285 3350 2690 2060
Zr Nb Mo Tc
1857 2468 1620 2200
4200 4758 4650 4567
Hf Ta W Re
2267 2980 3422 3180
4450 5534 5500 (5650)
Physical properties
In the first transition series V is the last element
before some of the (n-1)d electrons begin to
enter the inert electron-core of the atom. As a
result, it has the highest melting point in the
series and it is the last element whose
compounds in the group oxidation state are not
strongly oxidizing.
In the second and third transition series, the
entry of (n-1)d electrons into the electron core is
delayed somewhat and it is molybdenum and
tungsten whose melting points are the highest.
Chemical properties
V and Nb are attacked by hot conc. mineral
acids but are resistant to fused alkalis.
Ta , unless heated, is only attacked by oleum,
HF or more particularly HF/HNO3 mixture and
fused alkalis.
Generally resistant to corrosion due to the
formation of surface films of oxides which are
particularly effective in the case of Ta.
Chemical properties
Lower oxidation states become unstable down the
group. Thus the most stable oxidation state for V
is +4, but even +3 and +2 (which are admittedly
strongly reducing) have well characterized cationic
aqueous chemistry (i.e. they form such ions as
[V(H2O)6]3+and [V(H2O)6]2+ in aqueous media).
In contrast most of the chemistries of Nb and Ta
are confined to the group oxidation state +5. They
provide no counterparts to the cationic chemistry
of V in the +2 and +3 oxidation states.
Chemical properties
In vanadium, the +4 oxidation state is predominantly
found as VO2+ (vanadyl) ion. It is the most stable
diatomic cation known and retains its identity
throughout a wide variety of reactions and forms
many complexes. For Nb and Ta this is best
represented by their halides.
In low oxidation states Nb and Ta form a series of
cluster compounds based on octahedral M6X84+ or
M6X126+ units. These are formed as a consequence of
the strength of metal-metal bonding in this part of
the periodic table (reflected by high mp and
enthalpies of atomization).
Binary compounds
Oxidation +5 +4 +3 +2
state
V V2O5 VO2 V2O3 VO
Nb Nb2O5 NbO2 - (NbO)
Ta Ta2O5 TaO2 - (TaO)

The M2O5 are most important.


They are all amphoteric with V2O5 more so.
V2O5 is the most important and most studied. It is used
as a catalyst in the contact process of producing
sulphuric acid.
Vanadium pentoxide
Amphoteric
It is soluble in acids giving salts of the VO2+
(dioxovanadium) cation.
It dissolves in alkalis to give colourless solutions which
contain the orthovanadate ion VO43- at high pH. At
intermediate pHs a series of hydrolysis-polymerization
reactions occur yielding isopolyvanadates.
The equilibria involved in their formation as well as
their stoichiometries and structures have been
confused and disputed.
Vanadium pentoxide

It is sparingly soluble in water to give pale yellow


acidic solutions.
Mild oxidizing agent when compared to those of
Cr Mn and Fe.
The potential application of these metallates is in
catalysis either as catalysts or catalyst supports.
Vanadium pentoxide
Best prepared by decomposition of NH4VO3
Heat
NH4VO3 V2O5 + 2NH3 + H2O

Also reaction of V with excess O2 which gives V2O5


as the ultimate compound. This is however
contaminated with lower oxides and is therefore
not a good preparative method.
V2O5 losses oxygen reversibly. This may be the
reason why it is such a versatile catalyst.
Niobates and tantalates

Fusion of the M2O5 (M = Nb and Ta) with excess


alkali hydroxides or carbonates followed by
dissolution in water produces solutions of
isopolyanions.
These are not as extensive as those of vanadium.
For example, the presence of MO43- in strongly
alkaline solutions is uncertain.
Below pH 7 for Nb and pH 10 for Ta precipitation
of hydrous oxides occurs.
LiNbO3 and LiTaO3 have been found to be
attractive than quartz as frequency filters in
communication devices
The halides
Oxid
Fluorides Chlorides Bromides Iodides
state
VF5 - - -
+5 NbF5 NbCl5 NbBr5 NbI5
TaF5 TaCl6 TaBr5 TaI5
VF4 VCl4 VBr4 -
+4 NbF4 NbCl4 NbBr4 NbI4
- TaCl4 TaBr4 TaI4
VF3 VCl3 VBr3 VI3
+3 NbF3(?) NbCl3, NbBr3 NbI3
TaF3(?) TaCl3 TaBr3 -
+2 VF2 VCl2 VBr2 VI2
The halides
There are no VX5 (X = Cl, Br, I). It only forms VF5.
This is because V5+ is too strong an oxidizing agent to coexist
with the large Cl-, Br-, and I- anions.
Nb and Ta are less polarizing and can give all the halides
including MI5 (the only elements to do so apart from
protactinium).
F- is a hard base and can stabilize high oxidation states.
V does not form VI4 for the same reason as above.
There are no MX2 (M = Nb, Ta; X = F, Cl, Br and I).
This is because the metals form strong metal-metal bonds such
that to separate the metal atoms and keep them apart requires high
energy and many ligands.
There are no known TaF4, and TaI3.
The Pentahalides
The MX5 are prepared by direct action of the
halogens on the metal.
They are all relatively volatile, hydrolysable
solids in which the metals attain octahedral
coordination by halide bridges.
For example, VF5 is a viscous liquid because it
forms infinite chains with V-F-V bridges,
NbF5 and TaF5 form tetramers similar to MoF5
and WF5
The pentabromides and pentachlorides of Nb
and Ta form dimers
The Pentahalides

Alternative representations of: (a) infinite chains of vanadium atoms


in VF5, (b) tetrameric structures of NbF5 and TaF5, and (c) dimeric
structure of MX5 (M = Nb, Ta; X = C1, Br).
F F
F F F
F F
F V F F F F
V V
V F
F F F F F
F F F
F F Cl Cl
F Cl Cl
Nb Cl Nb
F F F Nb Cl
F F F Cl Cl
F Cl
Nb Nb Cl
F F
F F F F F
Nb
F F
F
The Pentahalides
The MX5 are sublimable giving trigonal bipyramidal
structures. They are Lewis acids, forming adducts with
Lewis bases with diminishing ability from fluorides to
iodides (why?).
reflux
NbCl5 + 2py o NbCl4(py)2
140 C
The colours of the pentahalides vary from white
fluorides yellow chlorides, orange bromides to brown
iodides due to LM charge transfer.
The decreasing energy of the charge transfer bands
responsible for these colours is a reflection of the
increasing polarizability of the anions from F- to I-.
The tetrahalides
The VX4 can be prepared by direct action of the
elements but are unstable.
For example, VF4 dispropotionates to VF5 + VF3.
VCl4 and VBr4 tend to dissociate to VX3 + X2 and
so require presence of excess halogen during
preparation.
The tetrahalides
The known tetrahalides of Nb and Ta (except NbI4
which is prepared by thermal decomposition of
NbI5) are generally prepared by reduction of the
corresponding pentahalide and are readily
hydrolyzed.
The MX4 (X = Cl, Br, M = Nb, Ta) are brown to
black solids with a chain structure in which pairs
of metal atoms are displaced towards each other,
so facilitating the interaction which leads to their
diamagnetism.
The tetrahalides

a) The sheet structure of NbF4


b) The chain structure of MX4 (M = Nb, Ta; X = C1, Br, I)
showing the displacement of the metal atoms which
leads to diamagnetism.
The trihalides
The vanadium trihalides are all crystalline,
polymeric solids in which the vanadium is 6-
coordinate.
They are coloured and have magnetic moments
slightly lower than the spin-only value of 2.83BM
corresponding to 2 unpaired electrons.
They are easily oxidized by air and are very
hygroscopic, forming aqueous solutions of
[V(H2O)6]3+. VF3 is neither very soluble nor readily
oxidized
The trihalides
NbF3, TaF3 and TaI3 may not exist. The 5 known
trihalides of Nb and Ta are dark coloured, rather
unreactive materials. The Nb-Cl system has been
the most thoroughly.
They are nonstoichiometric and the composition
"MX3" is best considered as a single unexceptional
point within a broad homogeneous phase based
on hcp halide ions.
The dihalides
The dihalides of V are prepared by reduction of
the corresponding trihalides.
They have simple structures based on the close-
packing of halide ions: the rutile structure for VF2,
and the CdI2 structure for the others.
They are strongly reducing and hygroscopic,
dissolving in water to give lavender- coloured
solutions of [V(H2O)6]2+.
Q. Compare and contrast the halides of V, with
those of Nb and Ta in high and low oxidation states
Rutile (TiO2) structure

Ti atoms are grey;


O atoms are red.

Rutile has a primitive tetragonal unit cell, with unit cell


parameters a=4.584, and c=2.953. The titanium cations
are surrounded by an octahedron of 6 oxygen atoms. The
oxygen anions have a co-ordination number of 3 resulting in
a trigonal planar co-ordination
CdI2 structure

In cadmium iodide the iodide anions form a hexagonal close


packed arrangement while the cadmium cations fill all of the
octahedral sites in alternate layers. The resultant structure
consists of a layered lattice.
The dihalides
The dihalides of Nb and Ta are cluster compounds
obtained by high-temperature reductions of NbX5
or TaX5 with the metals (or Na or Al).
Their structures are based on the cluster unit
[M6X12]n+ consisting of octahedral clusters of metal
atoms with the halogen atoms situated above each
edge of the octahedra.
The dihalides
These may be surrounded by:
a) Four similar units, with each of which a halogen
atom is shared, producing a sheet structure with
the composition [M6X12]X4/2 = M6X14 (i.e. MX2.3).
These compounds are diamagnetic as a result of
the metal-metal bonding.
b) Six similar units, with each of which a halogen
atom is shared, producing a three-dimensional
array with the composition [M6X12]X6/2 = M6X15
(i.e. MX2.5).
They have magnetic moments corresponding to 1
unpaired electron per hexamer and so indicate
the same metal-metal bonding within the cluster
as in (a).
Compounds with Oxoanions
The only simple oxoanion salts are the sulfates of
vanadium in the oxidation states +3 and +2.
These can be crystallized from aqueous solutions as
hydrates and are both strongly reducing.
They give rise to blue-violet alums,
MV(SO4)2.12H2O, the ammonium alum being air-
stable when dry.
They also form the reddish-violet Tutton's salts,
M2V(SO4)2.6H2O , the ammonium analogue of
which is again relatively more stable to oxidation.
Biochemistry of Vanadium
[V(5-C5H5)2Cl2] has anti-tumor activity.
A number of nitrogen fixing bacteria contain
vanadium.
Example,
Azotobacter contains three distinct nitrogenase
systems based in turn on Mo, V and Fe, each of which
has an underlying functional and structural similarity.
Models are being sought that can convert N2 to
NH3 at ambient conditions. To this end complexes
such as [Na(thf)]+[V(N2)2(dppe)2 (dppe =
Ph2PCH2CH2PPh2) have been prepared from VCl3
and shown to liberate NH3 on acidification.