SG Chemistry Classes

THE TRANSITION ELEMENTS (d-BLOCK)

d block elements are known as transition elements except Zn, Cd, Hg.
Why d block elements are known as transition element?
I) They have incompletely filled d orbitals.
ii) Their position is between s–and p–block elements .They correlate the property
between pure metal and non metal.
iii) Electrons are filled in penultimate energy level.
Zn Cd Hg are not considered as transition element as they have completely filled d
sub shell.

Electronic Configurations of the d-Block Elements

In general the electronic configuration of these elements is (n-1)d 1–10 ns 1–2
The elements of d and f block element has variable oxidation state and exhibit
colour.
Properties of the Transition Elements (d-Block)
With the exceptions of Zn, Cd, Hg and Mn, all of them exhibit typical metallic
structure.
Melting Points
In any row the melting points of
transition metals increases upto
middle of the period and then
decreases (due to increase in
metalling bond strength upto centre
then decrease the metallic bond
strength.)
Exception- Mn, Tc have
exceptionally lower melting point.
Variation in Atomic and Ionic Sizes of Transition Metals
There is an increase from the first (3d) to the second (4d) series of the elements but
the radii of the third (5d) series are nearly same as 4d series.The nearly equal size of
5d series and 4d series due to lower shielding of 4f sub shell electron.

Why do the transition elements exhibit higher enthalpies of atomisation?

Due to large number of unpaired electrons in d sub shell, the d block elements
exhibit strong metallic bond with each other.
Due to strong interaction d block elements exhibit strong enthalpy of atomisation.
Ionisation enthalpy
The second ionisation enthalpy of Cr and Cu is high due to d5 and d10 configuration
respectively.
The third ionisation enthalpy of Mn and Zn is high due to d5 and d10 configuration
respectively.

Ionization enthalpies are found to increase in the given series due to a

continuous filling of the inner−d orbitals. The irregular variation of ionization
enthalpies can be attributed to the extra stability of configuration such as
d5,d10.
Oxidation States

Trends in Stability of Higher Oxidation States

• Mn does not exhibit +7 oxidation state with simple halides.Only MnO3F is known
in which Mn is in +7 oxidation state.
• All CuII halides are known except the iodide. In this case, Cu2+ oxidises I– to I2:
2+ −
2Cu + 4I → Cu2I2 (s) + I2

• However, many copper (I) compounds are unstable in aqueous solution and
+ 2+
undergo disproportionation. 2Cu → Cu + Cu

• Cu+2 is more stable than Cu+ due to high hydration enthalpy of Cu+2.
• Stability of Cu > Cu+2 > Cu+ due to hydration enthalpy.
• N.B - Hydration enthalpy is the amount of energy released when a particular
substance gets dissolve in water.More the hydration enthalpy more will be the
stability of species.

• Cu+1 doesn’t exist in aqueous solution as it’s hydration enthalpy is minimum.

Magnetic Properties
• Two types of magnetic behaviour are observed: diamagnetism and
paramagnetism. Diamagnetic substances are weakly repelled by the magnetic
field while the paramagnetic substances are weakly attracted .

• An element having unpaired electron are paramagnetic in nature and element

having zero unpaired electron will be diamagnetic in nature.

• Where n is the number of unpaired electrons and μ is

the magnetic moment in units of Bohr magneton (BM).

• Substances which are attracted very strongly are said to be ferromagnetic. In

fact, ferromagnetism is an extreme form of paramagnetism.

Formation of Coloured Ions

The substance having unpaired electron will have produce colour
Sc3+ colourless, Ti +4 colourless , Zn +2 colourless

Complex forming ability

• The transition metal act as central metal atom in different co ordination
compound.
• This ability arises due to -
i) Comparatively smaller sizes of the metal ions, ii)their high ionic charges

ii)The availability of d orbitals for bond formation.

Catalytic Properties
The transition metals act as good catalyst.
Ex-Vanadium(V) oxide (in Contact Process) ,finely divided iron (in Haber’s
Process) ,nickel (in Catalytic Hydrogenation).

Catalyst makes a bond between the reactant molecule and it’s own surface
using 3d and 4s vacant orbital.

It helps in increasing the concentration of reactant at a particular surface.

It weakens the bond of reactant molecule.
It lowers the activation energy of reactant molecule.
For example, iron(III) catalyses the reaction between iodide and persulphate
ions.
– 2– 2–
2I +S2O8 →I2 +2SO4
An explanation of this catalytic action can be given as:
3+ – 2+
2Fe +2I →2Fe +I2
2+ 2– 3+ 2–
2 Fe + S2O8 →2 Fe + 2SO4

Formation of Interstitial Compounds

When small atoms like H, C or N are trapped inside the crystal lattices of metals it is
known as interstitial compound.
They are usually non stoichiometric .
They are neither typically ionic nor covalent.
Example, TiC, Mn4N, Fe3H, VH0.56 and TiH1.7.
Physical and chemical characteristics
(i) They have high melting points, higher than those of pure metals.
(ii) They are very hard, some borides approach diamond in hardness.
(iii) They retain metallic conductivity.
(iv) They are chemically inert.
Alloy Formation
• Alloys are homogeneous solid solutions in which the atoms of one metal are
distributed randomly among the atoms of the other.
• The alloys are hard and have often high melting points.
• Alloys of transition metals with non transition metals such as brass (copper-
zinc) and bronze (copper-tin) .
Some Important Compounds of Transition Elements Potassium
dichromate K2Cr2O7
i) It is an oxidising agent
ii) It is weaker oxidising agent than KMnO4.
iii) In acidic medium it acts as effective oxidant agent.
iv) In alkaline medium it doesn’t undergo any redox change.( No Change )

K2Cr2O7 act as a primary standard in redox titration due to it’s non hygroscopic
character i.e. it doesn’t absorb moisture from atmosphere .
N.B - Na2Cr2O7 is used as extensive oxidising agent due to high solubility in water.
Preparation of K2Cr2O7

FeCr2O4 +Na2CO3 +O2 →Na2CrO4 +Fe2O3 +CO2

Na2CrO4 + 2H+ →Na2Cr2O7 + Na+ + H2O

Properties
(In Acidic Medium)

Cr2O7 2– + 6I-→ 2Cr3+ + 3I2+ 7H2O

2–
Cr2O7 + H2S→ 2Cr3+ + 3S
Cr2O7 2– + Sn+2→ 2Cr3+ +Sn+4
Cr2O7 -2 + Fe+2———-> Fe+3 +Cr+3

Potassium permanganate KMnO4

i) It is an oxidising agent.
ii) It is stronger oxidising agent than K2Cr2O7 and O3.
iii) It is a secondary standard contain impurity (absorb moisture) and partially
decomposed in to MnO2.
iv) It is iso structural to KClO4 but KMnO4 is stronger oxidising agent than KClO4.
v) In all medium KMnO4 can act as oxidising agent and prefer to undergo
reduction.

Preparation Of KMnO4

MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O

–
MnO42–+4H+ →2MnO4 +MnO2 +2H2O
– 2–
2Mn2+ + 5S2O82– →2MnO4 +10SO4
Properties
i) Manganate ion is unstable and undergo disproportionation
reaction.(Same
Manganate element
ion is unstable will undergo
and undergo oxidation reaction
disproportionation and reduction)
(Same element
will undergo
both in oxidation and alkaline
acidic and reduction)medium
both in acidic and permanganate
to give alkaline medium to
andgive
-1 )and manganese dioxide (MnO ).
permanganate(MnO
MnO2. 4 2

MnO4 -2. MnO4 -1 + MnO2

MnO4 -2 MnO4 -1 + MnO2

2KMnO4 → K2MnO4 + MnO2 + O2 (Heat)

f-Block element
KMnO4 can act as oxidising agent in the following condition
i) The
—
last electron of f block elements must enter into f-subshell.
+2
MnO4 +C2O4-2————-> CO2 +Mn
ii) The 28 f- block element present in group III B
— +2
MnO4 +5Fe2+ →5Fe3++Mn
iii) 4f - series elements are otherwise known as Lanthanoid. (Rare earth elements
— – –
MnO4 +5NO2 →5NO +Mn+2
iv) 5f- series elements are known as Actinoide (Radioactive element).
MnO4–+10I– → 5I2 + Mn+2
v) General electronic configuration ns2 (n-1)d 0/1 (n-2)f1-14.
f-Block element
i) The last electron of f block elements must enter into f-subshell.
ii) The 28 f- block element present in group III B
iii) 4f - series elements are otherwise known as Lanthanoid. (Rare earth elements)
iv) 5f- series elements are known as Actinoide (Radioactive element).
v) General electronic configuration ns2 (n-1)d 0/1 (n-2)f1-14.

Lanthanoids

Actinoids
Atomic radii
Atomic radii gradually decreases on moving from ‘Ce’ to ‘Lu’ due to negligible
shielding effect given by inner d and f sub shell electrons e.g. La > Ce >...........>Lu
• This decrease in atomic radii is known as Lanthanoid contraction .
• This arises due to lower shielding effect of 4f subshell electrons.
• The effective nuclear charge increases across the period and the size gradually
decreases.

Polarising power of Cations

i) Polarising power is inversely proportional to small size. Lu >.........> Ce > La
ii) Smaller the size more is the polarity power of the cations.

Nature of Hydroxides
All the elements of Lanthanoid and Actinoids series produce ionic hydroxides and
basic in nature.
Basic character of hydroxide of Lanthanoid series is La > Ce > ........> Lu

Size is directly proportional to basic character . La(OH)3 > Ce(OH)3 > .......>Lu(OH)3
Oxidation State
Common oxidation state exhibited by f block element is +3.
N.B - Ce +4 , Eu +2 , Yb +2 , Tb +4 of 4f series element exhibit oxidation state
other than +3.
• Elements exhibiting higher oxidation state than +3 acts as good oxidising agent.
• Elements exhibiting lower oxidation state than +3 acts as good reducing agent.

Other Common characteristics Lanthanoids

• Reducing nature of Lanthanoids and Actinoids directly proportional to size of
atom.
La > Ce >.......> Lu
Atomic Size is inversely proportional to Ionisation Energy.
• Lanthanoids produces coloured salt due to presence of unpaired electrons in
them and due to f -f transition of electron.
• Lanthanoids are paramagnetic due to presence of unpaired electron in them.
Actinoids
• Actinoid series start from Th to Lr.
• Elements having atomic number greater than 92 are known as man made element
or transuranic element.
• Elements having atomic number < 92 are known as Natural element.
Atomic size
Th >.........> Lr
The decrease in atomic size across the f block element is known as actinide
contraction.

Basic Character of hydroxides

Th(OH)3 > ........>Lr(OH)3

Other common characteristics of Actinoids

Reducing power directly proportional to atomic size.
Ac > Th >…….> Lr
• Common oxidation state of Actinoid series is +3.
• Common oxidation state of Actinoid series is +3.
• 5f Series elements or Actinoids can exhibit highly variable oxidation states
other than +3. ( Reasons at N.B )
N.B- Elements of actinides can exhibit variable oxidation state and higher sate of
+5 , +6, +7 , +8 and +9.
• +9 is the highest oxidation state seen in nature i.e shown by Pu but
Lanthanoids can’t show higher oxidation state like actinoids.
• The 5f orbitals extends into space beyond the 6s and 6p orbital .But in case
of Lanthanoids the 4f orbital are placed deep inside in the atom.
• The participation of 5f orbitals in bonding explain the higher oxidation star of
actinoids.