The d and f-Block Elements

SHORT NOTES
GENERAL PROPERTIES OF d-BLOCK  Beyond Mn, trihalides are not observed except FeX3
(X = Cl/Br/I) & CoF3
ELEMENTS  V2O3 V2O4 V2O5
Atomic Radius basic basic    amphoteric
3d series Sc > Ti > V > Cr < Mn ≥ Fe  Co  Ni ≤ Cu < Zn
Magnetic Properties
Melting Point Most of the transition elements show paramagnetic behaviour
Melting point : s-block metals < d-block metals due to presence of unpaired electrons. Substances that are not
attracted by applied magnetic field are diamagnetic, they have all
In a series on increasing number of unpaired e– melting point the electrons paired. d-block elements and ions having d0 and d10
increases upto Cr then decreases. configuration are diamagnetic.
Sc < Ti < V < Cr > Mn < Fe > Co > Ni > Cu > Zn
Colour
↓ ↓ Colour in transition metal ions is associated with d-d transition of
Half filled d 5 Fully filled d10 unpaired electron from t2g to eg set of energies. Colourless – Sc3+,
∴weak metallic bond ∴weak metallic bond Ti4+, Zn2+ etc.
Coloured – Fe3+ (yellow), Fe2+ (green), Cu2+ (blue), Co3+ (blue) etc.
Zn > Cd > Hg
Melting point (data based) Alloys Formation
Cu > Ag ≤ Au
Solid mixture of metals in a definite ratio (15% difference in
E.N. Exception Zn < Cd < Hg
metallic radius) They are hard and have high melting point.
Density eg. Brass (Cu + Zn)
Density : − s − block metals < d − block metals. Bronze (Cu + Sn) etc.
Hg when mixed with other metals from semisolid amalgam except
3d series Fe, Co, Ni, Pt.
Sc < Ti < V < Cr < Mn < Fe < Co ≤ Ni < Cu > Zn Interstitial Compound
When less reactive nonmetals of small atomic size eg. H, B, N, C,
Density in a Group: 3d < 4d << 5d
trapped in the interstitial space of transition metals, interstitial
Metallic Character compounds are formed, like :- TiC, Mn4N, Fe3H etc.
They are non-stoichiometric compounds.
Metallic character: They are solid, hard, ductile, malleable, good
conductor of heat and electricity and exhibit metallic lusture, high They have high melting point than metals.
tensile strength. Hg is liquid They are chemically inert.
Ag > Cu > Au Al
 > p – block
Catalytic Properties
Electrical conductor 
d – block Most of the d-block compounds act as catalyst due to their variable
oxidation state or complex formation tendency or adsorption on
Oxidation State their surface.
Transition elements exhibit variable oxidation state due to small
energy difference of ns and (n–1)d electrons. IMPORTANT REACTIONS OF d-BLOCK
™ Sc(+3) and Zn(+2) exhibit only one oxidation state. ELEMENTS
™ Common oxidation state is +2 and +3 (a) Cu2+ + 4I– —→ Cu2I2(s) + I2
™ In 3d series highest oxidation state is +7 (Mn) (b) CuSO4 + KCN —→ K2SO4 + Cu(CN)2
Excess Unstable
™ In d-block series highest oxidation state is +8 (Os, Ru) 2Cu(CN)2 —→ 2CuCN + (CN)2
™ In carbonyl compound oxidation state of metals is zero due Cyanogen
to synergic effects. CuCN + 3KCN —→ K3[Cu(CN)4]
™ Their higher oxidation states are more stable in fluoride and H2O + CO2
(c) Cu CuCO3.Cu(OH)2
oxides. moist air green
™ Higher oxidation states in oxides are normally more stable Aqua regia
than fluorides due to capability of oxygen to form multiple Au H[AuCl4] + NO + H2O
(3HCl + HNO3)
bonds.
e.g. stable fluoride in higher oxidation state of Mn is MnF4 Heating 1
(d) AgNO3(s) Ag + NO2 + O 2
while oxide is Mn2O7 2
 Mn show maximum number of oxidation state (+2 to +7)
Heating 1
among 3d series. AgCO3(s) Ag + CO2 + O 2
2

1
(e) CuSO4.5H2O 100ºC CuSO4.H2O
720ºC
CuSO4 Cr2O72–/H+ (Orange)
light greenish blue Colourless

230ºC 1
CuO + SO2 + O 2
2 H2O2 H2O

NH2
(f) Hg2Cl2 + NH4OH Hg + Hg
Cl Black
CrO5
FeSO4 + H2SO4 (Blue)
(g) NO3–/NO2– [Fe(H2O)5 NO+]SO4
Brown ring complex
Reactions of MnO4–
(h) AgBr + 2Na2S2O3 Na3[Ag(S2O3)2] + NaBr
MnO4–(Purple)
Photographic
complex C2O42– CO2
SO2 SO42–
(i) Chemical volcano:
H2S S
(NH4)2Cr2O7 → N2 + 4H2O + Cr2O3 S2O32– S + SO42–
NO2– NO3–
Reactions of Cr2O72– I– I2
Cr2O72– (Orange) Br– Br2
Cl– Cl2
SO2 SO42– C2H5OH CH3 –COOH
H2S S Sn2+ Sn4+
SO32– SO42– Fe2+ Fe3+
NO2 NO3–
I– I2 Mn2+(Purple colour is decolourise)
Br– Br2
Strongly, ∆
MnO4– MnO42–
S2O32– S + SO42– Basic
purple solution green
C2H5OH CH3COOH
Sn2+ Sn4+ MnO4–/OH–
Fe2+ Fe3+
I IO3–

Cr3+(green)
CH2 = CH2 CH2 – CH2
OH OH
H+
CrO 24 − 
  Cr2 O7
2−

Yellow
–OH
( Orange ) MnO2
(Brown PPT)