d and f- Block Elements 1

08. d and f- Block Elements

8.0. : Prominent scientists

d- block elements
8.1 : General introduction and electronic configuration
Q.1. What are d-block elements?
Ans: The elements in which the last electron enters the d-orbital of the penultimate shell i.e.(n-1)d-orbital
where 'n' is the outermost shell, are called d-block elements. Their general electronic configuration is
(n –1 )d1–10ns1–2.
Q.2. Explain the position of d-block elements in the periodic table.
Ans: Position of d-block elements :
i) The d-block elements lie in between s- and p-block elements, i.e., these elements are located in the
middle part of the periodic table.
ii) The d-block elements are present in
4th period (Sc to Zn, 10 elements),
5th period (Y to Cd, 10 elements),
6th period (La, Hf to Hg, 10 elements) and
7th period (Ac, Rf to Uub, 10 elements)
iii) d-block elements are present in the groups 3 to 12. Each series starts with elements of Group 3 and
ends with elements of Group 12.
 d and f- Block Elements 2
Q.3. Explain the meaning of transition series.
Ans: i) d-block elements are also known as transition elements. The long form of periodic table contains four
series of transition elements, known as transition series.
ii) Four transition series are 3d, 4d, 5d and 6d serie-s wherein orbitals of (n – l)th main shell gets filled
respectively.
iii) The 3d series contains the elements from Sc (Z = 21) to Zn (Z = 30) belonging to the 4th period.
iv) The 4d series contains the elements from Y (Z = 39) to Cd (Z = 48) belonging to the 5th period.
v) The 5d series begins with La (Z = 57) and contains elements from Hf (Z = 72) to Hg (Z = 80)
belonging to the 6th period.
vi) The 6d series begins with Ac (Z = 89) and contains elements from Rf (Z = 104) to Uub (Z = 112)
belonging to the 7th period.
Q.4. Why are d-block elements called transition elements? (NCERT)
Ans:i) Transition elements are defined as those elements which have partly or incompletely filled
(n–l)d orbitals in their elementary state or in any of their common oxidation states.
ii) The 3d, 4d, 5d and 6d series of the d-block elements correspond to the filling of 3d, 4d, 5d and 6d
orbitals of the (n - l)" main shell. The last electron enters the (n - 1) d-orbital.
iii) d-block elements are called transition elements as they show transition in the properties from the most
electropositive s-block elements to the less electropositive p-block elements.
Q.5. Give the general electronic configuration of four series of d-block elements.
Ans: d-block elements have general electronic configuration (n – l)dl–10nsl–2. The four series of d-block elements
have the general electronic configuration as shown below :
i) 3d series: [Ar] 3d1–10 4s1–2
ii) 4d series: [Kr] 4d1–10 5s0–2
iii) 5d series: [Xe] 5dl–106s2
iv) 6d series: [Rn] 6d1–10 7s2
Q.6. Give the electronic configuration of all the elements belonging to the 3d series of d-block
elements.
Ans: 3d series or first row transition series (Sc to Zn) belonging to the fourth period has the general electronic
configuration [Ar] 3dl–10 4S1–2.The following table lists the general electronic configuration of first row
transition elements.

Q.7. In which period of the periodic table, will an element, be found whose differentiating electron is
a 4d electron ?
Ans: Fifth period of the periodic table consist of elements in which the differentiating electron is a 4d electron.
Q.8. Silver atom has completely filled d-orbitals (4d10) in its ground state. How can you say that it is
a transition element? (NCERT)
Ans: The outer electronic configuration of Ag (Z = 47) is 4d105s1. In addition to +1, it shows an oxidation state
of +2 (eg. AgO and AgF2 exist). In +2 oxidation state, the configuration is d9 , i.e. the d subshell is
incompletely filled, hence it is a transition element.
 d and f- Block Elements 3
Ag2+: [Kr]364d9. Therefore, Ag is a transition element.
Q.9. Write observed electronic configuration of elements from first transition series having half
filled dorbitals.

Ans:

Q.10. In what way is the electronic configuration of transition elements different from that of the
nontransition elements ?
Ans: Transition elements contain incompletely filled d subshell, i.e., their electronic configuration is (n–l) d1–10
nsl–2 whereas non-transition elements have no d subshell or their d subshell is completely filled and they
have the outer electronic configuration of ns1–2 or ns2 np1–6
and they have the outer electronic configuration of ns1–2 or ns2 np1–6
Q.11. Write down the electronic configuration of :
i) Cr3+ ii. Cu + iii. Co 2+ iv. Mn 2+
3+ 2 2 6 2 6 3
Ans: i) Cr = Is 2s 2p 3s 3p 3d ii) Cu = 1s 2s22p63s23p63d10
+ 2

iii) Co2+ = Is2 2s22p6 3s2 3p63d7 iv) Mn2+ = 1s2 2s22p63s23p63d5
Q.12. Why does copper show abnormal electronic configuration?
Ans: Copper has atomic number 29. Its expected and actual electronic configurations are :
29
CU (Expected): Is22s22p63s23p63d9 4s2
(Actual): 1s22s22p63s23p63d104S1
Explanation :
i) The energy difference between the 3d and 4s orbitals is very low.
ii) The d-orbital being degenerate, acquires more stability when it is half-filled (3d5) or completely filled
(3d10)
iii) Due to the inter-electronic repulsion, one electron from the 4s orbital is transferred to the 3d orbital in
Cu so that Cu has completely filled 3d10 orbital, thus acquiring more stability.
Q.13.Why chromium has electronic configuration 3d54s1 and not 3d44s2?
Ans: Chromium has atomic number 24. Its expected and actual electronic configurations are:
24
Cr (Expected): 1s22s22p63s23p63d44s2
(Actual): 1s22s22p63s23p63d54s1
Explanation :
i) The energy difference between the 3d and 4s orbitals is very low.
ii) The d-orbital being degenerate, acquires more stability when it is half-filled (3d5) or completely filled
(3d10)
iii) Electron - electron repulsion results in transfer of one electron from 4s orbital to 3d orbital of Cr. This
results in half filled 3d5 orbital which in turn results in extra stability.
8.2 : Occurrence and characteristics of transition elements
Q.14. Explain the occurrence of d-block elements.
Ans: i) d-block elements occur in free state as well as in combined states.
ii) Soft d-block elements occur as sulphide minerals. Roasting of sulphide minerals in air gives metal or
metal oxide, which on reduction gives metal.
iii) Hard d-block elements occur as oxide minerals. Reduction of oxide minerals with carbon gives metal.
iv) Hard d-block elements (metals) are more electropositive than soft d-block elements.
v) Occurrence of some d-block elements:
a) Titanium (in the combined state) is present in small quantities in coal, clay, rocks, sand, etc. eg.
Rutile (TiO2), Ilmenite (FeTiO3).
b) Vanadium occurs in the ores vanadinite and carnotite. It is present in the form of vanadate of
lead, zinc, copper, etc.
c) Some of the ores of chromium include chromite (FeO, Cr2O3), chrom ochre (Cr203), crocoisite
(PbCrO4).
 d and f- Block Elements 4
d) Manganese is present in pyrolusite ore (MnO2) and other minerals. It is not present in free state.
e) Iron occurs in free and combined states. In the earth's crust, the abundance of iron is next to
aluminium.
f) Cobalt is usually associated with nickel and arsenic and it is also found in traces in the soil.
g) Nickel is found in cobalt ores.
h) Copper is present in rocks, soil, sea, mineral waters. Some of the ores of copper include cuprite
(Cu2O), malachite [CuCO3,Cu(OH)2], azurite [2CuCO3,Cu(OH)2],etc.
i) Zinc is found in association with silver, copper, lead and platinum and in their ores.
Q.15. State the general characteristics of transition elements or d-block elements.
OR
What are the characteristics of the transition elements ? (NCERT)
Ans: Characteristics of transition elements:
i) Most of the transition elements are metals and thereby they show metallic properties such as ductility,
malleability, electrical conductivity, high tensile strength and metallic lustre.
ii) Except mercury which is liquid at room temperature, other transition elements have typical metallic
structures.
iii) Their compounds generally contain unpaired electrons, hence they are paramagnetic in nature and
form coloured compounds.
iv) They show variable oxidation states.
v) They have tendency to form large number of complexes.
vi) They have higher densities as compared to the metals of IA and IIA group (s-block).
vii) They are heavy metals with higher melting and boiling point as well as higher heats of vaporisation.
viii) Transition elements are less reactive than s-block elements due to their higher ionisation energy.
ix) Most of the transition metals such as Mn, Ni, Co, Cr, V, Pt, etc., and their compounds are used as
catalysts.
x) They have good thermal and electrical conductivity.
xi) They form alloys with different metals.
xii) They form interstitial compounds with elements such as hydrogen, boron, carbon, nitrogen, etc.
xiii) They form organometallic compounds.
Q.16. Why do transition metals possess high density and high melting and boiling points?
Ans:i) The densities of d-block elements are relatively higher as compared to the s-block elements due to the
decrease in the size of the atoms and the consequent increase in the nuclear charge, which results in
the compact structure of the elements.
ii) The density of the atoms increases with the decrease in the size of the atom. Therefore the density of
the elements increases from left to right across a period.
iii) Transition elements form strong metallic bond in which both (n–l) d and ns electrons take part. Due to
the notable covalent character of the strong metallic bond, considerable amount of energy is required
to break the metallic bond in order to melt the metal. Hence, these metals possess high melting and
boiling points.
Note:
Atomic properties of 3d series:
 d and f- Block Elements 5
Q.17. All d-block elements are not transition elements. Explain.
OR
Which of the d-block elements may not be regarded as the transition elements? (NCERT)
Ans: i) The d-block elements are those in which the last electron enters the d-orbital.
ii) The transition elements are those elements which have incompletely filled (partly filled) d-subshells in
their elementary state or in anyone of their oxidation states.
iii) Hence, only those d-block elements which have completely filled d-orbitals, (n–1)d10 are not transition
elements.
eg. Zn, Cd and Hg atoms have completely filled d-orbitals (3d10) in their ground state as well as in their
oxidation states. Hence they are d-block elements, but not transition elements.
8.3 : General trends in properties of the first row transition metals
Q.18. Explain the metallic characters of the d-block elements.
Ans: i) Except mercury which is a liquid, all the transition elements are metallic in nature.
ii) They are hard, lustrous, malleable and ductile with high melting and boiling points, and having good
thermal and electrical conductivities.
iii) Low ionization enthalpies and presence of vacant orbitals in the outermost shell results- in metallic
character due to formation of metallic bonds.
iv) In addition to the electrons from outermost energy level, the unpaired d-electrons also contribute for
the bond formation.
v) So, greater the number of unpaired d-electrons, stronger is the bonding. This is due to the formation of
covalent bonds by the overlapping of the d-orbitals containing unpaired electrons.
Q.19. Why are Cr, Mo and W hard metals while Zn, Cd and Hg are not very hard metals?
Ans: i) The d-orbitals containing unpaired electrons may overlap to form covalent bonds which are responsible
for the hardness. ,
ii) As the number of unpaired electrons increases, the number of covalent bonds and the strength of the
metallic bonds increases. The increase in the number of covalent bonds result in increase in the
strength and hardness of metal.
iii) Cr, Mo and W have maximum number of unpaired d-electrons which makes them very hard due to
increase in the number of covalent bonds. Zn, Cd, and Hg on the other' hand do not have unpaired
delectrons. Hence, they are not very hard.
Q.20. Explain the trends in melting and boiling points of first row transition metals.
Ans: i) Transition metals have close - packed structures. They are held together by strong metallic bonds with
significant covalent character.
ii) To melt the metal, metallic bonds should be broken. This requires significant energy. Hence transition
metals have very high melting and boiling points.
iii) The strength of metallic bonds, the melting and boiling points increases with increase in the number of
unpaired electrons.
iv) In a given period of transition elements, the number of unpairedelectrons in (n–1) d-orbital increases
upto d5 configuration. This results in increase in the strength of metallic bonds and the melting and
boiling points. .
v) Pairing of electrons results in decrease in the number of unpaired electrons from d6 to d9 configuration.
This decreases the strength of metallic bonds and results in progressive decrease in the melting and
boiling points, after the middle of the series.
vi) In the first transition series, the number of unpaired electrons increases from Sc to Cr and then
decreases. Thus, the strength of metallic bonds and the melting and boiling points increases from Sc to
Cr and then decreases.

vii) Zn, Cd, and Hg do not have unpaired d-electrons. Hence, they are soft and have low melting and
 d and f- Block Elements 6
boiling points. Mercury (Hg) is liquid at room temperature (melting point 234 K). Mn and Tc have
unexpectedly lower melting points due to complicated lattice structure. They have low enthalpies of
atomization.
Q.21. Define ionisation enthalpy.
Ans: Ionisation enthalpy is defined as the amount of energy required to remove the outermost electron
completely from a gaseous atom in its ground state.
Q.22. Explain the trends observed in the ionisation enthalpies of the d-block elements.

Ans:i) The ionization enthalpies of transition elements are higher than the ionization enthalpies of s-block
elements and lower than the ionization enthalpies of p-block elements. This is due to the trends in
atomic radii and nuclear charge.
ii) The atomic radii of transition elements are lower than the atomic radii of s-block elements and higher
than the atomic radii of p-block elements.
iii) The nuclear charges of transition elements are higher than the nuclear charges of s-block elements
and lower than the nuclear charges of p-block elements.
iv) As the atomic number increases across a transition series, the first ionization energy increases with
some irregularities. The irregularities are due to shielding of the valence electrons from the nucleus by
the added (n–l) d-electrons. Thus, the effect of increased nuclear charge is opposed by the screening
effect.
vi) The increasing order of the first ionization enihalpies of elements is :
First transition series < second transition series < third transition series
vii) The third transition series comprises of elements having atoms which possess filled 4f-orbitals. On
account of the peculiar diffused shape of 4f-orbitals, they exhibit poor shielding. Thus, the valence
electrons experience greater nuclear attraction. As a result, greater amount of energy is required to
ionise the elements of the third transition series. Thus, the ionization enthalpies of the third transition
series elements are much higher than those of the first and second series.
Note:
The energy required to remove first electron from gaseous atom in its ground state is called first
ionisation enthalpy, to remove second electron, it is called second ionisation enthalpy and for removal
of third electron it is called third ionisation enthalpy.
Q.23. Explain thermodynamic stability of transition metal compound on the basis of ionization enthalpy.
Ans: i) The thermodynamic stability of transition metal compounds can be predicted on the basis of their
ionization enthalpy value.
ii) When the sum of the ionization enthalpies required to attain a particular oxidation state of transition
metal ions is small, the thermodynamic stability of the compounds of the metal in that oxidation state
is high.
eg
a) Compounds containing Ni (II) are more stable than compounds containing Pt (II). Less amount of
energy is required for the ionization of Ni to Ni2+, than the energy required for the ionization of Pt to
 d and f- Block Elements 7
Pt 2+ .
This is because the sum of first and second ionization enthalpies (IE1 + IE2) for nickel is lesser as
compared to that of platinum.
Ni   Ni2+ (IE1 + IE2 = 2.49 × 103 kJ mol–1)
Pt   pt2+ (IE1 + IE2 = 2.66 × 103kJ mol–1)
b) Compounds containing Pt (IV) are more stable than compounds containing Ni (IV). Less amount of
energy is required for the ionization of Pt to Pt4+ than the energy required for the ionization of Ni to
Ni4+. This is because the sum of first four ionization enthalpies (lE1 + IE2 + IE3 + IE4) for platinum is
lesser as compared to that of nickel.
Ni   Ni4+ (lE1 + IE2 + IE3 + IE4 = 11.29 × 103 kJ mol–1)
Pt   Pt4+ (IE1 + IE2 + IE3 + IE4 = 9.36 × 103kJ mol–1)
Note:
K2PtCl6 is a well known compound of Pt (IV). The corresponding compound of nickel is not known.
Q.24. Explain the oxidation states of first row elements of transition series.
Ans:i) The oxidation states of transition elements are related to the electronic configuration. Transition elements
have last two orbitals incompletely filled i.e., they contain ns and (n–l)d orbitals.
ii) Transition elements have variable oxidation states as both (n –1)d and ns electrons participate in
bonding, due to nearly same energy levels.
iii) Elements of first transition series show + 1 and + 2 as the lowest oxidation states due to presence of
two 4s electrons, with the exception of copper and chromium which have only one 4s electron.
iv) As the 3d electrons take part in the chemical bonding one after another, in addition to the +2 oxidation
state, there are number of other oxidation states as illustrated below.
Oxidation states of first transition (3d) series elements:

v) The common oxidation states are +2 and +3. The number of oxidation states increases with increase
in the number of unpaired 3d electrons.
Q.25. Compare the stability of +2 oxidation state for the elements of the first transition series.
(NCERT)
Ans: i) In the beginning of 3d transition series, Sc2+ is virtually not known or in other words it is not stable in
comparison to Sc3+. Te2+, V2+, Cr2+ are known but less stable in comparison to their most common
oxidation state of +3.
ii) In the middle of the 3d transition series, Mn2+, Fe2+,CO2+ are known and quite common. Mn2+ and
Mn7+ are most stable in Mn. Fe2+ is less stable in comparison to Fe3+, due to fact that Fe2+ tends to lose
one electron to acquire d5 structure, which has extra stability: Co2+ is less stable as compared to CO3+
Ni2+ is most common and most stable among its +2, +3 and + 4 states. Cu+ is more stable and is most
common species as compared to Cu2+.
iii) At the end of the 3d transition series, Zn forms only Zn2+ which is highly stable as it has 3d10 configuration.
Q.26Explain briefly how +2 state becomes more and more stable in the first half of the first row
transition elements with increasing atomic number? (NCERT)
Ans: i) In the first half of the first row transition elements, as the atomic number increases, the stability of +2
oxidation state increases.
ii) Sc2+ is virtually not known.
iii) Ti2+,Y2+, and Ce2+ are known, but less stable in comparison to their most common oxidation state of +3.
iv) Mn2+, Fe2+ and CO2+ are known and quite common.
Q.27. Write the different oxidation states of manganese. Why +2 oxidation state of manganese is
more stable? [Mar 2013]
OR
 d and f- Block Elements 8
Explain why Mn2+ ion is more stable than Mn3+? (Given: Mn  Z = 25) [Mar ~014]
Ans: Oxidation states of Mn:
+ 2, + 3, + 4, + 5, + 6 and +7.
Electronic configuration of Mn:
1s22s22p63s23d54s2
Due to the presence of half filled 'd' orbital, the +2 oxidation state of Manganese is more stable.
Q.28.To what extent do the electronic configurations decide the stability of oxidation states in the
first series of transition elements? Illustrate with example. (NCERT)
Ans: In a transition series, the oxidation states which lead to noble gas or exactly half-filled or completely filled
d-orbitals are more stable.
eg. In the first transition series, electronic configuration of Mn (Z = 25) is [Ar]3d54s2. It shows oxidation
states + 2 to + 7, but Mn (II) is most stable because it has the half-filled configuration [Ar] 3d5. Similarly,
Sc3+ and Zn2+ are more stable as illustrated below:
Sc = [Ar]3d14s2, Sc3+ = [Ar] i.e., noble gas configuration.
Zn = [Ar] 3d104s2, Zn2+ = [Ar]3d10 i.e., completely filled configuration.
Q.29. How is the variability of oxidation states of the transition elements different from that of the
nontransition elements? Illustrate with examples. (NCERT)
Ans: i) The variability in oxidation states of transition metals is due to the incomplete filling of d-orbitals in
such a way that their oxidation states differ from each other by unity. eg. Fe2+ and Fe3+,Cu2+ and
Cu 2+,etc. In case of non-transition elements, the oxidation states differ by units of two.
eg. Pb2+ and Pb4+, Sn2+ and Sn4+, etc.
ii) In transition elements, the higher oxidation states are more stable for heavier elements in a group.
eg. In group 6, Mo (VI) and W (VI) are more stable than Cr (VI). In p-block elements, the lower
oxidation states are more stable for heavier members due to inert pair effect. eg. In group 14, Pb (II)
is more stable than Pb (IV).
Q.30.Why does scandium show only +2 and +3 oxidation states?
Ans: Scandium (Sc) has electronic configuration,
Sc: Is22s22p63s23p63dl4s2
Due to the loss of two electrons from the 4s-orbital, Sc acquires + 2 oxidation state.
Sc2+: Is22s22p63s23p63d1
By the loss of one more electron from the 3d-orbital, it acquires + 3 oxidation state.
Sc3+ : Is22s22p63s23p6
Since Sc3+ acquires extra stability of inert element [Ar], it does not form higher oxidation state.
Q.31.Why is manganese more stable in the +2 state than in the +3 state and the reverse is true for
iron?
OR
Why Mn compounds are more stable than Fe2+ towards oxidation to their + 3 state? (NCERT)
2+

Ans:Electronic configuration of Mn2+ is [Ar] 3d5 which is half filled and hence it is stable. So third ionisation
enthalpy is very high i.e,. third electron cannot be easily removed. Whereas, in case of Fe2+, the electronic
configuration is 3d6. Therefore, Fe2+ can easily lose one electron to acquire 3d5 stable electronic configuration.
Q.32. Why Zn does not exist in variable oxidation states ?
Ans: The oxidation state of an element depends on its electronic configuration.
Zn: Is22s22p63s23p63d104s2
When Zn loses two electrons from 4s-orbital thus acquiring +2 oxidation state, it gets a very stable electronic
configuration wherein all the electrons in d-orbital are paired.
Zn2+: 1s22s22p63s23p63d10
Since all the orbitals are completely filled with paired electrons, it has a very stable electronic configuration.
Therefore, Zn shows only one oxidation state of +2.
Q.33.Which element of 3d series of the transition metals exhibits the largest number of oxidation
states and why? (NCERT)
Ans:i) The electronic configuration of Mn is:
Mn: 1s22s22p63s23p63d54s2
ii) Manganese has maximum number of unpaired electrons.
iii) As the number of unpaired electrons in 3d subs hell increases, the number of oxidation state increases.
iv) Hence, among transition metals, Manganese exhibits the largest number of oxidation states ranging
 d and f- Block Elements 9
from +2 to +7.
v) Different oxidation states shown by Mn are:
2 3 4 5 6 7
MnCl2 , Mn 2 O3 , MnO2 , MnF5 , K 2 MnO4 , KMnO4

vi) Mn2+ state is very stable due to extra stability of half filled 3d5 subshell.
vii) Mn7+ is a good oxidising agent, since it can be easily reduced to Mn4+ and Mn2+.
Q.34. Explain why iron, cobalt and nickel do not show the expected highest oxidation states of +8, +9
and +10 respectively.
Ans: i) The oxidation states of an element depends on its electronic configuration and the number of unpaired
electrons.
ii) The electronic configuration of Fe, Co and Ni are as follows:

Ans:

iii)Hence the expected oxidation states of Fe, Co and Ni shall be + 8, + 9 and + 10 respectively.
iv) Fe by the loss of two electrons from 4s subshell forms Fe2+ and further loss of one more electron from
3d-orbital forms Fe3+, which is very stable due to half filled orbital, 3ds. Hence, there is no further loss
of electrons from the 3d subshell and thus Fe does not show + 8 oxidation.
v) Co forms CO2+due to the loss of two electrons from 4s subshell and further loss of one more electron
from 3d-orbital forms CO3+. In cobalt, + 2 and + 3 oxidation states are more stable and it does not lose
electrons further. Hence Co does not show + 9 oxidation state.
vi) Ni forms Ni2+ by the loss of two electrons from 4s-orbital and by the loss of one more electron from
3-dorbital, it forms Ne3+. The amount of energy required for the ionization of Ni to Ni2+ is less when
compared to that required for the ionization of Ni to Ni4+. Hence, Ni2+ oxidation state is comparitively
more stable. There is no further loss of electrons and therefore Ni does not show + 10 oxidation state.
Q.35.Which metal in the first transition series exhibits +1 oxidation state most frequently and why?
(NCERT)
Ans: Copper has electronic configuration [Ar] 3d104sl. It can easily lose one (4S1) electron to give stable 3d10
configuration.
Q.36. With suitable examples explain the following terms:
i) Chromous salts ii) Chromic salts
iii) Manganous salts iv) Ferrous compounds
v) Ferric compounds vi) Ferrates
vii) Cuprous salts viii) Cupric salts
Ans: i) Chromous salts: They are salts of chromium in + 2 oxidation state. eg. Chromous chloride (CrCl2)
and chromous sulphate (CrSO4)
ii) Chromic salts: They are salts of chromium in +3 oxidation state. They are also known as chromium
salts.
eg. Chromic chloride (CrCl3)
iii) Manganous salts: They are salts of manganese in +2 oxidation state. They are also known as
manganese salts.
eg. Manganese chloride (MnCl2)
iv) Ferrous compounds: They are compounds of iron in + 2 oxidation state.
eg. Ferrous sulphate (FeSO4)
v) Ferric compounds: They are compounds of iron in + 3 oxidation state.
eg. Ferric chloride (FeCl4)
vi) Ferrates: They are the compounds of iron in + 6 oxidation state.
eg. Potassium ferrate (K2FeO4)
vii) Cuprous salts: They are salts of copper in + 1 oxidation state.
eg. Cuprous iodide (Cu2I2)
viii) Cupric salts: They are salts of copper in +2 oxidation state. They are also known as copper salts.
 d and f- Block Elements 10
eg. Copper sulphate (CuSO4), Copper (II) chloride (CuCl2)
Q.37.Why is the highest oxidation state of a metal exhibited in its oxide or fluoride only? (NCERT)
Ans: Oxygen and fluorine have small size and high electronegativity, so they can easily oxidise the metal to its
highest oxidation state.
Q.38.Name the oxometal anions of the first series of the transition metals in which the metal exhibits
the oxidation state equal to its group number. (NCERT)
Ans: MnO4 : Oxidation state of Mn = +7 (Group No = 7)
CrO24 : Oxidation state of Cr = +6 (Group No = 6)
Note:
i) + 8 oxidation state is shown by both Os and Rh. However Os in OS04 has the most stable oxidation
state.
ii) Atoms having high electronegativity such as O or F stabilize higher oxidation states. However ligands
which have the ability to accept electrons from the metal (such as CO) through 1t bonding stabilize
lower oxidation states (zero or + 1).
iii) Fe+3 has higher oxidizing power than Fe2+.
Q.39.Comment on the statement that the "elements of the first properties different from those of
heavier transition elements".
Ans: The given statement is true because:
i) Atomic radii of the heavier transition elements (4d and 5d series) are larger than the corresponding
elements of the first transition series though those of 4d and 5d series are very close to each other.
ii) For first transition series, +2 and + 3 oxidation states are more common whereas for heavier transition
elements, higher oxidation states are more common.
iii) Melting and boiling points of heavier transition elements are greater than those of the first transition
series due to stronger intermetallic bonding (M–M bonding).
iv) Ionisation enthalpies of 5d series are higher than the corresponding elements of 3d and 4d series. The
elements of the first transition series form low spin or high spin complexes depending upon the strength
of the ligand field. However, the heavier transition elements form low spin complexes irrespective of
the strength of the ligand field.
Q.40.Explain the trend in atomic size of first row elements of transition series.
Ans: i) The atomic radii for transition metals are smaller than their corresponding s-block elements.
ii) The atomic radii of the elements of a given series decrease with the increase in atomic number but
this decrease becomes small after middle of the series.

iii) In the first transition series, the atomic radius gradually decreases from scandium to chromium but
from chromium to copper, it is nearly the same. Similar behaviour has been observed in the second
and third transition series. .
iv) The decrease in atomic radii in each series, in the beginning, is due to an increase in nuclear charge
across the period, which tends to pull the ns electrons inward, i.e. it tends to reduce the size.
v) The addition of extra electrons to (n–1) d-orbitals provides the screening effect. As the number of
delectrons increases, the screening effect increases. Thus, there are two operating effects namely
screening effect and nuclear charge effect which oppose each other.
vi) In the midway onwards of the series, both these effects become nearly equal and thus, there is no
change in atomic radii inspite of the fact that atomic number increases gradually.
vii) The values of atomic radii at the end of each series are slightly higher which is due to electronelectron
repulsions among (n–1) d-electrons. These repulsions become predominant at the end of each series
and thus resulting in the increase in size.
viii) In a vertical row, the atomic radii is expected to increase from top to bottom. Therefore, the atomic
radii of transition metals of second series have larger values than those of the first transition series.
However, the transition metals of third series except the first member, lanthanum, have nearly the
same radii as metals of second transition series above them which is due to the Lanthanoid contraction.
 d and f- Block Elements 11
Q.41. Explain the trend in ionic size of first row elements of transition series ?
Ans: i) The trend in ionic radii is illustrated by the following table.

ii) As the oxidation state increases, ionic radii decreases due to increase in effective nuclear charge.
iii)For a given oxidation state, as the nuclear charge increases, the ionic radii decreases. eg. With
increase in the effective nuclear charge, the ionic radii decreases gradually from Ti2+ to Cu2+.
iv) In a given period, transition elements have small ionic radii than representative elements.
Q.42. Explain the splitting of d-orbitals in transition elements.

Ans:i) In a free transition metal ion, the five (n –1)d orbitals are degenerate. This means that they have
same energy. I
ii) In transition metal compounds, the five (n –1)d orbitals of the transition metal ion split into two groups
(crystal field splitting):
a) Lower energy level containing three orbitals
dxy,dyz and dxz.
b) Higher energy level containing two orbitals.
dx2–y2 and dz2Splitting of d-Orbltals I
iii) The groups linked to the metal ions cause the splitting of d-orbitals.
iv) The difference between the two energy levels (E) is small.
Q.43.Explain, most of the transition metal compounds are remarkably coloured.
OR
Explain giving reasons: The transition metals generally form coloured compounds. (NCERT)
Ans:i) The colour of a substance is due to the absorption of light of a particular wavelength in visible region.
ii) Transition metal compounds contain partially filled (n–l) d-orbitals which become non-degenerate i.e.,
the energies of five d-orbitals are not same.
iii) The amount of energy required to excite some of the electrons to the higher energy states within the
same d-subshell, is quite small.
iv) In case of transition metal ions, the electrons can be easily promoted from one energy level to other
within the same d-subshell. This transition is called the d-d transition.
v) The energy required for d-d transition falls within visible region. Hence transition metal compounds
are remarkable coloured.
vi) The colour observed is different from the colour absorbed. The colour observed is the colour transmitted
and is complementary to the colour absorbed. In the following diagram, the complimentary colours are
placed diagonally opposite.
 d and f- Block Elements 12

eg. Absorption of red colour results in transmission of green colour. Thus, the transition metal compound
appears green.
Q.44. What are the factors responsible for colour of a transition metal ions ?
Ans: Factors responsible for colour of a transition metal ions:
i) The presence of incompletely filled d-orbitals in metal ions.
ii) The presence of unpaired electrons in d-orbitals.
iii) d-d transitions of electrons due to absorption of radiation in the visible region.
iv) Nature of groups (anions or ligands) linked to the metal ion in the compound or a complex.
v) Type of hybrid isation in metal ion in the complex.
vi) Geometry of the complex containing transition metal ion.
Note:
Colour of 3d transition metal ions:

Q.45. Why are some of the transition metal ions colourless ?

Ans: i) Transition metal ions exhibit colour due to the presence of unpaired electrons in (n–l )d-orbitals which
undergo d-d transition.
ii) The metal ions which does not have unpaired electrons i.e., (n–l )do or which have completely filled
d-orbital i.e., (n–1)d10 do not absorb radiations in visible region, since d-d transitions are not possible.
Hence, they are colourless ions.
eg. Cu+(3d10),Ag+ (4d10),Zn2+(3d10), Cd2+(4d10), Hg2+(5d10), etc.
Q.46. Predict which of the following will be coloured in aqueous solution? Te3+, V3+,Cu+, Sc3+, Mn2+,
Fe3+ and CO2+. Give reasons for each. (NCERT)
Ans: i) Transition metal ions exhibit colour due to the presence of unpaired electrons in (n–l )d-orbitals which
undergo d-d transition.
ii) The metal ions which does not have unpaired electrons i.e., (n–l )do or which have completely filled d-
orbital i.e., (n–l)d10 do not absorb radiations in visible region, since d-d transitions are not possible.
Hence, they are colourless ions.
iii) Ti3+, V3+, Mn2+, Fe3+ and CO2+ contain 1,2,5,5 and 3 unpaired electrons respectively in their (n–1) d-
orbital. Hence they are coloured in aqueous solution.
iv) Cu+ and Sc3+ do not contain unpaired electrons. Hence, they are colourless.
Q.47. Why salts of Sc3+,Ti4+,V5+ are colourless?
Ans: i) Electronic configurations of Sc3+, Ti4+, V5+ are:
Sc3+:[Ar]3d0
 d and f- Block Elements 13
Ti4+: [Ar] 3d0
V5+ [Ar] 3d0
ii) The ions Sc3+,Ti4+ and V5+ have completely empty d-orbitals i.e., no unpaired electrons are present.
Thus, their salts are colourless, as d-d transitions are not possible.
Q.48. Explain why the compounds of copper (II) are coloured, but those of zinc are colourless.
Ans:i) The electronic configuration of
Cu: [Ar]3d104s2 and Cu2+: [Ar] 3d9
ii) In copper compounds, Cu2+ ions have-incompletely filled 3d-orbital (3d9)
iii) The presence of one unpaired electron in 3d-orbital results in d-d transition due to which, Cu2+ ions
absorb red light from visible spectrum and emit blue radiation. Therefore, copper compounds are
coloured.
iv) In case of zinc, the electronic configuration is Zn:[Ar] 3d104s2 and Zn2+:[Ar]3d10
v) Since 3d subshell is completely filled and there are no unpaired electrons, d-d transition is not possible
and hence Zn2+ ions do not absorb radiation in visible region. Therefore, the compounds of Zn are
colourless.
Q.49. Explain why the solution of Ti3+ salt is purple in colour?
Ans:i) In [Ti(H2O)6]3+, Te3+ has 3d1 configuration.
ii) This one electron will occupy one of the orbital of lower energy and the complex (ion) will absorb
suitable wavelength of white light and promote the electron from lower energy level to higher energy
level.
iii) Since the complex absorbs light around 500 nm region, yellow and green lights are absorbed to excite
the electron and the transmitted light is of the complementary colour i.e., red blue (purple).
iv) Hence, solution containing hydrated Ti3+ ion is purple in colour.
Q.50.Explain why copper sulphate is blue in colour when dissolved in water but turns yellow when
treated with concentrated BCI.
Ans:i) The electronic configuration of Cu: [Ar] 3d104sl and Cu2+: [Ar] 3d9
ii) In the aqueous solution of copper sulphate, Cu2+ forms blue hydrated complex [Cu(H2O)6]+2 because
it has one unpaired electron in 3d subshell. The complex has octahedral geometry.
iii) When CuSO4 solution is treated with concentrated HCI solution, it forms a new complex [CuCl4]2–.
[Cu(H2O)6]2++ 4Cl–   [CuCl4]2–+ 6H2O
iv) The complex [CuC4]2– has a tetrahedral geometry. Due to a change in geometry and hybridisation of
the complex, the colour of the solution changes from blue to yellow.
Q.51. Explain the colour of MnO-4 ion.
Ans:i) MnO-4 ion is intense purple coloured in solution.
ii) The colour is due to charge transfer.
iii) An electron is temporarily transferred from O2– to Mn+7 in MnO-4 .
iv) Due to this, there is a temporary change in the oxidation state of oxygen from –2 to –1 and manganese
from + 7 to + 6.
v) Charge transfer is possible when the energy levels on two different atoms. are appreciably close.
Note: The complexes Cr2 O72- ,CrO 42 , MnO 4 , Cu2O and Ni-DMG are coloured due to charge transfer
transitions.
Q.52. Explain catalytic activity of transition metals.
OR
Explain giving reasons: Transition metals and their many compounds act as good catalyst. (NCERT)
Ans:i) Many transition metals and complexes are used as catalysts which influence the rate of chemical
reaction. The rate of a chemical reaction increases by the decrease in activation energy of the reactants.
This decrease is caused by the catalyst which probably alter the path of the reaction.
ii) Bonds are formed between reactant molecules and atoms on the surface of the catalyst (first row
transition metals utilise 3d and 4s-electrons for bonding). This results in the formation of reaction
intermediates which provides path of lower activation energy and therefore, increase the rate of the
reaction.
A+B+ C   [A – B – C]   A–B+C
Reactants Catalyst Intermediate Product Catalyst
 d and f- Block Elements 14
iii)
These reaction intermediates decompose to form the products and regenerate the original catalyst.
iv)Many transition metals are used as catalysts for reactions. Fe, Co, Pt, Cr, Mn, etc, are the commonly
used transition metal catalyst.
v) Following table lists some reactions catalyzed by transition metak
Q.53.Explain catalytic property of 3d series elements.
Ans: i) Transition metals posses variable oxidation states. Hence they can absorb and re-emit a wide range of
energies. Thus, they can provide necessary activation energy.
3
ii) Mechanism of 2I   S2 O82  
Fe
 I 2  2SO 24  is as shown below..
a) 2Fe3+ + 2I–   2Fe2+ + I2
b) 2Fe2  S2 O82   2Fe3  2SO24 
iii) Transitionmetals posses free valencies on the surface. Hence, they can absorb the reacting molecules.
Thus, the concentration of the reactants increases on the surface. This increases the rate of reaction.
Q.54. Transition metals and many of their compounds show paramagnetic behaviour. Explain. (NCERT)
Ans:i) Paramagnetism is a property due to the presence of unpaired electrons.
ii) In case of transition metals, as they contain unpaired electrons in the (n–l)d orbitals, most of the
transition metal ions and their compounds are paramagnetic in nature.
iii) The paramagnetic character increases with increase in the number of unpaired electrons.
Note:
i) Paramagnetism :
The substances which are attracted by the applied magnetic field are called paramagnetic
substances. This property of substances is known as paramagnetism. (They have unpaired electrons)
eg. Magnesium, Lithium
ii) Diamagnetism :
The substances which are repelled by the applied magneticfield are called diamagnetic substances.
This property of substances is known as diamagnetism. (They have paired electrons)
eg. Copper, Silver, Gold
iii) Ferromagnetism:
The substances which exhibits permanent magnetism even when the magnetic field is removed are
called ferromagnetic substances. Thisproperty of substances is known as ferromagnetism.
eg. Iron, Nickel, Cobalt
Q.55. Explain magnetic moment for transition elements and give formula for its calculation.
Ans:i) The magnetic moment of an electron is partly due to its orbital motion and partly due to its spin motion.
ii) In the compounds containing transition metal ions, the electrostatic field of other atoms, ions or molecules
(which surround the metal ion) suppresses the orbital contribution to the magnetic moment. Thus it is the
spin of the electrons, that contributes towards the effective magnetic moment ( eff ) is
iii) The expression for the effective magnetic moment ( eff ) is,
 eff  n(n  2)B.M
where, n is number of unpaired electrons. B.M stand for Bohr magneton (unit of magnetic moment)
A paramagnetic substance is characterized by its effective magnetic moment ( eff ) .
iv) Magnetic moment of a substance varies only with the number of unpaired electrons present.
eh
1B.M. 
4mc
where, 'h' represents planck's constant, 'e' represents charge on electron, 'm' represents mass of an electron
and 'c' represents the velocity of light.
Q.56. The d-electronic configuration of Co2+and Cu2+ is d7 and d9 respectively. Which one of these
ions will be more paramagnetic?
Ans: CO2+, (electronic configuration: 3d7) contains three unpaired electrons while Cu2+, (electronic configuration:
3d9) contains only one unpaired electron. Greater the unpaired electrons present, more paramagnetic is the
substance. So, CO2+ is more paramagnetic.
Q.57. Why does Mn(II) ion show maximum paramagnetic character amongst bivalent ions of first
transition series ?
 d and f- Block Elements 15
Ans: The electronic configuration of Mn(II) ion (atomic number of Mn = 25) is [Ar] 3d54s0. It has five unpaired
electrons in its d-orbitals which is a maximum value among the bivalent ions of first transition elements. As
the paramagnetic character is due to the presence of unpaired electron, Mn(II) ions shows maximum
paramagnetic character.
Q.58. Why are zinc metal and Zn++ ions diamagnetic ?
Ans: The atomic number of zinc is 30 and the electronic configuration of Zn is [Ar] 3d104s2 and Zn++ is [Ar] 3d10
In zinc metal and zn++, ions all electrons are paired and hence they are diamagnetic.
Q.59. Calculate the magnetic moment of Fe3+ ion (atomic number of Fe = 26).
Ans: Electronic configuration of Fe3+ ion is [Ar] 3d54s0.
So d-orbital has following distribution of electrons,

It has 5 unpaired electrons,
 Magnetic moment,
  n(n  2)  5(5  2) = 5.9 B.M.
Q.60. Calculate the magnetic moment of divalent ion in aqueous solution if its atomic number is 24.
Ans: The electronic configuration of the divalent ion (atomic number = 24) is [Ar]3d4 So d-orbital has following
distribution of electrons.

It has 4 unpaired electrons.

 Magnetic moment
  4(4  2) = 4.89 B.M.
Q.61. Calculate the 'Spin only' magnetic moment of M2+(aq) ion (Z = 26).
Ans: Atomic number = 26
Electronic configuration of M atom = [Ar]3d64s2.
Electronic configuration of M2+ = [Ar]3d6
So d-orbital has following distribution of electrons.

There are 4 unpaired electrons.

 Spin only magnetic moment () = ()  n(n  2) B.M.
= 4(4  2) B.M.
= 4.89 B.M.
Q.62.Calculate magnetic moment of Fe2+(aq) ion (Z = 26) [Mar 2013]
Ans: Refer Q.6J
Q.63. Calculate the 'Spin only' magnetic moment of M2+(aq) ion (Z = 27). (NCERT)
Ans: Atomic number = 27
Electronic configuration of M atom = [Ar]3d74s2.
Electronic configuration of M2+ = [Ar]3d7
So d-orbital has following distribution of electrons.

There are 3 unpaired electrons .

 Spin only magnetic mome ()  n(n  2) B.M.

= 3(3  2) B.M.
= 3.87 B.M.
Q.64. What are interstitial compounds? Why are such compounds well known for transition metals?
(NCERT)