D and f block elements

D & F BLOCK ELEMENTS

Electronic Configuration of d – Block Elements
The general electronic configuration of the d-block elements are: [Inert gas] (n-1)
d1-10 n s1-2 . The d-sub-shell is penultimate subshell and is denoted as (n-1) d-subshell,
the number of electrons may vary from one to ten. The s-sub shell is the valance shell is
represented as ns sub – shell and it may have one to two electrons e.g.
Consider the case of Cr which have 3d5 4s1 instead of 3d4 4s2 the energy
difference between the two sets (3d and 4s) of orbitals is small, similarly in case of Cu,
the configuration is 3d10 4s1 and not 3d9 4s2. It is due to extra stability of half and fully
filled sub-shell.

Classification of d- Block Elements

The d-block is present in the centre of the periodic table and have metals of s-block
on the left and non-metals of p-block on the right. Thus, they represent a transition
between the metals and non-metals.
a) These elements possess properties that are transitional between the s and p-block
elements. In other words they represent transition or change in properties from s-block
to p-block.
b) On the basis of d-orbitals these elements are classified into three series, known as 3d ,
4d and 5d series, each containing 10 elements. There is also 6d series, which is
incomplete.
i. First transition series or 3d – series: Elements from atomic number 21 to 30 are
included in this series. There are 10 elements in this series i.e Sc (21), Ti (22), V (23).
Cr(24), Mn (25).
ii. 4d series:-This series contains 10 elements with atomic number Z = 39 to 48 (Y –
Cd).
iii. 5d series:- This series also contains 10 elements with atomic number Z = 57 to
80.
c) Strictly speaking, a transition element is defined as the one which has incompletely
filled d orbitals in its ground state or in any one of its common oxidation states.
d) In Cu (3d10 451), Ag (4d10 5s1) and Au (5d10 6s1) the d-sub shells are completely filled
and even then d- electrons in these elements take part in chemical bonding. Thus Cu,

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 D and f block elements
Ag and Au are called typical transition elements, while Zn, Cd and Hg, which are the
last members of each d-block series, are excluded from transition elements.
 They also do not show properties characteristic of transition elements.
 Hence, all the transition elements are d-block elements, but all d- block elements
are not the transition elements.
e) Transition metals show greater horizontal similarities in properties due to same
valence shell electronic configuration i.e ns2.

Questions
1. Explain why zinc, cadmium and mercury are not regarded as transition
elements.
Ans:- The electronic configurations of zinc, cadmium and mercury are represented by the
general formula (n-1) d10 ns2. The d-orbitals in these elements are completely filled in
their ground states as well as in their common oxidation state. Hence, these elements do
not exhibit characteristic properties of transition elements. Therefore, they are not
regarded as transition elements.

2. On what ground can you say that scandium (Z = 21) is a transition element but
zinc (z = 30) is not?
Ans:-On the basis of incompletely filled 3d orbitals in case of scandium atom in its
ground state (3d1) it is regarded as transition element. On the other hand, zinc atom has
completely filled d orbitals (3d10) in its ground state as well as in its oxidized states
hence, it is not regarded as a transition element.

3. Silver atom has completely filled d-orbitals (4d10) in its ground state. How can
you say that it is a transition element?
Ans:- For an element to be classified as a transition element it should have partially filled
d–orbitals in its atom or common oxidation states. Silver can exhibit + 2 oxidation state
wherein it has incompletely filled d-orbitals, hence we can say it is a transition element.

Metallic Character
a) Nearly all the transition metals display metallic properties such as high tensile strength
, ductility, malleability, high thermal and electrical conductivity and metallic luster.
b) The transition elements are hard, less volatile, and have high enthalpy of atomization.

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 D and f block elements
c) Transition metals have high melting points. The high melting points are due to strong
inter -atomic bonding which involves both (n-1) d and ns electrons participation.
d) In a transition series, the melting points first increases and then decreases i.e. it
becomes maximum in the middle of series.
e) The maximum at about the middle of each series indicates that one unpaired electron
per d- orbital is particularly favourable for strong inter-atomic interaction.
f) The elements of 4d and 5d series have greater enthalpies of atomization than the
elements of 3d series. That’s why the elements of 4d and 5d series have more frequent
metal-metal bonding in their compounds.

4. Why Cr and Cu show exceptional configuration?

5. Why do some exceptions to the general electronic configuration of d-block

elements exists?
Ans:- There is a very less energy difference between (n-1) d and ns orbitals because of
which there exists exceptions to the general electronic configuration.

6. What is the reason of high enthalpies of atomization for transition elements?

Or
7. What is the reason for the high melting points of d-block elements?
Or
8. Why does the melting point of the d-orbitals increases upto the middle of the
series and then decrease again?
Ans:-The melting points depend upon the inter-atomic bonding, more the number of
electrons given by a metal higher is its inter-atomic bonding (metallic bonding) and thus
higher will be its melting point.
In d-block elements due to the involvment of both ns and (n-1) d electrons, the number of
electrons involved are higher and therefore stronger interatomic bonding and higher
melting point.
The number of unpaired electrons in the d-orbitals increases upto the middle of the series
and then decreases due to their paring. Thus, the strength of inter-atomic bonds increases
upto the middle and then decrease.

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 D and f block elements
9. Why is enthalpy of atomization increases upto the middle of the transition series
and then decreases?
Ans:-Upto the middle of the series, the number of unpaired electrons increases and then
decreases due to their pairing. This results first in the increase and then decrease in the
value of enthalpy of atomization.

10. In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomization of zinc is the
lowest i.e 126kJ mol-1. Why?
Ans:-In the series Sc to Zn, all elements have one or more unpaired electrons except zinc
which has no unpaired electron as its outer electronic configuration is 3d104s2. Hence,
atomic inter metallic bonding (M-M bonding) is weaker in zinc. Therefore, enthalpy of
zinc is the lowest.

11. Why are Zn, Cd and Hg softer and volatile metals?

Ans:-Due to their completely filled d-orbitals (e.c. is (n-1) d10 ns2), they have weak
metallic bonding and least compact packing, therefore they all are volatile in nature.

12. Why do the atomic and ionic radius decreases gradually in a given series?
Ans:-The atomic and ionic radii decreases gradually along the series because with the
extra electron entering the d-orbital each time the nuclear charge increases by one unit.
The shielding effect of the d-electrons is small. Due to this the electrostatic attraction
between the nuclear charge and the outermost electron increases and the atomic/ionic
radius decreases.

13. Why the density of the transition elements increases from left to right in the
series?
Ans:- The density increases in a series with increasing atomic number because the
metallic radius decrease and atomic mass increases. This makes their densities to
increase.

14. What is periodicity for atomic size along a group for transition elements?
Ans:-Along a group, while there is some increase in atomic radius in moving from first to
second member. The value remains unchanged while moving from second to third
member. This can be explained in terms of lanthanoid contraction size: 3d < 4d 5d.

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 D and f block elements

Ionization Enthalpies
The ionization enthalpies of transition elements are higher than those of s-block
elements but lower than p-block elements. In a particular transition series, ionization
enthalpy increases gradually as we move from left to right. However, the relative
difference of ionization enthalpy values of any two consecutive d-block elements of
particular period is much smaller than those of s- and p-block elements.

Reason
The increase in ionization enthalpy is primarily due to decrease in size and increase
in nuclear charge. As the transition elements involve the gradual filling of (n-1) d-
orbitals, the effect of increase in nuclear charge is partly cancelled by the increase in
screening effect. Consequently, the increase in ionization enthalpy along the period of d-
block elements is very small.

15. Cr and Cu have very high IInd ionization enthalpy values. Why?
Ans:-Second I.E increases almost regularly from Sc to Zn. Values for Cr and Cu are,
however, much higher than those of their neighbours on the left as well as on the right is
due to the stable configuration of Cr+ (3d5 – exactly half filled) and Cu+(3d10 completely
filled) .Removal of one electron means they change from a more stable to less stable
configuration.

16. Why are Mn2+ compound more stable than Fe2+ towards oxidation to their +3
state?
Ans:- The electron configuration of Mn2+ is 3d5, which is stable due to half filled sub
shell. Hence , Mn2+ is not easily oxidized to Mn3+. On the other hand, Fe2+ has electronic
configuration 3d6. After losing one electron it change to Fe 3+ which has stable 3d5
electronic configuration. Hence, Fe2+ is relatively easily oxidized to Fe3+.
Mn2+ → Mn3+ + e− Fe2+ → Fe3+ + e−
3d5 (stable) 3d4 3d6 3d5(stable)

17. The third ionization enthalpy of Mn, and Zn are quite high in comparison to Fe.
Explain.
Ans:- In Mn, and Zn, the third electron is taken out from the half filled or fully filled d-
orbitals due to which they have high third ionization enthalpies whereas in Fe third
electron is taken out from the 3d6 subshell due to which its value is not high.
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 D and f block elements

Variable Valency or Variable Oxidation State

a) All transition elements, except the first and last members of each series, exhibit a
variety of oxidation state.
b) The variation in the oxidation states is due to the involvement of incomplete d-orbitals
in addition of the electrons of the outermost s-orbital i.e (ns) as well as (n-1) d e . It is
due to slight energy difference between (n-1) d and ns orbitals and so electrons from
both the energy levels can be used for bonding.
c) The lesser number of oxidation states are shown by elements which occur at the
extreme ends of the transition series. This is because there are very few electrons to
lose or share.
d) The maximum number of oxidation state is shown by the element which occurs in or
near the middle of the series, e.g. Mn exhibits all the oxidation states from +2 to +7.
(3d5 4s2).
Sc Ti V Cr Mn Fe Co Ni Cu Zn
+2 +2 +2 +2 +2 +2 +2 +1 +2
+3 +3 +3 +3 +3 +3 +3 +3 +2
+4 +4 +4 +4 +4 +4 +4
+5 +5 +5
+6 +6 +6
+7

18. The number of oxidation state shown by the transition elements increases upto
the middle of the series and then decreases. Why?
Ans:- The number of unpaired electrons in the d-orbitals increases upto the middle of the
series and then decreases due to the pairing of the electrons, this pairing of electrons
decreases, the availability of electrons for reaction and therefore number of oxidation
states decreases.

19. Why are transition element series show fewer oxidation states at their extreme
ends. e.g. Sc, Ti, Cu, and Zn
Ans:-The lesser number of oxidation states at the extreme ends is because there are few
electrons to lose or share (Sc, Ti) or too many electrons (hence fewer orbitals available in
which to share electrons with others) for higher valence (Cu, Zn).

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 D and f block elements
20. To what extent do the electronic configurations decide the stability of oxidation
states in the first series of the transition elements? Illustrate your answer with
example.
Ans:-The stability of an oxidation state is determined to a large extent by the electronic
configuration of the element, in case of transition element those oxidation states in which
the element acquires stable configuration such as noble gas configuration, exactly half-
filled or fully filled d-subshell, are exceptionally stable. For example, Sc 3+, Mn2+ and
Zn2+ are relatively more stable.
Sc: [Ar] 3d1 4s2 ; Sc3+: 3d0 4s0 ; Mn: [Ar] 3d5 4s2 ; Mn2+: [Ar] 3d5
Zn: [Ar] 3d10 4s2 ; Zn2+: [Ar] 3d10

21. How is the variability in oxidation states of transition metal different from that of
the non-transition metals? Illustrate with examples.
Ans:-In case of transition elements, the oxidation states differ from each other by unity
whereas in case of non-transition elements oxidation states normally differ by units of
two. For example, Fe exhibits oxidation states of +2 and +3. Similarly, Cu exhibits
oxidations states of +1 and +2. On the other hand, Sn and Pb exhibit oxidation state of +2
and +4. Also in the p-block the lower oxidation states are favoured by the heavier
members (due to inert pair effect), the opposite is true in the groups of d-block. For
example, in group 6, Mo[VI] and W (VI) are found to be more stable than Cr (VI).

22. What may be the stable oxidation state of the transition element with the
following d-electron configurations in the ground state of their atoms: 3d3, 3d5,
3d8, 3d4?
Ans:-For 3d34s2, the most stable oxidation state is +5 (V)
For 3d54s2, the stable oxidation states are +2 and +7 (Mn)
For 3d84s2, the stable oxidation state is +2 (Ni)
For 3d44s2, (or 3d54s1, the stable oxidation states are +3 and +6. (Cr)

23. Name of the oxometal anions of the first series of the transition metals in which
the metal exhibits the oxidation state equal to its group number.
Ans:- Chromate ion, CrO42- Oxidation state + VI.
Dichromate ion, Cr2 O72-Oxidation state + VI
Permanganate ion, MnO4- Oxidation state + VII
Group number of chromium is 6 while that of manganese is 7.

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 D and f block elements
24. Name a transition metal which does not exhibit variation in oxidation state in its
compounds.
Ans:-Scandium (3d44s2). It shows +3 only (by loss of 3d1 4s2 e –s ) it aquires noble gas
electronic configuration , Zn (3d104s2) shows + 2 oxidation state only and Zn2+ has stable
3d10 etc.

25. What is the highest oxidation state shown by any transition metal?
Ans:-The highest oxidation state shown by any metals is +8by Ru & Os in RuO4,OsO4 .

Magnetic Properties
Transition elements and many of their compounds are paramagnetic, i.e., they are
weakly attracted by a magnetic field. This is due to the presence of unpaired electrons in
atoms, ions or molecules. The paramagnetic character increases as the number of
unpaired electrons increases. The paramagnetic character is measured in terms of
magnetic moment () and is given by  = √n(n + 2) Bohr magneton (B).

Formation of coloured ions

Most of the transition metal ions are coloured. The colour depends upon the nature
of the ligand bonded to the central ion. e.g. in aq. Solution , H2O acts as ligand . The
colour is attributed to the presence of unpaired d-electrons which are promoted to higher
energy levels within the d-shell and the transition metal ion gets the complementary
colour.
Since there are completely filled d-orbitals in Zn2+ (3d10) ,Cd2+ (4d10) and Hg2+(5d10) ions,
these are colourless . Sc3+, Ti4+are dcolourless.

Formation of Interstitial Compounds

 Transition element has a unique ability to form such compounds by accommodating
non metal atoms such as H,B,C, N etc. in between the metallic atoms in crystal.
 These voids may be tertrahedral or octahedral and called as interstices and occupied
by the non-metals to form metallic or interstitial hydrides, Carbides, nitrides, for
example. TiC, Mn4N, Fe3H, VH0.56 and TiH1.7 etc.
The principal physical and chemical characteristics of these compounds are as
follows:
a) They have high melting points, higher than those of pure metals.
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 D and f block elements
b) They are very hard, some borides approach diamond in hardness.
c) They retain metallic conductivity.
d) They are chemically inert.

26. The magnetic moment of the transition series elements increases upto the middle
of the series and then decreases why?
Ans:- The number of unpaired electrons increases upto the middle of the series and then
decreases due to their pairing. The magnetic moment depends upon the number of
unpaired electrons according to spin only formula. Therefore, its value increases upto
middle of the series and then decreases in a transition series μ = √n (n + 2) B.M

27. [Ti (H2O)6]3+ is coloured whereas [Sc(H2O)6]3+ is colourless. Why?

Ans:-In [Ti (H2O)6]3+(hexaaquatitanium ion) the titanium ion is present in Ti3+ form with
3d1 4s0 configuration. The single unpaired electron of 3d 1 orbital makes the compound to
show colour. [Sc(H2O)6]3+ is having scandium in Sc3+ state with 3d0 4s0 configuration.
Since no electron is present in the 3d and 4s orbitals, it remains colourless.

28. Predict which of the following will be coloured in an aqueous solution? Ti 3+,V3+,
Cu+, Sc3+,Mn2+,Fe3+,Co2+ reason for each.
Ans:- Species having unpaired electrons imparts colour in an aqueous solution:
Cu+ (3d10), Sc3+ (3d0) are colourless due to absence of any unpaired e – in d – subshell
Ti3+ (3d1), V3+ (3d2), Mn2+(3d5), Fe3+ (3d5) are coloured due to unpaired ‘d’ electrons
causing d-d transition.

Alloy Formation
1. An alloy is a blend of metals prepared by mixing the components. Alloys may be
homogeneous solid solutions in which the atoms of the metal are distributed randomly
among the atoms of the other.
Such alloys are formed by atoms with metallic radii that are within about 15
percent of each other.
2. The reason is that they have almost similar sizes and the atoms of one metal can easily
take up positions in the crystal lattice of the other. Also, ability of transition metals to
form strong metallic bonds is responsible for alloys formation.
The alloys so formed are hard and have often high melting points. The best
known are ferrous alloys: chromium, vanadium, tungsten, molybdenum and

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 D and f block elements
mangenese are used for the production of variety of steels and stainless steel. Brass
(copper –zinc) and bronze (copper tin) are also of considerable industrial importance.

29. What is the reason of the greater tendency of transition metals to form complex
compounds?
Ans:-The transition metals have great tendency to form complex compounds and they
form large number of such compounds due to:
a) Small sizes of the metal ions.
b) High ionic charge in them.
c) Availability of d-orbital for bond formation.

30. Why the transition metals and their compounds are widely used as catalysis.
Ans:- Transition metals and their compounds are extensively used as catalysts due to the
following:
a) They possess variable Oxidation state and thus easily form intermediate complex
providing d-subshells for complex formation and a new pathway for the reaction with
lower Ea.
b) They provide larger surface area for the reactant to be adsorbed.
c) The 3d electrons of the first transition series elements are used in bonding in addition
to 4s electrons. Thus, the concentration of the reactants at the catalyst surface
increases and the bonds of the reactant molecules weaken.
d) Also because the transition metal ions can change their oxidation states. They become
more effective as catalysis.

Standard reduction potentials and reducing properties :

The standard reduction potentials (E) of the elements present in the first transition
series for the divalent cation (M+2/M) are given:

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
+2
E (M )/ M(s)
in volts (V) - -1.6 -1.2 -0.91 -1.18 -0.44 -0.28 -0.25 +0.34 -0.76
From the values listed, it is evident that the trends in the reduction potentials (or
oxidation potential) is not regularly.
M (s)  M2+ (aq) + 2e -
The process is completed in three steps:
M (s)  M(g) ; Sublimation enthalpy (Hsub) is required
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 D and f block elements
M(g)  M2+(g) + 2e ; Ionisation enthalpy (Hion) is required(IE1+IE2)
M n+(g) + aq Mn+ (aq): Hydration enthalpy (Hhydiration) is released
(Hreaction) =Hsub +H( ion ) +H(hydration)

We have already seen the irregular trends in the values of ionization enthalpies.
Same is the case with the sublimation enthalpies as well. This means that the enthalpies
of the reactions do not show regular trend. Consequently, there is no regular gradation in
the standard reduction (or oxidation) potentials of these metals.

Reactivity of transition metals and standard reduction

potential values
From the values of the reduction potentials listed above, following Points are
noteworthy.
a) Except copper, all other elements have negative reduction potentials values. This
means that they should liberate hydrogen quite readily from dilute acids M(s) +
2H+(aq) M2+(aq) + H2(g).
But in actual practice, the rate of liberation of hydrogen is very poor. Actually some of
these metals get protected due to the formation of an inert oxide film on their surface.
Chromium, for example, inspite of its high negative reduction potential is so unreactive
that it does not liberate hydrogen from dilute HCl on account of the formation of coating
of Cr2 O3 on its surface.
b) With the exception of copper, all of them are excepted to be good reducing agents.

For the first row transition metals the E0 values are:

V Cr Mn Fe Co Ni Cu
-1.18 -0.91 -1.18 -0.44 -0.28 -0.25 +0.34

31. Explain the irregularity in the above values.

Ans:- The E0 (M2+/M) values are not regular which can be explained from the irregular
variation of ionization enthalpies (HI +HII) and also the sublimation enthalpies:
Element H (M) ∆𝟏 𝐇𝟏𝟎 ∆𝟏 𝐇𝟐𝟎 ∆𝐡𝐲𝐝𝐇 𝟎 (𝐌 𝟐 ) Eo/V
(M)
Ti 469 661 1310 -1866 -1.63
V 515 648 1370 -1895 -1.18
Cr 398 653 1590 -1925 -0.90

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 D and f block elements
Mn 279 716 1510 -1862 -1.18
Fe 418 762 1560 -1998 -0.44
Co 427 757 1640 -2079 -0.28
Ni 431 736 1750 -2121 -0.25
Cu 339 745 1960 -2121 -0.34
Zn 130 908 1730 -2059 -0.76

32. What is the reason for the decreasing tendency to form divalent cation across the
series as indicated by the decreasing E oM2+/M values?
Ans:-The decreasing values of Eo for M2+/M indicates that the tendency to form divalent
cation decreases across the series because the sum of the first and the second ionization
enthalpies increases across the series.

33. The Eo( M2+/M) value for copper is positive (+0.34V). What is possibly the
reason for this?
Ans:-The positive value of Eo ( M2+/M) for copper is due to its high enthalpy of
atomization and high values of enthalpies of ionization (∆i HI0 + ∆i HII0).

34. For M2+/M and M3+/M2+ systems the E values for some metals are as follows:
𝐂𝐫 𝟐+ ⁄𝐂𝐫 − 𝟎. 𝟗𝐕 𝐂𝐫 𝟑+ ⁄𝐂𝐫 𝟐+ − 𝟎. 𝟒𝐕
𝟐+ ⁄ 𝟑+ ⁄ 𝟐+
𝐌𝐧 𝐌𝐧 − 𝟏. 𝟐𝐕 𝐌𝐧 𝐌𝐧 + 𝟏. 𝟓𝐕
𝟐+ ⁄ 𝟑+ ⁄ 𝟐+
𝐅𝐞 𝐅𝐞 − 𝟎. 𝟒𝐕 𝐅𝐞 𝐅𝐞 + 𝟎. 𝟖 𝐕
Use this data to comment upon:
a) The stability of 𝐅𝐞𝟑+ in acid solution as compared to that of 𝐂𝐫 𝟑+ or 𝐌𝐧𝟑+ .
b) The ease with which iron can be oxidized as compared to the similar process for
either chromium or manganese metal.
Ans:- (a) We know that higher the reduction potential of a species, larger is the tendency
for its reduction to take place. Thus, Mn3+ with highest reduction potential would be most
readily reduced to Mn2+ and hence is least stable.
From values of reduction potential, it is clear that the stability of Fe3+ in acid
solution is more than Mn3+ but less than Cr 3+stability: Cr 3+ > Fe3+ > Mn3+ .
(b) The lower the reduction potential of a species, greater is the ease with which its
oxidation will take place.

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 Mn is oxidized most readily to Mn and Fe is oxidized to Fe2+ least readily among
2+

given metals Mn, Cr and Fe. Thus, order of their tendency to undergo oxidation is Mn>
Cr> Fe.

35. Why is the Eo value for the 𝐌𝐧𝟑+ ⁄𝐌𝐧𝟐+ couple much more positive than that for
𝐂𝐫 𝟑+ ⁄𝐂𝐫 𝟐+or 𝐅𝐞𝟑+⁄𝐅𝐞𝟐+? Explain.
Ans: - Much larger third ionization energy of Mn (where the required change is d 5 to d4)
is mainly responsible for this. This also explains why the +3 state of Mn is of little
importance.

36. List the factors on which the stability of a particular oxidation state of a
transition metal ion in solution depends.
Ans:-Enthalpy of sublimation, ionization enthalpy and enthalpy of hydration.

37. Which is stronger reducing agent 𝐂𝐫 𝟐+ 𝐨𝐫 𝐅𝐞𝟐+ and why.

Ans:-Cr 2+ is stronger reducing agent than Fe2+ . This can be explained in terms of
Eo( M3+/M2+) values , Eo( Cr3+/Cr2+) has negative value (-0.41V) indicating that Cr3+
would change into Cr 2+ with difficulty whereas reverse would take place readily.

38. How would you account for the following:

a) Of the d4 species 𝐂𝐫 𝟐+ is strongly reducing while managanese (III) is strongly
oxidizing.
b) The d1 configuration is very unstable in ions.
Ans:- (a) For chromium + III state is more stable as compared to + II. Therefore,Cr 2+
readily changes into Cr 3+ and behaves as a strong reducing agent. On the other hand, for
manganese, +II state is more stable than +III state. Hence, Mn3+ readily changes into
Mn2+ (3d5) by gaining an electron and behaves as strong oxidizing agent.
(b)The ions in d1 configuration have great tendency to acquire more stable d o
configuration by losing the lone d-electron.

39. Explain why Cu+ ion is not stable in aqueous solutions?

Ans:-Cu+ in aqueous solution undergoes disproportionation, i.e. 2Cu+(aq)  Cu2+ (aq) +
Cu(s) . The E0 value for this is favourable. The stability of Cu2+ (aq) rather than Cu+(aq)
is due to the much more negative hyd H 0 of Cu2+ (aq) than Cu+, which more than
compensates for the second ionization enthalpy of Cu.

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40. Why is the highest oxidation state of a metal exhibited in its oxide or fluoride
only?
Ans:-Because of small size and high electronegativity and high REP 0, oxygen or fluorine
can oxidize the metal to its highest oxidation state.

41. Why is the 𝐄 𝟎 value for the 𝐌𝐧𝟑+ ⁄𝐌𝐧𝟐+ couple much more positive than that for
𝐂𝐫 𝟑+ ⁄𝐂𝐫 𝟐+or 𝐅𝐞𝟑+⁄𝐅𝐞𝟐+? Explain.
Ans:-Much larger third ionization energy of Mn ,where the required change is d5 is
mainly responsible for this, this also explains why the +3 state of Mn is of little
importance.

42. Give a reaction to show that 𝐂𝐫 𝟐+ acts as a reducing agents?

Ans:-Cr 2+ liberates hydrogen as when treated with dilute acids. 2Cr2+(aq) + 2H+(aq) 
2Cr3+(aq) + H2(g)  .

43. What does the E0 value of 𝐌 𝟑+ ⁄𝐌 𝟐+ show for 𝐌𝐧𝟑+ 𝐚𝐧𝐝 𝐂𝐨𝟑+ (+1.57 and +1.97
V respectively)?
Ans:-The high E0 value of M3+ ⁄M 2+ for Mn3+ and Co3+ show that they are the
strongest oxidizing agents in aqueous solution among all the rest of the transition series
elements.

44. The E0 value of Zn2+/Zn and Mn2+/Mn and Ni2+/Ni quite high why?
Ans:-The high E0 value of Mn2+/Mn is related to the extra stability of its Mn2+ ion due to
half filled d-orbitals. Whereas, for the Zn2+/Zn, it is due to extra-stability of fully filled d-
orbitals of Zn2+ion.
For nickel high negative Eo value is related to the highest negative enthalpy of hydration
of Ni2+.

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 D and f block elements

Inner –Transition Elements

Inner- transition elements are defined as those elements which have partly filled (n-2) f-
orbitals in the neutral atom or in any of their usual positive oxidation state (i.e. ions).
Since in these elements the differentiating electron enters the f-orbitals, these are also
called f-block elements.(n-2) f-orbitals may be either 4f-orbitals of 5f-orbitals. Thus
corresponding to the filling of 4f and 5f-orbitals, these elements are divided into two
series: namely the lanthanoids and actinoids series.
a) The general electronic configuration of the lanthanoids is [Xe]4f1-14 5d0-16s2.
b) However, the electronic configurations of all the tripositive ions (the most stable
oxidation state of all lanthanoids) are of the form 4fn (n=1 to 14) with increasing
atomic number.
c) The electronic configurations of the elements with fully filled (f14) and half –filled (f7)
orbitals are relatively more stable; eg., europium (4f7 6s2 ),gadolinium (4f7 5d16s2),
ytterbium (4f14 6s2) and the extra electron in lutetium goes in 5d orbitals (4f14 5d16s2).
Although lanthanum-itself does not possess any 4f electrons but due to chemical
similarity with other lanthanoids it is also included.

Oxidation States of Lanthanoid Elements

The common oxidation shown by all the lanthanoids is +3. Some elements
display +2 and +4 states, but these are always less stable than the group valency +3. The
unusual oxidation states such as +2 or +4 exhibited by the lanthanoids can be explained
on the basis of extra stability associated with empty, half-filled or fully filled 4f subshell.
Some examples are given below:
a) Eu and Yb exhibit +2 oxidation states. This is because in +2 oxidation state europium
and ytterbium acquire f7 and f14 electronic configuration as:
Eu2+[Xe]4f7, Yb+2 [Xe]4f14. So Eu2+,Yb2+ act as good reducing agents and form Ln3+
easily.
b) Ce and Tb exhibit +4 oxidation states. This is because in +4 oxidation state cerium
and terbium acquire f0 and f7 electronic configuration which are supposed to be stable
configurations.
Ce4+ [Xe]4f0 (extra stable noble gas electronic configuration ) Tb4+ [Xe]4f 7, these are
converted to Ln3+ so act as good oxidising agents.

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 D and f block elements
Element Symbol Atomic Number Configuration
Lanthanum La 57 [Xe]5d1 6s 2
Cerium Ce 58 [Xe]4f 15d1 6s 2
Praseodymium Pr 59 [Xe]4f 3 6s 2
Neodymium Nd 60 [Xe]4f 4 6s 2
Promethium Pm 61 [Xe]4f 5 6s 2
Samarium Sm 62 [Xe]4f 6 6s 2
Europium Eu 63 [Xe]4f 7 6s 2
Gadolinium Gd 64 [Xe]4f 7 5d1 6s 2
Terbium Tb 65 [Xe]4f 9 6s 2
Dysprosium Dy 66 [Xe]4f 106s 2
Holmium Ho 67 [Xe]4f 116s 2
Erbium Er 68 [Xe]4f 126s 2
Thulium Tm 69 [Xe]4f 136s 2
Ytterbium Yb 70 [Xe]4f 146s 2
Lutetium Lu 71
[Xe]4f 145d1 6s 2

45. What is the common symbol used for lanthanoids?

Ans:-Ln.

46. Why are the 4f and 5f inner transition metals called lanthanoids and actinoids,
respectively?
Ans:-The lanthanum closely resembles the lanthanoids and is included in all its
properties (physical and chemical both). Hence, the series is named after the nature of the
metal as lanthanoids. Similarly, the name has been given to 5f series metals as actinoids.

47. Give the general electronic configurations of lanthanoids and actionids.

Ans:-Lanthanoids have general electronic configurations of 4f1-14 5d0-1 6s2, and actionoids
the general electronic configuration of 5f1-146d0-17s2.

48. Comment on the oxidation states of lanthanoids.

Ans:-All the lanthanoids generally shows Ln3+ oxidation state. But some of them also
show +2 and +4 states in solution and solid form like Ce 4+, Eu2+, Yb2+, Tb+4, etc. these
irregular state of +2 and +4 are shown because of the extra stability of empty, half filled
or fully filled 4f subshell e.g. Ce4+ has 4f0, Eu2+ has 4f7,Tb+4 has 4f7,Yb2+ has 4f14.

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 D and f block elements
49. Why is cerium a good analytical reagent?
Ans:-Cerium (Ce) shows + 4 oxidation state as in this it acquires stable noble gas
configuration but it is a strong oxidizing agent and reduces to Ce 3+(common) state. Its Eo
value for Ce4+/Ce3+is 1.74 V. It oxidizes water but the rate of reaction is slow.
Hence Ce acquires great use is analytical regents. As good oxidizing agent .

50. Eu2+, Yb2+ are good reductant whereasTb+4 is an oxidant. Why?

Ans:-Eu and Yb in +2 oxidation states acquires half filled (4f7) and fully filled (4f
14
)configuration but still they oxidizes to their common +3 state and thus acts as strong
reducing agents or reductants. Tb in +4 state has 4f7 half filled stable configuration but it
readily gets reduced to common +3 state and hence acts as oxidant.

51.What is so special about oxidizing state of Pr , Nd , Tb and Dy lanthanoids.

Ans:-Pr, Nd , Tb and Dy lanthanoids along with usual + 3 oxidation state also shows + 4
oxidation state only in their oxide form as MO2.

52.Use Hunds rule to derive the electronic configuration of Ce 3+ ion and calculate
the magnetic moment on the basic of ‘spin only’ formula.
Ans:-Cerium in ground state has 4f15d1 6s2 configuration. In Ce3+ state its configuration
becomes 4f 1 5d0 6s0, which means it contain only one unpaired electron. Hence, its
magnetic moment by spin only formula will be μ = √n(n + 2) B. M.
n = 1, ∴ μ = √1(1 + 2) = √3 = 1.732 B. M.

53. Name the members of lanthanoid series having +4 oxidation states and those
having +2 oxidation states. Try to co-relate this type of behavoiur with the electronic
configuration of these elements.
Ans:-+4 oxidation state are exhibited by Ce , Tb mainly (Ce = 4f 1 5d1 6s2, Tb= 4f 9 6s2)
as by doing they acquired 4f 0 and 4f 7 stable , empty and half filled 4f sub-shells
respectively. +2 oxidation states are shown by Eu (4f 7 6s2) and Yb (4f146s2) as in +2 state
they acquires 4f 7,4f14 stable half-filled and fully filled stable configuration.

54.Which is the most common oxidation state of lanthanoids?

Ans:-Ln3+ (+III).

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Colour of Lanthanoid Compounds

The colour of lanthanoid ions is due to the presence of partly filled f-orbitals. As a result
it is possible to absorb certain wavelength from the visible region of the spectrum. This
results in transition from one orbital to another 4f orbital known as f-f transition. The
colour transmitted is the colour shown by the substance. La 3+ (fo) , Lu3+(f 14) are
colourless.

Magnetic Properties of Lanthanides

Magnetism is a property associated with unpaired electrons. All lanthanoid ions with the
exception of La3+, Lu3+, Yb2+ and Ce4+ are paramagnetic because they contain unpaired
electrons.

55. La3+, Lu3+ are colourless while rest of the Ln3+coloured both in the solid as well
as in the aqueous state. Why?
Ans:-La3+, Lu3+ have 4f 0 and 4f 14 in their valence shell .Hence , due to the absence of
any unpaired f-electrons, they are colourless but all other lanthanoids have f-electrons
(unpaired) which impart colour.

56.Why are the absorption bands of lanthanoids narrow?

Ans:-The absorption band of lanthanoids are narrow due to the excitation of electrons
within f – level orbitals. (having small energy ).

57.Except La3+,Ce4+ and Yb2+, Lu3+ all lanthanoids are paramagnetic. Why?
Ans:-La3+, Ce4+ have 4f 0 configuration whereas Yb2+ and Lu3+ have 4f 14 configuration
which makes all these four deficient of unpaired electrons and thus they all are
diamagnetic .Whereas, rest of the lanthanoids have atleast one or more unpaired electron
which makes them paramagnetic.

58. What is lanthanoids contraction? Discuss its cause and consequences.

Ans:- The steady decrease in atomic and ionic radii of lanthanoids ions as we move from
La to Lu is known as lanthanoid contraction.
Cause: In lanthanoids, last electron enters the 4f sub-shell i.e., second last shell. The
shape of f – orbitals is very much diffused, because of this reason the mutual shielding of
4f – electrons is very little. The nuclear charge increases at each step due to the increase
in atomic number, while the mutual shielding effect of 4f-electrons is comparatively
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 D and f block elements
negligible. This causes a decrease in size of the 4f sub-shell with the increase in atomic
number.
Consequences: Following are the main consequence of lanthanoid contraction .
Similar sizes of second and third transition series elements: Lanthanoid contraction
also effect the chemistry of the elements which follow lanthanoids. Normally the atomic
radii increases with the increase in atomic number in the same subgroup, but after
lanthanoids the atomic radii of the elements of second and third transition series are
almost similar.
3 4 5
21Sc – 144 pm 22Ti – 132 pm 23V– 122 pm
39Y – 162pm 40Zr – 145 pm 41Nb – 134 pm
57La – 169pm Lanthanoids 72Hf – 144 pm 73Ta – 134 pm
58Ce – 71Lu

The expected increase in size from second to third transition series is cancelled by the
decrease in size due to lanthanoid contraction. Due to the similar atomic radii of second
and third transition series elements, they resemble each other very closely.
Separation of Lanthanoids: The properties of lanthanoids are very similar, therefore, it
is difficult to separate them.

59.What is the general trend of the ionization enthalpies in the lanthanoids?

Ans:-The ionization enthalpies increases from lanthanum to lutetium due to the decrease
in the sizes. However, the decrease in not much prominent.

60. Why La, Gd and Lu has low value of 3rd ionization enthalpies?
Ans:-The lanthanum (La), gadolinium (Gd) and lutetium (Lu) acquires empty, half filled
and fully filled 4f subshell respectively in their M3+ state and this state acquired extra-
stability and they have low 3rd ionization enthalpy.

61. Briefly explain the physical properties of lanthanoids.

Ans:-All lanthanoids are silvery white soft-metals which tarnish rapidly in air. Their
hardness increases along the series. Their melting point varies from 1000 to 1200K. They
are all typical metal and are good conductors of heat and electricity. Density increases
along the series, exception (Eu and Yb).

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 D and f block elements
62.Why does the hardness of lanthanoids increase along the series?
Ans:-The hardness increase as size decreases and the packing becomes more compact in
solid state in lanthanoids.

63.What is the range of E0 value of lanthanoids for Ln3+/ Ln?

Ans:-The value of E0 of lanthanoids for Ln3+/ Ln varies from -2.2 to -2.4 volts. (except
for Eu).

64. The chemical reactivity of lanthanoids resembles to which other elements of the
periodic table.
Ans:-The chemical reactivity of the starting lanthanoids resembles calcium but latter
lanthanoids resembles Al.

65.Briefly explain the uses of lanthanoids.

Ans:- Their best use is in the making of steel alloy for plates and pipes. They also forms
misch metal. Their oxides are used as catalysts in petroleum cracking. Few lanthanoids
are used as phosphors in T.V. screens and in fluorescent surfaces.

66.Give composition and uses of misch metal.

Ans:-Misch metal contains lanthanoid metals- 95% ,iron near to 5% and sulphur, carbon,
calcium and aluminium in traces. It is used in making Mg based alloy which is used to
make bullets shell and lighter flint.

Actinoids
The actinoids are the fourteen elements from Th to Lr in which the filling of electrons
takes place in the (n-2) f i.e., 5f subshell. The general electronic configurations for the
actinoids is [Rn] 5f 1-14 6d0-17s2. The fourteen electrons are formally added to 5f though
not in Thorium (Z=90) but onwards from it and the 5f subshell is complete at Lr (Z=103).
The irregularities in the electronic configuration of the actinoids are related to the
stabilities of 5f 0, 5f 7 and 5f 14 subshell

67.What is exceptional about Thorium?

Ans:-In Thorium the 5f orbital has no electron, instead its last electron is in 6d subshell
(6d2), but still it is placed in 5f actinoid series.

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 D and f block elements
68.Why Am and Cm have exceptional configuration in actinoids.
Ans:-Am and Cm has 5f 7 7s2 and 5f 7 6d1 7s2, i.e., half filled stable 5f subshell.
Element Symbol Atomic Number Configuration
Actinium Ac 89 [Rn]6d1 7s 2
Thorium Th 90 [Rn]6d2 7s 2
Protactinium Pa 91 [Rn]5f 2 6d1 7s 2
Uranium U 92 [Rn]5f 3 6d1 7s 2
Neptunium Np 93 [Rn]5f 4 6d1 7s 2
Plutonium Pu 94 [Rn]5f 6 7s 2
Americium Am 95 [Rn]5f 7 7s 2
Curium Cm 96 [Rn]5f 7 6d1 7s 2
Berkelium Bk 97 [Rn]5f 9 7s2
Californium Cf 98 [Rn]5f 10 7s2
Einsteinium Es 99 [Rn]5f 11 7s2
Fermium Fm 100 [Rn]5f 12 7s2
Mendelevium Md 101 [Rn]5f 13 7s2
Nobelium No 102 [Rn]5f 14 7s2
Lawrencium Lr 103 [Rn]5f 14 6d1 7s 2

69.Comment on the oxidation states of actinoids.

Ans:-Actinoids show no regular trend in oxidation states as they shows irregular
oxidation states ranging from most common +3 to +7. Their behavior of showing
different oxidation states follows no regular trend.
70.Why the actinoids shows more variable oxidation states than lanthanoids?
Ans:-In actinoids, the difference of the energy between 5f, 6d and 7s is small. Hence, the
electrons from 5f subshell also takes part in bonding and they shows variable oxidation
state.

71.The chemistry of actinoids elements is not as smooth as that Ln. justifies this
statement by giving some examples from oxidation state of these elements.
Ans:-Lanthanoids shows a common oxidation state of +3 with few +2 and +4 by Eu , Ce,
Yb etc. also whereas in actinoids due to Very weak shielding of 5f elements and less
difference of energies of 5f , 6d and 7s orbitals they show variable oxidation states from
+3 to +7 with no common trend. 5f orbital are more diffused than 4f . Hence , 5f electron
can easily participate in bonding in actinoids. This shows no smooth chemistry of
actinoids.

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 D and f block elements
72.Which is the last element in the series of the actinoids? Write the electronic
configuration of the element. Comment on the possible oxidation state of this
element.
Ans:-Lawrencium with atomic number 103 is the last element of actinoid series. Its
electronic configuration is 5f 146d 1 7s2 and it show oxidation state of +3 as in +3 state it
acquires fully filled 5f 14 stable configuration.

73.Compare the magnetic behavior of actinoids with lanthanoids.

Ans:-Most of actinoids are paramagnetic due to unpaired electrons but the magnetic
behavior of actinoids is more complex and cannot be explained, whereas for lanthanoids
it can be explained and calculated by spin only formula.
Though the magnetic behavior variation is similar to that of lanthanoids but still
lanthanoids have higher magnetic moment.

74.What is actinoid contraction? How is it different from lanthanoid contraction?

Ans:-The decrease in the atomic as well as ionic sizes of actinoids along the series is
called actinoids contraction. The actinoid in +3 oxidation states shows regular decrease in
their ionic size. It is different from the lanthanoid contraction by the fact that the decrease
in size or contraction between two successive elements is higher in actinoids due to poor
screening by 5f electrons.

75. What is the trend of ionization enthalpies of actinoids?

Ans:-The ionization enthalpy of the earlier actinoids are lower than for the earlier
lanthanoids. The reason is that 5f orbitals penetrate less into the inner core of electrons
i.e., its e – are more diffused as compared to the 4f electrons of the corresponding
lanthanoids. As the outer electrons are less tightly held, less amount of energy is required
to ionize an atom. These outer electrons are more readily available for bonding in
actinoids.

76.Briefly comment on physical properties of actinoids.

Ans:-Actinoids are silvery white metals. Radioactive in nature. They all show variety of
structures which is due to irregularities in their metallic radii.

77.Compare the chemical reactivity of actinoids with lanthanoids.

Ans:-Actinoids are far more reactive than lanthanoids especially in the powered form.
They react with non-metals at moderate temperatures whereas lanthanoids needs high
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 D and f block elements
temperature. They are not affected by acid as protective oxide layer prevents their further
reaction. They don’t react with alkalies. With water they form both oxides and hydrides
whereas lanthanoids forms hydroxide and H2 gas.
Ln + H2O  Ln (OH)3+ H2
Ac + H2O  Ac2O3 + AcH3

78.What are the inner transition elements? Decide which of the following atomic
numbers are the atomic numbers of the inner transition elements – 29, 59, 74, 95,
102, 104?
Ans:-The f–block elements are called inner transition elements. They consist of two
series lanthanoids series having elements with atomic number – 57 to 71 and actinoid
series having elements with atomic number-89 to103.

79.Compare the chemistry of lanthanoids and actinoids.

Lanthanoids Actinoids
1-14 0-1 2 1-14 0-1 2
a) 4f 5d 6s a) 5f 6d 7s
b) They all show +3 common state +2 is b) They shows along with +3,+4,+5,+7
shown by Eu and Yb and +4 by Ce and other oxidation states also.
Tb.
c) Difference between the two successive c) Difference between the two successive
lanthanoids sizes smaller than actinoid. actinoid is larger than lanthanoids.
d) Decrease in size in series called lanthanoid d) Decrease in size in series is called
contraction. actinoid contraction.
e) Their ionization enthalpies are high. e) Their ionization enthalpies are lower
than lanthanoids.
f) The magnetic character is explained by f) Their magnetic characteristic cannot be
using spin only formula. explained.
g) Most of these are non-radioactive (except g) All are radioactive.
promethium).
h) When reacted with water form hydroxide h) They form oxides and hydrides.
and H2 gas.
i) Reacts with non-metals at higher i) Reacts with non-metal at moderate
temperature. temperature.

 Transition metals form oxides on reaction with oxygen at elevated temperature.

transition metal form oxides in oxidation state of +1 (in Ag2O) to +7 (Mn2O7) to +8
(in Os O4). For the same elements, as the oxidation number increases:

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 D and f block elements
a) The covalent character of oxides increases, e.g. MnSO4 is ionic but Mn2O7 is covalent.
b) The oxidizing power of oxides increases and
c) The acidic strength of the oxides increases.

 In vanadium there is gradual change from the basic V 2 O3 to less basic V2 O4 and to
amphoteric V2 O5. e.g., MnO is basic, Mn2 O7 is acidic & Cr2 O3 is amphoteric while
CrO is basic and CrO3 is acidic.

80. Describe the preparation of potassium dichromate from ferrochrome (iron

chromite) ore.
Ans:-Potassium dichromate is prepared from ferrochrome in three major steps-
a) Fusion of chromite ore with sodium carbonate and O2.
4Fe Cr2 O 4 8Na2 CO3 + 7O2 8Na2 CrO4 + 2Fe2 O3 + 8CO2
+ →
(Chromite ion) (sodium carbonate) (sodium chromate) (Ferric oxide)

b)Acidification of chromate ion: The yellow solution of sodium chromate is acidified

with sulphuric acid.

2Na2 CrO4 +8H2 SO 4 → Na2 Cr2 O7

+ Na2 SO 4 + H2 O
yellow orange

d) Conversion of sodium dichromate to potassium dichromate: The orange red crystals of

sodium dichromate are dissolved in a solution and treated with KCl solution which
form potassium dichromate. (which is less soluble)
Na2 Cr2 O7 + 2KCI → K 2 Cr2O7 + 2NaCI
orange crystals
81.What is the action of increasing pH on a solution of potassium dichromate?
Ans:-When any alkali or KOH is added to the orange red solution of potassium
dichromate, it gets transformed to yellow coloured potassium chromate.
On adding the acids to the above yellow potassium chromate solution, the colour
again changes to orange red colour due to the formation of dichromate again.
K 2Cr2 O7 + 2KOH → 2K 2 CrO4 + H2O
(potassium dichromate) (potassium chromate )
orange, red yellow

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 D and f block elements
2K 2CrO4 + H2SO4 → K 2Cr2 O7 + K 2SO4 + H2 O
(potassium dichromate) (potassium dichromate )
yellow orange, red

low pH
→ Cr2 O2−
7 + H2 O
2CrO2−
4 + 2H +
← Orange
High pH

82.Explain the structures of dichromate and chromate ion.

Ans:- The chromate ion (CrO2− 4 ) has a tetrahedral shape, whereas dichromate ion has
two tetrahedral units with one common oxygen having Cr-O-Cr bond angle of 126.
O 2- O O 2-

O
Cr Cr Cr
O O O
O O O O

Chromate ion dichromate ion

83.Describe the oxidizing action of potassium dichromate and write the ionic
equation for its reaction with
a) Iodide ion
b) Iron (II) solution
c) H2S
d) Tin (II) solution
Ans:-Ionically:
Cr2O2− +
7 + 14H + 6e
−
→ 2Cr 3+ + 7H2 O
6I − → 3I2 + 6e−
Cr2O2− +
7 + 14H + 6I
−
→ 3I2 + 2Cr 3+ + 7H2 O

(b) Iron (II) solution:- Ferrous salts (Fe2+) are oxidized to ferric (Fe3+) salts
Cr2O2− +
7 + 14H + 6e
−
→ 2Cr 3+ + 7H2 O
6Fe2+ → 6Fe3+ + 6e−
Cr2O2−
7 + 6Fe2+ + 14H + → 2Cr 3+ + 6Fe3+ + 7H2 O

(c) Sulphide ion (S2-)

Cr2O2− +
7 + 14H + 6e
−
→ 2Cr 3+ + 7H2 O
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 D and f block elements
− +
3H2S → 3S + 6e + 6H
Cr2O2−
7 + 8H + 3H2 S → 3S + 2Cr 3+ + 7H2 O
+

(d) Tin (Sn2+) solution

Cr2O2− +
7 + 14H + 6e
−
→ 2Cr 3+ + 7H2 O
3Sn2+ → 3Sn4+ + 6e−
Cr2O2− +
7 + 14H + 3Sn
2+
→ 3Sn4+ + 2Cr 3+ + 7H2 O

84.Describe the preparation of Potassium permanganate.

Ans:- (i) Potassium permanganate is prepared by fusion of MnO2 with an alkali metal
hydroxide and an oxidizing agent like KNO3. This produces the dark green K2MnO4
which disproportionate in a neutral or acidic solution to give permanganate.
2MnO2 + 4KOH+O2  2K2 MnO4 + 2H2O
3MnO2−4 + 4H
+
→ 2MnO4− + MnO2 + 2H2 O

(ii)Commercially it is prepared by the alkaline oxidative fusion of MnO2 followed by the

electrolytic oxidation of manganate (VI).
fuse with KOH,oxidise
with air or KNO3
MnO2 → MnO2−
4
electrolytic oxidation
manganate
2− in alkaline solution
MnO4 → MnO4−
(green) (pink)

In the laboratory, a manganese (II) ion salt is oxidized by peroxodisulphate to

permanganate.
2Mn2+ + 5S2O82- + 8H2O 2MnO4− + 10SO42- + 16H+
Potassium permanganate forms dark purple (almost black) crystals.

85.What is effect of heat on kMnO4?

Ans:- When heated it decomposes at 513K.
2KMnO4 K2MnO4 + MnO2 +O2.

86.Give structure of MnO42- and MnO4-. Also give their magnetic nature.
Ans:-The manganate and permanganate ions are tetrahedral. The green manganate is
paramagnetic with one unpaired electron but the permanganate is diamagnetic.

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 D and f block elements

O
O

Mn
Mn
O O
O O O
O
Tetrahedral permanganate
Tetrahedral manganate (purple) ion
(green) ion

87. Give some reactions of KMnO4 showing its oxidizing nature in (i) acidic medium
(ii) neutral or faintly alkaline medium.
Ans:-Acidic solution: MnO4- + 8H++ 5e  Mn2++4H2O
(a) Iodine is liberated from potassium iodide:
yields
10I − + 2MnO4- + 16H+→ 2Mn2+ +8H2O + 5I2

(b) Oxalate ion or oxalic acid is oxidized at 333K.

yields
5C2 O42- + MnO4- + 16H+→ 2Mn2+ +8H2O + 10CO2
(c) Hydrogen sulphide is oxidized, sulphur being precipitated:
H2S  2H+ + S2-
yields
5S 2− + 2MnO4− + 16H + → 2Mn2 + 8H2 O + 5S
(d) Sulphurous acid or sulphite is oxidized to sulphate or sulphuric acid:
yields
5SO2− − +
3 + 2MnO4 + 6H → 2Mn2+ + 3H2 O + 5SO 2−
4

(e) Nitrite is oxidized to nitrate:

yields
5NO2− + 2MnO4− + 6H + → 2Mn2+ + 5NO3 − + 3H2 O

(f) 𝐅𝐞𝟐+ion (green) is converted to 𝐅𝐞𝟑+(yellow):

yields
5Fe2+ + MnO4− + 8H + → Mn2+ + 4H2O− + 5Fe3+

Note:-Permanganate titrations in presence of hydrochloric acid are unsatisfactory since

hydrochloric acid is oxidized to chlorine.

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 D and f block elements
(ii) In netural or faintly alkaline solutions:
yields
MnO4− + 2H2 O + 3e− → MnO2 + 4OH −

a) A notable reaction is the oxidation of iodide to iodate:

yields
2MnO− −
4 + H2 O + I → 2MnO2 + 2OH − + IO−
3

b) Thiosulphate is oxidized almost quantitatively to sulphate:

yields
8MnO4− + 3S2 O32− + H2O → 8MnO2 + 6SO2− 4 + 2OH
−

c) Manganous salt is oxidized to 𝐌𝐧𝐎𝟐 ; the presence of zinc sulphate or zinc oxide
catalyses the oxidation.
yields
2MnO4− + 3Mn2+ + 2H2O → 5MnO2 + 4H +

88. What is meant by disproportionation ? Give two examples of disproportionation

reaction in aqueous solution.
Ans:-Sometimes a particular oxidation state becomes less stable relative to other
oxidation states, one lower and the other higher. In such a situation a part of the species
undergoes oxidation while a part undergoes reduction. Such species is said to undergo
disproportionation.
yields
2Cu+(aq) → Cu2+(aq) + Cu(s)
yields
3MnO2− +
4 + 4H → 2MnO4− + MnO2 + 2H2O
(+𝐕𝐈) (+𝐕𝐈𝐈) (+𝐕𝐈)

89. Why is hydrochloric acid not used to acidify a permanganate solution in

volumetric estimation of Fe2+ or C2O42- ?
Ans:-KMnO4 acts as strong oxidizing agent in acidic medium. HCl is not used to acidify
KMnO4 solution, because KMnO4 will oxidize HCl itself to Cl2 .So , correct quantitative
determination of the other reducing agent (i.e. Fe2+ or C2O42-) will not be possible.
yields
2MnO4− + 10 Cl− + 16H + → 2Mn2+ + 5Cl2 + H2 O

90. Give examples and suggest reasons for the following features of the transition
metal chemistry:
The lowest oxide of transition metal is basic, the highest is amphoteric/acidic.

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 D and f block elements
Ans:-The lowest oxide is basic because the metal is presence in lower oxidation state i.e.,
some of the d-electrons are not involved in bonding and thus its nuclear charge is not
very high , due to this reason these oxide can donate electrons and behave like a base. On
the other hand, oxide of higher oxidation state have the tendency to accept the electrons
due to the high effective nuclear charge in these oxide. So they are acidic in nature.
𝑀𝑛𝑂 𝑀𝑛2 𝑂3 𝑀𝑛2 𝑂3 𝑀𝑛𝑂2 𝑀𝑛2 𝑂7
+2 +3 +8/3 +4 +7
Amphoteric in nature Acidic nature
Basic in nature

91. Comment on the statement that elements of first transition series possess many
properties different from those of heavier transition elements.
Ans:-The elements of first transition series have following properties different from the
elements of second and third series.
a) Atomic radii of elements of first transition series are smaller than that of the
corresponding 4d- and 5d- elements which have nearly same atomic radii. Size 3d< 4d
 5d.
b) Melting points of the elements of first transition series are found lower than of the
elements of second and third series.
c) Metal-metal bonding is rare in the elements of first series while it is common is
heavier transition elements.
d) Enthalpies of atomization of the element of first transition elements are lower than
that of heavier transition elements.
e) Elements of first series do not form the complexes having 7 and 8 coordination
number which are formed by heavier transition elements.

92. Pyrolusite on heating with KOH in the presence of air gives a dark green
compound (A). The solution of (A) on treatment with H2SO4 gives a purple coloured
compound (B), which gives following reactions.
a) KI on reaction with alkaline solution of (B) changes into a compound(C).
b) The colour of the compound (B) disappears on treatment with the acidic solution
of FeSO4.
c) With conc. H2SO4 compound (B) gives (D) which can decompose to yield (E) and
oxygen.
Identify (A) to (E) and write balanced chemical equations for the formation of (A)
and (B) and for the steps (i) to (iii)
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 D and f block elements
Ans:-Pyrolusite on heating with KOH in presence of air forms dark green compound,
potassium manganate (A).
yields
2MnO2 + 4KOH + O2 → 2K 2 MnO4 + 2H2 O
Pyrolusite (Green compounds)
(A)
The solution of potassium manganate on treatment with H2SO4 forms purple coloured
potassium permanganate (B).
yields
3K 2 MnO4 + 2H2SO4 → 2K 2 SO4 + MnO2 + 2KMnO4 + 2H2 O
(A) (purple colour)
(B)
a) Alkaline solution of potassium permanganate changes KI into KIO3 i.e, potassium
iodate
yields
2KMnO4 + H2O + KI → MnO2 + 2KIO3 + 2KOH
(C)
b) Acidic solution of FeSO4 reduces the potassium permanganate (purple) coloured to
manganese sulphate (colourless)
yields
2KMnO4 + 8H2 SO4 + 10FeSO4 → K 2 SO4 + MnSO4 + 5Fe2 (SO4)3 + 8H2O
c) With conc. H2SO4 , potassium permanganate gives Mn2O7 (D) which on heating
decomposes to MnO2(E).
yields
2KMnO4 + 2H2 SO4 → Mn2 O7 + 2KHSO4 + H2 O
(D)
yields
2Mn2 O7 → 4MnO2 + 3O2
(green oil) (E)

93.(a) Out of Ag2SO4, CuF2, MnF2 and CuCl , which compound will be coloured and
why? explain: (i) CrO42- is a strong oxidizing agent while MnO42- is not.(ii) Zr and
Hf have identical sizes.
Ans:-(a) In Ag2SO4, CuF2, MnF2 and CuCl, metal ions present are: Ag(I) (d
configuration), Cu(II) d9 configuration), Mn(II) (d5 configuration) and Cu(I) d10
configuration). Cu(II) in CuF2 and Mn(II) in MnF2 would be coloured because of unfilled
d-orbitals as they show d d transition.

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 D and f block elements
2-
(b)(i) In CrO4 , the Cr(VI) has a tendency to get reduced into more stable Cr(III) in
solution, therefore it is a strong oxidizing agent while Mn (VI) in MnO42-, has a tendency
to get oxidized into Mn (VII) (in MnO4-) in solution thus it is not an oxidizing agent.

(ii)Hf has filled 4f- orbital, the expected increase in size down the group i.e. from Zr to
Hf is cancelled by the decrease in size due to lanthanoid contraction present in Hf. Due to
this reason sizes of Zr and Hf are same.

94.Compare the important properties of transition elements and representative

elements.
Transition Elements Representative Elements
1. Last electron goes to d-orbitals of (n-1) shell Last electron goes either s or p-orbitals of nth shell.
2. Two outermost shells are incomplete. Only outer most shell in incomplete.
3. They are all metals. They may be metals, metalloids or non-meals.
4. They exhibit variable oxidation states due to a The p-block elements may also exhibit variable
very small differences between the energies oxidation states due to inert pair effect. The oxidation
of (n-1) d and ns orbitals. The oxidation state state differ by two units from each other. Examples:
differ by one unit only. Examples: Cu+ and TI+1 and TI3, Pb2+ and Pb4+.
Cu++, Fe2+ and Fe3+.
5. Most of the transition elements form coloured Their ions in aqueous solution are colourless.
ion in aqueous solution due to d d transition yields
Na+ → colourless
of unpaired electron. yields
3+
yields Al → colourless
Co2+ → Pink or blue yields
−
yields yields Cl → colourless
Ni2+ → green Co2+ → blue
6. In a particular series of transition elements the If we move across a period, there is a regular and
increase in ionization energy is not regular pronounced increase in the value of ionization energies.
and pronounced.
7. They form complexes e.g., [Fe(CN)6]4, They generally don’t form complexes.
[Ag(NH3)2]+.
8. Their compounds are generally paramagnetic. Their compounds are generally diamagnetic.

95.How would you account for the increasing oxidizing power in the series:
𝐕𝐎+ 𝟐−
𝟐 < 𝐂𝐫𝟐 𝐎𝟕 < 𝐌𝐧𝐎𝟒 ?
−

Ans:-This is due to the increasing stability of the lower species to which they are
reduced.

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 D and f block elements
96. Actinoid contraction is greater from element to element than lanthanoid
contraction. Why?
Ans:-This is due to poor shielding by 5f electrons in the actinoids than that by 4f
electrons in lanthanoids.

97.Osmium forms +8 oxidation state compound with oxygen but no such compound
with fluorine. Explain this behavior.
Ans:-This is because there is space around the osmium atom for four bonded oxygen
atoms and not for eight fluorine atoms. Also ability of oxygen to form multiple bonds.
98.Among ionic species Sc3+, Ce4+ and Eu2+ which is a good oxidizing agent?
Ans:- Ce4+, because after oxidation Ce4+ is reduced to Ce3+. So , +3 state is the most
stable oxidation state of the lanthanoids.
99. 4d and 5d transition metals have almost same size. Why?
Ans:-Size increase from the first (3d) to the second (4d) series of the elements but the
radii of the third (5d) series are virtually the same as those of the corresponding members
of the second series. This phenomenon is associated with the intervention of the 4f
orbitals which must be filled before the 5d series of elements begin. The filling of 4f
before 5d orbital results in a regular decrease in atomic radii called lanthanoid contraction
which essentially compensates for the expected increase in atomic size with increasing
atomic number .The net result of the lanthanoid contraction is that the second and the
third d-series exhibit similar radii (e.g., Zr 160pm , Hf 159pm) and have very

similar physical and chemical properties much more than that expected on the basis of
usual family relationship.

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 D and f block elements

CBSE EXAMINATION QUESTIONS

1. (a) How do you prepare:
(i) K2MnO4 from MnO2?
(ii) Na2Cr2O7 from Na2CrO4?
(b) Account for the following:
(i) Mn2+ is more stable than Fe2+ towards oxidation to + 3 states.
(ii) The enthalpy of atomization is lowest for Zn is 3d series of the transition
elements.
(iii) Actinoid elements show wide range of oxidation states.
2. (i) Name the element of 3d transition series which shows maximum number of
oxidation states. Why does it show so?
(ii) Which transition metal of 3d series has positive E0 (M+/M) value and why?
(iii) Out of Cr2+ and Mn3+, which is a stronger oxidizing agent and why?
(iv) Name a member of the lanthanoid series which is well known to exhibit + 2
oxidation state.
(v) Complete the following equation:
MnO4- + 8H+ + 5e- →
3. What are the transition elements? Write two characteristics of the transition
elements?
4. (a) How would you account for the following:
(i) Actinoid contraction is greater than lanthanoid contraction.
(ii) Transition metals form coloured compounds.

(b) Complete the following equation:

2MnO4- + 6H+ + 5NO2- →
5. When chromite ore FeCr2O4 is fused with NaOH in presence of air, a yellow
coloured compound (A) is obtained which on acidification with dilute sulphuric acid
gives a compound (B). Compound (B) on reaction with KCl forms an orange
coloured crystalline compound (C).
(i) Write the formulae of the compounds (A), (B) and (C).
(ii) Write one use of compound (C).
6. Complete the following chemical equations:
(i) 8MnO4- + 3S2O32- + H2O→
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 D and f block elements
(ii) Cr2O72- + 3Sn2+ + 14H+ →
7. Give reasons:
(i) Mn shows the highest oxidation state of +7 with oxygen but with fluorine it
shows the highest oxidation state of +4.
(ii) Transition metals show variable oxidation states.
(iii) Actinoids show irregularities in their electronic configurations.
8. (a) Account for the following:
(i) Transition metals form large number of complex compounds.
(ii) The lowest oxide of transition metal is basic whereas the highest oxide is
amphoteric or acidic.
(iii) E° value for the Mn3+/Mn2+ couple is highly positive (+ 1.57 V) as compared
to Cr 3+/Cr2+.
(b) Write one similarity and one difference between the chemistry of lanthanoid
and actinoid elements.

9. (a) (i) How is the variability in oxidation states of transition metals different from
that of the p – block elements?
(ii) Out of Cu+ and Cu2+, which ion is unstable in aqueous solution and why?
(iii) Orange colour of Cr2O72- ion changes to yellow when treated with an alkali.
Why?
(b) Chemistry of actinoids is complicated as compared to lanthanoids. Give two
reasons.

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