2021

TRANSITION METALS or
d – Block and f – Block elements

[DR. SHASHI KUMAR]

[ASSOCIATE PROFESSOR G.J COLLEGE RAMBAGH BIHTA (PATNA) OF HOD
DEPATMENT OF CHEMISTRY]

[B.SC – II (HONS)]
 d – Block and f – block element
d – block element
or
Transition metals
Definition:- Those elements are called as d – block elements
whose last electron enters into d – orbital.
General electronic configuration of valance electron (V.E):-
(n-1) d1 to 10 ns1 or 2
Here, n = outermost orbit number.
There are four series of transition metals:-
(1) 3d – series:-
Those transition metals are placed in 3d – series whose last
electron enters into 3d – orbital.
Ex:- Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn
Here total 10 elements are found.
(2) 4d – series:-
Those transition metals are placed in 4d – series whose last
electron enters into 4d – series whose last electron enters into
4d – orbital. Here also 10 elements are found.
Ex:- Y to Cd – 10 elements.
(3) 5d – series:-
Those transition metals are placed in 5d – series whose last
electron enters into 5d – orbital.
Ex:- La to Hg – 10 elements.
(4) 6d – series:-
Those transition metals are placed in 6d – series whose last

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electron enters in 6d – series whose last electron enters into
6d – orbital. This is incomplete series.
Ex:- Ac, Uuq, Uup, Uuh, Uus, Uuo.
Also those elements are called as transition metals in which
incomplete d – orbitals are found.
(Q) Why Zn, Cd, Hg, Cu, Ag, Au, are placed in transition metals?
Ans:- Some properties of those elements (for ex- complex
formation) resemble with transition metals. Also, for
convenience these metals are placed with transition metals
although most of the properties of these metals are different
from transition metals.
Characteristisc of Transition metals:-
(1) Metallic character:-
(a) All elements of transition elements are metals because in
the outermost orbit of transition metals only one or two
electrons are found, that can be easily lost.
(b) These elements are called as transition elements because
the properties of these elements are in between S – block
and P – block elements.
(c) Since from left to right of transition metals in a period the
value of IP increases, the electropositive character
decreases.
(d) The strength of metallic bond of transition metals are very
high due to high effective nuclear charge and large number
of valence electrons.

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(e) Due to above reason transition metals are very hard and
pocess high density.
(f) Most of transition metals have density 5gm/cm3 O.S being a
transition metal have highest density 22.6gm/cm3.
(2) Melting point and Boiling point:-
(Q) Why melting point and boiling point of transition metals
are very high?
Ans:- Since in transition metals incomplete d – orbitals are found,
the number of V.E (valence electron) in these metals are larger.
So, these metals also form covalent bond with its own atom. That
is why the interparticle attractive forces in transition metals are
very high. Thus, melting point and boiling point of transition
metals are high.
(Q) Why from left to right in a period of transition metals
melting point first increases and then decreases.

Since in transition series first there is increase of number of

unpaired electron and than after there is decrease of no. of
unpaired electron. Hence due to presence of increasing no. of
unpaired electron there is increase in number of covalent bonds
formed by similar atoms of transition metals at first and then due

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to decrease of number of unpaired electron, there is also
decrease of number of covalent bond between similar atoms of
transitions metals. So, in a series of transition metals at first
there is increase of melting point and then there is decrease of
melting point.
Note:- Mn and Tc have abnormally low melting point.
(3) Ionisation energy:-
(Q) Why in a series of Transition metals from left to right in a
period there is slow increase of ionisation potential to S, P –
block element?
Ans:- From left to right in a transition series there is increase of
inner d – orbitals. Hence there is increase of screening effect of
outer electrons by inner d – electrons. Thus, the energy required
to remove from outer most orbit will not increase so much from
left to right in a d – series as it is in S and P – block elements. So,
IP of transition metals increase very slowly form left to right in a
series.
Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn
IP – 6.6, 6.8, 6.7, 6.8, 7.4, 7.9, 7.9, 7.6, 7.7, 9.4
(Q) Why IP is 5d – series elements are greater than 3d and
4d – series elements?
Ans:- Since in 5d – series elements 4f orbital are fulfilled which
have got lesser screening effect, this increases the effective
nuclear charge of 5d – series. This is why IP of 5d – series are
greater than 4d and 3d – series elements.
(Q) Why Ni2+ compounds are more stable than Pt2+ compounds?

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Ans:- Sum of the value of IP1 + IP2 of Ni = 2.49 × 103 kj/mole and
IP1 + IP2 of Pt = 2.66 × 103 kj/mole. So, Ni+2 is more stable than
Pt+2 compounds.
(Q) Why K2[Pt+4Cl6] is well known complex while K2[Ni+4Cl6]
complex is not found?
Ans:- The some of the value of I.P1 + I.P2 + I.P3 + I.P4 of Ni =
11.29×103kj/mole
and I.P1 + I.P2 + I.P3 + I.P4 of Pt = 9.36×103kj/mole
Since the sum of the values of four successive IP of Pt is lower
than Ni. So, Pt can form Pt+4 ion but Ni cannot form Ni+4 ion. So,
K2[PtCl6] is found but K2 [NiCl6] is not found.
(Q) What are features which determine the stability of
particular oxidation state?
Ans:- Following features determine the stability of particular
oxidation state of transition metals.
(a) Enthalpy of sublimation [∆HS(+)]
(b) Ionisation potential [∆H(+)]
(c) Hydration energy [∆H(-)]
Lower the value of sum of the above parameters for a transition
metal higher will be the stability of oxidation state.
∆HT = ∆HS + ∆HI.P + ∆HHydrate
(Q) How stability of oxidation state is explained on the basis of
electrode potential?
Ans:- Electrode potential is the measure of ∆HT and hence the
stability of particular oxidation state. Lower the value of
electrode potential larger will be the stability of the particular

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oxidation state.
V, Cr, Mn, Fe, Co, Ni
E0(m+2/m) = -1.19, -0.19, -1.18, -0.44, -0.28, -0.24
In the above example it is clear that +2 state of V is most stable.
(4) Atomic and Ionic Radii:-
(Q) Why atomic radii of transition metals first decrease till
middle than almost become constant and towards the end it
increases?
Ans:- From left to right in a transition series there is successive
increase in the 3d – electrons and hence increase of screening
effect due to this 3d – electrons. Up to middle transition metal
nuclear charge exceeds over screening effect and hence there is
decrease of radii. But after the middle of a transition series, the
screening effect of d – orbitals just counterbalance the nuclear
charge and hence there is not any measurable change in atomic
radii.
But towards the end d – orbitals are fulfilled and due to this
strong repulsion between d – orbitals and outermost ns
electrons. So, now there is increase of atomic radius.
(Q) Why elements of second and third transition series
belonging to particular group have almost equal atomic radii?
Ans:- In third transition series (5d – series) 4f – orbitals are
fulfilled. Due to very small screening effect of 4f – orbitals there is
Lanthanide contraction. So, in a particular group of second and
third transition series there is not any increase in atomic radii.
(5) Oxidation state:-

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 Transition metals show variable oxidation state due to presence
of incomplete d – orbitals.
The following points may be noted regarding the
oxidation state of transition metals.
(i). From beginning to the middle of a transition series (Ex:- Sc, to
Mn) the minimum oxidation states are equal to +2 and maximum
oxidation states are equal to total number of valance electron.
Example:-
Elements Oxidation states
Sc (3d14s2) +2, +3
Ti (3d24s2) +2, +3, +4
V (3d34s2) +2, +3, +4, +5
Cr (3d54s1) +2, +3, +4, +5, +6 (K2Cr2+6O7).
Mn (3d54s2) +2, +3, +4, +5, +6, +7 (KMn+7O4).
(ii). The most common oxidation state of transition metals is (+2).
(iii). But in case of Fe, Co, Ni, Cu, Zn (these are more than half
fulfilled 3d - subshells), the minimum oxidation states are (+2)
where as the maximum oxidation states are not equal to the total
number of valance electron rather the maximum oxidation states
are less than total number of valance electron.
Examples:-
Elements Oxidation state
(a). Fe (3d64s2) +2, +3
It forms +4, +5, +6 oxidation states in rare cases +8 O.S of Fe is
not found.
(b). Co (3d14s2) +2, +3, +4

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 (c). Ni (3d14s2) +2, +3, +4
(d). Cu (3d14s2) +1, +2
(e). Zn (3d14s2) +2
(iv). Highest oxidation states shown by transition metals is +8.
Ex:- Os and Ru
(v). Some transition metals show 0 oxidation states.
Ex:- [Fe0(Co)5] [Ni0(Co)5]
(6) Complex formation:-
Transition metals form complexes due to the following reasons:-
(a) Due to small size and high charge density of metal ions.
(b) Due to presence of vacant d – orbitals.
(7) Magnetic property:-
In transition metals or ions there are good number of unpaired
electrons due to presence of incomplete d – orbitals.
Paramagnetic:- Those substance are called as paramagnetic in
which unpaired electrons are present.
The unpaired electrons present in transition metals and
ions create net magnetic moment.
Origin of paramagnetic:-
Paramagnetic character develops is substance due to presence
of unpaired electrons. These unpaired electrons produces net
magnetic moment due to orbital angular momentum and spin
angular momentum.
Here for convenience orbital angular momentum is
not taken. For the calculation of magnetic momentum of a
substance but with the help of spin angular momentum magnetic

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moment is calculated which gives the following relationship of
magnetic moment with unpaired electron.
Meff = √𝑛(𝑛 + 2) B.M
Here n = Number of unpaired electrons
Meff = Effective magnetic field
B.M = Bohr magneton
𝑒ℎ
B.M =
4𝜋𝑚𝑐
Here, e = Charge of electron
H = Planck’s constant
m = Mass of electron
c = Velocity of light
Ex:- Unpaired Configuration Magnetic Theoretical
electron Momentum
(experiment)
Sc+3 0 3d0 0 0
Ti+3 1 3d1 1.73 B.M 1.732 B.M
Ti+2 2 3d2 2.84 B.M 2.828 B.M
From above examples it is clear that, there is some difference
between experimental and theoretical value of magnetic moment
of a species. This is due to the fact that in theoretical value
magnetic moment due to orbital angular momentum has been
neglected.
Characteristrics of Paramagnetic substance:-
(a) When paramagnetic substance is placed in a magnetic, filed
the magnetic lines of fore Co through the paramagnetic
substance pass with greater density than in vacuum.
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(b) Due to the intraction of enternal magnetic field and magnetic
filed due to the paramagnetic substance, an attactive force
develops between magnet and paramagnetic substance.
Dimagnetic:- The substance which when placed in a magnetic
filed decreases the intensity of magnetic filed than in vaccum are
called as dimagnetic substance. The property due to which they
show this behavior is called as dimagnetism.

The magnetic lines of force tends to avoid to pass through such

substances and as such dimagnetic substances are repelled by the
magnetic filed. And set themselves at right angles to the
magnetic filed.
(8) Coloured compounds:-
Most of the transition metals ions or compounds are coloured
due to presences of incomplete d – orbitals.
But S and P – block elements generally
do not form coloured compounds because S and P – orbitals do
not split by the absorption of energy.
Those transition metal ions are not coloured in
which d – subshell is completely filled or empty.
Ex:- Zn2+ (3d10) = colourless
Cu+1 (3d10) = colourless
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 Sc3+ (3d0) = colourless
Ti4+ (3d0) = colourless
But in those transition metal ions in which incomplete
d – subshells are present show colour due to d -d transition.
d – d tansition:-
(a) Let us take an example to explain the d – d transition for
colouration [Co2+(H2O)6]2+. Here Co is found in oxidation state
= +2.
Co2+ (25) : 1s22s22p63s23p63d74s0
Now, here 3d – subshell splits up in to t2g and eg set in the
presence of octahedral legand field.

This complex requires high energy for excitation of electron

from t2g set to eg set so it absorbs energy of blue radiation. And
the complementry colour of blue radiation is red. So, this complex
emits red colour that’s why the colour of this complex is red.
(b) The tetrahedral cobalt (+2) complexes of type [CoX4]2- need
smaller energy for the excitation because ∆t < ∆o. So, it
absorbs red colour and emits its complementry blue colour.
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 Actually in tetrahedral field d – subshell split in to e and t2
set. e set has lower energy than t2 set.

(9) Catalytic property:-

Transition metals and their some compounds show catalytic
behavior due to their variable valency.
Example:-
(a) Fe behaves as catalyst in the manufacture of NH3 gas by
Haber process.
(b) V2O5 behaves as catalyst in the converson of SO2 in to SO3 in
the following ways.
V2+5 O5 + S+4O2 S+6O3 + V2+4
1
V2O4 + O2 V2O5 catalyst
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(10) Formation of Allays:-
Transition metals form Allays very often because their sizes are
almost the same. So, they can interchange their atoms by another
transition metals.
Ex:- Brass = Cu + Zn
Moneel metal = Cu + Fe + Ni
(11) Interstitial compounds:-
Transition metals form interstitial compounds. In the interstitial
sites of transition metals some foreign elements are trapped

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which makes the metal less maleable, ductile and more tensile
and hard.
General properties of 1st row of Transition metals (3d - series):-
(1) Oxides:-
(a) Transition metals form basic Amphoteric and acidic oxides.
(b) Generally in lower oxidation state they form basic oxides.
Ex:- Mn+2O, Mn2+3, V2+3O3, Cr+2O, Fe+2O, Co+2O, Ni+2O, Cu2+1O.
(c) Generally in the intermediate oxidation state they form
amphoteric oxides.
Ex:- Mn3O4, Mn+4O2, Cu+2O, Zn+2O, Fe2O3, MnO2, CrO2, Cr2O3, VO2,
TiO2.
(d) Generally in higher oxidation states they form acidic oxides.
Ex:- V2O5, CrO3, Mn2+7O7 etc.
(2) Halides:-
(a) Transition metals react with halogens at hightemperature to
give metallic halides.
(b) The order of reactivity is as under.
F>Cl>Br>I
Due to difference of electronegativity and size.
(c) Florides of transition metals form ionic compounds. While
chlorides Bromides and Iodides of transition metals are
covalent.
Ex:- CuF2 is ionic, CuCl2 is covalent, CuBr is covalent.
(d) Halides of transition metals in higher oxidation state are
relatively unstable and get hydrolised easily.
(3) Sulphides:-

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(a) Sulphides of transition metals are prepared by heating them
with sulphur or reaction with H2S or Na2S.
(b) In sulphides the oxidation states of transition metals are low
because of E.N of S atom is low.
Ex:- Fe+2S, Ni+2S, Zn+2S, Mn+S.
(c) Sulphides of transition metals are coloured or black.
Ex:- (i) NiS, CoS, CuS, ZnS = Black
(ii). MnS, CdS, etc. = coloured
(iii). MnS = Pink
(iv). CdS = Yellow
(d) They are insoluble in water.
Group trends in the chemistry transitions metals:-
(A) Group 4 – elements:-
(i) In this group Ti, Zr and Hf are found.
(ii) Ti is strong, has high melting point and is resistant to
corrosson.
(iii) Zr and Hf are silvery white metals.
(iv) The most stable oxidation state of this group is +4.
Are of Ti – Rutile, Ilmenite [FeTiO3]
(v) ZrO2 is a refractory metarial.
(Q) Why atomic radii of Zr (160 pm) and Hf (159 pm) are almost
equal?
Ans:- Due to Lanthenide contraction it happens.
(vi) Zr and Hf are important for the nucler energy.
(B) Group 5 – elements:-
(i) This group consits of V, Nb, Ta, Db.

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(ii) The most important oxidation state is +5.
(iii) Vd is used as additive to steel.
(iv) V2O5 is used as calalyst.
(v) Nb alloys are used in jet engines.
(vi) Ta is very resistant to corrossion and is used for making
apparaes is chemical plants.
(vii) Ta is used in surjery are also bone pins.
(C) Group 6 – elements:-
(i) It consists of Cr, Mo, W.
(ii) The most important oxidation states of Cr are +3, +6.
(iii) The most important oxidation states of Mo and W are +5
and +6.
(iv) In Cr(Co)6 the oxidation state Cr is O.
(v) W has highest melting point.
(vi) Cr is used for electroplating of Iron to prevent resting.
(vii) The ore of Cr is chromite – FeCr2O4.
(viii) The ore of Mo is molibdenite – MoS2.
(ix) The ore of W is wolframite – FeWO4.
(x) Mo and W form very hard alloys with Fe and used for
cutting purpose.
(xi) W is used as filament in electric bulb.
(xii) MoS2 acts as lubricant.
(D) Group 7 – elements:-
(i) It consist of Mn, Tc and Re.
(ii) Most stable oxidation state of Mn are +2, +4 and +7.
(iii) Most stable oxidation state of Tc and Re are +4 and +7.

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(iv) Mn is found in ores – named pyrolucite – MnO2, Braunite –
Mn2O3, Hausmanite – Mn3O4.
(v) Tc does not occur in nature. It is first man – made element.
It is Radioactive.
(vi) Re is a rare element and occurs in ore of Mo.
(vii) Ferromaganese Aloy – Fe + Mn. Manganese Bronze – Mn +
Cu + Zn.
(viii) Re is used as electronic filament.
(E) Group 8, 9 and 10 – elements:-
(i) Fe, Co, Ni are ferromagnetic substances.
Ferromagnetic:- Those substance are called as feromagnetic in
which paramagnetic property is found in large amount. This is
because the unpaired electrons in these elements have get
magnetic filed in the same direction. So, the net magnetic filed
becomes. Very larger
Ferromagnetic elements can be magnetized and
hence magnets are formed. With the help of these elements.
(ii) Fe has oxidation state +2 and +3.
(iii) Co shows +2 oxidation state.
(iv) Ni shows +2 oxidation state.
(v) After Al, Fe is the most abundant metal.
(vi) Rest metals of these groups are innert.
(F) Group 11 – elements:-
(i) This group includes Cu, Ag and Au.
(ii) These metals are known as coinage metals.
(iii) The most stable state of Cu is +2.

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(iv) The most stable state of Ag and Au is +1.
(v) The metals of this group have highest thermal and
electrical conductivity.
(vi) Metals of this group are found in free state and combined
state.
(G) Group 12 – elements:-
(i) It consists of Zn, Cd and Hg.
(ii) These metals do not show characteristrics of transition
metals.
(iii) These metals do not show oxidation state more than +2.
(iv) Hg is found in Liquid state.
Iron metal:-
Important ores:-
(a) Haematite (Red oxide of Fe) – Fe2O3.
(b) Magnetite (Magnetic oxide of Fe) Fe3O4.
(c) Limonite (2Fe2O3 . 3H2O).
(d) Siderite – FeCO3.
(e) Iron pyrite – FeS2.
Types of Iron:- There are three types of iron-
(a) Cast iron or pig iron:- In this iron carbon (2 – 5%), Silicon P,
Mn etc, impurities are present in large amount. It contracts
when it is heated. Belding of cast Iron is not possible. It is
resistance to corrossion.
(b) Wrought Iron:- (Maleable Iron) In this iron only carbon
Impurity (0.2%) is present. It can be changed in to rod sheat
etc. it can not be magnetised permantly.

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(c) Steal:- In this iron C, Si, P, Mn etc. imputies are present in
very small amount.
Extraction of cast Iron:-
Cast iron is mainly extracted from Haemotite (Fe2O3) or iron
pyrite. This is performed in the following steps.
(A) Concentration of ores:-
Haemotite cast iron pyrite are is concentrated by washing or
magnetic separation process.
(B) Calcination:-
Here concentrated ore is calcinated in a furance. Due to this
proccess following changes take place-
(i) C impurities is changed into CO2.
(ii) H2O changes into water vapour.
(iii) S change into SO2 .
(iv) FeS2 changes into Fe2O3.
4FeS2 + 11 O2 Fe2O3 + 8SO2.
In this way after this process we get Fe2O3 (Porous).
(C) Reducing or Smelting:-
Calcinated ore is mixed with coke, and CaCO3 and then it is taken
in a blast furnace.
Blast furnace:- Its length is about 50 to 100 fit and breadth is
about 15 to 20 fit. When charge (C + CaCO3 + calcinated ore) is
dropped through cup and cone arrangement following reactions
take place and altimately cast iron is obtained.

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(a) Zone of fusion (Lower zone):-
The temperature of this zone is 15000c. Here very small amount
or iron is obtained and mainly CO2 gas is formed.
C + O2 CO2
Fe2O3 2Fe + 3CO
(b) Middle zone or zone of Heat absorption:-
The temperature of this zone is 8000c to 10000c. Here mainly CO
gas is formed and also formation of slag takes place here.
CO2 + C 2CO
CaCO3(flux) CaO + CO2
SiO2 (Gangul) + CaO CaSiO3 (slag)
(c) Upper zone or zone of Reduction:-
The temperature of this zone is 4000c to 5000c. Here mainly
Iron is obtained by the reduction of Fe2O3. Here only reduction
takes place
3Fe2O3 + CO 2Fe3O4 + CO2
Fe3O4 + CO 3FeO + CO2
FeO + CO Fe + CO2 (Cast Iron)
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