Ln 8- d and f block

elements
SUGAIRA BANU. V
PGT CHEMISTRY

ST. BRITTO'S ACADEMY STD XII

Position in the Periodic table
Electronic Configuration of d-block elements
General properties of the Transition Elements
Some important compounds of Transition elements
The Lanthanoids
The Actinoids
Some Applications of d- and f- block elements
Position & Electronic Configuration
Of d block elements
 As the d-block elements lies between the s and
p block elements, they are also referred to as
the transition elements.

The elements of the group 3 – 12 in which the d – orbitals

are progressively filled are called d – block elements.
As the d-block elements lies between the s and p block elements, they are
also referred to as the transition elements.
Three main series of Transition Elements
 3d series

The 3d series or first transition series involves filling up of 3d orbitals. It

starts from Scandium (Z=21) and goes up to Zinc (Z=30).
 4d series

The 4d series or second transition series involves filling up of 4d orbitals. It

starts from Yttrium (Z=39) and goes up to Cadmium (Z=48).
 5d series

The 5d series or third transition series involves filling up of 5d orbitals. The first
element of this series is Lanthanum(Z=57). It is followed by fourteen elements called
lanthanides which involves filling up of 4f orbitals. The next nine elements from
Hafnium (Z=72) to Mercury(z=80) belong to 5d series.
 6d series

The 6d series or fourth transition series involves filling up of 6d orbitals. The first
element of this series is Actinium(Z=89). It is followed by fourteen elements called
actinides which involves filling up of 5f orbitals. The 6d series is an incomplete series.
 What are Transition elements?
The element which has incomplete d-orbital in its ground state or in any one of its
oxidation state.

Zinc, cadmium and mercury are not regarded as transition metals.(non-transition elements)
As they have full Filled configuration in their ground state as well as in their common
oxidation. [General outer EC = (n-1) ]

Scandium is a transition element but Zinc is not.

Because Scandium has incompletely filled d orbitals in its ground state but
Zn have full configuration in their ground state & +2 oxidation state.

Copper atom has completely filled d orbital (3) in its ground state, yet it is transition element.
Copper (Z = 29) can exhibit +2 oxidation state wherein it will have incompletely filled d-
orbitals (3d), hence a transition element.
 Electronic Configuration of the d-block elements

3d series

General electronic configuration:

(n-1) d1-10ns1-2.
 Exceptional Configuration of Copper & Chromium

 This is due to the fact that half-filled or completely filled orbitals impart greater
stability to an atom.
 Because of very little energy difference between (n-1)d and ns orbitals.
 General Characteristics
Of
d-block Elements

ST. BRITTO'S ACADEMY STD XII

 Characteristics of Transition elements

1. They show paramagnetic behavior.

2. They show variable oxidation state.
3. They exhibit catalytic properties.
4. They generally form complex compounds.
5. They generally form coloured compounds.

What are transition elements? Write two

characteristics of transition elements.

ST. BRITTO'S ACADEMY STD XII

 Why transition elements exhibit these properties?

The d orbitals of the transition elements project to the

periphery of an atom more than the other orbitals (i.e., s & p)
and hence they are more influenced by the surroundings as
well as affecting the atoms or molecules surrounding them.

Transition elements show greater period similarities and

1
some group similarities.

ST. BRITTO'S ACADEMY STD XII

 Physical Properties of Transition Elements
 They have high tensile strength.
 The are malleable & ductile.
 They have high thermal and electrical conductivity.
 They are lustrous.
 They are very hard and low volatile.(Except Zn, Cd & Hg).
 They have high boiling point and melting point.
Why Zn, Cd and Hg are soft metal?
Due to the absence of unpaired electrons.

(Weak interatomic metallic bonding)

 Lattice Structures of Transition Metals

 Except Zn, Cd, Hg & Mn, they have one or more typical metallic structures at room
temperature.
 This is because they have full filled & half filled configuration, their chemistry
revolves more around the s electrons.
 Therefore they show more typical metallic structures like s block elements.
ST. BRITTO'S ACADEMY STD XII
 Why Transition metals have high boiling point &
melting point?

 Transition elements have unpaired (n-1)d

electrons in addition to ns electrons.
 Due to these unpaired electrons, they form
strong interatomic metallic bond.
 As the number of unpaired electrons
increases, strength of the metallic bond
increases.

ST. BRITTO'S ACADEMY STD XII

 Trends in boiling point & melting point in a series
 As we move from left to right along the transition metal
series, melting point first increases as the number of
unpaired d electrons available for metallic bonding increases,
reach a maximum value and then decreases, as the
d electrons pair up and become less available for bonding.

 In any row the melting points of these metals rise to a

maximum at (Cr, Mo) except for anomalous values of Mn
and Tc and fall regularly as the atomic number increases.

 Mn ([Ar] ) & Tc ([Kr] ) has stable half filled configuration, as a

result 3d electrons are more tightly held by its nucleus and
this reduces delocalization of electrons. Thus resulting in
weaker interatomic metallic bond.
 Enthalpy Of Atomisation
 It is defined as enthalpy change for the total separation of all the atoms present in an element or compound.
 Transition elements have high enthalpy of atomization.
 This is because they have high effective nuclear charge and large number of unpaired electrons.
 Hence, they form strong metallic bonds.
 Thus large amount of energy is required to separate the atoms i.e., high enthalpy of atomisation,.

1. Why transition elements have high enthalpy of atomisation?

2. Why iron has higher enthalpy of atomisation than that of copper?
(Hints: Iron has more number of unpaired electrons than copper)
ST. BRITTO'S ACADEMY STD XII
 Trends in enthalpy Of Atomisation down the series

 Metals of 2nd and 3rd transition series have greater

enthalpy of atomisation than corresponding elements
of first transition series.
 As a result of frequent M-M bonding due to greater
special extension of 4d & 5d orbitals as compared to 3d
orbitals.

ST. BRITTO'S ACADEMY STD XII

 Variation in atomic and ionic sizes of transition metals
 Generally along the period atomic radius ↓
 But for the 3d transition elements, atomic radius ↓ from Sc to V ,
thereafter up to Cu the atomic radius nearly remains the same.
Reason: Poor shielding effect of d electrons &
repulsion of 3d & 4s electrons
 As we move from Sc toZn in 3d series the extra electrons are added to
the 3d orbitals, the added 3d electrons only partially shield the increased
nuclear charge and hence the effective nuclear charge increases slightly.
 However, the extra electrons added to the 3d sub shell strongly repel the
4s electrons and these two forces are operated in opposite direction and
as they tend to balance each other, it leads to constancy in atomic radii.
 At the end of the series, d – orbitals of Zinc contain 10 electrons in which
the repulsive interaction between the electrons is more than the
effective nuclear charge and hence, the orbitals slightly expand and
atomic radius slightly increases.

ST. BRITTO'S ACADEMY STD XII

 Variation in atomic and ionic sizes of transition metals
 Generally down a group atomic radius ↑.
 The same trend is expected in d block elements also.
(ie) 3d<4d<5d but 3d<4d≈5d.
 This is due to lanthanoid contraction.
Along the period Z ↑, Z*↑, Shielding effect ↓ Size ↓
In 5d series, electrons are getting filled in 4f subshell
before 5d, as f electrons have very poor shielding effect,
The greater effective nuclear charge pulls the electrons in
more closely, shrinking the atoms. So, there is an expected
decrease in atomic radius
 Because of the similar atomic radii of 4d & 5d series, they
exhibit much more similar physical and chemical properties
than expected on the usual family relationship.
 Variation in atomic and ionic sizes of transition metals
Why atomic radii of third (5d) transition series are similar to that of second (4d) transition
series?
Or
Why Zr & Hf have almost similar atomic radii?
 This is due to Lanthanoid contraction.
 It can be explained on the basis of shielding effect.
 We know that 4f sub shell have a diffused shapes and therefore the shielding effect of 4f
electrons relatively poor.
 As a result, the effective nuclear charge experienced by the 4f electrons increases, which
results in more attractive pull of nucleus on outer electron.
 In the case of post lanthanoid elements like 5d series, 4f subshell is filled and is not very
effective at shielding the outer electrons.
 Density of transition elements
 The transition elements are much denser
than the s-block elements.
Due to the decrease in the size of the
atoms because of consequent increase in
the nuclear charge results in the compact
structure of the elements.
 Along the period, Density of transition
metals ↑ from Sc to Cu & slightly ↓ for Zn
(Zinc contain 10 electrons in which the
repulsive interaction between the
electrons is more than the effective
nuclear charge and hence, the orbitals
slightly expand and atomic radius
slightly increases.
 Ionization Enthalpies of transition elements
 Ionization energy of transition element is intermediate between those of s and p block
elements.
 As we move from left to right in a transition metal series, the ionization enthalpy
increases as expected.
 This is due to increase in nuclear charge corresponding to the filling of d electrons.
 I.E1 < I.E2 < I.E3
 The irregular trend in the first ionization enthalpy of 3d series is because of exchange
energy (Re-organization of electrons and transfer of s electron into d-orbital).
 To form ion from the gaseous atom, three enthalpies are taken into consideration
namely,
i. Enthalpy of atomisation.
ii. First ionization enthalpy.
iii. Second ionization enthalpy.
 Practice questions based on Ionization Enthalpies
Why Chromium has lower first ionization enthalpy?
Cr - [Ar] 34
- [Ar] 3
On removing an electron, Chromium attains half filled stable configuration.
Why zinc has higher first ionization enthalpy?
Zn - [Ar] 34
- [Ar] 34
On removing an electron, Zinc loses its fully filled stable configuration, so it has higher first
ionization enthalpy.

Why Manganese has very high third ionization enthalpy?

- [Ar] 3
- [Ar] 3
On removing an electron, loses its half filled stable configuration, so it has higher third
ionization enthalpy.
 Try it out….
1. Why zinc has considerably low second ionization enthalpy?
2. Why Manganese has considerably low second ionization enthalpy?
3. Why Cu, Ni & Zn have very high third ionization enthalpy?
4. Why has very high third ionization enthalpy?

ST. BRITTO'S ACADEMY STD XII

 Oxidation States of transition elements
 Transition elements exhibit variable oxidation states:
Reason: due to incompletely filled d-orbitals & energy difference between
(n-1)d orbital and ns orbital is very small.
 The first transition metal Scandium exhibits only +3 oxidation state. But all other
transition elements exhibit variable oxidation states.
 At the beginning of the series, +3 oxidation state is stable but towards the end +2
oxidation state becomes stable.
 The number of oxidation states increases with the number of electrons available, and it
decreases as the number of paired electrons increases.
 Hence, the first and last elements show less number of oxidation states and the middle
elements with more number of oxidation states.
 For example, the first element Sc has only one oxidation state +3; the middle element
Mn has six different oxidation states from +2 to +7. The last element Cu shows +1 and +2
oxidation states only.
 Oxidation States of transition elements

ST. BRITTO'S ACADEMY STD XII

 Oxidation States of transition elements
 In transition series, oxidation states differ from each other by unity
(eg:, , whereas in non transition elements OS differ by two.
 In p–block , heavier members -lower os (due to inert pair effect).
In d-block, heavier members -higher os
 Ex: In group 6,(Cr, Mo, W)
Mo(VI) and W(VI) more stable than Cr(VI).
Thus Cr(VI) in the form of dichromate in acidic medium is a strong
Oxidising agent, whereas MoO3 and WO3 are not.
 Transition elements has low os, when they form complex with ligands
having both π- and σ- character. Example: Ni(CO)4, Fe(CO)5
(os of Ni & Fe is Zero)

ST. BRITTO'S ACADEMY STD XII

 Try it out….

Frequently Asked Questions….

1. Why do transition elements show variable oxidation state?
Due to small energy difference between (n-1)d & ns orbital as a result both
(n-1)d &ns electrons take part in bond formation.
2.Which element shows the maximum oxidation state?
Mn, due to maximum number of unpaired electrons present in (n-1)d orbital.
3. Which element in the first transition series exhibits +1 oxidation state most frequently? why?
Cu. This is because after losing an electron it attains stable 3 configuration.
4. Which element in the first transition series of transition elements doesnot exhibit variable
oxidation states? Why?
Sc, After losing three electrons all the orbitals in are fully filled.

ST. BRITTO'S ACADEMY STD XII

 Standard electrode potentials
Of
d block elements

ST. BRITTO'S ACADEMY STD XII

 Standard Electrode Potential Of transition metals
 Redox reactions involve transfer of electrons from one reactant to another.
 Such reactions are always coupled, which means that when one substance is
oxidised, another must be reduced.
 The substance which is oxidised is a reducing agent and the one which is reduced is
an oxidizing agent.
 The oxidizing and reducing power of an element is measured in terms of the
standard electrode potentials.
 Standard electrode potential is the value of the standard emf of a cell in which
molecular hydrogen under standard pressure ( 1atm) and temperature (273K) is
oxidised to solvated protons at the electrode.
 If the standard electrode potential (), of a metal is more negative, the metal is a
powerful reducing agent, because it loses electrons easily.
 If the standard electrode potential (), of a metal is positive, the metal is powerful
oxidizing agent, because it gains electron easily.
 Trends in the / M Standard electrode potentials
 / M Standard electrode potential is defined as enthalpy change, when
solid metal atoms
are converted to ions in solution.
 /M standard electrode potential value
/ M = ∆a∆i depends
∆i + ∆ on three parameters
namely,

ST. BRITTO'S ACADEMY STD XII

 Trends in the / M Standard electrode potentials
• In 3d series as we move from Ti to Zn, the standard
reduction potential / M value is approaching towards
less negative value.
• Among 3d series, high energy required to transform
M - (∆a∆i, ∆i) is balanced by its hydration
enthalpy.
• Across the series, sum of first and second ionization
enthalpy generally increases. So / M value becomes
less negative.
/ M = less negative
∆a∆i ∆i > ∆

ST. BRITTO'S ACADEMY STD XII

 W / M Standard electrode potentials?

The Eθ(M2+/M) value for copper is positive (+0.34V).

/ M ἀ ∆a∆i ∆i + ∆
 Trends in the / M Standard electrode potentials
 There are two deviations., In the general trend, value
for manganese, nickel and zinc are more negative
than the regular trend.
 Nickel has more negative hydration enthalpy, so it
has more negative / M value.
 In the case of manganese and zinc, due to extra
stability which arises due to the half filled d5
configuration in Mn2+ and completely filled d10
configuration in Zn2+. They have relatively low
second ionization enthalpy. so it has more negative /
M value.
/ M = more negative
∆a∆i ∆i < ∆

ST. BRITTO'S ACADEMY STD XII

 Trends in the / Standard electrode potentials

 The standard electrode potential for the / half-cell gives the relative stability
between and
 If the standard electrode potential for the / is high, then the ion is more stable than its
ion.
 If the standard electrode potential for the / is low, then the ion is less stable than its ion.
 Trends in the / Standard electrode potentials

ST. BRITTO'S ACADEMY STD XII

 Frequently Asked Questions….
Give reasons for the following:
i. Of the species, is strongly reducing while manganese(III)is strongly oxidizing. is
reducing as its configuration changes from 3 to 3, the latter having a stable
configuration ,half-filled t2g level. On the other hand, the change from toresults in the half-
filled (3d5) configuration which is an extra stable configuration.
ii. is a stronger reducing agent than .
Ans: Because change in 3→ 3 occurs in case of to But 3→ 3 occurs in case of to .In a
medium (like water) is more stable as compared to
iii. ion is not stable in aqueous solutions.
in aqueous solution undergoes disproportionation, i.e.,2(aq) →(aq) + Cu(s) .The value for
this is favourable.
IV. For the first row transition metals the (M) , explain the irregularities in the values.
Ans:The (M) values are not regular which can be explained from the irregular variation of
ionisation enthalpies (Δi H1 + Δi H2) and also the sublimation enthalpies
 Frequently Asked Questions….
Give reasons for the following:
V. Cobalt (II) is stable in aqueous solution but in the presence of complexing reagents it is
easily oxidized. .
Ans:Because is more stable than .OR Due to CFSE, which more than compensates the 3rd
IE.
vi. E0value for the /couple much more positive than that /or /
Ans: Much larger third ionisation energy of Mn (where the required change is to ) is
mainly responsible for this. This also explains why the +3 state of Mn is of little importance.
vii. Following are the transition metal ions of 3d series:
, , , (Atomic number :Ti = 22,V= 23, Mn = 25, Cr = 24)
Answer the following : (a) Which ion is most stable in an aqueous solution and why? (b)
Which ion is a strong oxidizing agent and why?
(a) Cr3+, half filled t
(b) , due to stable configuration in
 Trends in stability of higher oxidation states

List of the stable halides of the 3d series of the transition elements

 Trends in stability of higher oxidation states
 TiX4, VF5 and CrF6 have the highest oxidation numbers.
 The highest oxidation state +7, for manganese is not seen in simple halides, but MnO3F is
known.
 VF5 is stable, while the other halides undergo hydrolysis to give oxohalides of the type
VOX3.
 Fluorine stabilises higher oxidation states either because of its higher lattice energy or
higher bond enthalpy.
 Fluorides are unstable in their lower oxidation states, and, therefore, chlorides, bromides
and iodides exist in +2 oxidation state, while fluorides do not.
 Copper in +2 oxidation state forms all the halides, except iodides, because cupric ion
oxidises iodide to iodine.
 The stability of Cu +2ions rather than Cu+ ions is due to the higher negative hydration
enthalpy of cupric ion (Cu +2 ) than cuprous ion (Cu+ ), which more than compensates for
the second ionisation enthalpy of copper.
 Trends in stability of higher oxidation states

List of the stable oxides of the 3d series of the transition elements

 Transition Metal oxides with ↓ OS are basic Oxides, ↑ OS are acidic Oxides, Intermediate OS
amphoteric Oxides. (OS – Oxidation State)
 Frequently Asked Questions….
Give reasons for the following:
i. Mn shows the highest oxidation state of +7 with oxygen but with fluorine, it shows
oxidation state of +4.
Solution:

ii.O2​and F2​both stabilize higher oxidation states of metals but O2​exceeds F2​in doing so.
Solution:
 Chemical reactivity and

 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.
 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.
 Chemical reactivity and
 Chemical reactivity of transition metals are related to their E0 values

 WKT: E0 = -ve (Oxidation, Reducing agent) , E0 = +ve (Reduction, Oxidising agent)

 E0 M2+/M means M2+ → M , E0 = -ve (Reduction is less feasible, Oxidation is possible)
 less negative E0 values for M2+/M along the series indicate a decreasing tendency to
form divalent cations.
 More negative E0 values than expected for Mn, Ni and Zn show greater stability for
Mn2+, Ni2+ and Zn2+.
 E0 values for the redox couple M3+/M2+ indicate that Mn3+ and Co3+ ions are the
strongest oxidizing agents in aqueous solution whereas Ti 2+ , V 2+ and Cr 2+ are
strongest reducing agents and can liberate hydrogen from a dilute acid, e.g.,
 General Properties of
d block elements

ST. BRITTO'S ACADEMY STD XII

 Magnetic Properties
Substances, depending on their behaviour in an
external magnetic field, are classified into 2 types
Paramagnetic substances:
 These are weakly attracted to a magnetic field.
 This is due to the presence of unpaired electrons.
 They have incompletely filled d orbitals.
Diamagnetic substances:
 These are repelled to a magnetic field.
 This is due to the absence of unpaired electrons in
the atom.
 The have completely filled d orbitals.

ST. BRITTO'S ACADEMY STD XII

 Magnetic moment of transition elements
 The magnetic moment of the electron is due to spin angular momentum as well as
orbital angular momentum.
 For 3d series of elements, the orbital angular momentum of the electrons is small,
and hence, its contribution in these elements can be ignored.
 Therefore, the observed magnetic moment can be ascribed to the spin of the
unpaired electrons only.
 The magnetic moment for these elements is determined by the spin only formula
μ = √(n(n+2))
n = number of unpaired electrons orbital motion
μ = magnetic moment in units of Bohr Magneton (BM) Spin motion
When n=1, µ= 1.73 BM
nucleus
When n =2, µ=2.83
 Calculated and observed magnetic moments for few 3d series ions

Along the 3d-series paramagnetism increases upto the middle and then decreases. (Pairing start)
o In case of iron, cobalt and nickel, the unpaired electron spins are much pronounced.
o As a result, these elements are much more paramagnetic than the rest of the elements.
o These elements are called ferromagnetic substances.
 Frequently Asked Questions….
Give Reason:

1. Most of the transition metal ions are paramagnetic.

Because transition elements contain unpaired electrons in their (n-1) d sub shells.
2. exhibits paramagnetism.
Because contain unpaired electrons in d sub shells.
3. The magnetic moment of a +2 ion in aqueous solution if its at.no is 25.

ST. BRITTO'S ACADEMY STD XII

 Formation of complex compounds
 The transition elements have a tendency to form coordination compounds or complex
compounds.
 Complex compounds are those in which a central atom or ion is surrounded by a number
of anions or neutral molecules possessing a lone pair of electrons.
 These surrounding anions or molecules are called ligands.
EX: Hexaamminecobalt (III) Chloride, Potassium ferrocyanide (ll),
and Nickel Tetracarbonyl (0).
 The tendency of the transition metals to form large number of complexes is due to:
 Their relatively small size of the metal ions.
Give reason:
 High positive charge density on metal ions.
The transition metals form a large
 Presence of vacant d-orbitals for bond formation. number of complex compounds.

ST. BRITTO'S ACADEMY STD XII

 Formation of coloured ions
 Most d-block metal compounds are coloured in their solid or liquid states.
due to
 Unpaired electron result in d-d transition.
 Charge transfer spectrum.
 Polarisation.
 In the case of transition metal ions, under the influence of ligands, the degeneracy of the
5 d-orbitals is lost and they separate into two distinct energy levels. eg set and t2g set.
 When white light is incident on a transition metal ion, the electron in the lower energy d-
orbital set absorbs certain radiations and gets promoted to a d-orbital set of higher
energy. (d-d transition)

 The transmitted radiation free from the absorbed radiations is the complementary colour
of the absorbed light.
 This complementary colour is the colour of the substance.
Formation of coloured ions
 Formation of coloured ions
 Charge transfer spectrum:
Absorption and emission of light
in d-block metal cation having
d0 or d10 configuration is induced
by charge transfer spectra.
K2 Cr2 O7 → d0 → Orange red
K2 CrO4 → d0 → Yellow
KMnO4 → d0 → Purple
Cu2 O → d10 → Ruby red

 Polarisation:
 Frequently Asked Questtions….
Give Reason:
1. Transition elements form coloured complex.
Transition metal ions generally possess one or more unpaired electrons. When visible light falls on a transition
metal compound or ion, the unpaired electrons present in the lower energy d-orbital get promoted to high
energy d-orbitals, called d-d transition, due to the absorption of visible light. Since, the energy involved in d-d
transition is quantised, only a definite wavelength gets absorbed, remaining wavelengths present in the visible
region got transmitted. Therefore, transmitted light shows some colour complementary to the absorbed colour.

2. Most of the transition metal ions in solution as well as in solid states are coloured.
This is due to the presence of unpaired electrons in d-orbitals of the transition metal ions. It is because of
these d – d transitions.
3. salts are white ,but are blue.
are blue due to the unpaired electrons in d-orbitals.
4. salts are colourless while salts are Coloured.
are Coloured due to the presence of unpaired electrons in d-orbitals
 Catalytic Properties
 The transition metals and their compounds are known for their catalytic activity. Many industrial processes
use transition metals or their compounds as catalysts.
 Ex: i. V2O5 is used in the manufacture of sulphuric acid by the contact process
ii. Finely divided iron is used in Haber's process for the manufacture of ammonia.
iii. Nickel is used in the hydrogenation of oils.
Catalytic action:
• Formation of bonds between reactant molecules and atoms of the surface of catalyst.
(first row transition metals utilise 3d and 4s electrons for bonding).
• Concentration of the reactants at the catalyst surface increases and also weakens the bonds in the
reacting molecules. (the activation energy is lowering)
• For example, iron(III) catalyses the reaction between iodide and persulphate ions.
 Catalytic Properties

 Reasons:
 ability to show variable oxidation state and form complexes.
 form unstable intermediate compounds with reactant molecules.
 provide a new path with lower activation energy for a reaction.
 provide a suitable surface for the reaction to occur.

Most of the transition metals and their compounds possess catalytic properties. Why?
 Formation of interstitial compounds
 An interstitial compound is a compound that is formed when
small atoms like hydrogen, boron, carbon or nitrogen are
trapped in the interstitial holes in a metal lattice.
 They are usually non-stoichiometric compounds.
 Transition metals form a number of interstitial compounds
Ex: TiC, Fe3H , Mn4N, VH0.56 and TiH1.7 etc.
 Interstitial compounds are neither ionic nor covalent in nature.
 Characteristics of interstitial compounds are:
 They have high melting points, higher than those of pure metals.
 They are very hard
(some borides approach diamond in hardness).
 They retain metallic conductivity.
 They are chemically inert.
Transition metals form interstitial compounds. Why?
Because size of C, N, O, and B is similar to size of interstitial voids of transition metals.
 Alloy Formation
 An alloy is a blend of metals prepared by mixing the components.
 Alloys may be homogeneous solid solutions in which the atoms of one metal are distributed randomly among
the atoms of the other.
 To form an alloy the difference between the atomic radii of solvent and solute is less than 15%.
Hence, one metal atom can be easily replaced by another metal atom from its crystal lattice to form an alloy.
 Because of similar radii and other characteristics of transition metals, alloys are readily formed by these metals.
 Alloys are classified according to their components into two distinct types, namely, ferrous and non-ferrous.
Ferrous alloys:
Ferrous alloys contain iron, carbon, and one or two of the other elements like
chromium, vanadium, tungsten and molybdenum.
EX: Steel & Stainless steel
Non-ferrous alloys:
These alloys do not contain iron as one of the components.
EX: Brass (copper & zinc), Bronze (copper & tin)

Most of the transition metals form alloys. Why?

This is because of their similar radii
Some Important Compounds of Transition Elements

Oxide and Oxoanions of Metals :

 Oxides are formed by the reaction of metals with
O2 at high temperature.
 Except the first member of 3d series- Scandium,
all other transition elements form ionic metal oxides.
 The oxidation number of metal in metal oxides
ranges from +2 to +7.
As the oxidation number of a metal ↑, ionic character ↓
EX: Mn2O7 , CrO3 and V2 O5 are covalent,
‫ ؞‬have low melting points.
 Some Important Compounds of Transition Elements
Oxide and Oxoanions of Metals :
Transition Metal oxides with
↓ OS are basic Oxides, ↑ OS are acidic Oxides,
Intermediate OS amphoteric Oxides. (OS – Oxidation State)
 Mostly higher oxides are acidic in nature.
EX: Mn2O7 dissolves in water to give permanganic acid (HMnO4 )
CrO3 gives chromic acid (H2CrO4)
dichromic acid (H2Cr2O7).
 lower oxides may be amphoteric or basic.
EX: Chromium (III) oxide - Cr2O3, is amphoteric
Chromium(II) oxide - CrO, is basic in nature.
V2 O3 - basic
V2 O4 - less basic
V2ACADEMY
ST. BRITTO'S O5 - amphoteric
STD XII
 Some Important Compounds of Transition Elements
Potassium Dichromate (K2 Cr2 O7 )
 Ore: Ferrochrome or chromite (FeO.Cr2 O3 ) or (FeCr2 O4 )
 Preparation:
Step:1 Fusion of chromite ore with Na2 CO3 or K2 CO3 in excess air.

Step:2 Yellow solution ( Na2 CrO4) is filtered and acidified

with H2 SO4 to give a solution from which
orange sodium dichromate Na2 Cr2O7 .2H2 O is crystallised.

Step:3 Solution of sodium dichromate is treated with potassium chloride.

Orange crystals of potassium dichromate crystallise out.
ST. BRITTO'S ACADEMY STD XII
 Some Important Compounds of Transition Elements
Potassium Dichromate (K2 Cr2 O7 )
 Properties:
 Sodium dichromate is more soluble than potassium dichromate.
 Chromates and dichromates are interconvertible in aqueous solution
depending upon pH of the solutions as their oxidation states are same.
Low pH – dichromate (acidic)
High pH – Chromate (basic)

 Structures of Chromate & Dichromate ion

The chromate ion is
tetrahedral whereas the
dichromate ion consists of
two tetrahedra sharing
one corner with Cr–O–Cr
ST. BRITTO'S ACADEMY STD XII
bond angle of 126°.
 Some Important Compounds of Transition Elements
Potassium Dichromate (K2 Cr2 O7 )
 Properties:
 Sodium and potassium dichromates are strong oxidizing agents
Acidified K2 Cr2 O7 will oxidise iodides to iodine,
sulphides to sulphur, tin (II) to tin (IV) and iron (II) salts to iron (III).
In acidic solution, its oxidising action can be represented as follows:
half-reaction for potassium dichromate
Cr2 O7 2– + 14 H+ + 6 e - → 2 Cr 3+ + 7 H2 O (E0 = 1.33V)
half-reaction for the reducing agents
6 I– → 3I2 + 6 e– 6 Fe 2+ → 6Fe 3+ + 6 e-
3 Sn 2+ → 3Sn 4+ + 6 e - 3 H2 S → 6H+ + 3S + 6e–

ST. BRITTO'S ACADEMY STD XII

 Some Important Compounds of Transition Elements
Potassium Dichromate (K2 Cr2 O7 )
 Properties:
 full ionic equation may be obtained by adding the half-reaction for
potassium dichromate to the half-reaction for the reducing agent.
EX:
Cr2 O7 2– + 14 H+ + 6 e - → 2 Cr 3+ + 7 H2 O
6 Fe 2+ → 6Fe 3+ + 6 e-

Cr2 O7 2– + 14 H+ + 6 Fe 2+ → 2 Cr 3+ + 6 Fe 3+ + 7 H2 O

Cr2 O7 2− + 14H+ + 6I− → 2Cr3+ + 7H2 O + 3I2

Cr2 O7 2− + 3H2 S + 8H+ → 2Cr3+ + 3S + 7H2 O
Cr2 O7 2− + 14H+ + 3Sn2+ → 3Sn4+ + 2Cr3+ + 7H2 O
CrSTD
ST. BRITTO'S ACADEMY
2 OXII 2– + 14 H+ + 6 Fe 2+ → 2 Cr 3+ + 6 Fe 3+ + 7 H2 O
7
 Some Important Compounds of Transition Elements

Sodium & Potassium Dichromate (K2 Cr2 O7 )

 Uses:
 Sodium dichromate:
used as an oxidising agent in organic chemistry.
(has a greater solubility in water )
 Potassium dichromate:
a very important chemical
used in leather industry
used as an oxidant for preparation of many azo compounds.
used as a primary standard in volumetric analysis.

ST. BRITTO'S ACADEMY STD XII

 Some Important Compounds of Transition Elements
Potassium Permanganate (KMnO4 )
 Ore: Pyrolusite (MnO2 )
 Preparation: Fusion of MnO2 with an alkali metal hydroxide and an
oxidising agent like KNO3 , produces K2 MnO4 which
disproportionates in a neutral or acidic solution
to give permanganate.

 Commercial preparation:

ST. BRITTO'S ACADEMY STD XII

 Some Important Compounds of Transition Elements
Potassium Permanganate (KMnO4 )
 Laboratory Preparation: manganese (II) ion salt is oxidised by
peroxodisulphate to permanganate.

 Structure:
• pπ-dπbonding takes place by
overlap of p orbitals of oxygen
with d orbitals of manganese.
• Manganate (paramagnetic)
because of one unpaired
electron but the
permanganate is diamagnetic
due to the absence of
unpaired electron.
ST. BRITTO'S ACADEMY STD XII
 Some Important Compounds of Transition Elements
Potassium Permanganate (KMnO4 )
 Properties: .

 dark purple (almost black) crystals which are isostructural

with those of KClO4 .
 The salt is not very soluble in water (6.4 g/100 g of water at
293 K), but when heated it decomposes at 513 K.
2KMnO4 → K2 MnO4 + MnO2 + O2
 Intense colour and diamagnetism:
due to charge transfer spectrum.

ST. BRITTO'S ACADEMY STD XII

 Some Important Compounds of Transition Elements
Potassium Permanganate (KMnO4 )
 Properties: A good oxidising agent in acidic, basic or neutral medium.
 In acidic medium , KMnO4 is reduced to manganous salt.
MnO4 − + 8H+ + 5e− → Mn 2+ + 4H2 O
Acidified permanganate solution oxidises oxalates to carbon dioxide,
iron(II) to iron(III), nitrites to nitrates and iodides to free iodine.
The half-reactions of reductants are:
5 C2 O4 2− → 10 CO2 + 10 e−
5 Fe2+ → 5 Fe3+ + 5e –
5NO2– + 5H2 O → 5NO3– + 10H+ + l0e –
10I– → 5I2 + 10e –
NOTE:
To acidify KMnO4 , only H2 SO4 is used and not HCl or HNO3 because HCl reacts
with KMnO4 and produce Cl2 while HNO3 , itself acts as oxidizing agent.
ST. BRITTO'S ACADEMY STD XII
 Some Important Compounds of Transition Elements
Potassium Permanganate (KMnO4 )
 Properties: A good oxidising agent in acidic, basic or neutral medium.
 In slightly alkaline or neutral medium ,
KMnO4 is reduced to insoluble MnO2.
MnO4 − + 3e− + 2H2 O → MnO2 + 4OH−

Alkaline or neutral KMnO4 solution oxidizes

I− to IO3 − , S2 O3 2− to SO4 2− , Mn 2+ to MnO2 etc.

The full reaction can be written by adding the half-

reaction for KMnO4 to the half-reaction of the
reducing agent, balancing wherever necessary.

ST. BRITTO'S ACADEMY STD XII

 Some Important Compounds of Transition Elements
Potassium Permanganate (KMnO4 )
Important oxidising reactions :

ST. BRITTO'S ACADEMY STD XII

 Some Important Compounds of Transition Elements
Potassium Permanganate (KMnO4 )
Important oxidising reactions :

Uses:  In analytical chemistry

 Oxidant in preparative organic chemistry.
 bleaching of wool, cotton, silk and other textile fibres
 for the decolourisation of oils.
ST. BRITTO'S ACADEMY STD XII
Frequently Asked Questions….
 Write the formula of an oxo-anion of Manganese (Mn) in which it shows the
oxidation state equal to its group number.
Answer: Permanganate ion, i.e., MnO4– with oxidation number +7.

 Write the formula of an oxo-anion of Chromium (Cr) in which it shows the

oxidation state equal to its group number.
Answer: Cr2O72- (dichromate ion) in which oxidation state of Cr is +6
which equal to its group number 6.
 Complete the following chemical equations :
(i) MnO4- (aq) + S2O32- (aq) + H2O (l) →
(ii) Cr2O72- (aq) + Fe 2+ (aq) + H+ (aq) →

ST. BRITTO'S ACADEMY STD XII

Frequently Asked Questions….
 What is meant by ‘disproportionation’? Give an example of a
disproportionation reaction in aqueous solution.
Ans: In a reaction an element undergoes self-oxidation as well as self-reduction
forming two different compounds is called disproportionation reaction.
EX:

 Describe the preparation of potassium permanganate. How does the acidified

permanganate solution react with oxalic acid? Write the ionic equations for the
reactions.

 Describe the oxidising action of potassium dichromate and write the ionic
equations for its reaction with
(i) iodine (ii) H2S.
ST. BRITTO'S ACADEMY STD XII
Frequently Asked Questions….
 When chromite ore FeCr2O4 is fused with NaOH in presence of air, a yellow coloured
compound (A) is obtained which on acidification with dilute sulphuric acid gives a
compound (B). Compound (B) on reaction with KCl forms an orange coloured
crystalline compound (C).
(i) Write the formulae of the compounds (A), (B) and (C).
(ii) Write one use of compound (C).
Ans: (i) (A) → Sodium chromate Na2CrO4
(B) → Sodium dichromate Na2Cr2O7
(C) → Potassium dichromate K2Cr2O7
(ii) (C) is used as a strong oxidising agent in acidic medium in volumetric analysis.
 Write the balanced ionic equation for the reaction between ferrous sulphate
and acidified potassium permanganate solution.
Ans: MnO4– + 5Fe+2 + 8H+ → Mn+2 + 5Fe+3 + 4H2O
ST. BRITTO'S ACADEMY STD XII
Frequently Asked Questions….
 Describe the preparation of potassium dichromate from chromite ore.
What is the effect of change of pH on dichromate ion?
 Complete the following chemical reaction equations :

ST. BRITTO'S ACADEMY STD XII

 The inner transition elements
(f block )

ST. BRITTO'S ACADEMY STD XII

 What are inner transition elements?

++++++++++++++++++++++
+++++++++++++++++

 The elements in which last electron enters the anti penultimate shell i.e., (n-2) f
orbital are called f block elements.
 Due to such electronic configuration where the last electron enters the 4f or 5f
orbitals that are lower than the outermost electrons, f-block elements are also
named as inner transition elements.
 Lanthanoids

++++++++++++++++++++++
1) +++++++++++++++++
In the inner transition elements there are two series of elements.
Lanthanoids ( previously called lanthanides)
2) Actinoids ( previously called actinides)
 The elements in which the last electron enters the 4f orbitals are called 4f–block
elements or first inner transition series.
 These are also called lanthanides or lanthanons, because they come immediately
after lanthanum.
 Lanthanoid series consists of fourteen elements from Cerium (58Ce) to Lutetium
(71Lu) following Lanthanum (57La).
 Electronic Configuration of Lanthanoids

Atoms of these elements have electronic configuration with

6s2 common but with variable occupancy of 4f level
++++++++++++++++++++++
+++++++++++++++++
In Gadolinium (Gd) and Lutetium (Lu) the 4f orbital, are half-filled
and completely filled, so one electron enters 5d orbitals.
 Hence the general electronic configuration of 4f series of elements
can be written as [Xe] 4f1-145d0-16s2 beginning at cerium and ending at
lutetium(Z = 71).
 Electronic Configuration of Lanthanoids

++++++++++++++++++++++
+++++++++++++++++
 Atomic and Ionic Radii of Lanthanoids
Lanthanoid contraction
 As we move across 4f series, the
++++++++++++++++++++++
atomic and ionic radii of
lanthanoids show gradual
+++++++++++++++++
decrease with increase in atomic
number.
This continuous decrease in size
of atoms and ions is known as
lanthanoid contraction..
 Atomic and Ionic Radii of Lanthanoids
Cause of Lanthanoid contraction
 As we move from one element to another in 4f series ( Ce to Lu)
++++++++++++++++++++++
the nuclear charge increases by one unit and an additional
electron is added into the same inner 4f sub shell.
+++++++++++++++++
 We know that 4f sub shell have a diffused shapes and therefore
the shielding effect of 4f electrons relatively poor.
 Hence, with increase of nuclear charge, the valence shell is pulled
slightly towards nucleus.
 As a result, the effective nuclear charge experienced by the 4f
electrons increases and the size of Ln 3+ ions decreases.
 Consequences of Lanthanoid contraction

++++++++++++++++++++++
+++++++++++++++++
 Consequences of Lanthanoid contraction
Similarities among lanthanoids in chemical properties:
 In the complete f - series only 10 pm decrease in atomic radii and 20 pm decrease in
ionic radii is observed.
 Because of this very small change in radii of lanthanoids, their chemical properties
++++++++++++++++++++++
are quite similar.
Hence lanthanoids are not separated based on their chemical properties but on their
+++++++++++++++++
difference in physicalproperties like solubility, fractional crystallization,
chromatography etc.
Basic nature of hydroxides:
 As we move from to , the basic character of ions decrease.
 Due to the decrease in the size of ions, the ionic character of Ln OH −bond decreases (covalent
character increases).
 If ionic character decreases, readily M-OH bond will not break to release OH- ions.
 This results in the decrease in the basic nature of hydroxides.
Ce(OH)3 – Most basic hydroxide
Lu(OH)3 – Least basic hydroxide
 Consequences of Lanthanoid contraction
Similarities in atomic radii of 2nd and 3rd transition series:
The elements of the second and third transition series resemble each other more
closely than the elements of the first and second transition series. For example
++++++++++++++++++++++
Series Element Atomic radius

+++++++++++++++++
3d Series Ti 132 pm
4d Series Zr 145 pm
5d Series Hf 144 pm

Electronegativity ,Ionisation enthalpy , Electrode potential , Reducing power, Density:

Electronegativity ↑, IE ↑ , E0 ↑, Reducing power ↓, Density ↑ from the element La to Lu
 Oxidation State of Lanthanoids
 The lanthanides contains two s-electrons in the outermost shell, ‫ ؞‬expected to exhibit a
characteristic oxidation state of +2. But for the lanthanides, the +3 oxidation is common.

++++++++++++++++++++++
+++++++++++++++++
 Some of the lanthanoids also show either +2 or +4 oxidation states, when they lead to :
(i) A inert gas configuration e.g. Ce 4+ ()
(ii) A half filled ‘f’ orbital e.g. Eu 2+, Tb 4+, ()
(iii) A completely filled ‘f’ orbital e.g.. Yb 2+ ()
 and ions have extra stability, it is due to the fact that they have exactly half filled and
completely filled f-orbitals respectively.
 Oxidation State of Lanthanoids
 Lower oxidation state act as reducing agent (Eu 2+, Yb 2+) and higher oxidation state
act as oxidising agent (Ce 4+, Tb 4+).
++++++++++++++++++++++
EX: Formation of Ce IV is favoured by its noble gas configuration,
but it is a strong oxidant reverting to the common +3 state.
+++++++++++++++++
Eo value for Ce 4+/ Ce 3+ 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.
Eu 2+ is a strong reducing agent changing to the common +3 state.
Similarly Yb 2+ which has f 14 configuration is a reductant.
TbIV has half-filled f-orbitals and is an oxidant.
 Lanthanoids show limited no. of oxidation state
Reason : as the energy gap between 5d and 4f subshell is significant.
 Frequently Asked questions….
Why and are good oxidizing agents in aqueous solution?
is more stable than ce4+. Hence gains an electron to become .
Hence acts as good oxidizing agent.
Similarly for
++++++++++++++++++++++
is more stable than .

+++++++++++++++++
Name a member of the lanthanoid series that is well known to exhibit +2 oxidation state?
Europium. Since has half filled configuration.

Why , andare good reducing agents in aqueous solution?

lose an electron to attain +3 oxidation state.

ST. BRITTO'S ACADEMY STD XII

 General characteristics of lanthanoids
Physical properties
++++++++++++++++++++++
 Nature: White silvery soft metals , tarnish in air readily.
 Hardness : increases with increase in atomic number.

+++++++++++++++++
 Melting points : range between 1000 to 1200 K but Sm being steel hard melts at 1623 K.
 Structure: Have typical metallic structure
 Conductivity: good conductors of heat and electricity.
 Colour: Except and ions are coloured due to excitation of electrons within f- level (f-f
transition).
 Magnetic property:
Except ,
all lanthanoid ions are paramagnetic due to presence of unpaired f electrons.
 General characteristics of lanthanoids
 Ionization enthalpy :
∆iH1- around 600 kJ mol–1, ∆iH2 - about 1200 kJ mol–1 comparable with calcium
but, with increasing atomic number, they behave more like aluminum.
++++++++++++++++++++++
Lanthanum, Gadolinium and lutetium have low 3rd ionization enthalpy,
because on losing their 3rd electron they attain stable configuration.
+++++++++++++++++
 Standard Electrode potential:
E0 for the half-reaction: Ln 3+ (aq) + 3e– → Ln (s) are in the range of –2.2 to –2.4 V
except for Eu for which the value is –2.0 V.
 Electropositive Character : High due to high IP
 Complex formation:
Do not have much tendency to form complexes
due to low charge density, their large size.
Lu +3 is smallest in size can only form complex.
 General characteristics of lanthanoids
Chemical properties

++++++++++++++++++++++
+++++++++++++++++
 General characteristics of lanthanoids
Uses

++++++++++++++++++++++
 For the production of alloy steels for plates and pipes.
Mischmetal (A well known alloy) which consists of a
+++++++++++++++++
lanthanoid metal (~ 95%), iron (~ 5%) & traces of S, C, Ca and Al.
used in Mg-based alloy to produce bullets, shell and lighter flint.

 Mixed oxides of lanthanoids are employed as catalysts in petroleum cracking.

 Some individual Ln oxides are used as phosphors in television screens

and similar fluorescing surfaces.
 Actinoids

++++++++++++++++++++++
+++++++++++++++++

 The elements in which the last electron enters one of the 5f orbitals are called 5f–
block elements or second inner transition series.
 Actinoids

 These are also called actinides or actinons or actinoids because they

come immediately after actinium.
++++++++++++++++++++++
 Actinoids consists of 14 elements from Thorium (90Th) to Lawrencium
(103Lr) following Actinium (89Ac)
+++++++++++++++++
 These actinoids are radioactive in nature and lie below the lanthanides.
 The man-made 11 elements Np (93) – Lr (103) are placed after
uranium in the periodic table and are collectively called
trans-uranic elements.
 Th, Pa and U first three actinides are natural elements.
 Electronic Configuration of Actinoids
7s2 common but with variable occupancy of 5f & 6d subshell

++++++++++++++++++++++
+++++++++++++++++
 Electronic Configuration of Actinoids
 General configuration of actinides may be given as 5f1–14 6d0–1, 7s2.

++++++++++++++++++++++ There are irregularities

in the electronic
+++++++++++++++++ configurations of the
actinoids :
due to the stabilities of
the f 0, f 7 and f 14
occupancies of the 5f
orbitals.
 Atomic (or)Ionic size

gradual decrease in the size of atoms or M 3+ ions across

the series.
++++++++++++++++++++++
Due to actinoid contraction.
+++++++++++++++++
The contraction is, however, greater from element to
element in this series resulting from poor shielding by 5f
electrons.
Actinide contraction is greater than lanthanoid contraction
due to poor shielding by 5f-electorns in actinides than that
of 4f-electrons in the lanthanoids.
 Oxidation state
 General oxidation state is +3
 Actinoids show a variety of oxidation state.
It is because of a small energy difference between 5f, 6d and 7s subshells.

++++++++++++++++++++++
 The element in the first half of the series frequently exhibit higher oxidation states.
Ex: the maximum oxidation state increases from +4 in Th to +5, +6 and +7

+++++++++++++++++
respectively in Pa, U , Np and Pu but decreases in succeeding elements.
 General characteristics
 Nature: silvery in appearance
 Structure: display a variety of structures.
++++++++++++++++++++++
due to irregularities in metallic radii (more than lanthanoids)
 Reactivity: highly reactive metals, especially when finely divided.
+++++++++++++++++
Action with non-metals – Reacts at moderate temperature
action of boiling water - gives a mixture of oxide and hydride.
action of acid - Hydrochloric acid attacks all metals but most are
slightly affected by nitric acid owing to the formation
of protective oxide layers;
action of alkalis : No action
 General characteristics

++++++++++++++++++++++
 magnetic properties : more complex than those of the lanthanoids.
magnetic property of actinods = magnetic property of Lanthanoids
+++++++++++++++++
 Ionisation enthalpy : lower than lanthanoids
5f electrons, be more effectively shielded from the nuclear charge
than the 4f electrons of the corresponding lanthanoids.
 Colour: Actinoids compound or their ions are coloured most probably
due to f-f transition.
Difference between Lanthanoids & Actinoids

++++++++++++++++++++++
+++++++++++++++++
Some important applications of d & f block elements

 Iron and steels are the most important construction materials.

Production: Based on the reduction of iron oxides, the removal of
impurities and the addition of carbon and alloying metals such as Cr, Mn and Ni.
++++++++++++++++++++++
 TiO for the pigment industry.
 MnO2 for use in dry battery cells.
+++++++++++++++++
 Zn and Ni/Cd - battery industry.
 Ag and Au are restricted to collection items
 Coinage metals (elements of Group 11),
UK ‘copper’ coins - copper-coated steel
UK ‘silver’ coins - Cu/Ni alloy
Some important applications of d & f block elements

 Many of the metals and/or their compounds are essential catalysts in the
chemical industry.
• V2 O5 catalyses the oxidation of SO2 in the manufacture of sulphuric acid.
++++++++++++++++++++++
• TiCl4 with Al(CH3)3 -Ziegler catalysts
used to manufacture polyethylene (polythene).
+++++++++++++++++
• Iron catalysts are used in the Haber process for the production of ammonia from
N2 /H2 mixtures.
• Nickel catalysts enable the hydrogenation of fats to proceed.
• In Wacker process the oxidation of ethyne to ethanal is catalysed by PdCl2 .
• Nickel complexes are useful in the polymerisation of alkynes and other organic
compounds such as benzene.
• The photographic industry relies on the special light-sensitive properties of AgBr.
THANK YOU