Transition Elements and

their Properties

Prof. Amala Shrestha

Introduction
• Definition
• Transition elements are those elements in which 2 outermost
shells are incomplete. In those elements the last electron or
differentiating electron enters into (n-1)d orbitals of the (n-
1)th main shell as such these are also called d block
elements.
• These elements either in elementary form or atomic form
and in any common oxidation state have partially filled (n-
1)d orbital of the (n-1)th main shell.
• If all definitions fulfilled by elements such elements are
called typical transition elements..
• If the elements are d block but not fulfilled all the conditions
such elements are nontypical transitional elements.
Introduction
• The elements of all subgroups B including eight group,
subgroup IIIB to VIIB, VIII, IB and IIB are transitional
elements.
• These are so called as their position in the periodic table
lie in between S and P block elements and their properties
are also between highly electropositive elements of S
block which form ionic compounds and less electropositive
elements of P block which largely for covalent compounds.
Introduction
• The electronic configurations clearly show that according to the
definition of d block elements the elements of IB (Cu, Ag, Au) should
be excluded from d block elements. Since these elements both in
their atomic form with configuration (n-1)d10 ns1 and in their +1
oxidation state with configuration (n-1)d10 , do not have partly filled
(n-1)d orbitals.
• Similarly in the elements of IIB (Zn, Cd, Hg) which in both atomic
state with configuration (n-1)d10 ns2 and in +2 oxidation states they
have (n-1)d10. They do not contain partly filled d orbitals, should
also be excluded from d block elements.
• Similar in the case with Pd (Palladium) it has 4 d105s0 configuration,
yet in order to main a rational classification, these elements (Cu,
Ag, Au, Zn, Cd, Hg, Pd) are also generally studied with d block
elements.
Introduction
• The valence electronic configurations of these elements
can be represented by (n-1)d1-10 ns0, 1-2. The penultimate
shell contains d orbitals which contains 1 through 10
electrons and valence shell contains S orbital which
contains either no electrons or 1 - 2 electrons i.e. the
outermost shell contains maximum 2 electrons.
• There are 4 transition series 1st, 2nd , 3rd , and 4th transition
series corresponding to the filling of 3d, 4d, 5d, 6d orbitals
respectively and are known as 3d, 4d, 5d and 6d series.
Each series consist of ten elements and is known as
complete transition series.
General Characteristics of Transition
Elements
Some important properties of transition elements are given below
1. They are all metals. They are very hard malleable and ductile
except Hg. They are all good conductors of heat and electricity
2. They have high melting and boiling points as compared to s and
p block elements
3. They have high specific gravity i.e. they have high densities
more than five hence are heavy metals
4. They form complex compounds e.g. [Cu(NH3)4]SO4, K4[Fe(CN)6]
5. They show variable oxidation states i.e. they have more than
one valency except Zn
General Characteristics of Transition
Elements
6. They form coloured compounds. It is due to the presence
of unpaired electron in (n-1)d orbitals of the (n-1)th shell
7. The transition metals and their compounds are generally
paramagnetic i.e. they are attracted by magnet. It is also
due to the presence of unpaired electrons.
8. They form alloys with one another or with other non
transitional elements
9. Most of the transition metal and their compounds have
good catalytic properties
10.They are generally soluble in dilute mineral acids (HCl,
H2SO4, HNO3) with few exceptions
Detailed Properties of 3d Elements
The elements belonging to 3d series are known as 3d
elements. There are 10 elements. Some important
properties of 3d elements are mentioned below.

1. Electronic configuration: some of the elements of the 3d

series have irregularities in configuration. The electronic
configurations of 3d series are given in tabular form.
Observed and predicted electronic
configuration of 3d elements
Element Electronic configuration • Note the irregularities in the
Predicted Observed configuration from the table
we observed two facts
Scandium (Sc) 21 1S22S22p63s23p63d14s2 or [Ar]3d14s2 Same i. The atoms of all transition
Titanium (Ti) 22 1S22S22p63s23p63d24s2 or [Ar]3d24s2 Same elements consist of inner
Vanadium (V) 23 1S22S22p63s23p63d34s2 or [Ar]3d34s2 Same core of electron (when
valence electron is
Chromium (Cr) 1S22S22p63s23p63d44s2 or [Ar]3d44s2 [Ar]3d54s1 removed the remaining
24 portion is known as core)
Manganese (Mn) 1S22S22p63s23p63d54s2 or [Ar]3d54s2 Same having noble gas
25 configuration. The 3d
Iron (Fe) 26 1S22S22p63s23p63d64s2 or [Ar]3d64s2 Same series has argon
configuration
Cobalt (Co)27 1S22S22p63s23p63d74s2 or [Ar]3d74s2 Same ii. The two elements Cr and
Nickel (Ni) 28 1S22S22p63s23p63d84s2 or [Ar]3d84s2 Same Cu have irregularities
Copper ( Cu)29 1S22S22p63s23p63d94s2 or [Ar]3d94s2 [Ar]3d104s1 electronic configurations
which are explained on
Zinc (Zn)30 1S22S22p63s23p63d104s2 or Same the basis of extra stability
[Ar]3d104s2
of half filled and
completely filled d orbitals
Detailed properties of 3d series
2. Tendency to form complex compounds: The cations of the
transition metals have a great tendency to form complexes with
several ligands such as neutral molecules (NH 3, H2O, CO etc.)
and anions (CN-, Cl- etc.). These ligands possess invariably lone
pairs of electrons which they donate to the transition metals
cations in the formation of complex compounds.
The tendency of transition metals cations to form complexes is
due to the following reasons:
i. The transition metals cations are relatively small in size and have high
positive charge density in the nucleus which makes it easy for the transition
metals cations to accept the lone pairs of electrons from the ligands
ii. The transition metals cations have ( n-1)d orbitals in which they can
accommodate the lone pairs of electrons donated by the ligands and thus can
form L  M bond
iii. The transition metals are capable of showing several oxidation states.
Detailed Properties of 3d Elements
Relative stability of the complexes
i. The stability of the complexes decreases with the
increase in atomic number of central metal atom.
ii. The same ligand forms a complex compound with the
same metal atom in different oxidation state, the
metal ions having higher oxidation state is more
stable than lower oxidation state e.g.. [Fe+2(CN)6]4-,
[Fe+3(CN)6]3-, [Fe(CN)6]3- is more stable than [Fe(CN)6]4-.
This is due to the following reasons
a. Fe+3 has smaller ionic size than Fe+2
b. Fe+3 has stable electronic configuration. It has half filled
d orbitals d5
Detailed Properties of 3d Elements
3.Oxidation state
One of the most important property that distinguish transition
elements from s and p block elements is that they show variable
oxidation states except zinc. It has only one oxidation state of +2
This unique property is due to the following reasons:
i. The cations of the transition metals atoms can not achieve the inert gas
configuration or stable configuration in any common oxidation state, such
configuration is said to be pseudo inert gas configuration which is less stable.
Hence one or more electrons are lost during cations formation. This gives several
oxidation states to transition metals. E.g..
21Sc [Ar]3d14s2
Sc++  [Ar]3d1 (less stable)
Sc+++  [Ar]3d0 (more stable)
26Fe  [Ar]3d64s2
Fe++  [Ar]3d6 (less stable)
Fe+++  [Ar]3d5 (more stable)
Detailed Properties of 3d Elements
3. Oxidation state
ii. The energy levels of 3d, 4d and 5d orbitals are fairly close
to those of 4s 5s and 6s orbitals respectively and
therefore in addition to ns electrons a variable number of
(n-1)d electrons are also lost in getting variable oxidation
states.
The valance electronic configuration and possible oxidation
states of the 3d elements are shown in the next slide
 Different oxidation states exhibited by 3d transition metals
(most stable oxidation states are in brackets)
Gr. No. IIIB IVB VB VIB VIIB VIII IB IIB
Elements Sc21 Ti22 V23 Cr24 Mn25 Fe26 Co27 Ni28 Cu29 Zn30
Valence
electronic 3d104s
3d14s2 3d24s2 3d 4s
3 2
3d 4s
5 1
3d 4s
5 2
3d 4s
6 2
3d 4s
7 2
3d 4s
8 2
3d 4s10 1
configurati 2

on
Minimum
oxidation +2 +2 +2 +1 (+2) (+2) (+2) (+2) +1 (+2)
state
Intermedia +2 +3
(+3)
te +3 (+3) (+4) (+3)
- +3 +4 +3 (+2) -
oxidation +4 +4 +5 +4
+5
state +5 +6
Maximum (+3) (+4) (+5) (+6) (+7) +6 +5 +4 +3 -
oxidation
state increases decreases
The following points may be noted from this table.
i. Minimum oxidation state : All the 3d elements with the exception
of the Cr and Cu have a minimum oxidation state of +1 exhibit a
minimum oxidation state of +2. The minimum oxidation state arise
due to the loss of s electrons. Hence minimum oxidation state is
related to the valence electronic configuration
ii. Maximum oxidation state: The maximum oxidation state of
transition metals is due to use of ns and (n-1)d electrons in cation
formation. For the 1st five elements of 3d series Sc to Mn the
maximum oxidation state increases from +3 to +7. But for the last
five elements of 3d series Fe to Zn the maximum oxidation state
decreases from +6 to +2. There is an increase in the number of
oxidation states in going left to right. However the elements
towards the middle of the period show more oxidation state than
those towards the end of the period. The increase in the number of
oxidation states from left to right in the period is due to the ready
availability of s and d electron in bonding. Once d 5 configuration is
exceeded the number of unpaired electron in d orbital decreases.
Only the unpaired electron takes part in bond formation
The following points may be noted from this table.
iii. Immediate oxidation state: In between minimum and
maximum oxidation states there are several other
oxidation states which is increased by one unit. This
is quite contrast to s and p block. In s block elements
the oxidation state is equal to group number G. While
in p block elements have oxidation states either equal
to group number G or equal to (8 - G).
iv. Some metals form stable complexes in zero oxidation
state. E.g.. : [Ni(CO)4]0
The following points may be noted from this table.
v. Relative stability of various oxidation states: It has been
experimentally found that the metal ions having d 0, d5 and d10
configurations are more stable oxidation states. Thus Ti +4(3d0) is
more stable than Ti+3(3d1), Fe+3(3d5) is more stable than
Fe+2(3d6). But this generalization is not valid for Co to Cu. In Cu,
Cu+2(3d9) is more stable than Cu+(3d10). Because Cu+ in
aqueous undergoes disproportion forming Cu and Cu+2.
Cu+ (aq) Cu+2 + Cu0
Again Cu+2 compounds are highly hydrated. During hydration a
large amount of energy is released known as hydration
energy. This energy is used to remove the electron from d 10
configuration and makes unpaired electron in d orbital. So d
electron can be used in bond formation. While in Zn d10
configuration is more stable. The hydration energy is not
sufficient to remove the d electrons. So Zn can’t make unpaired
electron in d orbital only s electrons are used. So zinc has only
one oxidation state.
Detailed Properties of 3d Elements
4. Colour of transition metal ions
• Most of the transition metal compounds are coloured in
solid as well as in aqueous form. This is due to presence
of unpaired electron in (n-1)d orbitals. The colour of the
transition metal compounds are explained with help of
crystal field theory (CFT).
Detailed Properties of 3d Elements
4. colour of transition metal ions
• In an isolated or free gaseous metal ions there are five d orbitals in the
inner shell which have equal energy and is said to be ground stat
degenerate d orbitals (a)
a. When the combining anions or ligands come little close to the metal
ion, the ground state degenerate d orbitals become excited state
which have also equal energy and is said to be excited degenerate
d orbitals (b)
b. On approaching the combining anions or ligands close to the metal
ion, the excited degenerate d orbitals do not have equal energy. The
excited degenerate d orbitals split into 2 sets of d orbitals. One set
consist of three d orbitals (dxy, dyz, dzx), which forms the t2g set.
Another set consists of two d orbitals (dx2-y2 and dz2) which forms
the eg set. The one set of d orbital has higher energy compared to
another. In case of Octahedral complexes the e.g. set has higher
energy than t2g set. While in tetrahedral complexes e.g. set has
higher energy than t2g set. The splitting of d orbitals into 2 sets is
Excitation of unpaired electron from lower energy d orbital to higher energy d
orbital by absorbing certain colour of white light
Detailed Properties of 3d Elements
4.Colour of transition metal ions
• If the transition metal ion contains one or more unpaired electrons in d orbitals,
the unpaired electron can be excited from lower energy d orbital to higher
energy d orbital of the same d subshell. For the excitation of electron a very
small amount of energy is sufficient. The wavelength of light corresponding to
very small amount of energy is present in white light or sunlight or visible light.
Thus when the transition metal compounds are placed in the way of white light,
the metal ion absorbs certain colour of light whose wavelength is in the visible
region λ = (4000 -7000)A. The unpaired electron gets excited from the lower
energy d orbital to higher energy d orbital. The unabsorbed colour or excess
colour is reflected back which is no more white. The complementary colour of
the absorbed colour is the colour of the substance i.e. colour of the substance is
equal to the white light- absorbed colour.
Colour of substance= White light – Absorbed colour
Detailed Properties of 3d Elements
4. Colour of transition metal ions
• Different metal ions absorbed different colour of white light or radiation and
reflected different colour. Cu+2 ion absorbs all red colour and reflects blue
colour, so compounds of Cu+2 are all blue.
• The excitation of unpaired electron from lower energy d orbitals to higher
energy d orbital is known as d to d transition. The colour formation is mainly
due to d to d transition. For d to d transition there must be colour absorbed.
For colour absorption there must be one or more unpaired electrons in d
orbitals.
• If there is the transition metal compounds whose metal ions contain no
unpaired electrons i.e. completely vacant d orbitals d0 or paired electrons in
d orbitals d10 configurations, the compounds of such metal ions are all
white. Because in these cases d to d transition is not possible hence no light
of any colour is absorbed all the white light is reflected back and the
compounds appears white. Thus compounds of Sc+3, Ti+4, V+5(d0), Cu+, Ag+,
Zn+2, Cd+2 , Hg+, Hg+2and Zn+2(d10) are all white.
Detailed Properties of 3d Elements
5. Magnetic Properties
• Most of the compounds of the transition metals are para magnetic i.e. they
are attracted by magnet. On the basis of magnetic field, the transition
metals compounds are classified to two types.
1) diamagnetic substance 2) paramagnetic substance
• The highly paramagnetic substances are known as ferromagnetic
substances
• The paramagnetic character is due to the presence of unpaired electrons.
The paramagnetic character increases as the number of unpaired electrons
in orbitals increases . The paramagnetic character is expressed in magnetic
moment (μ) The value of μ increases as the number of unpaired electrons
increases. If there is some value of μ, μ = 1…,2…,3…,4… BM, then the
substance is paramagnetic. If there is no value of μ, μ = 0 then the
substance is diamagnetic. The magnetic moment (μ) is given by
μ = BM (Bohr Magnetron) where n=number of unpaired electrons
Detailed Properties of 3d Elements
5. Magnetic Properties
• The orbital motion and the spin motion of the electron creates
the magnetic field. Thus each electron is regarded as a micro
magnet having a definite value of magnetic moment. The total
magnetic moment of the substance is the resultant of the
magnetic moment of all the individual electron. If μ is the total
magnetic moment of the electron then total magnetic moment is
the sum of the spin moment (μs) and orbital moment (μl)
Then
μ = μl + μs ……………………….. (i)
The orbital moment is given by
μl = and μs = 2 …………….. (ii)
Detailed Properties of 3d Elements
Now
μ = μl + μs
Then from (ii)
μ= +2
μ = [ + 2 = [ + 2 BM
1 BM = = 9.27 x 10-27 erg /gauss
where
e = charge of electron, h = Planck’s constant, m = mass of electron
and
c = velocity of light.
In case of transition metal ions due to crystal field effect i.e. the
effect cause by the combining ions or ligands) restrict the orbital
motion of the electron. Hence
μl or becomes zero
Detailed Properties of 3d Elements
Now
=0
Then, the magnetic moment of the electron is
μ = [0 + 2 BM
If there is one unpaired electron n=1 then s=+1/2 or-1/2
So,
μ = 2 BM = BM = 1.732 BM
One unpaired electron gives the value of μ. So the unpaired
electron makes the substance paramagnetic.
If there are two unpaired electron n = 2 then
μ = 2 BM = 2 BM = 2.82 BM
Detailed Properties of 3d Elements
As the number of unpaired electron increases the value of μ also
increases as a result the paramagnetic character is also increased.
If there are n number of electrons then,
μ = 2 BM = BM
This formula is known as spin only formula and can be directly
used to calculate magnetic moment. If there are five unpaired
electrons n = 5. Then
μ = BM = BM = 5.92 BM
Detailed Properties of 3d Elements
• The transition metal ions having no unpaired electron i.e.
completely vacant d orbitals (d0) or paired electrons in d
orbitals (d10). The compounds of such metal ions are all
diamagnetic. Because the magnetic moment becomes
zero, if the metal ion has d10 configuration, the magnetic
moment produced by one electron is cancelled by another
electron. Because an equal and opposite magnetic
moment are produced. Thus compounds of Sc+3, Ti+4 and
V+5(d0) are all diamagnetic. Cu+, Ag+, Zn+2, Cd+2, Hg+, Hg+2
compounds (d10) are also diamagnetic.
Detailed Properties of 3d Elements
6. Alloy formation
• Many of the transition metals have similar atomic sizes. Due to
this the atom of one metal can be replaced by the atoms of the
another metal. This replacement forms alloys. When one metal is
mixed with another metal in molten state, stirred and cooled the
alloys are obtained. Thus when Mn is dissolved in molten iron,
the manganese iron alloy is obtained. Such alloys are hard, have
high melting point and boiling point and are more resistant to
corrosion.
Applications of 3d Transition Elements
1. Sc3+ is smaller than that of other ions of this sub-group. It has greater
tendency to form complexes e.g. [ScF4]-, [ScF5]2-, [ScF6]3- etc.
2. Due to the strength, lightness, corrosion resistance and low thermal
expansion of Ti, it is used in high speed air craft, military projects and
in chemical industry
3. Ti is used to remove traces of gases like O 2, H2, N2 from evacuated
vessels.
4. TiCl4 is a Ziegler-Natta catalyst used in polymerization of alkenes.
5. Alloys of Ti are used as deoxidizers and in construction of tanks,
automobiles and ships. Ferro-titanium which is an alloy of titanium
with iron is obtained in electric furnace by reducing ilmenite ore
(FeTiO3) with carbon or aluminum is used in steel as a scavenger to
removed absorbed O2,H2, N2 and hence cleansing deoxidizing agent.
Applications of 3d Transition Elements
6. Alloy of Ti with Cr, Fe and Mn are used for making rails,
gears, propellers, car wheels etc.
7. TiO2 is used in the manufacture of paints and pigments.
Mixed with BaSO4, It is sold under the name of titamox.
8. Titanium dioxide can also be used in making non
greasable paper, in the manufacture of arc lamp
electrodes and for the preparation of glazes.
9. TiCl4 is used in making smoke screens while dichloride
and oxalate are used in dyeing and mordanting.
Applications of 3d Transition Elements
10.About 90%of the vanadium is used for making ferro-vanadium alloy
which is used in the manufacture of steel and as a scavenger(removal of
N2 and O2). Addition of the 0.1-0.3 % vanadium to steel increases
toughness, tensile strength. The resulting special steel is much used in
construction of motor cars. Alumino-valadium alloy is used in
manufacture of aircrafts. Vanadium is an essential constituent of high
speed tool
11.V2O5 is used as a catalyst in the manufacture of sulphuric acid by contact
process and oxidation of naphthalene. Vanadium compounds find
application in the manufacture of ink, dyeing, as accelerators in drying
paints and varnish, in insecticides, photographic chemicals, medicine and
in glass industry
12.Chromium is used mostly for chrome plating and making alloys (stellite is
an alloy containing Cr, 20 - 35%, Co 40 - 80%, Ni 0.25%, C 0.75 - 2.5%, W
(tungsten) remaining part is employed for making surgical instruments.
Applications of 3d Transition Elements
13.Cr2O3 dissolved in glacial acetic acid is used as an oxidizing agent
and as a disinfectant to wash foul ulcers and sores.
14.K2Cr2O7 is used as a lab reagent, indicator.
15.A mixture of potassium dichromate and conc. Sulphuric acid known
as chromic acid has strong oxidizing properties and is used as a
cleansing agent for glass wares etc. it is also used in leather industry
(chrome tanning)
16.A number of alloy and manganese are of very good importance.
Ferro manganese; 70 - 80% Fe and 12% Mn is very hard and
resistant to wear and is used for making rock crushers, railroads,
and armor plate
17.KMnO4 is used as disinfectant, oxidizing agent , in volumetric
reagent and is used for estimation of ferrous salts
Applications of 3d Transition Elements
18.MnO2 is used as an oxidizing agent
19.Iron is used in constructing buildings , bridges, making
magnets, steel. Alloy steels are used in industry
20.Cobalt is used in electroplating and in formation of alloys.
Cobalt-chrome is an alloy of 60% Co, 15% Cr, and 25% Fe
and is used for making resistance wire similar to nickel-
chrome, Stellite is used for making surgical instruments
21.Ni finds use in making crucibles , dishes and other chemical
wares due to high melting point, greater resistance to
corrosion in acids and alkalis.
22.Finely divided Ni is used as a catalyst in the hydrogenation
of oils
Applications of 3d Transition Elements
23.Invar is an alloy containing 35% Ni with Fe and C is used for
making meter scale, measuring instruments and clock
pendulum
24.Copper is extensively employed for making electrical wires
for making vacuum pans, heating utensils, calorimeters and
conductor coils, for making coins and in electroplating and
electrotyping. Compounds of Cu are used as insecticides and
colouring materials
25.Zinc is used for the galvanization of iron to prevent from
rusting. Zn is used for the making alloys e.g. brass.
Granulated zinc is used in lab for the preparation of hydrogen
gas. Zn is used in metallurgy of silver and gold, as reductant ,
for the manufacture of dyes, drugs and perfumes.