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TRANSITION AND INNER TRANSITION ELEMENTS
PRESENTE
D BY:
FREYA
CARDOZO
BY FREYA CARDOZO
TRANSITION ELEMENTS
THE GENERAL ELECTRONIC CONFIGURATION OF TRANSITION ELEMENTS IS
(N-1)D1-10 NS1-2.
THE TRANSITION ELEMENTS ARE PLACED IN THE PERIODS 4 TO 7 AND GROUPS 3 TO 12
THOSE CONSTITUTE 3D,4D,5D AND 6D SERIES
BY FREYA CARDOZO
WHAT ARE TRANSITION ELEMENTS
 Elements that have a partially filled d orbital in their ground state or one of its oxidation state.
 G.R why Zn is not a transition element but Cu is.
Since zinc has completely filled (n - 1)d orbital in the ground state (3d104s2) and (3d10) in its common
oxidation state +2, it is not regarded as transition element.
Copper in the elementary state (3d104s1) contains filled 3d orbitals but in the +2 oxidation state it has partly
filled 3d orbital (3d9), hence copper is a transition element.
BY FREYA CARDOZO
BY FREYA CARDOZO
OXIDATION STATE
BY FREYA CARDOZO
GIVE REASON
 Why Cu and Cr show anomalous E.C
 Mainly due to the fact that half filled and fully filled orbitals have extra stability
 The general electronic configuration of the elements of the 3d series is 3d1-10 4s2 with the exceptions of
Cr and Cu.
 The 3d and 4s orbitals are close in energy and in order to gain extra stability the last electron instead of
occupying 4s orbital occupies the 3d orbital that assigns Cr the 3d5 4s1 and Cu 3d10 4s1configuration
BY FREYA CARDOZO
PHYSICAL PROPERTIES
 They are hard, lustrous, malleable and ductile
 They are good conductors of heat and electricity
 They possess high MP BP
 Except Zn, Cd, Hg and Mn, all the other transition elements have one or more typical metallic structures
at ambient temperature.
 These transition metals (with the exception of Zn, Cd and Hg) are very hard and have low volatility
BY FREYA CARDOZO
IONIC RADIUS
 For the same oxidation state, with an increase of nuclear
charge a gradual decrease in ionic radii was observed.
The trend is pronounced for the divalent ions of the first
transition series (Cr2⊕ - 82 pm, Cu2⊕ - 72 pm).
 The oxidation states of the same element shows
difference of one unit such as M⊕, M2⊕, M3⊕,M4⊕ and so
on.
With higher oxidation state the effective nuclear charge also
increases and hence, decrease of ionic radii can be observed
from M2⊕ to M3⊕
BY FREYA CARDOZO
ATOMIC RADII DECREASES GRADUALLY
ACROSS THE PERIOD
 As we move across a transition series from left to right the nuclear charge increases by one unit at a
time.
 The last filled electron enters a penultimate (n-1)d subshell.
 However, d orbitals in an atom are less penetrating or more diffused and, therefore d electrons offer
smaller screening effect.
 The result is that effective nuclear charge also increases as the atomic number increases along a
transition series.
 Hence the atomic radii decrease gradually across a transition series from left to right.
BY FREYA CARDOZO
Size decreases across a period
IONIZATION ENTHALPY
 The I.E for d block elements lies between the s and p blocks
 Across the group as the size decrease
 Ionization enthalpy increases
 IE3>IE2> IE1
 Depending on condition the type of bond is decided
 Lower O.S – Ionic bond
 High o.s – Covalent bond
BY FREYA CARDOZO
Ionization energy or Ionisation
energy, denoted Eᵢ, is the minimum
amount of energy required to
remove the most loosely bound
electron, the valence electron, of an
isolated neutral gaseous atom or
molecule
Size decreases across a
period
I.E ↑
Acros
s the
period
IONISATION ENTHALPY
 G.R ionization enthalpy for 3rd transition series is
more than 1st and 2nd series
 The atoms of elements of third transition series
possess filled 4f- orbitals. 4f orbitals show poor
shielding effect on account of their peculiar diffused
shape.
 As a result, the valence electrons experience greater
nuclear attraction.
 A greater amount of energy is required to ionize
elements of the third transition series
BY FREYA CARDOZO
METALLIC CHARACTER
 Metallic character is due to the :
1. VACANT d orbitals
2. Low ionisation enthalpy
 Hardness of metals is due to the covalent bond which is possible because of the unpaired (n-1)d
electrons in these elements
 Mostly they show HCP, ccp, bcc lattice structure
 Hardness, high melting points and metallic properties of the transition elements indicate that the metal
atoms are held strongly by metallic bonds with covalent character.
BY FREYA CARDOZO
MAGNETIC PROPERTIES
 They show magnetic properties due to the unpaired electrons
 3 types
1. Dimagnetic – Replled by magnetic field
2. Paramagnetic- attracted to mag field
3. Ferromagnetic- strongly attracted. EG. Fe, Co, Ni
 Magnetic moment is sum of spin angular momentum and orbital angular momentum
 µ= n(n + 2) BM
 n = no.of unpaired ELECTRONS
BY FREYA CARDOZO
Paired e- : Diamagnetic
Unpaired e-:
Paramagnetic
QUESTIONS
Which one of the following is dimagnetic
a. Cr2⊕ b. Fe3⊕
c. Cu2⊕ d. Sc3⊕
Magnetic moment of a metal
complex is 5.9 B.M. Number of
unpaired electrons in the complex is
a. 2 b. 3
c. 4 d. 5
BY FREYA CARDOZO
QUESTIONS
 What is the magnetic moment for Cr3+
a. equal to 1.73 BM,
b. less than 1.73 BM or
c. more than 1.73 BM ?
Why salts of Sc3⊕, Ti4⊕, V5⊕ are colourless ?
 Calculate the spin only magnetic moment of divalent cation of a transition metal with atomic number 25.
BY FREYA CARDOZO
BY FREYA CARDOZO
D BLOCK ELEMENTS ARE REMARKABLY
COLOURED
BY FREYA CARDOZO
A substance appears coloured if
it absorbs a portion of visible light. The colour
depends upon the wavelength of absorption in
the visible region of electromagnetic radiation
BY FREYA CARDOZO
REASONS FOR COLOR IN TRANSITION METALS
1. presence of unpaired d electrons
2. d - d transitions
3. nature of ligands attached to the metal ion
4. geometry of the complex formed by the
metal ion
BY FREYA CARDOZO
UNPAIRED ELECTRONS AND D-D TRANSITION
REASON FOR COLOUR- d-d transition
BY FREYA CARDOZO
GEOMETRY OF COMPLEX ION
 When cobalt chloride (Co2⊕) is dissolved in water, it forms a pink solution of the complex
[Co(H2O)6]2⊕ which has octahedral geometry.
 But when this solution is treated with concentrated hydrochloric acid, it turns deep blue.
 This change is due to the formation of another complex [CoCl4]2 which has a tetrahedral structure.
BY FREYA CARDOZO
CHARGE TRANSFER
 MnO4- ion has an intense purple colour in solution.
 In MnO4- , an electron is momentarily transferred from oxygen (O) to metal, thus momentarily changing
O2 to Oand reducing the oxidation state of manganese from +7 to +6.
 For charge transfer transition to take place, the energy levels of the two different atoms involved should
be fairly close.
 Colours of Cr2O7
2- , CrO4 , Cu2O and Ni-DMG (where DMG = dimethyl glyoxime) complex are other
examples
BY FREYA CARDOZO
CATALYTIC PROPERTIES
 because of their ability to participate in different oxidation-reduction steps of catalytic reactions.
 This possible due to
1. unpaired e-s in incomplete d orbitals
2. variable o.s
3. Large surface area
 In homogeneous catalysis reactions, the metal ions participate by forming unstable intermediates.
 In heterogeneous catalysis reactions on the other hand, the metal provides a surface for the reactants to
react.
BY FREYA CARDOZO
EXAMPLES OF IMPORTANT CATALYST
 Mo/Fe – Habers process
 Co-Th Fischer Tropsch process --- gasoline synthesis
 Ni – cataylic hydrogenation
 Platinised asbestos- solid catalyst --- contact process for manu of sulfuric acid from SO2 and O2
 Fe-Cr – production of CO2 frm CO
BY FREYA CARDOZO
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 interstitial compounds
 Steel and cast iron are examples of interstitial compounds of carbon and iron
 Properties
1. Good conduction
2. MP BP higher than parent
3. Density less than parent
 carbides of metals are inert and hard
 hydrides of transition metals are Powerful reducing agents
BY FREYA CARDOZO
ALLOYS
 Alloys are mixtures of metals
 classification
1. Ferrouss alloys have atoms of other elements distributed randomly in atoms of
iron in the mixture.
As percentage of iron is more, they are termed ferrous alloys eg. nickel steel,
chromium steel, stainless steel etc. All steels have 2% carbon
2. Non-ferrous alloys are formed by mixing atoms of transition metal other than iron
with a non transition element.
eg. brass, which is an alloy of copper and zinc. Ferrous and non-ferrous alloys are
of industrial importance.
BY FREYA CARDOZO
USES
 Bronze=Cu+Tin Tough, strong and corrosion resistant
 Cupra nickel – machine parts of ships
 stainless steel – air crafts
 Nichrome=Ni+Cr – turbine engines
 Titanium alloys --- can withstand high temp
Components of Nichrome alloy are
are
a. Ni, Cr, Fe b. Ni, Cr, Fe, C
c. Ni, Cr d. Cu, Fe
BY FREYA CARDOZO
PREPERATION OF POTASSIUM DICHROMATE
K2CR2O7
1. Chromite ore =FeO.Cr2O3 to Sodium chromate Na2CrO4 --- anhydrous
sodium carbonate And flux of like in air
2. Sodium chromate to Sodium dichromate Na2Cr2O7 ---- Sulphuric acid
and water
3. Sodium dichromate to potassium dichromate K2Cr2O7 --- Potassium
chloride
BY FREYA CARDOZO
FeO.Cr2O3
Na2CrO4
Na2Cr2O7
K2Cr2O7
OUTLINE
STEP 1
STEP 1
BY FREYA CARDOZO
STEP 2
STEP 2
BY FREYA CARDOZO
STEP 3
STEP 3
BY FREYA CARDOZO
CHEMICAL PROPERTIES OF POTASSIUM
DICHROMATE
Reactant Colour
(Before)
K2SO4 Cr2(SO4)3 H2O Special
byproduct
Color
K2Cr2O7+H2SO
4
KI
Potassium
iodide
Orange ✓ ✓ ✓ I2 Brown
K2Cr2O7+H2SO
4
H2S
Hydrogen
sulphide
Orange ✓ ✓ ✓ S Green
solution
+
Yellow
ppt
BY FREYA CARDOZO
REACTION WITH KI
 The oxidation of KI with acidified potassium dichromate produces I2
 This changes the solution to brown
 Potassium dichromate is reduced to chromic sulphate
BY FREYA CARDOZO
REACTION WITH H2S
 The reaction leads to the pptn of S which appears as pale yellow ppt
 Potassium dichromate is reduced to chromic sulphate
 Due to the production of chromic sulphate the orange solution turns green
BY FREYA CARDOZO
KMNO4 – POTASSIUM PERMANGANATE
Preparation method
1. Chemical oxidation
2. Electrolytic oxidation
BY FREYA CARDOZO
CHEMICAL METHOD
 MnO2 manganese dioxide  K2MnO4 Potassium mangante(green) –
1. Caustic potash KOH
2. Potassium chlorate KClO3 – oxidising agent
 Dispropotionation in neutral or acidic medium  KMnO4 + MnO2
 Filteration to glass wool
BY FREYA CARDOZO
ELECTROLYTIC OXIDATION
 Alkaline solution of manganate ion is electrolysed between iron electrodes seperated by a diaphram
 At anode the oxygen evolved is used to reduce manganate to permanganate
 Overall reaction
 The solution is evaporated and filtered to obtain the crystals
BY FREYA CARDOZO
CHEMICAL PROPERTIES OF KMNO4
 In acidic medium- Oxidising action
1. Iodide to Iodine
2. Fe2+ to Fe3+
3. H2S to S
4. Oxidation of oxalic acid H2C2O4
 In neutral medium or weakly alkaline medium
1. Iodide to Iodate
2. Oxidation of thiosulphate to sulphate
3. Manganous salt to manganese dioxide
BY FREYA CARDOZO
IN ACIDIC MEDIUM
BY FREYA CARDOZO
ACIDIC MEDIUM
BY FREYA CARDOZO
NEUTRAL OR ALKALINE MEDIUM
BY FREYA CARDOZO
USES
 Antiseptic
 Test for unsaturation
 Quantitative analysis- Halide detection
 Volumetric analysis- For reducing agents
 Oxidising agent- labs and industry
 Why is KMnO4 such a good oxidising agent?
BY FREYA CARDOZO
QUESTIONS
BY FREYA CARDOZO
INNER TRANSITION ELEMENTS
 Orbital lies much inside the d orbital,in relation to the transition metals the f
block elements are called inner transition elements.
 f – 1 to 14 electrons, d – 0 or 1 and s – 2 electrons
 2 series : Lanthanoids and Actinoids
 Lanthanoids – characterizied by filling of 4f
 Actinoids - characterizied by filling of 5f
 14 elements in each
BY FREYA CARDOZO
F BLOCK ELEMENTS
 Those elements in which the outermost electrons enter the f subshell
 They belong to the 6th and 7th period
 Placed seperately at the bottom of the table
BY FREYA CARDOZO
PROPERTIES OF F BLOCK ELEMENTS
 These metals are soft with moderate densities of about 7 g cm-3.
 They have high melting point
 They are quite reactive similar to the alkali metals than d block metals
 common oxidation state for lanthanoids is +3
 +2 is also very common among these, higher O.S like +4 is unusual (exptn- Ce)
BY FREYA CARDOZO
LANTHANOIDS- RARE EARTH ELEMENTS
They were know as rare because it was difficult to extract them economically from their ores
BY FREYA CARDOZO
G.R: LANTHANOIDS HAVE LOWER HEAT OF
ATOMIZATION THAN TRANSITION METALS.
The energy required to break up the metal lattice is heat of atomization.
This is because with d electrons, transition metals
are much harder and require high heat of
atomization.
Europium and ytterbium have the
lowest enthalpies of vaporization and largest
atomic radii of lanthanoids, resemble barium.
BY FREYA CARDOZO
RADII
Their ionic radii decrease from 117 pm of La to 100 pm for Lu.
This is because 5f orbitals do not shield the outer 5s and 5p electrons
effectively, leading to increase in effective
nuclear charge and decrease in the ionic size.
BY FREYA CARDOZO
REACTIONS WITH LN
Reactants Reactants Product
Ln C LnC
Ln H2O Ln(OH)3
Ln O2 Ln2O3
Ln N2 LnN
Ln X LnX3
Ln= Lanthanoids
BY FREYA CARDOZO
BASICITY OF LANTHANOIDS
All the lanthanoids form hydroxides ofthe general
formula Ln(OH)3
These are ionic and basic.
 Since the ionic size decreasesfrom La3+ to Lu3+,
the basicity of hydroxides decreases.
La(OH)3 is the strongest base while Lu(OH)3 is the
weakest base.
BY FREYA CARDOZO
ELECTRONIC CONFIGURATION
 Generally the E.C for lanthanoids is represented as [Xe] 4f0-14 5d0-1 6s2
 Xe = Xenon, Z= 54
 The E.C for Xe is 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10
BY FREYA CARDOZO
EXCEPTIONS
 The electrons first fill up the 6s
 4f and 5d are very close in energy
 In case of lanthanum the 5d oribtal has lower energy
 In case of Gd and Yb the anamolous behaviour is
observed
 As half filled and fully filled electrons have extra stability
 Thus general E.C for lanthanoids is [Xe] 4f0-14 5d0-1 6s2
BY FREYA CARDOZO
IONISATION ENTHALPY
 What is ionisation enthalpy?
 As size increases, ionisation enthalpy decreases since the
last electron experiences lesser pull from the nucleus
 Across the period, size decreases thus I.E increases
 Why some elements have variable O.S states but others only
a few? Can ionisation enthalpy justify these?
BY FREYA CARDOZO
QUESTION
HINT:
-Energy required to remove unpaired electrons is lesser than that
to remove paired electrons
- Check the energy of subshell, lower the energy easy to remove
the last electron
- n+l lower: lesser energy the subshell has
BY FREYA CARDOZO
OXIDATION STATE
 G.E.C = [Xe] 4f0-14 5d0-1 6s2
 thus the common O.S is +3 i.e 2 e- from 6s and the order from d/f
subshell
 The 4f electrons are shielded by the inner 5s and 5p orbitals, they are
tightly bond to the nucleus. Thus they do not take part in the bonding
 Some show O.S +2 and +4 this is due to f0, f7, f14 E.C
BY FREYA CARDOZO
COLOUR
 These elements are coloured due to the f-f
transition which corresponds to the energy in
the visible spectrum
 The colour of ions with nf electrons= (14-n)f
electrons
COLOUR IN LANTHANOIDS
BY FREYA CARDOZO
WHAT IS SHIELDING EFFECT
The decrease in the net force of attraction between
the electrons present in the outer shell of an atom in
the direction of nucleus due to change in linearity of
the electric lines of forces between them due to the
presence of high election density in the inner shells
in the same atom is known as screening effect.
BY FREYA CARDOZO
ATOMIC RADII
 Across the period the radii decreases as the size
decreases
 The decrease in lanthanoids is very steady this is
called the LANTHANOID CONTRACTION
 As we move left to right the nuclear charge
increases by +1 and an electron is added
 The electron is added to the same 4f subshell
 Due to their diffused shape the 4f electrons shield
each other poorly from the nuclear charge
 With increasing atomic no. the effective nuclear
charge increases thus pulling the 4f shell closer,
causing it to cntract
BY FREYA CARDOZO
MAGNETIC MOMENT
 µ=square root of n(n + 2) BM
 n = no.of unpaired ELECTRONS
 Calculate magnetic moment for La3+
 La -57
 [Xe]4f05d16s2 n=1
Magnetic moment
BY FREYA CARDOZO
APPLICATIONS
 In hybrid cars, superconductors and permanent magnets
 Used in the colour tubes of computers and T.Vs since they
produce visible light over a small wavelength upon bombarding
with e-s
 (Eu,Y)2O3 – red colour
 There types of Ln are used to get 3 primary colours
 Luminescent materials Nd: YAG laser
Applications of Lanthanoids
BY FREYA CARDOZO
ACTINOIDS
BY FREYA CARDOZO
ACTINOIDS
 Starts with Thorium Z=90 and ends with Lawrencium Z=103
 They are all radioactive and man-made
 High M.P, B.P, density
 The electronic configuration of actinoids is
[Rn] 5f0-14 6d0-2 7s2, where Rn is the electronic
configuration of radon.
 most stable oxidation state in actinoids
is +3. The highest however actinoids show a variety of O.S from +2 to +8
BY FREYA CARDOZO
DIFFERENCES
BETWEEN
LANTHANOIDS AND
ACTINOIDS
BY FREYA CARDOZO
OXIDATION STATE
 Early lanthanoids show variable O.S this is similar to transition
elements than lanthanoids
 This pattern is seen mostly due to the ability of 5f orbital to
participate in bonding
 A ready loss of 5f electrons by early actinoids indicates that these
electrons are much closer in energy to 7s and 6d electrons than
the 4f electrons to 6s and 5d electrons as in lanthanoids
 G.E.C [Rn] 5f0-14 6d0-2 7s2
 Eg. uranium has electronic configuration of [Rn]7s2 5f 36d1. The
formation of +6 oxidation state corresponds to an electronic
configuration of [Rn].
BY FREYA CARDOZO
Half filled and fully filled
orbitals have extra stability.
Thus one electron from f is
promoted to d
BY FREYA CARDOZO
The overall gradations
among the different blocks
of the periodic table
Transition elements- d
block
Lanthanoids-f block
Pre- transition – s block
BY FREYA CARDOZO
ACTINOID CONTRACTION
 5f 6d 7s are almost same energy in actinoids
 The 7s electrons shield the 5f and 6d orbitals from nuclear
charge , thus they expand a little. Therefore, they have size
greater than lanthanoids
 But the decreases in radii is not as prominent, due to the
shielding effect of f orbitals
BY FREYA CARDOZO
APPLICATION OF ACTNOIDS
 Half lives of Thorium & Uranium are so long that
the amount of radiation emitted is negiligble, thus
they can be used in everyday life.
 Th(IV) oxide, ThO2 with 1% CeO2 was used as a
major source of indoor lighting before
incandescent lamps came into existence only
because these oxides convert heat energy from
burning natural gas to an intense light.
 Even today, there is a great
BY FREYA CARDOZO
POSTACTINOID ELEMENTS
POST ACTINOID ELEMENTS
 Elements with atomic number greater than 92 are called ‘Transuranium’.
 Elements from atomic number 93 to 103 now are included in actinoid series and
those from 104 to 118 are called as postactinoid elements.
 They are included as postactinoids because similar to actinoid elements, they can
be synthesized in the nuclear reactions.
 So far, nine postactinoid elements have been synthesized.
 Half life is in secs 2.8 x 10^-4, thus difficult to study reactions
 Rutherfordium forms a chloride, RfCl4, similar to zirconium and hafnium in the +4
oxidation state.
 Dubnium resembles to both, group 5 transition metal, niobium(V) and actinoid,
protactinium(V).
BY FREYA CARDOZO
Questions
ix. In which of the following series
all the elements are radioactive in
nature
a. Lanthanides b. Actinides
c. d-block elements d. s-block elements
x. Which of the following sets of ions
contain only paramagnetic ions
a. Sm3⊕, Ho3⊕, Lu3⊕ b. La3⊕, Ce3⊕, Sm3⊕
c. La3⊕, Eu3⊕, Gd3⊕ d. Ce3⊕, Eu3⊕, Yb3⊕
xi. Which actinoid, other than uranium,
occur in significant amount
naturally?
a. Thorium b. Actinium
c. Protactinium d. Plutonium
BY FREYA CARDOZO
METAL EXTRACTION
BY FREYA CARDOZO
DEFINITION
 Mineral : naturally occuring substance found in the earth’s crust containing inorganic salts, solids,
siliceous matter etc, is called a mineral.
 Ore: The mineral which contains high percentage of the metal and from which the metal can be
extracted economically is called an ore
DEFINITONS
BY FREYA CARDOZO
METALLURGY
Commercial extraction of metals from their ores is called
metallurgy.
BY FREYA CARDOZO
TYPES OF METALLURGY
 Pyrometallurgy: A process in which the ore is reduced to
metal at high temperature using reducing agents like carbon,
hydrogen, aluminium, etc. is called pyrometallurgy.
 Hydrometallurgy : The process of extracting metals from the
aqueous solution of their salts using suitable reducing agent
is called hydrometallurgy.
 Electrometallurgy : A process in which metal is extracted by
electrolytic reduction of molten (fused) metallic compound is
called electrometallurgy
TYPES OF METALLURGY
BY FREYA CARDOZO
GENERAL METHODOLOGY
 Extraction of ore
 Concentration of ore – removing impurities of other metals, sand, dust
particles
impurities termed as gangue are removed from the ore and the ore gets
concentrated.
The sand, mud and other unwanted impurities which remain mixed with the
ore deposit are called gangue.
Methods –
1. Hydraulic classifiers
2. Froth floation
3. Magnetic seperation
 Convert to its oxides – Can be done by either
1. Roasting .
2. Calcination
 Obtaining pure metal
BY FREYA CARDOZO
STEPS
BY FREYA CARDOZO
EXTRACTION OF IRON
 Ore – Haematite ore (Fe2O3)
 Gangue -SiO2 + Al2O3+ phosphates
 Concentration – Hydraulic classifier
The powdered ore is washed in a powerful current of water introduced
into the hydraulic classifier.
The lighter gangue particles are separated and the concentrated ore is
collected at the bottom.
 Converting into the oxide
Roasting : The concentrated ore is heated In a current of air. The sulfur
and arsenic impurties present in the ore get converted into their oxides
and escape as vapour. Ferrous oxide in the ore is converted to Fe2O3
4FeO + O2 -- 2 Fe2O3
STEPS IN EXTRACTION OF Fe ore
BY FREYA CARDOZO
HYDRAULIC CLASSIFIER
CONCENTRATION
OF ORE !
BY FREYA CARDOZO
BY FREYA CARDOZO
BLAST FURNANCE- Smelting
Tall cylindrical steel tower lined with
refractory bricks.
The height=25 m and diameter =5 to10
m.
 Working- counter current principle :
Charge comes down and hot gases move
up the tower.
 The furnace is comprised of 3 parts –
1. Hearth, 2. Bosh and 3. Stack
Ore is introduced in the furnace through
a cup and cone arrangement
Ensures uniform distribution and
prevents loss of gases
A blast of preheated air is introduced into
the furnance below the bosh through
BY FREYA CARDOZO
BY FREYA CARDOZO
1.ZONE OF COMBUSTION
 The formation of CO is exothermic and thus temperature is 2000K
 Some CO decomposes to C
 The hot CO gas moves upward and thus heats up the incoming charge
 Therefore CO acts as a fuel and reducing agent
BY FREYA CARDOZO
ZONE OF REDUCTION
BY FREYA CARDOZO
ZONE OF SLAG FORMATION
The gangue present in the ore is converted to slag. This slag can be used for making road foundation.
Temperature of this zone is 1200 K. The gangue contains silica, alumina and phosphates. A removal of this
gangue is effected by adding lime-stone in the charge, which acts as flux. Limestone decomposes to give
CaO (quick lime)
3.Zone of slag formation
BY FREYA CARDOZO
• ZONE OF FUSION
MnO2 and Ca3(PO4)2 present in the iron ore are reduced to Mn and P. Some of the silica is also reduced to
Si.
The spongy iron coming down in the furnace melt absorbs impurities like C, Si, Mn, P and S. This molten
iron collects at the bottom in the furnace.
The slag which is lighter floats on the surface of molten iron. Molten slag and iron are collected through
separate outlets.
Molten iron is poured into moulds.
These solid blocks are called pigs. This iron contains about 4% of carbon.
When pig iron is remelted, run into moulds and cooled, it becomes cast iron. The waste gases containing
N2, CO and CO2 escape through the outlet at the top. These hot gases are used for preheating
the blast of air
BY FREYA CARDOZO
ZONES OF BLAST FURNACE
BY FREYA CARDOZO
FACTORS AFFECTING EXTRACTION TECHNIQUE
Pure iron can be obtained by electrolytic refining of impure iron or other methods given in the flow chart.
The choice of extraction technique is governed by the following factors.
1. Nature of ore
2. Availability and cost of reducing agent, generally cheap coke is used
3. Availability of hydraulic power.
4. Purity of product (metal) required.
5. Value of byproducts for example, SO2 obtained during roasting of sulphide ores is vital for manufacture
of H2SO4. Knowledge of electrochemical series provides solutions to many problems.
BY FREYA CARDOZO
TYPES OF IRON
BY FREYA CARDOZO
BY FREYA CARDOZO
THANKYOU

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transitionandinnertransitionelements-200708043110.pdf

  • 1. TRANSITION AND INNER TRANSITION ELEMENTS PRESENTE D BY: FREYA CARDOZO BY FREYA CARDOZO
  • 2. TRANSITION ELEMENTS THE GENERAL ELECTRONIC CONFIGURATION OF TRANSITION ELEMENTS IS (N-1)D1-10 NS1-2. THE TRANSITION ELEMENTS ARE PLACED IN THE PERIODS 4 TO 7 AND GROUPS 3 TO 12 THOSE CONSTITUTE 3D,4D,5D AND 6D SERIES BY FREYA CARDOZO
  • 3. WHAT ARE TRANSITION ELEMENTS  Elements that have a partially filled d orbital in their ground state or one of its oxidation state.  G.R why Zn is not a transition element but Cu is. Since zinc has completely filled (n - 1)d orbital in the ground state (3d104s2) and (3d10) in its common oxidation state +2, it is not regarded as transition element. Copper in the elementary state (3d104s1) contains filled 3d orbitals but in the +2 oxidation state it has partly filled 3d orbital (3d9), hence copper is a transition element. BY FREYA CARDOZO
  • 6. GIVE REASON  Why Cu and Cr show anomalous E.C  Mainly due to the fact that half filled and fully filled orbitals have extra stability  The general electronic configuration of the elements of the 3d series is 3d1-10 4s2 with the exceptions of Cr and Cu.  The 3d and 4s orbitals are close in energy and in order to gain extra stability the last electron instead of occupying 4s orbital occupies the 3d orbital that assigns Cr the 3d5 4s1 and Cu 3d10 4s1configuration BY FREYA CARDOZO
  • 7. PHYSICAL PROPERTIES  They are hard, lustrous, malleable and ductile  They are good conductors of heat and electricity  They possess high MP BP  Except Zn, Cd, Hg and Mn, all the other transition elements have one or more typical metallic structures at ambient temperature.  These transition metals (with the exception of Zn, Cd and Hg) are very hard and have low volatility BY FREYA CARDOZO
  • 8. IONIC RADIUS  For the same oxidation state, with an increase of nuclear charge a gradual decrease in ionic radii was observed. The trend is pronounced for the divalent ions of the first transition series (Cr2⊕ - 82 pm, Cu2⊕ - 72 pm).  The oxidation states of the same element shows difference of one unit such as M⊕, M2⊕, M3⊕,M4⊕ and so on. With higher oxidation state the effective nuclear charge also increases and hence, decrease of ionic radii can be observed from M2⊕ to M3⊕ BY FREYA CARDOZO
  • 9. ATOMIC RADII DECREASES GRADUALLY ACROSS THE PERIOD  As we move across a transition series from left to right the nuclear charge increases by one unit at a time.  The last filled electron enters a penultimate (n-1)d subshell.  However, d orbitals in an atom are less penetrating or more diffused and, therefore d electrons offer smaller screening effect.  The result is that effective nuclear charge also increases as the atomic number increases along a transition series.  Hence the atomic radii decrease gradually across a transition series from left to right. BY FREYA CARDOZO Size decreases across a period
  • 10. IONIZATION ENTHALPY  The I.E for d block elements lies between the s and p blocks  Across the group as the size decrease  Ionization enthalpy increases  IE3>IE2> IE1  Depending on condition the type of bond is decided  Lower O.S – Ionic bond  High o.s – Covalent bond BY FREYA CARDOZO Ionization energy or Ionisation energy, denoted Eᵢ, is the minimum amount of energy required to remove the most loosely bound electron, the valence electron, of an isolated neutral gaseous atom or molecule Size decreases across a period I.E ↑ Acros s the period
  • 11. IONISATION ENTHALPY  G.R ionization enthalpy for 3rd transition series is more than 1st and 2nd series  The atoms of elements of third transition series possess filled 4f- orbitals. 4f orbitals show poor shielding effect on account of their peculiar diffused shape.  As a result, the valence electrons experience greater nuclear attraction.  A greater amount of energy is required to ionize elements of the third transition series BY FREYA CARDOZO
  • 12. METALLIC CHARACTER  Metallic character is due to the : 1. VACANT d orbitals 2. Low ionisation enthalpy  Hardness of metals is due to the covalent bond which is possible because of the unpaired (n-1)d electrons in these elements  Mostly they show HCP, ccp, bcc lattice structure  Hardness, high melting points and metallic properties of the transition elements indicate that the metal atoms are held strongly by metallic bonds with covalent character. BY FREYA CARDOZO
  • 13. MAGNETIC PROPERTIES  They show magnetic properties due to the unpaired electrons  3 types 1. Dimagnetic – Replled by magnetic field 2. Paramagnetic- attracted to mag field 3. Ferromagnetic- strongly attracted. EG. Fe, Co, Ni  Magnetic moment is sum of spin angular momentum and orbital angular momentum  µ= n(n + 2) BM  n = no.of unpaired ELECTRONS BY FREYA CARDOZO Paired e- : Diamagnetic Unpaired e-: Paramagnetic
  • 14. QUESTIONS Which one of the following is dimagnetic a. Cr2⊕ b. Fe3⊕ c. Cu2⊕ d. Sc3⊕ Magnetic moment of a metal complex is 5.9 B.M. Number of unpaired electrons in the complex is a. 2 b. 3 c. 4 d. 5 BY FREYA CARDOZO
  • 15. QUESTIONS  What is the magnetic moment for Cr3+ a. equal to 1.73 BM, b. less than 1.73 BM or c. more than 1.73 BM ? Why salts of Sc3⊕, Ti4⊕, V5⊕ are colourless ?  Calculate the spin only magnetic moment of divalent cation of a transition metal with atomic number 25. BY FREYA CARDOZO
  • 17. D BLOCK ELEMENTS ARE REMARKABLY COLOURED BY FREYA CARDOZO
  • 18. A substance appears coloured if it absorbs a portion of visible light. The colour depends upon the wavelength of absorption in the visible region of electromagnetic radiation BY FREYA CARDOZO
  • 19. REASONS FOR COLOR IN TRANSITION METALS 1. presence of unpaired d electrons 2. d - d transitions 3. nature of ligands attached to the metal ion 4. geometry of the complex formed by the metal ion BY FREYA CARDOZO
  • 20. UNPAIRED ELECTRONS AND D-D TRANSITION REASON FOR COLOUR- d-d transition BY FREYA CARDOZO
  • 21. GEOMETRY OF COMPLEX ION  When cobalt chloride (Co2⊕) is dissolved in water, it forms a pink solution of the complex [Co(H2O)6]2⊕ which has octahedral geometry.  But when this solution is treated with concentrated hydrochloric acid, it turns deep blue.  This change is due to the formation of another complex [CoCl4]2 which has a tetrahedral structure. BY FREYA CARDOZO
  • 22. CHARGE TRANSFER  MnO4- ion has an intense purple colour in solution.  In MnO4- , an electron is momentarily transferred from oxygen (O) to metal, thus momentarily changing O2 to Oand reducing the oxidation state of manganese from +7 to +6.  For charge transfer transition to take place, the energy levels of the two different atoms involved should be fairly close.  Colours of Cr2O7 2- , CrO4 , Cu2O and Ni-DMG (where DMG = dimethyl glyoxime) complex are other examples BY FREYA CARDOZO
  • 23. CATALYTIC PROPERTIES  because of their ability to participate in different oxidation-reduction steps of catalytic reactions.  This possible due to 1. unpaired e-s in incomplete d orbitals 2. variable o.s 3. Large surface area  In homogeneous catalysis reactions, the metal ions participate by forming unstable intermediates.  In heterogeneous catalysis reactions on the other hand, the metal provides a surface for the reactants to react. BY FREYA CARDOZO
  • 24. EXAMPLES OF IMPORTANT CATALYST  Mo/Fe – Habers process  Co-Th Fischer Tropsch process --- gasoline synthesis  Ni – cataylic hydrogenation  Platinised asbestos- solid catalyst --- contact process for manu of sulfuric acid from SO2 and O2  Fe-Cr – production of CO2 frm CO BY FREYA CARDOZO
  • 25. 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 interstitial compounds  Steel and cast iron are examples of interstitial compounds of carbon and iron  Properties 1. Good conduction 2. MP BP higher than parent 3. Density less than parent  carbides of metals are inert and hard  hydrides of transition metals are Powerful reducing agents BY FREYA CARDOZO
  • 26. ALLOYS  Alloys are mixtures of metals  classification 1. Ferrouss alloys have atoms of other elements distributed randomly in atoms of iron in the mixture. As percentage of iron is more, they are termed ferrous alloys eg. nickel steel, chromium steel, stainless steel etc. All steels have 2% carbon 2. Non-ferrous alloys are formed by mixing atoms of transition metal other than iron with a non transition element. eg. brass, which is an alloy of copper and zinc. Ferrous and non-ferrous alloys are of industrial importance. BY FREYA CARDOZO
  • 27. USES  Bronze=Cu+Tin Tough, strong and corrosion resistant  Cupra nickel – machine parts of ships  stainless steel – air crafts  Nichrome=Ni+Cr – turbine engines  Titanium alloys --- can withstand high temp Components of Nichrome alloy are are a. Ni, Cr, Fe b. Ni, Cr, Fe, C c. Ni, Cr d. Cu, Fe BY FREYA CARDOZO
  • 28. PREPERATION OF POTASSIUM DICHROMATE K2CR2O7 1. Chromite ore =FeO.Cr2O3 to Sodium chromate Na2CrO4 --- anhydrous sodium carbonate And flux of like in air 2. Sodium chromate to Sodium dichromate Na2Cr2O7 ---- Sulphuric acid and water 3. Sodium dichromate to potassium dichromate K2Cr2O7 --- Potassium chloride BY FREYA CARDOZO FeO.Cr2O3 Na2CrO4 Na2Cr2O7 K2Cr2O7 OUTLINE
  • 29. STEP 1 STEP 1 BY FREYA CARDOZO
  • 30. STEP 2 STEP 2 BY FREYA CARDOZO
  • 31. STEP 3 STEP 3 BY FREYA CARDOZO
  • 32. CHEMICAL PROPERTIES OF POTASSIUM DICHROMATE Reactant Colour (Before) K2SO4 Cr2(SO4)3 H2O Special byproduct Color K2Cr2O7+H2SO 4 KI Potassium iodide Orange ✓ ✓ ✓ I2 Brown K2Cr2O7+H2SO 4 H2S Hydrogen sulphide Orange ✓ ✓ ✓ S Green solution + Yellow ppt BY FREYA CARDOZO
  • 33. REACTION WITH KI  The oxidation of KI with acidified potassium dichromate produces I2  This changes the solution to brown  Potassium dichromate is reduced to chromic sulphate BY FREYA CARDOZO
  • 34. REACTION WITH H2S  The reaction leads to the pptn of S which appears as pale yellow ppt  Potassium dichromate is reduced to chromic sulphate  Due to the production of chromic sulphate the orange solution turns green BY FREYA CARDOZO
  • 35. KMNO4 – POTASSIUM PERMANGANATE Preparation method 1. Chemical oxidation 2. Electrolytic oxidation BY FREYA CARDOZO
  • 36. CHEMICAL METHOD  MnO2 manganese dioxide  K2MnO4 Potassium mangante(green) – 1. Caustic potash KOH 2. Potassium chlorate KClO3 – oxidising agent  Dispropotionation in neutral or acidic medium  KMnO4 + MnO2  Filteration to glass wool BY FREYA CARDOZO
  • 37. ELECTROLYTIC OXIDATION  Alkaline solution of manganate ion is electrolysed between iron electrodes seperated by a diaphram  At anode the oxygen evolved is used to reduce manganate to permanganate  Overall reaction  The solution is evaporated and filtered to obtain the crystals BY FREYA CARDOZO
  • 38. CHEMICAL PROPERTIES OF KMNO4  In acidic medium- Oxidising action 1. Iodide to Iodine 2. Fe2+ to Fe3+ 3. H2S to S 4. Oxidation of oxalic acid H2C2O4  In neutral medium or weakly alkaline medium 1. Iodide to Iodate 2. Oxidation of thiosulphate to sulphate 3. Manganous salt to manganese dioxide BY FREYA CARDOZO
  • 39. IN ACIDIC MEDIUM BY FREYA CARDOZO
  • 41. NEUTRAL OR ALKALINE MEDIUM BY FREYA CARDOZO
  • 42. USES  Antiseptic  Test for unsaturation  Quantitative analysis- Halide detection  Volumetric analysis- For reducing agents  Oxidising agent- labs and industry  Why is KMnO4 such a good oxidising agent? BY FREYA CARDOZO
  • 44. INNER TRANSITION ELEMENTS  Orbital lies much inside the d orbital,in relation to the transition metals the f block elements are called inner transition elements.  f – 1 to 14 electrons, d – 0 or 1 and s – 2 electrons  2 series : Lanthanoids and Actinoids  Lanthanoids – characterizied by filling of 4f  Actinoids - characterizied by filling of 5f  14 elements in each BY FREYA CARDOZO
  • 45. F BLOCK ELEMENTS  Those elements in which the outermost electrons enter the f subshell  They belong to the 6th and 7th period  Placed seperately at the bottom of the table BY FREYA CARDOZO
  • 46. PROPERTIES OF F BLOCK ELEMENTS  These metals are soft with moderate densities of about 7 g cm-3.  They have high melting point  They are quite reactive similar to the alkali metals than d block metals  common oxidation state for lanthanoids is +3  +2 is also very common among these, higher O.S like +4 is unusual (exptn- Ce) BY FREYA CARDOZO
  • 47. LANTHANOIDS- RARE EARTH ELEMENTS They were know as rare because it was difficult to extract them economically from their ores BY FREYA CARDOZO
  • 48. G.R: LANTHANOIDS HAVE LOWER HEAT OF ATOMIZATION THAN TRANSITION METALS. The energy required to break up the metal lattice is heat of atomization. This is because with d electrons, transition metals are much harder and require high heat of atomization. Europium and ytterbium have the lowest enthalpies of vaporization and largest atomic radii of lanthanoids, resemble barium. BY FREYA CARDOZO
  • 49. RADII Their ionic radii decrease from 117 pm of La to 100 pm for Lu. This is because 5f orbitals do not shield the outer 5s and 5p electrons effectively, leading to increase in effective nuclear charge and decrease in the ionic size. BY FREYA CARDOZO
  • 50. REACTIONS WITH LN Reactants Reactants Product Ln C LnC Ln H2O Ln(OH)3 Ln O2 Ln2O3 Ln N2 LnN Ln X LnX3 Ln= Lanthanoids BY FREYA CARDOZO
  • 51. BASICITY OF LANTHANOIDS All the lanthanoids form hydroxides ofthe general formula Ln(OH)3 These are ionic and basic.  Since the ionic size decreasesfrom La3+ to Lu3+, the basicity of hydroxides decreases. La(OH)3 is the strongest base while Lu(OH)3 is the weakest base. BY FREYA CARDOZO
  • 52. ELECTRONIC CONFIGURATION  Generally the E.C for lanthanoids is represented as [Xe] 4f0-14 5d0-1 6s2  Xe = Xenon, Z= 54  The E.C for Xe is 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 BY FREYA CARDOZO
  • 53. EXCEPTIONS  The electrons first fill up the 6s  4f and 5d are very close in energy  In case of lanthanum the 5d oribtal has lower energy  In case of Gd and Yb the anamolous behaviour is observed  As half filled and fully filled electrons have extra stability  Thus general E.C for lanthanoids is [Xe] 4f0-14 5d0-1 6s2 BY FREYA CARDOZO
  • 54. IONISATION ENTHALPY  What is ionisation enthalpy?  As size increases, ionisation enthalpy decreases since the last electron experiences lesser pull from the nucleus  Across the period, size decreases thus I.E increases  Why some elements have variable O.S states but others only a few? Can ionisation enthalpy justify these? BY FREYA CARDOZO
  • 55. QUESTION HINT: -Energy required to remove unpaired electrons is lesser than that to remove paired electrons - Check the energy of subshell, lower the energy easy to remove the last electron - n+l lower: lesser energy the subshell has BY FREYA CARDOZO
  • 56. OXIDATION STATE  G.E.C = [Xe] 4f0-14 5d0-1 6s2  thus the common O.S is +3 i.e 2 e- from 6s and the order from d/f subshell  The 4f electrons are shielded by the inner 5s and 5p orbitals, they are tightly bond to the nucleus. Thus they do not take part in the bonding  Some show O.S +2 and +4 this is due to f0, f7, f14 E.C BY FREYA CARDOZO
  • 57. COLOUR  These elements are coloured due to the f-f transition which corresponds to the energy in the visible spectrum  The colour of ions with nf electrons= (14-n)f electrons COLOUR IN LANTHANOIDS BY FREYA CARDOZO
  • 58. WHAT IS SHIELDING EFFECT The decrease in the net force of attraction between the electrons present in the outer shell of an atom in the direction of nucleus due to change in linearity of the electric lines of forces between them due to the presence of high election density in the inner shells in the same atom is known as screening effect. BY FREYA CARDOZO
  • 59. ATOMIC RADII  Across the period the radii decreases as the size decreases  The decrease in lanthanoids is very steady this is called the LANTHANOID CONTRACTION  As we move left to right the nuclear charge increases by +1 and an electron is added  The electron is added to the same 4f subshell  Due to their diffused shape the 4f electrons shield each other poorly from the nuclear charge  With increasing atomic no. the effective nuclear charge increases thus pulling the 4f shell closer, causing it to cntract BY FREYA CARDOZO
  • 60. MAGNETIC MOMENT  µ=square root of n(n + 2) BM  n = no.of unpaired ELECTRONS  Calculate magnetic moment for La3+  La -57  [Xe]4f05d16s2 n=1 Magnetic moment BY FREYA CARDOZO
  • 61. APPLICATIONS  In hybrid cars, superconductors and permanent magnets  Used in the colour tubes of computers and T.Vs since they produce visible light over a small wavelength upon bombarding with e-s  (Eu,Y)2O3 – red colour  There types of Ln are used to get 3 primary colours  Luminescent materials Nd: YAG laser Applications of Lanthanoids BY FREYA CARDOZO
  • 63. ACTINOIDS  Starts with Thorium Z=90 and ends with Lawrencium Z=103  They are all radioactive and man-made  High M.P, B.P, density  The electronic configuration of actinoids is [Rn] 5f0-14 6d0-2 7s2, where Rn is the electronic configuration of radon.  most stable oxidation state in actinoids is +3. The highest however actinoids show a variety of O.S from +2 to +8 BY FREYA CARDOZO
  • 65. OXIDATION STATE  Early lanthanoids show variable O.S this is similar to transition elements than lanthanoids  This pattern is seen mostly due to the ability of 5f orbital to participate in bonding  A ready loss of 5f electrons by early actinoids indicates that these electrons are much closer in energy to 7s and 6d electrons than the 4f electrons to 6s and 5d electrons as in lanthanoids  G.E.C [Rn] 5f0-14 6d0-2 7s2  Eg. uranium has electronic configuration of [Rn]7s2 5f 36d1. The formation of +6 oxidation state corresponds to an electronic configuration of [Rn]. BY FREYA CARDOZO
  • 66. Half filled and fully filled orbitals have extra stability. Thus one electron from f is promoted to d BY FREYA CARDOZO
  • 67. The overall gradations among the different blocks of the periodic table Transition elements- d block Lanthanoids-f block Pre- transition – s block BY FREYA CARDOZO
  • 68. ACTINOID CONTRACTION  5f 6d 7s are almost same energy in actinoids  The 7s electrons shield the 5f and 6d orbitals from nuclear charge , thus they expand a little. Therefore, they have size greater than lanthanoids  But the decreases in radii is not as prominent, due to the shielding effect of f orbitals BY FREYA CARDOZO
  • 69. APPLICATION OF ACTNOIDS  Half lives of Thorium & Uranium are so long that the amount of radiation emitted is negiligble, thus they can be used in everyday life.  Th(IV) oxide, ThO2 with 1% CeO2 was used as a major source of indoor lighting before incandescent lamps came into existence only because these oxides convert heat energy from burning natural gas to an intense light.  Even today, there is a great BY FREYA CARDOZO
  • 70. POSTACTINOID ELEMENTS POST ACTINOID ELEMENTS  Elements with atomic number greater than 92 are called ‘Transuranium’.  Elements from atomic number 93 to 103 now are included in actinoid series and those from 104 to 118 are called as postactinoid elements.  They are included as postactinoids because similar to actinoid elements, they can be synthesized in the nuclear reactions.  So far, nine postactinoid elements have been synthesized.  Half life is in secs 2.8 x 10^-4, thus difficult to study reactions  Rutherfordium forms a chloride, RfCl4, similar to zirconium and hafnium in the +4 oxidation state.  Dubnium resembles to both, group 5 transition metal, niobium(V) and actinoid, protactinium(V). BY FREYA CARDOZO
  • 71. Questions ix. In which of the following series all the elements are radioactive in nature a. Lanthanides b. Actinides c. d-block elements d. s-block elements x. Which of the following sets of ions contain only paramagnetic ions a. Sm3⊕, Ho3⊕, Lu3⊕ b. La3⊕, Ce3⊕, Sm3⊕ c. La3⊕, Eu3⊕, Gd3⊕ d. Ce3⊕, Eu3⊕, Yb3⊕ xi. Which actinoid, other than uranium, occur in significant amount naturally? a. Thorium b. Actinium c. Protactinium d. Plutonium BY FREYA CARDOZO
  • 73. DEFINITION  Mineral : naturally occuring substance found in the earth’s crust containing inorganic salts, solids, siliceous matter etc, is called a mineral.  Ore: The mineral which contains high percentage of the metal and from which the metal can be extracted economically is called an ore DEFINITONS BY FREYA CARDOZO
  • 74. METALLURGY Commercial extraction of metals from their ores is called metallurgy. BY FREYA CARDOZO
  • 75. TYPES OF METALLURGY  Pyrometallurgy: A process in which the ore is reduced to metal at high temperature using reducing agents like carbon, hydrogen, aluminium, etc. is called pyrometallurgy.  Hydrometallurgy : The process of extracting metals from the aqueous solution of their salts using suitable reducing agent is called hydrometallurgy.  Electrometallurgy : A process in which metal is extracted by electrolytic reduction of molten (fused) metallic compound is called electrometallurgy TYPES OF METALLURGY BY FREYA CARDOZO
  • 76. GENERAL METHODOLOGY  Extraction of ore  Concentration of ore – removing impurities of other metals, sand, dust particles impurities termed as gangue are removed from the ore and the ore gets concentrated. The sand, mud and other unwanted impurities which remain mixed with the ore deposit are called gangue. Methods – 1. Hydraulic classifiers 2. Froth floation 3. Magnetic seperation  Convert to its oxides – Can be done by either 1. Roasting . 2. Calcination  Obtaining pure metal BY FREYA CARDOZO
  • 78. EXTRACTION OF IRON  Ore – Haematite ore (Fe2O3)  Gangue -SiO2 + Al2O3+ phosphates  Concentration – Hydraulic classifier The powdered ore is washed in a powerful current of water introduced into the hydraulic classifier. The lighter gangue particles are separated and the concentrated ore is collected at the bottom.  Converting into the oxide Roasting : The concentrated ore is heated In a current of air. The sulfur and arsenic impurties present in the ore get converted into their oxides and escape as vapour. Ferrous oxide in the ore is converted to Fe2O3 4FeO + O2 -- 2 Fe2O3 STEPS IN EXTRACTION OF Fe ore BY FREYA CARDOZO
  • 81. BLAST FURNANCE- Smelting Tall cylindrical steel tower lined with refractory bricks. The height=25 m and diameter =5 to10 m.  Working- counter current principle : Charge comes down and hot gases move up the tower.  The furnace is comprised of 3 parts – 1. Hearth, 2. Bosh and 3. Stack Ore is introduced in the furnace through a cup and cone arrangement Ensures uniform distribution and prevents loss of gases A blast of preheated air is introduced into the furnance below the bosh through BY FREYA CARDOZO
  • 83. 1.ZONE OF COMBUSTION  The formation of CO is exothermic and thus temperature is 2000K  Some CO decomposes to C  The hot CO gas moves upward and thus heats up the incoming charge  Therefore CO acts as a fuel and reducing agent BY FREYA CARDOZO
  • 84. ZONE OF REDUCTION BY FREYA CARDOZO
  • 85. ZONE OF SLAG FORMATION The gangue present in the ore is converted to slag. This slag can be used for making road foundation. Temperature of this zone is 1200 K. The gangue contains silica, alumina and phosphates. A removal of this gangue is effected by adding lime-stone in the charge, which acts as flux. Limestone decomposes to give CaO (quick lime) 3.Zone of slag formation BY FREYA CARDOZO
  • 86. • ZONE OF FUSION MnO2 and Ca3(PO4)2 present in the iron ore are reduced to Mn and P. Some of the silica is also reduced to Si. The spongy iron coming down in the furnace melt absorbs impurities like C, Si, Mn, P and S. This molten iron collects at the bottom in the furnace. The slag which is lighter floats on the surface of molten iron. Molten slag and iron are collected through separate outlets. Molten iron is poured into moulds. These solid blocks are called pigs. This iron contains about 4% of carbon. When pig iron is remelted, run into moulds and cooled, it becomes cast iron. The waste gases containing N2, CO and CO2 escape through the outlet at the top. These hot gases are used for preheating the blast of air BY FREYA CARDOZO
  • 87. ZONES OF BLAST FURNACE BY FREYA CARDOZO
  • 88. FACTORS AFFECTING EXTRACTION TECHNIQUE Pure iron can be obtained by electrolytic refining of impure iron or other methods given in the flow chart. The choice of extraction technique is governed by the following factors. 1. Nature of ore 2. Availability and cost of reducing agent, generally cheap coke is used 3. Availability of hydraulic power. 4. Purity of product (metal) required. 5. Value of byproducts for example, SO2 obtained during roasting of sulphide ores is vital for manufacture of H2SO4. Knowledge of electrochemical series provides solutions to many problems. BY FREYA CARDOZO
  • 89. TYPES OF IRON BY FREYA CARDOZO