d and f block (properties of T. E.

depends on partially filled (n -1) d – orbitals)

Those elements which have unpaired electrons in( n-1) d orbitals in their ground state or any of
the oxidation state are called transition elements.

1. T. E. has high M.P. and T.E. have high enthalpy of atomization :-

Reason:- It is due to – 1. Strong interatomic metallic bonding.

2. Involvement of partially filled d-orbitals in covalent bonding
between the atoms.

2. Mn and Tc have exceptionally low m.p. due to weak metallic bonding as they have stable
half-filled subshell (d5)
3. T.E. show variable oxidation state as (ns) and (n-1) d orbitals have similar energy, so d
orbitals can involve in binding
4. Generally transition elements from coloured ions:- they have unpaired e- which undergoes
transition from lower energy d-orbital to higher energy d-orbital by absorbing a part of white
light (d–d transition) and rest of the part is emitted, which gives its complementary colour.
5. Zn2+ salts are white as it has fully filled 3d10 subshell therefore: no d-d transition is possible
Cu+ colourless fully filled 3d10 subshell, cu2+ is coloured due to one unpaired e- in 3d (3d9)
which can show d-d transition.
6. T.E. and their compounds are generally paramagnetic due to unpaired e- in d-orbitals. More
the number of unpaired e- greater will be the paramagnetic character,µ = √𝑛(𝑛 + 2) 𝐵𝑀,
where n = number of unpaired e-.
7. Zn, Cd, Hg are diamagnetic due to all pair electrons. [(n-1) d10].
Due to fully filled d-subshell they do not show T.E. properties.
8. Sc shows only +3 oxidation state as Sc3+ gains stable argon configuration.
9. E0Ni2+/Ni is -0.25V due to highly -ve hydration enthalpy as Ni2+ is small in size.
Eocu2+/cu is +0.34V due to high enthalpy of atomization and less -ve hydration enthalpy.
EoZn2+/Zn is -0.76V as Zn2+ attain stale d10 state so Zn can easily change in Zn2+
EoCr3+/cr2+ is -0.40V as Cr3+ is stable due to half-filled stable t2g3 stable so Cr2+can change to Cr3+
easily
EoMn3+/Mn2+ is +v e as Mn2+ has stable d5 half -filled state and its IE3 valve is high.
10. Cr2+ and Mn3+ have d4 configuration Cr2+ is reducing agent and Mn3+ is oxidation agent.
Reason :- Cr3+ has stable t2g3 half state Cr2+ easily change to Cr3+ by releasing one electron
and acts as good reducing agent Cr2+ → Cr3+ + e-
Mn2+ is stable due to stable half -filled 3d5 state, therefore Mn3+ gains one e- to attain stable
Mn2+ state and is good oxidation agent Mn3++e- → Mn2+
11. Cu+ undergoes disproportionation / Cu+ is unstable in the solution / Cu2I2 changes to CuI2 in
solution
Reason→ Cu2+ has small size and highly -ve hydration enthalpy so it compensates IE2 value
therefore Cu+ changes to Cu2+ in solution
OR Cu2+ is stable 2Cu+ → Cu2+ +Cu
12. T.E. in higher oxidation states from fluorides and oxides as fluorine and oxygen are highly
electro -ve and small in size
13. Oxides are preferred (Dominated) over fluorides in higher oxidation states due to the ability
of oxygen to form multiple bonding with transition metal (pπ- dπ). e.g. Mn2O7 is known not
MnF7.
14. In [Ni(CO)4] →Ni show ‘zero’ ox state, In OsO4 →Os shows highest +8 state.
15. In 1st row of T.E. Mn shows highest +7 State due to 4s2 3d5 configuration.
16. d1 configuration of transition metal ion is unstable as by releasing one e- they attain stable
noble gas configuration.
17. E0M2+/M of 1st row of T.E. are irregular due to irregularity in (IE1 +IE2) as well as sublimation
enthalpy.
18. The increasing oxidizing power of VO2+< Cr2 O72- <MnO4- is due to increasing stability of their
lower oxidation state in which they are reduced.
19. Cr2+ is stronger reducing agent then Fe2+ as d4 →d3 in Cr2+ to Cr3+ and d6 to d5 in Fe2+ to Fe3+.
In aqueous medium d3 (t2g3) is stale than d5 stable according to CFSE.
20. Irregular variation in I.E. in T.E. is due to variation in the stability of 3d configuration eg d0,
d5, d10 are exceptionally stable.
21. Ag can exist in +2 stable and have partially filled d9 configuration it shows T.E. properties.
(AgF2)
22. In 1st row of T.E. , only Cu shows +1 ox state as Cu+ attain stable d10 configuration.
23. 2nd and 3rd transition series (4d and 5d) element have similar atomic size [ Zirconium (Zr) and
Hafnium (Hf)] due to Lanthanoids contraction. Hence due to similar size their properties are
very close to each other.
24. T.E. form alloys as they have similar atomic size so atom of one element can be easily
replaced by the atom of other element from lattice hence, they form alloys. Alloys have high
m.p.
25. T.E. form interstitial compounds:
Reason → In the voids of T.E. crystal lattice, the small atoms of element i.e. B, C, N, O are
trapped and form the bonds with their free valences due to partially filled d-orbitals hence
they form interstitial compound.
Properties of interstitial compounds ------
i) They are harder than pure metal.
ii) They have high m.p.
iii) They are chemically inert and
iv) They retain metallic conductivity.
26. T.E. form complexes due to →
1. Small size and high charge density.
2. Presence of vacant d-orbitals to accept lone pair of electrons from ligand to form dative
bonds.

• V2+ is stable due to high lattice enthalpy t2g3 state.

• CoF3 is stable due to high lattice enthalpy
• Vf5 and CrF6 are stable as they have high bond enthalpy due to higher covalent
nature
• Ni2+ is more stable than Pt2+ as IE1 +IE2 (2.49 KJ/mol) for Ni is lower than Pt. Pt4+ is
stable due to lower sum of first four IE (6.70 KJ/mol) than Ni4+
• In presence of a stronger ligand Co2+ oxidases to Co3+ (3d6) a more stable from
because in presence of strong ligand ‘t2g6’ all e- become paired and stable.
• Central element of T.E. series shows the highest ox state and variable ox state due to
presence of maximum no. of unpaired e- in d-orbital.
• Promethium is the man-made Lanthanoids but after U all Actinoids are man-made.
• Highest ox state of T.E. is in oxoanions as oxygen is highly electro -ve and can form
multiple bonding with metal atom.
• MnO42- (Manganite ion) under goes disproportionation on a acidification as:-
3MnO42- + 4H+ → 2MnO4- + MnO2 + H2O
• KMnO4 in acidic medium is stronger oxidizing agent than basic medium as 1 mol in
acid medium gains 6 e- MnO4- + 8H+ + 5e- → 2MnO4- + Mn2+ +
4H2O
but in alkaline medium only 3e- MnO4- + 2H2O + 3e- → MnO2- + 4OH-
• In first T.E. series (3d), Cu show +1 oxidation state due to stable 3d10 configuration.
• In lower oxidation state, TE oxides are basic as metal ion can oxidizes to higher ox.
state by releasing electron. MnO, VO
In higher ox. state they are acidic as by gaining electron they attain lower ox. state.
Mn2O7, CrO3
• +2 state in first row is common except Sc (Shows only +3). On moving L-R, +2 state
become more stable, as d-orbital electrons shows poor screening effect so effective
nucleus attraction becomes strong and only 4s e- can take part in bonding easily eg.
Zn2+, Cu2+, Mn2+
• Cr is more paramagnetic than Mn, Cr → [Ar] 4s1 3d5 (6 unpaired e-)
Mn → [Ar] 4s2 3d5 (5 unpaired e-)
Cr2+ is less paramagnetic than Mn2+, Cr2+ → [Ar] 3d4 (4 unpaired e-)
Mn2+ → [Ar] 3d5 (5 unpaired e-)
• Colour of K2Cr2O7 changes in pH →
→ In basic medium (pH>7) Cr2O72- changes to CrO42- and colour becomes orange to
yellow. Cr2O72- + 2OH- → 2CrO42- + 2e-

→ In acidic medium (pH<7) Cr2O42- changes to Cr2O72- and colour becomes yellow to
orange. 2CrO42- + 2H+ → Cr2O72- + H2O

• : →– (n-1) d1-10 n s0-2

Electronic configuration(T.E.
(General) Lanthanoids – [Xe] 4f1-14 5d0-1 6s2
Actinoids – [Rn] 5f1-14 6d0-1 7s2

• Lanthanoid contraction: - The steady decrease in the size of tripositive ion

Lanthanoids with increase in atomic number is called LC
 Reason: Due to poor screening effect 4f electrons, the effective nuclear attraction
regularly increases with increase in size therefore size shrinks.
Consequences of LC → 1. Similar size of 4d and 5d elements.
2. Separation of Lanthanoids.
• (+)3 is the stable oxidation state of lanthanoids.
Therefore Ce4+ gains one e- to attain stable +3 state and is a good oxidizing agent
(Cerium) Ce4+ +e- -----→ Ce3+
(Terbium) Tb4 + + e- ------→ Tb+4
Eu2+/Sm2+ is a good reducing agent as it changes to Eu3+/ Sm3+ stable state by
realizing one e-
(Samarium) Sm2+ -------→ Sm3+ +e-
Eu2+ -------→ Eu3+ +e-
• Ce4+ is stable due to stable xenon configuration [Xe] 4fo 5 do 6s0
Eu2+ is stable due to stable half-filled 4f subshell [Xe] 4f7 5d0 6s0
Tb+4 is stable due to 4f7 configuration.
• Actinoids show variable oxidation state (+3 to +7)
Reason :- 5f, 6d and 7s have similar energy so 5f electrons can easily take part in
bonding and show variable ox state.
• Actinoids are more reactive then Lanthanoids.
Reason :- 5f electrons in Actinoids are less penetrates in inner core electron than 4f
of Lanthanoids therefore the shielding effect of 5f is stronger than 4f. So the outer
shell electron feels poor nuclear attraction and is easily available for bonding.

• Misch metal →Alloy of ≈ 95 % Lanthanides ≈ 5% iron and traces of C, Al, Si, S.

Magnesium based alloy is used for making shells of bullets, flints of higher etc.
•