Chemistry Notes

Topic:-Transition and Inner Transition elements

d- block elements→Transition elements.
f- block elements→Inner transition elements.

s-block d-block p-block

f- block

As d-block elements are present between s-block and p-block, so these elements exhibit
properties between those of s and p-block elements.
3d series 4d
series
element →d series
d-block 5d series 6d series

 Position of d-block elements

(transition series elements) in the periodic table.
All d-block elements are placed in periods 4 to7 and groups 3 to 12

 General electronic configuration of four series of d- block elements of periodic table.

3d series – [ 1-10 2
Ar] 3d 4s 4d series – [Kr]
1-10 0-2 1-10 2
4d 5s 5d series – [Xe] 5d 6s 6d
1-10 2
series – [Rn] 6d 7s

 Rule of special stability-

 Subshell Empty or vacant Half filled Fully or completely filled

s 0 1 2

p 0 3 6

d 0 5 10

f 0 7 14

According to rule of special stability, if any subshell/orbit having empty or half-filled or

completely filled electronic configuration have higher stability.

 Exceptional electronic configuration of (Cr) Chromium and Copper (Cu)-

The expected valence shell electronic configuration of Chromium (Cr)- [ 4 2
1. Ar]3d 4s
The 3d and 4s orbitals are close in energy and in order to gain extra stability one electron
from 4s orbitals gets shifted to 3d orbitals and as a result of which 3d orbitals becomes
5
(3d ) half filled which is highly stable. So the observed valence shell electronic
9 1
configuration of Copper (Cu)-[Ar] 3d 4s chromium
The expected valence shell electronic configuration of copper (Cu)- [ 9 2
2. Ar] 3d 4s
The
3d and 4s orbitals are very close in energy and in order to gain extra stability, one
electron from 4ss orbitals get shifted to 3d orbitals and as a result of which 3d orbitals
10
becomes (3d ) completely filled so it is highly stable. So the observed the electronic
10 1
configuration of Copper (Cu) is – [Ar] 3d 4s
 Oxidation state of first transition series element (3d series elements)-

Elements Outer electronic Oxidation states

configuration
3d1 2
Sc 4s +2, +3
3d2 2
Ti 4s +2,+3,+4
3d3 2
V 4s +2,+3,+4,+5
3d5 1
Cr 4s +2,+3,+4,+5,+6
3d5 2
Mn 4s +2,+3,+4,+5,+6,+7
3d6 2
Fe 4s +2,+3,+4,+5,+6
3d7 2
Co 4s +2,+3,+4,+5
3d8 2
Ni 4s +2,+3,+4
3d10 1
Cu 4s +1,+2
3d10 2
Zn 4s +2

MCQ type
The element which gives the greatest number of
oxidation states (+2 to +7) is Manganese (Mn).


+1
1. Loss of one 4s electron forms M ion.
+2
2. Loss of two 4s electron forms M ion
+3
3. Loss of two 4s electron and one 3d electron forms M ion.
  Physical properties of just transition series-
a. All transition elements are metals and shows properties such as hardness, lustre,
malleability, ductility, forms alloys.
b. The transition elements are good conductors of heat and electricity.
c. They processes high melting and boiling point.
 Trends in atomic properties of the first transition series
(3d series)

Ionization enthalpy Colour

Atomic and ionic
radii Metallic
character

Magnetic properties

Catalytic properties

Formation of
interstitial compounds

Formation of Alloys
 1. Atomic and Ionic radii-
1. As we move from left to right along a transition series, the nuclear charge increases by one unit
at a time
2. The last filled electron enters a penultimate
(n-1)d-shell. However d-orbitals are less penetrating and more diffuse and offers smaller
screening effect.
3. So, as a result of which, atomic and ionic radii decreases gradually from left to right

2. Ionization enthalpy-
1. As we move from left to right, along a transition series, a slight variation is observed in the
successive enthalpies IE1, IE2, IE3.
2. The atoms of elements of third transition series (5d series) possess filled 4f-orbital also 4f-orbital
shows poor shielding effect due to its diffuse shape.
3. Due to which the outermost (valence) electrons experience greater nuclear attraction, so greater
amount of energy is required to ionize the 5d series elements.
4. So, the ionization enthalpies of 5d series or third transition series are much higher than first
and second transition series.

3. Metallic character-
1. Low ionization enthalpies and vacant d-orbitals in the outermost shell are responsible for
metallic character of transition series elements for metallic character of transition series
elements.
2. All transition metals have simple hexagonal closed packed (hcp), cubic closed packed (ccp) or
body centered cubic (bcc) lattices.
3. Cr, Mo, W shows highest melting point in their respective series.

4. Magnetic properties-

The compounds of the transition metals exhibit magnetic properties due to the unpaired
electrons present in their atoms or ions.

Magnetic substances

Paramagnetic
Diamagnetic Ferromagnetic
The substances which
The substances The substances which
are weakly attracted towards
which are repelled by the are strongly attracted towards
the applied
magnetic field, the applied
magnetic are
are called as diamagnetic magnetic field are called
substances called as as
paramagnetic Ferromagnetic substances
substances
  Examples of Ferromagnetic substance- Iron (Fe), Cobalt(Co), Nickel
(Ni)

 Magnetic moment (μ)- Due to

Spin angular and orbital angular

momentum momentum

o In first row transition element or first transition series elements or 3d series elements
Only contribution from spin angular momentum is present and orbital angular momentum is
quenched (not present).

𝜇= √n(n + 2) B.M.
So the magnetic moment (𝜇) can be calculated for 3d series elements by formula

o In second and third transition series elements (4d and 5d series elements)-
Both spin & orbitals angular momentum are present or significant.
So the magnetic moment (𝜇) for 4d and 5d series, cannot be calculated by using the formula.

o Magnetic moment-
Metal outer Metal Outer Representation No’s Calculat
ion configurat ion ion configurati on of unpa e value of
atom ired e- magneti c
moment
(𝜇)

Sc 3d1 4s2 Sc+3 3d0 4s0 . . . .0 0

Ti 3d2 4s2 Ti+3 3d1 4s0 ↑ . . .1 1.7

V 3d3 4s2 3d2 4s0 ↑ ↑ . .2 2.8

V+3
Cr Cr+3 3𝑑34𝑠0 ↑ ↑ ↑ .3 3.9
3d5 4s1 .
3𝑑44𝑠0 ↑ ↑ ↑ ↑4 4.9
Cr+2

Mn 3d5 4s2 M n+2 3d5 4s0 ↑ ↑ ↑ ↑ ↑ 5 5.9

Typ ↿ ↿ ↿
Fe 3d6 4s2 F e+2 3d6
3d4s0 ↿ ↿ ↿ ↿ 4 4.9
7 2
Typ Typ ↿ ↿
7 0
CO 3d 4s Co+
4s 3 3.9
3d8 4s0
Ty
Ni 8 1 2 2.8
Typ Typ ↿
3d 4s 2
9 0 10 1.7
Typ
1
Ty Ty
Cu 9
3d 4s
1 Ni+ 3d 4s 3d

Typ Typ
Zn 10 2 0
3d 4s

Ty Ty
2 Cu+
4s
2
Zn+
2
  Colour –
a. A substance appear coloured. If it absorbs a portion of visible light.
b. The observed coloured of the compounds corresponds to the complimentary colour of the
light absorbed.

 The colour of a transition metal ion depends on the following figure.

1. presence of unpaired d-electrons
2. 2 .d-d transition
3. nature of ligands
4. geometry of complex
 The ion having no unpaired electron are colourless. Ex.
+3
1. Sc ion-
The 1 2
outer electronic configuration of Sc is 3d 4s
+3
The outer electronic configuration of Sc ion

+3
As there are zero (no) unpaired electrons, so Sc is
colourless

2. Ti+4 ion-
The 2 2
outer electronic configuration of Ti is 3d 4s
The +4 0 0
outer electronic configuration of Ti ion is 3d 4s

+4
As there are zero (no) unpaired electrons, so Ti is colourless.
 3. Cu+1 ion-
The 9
outer electronic configuration of Cu is 3d
2
34s
The +1 9 10 0
outer electronic configuration of Cu ion 3d 3s ↔ 3d 4s

+1
As all the electrons are paired, so no unpaied is present. So Cu ion is colourless.

4. Zn+2 ion-
10 2
The outer electronic configuration of Zn is 3d 4s The outer electronic configuration of
+2 10 0
Zn ion is 3d 4s

As all the electrons are paired, so no unpaired

+2
electrons is present, so Zn ion is colourless

+2
 When (Co ) or CoCl2 or cobalt chloride is dissolved in water to form pink solution

+2 2-
[Co(H2O)] [CoCl4] + 6H2O
Pink colour deep blue colour Octahedral
geometry tetrahedral geometry
 Catalyst properties-
Transition metals and their compound exhibit good catalytic properties.
Catalyst

Homogenous catalyst Heterogeneous catalyst

In these, metal ion participate by forming In these type, the metal provides a surface
unstable intermediates for the reactant to react
Name of Process Reactions

catalyst
mnO2 For
decompositions of KClO3

Mo/Fe Haber’s process

in manufacture of ammonia
Ni Hydrogenation of ethene

Platinized Contact process

asbestos of industrial
production of
Sulfuric acid
Fe-Cr catalyst Reaction of carbon
monoxide (CO) and steam
(H2O)

Formation of interstitial compound- Interstitial compounds-

When small atoms like hydrogen, carbon or nitrogen are trapped in the interstitial spaces
within the crystal lattice, the compounds formed are called as interstitial compounds
Ex. steel and cast iron are the example of intestinal compounds.

 Propertied of interstitial compounds-

1. They are hard and good conductors of heat and electricity
2. They have higher melting points than pure metal
3. They have density than the parent metal.
4. Their chemical properties are similar to parent metal.
5. Density are less than parent metal 6.M + C carbides – hard as
diamond M+ H – Hydrides – reducing agent
 Alloys

Ferrous Non ferrous

[Link] alloys are formed by mixing the
atoms of other 1. Nonferrous alloys are formed by mixing the
elements in atoms of Fe(iron) atoms of transition metal other than Fe,
with non-transition element

Ex. Ni-steel, Cr-steel, Ex. Brass = Cu+Zn Stainless

steel

 Alloy uses-
[Link] = Cu + in
Strong, corrosion resistant, making status, medals
3. Cu-Ni, making ships, boats
4. Steel- construction, utensils
5. Nichrome- (Ni+Cr) for gas turbines
6. Titanium alloy- used for high speed height, fire proof bulkheads
  Compounds of Mn & Cr (KMnO4)
(K2Cr2O7)
Classification

Prep Chemical Uses

Properties

(Method)

1.KMnO4
Chemical oxidation-
MnO2 + KOH + KClO3→ 3K2MnO4 + KCl + 3H2O

Neutral - 3K2MnO4 + 4Co2 + 2H2O → 2KMnO4 medm + Mn + 4KHCO3

(Disproportion reaction)

MnO2 =Manganese oxide KOH = caustic potash

KClO3 = potassium chlorite = oxidizing agent KMnO4 = potassium permanganate
K2MnO4 = potassium magnate

m 2- +
Acidic med – 3Mno4 + H → 2Mno4 = Mno2 + 2H2O

 Electrolytic oxidation-
K2MnO4 + H2O + [O] KMno4 + KOH
Alkaline solution permanganate Magnate (deep purple black colored crystals)
 Chemical prop of KMnO4

In acidic In basic In neutral

In m
a. acidic med

[Link] of iodide to iodine

- - + +2
2MnO + 10 I4 + 16H → 2Mn + 8H O + I 2 2

+2 +3 - +2 + +3 +2
2. Oxidation
4 of Fe to Fe MnO +5Fe + 8H → 5Fe + Mn +2 4H O

+
3. Oxidation of H2S H2S → 2H
 2-
S
2- (-) (+) +2
5S + 2MnO + 16H 4 → 2Mn +5S+ 8H O 2

[Link] of oxalic acid

- + +2
2MnO4 + 5H2C2O4 + 6H → 2Mn + 10CO2+ 8H2O
m
(Alkaline =Basic med )
b. In neutral or weakly alkaline med

1-- -
General reaction → MnO + H O + x → MnO +4y + OH 2
2
Oxidation (-) - 3
1. of iodide (I ) to iodate (IO )
2MnO 4(-) 2 - 2 (-) ( 3- )
+HO + I → 2MnO + 2OH + IO

2- 2-
2. Thiosulphate (S2O3 ) is oxidized to sulphate (SO )
8MnO (-) 2- -
4 4 + 3S2O 3 + H2O → 8MnO2 = 6SO4 + 2OH

3. Magnous salt is oxidized to MnO2

4(-) +2 2
2MnO + 3Mn + 2H O → 5MnO2 (+)
+ 4H
 Uses of KMnO4-
a. As an antiseptic
b. For unsaturation test in laboratory
c. In volumetric analysis of reducing agents
d. For detecting halides in qualitative analysis
e. Powerful oxidizing agent in laboratory & industry

2. Compounds of Cr
K2Cr2O7
Preparation of K2Cr2O7 (Potassium dichromate)

(FeOCr2O3) + Na2CO3 + O2→ Na2 CrO4 + Fe2O3 + CO2

Chromite sod

Ore carbonate

From Na2CrO4

1.
Na2Cr2O7 2. K2Cr2O7

1. Na2Cr2O4 + H2SO4 Na2Cr2O7 + Na2SO4+ Na2Cr2O7

.H2O

2. Na2Cr2O4 + KCl K2Cr2O7 + NaCl

Chemical properties of
Frame reaction or simplest reaction
K2Cr2O7 + H2SO4 + x → Y + Cr2 (SO4)3 + H2O + K2SO4
1-
a. Oxidation of I (i.e KI) to I2
K2Cr2O7 + KI + H2SO4→ K2SO4 + I2 +H2O + Cr2(SO4)3
b. H2s is oxidized to S (Sulphur)
K2Cr2O7 + H2SO4 + H2S → S + K2SO4 + Cr2(SO4)3
 Mineral
A naturally occurring substances found in the earth’ crust containing inorganic salt, solids,
silicon’s matter is called as mineral.

 Ore
The mineral which contains high percentage of metal and from which the metal can be
extracted profitably or economically is called as ore.

 List of minerals and ores of some transition metal

Mineral Ore
1. Iron Hematite(Fe2O3) Hematite
Magnate (Fe3O4)

Limonite (2Fe2O3.3H2O) Iron pyrite (FeS2)

Siderite (FeCO3)

2. Copper chalcopyrite (CuFeS2) chalcopyrite

Or or
Chalcocite chalcocite Cuprite

(Cu2O)

3. Zinc Zinc Blende (Zns) Zincate

Zinc Blende
(ZnO) Calamine (ZnCO3)
 Metallurgy

Pyro metallurgy Hydrometallurgy electrometallurgy Ore → metal

n
[Link] → metal molten → metal

of salt metallic
compound
by reducing by reducing agents
agents

n
C,H,Al electrolytic Red

 Steps involved in process of extraction Concentration-

The step in which impurities called as gangue are removed form ore and ore gets concentrated
is called as concentration

Gangue-
The sand, mud and other unwanted impurities which remain mixed with the ore deposit are
called as Gangue.
 Extraction of Iron from Hematite ore using Blast
furnace
 Composition of Hematite ore – Fe2O3 + SiO2 + Al2O3 +
phosphates

Gangue

 Process involved in the extraction of Fe (Iron) from Hematite ore-

a. Concentration
The powdered ore is washed in a powerful flow of water using Hydraulic classifier.

The lighter gangue particles are separated and the concentrated ore is collected at the Bottom

b. Roasting-
The ore which is concentrated is then heated ion a current of air.
FeO + O2→Fe2O3
The roasted ore is converted into lumps by
sintering

c. Reduction (smelting) –
Smelting is done in a blast furnace.
 Blast furnace-
The tall cylindrical steel tower, is lined with
refractory bricks forms blast furnace.

 3 temperature zones in the furnace-

Zone of Zone of slag

combustion Zone of reduction
formation

Combustion of coke Reduction of fe2O3 to fe Gangue→ slag

(carton) with O2 in air (metallic) CaCO3→CaO+CO2
Fe2O3 + CO → Fe + CO2 Fe2O3 CaO + SiO2→ CaSiO3
C + 1/2O2→ CO 2CO
→ 2C + O2 + C → Fe + CO

 Zone of fusion
a. MnO2& Ca3 (PO4) present in iron ore are reduced to Mn & P.
b. Silica is reduced to Si.
c. Spongy Fe absorbs impurities like C, Si, Mn, P & S.
d. Molten Fe is powered into molds.
These solid blocks are called as Pigs. Pig iron contains 4l % of carbon

Pig iron cast iron Remelt

 Refining-
Pure Fe can be obtained by electrolyte refining of Impure iron.
Refining technique depends upon some factors-
a. Nature of ore
b. Cost and Availability of reducing agent
c. Availability of Hydraulic power
d. Purity of product
e. Value of byproduct

 Commercial forms of Fe

Cast Wrought Steel

Cast iron Wrought Iron Steel

Nature
hard + Brittle Soft Neither hard nor soft
%of carbon
4% C Less than 0.2% C 0.2-2% of C
Uses- Building infrastructure
making pipes Pipes, engine bolt
automotive parls utensils ships, toops, weapons
 Inner transition elements-
OR
f-block elements
OR
Lanthanides and Actinides series

The elements in which, the last electrons enters into the f-subshell are called as f-block
elements.

Position of f-block elements-

i. They are placed separately at the bottom of the periodic table.
th th
ii. They are subset of 6 and 7 period
Reason? Why f-block elements are also called as Inner transition elements?

-f-orbital lies or is present inside the d-orbital, so these elements are also called as Inner
transition elements (i.e inner to transition (d) block elements)

 Properties of f-block elements

a. They have similar properties as that of d-block elements
-
b.e are added into f-subshell

c. Placed between (n-1) and ns subshell

d. The start from atomic no-57 and end at atomic no- 71
e. They are also called as Rare earth elements
 Reactions of lanthanide elements
[Link] + H2O Ln(OH3)
Hydroxide of lanthanide

[Link] + C LnC2
Carbon carbides of lanthanides

[Link] + N LnN
Nitrogen Nitrides of lanthanides

[Link] + X LnX3
Halogen Halides of lanthanides
 Prop of lanthanides
i. As they are metals, so they are good conductors of heat and electricity.

ii. They show silvery white colour

iii. They are all Radioactive in nature, (except Promethium)
iv. Gadolinium is highly ferromagnetic in nature
v. They show lanthanides contraction.
 Electronic configuration
Atomic no’s electronic configuration

La 57 [Xe] 4f0 5d1 6s2

Ce 58 [Xe] 4f1 5d1 6s2

Pr 59 [Xe] 4f3 5d0 6s2

Nd 60 [Xe] 4f4 5d0 6s2

Pm 61 [Xe] 4f5 5d0 6s2

Sm 62 [Xe] 4f6 5d0 6s2

Eu 63 [Xe] 4f7 5d0 6s2

Gd 64 [Xe] 4f8 5d1 6s2

Tb 65 [Xe] 4f9 5d0 6s2

Dy 66 [Xe] 4f10 5d0 6s2

HO 67 [Xe] 4f11 5d0 6s2

Er 68 [Xe] 4f12 5d0 6s2

Tm 69 [Xe] 4f13 5d0 6s2

Yb 70 [Xe] 4f14 5d0 6s2

Lu 71 [Xe] 4f14 5d1 6s2

 Oxidation states of lanthanides
a. +3 is the common oxidation states of lanthanides series elements
b. The order in which the electrons are removed are firstly from s-subshell (2e-) and then
-
from d- subshell (le ) and lastly from f-subshell.
+4 0 +4 7
c. Ce f – vacant Tb f

– half filled

+2 7
Eu f -

+2 14
Yb f – completely filled

 Colour of lanthanide elements?

I. The colour is due to the presence of f-f- transitions occurring in the
elements.
n 14-n
II. The f and f have same colour.

Ex
No of f- electrons (14-n)

Pr+3 n=2 4f2 =12 Green

Tm+3 n=12 4f12 =2 Colour
Nd+3 n=3 4f3 =11 Pink
Er+3 n=11 4f11 =3 Colour

Atomic radii and ionic radii of lanthanide series OR

Lanthanide construction
1. As we move from left to right, nuclear charge
increases
2. As f-subshell have diffused shape so shows less screening effect
or shielding effect.
3. So (ENC) effective nuclear charges increases.
4. As a result of the above reasons the atomic or Ionic radius decrease from left to right.
5. These decreases in the values of radius observed in case of lanthanide series and hence is
called as lanthanide contraction.
 Applications of lanthanides
1. They are used inside the colour tubes in TV
(television)
2. Mixed oxide of europium releases or shows red
colour
3. They are used in superconductors and permanent magnet
4. They are also used in fiber-optics communication system.
 Actinides-
o The last row of elements in the periodic table is
called as actinide series

o They are all radioactive

o They start from z=89 to z=103 (where z=atomic number)

o They have high densities as they are also metals.

o They show high melting and Boiling point

o They show +2 to +8 oxidation states

-
o General e configuration
[ 0-14 0-2 2
o Rn] 5f 6d 7s
o Most stable oxidation state is +3
 Electronic configuration of actinoids
Atomic no’s electronic configuration

Ac 89 [Rn] 5f 6d1 7s2

Th 90 [Rn] 5f 6d 7s2

Pa 91 [Rn] 5f2 6d1 7s2

U 92 [Rn] 5f3 6d1 7s2

Np 93 [Rn] 5f4 6d1 7s2

Pu 94 [Rn] 5f6 6d1 7s2

Am 95 [Rn] 5f7 6d10 7s2

Cm 96 [Rn] 5f7 6d1 7s2

Bk 97 [Rn] 5f9 6d0 7s2

Cf 98 [Rn] 5f10 6d0 7s2

Es 99 [Rn] 5f11 6s0 7s2

Fm 100 [Rn] 5f12 6d0 7s2

Md 101 [Rn] 5f13 6d0 7ss

No 102 [Rn] 5f14 6d0 7s2

Lr 103 [Rn] 5f14 6d1 7s2

 Actinoid contraction-
a. As we move from left to right nuclear charge
increases
b. As f-subshell have diffused shape so it shows less shielding or screening effect
c. As a result of which the effective nuclear charge increases
d. 6d,5f,7s subshell have almost similar energies
e. Due to the above reasons atomic and ionic radii of actinoids decreases.
f. These is also called as actinoid contraction

 Properties of actinoids-
1. They show silvery white colour
2. They are highly reactive metals
3. They show +3 oxidation state as common
4. They show actinoid contraction

 Application of actinoids
a. Tho2 with 1% CeO2 is used as major indoor
lightning source
b. They are mostly used during outdoor camping

 Postactinoid element
Element with atomic no> 92 are called as
transurnium elements.
93 – 103 104-118

Actinoids post actinoid element