INTODUCTION

Element Symbol Electronic

structure

Vanadium V [Ar]3d34s2
Niobium Nb [Kr]4d35s2
Tantalum Ta [Xe]4f145d36s2
Vanadium
Vanadium is found only in
chemically combined form in nature.
Andrés Manuel del Río discovered
vanadium in 1801 by analyzing a
new lead-bearing mineral he called
"brown lead," and named the new
element erythronium (Greek for
"red") since, upon heating, most of
its salts turned from their initial color
to red. The element was
rediscovered in 1831 by Nils Gabriel
Sefström, who named it vanadium
after the Scandinavian goddess of
beauty and fertility, Vanadis (Freya).
Niobium
Niobium has physical and
chemical properties similar to
those of the element tantalum,
and the two are therefore difficult
to distinguish. The German
chemist Heinrich Rose determined
in 1846 that tantalum ores contain
a second element, which he
named niobium.
Niobium also usually called
Columbium
Tantalum
Tantalum is is a chemical
element with the symbol Ta and
atomic number 73. Previously
known as tantalium, the name
comes from Tantalus, a hero in
Greek mythology
Tantalum was discovered in
Sweden in 1802 by Anders
Ekeberg.
 ABUNDANCE
Element ppm Relative
Abundance

Vanadium 136 19
Niobium 20 32
Tantalum 1,7 53
 Vanadium
Vanadium is the nineteenth most abundant
element by weight in the earth’s crust, and is the
fifth most abundant transition element. The
element occurs naturally in about 65 different
minerals and in fossil fuel deposits.
Vanadium is also present in bauxite and in
fossil fuel deposits such as crude oil, coal, oil shale
and tar sands. In crude oil, concentrations up to
1200 ppm have been reported. Vanadium has also
been detected spectroscopically in light from the
Sun and some other stars.
 Vanadinite Carnotite
PbCl2.3Pb3(VO4)2 (K2(UO2)2(VO4)2·3H2O)

Patronite
(VS4)
 Niobium and Tantalum
Niobium and tantalum usually occurs together.
Niobium is the 33rd most abundant element by
weight in the earth’s crust, and tantalum is 53rd
The free element is not found in nature, but it
does occur in minerals.

Columbite
[(Fe, Mn)Nb,2O6]
 Pyrochlorite Tantalite
[CaNaNb2O6F] [(Fe,Mn)Ta2O6]
 OXIDATION STATE
 The maximum oxidation state is (+V)
 All three elements show the full range of
oxidation state from (-I) to (+V)
 For vanadium the (+II) and (+III) states
are reducing, (+IV) is stable, and (+V) is
oxidizing.
 For Nb and Ta the (+V) state is by far most
stable
 V(+V) is reduced by zinc and acid to V2+ ,
Nb(+V) is reduced to Nb3+ but Ta is not
reduced
 SIZE
Electronic Covalen Ionic Radius
Structure t Radius M2+ M3+
V [Ar] 3d3 4s2 1,22 0,79 0,64
Nb [Kr] 4d3 5s2 1,34 - 0,72
Ta [Xe] 4f14 5d3 6s2 1,34 - 0,72

The atom are smaller than those of the Ti group

do to the poor shielding of the nucleus by d
electrons
The covalent and ionic radii of Nb and Ta are
identical because of the lanthanida contraction
Consequently these two element have very
similar properties, occur together, and very
difficult to separated
Vanadium metal is obtained via a multistep process that begins with the
roasting of crushed ore with NaCl or Na2CO3 at about 850 °C to give sodium
metavanadate (NaVO3). An aqueous extract of this solid is acidified to give
"red cake", a polyvanadate salt, which is reduced with calcium metal. As an
alternative for small scale production, vanadium pentoxide is reduced
with hydrogen or magnesium.
the first step in the processing is the reaction of the oxides with hydrofluoric acid
Ta2O5 + 14 HF → 2 H2[TaF7] + 5 H2O
Nb2O5 + 10 HF → 2 H2[NbOF5] + 3 H2O

Exploits the differing solubilities of the complex niobium and tantalum fluorides,
dipotassium oxypentafluoroniobate monohydrate (K2[NbOF5]·H2O) and
dipotassium heptafluorotantalate (K2[TaF7]) in water

The complex niobium and tantalum fluorides are extracted separately from
the organic solvent with water and either precipitated by the addition
of potassium fluoride to produce a potassium fluoride complex, or precipitated
with ammonia as the pentoxide:

H2[NbOF5] + 2 KF → K2[NbOF5]↓ + 2 HF

Followed by:

2 H2[NbOF5] + 10 NH4OH → Nb2O5↓ + 10 NH4F + 7 H2O

 vanadium produced is used as ferrovanadium or as a steel additive

 vanadium steel was used for applications in axles, bicycle

frames, crankshafts, gears, and other critical components

 Vanadium stabilizes the beta form of titanium and increases the strength
and temperature stability of titanium. Mixed with
aluminium in titanium alloys it is used in jet engines and high-speed
airframes

 Vanadium is compatible with iron and titanium, therefore vanadium foil is

used in cladding titanium to steel

 vanadium pentoxide V2O5, is used as a catalyst in manufacturing sulfuric

acid by the contact process and as an oxidizer in maleic anhydride
production
 Vanadium pentoxide is also used in making ceramics.

 vanadium dioxide VO2, is used in the production of glass coatings, which

blocks infrared radiation (and not visible light) at a specific temperature

 Vanadium oxide can be used to induce color centers in corundum to create

simulated alexandrite jewelry, although alexandrite in nature is
a chrysoberyl.

 Vanadate can be used for protecting steel against rust and corrosion
by electrochemical conversion coating.

 Lithium vanadium oxide has been proposed for use as a high energy density
anode for lithium ion batteries
• Lithium niobate, which is a ferroelectric, is used extensively in mobile
telephones and optical modulators, and for the manufacture of surface
acoustic wave devices

• Niobium is used as a precious metal in commemorative coins, often with

silver or gold

• Niobium is used with iron and other elements in stainless steel alloys and
also in alloys with a variety of nonferrous metals, such as zirconium, Niobium
alloys are strong and are often used in pipeline construction.

• Niobium is also used for jewelry.

• At cryogenic temperatures, niobium is a superconductor

• Niobium is an effective microalloying element for steel

 The oxide is used to make special high refractive index glass for camera
lenses.

 The high melting point and oxidation resistance lead to the use of the metal
in the production of vacuum furnace parts.

 It is also occasionally used in precious watches e.g. from Hublot, Montblanc

and Panerai.

 Tantalum is also highly bioinert and is used as an orthopedic implant material

 Tantalum is also used to produce a variety of alloys that have high melting
points, are strong and have good ductility
GENERAL PROPERTIES
• V, Nb, and Ta are silvery coloured
metals with high melting points.
• V has the highest melting point in
the first row transition elements.
This is associated with the maximum
participation of d electrons in
metallic bonding.
• The pure metals V, Nb, and Ta are
moderately soft and ductile.
• They are extremely resistant to corrosion due to the
formation of a surface film of oxide.
• At room temperature, they are not affected by air, water, and
acids.
• V also dissolves in oxidizing acids such as hot concentrated
H2SO4, HNO3, and aqua regia.
• V is unaffected by alkali, showing that it is completely basic,
but Nb and Ta dissolve in fused alkali.
 Some physical properties

Covalent Ionic radius (Ǻ) Melting Boiling Density Pauling’s

radius (Ǻ) point point (g.cm-3) electroneg
M2+ M3+ (OC) (OC) ativity
V 1.22 0.79 0.640 1915 3350 6.11 1.6
Nb 1.34 - 0.72 2468 4758 8.57 1.6
Ta 1.34 - 0.72 2980 5534 16.65 1.5

 At high temperature, all three metals react with many non-

metals.
 V forms many different positive ions, but Nb and Ta form
virtually none.
 The tendency to form simple ionic compounds decreases as
the oxidation state increases.
 The basic properties of the oxides M2O5 (V2O5, Nb2O5, and
Ta2O5) increase down the group.
 Whilst V2+ and V3+ are well known, Nb(II), Ta(II), Nb (III), and
Ta (III) are not ionic but exist as cluster compounds M6X12, in
which groups of metal atoms are bonded together.
COLOUR
 COLOUR
• Commonly arises from d-d electronic
transitions.
• From defects in the solid state and from
charge transfer spectra.
• The particular COLOUR
energies of radiation
that a substance
absorbs dictate the
colors that it
exhibits
 COLOUR
• The oxidation states below (+V) are colored
because they have an incomplete d shell of
electrons and give d-d spectra.
• NbF5, TaF5 and TaCl5 are white, but V2O5 is red
or orange, NbCl5 is yellow, NbBr2 is orange and
NbI5 is brass colored. The colors arise because
of charge transfer.
Compounds with Nitrogen,
Carbon and Hydrogen
 Compounds with Nitrogen

HIGH TEMPERATURE

Vanadium Interstitial
group
nitrogen
nitrides (MN)
 VanadiumCompounds with Carbon
group
carbon MC and MC2

Example:
NbC and TaC are interestial, refractory and very hard.
TaC has the highest melting point (3800 C)
VC2 are ionic and react with water, liberating ethyne.
 VanadiumCompound wit
hydrogen
Hydrogen
Nonstoichiometric
group hydrydes

Note:
*The amount of hydrogen absorbed depends on the
temperature and pressure.
*The metal lattice expands as hydrogen interstitial positions.
*The density of hydrides are less then that of the metal
*It’s difficult to decide if these are true compounds or solids
solution
‫هللا‬ • V [Ar] 3d3 4s2
Preface
(-I), (0), (I), (II), III, IV, V
• Nb [Kr] 4d3 5s2 (-I), (0), (I), (II), III, (IV), V
• Ta [Xe] 4f14 5d3 6s2 (-I), (0), (I), (II), III, (IV), V

• Poor shielding effect by the d and f nucleus at

Tantalum make its radii become smaller as same
as Nb (1,34 Å)
• Covalent and ionic radii of Nb and Ta are
identical because the lanthanide contraction
• Nb and Ta have very similar properties
• V stable in +IV oxidation states, Nb and Ta in +V.
‫هللا‬

HALIDES (+V)
‫هللا‬ • When Vanadium is heated with halogen,
halides of different oxidation states are
formed. They are VF5, VCl4, VBr3,VI3.
• While Nb and Ta react with all of halogens
on heating to give pentahalides MX5.
• All the halides are volatile, covalent and
hydrolyzed by water (ionic properties)
‫هللا‬ • V forms pentafluorides, but Nb and Ta
form the full of the elements or by the
reactions
M2O5 + F2 MF5

heat 600C
2VF4 VF5 + VF3
disproportionates

NbCl5 or TaCl5 + F2 MF5

NbCl5 or TaCl5 + HF MF5

‫هللا‬
Oxidation states
(+II) (+III) (+IV) (+V)
VF2 , blue VF3 , yellow- VF4 , green VF5 , colorless
VCl2 , pale green green VCl4, reddish (liquid)
VBr2 , orange- VCl3 , red-violet brown -
brown VBr3 , brown VBr4 , magenta -
VI2 , red solution VI3 , black - -
- brown NbF4 , black NbF5, white
- (NbF3) * , blue NbCl4 , violet NbCl5 , yellow
- NbCl3, black NbBr4 , Brown NbBr5 , orange
- NbBr3 , brown NbI4 , grey NbI5 , brass
- NbI3 , - TaF5 , white
- (TaF3) *, blue TaCl4 , black TaCl5 white
- TaCl3, black TaBr4 , Blue TaBr5 , yellow
- TaBr3 TaI4 , TaI5 , black
-
‫هللا‬ • The oxidation states blelow (+V) are
coloured because they have incomplete d
shell of electrons and give d-d spectra.
• The (+V) states has d0 configuration and
VF5 is colourless. But NbF5, TaF5, V2O5, and
etc have colour because charge transfer.
• Electron from ligand (halogen atom)
transferred into central ion and give
spectra by excitation between t2g and eg
orbital
• VF5 are colourless, but NbF5 and TaF5 are
solids
‫هللا‬ • The fluorides are built if octahedral MF6
units with two cis fluorine atoms in each
octahedron acting as bridging groups V-F-
V with other octahedra
• VF5 forms long chain of octahedra , but
NbF5 and TaF5 form cyclic tetramers with
with four octahedra joined in this way
‫هللا‬ • Solid NbCl5 and TaCl5 are dimeric with
two octahedra joined by sharing two
corners, i.e. one edge
‫هللا‬ • All of the pentahalides can be sublimed
under an atmosphere of the appropriate
halogen. In the vapour phase they
probably exist as monomeric trigonal
bipyramides.
‫هللا‬ • The pentafluorides all react with F- ion,
forming octahedral [MF6]- complexes
• As in Titanium group, the heavier element
can form complexes with higher
coordination number
• With high concentration of F- the complexes
[NbOF5]2-,[NbF7]2-,[TaF7]2- are formed
• The structures of the seven seven-
coordinate species are capped trigonal
prisms
• With an even higher concentration of F-, Ta
forms [TaF8]3- which is an an octahedron
with an extra atom in one of the faces.
‫هللا‬ • On warming, the halides MF5 and MCl5
with donors such as dimethyl ether
(CH3)2O or dimethyl sulphoxide (CH3)2SO,
the halides extract O and form
oxochlorides MOCl3.
• Oxohalides are also form the
pentahalides are heated in air.
• VOCl3 can also be made by heating any
V2O5 with Cl2 (or sometimes C and Cl2)
• The oxohalides are tetrahedral in shape
‫هللا‬ • The pentahalides react with N2O4 in
giving solvated nitrates such as
NbO2.NO3.0,67MeCN, and unhydrous
nitrates such as NbO(NO3)3
• The (+V) halides have a d0 configuration,
and cannot give d-d spectra.
• The fluorides are white but the other
halides are coloured due to charge
transfer spectra.
‫هللا‬

HALIDES (+IV)
‫هللا‬ • All the tetrahalides are known except
TaF4. whose nonexistence is consistent
with the fact that [TaF5]4 should be the
least reducible halide of these elements
• these may be prepared as follows:
V + Cl2 VCl4

Reduce with
NbX5 or TaX5 H2, Al, Nb or Ta
MX4

V + HF VF4
‫هللا‬ • VCl4 is tetrahedral in the gas.
• The d1 configuration of V(+IV) would be
expected to make this unstable and to
cause distortion.
• In the liquid it is dimeric.
• NbF4 is a black, paramagnetic involatile
solid made up of regular octahedra joined
in a chain by their edges.
• The tetrachlorides, tetrabromides and
tetraiodides of Nb and Ta are also brown-
black solids and are diamagnetic.
‫هللا‬ • In NbI4, the structure is a chain of
octahedra joined by their edges.
• The Nb atoms are displaced from the
centre of the NbI6 octahedron and
occur in pairs, thus permitting weak Nb-
Nb bonds of lenght 3.20 Ȧ, and pairing
the previosly unpaired electron spins.
‫هللا‬ • NbCl4 is similar and has M-M bonds of
lenght 3.06 Ȧ.
Room temperature
2VCl4 2VCl3 + Cl2 (VCl5 does
not exist)
‫هللا‬ 2VF4
600oC
VF3 + VF5

400oC
2TaCl2 TaCl3 +TaCl5

• They also hydrolyse with water:

HO
VCl4 2
VOCl2

5H2O
4TaIVCl4 Ta2VO5 + 2TaIIICl3 +10HCl
 (+III) HALIDES

 V and Nb are known as trihalides but Ta is not.

 V, Nb, and Ta are reducing, have a d2
configuration and are brown or black in colour.
 V-Halides

Example :
 VCl3 and VBr3 (They can be made from the
elements)
 VF3 (it is made from VCl3 and HF)
It can be crystallized from water giving [VF3
(H2O)3]
 VI3 (It dispropriates VI3  VI2 + VI4 )
 Nb and Ta Halides

 The trihalides of Nb and Ta are typically non

stoichiometric.
 In NbCI3, the Nb ions occupy octahedral holes in a
distorted hexagonal closed-packed array of Cl- ions
in such a way that Niobium atom in three adjacent
octahedral are close enough to be bonded together
into a metal cluster.
 Spectra
• The V3+ has a d2 configuration
• The two d electrons occupy two of the t2g
orbitals, i.e. any two from dxy, dxz, and dyz.
• The groud state is triply degenerate and has the
symbol 3T1g.
• There are three degenerate ways of arranging
these two electrons in orbitals perpendicular to
each other :
(dxy)1 (dz2)1 (dxz)1 (dx 2- y 2)1 and (dyz)1 (dx 2- y 2)1
• This state is the 3T2g, somewhat higher in
energy is another triply generate state written
as 3T2g in which the orbitals occupied are at
450 to each other :
(dxy)1 (dx2y2)1 (dxz)1 (dz 2)1 and (dyz)1 (dz 2)1
• if both electrons are promoted to the eg level
then assuming they remain unpaired the only
arrangement possible is :
(dx 2- y 2)1 (dz2)1
• This state has the symbol 3A2g. Thus there are
three possible transitions from the ground
state to excited states with the same
multiplicity
3T (F) → 3T
1g 2g
3T (F) → 3T (F)
1g 1g
3T (F) → 3A
1g 2g
 (+II) HALIDES

 All the vanadiuum dihalides are known

 The VX2 compounds are prepared by reducting the

trihalides with Zn/ acid in aqueous solution

 VF2 has a rutile TiO2 structure and the other have a CdI2

type layer structure

 The dihalides are dissolve in water to yield blue–purple

solutions of [V(H2O)6]2+
 High temperature reduction of the pentahalides NbX5 and TaX5
with sodium or aluminium yields a series of lower halides such as
M6Cl14, M6I14, Nb6F15, Ta6Cl15 and Ta6Br17. these are all based on
the [M6X12]n+ unit. For example:
• If one of these cllusters is inked by halogen bridges
to four other clusters, the composition is [M6X12]
(the cluster) + ½ X4 (the halogens bridges)
• The structure of this type are sheet-like, and
diamagnetic because of the metal-metal bonding.
• If a cluster may be linked to six other clusters by
halogen bridges, giving a three-dimensional structure
and a formula of [M6X12] + ½ X6
• These are paramagnetic and the magnetic moment
corresponds to one unpaired electron.
• A very unusual structure is found in Nb6I11, where the
six Nb atoms form ann octahedral cluster, but eight
iodin atoms are situated above the eight faces of the
octahedral.
 STANDARD REDUCTION POTENTIALS
Acid Solution
Oxidation state
+V IV III +II +I 0
V(OH)4+ +1.0 VO2+ +0.34 V3+ -0.26 V2+ -1.18 V

-0.26
Nb2O5 0.05 Nb3+ -1.10 Nb

-0.64
T2O5 Ta
OXIDE

The metals all react with oxygen at elevated

temperatures and give pentoxide M2O5. V2O5 is orange
or red and can be obtained by acidifying ammonium
metavanadate.

or heating it
 (+ V) Oxide
M2O5 making
• V2O5 is best made by heating ammonium
metavanadate.
• Nb2O5 and Ta2O5 commonly made by ignition of other
Nb or Ta compound in air

Color
Nb2O5 and Ta2O5 are white.
V2O5 is orange or red due to the charge of transfer
Oxidation states of vanadium, from left +2 (lilac), +3 (green), +4
(blue) and +5 (yellow).
 Table 21.5 Oxides

Oxidation State
(+II) (+III) (+IV) (+V)
VO V2O3 VO2 V2O5
NbO - NbO2 Nb2O5
(TaO) - TaO2 Ta2O5
Properties
• V2O5 is amphoteric, but mainly acidic.
• With very strong NaOH form colourless orthovanadate ions
VO43-
• At slightly higher pH these polymerize to form a wide range of
isopolyacids called polyvanadates.

Na6(H2O)20(V10O28)·4H2O
• Dissolves in very strong acis, forming eventually the pale yellow
dioxovanadium(V) or ion VO2+
Some others reaction:

V2O5 + 6HCl + 7H2O → 2[VO(H2O)5]2+ + 4Cl− + Cl

V2O5 + 2HNO3 → 2VO2(NO3) + H2O
V2O5 + 3SOCl2 → 2VOCl3 + 3SO2
• Though Nb2O5 and Ta2O5 react with HF and form niobates and
tantalates when fused with NaOH, they are described as
unreactive rather than amphoteric

Structure

• V2O5 is unusual and consist of distorted trigonal bypiramids of

VO5 units sharing edges with other units to form zig-zag double
chains. Its use as catalyst in the Contact Process has been
mentioned previously. The catalytic may be because it can
reversibly lose or gain oxygen when heated.
(+IV) oxides

• V2O5 can be made from V2O5 with mild reducing

agents such as Fe2+ , SO2 or axlic acid.
• Vanadium(+IV) has a d1 configuration and VO2
dark blue color.
• The oxide is amphoteric, but is more basic than
acidic. In acids it forms blue solutions containing
the oxovanadium(IV) ion VO2+ .
• This is commonly called the vanadyl ion.
• A large number of vanadyl compounds are
known: vanadyl sulphate VOSO4 and vanadyl
halides VOX2.
• Several vanadyl complexes are also known,
[VOX4]2-,[VO(oxalate)2]2-,
[VO(bipyridi)2Cl]+,[VO(NCS)4]2- and
[VO(acetylacetone)2].
The Structure of Vanadyl acetylactone
[VO(acetylactone)2]
 (+III) oxides
• V2O3 is nonstochiometric (VO1.35-1.5) and contain simple ions
arranged in the corundum Al2O3 type of structure.
• It can be produced by high temperature reduction of V2O5 with
carbon orhydrogen, or by electrolytic reduction of a vanadate.
• The oxide is completely basic.
• It dissolve in acids, forming blue or green hydrated ions [V(H2O)]3+,
and these solutions are quite strongly reduction.
• Addition of NaOH precipitates hydrated V(OH)3, but this has no
tendency to dissolve in excess NaOH.
• The oxidation state (+III) has a d2 configuration, and the oxide is
black and the hydrated ions is blue.
• A considerable number of octahedral complexes are known such
as [V(H2O)6]3+ , [VF6]3- , [V(CN)6]3- and [V(oxalate)3 ]3-
• vanadium also forms a triacetate complex ,
which is dimeric [VIII 2(acetate)3]3-.
• The structure is related to the structures of
chromium (II) acetate [Cr2(acetate)4.(H2O)2]
and copper acetate [Cu(acetate) 4.(H2O)2].
• In water, [V(H2O)6]3+ partially hydrolyses to
V(OH)2+ and VO+
 (+ II) OXIDES
• VO is nonstoichiometric
• The solid is ionic and has defect NaCl type of
structure.
• It is has a d3 configuration
• The oxide is grey-black and has a metallic lustre
• It is made by reducing V2O5 with hydrogen at
1700 ͦC
• The oxide soluble in water
• Addition of NaOH form precipitates V(OH)2
• Dissolve in acids and form violet coloured
[V(H2O)6]2+ ions and soon turn green through
oxidation to [V(H2O)6]3+
• It is has a fairly high electrical conductivity due
to metal-metal bonding in the structure
 ORGANOMETALLIC COMPOUNDS
This group doesn’t for many compounds with M-
C σ bonds.
The main complex is:

V forms bis(cyclopentadienyl), for example:

Hapticity is used to describe how a group of contiguous

atoms of a ligand are coordinated to a central atom.