Chapter – 8 D BLOCK ELEMENTS

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

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

2nd Transition Series: Involves e– filling Ans. Due to half-filled d5 configuration the
in 4d-orbital and includes 10 elements electrons are held tightly by the nucleus
from Y-39 to Cd-48. so that the de-localization is less. This
results into weak inter metallic bond and a
3rd Transition Series: Involves e– filling dip in melting point.
in 5d-orbital has 10 elements from La-57
and is followed by 14 elements 2) Enthalpy of atomization: Heat
(Lanthanide Series) which involves the required to break metal lattice to get free
filling in 4f-orbital and next 9 elements atoms.
from Hf-72 to Hg-80.
Q6 Why do the transition elements
Physical Properties: exhibit higher enthalpies of
atomization?
1) Melting and Boiling point:
Ans. Because of large number of unpaired
Transition metals have high melting and electrons in their atoms they have
boiling point, which is attributed to stronger interatomic interaction and hence

1
 Chapter – 8 D BLOCK ELEMENTS

stronger bonding between atoms resulting They have greater I.E. values than s-block
in higher enthalpies of atomization. and lower than p-block. I.E. increases on
LR as the nuclear charge increases.
Q7 In the series Sc (Z = 21) to Zn (Z =
30), the enthalpy of atomization of Irregular variation of I.E.1: Because
zinc is the lowest, i.e, 126 kJmol–1. removal of the electron alters the relative
Why? energies of 4s and 3d ortbitals. Cr has low
I.E.1 because loss of one electron gives
Ans. Zinc which has no unpaired electron stable configuration of (3d5). Zn has very
as its outer electronic configuration is 3d10 high I.E.1 because electron has to be
4s2 has weakest atomic intermetallic removed from fully filled 4s orbital with
bonding. configuration (3d104s2).
3) Metallic character: It decreases on Irregularities of I.E.2: After the loss of
moving L-R as the electropositive one electron, the removal of second
character decreases. It is due to greater electron becomes difficult. Hence I.E.2 are
E.N.C. and larger number of valence e–. much higher and increases from L  R.
Due to the presence of strong metallic However, Cr and Cu show much higher
bonds, the transition metals are hard, values because the second electron has to
possess high densities and high enthalpies be removed from the stable configurations
of atomization. of Cr+(3d5) and Cu+ (3d10).

4) 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?
Atomic/Ionic sizes: The size first Ans. The sum of first four ionization
decreases with increase in atomic number, enthalpy of Ni is extremely high.
then remains constant and then slightly
increases. 7) Standard Electrode Potential:

 The size , because there is an in a) Trends in the M2+|M standard

nuclear charge i.e. ENC. Electrode Potentials:
 Then size remain constant ased  The general trend towards less
nuclear charge is partially negative E0 values across the
cancelled by ed shielding effect. series is related to the general
 The size as the interaction increase in the sum of the first and
between e– – e– repulsion  when second ionization enthalpies.
the pairing takes place.  The unique behavior of Cu,
having a positive E0, accounts
 The atomic radii of the elements of for its inability to liberate H2 from
the second and third transition
acids. The high ionization energy to
metals are nearly same due to
transform Cu(s) to Cu2+ (aq.) is not
lanthanide contraction.
balanced by its hydration enthalpy.
6) Ionization enthalpy:

2
 Chapter – 8 D BLOCK ELEMENTS

 The stability of the half-filled d As a result, the standard electrode

subshell in Mn2+ and the completely potential (E°) become less and less
filled d10 configuration in Zn2+ are negative. Hence, the tendency to
related to their large negative E0 form M2+ ion decreases.
values.  All Cu2+ halides are known except
 More negative E0 value of Ni is the iodide as Cu2+ oxidizes I– to I2.
related to their highest negative
hydration enthalpy. 2Cu2+ + 4I–  Cu2I2 (s) + I2.

(b) Trends in the M3|M2+ Electrode Q10 Why is Cr2+ reducing and Mn3+
Potential: oxidizing when both have d4
configuration?
 The low value for Sc reflects noble
gas configuration. Ans. Cr2+ is reducing as its configuration
 The highest +ve REP value for Zn is changes from d4 to d3, the latter having a
due to the removal of an electron half-filled t2g level. On the other hand, the
from the stable d10. change from Mn2+ to Mn3+ results in the
 The stability of V2+ (half-filled t2g half-filled (d5) configuration which has
level). extra stability.

Q9 Why E0 for Mn3+|Mn2+ couple is Q11 Explain why Cu+ ion is not stable
more positive than that for Fe3+|Fe2+? in aqueous solution?

Ans. The third ionization of Mn is very OR

high to change Mn2+ (3d5) to Mn3+. Mn2+ Cu+ disproportionate in aq. Solution.
(d5) is particularly stable, low value for Fe Why?
shows the extra stability of Fe3+ (d5).
Ans. Cu+ compounds are unstable in
8) Oxidation state: aqueous solution and therefore undergo
Oxidation State: The variable oxidation disproportionation Cu2+ and Cu.
state is due to participation of ns (lower 2Cu+ Cu2+ + Cu.
oxidation state) and (n–1) d (higher
oxidation state), because ns and (n-1)d The stability of Cu2+ (aq) rather than Cu+
have similar energy. (aq) is due to the much more negative
hydH of Cu2+ (aq) than Cu+, which more
 Sc show only +3 oxidation state than compensates for the second
because after losing two electrons ionization enthalpy of Cu.
it attain 3d1 configuration which is
very unstable. Q12 Why is the highest oxidation
 Zinc do not show variable oxidation state of a metal exhibited in its oxide
state because after losing two or fluroide only?
electrons it attains noble gas
Ans. Oxygen and fluorine have small size
configuration.
and high electronegativity. Hence, they
 Mn (Z=25) shows maximum
can oxidize the metal to the highest
number of oxidation states due to
oxidation state.
electronic share from both (n-1) d
and ns orbital. Q13 Why oxygen stabilizes the
 +2 oxidation state becomes more highest oxidation state more than
and more stable in the first half of fluorine?
the first row transition elements
with increasing atomic number. Ans. The ability of oxygen to stabilize
This is because the sum of first and these high oxidation states exceeds that
second ionization energy increases. of fluorine. Thus the highest Mn fluoride is

3
 Chapter – 8 D BLOCK ELEMENTS

MnF4 whereas the highest oxide is Mn2O7.  It increases with increase in no. of
The ability of oxygen to form multiple unpaired e–s. The paramagentism
bonds to metals explains its superiority. is expressed in terms of magnetic

Q14 Which is a stronger reducing √

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

4
 Chapter – 8 D BLOCK ELEMENTS

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.
 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

highest is acidic?

Ans. In the low oxidation state of metal

some of the valence electron of metal
atom are not evolved in bonding. Hence it
can donate electron and hence behave as pH effect on K2Cr2O7
basic. In higher oxidation state, valence The (Cr2O72–) and CrO42– exist in equilibrium
electron are involved in bonding and are with each other at pH 4 and are
not available and also they have high interconvertable by changing pH. The
effective nuclear charge. CrO42– on addition of acid change into
POTASSIUM DICHROMATE Cr2O72– and Cr2O72– on addition of alkali
changes into CrO42–.
Dichromate are obtained from chromates,
which are obtained by fusion of chromite 2CrO42– + 2H+  Cr2O72– + H2O
ore with Na or K2CO3 in air. Cr2O72– + 2OH–  2CrO42– + H2O
Preparation from Chromite ore:

1) 4FeCr2O4 + 8Na2CO3 + 7O2  8Na2CrO4

+ 2Fe2O3 + 8CO2
Properties:
2) Na2CrO4 is then filtered and acidified
with H2SO4 to give crystals of 1. It is orange crystalline solid with m. pt.
Na2Cr2O7.2H2O. 670K.

2Na2CrO4 + 2H+  Na2Cr2O7 + 2Na+ + H2O 2. It is soluble in hot water but moderately
in cold water.
3) KCl is reacted with Na2Cr2O7, as
Na2Cr2O7 is more soluble than K2Cr2O7 3. Action of Heat:

Na2Cr2O7 + 2KCl  K2Cr2O7 + 2NaCl. 4K Cr O  
2 2 7
4K CrO  2Cr O  3O
2 4 2 3 2
Chromic
oxide
Orange crystals of K2Cr2O7 are thus
separated out. 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]

5
 Chapter – 8 D BLOCK ELEMENTS

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

(iii) It oxidizes H2S to S.

Cr2O72– + 3H2S + 8H+  2Cr3+ + 3S +

7H2O 3. In lab. Manganese salt is oxidized by
peroxodisulphate to permanganate.
(iv) Tin (II) to Tin(IV)
2Mn2+ + 5S2O82– + 8H2O  2MnO4– +
Cr2O72– + 3Sn2+ + 14H+  2Cr3+ + 3Sn+4 +
10SO42– + 16H+
7H2O
Properties:
(v) Test for Drunken Driver:
1. It is a violet crystalline solid with 523K
Cr2O72– + C2H5OH + 14H+ 2Cr3+ +
as melting point.
CH3COOH+ 7H2O
2. It is soluble in water and its aq. solution
KMnO4
is purple in color.
Preparation:
3. Effect of Heat:
1. On large scale it is obtained by
pyrolusite ore (MnO2).
2KMnO4  

K 2MnO 4  MnO 2  O 2
KNO3 (O.A.)
MnO2  4KOH  O2      K 2MnO4  2H2O 4. Oxidizing Properties: Acts as a
Green powerful O. A. in acidic, neutral and
alkaline media.
K2MnO4 then undergoes disproportionate
reaction in neutral or acidic medium to MnO4– + e–  MnO42– ;(Eº = + 0.56 V)
give permanganate.
MnO4– + 4H+ + 3e– MnO2 + 2H2O ;(Eº =
3MnO4  4H   2MnO4  MnO2  2H 2O
2  
+ 1.69 V)
Manganate Permanganate
MnO4– + 8H+ + 5e–  Mn2+ + 4H2O ;(Eº = +
2. Commercially it is prepared by alkaline 1.52 V)
oxidative fusion of MnO2 followed by
electrolytic oxidation of manganate (VI) In Acidic Medium:

MnO2    with
air/
Fused with KOH
Oxidised 
KNO3 MnO 2– (i) Fe2+ to Fe3+ salts:
4

MnO4– + 5Fe2+ + 8H+  Mn2+ + 5Fe3+ +

MnO24      MnO4
  solution
Electrolytic oxidation in
Alkaline
Manganate Permanganage 4H2O.

(ii) Oxalates to CO2:

2MnO4– + 5C2O42– + 16H+  2Mn2+ + 10CO2

+ 8H2O.

(iii) Iodides to I2:

10I– + 2MnO4– +16H+  2Mn2+ + 5I2+

8H2O.

6
 Chapter – 8 D BLOCK ELEMENTS

(iv) Sulphites to Sulphates: having low tensile strength. They are good
conductor of heat and electricity.
5SO32– + 2MnO4– + 6H+  2Mn2+ + 5SO42+
+ 3H2O. 1. E. C.: 4f1-145d0-16s2.

(v) Nitrite to Nitrate: 2. Density: They have high densities

and it increases with increase in atomic
5NO2– + 2MnO4– + 6H+  2Mn2+ + 5NO3– + number.
3H2O.
3. M.P. and B.P.: High melting point
(vi) Sulphides to Sulphur: and has no definite trends.
5S2– + 2MnO4– + 16H+  2Mn2+ + 8H2O + 4. I.E.: Low IE. The IE1 and IE2 are
5S quite comparable to those of alkaline
In Neutral of Faintly Alkaline solution: earth metals particularly Ca.

(vii) Iodide to Iodate: 5. Colored ion: Are colored in solid &

solution. The color is due to f-f transition
2MnO4– + H2O + I–  2MnO2 + 2OH–+ IO3– since they have partly filled f-orbital.

6. Magnetic Behaviour: The

lanthanoides ion (Ln3+) generally show
(viii) Thiosulphate to Sulphate:
paramagnetism due to the unpaired e– in
8MnO4– + 3S2O32– + H2O  8MnO2 + 6SO42– f-orbital.
+ OH–.
7. At./Ionic Radii and Lanthanoid
(ix) Manganous salt to MnO2: Contraction:

2MnO  3Mn  2H O  
4
 2

ZnSO4
or ZnO
2
 5MnO  4H 2

Although the atomic radii do show
some irregularities but ionic radius (Ln3+)
MnO4– titration in HCl are unsatisfactory decreases steadily from La to Lu.
since HCl is oxidized to Cl2.
This steady decrease in size of Ln3+
Uses: ions with the in atomic number is called
lanthanide contraction.
1. As an O.A. in lab and industry.
Cause of L.C.: As atomic number
2. For volumetric estimation of Fe2+ salts, increases, e– goes to 4f-orbital and are
oxalates and other R.A. ineffective in screening nuclear charge.
3. For qualitative detection of halides, Hence, there is a gradual in the Effective
oxalates, tartrates, sulphites, etc. N.C.

4. As disinfectants for water, in dry cells. Consequently the force of attraction b/w
nucleus and valance shell increases & the
5. As lab reagent (Baeyer's reagent). e– cloud shrinks. This results in gradual
decrease in size of lanthanides with
F BLOCK ELEMENTS
increase in atomic number.
It consist of 2 series of inner transition
Consequence of Lanthanide
elements i.e. lanthanides and actinides
Contraction:
and are called rare earth elements.
(i) Similarity of 2nd and 3rd T.S: The
E.C.: (n – 2)f1-14 (n – 1)d0-1 ns2.
atomic radii of 2nd and 3rd row are almost
Lanthanides: Involves filling of 4f- similar.
orbitals. They are silvery white metals

7
 Chapter – 8 D BLOCK ELEMENTS

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.
Uses:
This slight variation in properties is
utilized in the separation of lanthanides by 1. Misch metal an alloy of Ce, La,
ion exchange methods. Neodymium, Fe, & traces of C, S, Si, Cu,
Al. is used in cigarette and gas lighters,
(iii) Variation in Basic Strength of
flame throwing tanks, tracer bullets and
Hydroxides: It decreases from La(OH)3
shells.
to Lu(OH)3, due to L.C. as the size of Ln3+
ions decreases. Hence, there is increase in 2. An alloy of Mg and Misch metal is
the covalent character in Ln-OH bond. used in jet engine parts.
8. Oxidation States: Common O.S is 3. Ceric sulphate Ce(SO4)2 is used as
+3. The +3 is extra stable for La, O.A. in volumetric analysis.
gadolinium and lutetium because these
elements have an empty, half-filled and 4. Cerium salts are used in dying
completely filled 4f. cotton, in Pb accumulators and as
catalyst.
 Cerium and Terbium show +4 O.S,
because empty (Ce4+) and half- 5. La2O3 is used in Crookes lens,
filled 4f orbitals (Tb4+). which gives protection from U.V. light by
 Europium and Ytterbium show +2 absorbing it.
O.S, because of their stable E.C 6. Many Lanthanide oxides are used
Eu2+(Half filled), Yb2+ (completely as phosphors in colour TV tubes.
filled).
7. CeO2 is used to polish glass.
Chemical Reactivity: Lanthanides form
salts like carbides and hydride, and oxide Actinides
(M2O3) and sulphides (M2S3) but cerium
gives CeO2. The M2O3 oxides react with They involve filling of 5f-orbitals and follow
water to form insoluble hydroxides and Ac (89) and include elements from Th(90)
with CO2 give M2(CO3)3. and Lr(103).

 They are ionic, coloured & exhibit All these are radioactive, therefore their
paramagnetism. accessibility for lab. Investigation is
 These occur together due to limited. The elements beyond U are all
chemical similarity and are difficult man-made (Transuranic) elements and are
to separate. 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.

8
 Chapter – 8 D BLOCK ELEMENTS

2. Physical Appearance: Silvery Ans. This is due to poor shielding by 5f

white and get tarnished when exposed to electrons in the actinoids than that by 4f
attack of alkaline. electrons in the lanthanides.

3. Density: Have high density except Q19 The chemistry of the actinoid
Thorium and Americium. elements is not so smooth as that of
the lanthanides. Explain.
4. I.E.: Low.
Ans. Lanthanides show limited number of
5. Radioactive Nature. oxidation state, i.e., +2, +3 and +4 (+3 is
6. Color: Are colored, which depends common). This is because of large energy
on 5f e–. The ions of 5f° and 5f7 are gap between 4f, 5d and 6s subshells. But
colorless, while those of 2 to 6 e– in 5f the dominant oxidation state of actinoids
shell are colored. E.g.: U3+(5f3) = Red, is also +3 and they show other oxidation
Np3+(5f4) = Bluish, Pu3+(5f5) = Blue, states also.
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:

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?