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The d and f Block Elements
Elements from 3rd group to 12th group in the Modern Periodic table are called d-block elements. In these
elements their last electron enters in the penultimate d- sub shell. They are placed in between s-block and p-
block elements. They show a regular transition from the highly electropositive metals of s- block elements to the
less electropositive p-block elements. So they are called transition elements.
Transition elements can be defined as elements which contain partially filled d orbitals in their atomic
state or in any of their oxidation state. The elements Zn, Cd and Hg contain only completely filled d-orbitals. So
they are not regarded as transition elements. Or, they are called pseudo transition elements.
There are four series of transition elements.
1) 3d series [from Scandium (Sc, z = 21) to zinc (Zn, z = 30)]
2) 4d series [from Yttrium(Y, z = 39) to cadmium, (Cd, z = 48)]
3) 5d series [from Lanthanum, (La, z =57), Hafnium, (Hf, z = 72) to Mercury, (Hg, z=80)]
4) 6d series [from Actinium, (Ac, z=89), Rutherfordium, (Rf, z=104) to copernicium, (Cp, z=112)]
Electronic Configuration

General outer electronic configuration of d-block elements is (n-1) d1-10 ns1-2. There is only a small
difference in energy between (n-1)d orbital and ns orbital. So in some cases ns electrons are also transferred to
(n-1)d level.
The electronic configurations of Cr and Cu in the 3d series show some exceptions.
24Cr – [Ar] 3d5 4s1
29Cu – [Ar] 3d10 4s1
This is due to the extra stability of half-filled (d5) and completely-filled electronic configurations (d10).
The electronic configurations of Zn, Cd and Hg are represented by the general formula (n-1)d10 ns2.
The orbitals in these elements are completely filled in the ground state as well as in their common oxidation
states. So they are not regarded as transition elements.

Electronic configuration of first row transition series elements:

Atomic number Element Symbol Electronic configuration

21 Scandium Sc [Ar] 3d1 4s2
22 Titanium Ti [Ar] 3d2 4s2
23 Vanadium V [Ar] 3d3 4s2
24 Chromium Cr [Ar] 3d4 4s2
25 Manganese Mn [Ar] 3d5 4s1
26 Iron Fe [Ar] 3d6 4s2
27 Cobalt Co [Ar] 3d7 4s2
28 Nickel Ni [Ar] 3d8 4s2
29 Copper Cu [Ar] 3d10 4s1
30 Zinc Zn [Ar] 3d10 4s2
General trends in the properties of transition elements:

1) Atomic and Ionic radii

2) Metallic character
3) Melting and boiling points
4) Density
5) Ionisation Enthalpy
6) Standard electrode potential and chemical reactivity

1) Atomic Radii and Ionic Radii:

a) The atomic radii of the transition metals lie in between those of s- and p-block elements.
b) In a given transition series, the atomic and ionic radii first decreases, then become constant and increases
towards the end of the series.
i. First decreases- Effective nuclear charge increases poor shielding effect of d-electrons increases
ii. Last increases- Electron-Electron Repulsion overcome the effective nuclear charge
iii. Constant- Effective nuclear charge is balanced by the shielding effect

Ex: Sc, Cr  Atomic Radii decreases

Mn, Fe  Constant

Co, Zn  Atomic radii increases

c) The atomic radii increase down the group:

This means that atomic radii of 4d series are larger than those of 3d transition series [4d > 3d]. But 5d and
6d series atomic radii are almost the same.
Reason:
i. Since, in 4d series number of shell increases, their atomic radii are larger than those of the elements of 3d
series.
ii. For 4d and 5d series, the atomic radii are nearly same due to the presence of 4f and 5f electrons. Because
of the poor shielding effect of 4f and 5f electrons, lanthanoid contraction occurs. Due to this lanthanoid
contraction, 4d and 5d series elements exhibit similar atomic radii.

2) Metallic character:
Except for mercury (Hg) which is a liquid, all the transition elements have typical metallic structure (hcp, ccp or
hcc). They exhibit all the characteristic of metals.
Explanation: Transition elements have relatively low ionisation enthalpies.
i. They have 1 or 2 electrons in their outermost energy level (ns 1 and ns2). As a result, metallic bonds are
formed. Hence, they behave as metals.
ii. The unpaired d-electrons also results in the formation of metallic bonds. Greater the number of unpaired
d-electrons, stronger is the bonding due to the overlapping of inpaired electrons between different metal
atoms.
Ex: Cr, Mo, W- Hard metals (Maximum number of unpaired d-electrons)
Zn, Cd, Hg- They are not very hard metals due to the absence of unpaired electrons

3) Melting and boiling points:

They have very high melting and boiling points.
Explanation:
i. Strong metallic bonds between the atoms of these elements are responsible for the high melting and
boiling points. This is due to their high enthalpies of atomization (i.e., heat required to break the metal
lattice to get free atoms)
ii. The metals of 4d and 5d series have greater enthalpies of atomisation than the corresponding elements of
the 3d series. This is due to more frequent metal-metal bonding present in them.
4) Ionization enthalpy:
(i)The first ionization enthalpies of d block elements lie between s-block and p-block elements. They are higher than
those of s-block and lesser than those of p-block elements

 The ionization enthalpy gradually increase with increase in atomic number along a given transition series though
some irregularities are observed

 IE of transition elements generally increases from left to right . This is due to increase in nuclear charge. But the
increase is not regular . This can be explained as follows.

Explanation: After the removal of one electron the relative energies of 4s and 3d orbital get changed. Hence the
remaining electron is 4s level is transferred to 3d level.So the unipositive ions have d n configuration with no 4s
electrons. During this reorganization of electrons some energy is released and it is known as exchange energy. So the
net energy required to remove the first electron is equal to the sum of IE and exchange enthalpy.

 The first IE of Cr and Cu are low. [Cr – 3d5 4s1 ; Cu – 3d104s1] This is because the removal of one electron
does not change their d- configuration and they attain stable configuration.

 First IE of Zn is high because after the removal of one electron there is no change in the d- configuration

Zn(3d104s2) -- Zn+ +e- [3d54s1]

Zn has very high IE because electron has to be removed from 4s orbital of the stable configuration

(ii) The first ionization enthalpy of Zn, Cd,Hg are however very high because of the fully filled (n-1)d10ns2 configuration

(iii)Although second and third ionization enthjalpies also in general increase along a period. Moreover exceptions are
observed from the regular increase as under

 The values of IE2 higher for Cr & Cu. It is because Cr + has stable 3d5 and Cu+ has stable 3d10 configuration and
the removal of second electron is very difficult

 The order for IE2 is V23 <Cr24 > Mn25

Cr+ (3d5) - Cr2+ (3d4) IE2 is high

Cu+ (3d10)-- Cu2+(3d4) IE2 is high

 IE3 (Third ionization enthalpy ) of Mn is very high because the third electron has to be remove from the stable
half filled 3d orbital

Mn2+ (3d5) -- Mn3+ (3d4 ) [IE3 –high}

 Third ionization enthalpy of Fe is very small. Because loss of 3 rd electron gives the stable configuration of 3d5

Fe has 3d6 4s2 configuration.

Fe - Fe+[3d64s1] +1 electron

Fe+ - Fe2+ [3d64s2] + 1electron

Fe2+  Fe3+ [3d64s3] + 1 electron

 Hence IE3 for Fe << IE3 for Mn

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

(v) The first ionization enthalpies of 5d elements are higher as compared to those of 3d and 4d elements. This is because
the weak shielding effect of nucleus by 4f electrons in 5d elements results in greater effective nuclear charge acting
on the outer valence electrons (lanthanoid contraction)

 The magnitude of ionization enthalpy gives a clue to the amount of enthalpy required to raise the metal to a
particular oxidation state in a compound

 In other words thermodynamic stability of the compounds of transition elements can be evaluated in terms of the
magnitude of ionization enthalpies of the metals

 Smaller the IE of metal stbler is its compound

Eg; (i) Ni(II) more stable than Pt(II)

IE2 for Ni= 2.49x 103 < IE2 for Pt =2.66x103

(ii) Pt(IV) more stable than Ni (IV)

IE4 for Pt = 9.36x103 < 11.29 x103

 K2PtCl6 is known but K2NiCl6 is not known

Standard electrode potential (E°) and chemical reactivity:

In solution the stability of the compounds depends upon electrode potentials rather than ionization enthalpies.
Electrode potential values depend upon factors such as enthalpy of sublimation (or atomization) of the metal
the ionization enthalpy and the hydration enthalpy, i.e.

M(s) -- M(g) (ΔHsub enthalpy of sublimation/atomization)

M(g) -- M+(g) + e- (ΔHIE is ionization enthalpy)

M+ (g) + aq -M+ (aq) (ΔHhyd is enthalpy of hydration)

Electrode potential E = ΔHsub + ΔHIE + ΔHIE

Thus E gives the enthalpy change required to change the metal M(solid) to the M+(aq) .

 Smaller the value of E greater is the stability of M+(aq)

 Electrode potentials are measure of the total energy (E). Therefore stability of transition metal ions in
different oxidation states may be compared on the basis of their electrode potentials (E°)

 Smaller the reduction potential (E°) i.e,more negative the standard negative potential of the electrode
Mn+/M more stable is the oxidation state of the transition metal in aqueous solution.

Trends in the M2+ /M standard electrode potentials

 There is no regular trend in the E ° M2+ /M values. This is because their ionization enthalpies (IE 1+IE2)
and sublimation enthalpies do not show any regular trend

 The general trend towards less negative E° values along the series is due to the general increase in the
sum of the first and second ionization enthalpies

 Copper shows a unique behavior in the series as it is the only metal having positive value for E °.
This explains why it does not liberate H2 gas from acids. It reacts only with the oxidizing acids (HNO3
and H2SO4) which are reduced. The reason for positive E° value for copper is that the sum of enthalpies
of sublimation and ionization is not balanced by hydration enthalpy.
  The values of E° for Mn and Zn are more negative than expected from the general trend. This is due to
greater stability of half-filled d-sub shell (d5) in Mn2+, and completely filled d-sub shell (d10) in Zn2+. The
exceptional behavior of Ni towards E° value from the regular trend is due to its high negative enthalpy of
hydration.

Trends in the M3+ /M2+ standard electrode potentials

 A very low value for E° (Sc3+/Sc2+) (not given in the Table above) reflects the stability of Sc3+ ion which
has noble gas configuration.

 The highest value for Zn is on account of very high stability of Zn2+ ion with d10 configuration. It is
difficult to remove an electron from it to change it into +3 state.

 The comparatively high value of E° (Mn3+/Mn2+) shows that Mn2+ is very stable which is on account of
stable d5 configuration of Mn2+.

 The comparatively low value of E° (Fe3+/Fe2+) is on account of extra stability of Fe3+ (d5), i.e., low third
ionization enthalpy of Fe.

 The comparatively low value for V is on account of the stability of V2+ ion due to its half-filled t32g
configuration.

Chemical Reactivity and E° Values:

The transition metals vary very widely in their chemical reactivity. Some of them are highly electropositive and dissolve
in mineral acids whereas a few of them are ‘noble’, i.e., they do not react with simple acids. Some results of chemical
reactivity of transition metals as related to their E° values are given below:

 The metals of the first transition series (except copper) are relatively more reactive than the other series.
Thus, they are oxidized by H+ ions though the actual rate is slow, e.g. , Ti and V are passive to dilute non-
oxidizing acids at room temperature.

 As already explained, less negative E° values for M2+/M along the series indicate a decreasing tendency to
form divalent cations.

 More negative E° values than expected for Mn, Ni and Zn show greater stability for Mn2+, Ni2+ and Zn2+.

 E° values for the redox couple M 3+/M2+ indicate that Mn3+ and Co3+ ions are the strongest oxidizing
agents in aqueous solution whereas Ti2+, V2+ and Cr2+ are strongest reducing agents and can liberate
hydrogen from a dilute acid, e.g., 2Cr 2+ (aq) + 2H+ (aq)  2Cr3+ (aq) + H2 (g)

Cause of variable oxidation states:

 In transition elements, electrons are present in (n-1) d orbitals also take part in chemical bonding. It is
because the energy difference between (n-1) d orbitals and ns orbitals is small. In lower oxidation states,
only the ns electron take part in bonding. In higher oxidation states (n-1) d orbitals take part in bonding.

 Since fluorine and oxygen are most electronegative elements and smaller size transition elements show
highest oxidation states in their fluorides and oxides. The highest oxidation state shown by any transition
element is +8 (osmium).

 In p-block, lower oxidation states are favored by the heavier elements due to inert pair effect. But in d-
block higher oxidation states are shown by heavier elements.
Ex: In group-6, Mo (VI) and W (VI) are more stable than Cr (VI) because in K 2Cr2O7 in acidic medium
Cr (VI) reduced to Cr (III). But MoO3 and WO3 do not exist.

 Transition elements form compounds in low oxidation state of +1 and 0 also. In Ni(CO)4 and Fe(CO)5,
the transition element is present in Zero oxidation state. Lower oxidation states are found when a complex
compound has ligands capable of 𝝅 acceptor in addition to σ bonding.

 The maximum oxidation state of reasonable stability is equal to the sum of s- and d- electrons upto
manganese. After Mn, there is abrupt decrease in stability of higher oxidation states. Thus, both Iron and
Cobalt show stable oxidation states of +2 and +3 while Ni, Cu and Zn show stable oxidation state of +2
only.
  In transition elements, the different oxidation states differ by one unit. But in non transition elements, the
different oxidation states differ by two units. Ex: V shows +2,+3,+4,+5, Cl shows +1,+3,+5,+7.

 The relative stabilities of the different oxidation states of an element can be compared from their E°
values. Smaller the value of E° for Mn+/ M couple greater is the stability of the +n oxidation state in
aqueous solutions.
Ex: Cu+ (aq) + e-  Cu (s) [E° = +0.52 V]
Cu2+ (aq) + 2e-  Cu (s) [E° = +0.34 V] Thus
Cu2+ is more stable than Cu+.

Trends in the stability of higher oxidation states of metal halides:

 The highest oxidation state of +4 is achieved for Ti in TiX4, +5 for VF5, +6 for Cr in CrF6, +7 for Mn in
MnO3F. Manganese does not show +7 oxidation states in simple halides. Beyond Mn, no metal has a
trihalide except FeX3 and CoF3.

 The highest oxidation state of a metal is shown in its fluorides. It is due to either higher lattice
enthalpy.
Ex: CoF3 or higher bond enthalpies for the covalent compounds (e.g) VF5 and CrF6. Vanadium
shows +5 oxidation state in VF 5. Other halides of vanadium undergo hydrolysis to give oxo-halides
VOX3 in which oxidation state of V is +5.

 In the lower oxidation states, fluorides are unstable. The stable halides in lower oxidation states are VX 2
(X= Cl, Br, I) similarly copper (I) halides CuX (X= Cl, Br, I) are stable.

 The stable halides of copper in +2 oxidation state are CuF 2, CuCl2 and CuBr2. Cupric iodide (CuI2) is
unstable. Cu2+ ion oxidizes iodide ion to iodine. Cu2+ ion itself is reduced to cuprous ion.
2Cu2+ + 4I-  Cu2I2 + I2

 Many copper (I) compounds are unstable in aqueous solution and undergo disproportionation
2Cu+  Cu2+ + Cu. The greater stability of Cu2+ is due to much more negative enthalpy for Cu2+
than Cu+. The negative enthalpy of hydration for Cu2+ is more and it compensates the high energy
required for the second ionization of copper to form Cu+.

Trends in the stability of higher oxidation states of metal oxides:

 The highest oxidation state of the metal in the oxides is equal to the group number up to group-7 (Sc2O3,
TiO2, V2O5, CrO3, Mn2O7).

 Beyond group-7, the maximum oxidation state of the metal in the oxides is +3. Ex: Fe2O3. Ferrates
(FeO5)2- are formed in alkaline medium oxidation state of Fe in ferrates is +6 but these are readily
decompose to give Fe2O3 and O2.

 The higher oxidation states are also shown in oxidations, Ex: VO2+ (V=+5), VO2+ (V=+4), TiO2+ (Ti=4)

 Oxygen stabilizes the highest oxidation state even more than fluorine. Ex: The highest fluoride of
Mn is MnF4 whereas the highest oxide is Mn2O7. It is because oxygen has the ability to form double
bonds with the metal atoms. Ex: Each Mn atom is tetrahedrally surrounded by four O atoms
including Mn-O-Mn Bridge. Other examples of tetrahedral ion are (MO4)n+ where M=V(+5),
Cr(+6) and Mn(+5,+6,+7).

5) Magnetic Properties:
Transition metals show mainly two types of magnetic properties- paramagnetism and diamagnetism. Some
transition metals also show ferromagnetism which is an extreme case of paramagnetism.
Paramagnetism arises from the presence of unpaired electrons. Each unpaired e- is associated with a spin magnetic
moment and an orbital magnetic moment. For the compounds of 1st row transition elements, the contribution of orbital
magnetic moment is effectively cancelled and so only spin magnetic moment is considered. It is determined by the no. of
unpaired e-s and is calculated by the spin only formula:
µs = √n(n+2) where n is the no. of unpaired electrons and µs is the spin only magnetic moment in the unit of Bohr
Magneton (B.M).
The magnetic moment increases with increase in no. of unpaired e-s. Thus the observed magnetic moment gives an idea
about the no. of unpaired e-s present in the atom or ion.
6) Formation of coloured ions or compounds:
Most of the Transition metals ions or compounds are coloured. This is because of the presence of partially filled d
orbitals. When an electron from a lower energy d orbital is exited to higher d level, it absorbs energy and this is equal to the
energy of certain colours in visible region. So the colour observed is the complementary colour of the light absorbed.
In aqueous solution most of the Transition metal ions are coloured since water molecules act as the ligands.
Among Ti2+ and Ti4+, Ti2+ is coloured while Ti4+ is colourless. This is because Ti4+ has no partially filled d orbitals.
Ti2+ -[Ar] 3d2 Ti4+ - [Ar] 3d0
Similarly among Cu and Cu , Cu2+ is coloured while Cu+ is colourless. This is due to the lack (absence) of partially
+ 2+

filled d orbitals in Cu+.

7) Formation of Complexes:
Transition metals form a large no. of complexes. This is due to:
a. Comparatively smaller size
b. High ionic charge
c. Presence of partially filled d orbitals
d. Ability to show variable oxidation state Eg:
K4[Fe(CN)6], K3[Fe(CN)6], [Ni(CO)4] etc.
8) Catalytic Property:
Transition metals act as catalysts in a large no. of chemical l reactions. This is due to their large surface area and
their ability to show variable oxidation state.
 Many transition metals and their compounds are good catalysts.
 Finely divided Iron (Spongy Iron) is used as a catalyst in the manufacture of ammonia byHaber process.
 V2O5 or Pt is used in contact process for the manufacture of H2SO4.
 The catalytic activity of transition metal is due to the following reasons.
(i) Variable valencies enable transition metals to form unstable intermediate compoundsreadily.
(ii) This provides a new path with lower activation energy for the reaction.
(iii) Transition metals can provide a large surface area for the reactants to be adsorbed
9) Interstitial Compound Formation:
These are formed when smaller atoms like H, N, C, B etc. are trapped inside the crystal lattice of the metal. They
are usually non-stoichiometric and neither typically ionic nor covalent.
E.g.: Fe3H, Mn4N, TiC, VH0.56, TiH1.7 etc.
. Some the properties of these compounds are:
1) They have high melting point.
2) They are very hard.
3) They retain metallic conductivity.
4) They are chemically inert.

10) Alloy Formation:

Alloys are homogeneous solid solutions of elements in which at least one element is a metal. They are formed by atoms
with metallic radii within about 15% of each other. Because of similar radii and other characteristics of Transition metals,
they readily form alloys. The alloys formed are hard and have high m.p. e.g.: Bronze (Cu, Zn), Stainless steel (Fe, C, Ni, Mn
and Cr).
Some Important Compounds of Transition Elements
1. Potassium dichromate ( K2Cr2O7)
Potassium dichromate is generally prepared from chromite ore (FeCr2O4). The preparation involves three steps.
1. Conversion of chromite ore to sodium chromate
Chromite ore is first fused with sodium carbonate in presence of air to form sodium chromate.
4 FeCr2O4 + 8 Na2CO3 + 7 O2 → 8 Na2CrO4 + 2 Fe2O3 + 8 CO2
2. Acidification of sodium chromate to sodium dichromate
The yellow solution of sodium chromate is filtered and acidified with sulphuric acid to orange sodium
dichromate.
 2Na2CrO4 + 2 H+ → Na2Cr2O7 + 2 Na+ + H2O
3. Conversion of sodium dichromate to potassium dichromate
The solution of sodium dichromate is treated with potassium chloride so that orange crystals of potassium
dichromate crystallise out.
Na2Cr2O7 + 2 KCl → K2Cr2O7 + 2 NaCl
Properties: The chromate and dichromate are inter convertible in aqueous solution depending upon pH of the solution.
Chromate on acidification gives dichromate and the dichromate on treating with alkali gives chromate.
2 CrO 2– + 2H+ → Cr O 2– + H O
4 2 7 2

Cr2O72– + 2OH- → 2 CrO42– + H2O

The oxidation state of chromium in chromate and dichromate is
+6.
Structure
The chromate ion is tetrahedral while, 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. Sodium dichromate is most commonly used
as oxidizing agent, due to its greater solubility in water. Potassium dichromate is used as a primary standard in
volumetric analysis.

USES: It is used as a primary standard in volumetric analysis, as an oxidising agent in many reactions, in leather
industry etc.
2. Potassium permanganate ( KMnO4)
Potassium permanganate is commercially prepared from MnO2 (Pyrolusite). The preparation involves two
steps:
i) Conversion of MnO2 to potassium manganate (K2MnO4) by fusing with KOH in presence of air (or an
oxidizing agent like KNO3).
2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O
ii) Potassium manganate is oxidised to potassium permanganate either by electrolysis or by
acidification.
 Or

Properties:
Potassium permanganate forms dark purple crystals which are iso-structural with those of potassium perchlorate
(KClO4).
When heated it decomposes and liberate O2.
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.
Note: In permanganate ion, Mn is in +7 oxidation state with no d-
electrons. So the colour of permanganate is due to ligand to metal
charge transfer. i.e. an electron is transferred from oxygen atom to
the vacant d-orbital of Mn.

Oxidising Property of KMnO4

KMnO4 is a good oxidizing agent in acidic, basic and neutral media. The oxidizing action in acidic medium is
due to the reaction:
MnO4- + 8H++ 5e-→ Mn2+ + 4H2O
Acidified permanganate solution oxidises:
 4 2 2

Note: For acidification of permanganate, hydrochloric acid (HCl) is not used, since it is oxidised to chlorine. Uses: It is used
as an oxidising agent in acidic, basic and neutral medium. It is used as a primary standard in volumetric analysis. It is used
for the bleaching of wool, cotton, silk and other textile fibres and also for the decolourisation of oils.
THE INNER TRANSITION ELEMENTS ( f-BLOCK)
The elements in which the last electron enters in the anti-penultimate f-subshell are called f-block elements.
They include lanthanides of the 6th period and actinides of the 7th period. They are also called inner transition elements.
Since lanthanum (57La) closely resembles lanthanides, it is also included along with them. Similarly, actinium (89Ac)
is included along with actinoids because of its close resemblance with them.
The Lanthanoids or lanthanides
The 14 elements after lanthanum of the 6th period are called lanthanides or lanthanoids or lanthanones or
rare earths. They include elements from 58Ce to 71Lu. They are generally represented as Ln.

Atomic and ionic radii - Lanthanide Contraction

In lanthanides, the atomic and ionic radii decrease regularly from lanthanum to lutetium. This regular decrease in the
atomic and ionic radii along lanthanide series (though very slightly) is called lanthanide contraction.

Reason: In lanthanides, as the atomic number increases, the nuclear charge increases one by one and the electrons are
added to the anti-penultimate f subshell. Due to its diffused shape, f orbitals have poor shielding effect. So the nucleus
can attract the outer most electrons strongly and as a result the radii decreases.
Consequences of Lanthanide contraction:
1) Due to Lanthanide Contraction the 2nd and 3rd row transition series elements have similar radii.
E.g. Zr – 160pm and Hf -159pm

2) Lanthanides have similar physical properties and they occur together in nature. So their isolation is
difficult.
3) The basic character of their hydroxides decreases from lanthanum to lutetium. i.e, La(OH)3 is more
basic than Lu(OH)3.
Oxidation number
In lanthanoids, the most common oxidation state is +3. However, +2 and +4 ions in solution or in solid
compounds are also obtained. This irregularity arises mainly from the extra stability of empty, half-filled or filled f
subshells. Cerium shows the oxidation state +4 due to its noble gas configuration. Praseodymium (Pr), neodymium
(Nd), terbium (Tb) and dysprosium (Dy) also exhibit +4 state but only in oxides, MO2.
Europium (Eu) and ytterbium (Yb) shows +2 oxidation state because of the stable f7 or f14 configuration. Samarium
(Sm) shows +2 oxidation state also.
General properties of Lanthanoids
All the lanthanoids are silvery white soft metals and tarnish rapidly in air. Their hardness increases with
increasing atomic number. They have typical metallic structure and are good conductors of heat and electricity.
Most of the lanthanoid ions are coloured both in the solid state and in aqueous solutions. Colour of these ions
 is due to the presence of f electrons. But La3+ or Lu3+ ion are colourless. The lanthanoid ions other than the f 0 type
(La3+ and Ce4+) and the f 14 type (Yb2+ and Lu3+) are all paramagnetic. The paramagnetism rises to maximum in
neodymium.

Uses of Lanthanides
The main use of the lanthanoids is for the production of alloy steels. An important alloy is mischmetall
which consists of a lanthanoid metal (~ 95%) and iron (~ 5%) and traces of S, C, Ca and Al. It is mainly used

in Magnesium based alloy to produce bullets, shell and lighter flint.

Mixed oxides of lanthanoids are used as catalysts in petroleum cracking. Some lanthanide oxides are
used as phosphors in television screens and similar fluorescing surfaces.
The Actinoids or Actinones
The 14 elements after actinium in the 7th period of modern periodic table are called actinides or
actinoids or actinones. They include elements from 90Th to 103Lr. Most of them are artificially prepared
and are short lived. They are radioactive. The elements after Uranium are artificially prepared and so they
are called trans-uranium elements or trans-uranic elements.
Atomic and ionic radii
In actinoid series the atomic and ionic radii decrease regularly from left to right. This is known as
Actinoid contraction.
Oxidation state
Common oxidation state of actinoids is +3. The elements in the first half of the series show higher
oxidation states. The maximum oxidation state increases from +4 in thorium (Th) to +5, +6 and +7
respectively in protactinium (Pa), uranium (U) and neptunium (Np) but decreases in succeeding elements.
The actinoids resemble the lanthanoids in having more compounds in +3 state than in the +4 state.
Comparison between lanthanoids and acinoids
1. Most of the actinoids are artificially prepared and are radioactive.
2. The first ionisation enthalpy of early actinoids is lower than those of lanthanoids.
3. Actinoid contraction is greater from elements to elements than lanthanoid contraction. This is due to
greater shielding effect of 5f electrons.

Uses of Lanthanoids
1. Misch Metal
95% Ce + 5% Fe, it is alloy.
 2. Crooke Glass
CeO2 in ordinary glass SiO 2 is present. Crookeglass prevents UV light.
3. Lanthanoid Oxide (LnO): It is used in T.V. screen and used as catalyst in petroleum
cracking.

 shielding by 5f-electorns in actinides than that of 4f-electrons in the lanthanoids.

Differences :

S.N. Lanthanides S.N. Actinides

In addition to +3 oxidation In addition to +3 oxidation state,

1. state, they exhibit +2 and they show +4, +5, +6 and +7
1.
+4 oxidation states only. oxidation states.

2. Most of their ions arecolourless. 2. Most of their ions are coloured.

3. They do not form They have much greater tendency

3.
complexes easily. to form complexes.

4. They form oxo cations such as

They do not form oxo
4. UO 2+, PuO 2+
cations.
2 2

5. Their compounds are lessbasic. 5. Their compounds are more basic.

6. Except promethium, they

6. They are radioactive.
are non-radioactive.

7. Their magnetic properties Their magnetic properties cannot

7.
can be easily explained. be explained.