D And F- Block Elements

D-Block Elements
Introduction:- A transition element may be defined as an element whose atom in the ground state or ion in
common oxidation state has incomplete sub-shell, has electron 1 to 9. It is called transition element due to
fact that it is lying between most electropositive (s-block) and most electronegative (p-block) elements and
represent a transition from them. The general electronic configuration of these element is (n-1)d1-10 ns1-2.
The definition of transition metal excludes Cd, Zn and Hg because they have complete d- orbital. Their common
oxidation state is Zn++,Cd++,Hg++ . They also do not show the characteristics of transition element. Element of
group 3 (Sc, Y, La and Ac) and group 12 (Zn, Cd, Hg) are called non typical transition element.
First Transition or 3d- Series

Second Transition or 4d-series

Third Transition or 5d-Series

Fourth Transition or 6d-Series

Exceptional Electronic Configuration:-

There are several exceptions because of very little energy difference between (n–1)d and ns orbitals.
Furthermore, half and completely filled sets of orbitals are relatively more stable. A consequence of this factor is
reflected in the electronic configurations of Cr and Cu in the 3d series.
Consider the case of Cr, which has 3d5 4s1 instead of 3d44s2; the energy gap between the two sets (3d and 4s)
of orbitals is small enough to prevent electron entering the 3d orbitals. Similarly in case of Cu, the configuration is
3d104s1 and not 3d94s2.
The other exceptions is Pd,Nb,Mo,Ru,Rh,Ag,Pt,Au.
GENERAL PROPERTIES OF THE TRANSITION ELEMENTS (d-BLOCK ELEMENTS):-
The transition elements exhibit typical characteristic properties. This is due to their small atomic sizes, large
nuclear charges and the presence of unpaired d - electrons.
(1) Atomic radii :
The atomic radii of 3d-series of elements are compared with those of the neighbouring s and p-block elements
are given below.
(i) The atomic radii and atomic volumes of d-block elements in any series decrease with increase in the atomic
number. The decrease, is not regular. The atomic radii tend to reach minimum near at the middle of the series, and
increase slightly towards the end of the series.
Explanation : When we go in any transition series from left, to right, the nuclear charge increases gradually by
one unit at each elements. The added electrons enter the same penultimate shell. These added electrons shield the
outermost electrons from the attraction of the nuclear charge. The increased nuclear charge tends to reduce the
atomic radii. At the beginning of the series, due to smaller number of electrons in the d-orbitals, the effect of
increased nuclear charge predominates, and the atomic radii decrease. Later in the series, when the number of d-
electrons increases, the increased shielding effect and the increased repulsion between the electrons tend to
increase the atomic radii.
(ii) The atomic radii increase while going down in each group. However, in the third transition series from Hafnium
(Hf) and onwards, the elements have atomic radii nearly equal to those of the second transition elements.
Explanation : The atomic radii increase while going down the group. This is due to the introduction of an
additional shell at each new element down the group. Nearly equal radii of second and third transition series
elements is due to a special effect called lanthanide contraction.
(2) Ionic radii :
For ions having identical charges, the ionic radii decrease slowly with the increase in the atomic number
across a given series of the transition elements.
Explanation :- The gradually decrease in the values of ionic radius across the series of transition elements is due
to the increase in the effective nuclear charge.
(3) Ionisation Energies :-
The ionisation energies of the elements of first transition series are given below:

1st 2nd 3rd

in KJ/Mol
(i) The ionisation energies of these elements are high and in the most cases lie between those of s- and p-block
elements. This indicates that the transition elements are less electropositive than s-block elements.
(ii) The ionisation energy in any transition series increases with atomic number; the increase is not smooth and sharp
as seen in the case of s and p-block elements.
(iii) The first ionisation energies of 5d-series of elements are much higher than those of the 3d and 4d series
elements.
Explanation : In the 5d-series of transitions elements, after lanthanum (La), the added electrons go to the next inner
4f orbitals. The 4f electrons have poor shielding effect. As a result, the outermost electrons experience
 greater nuclear attraction. This leads to higher ionisation energies for the 5d- series of transition elements.
(4) Metallic character : All the transition elements are metals. These are hard, and good conductor of heat and
electricity. All these metals are malleable, ductile and form alloys with other metals.
These elements occur in three types e.g., face- centered cubic (fcc), hexagonal close-
packed (hcp) and body-centered cubic (bcc), structures.
The transition elements shows both covalent as well as metallic bonding amongst their atoms.
Explanation : The ionisation energies of the transition elements are not very high. The outermost shell in their
atoms have many vacant, partially filled orbitals. These characteristics make these elements metallic in character.
(5) Melting and boiling points : The melting and boiling points of transition elements except Cd and Hg, are
very high as compared to the s block and p-block elements. The melting and boiling points first increase,
pass through maxima and then steadily decrease across any transition series. The maximum occurs around
middle of the series.
Explanation : Atoms of the transition elements are closely packed and held together by strong metallic bonds
which have appreciable covalent character. This leads to high melting and boiling points of the transition elements.
The low melting points of Zn, Cd, and Hg may be due to the absence of unpaired d-electrons in their atoms.
(6) Enthalpies of atomization : Transition metals exhibit high enthalpies of atomization.
Explanation : This is because the atoms in these elements are closely packed and held together by strong metallic
bonds. The metallic bond is formed as a result of the interaction of electrons in the outermost shell. Greater
the number of valence electrons, stronger is the metallic bond.
(7) Oxidation states : Most of the transition elements exhibit several oxidation states i.e., they show variable
valency in their compounds. Some common oxidation states of the first transition series elements are given
below in table,

Explanation : The outermost electronic configuration of the transition elements is (n - 1)d1-10 ns2 . Since, the
energy levels of (n-1)d and ns orbitals are quite close to each other, hence both the ns and (n-1) d electrons are
available for bonding purposes. Therefore, the number of oxidation states show by these elements depends upon
the number of d-electrons it has.
For example, Sc having a configuration 3d1 4s2 may show an oxidation state of + 2 (only s-electrons are lost) and
+ 3 (when d-electron is also lost). The highest oxidation state which an elements of this group might show is given by
the total number of ns and (n -1) d-electrons.
An examination of the common oxidation states reveals the following conclusions.
(i) The variable oxidation states shown by the transition elements are due to the participation of outer ns and inner
(n–1)d-electrons in bonding.
(ii) Except scandium, the most common oxidation state shown by the elements of first transition series is +2. This
oxidation state arises from the loss of two 4s electrons. This means that after scandium, d-orbitals become more
 stable than the s-orbital.
(iii) The highest oxidation states are observed in fluorides and oxides. The highest oxidation state shown by any
transition elements (by Ru and Os) is 8.
(iv) The transition elements in the +2 and +3 oxidation states mostly form ionic bonds. In compounds of the higher
oxidation states, the bonds are essentially covalent. For example, in permanganate ion MnO4 , all bonds formed
between manganese and oxygen are covalent.
(v) Within a group, the maximum oxidation state increases with atomic number. For example, iron shown the
common oxidation state of +2 and +3, but ruthenium and osmium in the same group form compounds in the
+4, +6 and +8 oxidation states.
(vi) Transition metals also form compounds in low oxidation states such as +1 and 0.
For example, Nickel,in Nickel tetracarbonyl, Ni(CO)4 has zero oxidation state. Similarly Fe in Fe(CO)5 has zero
oxidation state.
(vii) Transition elements like Sc, Y, La and Ac do not show variable valency.
(8) Electrode potentials (E0) : Standard electrode potentials of some half–cells involving 3d-series of transition
elements and their ions in aqueous solution are given in table,
Standard electrode potentials for 3d-elements

The negative values of E° for the first series of transition elements (except for Cu2+ / Cu ) indicate that,
(i) These metals should liberate hydrogen from dilute acids
M + 2H+  M2+ + H2(g); 2M + 6H+  2M3+ + 3H2 (g)
The reactions are favourable in the forward direction. In actual practice however, most of these metals react
with dilute acids very slowly. Some of these metals get coated with a thin protective layer of oxide. Such an oxide
layer prevents the metal to react further.
(ii) These metals should act as good reducing agents. There is no regular trend in the E° values. This is due to
irregular variation in the ionisation and sublimation energies across the series.
(9) Formation of coloured ions : Most of the compound of the transition elements are coloured in the solid
state and /or in the solution phase. The compounds of transition metals are coloured due to the presence of
unpaired electrons in their d-orbitals.
Explanation : In an isolated atom or ion of a transition elements, all the five d-orbitals are of the same energy
(degenerate). Under the influence of the combining anion , or electron- rich molecules, the five d-orbitals split into
two (or sometimes more than two) levels of different energies. The difference between the two energy levels
depends upon the nature of the combining ions, but corresponds to the energy associated with the radiations in
the visible region, ( 760 380 nm) . Typical splitting for octahedral and tetrahedral geometries are shown in fig.

The splitting of d-orbital energy levels in (a) an octahedral (b) a tetrahedral, geometry.
This spllitting is termed as the crystal field splitting.
 The transition metals in elements form or in the ionic form have one or more unpaired electrons. When visible
light falls on the sample, the electrons from the lower energy level get promoted to a higher energy level due to the
absorption of light of a characteristic wavelength. This wavelength of the absorbed light depends upon the energy
difference of the two levels. Rest of the light gets transmitted. The transmitted light has a colour complementary to
the absorbed colour. Therefore, the compound or the solution appears to be of the complementary colour.
e.g. ions absorb red radiation, and appear blue-green (blue-green is complementary colour
to red). Hydrated Co2+ ions absorb radiation in the blue-green region, and therefore, appear red in sunlight.

Relationship between the colours of the absorbed and transmitted light: the
complementary colours.

Colours and the outer- electronic configurations of the some important ions of the first transition series
elements are given bellow,
(10) Magnetic properties : Most of the transition elements and their compounds show paramagnetism. The
paramagnetism first increases in any transition element series, and then decreases. The maximum
paramagnetism is seen around the middle of the series. The paramagnetism is described in Bohr Magneton
(BM) units. The paramagnetic moments of some common ions of first transition series are given below in Table
Magnetic moments of some ions of the 3d-series elements

Explanation : A substance which is attracted by magnetic filed is called paramagnetic substance. The substances
which are repelled by magnetic filed are, called diamagnetic substances. Paramagnetism is due to the
presence of unpaired electrons in atoms, ions or molecules.
The magnetic moment of any transition element or its compound/ion is given by-

where, S is the total spin (n s) : n is the number of unpaired electrons and s is equal to ½ (representing the spin of
an unpaired electron).
From the equation given above, the magnetic moment ) ( s  increases with an increase in the number of unpaired
electrons.
(11) Formation of complex ions : Transition metals and their ions show strong tendency for complex
formation. The cations of transition elements (d-block elements) form complex ions with certain molecules
containing one or more lone-pairs of electrons, viz., CO, NO, NH3 etc., or with anions such as, F , Cl , CN etc. A few
complex ions are,

Explanation : This complex formation tendency is due to,

(i) Small size and high nuclear charge of the transition metal cations.
(ii) The availability to vacant inner d-orbitals of suitable energy.
(12) Formation of interstitial compounds : Transition elements form a few interstitial compounds with
elements having small atomic radii, such as hydrogen, boron, carbon and nitrogen. The small atoms of these
elements get entrapped in between the void spaces (called interstices) of the metal lattice. Some characteristics of
the interstitial compound are,

(i) These are non-stoichiometric compounds and cannot be given definite formulae.
(ii) These compounds show essentially the same chemical properties as the parent metals, but differ in physical
properties such as density and hardness. Steel and cast iron are hard due to the formation of interstitial compound
with carbon. Some non-stoichimetric compounds are, VSe 0.98 (Vanadium selenide), Fe 0.94 O and titanium nitride.
(13) Catalytic properties : Most of the transition metals and their compounds particularly oxides have good
catalytic properties. Platinum, iron, vanadium pentoxide, nickel etc., are important catalysts. Platinum is a general
catalyst. Nickel powder is a good catalyst for hydrogenation of unsaturated organic compound such as,
hydrogenation of oils some typical industrial catalysts are,
(i) Vanadium pentoxide (V2O5 ) is used in the Contact process for the manufacture of sulphuric acid.
(ii) Finely divided iron is used in the Haber’s process for the synthesis of ammonia.
Explanation : Most transition elements act as good catalyst because of
(i) The presence of vacant d-orbitals.
(ii) The tendency to exhibit variable oxidation states.
(iii) The tendency to form reaction intermediates with reactants.
(iv) The presence of defects in their crystal lattices.
(14) Alloy formation : Transition metals form alloys among themselves. The alloys of transition metals are hard
and high metals are high melting as compared to the host metal. Various steels are alloys of iron with metals such as
chromium, vanadium, molybdenum, tungsten, manganese etc.
Explanation : The atomic radii of the transition elements in any series are not much different from each other. As
a result, they can very easily replace each other in the lattice and form solid solutions over an appreciable
composition range. Such solid solutions are called alloys.
(15) Chemical reactivity : The d-block elements have lesser tendency to react, these are less reactive as
compared to s block elements.
Explanation : Low reactivity of transition elements is due to
(i) Their high ionisation energies.
(ii) Low heats of hydration of their ions.
(iii) Their high heats of sublimation.
Chromium containing compounds
Potassium dichromate, (K2Cr2O7)- Potassium dichromate is one of the most important compound of
chromium, and also among dichromates. In this compound Cr is in the hexavalent (+6) state.
Preparation : It can be prepared by any of the following methods-
(i) From potassium chromate : Potassium dichromate can be obtained by adding a calculated amount of
sulphuric acid to a saturated solution of potassium chromate.

K2Cr2O7 Crystals can be obtained by concentrating the solution and crystallisation.

(ii) Manufacture from chromite ore : K2Cr2O7 is generally manufactured from chromite ore (FeCr2O4).The
process involves the following steps.
(a) Preparation of sodium chromate : Finely powdered chromite ore is mixed with soda ash and quicklime.
The mixture is then roasted in a reverberatory furnace in the presence of air. Yellow mass due to the formation of
sodium chromate is obtained.

The reaction may also be carried out by using NaOH instead of Na2CO3 . The reaction in that case is

(b) Conversion of chromate into dichromate : Sodium chromate solution obtained in step (a) is treated
with concentrated sulphuric acid when it is converted into sodium dichromate.

(c) Concentration of sodium dichromate to potassium dichromate : Hot concentrated solution of

sodium dichromate is treated with a calculated amount of potassium chloride. When potassium dichromate being
less soluble crystallizes out on cooling.
Physical properties
(i) Potassium dichromate forms orange-red coloured crystals.
(ii) It melts at 699 K.
(iii) It is very stable in air (near room temperature) and is generally, used as a primary standard in the volumetric
analysis.
(iv) It is soluble in water though the solubility is limited.
Chemical properties
(i) Action of heat : Potassium dichromate when heated strongly. Decomposes to give oxygen.

(ii) Action of acids

(a) In cold, with concentrated H2SO4 , red crystals of chromium trioxide separate out.

On heating a dichromate-sulphuric acid mixture, oxygen gas is given out.

(b) With HCl, on heating chromic chloride is formed and Cl2 is liberated.

(iii) Action of alkalies : With alkalies, it gives chromates. For example, with KOH

On acidifying, the colour again changes to orange-red owing to the formation of dichromate.

Actually, in dichromate solution, the Cr2O7 2-ions are in equilibrium with CrO42ions.

(iv) Oxidising nature : In neutral or in acidic solution, potassium dichromate acts as an excellent oxidising
agent, and Cr2O72gets reduced to Cr 3+ . The standard electrode potential for the reaction

This indicates that dichromate ion is a fairly strong oxidising agent, especially in strongly acidic solutions. That is why
potassium dichromate is widely used as an oxidising agent
(a) Ferrous salts to ferric salts

Ionic equation

(b) Sulphites to sulphates and arsenites to arsenates.

Ionic equation
Similarly, arsenites are oxidised to arsenates.

(c) Hydrogen halides to halogens.

(d) Iodides to iodine

(e) It oxidises H2S to S

(v) Formation of insoluble chromates : With soluble salts of lead, barium etc., potassium dichromate gives
insoluble chromates. Lead chromate is an important yellow pigment.

(vi) Chromyl chloride test : When potassium dichromate is heated with conc. H2SO4 in the presence of a
soluble chloride salt, the orange-red vapours of chromyl chloride (CrO2Cl2) are formed.

Chromyl chloride vapours when passed through water give yellow coloured solution containing chromic acid.

Chromyl chloride test can be used for the detection of chloride ion is any mixture.
Uses:- (i) An oxidising agent
(ii) In chrome tanning
(iii) The raw meterial for preparing large number of chromium compounds
(iv) Primary standard in the volumetric analysis.
Structures of Chromate and Dichromate Ions

Manganese containing compound

Potassium Permanganate (KMnO4)
Potassium permanganate is a salt of an unstable acid HMnO4 (permanganic acid). The Mn is an +7 state in this
compound.
Preparation : Potassium permanganate is obtained from pyrolusite as follows.
Conversion of pyrolusite to potassium manganate : When manganese dioxide is fused with potassium
hydroxide in the presence of air or an oxidising agent such as potassium nitrate or chlorate, potassium manganate is
formed via potassium manganite.

Oxidation of potassium manganate to potassium permanganate : The potassium manganate is oxidised to

potassium permanganate by the following methods.
By chemical method : The fused dark-green mass is extracted with a small quantity of water. The filtrate is
warmed and treated with a current of ozone, chlorine or carbon dioxide. Potassium manganate gets oxidised to
potassium permanganate and the hydrated manganese dioxide precipitates out. The reactions taking place are-
When CO2 is passed

When chlorine or ozone is passed

The purple solution so obtained is concentrated and dark purple, needle-like crystals having metallic lustre are
obtained.
Electrolytic method : Presently, potassium manganate (K2MnO4) is oxidised electrolytically. The electrode
reactions are

The purple solution containing KMnO4 is evaporated under controlled condition to get crystalline sample of
potassium permanganate.
Physical properties
KMnO4 crystallizes as dark purple crystals with greenish luster (m.p. 523 K).

It is soluble in water to an extent of 6.5g per 100g at room temperature. The aqueous solution of KMnO4 has a
purple colour.
Chemical properties : Action of heat :

Oxidising actions : KMnO4 is a powerful agent in neutral, acidic and alkaline media. The nature of reaction is
different in each medium. The oxidising character of KMnO4 is indicated by high positive reduction potentials for the
following reactions.

In strongly alkaline solutions and with excess of MnO4 , the reaction is

There are a large number of oxidation-reduction reactions involved in the chemistry of manganese compounds.
Some typical reactions are-
1- In the presence of excess of reducing agent in acidic solutions permanganate ion gets reduced to manganous ion,
e.g.-
2- An excess of reducing agent in alkaline solution reduces permanganate ion only to manganese dioxide e.g.-

3- In faintly acidic and neutral solutions, manganous ion is oxidised to manganese oxidised to manganese dioxide by
permanganate.

4- In strongly basic solutions, permangante oxidises manganese dioxide to manganate ion.

In acidic medium, KMnO4 oxidises:- 1- Ferrous salts to ferric salts

The reaction forms the basis of volumetric estimation of Fe2+ in any solution by KMnO4 .
2- Oxalic acid to carbon dioxide

3- Sulphites to sulphates
4- Iodides to iodine in acidic medium

5- Hydrogen peroxide to oxygen

6- Manganous sulphate (MnSO4 ) to manganese dioxide (MnO 2)

7- Ammonia to nitrogen

Uses : (i) As an oxidising agent.

(ii) As a disinfectant against disease causing germs.
(iii) For sterilizing wells of drinking water.
(iv) In volumetric estimation of ferrous salts, oxalic acid etc.
(v) Dilute alkaline KMnO4 solution known as Baeyer’s reagent.
Structure of Permanganate Ion (MnO4-) :-

Iron and its Compounds

(1) Ores of iron : Haematite Fe2O3, Magnetite (Fe3O4) , Limonite (Fe2O3 . 3H2O) ,Iron pyrites (FeS2),
Copper pyrities (CuFeS2) etc.
(2) Extraction : Cast iron is extracted from its oxides by reduction with carbon and carbon monoxide in a blast
furnace to give pig iron.
Roasting : Ferrous oxide convert into ferric oxide.

Smelting : Reduction of roasted ore of ferric oxide carried out in a blast furnace.
(i) The reduction of ferric oxide is done by carbon and carbon monoxide (between 1473k to 1873k

(ii)
It is a reversible and exothermic reaction. Hence according to Le-chatelier principle more iron will be produced in
the furnace at lower temp.

The gases leaving at the top of the furnace contain up to 28% CO and are burnt in cowper's stove to pre-heat
the air for blast
Varieties of iron : The three commercial varieties of iron differ in their carbon contents. These are;
(1) Cast iron or Pig-iron : It is most impure form of iron and contains highest proportion of carbon (2.5–4%).
(2) Wrought iron or Malleable iron : It is the purest form of iron and contains minimum amount of carbon
(0.12–0.25%).
(3) Steel : It is the most important form of iron and finds extensive applications. Its carbons content (Impurity) is
mid-way between cast iron and wrought iron. It contains 0.2–1.5% carbon. Steels containing 0.2–0.5% of carbon
are known as mild steels, while those containing 0.5–1.5% carbon are known as hard steels.
Steel is generally manufactured from cast iron by three processes
(i) Bessemer Process which involves the use of a large pear-shaped furnace (vessel) called Bessemer converter
(ii) L.D. process
(iii) open hearth process, Spiegeleisen (an alloy of Fe, Mn and C) is added during manufacture of steel.
Heat treatment of steels : Heat treatment of steel may be defined as the process of carefully heating the
steel to high temperature followed by cooling to the room temperature under controlled conditions. Heat
treatment of steel is done for the following two purposes-
(i) To develop certain special properties like hardness, strength, ductility etc. without changing the chemical
composition.
(ii) To remove some undesirable properties or gases like entrapped gases, internal stresses and strains.
The various methods of heat treatment are-
(a) Annealing : It is a process of heating steel to redness followed by slow cooling.
(b) Quenching or hardening : It is a process of heating steel to redness followed by sudden cooling by
plunging the red hot steel into water or oil.
(c) Tempering : It is a process of heating the hardened or quenched steel to a temperature much below redness
(473–623K) followed by slow cooling.
(d) Case-hardening : It is a process of giving a thin coating of hardened steel to wrought iron or to a strong and
flexible mild steel by heating it in contact with charcoal followed by quenching in oil.
(e) Nitriding : It is a process of heating steels at about 700oC in an atmosphere of ammonia. This process imparts
a hard coating of iron nitride on the surface of steel.
Properties of steel : The properties of steel depend upon its carbon contents. With the increase in carbon
content, the hardness of steel increases while its ductility decreases.
(i) Low carbon or soft steels contain carbon upto 0.25%.
(ii) Medium carbon steels or mild steels contain 0.25–0.5% carbon.
(iii) High carbon or hard steels contains 0.1 – 1.5 percent carbon.
(iv) Alloy steels or special steels are alloys of steel with V, Mn, W, Co, Cr, Ni etc.
For example-
(a) Stainless steel (Fe = 73%, Cr = 18%, Ni = 8% + C) is resistant to corrosion and is used for making ornamental
pieces, cutlery etc.
(b) Invar (Fe = 64%, Ni = 36%) has small coefficient of expansion and is used for making metre scales, pendulum rods
and watches.
(c) Manganese steel (Fe = 86%, Mn 13% + carbon) is very hard and resistant to wear and hence is used for making
rock drills, safes etc.
(d) Tungsten steel (Fe = 94%, W = 5% + carbon) is quite hard and is used for making high speed cutting tools.
(e) Permalloy (Fe = 21%, Ni = 78% + carbon) is strongly magnetised by electric current but loses magnetism when
current is cut off. It is used for making electromagnets, ocean cables etc.
Properties of iron
(1) Dry or moist air has no action on pure iron but impure iron when exposed to moist air is covered with a layer of
rust Fe2O3 + Fe(OH)3. However, finely divided pure iron burns in air or oxygen forming Fe3O4.
3Fe + 2O2  Fe3O4
(2) Iron decomposes steam at red heat

(3) Action of acids : Iron reacts with dil. HCl and dil.H2SO4 liberating hydrogen. with hot conc. H2SO4, it gives SO2, with
dil. HNO3, it gives NH4NO3 and moderately conc.HNO3 reacts with iron forming NO2.
Cold conc. HNO3 makes iron passive due to the deposit of a thin layer of iron oxide (Fe3O4) on the surface.
Hot conc. HNO3 reacts with iron liberating NO.

(4) Iron does not react with alkalies.

(5) It displaces less electropositive metals (e.g., Cu, Ag etc.) from their salts

(6) Finely divided iron combines with CO forming penta carbonyl

(7) Iron does not form amalgam with Hg.

(8) Iron is the most abundant and most widely used transition metal.
Compounds of iron
(1) Oxides of Iron : Iron forms three oxides FeO, Fe2O3 (Haematite),Fe3O4 (magnetite also called magnetic oxide
or load stone).
(i) Ferrous oxide FeO: It is a black powder, basic in nature and reacts with dilute acids to give ferrous salts.

It is used in glass industry to impart green colour to glass.

(ii) Ferric oxide Fe2O3 : It is a reddish brown powder, not affected by air or water; amphoteric in nature and
reacts both with acids and alkalis giving salts. It can be reduced to iron by heating with C or CO.

It is used as red pigment to impart red colour to external walls and as a polishing powder by jewellers.
(iii) Ferrosoferricoxide Fe3O4 (FeO.Fe2O3): It is more stable than FeO and Fe2O3, magnetic in nature and
dissolves in acids giving a mixture of iron (II) and iron (III) salts.

(2) Ferrous sulphide FeS: It is prepared by heating iron filing with sulphur. With dilute H2SO4, it gives H2S.

(3) Ferric chloride FeCl3: (i) preparation : It is prepared by treating Fe(OH)3with HCl

(ii) Properties : (a) Anhydrous FeCl3 forms reddish-black deliquescent crystals.

(b) FeCl3 is hygroscopic and dissolves in H2O giving brown acidic solution due to formation of HCl

(c) Due to oxidising nature Fe3 ions FeCl3 is used in etching metals such as copper

(d) In vapour state FeCl3 exists as a dimer, Fe2Cl6

(e) FeCl3 is used as stypic to stop bleeding from a cut.
(4) Ferrous sulphate, FeSO4.7H2O (Green vitriol) : It is prepared as follow

(i) On pressure to moist air crystals become brownish due to oxidation by air.

(ii) On heating, crystals become anhydrous and on strong heating it decomposes to Fe2O3, SO2 and SO3.

(iii) It can reduce acidic solution of KMnO4 and K2Cr2O7

(iv) It is generally used in double salt with ammonium sulphate.

Mohr’s salt is resistant to atmospheric oxidation.

(v) It is used in the ring test for nitrate ions where it gives brown coloured ring of compound FeSO4. NO.

(vi) FeSO4 is used in manufacture of blue black ink.

(vii) FeSO4  H2O2 is known as a name of Fenton’s reagent.
(5) Mohr's salt FeSO4. (NH4) 2SO4. 6H2O : It is a double salt and is prepared by crystallising a solution
containing equivalent amounts of FeSO4.7H2O and (NH4)2SO4. It may be noted that Mohr’s salt contains only Fe2
ions without any trace of Fe3 ions.
In contrast FeSO4.7H2O always contains some Fe3 ions due to aerial oxidation of Fe2 ions.
Mohr salt is,used as a primary standard in volumetric analysis since a standard solution of Fe2 ions can be
obtained directly by weighing a known amount of the Mohr salt.
+It acts as a reducing agent and as such reduces acidified KMnO4 and K2Cr2O7 solutions.

Copper and its Compounds

(1) Ores : Copper pyrites (chalcopyrite) CuFeS2, Cuprite (ruby copper) Cu2O, Copper glance Cu2S, Malachite
[Cu(OH)2.CuCO3], Azurite [Cu(OH)2.2CuCO3] .
(2) Extraction : Most of the copper (about 75%) is extracted from its sulphide ore, copper pyrites.
Concentration of ore : Froth floatation process.
Roasting : Main reaction :

Side reaction :

Smelting :

The mixture of copper and iron sulphides melt together to form 'matte' (Cu2S +FeS) and the slag floats on its
surface.
Conversion of matte into Blister copper (Bessemerisation) : Silica is added to matte and a hot blast
of air is passed
FeO + SiO2  FeSiO3(slag) .
Slag is removed. By this time most of iron sulphide is removed. Cu2S +2Cu2O 6Cu + SO2
Blister copper : Which contain about 98% pure copper and 2% impurities (Ag, Au, Ni, Zn etc.)
Properties of copper :
It has reddish brown colour.
It is highly malleable and ductile.
It has high electrical conductivity and high thermal conductivity. Copper is second most useful metal (first being
iron).
It undergoes displacement reactions with lesser reactive metals e.g. with Ag. It can displace Ag from AgNO3. The
finally divided Ag so obtained is black in colour.
Copper shows oxidation states of +1 and +2. Whereas copper (I) salts are colourless, copper (II) salts are blue in
colour.
Cu (I) salts are less stable and hence are easily oxidised to Cu (II) salts (2Cu+ Cu2+ + Cu) . This reaction is called
disproportionation.
(1) In presence of atmospheric CO2 and moisture, copper gets covered with a green layer of basic copper carbonate
(green layer) which protects the rest of the metal from further acton.

(2) In presence of oxygen or air, copper when heated to redness (below 1370K) first forms red cuprous oxide which
changes to black cupric oxide on further heating. If the temperature is too high, cupric oxide changes back to
cuprous oxide

(3) Action of acids. Non oxidising dil. acids such as H2SO4 , HCl have no action on copper. However, copper dissolves
in these acids in presence of air.

Compounds of Copper
(1) Halides of copper : Copper (II) chloride, CuCl2 is prepared by passing chlorine over heated copper.
Concentrated aqueous solution of CuCl2 is dark brown but changes first to green and then to blue on dilution.
On heating, it disproportionates to copper (I) chloride and chlorine

It is used as a catalyst in the Daecon’s process for the manufacture of chlorine.

Copper (I) chloride, CuCl is a white solid insoluble in water. It is obtained by boiling a solution of CuCl2 with
excess of copper turnings and conc. HCl .

It dissolves in conc. HCl due to the formation of complex H[CuCl2]

It is used as a catalyst alongwith NH4Cl in the preparation of synthetic rubber.

(2) Cuprous oxide Cu2O: It is a reddish brown powder insoluble in water but soluble in ammonia solution,
where it forms diammine copper (I) ion. Cu+ + 2NH3 [Cu(NH3)2]+ . It is used to impart red colour to glass in
glass industry.
(3) Cupric oxide CuO : It is dark black, hygroscopic powder which is reduced to Cu by hydrogen, CO etc. It is
used to impart light blue colour to glass. It is prepared by heating copper nitrate.
(4) Copper sulphate CuSO4.5H2O (Blue vitriol) : It is prepared by action of dil H2SO4 on copper scrap in
presence of air.

(i) On heating this blue salt becomes white due to loss of water of crystallization.

At about 1000 K, CuSO4 decomposes to give CuO and SO3.

(ii) It gives a deep blue solution of tetrammine copper (II) sulphate with NH4OH.

(iii) With KCN it first gives yellow precipitate of CuCN which decomposes of give Cu2(CN)2 . Cu2(CN)2 dissolves in
excess of KCN to give K3[Cu(CN)4.

(iv) With KI it gives white ppt. of Cu2I2

(v) With K4[Fe(CN)6,CuSO4 gives a reddish brown ppt. of Cu2[Fe(CN)6]

Uses :
1-For electroplating and electrorefining of copper.
2-As a mordant in dyeing.
3-For making Bordeaux mixture (11 parts lime as milk of lime + 16 parts copper sulphate in 1,000 parts of water). It is
an excellent fungicide.
4-For making green pigments containing copper carbonate and other compounds of copper. Like Verdigris which is
Cu(CH3COO)2 Cu(OH)2 i.e. basic copper acetate and is used as a green pigment in paints.
5-As a fungicide in starch paste for book binding work.
(5) Cupric sulphide : CuS It is prepared as follows

(6) Basic copper carbonates : Because of lower solubility of the hydroxide, the normal carbonate does not
exist. Two basic copper carbonates occur in nature viz malachite CuCO3.Cu(OH)2 which has a fine green colour,
and azurite 2CuCO3.Cu(OH)2 which is deep blue in colour.
Malachite is prepared by heating a mixture of CuSO4 solution and limestone in a sealed tube at 423 – 443 K

At lower temperature azurite is formed

On heating, both decompose to give black cupric oxide, water and CO2.
They are used as green and blue painter’s pigments under the name ‘malachite green’ and azurite blue’.
Silver and its Compounds
(1) Ores : Argentite (silver glance) Ag2S, Horn silver (AgCl), Ruby silver (Pyrargyrite) 3Ag2S.Sb2S3.
(2) Extraction : Cyanide process or Mac Arthus-Forrest cyanide process : This method depends on the fact
that silver, its sulphide or chloride, forms soluble complex with alkali cyanides in the silver. This implies that
silver compounds will dissolve in solution of alkali cyanides in the presence of blast of air.
 The reaction with the sulphide is reversible and accumulation of Na2S must be prevented. A free excess of air
is continuously passed through the solution which oxidizes Na2S into sulphate and thiosulphate.

(3) Extraction of Ag from argentiferrous lead (PbS + Ag2S)– Parke’s Process : It is based upon the
following facts
(i) Molten Zn and Pb are immiscible, zinc forms the upper layer
(ii) Ag is more soluble in molten Zn
(iii) Zn-Ag alloy solidifies earlier than molten Pb
(IV) Zn being volatile can be separated from Ag by distillation. Ag is purified by cupellation.
Properties of Silver: Silver is a white lustrous metal, best conductor of heat and electricity. Being soft, it is
alloyed. The silver alloy used for making jewellery contain 80% Ag and 20% Cu. The composition of a silver alloy is
expressed as its purity i.e. the amount of Ag present in 1000 parts of the alloy Ag does not react with dilute HCl or
dil. H2SO4 and aqua regia but reacts with dil. HNO3 and conc. HNO3 forming NO and NO2 respectively. Chlorine
also reacts with Ag to form AgCl.

Hot conc. H2SO4 reacts with Ag forming SO2 like Cu

Compounds of Silver:
(1) Silver oxide (Ag2O): It is unstable and decomposes into Ag and O2 on slow heating.

(2) Silver halides (AgF, AgCl, AgBr and Agl) : Only AgF is soluble in H2O. AgCl is insoluble in H2O but
dissolves in NH4OH,Na2S2O3 and KCN solutions. AgBr is partly soluble whereas Agl is completely insoluble in
NH4OH. Except AgF, all the remaining three silver halides are photosensitive.

(3) Silver nitrate (AgNO3 ) : Silver nitrate (AgNO3 ) is called lunar caustic silver nitrate on heating above its
m.p. (485 K) decomposes to silver nitrite but on heating to red heat gives silver.

When treated with alkali, AgNO3 forms silver oxide which in case of NH4OH dissolves to form complex ion.

AgNO3 reacts with iodine in two ways

In contact with organic matter (skin, cloth, paper etc.) AgNO3 is reduced to metallic silver (black)

AgNO3 gives different coloured ppt. with different anions like etc.
Photography : The photographic plate is coated with a colloidal gelatinised solution of AgBr. During exposure,
AgBr is reduced to metallic silver.

The exposed film is developed. The developer used is an alkaline solution of hydroquinone or quinol which reduces
some of the exposed AgBr to black silver.

The film is finally fixed by dipping in a solution of sodium thiosulphate or hypo which removes unchanged AgBr as
complex ion.

After taking a print of the photograph it is finally toned by dipping in a dilute solution of gold chloride to impart a
beautiful golden colour or it is dipped in potassium chloro platinate K2PtCl6 solution to get a shining grey tinge.

Gold and its Compounds

(1) Occurrence of gold : Gold is mainly found in native state either as vein gold, placer gold or alluvial gold. It is
also present to a small extent in the combined state as sulphide, telluride and arsenosulphide. It is considered to be
the king of metal.
Some important ores of gold are:
(i) Calaverite, AuTe2
(ii) Sylvanite, AuAgTe2
(iii) Bismuth aurite, BiAu2
(2) Extraction of gold :
(i) Mac-Arthur-Forest Cyanide process : The powdered gold ore, after concentration by Froth-floatation
process, is roasted to remove easily oxidisable impurities of tellurium, arsenic and sulphur. The roasted ore is
then treated with a dilute solution of KCN in presence of atmospheric oxygen when gold dissolves due to the
formation of an aurocyanide complex.

The metal is then extracted by adding zinc dust.

(ii) Plattner’s chlorine process : The roasted ore is moistened with water and placed in wooden vats with
false perforated bottoms. It is saturated with current of chlorine, gold chloride thus formed is leached with water
and the solution is treated with a reducing agent such as FeSO4 or H2S to precipitate gold.

The impure gold thus obtained contains impurities of Ag and Cu. The removal of Ag and Cu from gold is called
parting. This is done by heating impure gold with conc. H2SO4 (or HNO3) when Ag and Cu dissolve leaving behind Au.

Properties of Gold: Gold is a yellow, soft and heavy metal. Gold and Ag are called noble metals since they are
not attacked by atmospheric oxygen. However, Ag gets tarnished when exposed to air containing traces of H2S.
Gold is malleable, ductile and a good conductor of heat and electricity.
 Pure gold is soft. It is alloyed with Ag or Cu for making jewellery. Purity of gold is expressed in terms of carats.
Pure gold is 24 carats. Gold ’14 carats’ means that it is an alloy of gold which contains 14 parts by weight of pure gold
and 10 parts of copper per 24 parts by weight of the alloy. Thus the percentage of gold in ’14 carats” of gold is-

Most of the jewellery is made from 22 carat gold (91.66% pure gold). Gold is quite inert. It does not react with
oxygen, water and acids but dissolves in aqua regia

Oxidation states of gold: The principal oxidation states of gold are + 1 and + 3 though + 1 state is more stable
than + 3.
Compounds of gold
(1) Auric chloride, AuCl3 : It is prepared by passing dry Cl2 over finely divided gold powder at 573 K

It is a red coloured crystalline solid soluble in water and decomposes on heating to give gold (I) chloride and Cl2

It dissolves in conc. HCl forming chloroauric acid

Chloroauric acid is used in photography for toning silver prints and as an antidote for snake poisoning.
(2) Aurous sulphide, Au2S : It is prepared when H2S is passed through an acidified solution of potassium
aurocyanide, K[Au (CN)2]

It is a dark brown solid, not attached by dilute mineral acids and hence is probably the most stable gold compound.
Zinc and its Compounds
(1) Occurrence of zinc: Zinc does not occur in the native form since it is a reactive metal. The chief ores of zinc
are-
(i) Zinc blende (ZnS)
(ii) Calamine or zinc spar (ZnCO3)
(iii) Zincite (ZnO)
(2) Extraction of zinc : Zinc blende, after concentration by Froth floatation process, is roasted in air to convert
it into ZnO. In case of calamine, ore is calcined to get ZnO. The oxide thus obtained is mixed with crushed coke
and heated at 1673 K in fire clay retorts (Belgian Process) when ZnO gets reduced to metallic zinc. Being volatile
at this temperature, the metal distils over and is condensed leaving behind Cd, Pb and Fe as impurities. The
crude metal is called spelter. The metal may be refined either by electrolysis or by fractional distillation.
Properties of Zn : Zinc is more reactive than mercury. It is a good conductor of heat and electricity. Zinc readily
combines with oxygen to form ZnO. Pure zinc does not react with non-oxidising acids (HCl or ) H2SO4 but the
impure metal reacts forming Zn2 ions and evolving H2 gas.

Hot and conc. H2SO4 attacks zinc liberating SO2 gas

Zinc also reacts with both dilute (hot and cold) HNO3 and conc. HNO3 liberating nitrous oxide (N2O), ammonium
nitrate (NH4NO3) and nitrogen dioxide (NO2) respectively.
 Zinc dissolves in hot concentrated NaOH forming the soluble sod. Zincate

(3) Special varieties of zinc. (i) Zinc dust : It is prepared by melting zinc and then atomising it with a blast
of air.
(ii) Granulated zinc : It is prepared by pouring molten zinc into cold water. Both these varieties of zinc are used
as reducing agents in laboratory.
Compounds of zinc
(1) Zinc oxide (Zinc white or Chinese white), ZnO : It is obtained by burning zinc in air or by heating zinc
carbonate or zinc nitrate.

It is a white powder but becomes yellow on heating and again white on cooling.
It is insoluble in water and is very light and hence commonly known as philosopher’s wool.
It is amphoteric in nature.

It is reduced both by carbon and H2 and is used as a white paint

(2) Zinc chloride, ZnCl2 : It is obtained when Zn metal, ZnO or ZnCO3 is treated with dil. HCl. It crystallizes as
ZnCl2 2H2O. and becomes anhydrous on heating. ZnCl2 is highly deliquescent and is highly soluble in H2O and also
readily dissolves in organic solvents like acetone, alcohol, ether etc. its aqueous solution is acidic due to
hydrolysis.

Anhydrous ZnCl2 is used as a Lewis acid catalyst in organic reactions. Mixed with moist zinc oxide, it is used for
filling teeth and its solution is used for preserving timber. Anhydrous ZnCl2 used as a Lucas reagent with conc. HCl.
(3) Zinc sulphide, ZnS : It is a white solid. It is soluble in dil. HCl and thus does not get precipitated by H2S in the
acidic medium.

It is a constituent of lithopone (ZnS  BaSO4)

(4) Zinc sulphate, ZnSO4 .7H2O : It is commonly known as white vitriol and is obtained by the action of dil.
H2SO4 on zinc metal, ZnO or ZnCO3. On heating, it first loses six molecules of water of crystallization at 373 K. At
723 K, it becomes anhydrous and on further heating, it decomposes.

It is used to prepare lithopone (ZnS  BaSO4) , a white paint and also in galvanising iron.
 It is also used as an eye lotion.
Mercury and its compounds
(1) Occurrence and extraction of mercury : Cinnabar (HgS) is the only important ore of Hg. It is
concentrated by froth floatation method and mercury is extracted from this ore by heating it in air at 773-873 K.

The mercury vapours thus obtained are condensed to give liquid metal. Hg thus obtained contains impurities of
Zn, Sn and Pb. These are removed by treating the impure metal with dil HNO3, mercurous nitrate, Hg2(NO3)2 thus
formed react with metals present as impurities forming their nitrates which pass into solution leaving behind pure
mercury. However, it is best purified by distillation under reduced pressure.

Similar reaction is given by Pb and Sn

Properties of mercury : Mercury is less reactive than Zn. It is a liquid at room temperature and has low
thermal and electrical conductivity. Mercury forms dimeric mercury (I) ions, Hg22 in which the two atoms are
bonded by a covalent bond. It is slowly oxidised to HgO at about its boiling point. Hg does not react with dil.
HCl or dil. H2SO4 but reacts with hot concentrated H2SO4 to form HgSO4 , it reacts with both warm dil. and
conc. HNO3 evolving NO and NO2 respectively.

Hg does not react with steam or water hence can’t form any hydroxide.
Compounds of mercury
(1) Mercuric oxide, HgO : It is obtained as a red solid by heating mercury in air or oxygen for a long time at
673 K

or by heating mercuric nitrate alone or in the presence of Hg

When NaOH is added to a solution of HgCl2 , yellow precipitate of HgO are obtained.

Red and yellow forms of HgO differ only in their particle size. On heating to 673 K, yellow form changes to red
form.

It is used in oil paints or as a mild antiseptic in ointments.

(2) Mercuric chloride, HgCl2 : It is obtained by treating Hg with Cl2 or by heating a mixture of NaCl and HgSO4
in presence of small amount of MnO2 (which oxidises any Hg(I) salts formed during the reaction).

It is a white crystalline solid and is commonly known as corrosive sublimate. It is a covalent compound since it
dissolves in organic solvents like ethanol and ether.
It is extremely poisonous and causes death. Its best antidote is white of an egg.
When treated with stannous chloride, it is first reduced to white ppt. of mercurous chloride and then to mercury
(black).

With ammonia it gives a white ppt. known as infusible white ppt.

 A dilute solution of HgCl2 is used as an antiseptic.
(3) Mercuric iodide, HgI2 : It is obtained when a required amount of KI solution is added to a solution of HgCl2.

Below 400 K, HgI2 is red but above 400 K, it turns yellow

HgI readily dissolves in excess of KI solution to form the (HgI4)2 complex ion.

An alkaline solution of K2[HgI4] is called Nessler’s reagent and is used to test NH4 ions.
It gives a brown ppt. of (Iodide of Millon’s base) with NH4 ions.

It is used in ointments for treating skin infections.

(4) Mercurous chloride, Hg2Cl2 : It is obtained as under :

It is purified by sublimation. Mercurous chloride is also called calomel. It is a white powder insoluble in H2O. On
heating, it decomposes to give HgCl2 and Hg.

It dissolves in chlorine water forming mercuric chloride.

With ammonia, it turns black due to the formation of a mixture of finely divided black Hg and mercuric amino
chloride.

It is used to prepare standard calomel electrode and as a purgative in medicine.

(5) Mercuric sulphide, HgS : The solubility product of HgS is lower than that of ZnS and hence it gets
precipitated as black solid when H2S is passed through an acidic solution of any mercury (II) salt.

It is insoluble in water and HCl but dissolves in aqua regia (1 part conc. HNO3  3 parts conc. HCl)

(6) Mercuric sulphate, HgSO4 : It is obtained when HgS is treated with conc. H2SO4.

It is a white solid which decomposes on heating to give mercurous sulphate.

It is used as a catalyst in the hydration of alkynes to give aldehydes or ketones. It is also used as a cosmetic
under the name Vermillon and in ayurvedic medicine as makardhwaj.
(7) Amalgams : Mercury forms alloys commonly known as amalgams, with all metals except iron and platinum.
Hence it is transported in iron containers.

F-BLOCK ELEMENTS
Inner Transition Elements-The elements in which the additional electron enters in (n-2)f orbitals are called
inner transition elements or f-block elements.
Position in the periodic table-The lanthanides resemble with Yttrium in most of their properties. So it
became necessary to accommodate all the fifteen elements together at one place. This has been done by
placing the first element, lanthanum below yttrium and placing the remaining fourteen elements separately in
the lower part of the periodic table.
Lanthanide series (Z = 58 -71) (Ce -Lu)
Actinide series (Z = 90 -103) (Th -Lr)
Lanthanides (Rare Earths or Lanthanones)
(i) Lanthanides are reactive elements so do not found in free state in nature.
(ii) Most important minerals of lighter Lanthanides are Monazite, cerites and of heavier lanthanides Gadolinite and
Xenotime
Electronic configuration
(i) The general configuration of lanthanides may be given as 4f1- 14 5s2 5p6 5d0- 1 6s2 .

(ii) It is to be noted that filling of 4f orbitals in the atoms is not regular. A 5d electron in gadolinium (Z = 64) with an
outer electronic configuration of 4f7 5d1 6s2 (and not 4f8 6s2 ). This is because the 4f and 5d electrons are at
about the same potential energy and that the atoms have a tendency to retain stable half filled configuration.
(iii) On the other hand, the filling of f-orbitals is regular in tri positive ions.
(iv) After losing outer electrons, the f-orbitals shrink in size and became more stable.
(v) Pm is the only synthetic radioactive lanthanide

Oxidation states:-
 (Oxidation states in brackets are unstable states)
(i) The lanthanides contains two s electrons in the outermost shell, they are therefore expected to exhibit a
characteristic oxidation state of +2. But for the lanthanides, the +3 oxidation is common.
(ii) This corresponds to the use of two outermost electrons (6s2 ) alongwith one inner electron. The inner electron
used is a 5d electron (in La, Gd and Lu), or one of the 4f electron if no 5d electrons present.
(iii) All the lanthanides attains +3 oxidation state and only Cerium, Praseodymium, and Terbium exhibit higher
oxidation state (+4). Eu and Yb exhibit +2 oxidation state.
(iv) Oxidation states +2 and +4 occur particularly when they lead to -
(a) A noble gas configuration Ex. Ce4+ (f0 ) The formation of Ce (IV) is favoured by its noble gas configuration, but it
is a strong oxidant reverting to the common +3 state. The E° value for Ce4+/Ce3+ is + 1.74 V which suggests that
it can oxidise water. However, the reaction rate is very slow and hence Ce(IV) is a good analytical reagent.
(b) A half filled 'f ' orbital Ex. Eu2+, Tb4+, (f7 ) Pr, Nd, Tb and Dy also exhibit +4 state but only in oxides, MO2. Eu2+ is
formed by loosing the two s electrons and its f7 configuration accounts for the formation of this ion. However,
Eu2+ is a strong reducing agent changing to the common +3 state. Similarly Yb2+ 14 configuration is a reductant.
(c) A completely filled 'f ' orbital is Yb2+ (f14)
(v) Therefore, in higher oxidation state, they act as oxidizing agent while in lower state they act as reducing agents.
Magnetic properties-
(i) In tripositive lanthanide ions the number of unpaired electrons regularly increases from lanthanum to Gadolinium
(0 to 7) and then continuously decreases upto lutecium (7 to 0).
(ii) lanthanum and lutecium ions are diamagnetic, while all other tripositive lanthanide ions are paramagnetic.
(Exception Neodyomium is the most paramagnetic lanthanide).
(iii) Ce+4 and Yb+2 are also diamagnetic ions.
(iv) magnetic moments of lanthanides are calculated by taking into consideration spin as well as orbital contributions
and a more complex formula

which involves the orbital quantum number L and spin quantum number S.
Colour
(i) The lanthanide ions have unpaired electrons in their 4f orbitals. Thus these ions absorbs visible region of light and
undergo f-f transition and hence exhibit colour.
(ii) The colour exhibited depends on the number of unpaired electrons in the 4f orbitals.
(iii) The ions often with 4fn configuration have similar colour to those ions having 4f14 n configuration.
(iv) Lanthanide ions having 4f0 , 4f14 are colorless.
 Other Properties:-
• All the lanthanoids are silvery white soft metals and tarnish rapidly in air.
• The hardness increases with increasing atomic number, samarium being steel hard.
• Theirmelting points range between 1000 k to 1200 K but samarium melts at 1623 K.
• They have typical metallic structure and are good conductors of heat and electricity.
• Highly dense metals with high m.pts. do not show any regular trend.
• Ionisation Energies : Lanthanides have fairly low ionisation energies comparable to alkaline earth metals.
• Electro positive character : High due to low I.P.
• Complex formation : Do not have much tendency to form complexes due to low charge density because of their
large size. Lu+3 is smallest in size can only form complex.
• Reducing Agent : They readily lose electrons so are good reducing agent. Alloy : Alloys of lanthanides with Fe are
called Misch mish metals. which consists of a lanthanoid metal (~ 95%) and iron (~ 5%) and traces of S, C, Ca and Al.
• Basic Nature : La(OH)3 is most basic in nature while Lu(OH)3 least basic.
• Carbide : Lanthanides form MC2 type carbide with carbon, which on hydrolysis gives C2H2.
• The lanthanide elements Eu and Yb dissolve directly in very high concentration in liquid ammonia.
Chemical reactions of the lanthanoids:-

Lanthanide contraction :
The regular decrease in the size of lanthanide ions from La3to Lu3 is known as lanthanide contraction. It is
due to greater effect of the increased nuclear charge than that of the screening effect.
Consequences of lanthanide contraction
(a) It results in slight variation in their chemical properties which helps in their separation by ion exchange
(b) Each element beyond lanthanum has same atomic radius as that of the element lying above it in the group (e.g.
Zr145 pm, Hf144 pm); Nb134 pm, Ta134 pm ; Mo129 pm, W130 pm).
(c) The covalent character of hydroxides of lanthanides increases as the size decreases from La 3 to Lu3. However
basic strength decreases. Thus La(OH)3 is most basic whereas Lu(OH)3 is least basic. Similarly, the basicity of
oxides also decreases in the order from La3 to Lu3.
(d) Tendency to form stable complexes from La3 to Lu3 increases as the size decreases in that order.
(e) There is a slight increase in electronegativity of the trivalent ions from La to Lu.
(f) Since the radius of Yb3 ion (86 pm) is comparable to the heavier lanthanides Tb, Dy, Ho and Er, therefore they
occur together in natural minerals.
Application of lanthanides
Cerium is most useful element in the lanthanides-
• Ceramic application CeO2, La2O3, Nd2O3 and Pr2O3 are used as decolourizing agents for glasses.
• CeS (m.p. 20000C) is used in the manufacturing of a special type of crucibles and refractories.
• Lanthanide compounds like cerium molybdate, cerium tungstate are used as paints and dyes.
• In textile and leather industries (Ce salts).
• Mish metal is pyropheric and is used in cigarette & gas lighter.
 Actinides ( f-Block Elements)
(i) The elements in which the extra electron enters 5f-orbitals of (n-2)th Main shell are known as actinides.
(ii) The man-made eleven elements 93Np - 103 Lr are placed beyond uranium in the periodic table and are collectively
called trans-uranium elements.
(iii) Th, Pa and U first three actinides are natural elements.
Electronic configuration
The general configuration of actinides may be given as 5f1- 14 6d0- 1 ,7s2 .

Oxidation states
(i) In lanthanides and actinides +3 oxidation is the most common for both of the series of elements.
(ii) This oxidation state becomes increasingly more stable as the atomic number increases in the actinide series.
(iii) Highest oxidation states in the actinides is +7 exhibited by 93Np & 94Pu, it is unstable.
(iv) Highest stable oxidation state is +6 shown by 92U.
Other Properties
• Physical appearance : Acitinides are silvery white metals. They get tarnished when exposed to the attack of
alkalies.
• Density : All the actinides except thorium and americium have high densities.
• Colour : Actinide ions are generally coloured. The colour of actinide ions depends upon the number of 5f-electrons.
The ions containing no unpaired 5f-electrons (exactly full filled f subshell) are colourless, as expected.
• Ionisation energies : Ionisation energies values of actinides are low.
• Electropositive character : All the known actinide metals are highly electropositive. They resemble lanthanide
series in this respect.
• Melting Boiling properties : They have high melting and boiling points. They do not follow regular gradation of
melting or boiling points with increase in atomic number.
• Magnetic properties : The actinide elements are paramagnetic due to the presence of unpaired electrons.
• Radioactive nature : All the actinides are radioactive in nature.
• Actinide contraction : The size of atom/cation decrease regularly along the actinides series.
The steady decrease in ionic radii with increase in atomic number is referred to as actinide contraction. This is due
to poor shielding of 5f-electrons.
•Complex formation : Actinides have a greater tendency to form complexes because of higher nuclear charge and
smaller size of their atoms. They form complexes even with -bonding ligands such as alkyl phosphines, thioethers
etc, besides EDTA, -diketones, oxine etc. The degree of complex formation decreases in the order.
M4+> MO22+ > M3+ > MO2+
 Where M is element of actinide series. There is a high concentration of charge on the metal atom in MO 22
which imparts to it relatively high tendency towards complex formation.
Comparison of lanthanides and Actinides
Points of Resemblance
(i) Both lanthanides and actinides show a dominant oxidation state of +3.
(ii) Both are electropositive and act as strong reducing agents.
(iii) Cations with unpaired electrons in both of them are paramagnetic.
(iv) Most of the cations of lanthanides and actinides are coloured.
(v) Both of them show a steady decrease in their ionic radii along the series. Thus, lanthanides show lanthanide
contraction and actinides show actinide contraction.

Difference between lanthanides & Actinides

Some important uses of actinides are as follows

Thorium : Thorium is used in atomic reactors as fuel rods and in the treatment of cancer.
Uranium : Uranium is used as nuclear fuel. Its salts are used in glass industry (for imparting green colour). textile
industry and also in medicines.
Plutonium : Plutonium is used as fuel for atomic reactors as well as in atomic bombs.