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TRANSITION ELEMENTS
d-block elements: The elements in which the differentiating electrons enter into d-orbitals of penultimate
shell are known as d-block elements.
These are present in the middle of the periodic table between s and p blocks.
The general electronic configuration of these elements is (n-1)d1-10 ns0 or 1 or 2.

S-BLOCK P-BLOCK
1 18

2 D-BLOCK 13 14 15 16 17

3 4 5 6 7 8 9 10 11 12

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IIIB IVB VB VIB VIIB VIII IB IIB
Sc Ti V Cr Mn Fe Co Ni Cu Zn
21 22 23 24 25 26 27 28 29 30

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Y Zr Nb Mo Tc Ru Rh Pd Ag Cd

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39 40 41 42 43 44 45 46 47 48
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La Hf Ta W Re Os Ir Pt Au Hg
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57 72 73 74 75 76 77 78 79 80
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Ac Rf Ha Dh Bh Hs Mt Uun Uuu Uub


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89 104 105 106 107 108 109 110 111 112


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Transition elements: The elements in which the d-orbitals are partially filled in either native state or in
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their stable oxidation state are known as transition elements.


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The general electronic configuration of these elements is (n-1)d1-10 ns1-2.


Except group 12 (IIB) elements (Zn,Cd & Hg), all the d-block elements are the transition elements.
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In case of Zn, Cd & Hg the d-orbitals are completely filled both in native state as well as in their oxidation
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states.
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Classification of d-block elements: Based on the principal quantum number of d-orbital being filled
with the differentiating electron, d-block elements are classified into four series viz., 3d,4d,5d and 6d
series.
i) 3d series Sc(Z=21) to Zn(Z=30)
ii) 4d series Y(Z=39) to Cd(Z=48)
iii) 5d series La(Z=57) to Hg(Z=80) excluding Ce(Z=58) to Lu(Z=71)
iv) 6d series starts with Ac(Z=89) and is still incomplete.
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3d series
3 4 5 6 7 8 9 10 11 12
IIIB IVB VB VIB VIIB VIII IB IIB

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic number 21 22 23 24 25 26 27 28 29 30

Electronic 1 2 2 2 3 2 5 1 5 2 6 2 7 2 8 2 10 1 10 2
3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s
Configuration

4d Series
3 4 5 6 7 8 9 10 11 12
IIIB IVB VB VIB VIIB VIII IB IIB

Element Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
Atomic Number 39 40 41 42 43 44 45 46 47 48

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Electronic 1 2 2 2 3 5 5 6 2 7 2 10 10 10 1 10 2
4d 5s 4d 5s 4d 5s2 4d 5s1 4d 4s2 4d 5s 4d 5s 4d s 4d 5s 4d 5s
Configuration

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5d series
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3 4 5 6 7 8 9 10 11 12
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IIIB IVB VB VIB VIIB VIII IB IIB


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Element La Hf Ta W Re Os Ir Pt Au Hg
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Atomic Number: 57 72 73 74 75 76 77 78 79 80
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0 1 14 2 14 3 14 5 14 5 14 6 14 7 14 8 14 10 14 10
Electronic 4f 5d 4f 5d 4f 5d 4f 5d 4f 4d 4f 5d 4f 5d 4f 5d 4f 5d 4f 5d
2 2 2 1 2 2 2 2 1 1
Configuration 6s 6s 6s 6s 6s 6s 6s 6s 6s 6s
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6d series
3 4 5 6 7 8 9 10 11 12
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IIIB IVB VB VIB VIIB VIII IB IIB

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Element Ac Ku
(Unp) (Unh) (Uns) (Uno) (Une)
Atomic Number 89 104
105 106 107 108 109
0 14 14
Electronic 5f 5f 5f
1 2 2 2 3 2
Configuration 6d 7s 6d 7s 6d 7s

General characteristics
Transition elements exhibit following typical characteristic properties due to presence of partiallyfilled
d-orbitals.
1) All the d-block elements are hard metals.
2) Their melting and boiling points are very high.
3) These are good conductors of heat and electricity.
4) These metals are malleable, ductile.
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5) They have alloy forming tendency.
6) They exhibit variable oxidation states.
7) Most of them form colored atleast in one oxidation state.
8) These metals are paramagnetic due to presence of unpaired electrons.
9) They form coordination compounds.
10) They can form interstitial compounds.
11) These metals and their compounds have catalytic properties.

Electronic configuration
The general electronic configuration of these elements is (n-1)d1-10 ns1-2. But some of the elements
show anomolous electronic configurations due to very small energy difference between (n-1)d and ns
orbitals.To get extra stability, electrons are exchanged between these orbitals and give rise to anomalous
configurations.
Eg., Following elements show anomalous electronic configurations as the atoms with half filled or full filled
d-orbitals are more stable due to greater exchange energy.
1) Cr 3d5 4s1
2) Mo 4d5 5s1

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3) W 5d5 6s1
4) Cu 3d10 4s1

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5) Ag 4d10 5s1

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6) Au 5d10 6s1

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7) Pd 4d10 5s0
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Atomic and ionic radii


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The atomic sizes of d-block elements are in between those of s and p-block elements.
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In the periodic table, atomic and ionic radii decrease from left to right across a period with increase
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in atomic number. But in d-block elements, this decrement is very small due to shielding effect of electrons
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in inner d-orbitals.
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For example, in 3d series, the atomic radii decreases from Sc to Cr but then remains almost constant
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up to Cu and then increased to Zn.


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3 4 5 6 7 8 9 10 11 12
3d series
IIIB IVB VB VIB VIIB VIII IB IIB
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E lement Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic radius (pm) 164 147 135 129 137 126 125 125 128 137

In IIIB group (Sc --> Y --> La), atomic size increase regularly from top to bottom.
But in case of other d-block elements, the atomic radius increases from 3d series to 4d series and
remains almost same for 4d and 5d series due to lanthanoid contraction.
Eg., Hf (4d series) and Zr(5d series) almost equal atomic size.

Atomic radius Atomic radius


IIIB (Ao) IVB (Ao)
Sc 1.62 Ti 1.47
Y 1.80 Zr 1.60
La 1.87 Hf 1.58
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Metallic properties
Transition elements show typical metallic properties like ductility, malleability, high thermal and electri-
cal conductivities and metallic lustre.
These are hard metals with high melting and boiling points due to involvement of greater number of
electrons from ns and (n-1)d electrons in metallic bonding. Melting points in a series increase up to VB
group element and then decreases.
These metals are less reactive than s-block elements due to relatively small size and higher ionization
energies.

Densities
The densities of transition elements are very high due to small size and close packed crystalline struc-
tures. The densities increase across a period in a given series with increase in atomic mass and decrease
in atomic volume.
Eg., Increases from Sc to Cu and then decreases to Zn.
Usually VIII group elements have maximum densities. Among transition metals, Iridium has highest
density (22.61× 10- 3 kg/cc).

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Ionization energies
Ionization energy increases with decrease in atomic radius and increase in nuclear charge. In case of

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d-block elements, the ionization energies in a series increase irregularly. Elements with stable electronic

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configurations (with half filled or full filled d-orbitals) have higher ionization energies.

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Eg., The first ionization energy in 3d series is shown below.
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3 4 5 6 7 8 9 10 11 12
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3d series
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IIIB IVB VB VIB VIIB VIII IB IIB


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Sc Ti V Cr Mn Fe Co Ni Cu Zn
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1st Ionization Energy (in kJ/mol) 631 656 650 652 717 762 758 736 745 906
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The second ionization energies of Cr and Cu are very high due to stable electronic configurations of
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their M+ ions.
Cr+ ---- 3d5
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Cu+ ---- 3d10


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In case of s and p-block elements, the ionization energy decreases from top to bottom in a group. In
IIIB group (Sc --> Y --> La), ionization energy decreases regularly with increase in atomic size.
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But in case of other d-block elements, the ionization energy decreases from 3d series to 4d series.
But it increases from 4d series to 5d series. It is because, the atomic size remains almost same (as
consequence of lanthanoid contraction) and at the same time nuclear charge increases.

Element Atomic IP Element Atomic IP


-1 -1
radius kJ.mol radius kJ.mol
0
(A ) (A)
Sc Ti
1.62 631 1.47 656
21 22
Y Zr
1.8 616 1.6 674
39 40
La Hf
1.87 541 1.58 760
57 72
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Oxidation states
* Transition elements exhibit variable oxidation states due to
i) availability of ns and (n-1)d electrons.
ii) small difference between ns and (n-1)d electrons.
* These elements show common oxidation of +2 which is due to loss of electrons from ns level.
* The lowest oxidation number shown by a transition element is equal to the number of electrons in 'ns'
orbital.
e.g., Sc2+, Cu+
* The maximum oxidation state exhibited is equal to the sum of ns and (n-1)d electrons.
e.g., Mn7+, Os8+ (stable) and Ru8+ (unstable)
* The oxidation states with half filled (d5) and completely filled (d10)electrons are more stable.
e.g., Fe3+, Zn2+
* In a given series, the elements with maximum number of oxidation states are present in the middle of
the series.
e.g., Mn exhibits oxidation states from +1 to +7.
The elements at the beginning of the series exhibit fewer oxidation states due to presence of less
number of d-electrons. Also the elements at the end of a series exhibit fewer number of oxidation states

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due to availability of few vacant d-orbitals for bonding.
* In 3d series, the ions with minimum oxidation states are more stable where as in 4d and 5d series, the

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maximum oxidation states are more stable.

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* Some elements exhibit zero oxidation numbers in their compounds. e.g., Ni(CO)4, Fe(CO)5 etc.,

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* Transition elements with lower oxidation states generally form ionic bonds and those in higher oxidation
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Magnetic properties
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Diamagnetic substances are repelled from the magnetic fields where as paramagnetic substances are
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attracted in the magnetic field. Ferromagnetic substances are strongly attracted towards the magnetic
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field.
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Most of the transition elements exhibit paramagnetic nature due to presence of unpaired electrons.
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e.g., Ti3+, Fe2+, Fe3+ etc.,


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The metal ions with d0 and d10 configurations have no unpaired electrons and hence exhibit diamag-
netism. e.g., Sc3+, Cu+, Zn2+ etc.,
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Fe, Co and Ni exhibit ferromagnetism. But they become paramagnetic in solution state.
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The magnetic moment of an ion which arise due to spin and orbital motion of the electron can be
calculated by using the following formula.

( S  L )  4 S (S  1)  L( L  1) BM
Where S =  m  (n.m )  sum of spin quantum numbers of all the unpaired electrons
s s

L   l  sum of azimuthal quantum numbers of all the unpaired electrons


BM = Bohr magneton = 9.273 x 10-27 erg.Gauss 1
But in most cases the contribution from orbital motion of electron can be neglected and the magnetic
moment can be alone calculated by considering only the spin of electrons. This spin only formula can be
given as follows.
 S  4S ( S  1) BM  n(n  2) BM
Where n = number of unpaired electrons.

Colour
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Most of the transition elements exhibit color in their compounds. This is due to d-d electronic transi-
tions. The energy required for these transitions is very small and is in the visible region of electromagnetic
spectrum. The metal ions will absorb radiation of any one color for d-d electronic transitions and transmit
the remaining color radiations. The color of the ion is decided by the transmitted light and this color is
called complementary color. Thus the ion appears to have color.
The d-orbitals in isolated gaseous metal ion are degenerate (possess same energy). But they get
different energies when the metal ion is surrounded by ligands in complexes or by water molecules in
solutions or by counter ions in the crystals. The d-orbitals which are facing the ligands or water molecules
or counter ions get more energy and the rest will get lower energy. This phenomenon is called d orbital
splitting.
For example, the d-orbitals are split into two sets viz., t2g (dxy, dxz & dyz ) and eg ( d x 2 -y2 & d z 2 ) when
surrounded by ligands octahedrally. The energy of t2g set is lowered and the orbitals in eg set get higher
energy. But the energy difference between these two sets is usually very small and the energy required for
the electronic transitions between them is available in the visible region of light.

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d-orbitals with higher energy

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d-orbitals with lower energy


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The d-d electronic transitions are only possible when d-orbitals in the metal ion are partially filled.
Hence the metal ions with partially filled d-orbitals can only show colors. The ions with empty or full-filled
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d-orbitals (d0 or d10) do not exhibit colors.


e.g. i) [Ti(H2O)6]3+ is pink in color. The Ti3+ ion has d1 configuration. It absorbs green and yellow
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colors and transmit the complementary colors rich in red and violet. Hence the hydrated
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Ti3+ is pink in color.


e.g. ii) Hydrated Cu2+ (3d9 configuration) has intense blue color because it absorbs red color for d-
d transitions and transmits its complementary blue color.
e.g. iii) Sc3+, Ti4+ have 3d0 configuration. Hence these are colorless.
e.g. iv) Cu+, Zn2+ have 3d10 configuration. Hence these are also colorless.

Transition metals show different colors in different oxidations states.


e.g.
Mn2+ is pink, Mn3+ is blue, Mn6+ is green
Fe2+ is green, Fe3+ is yellow
Cr2+ is blue, Cr3+ is green, Cr6+ is yellow

Cr6+, Mn7+ also have d0 configurations and hence expected to be colorless. But their oxo-anions are
strongly colored due to charge transfer from ligands to metal. e.g. Cr2O72- is orange red, CrO42- is yellow
and MnO4- is purple.

Catalytic properties
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Transition elements and their compounds show catalytic properties due to their ability to exist in
different oxidation states and ability to form coordination compounds.

e.g.
1) In contact process, V2O5 is used as catalyst to oxidize SO2 to SO3 . This reaction occurs in
following steps.
i) Oxidation of SO2 to SO3 and V5+ is reduced to V4+.
ii) Regeneration of V5+ from V4+ by oxygen.

2) In some cases, the catalyst provide a suitable surface for the reaction and decreases the activation
energy by binding the reactant molecules. This is possible due to presence of partially filled d-orbitals and
ability of the metal to show multiple oxidation states.

Catalysts formed by transition elements – their industrial uses


Name of the catalyst & its
S.No Applications

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composition
Haber’s process for the preparation of NH3 In
1 Fe & Mo contact process for the oxidation

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of SO2 to SO3

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In contact process for the oxidation
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2 Platinized asbestos

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of SO2 to SO3
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3 Pt/Ir mixture In Ostwald’s process oxidation of NH3 to NO.


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4 Raney nickel Catalyst in hydrogenation reactions.
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Oxidation of 10- alcohols to aldehydes


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Fenton’s reagent FeSO4 /


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H2 O2
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Alloys
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An intimate mixture of metal with other metals or metalloids or sometimes non metals, which has
similar physical properties to that of metal is called an alloy
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* Alloys have improved mechanical properties like malleability, ductility, toughness, resistance to corro-
sion etc.,
* Alloys are formed effectively when the difference in atomic radii of metals are with in 15%.

Preparation: Alloys are prepared by following methods.


1) Melting a mixture of metals: An alloy can be easily prepared by melting a mixture of metals in proper
proportions. e.g. Brass is made by melting a mixture of copper and zinc.

2) Simultaneous electrolytic deposition of metals: It is possible to get an alloy by the deposition of metals
simultaneously from their ionic solutions. e.g. Brass can be prepared by the electrolysis of a mixture of Cu
and Zn cyanides.

3) Amalgamation: Alloys of mercury are called amalgams. These are prepared by mixing the metal with
mercury. e.g. M-Hg where M = Zn, Na, Cu, Ag, Au etc.,

4) Reduction: In this method, compounds of two metals are reduced to get the alloy. e.g. Fe-Cr alloy can
be prepared by the reduction of chromite ore FeCr2O4.
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5) Compression method or powdered metallurgy: In this method, finely powdered metals are mixed and
compressed below their melting points to get the alloy. Diffusion of fine particles of metals and strong
binding with one another results in proper structures. No raw material is wasted in this method.
e.g. Mo-W alloy is prepared by this method.

6) Quenching: In this method, Fe-C alloy is produced. Red hot steel is suddenly immersed into oil or
water. Steel prepared by this method is tougher and its properties depend on the percentage of carbon.

Ferrous alloys
Name of Composition of
S.No Common uses
the alloy the alloy
It has a low temperature
It is a nickel steel. 64%Fe: 35%
1 Invar coefficient, Used for
Ni, Mn & C in trace amounts
pendulum rods

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It is a nickel chromium steel Used in heating elements
2 Nichrome
60% Ni;25% Fe, 15%Cr of fire stoves and furnaces

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Non-Ferrous alloys

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alloy the alloy
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Used to reduce nitrites or


1 Devarda’s alloy 50%Cu;45%Al;5%Zn
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nitrates to NH3
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95% Al;4%Cu; Widely used for stressed


2 Duralumin
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0.5Mn; 0.5% Mg; structures like aircraft


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Aluminum Used in ornaments


3 88-90% Cu; 10-12%Al
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Bronze Photo frames etc.


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50-60% Cu; 10-30%Ni 20- Used in spoons; forks and


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4 German Silver
30% Zn utencils
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5 Bell metal 80% Cu;20%Sn Used in Bells


Used in utencils, coins and
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6 Bronze 75-90% Cu;10-25% Sn


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7 Gun metal 88%Cu;10%Sn; 2% Zn Used in bearings; Guns


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8 Brass 60-80% Cu;20-40%Zn Used in machinery parts

Interstitial compounds
These are the non-stoichiometric compounds formed when the small atoms like H, B, C and N
occupy the interstices of transition metals. In these compounds, the elements do not combine in definite
ratios and hence do not possess definite formula.
E.g.., TiC, Mn4N, Fe3H, VH0.56, Fe0.89S, WO2.88
Interstitial compounds retain metallic properties. They posses higher melting and boiling points. They
are very hard and chemically inert. They conduct electricity.
The metallic lattice does not alter but expands a little hence the density of interstitial compounds is less
than that of the metal.
Hydrogen always occupies the tetrahedral holes where as C & N occupy the larger octahedral holes.
Some times stoichiometric compounds may becomes non stoichiometric at high temperatures and
become colored.
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E.g. ZnO is white in cold and yellow when hot

Test your understanding


State whether the following statements are True or False.
1) The differentiating electron enters into 4d orbitals in the d-block elements which belong to 4th period.
2) Copper is not a transition element because it has completely filled d-orbitals.
3) The atomic radii of Zr and Hf are equal because of Lanthanoid contraction.
4) The ionization energies of transition metals are higher than those of alkali metals.
5) CuCl is diamagnetic and colorless.
6) The maximum oxidation state of osmium is +7.
7) ZnSO4 is dark blue in color due to presence of d10 configuration.
8) ZnO becomes yellow upon heating due to formation of non - stoichiometric compound.
9) German silver contains 25% of silver.
10) Fe3+ ion is more stable than Fe2+ ion.

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