REVISION – d AND f BLOCK ELEMENTS.

d BLOCK ELEMENTS / TRANSITION ELEMENTS ARE THOSE ELEMENTS IN

WHICH THE LAST ELECTRON ENTERS INTO (n-1) d ORBITALS.
GENERAL OUTERMOST CONFIGURATION : (n-1) d1-10 ns2 .
ALL 3d MEMBERS AND THEIR ELECTRONIC CONFIGURATIONS.
Sc = [Ar] 3d1 4s2

Ti = [Ar] 3d2 4s2

V = [Ar] 3d34s2

Cr = [Ar] 3d54s1

Mn = [Ar] 3d54s2

Fe = [Ar] 3d64s2

Co = [Ar] 3d74s2

Ni = [Ar]3d84s2

Cu = [Ar]3d104s1

Zn = [Ar]3d104s2

MODERN DEFINITION ; ELEMENTS HAVING UN PAIRED d ELECTRONS EITHER IN ATOMIC

STATE OR IONIC STATE.
Zn,Cd,Hg NOT REGARDED AS TRANSITION ELEMENTS AS THEY HAVE FULL FILLED d
CONFIGURATION IN BOTH ATOMIC AND IONIC STATE.
Zn : [Ar] 3d10 4s2 Zn(II) : [Ar] 3d10
Cd : [ Kr] 4d10 5s2 Cd(II) : [Kr] 4d10 .
Hg : [Xe] 5d10 6s2 Hg(I) : [Xe] 5d10 6s1 and Hg(II) : [Xe] 5d10.
*PROPERTIES OF TRANSITION ELEMENTS AND REASONS

PROPERTY REASON

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 HIGH [METALLIC CHARACTER METALLIC BONDING ,ATOM-ATOM
,MELTING POINT AND BOILING BONDING ,HIGH INTER ATOMIC
POINT ,ENTHALPY OF FORCE [ INCREASES WHEN NO OF
ATOMISATION] UN PAIRED ELECTRONS INCREASES]
MOST OF ATOMS AND IONS PRESENCE OF UNPAIRED
PARAMAGNETIC ELECTRONS . {PARA MAGNETIC
MOMENT CALCULATED BY √n (n+2).
n = no of unpaired electrons.]
FORMATION OF INTERSTITIAL PRESENCE OF VOIDS
COMPOUNDS /INTERSTITIAL SPACES IN THE
METALLIC LATTICE WHICH ARE
FILLED BY SMALL ATOMS LIKE
HYDROGEN.
FORMATION OF ALLOYS ALMOST SIMILAR ATOMIC SIZE ;
ATOMS OF ONE CAN BE REPLACED
BY ATOMS OF ANOTHER.
FORMATION OF COMPLEXES COMPARATIVELY SMALLER
SIZE,HIGH NUCLEAR CHARGE AND
PRESENCE OF EMPTY d ORBITALS
TO ACCEPT THE ELECTRON PAIRS
DONATED BY LIGANDS.
COLOUR OF COMPOUNDS AND d – d TRANSITION ; PRESENCE OF
COMPLEXES UNPAIRED d ELECTRONS.
CATALYTIC PROPERTIES *CAN FORM REACTION
INTERMEDIATES BY EXHIBITING
VARIABLE OXIDATION STATES.
* METAL PROVIDES LARGE SURFACE
AREA ON WHICH REACTANTS GET
ADSORBED.

STABLE d CONFIGURATIONS :
d0 d3 d5 d10
EMPTY d t2g half filled half fiilled d fulfilled d
Sc (III) V(II) Mn(II) Cu(I)
Ti(IV) Cr(III) Fe(III) Zn(II)
V(V) Mn(IV)
Cr(VI)
Mn(VII)
HIGHEST OXIDATION STATES SEEN IN OXIDES AND FLOURIDES ----OXYGEN AND FLUORINE
ARE THE MOST ELECTRONEGATIVE AND THE STRONGEST OXIDISING AGENTS .

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 • LOWER OXIDES OF TRANSITION METALS ARE IONIC AND BASIC : HIGHER OXIDES ARE
ACIDIC AND COVALENT ; SOME MAY BE AMPHOTERIC.
• WHEN THE OXDN STATE OF CENTRAL METAL ION INCREASES ,COVALENT AND ACIDIC
CHARACTER INCREASES.
• IN HIGHEST OXIDATION STATE METAL PREFERS TO BOND WITH OXYGEN BCZ METAL-
OXYGEN BOND STABILISED BY MULTIPLE BOND FORMATION.
• STABLE OXIDATION STATE OF Co & Cr IN COMPLEXES IS : +3
• IONISATION ENTHALPY : IE IS HIGH WHEN THE ELECTRON IS TO BE REMOVED FROM
STABLE CONFIGURATION. IE IS LESS WHEN REMOVAL OF ELECTRON RESULTS IN
STABLE CONFIGURATION.
• ELECTRODE POTENTIAL: WHEN THE TENDENCY TO UNDERGO THE CHANGE IS HIGH
ACCORDING TO THE NOTATION –POTENTIAL HIGH WHERE THE SHIFT IS FROM LESS
STABLE TO MORE STABLE.
NOTE : 1.IE1 OF Mn and Zn high. ( first electron to b removed frm stable d 5 & d10
configuration)
IE2 of Mn and Zn less. ( removal of second electron results in stability)
IE3 of Mn and Zn high.
IE1 of Cr and Cu less.( removal of first electron results in stable d 5 ,d10 configuration)
IE2 of Cr and Cu high.
* Mn = [Ar] 3d5 4s2
Mn(II) = [Ar] 3d5 (stable half filled d) & Mn(III) = [Ar] 3d4
Mn (II) more stable than Mn(III) .
So E0 Mn3+ / Mn2+ is high.
Mn (III) gets reduced to Mn(II) very easily.
Mn (III) is an oxidizing agent or is oxidizing in nature.

• Cr = [Ar] 3d5 4s1

Cr(II) = [Ar] 3d4 & Cr (III) = [Ar] 3d3 (stable half filled t2g)

Cr(III) more stable than Cr (II) . Cr (II) gets oxidized into Cr (III)

Cr(II) is reducing agent / reducing in nature.

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 • No of unpaired electrons proportional to paramagnetism ,paramagnetic moment
,MP,BP and enthalpy of atomization.
• Presence of unpaired d electrons is the reason for colour and being a transition
element .

AMONG 3d series
• Most metallic = highest MP ,BP ,ΔH at === Cr
• MP & BP OF Mn is less than the expected value bcz Mn has a stable configuration
( [Ar] 3d5 4s2 ] and the valence electrons do not show much tendency to enter into metallic
bonding.

• SOFT METAL ==Zn ( least enthalpy of atomization )

• Common oxdn state : +2
Sc(II) not there
Sc = [Ar] 3d1 4s2
Sc (II) = [Ar] 3d1
3d1 is oxidized into 3d0 . Sc (II) to Sc(III)
• SHOWING +1 OXDN STATE = Cu.
Cu (I) : 3d10 stable.
Cu (I) changes to Cu(II) --- Cu(II) has higher hydration enthalpy .
Cu(I) undergoes disproportionation.
Cu+ ---------→ Cu2+ + Cu.

• MAXM OXDN STATES FOR = Mn. ( maxm no of electrons available for bonding)
• Reducing agents in +2 state = Cr2+ ,Fe2+ .
* Oxidising agent in +3 state = Mn3+ .
* HIGHEST ENTHALPY OF ATOMISATION IN 5 D SERIES : W.
* WHEN THE NO OF UNPAIRED ELECTRONS INCREASES == MP,BP ,ΔHat INCREASES.
PARAMAGNETISM INCREASES.
METALLIC BONDING INCREASES.

• Density increases along 3 d series.

Density = Mass / Volume
Mass increases along the series but atomic size at first decrease , then constant and
then increases.
• Mn2 O7 and CrO3 acidic and covalent == forms oxo anions.
V2O5 amphoteric.== form oxo anion and cation == VO43- & VO2+ .

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MnO = Basic oxide (ionic)
* 3d to 4d to 5d == frequency of atom-atom bond increases.
* ATOMIC SIZE : VARIATION ALONG 3d SERIES
AT FIRST DECREASES ,THEN CONSTANT ,INCREASES TOWARDS THE END.
Factors affecting atomic size : Nuclear charge, shielding effect.
d orbitals have poor shielding effect ; increases with increase in the no f d electrons.
At the beginning nuclear charge is dominant : in the middle part nuclear charge balanced by
shielding effect and at the end shielding effect is dominant
4d BIGGER THAN 3d . BUT 4d AND 5d ALMOST SIMILAR –CONSEQUENCE F LANTHANOID
CONTRACTION .

• LANTHANOID CONTRACTION : Gradual decrease in atomic and ionic size along the
lanthanoid series from lanthanum to lutetium.
CAUSES : Increase in nuclear charge & poor shielding effect of 4 f orbitals.
Consequences : 1.Corrsponding members of 4d and 5d have almost similar atomic size,ionic
size , ionization enthalpy and electronegativity.Hence thy resemble in chemical properties.
Ex: Zr resembles Hf & Nb resembles Ta.
2.Basic character decreases from lanthanum hydroxide to lutetium hydroxide.
PREPARATIONS :

1. K2Cr2O7 –Potassium dichromate .

Step 1 : Chromite ore into sodium chromate

4 FeCr2O4+ 8 Na2CO3 + 7 O2 → 8 Na2CrO4 + 2 Fe2O3 + 8 CO2

Step 2 : Sodium chromate into sodium dichromate.

2Na2CrO4 + H2SO4 → Na2Cr2O7 + Na2SO4 + H2O.

Step 3 : Sodium dichromate into potassium dichromate.

Na2Cr2O7 + 2 KCl → K2Cr2O7 + 2 NaCl

2. KMnO4 – Potassium permanganate

Step 1 : Pyrolusite into potassium manganate
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2MnO2+ 4KOH + O2 → 2K2MnO4 + 2H2O

Step 2 : Potassium manganate into potassium permanganate in acid medium.

3MnO42- + 4H+ → 2MnO4- + MnO2 + 2H2O.

Manufacture of KMnO4:
alkaline oxidative fusion of MnO2 followed by the electrolytic oxidation of manganate into
permanganate.

MnO2 --------------→ K2MnO4 ( treatment with KOH & O2 )

MnO42- -------------→ MnO4- + e- ( electrolytic oxidation )

Preparation from Mn (II) salt

2Mn 2+ + 5S2O82- +8H2O -------→ 2 MnO4- + 10 SO42- + 16H+

REACTIONS :
1. Decomposition of KMnO4 :
2KMnO4 -------→ K2MnO4 + MnO2 + O2

1. KMnO4 as an oxidant :
i. Acid medium
MnO4- + 5e- + 8H+ -------→ Mn2+ + 4 H2O .
ii. Basic medium
MnO4- + 3e- + 2 H2O -----→ MnO2 + 4OH-
NOTE : Number difference is 5 in acid medium and 3 in basic medium.
2. K2Cr2O7 as an oxidant :
Cr2O7 2- + 6e - + 14H+ ----→ 2Cr3+ + 7 H2O
NOTE : Number difference 6.
3. Self reduction of MnO4- .
MnO4- + 5e- + 8H+ -------→ Mn2+ + 4 H2O .
MnO4- + 3e- + 2 H2O -----→ MnO2 + 4OH-
MnO4- + e- ------→ MnO42- .

4. Remember the number difference in writing examples where KMnO4 & K2Cr2O7
Act as oxidizing agents .

Acid medium MnO4- ----→-Mn2+ [ No difference 5]

Basic medium MnO4- ----→MnO2 [ No difference 3]

[ 2I- --→ I2 , H2S ---→ S , S2- ---→ S , SO2 ---→ SO42 ,

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 SO32- ---→ SO42- , NO2- ----→ NO3- , Sn2+ --→ Sn4+ ,
SO2 ---→ HSO4- , C2O42- -→ 2CO2 == Number difference is 2]

[ Fe2+ ---→ Fe3+ ======No difference s 1]

[I- ----→ IO3- ==No difference s 6] -- { basic medium}

[S2O32- ---→ 2SO42- ==No difference s 8]—{ basic medium}

6. Chromate to dichromate in acid medium & Dichromate to chromate in basic

medium.
2 CrO42- + 2H+ ---→ Cr2O72- + H2O
Cr2O72- + 2OH- ----→ 2CrO42- + H2O

7. Ln + O2 ----→ Ln2O3 ; Ln + N2 -----→ LnN

Ln + H2O -----→ Ln (OH)3 + H2 ; Ln + HCl ----→ LnCl3 + H2
( all rxns at high temp)

8. Disproportionations :
2Cu+ -------→ Cu2+ + Cu .
3MnO42- + 4 H+ --------→2 MnO4- + MnO2 +2 H2O.

9. Fe3+ catalysing the rxn between I- and S2O82-

Step 1 : 2 Fe3+ + 2 I- --→ Fe2+ + I2

Step 2 : 2 Fe2+ + S2O82- ---→ 2Fe3+ + 2SO42- .

10. MnO4- on Mn2+ .

2 MnO4- + 3Mn2+ + 2 H2O ----→ 5 MnO2 + 4H+

11.Unstable nature of CuI2

Cu2+ + 4I- --------→ Cu2I2 + I2 .

LANTHANOIDS & ACTINOIDS : Important configurations :

Lanthanoids :

1 8 15

La Gd Lu

La : [Xe] 4f0 5d1 6s2 Gd : [Xe] 4f7 5d1 6s2 Lu : [Xe] 4f14 5d1 6s2 .
7 14
Eu Yb

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Eu : [Xe] 4f7 5d0 6s2 Yb : [Xe] 4f14 5d06s2
2 9

Ce : [Xe] 4f1 5d1 6s2 Tb [Xe] 4f9 5d16s2

ACTINOIDS: Ac : [ Rn] 5f0 6d1 7s2 & Last actinoid – Lr : [Rn] 5f14 6d1 7s2 .

NOTE : COMMON OXDN STATE OF LANTHANOIDS :+3

La : [Xe] 4f0 5d1 6s2 La (III) 4f0
Gd : [Xe] 4f7 5d1 6s2 . Gd(III) 4f7
Lu ; [Xe] 4f14 5d1 6s2 . Lu(III) 4f14 [ 3 are stable ] most stable in +3.
Eu : [Xe] 4f7 5d0 6s2 Yb : [Xe] 4f14 5d06s2 .
Eu(II) : [Xe] 4f7 & Yb(II) : [Xe] 4f14 === stable in +2.
Eu(II) and Yb (II) undergo oxdn to Eu(III) and Yb(III) acting as reducing agents.
== reducing in nature.
Ce : [Xe] 4f1 5d1 6s2 Ce(IV) [Xe] 4f0 stable.
Ce(IV) reduced to Ce(III) – act as oxidizing agent /oxidizing in nature.
Being lanthanoids +3 common.
Tb : [Xe] 4f9 5d0 6s2 Tb ( IV) [Xe] 4f7
Ce(IV) & Tb (IV) stable in +4.

COMPARISON BETWEEN LANTHANOIDS AND ACTINOIDS

Lanthanoids Actinoids
1.4f series 1.5f series.
2.Atomic size :
Lanthanoid contraction 2.Actinoid contraction.
Gradual decrease in atomic and Gradual decrease in atomic and
Ionic size along the 4 f series ionic size of actinoids along
From La to Lu 5f series from Ac to Lr.
*The magnitude of contraction is more in actinoid contraction.

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5f has poorer shielding effect than 4f.
3.Electronic configuration :
[Xe] 4f0-14 5d0-1 6s2 3.[Rn] 5f0-14 6d0-2 7s2
4.Reactivity :
Reactive metals 4.More reactive.
Highly reactive in finely powdered state
5.Radioactivity:
Except Pm , all non radio active 5. All radioactive

6. Oxidation state :

Common : +3 6. Common : +3
+2 & +4 shown +4,+5,+6,+7 shown
Actinoids show higher oxdn state bcs 5f ,6d and 7s orbitals are of comparable energy and
hence electrons of these 3 orbitals can take part in bonding.
Note : The chemistry of actinoids is more complex bcs
1.Actinoids are radio active and of short life.

2. They show variable oxidation state.

USES :

1. KMnO4 & K2Cr2O7 act as oxidizing agents in organic and inorganic reactions and in
volumetric estimations.
2. Misch metal is used in magnesium based alloys to make bullets and shells.
3. Mixed oxides of lanthanoids are used as catalysts for cracking of petroleum.
4. Some Ln oxides are used as phosphors in television screen.
Note : In permanganometry , acid medium is preferred bcz oxidation is comparatively
faster in acid medium and in basic and neutral medium MnO 2 formed may impart a
brown colour to solution and then detection of endpoint wont be smooth.
• HNO3 is not used to acidify bcs HNO3 itself is an oxidizing agent.
• HCl cant be used bcs KMnO4 oxidises HCl to chlorine.
• H2SO4 is used.
Structure of permanganate , manganate ,dichromate and chromate.

REMEMBER ==➔ 1. In 3d Series :

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*Most metallic metal : Cr

* metal with highest MP,BP, ΔHat : Cr

* metal with least ΔHat : Zn

* +1 oxidation state for : Cu

* Common oxidation state : +2

* +2 not shown by : Sc

* Maxm no of oxdn states : Mn

* Maxm no of unpaired electrons : Cr

*Soft metal : Zn

* Stable oxdn state of Cr & Co in complexes : +3

* IE1 high for : Mn , Zn

* IE1 less for : Cr,Cu

*IE2 less for : Mn ,Zn

* IE2 high for : Cr ,Cu

* Oxidising agent in +3 : Mn

* Reducing agent in +2 : Cr ,Fe

* Colourless in +2 :Zn

* Colourless in +4 : Ti

* d5 in +2 : Mn

* d5 in +3 : Fe

*d3 in +2 :V

*Stable chloride of Copper : CuCl2 .

*Non existing halide of copper : CuI2

* acidic oxides : Mn2O7 , CrO3

* amphoteric oxide : V2O5

* Basic & amphoteric oxide f Mn : MnO , MnO2 .

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* Oxo anion of Mn : MnO4- & corresponding acid and salt : HMnO4 , KMnO4 .

* Oxo anion of Cr :Cr2O72- & corresponding acid and salt : H2Cr2O7 , K2Cr2O7 .

: CrO42- ; H2CrO4 ; K2CrO4

• Highest fluoride of Cr : CrF6.

• Highest oxy fluoride of Mn : MnO3F { MnF7 doesn’t exist}
0 2+
• E M / M is +ve for : Cu ( sublimation enthalpy & ionization enthalpy
comparatively high and hydration enthalpy comparatively less for Cu)
• Colour of compounds : d-d transition ( needs unpaired d electron)

2. Lanthanoids & Actinoids :

* Common oxdn state of 4f & 5f : +3

* Ln stable in +3 : La ,Gd,Lu

* Ln stable in +2 : Eu,Yb

* Ln stable in +4 : Ce, Tb

* Alloy of Ln : Misch metal { nearly 95% Ln , nearly 5% Fe, traces of S,Ca,C,Al}

* Ln as oxidant in +4 : Ce

* Ln as reductant in +2 : Eu,Yb

* Actinoid showing +7 : Np

* Last actinoid : Lr

* Ionic oxide of Ln : La2O3

* Covalent oxide of Ln : Lu2O3 .

* Colour of Ln compounds : f-f transition . ( needs unpaired f electrons)

3. KMnO4 & K2Cr2O7

* Oxdn state of Mn in KMnO4 : +7 & K2MnO4 : +6

* Oxdn state of Cr in in K2Cr2O7 & K2CrO4 : +6

* Violet coloured compound of Mn acting as oxidant : KMnO4

* Green coloured compound of Mn undergoing disproportionation : K2MnO4

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* Orange coloured compound of Cr acting as oxidant : K2Cr2O7

* K2Cr2O7 prepared from : Chromite ore , FeCr2O4

* KMnO4 prepared from : Pyrolusite , MnO2 .

* Colour of KMnO4 due to : Charge transfer from oxygen to Mn.

( Mn in +7 , strong +ve attracts electrons / -ve charge from surrounding oxygen.)

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