d– & f-Block Elements

Those elements whose last electron fall in the d-orbitals known as d-Block elements.

Transition Element:- Those element whose d – configuration is incompletely/partially filled

either in ground state or any stable oxidation state known as Transition Element.

d1 - d10 – d – Block
d1 - d9 – Transition element
d10 – Non Transition element.
Note:- All transition element are d – block element but vice- versa is not true.
General Electronic Configuration of d – Block elements are ( n – 1) d 1 to 10 ns0 – 2 , where n=
outermost shell. (n – 1) = penuiltimate shell i.e. one inner than outermost shell.
(Q) (1) Why transition element is so called?
Ans. Because it is placed between s- and p- Block element that’s why it is known as transition
element.
3 4 5 6 7 8 9 10 11 12
3d / 1st T S. Sc Ti V Cr Mn Fe Co Ni Cu Zn
4d / 2nd T S. Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
5d / 3rd T S. La Hf Ta W Re Os Ir Pt Au Hg

(Q) (2) Why copper acts as a transition element although its d – configuration is full filled?
Ans. Cu (29) - 4s1 3d10
Cu + - 4s0 3d10
Cu 2+ - 4s0 3d9

Copper can show or form two oxidation state Cu + and Cu2+. In Cu2+ oxidation state, the d –
configuration is partially filled that’s why copper acts as a transition element.
(Q) (3) Why Zinc do not acts as a transition elements?
Ans. Zn (30) - 3d104S2
Zn2+ - 3d104S0
The d – configuration of Zinc is full filled both in ground state and stable oxidation state
i.e. Zn2+ that is why Zinc acts as a non – transition element.
(Q) (4) Why Zinc studied along with transition element although its d-Configuration is full filled?
Ans. Because the properties of Zinc is similar with the properties of transition element i.e. why
they are studied along with transition element.

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(Q) (5) Why transition elements are very hard and have high density?
Ans. Due to presence of strong metallic bond, transition elements are hard and have high
density.
(Q) (6) Why transition elements have high enthalpy of atomisation?
Ans. It is due to presence of strong metallic bond.
Enthalpy of Atomisation
It is the amount of enthalpy change when one mole of a substance is converted into its gaseous
atom is known as enthalpy of atomisation.
For eg. H2 (g) a H 2H(g)
(Q) (7) Why the enthalpy of atomisation of 3 rd transition series is higher than 2 nd transition series is
higher than 1st T. series.
Ans. In Case of 3rd transition series due to strong interatomic bonding or due to strong metal-
metal bonding, the enthalpy of atomisation of 3rd transition series is higher than 2nd then 1st.
(Q) (8) Why the melting point and boiling points of transition elements are very high?
Ans. It is due to presence of strong metallic bond and interatomic forces.
 The strength of inter atomic bonding depends upon no. of half filled d orbital.
3 4 5 6 7 8 9 10 11 12
Sc Ti V Cr Mn Fe Co Ni Cu Zn

No. of half filled d – orbital increases no. of half filled d – orbital decreases.

Strength of inter atomic forces increases strength of inter atomic forces decrease
(Q) (9) In the series S.C. (Z=21) to Zn (Z=30), the enthalpy of atomisaton of Zinc is the lowest i.e.
126 Kj mol-1 why?
Ans. In case of Zinc, 3d e- are not involved in metallic bonding due to having 3d 10
configuration, Because of poor metallic bonding the enthalpy of atomization of Zinc is
lowest.
(Q) (10) Chromium is a typical hard metal while mercury is a liquid. Explain.
Ans. In chromium, the interatomic bonding is very strong due to presence of five unpaired e- in
3d subshell (3d54s1). Therefore, it is hard metal. In mercury, on the contrary, the 3d-
subshell is filled maximum capacity (5d106s2), i.e. these e- are not available for interatomic
bonding and thus bonding is very weak in mercury. Therefore. Hg is a liquid at room
temperature.

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(Q) (11) Why are the ionisation energies of 5d elements greater than 3d elements?
Ans. In the 5d series, after lanthanum, there is lanthanide contraction. As a result, the atomic size
does not increase to the extent as expected, i.e. it is smaller than expected while the nuclear
charge is larger in comparison to 3d elements. Hence the ionization energies of 5d elements
are greater than 3d elements.
(Q) (12) The melting and boiling points of Zn, Cd and Hg are low why?
Ans. In Zn, Cd and Hg the (n-1) d-orbitals are filled to their maximum capacity. These d-e - do
not take part in metallic bonding. Thus metallic bonding is weak in Zn, Cd and Hg. That is
why they have low melting point and boiling point.
(Q) (13) Name the lightest and heaviest elements in terms of density among the transition.
Ans. Lightest element - Sc density 3.43 gm cm-3
Heaviest element - Osmium densiy 22.59 gm cm-3
Or
Iridium density 22.61 gm cm-3
Atomic Size and Ionic Size
Sc Ti V Cr Mn Fe Co Ni Cu Zn

Atomic size decreases till the middle. Constant It increases till the end.
 Nuclear charge (N.C) partially Increase N.C. Due to repulsion of paired e -,
cancelled by increased screening e- cloud expanded which
balance by
effect increases the atomic size.
Increase S.E.

Oxidation State
(Q) (1) Why transitions element show variable oxidation state.
Ans. Due to participation of ns and (n–1) d-e- in chemical bonding, it shows variable oxidation
state.
Note: +2 Oxidation state is the common oxidation state of the transition element except
scandium. (It show +3 oxidation state only)
(Q) (2) Write the name of transition element which can’t show variable oxidation state or which can
only show +3 oxidation states.
Ans. SC
(Q) (3) Write the name of element in 1st transition series which shows large no. of different types of
oxidation state?
Ans. Manganese (Mn) it shows +2, +3, +4, +5, +6, +7 oxidation state.

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(Q) (4) Write the name of element is 1st transition series which show highest no. of oxidation state?
Ans. Manganese i.e. +7.
(Q) (5) Write the name of transition element which shows highest oxidation state in any transition
Ans. series?
OS = +8 Ru = +8
(stable) (unstable)

OSO4 Ruthenium

Osmium
tetra oxide

(Q) (6) Why the highest oxidation state of Transition element show only with oxygen or fluorine?
Ans. Due to high electron negativity of oxygen and fluorine.
(Q) (7) Why the highest oxidation state is more stable with oxygen then fluorine?
Ans. Because transition elements form multiple bonds with oxygen while fluorine can’t form
multiple bond with transition element i.e. why highest oxidation state of transition
element is more stable with oxygen than fluorine.
Oxidation
* M(S) M+(aq) + e-
H (E0Oxidation)
Sub.H HHyd
e
M(g) M+(g)
iH
E0 oxidation ( H) = sub H + iH + HHyd
 The stability of oxidation state depends upon the following factors:-
(i) Enthalpy of sublimation
(ii) Enthalpy of atomization.
(iii) Ionization enthalpy
(iv) Hydration enthalpy
(v) Electronic configuration of d-sub shell.
Note:- Half filled t2g level (d3) is more stable than half filled d-sub shell (d5)
(Q) Explain why Cu+ is not stable is aqueous solution?
Ans. Cu+ disproportionate into Cu2+ and Cu.
2Cu+ Cu + Cu2+
The stability of Cu2+ is more than Cu+ due to much more negative hydration enthalpy of
Cu2+ than Cu+, which more than compensates for the 2nd Ionisation enthalpy of Cu.
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 (Q) Why Cr2+ reducing and Mn3+ oxidising when both have d4 configuration?
Oxidation Reduction
Ans. Cr2+ Cr3+ + e-, Mn3+ + e- Mn2+
3d4 3d3 3d4 3d5
Cr2+ easily converted into Cr3+ Mn3+ converted into Mn2+ due to stable
due to stable half filled t2g level. half filled (d5) d- configuration.

(Q) Which is stronger reducing agent Cr2+ or Fe2+ and why?

Ans. Oxidation
Cr = 4s13d5 Cr2+ Cr3+ + e-
3d4 3d3 (half filled t2g level)
Oxidation
Fe = 4s23d6 Fe2+ Fe3+ + e-
3d6 3d5 (half filled)
d3 half filled t2g level is more stable than d5 that is why Cr2+ is stronger reducing agent then Fe2+.
 Transition element in lower oxidation state form ionic compound, while transition elements
in higher oxidation state form covalent compound.

Magnetic Property
(Q) Why transition elements show paramagnetic behaviour ?
Ans. Due to presence of unpaired e- in transition element it show paramagnetic behaviour.
Note:- Paramagnetic behaviour express in the terms of magnetic moment i.e. .
= M
= magnetic moment
n = Total no. of unpaired e-
M = Bohr magneton (unit of Magnetic moment).
OR
M 1 M =

s = Total spin Q.No.

(Q) [Ti (H2O)6]3+ is paramagnetic or diamagnetic. Explain.
Ans. x + 0 x 6 = +3
x = +3
Ti (22) = 4s23d2
Ti3+ = 4s03d1
d0
Diamagnetic d1 – d9 – paramagnetic.
d10

Catalytic Property
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(Q) Why transition element show catalytic behaviour?
Ans. It is due to two factors;
1) Due to variable valency it provides new path for the reaction whose activation energy is
low.
V2O5
Example: SO2 + O2 SO3

SO2 + V2O5 SO3 + V2O4

V2O4 + O2 V2O5

2) In some reaction catalyst also provide the surface / solid surface for the reaction.
Ni(s)
CH2 = CH2 + H2 CH3 – CH3

Formation of Complex Compound

(Q) Why transition element form complex compound?
Ans. It is due to two factors;-
(i) Small size and high charge density.
(ii) Presence of vacant d-orbital.

Formation of Alloy
(Metal – Metal Solution)
(Q) Why transition element form alloy?
Ans. Due to similar size of transition element, it can replaces to each other and form alloy.

Formation of Interstitial Compound

(Q) Why transition element form interstitial compound?
Ans. Transition element have lattice structure due to which it contain some void or holes or
interstitial sites. Small element like hydrogen, boron, carbon, nitrogen, etc. can easily trap
and form interstitial compound..
 Properties of Interstitial compounds;
1) They have high melting point.
2) They are very hard.
3) They retain metallic conductivity.
4) They are chemically inert.

Colouring Perperty – it is due to following factors;

(1) d – d transition.
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 (2) Charge transfer.
(3) Lattice defect or solid defect.
Charge Transfer;
+7
Mn(25) 4s23d5 KMnO4

K+ + MnO
+7 e-4 hv MnO
+6 4 MnO
+7 e-4
+7
E.S.
(10-8 sec)
KMnO4 and K2Cr2O7 both show colouring property due to charge transfer.
 Due to interaction between ligand and metal d-orbital’s the degeneracy of d-orbital is
lifted/splitted into two parts known as crystal field splitting.
d – d transition:-
Partially or Incompletely filled d-orbital (d 1 to d9) absorb energy from visible light and go to
higher d–orbital’s, after a certain time of interval these e - again back to ground state and releases
energy in the form of radiation which appears as a colour.
Complementary colour

(Q) Ti (H2O)6]3+ is coloured or colourless.

Here,
x + 0x6 = +3 Ti (22) 3d24s2
x = +3 Ti 3+ 3d14s0
eg

h eg
E
t2g

t2g

(Q) [ Co (NH3)6] Cl3 is coloured or colourless / paramagnetic or diamagnetic.

Ans. Here,

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 x + 0 x 6 + (-1) x 3 = 0
x = +3
Co (27) = 3d74s2
CO3+ = 3d6

Due to 3d6 configuration, it show d – d transition that’s’ why it shows colouring property.
Magnetice property;-

Due to presence of four un-paired e-. It show paramagnetic behavior.

M or M = M

Po-Lassium dichromate (K2Cr2O7)

Preparation
K2Cr2O7 is prepared from chromite ore (FeCr2O4)
4FeCr2O4 + 8Na2CO3 + 7O2 8Na2CrO4+ 2Fe2O3 + 8CO2
2Na2CrO4 + H2SO4 Na2Cr2O7 + Na2SO4 + H2O
Na2Cr2O7 + 2KCl K2Cr2O7 + 2Nacl
2CrO42- + 2H+ Cr2O72- + H2O
Yellow Acid Orange
(Chromate ion) (dichromate ion)

Cr2O72- + 2OH- 2CrO42- + H2O

(base)
CrO42- Cr2O72-
O 2- O O O 2-

Cr Cr Cr Cr

O O O O O O O
O O O O

O O

Cr Cr

O O O
O O

K2Cr2O7 acts as a strong oxidizing agent. It also used as a primary standard in volumetric
Analysis.
(Q) What happens when chromates are kept in acidic solution and dichromates in the alkaline
solution?
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Ans. Chromates are converted into dichromates in acid medium and dichromates are converted
into chromates in alkali medium.
Acid
2CrO42- + 2H+ Cr2O72- + H2O
Alkali

Oxidising properties in acidic medium

 It oxidizes ferrous to ferric

Cr2O72- Cr3+

Reduction
(Cr2O7)2- + 14H+ + 6e- 2Cr3+ + 7H2O

Oxidation
[ Fe2+ Fe3+ + e-] x 6

Cr2O72- + 6Fe2+ + 14H+ 2Cr3+ + 6Fe3+ + 7H2O

 It oxidises stannous to stannic

Reduction
(Cr2O7)2- + 14H+ + 6e- 2Cr3+ + 7H2O
Oxidation
[ Sn2+ Sn4+ + 2e-] x 3
Cr2O72- + 3Sn2+ + 14H+ 2Cr3+ + 3Sn4+ + 7H2O

 It oxidizes Hydrogen sulphide to Sulphur

+6e-
(Cr2O7)2- + 14H+ Reduction 2Cr3+ + 7H2O
[ H2S-2 Oxidation S0 + 2e- + 2H+] x 3
Cr2O72- + 3H2S + 14H+ 2Cr3+ + 3S + 7H2O + 6H+
Cr2O72- + 3H2S + (14H+ - 6H+) 2Cr3+ + 3S + 7H2O
Cr2O72- + 3H2S + 8H+ 2Cr3+ + 3S + 7H2O
 It oxidizes iodides to iodine
+6e-
(Cr2O7)-2 + 14H+ Reduction 2Cr3+ + 7H2O
Oxidation
[ 2 I- I2 + 2e- ] x 3

Cr2O72+ + 14H+ + 6 I- 2Cr3+ + 7H2O + 3I2

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Potassium permanganate (KMnO4):- it is prepared by fusion of pyrolusite
(MnO2) with KOH in the presence of oxidizing agent like KNO 3. This produces the
dark green potassium manganate K2MnO4 which disproportionate in a neutral or
acidic solution to give purple permanganate.
2MnO2 + 4KOH + O2 2K2MnO4 + 2H2O
Green

3MnO42- + 4H+ 2MnO4- + MnO2 + 2H2O

Purple

Commercially, it’s prepared by the alkaline oxidative fusion of MnO 2 followed by the
electrolytic oxidation of manganate VI.
MnO2 Fused with KOH MnO42-
Oxidised with air or KNo3 Manganate ion

Electrolytic oxidation
MnO42- MnO4-
In alkaline Solution permanganate ion
 Laboratory preparation
2Mn2+ + 5S2O82- + 8H2O 2MnO4- + 10SO42- + 16H+
 MnO42- MnO4-
O O
Mn Mn

O O O O O O

Oxidising action of KMnO4 in Acidic medium

(1) Ferrous salt to Ferric salts
Reduction
[ MnO4- + 8H+ + 5e- Mn2+ + 4H2O]
Oxidation
[ Fe2+ Fe3+ + e- ] x 5
MnO4- + 5 Fe2+ + 8H+ Mn2+ + 5Fe3+ + 4H2O
(2) Oxalate to Carbon-dioxide
Reduction
[ MnO4- + 8H+ + 5e- Mn2+ + 4H2O] x 2
Oxidation
on
[ C2O42- 2CO2 + 2e- ] x 5
2MnO4- + 5 C2O42- + 16H+ 2Mn2+ + 10CO2 + 8H2O
(3) Iodide to iodine.
Reduction
[ MnO4- + 8H+ + 5e- Mn2+ + 4H2O] x 2
on
Oxidationo
[ 2 I- I2 + 2e- ] x 5
n
2 MnO4- + 10I- + 16H+ 2Mn2+ + 5 I2 + 8H2O

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Oxidationo
Oxidationo
 (4) Nitrite to nitrate.
Reduction
[ MnO4- + 8H+ + 5e- Mn2+ + 4H2O]x 2
Oxidationo
[NO2- + H2O NO3- + 2e- + 2H+ ] x5
n
2 MnO4- + 16H+ + 5NO2- + 5H2O 2Mn2+ + 8H2O + 5NO3- + 10H+
2 MnO4- + 6H+ + 5NO2- 2Mn2+ + 3H2O + 5NO3-
(5) [ MnO4- + 8H+ + 5e- Reduction Mn2+ + 4H2O ] x 2
on
[H2S 2H+ + S + 2e- ] x 5
2 MnO4- + 16H+ + 5H2S 2Mn2+ + 8H2O + 10H+ + 5S
(6) [MnO4- + 8H+ + 5e- Reduction Mn2+ + 4H2O ] x 2
on
[SO32- + H2O SO42- + 2H+ + 2e- ] x 5
2MnO4- + 16H+ + 5SO32- 2Mn2+ + 8H2O + 5SO42- + 10H+
2MnO4- + 6H+ + 5SO32- 2Mn2+ + 3H2O + 5SO42-
Oxidising property in Basic Meduim / Neutral Medium

(i) Iodide to Iodate

Reduction
[MnO4- + 2H2O + 3e- MnO2 + 4OH- ] x 2
Oxidation
6OH- + 3H2O + I- IO3- + 6e- + 6H2O
2MnO4- + I- + 7H2O + 6OH+ 2MnO2 + 8OH- + + IO3- + 6H2O
2MnO4- + I- + H2O 2MnO2 + 2OH- + + IO3 -
(ii) Thio sulphate to Sulphate
Reduction
[MnO4- + 2H2O + 3e- MnO2 + 4OH- ] x 8
+2 +6
S2O32- + 5H2O + 10OH- Oxidation 2SO42- + 8e- + 10H2O ] x 3
8MnO4- + 16H2O + 3S2O32- + 15H2O + 30OH- 8MnO2 + 32OH- +
6SO42- + 30H2O
8MnO4- + 3S2O32- + H2O 8MnO2 + 6SO42- + 2OH-
(iii) Magnous salt is oxidized to MnO2
[2MnO4- + 3Mn2+ + 2H2O 5MnO2 + 4H+

f- Block Elements Or Inner Transition Element

Those elements whose last e- fall in the f-orbital known a f-block element.
It is of two type;-
(1) Lanthanoids
(2) Antinoids

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 f – Block
Lanthanoids Antinoids
It comes after La (57) i.e. from Ce (58) to Lu It comes after Ac(89) i.e. Th (90) to Lr (103).
(71). In this case there is regularly filling of 4f In this case there are regularly filling of 5F
sub shell. They are altogether 14 elements. subshell they also have altogether 14 elements
Cerium (Z = 58) to Lutetium (z = 71) Thorium (Z = 90) to Lr (Z = 103)

Atomic No. Elements Symbol Electronic Configuration

57 Lanthanum La 5d16S2
58 Cerium Ce 4f15d16S2
59 Praseodymium Pr 4f36S2
60 Neodymium Nd 4f46S2
61 Promethium Pm 4f56S2
62 Samarium Sm 4f66S2
63 Europium Eu 4f76S2
64 Gadoliuium Gd 4f75d16S2
65 Terbium Tb 4f96S2
66 Dys Prosium Dy 4f106S2
67 Holmium Ho 4f116S2
68 Erbium Er 4f126S2
69 Thulium Tm 4f136S2
70 Ytterbium Yb 4f146S2
71 Lutetium Lu 4f145d16S2

Atomic No. Elements Symbol Electronic Configuration

89 Actinium 6d17S2
90 Thorium 6d27S2
91 Protactinium 5f26d17S2
92 Uranium 5f36d17S2
93 Neptunium 5f46d17S2
94 Plutonium 5f67S2
95 Americium 5f7 7S2
96 Curium 5f76d17S2
97 Berkelium 5f9 7S2

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 98 Californium 5f10 7S2
99 Einsteinium 5f117S2
100 Fermium 5f12 7S2
101 Mendelevium 5f13 7S2
102 Nobelium 5f14 7S2
103 Lawrencium Lr 5f146d17S2

(Q) What is lanthanoid contraction?

Ans. The steady decrease in the size of lanthanoid ions (M 3+) with the increase in atomic
number is called lanthanoid contraction.
(Q) What is the cause of lanthanoids contraction?
Ans. Due to poorest shielding power of f-e -, the outer most electron experiences more effective
nuclear charge or force of attraction from the nucleus which decreases its atomic size.
(Q) What is the consequence of lanthanoid contraction?
(1) Atomic size or atomicradi of elements of 2nd and 3rd transition series are similar.
(2) Due to lanthanoid contraction, lanthanoid element separated from its mixture by ion
exchange method.
(3) The basic character of hydroxide of lanthanoid element is decreases from La(OH) 3 to
Lu(OH)3 because due to decrease in atomic size from La to Lu, the expulsion of OH -
decreases which decrease its basic character.
Note:- Both lanthanoids and actinoid has +3 oxidation state which is common oxidation
state of Lanthanoid and Actinoid.
(Q) Why Ce4+ acts as a oxidizing agent while Sm2+ acts as reducing agent?
Reduction
Ce4+ + e- Ce3+
Sm2+ Oxidation Sm3+ + e-
Ce4+ is easily converted into Ce3+ by taking e- that is process is reduction agent will be
oxidizing while Sm2+ easily changes into Sm3+ by losing electron that is process is
oxidation and agent will be reducing.
(Q) What is mishmetal?
An alloy which contain 95% lanthanoids metal and 5% iron and traces of sulphur,
Carbon, Calcium and Aluminium.

(Q) Write the difference between Lanthanoinds and actinoids?

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 Lanthanoids Actinoids
It show +2, +3 and +4 oxidation state. It show +2, +3, +4, +5, +6 and +7 oxidation
state.
except promethium all lanthanoids are non- They are radioactive in nature.
radioactive.
They can’t form oxo ions. They can form oxo ion.
They are less basic in nature. They are more basic in nature.
They have small tendency of complex They have strong tendency of complex
formation. formation.

(Q) Why lanthanoids and actinoids show colouring property?

Ans. Due to f-f transition.
(Q) Why lanthanoids and actinoids show para-mangnetic nature?
Ans. Due to presence of unpaired electron. It show para-magnetic nature.
(Q) Actionoid Contraction is greater from element to element than Lanthanoid contraction. Why?
Ans. The 5f-e- are more effectively shielded from nuclear charge. In other works the 5f-e -
themselves provide poor shielding from element to element in the series.
(Q) Why are +3 Oxidation state of gadolinium (Z=64) and lutetium (Z=91) especially stable?
Ans. This is because Gd in +3 state has half filled 4f-subshell (4f 7) and lutetium in +3 state has
completely filled 4f-sub shell, which are very stable configuration.
(Q) The outer electronic configuration of two members of the lanthanide series are as follows;
4f’ 5d1 6s2 and 4f7 5d0 6s2
What are their atomic no.? Predict the oxidation states exhibited by these elements in their
compounds.
Ans. Complete E.C. of 1st element = [Xe]54 4f15d16s2=58 i.e. the element is cerium.
Complete electronic configuration of 2nd element = [Xe]54 4f 7 5d0 6s2= 63 i.e the element is
europium. The expected oxidation state of 1st element = +3 and +4. The expected oxidation
state of 2nd element = +2 and + 3
(Q) Briefly explain why electronic configuration of lanthanides is not known with certainty?
Ans. In the lanthanide series, 4f and 5d-sub shell are having nearly same energies. The e - can
easily Jump from 4f to 5d or vice versa. Hence their e - configurations are not known with
certainty.
(Q) Why the separations of Lanthanide elements are difficult?
Ans. The lanthanides have similar chemical properties.

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