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INORGANIC
CHEMISTRY
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CHAPTER
06 d-BLOCK (Transition Elements)
DEFINITION
Incomplete n and n–1 shell in atomic or in ionic state. Zn, Cd & Hg – are d-block nontransition elements.
GENERAL ELECTRONIC CONFIGURATION TRANSITION SERIES
ns
0–2
(n–1)d
1–10
1st 3d series Sc21 — Zn30 9 + 1 = 10
2nd 4d series Y39 — Cd48 9 + 1 = 10
Cr = 4s1 3d 5
Exceptions , Pd = 5s04d10 3rd 5d series La57, Hf72 — Hg80 9 + 1 = 10
1 10
Cu = 4s 3d 4
th
6d series Ac89, Unq104 — Uub112 9 + 1 = 10
ATOMIC RADIUS OXIDATION STATE
3d series Sc > Ti > V> Cr >Mn ≥ Fe CO Ni ≤ Cu<Zn Transition elements exhibit variable oxidation state
due to small energy difference of ns and (n–1)d
In a group 3d to 4d series increases but 4d and 5d electrons.
series nearly same due to poor shielding of f electron. Sc(+3) and Zn(+2) exhibit only one oxidation
(Lanthanide contraction) state
Common oxidation state is +2
3d < 4d 5d 3d series highest oxidation state is +7 (Mn)
Smallest radius – Ni In d-block series highest oxidation state is +8
e.g. Ti < Zr Hf
Largest radius – La (Os, Ru)
In carbonyl compound oxidation state of
Melting point : s-block metals < d-block metals metals is zero due to synergic effects.
Their higher oxidation states are more stable in
In a series on increasing number of unpaired e– mpt
fluoride and oxides.
increases upto Cr then decreases.
Higher oxidation states in oxides are normally
Sc < Ti < V < Cr > Mn < Fe > Co > Ni > Cu > Zn more stable than fluorides due to capability of
↓ ↓ oxygen to form multiple bonds.
Half filled d5 Fully filled d10
∴weak metallic bond ∴weak metallic bond eg. stable fluoride in higher oxidation state of
Mn is MnF4 while oxide is Mn2O7
Zn > Cd > Hg
Melting point (data based) Some more stable oxidation states
Cu > Ag ≤ Au
of d-block elements
E.N. Exception Zn < Cd < Hg
Cu +2 Mn +2 Pt +4 Ag +1
Density : s-block metals < d-block metals.
Cr +3 Sc +3 Au +3 Ni +2
3d series
Common oxidation states
Sc < Ti < V < Cr < Mn < Fe < Co ≤ Ni < Cu > Zn
Ti(+4), V(+5) Cr(+3,+6) Mn(+2,+4,+7)
Density in a Group 3d < 4d << 5d
Metallic character : They are solid, hard, ductile, Fe(+2, +3), Co(+2,+3) Ni (+2) Pt (+2+4)
malleable, good conductor of heat and electricity and In p-block lower oxidation states of heavier
exhibit metallic lusture, high tensile strength. Hg is elements are more stable while in d-block
liquid heavier element, higher oxidation state are
more stable.
Elect. cond. Ag > Cu > Au > Al eg. In VIB gp Mo(+6) & W(+6) are more stable
p −block
d − block
than Cr(+6)
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MAGNETIC PROPERTY
All transition elements are paramagnetic due to presence of unpaired electrons. They attract when magnetic
field is applied. Magnetic moment of unpaired electron is due to spin and orbital angular momentum.
"Spin only" magnetic moment can be calculated by using formula=µ n(n + 2) Bohr magneton. (n is number
–
of unpaired e .)
If n is 1 µ = 1.73 BM n is 2 µ = 2.84 BM n is 3 µ = 3.87 BM
n is 4 µ = 4.90 BM n is 5 µ = 5.92 BM
Substances that are not attracted by applied magnetic field are diamagnetic. They have all the electrons paired.
d-block element and ions having d0 and d10 configuration are diamagnetic.
COLOUR
Colour in transition metal ions is associated with d–d transition of unpaired electron from t2g to eg set of
energies.
This is achieved by absorption of light in the visible spectrum, rest of the light is no longer white.
3+ 4+ 2+
Colourless – Sc , Ti , Zn etc
Coloured – Fe3+ yellow , Fe2+ green, Cu2+ blue, Co3+ blue etc.
Interstitial compounds : When less reactive nonmetals of small atomic size eg. H, B, N, C, Trapped in the
interstitial space of transition metals, interstitial compounds are formed, like :- TiC, Mn4N, Fe3H etc.
They are nonstoichiometric compounds. They have high melting point than metals. They are chemically inert.
ALLOYS CATALYST
Solid mixture of metals in a definate ratio Transition metals & their compounds act as catalyst
due to –
(15% difference in metallic radius)
– Variable oxidation state
They are hard and having high melting point.
– Tendency to form complex
eg. Brass (Cu + Zn)
eg. V2O5 – Contact process
Bronze (Cu + Sn) etc.
Fe – Haber process
Hg when mix with other metals form semisolid
amalgam except Fe,Co,Ni, Li. Ni – Catalytic hydrogenation
IMPORTANT REACTIONS OF d-BLOCK ELEMENTS
(a) Cu2+ + 4I– → Cu2I2(s) + I2 (e) 100° C
CuSO4 .5H2 O 230° C
→ CuSO4 .H2 O → CuSO4
light greenish blue Colourless
(b) CuSO4 + KCN → K2SO4 + Cu(CN)2
Excess Unstable 720° C 1
→ CuO + SO2 + O2
2Cu(CN)2 → 2CuCN + (CN)2 2
Cyanogen
CuCN + 3KCN → K3[Cu(CN)4] NH2
(f) Hg2Cl2 + NH4OH → Hg
Cl
H2O + CO2
(c) Cu
moist air
→ CuCO3 .Cu(OH)2 Black
green
Aqua regia
(g) FeSO4 + H2 SO4
NO3− / NO2− → Fe ( H2O )5 NO + SO4
Au
(3HCl + HNO3 )
→ H[AuCl 4 ] + NOCl + H2O
Brown ring complex
Heating 1 (h) AgBr + 2Na2S2O3 → Na3[Ag(S2O3)2] + NaBr
(d) AgNO3 → Ag + NO2 + O2 Photographic
2
complex
Heating 1
AgCO3 → Ag + CO2 + O2
2
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COMPOUNDS OF d-BLOCK ELEMENT
A. K2Cr2O7 :
Method of preparation :
4FeO.Cr2O3 + 8Na2CO3 + 7O2 8Na2CrO4 + 2Fe2O3 + 8CO2
(Chromite)
K2Cr2O7
Important point :
H+
CrO4−2 Cr2 O7−2
−
OH
Yellow Orange
K2Cr2O7 used in volumetric analysis not Na2Cr2O7.
∆ 3
Hetaing effect → 2K 2 Cr2 O7 → 2K 2 CrO4 + Cr2 O3 + O
2 2
Chromyl chloride test → Used to detect ionic chloride (Cl–)
NaCl + K2Cr2O7 + H2SO4 → CrO2Cl2 (Red orange)
With H2O2 → Cr2O7–2 + H+ + 4H2O2 → CrO5 (Deep Blue sol.)
Act as an oxidising agent.
Acidified K2Cr2O7 (Orange)
H2S S
SO2 SO4
–2
–
NO2 NO3
–
SO3–2 SO4–2
Sn+2 Sn+4
Fe+2 Fe+3
–
Br Br
–
I I2
C2H5OH CH3COOH (drunken drive test)
+3
Cr (green)
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B. KMnO4 :
Method of preparation :
Cl2
KMnO4
KOH
K2MnO4 H2O + O3
KMnO4
MnO2
K2CO3 CO2
K2MnO4 KMnO4
(Green) (Purple)
Property :
Effect of heating :
2KMnO4 → K2MnO4 + MnO2 + O2
With conc. H2SO4 :
conc.
KMnO4
H2 SO4
→ Mn2 O7 (explosive)
acts as oxidising agent in Acidic/Neutral/Alkaline
(a) Acidic (b) Neutral/Weak alkaline
KMnO4 KMnO4
H2S S Br– BrO3–
SO2 SO4–2 I– IO3–
–
NO2 NO3– S2O3–2 SO4–2
+2
Fe Fe
+3
Mn+2 MnO2
MnO2
Cl– Cl2
H2C2O4 CO2 + H2O
–2
S2O3 S4O6–2
+2
Mn
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IMPORTANT NOTE
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