MINIMUM LEARNING MATERIAL

8. d & f BLOCK ELEMENTS

● The d-block of the periodic table contains the elements of group 3-

12 in which the d orbitals are progressively filled in each of the
four long periods.
● There are four series of the transition metals
3d series (Sc to Zn),
4d series (Y to Cd)
Position in the Periodic 5d (La, Hf to Hg) and
Table 6d series (AC, unq to Uub).

Definition of Transition A transition element is defined as the one which has incompletely filled d
Element orbitals in its ground state or in any one of its oxidation state.

For 3d series 3d 1–10 4s1–2

For 4d series 4d1–10 5s1–2

For 5d series 5d1–10 6s1–2

Electronic For 6d series 6d1–10 7s1–2

Configurations of the d- Overall (n–1) d1–10 ns1–2
Block Elements

Why do the transition Because of large number of unpaired electrons in their atoms they have
elements exhibit higher stronger interatomic interaction and hence stronger bonding between
enthalpies of atomisation? atoms resulting in higher enthalpies of atomisation.

The E V (M2+/M) value The high energy to transform Cu(s) to Cu2+(aq) is not
for copper is positive balanced by its hydration enthalpy ∆hydH. The general trend
(+0.34V). What is possible towards less negative E V values across the series is related to the general
reason for this? increase in the sum of the first and second ionisation enthalpies (OR)

Why is Cr2+ reducing and
Mn3+ oxidising when both
have d4configuration?
Trends in the M3+/M2+
Standard Electrode
Potentials
Which is a stronger
reducing agent Cr2+ or Fe2+
and why ?
● Cr2+ is reducing as its configuration changes from d4 to d3, the latter
having a half-filled t2g level.
● On the other hand, the change from Mn3+ to Mn2+ results in the
half-filled (d5) configuration which has extra stability.
● The low value for Sc reflects the stability of Sc3+ which has a
noble gas configuration
● The highest value for Zn is due to the removal of an electron from
the stable d10 configuration of Zn2+.
● The comparatively high value for Mn shows that Mn2+(d5) is
particularly stable, whereas comparatively low value for Fe shows
the extra stability of Fe3+ (d5).
● The comparatively low value for V is related to the stability of V2+
(half-filled t2g level)
Cr2+ is a stronger reducing agent than Fe2+. This can be explained on the
basis of the standard electrode potential values E°(Cr3+/Cr2+ = –0.41 V)
and E° (Fe3+/Fe2+ = + 0.77 V). Thus Cr2+ is easily oxidised to Cr3+ but Fe2+
cannot be as readily oxidised to Fe3+.
Why is the highest Both fluorine and oxygen have small size, high electronegativity and also
oxidation state of a metal high negative electron gain enthalpy. They can oxidise a metal to the
exhibited in its oxide or highest oxidation state. Thus, the highest oxidation states are shown in the
fluoride only? oxides and fluorides of transition metals.

Copper (I) compounds are unstable in aqueous solution and undergo

disproportionation.

2Cu+ → Cu2+ + Cu

The stability of Cu2+ (aq) rather than Cu+(aq) is due to the much
more negative ∆hydH

of Cu2+ (aq) than Cu+, which more than compensates for the second
Explain why Cu+ ion is not ionisation enthalpy of Cu
stable in aqueous
solutions?

● Diamagnetic substance contain no unpaired electron and repelled

by magnet while paramagnetic substances are attracted and contain
one or more unpaired electron.
● The substance which are strongly attracted by magnet are said to
be ferromagnetic. Paramagnetism arises due to presence of
unpaired electrons, each such electron having a magnetic moment
associated with its spin angular momentum and orbital angular
momentum.
Magnetic Properties where n is number of unpaired electron and BM–Bohr magneton.

● The d-orbitals are non-degenerated in presence of ligands. When

an electron from a lower energy d-orbital is excited to a higher
energy d-orbital, (d-d transition), the energy of required
wavelength is absorbed and rest light is transmitted out,
● This frequency absorbed generally lies in the visible region.
Formation of Coloured Therefore, the colour observed corresponds to the complementary
Ions colour of the light absorbed.

● Due to smaller size of the metal ions

● high ionic charges and
Formation of Complex ● the availability of d orbitals for bond formation, transition elements
Compound form a number of complex compounds
 The transition metals and their compounds are known for their catalytic
activity. This activity is due to their ability

● To adopt multiple oxidation states

● To form complexes
● Transition metals also provide larger surface area for the reactant
to be adsorbed.
(Catalyst at a solid surface involve the formation of bonds between
reactant molecules and atoms of the surface of catalyst. This has the effect
of increasing the concentration of the reactants at the catalyst surface
and also weakening of the bonds in the reacting molecules (the
Catalytic Properties activation energy is lowering).

● Interstitial compounds are those which are formed when small

atoms like H, C or N are trapped inside the crystal lattices of
metals. They are usually non stoichiometric and are neither
typically ionic nor covalent, for example, TiC, Mn4N, Fe3H,
VH0 .56 and TiH1.7, etc.
● Characteristics of these compounds are as follows: (i) They have
high melting points, higher than those of pure metals. (ii) They are
very hard, some borides approach diamond in hardness. (iii) They
Formation of Interstitial retain metallic conductivity. (iv) They are chemically inert.
Compounds

● Alloy is the homogeneous mixture of two or more metals.

Transition metals have approximate same size therefore, in molten
form they can fit to each other crystalline structure and form
homogeneous mixture and form the alloy
Alloy Formation ● E.g., Brass (copper-zinc) and bronze (copper-tin) etc.

Potassium Dichromate (K2 Ore

Cr2 O7 )
Ferrochrome or chromate (FeO.Cr2 O3 ) or (FeCr2 O4 )

Preparation

4FeO.Cr2 O3 + 8Na2 CO3 + 7O2 → 8Na2 CrO4 + 2Fe2 O3 + 8CO2 (yellow)

2Na2 CrO4 + 2H+ → Na2 Cr2 O7 + 2Na+ + H2 O (orange)

Na2 Cr2 O7 + 2KCl → K2 Cr2 O7 + 2NaCl

 Sodium dichromate is more soluble than potassium dichromate

Potassium Dichromate (K2

Cr2 O7 )

Potassium Dichromate (K2

Cr2 O7 )

Ore

Pyrolusite (MnO2 )

Preparation

2MnO2 + 4KOH + O2 → 2K2 MnO4 + 2H2 O (green)

Potassium Permanganate
(KMnO4 ) 3MnO4 2− + 4H+ → 2MnO4 − + MnO2 + 2H2 O
Potassium Permanganate
(KMnO4 )

Potassium Permanganate
(KMnO4 )
2KMnO4 → K2MnO4 + MnO2 + O2

Potassium Permanganate In acid solutions:

(KMnO4 )
(a) Iodine is liberated from potassium iodide :

10I– + 2MnO4 – + 16H+ ——> 2Mn2+ + 8H2O + 5I2

(b) Fe 2+ ion (green) is converted to Fe3+ (yellow):

5Fe2+ + MnO4 – + 8H+ ——> Mn2+ + 4H2O + 5Fe3+

(c) Oxalate ion or oxalic acid is oxidised at 333 K:

5C2O4 2– + 2MnO4 – + 16H+ ——> 2Mn2+ + 8H2O + 10CO2

(d) Hydrogen sulphide is oxidised, sulphur being precipitated:

H2S —> 2H+ + S2–

5S2– + 2MnO4 - + 16H+ ——> 2Mn2+ + 8H2O + 5S

(e) Sulphurous acid or sulphite is oxidised to a sulphate or sulphuric

acid:
 5SO3 2– + 2MnO4 – + 6H+ ——> 2Mn2+ + 3H2O + 5SO4 2–

(f) Nitrite is oxidised to nitrate:

5NO2 – + 2MnO4 – + 6H+ ——> 2Mn2+ + 5NO3 – + 3H2O

In neutral or faintly alkaline solutions:

(a) A notable reaction is the oxidation of iodide to iodate:

2MnO4 – + H2O + I– ——> 2MnO2 + 2OH– + IO3 –

(b) Thiosulphate is oxidised almost quantitatively to sulphate:

8MnO4 – + 3S2O3 2– + H2O ——> 8MnO2 + 6SO4 2– + 2OH–

(c) Manganous salt is oxidised to MnO2 ; the presence of zinc

sulphate or zinc oxide catalyses the oxidation:

2MnO4 – + 3Mn2+ + 2H2O ——> 5MnO2 + 4H+

Note: Permanganate titrations in presence of hydrochloric acid are

Potassium Permanganate unsatisfactory since hydrochloric acid is oxidised to chlorin
(KMnO4 )

Potassium Permanganate
(KMnO4 )

Properties of the General electronic configuration is [Xe] 4f1-14 5d0-1 6s2.

lanthanides (b) The metals are silvery-white in colour. They are malleable, ductile,
have low tensile strength and are good conductors of heat and electricity.
(c) They have relatively high density and possess high melting points.
 (d) The lanthanides exhibit a principle oxidation state of + 3. However,
some elements also exhibit + 2 (Eu2+) and + 4 (Ce4+)oxidation states.
(e) Many of the lanthanide ions are coloured due to the electronic
transition between different 4 f-levels.
(f) The majority of the lanthanide ions exhibit paramagnetism due to the
presence of unpaired electrons. The lanthanoid ions that do not exhibit
paramagnetism are those with either no 4f-electrons, e. g., La3+ and Ce4+
or with a completed 4f-level, e.g., Yb2+ and Lu3+.
(g) The lanthanides readily tarnish in air and bum to give trioxides (except
cesium, which forms Ce02).
(h) The oxides and hydroxides of the lanthanides are basic in character.
(i) The lanthanoid compounds are generally predominantly ionic.
20. This gradual decrease in atomic size across the first f- transition
element series is called lanthanoid contraction.

General electronic configuration is [Rn] 5f0-14 6ds0-1 7s2.

Properties of actinides:
(b) The elements are all silvery-white metals.
(c) The melting points of the actinides are moderately high.
(d) The ionic size of the actinides decreases gradually along the series.
(e) The actinides have the ability to exhibit several oxidation states.
However, +4 oxidation state is preferred in actinides.
(f) Some actinoid elements can exist in + 6 oxidation state, e.g., uranium,
neptunium and plutonium.
(g) Many actinoid elements are radioactive. The elements beyond uranium
are man-made.
(h) The actinides have a much greater tendency to form complexes than
lanthanides.

1 d-block elements are called transition as they have incomplete d-orbitals in neutral or most
elements stable oxidation state.
2 Zn, Hg, Cd, are not included as transition as they have filled d-orbitals in neutral and most stable +2
elements and why? oxidation state.

3 Sc3+ has d0 configuration but it is transition Because of partially filled d1 configuration of Sc

metal
4 First series transition elements shows Due to shielding effect of inner 3d electrons which
irregular trend of atomic radii overcome ENC.

5 Atomic radii of Zr to Hf are almost same. due to Lanthenoid Contraction.

6 First series transition elements shows
irregular trend of IE
7 Transition metals have strong metallic
bond, have high enthalpy of atomization
and melting point.
8 Zn, Cd, Hg are not very hard and have low
M.P. and B.P.
9 d-block elements shows a large no. of
oxidation state
10 Which first series transition metal shows
highest number of oxidation states and
why?
11 Which first series transition metal do not
show variable oxidation states and why?
12 Cr3+ is more stable as compared to Cr2+
13 Cu2+ is more stable in solution than Cu+
14 Which first series transition metal shows
+1 oxidation states and why?
15 Higher oxidation states of transition metals
found in their oxides and fluorides
16 higher oxidation states are more common
in oxides rather than fluorides of transition
metals.
17 +2 O.S becomes more stable in first series
transition elements moving from left to
right
18 Write oxoanions of first series transition
metals in which group number and O.N. of
transition metal are same-
19 Moving from left to right E0 for M2+/M trends due to irregular variation of IE1 + IE2.
becomes less negative but it shows
irregular trend
20 For copper E0 Cu2+/Cu is +ve (+0.34 V) it is due to low hydration enthalpy of Cu 2+ which cannot
compensate ∆subH0 + IE1 + IE2.
It is because of mutual exchange of energy between d and
f orbitals after removal of one electron.
due to presence of unpaired electrons.
Due to presence of all paired electrons they have least
enthalpy of atomization, very weak metallic bond & are
not very hard with low M.P. and B.P.
due to presence of unpaired electrons or partially filled d-
orbitals.
Mn shows highest number of oxidation state due presence
of highest number of unpaired electrons.
Sc , due to achieving noble gas configuration in +3 O.S
due to stable half filled t2g3 configuration.
due to high hydration enthalpy of Cu2+ ion in solution.
Cu shows +1 oxidation state in gaseous form due to stable
full filled 3d10 configuration.
because higher oxidation states stabilized by highly
electronegative elements such as O and F
due to formation of dπ-pπ bond between metal and
oxygen.
as number of unpaired electrons decreases.
MnO4-, Cr2O72-, VO3-, CrO42-
21 For Mn , E0 Mn3+/Mn2+ is +ve because by converting into Mn2+ it achieves half filled
configuration.

22 For Cr , E0 Cr3+/Cr2+ is −ve because Cr3+ is more stable due to half filled t 2g
configuration.

23 Most of the compounds of transition metal It is due to d-d transition

are coloured in solid state as well as in their
solution form.

24 (Sc3+, Ti4+) does not exhibit any colour Ions with vacant d-orbitals (d0) as d-d transition is not
possible in this type of ions.

25 (Zn2+, Cu+) does not exhibit any colour full filled d-orbitals (d10) as d-d transition is not possible
in this type of ions.

26 Transition metals or ions are paramagnetic Due to presence of unpaired electrons (d1-9)
in nature

27 Transition metal form large number of High charge by mass ratio, availability of vacant d-orbital
coordination complexes & Variable oxidation state

28 What are Interstitial compounds? Compounds in which small elements like H, B, C, N

trapped in the interstitial space of metal lattice.

29 Transition metals form Interstitial due to availability of interstitial space in metal lattice.
compounds.
30 Why interstitial compounds are found to be These compounds have high M.P as compared to pure
more useful than pure metal? metals. These are very hard. Retain metallic conductivity
and are Chemically inert.

31 Transition metals and their compounds are Due to large surface area, variable oxidation state &
widely used as catalyst Availability of vacant d-orbitals

32 transition metals form alloy. Due to comparable metallic radii

33 Why oxides of Higher oxidation states of
transition metals are acidic in nature
whereas lower O.S. are basic in nature?
34 Actinoids shows greater number of
oxidation states then lanthanoids
35 It is difficult to study chemistry of actinoids.
36 Ce(IV) is a good oxidizing agent in aq. soln
37 Actinoid contraction is greater from
element to element as compared to
Higher oxidation states are more polarizing in nature .
hence are acidic in nature whereas lower O.S. are less
polarizing hence are basic in nature.
Due to comparable energy of 5f, 6d, and 7s orbitals.
Due to radio active nature and small half life
because in aq. solution its E0Ce4+/ Ce3+ is +1.74 V
because of poor shielding by 5f orbitals due to its
superficial position.
 lanthanoids .
Potassium Dichromate [K2Cr2O7] Potassium Permanganate [KMnO4]
Preparation: Preparation: from pyrolucite ore [MnO2]
It is prepared from chromite ore : FeCr 2O4 / Step 1:
FeO Cr2O3 2MnO2 (Black)+4KOH+O2 2K2MnO4 (Green)+ 2H2O
Step 1: Step 2:
4FeCr2O4 + 8Na2CO3 +7O2 8Na2CrO4 + 2Fe2O3 3MnO42- (Green)+4H+ 2MnO4-( Purple)+MnO2+ 2H2O
+ 8CO2 Oxidizing Character: (Oxidation in acidic medium)
Step 2: 2Na2CrO4 (Yellow)+ H2SO4 MnO4- + 8H+ + 5e- Mn2+ + 4H2O
Na 2Cr2O7(Orange)+ Na2SO4 + Eq. mass of KMnO4 = 158/5 = 31.6
H2O MnO4-+5Fe2++8H+ Mn2++5Fe3++ 4H2O
Step 3: Na2Cr2O7 + 2KCl K2Cr2O7 + 2MnO4- + 10Cl- + 16H+ 2Mn2+ + 8H2O + 5Cl2
2NaCl 2MnO4- +5C2O42-+ 16H+ 2Mn2++10CO2+ 8H2O
Orange Orange 2MnO4 +5SO3 +6H
- 2- +
2Mn2+ + 5SO42- + 3H2O
Effect of pH: 2MnO4-+5NO2-+6H+ 2Mn2+ + 5NO3- + 3H2O
Cr2O72- (Orange) + 2OH- 2CrO42- (Yellow) 2MnO4-+5S2-+16H+ 2Mn2+ + 5S + 8H2O
+ H2O 2MnO4 +3H2O+ I
- -
2MnO2 +IO3- + 2OH-
2CrO42- (Yellow) + 2H+ Cr2O72- (Orange) + 8MnO4- +3S2O32-+H2O 8MnO2 + 6SO42- + 2OH-
H2O 2MnO4- +3 Mn2++2 H2O 5MnO2 +4H+
Oxidizing Character: Dichromate ion acts as
strong oxidizing agent in acidic medium.
Cr2O72- + 14H+ + 6e- 2Cr3+ + 7H2O
Cr2O72- + 14H+ + 6I- 2Cr3+ + 7H2O + 3I2
Cr2O7 + 14H + 6Fe
2- + 2+
2Cr3+ 7H2O + 6Fe3+
Cr2O72- + 14H+ + 3Sn2+ 2Cr3+ 7H2O + 3Sn4+
Cr2O72- + 8H+ + 3H2S 2Cr3+ + 7H2O + 3S
f-Block Elements Consequences: 1. Resemblance in the properties of
General configuration (n – 2) f 1-14 (n – 1)d 0-1 second and third transition series from Zr & Hf) atomic
ns2 size of 2nd and 3rd transition series become same.
57La [Xe] 5d1 6s2 89Ac 2. Similarity in the properties of Lanthanoids:- The
[Rn] 6d1 7s2 -
58Ce [Xe] 4f 5d 6s
1 1 2
91Pa decrease in atomic radii from Lanthenoid to Lanthenoid is
[Rn] 5f2 6d1 7s2
63Eu [Xe] 4f7 5d0 6s2 92U very less hence it is very difficult to separate these
[Rn] 5f3 6d1 7s2
64Gd [Xe] 4f7 5d1 6s2 94Pu elements in pure state.
[Rn] 5f6 6d0 7s2
70Yb [Xe] 4f14 5d0 6s2 3. Basic strength of hydroxides of Lanthanoids decreases
from Lanthenium (La) to Lutesium (Lu).
Misch Metal – It is alloy of Lanthanoids(95%) with iron
(5%)and Trace of S, C, Al ,Ca Lanthenoid – 95% Metal +
Trace of S, C, Al ,Ca + Iron – 5%
Lanthanoid Contraction- Regular decrease in
Uses- making bullet shells and flinter of lighters.
atomic or ionic radii of Lanthenoid with increase
in atomic number is called Lanthenoid
contraction.
Cause: It is due to imperfect shielding of one 4f
orbital by another 4f orbital due to which ENC
regularly increases with increase in atomic
number.
Lanthanoids Actinoids
Last electron enters in 4f orbital Last electron enters in 5f orbital
Are natural elements and non radioactive in Are radioactive in nature and after Np they are synthetic
nature elements
Shows less number of oxidation states Shows greater number of oxidation states
[+2,+3,+4] [+3,+4,+5,+6,+7]
Element to element lanthanoid contraction is Element to element actinoid contraction is more
less