STUDYMATE

Chapter – 8 D BLOCK ELEMENTS

Transition Elements: A transition element unpaired electrons in (n-1)d orbital which

is defined as the one which has lead to interatomic metallic bonding.
incompletely filled d orbitals in its ground
state or in any one of its oxidation states.

General E.C.: (n – 1)d1–10 ns0–2

Q1 Though copper, silver and gold have

completely filled sets of d-orbitals yet
they are considered as transition metals.
Why?

Ans. Because in their common oxidation

states they have incompletely filled d-
orbitals.

Q2 Why zinc, cadmium and mercury are

generally not considered as transition
metals?

Ans. Due to completely filled d orbitals in
their ground as well as common oxidation
state of +2.
Q3 On what ground can you say that
scandium (Z = 21) is a transition element
but zinc (Z = 30) is not?
Ans. Scandium atom in its ground state
has incompletely filled d-orbital (3d1), is
regarded as a transition element. Whereas,
Zinc atom has completely filled d orbitals
(3d10).
Ist Transition Series: Involves e filling in
– of Mn?
3d-orbital and includes 10 elements from
Sc-21 to Zn–30.
2nd Transition Series: Involves e– filling in
4d-orbital and includes 10 elements from
Y-39 to Cd-48.
But melting and boiling point first increases
and then decreases. It increases, because
the no. of unpaired electrons in d-orbitals,
increases but then decreases because the
pairing of d-orbitals takes place, which
decreases the strength.
Q4 Why Zn, Cd and Hg has lowest
melting point?
Ans. As they have fully filled d-orbitals and
therefore they have weak metallic bonds.
Q5 Why there is dip in the melting point
Ans. Due to half-filled d5 configuration the
electrons are held tightly by the nucleus so
that the de-localization is less. This results
into weak inter metallic bond and a dip in
melting point.

3rd Transition Series: Involves e– filling in 2) Enthalpy of atomization: Heat required

5d-orbital has 10 elements from La-57 and
is followed by 14 elements (Lanthanide
Series) which involves the filling in 4f-
orbital and next 9 elements from Hf-72 to
Hg-80.
Physical Properties:
1) Melting and Boiling point:
Transition metals have high melting and
boiling point, which is attributed to
to break metal lattice to get free atoms.
Q6 Why do the transition elements
exhibit higher enthalpies of
atomization?
Ans. Because of large number of unpaired
electrons in their atoms they have stronger
interatomic interaction and hence stronger
bonding between atoms resulting in higher
enthalpies of atomization.

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 STUDYMATE
Chapter – 8 D BLOCK ELEMENTS
Q7 In the series Sc (Z = 21) to Zn (Z =
30), the enthalpy of atomization of zinc
is the lowest, i.e, 126 kJmol–1. Why?
Ans. Zinc which has no unpaired electron
as its outer electronic configuration is 3d10
4s2 has weakest atomic intermetallic
bonding.
3) Metallic character: It decreases on
moving L-R as the electropositive character
decreases. It is due to greater E.N.C. and
larger number of valence e–.
Due to the presence of strong metallic
bonds, the transition metals are hard,
possess high densities and high enthalpies
of atomization.
4) Atomic/Ionic sizes: The size first
decreases with increase in atomic number,
then remains constant and then slightly
increases.
 The size , because there is an in
nuclear charge i.e. ENC.
 Then size remain constant ased
nuclear charge is partially cancelled
by ed shielding effect.
 The size as the interaction
between e– – e– repulsion  when the
pairing takes place.
 The atomic radii of the elements of
the second and third transition
metals are nearly same due to
lanthanide contraction.
6) Ionization enthalpy:
They have greater I.E. values than s-block
and lower than p-block. I.E. increases on
LR as the nuclear charge increases.
2
Irregular variation of I.E.1: Because
removal of the electron alters the relative
energies of 4s and 3d ortbitals. Cr has low
I.E.1 because loss of one electron gives
stable configuration of (3d5). Zn has very
high I.E.1 because electron has to be
removed from fully filled 4s orbital with
configuration (3d104s2).
Irregularities of I.E.2: After the loss of one
electron, the removal of second electron
becomes difficult. Hence I.E.2 are much
higher and increases from L  R. However,
Cr and Cu show much higher values
because the second electron has to be
removed from the stable configurations of
Cr+(3d5) and Cu+ (3d10).
V < Cr > Mn and Ni < Cu> Zn
 The first ionization enthalpy of 5d
elements are higher than 4d and 3d
because of poor shielding of nucleus
by 4f electrons which result in
greater effective nucleus charge.
Q8 Why K2PtCl6 exist but K2NiCl6 does
not?
Ans. The sum of first four ionization
enthalpy of Ni is extremely high.
7) Standard Electrode Potential:
a) Trends in the M2+|M standard
Electrode Potentials:
 The general trend towards less
negative E0 values across the series
is related to the general increase in
the sum of the first and second
ionization enthalpies.
 The unique behavior of Cu, having
a positive E0, accounts for its
inability to liberate H2 from acids.
The high ionization energy to
transform Cu(s) to Cu2+ (aq.) is not
balanced by its hydration enthalpy.
 The stability of the half-filled d
subshell in Mn2+ and the completely
filled d10 configuration in Zn2+ are
related to their large negative E0
values.
 STUDYMATE
Chapter – 8 D BLOCK ELEMENTS

 More negative E0 value of Ni is  All Cu2+ halides are known except

related to their highest negative
hydration enthalpy.
(b) Trends in the M3|M2+ Electrode
Potential:
 The low value for Sc reflects noble
gas configuration.
 The highest +ve REP value for Zn is
due to the removal of an electron
from the stable d10.
 The stability of V2+ (half-filled t2g
level).
Q9 Why E0 for Mn3+|Mn2+ couple is more
positive than that for Fe3+|Fe2+?
Ans. The third ionization of Mn is very high
to change Mn2+ (3d5) to Mn3+. Mn2+ (d5) is
particularly stable, low value for Fe shows
the extra stability of Fe3+ (d5).
8) Oxidation state:
Oxidation State: The variable oxidation
state is due to participation of ns (lower
oxidation state) and (n–1) d (higher
oxidation state), because ns and (n-1)d
have similar energy.
 Sc show only +3 oxidation state
because after losing two electrons it
attain 3d1 configuration which is
very unstable.
 Zinc do not show variable oxidation
state because after losing two
electrons it attains noble gas
configuration.
 Mn (Z=25) shows maximum number
of oxidation states due to electronic
share from both (n-1) d and ns
orbital.
 +2 oxidation state becomes more
and more stable in the first half of
the first row transition elements
with increasing atomic number. This
is because the sum of first and
second ionization energy increases.
As a result, the standard electrode
potential (E°) become less and less
negative. Hence, the tendency to
form M2+ ion decreases.
the iodide as Cu2+ oxidizes I– to I2.
2Cu2+ + 4I–  Cu2I2 (s) + I2.
Q10 Why is Cr2+ reducing and Mn3+
oxidizing when both have d4
configuration?
Ans. Cr2+ is reducing as its configuration
changes from d4 to d3, the latter having a
half-filled t2g level. On the other hand, the
change from Mn2+ to Mn3+ results in the
half-filled (d5) configuration which has extra
stability.
Q11 Explain why Cu+ ion is not stable in
aqueous solution?
OR
Cu+ disproportionate in aq. Solution.
Why?
Ans. Cu+ compounds are unstable in
aqueous solution and therefore undergo
disproportionation Cu2+ and Cu.
2Cu+ Cu2+ + Cu.
The stability of Cu2+ (aq) rather than Cu+
(aq) is due to the much more negative hydH
of Cu2+ (aq) than Cu+, which more than
compensates for the second ionization
enthalpy of Cu.
Q12 Why is the highest oxidation state
of a metal exhibited in its oxide or
fluroide only?
Ans. Oxygen and fluorine have small size
and high electronegativity. Hence, they can
oxidize the metal to the highest oxidation
state.
Q13 Why oxygen stabilizes the highest
oxidation state more than fluorine?
Ans. The ability of oxygen to stabilize these
high oxidation states exceeds that of
fluorine. Thus the highest Mn fluoride is
MnF4 whereas the highest oxide is Mn2O7.
The ability of oxygen to form multiple bonds
to metals explains its superiority.

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 STUDYMATE
Chapter – 8 D BLOCK ELEMENTS
Q14 Which is a stronger reducing agent
Cr2+ or Fe2+ and why?
Ans. E°(Cr3+|Cr2+) is –ve (–0.41 V) whereas
is +ve (+0.77V). Thus, Cr2+ is easily oxidized
to Fe3+ but Fe2+ cannot be easily oxidized to
Fe3+.
Q15 How would you account for the
increasing oxidizing power in the series
VO2+ < Cr2O72– < MnO4–?
Ans. This is due to the increasing stability
of the lower species to which they are
reduced.
Q16 Name the Oxo metal anions of the
first series of the transition metals in
which the metal exhibits the oxidation
state equal to its group number.
Ans. MnO4– .
Characteristic Properties of Transition
Metals
1. Complex Formation: They form many
coordination complexes due to following
reasons:
(i) Small size and high charge density
of ions of transition metal.
(ii) Presence of vacant d orbitals of
appropriate energy which can accept lone
pair of e– donated by other groups.
2. Coloured Complexes: Transition metals
forms coloured complexes. Except: Sc+3, Ti+4
(3d0) & Zn+2 (3d10).
Reason: The transition of e– can take place
from lower d-orbital to higher d-orbital
within same sub-shell. If the energy
released falls in visible region, then they
emit the colors when white light falls on
these substance. (d-d transition)
3. Magnetic Properties: Due to presence of
unpaired e–, their complexes are
paramagnetic (weakly attracted).
 It increases with increase in no. of
unpaired e–s. The paramagentism is
expressed in terms of magnetic
4
moment  = ❑ n ( n+2 ) B.M., (spin
√
only formula) where n is no. of
unpaired e–s and B.M. is Bohr
Magneton.
4. Catalytic Properties: Many transition
metals acts as catalyst, E.g.: Fe in
manufacture of NH3 by Haber process, V2O5
or Pt for oxidation of SO2 to SO3 in contact
process, etc. because of following reason:
(i) Transition metal has tendency to show
variable O.S to form unstable intermediates
and provide new path with lower Ea for
reaction.
2I– + S2O82–  I2 + 2SO42–
Mech: (a) 2Fe3+ + 2I–  2Fe2+ + I2
(b) 2Fe2+ + S2O82 –  2Fe3+ + 2SO42–
(ii) Transition metals provides a suitable
surface for the reaction to take place. The
reactants are adsorbed on the surface of
the catalyst where reaction occurs.
5. Formation of Alloys: Since they have
almost similar atomic sizes, they can
mutually substitute their position in their
crystal lattices and can form alloys. Eg:
Brass, Bronze, Steels, etc.
6. Interstitial Compounds: They can
entrap smaller atoms like H,C,N, etc. in
their interstitial sites of crystal lattice.
 These trapped atoms get bounded to
the atom of metals. The presence of
atoms results in decease in
malleability and ductility of metal,
but increases their tensile strength.
Eg: Steel and Cast iron are hard due
to entrapped C.
Oxides and Oxo metal Ions
 All metals except Sc form MO oxides
which are ionic. The highest
oxidation no. in oxides coincides
with the group no. and is attained in
Sc2O3 to Mn2O7. Beyond group 7, no
higher oxides of iron above Fe2O3
(which gives O2) are known.
 STUDYMATE
Chapter – 8 D BLOCK ELEMENTS

 Besides the oxides, some metals

stabilizes by forming Oxo cations
like V as VO2+, VO2+ and TiO2+, etc.,
i.e. O2 can form higher states then F
(MnF4) because O2 can form multiple
bonds. As oxdn no. , ionic
character .

Q17 Why lowest oxides are basic and

pH effect on K2Cr2O7
highest is acidic?
The (Cr2O72–) and CrO42– exist in equilibrium
Ans. In the low oxidation state of metal
with each other at pH 4 and are
some of the valence electron of metal atom
interconvertable by changing pH. The
are not evolved in bonding. Hence it can
CrO42– on addition of acid change into
donate electron and hence behave as basic.
Cr2O72– and Cr2O72– on addition of alkali
In higher oxidation state, valence electron
changes into CrO42–.
are involved in bonding and are not
available and also they have high effective 2CrO42– + 2H+  Cr2O72– + H2O
nuclear charge.
Cr2O72– + 2OH–  2CrO42– + H2O
POTASSIUM DICHROMATE

Dichromate are obtained from chromates,

which are obtained by fusion of chromite
ore with Na or K2CO3 in air.
Properties:
Preparation from Chromite ore:
1. It is orange crystalline solid with m. pt.
1) 4FeCr2O4 + 8Na2CO3 + 7O2  8Na2CrO4 + 670K.
2Fe2O3 + 8CO2 2. It is soluble in hot water but moderately
2) Na2CrO4 is then filtered and acidified in cold water.
with H2SO4 to give crystals of 3. Action of Heat:
Na2Cr2O7.2H2O.
4K Cr O 

4K CrO  2Cr O  3O
2Na2CrO4 + 2H+  Na2Cr2O7 + 2Na+ + H2O 2 2 7 2 4 2
Chromic
3 2

3) KCl is reacted with Na2Cr2O7, as
Na2Cr2O7 is more soluble than K2Cr2O7
Na2Cr2O7 + 2KCl  K2Cr2O7 + 2NaCl.
Orange crystals of K2Cr2O7 are thus
separated out.
oxide
4. Oxidizing Properties: Acts as strong
O.A. in acidic medium.
K2Cr2O7 + 4H2SO4  K2SO4 + Cr2(SO4)3 +
4H2O + 3[O]
Cr2O72– + 14H+ + 6e–  2Cr3+ + 7H2O

[E° = – 1.33 V]

Eg: (i) Oxidizes Iodides to I2

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

(ii) Acidified FeSO4 to Fe2(SO4)3

Cr2O72– + 14H+ + 6Fe2+  2Cr3+ + 6Fe3+ +

7H2O

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 STUDYMATE
Chapter – 8 D BLOCK ELEMENTS

(iii) It oxidizes H2S to S. 1. It is a violet crystalline solid with 523K

as melting point.
Cr2O72– + 3H2S + 8H+  2Cr3+ + 3S + 7H2O
2. It is soluble in water and its aq. solution
(iv) Tin (II) to Tin(IV) is purple in color.
Cr2O72– + 3Sn2+ + 14H+  2Cr3+ + 3Sn+4 + 3. Effect of Heat:
7H2O
2KMnO 

4
K MnO  MnO  O
2 4 2 2
(v) Test for Drunken Driver:
4. Oxidizing Properties: Acts as a powerful
Cr2O72– + C2H5OH + 14H+ 2Cr3+ +
O. A. in acidic, neutral and alkaline media.
CH3COOH+ 7H2O
MnO4– + e–  MnO42– ;(Eº = + 0.56 V)
KMnO4
MnO4– + 4H+ + 3e– MnO2 + 2H2O ;(Eº = +
Preparation:
1.69 V)
1. On large scale it is obtained by
pyrolusite ore (MnO2). MnO4– + 8H+ + 5e–  Mn2+ + 4H2O ;(Eº = +
1.52 V)
KNO3 (O.A.)
MnO  4KOH  O   K MnO  2H O
2 2 2
Green
4 2
In Acidic Medium:

K2MnO4 then undergoes disproportionate (i) Fe2+ to Fe3+ salts:

reaction in neutral or acidic medium to give
permanganate. MnO4– + 5Fe2+ + 8H+  Mn2+ + 5Fe3+ + 4H2O.

3MnO24  4H  2MnO4  MnO2  2H2O (ii) Oxalates to CO2:

Manganate Permanganate
2MnO4– + 5C2O42– + 16H+  2Mn2+ + 10CO2
2. Commercially it is prepared by alkaline + 8H2O.
oxidative fusion of MnO2 followed by
electrolytic oxidation of manganate (VI) (iii) Iodides to I2:

MnO2 
Fused with KOH 10I– + 2MnO4– +16H+  2Mn2+ + 5I2+ 8H2O.
Oxidised with air/KNO3
MnO42–
(iv) Sulphites to Sulphates:
MnO24 
Electrolytic oxidation in
Alkaline solution  MnO4
Manganate Permanganage
5SO32– + 2MnO4– + 6H+  2Mn2+ + 5SO42+ +
3H2O.

(v) Nitrite to Nitrate:

5NO2– + 2MnO4– + 6H+  2Mn2+ + 5NO3– +

3H2O.

(vi) Sulphides to Sulphur:

5S2– + 2MnO4– + 16H+  2Mn2+ + 8H2O + 5S

In Neutral of Faintly Alkaline solution:

3. In lab. Manganese salt is oxidized by
(vii) Iodide to Iodate:
peroxodisulphate to permanganate.
2MnO4– + H2O + I–  2MnO2 + 2OH–+ IO3–
2Mn2+ + 5S2O82– + 8H2O  2MnO4– + 10SO42–
+ 16H+

Properties: (viii) Thiosulphate to Sulphate:

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 STUDYMATE
Chapter – 8 D BLOCK ELEMENTS
8MnO4– + 3S2O32– + H2O  8MnO2 + 6SO42–+
OH–.
(ix) Manganous salt to MnO2:
2MnO  3Mn  2H O 

4 or ZnO  5MnO  4H
ZnSO4
2
2 2

MnO4– titration in HCl are unsatisfactory
since HCl is oxidized to Cl2.
Uses:
1. As an O.A. in lab and industry.
2. For volumetric estimation of Fe2+ salts,
oxalates and other R.A.
3. For qualitative detection of halides,
oxalates, tartrates, sulphites, etc.
4. As disinfectants for water, in dry cells.
5. As lab reagent (Baeyer's reagent).
F BLOCK ELEMENTS
It consist of 2 series of inner transition
elements i.e. lanthanides and actinides and
are called rare earth elements.
E.C.: (n – 2)f1-14 (n – 1)d0-1 ns2.
Lanthanides: Involves filling of 4f-orbitals.
They are silvery white metals having low
tensile strength. They are good conductor of
heat and electricity.
1. E. C.: 4f1-145d0-16s2.
2. Density: They have high densities
and it increases with increase in atomic
number.
3. M.P. and B.P.: High melting point
and has no definite trends.
4. I.E.: Low IE. The IE1 and IE2 are
quite comparable to those of alkaline earth
metals particularly Ca.
5. Colored ion: Are colored in solid &
solution. The color is due to f-f transition
since they have partly filled f-orbital.
6. Magnetic Behaviour: The
lanthanoides ion (Ln3+) generally show
paramagnetism due to the unpaired e– in f-
orbital.
7
7. At./Ionic Radii and Lanthanoid
Contraction:
Although the atomic radii do show
some irregularities but ionic radius (Ln3+)
decreases steadily from La to Lu.
This steady decrease in size of Ln3+
ions with the in atomic number is called
lanthanide contraction.
Cause of L.C.: As atomic number
increases, e– goes to 4f-orbital and are
ineffective in screening nuclear charge.
Hence, there is a gradual in the Effective
N.C.
Consequently the force of attraction b/w
nucleus and valance shell increases & the
e– cloud shrinks. This results in gradual
decrease in size of lanthanides with
increase in atomic number.
Consequence of Lanthanide Contraction:
(i) Similarity of 2nd and 3rd T.S: The
atomic radii of 2nd and 3rd row are almost
similar.
But after lanthanides, atomic radii from 2nd
& 3rd transition series does not increases
because the increase in size on moving
down from 2nd and 3rd series is cancelled by
L.C.
(ii) Separation of Lanthanides: Due to
L.C. all Lanthanides have quite similar
properties therefore, they are difficult to be
separated. Because of L.C. their properties
vary slightly.
This slight variation in properties is
utilized in the separation of lanthanides by
ion exchange methods.
(iii) Variation in Basic Strength of
Hydroxides: It decreases from La(OH)3 to
Lu(OH)3, due to L.C. as the size of Ln3+ ions
decreases. Hence, there is increase in the
covalent character in Ln-OH bond.
8. Oxidation States: Common O.S is
+3. The +3 is extra stable for La,
gadolinium and lutetium because these
 STUDYMATE
Chapter – 8 D BLOCK ELEMENTS
elements have an empty, half-filled and
completely filled 4f.
 Cerium and Terbium show +4 O.S,
because empty (Ce4+) and half-filled
4f orbitals (Tb4+).
 Europium and Ytterbium show +2
O.S, because of their stable E.C Eu2+
(Half filled), Yb2+ (completely filled).
Chemical Reactivity: Lanthanides form
salts like carbides and hydride, and oxide
(M2O3) and sulphides (M2S3) but cerium
gives CeO2. The M2O3 oxides react with
water to form insoluble hydroxides and with
CO2 give M2(CO3)3.
 They are ionic, coloured & exhibit
paramagnetism.
 These occur together due to
chemical similarity and are difficult
to separate.
Uses:
1. Misch metal an alloy of Ce, La,
Neodymium, Fe, & traces of C, S, Si, Cu, Al.
is used in cigarette and gas lighters, flame
throwing tanks, tracer bullets and shells.
2. An alloy of Mg and Misch metal is
used in jet engine parts.
3. Ceric sulphate Ce(SO4)2 is used as
O.A. in volumetric analysis.
4. Cerium salts are used in dying
cotton, in Pb accumulators and as catalyst.
5. La2O3 is used in Crookes lens, which
gives protection from U.V. light by
absorbing it.
8
6. Many Lanthanide oxides are used as
phosphors in colour TV tubes.
7. CeO2 is used to polish glass.
Actinides
They involve filling of 5f-orbitals and follow
Ac (89) and include elements from Th(90)
and Lr(103).
All these are radioactive, therefore their
accessibility for lab. Investigation is limited.
The elements beyond U are all man-made
(Transuranic) elements and are made by
Nuclear- Chemical methods.
E. C.: 5f 1-14
6d0-1 7s2.
Properties:
1. Oxidation State: Common O.S is
+3, but show +4, +5, +6 also.
2. Physical Appearance: Silvery white
and get tarnished when exposed to attack
of alkaline.
3. Density: Have high density except
Thorium and Americium.
4. I.E.: Low.
5. Radioactive Nature.
6. Color: Are colored, which depends
on 5f e–. The ions of 5f° and 5f7 are
colorless, while those of 2 to 6 e– in 5f shell
are colored. E.g.: U3+(5f3) = Red, Np3+(5f4) =
Bluish, Pu3+(5f5) = Blue, Am3+(5f6) = Pink.
7. M.P. and B.P.: No regular trend
with increase in atomic number.
8. Magnetic Properties: Paramagnetic
due to presence of unpaired e–.
9. Actinoid Contraction: The size of
atom/cation decreases along actinoid
series. The steady decrease in ionic radii
with increase in atomic number is known
as Actinoid Contraction and it is due to
poor shielding of 5f e-.
Comparision between Lanthanides and
Actinoids:
 STUDYMATE
Chapter – 8 D BLOCK ELEMENTS

L.S. A.S.
1. +3, they +3 they show +4,
show +2 and +4 +5, +6, +7.
Shows more
variable O.S
2. Smaller Stronger tendency
tendency of of complex
complex formation formation.
3. Do not form Form oxo ions, like
oxo-ions. UO22+ PuO22+
UO2+ ,etc.
4. Except All are radioactive.
Promethium, they
are non-radioactive
5. Less basic More basic.

Q18 Actinoid contraction is greater from

element to element than lanthanide
contraction. Why?

Ans. This is due to poor shielding by 5f

electrons in the actinoids than that by 4f
electrons in the lanthanides.

Q19 The chemistry of the actinoid

elements is not so smooth as that of the
lanthanides. Explain.

Ans. Lanthanides show limited number of

oxidation state, i.e., +2, +3 and +4 (+3 is
common). This is because of large energy
gap between 4f, 5d and 6s subshells. But
the dominant oxidation state of actinoids is
also +3 and they show other oxidation
states also.