d-and f-block elements

➢ d-block of the periodic table contains elements of the group’s 3-12 in which the orbitals are progressively
filled in each of the four long periods.
➢ The elements constituting the f- block are those in which the 4f and 5f are progressively in the later two
long periods; these elements are formal members of group 3 from which they have been taken out to
form separate f-block of the periodic table.

Transition elements consist to of 4 rows: These series are called transition series.

Transition series- The d-block elements are called transition elements as they represent change in properties
from most electropositive s-block elements to least electropositive (or most electropositive) p-block elements.

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn

Mnemonic Second Tea Vo Cro Man Phe Kon Nahi Kyu Zin
(Ti)
Element Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
Mnemonic Year Zara Nawab Ma Tak Ru Rahega Padhoge Aage Caneda
Element La Hf Ta W Re Os Ir Pt Au Hg
Mnemonic Layenge Half Tha Tun Rahe Os Idhar To pitoge Aau Hoga
Element
Mnemonic AC

First transition series- 3d series

Sc Ti V Cr Mn Fe Co Ni Cu Zn

21 22 23 24 25 26 27 28 29 30
3d14s2 3d 24s2 3d34s2 3d54s1 3d54s2 3d64s2 3d74s2 3d84s2 3d104s1 3d104s2

Second Transition series – 4d series

Y Zr Nb Mo Tc Ru Rh Pd Ag Cd

39 40 41 42 43 44 45 46 47 48
4d15s2 4d25s2 4d45s2 4d5s1 4d65s1 4d75s1 4d85s1 4d105s0 4d105s1 4d105s2

Third transition Series – 5d series

La Hf Ta W Re Os Ir Pt Au Hg

57 72 73 74 75 76 777 78 79 80

Fourth transition Series- 6d Series

 Ac Rf Db Sg Bh Hs Mt Ds Rg Uub

89 104 105 106 107 108 109 110 111 112

➢ All the elements of d-block elements are not called as transition metal.
➢ The transition metals are those elements which have incompletely filled d-subshells in their ground
state or in any one of their oxidation states.

Cu, Ag and Au are transition metals because in their commonly occurring states, i.e Cu+2 Ag+2 Hg+2 they have
partly filled d-sub shells.
Zn, Cd and Hg of group 12 do not have partly filled d-sub shell in their elementary state or commonly
occurring oxidation state, and hence, are not considered as transition elements. However, being the end
members, their chemistry is studied with transition elements.

General Electronic Configuration of d block element- ( n-1)d 1-10 ns 1-2

GENERAL POPERIES OF TRANSITION ELEMENTS

Atomic radii: The Variation of size across the periods is due to two major reasons.
(a) Effective nuclear charge (Zeff)
Increase of Zeff decreases the atomic radii & vice versa.

(b) d – d electron repulsion

Increase in d – d electron repulsion increases the size and vice versa.
Following trends is observed in all the transition series:
Along the Period
➢ The atomic radii decrease from Sc to Cr because the effective nuclear charge increases.
➢ The atomic size of Fe, Co, Ni is almost same due to increase in nuclear charge is cancelled by the
repulsion between the electrons and increase in shielding effect.
➢ Cu and Zn have bigger size because the shielding effect decreases and electron-electron repulsion
increases.

Along the group

➢ The atomic radii increase while going down the group.
Reason – The atomic radii of second transition series is larger than that of first transition series because of
increase in no. of outermost shell.
➢ The third transition series have nearly the same radii as metals of second transition series.
Reason: This is because of lanthanide contraction. This is associated with the interventions of 4f- orbitals
which are filled before 5d-series. 4f- orbital have poor screening effect, this results in regular decrease in
atomic radii which compensates the expected increase in atomic size with increase in atomic no.

Graph for Size Variation along the period & group

In the above graph, we will see a Comparatively low increase in size as we go down from 3d to 4d to 5d. This
is because:
(a) Lanthanoid Contraction: There is regular decrease in the atomic and ionic radii of the transition metals
as the atomic number increases. This is because of filling of 4f orbitals before the 5d orbitals. This
contraction in size is quite regular. This is called lanthanoid contraction.
(b) Actinoid Contraction: Similarly, due to poor shielding of 5f orbital.

Ionic Radii- The ionic radii follow the same trend as atomic radii. Since metals exhibit different oxidation
states, radii of ions also differ. The ionic radii decrease with increase in nuclear charge.

Density-

Density = Mass/Volume
Across the period: Mass is increasing, as well size is decreasing (Volume decreases) almost till copper. So, both
the factor implies the increase in Density till copper but after Copper size increases (Volume increases) hence,
density decrease.

Down the group: Due to Lanthanoid & Actinoid contraction Volume does not increases more as comparison to
mass. So, Mass act a dominating factor, So the density down the group increases.
➢ In d-block Os and Ir have highest density and in 3d-series Cu have highest density.
➢ Order of Density (Due to Lanthanide Contraction) [ Ti < Zr <<< Hf ] & [Cu < Ag <<< Au]
➢ The density of transition element is high as compared to s-block element due to its low atomic volume.

Ionization Enthalpies-
➢ There is slight and irregular variation in ionization energies of transition metals due to irregular variation
of atomic size.
➢ The I.E. of 5d transition series is higher than 3d and 4d transition series because of lanthanoid contraction.
Order of IP of d-block Elements is 3d < 5d > 4d.
➢ There are various exceptions in the IP of d-block elements which is due to the following reasons.
(1) Exceptional electronic configuration.
(2) Irregular variation in size and Zeff.
(3) When e- is removed from ns orbital then remaining e- is shifted to (n-1) orbital due to which the no.
of exchanges are changed and IP also changes.
➢ On moving from top to bottom in d-block Zeff is dominating factor. y Order of IP of 3d series will be: -
Sc < Ti > V < Cr < Mn < Fe > Co > Ni < Cu < Zn

Some exceptions observed in ionization enthalpies are: -

a) Cr and Cu have high I.E. This is attributed to their half-filled (d5) and completely (d10) electronic
configuration.
b) The value of second I.E., for zinc is low because ionization involves removal of an electron resulting in
stable 3d10 configuration.
c) The trend in third I.E., shows high value for Mn+2 and Zn+2 because of stable 3d5 and 3d10 electronic
configuration.
d) I.E3 for Fe <I.E3 for Mn because of stable 3d5 in Fe. In general, third I.E., values are very high because of
filled 4f-orbitals which have poor shielding effect.

Oxidation States-

➢ Transition metals exhibit a larger number of oxidation states in their compound.

 Reason - This is because of participation of inner (n -1) d-electrons in addition to outer ns- electrons
because the energies of ns and (n -1) d-electrons are almost equal.
➢ Sc & Zn does not show variable Oxidation state.
➢ Most common oxidation state of d-block metals is +2.
➢ The elements which gave the greatest number of oxidations states occur in or near the middle of the
series. Eg. Mn; oxidation states from + 2 & +7
➢ Highest oxidation state of d-block metals is found in their compounds with oxygen and fluorine
because of high electronegativity. However, Mn shows highest O.S. with Oxygen because it can form
Π bond with Mn whereas fluorine cannot.

➢ In + 2 and + 3 oxidation state, bonds formed are ionic and in the compounds of higher oxidation state
bonds are covalent.
➢ Transition elements show low oxidation states in some compounds or complexes having ligands such
as CO, for e.g. in Ni (CO)4 , Ni has zero oxidation state.
➢ Compounds of d-block metal in their lowest oxidation state are ionic in nature while those of highest
oxidation state are covalent in nature.
➢ The lesser number of oxidation states at the extreme ends is either due to too few electrons to lose or
share or too many d-electrons, hence fewer orbital is available in to available to share electrons with
others, thus higher valence cannot be attained. E.g., Cu can have oxidation state of +1& +2 & Zn can
have oxidation state of +2 only
➢ Copper having positive E° values, does not liberate hydrogen from acids. It reacts only with oxidising
acids such as HNO3 and conc. H2SO4.
➢ Within a group, maximum oxidation state increases with atomic number. For e.g. in group 8 , Fe shows
+2 and +3 but Ruthenium and Osmium form compounds in +4 , +6 and + 8

Oxidation state of first row transition elements

Sc Ti V Cr Mn Fe Co Ni Cu Zn

21 22 23 24 25 26 27 28 29 30
3d1 4s2 3d 24s2 3d34s2 3d54s1 3d54s2 3d64s2 3d74s2 3d84s2 3d10 4s1 3d10 4s2
+3 +2 +2 +2 +2 +2 +2 +2 +1 +2
+3 +3 +3 +3 +3 +3 +3 +2
+4 +4 +4 +4 +4 +4 +4
+5 +5 +5
+6 +6 +6
+7

Standard electrode potential

➢ The stability of the compounds in solution depends upon standard electrode potentials rather than I.E.
Electrode potential values depend upon factors such as enthalpy of sublimation (or atomisation) of the
metal, the ionisation enthalpy, and the hydration enthalpy, i.e.,

➢ For the process, M(s) → M+(aq) + e–, will be the sum of the three types of enthalpies, i.e., ∆𝐻𝑇𝑜𝑡𝑎𝑙 =
∆𝐻𝑆𝑢𝑏 + ∆𝐻𝑖 + ∆𝐻ℎ𝑦𝑑𝑟𝑎𝑡𝑖𝑜𝑛
➢ Smaller the value of total energy change for a particular oxidation state in aqueous solution, greater will
be the stability of that oxidation state. The electrode potential is a measure of total energy change.
➢ The lower the electrode potential, i.e., more negative the standard reduction potential of the electrode,
more stable is the oxidation state of the transition metal in aqueous solution.
➢ More negative values of E0 for Mn and Zn are due to the stability of half filled (3d5 ) in Mn+2 and
completely filled (3d10 ) configuration in Zn+2 .

➢ Except copper, all other elements have negative reduction potential values, i.e., these elements except
copper should have the capacity to liberate hydrogen from dilute acids.
➢ E° value for Sc3+/Sc2+ is very low. Hence, Sc3+ is stable. This is due to its noble gas configuration.
➢ E° values for the redox couple M3+/M2+ indicate that Mn3+ and Co3+ ions are strong oxidising agents.

Metallic character-
➢ All transition elements are metals. They have high m.p.& b.p. & high tensile strengths, ductility, high,
thermal, and electrical conductivity, and lustre.
Reason – The metallic character is due to their relatively low ionization enthalpies and number of vacant orbitals
in the outermost shell.

Melting and boiling points

➢ As the number of d-electron increases the number of covalent bonds between the atoms are expected to
increase up to Cr-Mo-W family where each of the d-orbital has only unpaired electrons and the
opportunity for covalent sharing is greatest.
➢ Despite presence of five unpaired electrons in Mn, the unexpected low melting and boiling points is
due to (i) Stable electronic configuration (4s2 3d5) (ii) High ionisation energy. (iii) Less delocalisation of
electron. (iv) Weak metallic bond.
➢ The absence of unpaired electron [(n–1) d10 4s2 ] in Zn, Cd & Hg is responsible for its low melting and
boiling point.
 ➢ Tungsten (W) and Mercury (Hg) have highest and lowest melting points respectively.
➢ Along the 3d-series melting point increases up to the middle (Cr) and then decreases Order of Melting
point. (3d-series) Sc < Ti < V < Cr < Mn < Fe > Co > Ni > Cu > Zn

➢ The hardness of their metals suggests the presence of strong bonding due to overlap of unpaired
electrons between different metal atoms.
➢ Zn, Cd and Hg are soft in nature as they have fully filled d-orbitals whereas Cr, Mo and W are hardest
metals as they have max. no. of unpaired d-orbitals.

Enthalpy of atomisation:
➢ d-block metals have very high enthalpy of atomisation (E.O.A.) due to presence of strong metallic bond.
➢ In a series when we move from left to right E.O.A. is first increases then start decreases.
➢ Enthalpy of atomisation depends upon interatomic interaction.
➢ More no. of unpaired electron is particularly favourable for strong atomic interaction. Hence, max
enthalpy of atomization.
➢ There is low enthalpy of atomization for Cu because of no unpaired electron & weak metallic bonding.

Formation of coloured ions-

➢ Most of the compo undo of transition metals are coloured in solid or solution form.
Reason- The colour is due to the presence of unpaired electron which undergoes d-d electron transition
 ➢ Under the influence of approaching ions towards central metal ion, the d-ordinals of central metal split
into different energy levels. This phenomenon is called crystal field splitting.
➢ The electrons are easily promoted from one to another energy level in the same d-sub shell. There are
called d-d transition.
➢ The amount of energy required to excite some of the electrons to higher energy states within the same d-
sub shell corresponds to energy of certain colours of visible light.
➢ Therefore, when white light falls on the compounds, some part of its energy corresponding to certain
colour is absorbed and the electron gets raised from lower energy to higher energy & the excess colour
is transmitted.
➢ The observed colour is complementary of colour absorbed. Eg-Ti+3 (d1) is purple.

Magnetic Properties-
➢ On applying magnetic field to substances, mainly two types of magnetic behaviour are observed:
(i) Diamagnetism: Diamagnetic substance is one which is slightly repelled by a magnetic field.
(ii) Paramagnetism: Paramagnetic substance is one which is attracted by a magnetic field.
➢ Paramagnetism arises from the presence of unpaired electrons.
➢ Due to presence of unpaired electrons Paramagnetism occurs, each such electron having a magnetic
moment associated with its spin angular momentum.
➢ The magnetic moment is determined by the number of unpaired electrons.
Magnetic moment = √n(n + 2) B.M. Where, n = number of unpaired electrons.
➢ An unpaired electron spins and as it is a charged particle, magnetic field is created due to its spinning.
➢ If all electrons are paired, substance will be diamagnetic and magnetic moment will be zero.
Formations of complex compounds: -
The transition metals form a large no. of complex compo undo due to
(i) the comparatively smaller sizes of the metal ions,
(ii) their high ionic charges and
(iii) the availability of d-orbital for bond formation Eg .[PtCl4]2- , [Cu(NH3)4], [Fe(CN)6]4– etc.

Catalytic Properties-
a) Transition metals show catalytic property because of their ability to adopt multiple oxidation states.
Catalysts at a solid surface involve the formation of bond between reactant molecules and atoms of the
surface of the catalyst. This has the effect of increasing the concentration of the reactants at the catalyst
surface and weakening of the bonds in the reacting molecules & the activation energy is lowered, moreover
transition metals can change their oxidation states.
Eg- Fe3+ catalyses the reaction between I2 & persulphate ions.
b) The catalytic property of transition metals is due to their tendency to form reaction intermediates with
suitable reactants. These intermediates give reaction paths of low activation energy and therefore increase
the rate of reaction. The reaction intermediates decompose yielding products and regenerating the original
substance. The transition metals form reaction intermediates due to the presence of vacant orbitals &
tendency to form variable oxidation state.

Formation of interstitial compounds: -

Many of the transition metals form interstitial compounds which are formed when small atoms like B, H, N or
C are trapped inside the crystal lattices of metals. They are usually non-stoichiometric and are neither typically
ionic nor covalent. There small atoms enter into the void sites, eg In, Ti. If C enters the void going the composition
TiC or TiH1.7, VH0.56 etc.

Physical & Chemical characteristics of these compounds

(i) High m.pt, higher than pure metals.
(ii) Very hard, some borides approach diamond in hardness
(ii) Retain metallic conducting
(iii) They are less malleable and ductile.
(iv) Interstitial compounds are neither ionic nor covalent
(v) Chemically inert

Alloy Formation: -
Alloys are homogenous solid solutions in which the atoms of one metal are distributed randomly among the
atoms of the other but the metals should have similar metallic radii within 15% of each other.
 ➢ The alloys formed have high m.pt & are hard.
➢ Alloy containing mercury as one of the constituents’ elements are called Amalgams. Ex: Sodium
amalgam (Na–Hg).
➢ E.g., Alloys of Cr, V, W, Mo, Mn etc, stainless steel is or alloys of Fe, Ni, Cr
➢ Alloys of transition metals with non-transition metals, such as Brass (Cu-Zn), Bronze (Cu- Sn).
Properties of alloy:
➢ Alloy is resistive towards rusting.
➢ Melting point of alloy is more than pure metal.
➢ Alloys of transition metal like brass and bronze have industrial importance.
➢ Also ferrous alloys, Cr, W, Mo and Mn are used for the production of a variety of steels and stainless
steel.

Some important compounds of transition elements

Oxides & oxo metals ions

The oxides of transition elements are generally formed by the reaction of metals with O2 at high
temperature. (Metal + O2 high/ temp MxOy )
➢ All the metals except Sc form metal oxide which are ionic.
➢ For Mn with increase in oxidation number, ionic character decreases. Mn2O7 is a covalent green oil.
Even CrO3 and V2O5 as well as 2 VO+ salt. V2O5 react with alkalies as well as acids to give 𝑉𝑂4−3and
𝑉𝑂4+3 respectively.
➢ The well characterised CrO is basic but Cr2O3 is amphoteric.
➢ The higher oxidation state in the oxides coincides with the group no. eg, Sc2O3(Sc is +3), MN2O7(Mn is
+7).
➢ Beyond group 7- no higher oxides. Eg- Fe2O3(Fe is +3)
➢ As the oxidation number of metal increases, ionic character decreases, Acidic character increases,
stability increases.

Potassium Dichromate, K2Cr2O7 –

Preparation - From Chromite ore
➢ Chromates in turn are formed by fusion of Chromite ore (FeCr2O4) with Na2CO3 or K2CO3.
4 FeCr2O4 + Na2CO3 + 7O3 → 8Na2CrO4 + 2Fe2O3 + 8CO2.
Excess

➢ Na2CrO4 is filtered and treated with H2SO4 to obtain orange crystals of Na2CrO7.2H2O
➢ Sodium dichromate is more stable than pot. dichromate
Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl

Chromates and dichromate’s are interchangeable in aqueous solution depending upon pH of the solution.
The O.S. of Cr in CrO42- and Cr2O72- is same.
2CrO42- + 2H+ → Cr2O72- + H2O
(+6) (+6)

Cr2O72- + 2OH- → 2CrO42- + H2O

 Na2Cr2O7 & K2Cr2O7 : Strong oxidizing agents

Used in
Used as a primary
Organic
standard in volumetric
Chemistry analysis

Chemical properties of K2Cr2O7 :-

➢ In acidic solution, its oxidizing action can be represented as follows –
Cr2O72- + 14H+ + 6e- → 2Cr3+ + 7H2O
➢ Acidified K2Cr2O7 oxidises iodides to iodine, sulphide to S, Sn(II) to Sn(IV), Fe(II) to Fe(II) to
Fe(III)
6I- → 3I2 + 6e-
3 H2S → 6H+ +3S + 6e-
3Sn2+ → 3Sn4+ +6e- 6Fe2+ → 6Fe3+ 6e-
➢ The full ionic equation can be obtained by adding half equation for potassium dichromate to half
equation for the reducing agent, for eg., Cr2O72- + 14H+ + 6Fe2+ → 2Cr3+ + 6Fe3+ + 7H2O Uses – In
leather industry, preparation of azo dyes.

Potassium Permanganate (KMnO4)

Preparation –
KNO3
2MnO2 + 4KOH + O2 ---------→ 2K2MnO4 + 2H2O
Oxidizing agent

3MnO42- + 4H+ → 2MnO4- + MnO2 + 2H2O

(+6) (+7) (+4)

Commercially prepared by alkaline oxidative fusion of MnO2 followed by the electrolytic oxidation of
Manganate (VI)

Fuse with KOH

MnO2 ---------------------→ MnO42-
Oxidize with air or KNO3
Electrolytic oxidation
MnO42- -----------------------→ MnO4-
in alkaline solution
In the laboratory manganese (II) ion salt is oxidized by peroxodisulplate to permanganate
2Mn+2 + 5S2O82- + 8H2O → 2MnO4- + 10SO42- 16H+
Properties-
1. Forms dark purple crystals
2. Not very soluble in water
3. KMnO4 is a good oxidising agent in acidic, basic or neutral medium.
4. Decomposes when heated at 513K
2KMnO4 → K2MnO4 + MnO2 + O2

MnO4 is a strong oxidizing agent, both in neutral & acidic medium

Acidified KMnO4 oxidises oxalates to CO2, Iron(II) to iron (III), nitrites to nitrates and iodides to free iodine
The half reaction of reductants are-
COO-
5 → 10CO2 + 10e-
COO-

Fe+2 → 5Fe+3 + 5e-

5NO2 + 5H2O → 5NO3- + 10H+ + 10e-
-

10I- → 5I2 + 10e-

Full reactions can be written by adding the half reactions of KMnO4 to half reactions of the reducing agents
and balancing them.

Acidic solutions –
10I- + MnO4- + 16H+ → Mn+2 + 8H2O + 5I2 (iodides to KI)
5C2O42- + 2MnO4- + 16H+ → 2Mn+2 + 8H2O + 10CO2 (oxalate ions to CO2)
5Fe2+ + MnO4- + 8H+ → Mn+2 + 4H2O + 5Fe2+ (Fe2+(green) to Fe3+ (yellow))
5S2- + 2MnO4- + 16H+ → 2Mn+2 + 8H2O + 5S (H2S to S)
5SO32- + 2MnO4- + 6H+ → 2Mn+2 + 3H2O + 5SO42 (sulphites to sulphates)
5NO2- + 2MnO4- + 6H+ → 2Mn+2 + 3H2O + 5NO3- (nitrites to nitrates)

Neutral medium -
2MnO4- + H2O + I- → MnO2 + OH- + IO3- (iodides to iodates)
8MnO4- + H2O + 3S2O32- → 8MnO2 + 2OH- + 6SO42 (thiosulphates to sulphates)
MnO4- + 2H2O + 3Mn2+ → 4H+ + 5MnO2 (Manganese salt to Mn2+)

Uses- Used as oxidant, used for bleaching wool, cotton, silk and decolorization of oils.
 The Inner Transition elements (f- Block)

Consists of two series:-

Lanthanoids (Ln; general Symbol) Actinoids
(14elements following La ) (14 elements following Ac)

Have only one stable oxidation state (+3)

Lanthanoides :-

Electronic Configuration:-

Atomic No. Name Symbol E.C.

57 Lanthanum La 5d1 6s2

58 cerium Ce 4f15d16s1
59 praseodymium Pr 4f3 6s2
60 Neodymium Nd 4f4 6s2
61 Promethium Pm 4f56s2
62 Samarium Sm 4f6 6s2
63 Euroduim Eu 4f7 6s2
64 Gadolinium Gd 4f7 5d1 6s2
65 Terbium Tb 4f9 6s2
66 Dysprosium Dy 4f10 6s2
67 Holmium Ho 4f11 6s2
68 Erbium Er 4f12 6s2
69 Thulium Tm 4f13 6s2
70 Ytterbium Yb 4f14 6s2
71 Lutetium Lu 4f14 5d1 6s2

Atomic & Ionic Series :-

➢ Decrease from La to Lu is due to Lanthanoid Contraction (The shielding of one 4f electron by another
less than that by one d electron by another & the increase in nuclear charge along the series.
➢ The almost identical radii of Zr (160pm.) and Hf (159), a consequence of the lanthanoid contraction,
account their occurrence together in nature and for the difficulty faced in their separation.

Colour and Para magnetism

Ln3+ are coloured both in solid and in aqueous solution due to the presence of f electrons. La3+ and Lu3+ do not
show any colour. However absorption bands are narrow probably because of the excitants with in f level.
Ln3+ are paramagnetic except La3+ & Ce4+ (f0 type) & f14 type ( Yb2+ & Lu3+ ). Paramagnetism rises to maximum
in Neodymium.

Ionization enthalpies
➢ I.E. depends on the degree of stability of empty, half-filled and completely filled f-level.
➢ This is indicated from the abnormally low values of the third ionization enthalpy of La, Gd, Lu.
Oxidation states.:-
➢ Ln3+ compounds are predominant species. +2 & +4 ions in solution or in solid compounds are also
obtained occasionally.
➢ Ce (IV) formation is favoured due to extra stability of noble gas configuration, but it is a strong
oxidant reverting to the common +3 state .
➢ Pr, Nd, Tb and Dy also exhibit +4 state but only in oxides, MO2 Eu2+ is formed by losing the two s-
electrons & its +7 configuration.

Properties and use :-

➢ Ln are silvery white soft metals and tarnish rapidly in air. Hardness increases with increasing atomic
number. M.pt. ranges from 1000K – 1200K Sm is steel hard. (m.pt 1623K)

Chemical behavior
In general earlier members of the series are quite reactive similar to Ca, with increasing atomic number they
behave more like aluminum.
Ln3+ (aq) +3e-➔ Ln(s)

Ln2O3 H2

Burns in with acids

O2

Heated with S with halogens

Ln2S3 Ln LnX3

Heated with H2O

N2
Ln(OH)3 +H2
. Ln N C 2773K
Ln C2

Ln + C ---------→ Ln3C + Ln2C3 + LnC2 (carbides)

Use:- Used in the production of alloy steels for plates & pipes eg. Mischmetal is an alloy which consists of a
lanthanoid metal (95%) and iron (5%) and trace of S, C, Ca and Al. A good amount of this allay is used in Mg-
based alloy to produce bullets, shell & lighter flint.

• Mixed oxides of Ln are used as catalyst in petroleum cracking .

• Ln oxides are used as phosphors in television screens & similar fluorescing surfaces.

The Actinoids:-

Atomic no. Name Symbol E.C.

89 Actinium Ac 6d17s2
90 Thorium Th 5f16d17s2
91 Protactinium Pa 5f26d17s2
92 Uranium U 5f36d17s2
93 Neptunium Np 5f46d17s2
94 Plutonium Pu 5f67s2
95 Americium Am 5f77s2
96 Curium Cm 5f76d17s2
97 Berkelium Bk 5f97s2
98 Californium Cf 5f107s2
99 Einsteinium Es 5f117s2
100 Fermium Fm 5f127s2
101 Mendelevium Md 5f137s2
102 Nobelium No 5f147s2
103 Lawrencium Lr 5f146d17s2

Although the naturally occurring elements & the earlier member have relatively long half lives, the latter
members have values ranging from a day to 3 minutes for Lr (Z=103) These facts and high radioactivity
renders their study more difficult.

Electronic Configuration
The irregularities in the electronic configurations of the actinoids like those of in the lanthanoids are related to
the stability of fo , f7 and f14 occupancies of the 5f orloitals.
Eg. Am : [Rn] 5f77s2
Cm : [Rn] 5f76d17s2

5f orbital can & do participate in bonding.

Common oxidation state is +3
The maximum oxidation state increases from +4 in Th, +5 in Pa, +6 in U and +7 in Np but decreases in
succeeding elements.

Magnetic Properties:- the variation of magnetic properties with the no. of unpaired 5f electrons is similar to
that of Ln.

Ionic Sizes: Decrease in size due to increase in the effective nuclear charge on the outermost shell and poor
shielding by 5f electrons. This is referred to as actinoid contractions.

Ionization Enthalpy :
The I.E. of early actinoids is lesser than that of early Ln as when 5f orbitals are beginning to be occupied, they
will penetrate less into the inner core of electrons. The 5f electrons, will therefore, be more effectively shielded
from the nuclear charge than are the 4f electrons of the corresponding Ln. Because the outer electrons are less
firmly held, they are available for bonding in the actinoids.

Physical and Chemical Reactivity

The actinoids are highly reactive when they are finely divided.

Actinoid Boiling water MxOy + MHn

moderate temp
Actinoid + Non metal Corresponding compound
Actinoid + HCl ➔ MxOy oxide layer
Actinoid + HNO3 ➔ MxOy
Actinoid + Alkali ➔ No reaction
Metallic radii of actinoids is more as compared to lanthanoids.

Comparison With Lanthanoids

1. Structural variability in actinoids is obtained due to irregularities in metallic radii which are greater
then lanthanoids.
2. Magnetic properties in actinoids are more complex than lanthanoids.
3. Ionization enthalpies of early actinoids, though not accurately known are lower than early lanthanoids.
This is because 5f electrons penetrate less into the inner core and hence the outer electron are less firmly
held, they are available for bonding in actinoids.

Applications of d-and f Block Elements

1 Iron and steel are important construction materials. Their production is based on reduction of iron
oxides, removal of impurities, and addition of carbon and alloying metals such as Cr, Mn, and Ni.
2 TiO is used in pigment industry.
3 MnO2 is used in battery cell. Also Zn and Ni/Cd.
4 Elements of group II are coinage metals.
5 V2O5 catalyses oxidation of SO2 in contact process, 6 Iron catalyst is used in Haber’s process.
7 TiCl4 and Al(CH3)3 forms Ziegler-Natta Catalyst.
8 Ni complexes are used in polymerization of alkynes.