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D&FBlocks
D&FBlocks
Syllabus:
3d
4d
5d Lanthanide
series
6d Actinide
Series
4f
5f
D-Block:
1. General Points:
a. Outer e.c: (n-1)d1-10 ns1-2
Exception: Pd (4d10 5s0)
b. Coinage metals are Cu, Ag, Au
Due to ductile and malleable nature.
c. Noble Metals: Cu, Ag, Au, Pt, Hg
d. Transition Metal:
A metal which has an incompletely filled orbital in ground state or any common OS.
Zn(3d10), Cd(4d10) and Hg(5d10) are not considered as transition metals (though d-block)
as they have fully filled d-orbitals in ground state and oxidation states.
Zn, Cd and Hg are very much similar in properties to the alkaline earth metals
(representative elements).
i. mp: Zn: 420°C
Cd: 321°C
Hg: Liquid at room temp.
Other d-block elements have higher mp, bp and hardness.
This is why Zn, Cd, Hg are called volatile metals.
e. The d-orbitals of transition elements project more to the periphery of the atom than
s- and p-orbitals, and hence are more influenced by
other atoms/molecules (eg: ligands)
3. Lanthanide Contraction:
a. Observed in 4d series (Zr-Cd) and 5d series (Hf-Hg)
b. Atomic Size of 5d elements after La are of nearly the same size as 4d elements in the
corresponding group. This is called lanthanoid/lanthanide contraction.
c. It occurs due to the poor shielding effect of f-electrons filled after La (Ce to Lt). As a
result, zeff is very high from Hf.
4. mp, bp and ∆H :
a. mp, bp and ∆H of d-block elements are much higher
than those of s- and p-block elements due to strong
metallic bonding.
b. mp first increases, reaches max in the middle, and
again decreases.
c. In d-block metals, unpaired (n-1)d and ns electrons
take part in metallic bond formation. Hence, the greater
the unpaired d-electrons, greater will be the mp.
d. Mn has lower mp than Cr and Fe because of its stable
ec of 3d5 4s2, in which unpaired 3d5 and 4s2 electrons
are not delocalised, and strength of metallic bond is low.
e. Order of mp down a group: 3d < 4d < 5d
f. (n-1)d unpaired electrons in 4d and 5d have greater tendency to get involved in inter-
atomic bonding.
g. High ∆𝐻 is due to high strength of metallic bonds.
h. Strength of metallic bonding↑, mp↑, ∆H↑
5. Densities:
i. Density increases from L to R in d-block because size decreases from L to R while
molar mass increases from L to R.
ii. 𝜌 < 𝜌 due to the larger size of Zn-atom than Cu-atom
iii. Lowest density in d-block: Sc
iv. Highest density in d-block: Os ≈ Ir
6. Ionisation Enthalpies:
a. In general, IE of d-block elements increases from L to R with irregular trends due to
increase in zeff.
b. When one e ̄ is removed from ns-orbital, the relative energies of 3d and 4s change and
the other ns e ̄ shifts to (n-1)d orbital (if empty).
Eg: Fe: 3d6 4s2
Fe+: 3d6 4s1 ⎯ 3d7 4s0
(unstable)
c. IE2 of Cr and Cu are unusually high due to the 2nd e ̄ being removed from the stable 3d5
or 3d10 configurations.
d. IE1(Mn) > IE1(Cr)
IE2(Cr) > IE2(Mn)
7. Oxidation States:
a. Most common OS in d-block is +2
b. Sc(+3), Zn(+2), Cd(+2) show fixed OS in all compounds.
Sc Ti V Cr Mn Fe Ni Co Cu Zn
+3 +2 +2 +2 +2 +2 +2 +2 +1 +2
+3 +3 +3 +3 +3 +3 +3 +2
+4 +4 +4 +4 +4 +4 +4
+5 +5 +5
+6 +6 +6
+7
+OS indicates common OS of the element.
c. Mn+2 to Mn+3 form ionic compounds while Mn+4 to Mn+7 form covalent compounds.
d. Variety of OS increases from L to R, reaches maximum in middle (Mn), and decreases
towards the end. This is due to the number of unpaired (n-1)d electrons which can be
lost to form a cation in lower OS or to share e ̄ to form covalent bonds in higher OS.
e. Eg: MnO is ionic, MnO3 is covalent.
f. Unlike heavy members of p-block which show variable OS by a difference of 2 (eg: SnCl2,
SnCl4) due to inert pair effect, d-block elements form compounds in various OS due to
small IE difference in successive ionisation energies.
g. High OS of d-block elements are stabilised by O and F as these form strong bonds with
the d-block elements (Mn2O7 exists but MnF7 does not).
Eg: MnO4 ̄ , MnO42 ̄ , Mn2O72 ̄ , Cr2O72 ̄ , CrF6, MnF4, VF5, MnOF3, OsO4, FeO42 ̄ , V2O5,
VO2+, TiCl4, XeF6, XeF4, XeO3, XeO4, etc.
h. O can stabilise the highest OS of an element better than F due to its nature of forming
strong double bond.
i. Unlike in p-block, the stability of higher OS increases from top to bottom in d-block.
Eg: Cr2O7 is a powerful OA. However, MoO3 and WO3 under it have no oxidising ability
since they are stable compounds.
e. In aq. soln., Co+2 is more stable and Co+3 is highly unstable. However, Co+3 is highly
stable in complex compounds due to high CFSE released.
Eg: [Co(NH4)6]3+, [Co(H2O)6]3+, [Co(C2O4)3]3 ̄ .
(These are d2sp3 diamagnetic complexes)
f. +ve SRP for Cu indicates that it has less tendency to convert into Cu+2.
g. Cu does not liberate H2 gas with dilute HCl, but reacts with oxidising acids like HNO3
and H2SO4. This is attributed to high IE2 of Cu (3d10).
h. Extra stability of Mn+2 is due to half-filled stable configuration.
i. Mn+3 is a powerful OA (unstable) and converts into the more stable Mn+2 by reducing
other compounds.
j. Cr+2 is a good reducing agent as it converts into stable Cr+3 ion.
k. Cr+3 is stable as 3 electrons remain in t2g orbitals.
l. In aqua complex, Cr+3 (3d3 4s0), electrons are distributed as (t2g1, 1, 1 eg0, 0)
m. Cr+2, V+2, Ti+2 are good RA and liberate H2 from dilute acids.
2Cr+2 + 2H+ ⎯⎯ 2Cr+3 + H2↑
n. VF5 is stable at room temp, and other pentahalides undergo hydrolysis to give oxohalides
(VOX3).
Eg: VO+3, VO2+, BiO+ are oxycations.
o. Another feature of fluorides is their stability in low OS (CuF and VF2 do not exist) because
F2 is such a powerful OA that it forms more stable CuF2.
Eg: Cu + F2 ⎯⎯ CuF2
However, CuCl and CuBr exist.
p. CuI2 and FeI3 do not exist as I is a good RA
Eq: Cu+2 + I ̄ ⎯ CuI↓ + I2 or I3 ̄
q. Many Cu+ compounds in aq. soln. undergo disproportionation:
2Cu+(aq) ⎯⎯ Cu(s) + Cu+2(aq)
Cu+2 is more stable than Cu+ because ∆𝐻 of Cu+2 is very high (released)
9. Magnetic Properties:
a. Paramagnetic:
i. Weakly attracted in magnetic field
ii. One or more unpaired e-
iii. Non-zero spin magnetic moment
b. Diamagnetic:
i. Weakly repelled in magnetic field
ii. Zero unpaired e-
iii. Zero spin magnetic moment
c. Ferromagnetic:
i. Fe, Ni, Co
ii. Special case of diamagnetism
iii. Spin magnetic moment = 𝑥(𝑥 + 2) Bohr Magneton (BM), where x = no. of
unpaired e ̄.
10. Formation of Coloured Ions:
a. Colour of d-block metals can be explained mainly due to d-d transition.
b. Colours of some aq. ions:
i. Sc+3 – colourless
ii. Ti+4 – colourless
iii. Ti+3 – purple
iv. V+4 – blue
v. V+3 – green
vi. V+2 – violet
vii. Cr+3 – violet (pure)
viii. Cr+3 – green (impure)
ix. Fe+2 – green
x. Fe+3 – yellow
xi. Co+2 – pink
xii. Co+3 – blue
iii. Uses:
As white paint. Even in H2S atmosphere, it remains white as ZnS is also
white.
Used in making green paint (Rinman’s Green – ZnO.CoO or ZnCoO2)
iii. Properties:
Dark brown solid
Soluble in water
Dissolves in ether also, as FeCl3 is a good LA
Sublimes at 300°C to give dimeric gas
∆
FeCl3 ⎯⎯ FeCl2 + Cl2↑
Aq. soln. of FeCl3 is acidic:
FeCl3 + 6H2O ⎯⎯⎯ [Fe(H2O)6]+3 + 3Cl ̄ (aq)
Hydrolysis:
[Fe(H2O)6]+3(aq) + H2O ⇋ [Fe(H2O)5(OH ̄ )]+2 + H3O+
(acid) (base)
Hydroquinone Quinone
iii. Fixing the film:
Na2S2O7 is used to remove the unexposed AgBr.
AgBr(s) + 2Na2S2O7 (aq) (exc) ⎯⎯ Na3[Ag(S2O3)2] + NaBr
(unexposed) (fixer solution)
Now the film is light-insensitive and is called ‘negative’.
All Mn–O bond lengths are equal due to delocalisation of e ̄ .
KMnO4 is a purple solid
2KMnO4 ⎯⎯⎯⎯⎯ K2MnO4 + MnO2 + O2↑
KMnO4 + H2SO4 ⎯⎯ Mn2O7 + KHSO4 + H2O
(excess) (conc) (explosive)
KMnO4 + conc. HCl ⎯⎯ MnCl2 + Cl2 + H2O
While using KMnO4 as OA in quantitative or volumetric analysis, to make
the solution acidic, H2SO4 is preferred.
Stronger OA than K2Cr2O7 (SRP=1.52V vs 1.33V)
v. Oxidising Nature:
In acidic medium:
.
C2O42 ̄ → CO2↑
H2S → S↓
S2 ̄ → S↓
NO2 ̄ → NO3 ̄
I ̄ → I2
Fe+2 → Fe+3
H2O2 → O2
In basic medium:
.
I ̄ → IO3
S2O32 ̄ → SO42 ̄
MnO4 ̄ → MnO2↓
/
Mn+2 + MnO4 ̄ + H2O ⎯⎯⎯⎯⎯⎯⎯⎯ MnO2↓
Mn salt OA catalyst (comproportionation)
vi. Uses:
As an oxidising agent in laboratories
Bleaching agent for silk, cotton, wool, etc
Alkaline KMnO4 is called Bayer’s reagent
KMnO4 is a secondary titrant
Oxidising Nature:
In acidic medium, Cr2O72 ̄ (aq) converts to Cr+3(aq)
C2O42 ̄ → CO2↑
Na2SnO2 → Na2SnO3
S2 ̄ → S↓
NO2 ̄ → NO3 ̄
Fe+2 → Fe+3
I ̄ → I2
SO32 ̄ → SO42 ̄
Heating Effect:
∆
K2Cr2O7 ⎯⎯⎯ K2CrO4 + Cr2O3 + O2↑
iv. Uses:
As an OA in laboratory
Used as primary standard in volumetric analysis (titration)
In preparation of chrome alum (K2SO4.Cr2(SO4)3.24H2O)
In leather industry
To manufacture azo compounds.
F-Block:
1. 4f series:
a. General Points:
i. Outer e.c.: (n-2)f1-14 (n-1)d0-1 ns2
ii. Most common OS for lanthanoids and actinoids is +3
iii. The Lanthanoids (Ln):
Lanthanum is not part of f-block since it does not have f-electron.
However, it is still studied along with f-block elements because it shows
properties similar to the f-block elements.
b. Oxidation States:
i. The most common OS is +3, but they show +2 and +4 as well
The +3 OS has uniform ec through the block (4fn, where n=1, 2, 3, ... 14)
Ce+4 is a powerful OA used in analytical chemistry. It is favoured as it has
noble gas (Xe) configuration.
𝑆𝑅𝑃 / / = 1.74V (Powerful OA)
Ce can even oxidise water, but oxidation of water is kinetically slow.
+4
d. General Characteristics:
i. All lanthanoids are silvery-white metals, and tarnish rapidly in air
ii. Sm is very hard and has highest mp in 4f series
iii. Many Ln+3 ions (solid and aq) are coloured due to unpaired f-electron
(paramagnetic)
La+2 and Lu+3 do not show colour as there are no unpaired e ̄
iv. IE1 and IE2 of lanthanoids matches alkaline earth metals (Ca)
v. Reactivity also matches with Ca for first 5; but as atomic no. increases, they behave
like Al.
e. Uses:
i. For production of alloy steels for plates and pipes
Mischmetal: Ln + Fe + traces of C, S, Ca, Al
≈95% ≈5%
Mischmetal is used in Mg-based alloys to produce bullets, shells, and lighter flints
ii. Mixed oxides of Ln are used in petroleum cracking
2. 5f Series:
a. General Properties:
i. Outer e.c.: (n-2)f0-14 (n-1)d0-2 ns2
M+3 follows a regular trend of ec (n-2)fn, where 0 ≤ 𝑛 ≤ 14
c. General Characteristics:
i. All actinoids are silvery metals.
ii. They are highly active metals, particularly when finely divided.
They are more active than the lanthanoids.
iii. With hot water, they form oxides and hydrides.
M + H2O(l) ⎯⎯ M(OH)3 + H2↑
(hot water/steam)
M + H2 ⎯⎯⎯ MHx
iv. Do not react with alkalis
v. React with halogens
vi. Reaction of HNO3 is slow due to formation of protective oxide film on the surface
of actinoid.