REVISION SHEET

The d and f-Block Elements

Incomplete n and n − 1 shell in atomic or in ionic state. Zn,Cd & Hg - are d-block non-transition
elements.
◼ GENERAL ELECTRONIC CONFIGURATION
ns0−2 (n − 1)1−10

 Cr = 4 s 3 d
1 5

Exceptions  ,Pd = 5 s0 4 d10


Cu = 4 s 1
3 d10

◼ TRANSITION SERIES
3d series: Sc21 − Zn30

4d series: Y39 − Cd48

5d series: La57 ,Hf72 − Hg80

6d series: Ac89Unq104 − Uub112

◼ ATOMIC RADIUS
3d series Sc  Ti  V  Cr  Mn  Fe CO Ni  Cu  Zn
In a group 3d to 4d series increases but 4d and 5d series nearly same due to poor shielding of
f electron. (Lanthanide contraction)
3d  4 d 5d
Smallest radius − Ni
e.g. : TI  zr Hf
Largest radius − La
Melting point: s -block < d-block
In a series on increasing number of unpaired e –mpt increases upto Cr then decreases.
Sc  Ti  V  CR  Mn  Fe  Co  Ni  Cu  Zn
 
Half filled d5 Fully filled d10
 weak metallic bond  weak metalic bond
Zn  Cd  Hg
Melting point  (data based)
Cu  Ag  Au
E.N. Exception Zn  Cd  Hg
Density: s-block metals < d-block metals
3d series: Sc < Ti < V < Cr < Mn < Fe < CO ≤ Ni <Cu > Zn
 Density in a Group 3d  4d  5d
Metallic character: They are solid, hard, ductile, malleable, good conductor of heat and electricity
and exhibit metallic lusture, high tensile strength. Hg is liquid
Elect. Cond. Ag  Cu  Au  Al p − block
d−block

◼ OXIDATION STATE
Transition elements exhibit variable oxidation state due to small energy difference of ns and
(n-1) d electrons.
▪ Common oxidation state is +2
▪ 3d series highest oxidation state is +7(Mn)
▪ Their higher oxidation states are more stable in fluoride and oxides.
▪ Sc(+3) and Zn(+2) exhibit only one oxidation state
▪ In d-block series highest oxidation state is +8 (Os, Ru)
▪ In carbonyl compound oxidation state of metals is zero due to synergic effects.
▪ Higher oxidation states in oxides are normally more stable than fluorides due to capability of
oxygen to form multiple bonds.
e.g. stable fluoride in higher ox. St. of Mn is MNF4 while oxide is MN2O7
▪ Some more stable oxidation states of d-block elements
Cu + 2 & Mn + 2 & Pt + 4

Cr + 3 & Sc + 3 & & Au + 3 & Ni +

▪ Common oxidation states
Ti(+4), V(+5) Cr(+3, +6) Mn(+2, +4, +7)

Fe(+2, +3),Co(+2. + 3)Ni(+2) Pt(+2 + 4)

In p-block lower oxidation states of heavier elements are more stable while in d-block heavier
element, higher oxidation state are more stable.
e.g. In VIB gp Mo (+6) \& W (+6) are more stable than Cr(+6)

◼ MAGNETIC PROPERTY
All transition elements are paramagnetic due to presence of unpaired electrons. They attract
when magnetic field is applied. Magnetic moment of unpaired electron is due to spin and orbital
angular momentum.
"Spin only" magnetic moment can be calculated by using formula  = n(n + 2) Bohr magneton. (
n is number of unpaired e− .)
n is 1 = 1.73BM
n is 2 = 2.84BM
n is 3 = 3.87BM
n is 4 = 4.90BM
n is 5 = 5.92BM
◼ COLOUR
Colour in transition metal ions is associated with d − d transition of unpaired electron from t 2g

to e g set of energies. This is achieved by absorption of light in the visible spectrum, rest of the
light is no longer white.
 Colourless - Sc3+ , Ti4+ ,Zn2+ etc

Coloured −Fe3+ yellow Fe2+ green, Cu2+ blue, Co3+ blue etc
Interstitial compounds: When less reactive nonmetals of small atomic size e.g. H, B, N, C, Trapped
in the interstitial space of transition metals, interstitial compounds are formed, like:-
TiC,Mn4 N,Fe3H etc.

These compounds are called nonstoichiometric compounds and have higher melting point than
metals, but chemically inert.
Alloys
Solid mixture of metals in a definite ratio ( 15% difference in metallic radius)
They are hard and having high melting point.
e.g. Brass(Cu + Zn)
Bronze (Cu + Sn) etc.

Hg when mix with other metals form semisolid amalgam except Fe,Co,Ni , Li.

Catalyst
Transition metals \& their compounds act as catalyst due to-
Variable oxidation state
Tendency to form complex
e.g. V2O5 - Contact process

Fe - Haber process
Ni - Catalytic hydrogenation
◼ POTASSIUM DICHROMATE
K2Cr2O7 :

Prepared from chromite ore (FeCr2 O4 )

▪ 4FeCr2O4 + 8Na2CO3 + 7O2 → 8Na2CrO4 + 2Fe2O3 + 8CO2

▪ Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl
▪ 2Na2CrO4 + H2SO4 → Na2Cr2O7 + Na2SO4 + H2O
The chromates and dichromates are interconvertible in aqueous solution depending upon pH of
the solution.

2CrO24− + 2H+ → Cr2O27− + H2O

(orange)

Cr2O72− + 2OH− → CrO42− + H2O

( yellow)

Cr2O72− + 14H+ + 6e− → 2Cr3+ + 7H2O

Fe2+ → Fe3+ + e− ;2I− → I2 + 2e−

SO2 + 2H2O → SO42− + 2H+ + 2e− ; C2O42− → 2CO2 + 2e−

The full equation is obtained by adding the half reaction for potassium dichromate to the half
reaction for the reducing agent
 for e.g. Cr2O27 − + 14H+ + 6I− → 2Cr 3+ + 7H2O + 3I2
Green

Green-Chromylchloride Test: K2Cr2O7 + 4KCl + 6H2SO4 → 2CrO2Cl 2 + 6KHSO4 + 3H2O

(chromyl chloride)

◼ POTASSIUM PERMANGANATE
KMnO4 :
▪ Prepared from the mineral pyrolusite
2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O

3MnO24− + 4H+ → 2MnO4− + MnO2 + 2H2O

Oxidising properties:
In acidic medium: MnO4− + 8H+ + 5e− → Mn2+ + 4H2O

It oxidises I− to I2 ,NO2− to NO3− ,Fe2+ to Fe3+ , C2O42 − to CO2

In neutral or faintly alkaline medium,
MnO4− + 2H2O + 3e− → MnO2 + 4H2O

It oxidises S2O32 − to SO24− ,Mn2+ to MnO2 , I− to IO3− etc.

◼ F-BLOCK ELEMENTS
Actinoids Lanthanoids

General E.C. 5f 1−14 6d0− 1 7s2 6s2 5d0−1 4f 1−14

Ionic Size ▪ The general trend in lanthanoids ▪ In the lanthanoid series with increasing
is observable in the actinoids as atomic number, there is a progressive
well. decrease in the size from lanthanum to
▪ There is a gradual decrease in the (
lutetium La 3 + to Lu3 + . )
3+
size of atoms or M ions across ▪ In these elements the added electron
the series. enters in the deep seated f-orbitals and
▪ This may be referred to as the therefore experiences considerable pull
actinoid contraction (like by the nucleus.
lanthanoid contraction). ▪ Hence with increasing atomic number,
▪ The contraction is, however, the enhanced nuclear charge leads to
greater from element to element contraction in the size of atoms and ions.
in this series resulting from poor
shielding by 5f electrons.
Oxidation +3, +4, +5, +6 and +7 +2, +4
state

Properties ▪ These are mostly radioactive. ▪ Electropositive character: High due to

▪ Greater tendency to form low I.P.
complexes than lanthanides. ▪ Complex formation: Do not have much
tendency to form complexes.
▪ Reducing Agent: They readily lose
electrons so they act as good reducing
agents.