CHAPTER

10 The d & f-Block Elements

Definition E.N. Exception: Zn < Cd < Hg

Transition elements are those d-block elements which have Density : s − block metals < d − block metals.
partially filled (n – 1)d subshell either in their ground state or in
their most stable oxidation states. Therefore, Zn, Cd & Hg are 3d series
d-block elements and not transition elements. Sc < Ti < V < Cr < Mn < Fe < Co ≤ Ni < Cu > Zn
General electronic configuration Density in a Group: 3d < 4d << 5d
ns0–2 (n–1)d1–10
Metallic character: They are solid, hard, ductile, malleable,
Cr = 3d 5 4s1 good conductor of heat and electricity and exhibit metallic
Exceptions  10 1 10
Cu = 3d 4s , Pd = 4d 5s
0
lusture, high tensile strength. Hg is a liquid.
Electrical conductivity:-
Transition Series
Ag > Cu > Au
 Al
 > p – block
1st 3d series Sc21 — Zn30 9 + 1 = 10 d – block

2nd 4d series Y39 — Cd48 9 + 1 = 10 Oxidation State

Transition elements exhibit variable oxidation states due to small
3rd 5d series La57, Hf72 — Hg80 9 + 1 = 10
energy difference of ns and (n–1)d orbitals.
4th 6d series Ac89, Unq104 — Uub112 9 + 1 = 10
™ Sc(+3) and Zn(+2) exhibit only one oxidation state.
Common oxidation state is +2 & +3.
Atomic Radius ™

3d series: Sc > Ti > V > Cr > Mn ≥ Fe  Co  Ni ≤ Cu < Zn. In a ™ In 3d series, highest oxidation state is +7 (Mn).
group from 3d to 4d series, atomic radius increases but 4d and 5d ™ In d-block series, highest oxidation state is +8 (Os, Ru).
series have nearly same atomic radius due to poor shielding of f ™ In carbonyl compounds, oxidation state of metals is zero due
electrons (Lanthanide contraction).
to synergic effects.
3d < 4d  5d Their higher oxidation states are more stable in fluorides and
™

Smallest radius – Ni oxides.

e.g :Ti < Zr  Hf
Largest radius – La ™ Higher oxidation states in oxides are normally more stable

than fluorides due to capability of oxygen to form multiple
Melting point : s-block metals < d-block metals
bonds.
In a series, on increasing number of unpaired electrons, melting Eg. stable fluoride in higher oxidation state of Mn is MnF4
point increases upto Cr and then decreases. while oxide is Mn2O7.
Sc < Ti < V < Cr > Mn < Fe > Co > Ni > Cu > Zn
™ Mn shows maximum number of oxidation states (+2 to +7)
↓ ↓
among 3d series.
Half filled d 5 Fully filled d10 ™ Beyond Mn, trihalides are not observed except in FeX3 (X = Cl/
∴weak metallic bond    ∴weak metallic bond Br/I) & CoF3.
Zn > Cd > Hg ⇒ V2O3 V2O4 V2O5
Melting point (data based)
Cu > Ag ≤ Au Basic Basic Amphoteric
 ⇒ CrO Cr2O3 CrO3 They are non-stoichiometric compounds.
Basic Amphoteric Acidic
They have high melting point than the metals from which
⇒ MnO MnO2 Mn2O7
they are formed.
Basic Amphoteric Acidic
⇒ CuI2 does not exist as it decomposes to give CuI & I2 at room They are chemically inert.
temperature
1 Catalytic Properties
CuI 2 → CuI + I 2
2 Most of the d-block compounds act as catalyst due to their variable
⇒ In aqueous solution, Cu+ disproportionates into Cu & Cu2+. In oxidation state, complex formation tendency and adsorption of
p-block, lower oxidation states of heavier elements are more gases on their surface.
stable, while in d-block higher oxidation state of heavier
Example:
elements are more stable.
Eg. In VIB group, Mo(+6) & W(+6) are more stable than Contact process = V2O5
Cr(+6). Haber's process = Fe2O3 + Al2O3 + K2O

Magnetic Property Fenton’s reagent = FeSO4 + H2O2

All transition elements are paramagnetic due to the presence of Decomposition of KClO3 = MnO2
unpaired electrons. Magnetic moment of unpaired electrons is due Ostwald's process = Pt/Rh
to spin and orbital angular momentum.
Zeigler Natta = TiCl4 + (C2H5)3 Al
“Spin only” magnetic moment can be calculated by using the formula,
Hydrogenation of Alkene = Ni/Pd
=µ n(n + 2) Bohr magneton. (n is the number of unpaired e–s)
Wilkinson’s catalyst = RhCl + PPh3
If n is 1, m = 1.73 BM
n is 2, m = 2.84 BM Important reactions of d-block elements
n is 3, m = 3.87 BM (a) Cu2+ + 4I–→ Cu2I2(s) + I2
n is 4, m = 4.90 BM
(b) CuSO4 + KCN → K2SO4 + Cu(CN)2
n is 5, m = 5.92 BM Excess Unstable

Substances, that are not attracted by applied magnetic field are 2Cu(CN)2 → 2CuCN + (CN)2
Cyanogen
diamagnetic. They have all the electrons paired. d-block elements
CuCN + 3KCN → K3[Cu(CN)4]
and ions, having d0 and d10 configuration are diamagnetic.
H2O + CO2
(c) Cu CuCO3.Cu(OH)2
Colour moist air Green
Aqua regia
Colour in transition metal ions is associated with d-d transitions of Au(3HCl + HNO )
H[AuCl4] + NOCl + H2O
3
unpaired electrons from t2g to eg set of energies. This is achieved
Heating 1
by absorption of light in the visible spectrum, rest of the light is (d) AgNO3(s) Ag + NO2 + O 2
2
no longer white.
Heating 1
Colourless – Sc3+, Ti4+, Zn2+ etc. Ag2CO3(s) Ag + CO2 + O 2
2
Coloured – Fe3+ yellow, Fe2+ green, Cu2+ blue, Co3+ blue etc. 100ºC 720ºC
(e) CuSO4.5H2O CuSO4.H2O
Alloys Light greenish blue

230ºC 1
Solid mixture of metals in a definite ratio (15% difference in CuSO4 CuO + SO2 + O 2
Colourless 2
metallic radius). They are hard and have high melting point.
NH2
Eg. Brass (Cu + Zn) (f) Hg2Cl2 + NH4OH Hg + Hg
Bronze (Cu + Sn) etc. Cl Black

Hg when mixed with other metals form semisolid amalgam except (g) NO3–/NO– FeSO4 + H2SO4 [Fe(H O) NO+]SO
2 2 5 4
Brown ring complex
Fe, Co, Ni, Pt.
(h) AgBr + 2Na2S2O3 Na3[Ag(S2O3)2] + NaBr
Interstitial compound Photographic complex

When less reactive non-metals of small atomic size eg. H, B, N, C (i) Chemical volcano:
are trapped in the interstitial space of transition metals, interstitial D
(NH4)2Cr2O7 → N2 + 4H2O + Cr2O3
compounds are formed, like: TiC, Mn4N, Fe3H etc. orange solid Green residue

28 JEE (XII) Module-3 PW

Reactions of Cr2O72– MnO4–/OH–
Cr2O72– (Orange) I– IO3–
SO2 SO42–
H2S S CH2 = CH2 CH2 – CH2
SO3 2–
SO42– OH OH
NO2– NO3– MnO2
I– I2 (Brown ppt)

Br– Br2 Some important d-Block metal compounds

S2O3 2– S + SO4 2– Ferrous sulphate, FeSO4.7H2O (Green Vitriol)
C2H5OH CH3COOH Commonly known as harkasis.
Sn2+ Sn4+ Heating effect:
Fe2+ Fe3+ FeSO4.7H2O 
140° C
→ FeSO4.H2O 
300° C
→ 2FeSO4
 High
 → Fe2O3 + SO2↑ + SO3↑
Cr3+(green) Temp.

H 2 SO4


CrO 24 − 
H+ 2− Fe (from iron scrap)   FeSO 4
−  Cr2 O7
OH
 H2 
Yellow Orange

–2/H+
KCN
FeSO 4  → K 4 [Fe ( CN )6 ]
Cr2O7 (Orange) − K 2 SO4

Hydrolysis
FeSO 4  → Fe(OH) 2 + H 2SO 4
(Solution is acidic)
H2O2 H2O
Uses : For making laboratory reagents, like Mohr’s salt etc.
FeSO4 + (NH4)2 SO4 + 6H2O → FeSO4.(NH4)2 SO4.6H2O
CrO5 (Mohr’s salt)
(Blue)
FeSO4 + H2O2 known as Fenton’s reagant is used as catalyst.
2. Zinc Sulphate, ZnSO4.7H2O (White Vitriol)
Reaction of MnO4– NaOH NaOH
ZnSO 4 
− Na 2 SO4
→ Zn(OH) 2 ↓  − H2 O
→ Na 2 ZnO 2
MnO4–(Purple)/H+ White Soluble Complex

ZnSO 100° 200° 800°C

4 → ZnSO ⋅ 6H O  4 → ZnSO
2 4
C2O42– CO2
SO2 SO42– ZnO + SO3↑
H2S S 3. Copper sulphate, CuSO4.5H2O (Blue vitriol)
S2O32– S + SO42– Also known as ‘Nilathotha’
NO2– NO3– Physical Properties: Blue crystalline compound, soluble in
I– I2 water.
Br– Br2 air
CuSO4.5H2O  → CuSO4.4H2O 
100° C
→
Cl– Cl2 effloresces
250° C 750° C
C2H5OH CH3COOH CuSO4.H2O → CuSO4 → CuO + SO2↑ + O2↑
Sn+2 Sn+4 Cu + H 2SO 4 + O 2  → CuSO 4
Fe+2 Fe+3 − H2 O

CuSO 4 
NaOH / Na 2 CO3
− Na 2 SO 4 / − Na 2 SO 4 , CO 2
→ Cu ( OH )2 ↓
Mn+2(Purple colour is decolourised) blue
Strongly ∆ CuSO 4 
KSCN + SO + H O
MnO4 – → MnO4 2– 2
→ CuSCN ↓ (white) + K 2SO 4 + H 2SO 4
2

Basic
Purple Green
Solution
4. Ferric Chloride, FeCl3
FeCl3(anhyd.) + O2 
–Fe2O3
Fe + Cl2 (dry)  FeCl3
FeCl3.6H2O+SOCl2 –HCl, SO2
It sublimes at 300°C giving a dimeric gas.

P The d & f-Block Elements 29

W
 Cl Cl Cl (ii) The film is placed in a camera. When the photograph is
exposed, light from the subject enters the camera and is
Fe Fe focussed by the lens to give a sharp image on the film.
Cl Cl Cl The light starts a photochemical reaction by exciting a
Two 3C-4e– bond halide ion, which loses an electron. The electron moves
Four 2C-2e– bond in a conduction band to the surface of the grain, where it
5. Zinc Chloride reduces Ag+ ion to metallic silver. To remove the excess
of AgBr, hypo solution is used.
Prepration of hydrated ZnCl2(ZnCl2.2H2O)
2AgBr(s)  light
→ 2Ag + Br2
ZnCl2.  
ZnO +HCl ZnO+HCl AgBr + 2Na2S2O3(aq.) 
2H2O –HCl, H2O
Zn(OH)Cl light
→ Na3[Ag (S2O3)2] + NaBr

6. Cupric chloride, CuCl2, 2H2O f-block elements

150° C Lanthanoids are a series of elements that involve the filling of
Heating effect: CuCl2.2H2O →
HCl gas CuCl2 + 2H2O 4f- subshell. These are fourteen elements, following lanthanum,
7. Silver nitrate, AgNO3 (Lunar Caustic) from Cerium to Lutetium. Actinoids are a series of elements
Heating above that involve filling of 5f-subshell. These are fourteen elements
M.pt.
AgNO2 + O2 following Actinium from Thorium to Lawrencium. The common
 oxidation state of lanthanoids and actinoids is +3.
Ag+HNO3 (dil.) AgNO3
Red Hot
Ag + NO2 + O2 Some Applications of d- and f-Block Elements
Iron and steels are the most important construction materials. Their
Photography production is based on the reduction of iron oxides, the removal of
(i) A photographic film consists of a light sensitive emulsion impurities and the addition of carbon and alloying metals, such as
of fine particles (grains) of silver salts in gelatin, spread Cr, Mn and Ni. TiO for the pigment industry and MnO2 for use in
on a clear celluloid strip or a glass plate. AgBr is mainly dry battery cells. The battery industry also requires Zn and Ni/Cd.
used as the light sensitive material. The ‘silver’ UK coins are Cu/Ni alloy.

30 JEE (XII) Module-3 PW