Inorganic Chemistry Birendra Thapa (BT)

Chapter Hours Marks

3d – Transition elements 5 10 (2 x 5)
Co – ordination complexes 5 10 (2 x5)
3d – Transition Elements
 A A A A A

B B B B B
• The elements which involves the filling of d – orbitals in the (n – 1) or
penultimate shell are called d – block elements.

• Valence shell , penultimate shell and antepenultimate shell:

• General outer electronic configuration: ns1-2(n-1)d1-10.

• The elements belonging to group 3 – 12 are called d – block
elements.

• The d – block contain three complete rows called first, second and
third transition series which involve filling of 3d, 4d, and 5d orbitals
and one incomplete row which is fourth row.
• In P.T., lies in between s and p block elements.

• Properties are intermediate between the properties of highly reactive

metallic elements of the s – block, which typically forms ionic
compounds, and the elements of the p –block, which are largely
covalent.

• d – block elements represents change or transition in properties from

most electropositive s – block elements to least electropositive p –
block elements.

• These are called transition elements.

• But, all d – block elements are not typical transition elements.
• Atom or ion in common oxidation state having partially filled penultimate d –
subshell are called transition elements.
• Coinage metals IB (Cu, Ag, Au):
• are included in transition metal as their ions have partially filled (n-1) d
subshells although their atoms have filled (n – 1) d sub - shells in the ground
state.

• Elements of group IIB (Zn, Cd, Hg):

• are not included in transition elements as they do not have partly filled (n –
1) d subshell either in ground state or in ions. These are non – typical
transition elements.
Electronic configuration of 3d – block elements
GENERAL CHARACTERISTICS:
• They are solid metal which are hard, strong, high m. pt and b. pt. and conduct
heat and electricity well except Hg which is liquid metal (m. pt. = - 38.90C).
• They are all ductile and malleable.
• They form alloys with one another and with other metals.
• They form interstitial compounds with non – metals like C, B, N, H etc.
• Because of unpaired electrons, they form paramagnetic compounds.
• Most of the elements have great tendency to form stable complex ions.
• Most of them are electropositive enough to dissolve mineral acids.
• They exhibit catalytic properties for hydrogenation, oxidation, dehydration
etc.
• They exhibit variable oxidation state and their ions and compounds are
coloured.
• They are good reducing agents.
ATOMIC RADII

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic 1.44 1.32 1.22 1.17 1.17 1.17 1.16 1.15 1.17 1.25
Radii
(A0)

Melting point and boiling point

High melting
and boiling
points indicate
strong metallic
bonding.
VARIABLE OXIDATION STATE
• One of the striking feature of transition elements is that the elements usually exist in several
oxidation state in their compounds.
• Some common oxidation states of 3 d – transition elements are given as:

Element Outer Electronic Oxidation States The values

Configuration stated in the
Sc 3d14s2 (+2), +3 brackets are
for less
Ti 3d24s2 +2, +3, +4 common
V 3d34s2 +2, +3, +4, +5 oxidation
Cr 3d54s1 (+1), +2, +3, (+4), (+5), +6 states. These
states are
Mn 3d54s2 +2, +3, +4, (+5), +6, +7 exhibited only
Fe 3d64s2 +2, +3, (+4), (+5), (+6) in a few
complexes
Co 3d74s2 +2, +3, (+4), (+5)
and are
Ni 3d84s2 +2, +3, +4 unstable.
Cu 3d104s1 +1, +2, (+3)
Zn 3d104s2 +2
• The general outer electronic configuration of transition elements is (n –
1)d1-10ns1-2.
• There is very small difference in energy of electron in ns and (n – 1)d
orbitals.
• Thus both ns and (n – 1)d orbitals participate in compound formation
showing variable oxidation sates.
• The most common oxidation state shown by elements of 3d – series is
+2 which is attained by the loss of 4s electron.
• After removing ns – electrons, the remainder is called core.
• In the case of d – block elements, the core is usually unstable and hence
loses one or more electrons. The removal of one or more electrons
from unstable core gives variable oxidation states to transition metals.
• The variable oxidation states shown by these transition elements may
be related to their actual electronic configuration.
• Outer electronic configuration of Sc = 3d14s2.
• It shows +2 o. s. if both 4s electrons are used for bonding and +3 o. s.
when two 4s and one 3d – electrons are removed.
• Similarly, Ti (3d24s2)
• +2 o.s. if only 4s electrons are used.
• +3 o.s. if two 4s and one 3d electrons are used.
• +4 o.s. if two 4s and two3d electrons are used.
• On the same basis, we can account for different oxidation states for V,
Cr and Mn.
• Lower o. s. is exhibited if only 4s electrons are used in bonding and
higher o.s. is exhibited if 4s and one or more 3d – electrons are used
for bonding.
• For e. g., Mn = +2 o. s. if 4s electrons are used and +7 o. s. if all 4s and
3d – electrons are used.
• Thus correlation between electronic structure and minimum and
maximum o. s. for first five transition elements can be studied.
• In the remaining 5 elements, i.e., Fe, Co, Ni, Cu and Zn, the number of d
- electrons is more than five. The minimum o. s. in each case is equal to
number of 4s – electrons but the maximum o. s. is not at all related to
the total number of ns and (n – 1) d electrons.

• Once the d5 configuration is exceeded, the tendency of d – electrons to

participate in bonding decreases due to more effective nuclear charge.
Therefore, o. s. decreases after Mn. Hence, Fe has maximum oxidation
states VI due to participation of outer s – electrons and unpaired d –
electrons.
• Similar explanation can be given to remaining elements.
• The transition elements in the +2 and +3 oxidation states mostly form
ionic bonds. In compounds of the higher oxidation states, the bonds
are essentially covalent. For example, in permanganate ion MnO4-, all
bonds formed between manganese and oxygen are covalent.
• Transition metals also form compounds in low oxidation states such
as +1 and zero(0). For e.g., Ni in nickel tetracarbonyl, Ni(CO)4 has zero
oxidation state.
• The highest oxidation states are observed in fluorides and oxides. Os
and Ru shows +8 oxidation states (highest).
Q. Zn forms only Zn2+ and not Zn3+. Why?

Q. In between Cu+ and Cu2+, which is more stable. Give reason.

Q. Cu2+ (3d9) is more stable than Cu+ (3d10). Why?
• An ion carrying higher charge and smaller size is associated with
greater lattice and hydration energy. That is why Cu2+ is more stable
than Cu+. It is expected on the basis of electronic configuration that
Cu+ showed to be more stable because it has completely filled
orbitals. But the lattice and hydration energy facto dominate and as a
result Cu2+ is more stable.
• Furthermore, Cu+ disproportionates in water as:
[𝐶𝑢2+ ]
2Cu+ (aq.) ⇌ Cu2+ (aq.) + Cu; k = = 1.6 x 106
[𝐶𝑢+ ]2
• The equilibrium constant for the disproportination of Cu+ solution is
high showing that the equilibrium is largely to the right. Thus the
concentration of Cu+ is very low in solution and typically Cu+ ion exists
in aqueous solution for less than a second. The only copper (I)
compounds that are stable to water are either insoluble or present as
complexes. E.g., CuCl, CuCN, CuSCN.
 COLOUR
• Most of the transition metal compounds (ionic a well as covalent) are
coloured both in solid state and in aqueous solution in contrast to the
compounds of s – and p – block elements which are almost always white.

• When white light is passed through a material it absorbs light of certain

wavelength. If absorption occurs in the visible region (3800 – 7600A0),
the transmitted light is coloured to the complimentary colour of light
absorbed.

• Absorption in the visible and uv regions of the spectrum is caused by

changes in electronic energy. Thus the spectra are sometimes called
electronic spectra.
• The compounds of transition metals are coloured due to presence of
unpaired electrons in their d – orbitals.

• In an isolated atom or ion of transition element, all the five d – orbitals

are of the same energy, which are said to be degenerate.

• When the anions or the ligands approach the transitional metal ions,
their d – orbitals do not remain degenerate.

• They split into two sets, one consisting of lower energy orbitals (t2g
which include dxy, dyz, and dzx) and other consisting of higher energy
orbitals (eg which includes dx2-y2 and dz2).

• This is called crystal field splitting.

• In the transition elements or ions which have partly filled d – orbitals,
the transition of electron can take place from lower d – orbitals to
some higher d – orbitals within the same shell.
• This is called d – d transition.

• The energy required for this transition falls in the visible region.

• So, when white light falls on these complexes, they absorb a particular
colour from the radiation for the promotion of electron and the
remaining colours are emitted. The colour of complexes is due to their
emitted radiation.
• The colour of transition metal complex depend on how big the energy
difference is between the two d – levels.
• This is in turn depend on nature of ligand and the type of complex
formed.
• The colour changes with the ligand used. The colour also depends on
number of ligand and shape of complex formed.

• Thus the octahedral complex,

[Ni(NH3)6]2+ Blue
[Ni(H2O)6]2+ Green
[Ni(NO2)6]4- Brown red
• Cu2+ salts look like blue.
• Anhydrous cobalt II compounds are blue.
• A complex of Ti, [Ti(H2O)6] 3+ is purple in colour.

• The transition metal ions which have completely filled d – orbitals are
colourless, as there is no vacant d – orbitals to permit promotion of
electron.
Zn2+ compounds are Colourless.

• The transition metal ions which have completely empty d – orbitals are
colourless.
Sc3+, Ti4+ are Colourless.
 Ion Outer electronic Number of unpaired Colour of the ion
configuration electrons

Sc+ 3, Ti +4, V+5, Cr+6, Mn+7 3d0 0 Colourless

Cu+1, Zn+2 3d10 0 Colourless
Ti+3 3d1 1 Purple
V+3 3d2 2 Green
Cr+3 3d3 3 Violet
Mn+2 3d5 5 Light pink
Mn+3 3d4 4 Violet

Fe+2 3d6 4 Green

Fe+3 3d5 5 Yellow
Co+2 3d7 3 Pink
Ni+2 3d8 2 Green
Cu+2 3d9 1 Blue
Q. Illustrate [Ti(H2O)6]3+ has purple colour.
Q. The compounds formed by ‘V’ element in +5 oxidation state are
colourless but those formed in +3 oxidation state are colourful. Give
reason.
Q. TiO2 is white but TiCl3 is violet. Give reason.
Q. Illustrate V2O5 is colourless while VO2 is purple in colour.
Q. Explain why transition metals generally form coloured compounds.
Q. Transition metal complex ions with d0 or d10 configuration are
colorless, why?
Q. Explain why compounds of Ti3+ are coloured but those of zinc are
colourless.
 COMPLEX FORMATION
• Transition metal has unparalled tendency to form co – ordination
compounds with Lewis base.

• i.e. with groups which are able to donate an electron pair.

• The groups are called ligands.

• A ligand may be a neutral molecule like NH3 or ions like Cl- or CN-.

• The ability to form complex compound is in marked contrast to the s – and

p – block elements which can form only few complexes.

• The reason transition elements are so good at forming complexes is due to:
 (1) Small size of metal ions
(2) Their high ionic charge
Because of (1) and (2), they have large charge/size ratio, i.e. greater
+ve charge density so that they can strongly attract lone pair of electrons.

(3) Availability of vacant d – orbitals so that those orbitals can

accommodate lone pair of electrons donated by ligands.

• The stability of metal complex increases with decrease in size of the

metal cations.
• For M2+ ions, the general trend in stability for complexes is:
Mn2+ < Fe2+ < Co2+< Ni2+ < Cu2+ < Zn2+
• The stability of complexes increases with increase in oxidation state of
metal so complexes where the metal is in the (+III) oxidation state are
generally more stable than those where the metal is in (+II) oxidation
state.
• E.g., Co+2 compounds with ammonia is highly unstable and does not form
while Co+3 compounds with ammonia [Co(NH3)6]3+ is highly stable.
• The stability of complex increases as basic character of ligand increases. In
3d – series metal ion, order of stability of complex with NH3, H2O, and F-
is:
NH3 > H2O > F-
• The complex compounds with chelating ligand are more stable than the
complexes with non – chelating ligands.
• Stability of complex.pdf
 MAGNETIC PROPERTIES OF TRANSITION ELEMENTS
• Transition metal elements and their compounds have been classified in
following properties on the basis of their behaviour in magnetic field:
(i) Paramagnetic substances:
• Are those which are weakly attracted by magnetic field and this property is
associated with the unpaired electrons in an atom or a compound.
(ii) Diamgnetic substances:
• Are those which are slightly repelled by magnetic field and this property is
associated with paired electrons in an atom or compound.
(iii) Ferromagnetic substances:
• Are those which are strongly attracted by magnetic field, i.e., they are
paramagnetic in character.
• This property is associated with the substance which retain their magnetism
even after the removal of magnetic fields. Due to this property ferromagnetic
substances differ from paramagnetic substances which lose their magnetic
properties after removing the magnetic field.
• E.g., of ferromagnetic substances are Fe, Co, Ni,
EXPLANATION OF MAGNETIC PROPERTIES
• An electron is a charged particle (negatively charged) which revolves around the nucleus and
spins on its own axis.
• A magnetic field is generated due to the orbital motion and spin of the electron.
• The spinning of an electron in an orbit is very much similar to flow of electric current in a
closed circuit.
• Therefore, an unpaired electron is regarded as a micro magnet which has a definite magnetic
moment.
• A substance which contains an unpaired electron when placed in a magnetic field interacts
with the applied field. Consequently, an attractive force is exerted and the paramagnetic
property is shown.
• The number of unpaired electrons determines the magnitude of magnetic moment.
• Higher the number of unpaired electrons more is the magnetic moment and greater will be
the paramagnetic behaviour of the substance.
• In the case of paired electrons, the electrons in each pair will have opposite spin.
• The magnetic field created by the electrons of same pair is equal and opposite in nature.
• Hence, the magnetic field which is created by one electron is cancelled by the other. So the
net effect of the magnetic moment is zero. These kinds of substances show diamagnetic
property and are repelled by the applied magnetic field.
• The paramagnetism first increases in any transition element series, and
then decreases.
• The maximum paramagnetism is observed around the middle of the
series.
• The paramagnetism is noted in Bohr Magneton (BM) units.
• Relation between magnetic moment and number of unpaired electrons is
given by spin only formula as:
• Magnetic moment,  or S = 𝑛(𝑛 + 2) B.M.
• Where, n = no. of unpaired electrons
• B.M. = Bohr Magneton, a unit of magnetic moment
𝑒ℎ
• 1 B.M. =
4𝑚𝑐
• Where, e = electronic charge, m = mass of electron, h = Planck’s constant,
c = velocity of light.
• The magnetic field produced by unpaired electrons is partly due to their
spin and partly due to their orbital motion.
• The magnetic moment is given by:
 =  (S + L) = 4𝑆 𝑆 + 1 + 𝐿 𝐿 + 1
𝑛
where S is the total of the spin quantum numbers = , and
2
L is the resultant of the orbital angular momentum quantum
numbers of all the electrons in the molecule.
• But it has been found that in a number of compounds including first row
of transition elements, the orbital contribution is quenched or
suppressed by the electric fields of the surrounding atoms (i.e., L = 0).
• As the slight approximation the orbital contribution can be ignored and
the observed magnetic moment is considered to arise only form
unpaired spins.
• The spin – only magnetic moment S can be written as:
 = S = 4𝑆 𝑆 + 1

• The magnetic moment  (measured in Bohr magnetons, BM) is related

to the number of unpaired electrons, n by the equation:
 = S = 𝑛 𝑛 + 2 BM

Q. Compare the magnetic properties of Fe2+, Mn2+, Co2+ and Zn2+ by determining the
value of magnetic moment in BM.

Q. Cu (I) is diamagnetic whereas Cu(II) is paramagnetic. Give reason.

 ALLOY FORMATION
• A homogeneous mixture of metals or a metal with another element is
commonly called as alloy i.e., it is usually composed of two or more
metals.
• Transition metals mix freely with each other in the molten state and on
cooling a solution of different metal result in the alloy.
• E.g., chromium dissolves in nickel to form Cr – Ni alloy. Manganese
dissolves in iron to form manganese steels, brass (Cu + Zn) and bronze
(Cu + Sn).
• The alloy formation is explained on the basis of similar sizes of the atoms
of these metals which allow the atoms of one metal to take up the
positions in the crystal lattice of other.
• Alloys are generally harder, have higher melting points and more
resistant to corrosion than the individual metals.
 APPLICATION OF TRANSITION METALS
• Many transition metals and their compounds have catalytic properties.
(i) Finely divided iron (Fe) acts as catalyst in the manufacture of ammonia
by Haber’s process.
(ii) Vanadium pentoxide (V2O5) or platinum (Pt) acts as catalyst for the
oxidation of SO2 to SO3 in contact process for the manufacture of sulphuric acid.
(iii) Nickel powder is a good catalyst for hydrogenation of unsaturated
organic compounds such as oil.
(iv) Ferrous sulphate and hydrogen peroxide (Fenton’s reagent) are used
for the oxidation of alcohols to aldehydes.
(v) TiCl3 is used as the Ziegler – Natta catalyst in the production of
polythene.
(vi) MnO2 is used as catalyst to decompose KClO3 to give O2
• Iron and steels are important construction materials.
• Alloys of transition metals with non – transition metals such as brass(Cu – Zn)
and bronze (Cu – Sn) are also of considerable importance.
• KMnO4 is used as a disinfectant, oxidizing agent, in volumetric reagent and is
used for the estimation of ferrous salts.
Thank you