5.

d & f BLOCK ELEMENTS

1.2 Electronic configuration

1. INTRODUCTION
(1) In d-block elements with increase in atomic number, the d-
1.1 Definition orbitals of penultimate shell i.e. (n-1) d are gradually filled
by electrons. The general electronic configuration of d-
“The elements in which the last differentiating electron enters
block element is,
into the d-orbitals of the penultimate shell i.e.
(n-11) d1-10, ns0-2.
(n–1) d where n is the last shell are called d-block elements”.
(2) Depending upon the d-orbitals of which penultimate shell
A transition element may also be defined as the element
i.e. n = 4, 5, 6, 7 are filled, four rows (called series) os ten
which partially filled d-orbital in their ground state or most
elements each obtained. They correspond to 3d, 4d, 5d and
stable oxidation state.
6d subshells.
Cu (Z = 29) = 1s2 2s2 2p6 3s2 3p6 3d10 4s1
(3) Energy of ‘(n–1)d’ subshell is slightly greater than ‘ns’
Cu2+ = 1s2 2s2 2p6 3s2 3p6 3d9
subshell, hence orbital is filled first then (n – 1) d orbitals.
(Cupric ion)
(4) The general electronic configuration of d-block/d-series
The properties of these elements are intermediate between elements be shown as follows :
the properties of s-block and p-block elements.
1. First (3d) Transition Series (Sc–Zn)
These elements represent a change or transition in
properties from more electropositive elements (s-block) to
less electropositive elements (p-block). Therefore these
elements are called transition elements.
2. Second (4d) Transition Series (Y-Cd)
Position in the periodic table
The position of d-block element has been shown in periodic
table as follows :

3. Third (5d) Transition Series (La–Hg)

4. Fourth (6d) Transition Series

Exceptional configuration of Cr and Cu. The exceptions

observed in the first series are in case of electronic
(1) d-block elements lie in between ‘s’ and ‘p’ block elements, configurations of chromium (Z = 24) and copper (Z = 29). It
i.e. these elements are located in the middle of the periodic may be noted that unlike other elements, chromium and
table. copper have a single electron in the 4s-orbital. This is due
(2) d-block elements are present in, to the gain of additonal stability by the atom by either having
4th period (21Sc to 30Zn, 10 elements) o1st Transition series. half-filled configuration (i.e., containing 5 electrons in the
5th period (39Y to 48Cd, 10 elements) o2nd Transition series. d-sublevel) or completely filled configuration, (i.e.,
6th period (51La, 72Hf to 80Hg, 10 elements) o3rd Transition containing 10 electrons in the d-sublevel). The 3d-level in
series. case of chromium gets excatly half-filled with configuration
7th period (89Ac, 104Rf to 112Uub, 10 elements) o4th Transition 3d5 4s1 and that in case of copper, it gets completely filled
series. with configuration 3d10 4s1. This can be explained on the
basis of exchange energy
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 140 d AND f BLOCK ELEMENTS
Thus, the electronic configuration of chromium (Z = 24)
and copper (Z = 29) are 1s2 2s2 2p6 3s2 3p6 3d5 4s1 and 1s2 2s2 1.5 Metallic character
2p6 3s6 3p6 3d10 4s1 respectively.
Except for mercury which is a liquid, all the transition
elements have typical metallic structure. They exhibit all
1.3 Properties the characteristics of metals. ductile, have high melting and
boiling points, high thermal and electrical conductivity and
1. Atomic Raddii
high tensile strength.
(i) The atomic radii of the transition metals lie in-between those Transition elements have relatively low ionization energies
of s- and p-block elements. and have one or two electrons in their outermost energy level
(ns1 or ns2). As a result, metallic bonds are formed. Hence, they
(ii) Generally the atomic radii of d-block elements in a series behave as metals. Greater the number of unpaired d electrons,
decreas with increase in atomic number but the decrease in stronger is the bonding due to the overlapping of unpaired
atomic size is small after midway. electrons between different metal atoms.
Explanation 1.6 Melting Point
The atomic radius decreases with the increase in atomic
Transition metals have high melting points which is due to
number as the nuclear charge increases whereas the their strong metallic bond. The metallic bond. The metalic
shielding effect of d-electron is small. After midway, as the bonding depends upon the number of unpaired e–. The
electrons enter the last but one (penultimate) shell, the added melting point first increases (Sc-Cr), reaches a maximum value
d-electron shields (screens) the outermost electron. Hence, (Cr) and then decreases (Fe-Zn)
with the increase in the d-electrons, screening effect * Tungsten (W) has the highest melting point.
increases. This counterbalances the increased nuclear * Mercury (Hg) has the lowest melting point.
charge due to increase in atomic number. As a result, the * Mn has the lowest melting point in 3d series typicl
atomic radii remain practically same after chromium. For transition elements.
example in Fe, the two opposing tendencies almost
1.7 Ionisation energies or Ionisation enthalpies
counterbalance and there is no change in the size from Mn
to Fe. (i) The first ionisation enthalpies of d-block elements lie between
s-block and p-block elements. They are higher than those of s-
(iii) At the end of the period, there is a slight increase in the
block elements and are lesser than those of p-block elements.
atomic radii.
The ionisation enthalpy gradually increases with increase in
Explanation atomic number along a given transition series though some
irregularities are observed
Near the end of series, the increased electron-electron
Explanation
repulsions between added electrons in the same orbitals
(i) The increasing ionization enthalpies are due to increased
are greater than the attractive forces due to the increased
nuclear charge with increase in atomic number which reduces
nuclear charge. This results in the expansion of the electron
the size of the atom making the removal of outer electron
cloud and thus the atomic radius increases. difficult.
(iv) The atomic radii increase down the group. This means that (ii) In a given series, the difference in the ionisation enthalpies
the atomic radii of second series are larger than those of between any two successive d-block elements is very much
first transition series. But the atomic radii of the second less than the difference in case of successive s-block or p-
and third transition series are almost the same. block elements.
Explanation
The atomic radii of the elements of the second and third The addition of d electrons in last but one [(n — 1) or
transition metals are nearly same due to lanthanide penultimate] shell with increase in atomic number provides
contraction (or also called lanthanoid contraction) a screening effect and thus shields the outer s electrons
discussed later. from inward nuclear pull. Thus, the effects of increased
nuclear charge and addition of d electrons tend to oppose
1.4 Ionic radii each other.
(i) The trend followed by the ionic radii is the same as that
(iii) The first ionization enthalpy of Zn, Cd and Hg are, however,
followed by atomic radii. very high because of the fully filled (n-1) d 10 ns 2
(ii) Ionic radii of transition metals are different in different configuration.
oxidation states. (iv) Although second and third ionization enthalpies also, in
(iii) The ionic radii of the transition metals are smaller than those general, increase along a period, but the magnitude of
of the representative elements belonging to the same period. increase for the successive elements is much higher.
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 d AND f BLOCK ELEMENTS 141

(v) The high values of 3rd ionization enthalpies for Cu, Ni and In ‘3d’ series all element contain 2 electrons in ‘4s’ and hence
Zn explain why they show a maximum oxidation state of +2. they all give a common minimum oxidation state of +2.
(vi) The first ionisation enthalpies of 5d elements are higher as (Except ‘Cr’ and ‘Cu’ where minimum oxidation state is +1.]
compared to those of 3d and 4d elements. This is because The maximum oxidation state is given by Mn i.e. Mn+7 in
the weak shielding of nucleus by 4f electrons in 5d elements which two electrons are removed from 4s and five unpaired
results in greater effective nuclear charge acting on the electrons are removed from 3d orbitals.
outer valence electrons. (4) The highest oxidation state is shown by Ruthenium (Ru)
and Osmium (Os) i.e. +8.
1.8. Oxidation state
(5) Across the period oxidation state increases and it is maximum
at the centre and than decreases even if atomic number
“The net numerical charge assigned to an atom of an element
increases. The element which shows highest oxidation state
in its combined state is known as its Oxidation state or
occur in the middle or near the middle of the series and than
Oxidation number”.
decreases.
(1) With the exception of few elements, most of the d-block
(6) Transition metals also show zero oxidation states in metal
elements show more than one oxidation state i.e. they show
carbonyl complex. (Nickel tetracarbonyl).
variable oxidation states. The elements show variable
Example : Ni in Ni (CO)4 has zero oxidation state.
oxidation state because of following reasons:
(7) The bonding in the compounds of lower oxidation state
(i) ‘(n-1) d’ and ‘ns’ orbitals in the atoms of d-block elements
(+2, +3) is mostly ionic and the bonding in the compounds
have almost same energies and therefore electron can be
of higher oxidation state is mostly covalent.
removed from ‘(n-1)d’ orbitals as easily as ‘s’ orbitals
(8) The relative stabilities of some oxidation states can be
electrons.
explained on the basis of rule extra stability, according to
(ii) After removing ‘s’ electrons, the remainder is called Kernel which d0, d5 and d10 are stable configurations.
of the metal cations. In d-block elements, the kernel is
For example, the stability order of some ions is as follows:
unstable and therefore it loses one or more electrons from
Ti4+ (3d0, 4s0) > Ti3 (3d1, 4s0)
(n – 1)d electrons. This results in formation of cations with
different oxidation states. Mn2+ (3d5, 4s0) > Mn3+ (3d4, 4s0)
Fe3+, (3d5, 4s0) > Fe2+ (3d6, 4s0)
(2) All transition elements show variable oxidation state except
last element in each series. (9) Cu+2 is more stable than Cu+1 even when Cu+1 is 3d10 while
Cu+2 is 3d due to high heat of hydration.
(3) Minimum oxidation state = Total number of electrons in 4s
lost. Maximum oxidation state = (Total number of electrons Variable oxidation states shown by 3d-series of d-block elements.
in 4s + number of unpaired electrons in 3d lost).
Oxidation States

ELECTRONIC Sc Ti V Cr Mn Fe Co Ni Cu Zn

CONFIGURATION d 1s 2 d 2s 2 d 3s2 d 4s 2 d5s 2 d6s2 d 7s2 d8s2 d 9s 2 d 10 s 2

d 5s 1 d 10 s 1

+1 +1

+2 +2 +2 +2 +2 +2 +2 +2 +2 +2

+3 +3 +3 +3 +3 +3 +3 +3 +3

+4 +4 +4 +4 +4 +4 +4

+5 +5 +5 +5 +5

+6 +6 +6

+7
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 142 d AND f BLOCK ELEMENTS
(iv) The values of Eo for Mn, Ni and Zn are more negative than
1.9 Standard electrode potentials (Eo) and chemical expected from the generall trend. This is due to greater
reactivity stability of half-filled d-subshell (d5) in Mn2+, and completely
Thermodynamic stability of the compounds of transition filled d-subshell (d10) in Zn2+. The exceptional behaviour of
elements can be evaluated in terms of the magnitude of Ni towards Eo value from the regular trend is due to its high
ionisation enthalpies of the metals — smaller the ionisation negative enthalpy of hydration.
enthalpy of the metal, stabler is its compound. Trends in the M3+/M2+ Standard Electrode Potentials
In solution, the stability of the compounds depends upon (i) A very low value for Eo (Sc3+/Sc2+) reflects the stability of
electrode potentials rather than ionization enthalpies. Sc3+ ion which has a noble gas configuration.
Electrode potential values depend upon factors such as
enthalpy of sublimation (or atomisation) of the metal, the (ii) The highest value for Zn is on account of very high stability
ionisation enthalpy and the hydration enthalpy, i.e., of Zn2+ ion with d10 configuration. It is difficult to remove
an electron from it to change it into +3 state.
' sub H
M s  o M g , ('subH is enthalpy of sublimation/
(iii) The comparatively high value of Eo (Mn3+/Mn2+) shows
atomisation) that Mn2+ is very stable which is on account of stable d5
'iH configuration of Mn2+.
M s  o M  g  e , ('i H is ionisation enthalpy)
(iv) The comparatively low value of Eo (Fe3+/Fe2+) is on account
' hyd H
M  g  aq o M  aq , (' hyd H is enthalpy of of extra stability of Fe3+ (d5), i.e., low third ionization enthalpy
of Fe.
hydration)
(v) The comparatively low value for V is on account of the
The total energy, ' T H, for the process involving
sublimation, ionisation and hydration simultaneously, i.e., stability of V2+ ion due to its half-filled t 32g configuration
o M  aq  e  , will be the sum
for the process, M s  (discussed in unit 9).
of the three types of enthalpies, i.e., Chemical Reactivity and Eo Values. The transition metals
vary very widely in their chemical reactivity. Some of them
'TH ' sub H  ' i H  ' hyd H. are highly electropositive and dissolve in mineral acids
Thus, 'T H, is the total enthalpy change when solid meal, whereas a few of them are ‘noble’, i.e., they do not react with
M is brought in the aqueous medium in the form of simple acids. Some results of chemical reactivity of transition
monovalent ion, M+ (aq). metals as related to their Eo values are given below :
(i) The metals of the first transition series (except copper) are
relatively more reactive than the othr series. Thus, they are
oxidized by H+ ions though the actual rate is slow, e.g., Ti
and V are passive to dilute non-oxidizing acids at room
temperature.
(ii) As already explained, less negative Eo values for M2+/M
along the series indicate a decreasing tendency to form
Trends in the M2+/M Standard Electrode Potentials divalent cations.
(i) There is no regular trend in the Eo (M2+/M) values. This is (iii) More negative Eo values than expected for Mn, Ni and Zn
because their ionization enthalpies (I1 + IE2) and sublimation show greater stability for Mn2+, Ni2+ and Zn2+.
enthalpies do not show any regular trend.
(iv) Eo values for the redox couple M3+/M2+ indicate that Mn3+
(ii) The general trend towards less negative Eo values along and Co3+ ions ar the strongest oxidizing agents in aqueous
the series is due to the general increase in the sum of first solution whereas Ti2+, V2+ and Cr2+ are strongest reducing
and second ionization enthalpies. agents and can liberate hydrogen from a dilute acid, e.g., 2
(iii) Copper shows a unique behaviour in the series as it is the Cr2+ (aq) + 2 H+ (aq)  o 2 Cr3+ (aq) + H2 (g)
only metal having positive value for Eo. This explains why
is does not liberate H2 gas from acids. It reacts only with 1.10 Catalytic Property
the oxidizing acids (HNO3 and H2SO4) which are reduced.
The reason for positive Eo value for copper is that the sum Most transition elements and their compounds have good
of enthalpies of sublimation and ionization is not balanced catalytic properties because
by hydration enthalpy. (a) They possess variable oxidation state.
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d AND f BLOCK ELEMENTS 143

(b) They provide a large surface area for the reactant to be

absorbed. 2. COMPLEX FORMATION

Catalysts Uses Transition metal ions form a large number of complex

compounds. Complex compounds are those which have
TiCl4 + Al (C2H5)3 Ziegler-Natta catalyst, used in a metal ion linked to a number of negative ions (anions) or
neutral molecules having lone pairs of electrons. These
polymerisation of ethylene ions or molecules are called ligands. They donate lone
V2O5 Contact process SO2 o SO3 pairs of electrons to the central transition metal ion forming
coordinate bonds
Fe Haber Bosch process
A few examples are given below :
PdCl2 Wacker’s process for CH3CHO [Fe(CN)6]3–, [Fe(CN)6]4–, [Cu(NH3)4]2+, [Zn(NH 3)4]2+,
[Ni(CN)4]2– and [Ptcl4]2–
manufacturing
Such complex compounds are not formed by s - and p -
Pd Hydrogenation of alkene, alkyne
block elements.
etc
Explanation. The transition elements form complexes
Pt/PtO Adam’s catalyst for selective because of the following reasons :
reduction (i) Comparatively smaller size of their metal ions.
Pt Catalytic convertor, for (ii) Their high ionic charges.
cleaning (Because of (i) and (ii), they have large charge/size ratio)
car exhaust fumes (iii) Availability of vacant d-orbitals so that these orbitals can
Pt/Rh Ostwald’s process : accept lone pairs of electrons donated by the ligands.

NH3 o NO 2.1 Interstitital Compounds

Cu Oxidation of alcohols The transition metals form a large number of interstitial

compounds in which small atoms such as hydrogen,
1.11 Magnetic Behaviour carbon, boron and nitrogen occupy the empty spaces
(interstitial sites) in their lattices (Fig.).
When a substance is placed in a magnetic field of strength They are represented by formulae like TiC, TiH2, Mn4N,
H, the intensity of the magnetic field in the substance may Fe 3 H, Fe 3C etc. However, actually they are non-
be greater than or less than H. If the field in the substance stoichiometric materials, e.g., TiH1.7, VH0.56 etc. and the
is greater than H, the substance is a paramagnetic material bonds present in them are neither typically ionic nor
and attracts line of force. If the field in the substance is less covalent. Some of their important characteristics are as
than H, the substance is diamagnetic. Diamagnetic materials follows:
tend to repel lines of force. The magnetic moment of a (i) They are very hard and rigid, e.g., steel which is an
substance depends on the strength of magnetic field interstitial compound of Fe and Cis quite hard. Similarly,
generated due to electronic spin, there is a change in electric some borides are as hard as diamond.
flux which leads to induction of magnetic field. The electron (ii) They have high melting points which are higher than those
is also under orbital angular momentum or orbital spin. It of the pure metals.
leads to generation of magnetic moment. (iii) They show conductivity like that of the pure metal.
In first transition elements series the orbital angular magnetic (iv) They acquire chemical inertness.
moment is insignificant the orbital contribution is quenched
by the electric fields of the surrounding atoms so magnetic 2.2 Alloy formation
moment is equal to the spin magnetic moment only.
Alloys are homogeneous solid solutions of two or more
P eff n (n  2) BM metals obtained by melting the components and then
cooling the melt. These are formed by metals whose atomic
n o no. of unpaired electron. radii differ by not more than 15% so that the atoms of one
Maximum transition elements and compounds are metal can easily take up the positions in the crystal lattice
paramagnetic due to presence of unpaired electrons. of the other (Fig.)
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 144 d AND f BLOCK ELEMENTS
Now, as transition metals have similar atomic radii and (v) In general, the oxides in the lower oxidation states of the
other characteristics, hence they form alloys very readily. metals are basic and in their higher oxidation states, they
Alloys are generally harder, have higher melting points are acidic whereas in the intermediate oxidation state, the
and more resistant to corrosion than the individiual metals. oxides are amphoteric.
The most commonly used are the ferrous alloys the metals
For example, the behaviour of the oxides of manganese
chromium, vanadium, molybdenum, tungsten and
may be represented as follows :
manganese are used in the formation of alloy steels and
stainless steels. Some alloys of transition metals with non- 2 8 /3 3 4 7
transition metals are also very common. e.g., brass MnO Mn 3O 4 Mn 2 O 3 MnO 2 Mn 2 O 7
Basic Amphoteric
(Cu + Zn) and bronze (Cu + Sn) Amphoteric Amphoteric Acidic

Thus, Mn2O7 dissolves in water to give the acid HMnO4.

3.2 KMnO4 Potassium permanganate

It is prepared from the ore called chromite or ferrochrome

or chrome iron, FeO.Cr2O3. The various steps involved
are as follows :
(i) Preparation of sodium chromate. The ore is finely
powdered, mixed with sodium carbonate and quick lime
and then roasted, i.e., heated to redness in a reverberatory
furnace with free exposure to air when sodium chromate
(yellow in colour) is formed and carbon dioxide is evolved.
Quick lime keeps the mass porous and thus facilitates
oxidation.

4FeO.Cr2O3 + 8Na2CO3+ 7O2 

o 8Na2CrO4 + 2Fe2O3 + 8CO2
Chromite ore Sod. chromate Ferric oxide

After the reaction, the roasted mass is extracted with water

when sodium chromate is completely dissolved while ferric
3. COMPOUNDS OF TRANSITION ELEMENTS oxide is left behind. Ferric oxide is separated out by
filtration.
3.1 Oxides
(ii) Conversion of sodium chromate into sodium dichromate.
(i) The metals of the first transition series form oxides with The filtrate containing sodium chromate solution is treated
oxygen at high temperature. with concentrated sulphuric acid when sodium chromate
is converted into sodium dichromate.
(ii) The oxides are formed in the oxidation, states +1 to +7 (as
2Na 2 CrO 4  H 2SO 4 
o Na 2 Cr2 O7  Na 2SO 4  H 2 O
given in Table 8.10, page 8/14). Sod.chromate Conc. Sod. dichromate

(iii) The highest oxidation state in the oxides of any transition Sodium sulphate being less soluble crystallizes out as
metal is equal to its group number, e.g., 7 in Mn2O7. Beyond decahydrate, Na2SO4. 10H2O and is removed. The clear
group 7, no higher oxides of iron abov Fe2O are known. solution is then evaporated in iron pans to a specific
Some metals in higher oxidation state stabilize by forming gravity of 1.7 when a further crop of sodium sulphate is
oxocations, e.g., VV as VO2 , VIV as VO2+ and TiIV as TiO2+. formed. It is removed and the solution is cooled when
orange crystals of sodium dichromate, Na2Cr2O7. 2H2O
(iv) All the metals except scandium form the oxides with the separate on standing.
formula MO which are ionic in nature. As the oxidation
(iii) Conversion sodium dichromate into potassium
number of the metal increases, ionic character decreases,
dichromate. Hot concentrated solution of sodium
e.g., Mn2O7 is a covalent green oil. Even CrO3 and V2O5
dichromate is treated with calculated amount of potassium
have low melting points.
chloride when potassium dichromate, being much less
2 8/ 3 3 4 7 soluble than sodium salt, crystallizes out on cooling as
MnO Mn 3O 4 Mn 2O 3 MnO 2 Mn 2O 7 orange crystals.

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d AND f BLOCK ELEMENTS 145
(b) On heating the mixture, oxygen is evolved.
Na Cr O  2KCl 
2 2 7 o K 2 Cr2 O7  2NaCl
Sodium dichromate Potassium dichromate 2K 2 Cr2 O7  8H 2SO 4 
o 2K 2SO 4  2Cr2 SO 4 3 + 8H2O + 3O2

6. Oxidising properties. It is a powerful oxidising agent. In

3.3 Properties
the presence of dilute sulphuric acid, one molecule of
1. Colour and Melting point. It forms orange crystals which potassium dichromate furnishes 3 atoms of available
melt at 669 K. oxygen as indicated by the equation :

2. Solubility. It is moderately soluble in cold water but freely K 2 Cr2 O 7  4H 2SO 4 

o K 2SO 4  Cr2 SO 4 3
+ 4H2O + 3O
soluble in hot water.
or Cr2 O72  14H   6e 
o 2Cr 3  7H 2 O
3. Action of heat. When heated to a white heat, it
decomposes with the evolution of oxygen.
Mol. wt. 294
? Eq. wt. of K 2 Cr2 O 7 49
4K 2 Cr2 O7 
o 4K 2 CrO4  2Cr2 O3  3O 2 6 6

4. Action of alkalies. When an alkali is added to an orange (i) It liberates I2 from KI

red solution of dichromate, a yellow solution results due
K 2 Cr2 O 7  7H 2SO 4  6KI 
o 4K 2SO 4  Cr2 SO 4 3
to the formation of chromate.
3I2  7H 2 O
K 2 Cr2 O7  KOH 
o 2K 2 CrO4  H 2 O
Pot. dichromate Pot.chromate (ii) It oxidises ferrous salts to ferric salts

or Cr2 O72  2 OH  
o 2 CrO42   H 2 O K 2 Cr2 O7  7H 2SO 4  6FeSO 4 
o K 2SO 4  Cr2 SO4 3

On acidifying, the colour again changes to orange red 3Fe2 SO 4 3

 2H 2 O
due to the reformation of dichromate.
(iii) It oxidises H2S to sulphur
2 K 2 CrO4  H 2SO4 
o K 2 Cr2 O7  K 2SO4  H 2 O
K 2 Cr2 O 7  4H 2SO 4  3H 2S 
o K 2SO 4  Cr2 SO 4 3
2  2
or 2 CrO  2 H 
4 o Cr2 O  H 2O 7 + 7H2O + 3S
This interconversion is explained by the fact that in (iv) It oxidises sulphites to sulphates and thiosulphates to
sulphates and sulphur
dichromate solution, the Cr2 O72 ions are invariably in
K 2 Cr2 O 7  4H 2SO 4  3Na 2SO3 
o K 2SO4  Cr2 SO 4
equilibrium with CrO24 ions at pH = 4, i.e., 3

+ 4H2O + 3Na2SO4
2 pH 4 2 
Cr O2 7  H 2 O YZZZZ 2CrO  2H
ZZZZX 4
(v) It oxidises nitrites to nitrates
Orange red Yellow
dichromate chromate
K 2 Cr2 O7  4 H 2 SO 4  3NaNO2 
o K 2 SO 4  Cr2 SO 4 3

On adding an alkali (i.e., increasing the pH of the solution), + 3 NaNO3 + 4 H2O

the H+ ions are used up and according to the law of
chemical equilibrium, the reaction proceeds in the forward (vi) It oxidises halogen acids to halogen
direction producing yellow chromate solution. On the
K 2Cr2 O7  14 HCl 
o 2KCl  2CrCl3  7H2 O  3Cl2
other hand, when an when an acid is added (i.e., pH of the
solution is decreased), the concentration of H+ ions is (vii) It oxidises SO2 to sulphuric acid
increased and the reaction proceeds in the backward
K 2 Cr2 O 7  H 2 SO 4  3SO 2 
o K 2 SO 4  Cr2 SO 4  3H 2 O
direction producing an orange red dichromate solution. 3

5. Action of concentrated sulphuric acid (viii) It oxidises stannous salts to stannic salts

(a) In cold, red crystals of chromic anhydride (chromium Cr2O72   14 H   3Sn 2 

o 2 Cr 3  3 Sn 4  3 Sn 4  7 H 2 O
trioxide) are formed.
(ix) It oxidises ethyl alcohol to acetaldehyde and acetic acid.
K 2 Cr2 O7  2H 2SO 4 
o 2CrO3  2KHSO4  H 2O K 2 Cr2 O7  4H 2SO 4 
o K 2SO 4  Cr2 SO 4  4H 2 O  3O
3
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 146 d AND f BLOCK ELEMENTS
(iii) In organic chemistry, it is used as an oxidising agent.
CH 2 CH 2OH  O 
o CH3CHO  H 2 O Structures of chromate and dichromate ions.
Ethyl alcohol

CH 3 CHO  O 
o CH 3COOH
Acetaldehyde Acetic acid

or
Test for a drunken driver. The above reaction helps to
test whether a driver has consumed alcohol or not. he is
asked to breathe into the acidified K2Cr2O7 solution taken
in a test tube. If the orange colour of the solution changes
into green colour (due to Cr2(SO4)3 formed in the reaction),
the driver is drunk, otherwise not.
7. Chromyl chloride test (Reaction with a chloride and conc. or
sulphuric acid). When heated with concentrated
hydrochloric acid or with a chloride and strong sulphuric
acid, reddish brown vapours of chromyl chloride are
obtained. 3.4 Potassium Permanganate (KMnO4)
K 2 Cr2 O 7  4KCl  6H 2SO4 
o 2CrO 2 Cl2  6KHSO 4  3H 2 O Preparation
Chromyl chloride
Red vapour
On a large scale, it is prepared from the mineral, pyrolusite,
8. Reaction with hydrogen peroxide. Acidified K2Cr2O7 MnO2. The preparation involves the following two stesp:
solution reacts with H2O2 to give a deep blue solution (i) Conversion of MnO2 into potassium manganate. The finely
due to the formation of peroxo compound, CrO (O2)2. powdered pyrolusite mineral is fused with potassium
hydroxide or potassium carbonate in the presence of air
Cr2O72   2 H  4 H 2 O2 
o 2 CrO5  5 H 2 O or oxidising agent such as potassium nitrate or potassium
chlorate when green coloured potassium manganate is
The blue colour fades away gradually due to the formed.
decomposition of CrO5 into Cr3+ ions and oxygen.
2MnO2 + 4KOH + O2 
o 2K2MnO4 + 2H2 O

The structure of CrO5 is in which Cr is in +6 Potassium manganate

2MnO2 + 2K2CO3 + O2 
o 2K2MnO4 + 2 CO2
oxidation state.
Uses. MnO2 + 2KOH + KNO3 
o K2MnO4 + KNO2 + H2O

(i) In volumetric analysis, it is used as a primary standard for 3MnO2 +6KOH+KClO3 

o 3K2MnO4 +KCl+2H2O
the estimation of Fe2+ (ferrous ions) and I– (iodides) in
Potassium manganate thus formed undergoes
redox titrations.
disproportionation in the neutral or acidic solution as
Note follows, if allowed to stand for some time :
VI VII IV
Na2Cr2O7 is not used in volumetric analysis because it is 3 MnO 24   4 H  
o2 MnO4  MnO 2  2 H 2 O
Manganate ion Permanganate ion
deliquescent.
(ii) Oxidation of potassium manganate to potassium
(ii) In industry, it is used
permanganate.
(a) In chrome tanning in leather industry. (a) Chemical oxidation. The fused mass is extracted with
(b) In the preparation of chrome alum K2SO4.Cr2(SO4)3. water and the solution after filtration is converted into
24H2O and other industrially important compounds potassium permanganate by bubbling carbon dioxide,
such as Cr2O3, CrO3, CrO2Cl2, K2CrO4, CrCl3 etc. chlorine or ozonised oxygen through the green solution.

(c) In calico printing and dyeing. 3K 2 MnO 4  2CO2 

o 2KMnO 4  MnO 2 p 2K 2 CO3

(d) In photography and in hardening gelatine film. 2K 2 MnO4  Cl2 

o 2KMnO 4  2KCl
2K 2 MnO4  H 2 O  O3 
o 2KMnO4  2KOH  O 2
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 d AND f BLOCK ELEMENTS 147

The carbon dioxide process is uneconomical as one third Presence of ZnSO4 or ZnO catalyses the oxidation.
of the original manganate is reconverted to manganese (ii) It oxidises sodium thiosulphate to sodium sulphate.
dioxide. However, this process has the advantage that
the potassium carbonate formed as a by-product can be 8KMnO4  3Na 2S2 O3  H 2 O 
o 3K 2SO 4  8MnO 2 
used for the oxidative fusion of manganese dioxide. In 3Na 2SO 4  2KOH
the chlorine process, potassium chloride obtained as a
by-product is lost. (iii) It oxidises hydrogen sulphide to sulphur.

PROPERTIES 2KMnO4  4H 2S 
o 2MnS  S  K 2SO4  4H 2 O
1. Colour. Potassium permanganate exists as deep purple (b) In alkaline solution. In strongly alkaline solution, MnO24 
black prisms with a greenish lustre which become dull in
air due to superficial reduction. (manganate) ion is produced.

2. Solubility. It is moderately soluble in water at room 2KMnO4  2KOH 

o 2K 2 MnO 4  H 2 O  O or
temperature and it is more soluble in hot water. MnO14  e 
o MnO42 
3. Action of heat. When heated to 513 K, it readily Mol. wt. 158
decomposes giving oxygen. ? Eq. wt. of KMnO 4 158
1 1
2KMnO 4 
o K 2 MnO4  MnO 2  O2
Pot. manganate Potassium manganate is also further reduced to MnO2
At red heat, potassium manganate formed decomposes
into potassium manganite (K2MnO3) and oxygen. when a reducing agent is present.

2K 2 MnO4 
o 2K 2 MnO3  O2 K 2 MnO4  H 2 O 
o MnO2  2KOH  O
4. Action of heat in current of hydrogen. When heated in a
current of H2, solid KMnO4 gives KOH, MnO and water or MnO 24  2H 2 O  2 e  
o MnO2  4OH 
vapours. So the complete reaction is :
'
2KMnO4  5H2 
o 2KOH  2MnO  4H 2 O 2KMnO4  H2 O 
o 2MnO2  2 KOH  3O
5. Oxidising property. Potassium permanganate is powerful or MnO 4  2H 2 O  3 e 
o MnO2  4OH 
oxidising agent. The actual course of reaction depends
on the use of the permanganate in (a) neutral (b) alkaline which is the same as that for neutral medium. Hence,
or (c) acidic solution. equivalent weight of KMnO4 in weakly alkaline medium is
same as that in the neutral medium, viz., 52.67
(a) In neutral solution. Potassium permanganate acts as a
moderate oxidising agent in neutral aqueous solution Some oxidizing properties of KMnO4 in the alkaline medium.
because of the reaction : These are given below :

2KMnO4  H 2 O 
o 2KOH  2MnO2  3O (i) It oxidises potassium iodide to potassium iodate.
2KMnO 4  H 2 O  KI 
o 2MnO 2  2KOH  KIO3
or MnO 4  2H 2 O  3 e 
o MnO2  4OH  Pot. iodate

   
Thus, MnO 4 ion gains 3 electrons. Also, according to or I  6OH 
o IO  3H 2 O  6 e
3

the above equation, in neutral medium, from two moles of In this case, iodine is not liberated unlike the case of acidic
permanganate, three oxygen atoms are available. In fact, medium.
during the course of reaction, the alkali generated renders Similar reaction takes place with KBr.
the medium alkaline even when we start with neutral
(ii) It oxidises olefinic compounds to glycols, i.e., when an
solutions. Hence, Eq. wt. of KMnO4 in neutral or weakly
olefinic compound is shaken with alkaline KMnO4, pink
alkaline medium
colour of KMnO4 is discharged.
Mol. wt. 158
52.67
3 3
Some oxidizing properties of KMnO4 in the neutral medium.
These are given below :
(i) It oxidises hot manganous sulphate to manganese dioxide.

2KMnO4  3MnSO4  2H2 O 

o K 2SO4  2H2SO 4  5MnO2
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 148 d AND f BLOCK ELEMENTS
Alkaline KMnO4 used for this test is known as Baeyer’s (vii) It oxidises potassium iodide to iodine
reagent. It is used for oxidation of a number of organic
2KMnO 4  3H 2 SO 4  10KI 
o K 2SO 4  2MnSO 4 
compounds.
(c) In acidic medium. Potassium permanganate in the 8H 2 O  5I 2
presence of dil. sulphuric acid, i.e., in acidic medium, acts
as a strong oxidising agent because of the reaction (viii) It oxidises HX (where X = Cl, Br, l) to X2

2KMnO4  3H 2SO 4 
o K 2SO 4  2MnSO 4  3H 2 O  5O 2KMnO 4  3H 2SO4  10 HX 
o K 2SO4  2MnSO 4 

or MnO 4  8H   5 e  8H 2 O  5X 2
o Mn 2   4H 2 O.
(ix) It oxidises ethyl alcohol to acetaldehyde
Since in the above reaction, MnO 4 ion gains 5 electrons
2KMnO4  3H 2SO 4  5CH3 CH 2 OH 
o K 2SO 4  2MnSO4 
of five atoms of oxygen are available from two molecules
of KMnO4. Hence. 5CH 3 CHO  8H 2 O.
Mol. wt. 158 Uses.
Eq. wt. of KMnO 4 31.6
5 5
(i) It is often used in volumetric analysis for the estimation
Some oxidizing properties of KMnO4 in the acidic medium. of ferrous salts, oxalates, iodides and hydrogen peroxide.
These are given below : However, it is not a primary standard because it is difficult
to obtain it in the pure state and free from traces of MnO2.
(i) It oxidises H2S to S.
It is, therefore, always first standardised with a standard
2KMnO 4  3H2SO 4  5H 2 S 
o K 2SO4  2MnSO 4  2H 2 O  5O solution of oxalic acid.

(ii) It oxidises sulphur dioxide to sulphuric acid. Remember that volumetric titrations inolving KMnO4 are
carried out only in presence of dilute H2SO4 but not in the
2KMnO4  5 SO2  2H 2 O 
o K 2 SO4  2MnSO 4  2H 2SO 4 presene of HCl or HNO3. This is because oxygen produced
from KMnO4 + dill. H2SO4 is used only for oxidizing the
 
(iii) It oxidises nitrites NO 2 to nitrates NO3 , arsenites reducing agent. Moreover, H2SO4 does not give any
oxygen of its own to oxidiize the reducign agent. In case
AsO 33  to arsentates AsO 34 and sulphites and
HCl is used, the oxygen produced from KMnO4 + HCl is
thiosulphates to sulphates. partly used up to oxidize Hcl to chlorine and in case HNO3
is used, it itself acts as oxidizing agent and partly oxidizes
2KMnO 4  3H 2SO4  5KNO2 
o K 2SO4  2MnSO4 
the reducing agent.
3H 2 O  5KNO3 (ii) It is used as a strong oxidising agent in the laboratory as
well as in industry. It is a favourite and effective oxidising
(iv) It oxidises oxalates or oxalic acid to CO2
agent used in organic synthesis Alkaline potassium
2KMnO 4  3H 2SO4  5C2 H 2 O 4 
o K 2 SO4  2MnSO 4  permanganate is used for testing unsaturation in organic
chemistry and is known as Baeyer’s reagent.
8H 2 O  10 CO 2 (iii) Potassium permanganate is also widely used as a
(v) It oxidises ferrous sulphate to ferric sulphate (i.e., ferrous disinfectant and germicide. A very dilute solution of
salt to ferric salt). permanganate is used for washing wounds and gargling
for mouth sore. It is also used for purifying water of
2KMnO 4  8H 2SO4  10FeSO4 
o K 2SO4  2MnSO 4  stinking wells.
(iv) Because of its strong oxidizing power, it is also used for
5Fe2 SO4 3
 8H 2 O
bleaching of wool, cottong, silk and other textile fibres
(vi) It oxidises H2O2 to H2O and O2. This is because acidified and also for decolourisation of oils.
KMnO4 is a stronger oxidising agent than H2O2.

2KMnO 4  3H 2SO4  5H 2 O2 
o K 2SO4  2MnSO4 

8H 2 O  5O 2
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d AND f BLOCK ELEMENTS 149

THE LANTHANIDE SERIES

1. INTRODUCTION

These elements are classified by the filling up of the

antipenultimate 4f energy levels.

2. PHYSICAL PROPERTIES

Electronic Configuration and oxidation states

Element Electronic Electronic Oxidation States
Configuration Configuration of M3+

Lanthanum La [Xe] 5d1 6s2 [Xe] +3

Cerium Ce [Xe] 4f1 5d1 6s2 [Xe] 4f 1 +3 (+ 4)

Praseodymium Pr [Xe] 4f 3 6s2 [Xe] 4f 2 +3 (+ 4)

Neodymium Nd [Xe] 4f 4 6s2 [Xe] 4f 3 (+2) +3

Promethium Pm [Xe] 4f 5 6s2 [Xe] 4f 4 (+2) +3

Samarium Sm [Xe] 4f 6 6s2 [Xe] 4f 5 (+2) +3

Europium Eu [Xe] 4f 7 6s2 [Xe] 4f 6 (+ 2) +3

Gadolinium Gd [Xe] 4f 7 5d1 6s2 [Xe] 4f 7 +3

Terbium Tb [Xe] 4f 9 6s2 [Xe] 4f 8 +3 (+ 4)

Dysprosium Dy [Xe] 4f 10 6s2 [Xe] 4f 9 +3 (+ 4)

Holmium Ho [Xe] 4f 11 6s2 [Xe] 4f 10 +3

Erbium Er [Xe] 4f 12 6s2 [Xe] 4f 11 +3

Thulium Tm [Xe] 4f 13 6s2 [Xe] 4f 12 (+ 2) +3

Ytterbium Yb [Xe] 4f 14 6s2 [Xe] 4f 13 (+ 2) +3

Lutetium Lu [Xe] 4f14 5d1 6s2 [Xe] 4f 14 +3

2.1 Oxidation state Oxidation numbers (+II) and (+IV) do occur, particularly
when they lead to :
The sum of the first three ionization energies for each element
are low. Thus the oxidation state (+III) is ionic and Ln3+
1. a noble gas configuration e.g. Ce4+ (f 0)

dominates the chemistry of these elements. The Ln2+ and 2. a half filled f shell, e.g. Eu2+ and Tb4+ (f7)
Ln4+ ions that do occur are always less stable than Ln3+. 3. a completely filled f level, e.g. Yb2+ (f14).

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 150 d AND f BLOCK ELEMENTS

As we move along the lanthanide series, the nuclear charge

NOTE increases by one unit at each successive element. The new
electron is added into the same subshell (viz., 4f). As a result,
The 4f electrons in the antipenultimate shell are very the attraction on the electrons by the nucleus increases and
effectively shielded from their chemical environment this tends to decrease the size. Further, as the new electron
outside the atom by the 5s and 5p electrons. Consequently is added into the f-subshell, there is imperfect shielding of
the 4f electrons do not take part in bonding. They are one electron by another in this subshell due to the shapes
neither removed to produce ions nor do they take any of these f-orbitals. This imperfect shielding is unable to
significant part in crystal field stabilization or complexes. counterbalance the effect of the increased nuclear charge.
Crystal field stabilization is very important with the d- Hence, the net result is a contraction in the size though the
block elements. The octahedral splitting of f orbitals 'o is decrease is very small. It is interesting to note that in
only about 1kJ mol–1. Whether the f orbitals are filled or lanthanides, the decrease in the atomic radius for 14 elements
empty has little effect on the normal chemical properties. [Ce (58) to Lu (71)] is only 11pm (from 183 to 172 pm).
However, it does affect their spectra and their magnetic Similarly, decrease in ionic radii from Ce3+ to Lu3+ is only
properties. 17 pm (103 to 86 pm)
The contraction is similar to that observed in any transition
series. The cause is also similar, just as in the transition
2.2 Atomic radius
series where the contraction is due to imperfect shielding of
In lanthanide series, with increasing atomic number, there is one d electron by another. But the shielding of one 4f electron
a progressive decrease in the atomic as well as ionic radii of by another is less than one d electron by another with
increase in nuclear charge along the series.
trivalent ions from La3+ to Lu3+. This regular decrease in the
atomic and ionic radii with increasing atomic number is
known as lanthanide contraction.

Atomic and Ionic radii (pm) of lanthanum and lanthanoids.

Element La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Atomic Radii (Ln) 187 183 182 181 181 180 199 180 178 177 176 175 174 173 172

Ionic Radii (Ln3+) 106 103 101 99 98 96 95 94 92 91 90 89 88 87 86

2.3 Magnetic behaviour calculated by considering spin as well as orbital contribution,

i.e,
Paramagnetism is shown by the positive ions of lanthanides
except La3+ (lanthanum ion, f0) and Lu3+ (lutetium ion, f14). P eff 4 S (S  1)  L (L  1) B.M.
This property of the lanthanides is due to presence of where S is spin quantum number and L is orbital quantum
unpaired electrons in the incomplete 4f subshell. number.
lanthanides differ from transition elements in the fact that
their magnetic moments do not obey ‘spin only’ formula, NOTE

viz., P eff n ( n  2) B.M. where n is the number of Separation of the Lanthanide Elements
unpaired electrons. This because in case of transition Since the change in ionic radius is very small, the chemical
elements, the orbital contribution is quenched by the electric properties are similar. This makes the separation of the
field of the environment but in case of lanthanides, 4f orbitals element in pure state difficult. Separation is done by Ion
lie to deep to be quenched. Hence, their magnetic moment is Exchange methods which is based on the ionic size.

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d AND f BLOCK ELEMENTS 151

2.4 Colour
93 Neptunium Np 5f 4 6d1 7s2
The Lanthanides are silvery white metals. However, most of
+3, +4, +5,+ 6, +7
the trivalent metal ions are coloured, both in the solid state
and in aqueous solution. This is due to the partly filled-f- 94 Plutonium Pu 5f 6 7s2 +3, +4, +5, +6, +7
orbitals which permit f-f transition.
95 Americium Am 5f 7 7s2 +2, +3, +4, +5, +6
NOTE 96 Curium Cm 5f 7 6d1 7s2 +3, +4
Lanthanides ions with x f electrons have a similar colour 97 Berkelium Bk 5f 9 7s2 +3, +4
3+ 3+
to those with (14–x) f electrons e.g., La and Lu are
98 Californium Cf 5f 10 7s2 +2, +3
colourless, Sm and Dy are yellow and Eu and Tb3+
3+ 3+ 3+

are pink. 99 Einsteinium Es 5f 11 7s2 +2, +3

100 Fermium Fm 5f 12 7s2 +2, +3

2.5 Hydroxides 101 Mendelevium Md 5f 13 7s2 +2, +3
The hydroxides Ln(OH)3 are precipitated as gelationous 102 Nobelium No 5f 14 7s2 +2 ,+3
precipitates by the addition of NH4OH to aqueous solutions.
103 Lawrencium Lr 5f14 6d1 7s2 +3
These hydroxides are ionic and basic. They are less basic
than Ca(OH)2 but more basic than Al(OH) 3 which is 104 Rutherfordium Rf 4f14 6d2 7s2
amphoteric. The metals, oxides and hydroxides all dissolve
in dilute acids, forming salts. Ln(OH)3 are sufficiently basic
to absorb CO2 from the air and form carbonates. The basicity 1. OXIDATION STATE
decreases as the ionic radius decreases from Ce to Lu. Thus
Ce(OH)3 is the most basic, and Lu(OH3), which is the least Unlike Lanthanides, Actinides show a large number of
basic, is intermediate between Scandium and Yttrium in basic oxidation states. This is because of very small energy gap
strength. The decrease in basic properties is illustrated by between 5f, 6d and 7s subshells. Hence, all their electrons
the hydroxides of the later elements dissolving in hot can take part in bond formation. The dominant oxidation
concentrated NaOH, forming complexes. state of these element is +3 (similar to Lanthanides). Besides
+3 state, Actinides also exhibit an oxidation state of +4.
Yb(OH)3 + 3NaOH o 3Na+ + [Yb(OH)6]3– Some Actinides show still higher oxidation states. The
maximum oxidation state first increases upto the middle of
Lu(OH)3 + 3NaOH o 3Na+ + [Lu(OH)6]3– the series and then decreases, e.g., it increases from + 4
from Th to +5, +6, and +7 for Pa, U and Np but decreases in
ACTINIDES SERIES the succeeding elements.
The Actinides resemble Lanthanides in having more
The elements and their Oxidation States compounds in +3 state than in the +4 state. However, the
compounds in the +3 and +4 state tend to undergo
Atomic Element Symbol Outer Oxidation hydrolysis.

electronic states* Further, it may be noted that in case of Actinides, the distribution
of oxidation states is so uneven that it is of no use to discuss their
structure chemistry in terms of their oxidation states.

89 Actinium Ac 6d17s2 +3 2. ATOMIC RADIUS

90 Thorium Th 6d2 7s2 +3, +4 The Actinides show Actinide contraction (very much like
Lanthanide contraction) due to poor shielding effect of the
91 Protactinium Pa 5f 2 6d1 7s2 +3, +4, +5 5f-electrons. As a result, the radii of the atoms or ions of
these metals decrease regularly across the series. The
92 Uranium U 5f 3 6d1 7s2 +3, +4, +5, +6 contraction is greater from element to element in this series
due to poorer shielding by 5f electrons. This is because 5f
orbitals extend in space beyond 6s and 6p orbitals whereas
4f orbitals are buried deep inside the atom.
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 152 d AND f BLOCK ELEMENTS

Differences :
3. MAGNETIC BEHAVIOUR
The show differences in some of their characteristics as
Like Lanthanides, the Actinides elements are strongly follows :
paramagnetic. The variation in magnetic susceptibility of
Lanthanides Actinides
Actinides with the increasing number of unpaired electrons
is similar to that of Lanthanides but the values are higher (i) Besides + 3 oxidation state (i) Besides +3 oxidation state,
for the Actinides than the Lanthanides.
they show + 2 and +4 oxi- they show higher oxidation
4. COLOUR dation states only in few states of +4, +5, +6, + 7 also.
cases.
These metals are silvery white. However, Actinide cations
are generally coloured. The colour of the cation depends (ii) Most of their ions are (ii) Most of their ions are
upon the number of 5f-electrons. The cations containing colourless coloured
no 5f-electron or having seven 5f-electrons (i.e., exactly (iii) They have less tendency (iii) They have greater tendency
half-filled f-subshell) are colourless. The cations containing towards complex formation towards complex formation.
2 to 6 electrons in the 5f-subshell are coloured both in the
crystalline state as well as in aqueous solution. The colour (iv) Lanthanides compounds are (iv) Actinides compounds are
less basic. more basic
arises due to f–f transition e.g. Ac3+ (5f 0) = colourless, U3+
(5f 3) = Red, Np3+ (5f 4) = Blue, Pu3+ (5f 5) = Voilet, Am3+ (v) Do not form oxocation (v) From oxocations e.g.
6 3+ 7 3+ 0
(5f ) = Pink, Cm (5f ) = Colourless, Th (5f ) = Colourless UO22 , PuO22 and UO+
as so on.
(vi) Except promethium, they (vi) They are radioactive.
COMPARISON OF LANTHANIDES AND are non-radioactive
ACTINIDES
(vii) Their magnetic properties (vii) Their magnetic properties
Similarities : can be explained easily. cannot be explained easily,
as they are more complex.
As both Lanthanides and actinides involve filling of f-
orbitals, they show similarities in many respects as follows :
(i) Both show mainly an oxidation state of +3.
(ii) Both are electropositive and very reactive.
(iii) Both exhibit magnetic and spectral properties.
(iv) Actinides exhibit Actinide contraction like Lanthanide
contraction shown by Lanthanides.

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 d AND f BLOCK ELEMENTS 153

IMPORTANT COMPOUNDS OF TRANSITION ELEMENTS

1. ZINC SULPHATE (ZnSO4. 7H2O ­ WHITE VITRIOL) II. REACTIONS :

(a) ZnO + 2HCl ZnCl2 + H2O
I. PREPARATION :
(dil/conc.)
ZnCO3 + H2SO4 o ZnSO4 + H2O + CO2
(b) ZnO + HNO3 Zn (NO3)2 + H2O
II. REACTIONS :
(dil/conc.)
(a) ZnSO4  2H 2 O 
o Zn(OH)2  H2SO4
white ppt (c) ZnO + 2NaOH Na2ZnO2 + H2O
(d) ZnO + 2KOH K2ZnO2 + H2O
NaOH (e) ZnO + CoO CoZnO 2
( Rinmann 's green )

III. USES :
Na 2 ZnO 2  Na 2 SO 4  H 2 O
(sodium zincate) (i) As a white paint (It does not get tranished even in
presence of H2S because Zns is also white)
(b) ZnSO4.7H2O ZnSO4.6H2O ZnSO4 (ii) For preparing Rinmann’s green (Green Paint)
(iii) As catalyst for preparation of methyl alcohol
(iv) For making soft rubber
(v) For making cosmetic powders, creams and in
medicine

3. ZINC CHLORIDE ZnCl2.2H2O

(c) ZnSO4 + NH4OH o Zn (OH)2 + (NH4)2 SO4
Anhydride of zinc chloride cannot be obtained by
heating its aqueous salt.
I. PREPARATION :
(a) ZnO + 2HCl ZnCl2 + H2O
[Zn(NH3)4]SO4
(b) Zn + HgCl2 ZnCl2 + Hg
(d) Lithopone (ZnS + BaSO4) used as a white pigment.
II. PROPERTIES :
2. ZINC OXIDE, ZNO (CHINESE WHITE OR
(a) ZnCl2 + H2S o ZnS + 2HCl
PHILOSPHER’S WOOL) (b) ZnCl2 + 2NaOH o Zn(OH)2 + 2NaCl
It found in nature as zincite or red zinc ore. Zn(OH)2 + 2NaOH o Na2ZnO2 + 2H2O
I. PREPARATION : (c) ZnCl2 + 2NH4OH o Zn(OH)2 + 2NH4Cl
(a) 2Zn + O2 2ZnO

(b) ZnCO3 ZnO + CO2

(c) 2Zn(NO3)2 2ZnO + 4NO2 + O2

[Zn(NH3)4] Cl2 + 4H2O

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 154 d AND f BLOCK ELEMENTS

(b) Fe2O3 + 6HCl 2FeCl3 + 3H2O

4. FERROUS SULPHATE (FeSO4. 7H2O ­ GREEN
III. USES :
VITRIOL)
(i) As a red pigment
I. PREPARATION :
(ii) As abrasive polishing powder
(a) FeS + H2SO4 o FeSO4 + H2S n
(iii) As catalyst
'
(b) Fe  H 2SO 4 o FeSO 4  H 2 n
dil.
6. FERRIC CHLORIDE, FeCl3
2FeS2 + H2O + 7O2 o 2FeSO4 + 2H2SO4
It is known in anhydrous and hydrated form. It is a red
(Commercial preparation)
deliquiscent solid.
II. REACTIONS :
I. PREPARATION :
'
(a) 2 FeSO 4 o Fe 2 O 3  SO 2  SO 3 (a) 12FeCl2 (anhydrous) + 3O2 Fe2O3 + 8FeCl3
(light green) (brown) (anhydrous)

(b) Fe 2  [Fe (CN) 6 ]3 

o Fe3 [Fe (CN)6 ]2 II. REACTIONS :
Turnbull's blue
(used as pigment in ink and paint)
(a) 2FeCl3 2FeCl2 + Cl2
Or Fe4 [Fe (CN)6]3
(b) FeCl3 + 3NH4OH Fe(OH)3 + 3NH4Cl
(Prussian blue)
(Reddish brown)
(c) NO3 detection :
(c) 4FeCl3 + 3K4Fe(CN)6 Fe4 [Fe(CN)6 ]3 + 12 KCl
NO3
Prussian Blue
FeSO4 + + Conc. H2SO4 o [Fe(H2O)5 NO] SO4
.
Brown ring

(d) 2FeCl3 + 6NH4CNS Fe[Fe(CNS)6 ]  6NH4Cl

Deep red colour
(d) FeSO4 + 2KCN o Fe(CN)2 + K2SO4
brown Deep red colouration is produced due to formation
of complex.
(e) Till 750ºC it exists as its dimer Fe2Cl6.

4 6

2+ 3+ –
(e) 2Hg Cl2 + 2Fe o Hg 2Cl2 + 2Fe + 2Cl
white III. USES :
(f) FeSO4 + H2O2 o Fenton’s reagent for oxidation of (i) Its alcoholic solution is medicine, name (Tincture
alcohols to aldehydes ferri perchloride)
(g) FeSO4. (NH4)2 SO4. 6H2O o Mohr’s salt (ii) For detection of acetates and phenols
(iii) For making prussion blue & as an oxidising agent

5. FERRIC OXIDE, Fe2O3 7. COPPER SULPHATE

(CuSO4. 5H2O ­ BLUE VITRIOL)
I. PREPARATION :

(a) 2FeSO4 Fe2O3 + SO2 + 3SO3

I. PREPARATION :
II. REACTIONS:
(a) CuO  H 2SO 4 o CuSO 4  H 2O
(a) Fe2O3 + 2NaOH H2O + 2NaFeO2
(b) Cu(OH)2.CuCO3 + 2H2SO4 o 2CuSO4 + 3H2O + CO2
(sodium ferrite) Malachite Green
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 d AND f BLOCK ELEMENTS 155

Copper scrape ,,, USES :

Cu + H2SO4 + ½O2 (air) o CuSO4 + H2O (1) Bordeaux Mix o CuSO4 + CaO
(Commerical preparation) (to kill fungi)
II. REACTIONS :
8. CUPRIC OXIDE, CuO
(a) Effect of heat
It is called black oxide of copper and is found in nature as tenorite.
100 º C 230 º C
CuSO 4 .5H 2 O o CuSO 4 .H 2O o
I. PREPARATION :
pale blue. (a) By heating Cu2O in air or by heating copper for a
long time in air (the temperature should not exceed
CuSO4 o
750º
CuO  SO3
white above 1100ºC)
2Cu2O + O2 4CuO (black)
(b) [CuSO 4  KI o CuI 2  K 2 SO 4 ] u 2
2Cu + O2 2CuO
(Unstable
dirty white) (b) 2Cu(NO3)2 2CuO + 4NO2 + O2

2CuI 2 o Cu 2 I 2  I 2 (c) On a commercial scale, it is obtained by heating

white ppt.
malachite which is found in nature.
2CuSO4 + 4KI o Cu2I2 + 2K2SO4 + I2 CuCO3 . Cu(OH)2 2CuO + CO2 + H2O
2+
(c) Test of Cu II. REACTIONS :

CuSO 4  NH 4 OH o Cu (OH ) 2  ( NH 4 ) 2 SO 4 (a) When heated to 1100–1200ºC, it is converted into

 
cuprous oxide with evolution of oxygen.
4CuO 2Cu2O + O2

(Black) (Red)

Uses : Used to impart blue and green colour to glazes and glass.

9. CUPRIC CHLORIDE, CuCl2.2H2O

Schwitzer’s reagent I. PREPARATION :
(Deep blue solution) (a) CuO + 2HCl CuCl2 + H2O
Cu(OH)2 CuCO3 + 4HCl 2CuCl2 + 3H2O + CO2
(d) CuSO 4  KCN o Cu (CN) 2  K 2SO 4
(b) CuCl2 . 2H2O CuCl2 + 2H2O
2Cu (CN ) 2 o Cu 2 (CN ) 2  (CN ) 2 n
cyanogen gas II. REACTIONS :
(a) The anhydrous salt on heating forms Cu2Cl2 and Cl2
Cu 2 (CN)2  KCN o K 3 [Cu(CN)4 ]
excess 2CuCl2 Cu2Cl2 + Cl2

(e) CuSO4  K 4 [Fe(CN)6 ] o Cu2 [Fe(CN)6 ]  K 2SO4

Chocolate brown ppt. 3CuCl2. 2H2O CuO + Cu2Cl2 + 2HCl

(f) CuSO4 + H2S o CuS + H2SO4 + Cl2 + 5H2O

( black ppt .)

Dilute solution of CuCl2 is blue but concentrated solution

(g) In Fehling’s test & Benedict’s test
is green. Its dilute solution on adding HCl becomes yellow.
Aldehyde  Cu 2 o Cu 2O p  acid [Cu(H2O)4]2+ o Blue
( red ppt.)
On adding HCl o [CuCl4]2– o green
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 156 d AND f BLOCK ELEMENTS

(g) AgNO3 + 2NH4OH o Ag 2 O  2 NH 4 NO 3  H 2O

10. AgNO3 (LUNAR CAUSTIC) ( brown ppt .)

I. Preparation :

'
(a) 3Ag  4 HNO3 o 3AgNO3  NO  2H 2O
Colourless crystal
2[Ag(NH3)2] NO3 + 3H2O
II. REACTION :
(h) Ammonical AgNO3 o Tollen’s reagent used to test
' aldehydes
(a) 2AgNO3 o 2Ag  2NO 2  O 2
red hot

(i) It converts glucose to gluconic acid.

! 212º C
(b) 2AgNO 3 T o 2AgNO 2  O 2
Ag 2O  C6 H12O 6 
o 2Ag  C 6 H12 O7

(c) AgNO3 

KCN
o AgCN 
KCN
oK [Ag(CN)2 ] (j) It oxidises formaldehyde to formic acid
white ppts. soluble
Potassium
Dicyanidoargentate(I) Ag 2 O  HCHO 
o 2Ag  HCOOH

2 AgNO3  Na 2S2 O3 o Ag 2S2O3  2 NaNO3 Very dilute solution of AgNO3 is used as dental antiseptic.
(d) (limited) white ppt .
(k) Ag2O + H2O2 o 2Ag + H2O + O2
White ppt. of Ag2S2O3 which gracdually changes
11. SILVER BROMIDE, (AgBr)
Ag 2S2 O 3  H 2O o Ag 2S  H 2SO 4
black I. PREPARATION :
(e) AgNO3  Na 2S2 O 3 o Ag 2S2 O3  2NaNO 3 It is prepared by the reaction of silver nitrate with a soluble
bromide.

AgNO3  NaBr 
o AgBr  NaNO3

II. PROPERTIES
(a) It is a pale yellow solid. It is insoluble in water and
concentrated acids. It is partially soluble in strong solution
Sodium argentothic sulphate.
of ammonium hydroxide due to complex formation.
It is used in photography.
AgBr  2NH 4 OH 
o Ag(NH 3 ) 2 Br  2H 2 O
(b) On heating, it melts to a red liquid.
(c) It is most sensitive to light. It undergoes photoreduction.
(f) Light
2AgBr  o 2Ag  Br2
(d) It dissolves in potassium cyanide.

AgBr  2KCN 
o KAg(CN) 2  KBr
Potassium argento-
cyanide (Soluble)

(e) It dissolves in sodium thiosulphate.

AgBr  2Na 2S2 O3 

o Na 3 [Ag(S2 O3 )2 ]  NaBr
Sodium argento-
thiosulphate (Soluble)

(f) AgBr is reduced to silver, when treated with zinc and

dilute H2SO4.

Zn  H 2SO 4 
o ZnSO 4  2H

2AgBr  2H 
o 2Ag  2HBr
Mahesh Tutorials Science
d AND f BLOCK ELEMENTS 157

All above reactions are also observed in the case of

AgCl. However, it is white and fairly soluble in ammonium II. REACTION :
hydroxide. It is sensitive to light. (a) KI  HgCl 2 o KCl  HgI 2
red ppts .
III. USES :
It is used for making photographic films and plates because (b) HgI 2  KI o K 2 HgI 4
it is sensitive to light. colourless

Basic solution of K2HgI4 (K2HgI4 + KOH) is called as

12. MERCURY CHLORIDES Nessler’s Reagent.
(c) Test for ammonium ion
12.1 Mercurous Chloride (Hg2 Cl2 - Calomel)

I. PREPARATION : K 2 HgI 4  NH 4 Cl o NH 2 HgOHgI  KCl

Brown ppt.

2HgCl 2  SnCl 2 o Hg 2 Cl 2  SnCl 4

II. REACTIONS :

Hg 2 Cl2  SnCl2 o 2Hg  SnCl4

(a) black /
grey

(b) '
Hg2Cl2 o HgCl2 + Hg (grey deposit) Iodide of Millon’s Base

(c) Hg2Cl2 + 2NH3 o Hg  Hg( NH 2 )Cl  NH 4Cl (d) HgCl2 + 2NH3 o Hg( NH 2 )Cl + NH4Cl
  
 

black white

(e) HgCl2 + Cu o CuCl2 + Hg (grey deposit)

12.2 Mercuric Chloride (Hg Cl2 - Corrosive sublimate)
(f) HgCl2 is sparingly soluble in cold H2O but readily in hot
I. PREPARATION : water.
It is highly corrosive, poisonous and hence is called as
corrosive sublimate.

(a) Hg  2Cl aqua regia o HgCl2

SnCl2  2HgCl2 o Hg 2Cl2 p  SnCl4

(b) white ppts.

Hg 2Cl2  SnCl2 o 2Hg  SnCl4

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 158 d AND f BLOCK ELEMENTS

SOLVED EXAMPLES
Example - 1 Reason : d4 o d5 occurs in case of Cr2+ to Cr3+.
10
Silver atom has a completely filled d orbitals (4d ) in
But d6 od5 occurs in case of Fe2+ to Fe3+. In a medium (like
its ground state. How can you say that it is a transition water) d3 is more stable as compared to d5.
element ?

Sol. Silver (Z = 47) can exhibit +2 oxidation state wherein it will Example - 8
have incompletely filled d-orbitals (4d), hence a transition Calculate the ‘spin only’ magnetic moment of M(aq)2+ ion
metal. (Z = 27).
Example - 2
Sol. Atomic number (27) = [Ar]3d7 4s2
In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of
n=1
atomisation of zinc is the lowest i.e., 26, kJ mol. Why ?

Sol. In the formation of metallic bonds no electrons from 3d- P n n2

orbitals are involved in case of zinc, while in all other
metals of the 3d series, electrons from the d-orbitals are
1u 3 1.73 BM.
always involved in the formation of metallic bonds.
Example - 9
Example - 3
Which of the 3d series of the transition metals exhibits Explain why Cu+ ion is not stable in aqueous solutions ?
the largest number of oxidation states and why ? Sol. Cu+ in aqueous solution undergoes disproportionation
i.e.,
Sol. Manganese (Z = 25), as it atoms has the maximum number
of unpaired electrons.
2Cu  aq 
o Cu 2 aq  Cu s
Example - 4
The Eo, value for this is favourable.
o 2+
The E (M /M) value for copper is positive (+0.34 V).
What is possibility the reason for this ? Example - 10
Sol. Copper has high 'aHo and low 'hyd Ho. Actinoid contraction is greater from element to element
than lanthanoid contraction. Why ?
Example - 5 Sol. The 5f electrons are more effectively shielded from nuclear
How would you account for the irregular variation of charge. In other words, the 5f electrons themselves provide
ionisation enthalpies (first and second) in the first series poor shielding from element to element in the series.
of the transition elements ?
Example - 11
Sol. Irregular variation of ionisation enthalpies in mainly
On what ground can you say that scandium (Z = 21) is a
attributed to varying degree of stability of different 3d-
transition element but zinc (Z = 30) is not ?
configurations (e.g., d0, d5, d10 are exceptionally stable).
Sol. On the basis of incompletely filled 3d orbitals in case of
Example - 6 scandium atom is its ground state (3d1), it is regarded as a
Why is the highest oxidation state of a metal exhibited transition element. On the other hand, zinc atom has
in its oxide or fluoride only ? completely filled d orbitals (3d10) in its ground state as
well as in its oxidised state, hence it is not regarded as a
Sol. Because of small size and high electronegativity oxygen transition elements.
or fluorine can oxide the metal to its highest oxidation
state. Example - 12
Why Cr and Cu show exceptional configuration ?
Example - 7
Sol. By deviating from normal configuration, Cr and Cu acquires
Which is a stronger reducing agent Cr2+ or Fe2+ and
half-filled and fully filled configurations which gives them
why ? extra stability. Hence they show exceptional configuration.
Sol. Cr2+ is strong reducing agent than Fe2+. Cr o[Ar] 3d5 4s1 and Cu o[Ar] 3d10 4s1
Mahesh Tutorials Science
 d AND f BLOCK ELEMENTS 159

Example - 13 series (i.e., Cu and Zn). Thus electronic configuration, to

large extent, the existence and stability of oxidation states.
Why are Zn, Cd and Hg softer and volatile metals ?
The other factors which determine stability of oxidation
Sol. Due to their completely filled d-orbitals, they have weak state are:
metallic bonding and least compact packing therefore they
(i) Enthalpy of atomisation (ii) Ionisation energy
all are volatile in nature.
(iii) Enthalpy of solvation (iv) E.N. of other element.
Example - 14
Example - 16
Explain briefly how +2 state becomes more an more
What may be the stable oxidation state of the transition
stable in the first half of the first row transition elements
element with the following d electron configurations in
with increasing atomic number ?
the ground state of their atoms : 3d3, 3d5, 3d8 and 3d4 ?
Sol. In transition elements, there are greater horizontal
Sol. The stable oxidation state of transition element with the d
similarities in the properties in constrast to the main group
electron configuration in ground state of atoms are as
elements because of similar ns2 common configuration of
follows :
the outermost shell.
An examination of common oxidation states reveals that
excepts scandium, the most common oxidation state of
first row transition elements is +2 which arises from the
loss of two 4s electrons. This means that after scandium,
d-orbitals become more stable than the s-orbital.
Further, +2 state becomes more an more stable in the first
half of first row transition elements with increasing atomic
number because 3d orbitals acquire only one electron in It should be noted that lower stable oxidation state
each of five 3d orbitals (i.e. remains half filled) and electronic generally leads to ionic bond and higher oxidation state
repulsion is the least and nuclear charge increases. In 2nd corresponds to covalent bond.
half of first row transition elements, electrons starts pairing
up in 3d orbitals. (Ti2+ to Mn2+ electronic configuration Example - 17
changes from 3d2 to 3d5 but in 2nd half i.e. Fe2– to Zn2+ it Name the oxometal anions of the first series of the
changes from d6 to d10). transition metals in which the metal exhibits the
oxidation state equatl to its group number.
Example - 15
To what extent do the electronic configurations decide the Sol.
stability of oxidation states in the first series of the
transition elements ? Illustrate your answer with example.

Sol. One of the main characteristic of a transition element is

that it can show large variety of oxidation states in its
compounds. It is due to its characteristic electronic
configuration i.e., (n – 1) d and ns electrons take part in
bond formation either by loosing or by sharing of electrons
with other combining atoms. Example - 18
The stability of oxidation state depends mainly on What is lanthanoid contraction ? What are the
electronic configuration and also on the nature of other consequences of lanthanoid contraction ?
combining atom.
Sol. A group of fourteen elements following lanthanum i.e.
The elements which show largest number of oxidation from58Ce to71 Lu placed in 6th period of long form of periodic
states occur in or near the middle of series (i.e., 4s23d3 to talbe is known as lanthanoids (or lanthanide series). These
4s 23d 7 configuration). For example, Mn exhibits all fourteen elements are represented by common general
oxidation states from +2 to +7 as it has 4s 2 3d 5 symbol ‘Ln’. In these elements, the last electron enters the
configuration. The lesser number of oxidation states at 4f-subshells (pre pen ultimate shell). It may be noted that
extreme ends arise from either too few electrons to loose atoms of these elements have electronic configuration with
or share (e.g. Sc and Ti) or too many d electrons (hence 6s2 common but with variable occupancy of 4f level. However,
fewer orbitals available in which to share electrons with the electronic configuration of all the tripositive ions (the
others) for higher elements at upper end of first transition most stable oxidation state of all lanthanoids) are of the form
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 160 d AND f BLOCK ELEMENTS
4f n(n = 1 to 14) with increasing atomic number). These (vii) These metals form various alloys with other metals of the
elements constitute one of the two series of inner transition series.
elements or f-block.
(viii) These metals form interstitial compounds with C, N, B and
Lanthanoid contraction : In the lanthanoide series with H.
the increase in atomic number, atomic radii and ionic radii
decrease from one elements to the other, but this decrease The presence of partially filled d-orbitals in the electronic
is very small. the regular small decrease in atomic radii and configuration of atomic and ionic species of these elements
ionic radii of lanthanides with increasing atomic number is responsible for the characteristic properties of transition
along the series is called lanthanoid contraction. elements. They are called transition elements because of
their position in the periodic table. These elements lie in
Cause of lanthanoid contraction: When one moves from the middle of periodic table between s and p-block (i.e.,
58
Ce to 71Lu along the lanthanide series nuclear charge between group 2 and group 13). A transitio element may
goes on increasing by one unit every time. Simultaneously be defined as a element whose atom or at least one of its
an electron is also added which enters to the inner f simple ions contain partially filled d-orbitals, e.g., iron,
subshell. The shielding effect of f-orbitals in very poor copper, chromium, nickel etc.
due to their diffused shape. It results in the stronger force
of nuclear attraction of the 4f electrons and the outer The general characteristic electronic configuration may
electrons causing decrease in size. be written as (n – 1) d1–10ns1–2.

Consequences of lanthanoid contraction: The elements of group 12 i.e., Zinc, Cadmium, and Mercury
are generally not regarded as transition elements as their
(i) Similarly in the properties of elements of second and third atoms and all ions formed have completely filled d-orbitals
transition series e.g. Sr and Hf; Nb and Ta; Mo and W. i.e., these do not have partially filled d-orbitals in atomic
This resemblance is due to the similarity in size due to the state or common oxidation state (Zn2+, Cd2+, Hg2+)
presence of lanthanoids in between.
Zn (30) = [Ar] 4s23d10 Zn2+ = [Ar] 3d10 4s0
(ii) Similarity among lanthanoids : Due to the very small change
in sizes, all the lanthanoids resemble one another in Cd (48) = [Kr] 5s2 4d10 Cd2+ = [Kr] 4d10 5s0
chemical properties. Hg (80) = [Xe] 6s2 5d10 Hg2+ = [Xe] 5d10 6s0
(iii) Decrease in basicity : With the decrease in ionic radii,
covalent character of their hydroxides goes on increasing Example - 20
from Ce(OH)3 to Lu(OH)3 and so base strength goes on In what way is the electronic configuration of the
decreasing. transition elements different from that of the non-
transition elements ?
Example - 19
Sol. Transition elements have incomplete penultimate d-orbitals
What are the characteristics of the transition elements while penultimate orbitals of representative elements (s -
and why are they called transition elements ? Which of and p - block elements) are completely filled up. The
the d-block elements may not be regarded as the general valence shell configuration of s-block (group 1
transition elements? and 2) elements is ns1–2 and for p-block elements (group
Sol. The important characteristics of transition metals are: 13 to 18) is ns2 np1–6. The valence shell configuration of
transition elements can be written as (n – 1) d1–9 ns1–2 .
(i) All transition elements are metallic in nature, e.g., all are
metals. Example - 21

(ii) These metals exhibit variable oxidation states. Explain giving reasons :

(iii) Transition metal atoms or ions generally form the Sol.

complexes with neutral, negative and positive ligands. (i) Transition metals and many of their compounds show
(iv) Compounds of transition metals are usually coloured. paramagnetic behaviour.

(v) The compounds of these metals are usually paramagnetic (ii) The enthalpies of atomisation of the transition metals are
in nature. high.

(vi) Transition metals and their compounds act as good (iii) The transition metals generally form coloured compounds.
catalysts, i.e., they show catalytic activities. (iv) Transition metals and their many compounds act as good
catalyst.
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 d AND f BLOCK ELEMENTS 161

Example - 22 Example - 24
What are interstitial compounds ? Why are such Describe the preparation of potassium dichromate from
compounds well known for transition metals ? iron chromite one. What is the effect of increasing pH
on a solution of potassium dichromate ?
Sol. Interstitial compounds are those which are formed when
small atoms like H, C, N, B etc. are trapped inside the Sol. The following steps are involved in preparation of K2Cr2O7
crystal lattices of metals. They are generally non- from iron chromite (FeCr2O4) ore :
stoichiometric and neither typically ionic nor covalent. (i) Preparation of sodium chromate : The chromite ore
(FeO.Cr2O3) is finely powdered and mixed with sodium
Most of transition metals form interstitial compounds with carbonate and quick lime and then heated to redness in a
small non-metal atoms such as hydrogen, boron, carbon reverberatory furnace with free supply of air.
and nitrogen. These small atoms enter into the void sites 4FeO.Cr2O3 + O2 o 2Fe2O3 + 4Cr2O3
between the packed atoms of crystalline transition metals. [4Na2CO3 + 2Cr2O3 + 3O2 o 4Na 2CrO4 + 4CO2] × 2

For Example, steel and cast iron become hard by forming 4FeO.Cr2O3 + 8Na 2CO3 + 7O2 o 8Na2CrO4 + 2Fe2O3 + 8CO2
interstitial compound with carbon.
The mass is then extracted with water, when sodium
The exsitence of vacant (n – 1) d orbitals in transition chromate is completely dissolved while Fe2O3 is left
elements and their ability to make bonds with trapped small behind.
atoms in the main cause of interstitial compound formation. (ii) Conversion of sodium chromate into sodium dichromate
Other examples are : VH 0.5 6 , TiH 1. 7. Some main (NaCr2O7) : The sodium chromate extracted with water in
characteristics of these compounds are : previous step is acidified.

(i) They have high melting and boiling points, higher than 3Na2CrO4 + H2SO4 o Na2Cr2O7 + Na2SO4 + H2O
those of pure metals.
On cooling Na2SO4 separates out as Na2SO4. 10H2O and
(ii) They are very hard. Some borides of transition elements Na2Cr2O7 is remains in solution.
approach diamond in hardness. (iii) Conversion of Na2Cr2O7 into K2Cr2O7 : The solution
containing Na2Cr2O is treated with KCl
(iii) They are chemically inert but retain metallic conductivity.
Na2Cr2O7 + KCl o K2Cr2O7 + 2NaCl
Example - 23
Sodium chloride (NaCl) being less soluble separates out
How is the variability in oxidation states of transition on cooling. On crystallising the remaining solution, orange
metals different from that of the non-transition metals ? coloured crystals of K2Cr2O7 separate out.
Illustrate with examples
Effect of Change of pH : When pH of solution of K2Cr2O7
Sol. The variability in oxidation states is a fundamental is increased slowly the medium changes from acidic to
characteristic of transition elements and it arises due to basic. The chromates and dichromates are interconvertible
incomplete filling of d-orbitals in such a way that their in aqueous solution depending upon pH of solution.
oxidation states differ from each other by unity. For
example, vanadium, V show the oxidation states of +2, +3,
+4 and +5. Similarly, Cr shows oxidation states of +2, +3,
+4, +5 and +6; Mn shows all oxidation states from +2 to
+7. At low pH (acidic medium), K2Cr2O7 solution is oranged
coloured while at higher pH (alkaline medium) it changes
This is contrasted with variability of oxidation states of to yellow due to formation of chromate ions.
non-transition element where oxidation states generally
Example - 25
differ by units of two. For example, S shows oxidation
states of –2, +2, +4, +6 while P shows +3 and +5 oxidation Describe the oxidising action of potassium dichromate
states. Halogenes like Cl, Br and I show oxidation states and write the ionic equations for its reaction with :
of –1, +1, +3, +5 and +7 states. In non-transition elements (a) iodide (b) iron (II) solution and (c) H2S.
variability of oxidation states is caused due to unpairing
Sol. Potassium dichromate, K2Cr2O7 is a strong oxidising agent
of electrons in ns or np orbitals and their promotion to np
and is used as a primary standard in volumetric analysis
or nd vacant orbitals.
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 162 d AND f BLOCK ELEMENTS
involving oxidation of iodides, ferrous ion and S2– ions (a) It oxidises iron(II) salt to iron(III) salts.
etc. In acidic solution, its oxidising action can be
represented as follows : 2MnO42- + 16+ + 10Fe2+ o 2Mn2+ + 8H2O + 10Fe3+

Cr2O72– + 14H+ + 6e– o 2Cr3+ + 7H2O; (E+ = 1.33 V) (b) It oxidised sulphur dioxide to sulphuric acid.

(a) It oxidises potassium iodide to iodine. 2MnO4– + 5SO2 + 2H2O o 5SO42– + 2Mn2+ 4H+

Cr2O72– + 14H+ 6I– o 2Cr3 + 7H2O + 3I2 (c) It oxidises oxalic acid to CO2 and H2O

(b) It oxidises iron(II) salt to iron (III) salt 2MnO4– + 16H+ + 5C2O42– o 2Mn2+ + 8H2O + 10CO2

Cr2O72– + 14H+ + 6Fe2+ o 2Cr3+ + 6Fe3+ + 7H2O Example - 27

(c) It oxidises H2S to S For M2+/M and M3+/M2+ systems the Eo values for some
metals are as follows :
Cr2O72– + 8H+ + 3H2S o 2Cr3+ + 7H2O + 3S
Cr2+/Cr – 0.9 V Cr3+/Cr2+ – 0.4 V
Example - 26
Mn2+/Mn – 1.2 V Mn3+/Mn2+ + 1.5 V
Describe the preparation of potassium permanganate.
How does the acidified permanganate solution reacts Fe2+/Fe – 0.4 V Fe3+/Fe2+ + 0.8 V
with (a) iron(II) ions (b) SO2 and (c) oxalic acid ? Write Use this data to comment upon
the ionic equations for the reactions.
(a) The stability of Fe3+ in acid solution as compared
Sol. Preparation of KMnO 4 from pyrolusite ore (MnO 2) to that of Cr3+ or Mn3+ and
involves the following steps :
(b) In case with which iron can be oxidised as compared
(i) Fusion of ore with alkali in presence of air : Pyrolusite to the similar process for either chromium or
ore is fused with alkali in the presence of air when manganese metal.
potassium manganate is obtained as green mass.
2MnO2 + 4KOH + O2 o 2K2MnO4 + 2H2O Sol.
(green mass) (a) We know that higher the reduction potential of a specie,
The green mass is dissolved in water to obtain aqueous there is larger tendency for tis reduction to take place. Let
solution of potassium manganate. The insoluble impurities us represent the reduction potential i.e., Eo values of three
of sand and other metal oxides are removed by filtration. M3+/M2+ systems on number line.
Cr3+ / Cr2+ F3+/Fe2+ Mn3+/Mn2+
(ii) Oxidation of manganate into permanganate : The aqueous
solution of K2MnO4 is oxidised electrolytically or by using – 0.4 V 0.8 V 1.5 V
ozone or Cl2 to obtain potassium permanganate. The
process is carried out till green colour disappear and
solution acquires distinct pink colour. From values of reduction potentials, it is clear that the
stability of Fe3+ in acid solution is more than that Cr3+ but

MnO 42  
o MnO 4  e less than that of Mn3+.
at anode (oxidation at anode)
green coloure pink (b) Mn2+/Mn Cr2+/Cr Fe2+/Fe
H2O + e– o 1/2H2 + (OH)– (reduction at cathodes)
– 1.2 V 0.9 V –0.4 V 0V
(at cathode)
The lower the reduction potential of a species, its
oxidation will take place more readily.
or 2K 2 MnO 4  CI 2 o 2KMnO4  2KCI
green colour pink colour
? Mn is oxidised most readily to Mn2+ and Fe is oxidised
least readily among given metals Mn, Cr and Fe.
Potassium permanganate is crystallised out from the
solution.
Example - 28
Oxidising Properties : It acts as a powerful oxidising agent Write the electronic configurations of the elements with
in different media differentily. In acidic medium, it oxidises the atomic numbers 61, 91, 101 and 109.
iron(II) salts to iron(III) salts, SO2 to H2SO4 and oxalic acid
to CO2 and H2O. Sol. Atomic number (61) = [Xa] 4f5 6s2.

Atomic number (91) = [rn] 5f2 6d1 7s2

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d AND f BLOCK ELEMENTS 163
Atomic number (101) = [Rn] 5f14 7s1 2
3CrO 43  8H  o 2CrO 4  Cr 3  4H 2 O
Cr in  5 o.s. Cr in  o.s.
Atomic number (109) = [Rn] 5f14 6d7 7s2.
.
3MnO 43  4H  o 2MnO 4   MnO 2  2H 2 O
Mn in  6 o.s. Mn in Mn in
7 o.s 4 o.s.
Example - 29
How would you account for the following : Here, we can say that Cr in +5 oxidation state undergo
disproportionation into its +6 and +3 states. Similarly, Mn
(a) Of the d4 species Cr2+ is strongly reducing while in +6 oxidation state undergo disproportionation into +7
manganese(III) is strongly oxidising. and +7 oxidation states.

(b) Cobalt(II) is stable in aqueous solution but in the Example - 31

presence of complexing reagents it is easily
oxidized. Give reasons for the following :

(c) The d1 configuration is very unstable in ions? (a) Transition metals have high enthalpies of
atomisation.
Sol. (b) Among the lanthenoids Ce(III) is easily oxidised to
Ce(IV).
(a) Of d 4 species, Cr2+ has 3 d4 configuration and tends to
loose one electron to acquire d3 configuration as it is highly (c) Fe3+/Fe2+ redox couple has less positive electrode
stable and best metallic specie available for complex potential than Mn3+/Mn2+ couple.
formation. Cr3+ can accommodate six lone pair of electrons
from ligands due to sp3d2 hybridisation e.g. [Cr(NH3)6]3+ (d) Copper (I) has d10 configuration while copper(II) hs
Mn3+ although have d4 configuration but tends to become d9 configuration, still copper(II) is more stable in
Mn2+ stable specie by acquiring one electron to attain d5 aqueous solution than copper(I).
configuration. It becomes exactly half filled on one hand (e) The second and third transition series elements
and more energy is released in gain of electron due to have almost similar atomic radii.
higher nuclear charge.
Sol.
(b) Co 2+ is stable in aqueous solution because it get
surrounded and weakly bonded to water molecules. In (a) The metallic bonds in transition elements are very strong
presence of strong ligands and air it gets oxidised tc Co(III) due to participation of (n – 1) d electrons along with
as strong ligands get co-ordinated more strongly with valence s-electrons in the bond formation. Therefore, the
Co(III). The electronic configuration of Co(II) and Co(III) cleavage of these bonds is extremely difficult and
are : consequently, enthalpies of atomization are high.

Co(II) = [Ar]18 4s03d7 and Co(III) = [Ar]18 4s03d6 3

(b) C e o Ce 4   e 

4f 5d o 6so 4f o 5d o 6so
In Co(III) specie, 6 lone pairs of electrons from ligands are
accommodated by sp 3d 2 hybridisation which is not
possible in Co(II). Spontaneous oxidation due to more stability of Ce4+ ion
as compared to Ce3+ ion due to more stable configu-ration
(c) Some species with d1 configuration are reducing and tends of Ce4+ ion.
to loose one electron to acquire d4 stable configuration.
Some other species with d1 configuration like Cr(V) and (c) Mn 3  3e 
o Mn  2
Mn(VI) undergo disproportionation.
(more spontaneous due to higher stability of Fe3+)
Example - 30
Fe3  e 
o Fe 2
What is meant by disproportionation ? Give two examples
of disproportionation reaction in aqueous solution. (less spontaneous due to higher stability of Fe3+)

Due to stability of half filled d-orbitals, Mn2+ is more stable

Sol. Some time transition metal species in same oxidation state
than Mn3+ and thus its reduction is more spontaneous.
undergo a chemical change in such a way that some species
Similarly Fe3+ is more stable than Fe2+ and thus its
get oxidised and some other get reduced. For example, Cr(V)
reduction is less spontaneous.
and Mn(VI) species undergo disproportionation reaction
in acidic medium as follows:
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 164 d AND f BLOCK ELEMENTS
(d) Copper (II) has lower reduction electrode potential than An important alloy which contains some of the lanthanoid
copper (I), hence. Copper(I) is oxidised to copper (II) in is mischmetall. Mischmetall consists of a lanthanoid metal
the presence of strong ligands and air. (~95%) and iron (~5%) and traces of S, C, Ca and Al.
(e) It is due to lanthanoid contraction. It arises due to poor Uses : (i) Mischmetall is used in Mg based alloy to produce
shielding effect of d and f electrons. bullets, shell and lighter flint.
Example - 32 Some individual Ln oxides are used as phosphorus in
Indicate the steps in the preparation of : television screens and similar fluorescing surfaces.

(a) K2Cr2O7 from chromite ore Example - 34

(b) KMnO4 from pyrolusite ore. The Chemistry of the actinoid elements is not so smooth
as that of the lanthanoids. Justify this statement by giving
Sol. some examples from the oxidation state of these elements.

(a) The preparation of potassium dichromate from chromite Sol. Among the actinoids, there is a greater range of oxidation
involves the following main steps : states as compared to lanthanoids. This is in part due to
(i) The chromate ore is finely ground and heated strongly the fact that 5f, 6d and 7s levels are of very much
with molten alkali in the presence of air. comparable energies and the frequent electronic transition
2FeCr2 O4  8NaOH  7 / 2O2 o 4Na 2 Cr2 O 4 o Fe2 O3  4H 2 O among these three levels is possible. This 6d-5f transition
Chromite Sodium chromate and larger number of oxidation states among actinoids
(ii) The solution of sodium chromate is filtered and acidified make their Chemistry more complicated particularly among
with dilute sulphuric acid so that sodium dichromate is the 3rd to 7th elements. following examples of oxidation
obtained. states of actinoids. Justify the complex nature of their
Chemistry.
2Fe 2Cr2O 4  H 3SO 4 o Na 2Cr2O7  Na 2SO 4  H 2 O
Sodium Chromate Sodium dichromate
(i) Uranium exhibits oxidation states of +3, +4, +5, +6 in its
(iii) A calculated quantity of potassium chloride is added to a compounds. However, the dominant oxidation state in
hot concentrated solution of sodium dichromate. actinoides is +3.
Potassium dichromate is less soluble therefore it
crystallizes out first. (ii) Nobelium, No is stable in +2 state because of completely
filled f14 orbitals in this state.
Na 2 Cr2 O 7  2KCl o K 2 Cr2 O7  2NaCl
Sodium Potassium
dichromate dichromate (iii) Berkelium, BK in +4 oxidation state is more stable due to f7
(b) (i) Pyrolusite ore is fused with alkali in the presence of (exactly half filled) configuration.
air when potassium manganate is formed.
(iv) Higher oxidation states are exhibited in oxoions are UO22+,
2MnO 2  4KOH  O 2 o 2K 2 MnO 4  2H 2 O
PuO22+, NpO+ etc.
Potassium manganate
Example - 35
(ii) Potassium manganate is oxidised by using either CO2,
ozone or chlorine to potassium permanganate. Use Hund’s rule to derive the electronic configuration
of Ce3+ ion, and calculate its magnetic moment on the
2K 2 MnO 4  Cl2 o 2KMnO4  2KCl
Potassium basis of ‘spin only’ formula.
permanganate

(iii) Potassium permanganae is crystallized from the Sol. The electronic configuratio of Ce and Ce3+ ion is :
solution.
Ce(Z = 58) = 54[Xe] 4f15d16s2
Example - 33
What are alloys ? Mention an important alloy which Ce3+ = 54[Xe] 4f1
contains some of the lanthanoid metals. Mention its uses.
The no. of unpaired electron = 1
Sol. An alloy is a mixture of a metal with other metals or non-
metals. ‘Spin only’ formula for magnetic moment of a specie,

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d AND f BLOCK ELEMENTS 165

(i) Because of their variable oxidation states transition metals

P n n  2 B.M.
form unstable intermediate compounds and provide a new
path with lower activation energy for the reaction.
? Magnetic moment of Ce3+
(ii) In some cases, the transition metal provides a suitable
large surface area with free valencies on which reactants
P 1 1  2 B.M. are adsorbed.

(b) Because they have strong metallic bonds due to greater

3 B.M. 1.732 B.M. number of unpaired d electrons.

(c) this is due to d-d transition.

Example - 36
Name the members of the lanthanoid series which exhibit Example - 38
+4 oxidation states and those which exhibit +2 oxidation Discuss the relative stability in aqueous solutions of +2
state. Try to correlate this type of behaviour with the oxidation state among the elements: Cr, Mn, Fe and Co.
electronic configurations of these elements. How would you justify this situation ?
Sol. Cerium (Ce) and Terbium (Tb) show +4 oxidation state. (At. Nos. Cr = 24, Mn = 25, Fe = 26, Co = 27)
Their electronic configurations are given below :
Sol. On the basis of electrochemical series the standard
Ce = [Xn] 4f1 5d1 6s2 electrode potential shows the following order
Tb = [Xn] 4f0 6s2 E o Mn 2 / Mn  E o Cr 2 / Cr  E o Fe2 / Fe  E o Co2 / Co
It is clear from the configuration of Ce that Ce+4 is favoured
Therefore Co2+ gets easily reduced to metallic cobalt while
by its noble gas configuration i.e., [Xn] 4f0 5d0 5s0, but can
it is difficult to reduce Mn2+. Hence Mn2+ will be most
be easily converted into Ce3+ ([Xn]) 4f1 5d0 6s0). Due to
stable and the increasing stability order will be
this reason Ce+4 is an oxidising agent. Tb4+ ion is stabilized
due to half filled f-subshell i.e., [Xn] 4f7. It also acts as an Co2+ < Fe2+ < Cr2+ < Mn 2+
oxidant.
Example - 39
Europium (63) and ytterbium (70) show +2 oxidation state,
this acts as reducing agents because they can be Which metal in the first series of transition metals
converted into common oxidation state +3. The electronic exhibits +1 oxidation state most frequently and why ?
configuration of Eu and Y are as follows :
Sol. Copper metal (Cu, at, no. 29) shows + 1 oxidation state i.e.,
7
Eu = [Xn] 4f 6s 2 it exists as Cu+ in large number of copper compounds e.g.,
cuprous oxide (Cu2O), coprous sulphide 9Cu2S); cuprous
Y = [Xn] 4f14 6s2 chloride (Cu2Cl2) etc. The electronic configuration of Cu+
is [Ar] 3d10 4s0.
Formation of Eu2+ ion leaves 4f7 configuration and Y2+ ion
leaves 4f14 configuration. These configurations can stable This configuration is very stable as all five 3d orbitals are
due to half filled and full filled f-subshell. Samarium, Sm fully filled.
(62) 4f6 6s2 also shows both +2 and +3 oxidation states like
europium. Example - 40
Assign a reason for each of the following :
Example - 37
(i) The third ionization energy of Mn(Z = 25) is higher
Explain the following facts
than that of either Cr (Z = 24) or Fe (Z = 26).
(a) transition metals act as catalysts.
(ii) Simple copper (I) salts are not stable in aqueous
(b) chromium group elements have the highest melting solutions.
points in their respective series.
Sol.
(c) transition metals form coloured complexes.
(i) This is because Mn2+ is more stable as it has exactly half
Sol. filled configuration 3d5 4s0.

(a) The catalytic activity of transition metals is attributed to

the following reasons :
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 166 d AND f BLOCK ELEMENTS
2+ +
(ii) Cu (aq) is much more stable than Cu (aq). This is
because, although second ionization enthalpy of copper
is large but for Cu2+ (aq) is much more negative than that
of Cu + (aq) and therefore, it more compensate for the
second ionisation enthalpy of copper. Therefore, Cu+ ion
aqueous solution undergoes disproportionation.

2Cu 2 aq 
o Cu 2 aq  Cu s

Example - 41 Example - 42

Describe the trends in the following properties of the Complete the following chemical reaction equations:
first series of the transition elements:
(i) MnO4 aq  C2 O42  aq  H  aq 
o
(i) Oxidation states

(ii) Atomic sizes (ii) Cr2 O27  aq  Fe2  aq  H  aq 

o

(iii) Magnetic behaviour of dipositive gaseous ions (M2+).

  
o Mn 2   4H 2 O] u 2
Sol. (i) MnO 4  8H  5e 
Sol.
C 2 O 24 o 2CO 2  2 ] u 5

(i) As there is very little energy difference between 4s and 3d
orbitals, electrons from both energy levels can be used 2MnO4  5C2 O 42   16H  
o 2Mn 2   10CO 2  8H 2 O
for chemical bond formation. Therefore all elements except
Sc and Zn, of the first transition series show a number of
oxidation states as shown in table. (ii) Cr2 O72   14H   6e  
o 2Cr 3  7H 2 O
Sc Ti V Cr Mn Fe Co Ni Cu Zn Fe 2  o Fe3  e  ] u 6

2 2 2 2 2 2 2 1
3 3 3 3 3 3 3 3 2 2 Cr2 O72   6Fe2   14H  
o 2Cr 3  6Fe3  7H 2 O
4 4 4 4 4 4 4
5 5 5 Example - 43
6 6 6
7 How would you account for the following :

(ii) Atomic radii of the first transition series decreases from (i) Many of the transition elements and their
Sc to Cr, then reamins almost constant till Ni and then compounds can act as good catalysts.
increases from Cu to Zn.
(ii) The metallic radii of the third (5d) series of
The reason of this variation in atomic radii has been
transition elements are virtually the same as those
attributed to the increase in nuclear charge in the beginning
of the series. But as the electrons continue to be filled in of the corresponding members of the second series.
d-orbitals, they screen the outer 4s electrons from the (iii) There is a greater range of oxidation states among
influence of nuclear charge. When the increased nuclear
the actinoids than among the lanthanoids.
charge. When the increased nuclear charge and the
increased screening effect balance each other in the middle Sol.
of transition series, the atomic radii becomes almost
constant (Mn to Fe). Towards the end of the series, the (i) The catalytic activity of transition metals is attributed to
repulsive interaction between electrons in d orbitals the following reasons:
become very dominant. As a result there is an expansion
of the electron cloud; consequently, the atomic size (a) Because of their variable oxidation states transition
increases. metals form unstable intermediate compounds and
(iii) Except Zn2+, all other divalent gaseous ions of the first provide a new path with lower activation energy for
series of the transition elements contain unpaired electrons the reaction.
in their 3d subshell and are therefore paramagnetic in
nature. (b) In some cases, the transition metal provides a suitable
The magnetic moment (P) of the elements of the first large surface area with free vacancies on which
transition series can be calculated with the unpaired reactants are adsorbed.
electrons (n) by the spin-only formula
(ii) This due to filling of 4f orbitals which have poor shielding
P n n  2 B.M. effect or due to lanthanoid contraction.

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 d AND f BLOCK ELEMENTS 167
(iii) This is due to comparable energies of 5f, 6d and 7s orbital Cerium can lose four electrons (4f1 5d1 6s2) in aqueous
in actinoids. solution to acquire stable configuration of rare gas xenon.
Moreover due to small size and high charge, Ce4+ ion has
Example - 44 high hydration energy.
In transition series, with an increase in atomic number, (ii) The second and third members in each group of transition
the atomic radius does not change very much. Why is it elements have very similar atomic radii due to lanthanoid
so ? contraction. It arises due to poor shielding effect of 'f
Sol. With the increase in atomic number along a transition series electrons.
the nuclear charge increases which tends to decrease the
size of the atom. But the addition of electrons in the d Example - 47
subshell increases the screening effect which Among the ionic species Sc3+, Ce4+ and Eu2+ which one
counterbalances the increased nuclear charge. Hence, is a good oxidising agent? Give a suitable reason for
along a transition series the atomic radius does not change your answer. (Atomic numbers ; Sc = 21; Ce = 58;
very much. Eu = 63).

Example - 45 Sol. The electronic configurations of given species are:

Decide giving reasons which one of the following pairs o18 Sc3 
Sc 
21
exhibits the property indicated:

(i) Sc3+ or Cr3+ exhibits paramagnetism. Ar 3d1 4s 2 Ar 3d0 4s0

(ii) V or Mn exhibits more number of oxidation states.

58 o54 Ce 4 
Ce 
(Atomic Numbers: Sc = 21; Cr = 24; V = 23; Mn = 25)
[Xe] 4f1 3d1 6s2 [Xe]
Sol.

(i) The electronic configurations of Sc3+ and Cr3+ are given 63 o61 Eu 2 
Eu 
below.
Xe 4f 7 6s2 Xe 4f 7
3 0 0 3 3 0
Sc : Ar 3d 4s Cr : Ar 3d 4s
Ce4+ is a good oxidising agent because it can readily
Because of the presence of three unpaired electrons in change to the most stable +3 oxidation state by gaining
the 3d subshell Cr3+ is paramagnetic. Sc3+ is diamagnetic one electron.
as it does not have any unpaired electrons.
Ce4   e 
o Ce3
(ii) The electronic configurations of V and Mn are given
below: Because of their stable configuration Sc3+ and Eu2+ cannot
gain electrons.
23 V : Ar 3d3 4s 2 25 Mn : Ar 3d5 4s 2
Example - 48
Mn exhibits more number of oxidation states than V Write complete chemical equations for :
because of the greater number of electrons in its valence
shell. (i) Oxidation of Fe2+ by Cr2O72– in acid medium.

Example - 46 (ii) Oxidation of S2O32– by MnO4 in neutral aqueous

Account for the following: solution.

(i) Cerium (atomic number = 58) forms tetra positive

Sol. (i) 6Fe2+ + Cr2O72– + 14 H+ 
o 6Fe3+ + 2Cr3+ + 7H2O
ion, Ce4+ in aqueous solution.

(ii) The second and third members in each group of (ii) 2MnO4– + 3S2O32– + H2O 
o 2MnO2 + 3SO42– +
transition element have similar atomic radii. 3S + 2OH–.
Sol.

(i) The electronic configuration of Ce (Z = 58) is 58Ce = [Xe]

4f1 5d1 6s 2
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 168 d AND f BLOCK ELEMENTS

Example - 49 Sol.

What are the different oxidation states exhibited by the (i) 8MnO4 aq  3S2 O32  aq  H 2O A 
o 6 SO42 
lanthanoids ? (aq) + 8MnO2 + 2OH– (aq)
Sol. The most common oxidation states shown by lanthanoids (ii) Cr2O 72 aq  6Fe2 aq  14H  aq 
o 2 Cr 3
is +3. In some exceptional cases it may be +2 or +4 (+2 in (aq) + 6 Fe3+ (aq) + 7H2O (l)
Eu and Yb; +4 in Ce).
Or
Example - 50
(i) Cu2+ (aq) is much more stable than Cu+ (aq. This is due to
What is meant by ‘lanthanoid contraction’ ? more negative 'hydH more than compensates for 'iH2. As
Sol. The regular decrease (contraction) in the atomic and ionic a result Cu(I) is unstable in aqueous solution and
radii with increasing atomic number from lanthanum to undergoes disproportionation as below :
lutetium along the lanthanoid series is called lanthanoid
contraction. 2Cu  
o Cu 2   Cu

(ii) The valence shell electronic configuration of Cr3+, Mn2+,

Example - 51
Fe3+ is d3, d5 respectively. Due to symmetrical distribution
How would you account for the following :
of electrons (Either t 32g or t 32g eg2 ) they form stable
(i) Cr2+ is reducing in nature while with the same d-
orbital configuration 9d4) Mn3+ is an oxidising cationic complexes. The atomic radii of 4d and 5d transition
agent. metal at elements are more than those of 3d series. Hence.
(ii) In a transition series of metals, the metal which they generally do not form stable cationic complexes.
exhibits the greatest number of oxidation states
Example - 53
occurs in the middle of the series.
Explain giving reasons :
Sol.
(i) Transition metals and their compounds generally
(i) Eo value of Cr3+/Cr2+ is negative (–0.04V) while that of
exhibit a paramagnetic behaviour.
Mn3+/Mn2+ is positive (1.5 V). This means Cr2+ can lose
electrons to form Cr3+ and thus is reducing in nature while (ii) The Chemistry (XII) (XII) of actinoids is not so
Mn3+ can gain electrons to form Mn2+ and is thus oxidising smooth as that of lanthanoids.
in nature.
Sol.
(ii) In a transition series of maximum number of oxidation states
are shown by that element which has maximum number of (i) Paramagnetism is a property due to presence of unpaired
unpaired electrons. This is so in the element present in the electrons. In case of transition metals, as they contain
middle of the series. That is why the metal in the middle of unpaired electrons in (n – 1) d orbitals, most of the
the series exhibits maximum number of oxidation states. For transition metal ions and their compounds are
example, manganese, present in the middle of the first paramagnetic.
transition series exhibits maximum oxidation states i.e., +2, (ii) The general electronic configuration of lanthanoids is
+3, +4, +5, +6, +7. [Xe]54 4f0–4 5d0–1 6s2 and that of actinoids is [Rn]86 5f1–14
6d0–1 7s2. Unlike 4f orbitals, 5f orbitals are not deeply burried
Example - 52 and participate in bonding to a greater extent. In actinoids
Complete the following chemical equations : due to poor shielding effect of 5f orbitals, the effective
nuclear charge experienced by valence shell electrons is
(i) MnO 4 aq  S2O32  aq  H 2 O A o
more than those in lanthanoids. As a result the Chemistry
(ii) Cr2 O27  aq  Fe2  aq  H  aq o (XII) (XII) of actinoids is not so smooth as that of
lanthanoids.
Or
State reasons for the following : Example - 54
(i) Cu (I) ion is not stable in an aqueous solution.
Assign reasons for the following :
(ii) Unlike Cr3+, Mn2+, Fe3+ and the subsequent other (i) Copper (I) ion is not known in aqueous solution.
M2+ ions of the 3d series of elements, the 4d and the (ii) Actinoids exhibit greater range of oxidation states
5d series metals generally do not form stable than lanthanoids.
cationic species.

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 d AND f BLOCK ELEMENTS 169
Sol. Sol.

(i) Cu (I) ion is not known in aqueous solution because (i) CuF2 and CCl2 compounds will be coloured because they
Cu2+(aq) is much more stable than Cu+(aq). This is due to incompletely filled d-orbitals and unpaired electrons, they
more negative 'hydH for Cu2+ (aq) than Cu+(aq) although can undergo d-d transition by absorbing colour from
'iH2 for Cu2+ is large. Thus, 'hydH more than compensates visible region and radiating complementary colour.
for high value of 'iH2. As a result Cu (I) is unstable in
aqueous solution and undergoes disproportionation as (ii) Zr and Hf have identical sizes because passing of electrons
below : takes place in d-orbitals causing repulsion and effective
nuclear charge does not increase apprecialby.
2Cu  
o Cu 2  Cu
(iii) Manganese (Z = 25) exhibits the largest number of
(ii) Actinoids exhibit greater range of oxidation states than oxidation states because its atoms has the maximum
lanthanoids. this is because of very small energy gap number of npaired electrons. The lowest oxidation state
between 5f, 6d and 7s subshells. Hence, all their electrons of manganese is basic while the highest is acidic.
can take part in bond formation.
(iv) Mn(II) shows maximm paramagnetic character amongst
Example - 55 the divalent ions of the first transition series because it
Assign reasons for each of the following : has the largest number of unpaired electrons.

(i) Transition metals generally form coloured Example - 57

compounds.
Explain the following facts :
(ii) Manganese exhibits the highest oxidation state of
+7 among the 3d series of transition elements. (a) Transition metals acts as catalyst.

Sol. (b) Chromium group elements have highest meeting

points in their respectively series.
(i) Transition metals generally form coloured compounds. The
colour of compounds of transition metals may be attributed (c) Transition metals form coloured complexes.
to the presence of incomplete (n – 1) d subshell. In the
compounds of transition metals the d–orbitals split into Sol.

two sets-t 2g d x 2  y2 ,d z2 of lower energy and e g (a) Transition metals acts as catalyst due to the following
reasons :
d xy , d yz , d xz of high energy. The electron can jump from
lower energy t2g orbitals to higher energy eg orbitals (d–d (i) Their partially empty d-orbitals provide surface area for
transition) by absorption of light of some particular reactant molecules.
wavelength from visible light. The remainder light is emitted
as coloured light and the compound appears coloured. (ii) They combine with reactant molecules to form transition
(ii) In a transition series the element with maximum oxidation states and lowers their activation energy.
state occurs in or near the middle of the transition series
and maximum oxidation state exhibited is equal to sum of (iii) They show multiple oxidation states and by giving
(n – 1) d and ns electrons. In Mn (3d5 4s2) the sum of electrons to reactants they form complexes and lower their
(n – 1) d and (ns) electron is 7 and therefore it exhibits energies.
maximum o.s. of + 7. The lesser no. of oxidation states on
extreme ends are either due to too few electrons to lose or (b) The melting point of chromium groups elements have the
share or too many d-electrons so that fewer orbitals are
highest melting points in their respective serves due to
available to share electrons with others.
presence of strong intermetallic bonds (formed by valence
Example - 56 electrons and covalent bonds formed due to d–d
Explain: overlapping of impaired d-elelctrons.)

(i) CrO42– is a strong oxidizing agent while MnO42– is not. (c) Their colour due to the presence of incomplete d-subshell.
(ii) Zr and Hf have identical sizes. The electrons can be excited from one energy lavel to
another with in the d-subshell. The energy required to
(iii) The lowest oxidation state of manganese is basic
while the highest is acidic. cause such d–d promotions or transition falls within the
visible range for all transition elements. When white light
(iv) Mn (II) shows maximum paramagnetic character falls on an ion or compound, some of its wave lengths are
amongst the divalent ions of the first transition
series. absorbed due to d–d transition and others are reflected.
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 170 d AND f BLOCK ELEMENTS

Therefore, coloure of the transition metal ion is that of the

Example - 60
reflected light.
What happens when ?
Example - 58
(i) Ferric chloride is added to potassium ferrocyanide.
Give reasons :
(ii) Iron reacts with cold dilute nitric acid.
(i) Among transition metals, the highest oxidation state
is exhibited in oxoanins of a metal. (iii) Potassium ferricyanide is added to ferrous sulphate.
(ii) Ce4+ is used as an oxidising agent in volumetric (iv) Excess of potassium iodide is added to mercuric
analysis. chloride.
(iii) Transition metals form a number of interstitial
(v) Green vitriol is strongly heated.
compounds.

(iv) Zn2+ salts are white while Cu2+ salts are blue. (vi) Silver chloride is treated with aqueous sodium
cyanide and the product thus formed is allowed to
Sol. react with zinc in alkaline medium.
(i) Highest oxidation state is shown in flourides and oxides
because F2 and O2 are strong oxidising agents. (vii) Zinc oxide is treated with excess of sodium hydroxide
solution.
(ii) Ce4+ = [Xe], 4f0, 5d0, 6s0
Ce4+ has the tendency to accept one electron to get the +3 (viii) Ammonium thiocyanate is added to ferric chloride
oxidtion state, hence Ce4+ is a good oxidising agent. solution.
(iii) In these compounds small size atoms like hydrogen,
Sol. (i) Prussian blue is formed.
carbon, nitrogen, boron, etc. occupy the empty space of
metal lattice (interstices). The small entrapped atom in the
interstices form the bonds with metals due to which 4FeCl3  3K 4 Fe(CN )6 o Fe 4 [Fe(CN )6 ]3  12KCl
Prussian blue
mobility and ductility of the metals decrease, when as (Ferri ferrocyani de)
tensile strength increases. Example : steel is the interstitial
compound of iron and carbon. (ii) Ammonium nitrate is formed.
(iv) In Cu2+ salts (3d9) d–d transition is possible. Therefore
Cu2+ salts are coloured. [Fe + 2HNO3 o Fe(NO3)2 + 2H] × 4
In Zn2+ salts (3d10) no. d–d transition is possible due to HNO3 + 8H o NH3 + 3H2O
completely filled d-orbitals. Hence Zn2+ salts are white.
NH3 + HNO3 o NH4NO3
Example - 59
Write the main differences in lanthanides and actinides. 4Fe + 10HNO3 o 4Fe(NO3)2 + NH4NO3 + 3H2O

Sol. (iii) Ferrous ion is first oxidised to ferric ion while

ferricyanide ion is reduced to ferrocyanide ion. Then,
ferric ions react with ferrocyanide ions to form
potassium ferric ferrocyanide (Turnbull’s blue).

Fe2+ + K3 [Fe (CN)6]3– o KFe [Fe(CN)6 ]

(Turnbull's Blue )

(iv) First scarlet precipitate is formed which then dissolves

in excess of potassium iodide forming a complex.

HgCl2 + 2KI o HgI2 + 2KCl

HgI2 + 2KI o K2HgI4

Potassiumtetraiodomercurate(II)

(colourless)
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d AND f BLOCK ELEMENTS 171

(v) When heated strongly, a mixture of gases consisting K2Cr2O7 + 4H2SO4 o K2SO4 + Cr2(SO4)3 + 4H2O + 3 [O]
of SO2 and SO3 is evolved and a red residue, Fe2O3 is [Na2SO3 + [O] o Na2SO4] × 3
formed.
K2Cr2O7 + 3Na2SO3 + 4H2SO4 o K2SO4 + Cr2(SO4)3
[FeSO4.7H2O o FeSO4 + 7H2O] × 2
Green
2FeSO4 o Fe2O3 + SO2 + SO3 + 3Na2SO4 + 4H2O
SO3 + H2O o H2SO4 (ii) When zinc is exposed to moist air, the surface is
2FeSO4.7H2O o Fe2O3 + SO2 + H2SO4 + 13H2O affected with the formation of a film of basic zinc
carbonate on it. Due to this zinc becomes dull.
Green vitriol Red
[2Zn + 2H2O + O2 o 2Zn (OH)2] × 2
(vi) AgCl dissolves in KCN forming a complex, potassium Zn(OH)2 + CO2 o ZnCO3 + H2O
argentocyanide. The addition of zinc precipitates ZnCO3 + 3Zn(OH)2 o ZnCO3.3Zn (OH)2
silver.
4Zn + 3H2O + CO2 + 2O2 o ZnCO3.3Zn(OH)2
AgCl + 2KCN o KAg(CN)2 + KCl
Basic zinccarbonate
2KAg(CN)2 + Zn o K2Zn(CN)4 + 2Ag (iii) Ferrous sulphate is a salt of a weak base and a strong
Potassium zincocyanide acid. Thus, its hydrolysis occurs when it is dissolved
(vii) ZnO dissolves in NaOH forming sodium zincate. in water and solution becomes turbid due to formation
of ferrous hydroxide.
ZnO + 2NaOH o Na2ZnO2 + H2O
FeSO4 + 2H2O Fe(OH)2 + H2SO4
(viii) Deep red colouration due to the formation of a complex Addition of a small amount of acid shifts the
is developed. equilibrium towards left and thus prevents hydrolysis.
FeCl3 + NH4CNS o Fe(CNS)Cl2 + NH4Cl (iv) On addition of NaOH, a white precipitate of Zn (OH)2
is formed which dissolves in excess of NaOH forming
or FeCl3 + 3NH4CNS o Fe(CNS)3 + 3NH4Cl sodium zincate.
Example - 61 ZnCl2 + 2NaOH o Zn(OH)2 + 2NaCl
Zn (OH)2 + 2NaOH o Na2ZnO2 + 2H2O
Explain the following :
Soluble
(i) Acidified K 2 Cr 2O 7 solution turns green when (v) NH 4OH is a weak hydroxide. It ionises slightly
sodium sulphite is added to it. furnishing OH– ions. However, the OH– ions are
(ii) Zinc becomes dull in moist air. sufficient to cause the precipitation of Zn(OH)2 as its
solubility product is exceeded.
(iii) A little acid is always added in the preparation
ZnSO4 + 2NH4OH o Zn(OH)2 + (NH4)2SO4
of aqueous ferrous sulphate solution.
white ppt.
(iv) The addition of NaOH solution to a solution of zinc In presence of NH4Cl, the ionisation of NH4OH is
chloride produces a white precipitate which further suppressed and sufficient OH– ions are not
dissolves on further addition of NaOH. available to cause precipitation as the solubility
(v) The addition of NH 4 OH to ZnSO 4 solution product is not exceeded.
produces white precipitate but no (vi) Zinc is cheaper as well as stronger reducing agent in
comparison to copper.
precipitate is formed if it contains NH4Cl.
Zn + 2[Ag(CN)2]– o 2Ag + [Zn(CN)4]2–
(vi) Zinc and not copper is used for the recovery of silver
(vii) Copper sulphate dissolves in the ammonium hydroxide
from complex [Ag(CN)2]–. due to formation of a copper complex. Ferrous sulphate
(vii) Copper sulphate dissolves in NH 4OH solution reacts with NH4OH to form insoluble Fe(OH)2. It does
but FeSO4 does not. not form any complex with NH4OH.
CuSO4 + 4NH4OH o [Cu(NH3)4]SO4 + 4H2O
(viii) Copper hydroxide is soluble in ammonium Deep blue solution
hydroxide but not in sodium hydroxide. FeSO4 + 2NH4OH o Fe(OH)2 + (NH4)2SO4
Insoluble
Sol. (i) Na2SO3 is a reducing agent. It reduces acidified K2CrO7
(viii) Cu(OH)2 dissolves in NH4OH by forming a complex.
to chromic sulphate which is green in colour. Cu(OH)2 + 4NH4OH o [Cu(NH3)4] (OH)2 + 4H2O

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 172 d AND f BLOCK ELEMENTS

the compound (A) is ferrous sulphate, FeSO4.7H2O.

Cu(OH)2 is insoluble in NaOH as no such complex is
formed. Reactions :
FeSO 4 .7H 2 O 
Heat
7H 2O
o FeSO4 
Heat
o Fe 2 O3  SO 2  SO 3
Example - 62 ( A) (B) (C) ( D)
Blackish
brown powder
A metal chloride (x) shows the following reactions :
(a) When H2S is passed in an acidified solution of (x) a Fe 2O3  6HCl 
o 2FeCl3  3H 2 O
(B) (E)
black precipitate is obtained. Yellow solution

(b) The black precipitate is not soluble in ammonium

sulphide. 2FeCl3  H2S 
o 2FeCl 2  2HCl  S
(G) (F)
Apple White
(c) The solution of stannous chloride is added to an green solution turbidity

aqueous solution of (x), a white precipitate is

obtained which turns grey on addition of more FeCl3  3CNS 
o Fe(CNS)3  3Cl
stannous chloride. (E) Blood red
coloured solution
(d) When aqueous solution of KI is added to an aqueous
Example - 64
solution of (x), a red precipitate is obtained which
dissolves on addition of excess of KI. (i) A black mineral (A) on treatment with dilute sodium
Identify (x) and write down the equations for the cyanide solution in presence of air gives a clear
reactions. solution of (B) and (C).
Sol. The acidified solution of (x) gives a black sulphide with (ii) The solution (B) on reaction with zinc gives
H2S indicates that the chloride is of a basic cation of second precipitate of a metal (D).
group. The sulphide in insoluble in ammonium sulphide, (iii) (D) is dissolved in dilute HNO3 and the resulting
hence, the cation belongs to IIA group of mixture analysis. solution gives a white precipitate (E) with dilute HCl.
It gives white precipitate with SnCl2 which turns to grey (iv) (E) on fusion with sodium carbonate gives (D).
in excess of SnCl2 suggests that (x) is HgCl2. It is further (v) (E) dissolves in ammonia solution giving a colourless
confirmed by the reaction with KI. solution of (F). Identify (A) to (F) and give chemical
Reactions : equations for reactions at steps (i) to (v).
HgCl2 + H2S o HgS + 2HCl
Black
Sol. On the basis of the given data, the black mineral (A) is
silver glance, Ag2S. It is confirmed by the following :
2HgCl2 + SnCl2 o Hg2Cl2 + SnCl4
(i) It dissolves in sodium cyanide solution in presence of air.
white
Hg2Cl2 + SnCl2 o 2Hg + SnCl4 Ag2S + 4NaCN + 2O2 o 2[NaAg(CN) 2 ]  Na 2SO 4
Sodium Sodium
argento cyanide sulphate
Grey (B) (C)

HgCl2 + 2KI o HgI2 + 2KCl

Red ppt. (ii) 2[NaAg(CN) 2 ]  Zn o Na 2 Zn(CN) 4  2Ag
(B) (D)
HgI2 + 2KI o K2HgI4
Soluble (iii) 3Ag  4HNO 3 o 3AgNO3  NO  2H 2 O
(D)
Example - 63
A certain inorganic compound (A) on heating loses its AgNO3  HCl o AgCl  HNO 3
(E)
water of crystallisation. On further heating, a blackish
brown powder (B) and two oxides of sulphur (C and D) 1
are obtained. The powder (B) on boiling with hydrochloric (iv) 2AgCl Na 2 CO3 o 2Ag  2NaCl  CO 2  2 O 2
(E) (D)
acid gives a yellow solution (E). When H2S is passed in
(E), a white turbidity (F) and apple green solution (G) are AgCl  2NH 4 OH o Ag(NH 3 ) 2 Cl  2H 2 O
obtained. The solution (E) on treatment with thiocyanate (v) ( E) (F)
Colourless solution
ions gives a blood red coloured compound (H). Identify
the compounds from (A) to (H). (A) = Silver glance, Ag2S
(B) = Sodium argentocyanide, NaAg(CN)2
Sol. The compound (A) on strong heating gives two oxides of (C) = Sodium sulphate, Na2SO4
sulphur, it may be a sulphate. The solution (E) on treatment (D) = Silver metal, Ag
with thiocyanate ions gives blood red coloured compound (E) = Silver chloride, AgCl
(H) indicates that the solution (E) consists Fe3+ ions. Thus, (F) = Diamminsilver (I) chloride, Ag (NH3)2Cl
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 d AND f BLOCK ELEMENTS 173

EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS

D & F Block 9. Transition elements

1. Transition elements have (a) exhibit inert-pair effect

(a) completely filled d levels (b) show nonmetallic character

(b) completely filled s levels and d levels (c) do not form complex compounds

(c) incompletely filled s levels and completely filled d (d) exhibit variable oxidation states
levels 10. The oxidation states shown by transition elements is
(d) incompletely filled d levels related to their

2. The general electronic configuration of the transition (a) electropositive characters

elements is (b) electronic configurations
10 2
(a) (n – 1)d (n + 1)s (c) atomic weights (d) atomic sizes
1–10 1–2
(b) (n – 1)d (n + 1)s 11. The electronic configuration of chromium is actually
[Ar]3d54s1 instead of normally expected [Ar]3d44s2. This
(c) (n – 1)d1–10 np6 ns2
is because
(d) (n – 1)d1–10 ns0–2 (a) an exactly half-filled d level gives additional stability,
3. Which of the following transition elements has completely according to the Hund rule of maximum multiplicity
filled d orbitals (the d10 configuration) (b) the 4s orbital has higher energy than the 3d orbitals
(a) Co (b) Cr (c) the 4s orbitals has lower energy than the 3d orbitals
(c) Hg (d) Ni (d) the 3d and 4s orbitals have equal energies and hence
electron migration occurs readily
4. In which of the following transition elements are the d
orbitals not completely filled ? 12. Identify the species having an atom in +6 oxidation state.
(a) Zn (b) Hg (a) MnO4 (b) Cr(CN)36 
(c) Cd (d) Ag
(c) NiF63 (d) CrO2Cl2
5. The electronic configurations of the first four members of
the actinide series cannot be written accurately in a regular 13. Which of the following is not true about the transition
manner because of elements ?
(a) small difference in energy between 5f and 6d orbitals (a) They show variable oxidation states
(b) large difference in energy between 5f and 6d orbitals (b) Their ions have a strong tendency to form complexes
(c) small difference in energy between 5f and 6s orbitals (c) Their compounds usually do not absorb ultraviolet
(d) violation of the Pauli exclusion principle and visible lights

6. The electronic configuration of silver is (d) Their ions and complex ions usually possess magnetic
moments.
(a) [Ar]3d10 4s1 (b) [Ar]4d10 4s1
14. What of the following is an incorrect statement?
(c) [Kr]4d10 5s1 (d) [Kr]4d8 5s2 (a) The lowest oxide of a transition metal is acidic whereas
7. The electronic configuration of palladium is the highest one is usually basic.
(b) A transition metal usually exhibits higher oxidation
(a) [Ar]3d84s2 (b) [kr]4d85s2
states in its fluorides than it its iodides.
(c) [kr]5d86s2 (d) [Ar]4d105s0 (c) Transition metal halides become more covalent with
8. The electronic configuration of platinum is the increasing oxidation state of the transition metal
and are more susceptible to hydrolysis.
(a) [Ar] 4f145d96s1 (b) [Ar] 4f145d106s2
(d) The highest oxide of a transition metal is acidic whereas
14
(c) [Ar] 4f 6d 7s 10 2 14
(d) [Ar] 4f 6d 7s 9 1 the lowest one is usually basic.
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 174 d AND f BLOCK ELEMENTS
15. Which of the following transition metals does not show 25. Which of the following compounds is expected to be
variable oxidation states ? coloured ?
(a) Mercury (b) Zinc (a) Ag2SO4 (b) CuF2
(c) Gold (d) Silver (c) MgF2 (d) CuCl
16. Which of the following ions is colourless in solution ? 26. The covalent radii of transition metals decrease from left
to right in a period because
(a) V3+ (b) Cr3+
(a) the densities of the metals decrease with increasing
(c) Co2+ (d) Sc3+ atomic number due to poor shielding of electrons

17. Which of the following ions has the maximum number of (b) the screening of nuclear charge by d electrons is poor
unpaired d electrons ? and hence the nuclear charge attracts all the electrons
strongly, causing a decrease in size
(a) Fe3+ (b) V3+
(c) the ionization energies also decrease correspondingly
3+ 2+
(c) Ti (d) Mg (d) the metallic character decreases as the atomic number
increases
18. Which of the following ions possesses the maximum
number of unpaired electrons ? 27. The highest possible oxidation state shown by osmium
in its compounds is
(a) Ni2+ (b) Fe2+
(a) +4 (b) +8
+ 2+
(c) Cu (d) Zn (c) +6 (d) +10
19. Which of the following does not possess unpaired 28. Which of the following oxides of chromium is amphoteric
electrons ? in nature ?
(a) Co3+ (b) Cu2+ (a) CrO (b) CrO3

(c) Ti2+ (d) Hg2+ (c) Cr2O3 (d) CrO5

20. Which one of the following ionic species will impart colour 29. Permanent magnetic are generally made from the alloy of
to an aqueous solution ? (a) Co (b) Zn
4+ +
(a) Ti (b) Cu (c) Al (d) Pb

(c) Zn2+ (d) Cr3+ 30. CrO3 dissolves in aqueous NaOH to give

21. Which of the following elements shows the maximum (a) CrO24 (b) Cr(OH)2
number of different oxidation states in its compounds ?
(c) Cr2 O72  (d) Cr(OH)3
(a) Eu (b) La
31. Lanthanide elements have
(c) Gd (d) Am
(a) similar lattice energies but widely different solvation
22. Which of the following electronic configurations and ionization energies
represents Fe3+ ? (b) similar lattice and solvation energies but widely
different ionization energies
(a) [Ar]3d64s2 (b) [Ar]3d54s1 (c) similar lattice and ionization energies but widely
different hydration energies
(c) [Ar]3d54s2 (d) [Ar]3d54s0
(d) similar lattice energies, solvation energies and
23. The last electron of a d-block element occupies the orbital ionization energies
(a) (n – 1)d (b) nd 32. Among the transition metals, the melting points of Zn, Cd
and Hg are relatively low because
(c) np (d) (n – 1)s
(a) their d shells are not completely filled
24. Which of the following ions is expected to the coloured
(b) their d electrons do not participate in metallic bonding
in solution ?
(c) their densities are higher
(a) Cu+ (b) Cu2+
(c) Ti4+ (d) Sc3+ (d) of all the above
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d AND f BLOCK ELEMENTS 175
33. The noble character of platinum and gold is favoured by 39. Which of the following compounds is green in colour ?
(a) high enthalpies of sublimation, high ionization (a) KMnO4 (b) (NH4)2Cr2O7
energies and low enthalpies of solvation
(c) MnO2 (d) K2MnO4
(b) high enthalpies of sublimation, low ionization energies
and low enthalpies of solvation 40. Cr2O72 reacts with OH– as
(c) low enthalpies of sublimation, high ionization energies
and low enthalpies of solvation Cr2O72  2(OH ) o 2CrO24  H2O
(d) high enthalpies of sublimation, high ionization The change in oxidation number of Cr is
energies and high enthalpies of solvation
(a) +6 (b) +3
34. The transition elements are
(c) zero (d) +4
(a) more reactive than group 1 elements
41. CrO 24  reacts with H+ as
(b) more reactive than group 2 elements
(c) less reactive than group 1 elements but more reactive 2CrO24  2H o Cr2O72  H2 O
than group 2 elements
The change in oxidation number of Cr is
(d) less reactive than group 1 and 2 elements
(a) +5 (b) +7
35. Transition metals
(c) +6 (d) zero
(a) form only ionic compounds
42. Which of the following ions is paramagnetic ?
(b) form exclusively covalent compounds
(a) Zn2+ (b) N3–
(c) may form either ionic or covalent compounds
depending on the condition (c) Mn4+ (d) Cu+
(d) exclusively form coordination compounds but no 43. Which of the following ions is diamagnetic ?
simple compounds
(a) Ni2+ (b) Ti4+
36. Which of the following statements is incorrect ?
(a) The compounds formed by the 3d transition metals in (c) Cr3+ (d) Co3+
lower valence states are ionic but those in higher
44. The value of magnetic moment (P spin only) for Cu2+ in
valence states are covalent.
CuSO4.5H2O is
(b) The 4d and 5d transition metals form less ionic
compounds than do the 3d transition metals. (a) 5.92 BM (b) 4.92 BM

(c) The compounds formed by the 3d transition metals (c) 2.83 BM (d) 1.73 BM
are less ionic than the corresponding compounds 45. For a given ion, the magnetic moment is 2.83 BM. The
formed by the 4d and 5d transition metals. total spin (s) of all the unpaired electrons is
(d) The ionization energies of 3d, 4d and 5d transition (a) 2 (b) 1
metals are greater than those of group 1 and 2 metals.
(c) 3/2 (d) 1/2
37. Which of the following compounds is colourless?
46. Wilkinson’s catalyst consists of
(a) K2MnO4 (b) HgI2
(a) (C2H5)3 Al and TiCl4 (b) RhCl3 and Ph3P
(c) ZnSO4 (d) FeSO4
(c) HCo(CO)4 (d) trans-[(Rh(CO)(H)(PPh3)3]
38. The compound ZnSO4 is white because
47. Which of the following mixture is known as Fenton’s
(a) charge is transferred from the metal to the oxygen atoms reagent ?
(b) electron transfer to d level does not occur as the level (a) FeSO4 + K4[Fe(CN)6] (b) FeSO4 + PdCl2
is already filled to capacity in zinc
(c) FeSO4 + H2O2 (d) TiCl4 + (C6H5)3P
(c) Zn2+ has d10 configuration and d–d transition occurs easily

(d) Zn2+ ions absorb light of the visible range

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 176 d AND f BLOCK ELEMENTS
48. Which of the following is known as Adams catalyst ? 55. Deep red-yellow vapour of CrO2Cl2 is passed into an
(a) Pt/PtO (b) V2O5/TiCl4 aqueous solution of NaOH. The solution turns

(c) Cu/V (d) Pt/Rh (a) yellow due to the formation of Na2Cr2O7

49. The transition metals sometimes form nonstoichiometric (b) yellow due to the formation of Na2CrO4
compounds. These compounds have
(c) green due to the formation of CrCl3
(a) definite structures and definite proportions
(b) indefinite structures and definite proportions (d) red due to the formation of Na2CrO4

(c) definite structures and indefinite proportions 56. Acidified K2Cr2O7 on treatment with KI produces
(d) indefinite structures and indefinite proportions (a) KIO3 (b) I2
50. Which of the following statements is correct ?
(c) KIO4 (d) I3
(a) The second-row elements have smaller radii than the
corresponding third-row ones. 57. Na2CrO4 on treatment with lead acetate gives a precipitate.
(b) Because of lanthanide contraction, the radii of the This precipitate is dried and the solid is used as a pigment
third-row elements are almost the same as those of the for road signs and markings. The solid is known as
first-row elements.
(a) white lead (b) chrome green
(c) Because of lanthanide contraction, the radii of the
third-row elements are almost the same as those of the (c) chrome yellow (d) red lead
second-row elements. 58. Which of the following ores is known as pyrolusite ?
(d) Because of lanthanide contraction, the separation of
second-row elements from one another is easier. (a) Fe2O3 (b) SnO2

51. Sodium chromate is prepared by (c) MnO2 (d) PbS

(a) fusing chromite (FeCr2O4) with sodium chloride in air 59. Which of the following oxides of manganese is
amphoteric ?
(b) fusing chromite (FeCr2O4) with sodium hydroxide in
air (a) MnO (b) Mn2O3
(c) fusing (NH4)2Cr2O7 with sodium hydrogen sulphate (c) Mn2O7 (d) MnO2
in nitrogen
60. Which of the following oxides of manganese is stable as
(d) fusing sodium dichromate with carbon well as strongly acidic ?
52. When hydrogen peroxide is added to an acidic solution
(a) MnO2 (b) Mn2O7
of a dichromate, the most probable product is
(a) K2CrO4 (b) CrO3 (c) MnO3 (d) Mn2O3

(c) Cr2O3 (d) CrO(O2)2 61. KMnO4 is manufactured on a large scale by

53. Which of the following statements is incorrect for CrO3 ? (a) fusing MnO2 with KOH and then oxidizing the fused
(a) It is a bright orange solid. mixture with KNO3

(b) It is commonly called chromic acid. (b) fusing MnO2 with Na2CO3 in the presence of O2

(c) It is prepared by adding concentrated H2SO4 to a (c) fusing MnO2 with KOH and KNO3 to form K2MnO4
saturated solution of sodium dichromate. which is then electrolytically oxidized in an alkaline
(d) The colour arises due to d–d transition. solution

54. Chromyl chloride, CrO2Cl2, is prepared by heating a mixture of (d) fusing MnO2 with KNO3 and then acidifying the fused
mixture
(a) NaCl, K2Cr2O7 and NaOH
62. MnO4 is prepared by treating a solution containing Mn2+
(b) NaCl, K2Cr2O7 and concentrated H2SO4 ions with a very strong oxidizing agent such as
(c) NaCl, K2Cr2O7 and MnO2
(a) PbO2 (b) C2O24
(d) CrO3 and NaCl
(c) I2 (d) Fe3+
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d AND f BLOCK ELEMENTS 177
63. Which of the following is an incorrect statement ? 71. Which of the following statements is correct for the
lanthanoids ?
(a) In a redox reaction in acidic medium, KMnO4 produces
Mn2+ ions. (a) The 4f electrons do not take part in bonding.
(b) The 4f electrons can neither be removed to produce
(b) In a redox reaction in strongly alkaline medium, KMnO4
ions nor be made to take part in crystal field
produces MnO24 ions. stabilization of complexes.

(c) In a redox reaction in neutral medium, KMnO4 produces (c) The 4f electrons in the antepenultimate shell are very
effectively shielded by the 5s and 5p electrons.
MnO2.
(d) All of these
(d) In a redox reaction in alkaline medium, KMnO 4
produces Mn2O7. 72. The most common and stable oxidation state of a
lanthanide is
64. KMnO4 in an acidic medium oxidizes
(a) +II (b) +IV
2
(a) CrO 4 to CO2 (b) N2H4 to N2 (c) +VII (d) +III

(c) S2O32 to SO24  (d) all of these 73. The atomic and ionci radii (M3+ ions) of lanthanide
elements decrease with increasing atomic number. This
65. KMnO4 in an acidic medium will not oxidize effect is called
(a) lanthanide contraction
(a) NO2 (b) SO24
(b) lanthanide expansion
(c) HN3 (d) H2O2
(c) actinide contraction
66. Dilute and slightly alkaline KMnO4 is called (d) none of these
(a) Fenton’s reagent (b) Lucas reagent 74. Lanthanide contraction occurs because
(c) Baeyer’s reagent (d) Tollens reagent (a) the 4f electrons, which are gradually added, creat a
67. Which one of the following oxides of chromium is strong shielding effect
amphoteric in nature ? (b) the 4f orbitals are greater in size than the 3d and 3f
orbitals
(a) CrO (b) Cr2O3
(c) the 5f orbitals strongly penetrate into the 4f orbitals
(c) CrO3 (d) CrO5
(d) the poor shielding effect of 4f electrons is coupled
68. The electronic configuration of-block elements is with increased attraction between the nucleus and the
represented by added electrons
(a) (n – 2)f1–14 (n – 1)d0–1ns2 75. The hardness, melting point and boiling point of elements
increase from Ce to Lu because
(b) (n – 2)f1–14 (n – 1)d0–5ns0–2
(a) the attraction between the atoms increases as the size
(c) (n – 2)f1–14 (n – 1)d0–10ns1–2 increases
(d) (n – 2)f1–14 (n – 1)d0–2 (n – 1)s2 (b) the attraction between the atoms decreases as the size
increases
69. Lanthanides are characterized by the filling of the
(c) the attraction between the atoms increases as the size
(a) penultimate 4f energy level decreases
(b) antepenultimate 4f energy level (d) the attraction between the atoms remains the same as
(c) penultimate 3f energy level the size increases

(d) antepenultimate 3f energy level

70. The electronic configuration of cerium is

(a) [Xe]4f15d16s2 (b) [Xe]4f25d06s1

(c) [Xe]4f15d26s2 (d) [Xe]4f25d06s2

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 178 d AND f BLOCK ELEMENTS

EXERCISE - 2 : PREVIOUS YEAR COMPETITION QUESTIONS

2013
(c) It has no Cr – Cr bond and has six O – O bonds
1. Which of the following lanthanoid ions is diamagnetic ?
(d) It has one Cr – Cr bond and seven Cr – O bonds
(Atoms, Ce = 58, Sm = 62, Yb = 70) [CBSE AIPMT] 3+
2+ 2+
7. The spin only magnetic moment of Fe ion (in BM) is
(a) Yb (b) Ce approximately [KCET]
2+ 2+
(c) Sm (d) Eu (a) 4 (b) 7
2. KmnO4 can be prepared from K2MnO4 as per the reaction : (c) 5 (d) 6
8. Which of the following species is/are paramagnetic ?
3MnO 24  2H 2 O YZZ
ZZX 2MnO 4  MnO 2  4OH  2+ 0 2+ 4+
Fe , Zn , Hg , Ti [Kerala CEE]
–
The reaction can go to compition by removing OH ions by 2+ 0 4+
(a) Fe only (b) Zn and Ti
addings :- [CBSE AIPMT]
2+ 2+ 0 2+
(c) Fe and Hg (d) Zn and Hg
(a) SO2 (b) HCl
9. The acidic, basic or amphoteric nature of Mn2O7, V2O5 and
(c) KOH (d) CO2
CrO are respectively, [Kerala CEE]
2012
(a) acidic, acidic and basic
3. Which of the statements is not true ? [CBSE AIPMT]
(b) basic, amphoteric and acidic
(a) K2Cr2O7 solution becomes yellow on increasing the pH
(c) acidic, amphoteric and basic
beyond 7
(d) acidic, basic and amphoteric
(b) On passing H2S through acidified K2Cr2O7 solution, a
10. Ammonia will not form complex with [Kerala CEE]
milky colour is observed
2+ 2+
(a) Ag (b) Pb
(c) Na2Cr2O7 is preferred over K2Cr 2O 7 in volumetric
2+ 2+
analysis (c) Cu (d) Cd
(d) K2Cr2O7 solution in acidic medium is orange 11. The titanium (atomic number 22) compound that does not
exist is [Kerala CEE]
Transition Elements and Their Compounds
2011 (a) TiO (b) TiO2

4. For the four successive transition elements (Cr, Mn, Fe and (c) K2TiF6 (d) K2TiO4
Co), the stability of +2 oxidation state will be there in which 12. Copper exhibits only +2 oxidation state in its stable
of the following order ? [CBSE AIPMT] compounds. Why ? [Guj. CET]
(At. no. Cr = 24, Mn = 25, Fe = 26, Co = 27) (a) Copper is transition metal in +2 state.
(a) Cr > Mn > Co > Fe (b) Mn > Fe > Cr > Co (b) +2 state compounds of copper are formed by exothermic
(c) Fe > Mn > Co > Cr (d) Co > Mn > Fe > Cr reactions.
9
5. Acidified K2Cr2O7 solution turns green when Na2SO3 is (c) Electron configuration of copper in +2 state is [Ar]3d
0
added to it. This is due to the formation of 4s .
[CBSE AIPMT] (d) Copper gives coloured compounds in +2 state.
(a) CrSO4 (b) Cr2(SO4)3 13. When dil. H2SO4 is added to aqueous solution of potassium
chromate, yellow colour of solution turns to orange colour.
(c) CrO 24  (d) Cr2(SO3)3
It indicates [Guj. CET]
6. Which is the correct statement about Cr2 O72  structure ? (a) chromate ions are reduced

[DUMET] (b) chromate ions are oxidised

(a) It has neither Cr – Cr bonds nor O–O bonds (c) mono centric complex is converted into dicentric complex

(b) It has one Cr – Cr bond and six O – O bonds (d) oxygen gets removed from chromate ions
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d AND f BLOCK ELEMENTS 179

14. German silver alloy contains [Guj. CET] 23. In Cu (at. no. 29) [RPMT]
(a) zinc, silver and copper (a) 13 electrons have spin in one direction and 16 electrons
(b) nickel, silver and copper in other direction
(c) germanium, silver and copper (b) 14 electrons have spin in one direction and 15 electrons
(d) zinc, nickel and copper in other direction
2+ (c) one electron can have spin only in the clockwise
15. Experimental value of magnetic moment of Mn complex is
direction
5.96 BM. This indicates [Guj. CET]
(d) None of the above is correct
(a) axial and orbital motion of electron in same direction
24. Which one of the following ions is colourless ?
(b) axial and orbital motion of electron in opposite direction
(c) electron does not exhibit orbital motion, it only exhibits [Manipal, BVP]
+ 2+
axial motion (a) Cu (b) Co
(d) electron does not axial motion, it only exhibits orbital 2+ 3+
(c) Ni (d) Fe
motion
25. Which of the following statements concerning transition
2010
elements is false ? [Manipal, JCECE]
16. Which of the following pairs has the same size ?
(a) They are all metals
[CBSE AIPMT]
2+ 4+ 2+ 2+
(b) They easily form complex coordination compounds
(a) Zn , Hf (b) Fe , Ni
(c) They form compounds containing unpaired electrons
4+ 4+ 4+ 4+
(c) Zr , Ti (d) Zr , Hf and their ions are mostly coloured
17. Which of the following ions will exhibit colour in aqueous (d) They show multiple oxidation states always differing
solutions ? [CBSE AIPMT] by units of two
3+ 3+
(a) Sc (Z = 21) (b) La (Z = 57) 26. Choose the correct reaction to prepare mercurous chloride
3+ 3+ (calomel). [Guj. CET]
(c) Ti (Z = 22) (d) Lu (Z = 71)
'
18. Which of the following transition metal ions is not coloured? (a) HgCl2  Hg  o (b) Hg  Cl 2 
o
[AFMC]
+ 3+
(c) HgCl2  SnCl 2 
o
(a) Cu (b) V
2+ 2+ (d) Both options (a) and (c)
(c) Co (d) Ni 4
27. A transition element X has the configuration [Ar]d in its
19. Maximum number of unpaired electrons are present in
+3 oxidation state. Its atomic number is [JCECE]
[CPMT]
(a) 25 (b) 26
2+ 2+
(a) Fe (b) Mn
(c) 22 (d) 19
+ 2+
(c) Cu (d) Cr 28. In haemoglobin, the metal ion present is [WB JEE]
20. The colour of zinc sulphide is [MP PMT] 2+ 2+
(a) Fe (b) Zn
(a) white (b) black 2+ 2+
(c) Co (d) Cu
(c) brown (d) red
29. When Zn is treated with excess of NaOH, the product
21. The formula of mercurous ion is [MP PMT]
obtained is [BVP]
+
(a) Hg (b) Hg 2
(a) Zn(OH)2 (b) ZnOH
2
(c) Hg 2
(d) None of these (c) Na2ZnO2 (d) None of these
22. Which of the following has maximum unpaired d-electrons? 30. Which of the following is magnetite ? [VMMC]
[RPMT] (a) Fe2CO3 (b) Fe2O3
2+ 2+
(a) Zn (b) Fe (c) Fe3O4 (d) Fe2O3. 3H2O
2+ +
(c) Ni (d) Cu

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 180 d AND f BLOCK ELEMENTS
2009 39. The maximum number of unpaired electrons is preent in

31. Out of TiF62  ,CoF63 ,Cu 2 Cl 2 and NiCl 24  (Z of Ti = 22, [MHT CET]

Co = 27, Cu = 29, Ni = 28), the colourless species are (a) Fe (b) Cu

[CBSE AIPMT, AMU] (c) CO (d) Ni
40. The ion of least magnetic moment among the following is
(a) TiF62  and CoF63 (b) Cu 2 Cl 2 and NiCl24 
[J & K CET]
(c) TiF62  and Cu 2 Cl 2 (d) CoF63 and NiCl 42  3+ 2+
(a) Ti (b) Ni
32. Transition metals show paramagnetic behaviour. This is 2+ 2+
(c) Co (d) Mn
because of their [AFMC]
41. The atom of which one of the following elements has the
(a) high lattice energy
highest number of unpaired electrons ? [J & K CET]
(b) variable oxidation state
(a) 25Mn (b) 24Cr
(c) characteristic configuration
(d) unpaired electrons (c) 96Cm (d) 26Fe

33. For which of the following pairs, magnetic moment is same? 42. The amphoteric oxide among the following is
[AIIMS] [J & K CET]
(a) MnCl2, CuSO4 (b) CuCl2, TiCl3 (a) Cr2O3 (b) Mn2O7
(c) TiO2, CuSO4 (d) TiCl3, NiCl2 (c) V2O3 (d) CrO
34. Which compound is expected to be coloured ? [CPMT] 43. Which one of the following is a d-block element ?
(a) CuCl (b) CuF2 [J & K CET]
(c) Ag2SO4 (d) MgF2 (a) Gd (b) Hs
(c) Es (d) Cs
35. The magnetic moment of a transition metal ion is 15 BM.
2+ 2+ 2+ 2+
Therefore, the number of unpaired electrons present in it is 44. Out of Cu , Ni , Co and Mn those dissolve in dil. HCl
[KCET] only one gives a precipitate when H2S is passed. Identify
the corresponding one. [OJEE]
(a) 4 (b) 1
2+ 2+
(c) 2 (d) 3 (a) Ni (b) Cu
2+ 2+
36. The solid product formed on heating AgNO3 strongly to (c) Co (d) Mn
980 K is [Kerala CEE] 3+
45. Number of unpaired electrons in Mn is [OJEE]
(a) silver carbonate (b) silver nitride
(a) 2 (b) 3
(c) silver oxide (d) silver metal
(c) 4 (d) 5
37. The maximum oxidation state shown by Mn in its
2008
compounds is [Kerala CEE]
46. What is the correct order of spin only magnetic moment
(a) +4 (b) +5 2+ 2+ 2+
(in BM) of Mn , Cr and Ti ? [AFMC]
(c) +6 (d) +7
2+ 2+ 2+ 2+ 2+ 2+
38. Which one of the following sets correctly represent the (a) Mn > Ti > Cr (b) Ti > Cr > Mn
2+ 2+ 2+ 2+ 2+ 2+
increase in the paramagnetic property of the ions ? (c) Mn > Cr > Ti (d) Cr > Ti > Mn
[EAMCET] 47. Which of the following compounds is coloured ? [AIIMS]
2+ 2+ 2+ 2+
(a) Cu < V < Cr < Mn
(a) TiCl3 (b) FeCl3
2+ 2+ 2+ 2+
(b) Cu < Cr < V < Mn
(c) CoCl2 (d) All of these
2+ 2+ 2+ 2+
(c) Cu > V > Cr > Mn
2+ 2+ 2+ 2+
(d) V < Cu < Cr < Mn
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d AND f BLOCK ELEMENTS 181

48. An aqueous solution of CoCl2 on addition of excess of 55. The highest oxidation state exhibited by transition metals
conc. HCl turns blue due to the formation of [DUMET] is [J&K CET]
2– (a) +7 (b) +8
(a) [Co(H2O)]Cl2 (b) [Co(H2O)2Cl4]
2– (c) +6 (d) +5
(c) [CoCl4] (d) [Co(H2O)2Cl2]
56. Which one of the following statements is not true with
49. Mercury is a liquid metal because [KCET]
regard to transition elements ? [J&K CET]
(a) it has a completely filled s-orbital
(a) They readily form complex compounds
(b) it has a small atomic size
(b) They show variable oxidation states
(c) it has a completely filled d-orbital that prevents d-d
(c) All their ions are colourless
overlapping of orbitals
(d) Their ions contain partially filled d-electrons
(d) it has a completely filled d-orbital that causes d-d
overlapping 2007

50. A transition metal ‘A’ has ‘spin-only’ magnetic moment 57. Which one of the following ions is the most stable in
value of 1.8 BM. When it is reacted with dilute sulphuric aqueous solution ? (At. no. Ti = 22, V = 23, Cr = 24, Mn = 25)
acid in the presence of air, a compound ‘B’ is formed. ‘B’ [CBSE AIPMT]
reacts with compound ‘C’ to give compound ‘D’ with 3+ 3+
(a) Cr (b) V
liberation of iodine. Then, the metal A and compounds B, C
3+ 3+
and D are respectively [Kerala CEE] (c) Ti (d) Mn
(a) Ti, TiSO4, KI and TiI2 58. Acidified potassium permanganate solution is decolourised
by [AFMC]
(b) Zn, ZnSO4, KI and Zn2I2
(a) bleaching powder (b) white vitriol
(c) Cu, CuSO4, KI and Cu2I2
(c) Mohr’s salt (d) microcosmic salt
(d) Cu, CuSO4, Cu2I2 and CuI2 59. Assertion : Mercury vapour is shining silvery in
51. Which of the following pairs of transition metal ions are the appearance.
stronger oxidising agents in aqueous solutions ? Reason : Mercury is a metal with shining silvery appearance.
[Kerala CEE] [AIIMS]
2+ 2+ 2+
(a) V 2  and Cr (b) Ti and Cr (a) Both Assertion and Reason are true and Reason is the
3+ 3+ 2+ 2+ correct explanation of Assertion.
(c) Mn and Co (d) V and Fe
(b) Both Assertion and Reason are true but Reason is not
52. Which of the following group of transition metals is called the correct explanation of Assertion.
coinage metals ? [RPMT]
(c) Assertion is true but Reason is false.
(a) Cu, Ag, Au (b) Ru, Rh, Pd
(d) Both Assertion and Reason are false.
(c) Fe, Co, Ni (d) Os, Ir, Pt
60. Which of the following ions has the least magnetic moment?
53. Potassium dichromate is used [Guj. CET]
[AMU]
(a) in electroplating 2+ 2+
(a) Cu (b) Ni
(b) as a reducing agent
3+ 2+
(c) oxidise ferrous ions into ferric ions in acidic media as an (c) Co (d) Fe
oxidising agent 61. CuSO4 when reacts with KCN forms CuCN which is insoluble
(d) as an insecticide in water. It is soluble in excess of KCN, due to formation of
the following complex [Punjab PMET]
54. Calomel on reaction with ammonium hydroxide gives
[JCECE] (a) K2[Cu(CN)4] (b) K3[Cu(CN)4]

(a) HgO (b) Hg2O (c) CuCN2 (d) Cu[K Cu(CN)4]

(c) NH2 – Hg – Hg – Cl (d) HgNH2Cl

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 182 d AND f BLOCK ELEMENTS
62. Formula of ammonium manganate is [DUMET] 72. A transition metal ion exists in its highest oxidation state. It
is expected to behave as [KCET]
(a) NH4MnO4 (b) (NH4)2MnO4
(a) a chelating agent
(c) NH4(MnO4)2 (d) NH4Mn2O4
(b) a central metal in a coordination compound
63. The dark blue colour of the solution formed when excess of
ammonia is added to a solution of copper(II) sulphate is (c) an oxidising agent (d) a reducing agent
due to the presence of the ion [Kerala CEE] 73. The following is known as “bordeaux mixture” [Kerala CEE]
2– 2+ (a) Borax and copper sulphate
(a) [Cu(OH)4 (H2O)2] (b) [Cu(H2O)6]
4+ 2+ (b) Orthoboric acid and ferrous sulphate
(c) [Cu(NH3)2 (H2O)4] (d) [Cu(NH3)4 (H2O)2]
(c) Sodium borate and zinc sulphate
64. Among the following series of transition metal ions, the
2 6 (d) Copper sulphate and lime
one in which all metal ions have 3d , 3p electronic
configuration is (At. no. Ti = 22 ; V = 23 ; Cr = 24, Mn = 25) 74. Wich of the following metals form amphoteric oxide ?
[Manipal] [MP PMT]
3+ 2+ 3+ 4+ + 4+ 6+ 7+
(a) Ti , V , Cr , Mn (b) Ti , V , Cr , Mn (a) Fe (b) Cu
4+ 3+ 2+ 3+ 2+ 3+ 4+ 5+ (c) Zn (d) Ca
(c) Ti , V , Cr , Mn (d) Ti , V , Cr , Mn
75. The stability of ferric ion is due to [BCECE]
65. Among K, Ca, Fe and Zn, the element which can form more
than one binary compound with chlorine is [Manipal] (a) half-filled f-orbitals (b) hal-filled d-orbitals

(a) Fe (b) Zn (c) completely filled f-orbitals

(c) K (d) Ca (d) completely filled d-orbitals

66. Blue vitriol is [RPMT] 76. Which of the following is red in colour ? [JCECE]

(a) MgSO4 . 7H2O (b) CuSO4 . 5H2O (a) Cu2O (b) CuF

(c) CaSO4 . 2H2O (d) ZnSO4 . 7H2O (c) ZnF2 (d) ZnCl2

67. Reason of passivity of iron is [RPMT] 77. Fenton’s reagent is [JCECE]

(a) Fe2O3 (b) Fe3O4 (a) SnCl2 + HCl (b) AgNO3 + NH4OH

(c) FeO (d) Fe2O4 . 3H2O (c) CuSO4 + NaOH (d) FeSO4 + H2O2

68. Essential component of amalgam is [RPMT] 78. The coordination number in an ....... complex may increase
to 8. [J&K CET]
(a) Fe (b) Pb
(a) cobalt (b) osmium
(c) Hg (d) Cr
(c) nickel (d) iron
69. In which of the following ions, d–d transition is not
possible? [Guj. CET] 79. Which of the following is used as indelible ink ?
3+ 4+ [J&K CET]
(a) Cr (b) Ti
2+ 2+ (a) Aqueous CuSO4 solution
(c) Cu (d) Mn
70. Which of the following is used as purgative ? [BCECE] (b) Aqueous AgNO3 solution
(c) Aqueous NaCl solution
(a) HgS (b) Hg2Cl2
(d) Aqueous NaOH solution
(c) HgCl2 (d) ZnSO4
2005
2006
80. Four successive members of the first row transition elements
71. 4K 2 Cr2 O 7 
o 4K 2 CrO 4  3O 2  X . In the above
Heat are listed below with their atomic numbers. Which one of
them is expected to have the highest third ionisation
reaction X is [AMU]
enthalpy ? [CBSE AIPMT]
(a) CrO3 (b) Cr2O7 (a) Vanadium (Z = 23) (b) Chromium (Z = 24)
(c) Cr2O3 (d) CrO5 (c) Iron (Z = 26) (d) Manganese (Z = 25)
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d AND f BLOCK ELEMENTS 183

81. Which of the following is a highly corrosive salt ? 2004

[AFMC] 89. The transition metal used as a catalyst is [Punjab PMET]
(a) FeCl2 (b) PbCl2 (a) nickel (b) platinum
(c) Hg2Cl2 (d) HgCl2 (c) cobalt (d) All of these
82. Which of the following is obtained when auric chloride 90. Vanadium (III) oxide is the strong [Kerala CEE]
reacts with sodium chloride ? [AMU]
(a) drying agent (b) oxidising agent
(a) Na[AuCl] (b) Na[AuCl2]
(c) reducing agent (d) wetting agent
(c) Na[AuCl3] (d) Na[AuCl4] (e) precipitating agent
83. Green vitriol is formed by [Punjab PMET] 91. Which element is not found in nature ? [RPMT]
(a) FeS2 + H2O + O2 (b) FeS2 + H2O + CO2 (a) Tc (b) Y
(c) FeS2 + CO + CO2 (b) FeS2 + CO (c) Sr (d) Pt
84. Which of the following pairs of elements cannot form an 92. Mohr’s salt is [JCECE]
alloy ? [KCET]
(a) Na2SO4 . Al2(SO4)3 . 24H2O
(a) Zn, Cu (b) Fe, Hg
(c) Fe, C (d) Hg, Na (b) CuSO4 . Al2(SO4)3 . 24H2O
3+
85. Assertion : The spin only magnetic moment of Sc is 1.73 (c) FeSO4 . (NH4)2SO4 . 6H2O
BM
(d) K2SO4 . Fe2(SO4)3 . 24H2O
Reason : The spin only magnetic moment (in BM) of an ion
2003
is equal to n(n  2) , where n is the number of unpiared
93. The basic character of the transition metal monoxides
electrons present in the ion. [EAMCET] follows the order
(a) Both Assertion and Reason are true and Reason is the (At. no. Ti = 22, V = 23, Cr = 24, Fe = 26)
correct explanation of Assertion.
[CBSE AIPMT]
(b) Both Assertion and Reason are true but Reason is not
(a) TiO > FeO > VO > CrO
the correct explanation of Assertion.
(b) TiO > VO > CrO > FeO
(c) Assertion is true but Reason is false.
(c) VO > CrO > TiO > FeO
(d) Assertion is false but Reason is true.
86. The magnetic moment P, of transition metals is related to (d) CrO > VO > FeO > TiO
the number of unpaired electrons, n as [JCECE] 94. The colourless species is [AIIMS]

(a) P = n (n + 2)2 (b) P = n2 (n + 2) (a) VCl3 (b) VOSO4

(c) Na3VO4 (d) [V(H2O)6]SO4 . H2O

n
(c) P (n  2) (d) P n(n  2) 95. Assertion : Solution of Na 2CrO4 in water is intensely
coloured.
87. CrO3 dissolves in aqueous NaOH to give [J&K CET]
Reason : Oxidation state of Cr in Na2CrO4 is +VI.
2 
(a) CrO 4 (b) Cr(OH) 3 [AIIMS]

(c) Cr2 O72  (d) Cr(OH)2 (a) Both Assertion and Reason are true and Reason is the
correct explanation of Assertion.
88. Which of the following is the green coloured powder
(b) Both Assertion and Reason are true but Reason is not
produced when ammonium dichromate is used in fire works?
the correct explanation of Assertion.
[J&K CET]
(c) Assertion is true but Reason is false.
(a) Cr (b) CrO3
(d) Both Assertion and Reason are false.
(c) Cr2O3 (d) CrO(O2)
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 184 d AND f BLOCK ELEMENTS
96. Copper sulphate is commercially made from copper scrap Lanthanides and Actinides
by [AMU]
2010
(a) heating with sodium sulphate
104. Which of the ions is colourless inspite of the presence of
(b) heating with sulphur unpaired electrons ? [MHT CET]
3+ 3+
(c) action of dilute sulphuric acid and air (a) La (b) Eu
3+ 3+
(d) dissolving in hot conc. sulphuric acid (c) Gd (d) Lu
4+
97. Lunar caustic is [Punjab PMET] 105. Ce in stable. This is because of [MHT CET]
(a) AgCl (b) AgNO3 (a) half-filled d-orbitals

(c) NaOH (d) KNO3 (b) all paired electrons in d-orbitals

(c) empty orbitals
98. Which of the following is called white vitriol ? [DUMET]
(d) fully filled d-orbitals
(a) ZnCl2 (b) MgSO4 . 7H2O
106. The lanthanoid contraction relates to [CMC Ludhiyana]
(c) ZnSO4 . 7H2O (d) Al2(SO4)3 (a) atomic radii
99. Which gas is evolved, when ammonium dichromate is 3+
(b) atomic as well as M radii
heated ? [DUMET]
(c) valence electrons
(a) Hydrogen (b) Ammonia
(d) oxidation states
(c) Oxygen (d) Nitrogen
107. Across the lanthanide series, the basicity of the lanthanide
100. All the following statements about the transitional elements hydroxides [BVP]
are true except that [Kerala CEE] (a) increases
(a) all of the transitional elements are predominantly metallic (b) decreases
(b) in aqueous solution many of their simple ions are (c) first increases and then decreases
coloured.
(d) first decreases and then increases
(c) most of the transitional elements show pronounced 108. More number of oxidation state are exhibited by the actinoids
catalytic activity. than by the lanthanoids. The main reason for this is
(d) most of the transitional elements show only one valence [VMMC]
state.
(a) lesser energy difference between 5f- and 6d-orbitals than
101. Which of the following is more soluble in ammonia ? that between 4f- and 5d-orbitals.
[MHT CET] (b) greater metallic character of the lanthanoids than that of
the corresponding actionoids.
(a) AgCl (b) AgBr
(c) more active nature of the actinoids.
(c) AgI (d) None of these
(d) more energy difference between 5f and 6d-orbitals than
102. On going left to right in a period, in transition metals, their that between 4f and 5d-orbitals.
atomic volume [MP PMT]
2009
(a) decreases (b) increases
109. Which of the following is man-made element ? [AFMC]
(c) remain same (d) None of these
(a) Ra (b) U
103. Addition of HgCl2 to SnCl2 gives a black colour due to (c) Np (d) C
[JCECE] 110. The pair, that referred as ‘chemical twins’ is [MHT CET]

(a) oxidation of Sn (b) reduction of HgCl2 (a) Ac, Cf (b) Hg, Ta

(c) Tc, Re (d) La, Ac
(c) formation of amalgam (d) oxidation of Hg

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d AND f BLOCK ELEMENTS 185

111. Most basic hydroxide among the following is (c) As a result of lanthanoid contraction, the properties of
[MHT CET] 4d-series of the transition elements have no similarities
with the 5d-series of elements.
(a) Lu(OH)3 (b) Eu(OH)3
(d) Shielding power of 4f electrons is quite weak.
(c) Yb(OH)3 (d) Ce(OH)3
119. General electronic configuration of lanthanides are
2008
[Punjab PMET]
112. Which of the following is not an actinide ? [AMU]
1–14 2 6 0–1 2
(a) Curium (b) Californium (a) (n – 2) f (n – 1) s p d ns
10–14 0–1 2
(c) Uranium (d) Terbium (b) (n – 2) f (n – 1) d ns
113. Identify the incorrect statement among the following. 0–14 10 2
(c) (n – 2) f (n – 1) d ns
[BHU] 0–1 1–14 2
(d) (n – 2) d (n – 1) f ns
(a) d-block elements show irregular and erratic chemical
3+ 3+ 3+ 3+
properties among themselves. 120. The correct order of ionic radii of Y , La , Eu and Lu is
(b) La and Lu have partially filled d-orbitals and no other [Kerala CEE]
partially filled orbitals. 3+ 3+ 3+ 3+
(a) Y < La < Eu < Lu
(c) The chemistry of various lanthanoids is very similar.
3+ 3+ 3+ 3+
(d) 4f- and 5f - orbitals are equally shielded. (b) Lu < Eu < La < Y
3+ 3+ 3+ 3+
114. The point of dissimilarity between lanthanides and actinides (c) La < Eu < Lu < Y
is [MHT CET] 3+ 3+ 3+ 3+
(d) Y < Lu < Eu < La
(a) three outermost shells are partially filled.
121. Lanthanides are [Manipal]
(b) they show oxidation state of +3 (common).
(a) 14 elements in the sixth period (atomic no. = 90 to 103)
(c) they are called inner-transition elements.
that are filling 4f sub-level.
(d) they are radioactive in nature.
(b) 14 elements in the seventh period (atomic no. = 90 to
115. Most common oxidation states of Ce (cerium) are
103) that are filling 5f sub-level.
[MHT CET]
(c) 14 elements in the sixth period (atomic no. = 58 to 71)
(a) +3, +4 (b) +2, +3 that are filling 4f sub-level.
(c) +2, +4 (d) +3, +5
(d) 14 elements in the seventh period (atomic no. = 58 to 71)
116. On which factors, the stability of an oxidation state of that are filling 4f sub-level.
lanthanoide elements depends ? [Guj. CET]
2006
(a) Enthalpy
122. Which of the following is not an actinoid ? [DUMET]
(b) Internal energy
(a) Am (b) Cm
(c) Combined effect of hydration energy and ionisation
energy (c) Fm (d) Tm
(d) Electronic configuration 123. The lanthanoid contraction is responsible for the fact that
117. Differentiating electron in inner-transition elements enters [Guj. CET]
in the ........ orbital. [J&K CET] (a) Zr and Y have about the same radius
(a) s (b) p
(b) Zr and Nb have similar oxidation state
(c) d (d) f
(c) Zr and Hf have about the same radius
2007
(d) Zr and Zn have the same oxidation state
118. Identify the incorrect statement among the following
2005
[CBSE AIPMT]
(a) There is a decrease in the radii of the atoms or ions as 124. Europium is [DUMET]
one proceeds from La to Lu. (a) s-block element (b) p-block element
(b) Lanthanoid contraction is the accumulation of (c) d-block element (d) f-block element
successive shrinkages.
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 186 d AND f BLOCK ELEMENTS

125. Which belongs to the actinide series ? [J&K CET]

(a) Ce (b) Cf
(c) Ca (d) Cs
2004
126. Lanthanides and actinides resemble in [AFMC]
(a) electronic configuration
(b) oxidation state
(c) ionisation energy
(d) formation of complexes
127. Which of the following lanthanide is commonly used in the
manufacture of alloys ? [Manipal]
(a) Lanthanum
(b) Nobelium
(c) Thorium (d) Cerium
128. The atomic size of cerium and promethium is quite close,
because [JCECE]
(a) they are in same period in Periodic Table
(b) their electronic configuration is same
(c) f-electrons have poor shielding effect
(d) nuclear charge is higher on cerium than promethium
2003
129. Lanthanide for which +II and +III oxidation states are
common is [AIIMS]
(a) La (b) Nd
(c) Ce (d) Eu

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d AND f BLOCK ELEMENTS 187

ANSWER KEY

Exercise ­ 1 : (Basic Objective Questions)

1. (d) 2. (d) 3. (c) 4. (d) 5. (a) 6. (c) 7. (d) 8. (a) 9. (d) 10. (b)

11. (a) 12. (d) 13. (c) 14. (a) 15. (b) 16. (d) 17. (a) 18. (b) 19. (d) 20. (d)
21. (d) 22. (d) 23. (a) 24. (b) 25. (b) 26. (b) 27. (b) 28. (c) 29. (a) 30. (a)
31. (d) 32. (b) 33. (a) 34. (d) 35. (c) 36. (c) 37. (c) 38. (b) 39. (d) 40. (c)
41. (d) 42. (c) 43. (b) 44. (d) 45. (b) 46. (b) 47. (c) 48. (a) 49. (d) 50. (c)
51. (b) 52. (d) 53. (d) 54. (b) 55. (b) 56. (b) 57. (c) 58. (c) 59. (b) 60. (b)
61. (c) 62. (a) 63. (d) 64. (d) 65. (b) 66. (c) 67. (b) 68. (a) 69. (b) 70. (a)

71. (d) 72. (d) 73. (a) 74. (d) 75. (c)

Exercise ­ 2 : (Previous Year Competition Questions)

1. (a) 2. (d) 3. (c) 4. (b) 5. (b) 6. (a) 7. (d) 8. (a) 9. (c) 10. (b)
11. (d) 12. (b) 13. (c) 14. (d) 15. (a) 16. (d) 17. (c) 18. (a) 19. (b) 20. (a)
21. (c) 22. (b) 23. (b) 24. (a) 25. (d) 26. (d) 27. (a) 28. (a) 29. (c) 30. (c)
31. (c) 32. (d) 33. (b) 34. (b) 35. (d) 36. (d) 37. (d) 38. (a) 39. (a) 40. (a)
41. (c) 42. (a) 43. (b) 44. (b) 45. (c) 46. (c) 47. (d) 48. (c) 49. (c) 50. (c)
51. (c) 52. (a) 53. (c) 54. (d) 55. (b) 56. (c) 57. (d) 58. (c) 59. (d) 60. (a)
61. (b) 62. (b) 63. (d) 64. (d) 65. (a) 66. (b) 67. (b) 68. (c) 69. (b) 70. (b)
71. (c) 72. (c) 73. (d) 74. (c) 75. (b) 76. (a) 77. (d) 78. (b) 79. (b) 80. (d)
81. (d) 82. (d) 83. (a) 84. (b) 85. (d) 86. (d) 87. (a) 88. (c) 89. (d) 90. (c)
91. (a) 92. (c) 93. (b) 94. (c) 95. (b) 96. (c) 97. (b) 98. (c) 99. (d) 100. (d)
101. (a) 102. (d) 103. (b) 104. (c) 105. (c) 106. (b) 107. (b) 108. (a) 109. (c) 110. (c)
111. (d) 112. (d) 113. (d) 114. (d) 115. (a) 116. (c) 117. (d) 118. (c) 119. (a) 120. (d)

121. (c) 122. (d) 123. (c) 124. (d) 125. (b) 126. (b) 127. (d) 128. (c) 129. (d)

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