d – Block transition elements (group 3–12)

Uses Compounds of d-block elements

• Electronic configuration : (n –1)d1–10 ns1–2


• In production of iron and steels.
Cr=4s13d5 Non-typical transition elements • TiO in pigment industry
Exceptions • MnO2 in dry battery cells.
Cu=4s13d10,Pd=5s04d10 Zn,Cd & Hg
• As catalysts in industry.
• Physical properties: • Ni complexes:polymerization of Potassium permanganate KMnO4
alkynes and other organic compounds
Potassium dichromate K2Cr2O7
-High melting and boiling point
Melting point : s-block metals < d-block metals • AgBr in photographic industry.
Preparation : • Preparation : 2MnO2 + 4KOH + O2 → 2KMnO4 + 2H2O
Sc < Ti < V < Cr > Mn < Fe > Co > Ni > Cu > Zn (3d Series) 3MnO42-+ 4H+ →2MnO4− + MnO2 + 2H2O
4FeCr2O4 + 8Na2CO3 + 7O2→8Na2CrO4 + 2Fe2O3 +8CO2 2Mn2+ + 5S2O82- + 8H2O →2MnO4− + 10SO42− + 16H+
Zn > Cd > Hg 2Na2CrO4 + 2H+→ Na2Cr2O7 + 2Na+ + H2O •Intense colour
Melting point
Cu > Ag ≤ Au Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl •Paramagnetism
-High enthalpies of atomization(Highest for V in 3d, series)
Catalysts Properties : Strong oxidising agent •Strong oxidising agent
MnO4− + 8H+ + 5e– →Mn2+ + 4H2O
Cr2O72- + 14H+ + 6e–→2Cr3+ + 7H2O
Atomic Radius: Contact process = V2O5
3d series: Sc > Ti > V > Cr > Mn ≥ Fe Co  Ni≤ Cu < Zn
Haber process = Fe 2O3+ Al2O3 + K2O –
MnO4 (Purple)
Decomposition of KClO 3 = MnO2 Cr2O72– (Orange) -
In a group 3d 4d 5d (Lanthanide contraction) C 2O4
2–
CO2
SO2 SO4
2– O
Ostwald process = Pt/Rh SO2 SO4
2–
Smallest radius – Ni
eg : Ti Zr Hf H2S S 2–
Largest radius – La Zeigler Natta catalyst = TiCl4+(C2H5)3Al O H2S S
2– 2–
O O

pm
SO3 SO4 S2 O32– SO4
2–
Mn
Hydrogenation of Alkene = Ni/Pd

9
126°

17
- –
Density: NO2 NO3 O Cr Cr O NO2
–
NO3
–
Wilkinson‛s catalyst=RhCl(PPh3)3 I– I2
16
3p – O O
s-Block < d-Block
O m O I I2
Br– Br2 – O
Br Br2
3d series: Sc < Ti < V < Cr < Mn < Fe <Co ≤ Ni< Cu > Zn S2O3
2–
SO42– Cl
–
Cl 2
In a group C 2H5OH CH3COOH C 2H5OH CH3 –COOH
• Ionisation enthalpy:increases from left to right Sn2+ Sn4+ Sn
+2
Sn
+4

• Oxidation states : Variable; higher O.S. stable down the group Ln2S3 Fe
2+
Fe
3+
+2 +3
• Trends in E°M2+/M : E° for Mn, Ni and Zn are more negative
Fe Fe
Ln2O3
than expected.
+3
• Trends in E°M3+/M: variable Cr (green) Mn+2
• Chemical reactivity and E° values : Variable Ti2+ , V2+ and Cr2+ are strong (Purple colour decolourises)

ted
Hea S

s
Burn
reducing agents
+
2– H 2–
CrO4 Cr2O7 Strongly

2
– 2–

h
MnO4 MnO4

in O
t
–
Basic
• Magnetic properties : Diamagnetism and paramagnetism. µ = n(n + 2) BM OH

i
H2 (Orange)

w
(Yellow) (purple) solution (green)
• Formation of coloured ions : due to d – d transitions LnN
neutral
• Form a large number of complex compounds MnO 4
–
MnO2 Brown ppt
medium
• Forms interstitial compounds : Non - stoichiometric and are neither He ith
ionic nor covalent. wit ated W ids
• Alloy formation : Due to similar atomic sizes.(15% difference in metallic radius) hN ac
Actinoids
Ln • Electronic configuration : [Rn]5f1–14 6d0–1 7s2
• Ionic sizes : Gradual decrease along the series
Lanthanoids
PHYSICS
Wit • Oxidation states : Most common is +3 . They show
h Lnx3
halo
gen s O.S. of +4, +5, +6 and +7.
• Electronic configuration: 4f1–14 5d0–1 6s2 (Gd:4f7 5d1 6s2) C
th • General characteristics :
LnC2 Wi 3 K

WALLAH
• Atomic and ionic sizes: Decreases from La to Lu(Eu is the largest) 7 –Highly reactive metals
• Oxidation states: Most common is +3. 27
–Irregularities in metallic radii,greater than in Lanthanoids.
Wi

• Some elements: exhibit +2 and +4.

H 2O

–Magnetic properties more complex than lanthanoids

th

• General characteristics
- Silvery white soft metals and tarnish rapidly in air. Actinoid Contraction > Lanthanoid Contraction
- Hardness increases with increasing atomic number. Ln(OH)3+H2
- Metallic structure and good conductors of heat and electricity.
- Variable density
- Trivalent Lanthanoid ions are coloured.
• Ionisation Enthalpies : Low third ionisation enthalpies.
• Good reducing agents.
MISCH METAL-Alloy of Ln (95%), Fe (5%) & S,C,Ca,Al etc..
The element that usually does not Which of the following is not
show variable oxidation state is ? formed when H2S reacts with acidic
K2Cr2O7 solution ?
a) Cu b) Ti
a) CrSO4 b) Cr2(SO4)3

d & f BLOCK ELEMENTS

c) Sc d) V c) K2SO4 d) S