UNIT 8 - The d– and f– block elements

d-block elements (Group 3-12)

Position in the periodic table:-

The d- block occupies the middle section in between s- and p- blocks in the periodic table.
The name transition given to the elements of d- block, because of their position between s- and p-
block elements. The d- orbitals of the penultimate energy level in their atoms receive electrons
giving rise to the three rows of the transition metals i.e. 3d, 4d and 5d. The fourth row of 6d is
incomplete.

Transition element is defined as the one which has incompletely filled d – orbitals in its
ground state or in any one of its oxidation states.

The four transition series elements are given below.

Group 3 4 5 6 7 8 9 10 11 12
3d-series Sc Ti V Cr Mn Fe Co Ni Cu Zn
4d-series Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
5d-series La Hf Ta W Re Os Ir Pt Au Hg
6d-series Ac Rf Db Sg Bh Hs Mt Ds Rg Cn

Electronic configurations of the d- block elements:

General electronic configuration of d- block elements is [noble gas] (n — 1) d1 – 10ns1 – 2
Half and completely filled orbitals are more stable.
Eg. 1) Electronic configuration of Cr is [Ar] 3d54s1
2) Electronic configuration of Cu is [Ar] 3d104s1

The electronic configuration of Zn, Cd, Hg and Cn are represented by the general formula
(n – 1) d10ns2. The orbitals in these elements are completely filled in the ground state as well as
in their common oxidation states, but their properties are in similar with other d-block elements.
Hence they are called as pseudo transition elements.

Problem:-
1) Silver atom has completely filled d- orbitals (4d10) in its ground state. How can you say that it
is a transition element?
Answer: - The outer electronic configuration of Ag (z = 47) is 4d105s1. In addition to +1, it shows
an oxidation state of +2(e.g. AgO and AgF2). In +2 oxidation state, the configuration is 4d9 so the
d- sub shell is incompletely filled. Hence, it is a transition element.

General properties of the transition elements (d- block)

Physical properties:-
1) Nearly all transition elements display typical metallic properties such as conductivity,
malleability and ductility, lustre, high tensile strength with the exceptions of Zn, Cd, Hg and Mn,
they have one or more typical metallic structures at normal temperatures.
2) They have high melting and boiling points (elements with d5 configuration have maximum
MP’s. eg: Cr, Mo,W)
3) They have high enthalpies of atomisation and high enthalpies of hydration of their ions. These
properties depend upon the strength of the metallic bond in them.
4) The melting points and atomization enthalpy increase in the order: 3d< 4d<5d.
5) The transition metals (except Zn,Cd, Hg) are very much hard & have low volatility.

Variation in atomic and ionic radii (sizes) of transition metals:-

Atomic radii:-
Generally the atomic radii of d- block elements in a period decrease with increase in atomic
number.
This is due to with the increase in the atomic number, as the nuclear charge increases, the
shielding effects of d- electron is small.

The atomic radii increases down the group.

The atomic radii of second series (4d) are larger than those of first transition series (3d).
This is because in the atoms of the second series, the number of shells increases, so their atomic
radii are larger than those of the elements of the first transition series.

The atomic radii of the elements of the second (4d) and third (5d) series are nearly same due to
Lanthanoid contraction.

Ionic radii:- The trend of ionic radii is same as that of atomic radii.

Problem:-
1) In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomisation of zinc is the lowest, i.e.
126 kJ mol-1, why?
Answer: - In the 3d series Sc to Zn all elements have one or more unpaired electrons except zinc
which has no unpaired electrons (3d104s2). Hence atomic inter metallic bonding (metal – metal
bonding) is weaker in zinc. Therefore enthalpy of atomisation is lowest.

Ionisation enthalpies:-
The ionisation enthalpy gradually increases with increase in atomic number along a given
transition series.
The increasing ionisation enthalpies are due to increased nuclear charge with increase in atomic
number which reduces the size of the atom making the removal of outer electron difficult.

The irregular trend in the first ionisation enthalpy of 3d metals is due to the fact that the removal
of the electron alters the relative energies of 4s and 3d orbitals. Thus there is a reorganisation
energy accompanying ionisation. This results in the release of exchange energy between (n-1) d
and ns electrons.

Some irregularities are as follows;

(1) Cr has low first ionisation energy because loss of one electron gives stable configuration(3d5).

(2) Zn, Cd, Hg have very high first ionisation energy because electron should be removed from
ns2 subshell which has extra stability.
(3) The magnitude of increase in the 2nd and 3rd ionization energies along any series of transition
metals is higher when compared to the increase in their 1st ionization energy.

(4) There is a decrease in 2nd ionisation enthalpy from Cr to Mn and from Cu to Zn. This is
because after the removal 1st electron, Cr and Cu acquire a stable configuration (d5 and d10) and
the removal of 2nd electron is very difficult.

(5) Third ionisation enthalpy of Mn is very high because the 3rd electron has to be removed from
the stable half – filled 3d- orbital (25Mn is 3d54s2).

(6) Third ionisation enthalpy for change from Fe2+ to Fe3+ (26Fe = 3d64s2) is very small because
loss of 3rd electron gives the stable configuration of 3d5.
Hence IE3 for Fe <<IE3 for Mn.

(7) The high values of 3rd ionisation enthalpies for Cu, Ni and Zn explain why they show a
maximum oxidation state of +2.

Oxidation states:-
All the transition elements, except the first and last member of the series exhibit variable
oxidation states as shown below (3d series).

Elements Sc Ti V Cr Mn Fe Co Ni Cu Zn
+2
+3
+2 +2 +2
+2 +4 +2
(+2) +3
Oxidation +3 (+5) +1
+3 +3 +4 +3 +3 +2
stae +4 +6 (+3) +2
+4 +5 +4
+5 +7 (+4)
+6 (+6) +4

Note: Rare oxidation states are given in the brackets.

Most common oxidation states are given in the boxes.

Whenever transition metals form compounds, the electrons present in 4s-orbital as well as 3d-
orbitals participate in the bond formation. Hence, these elements exhibit variable oxidation states
depending on the number of electrons participating in the bonding.

From the oxidation states we observe the following points:

(1) The most common oxidation states of the 3d series are +2 except scandium (which has +3).
+2 states are due to the loss of two ns2 electrons.

(2) Mostly ionic bonds are formed in +2 and +3 oxidation states. In compounds of higher
oxidation states the bonds formed are mostly covalent since they are formed by sharing of
d- electrons.
e.g. All the bonds between manganese and oxygen are covalent in MnO4− (permanganate ion)
 (3) The elements which give the greatest number of oxidation states occur in or near the
middle of the series.
e.g. Manganese exhibits all the oxidation states from +2 to +7.
The highest oxidation state shown by any transition metal is +8 (by osmium or in a very few
compounds by Ruthenium).

(4) In the group of d- block elements the higher oxidation states are more stable for heavier
elements. For example in group 6, Mo(VI) and W(VI) are found to be more stable than
Cr(VI). For this reason, Cr(VI) in the form of dichromate is a stronger oxidising agent in
acidic medium where as MoO3 and WO3 are not.

(5) Transition metals also show low oxidation states in some compounds or complexes
having ligands like CO which not only form sigma bonds with the metal atom but also
have 𝜋 acceptor character.
E.g. Nickel in Ni(CO)4 or iron in Fe(CO)5 is in the zero oxidation state.

Problem:-
1) Name a transition element which does not exhibit variable oxidation states?
Answer:- Scandium (Z = 21) does not exhibit variable oxidation states (only +3 oxidation state).

2) Which of the 3d series of the transition metals exhibits the largest number of oxidation
states and why?
Answer:- Manganese (Z = 25) shows maximum number of oxidation states. This is because its
electronic configuration is [Ar] 3d54s2. As 3d and 4s are close in energy, it has
maximum number of electrons to lose or share (as all the 3d electrons are unpaired).
Hence it shows oxidation state from +2 to +7 (+2,+3,+4,+5,+6 and +7).

Stability of oxidation states:

+1 oxidation state is observed in the case of copper like CuCl, CuBr, CuI.
Many copper (I) compounds are unstable in aqueous solution and undergo disproportionation as
follows;
2Cu+ → Cu2+ + Cu
The greater stability of Cu2+(aq) than Cu+(aq) is due to much more negative enthalpy of hydration
for Cu2+(aq) than Cu+(aq), which more than compensates for the second ionisation enthalpy of Cu.

Trends in stability of higher oxidation states:

1) Halides of d-block elements are more stable in the higher oxidation states.
Eg: TiF4, VF5, CrF6 etc.
Iron and cobalt form FeF3 and CoF3
Fluorine increases the lattice energy in CoF3 and increases bond enthalpy in VF5 and CrF6.

2) The ability of oxygen to stabilize high oxidation states is higher that of fluorine.
Hence Mn forms MnF4(+4) but Mn forms Mn2O7(+7)
Oxygen can form multiple bonds. Mn2O7has a tetrahedral structure with Mn-O-Mn bond.
The tetrahedral [M4O]n- ions are known for V (+5), Cr (+6), Mn (+5), Mn(+6), Mn (+7).
Problem:-
(1) Why is the highest oxidation state of a metal exhibited in its oxide or fluoride only?
Answer:-Oxygen and fluorine have small size and high electronegativity. Hence they can oxidise
the metal to the highest oxidation state.

(2) Explain why Cu+ ion is not stable in aqueous solution?

Answer:- Cu2+(aq) is much more stable than Cu+(aq).
This is because although second ionisation enthalpy of copper is larger but ∆hyd H for Cu2+(aq)is
much more negative than that for 𝐶𝑢(𝑎𝑞)
+
and hence it compensates for the second ionisation
enthalpy of copper.
Therefore, many copper (I) compounds are unstable in aqueous solution and undergo
disproportion as follows;
2Cu+ Cu2+ + Cu.

Magnetic properties:-
When a magnetic field is applied to substance, three types of magnetic behavior are observed.
1) Diamagnetism substances are repelled by the applied magnetic field.

2) Paramagnetic substances are attracted by the magnetic field.

3) Substances which are attracted very strongly by the magnetic field are called
ferromagnetic (ferromagnetism is an extreme form of paramagnetism). Many of the
transition metal ions are paramagnetic.

Paramagnetism is a property due to the presence of unpaired electrons.

The transition elements which have no unpaired electrons are diamagnetic.

The magnetic moment of an electron is partly due to its orbital motion and partly due to its spin
motion.

Magnetic moment is calculated from spin only formula,

𝝁 = √𝒏(𝒏 + 𝟐)
B.M.

Where, “n” is the number of unpaired electrons.

𝜇 = magnetic moment in Bohr magneton(B.M.)

e.g. (1) Calculate the magnetic moment of Cu2+ ion.

𝝁 = √𝒏(𝒏 + 𝟐) B.M. For Cu2+, n = 1 (3d9)
= √1(1 + 2) B.M.
= √3 B.M.
= 1.73 B.M

Magnetic moment gives the number of unpaired electrons present in the atom, molecule or ion.
The calculated and observed magnetic moments of 3d series ions are given below.

Outer Number of Magnetic moment(B.M.)

Ion electronic unpaired
Calculated Observed
configuration electrons
Sc3+ 3d0 0 0.0 0.0
Ti3+ 3d1 1 1.73 1.75
Ti+2,(V3+) 3d2 2 2.84 2.76
V2+,(Cr3+) 3d3 3 3.87 3.86
Cr2+ 3d4 4 4.90 4.80
Mn2+ 3d5 5 5.92 5.96
Fe2+ 3d6 4 4.90 5.3 – 5.5
Co2+ 3d7 3 3.87 4.4 – 5.2
Ni2+ 3d8 2 2.84 2.9 – 3.4
Cu2+ 3d9 1 1.73 1.8 – 2.2
Zn2+,(Cu+) 3d10 0 0.0 0.0

Problem:- (1) Calculate the magnetic moment of a divalent ion in aqueous solution if its atomic
number is 25.
Answer :- Z = 25 is for Mn. Its E.C. = [Ar]3d54s2.
E.C. of its divalent ion [Ar]3d5.
Thus it has 5 unpaired electrons.
𝝁 = √𝒏(𝒏 + 𝟐) B.M.
= √5(5 + 2) B.M.
= √35 B.M.
𝜇 = 5.92 B.M.

(2) Calculate the “spin only” magnetic moment of M2+(aq) ion (z = 27)
Answer :- Electronic configuration of M atom with z = 27 is [Ar]183d74s2
∴ electronic configuration of M2+ will be [Ar]183d7
i.e.
↑↓ ↑↓ ↑ ↑ ↑
Thus, it has three unpaired electrons. ∴ n = 3
𝝁 = √𝒏(𝒏 + 𝟐) B.M.
= √3(3 + 2) B.M.
= √15 B.M.
= 3.87 B.M.

Note: 1) In the case of iron, cobalt and nickel the paramagnetic behavior is high, hence
they are ferromagnetic substances
2) Cuprous, Cu (I) ion (3d104s0) is diamagnetic while cupric, Cu (II) ion (3d94s0) is
paramagnetic because Cu2+ has one unpaired electron.
Formation of coloured ions:
Most of the compounds of transition elements are coloured in their solid state or in their aqueous
solution. The colour of these substances is due to the number of unpaired electrons present in d –
orbitals of the transition metal ions.

When an electron from a lower energy d – orbital is excited to a higher energy d – orbital, the
energy of excitation corresponds to the frequency of light absorbed. This frequency lies in the
visible region.
The colour observed corresponds to the complementary colour of the light absorbed.

The frequency of the light absorbed is determined by the nature of the ligand.
In aqueous solutions where the water molecules are the ligands.

e.g. Copper sulphate (CuSo4) solution is blue in colour because it absorbs red colour from white
light and transmit blue colour.

The colours of some of the hydrated transition metal ions are given in the following table.

Number of
Outer electronic
Ions unpaired Colour
configuration
electrons
Sc3+, Ti+4,V+5 3d0 0 Colourless
Ti3+, V4+ 3d1 1 Purple, blue
V3+ 3d2 2 Green
V2+,Cr3+ 3d3 3 Violet
Mn3+, Cr2+ 3d4 4 Violet, blue
Mn2+ , Fe3+ 3d5 5 Pink, yellow
Fe2+, Co3+ 3d6 4 Green, blue
Co2+ 3d7 3 Pink
Ni2+ 3d8 2 Green
Cu2+ 3d9 1 Blue
Zn2+,Cu+1 3d10 0 Colourless

Formation of Complex compounds:

Complex compounds are those in which the metal ions bind a number of anions or neutral
molecules giving complex species with characteristic properties.
e.g. 1) cuprammonium sulphate [Cu(NH3)4]SO4
2) potassium ferrocyanide K4[Fe(CN)6]
3) potassium ferricyanide K3[Fe(CN)6]

The formation of complex compounds by transition metal ions is due to

1) Compartively smaller size of the metal ions.
2) Their high ionic charges.
3) The availability of vacant d – orbitals for bond formation.
Catalytic properties of transition metals:
Transition metals and their compounds are used as catalysts in inorganic and organic chemical
reactions.
e.g. 1) Finely divided iron is used as a catalyst in the manufacture of ammonia by Haber’s
process.
2) Nickel catalyst is used in the hydrogenation of oils.

The catalytic properties of transition metals are due to:

1) Finely powdered transition metals provide large surface area. (The reacting molecules are
absorbed on the surface and react readily to form products).
2) Transition metal ions can change their oxidation states.

Change of oxidation states is explained in the following reaction

Iron (III) catalyses the reaction between iodide and persulphate ions.
2I- + S2O82- → I2 + 2SO42-
The explanation of this catalytic action can be given as,
2Fe3+ + 2I- → 2Fe2+ + I2
2Fe2+ + S2O82- → 2Fe3+ + 2SO42-

Formation of interstitial compounds:

Interstitial compounds are those which are formed when small atoms such as hydrogen, carbon,
boron and nitrogen are occupy the empty spaces (interstitial sites) in their lattices.
Eg: TiC, TiH2, Mn4N, Fe3H, TiH1.7, VH0.56 etc.
However they are non – stoichiometric materials. The bonds present in them are neither typically
ionic nor covalent.

Their important characteristics are as follows:

1. They have high melting points, higher than those of pure metals.
2. They are very hard.
3. They retain metallic conductivity.
4. They are chemically inert.

Alloy formation:
Alloys are homogeneous solid solutions of two or more metals obtained by melting the
components and then cooling.
These are formed by metals whose metallic radii are within about 15% of each other.
Because of similar radii and other characteristics of transition metals, alloys are readily formed
by these metals.
Alloys are generally harder, have higher melting points and more resistant to corrosion.
The commonly used are ferrous alloys. The metals chromium, vanadium, molybdenum, tungsten
and manganese are used in the formation of alloy steels and stainless steels.
Some alloys of transition metals with non – transition metals are;
1. Brass (Cu + Zn).
2. Bronze (Cu + Sn).
Some important compounds of transition elements:

Oxides and oxoanions of metals:

1. Potassium dichromate (K2Cr2O7):

It is prepared from the chromite ore (FeO.Cr2O3)

The chromite ore is mixed with sodium carbonate and roasted with free air.

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

Sodium chromate Ferric oxide

Sodium chromate is acidified with sulphuric acid to give sodium dichromate.

2 Na2CrO4 + 2 𝐇 + → Na2Cr2O7 + 2 𝐍𝐚+ + H2O

sodium chromate sodium dichromate

Sodium dichromate is then treated with calculated amount of potassium chloride to give
potassium dichromate.

Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl

sodium dichromate potassium dichromate

Chromate ion is tetrahedral.

Dichromate ion consists of two tetrahedral sharing one corner with Cr—O—Cr bond angle of
1260 .

When an alkali is added to an orange red solution of dichromate a yellow solution results due to
the formation of chromate.
Cr2O72- + 2OH- → 2CrO42- + H2O

On acidifying, the colour again changes to orange red due to the reformation of dichromate.
2CrO42- + 2H+ → Cr2O72- + H2O

The chromates and dichromates are inter-convertible in aqueous solution depending upon pH of
a solution.
Cr2O72- + H2O 2CrO42- + 2H+
Orange red PH = 4 Yellow
(dichromate ion) (chromate ion)
Oxidising properties:
Oxidising properties:
e.g.: 1) K2Cr2O7 oxidises iodides to iodine.
Cr2O72- + 14H+ + 6I- → 2Cr3+ + 7H2O + 3I2
2) It oxidises ferrous salts to ferric salts.
Cr2O72- + 6Fe2+ + 14H+ → 2Cr3++ 6Fe3++ 7H2O
3) It oxidises H2S to sulphur.
Cr2O72- + 8H+ + 3H2S → 2Cr3+ + 7H2O + 3S↓
4) It oxidises stannous salts to stannic salts.
Cr2O72- + 14H+ + 3Sn2+ → 2Cr3+ + 7H2O + 3Sn4+

Potassium permanganate (KMnO4):

Preparation:-
1. The finely powdered pyrolusite mineral(MnO2) is fused with potassium hydroxide in the
presence of an oxidising agent like potassium nitrate.
This produces the dark green coloured potassium manganate (K 2MnO4).

2MnO2 + 4KOH + O2 → 2 K2MnO4 + 2H2O

potassium manganate(dark green)

Potassium manganate formed undergoes disproportionation in the neutral or acidic

solution to give permanganate.

3 K2MnO4 + 4H+ → 2 KMnO4 + MnO2 + 2H2O

potassium manganate potassium permanganate

2. Commercially KMnO4 is prepared by the alkaline oxidative fusion of MnO2 followed by the
electrolytic oxidationof manganate (VI).
fused with KOH, oxidised
MnO2 𝑀𝑛𝑂42−
with air or KNO3 manganate

electrolytic oxidation
𝑀𝑛𝑂42− 𝑀𝑛𝑂4−
manganate in alkaline solution permanganate ion

3. In the laboratory, KMnO4 is prepared by the oxidation of manganese (II) ion salt by
peroxodisulphate.
2Mn2+ + 5𝑆2 𝑂82− + 8H2O → 2𝑀𝑛𝑂4− + 10𝑆𝑂42− + 16H+
peroxodisulphate

properties:-
I. KMnO4 is a dark purple crystal, which are iso-structural with those of KClO4.
II. When heated it decomposes at 513 K as follows;
2KMnO4 → K2MnO4 + MnO2 + O2.

STRUCTURE:
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 properties of KMnO4 in the acidic medium

1. KMnO4 oxidises oxalates or oxalic acid to CO2.
2𝑀𝑛𝑂4− + 16H+ + 5C2𝑂42− → 2Mn2+ + 8H2O + 10CO2↑
2. It oxidises ferrous to ferric.
𝑀𝑛𝑂4− + 8H+ + 5Fe2+ → Mn2+ + 4H2O + 5 Fe3+
3. It oxidises nitrites (𝑁𝑂2− ) to nitrates (𝑁𝑂3− )
2𝑀𝑛𝑂4− + 6H+ + 5𝑁𝑂2− → 2Mn2+ + 3H2O + 5𝑁𝑂3−
4. It oxidises iodide to iodine.
2𝑀𝑛𝑂4− + 16H+ + 10I- → 2Mn2+ + 8H2O + 5I2
5. It oxidises H2S (hydrogen sulphide) to sulphur (S).
2𝑀𝑛𝑂4− +16H+ + 5S2- → 2Mn2+ + 8H2O + 5S↓
6. It oxidises sulphites to sulphates.
2𝑀𝑛𝑂4− + 6H+ + 5𝑆𝑂32− → 2Mn2+ + 3H2O + 5𝑆𝑂42−
7. It oxidises sulphur dioxide to sulphuric acid
2MnO4- + 5SO2 + 2H2O → 2Mn2+ + 5SO42- + 4H+

Oxidising properties of KMnO4 in neutral or faintlyalkaline medium:-

e.g:- 1) It oxidises iodide to iodate.
2𝑀𝑛𝑂4− + H2O + I- → 2MnO2 + 2OH- + 𝐼𝑂3−
2) It oxidises thiosulphate to sulphate.
8𝑀𝑛𝑂4− + 3𝑆2 𝑂32− + H2O → 8MnO2 + 6𝑆𝑂42− + 2OH-
3) Manganous salt is oxidised to MnO2, in the presence of zinc sulphate or zinc oxide
catalyst.
2𝑀𝑛𝑂4− + 3Mn2+ + 2H2O → 5MnO2 + 4H+

USES OF KMnO4:-
1. KMnO4 is used as an oxidising agent in organic chemistry.
2. It is also used for bleaching of wool, cotton, silk and other textile fibres and also for
decolourising of oils.
3. It is used in analytical chemistry for the estimation of ferrous salts, oxalate and iodides
etc.
 f – block elements
(The inner transition elements)
The elements in which the last electron enters the anti – penultimate energy level,
i.e. (n -2) f – orbitals are called f – block elements. These elements have also been called inner
transition elements, because the last electron in them enters into (n – 2) f – orbitals, i.e. inner to
the penultimate energy level. General electronic configuration:
[Noble gas] (n – 2) f1 – 14 (n – 1) d0 – 1 ns2

Classification of f – block elements:-

1. Lanthanoids:-The elements in which the last electron enters one of the 4f – orbitals are
called 4f – block elements. These are also called lanthanides or lanthanons or lanthanoids,
because they come immediately after lanthanum. (14 elements from Z = 58 to 71).

2. Actinoids:- The elements in which the last electron enters one of the 5f – orbitals are
called 5f – block elements. The 14 elements (Z = 90 to 103) are called actinides or actinons
or actinoids because they come immediately after actinium.
Lanthanum though a d- block element, is included in the lanthanoid series because it
closely resembles lanthanoids. Similarly actinium is also induced in the actinoid series.

1) lanthanoids:- Electronic configurations:-

The members of this series along with their electronic configurations are given below.
Their common oxidation states are also included in the table.

Atomic. Electronic Oxidation

Symbol
No configuration state
Lanthanum La 57 [Xe]5d16s2 +3
Cerium Ce 58 [Xe]4f15d16s2 +3,+4
Praseodymium Pr 59 [Xe]4f35d06s2 +3,+4
Neodymium Nd 60 [Xe]4f45d06s2 +2,+3,+4
Promethium Pm 61 [Xe]4f55d06s2 +3
Samarium Sm 62 [Xe]4f65d06s2 +2,+3
Europium Eu 63 [Xe]4f75d06s2 +2,+3
Gadolinium Gd 64 [Xe]4f75d16s2 +3
Terbium Tb 65 [Xe]4f95d06s2 +3,+4
Dysprosium Dy 66 [Xe]4f105d06s2 +3,+4
Holmium Ho 67 [Xe]4f115d06s2 +3
Erbium Er 68 [Xe]4f125d06s2 +3
Thulium Tm 69 [Xe]4f135d06s2 +2,+3
Ytterbium Yb 70 [Xe]4f145d06s2 +2,+3
Lutetium Lu 71 [Xe]4f145d16s2 +3

Atomic and ionic radii of lanthanoids:-

The lanthanoid series, there is a regular decrease (contraction) in the atomic and ionic
radii of lanthanoids with increasing atomic number is known as lanthanoid contraction.
Reason: Imperfect shielding by 4f electrons.

Consequences of lanthanoid contraction:-

1) The separation of lanthanoids from their mixture can be achieved based on the lanthanoid
contraction.
2) Similarity in size of elements belonging to the same group of second and third series
Ex: The almost identical radii of Zr(160pm) and Hf (159pm).

. Oxidation states of lanthanoids:-

The oxidation state of lanthanoids is +3. The oxidation state of +2 and +4 are exhibited by
some of the elements. These are shown by those elements which by losing 2 or 4 electrons
aquaire a stable configuration of f0, f7 or f14.

Ce shows +4 oxidation state to attain stable noble gas configuration, [Xe] 4f0
Tb shows +4 oxidation state to attain half filled orbitals, [Xe] 4f7
Eu shows +2 oxidation state to attain half filled orbitals, [Xe] 4f7
Yb shows +2 oxidation state to attain completely filled orbidals, [Xe] 4f14

Exceptions:-
Some elements show an oxidation state of +2 or +4 even though their ions are not having f0 and f7
or f14 configuration.
e.g: Pr4+ (4f1), Nd2+ (4f4), Nd4+ (4f2), Sm2+ (4f6), and Dy4+ (4f8) etc.

NOTE:-
1. Lanthanoids show limited number of oxidation states because the energy gap between
4f and 5d sub shells is large.
2. In case of lanthanoids, the f – electrons are present in the deeper (n – 2) f – sub shell
which cannot participate in bond formation.

GENERAL CHARACTERISTICS:-
All the lanthanoids are silvery white metals and tarnish rapidly in the air.
Their hardness increases with increase atomic number, Samarium (Sm) is exceptionally hard like
steel.
They have high melting points
They are good conductors of heat and electricity.
They have high densities
Most of the trivalent lanthanoid metal ions coloured both in the solid state and in aqueous
solution. This is due to the partly filled f – orbitals which permit f – f transition.
e.g.: La3+ and Lu3+ are colourless,
Sm3+ and Dy3+ are yellow and
Eu3+ and Tb3+ are pink.
Paramagnetism is shown by the positive ions of lanthanoids except La3+ (Lanthanum ion, f0) and
Lu3+ (Lutetium ion, f14). This property is due to presence of unpaired electrons in the incomplete
4f sub shell. Para magnetism seems maximum in Neodymium.
They are highly electropositive because of their low ionisation enthalpies.
They are thus good reducing agents.
They show less tendency to form complexes due to low charge density because of their large size.
Chemical behavior:-
(1) They combine with H2 on gentle heating
(2) When heated with carbon they form carbides.
(3) On burning with halogens they form halides.
(4) They react with dilute acids to liberate H2 gas.
(5) They form oxides with oxygen.
(6) They form nitrides with nitrogen.
(7) They form hydroxides with water, which are basic.

with halogen LnX3

with C, 2773 K Ln3C, Ln2C3 and LnC2

with dilute acids liberates H2 gas

burns in O2 Ln2O3
Ln
(lanthanoid)
heated with N2
LnN

heated with S Ln2S3

with H2O
Ln(OH)3 + H2

USES OF LANTHANOIDS:-
1. Lanthanoids are used in the production of alloy steels for plates and pipes.
e.g.:- misch metal (lanthanoid metal ≃ 95% — about 50% Ce, 40% La and the rest other
lanthanoids).
Iron ≃ 5% and traces of S, C, Ca and Al.
Misch metal is used in making a magnesium based alloy to produce bullets, shells and
lighter flints.
2. Mixed oxides of lanthanoids are employed as catalysts in petroleum cracking.
3. Their oxides are used in glass industry, for polishing glass and for making optical glasses
(Crooke’s lenses).
4. Some individual ln oxides are used as phosphors in television screens and similar
flourescing surfaces.
2) Actinoids:-

Atomic. Electronic Oxidation

Elements Symbol
No. configuration state
Actinium Ac 89 [Rn]6d17s2 +3
Thorium Th 90 [Rn]6d27s2 +4
Protactinium Pa 91 [Rn]5f26d17s2 +3, +4, +5
Uranium [Rn]5f36d17s2 +3, +4, +5,
U 92
+6
Neptunium [Rn]5f46d17s2 +3,+4, +5,
Np 93
+6, +7
Plutonium [Rn]5f66d07s2 +3,+4, +5,
Pu 94
+6, +7
Americium [Rn]5f76d07s2 +3, (+4), +5,
Am 95
+6,
Curium Cm 96 [Rn]5f76d17s2 +3, +4
Berkelium Bk 97 [Rn]5f96d07s2 +3, +4
Californium Cf 98 [Rn]5f106d07s2 +3
Einsteinium Es 99 [Rn]5f116d07s2 +3
Fermium Fm 100 [Rn]5f126d07s2 +3
Mendelevium Md 101 [Rn]5f136d07s2 +3
Nobelium No 102 [Rn]5f146d07s2 +2
Lowrencium Lr 103 [Rn]5f146d17s2 +3

The actinoids are radioactive elements. The earlier members have relatively long half – lives, the
latter ones have half – lives ranging from a day to 3 minutes (for Lowrencium Z = 103,t½ = 3
minutes). The later members have prepared only in nanogram quantities.
Though 4f and 5f orbitals have similar shapes but 5f is less deeply buried than 4f. Hence 5f
electrons can participitate in bonding to a far greater extent.

Ionic sizes and actinoid contraction:-

There is a gradual decrease in the size of atoms or M3+ ions across the series. This is called
actinoid contraction.
The contraction is greater from elements to element in this series due to poor shielding by 5f
electrons.

Oxidation states of actinoids:-

Actinoids show variable oxidation states due to the comparable energies of 5f, 6d and 7s orbitals.
The actinoids show in general +3 oxidation state.
The elements in the first half of the series show higher oxidation states.
e.g.:- The maximum oxidation state increases from +4 in Th to +5, +6 and +7 respectively in (Pa)
Protactinium, Uranium (U) and Neptunium (Np). But decreases in succeding elements.
The actinoids resemble lanthanoids in having more compounds in +3 state than in the +4 state.
However the compounds in the +3 and +4 state tend to undergo hydrolysis.
General characteristics of actinoids:-
Actinoids are metals with silvery appearence.
The structural variability is due to irregularities in metalic radii which are for greater than in
lanthanoids.
The actinoids have high melting and boiling points.
All the actinoids except Thorium and Americium have high densities.
The actinoids have lower ionisation enthalpies than lanthanoids.
All the actinoid metals are highly electropositive.
Actinoid elements are strongly paramagnetic.
Actinoids are strong reducing agents.

Chemical properties:-
They react with boiling water to give a mixture of oxides and hydride.
They combine with most of the non-metals at moderate temperature.
All the metals are attacked by hydrochloric acid but the effect of nitric acid is very small due to
the formation of a protective oxide layer on their surface.
Alkalies have no action.

Problems:-
1. Name a member of the lanthanoid series which is well known to exhibit +4 oxidation
state?
Answer:- Cerium (Z = 58).
2. Actinoid contraction is greater from element to element than lanthanoid contraction why?
Answer:- This is due to poor shielding by 5f electrons in the actinoids than that by 4f
electrons in the lanthanoids.

Some applications of d- and f- block elements:-

1) Iron and steel production is based on the reduction of iron oxides, the removal of
impurities & the addition of carbon and alloying metals such as Cr, Mn and Ni.
2) Some compounds are manufactured for special purposes such as TiO for the pigment
industry and MnO2 for use in dry battery cells. The battery industry also requires Zn and
Ni/Cd.
3) Group-11 elements are called coinage metals. The ‘silver’ UK coins are Cu/Ni alloy.
4) Many of the metals and their compounds are used as catalysts.
Eg:
(1) V2O5 in the manufacture of H2SO4
(2) TiCl4 with Al(CH3)3 forms the basis of the Zeigler catalysts used to manufacture
polythene.
(3) Fe catalysts are used in the Haber’s process for the production of ammonia.
(4) Ni catalysts enable the hydrogenation of fats to proceed.
(5) In Wacker process, the oxidation of ethyne to ethanol is catalyzed by PdCl2.
(6) Ni complexes are useful in the polymerization of alkynes and other organic
compounds such as benzene.
5) The photographic industry relies on the special light sensitive properties of AgBr.