CHAPTER-8

d & f – Block elements

d- block elements lying between s-block and p-block elements in the
periodic table.
OR
The d-block elements are present in group 3 to group 12 and lie in between
s-block elements and p-block elements.OR
In d-block elements the last electron enters into the d-sub shell of the
penultimate (last by 1) main energy level.
d- block elements are also known as transition elements, because the
properties of these elements transit between s-block elements and p-block
elements.
d-block elements are present in Groups 3, 4, 5, 6, 7, 8, 9, 10, 11, 12.
Each series starts with elements of Group 3 and ends with elements of
Group 12.
Thus the elements of Group 3 to 12 belonging to the periods 4 to 7 are d-
block elements.
Zinc, cadmium, mercury are not regarded as transition metals due to
completely filled d – orbital.

The general electronic configuration of d-block elements are

[ Noble gas](n − 1)d 1−10 ns1 or ns 2
4d series-[Kr]4d1-10 5s1-2,
5d series-[Xe]5d1-106s1-2(Hf –Hg 4f14 is included before 5d) and
6dseries-[Rn]6d1-107s1-2(Ru –Cn 5f14 is included before 6d)

Classification of d-block elements:

d- block elements are classified into 4 transition series, they are 3d, 4d, 5d
and 6d series, each series contain 10 elements excepted 6d series.
3d series (Sc to Zn 10 elements), 4d series(Y to Cd 10 elements),
5d series (La, Hf to Hg 10 elements),6d series
(Ac, Rf toCn10 elements)
3d series elements:
3d series consists of 10 elements from scandium [Sc] [21] to Zinc [Zn][30] in
which sub shell is being progressively filled.
The elements present in 3d series are scandium, Titanium, Vanidium,
Chromium, Manganese, Iron, Cobalt, Nickel, Copper and Zinc.
Characteristics of transition elements:
 1. Most of the transition elements are metals they show metallic
properties such as ductility, malleability, electrical conductivity, high
tensile strength and metallic luster.
1. Except mercury which is liquid at room temperature, other transition
elements have typical metallic structures.
2. They have higher densities as compared to the metals of IA and IIA
group (s-block).
3. Their compounds generally contain unpaired electrons hence they are
paramagnetic in nature and form coloured compounds.
4. They exhibit several oxidation states.
5. They have good tendency to form complexes.
6. They are heavy metals with higher melting and boiling point as well as
higher heats of vaporisation.
7. Transition elements are less reactive than s-block elements due to
their higher ionisation energy.
8. Most of the transition metals such as Mn, Ni, Co, Cr, V, Pt, etc. and
their compounds are used as catalyst.
9. They form alloys with different metals.
10. They form interstitial compounds with elements such as
hydrogen, boron, carbon, nitrogen etc.
11. They are good conductors of heat and electricity.
Reason for the above properties:1.metallic bond 2.d-d overlap
General properties of 3d series:
1) Electronic configuration: As we move from scandium to zinc along 3d
series of transition elements, 3d-sub shell is successively filled hence,
1−10 1 2
the general electronic configuration of 3d series is [ Ar ] 3d 4s or 4s
the electronic configuration of 3d series are as follows.
Atomic Electronic
Element
number configuration
Scandium(Sc) 21 [ Ar] 3d 1 4s 2
Titanium (Ti) 22 [ Ar ] 3d 2 4s 2
Vanidium (V) 23 [ Ar] 3d 3 4s 2
Chromium
24 [ Ar ] 3d 5 4s1
(Cr)
 Manganese
25 [ Ar] 3d 5 4s 2
(Mn)
Iron (Fe) 26 [ Ar ] 3d 6 4s 2
Cobalt (Co) 27 [ Ar ] 3d 7 4s 2
Nickel (Ni) 28 [ Ar] 3d 8 4s 2
Copper (Cu) 29 [ Ar ] 3d 10 4s1
Zinc (Zn) 30 [ Ar] 3d 10 4s 2

The Electronics configuration of chromium is [ Ar ] 3d 5 4s1 but not

[ Ar ] 3d 4 4s 2
Half filled d sub shell is more stable then nearly filled one, when 3d
sub shells receives one electron from 4s orbital giving the most sable
configuration
10 1 9 2
The electronic configuration of copper is [ Ar ] 3d 4s but not [ Ar ] 3d 4s
Completely filled atomic orbital are more stable than nearly filled
ones, 3d10 configuration is more stable then 3d9configurations. 1 electron
from 4s orbital jumps to 3d sub shells giving more stable configuration
[ Ar ] 3d 10 4s1
1)Metallic character:
All transition elements are metallic in nature, i.e. they have strong metallic
bonds. This is because of presence of unpaired electrons. This gives rise to
properties like high density, high enthalpies of atomization, and high
melting and boiling points.
Except mercury which is a liquid, all the transition elements have metallic
structure.
ii. They are all metals show good thermal and electrical
conductivities. They are hard, lustrous and ductile.
(Cr, Mo and W are hard metals while Zn, Cd and Hgsoft in nature)
2) Variable oxidation state:
[Name the element in 3d series having highest oxidation state?] = Mn +7
Transition elements exhibits variable oxidation state. The oxidation state
shown by the transition elements are related to their electronic
configuration.
Wide variety of oxidation states exhibited by transition metals is due to the
availability of both 4s as well as 3d sub shell electrons for bond formation.
The stability of different oxidation states depends upon many factors
Example: Electronic structure, type of bonding, lattice energy etc.
+6 +7
+5 +6 +6
+5 +4 +5 +5 +5
+4 +4 +3 +4 +4 +4 +4 +3
+3 +3 +3 +2 +3 +3 +3 +3 +2
+2 +2 +2 +1 +2 +2 +2 +2 +1 +2
Sc(21) Ti(22) V(23) Cr(24) Mn(25) Fe(26) Co(27) Ni(28) Cu(29) Zn
(30)

When we proceeds from Mn towards the right of the series, the maximum
oxidation state decreases from +7 to +2. This is because from iron to copper
the pairing d electron takes place.
1. lower oxidation states are basic in nature & forms ionic bond
compounds(Reducing agent)
2. Higer oxidation statea are acidic in nature & forms covalent
compounds(oxidizing agent)
3. intermediate oxidation states act as both as acid as well as basic in
nature.
Eg-Mn+2, Mn+3, Mn+4, Mn+5 ,Mn+6,Mn+7
4.Transition metals shows lower oxidation state when a complexcompound
is formed with п-acid ligand (CO)

3) Magnetic property:
Many compounds of transition metals and their compounds exhibit
magnetic property due to the presence partially filled d orbital.
Dia magnetic: If the metals and their compounds repelled by external
magnetic field are known as dia magnetic Example: Zn
Para magnetic: If the metal or compound attract towards the external
magnetic field are known as Paramagnetic. Example Titanium ion, Cupric
ion etc.,
Ferro magnetic: If the metal and their compounds which are strongly
attracted towards the external magnetic field are known as Ferro magnetic.
Example: Fe, Co, Ni etc.,
The magnetic character is expressed in terms of magnetic moment.
 = n (n + 2) BM
Where  = Magnetic moment
N= Number of unpaired electrons.
BM = Bohr magneton
Calculate the magnetic moment of Ti2+.
The atomic number of titanium = 22
2 2
The electronic configuration of titanium is [ Ar ] 3d 4s
The atomic number of Ti2+ = 20
2 0
The electronic configuration of Ti is [ Ar ] 3d 4s
2+

The box diagram is

 = n (n + 2) BM
n= 2, It contains 2 unpaired electrons
 = 2 (2 + 2) BM
 = 8 BM
 = 2.8 BM

Why cuprous is diamagnetic? But cupric is paramagnetic

Atomic number of Cu = 20
10 1
The electronic configuration is [ Ar ] 3d 4s

Atomic number of Cu+ = 28

10 0
The electronic configuration is [ Ar ] 3d 4s
Cuprous does not contain unpaired electron hence they are diamagnetic.

Atomic number of Cu+2 = 27

9 0
The electronic configuration is [ Ar] 3d 4s
Box diagram is
Cupric ion contain one unpaired electron hence they are paramagnetic.

4. Colour:
Compounds of transition elements are coloured. The colour is due to
incomplete (half filled) d- orbital in the transition metal ion.
All 3d metals except zinc contain incomplete d-sub shell.
When visible light falls on these metal ions electrons jumps from lower level
to higher level within the same d-orbital, it absorbs a particular frequency
radiation and transmitted the remaining colour. The colour transmitted is
called complimentary colour to that of the colour absorbed.
Example: Copper sulphate is blue in colour, because copper ion absorbs red
colour from white light and transmittes blue colour.
[Fe(H2O)]SO4—Green colour,[Ti(H2O)6]2---purple coloured complex.(ligand
responsible splitting d subshell in to two sets like in octahedral
complex→t2g(dxy.dyz&dxz) & eg(dx2-y2&dz2))
Complementary colours:R→G, B→O & V→Y etc.
Factors responsible for colour of a transition metal ions:
i. The presence of incompletely filled d-orbitals in metal ions.
ii. The presence of unpaired electrons in d-orbitals.
iii. d-d transitions of electrons due to absorption of radiation in the visible
region.
iv. Nature of groups (anions or ligands) linked to the metal ion in the
compound or a complex.
v. Type of hybridisation in metal ion in the complex.
vi. Geometry of the complex of the metal ion.
Why is cuprous is colourless while cupric is colour
Atomic number of Cu = 20
10 1
The electronic configuration is [ Ar ] 3d 4s
Atomic number of Cu+ = 28
10 0
The electronic configuration is [ Ar ] 3d 4s
Cuprous does not contain unpaired electron hence they are colourless
Atomic number of Cu+2 = 27
9 0
The electronic configuration is [ Ar] 3d 4s
Cupric ion contain one unpaired electron hence they are blue in colour.
5.Catalytic behavior:
Many transition metals and their compounds acts as good
catalyst. The catalytic activity is due to following factors.
i) The transition elements have vacant d-orbital.
ii) They have the ability to exhibit variable oxidation states.
iii) They provide large surface area with free valencies in the finely
divided state
Example:
i) Iron acts a catalyst in the manufacture of ammonia from nitrogen
and hydrogen by Haber’s process.
ii) Vanidium pentoxide acts as a catalyst in the manufacture of
sulphuric acid by contact process
Example:iron(III) catalyses the reaction between iodide and persulphate
ions.
2 I− + S2O82− → I2 + 2 SO42−
An explanation of this catalytic action can be given as:
2 Fe3+ + 2 I– → 2 Fe2+ + I2
2 Fe2+ + S2O82− → 2 Fe3+ + 2SO42−

4) Atomic radius or atomic size:

Element Sc Ti V Cr Mn Fe Co Ni Cu
Atomic radium in 144 132 122 117 117 117 116 115 117
pm

The atomic radii of the elements of particular transition series decreases

from left to right. The atomic radii become almost constant after chromium,
because of the two factors, they are
i) Increase in nuclear chare [ variable oxidation state]
ii) Screening effect.
With increase in atomic number the new electrons enter inner (n-1) d
orbital. Since the new electron enters an inner orbital the atomic size
decreases, because increases the screening effect, but the increase in
nuclear charge by 1 unit brings about contraction in the size of atom. Due
to increase columbic force of attraction. Hence atomic and ionic radii
decrease with increase in atomic number.
Ionic size: varies similar to atomic radius from Sc to Zn if they carries like
oxidation number(+2).
5)Ionisation enthalpy or energyor potential:
 Ionisation energy increases from Sc to Zn because of decreases in atomic
radius along with increase in effective nuclear force. Cr has low first
ionisation enthalpy because loss of one electron gives stable electronic
configuration (3d5), Zn has very high ionisation enthalpy because
electron has to be removed from 4s orbital of thestable configuration
(3d104s2).
Note:
The energy required to remove first electron from gaseous atom in its ground
state is called first ionization enthalpy, for second electron it is called
second ionisation enthalpy and for removal of third electron it is
calledthird ionisation enthalpy.

6)Formation of interstitial compounds:

Transition metals have voids or interstitials in which C, H, N, B etc. can fit
into resulting in formation of interstitial compounds. They are non –
stoichiometric, i.e., their composition is not fixed .
Eg: TiC, Fe3H ,Mn4N etc.
Properties:1.They are hard,high melting point &less malleable & ductile in
nature
2.Chemically inert & metallic conductor.
7)Alloy formation:
They form alloys due to similar ionic size. Metals can replace each other in
crystal lattice, e.g., brass(Cu+Zn), bronze(Cu+Sn),stainless
steel(Fe+Cr),Mangnesesteel(Fe+Mn) &tungsten steel(Fe+W) etc.
Alloys are generally harder, have high melting points and more resistant to
corrosion than the
individual metals.

8)Standard electrodepotential of electrodes(trends)Eo:

1)M2+/M type:
When metal atoms are in equilibriumwith metal ions develops electrode
potentials. In general less electronegative electrode potentials across the
series depends on sum of first & second ionization enthalpies. Therefore E o
for Mn,Ni & Zn are more negative thanthe expected value because of half
filled d-sub shell in Mn2+,commpetely filled d-subshell in Zn2+,where as
highest hydration enthalpy of Ni2+ ion.
But in cu, the unique behavior of positive potential account inability to
liberate H2 from acids, but only oxidizing acids being reduced by Cu(HNO 3,
H2SO4).the high energy of Cu(g)---→Cu2+ is not balancedby hydration
enthalpy.

2)M3+/M2+:
Eo potential values for M3+/M2+ show variation i.elow value of Sc reflects
stability of Sc3+, high value of Zn due to d10 configuration,high value of Mn is
due to d5 configuration,low value of Fe shows the extra stability of
Fe+3(d5).low value for V due to stability of V 2+(half filled t2g set).

Stability of higher oxidation states:

Higher oxidation state of 3d series elements can be stabilized by both oxygen
& fluorine by forming oxides & fluorides.but the ability of oxygen exceeds
that of fluorine,because oxygen forms multiple bonds to metals, but fluorine
by lattice enthalpy & bond enthalpy.
Ex:TiX4,VF5,CrF6,Mn2O7,ScO3 etc
Fluorides of the metals exhibits instabilityin low oxidationstate but Cu(II)
halides are known,except iodides.
Note:The stability of cu2+ is mor than Cu1+due to high hydration enthalpy of
Cu2+, which more than compensates second ionisationenthalpy of Cu.
Chemical Reactivity and EΘ Values:
Metals of 3d series except cu, which have negative standard electrode
potentials.so they are more reactive & they are oxidized by 1M H+
The Eo values for M2+/M shows that,decreasing reducing tendency.this
trend is due to increase insum of first & second ionization energy.
Eo value for the couple M3+/M2+ shows that, M3+ are oxidizing agents in
aqueous solutions (Mn3+& C03+). M2+ ion are strong reducing agents (
Ti2+,Cr2+& v2+) & liberate hydrogen from dilute acids.2 Cr2+(aq) + 2 H+(aq) →
2 Cr3+(aq) + H2(g)
Oxides and Oxoanions of Metals
• Oxides are generally formed by the reaction of metals with oxygen at
higher temperatures.
• All the metals (except scandium) form MO oxides, which are ionic in
nature.
• As the oxidation number of a metal increases, ionic character
decreases.
Ex: In the case of Mn, Mn2O7 is a covalent green oil. Even
CrO3 and V2O5 have low melting points.
Higher oxidation statesexhibits acidic character (Mn 2O7,CrO3&
V2O5)
Lower oxides arebasic in nature EX: CrO
But Cr2O3 is amphoteric in nature

POTASSIUM DICHROMATE: (K2Cr2O7):

Potassium dichromate is an orange red crystalline solid, It is used in
laboratory in volumetric analysis. It is used as an oxidizing agent.

Describe the manufacture of Potassium dichromate from chromite ore:

The chemical composition of chromite is FeO.Cr2O3 .It is also called Ferro
chrome.
The chromite ore is finely powdered and concentrated by gravity separation
method.
The concentrated chromite ore is roasted with excess of sodium carbonate in
a reverberatory furnace in excess of air, yellow mass of sodium chromate is
obtained.
4FeO.Cr2O3 + 8Na2CO3 + 7O2 8Na2CrO4 + 2Fe2O3 + 8CO2
Sodium chromate is dissolved in water when Fe2O3 is left behind. The
sodium chromate solution is treated with concentrated sulphuric acid to get
sodium dichromate.
2Na2CrO4 + H2SO4 Na2Cr2O7 + Na2SO4 + H2O
When the solution is concentrated and cooled, the sodium sulphate
separates as crystals. More soluble sodium dichromate remains in the
solution.
The hot and concentrated solution of sodium dichromate is treated with a
calculated amount of KCl, when K2Cr2O7crystallizes outon cooling .
Na2Cr2O7 +2KCl  K2Cr2O7 +2NaCl
These crystals are separated and dried.
Uses of Potassium di chromate:
• Potassium di chromate is used in volumetric analysis for oxidation
titration and iodo metric titration.
• A mixture of Potassium di chromate and concentrated sulphuric
acid is known as chromic acid is used to cleaning glass apparatus
in the laboratory.
• It is used in qualitative analysis to confirm chloride radical by
chromyl chloride test.
• Potassium di chromate is used as an oxidizing agent in organic and
inorganic reaction.
• It is also used in the chrome tanning of leather as well as a
mordant in dyeing industry.

PHYSICAL PROPERTIES OF POTASSIUM DICHROMATE:

1. Potassium dichromate is a orange crystalline solids, they are solube
in water,
1. 2. The dichromate ion (𝐶𝑟2 𝑂72− ) exists in equilibrium with chromate
(𝐶𝑟𝑂42− ) ion at
pH =4. However, by changing the pH, they can be inter-converted.
Acid Acid
2− −
2𝐶𝑟𝑂4 2𝐻𝐶𝑟𝑂4 𝐶𝑟2 𝑂72−
Chromate Alkali Hydroge Alkali Dichromate
(yellow) chromate (orange)

2. The structures of chromate ion, CrO42− and the dichromate ion,

Cr2O72− are shown below. The chromate ion is tetrahedral whereas the
dichromate ion consists of two tetrahedra sharing one corner with Cr–
O–Cr bond angle of 126°. Sodium and potassium dichromates are
strong oxidising agents; the sodium salt has a greater solubility in
 water and is extensively used as an oxidising agent in organic
chemistry. Potassium dichromate is used as a primary standard in
volumetric analysis.
Structures:
CHEMICAL PROPERTIE OF POTASSIUM DICHROMATE:
a) Oxidation reaction:
Potassium dichromate is a powerful oxidizing agent in the acid
medium because it provides nascent oxygen needed for oxidation.
K2Cr2O7 + 4H2SO4 K2SO4 + Cr2(SO4)3 + 4H2O + 3(O)
OR
3+
⎯
⎯→ + 7 H 2O
2-
Ionic reaction: 2 7
+
Cr O + 14H + 6e - 2Cr
During oxidation reactions, six electrons are provided by the
substances that undergo oxidation. Thus, acidified potassium
dichromate oxidized iodide to iodine, sulphide to sulphur, stannous
(II) to stannic (IV) and ferrous (II) to ferric (III). Changes are
represented as
⎯→ 3I 2 + 6e −
6I - ⎯
⎯→ 6 H + + 3S + 3e −
3H 2 S ⎯
3Sn 2+ ⎯
⎯→ 3Sn 4+ + 6e −
⎯→ 6 Fe3+ 6e −
6 Fe 2+ ⎯
The net ionic equation may be obtained by adding half reaction
for K2Cr2O7 and the substance oxidized.
⎯→ 2Cr 3+ + 7 H 2O + 3I 2
+ 14H + + 6I - ⎯
2-
Cr2O7
POTASSIUM PERMANGANATE [KMnO4]:
It is prepared from pyrolusite mineral (MnO2) in following two steps as
below:
a) Conversion of MnO2 to potassium manganate, K2MnO4:
Powdered pyrolusite is fused with KOH in presence of oxidizing agent like
potassium nitrate to obtain green coloured mass of potassium mangante.
MnO2 + 2KOH + KNO3 ⎯ ⎯→ K2MnO4 + 2KOH
3MnO4 + 4H → 2MnO4– + MnO2 + 2H2O
2– +

b) Electrolytic oxidation:
The potassium manganate solution is electrolyzed between iron
electrodes separated by diaphragm. Oxygen evolved at anode converts
manganate to permanganate.
2K2MnO4+ H2O + (O) ⎯ ⎯→ KMnO4 + 2KOH
OR
2−
MnO4 ⎯ ⎯→ MnO4− +e −
The solution is filtered and evaporated to obtain crystals of potassium
permanganate.
3.Lab preparation:
A manganese (II) ion salt is oxidised by peroxodisulphate to permanganate.

2Mn2+ + 5S2O82− + 8H2O → 2MnO4− + 10SO42− + 16H+

 Physical Properties:
Potassium permanganate is a dark purple crystalline solid which
dissolved in water to form pink coloured solution. It decomposes on heating
at 513K forming dark green coloured potassium manganate.
2KMnO4 ⎯⎯→ K2MnO4 + MnO2 + O2.
Both manganate and permanganate ions are tetrahedral.
The manganate and permanganate ions are tetrahedral; the green
manganate is paramagnetic with one unpaired electron but the
permanganate is diamagnetic.

The π-bonding takes place by overlap of p orbitals of oxygen with d orbitals

of manganese.

Oxidising property: Potassium permanganate acts as oxidizing agent in

neutral, acidic as well as basic medium.

a) Oxidation in acidic medium: In presence of dilute sulphuric acid.

Potassium permanganate act as good oxidizing agent.
2KMnO4 + 3H2SO4 K2SO4 + 2MnSO4 + 3H2O + 5(O) OR
⎯→ Mn 2+ + 4 H 2O
MnO 4 + 8H + + 5e - ⎯
-

i) Oxidises ferrous salt to ferric salt.

5Fe 2+ + MnO 4 ⎯→ Mn 2+ + 4 H 2O + 5 Fe3+
+ 8H + ⎯
-

ii) Oxidises iodide to iodine

⎯→ 2Mn 2+ + 8H 2O + 5I 2
10I - + 2MnO 4 + 16H + ⎯
-

iii) Oxidises oxalates or oxalic acid to carbon dioxide.

5C2O42− + 2MnO 4 + 16H + ⎯
⎯→ 2 Mn 2+ + 8 H 2O + 10CO2
-

iv) Oxidises Hydorgen sulphide to sulphur

5S 2− + 2MnO 4 ⎯→ 2 Mn 2+ + 8 H 2O + 10 S
+ 16H + ⎯
-

Oxidation as neutral or ion faintly alkaline solution: In neutral aqueous

solution potassium permanganate acts as moderate oxidizing agent.
 2KMnO4 + H2O  2KOH+ 2MnO2 + 3(O)
OR
⎯→ MnO2 + 4OH −
+ 2H 2 O + 3e - ⎯
-
MnO 4

i) Oxidises sodium thiosulphate to sodium sulphate.

+ 3S 2O32− + H 2O ⎯
⎯→ 8MnO2 + 6SO42− + 2OH −
-
8MnO 4

ii) Oxidises iodide to iodate.

⎯→ 2MnO2 + 2OH − + IO3−
+ 2H 2O + I - ⎯
-
2MnO 4

Uses:
1. used as oxidisig agent.
2. Used as decolourising oil.
3.Bleaching cotton & silk cloth.

f-block Elements[The inner transition elements]:

The elements which are having partially filled f-subshell in their
elementary or ionic state are called f-block elements.
These f-block elements are also called as Inner transition elemtns
because the differentiating electron enters (n-2)f orbital in preference to (n-
1) d and ns orbital.
There are two series of f-block elements namely.
1. Lanthanoids or 4f series or I inner transition series.
2. Actinoids or 5f series or II inner transition series.
Lanthanoids:
Lanthanum with atomic number 57, followed by the next fourteen
elements from atomic number 58 to 71 (Cerium to Lutetium) are together
called Lantanoids because all these elements have properties very closely
resembling lanthanum, Lanthanoids are the first inner transition elements.
Actinoids:
Actinium, with atomic number 89 followed by the next fourteen
elements from atomic number 90 to 103 (Thorium to Lawrencium) are
together called actinoids because all these elements have properties very
closely resembling actinium. Actinoids are the second inner transition
elements.

Electronic configuration:
Generally electronic configuration of 4f-block elements is
[Noble gas](n-2) f1-14(n-1)d0-1ns.
[Xe] (n-2) f1-14 (n-1)d0-1 ns.
The 6s Orbital of Barium (Z=56) {Xe} 6s2 is completely filled and yet
lanthanum (Z=57) 5d orbital is singly occupied [Xe] 5d 1 6s2.
But after lanthanum further filling of 5d orbital is discontinued. As
the nuclear charge increasing by one unit form La(57) to Ce(58) , 4f orbitals
which were higher in energy upto La (57) falls slightly below the 5d level.
Hence 4f orbitals therefore begin to fill and are completely filled upto Lu
(71), before filling of 5d orbital.
Hence the electronic configuration of lanthanides is given by

LANTHANIDE CONTRACTION:
“ As going from La3+ to Lu3+ ion, ionic size decreases. The decrease in
the size of the trivalent cations along the series is called Lanthanide
contraction.
Causes:
As we move through the lanthanide series, 4f electron are added one at
each step. The mutual shielding effect of 4f-electrons is very little, due to
theshape of f-orbital. However the nuclear charge increases one at each
step. Hence the inward pull experienced by the 4f- electron increases. This
causes a reduction in the size of the entire 4fn shell. The sum of successive
reduction gives the total lanthanide contraction.

CONSEQUENCES:
1. Lanthanide contraction is an important factor in allowing the
separation of lanthanides from one another.
2. Electronegativity increases from Ce to Lu.
3. Basic strength decreases from Ce to Lu.
4. Complex formation increases from Ce to Lu.
5. Covalent character of cations increases.
6. Eo value increases
7. Zr & Hf almost same atomic radius(transition series).
OXIDATION STATE:
Lanthanides show a common oxidation state of +3 some of thelanthanides
also exhibit +2,+4, oxidation state. But +3 is most stable oxidation state,
because in lanthanide 6s2 and 5d electrons are lost during the formation of
tripositive ions. The outer shell 5s and 5p have the maximum number of
electrons and an inner 4f-shell have electrons starting from 1 to 14.

General properties of lanthanoids:

• Lanthanoids are silvery white metals.
• They are soft metals with melting points between 1000K to 1200K.
However samarium (Sm) has an abnormal melting point of 1623K.
• They are reactive metals because they are tarnished rapidly by air.

i)Coloures of lanthonoid ions:

They are coloured in their solid state as well as in aqueous solution This
colour is due to f-f transition of elements.

ii)Magnetic property: Most of the lanthanoid ions are paramagnetic

due to the presence of one or more unpaired electrons.

iii)Ionisation enthalpies: Second ionization enthalpies are high than

the first ionization enthalpies.but lanthanoids shows variations in their 3rd
ionization energydue to fo, f7,& f14 configuration.abnormal low value of 3rd
ionization energy for La, Gd & Lu.
iv)Chemical reactivity:
In general, the earlier members of the series
are quite reactive similar to calcium but, with increasing atomic number,
they behave more like aluminium. Values for E Θ for the half-reaction:
Ln3+ (aq) + 3e− → Ln(s)
are in the range of –2.2 to –2.4 V except for Eu for which the value is – 2.0
V. This is, of course, a small variation.
Lanthanoids combine with Hydrogen, carbon, water ,oxygen
and ammonia forming respective compounds.

Chemical recativity:All lanthanides are highly electropositive metals & are

chemically reactive
1.They react with air lose their shining nature.
2.They react with water forms insoluble hydroxides & libertaes H2
3.They react with hydrogen forms hydrides.(partial ionic in nature)
4.Theyreact with halogens,oyher non metals forms respective
halides,oxides,carbides etc
Uses
• In the production of alloy steels for plates and pipes
• Mixed oxides of lanthanoids are used as catalysts in petroleum
cracking.
• Some lanthanum oxides are used as phosphors in television screens
and other fluorescing surfaces.

Actinoids:
Actinium, with atomic number 89 followed by the next fourteen
elements from atomic number 90 to 103 (Thorium to Lawrencium) are
together called actinoids because all these elements have properties very
closely resembling actinium. Actinoids are the second inner transition
elements.
OR
In 5f series elements, the extra electron enters into 5f orbital. A group of 14
elements from thorium to Lawrencium are called actinoids.

Electronic configuration:
Generally electronic configuration of 5f-block elements is
[Noble gas] 5f1-14 6d0-17s2
Ie., [Rn] 5f1-14 6d0-1 7s2.
Oxidation state:
Actinides exhibit oxidation state of +2,+3,+4,+5,+6. The +2 state is shown
only by actinium and thorium in a few compound. The +3 oxidation state is
most common and it becomes more and more stable with increase in atomic
number. The +4 oxidation state is shown by first 8 elements.( Ac to Cm
only).The +5 oxidation state shown by 5 elements (Th to Pu).Where as +6
oxidation state exhibited only by 4 elements (Pa to Pu)
Actinide contraction:
The ionic radii of actinide elements decreases gradually with increase in
atomic number. These decrease in the ionic radii with increase in the atomic
number along the actinide series is called actinide contraction.
This contraction is due to the addition of successive electrons to an
inner 5f subshell. Due to poor shielding effect of 5f electrons, as the atomic
number increases the inward pull experienced by the 5f electron increases
consequently, steady decrease in the ionic radii occurs in actinide series.

General Characteristics and Comparing with Lanthanoids

• Silvery metals
• Have a variety of structures
• Highly reactive (especially when finely divided)
• Give a mixture of oxide and hydride when treated with boiling water
• Combine with most non-metals at moderate temperatures
• React readily with hydrochloric acid, but slowly with nitric acid due to
the formation of protective oxide film
• Do not react with alkalies
• Paramagnetic in nature.

Their magnetic properties are complex in comparison to lanthanoids.

• Lower ionization enthalpies than lanthanoids
• Reason -5f electrons are less effectively shielded than 4f electrons.

Comparison of actinoids with Lanthanoids:

Lanthanoids Actinoids
Usually shows a common oxidation Usually shows a common oxidation
state of +3 state of +3
 Undergo lanthanide contraction Undergo Actinide contraction
Lanthanoids are electropositve and Actinoids are also electropositive
act as strong reducing agents. and act as strong reducing agents.
They are paramagnetic in nature They are also paramagnetic in
nature
Most of the ions are coloured Most of the ions are coloured.
Steady decrease in their ionic radii Steady decrease in their ionic radii
along the series. along the series.

Distinction betweeen lanthanoids and actinoids:

Have lessr tendency of complex Have stronger tendency of complex
formation formation.
Magnetic properties can be easily Magnetic properties of actinoids
explained cannot by explained easily.
Except promethium, they are non- All actinoids are radioactive.
radioactive.

General Characteristics and Comparing with Lanthanoids

• Silvery metals
• Have a variety of structures
• Highly reactive (especially when finely divided)
• Give a mixture of oxide and hydride when treated with boiling water
• Combine with most non-metals at moderate temperatures
• React readily with hydrochloric acid, but slowly with nitric acid due to
the formation of protective oxide film
• Do not react with alkalies
• Paramagnetic in nature.

Their magnetic properties are complex in comparison to lanthanoids.

• Lower ionization enthalpies than lanthanoids
• Reason -5f electrons are less effectively shielded than 4f electrons.

Some Applications of d- and f-block Elements

• Iron is used in the construction materials.
• Fe, Cr, Ni, and Mn are used in the manufacture of steel, which is used
in construction.
• TiO is used in pigment industry whereas MnO2 , Zn, and Ni/Cd are
used in battery industry.
• Ag, Au, Cu and Ni are used in making coins.
• Some metals and /or their compounds (V, Ti, Al, Fe, Ni, and Pd) are
used as catalysts.
• AgBr is used in photographic industry as it has special light sensitive
properties.