CHAPTER

Transition Metals Including

19 Lanthanides and Actinides
Chapter Highlights
Electronic con guration, General properties, Oxidation states of transition metals, General properties of second
and third row transition elements, inner transition elements, General discussion with special reference to oxidation
states, Lanthanide contraction and various levels of multiple-choice questions.

d-BLOCK AND f-BLOCK ELEMENTS

Table 19.1 d-and f-Block Elements

IIIB IVB VB VIB VIIB VIII IB IIB
3d-series 21
Sc 22
Ti 23
V 24
Cr 25
Mn 26
Fe 27
Co 28
Ni 29
Cu Zn
30

4d-series 39
Y 40
Zr Nb
41 42
Mo Tc
43 44
Ru 45
Rh Pd
46 47
Ag Cd
48

5d-series 57
La 72
Hf 73
Ta 74
W 75
Re 76
Os 77
Ir 78
Pt 79
Au 80
Hg
6d-series 89
Ac 104
Rf

TRANSITION ELEMENTS Electronic Configuration

• Those elements which have their last valence elec- The general electronic configuration of transition elements
tron in d orbital or those elements which have two is (n–1) d1–10, ns1–2
outermost shells incomplete are called d-block
In case of 3d-series
elements.
• They are called transition elements as their proper- 3d1–10, 4s1–2
ties lie in between the properties of s-and p-block • 21Sc : [Ar], 3d1, 4s2
elements. • 24Cr : [Ar], 3d5, 4s1
• Here the first transition d-series is 3d-series having • 29Cu : [Ar], 3d10, 4s1
ten elements from 21Sc to 30Zn. • 30Zn : [Ar], 3d10, 4s2
• Here the second transition d-series is 4d-series hav-
ing ten elements from 39Y to 48Cd. In case of 4d-series
• Here the third transition d-series is 5d-series having 4d1–10, 5s0–2
ten elements from 57La, 72Hf to 80Hg.
• Here the fourth transition d-series is 6d-series having Some Exceptional Configuration
elements from 89Ac onwards. • Nb : [Kr], 4d4, 5s1
41
• Here group IIIB and IIB elements are non-typical • Mo : [Kr], 4d5, 5s1
42
transition elements.
19.2 Chapter 19

(b) Iridium(Ir) has maximum density in the peri-

• 44Ru : [Kr], 4d7, 5s1
odic table (22.61 g/ml) followed by osmium (OS)
• 45Rn : [Kr], 4d8, 5s1 (22.57 g/mL).
• 46Pd : [Kr], 4d10, 5s0
• 47Ag : [Kr], 4d10, 5s1 Melting Point and Boiling Point
Reason The exeptional configurations occur due to nuclear These elements have high value of boiling point, melting
electron and e––e– forces present in these atoms. point. Here, tungsten has highest melting point (3410oC)
among these metals.
In Case of 5d-Series Melting and boiling point ∝ metallic bond strength ∝
4f 0–14, 5d1–10, 6s2 Number of unpaired electrons
• 78
Pt : [54 Xe], 4f 14, 5d9 , 6s1 • Melting point, boiling point increase from group
• Au : [54 Xe], 4f 14, 5d10 , 6s1 III B to group VIII B then decreases due to decrease
79
in number of unpaired electrons.
Physicochemical Properties • Melting point, boiling point increase from top to bot-
tom except in group IB and IIB
Metallic character and related properties
• All transition elements are metals with metallic lus- W > Mo > Cr
ture due to low ionization energy values. Cu > Ag > Au
• All of these are generally hard, ductile, malleable, • Zn, Cd and Hg have relatively lower melting points
brittle and form alloys. than the other d-block elements. Since they have
• These are good conductors of heat and electricity due completely filled (n–1) d orbitals, their atoms are
to presence of free or mobile electrons. not expected to form covalent bonds amongst
• Cu, Ag, Au have high conductivity. themselves.
• They are hard due to strong metallic bonding.
Atomic radii
Hardness ∝ Metallic bond strength
1. In a period: The value of atomic radii first decreases
∝ No. of unpaired electrons
with the increase of atomic number and then becomes
For example, Cr, Mo, W are extremely hard due to almost constant and finally increases slightly.
presence of maximum number of unpaired electrons.
IIIB -----------VI B----VII B, VIII B ----- IB, IIB
• Zn, Cd, Hg are not very hard, as no unpaired electron
Decrease in size Slight increase
is present in them. Constant value
• Hg is soft and liquid, due to the presence of weakest (a) Slight increase in radii in elements of group IA
metallic bond. and IIB is due to pairing of electrons in d orbit-
als, that is, when more e––e– repulsion occurs, so
Atomic volume and density
Zeff decreases. The following list gives the atomic
These elements have a low atomic volume but higher radius of various elements in picometres.
density as compared to s - or p-block elements because of Sc Ti V Cr Mn Fe
the greater nuclear pull resulting from poorly screened as 162 147 134 127 126 126
nuclear charge is weakly screened. Volume decreases from Co Ni Cu Zn
group IIIB to group VIII and then increases from group IB 125 124 128 130
to group IIB. Density increases from group IIIB to group
VIII and then decreases. 2. In a group: Atomic radii increases from top to bottom
however sizes of 4d, 5d series elements are nearly same in
1. Reason: This is due to the presence of small radius and groups due to lanthanide contraction.
close packed structure of atoms of these elements. 3. Lanthanide contraction: It is a steady or a very lit-
(a) Density increases from top to bottom. Density of tle decrease in size of atoms due to poor screening
IIIrd series is nearly double as that of IInd series effect of 4f electrons because of the diffused shape of
because the atomic weight is nearly double. f-orbitals.
For example,
Ti Zr Hf
4.5 6.9 13.2 g/cm3
 Transition Metals Including Lanthanides and Actinides 19.3

Ionic radii • It is due to the fact that the energy of (n – 1)d and
ns electrons are nearly same, so removal of electrons
1. In a Period: Ionic size of cations with same oxidation num-
is easy. When ns electrons are removed, the remain-
ber decreases in a period with the increase in atomic number.
der is called core or Kernel (unstable). One or more
Ti+2 > V+2 > Cr+2 > Mn+2 > Fe+2 > Co+2 > Ni+2 > Cu+2 electrons can be further removed for stability. Hence,
(a) When oxidation numbers are different, ionic size more number of oxidation states are possible. For
decreases with the increase in oxidation number. example,
Ti+2 > Ti+3 > Ti+4 > Ir+2 > Cr+3 > Cr+4 > Cr+5 --------- Sc : +2, +3 Ti : +2, +3, +4, +5
--------- Cu+ > Cu+2. V : 0, +2, to +5 Cr : 0, +1 to +6
2. In a Group: Ionic radii increases from top to bottom. Zn : +2 Cd : +2 only
La+3 > Y+3 > Sc+3 • Highest oxidation state is shown by Ru, Os.
(a) 4d, 5d same group cations will have nearly same Ru : + 8 in RuO4
ionic size due to lanthanide contraction. Os : + 8 in OsO4
Ionization potential • Some specific examples of low oxidation state are:
The ionization energy of these elements is more than [Fe0(CO)5], [Cr0(CO)6],
that of s-block elements, but less than those of p-block [Cr0(C6H6)2], Na+[V-(CO)6],
elements. [V+1(di Py)3]I
• In a period, on moving from left to right there is a • [Ag+2 (di Py)2]+2 is an example of a compound show-
slow increase in ionization potential value as Zeff is ing high oxidation state.
reduced due to the shielding effect of (n – 1)d elec-
trons. for example,
FA C T TO R E M E M B E R
V < Cr < Mn < Fe < Co < Ni < Cu < Zn
• Elements of group IIB will have the highest value of  As a generalized rule, the first four elements of each tran-
sition series are more stable in their higher oxidation state,
ionization potential.
while the next five elements are more stable in lower oxi-
• The value of ionization energy of Cr and Cu are dation states.
comparatively higher, because of 3d5 and 3d10 stable  Covalent nature ∝ Oxidation number
configurations. VCl4 > VCl3 > VCl2
• Ionization energy decreases down the group in case More covalent
of group IIB and group IB elements. Ionization  Acidic character ∝ Oxidation number
energy decreases from top to bottom in case of only
for example,
IIIB group and IB group (Cu > Ag)
VO < V2O3 < VO2 < V2O5
• In the rest of the groups, there is an increase in ion- Basic Basic Amphoteric Acidic
ization potential value due to the poor shielding CrO < Cr2O3 < CrO2 < CrO3
effect by 4f electrons, so a greater effective nuclear Basic Amphoteric Acidic
charge (Zeff values) is observed in these elements. MnO<Mn3O4<Mn2O3<MnO2 < MnO3 < Mn2O7
• The ionization energy of 5d-series is more than that Basic Amphoteric Strongly
of 4d and 3d elements, due to higher effective nuclear acidic
charge, which is due to poor screening effect caused
by 4f-electrons. For example, Pt (IV) compounds are Reactivity
thermodynamically more stable than Ni (IV) com-
These elements are either less reactive or unreactive due
pounds, as formation of Pt4+ and Ni4+ requires 9.36
to following reasons: high ionization energy, low heat of
and 11.29 kJ of energy respectively.
hydration and high heat of sublimation.
Variable oxidation state • The property to remain unreactive is more common
Most of the transition metals show variable oxidation states in platinum and gold than in elements of the third
except the first and the last members of each series. transition series.
19.4 Chapter 19
Complex formation
The cations of these elements have a great tendency to
form complexes with several molecules or ions known as
ligands (CO, CN, NH3, X–).
It occurs due to following factors:
• Cations have a high effective nuclear charge and
a small size, that is, have a high positive charge
density. They can therefore easily accept lone pair of
electrons from ligands.
• Cations also have vacant inner d orbitals having
enough energy to accept lone pair of electrons from
the ligands, by forming coordinate bond with ligands.
For example, K4 [Fe(CN)6], [Ni(CN)4]–2
• Transition metal in high oxidation state form stable
complexes with small, highly electronegative and
basic ligands like X– and NH3.
• Transition metal in low oxidation state form stable
complex with acidic strong ligands like Co and CN.
• If two ligands have similar stability, then the tendency
to form complex is directly propotional to the oxida-
tion state of central metal atom. For example,
[Co(NH3)6] > [Co(NH3)6]
+3 +2
1. Coloured ion or coloured complex formation
(a) These elements can easily form coloured ions or
complexes, due to the presence of incomplete d
orbitals.
FA C T TO R E M E M B E R
 Colour of KMnO4, K2Cr2O7, Cr2O3 is due to charge transfer.
V B
R G
O Y
 Complementary colours can be identified by using the
Munsell colour wheel.
Here
V stands for Violet
R stands for Red
O stands for Orange
B stands for Blue
G stands for Green
Y stands for Yellow
(b) Complex ions or compounds of transition metals
can absorb light and then transmit it. The colour
exhibited is due to the transmitted light. For
example,
(i) Cupric salts or compounds are blue coloured
as Cu2+ absorbs blue -yellow light but trans-
mits only blue light.
(ii) Ti3+ ion absorbs green light but transmits
purple or violet light.
(iii) Co2+ absorbs blue -green light but transmits red
light.
Reason The main reason for colour formation is d– d elec-
tron transition or crystal field splitting (electron transition
from lower energy d orbital to higher energy d orbital.
• A complex containing a with transition metal with d0
or d10 orbitals will be colourless, as no d–d electron
transition will take place. For example,
Sc+3, Ti+4, Cu+, Ag+, Zn+2, Cd+2, Hg+2
3d0 3d10
Catalytic activity
Most of the transition metals [Fe, Ni, Pt], alloys [Fe–Mo]
and compounds [V2O3, V2O5, MnO2, Co+2 salt] are used as
catalysts in various processes.
1. Reason of catalytic property: It is due to the presence
of vacant d-orbital, tendency to show variable oxidation
state and their larger surface area. For example,
2H2O2 Pt 2H2O + O2
Black
Pt-gauge
4NH3 + 5O2 4NO + 6H2O
2CH3OH + O2 Pt 2HCHO + 2H2O
Black
Fenton’s Reagent [FeSO4 + H2O2] is used to convert
R– CH2OH into R– CHO.
Magnetic properties
• Most of the transition metals show paramagnetism
due to the presence of unpaired electrons.
• Paramagnetic nature ∝ Number of unpaired electrons.
• The magnetic nature of substance can be deter-
mined by weighing the substance in Gouy's magnetic
balance.
μ = √n(n+2) B.M.
μ = Magnetic moment
B.M. = Bohr’s Magneton
n = Number of unpaired electrons
 Transition Metals Including Lanthanides and Actinides 19.5

It can also be calculated as follows Some Important Compounds of

μ = √{4s(s+1) + l (l+1)}
Here s = Spin quantum number (n/2)
l = Orbital quantum number
• When n = 0 (d0 or d10 state), μ is 0 and diamagnetic in
nature. For example,
Zn, Cd, Hg and ions like Cu+, Ag+, Zn+2, Cd+2, Hg+2
(all have d10 state).
• When n = 1, 2, 3, μ is positive and paramagnetic in
nature. For example, Cu+2, Ni2+, Co2+.
• When n = 4, 5, 6 then μ has a highly positive value
and the element is ferromagnetic in nature. For
example, Mn+2, Fe+3, Fe+2.
Transition Elements
• Transition elements combine with many non-met-
als like O, N, C, X and S to form useful binary
compounds.
• Some general trends in oxides, halides, sulphides are
given below.
Oxides
The first row transition metals form many type of oxides
like MO, M2O3, M3O4, MO2, M2O5 and MO3 when they
are heated strongly at high temperature in an atmosphere
of oxygen.

Alloy Formation Table 19.2 Oxides of first row transition metal

These elements can easily form alloys as due to similarity Element Oxides
in atomic sizes, they can mutually substitute one another Sc Sc2O3 (b)
in the crystal lattice. Alloys having mercury as one of the
Ti TiO (b), Ti2O3 (b), TiO2 (c)
constituent element, are called amalgams.
V VO (b), V2O3 (b), VO2 (c), V2O5 (a)
Cr CrO (b), Cr2O3 (c), CrO2 (c), CrO3 (a)
Formation of non-stoichiometric compounds and
interstitial compounds Mn MnO(b), Mn2O3(b), Mn3O4(c), MnO2(b), Mn2O7 (a)

These elements can trap some of the small size atoms such Fe FeO (b), Fe2O3 (c), Fe3O4 (b)
as H, C, N, B in the vacant spaces between the crystal Co CoO (b)
lattice forming inter-orbital or interstitial compounds like Ni NiO (b)
FeC, TiH2, Fe8N. Cu Cu2O (b), CuO (b)
• This tendency makes these metals different from Zn ZnO (b)
non-transition elements, and products obtained are
hard and rigid. For example, cast iron and steel.
 The stable oxides have been shown in bold letters.
• Compounds like Fe0.86 S, Fe0.98 O, VH0.56, TiH1.7  The acidic, basic or amphoteric oxides are indicated by
are classified as interstitial or non-stoichiometric the italic letters (a), (b) or (c) respectively just after the
compounds. formula of the oxide.

Standard reduction potential and reducing property • Acidic nature of oxides ∝ Oxidation number of
The value of E oRP of most of the transition elements except Central atom
Cu and Hg is lower than that of hydrogen that is, a negative In lower oxidation states, the compounds exhibit
value, so they can easily displace hydrogen, from dilute basic nature, in intermediate oxidation states. They
acids. For example, become amphoteric in nature and in higher oxidation
M + 2H+ M2+ + H2 ↑ states, acidic nature is observed. For example,
+2 +3 +4 +6
• The value of Eo is governed mainly by these factors: CrO Cr2O3 CrO2 CrO3
heat of hydration, heat of sublimation and heat of Basic Amphoteric Acidic
ionization. +2 +3 +4 +6 +7
• The value of Eo in 3d-series (M2+) varies with some MnO Mn2O3 MnO2 MnO3 Mn2O7
irregularities as follows: Basic Amphoteric Acidic

V Cr Mn Fe Co Ni Cu • Generally the basic and amphoteric oxides dissolve

in non-oxidizing acids like HCl to form hexa aquo
–1.17 –0.91 –1.18 –0.44 –0.28 –0.25 0.35
ions [M(H2O)6 ]n+.
19.6 Chapter 19

• Some of these oxides also dissolve in acids or bases 2K2MnO4 + O3 + H2O 2KMnO4 + 2KOH +
to give oxo-metallic salts like chromates (K2CrO4), O2
dichromate (K2Cr2O7), permangnates (KMnO4). 2K2MnO4 + Cl2 2KMnO4 + 2KCl
Halides 3K2MnO4 + 2CO2 2KMnO4 + 2K2CO3
+ MnO2
These elements react with halogens at high temperature
due to high activation energy to form halides. The order of (c) The purple solution of KMnO4 is concentrated to
reactivity for the halogens is F > Cl > Br > I. get the purple crystals of KMnO4 .
(d) Basic solution of K2MnO4 on electrolytic oxida-
• In higher oxidation states, transition elements form
tion gives KMnO4 .
only fluorides as F is the most electronegative and –
reactive halogen. MnO4–2 – e– MnO4
magnate permagnate
• These fluorides are ionic in nature, however chlo-
rides, bromides and iodides may be ionic as well as (e) Oxygen is liberated at anode .
covalent. (f) Hydrogen is liberated at cathode.
Covalent nature ∝ Atomic weight of halogen 2H+ + 2e– 2H H2
CuF2 , CuCl2, CuBr2 2. Physical properties: It has dark purple, needle-like crys-
Covalent nature increases tals with greenish metallic lusture.

• The halides of these metals in higher oxidation states (a) Its melting point is 523 K.
are relatively unstable and can undergo hydrolysis (b) It is less soluble in cold water but readily in hot
easily. The aqueous solutions of transition metal water (aqueous solution is pink).
halide, in most of the cases, are acidic resulting from 3. Chemical properties
the formation of strong acids. (a) Affect of heat Here different products are obtained
For example, at different temperatures.
FeCl3 + 3H2O Fe(OH)3 + 3HCl
200o C
2KMnO 4 → K 2 MnO 4 + MnO 2 + O 2
Sulphides
These metals can form sulphides easily by the action of 500−700°C → 2K MnO
3K 2 MnO4  + MnO2 + O2
sulphur or H2S or Na2S on these elements or their salts. 3 4
Potassium-magnate
For example,
(b) Reation with concentrated H2SO4
Fe + S FeS
CuSO4 + H2S CuS + H2SO4 2KMnO4 + H2SO4 Mn2O7 + K2SO4 + H2O
AgNO3 + Na2S Ag2S + 2NaNO3 2Mn2O7 explodes to produce 4MnO2 + 3O2
• Most of these metal sulphides are coloured and insol- (c) Mn2O7 is a dark brown highly explosive liquid.
uble in water. (d) Oxidizing action: It is a powerful oxidizing agent
CuS, NiS, CoS –(Black) in neutral, acidic or alkaline medium.
MnS– (Light pink) (e) In neutral medium
Potassium permanganate (KMnO4) 2KMnO4 + H2O 2KOH + 2MnO2 + 3[O]

1. Methods of preparation of KMnO4 (f) Reaction with H2S it oxidizes H2S into sulphur
(a) From pyrolusite (MnO2 ) When finely powdered 2KMnO4 + 3H2S 2MnO2 + 2KOH + 3S
ore is fused with KOH or K2CO3 in air, green + 2H2O
coloured K2MnO4 is obtained. (g) Reaction with hypo it oxidozes hypo in Na 2SO4
2MnO2 + 4KOH + O2 2K2MnO4 + 2H2O 8KMnO4 +3Na2S2O3 + H2O
(b) Conversion of K2MnO4 into KMnO4 The green Hypo
mass of K2MnO4 is extracted with H2O and the 3Na2SO4 + 3K2SO4 + 8MnO2 + 2KOH
solution is treated with Cl2 or O3 or O2 to oxidize
K2MnO4 into KMnO4 (purple solution).
 Transition Metals Including Lanthanides and Actinides 19.7

(h) Reaction with alkalis 5. Uses of KMnO4

2KMnO4 + 2KOH 2K2MnO4 + H2O + [O] (a) As an oxidizing agent.
Colourless (b) As disinfectant and germicide.
(i) In Basic medium (c) In the manufacture of saccharin, boric acid,
CH2 H CH2OH acetaldehyde.
|| + | + [O] | (d) In volumetric estimation of Fe+2 salts, oxalate and
CH2 OH CH2OH H2O2.
Ethene Glycol
Potassium dichromate (K2Cr2O7)
where [O] is supplied by KMnO4
1. Preparation: It is prepared from chromite ore (FeCr2O4
(j) Reaction with toluene
or FeOCr2O3) in following steps
CH3 COOH
(a) Formation of Na2CrO4 Here the ore is fused with
3[O]
molten alkali, in presence of air in a reveberatory
furnace and the obtained fused mass is extracted
where [O] is supplied by KMnO4 with water, followed by filtration giving Na2CrO4.
(k) Reaction with KI 4FeCr2O4 + O2 2Fe2O3 + 4Cr2O3
KI + 3[O] KIO3 4Cr2O3 + 8Na2CO3 + 6O2 8Na2CrO4 + 8CO2
(l) Alkaline KMnO4 is called baeyer’s reagent and it 4FeCr2O4 + 8Na2CO3 + 7O2 2Fe2O3 + 8CO2
is used to test unsaturation in organic compounds. + 8Na2CrO4
(m) In Acids medium or
2KMnO4 + 3H2SO4 K2SO4 + 2MnSO4 + 3H2O 4FeCr2O4 + 16NaOH + 7O2 8Na2CrO4
+ 5[O] + 2Fe2O3 + 8H2O
Or (b) Conversion of Na2CrO4 into Na2Cr2O7
2MnO4 + 6H+ 2Mn+2 + 3H2O + 5[O] 2Na2CrO4 + H2SO4 Na2Cr2O7 + Na2SO4
(n) Reaction with ferious sulphate dil. + H2O separates first
10FeSO4 + 2KMnO4 +8H2SO4 K2SO4 + (c) Conversion of Na2Cr2O7 into K2Cr2O7
2MnSO4 + 5Fe2(SO4)3 + 8H2O
Na2Cr2O4 + 2KCl Δ K2Cr2O7 + 2NaCl
(o) Reaction with HX
less soluble
2KMnO4 + 3H2SO4 + 10HX K2SO4 +
2MnSO4 + 8H2O + 5X2 K2Cr2O7 being less soluble can be easily obtained
by fractional crystallization.
(p) Reaction with oxalic acid
2KMnO4 + 3H2SO4 + 5H2C2O4 K2SO4 +
2MnSO4 + 8H2O + 10CO2 FA C T TO R E M E M B E R
(q) Reaction with SO2 K2Cr2O7 is preferred over Na2Cr2O7 in volumetric analysis as
2KMnO4 + 5SO2 + 2H2O K2SO4 + 2MnSO4 it is not hygroscopic.
+ 2H2SO4
4. Structure of KMnO4 2. Properties of K2Cr2O2
(a) It has orange red coloured crystals with a melting
O
point of 669 K.
(b) It is moderately soluble in cold water but readily
Mn soluble in hot water.
O
O− (c) Affect of heat
4K Cr O Δ 4K CrO + 2Cr O + 3O
2 2 7 2 4 2 3 2
O Potassium Chromic
Figure 19.1 Tetrahedron structure KMnO4 chromate oxide

Mn – O is 1.63 Å, O – Mn – O is 109º
19.8 Chapter 19

(d) Reaction with H2SO4: with cold H2SO4 Red crys- K2Cr2O7 + H2SO4 + 4H2O2 2CrO5 + K2SO4
tals of chromic anhydride are formed. + 5H2O
K2Cr2O7 + H2SO4 2KHSO4 + 2CrO3 + H2O (p) Formation of insoluble chromates It forms insol-
Concentrated Red crystals uble chromates with soluble salts of Pb, Ba. For
with hot concentrated H2SO4: Chromium sulphate example,
is formed when it reactes. 2Pb(NO3)2 + K2Cr2O7 + H2O PbCrO4 +
2K2Cr2O7 + 8H2SO4 2K2SO4 + 2Cr2 (SO4)3 Lead chromate
+ H2O + 3O2 2KNO3 + 2HNO3
(e) Reaction with HCl: chromium chloride is formed (q) chromyl chloride test When it is treated with NaCl
when it reacts with HCl. and concentrated. H2SO4, orange red vapours of
chromyl chloride are formed which dissolve in
K2Cr2O7 + 14HCl 2CrCl3 + 2KCl + 7H2O NaOH to give yellow solution of sodium chromate.
+ 3Cl2
K2Cr2O7 + NaCl+ 6H2SO4 Δ 2KHSO4 + 4NaHSO4
(f) Reaction with KOH: here a yellow solution of conc. + 2CrO2Cl2 + 3H2O
potassium chromate is formed. orange red vapours
K2Cr2O7 + 2KOH 4K2CrO4 +H2O CrO2Cl2 + 4NaOH 2NaCl + 2H2O + Na2CrO4
Yellow solution Yellow solution
(g) On acidification, yellow solution again changes (r) Sodium chromate gives yellow precipitate with
into orange-red potassium dichromate solution. lead acetate.
(h) Oxidizing nature: it is a very powerful oxidizing
Na2CrO4 + Pb(CH3COO)2 2Na(CH3COO)2
agent in acidic medium.
+ PbCrO4
Cr2O7–2 + 14H+ + 6e– 2Cr+3 + 7H2O
CrO2Cl2 + 2H2O 2HCl + H2CrO4
(i) Reaction with FeSO4
(s) Chromyl chloride test is used for detection of Cl–
K2Cr2O7 + 6FeSO4 + 7H2SO4 in any mixture.
Orange

K2SO4 + 3Fe2(SO4)3 + Cr2 (SO4)3+ 7H2O Structure of Chromate and Dichromate

Green −2
O −2
(j) Reaction with KI O 180 O O
p.m
K2Cr2O7 + 7H2SO4 + 6KI 4K2SO4 + Cr 131°
Cr Cr
Cr2(SO4)3 + 7H2O + 3I2 O 1.61 O
O O O p.m
(k) SO (Sulphite) into SO (sulphate)
–2 –2 O O
3 4
(a)
Cr2O7–2 + 8H+ + 3SO3–2 2Cr+3 + 4H2O (b)
+ 3SO4–2 Figure 19.2 (a) Charomate and (b) Dichromate

(l) Reaction with AsO3–3 (arsenite) Uses K2Cr2O7

Cr2O7–2 + 8H+ + 3AsO3–3 2Cr+3 + 4H2O + • It is used in photography, for hardening of gelatin
3AsO4–3 and in dyeing as mordant [Cr(OH)3].
Arsenate
(m) Reaction with HX
INNER TRANSITION ELEMENTS OR
K2Cr2O7 + 4H2SO4 + 6HX K2SO4 +
Cr2(SO4)3 + 7H2O + 3X2 F-BLOCK ELEMENTS
(n) Reaction with H2S • Elements in which the last or differentiating electron
K2Cr2O7 + 4H2SO4 + 3H2S K2SO4 + is present in f orbital of the anti-penultimate orbit
Cr2(SO4)3 + 7H2O + 3S (n–2) are called f-block elements.
• These are also called inner transition elements as
(o) Reaction with hydrogen peroxide: Acidified
the (n–2)f orbitals lie comparatively deep within the
K2Cr2O7 gives a deep blue colour with H2O2, due
orbital.
to formation of CrO5.
 Transition Metals Including Lanthanides and Actinides 19.9

• Elements with atomic number 58 to 71 are called
4f-block elements or lanthanides or lanthanones or
rare earth elements.
• Elements with atomic number 90 to 103 are called
5f-block elements or actinides or actinones.
Oxidation of +2 Eu+2, Sm+2, Yb+2
Order of reducing power is: Sm+2 > Yb+2 > Eu+2
Oxidation of +4 is shown by Ce+4, Pr+4, Tb+4
Ce+4 is stable, the rest are unstable and act as good
oxidizing agents.

Lanthanides Colour
Most of M+3 (trivalent cations of these elements) are
La Ce Nd Pm Sm Eu Gd
57 58 59 61 62 63 64
coloured in both solid as well as in aqueous solution.
65
Tb 66
Dy 67
Ho 68
Er 69
Tm 70
Yb 71
Lu
• Colourless : La+3, Ce+3, Lu+3, Yb+3, Gd+3
• These elements are present in period VIth in peri-
• Green : Pr+3, Tm+3
odic table and the last electron in these elements goes
to 4f sub shell so these also called 4f-block elements. • Pale Pink : Eu+3 , Tb+3
They are called Lanthanides or rare earth elements or • Pink : Er+3 , Nd+3
Inner transition elements. • Yellow : Sm+3 , Dy+3
Lanthanides have following important properties: • The colour of these ions depend upon the number
of electrons present in 4f orbitals. (f–f electron
1. Electronic configuration: Their last valence electron is transition).
in 4f orbital and their general electronic configuration is
La+3 : n = 0
(n –2) f 0 – 14 (n –1) d 0 – 2 ns2 Lu+3 (4f 14) colourless
or 4f 0 – 14 5d 0 – 2 6s2
• Ce+3, Yb+3 are colourless
Expected
Properties dependent on standard reduction
La : (Xe), 4f 1, 5d 0, 6s2
57 54 potential (E°) values
Ce : (Xe), 4f 1, 5d 1 6s2
58 54 [Eº]
59
Pr : 54
(Xe), 4f 2 5d 1 6s2 M+3 + 3 e– Δ M
63
Eu : 54
(Xe), 4f 6 5d 1 6s2 (aq) (s)
64
Gd : 54
(Xe), 4f 7 5d 1 6s2 The value of Eº for the reaction increases from La to
Lu : (Xe), 4f 14 5d 1 6s2 Lu.
71 54
La --------------------------------------------------- Lu
Actual – 2.53 – 2.25
57
La : (Xe), 4f 0, 5d 1, 6s2 1. Eº Values explain the following properties:
58
Ce : (Xe), 4f 2 5d 0 6s2
• Reducing nature ∝ Negative values of Eº
59
Pr : (Xe), 4f 3 5d 0 6s2
• As lanthanides have high negative Eº value so
Eu : (Xe), 4f 7 5d 0 6s2
63 they are good reducing agents and this property
64
Gd : (Xe), 4f 7 5d 1 6s2 decreases from La to Lu.
71
Lu : (Xe), 4f 14 5d 1 6s2 • Since electropositive nature is the tendency to lose
electrons, electropositive nature decreases from
Oxidation states
La to Lu.
Like transition elements lanthanides also show variable
Electropositive nature ∝ Negative value of Eº
oxidation states.
• They react slowly with cold water, but rapidly
• The major oxidation state shown by all lanthanides with hot water to liberate H2 due to their negative
is +3 and they are most stable in this state also. It is EoRP.
the most favorable oxidation state, due to high lattice
energy and hydration energy. Physical properties
• The unusual oxidation state such as +2 , +4 is also All lanthanides are soft, malleable and ductile with low
shown by some lanthanides. It is due to the extra tensile strength.
stability associated with empty, half-filled and ful- • These are good conductors of heat and electricity.
ly-filled 4f sub-shell.
19.10 Chapter 19

• These elements have a high value of boiling point, attraction of nucleus for the e– in outermost shell, so Zeff
melting point but without any regular trend. Their increases gradually and atomic radii or ionic radii gradu-
densities are in between 6.77 to 9.7 g/ml. ally decreases.
• The value of atomic volumes and densities increase Consequences of lanthanide contraction
with increase in atomic number.
• Lanthanide contraction plays an important role in
• The value of electronegativity of these elements is explaining many properties of lanthanides.
nearly equal to s-block elements, so they form ionic
• Due to Lanthanide contraction, ionic size of M+3
compounds.
decreases from Ce+3 to Lu+3 continuously. Basic
Magnetic properties nature also decreases from Ce(OH)3 to Lu(OH)3 .
These are paramagnetic in nature as they have unpaired
1
Basic Nature ∝ ___________
Atomic number
electrons. 1
Covalent nature ∝ __________
size of cation
Paramagnetic nature ∝ Number of unpaired electrons.
• La+3 , Lu+3 and Ce4+ have no unpaired electron so they That means covalent nature in M(OH)3 will increase
are diamagnetic. from Ce(OH)3 to Lu(OH)3.
• Rest of the M+3 ions are paramagnetic as they have • Lanthanide contraction increases the value of elec-
unpaired e– . [1, 2---------7] tronegativity for M+3 .
• Ce+3 ------------------ Gd+3 ---------------------- Yb • Eº values increases slightly due to lanthanide
1 Unpaired 7 Unpaired 1 Unpaired contraction.
electron electrons electron • Basic nature of M2O3 also decreases from La2O3 to
Lu2O3 due to lanthanide contraction.
Increase in Decrease in
paramagnetic nature paramagnetic nature • The value of electronegativity of M3+ also increases
slightly.
• Maximum paramagnetic nature in shown by Dy+3.

Chemical reactivity Actinides or Actinones

All lanthanides have almost the same reactivity due to the 89
Ac 90
Th 91Pa 92U 93Np 94
Pu
fact that 4f electrons in lanthanides are very effectively 95
Am 96
Cu 97Bk 98Cy 99Es 100
Fm 101
Md
shielded from the interaction with other elements by over- 102
No 103
Lr
lapping 5s, 5p, 6s electrons.
• These elements are present in period VIth of the
• Due to their similar nature of reactivity, they occur periodic table and the last electron in these elements
together and their separation is difficult. goes to 5f subshell so they are called 5f-block ele-
ments. They are also called actinides or actinones
Lanthanide Contraction or post-uranium or transuranium elements.
• This steady decrease in the value of atomic radii
Actinides have Following Important
and ionic radii of lanthanides with increase of
atomic number is called lanthanide contraction. This Properties:
decrease is not much and is present with some abnor- Electronic Configuration
malities also. Their general electronic configuration is 5f 1–14, 6d0 –1, 7s2.
• Atomic radii decreases from La to Lu: 165 pm–156
pm that is, by 9 units only. Oxidation State
• Ionic radii (M+3) decrease from Ce+3 to Lu+3: 103 pm These elements show +2, +4, +5, + 6 but mainly exhibit
– 85 pm, that is, by 18 units only. +3 state which is the most stable and the most common
oxidation state.
1. Cause of lanthanide contraction: As we move from Ce
to Lu, the atomic number (nuclear charge) increases by Physical properties
+1 at each next element, thus, on moving from Ce to Lu, • These are silvery white in colour and get tarnished
the attraction between the nucleus and outermost orbit with alkalies.
electron increases gradually. As 4f orbitals are diffused
in shape, so the inner electrons are not able to hinder the • They have a high density, except Th, Am. Density
range is 7g/ml to 19.8 g/ml.
 Transition Metals Including Lanthanides and Actinides 19.11
• These have low ionization energy so these are highly
electropositive elements and have a strong reducing
nature.
• All have high boiling point and melting point val-
ues. However, an irregular variation in these values
is seen between the member elements.
• Most of M+3 ions are coloured due to f–f electrons
transition except 5f 0, 5f 7 which are colourless.
For example, Np+3 Bluish colour white
Am+3 is Pink.
Chemical reactivity
Due to their high electropositivity and low ionization
energy they react with hot water, HCl, O2 , X2 etc.
CONCEPT AT A GLANCE
 Sc, Y, La, Ac do not show variable valency.
 Sc is the lightest, while Os is the heaviest transition metal.
 Reactivity of transition elements decreases with the
increase of atomic number.
 Platinum dissolves in aqua regia and forms H2PtCl6.
 Molybdenum is used in X-ray tubes, while tantalum is used
in analytical weighing instruments.
 U235, Pu239 are nuclear fuel in the nuclear reactors and atom
bombs.
 A mixture of ThO2 and CeO2 is used for making incandes-
cent gas mantles.
 Lanthanides cannot form oxo ions while actinides can form
oxo ions like UO+ , UO2+, PuO2+2.
Magnetic property
All M+3 are paramagnetic, except Ac+3, Th+4 , U+6 which
have 5f 0 or Lr+3 (5f 14 ) therefore making them diamagnetic.
• Actinides have a greater tendency to form complexes
than lanthanides, due to high positive charge density
and smaller radii.
• The degree of complex formation for the ions M+4,
MO2+2, M+3 and MO2+ decreases as follows M+4 >
MO2+2 > M+3 > MO2+.
 Among lanthanides, only promethium (Pm) is radioactive,
while all actinides are radioactive.
 Misch metal are La, Ce, Nd (94% –95%) and Fe (4%) +
S, C, Si.
 Misch metal and magnesium are used to manufacture
engine parts.
 Ceric sulphate is used as an oxidizing agent in volumetric
analysis.
 Some metals release hydrogen very slowly as they are
protected from the attack of acids by the formation of an
impervious layer of an inert oxide. For example, Chromium
is so unreactive that it can be used as a protective non-ox-
idizing metal.
19.12 Chapter 19

EXERCISES

Single Option Correct Type

1. Among which of the following pairs of ions, the lower 10. Which of the following pairs of ions is colourless?
oxidation state in aqueous solution is more stable than (a) Ti3+, Cu2+ (b) Sc3+, Zn2+
the other? (c) Co2+, Fe3+ (d) Ni2+, V3+
(a) Ti+, Ti3+ (b) V2+, VO2+ 11. Which of the following pairs of ions have same para-
(c) Cr2+, Cr3+ (d) Cu+, Cu2+ magnetic moment?
2. Which of these ions is coloured as well as paramag- (a) Cu2+, Ti3+ (b) Ti3+, Ni2+
netic in nature? (c) Ti , Cu
4+ 2+
(d) Mn2+, Cu2+
(a) Cu2+ (b) Cu+ 12. Which of the following does not exist?
(c) Nl2+ (d) Both a and c
(a) [Cu Cl4]2– (b) [CuI4]2–
3. The aqueous solution containing which one of the fol- (c) [Zn (CN)4] 2–
(d) [HgI4]2–
lowing ions will be colourless?
13. Lanthanides and actinides resemble each other in
(a) Sc3+ (b) Fe3+
(a) oxidation state
(c) Fe2+ (d) Mn2+
(b) ionization energy
4. Which of the following is a highly corrosive salt? (c) formation of complexes
(a) FeCl2 (b) HgCl2 (d) electron configuration
(c) PbCl2 (d) Hg2Cl2 14. Among the following series of transition metal ions,
5. A complex compound of Co with molecular formula
3+ the one where all metal ions have 3d2 electronic con-
CoClx. yNH3 gives a total of 3 ions when dissolved in figuration is
water. How many Cl– ions satisfy both primary as well (a) Ti+, V4+, Cr6+, Mn7+
as the secondary valencies in this complex? (b) Ti2+, V3+, Cr4+, Mn5+
(a) 3 (b) 1 (c) Ti3+, V2+, Cr3+, Mn4+
(c) 4 (d) zero (d) Ti4+, V3+, Cr2+, Mn3+
15. Which of the following are coloured due to charge
6. In which of the following metal complex, does the
transfer spectra
central metal atom have zero Oxidation state?
(a) CrO3 (b) [Fe (H2O) NO] SO4
(a) [Cu(NH3)4]SO4 (b) K3[Fe(CN)6]
(c) K2 Cr2O7 (d) All of these
(c) [Ni(CO)4] (d) [Pt(NH3)2Cl2]
16. How many electrons are involved in the oxidation by
7. Misch metal is
KMnO4 in basic medium?
(a) an alloy of copper
(a) 5 (b) 3
(b) an alloy of lanthanoid metal
(c) 2 (d) 1
(c) an alloy of aluminium
(d) a mixture of chromium and lead chromate 17. For which lanthanide are +2 and +3 oxidation states
are common?
8. Which one of the following forms, with an excess of
(a) Eu (b) Na
CN–, a complex having coordination number two?
(c) Ce (d) La
(a) Ni2+ (b) Cu+
(c) Ag+ (d) Fe2+ 18. An alkaline solution of ______ and citrate ions is
called __________.
9. Which of the following order is correct for the size of (a) silver chloride; Tollen’s reagent
Fe3+, Fe and Fe2+? (b) cupric sulphate; Benedict’s solution
(a) Fe3+ < Fe2+ < Fe (b) Fe < Fe3+ < Fe2+ (c) silver nitrate; Fehling’s solution
(c) Fe < Fe2+ < Fe3+ (d) Fe2+ < Fe3+ < Fe (d) cupric sulphate; Schiff’s reagents
 Transition Metals Including Lanthanides and Actinides 19.13

19. Ferrous ion changes to X ion, on reacting with acidified 30. What is the oxidation state of Fe in the product formed
hydrogen peroxide. The number of d-electrons present when acidified potassium ferrocyanide is treated with
in X and its magnetic moment (in B.M.) are respectively H2O2?
(a) 5 and 4.9 (b) 4 and 5.92 (a) +2 (b) +6
(c) 6 and 6.95 (d) 5 and 5.92 (c) +1 (d) +3
20. Which one of the following characteristics of the tran- 31. Stainless steel vessels are made from steel containing
sition metal is associated with their catalytic activity?
(a) W (b) Mn
(a) variable oxidation states
(c) Cr (d) Ni
(b) colour of hydrated ions
(c) paramagnetic behaviour 32. Which of the following reacts with concentrated sul-
(d) high enthalpy of atomization phuric acid?
21. Iron loses its magnetic property at (a) Pb (b) Pt
(a) melting point (b) curie point (c) Ag (d) Au
(c) 1000 K (d) boiling point 33. Silver chloride dissolves in excess of NH4OH. The
22. In the extraction of zinc, the formation of blue flame cation present in this solution is
is due to the burning of (a) [Ag(NH3)6]+
(a) C (b) CO (b) [Ag(NH3)4]+
(c) Zn (d) ZnO (c) [Ag(NH3)2]+
23. Which one of the following ions exhibits colour in (d) Ag+
aqueous solution? 34. The number of moles of AgCl precipitated when
(a) Ti4+ (b) Zn2+ excess AgNO3 is added to one mole of [Cr (NH3)4 Cl2]
(c) Ni 2+
(d) Sc3+ Cl is
24. The number of un-paired electrons in [Fe (H2O)5 NO] (a) 3.0 (b) 2.0
SO4 (c) 1.0 (d) zero
(a) 1 (b) 2 35. The element that can exhibit the highest number of
(c) 3 (d) 4 oxidation states amongst the following is
25. Which one of the following ions is colourless in its (a) Mn (b) CO
aqueous solution? (c) V (d) Ni
(a) Ti3+ (b) Cu2+ 36. The oxidation number of cobalt in K3[Co(NO2)6] is
(c) Ni 2+
(d) Zn2+ (a) –3 (b) +3
26. Which one of the following ions exhibit highest mag- (c) –4 (d) +4
netic moment? 37. Which of the following is not correctly matched.
(a) Cu2+ (b) Ti3+ List I List II
(c) Ni 2+
(d) Mn2+ (a) Cu2O Red
27. Which one of the following is a diamagnetic ion? (b) Cu2I2 Blue
(a) Cu2+ (b) Mn2+ (c) Fe4 [Fe(CN)6]3 Blue
(c) Sc3+
(d) Co2+ (d) CuO Black
28. Which one of the following pairs of ions has the same 38. If NaOH is added to an aqueous solution of zinc ions,
electronic configuration? a white precipitate appears and on adding excess of
(a) Cr3+, Fe3+ (b) Fe3+, Mn2+ NaOH, the precipitate dissolves. In this solution, zinc
(c) Fe , Co
3+ 3+
(d) Sc3+, Cr3+ exists in the
29. Iron sulphide is heated in air to form 'A', an oxide of (a) anionic part
sulphur. 'A' is dissolved in water to give an acid. The (b) cationic part
basicity of this acid is (c) both in cationic and anionic parts
(a) zero (b) 1 (d) there is no zinc in the solution
(c) 2 (d) 3
19.14 Chapter 19

39. The black compound formed during the reaction 48. In the equation
between sodium thiosulphate and silver nitrate is 4M + 8CN– + 2H2O + O2 4[M(CN)2]– +
(a) silver sulphite (Ag2SO3) 4OH–
(b) silver sulphate (Ag2SO4) identify the metal M.
(c) silver sulphide (Ag2S) (a) zinc (b) iron
(d) silver thiosulphate (Ag2S2O3) (c) copper (d) silver
40. Zn gives H2 gas with H2SO4 and HCl but not with 49. Lanthanoides are
HNO3 because (a) 14 elements in the VI period (atomic number = 58
(a) in electrochemical series Zn is above hydrogen to 71) that are filling the 4f-sublevel
(b) NO3– ion is reduced in preference to hydronium ion (b) 14 elements in the VII period (atomic number =
(c) Zn acts as an oxidizing agent when reacts with HNO3 50 to 71) that are filling the 4f-sublevel
(d) HNO3 is weaker acid than H2SO4 and HCl (c) 14 elements in the VII period (atomic number =
90 to 103) that are filling the 5f-sublevel
41. Which of the following is obtained when Fe reacts
(d) 14 elements in the VI period (atomic number = 90
with dilute HNO3?
to 103) that are filling the 4f-sublevel
(a) NO (b) N2O
(c) NO2 (d) none of these 50. Which of the following compound is both paramag-
netic and coloured?
42. In the reaction
Δ (a) (NH4)2[TiCl6] (b) VOSO4
Zn + NaOH , the product A is (c) K2Cr2O7 (d) K3[Cu(CN)4]
(a) Zn(OH)2 (b) 2NaZnO2
(c) Na2ZnO2 (d) none of these 51. Gold is extracted by hydrometallurgical process,
based on its property
43. Which one of the following metals is found in gun
(a) of being electropositive
metal, monel metal and constantan alloys?
(b) of being less reactive
(a) Cu (b) Fe (c) to form complexes which are soluble
(c) Hg (d) Zn (d) to form salts which are water soluble
44. The basic character of the transition metal monoxides 52. A pair of amophoteric oxides from the following is
follow the order
(a) VO2 and CrO (b) VO2 and CrO3
(a) CrO > VO > Feo > TiO (c) VO and V2O5 (d) VO2 and Cr2O3
(b) TiO > VO > CrO > FeO
(c) TiO > FeO > VO > CrO 53. Corrosion of iron is essentially an electro-chemical
(d) VO > CrO > TiO > FeO phenomenon, where the cell reactions are
(a) Fe is oxidized to Fe2+ and dissolved oxygen in
45. The correct order of ionic radii of Y3+, La3+, Eu3+ and
water is reduced to OH
Lu3+ is
(b) Fe is oxidized to Fe3+ and H2O is reduced to O22–
(a) Lu3+ < Eu3+ < La3+ < Y3+ (c) Fe is oxidized to Fe2+ and H2O is reduced to O2–
(b) La3+ < Eu3+ < Lu3+ < Y3+ (d) Fe is oxidized to Fe2+ and H2O is reduced to O2
(c) Y3+ < La3+ < Eu3+ < Lu3+
(d) Y3+ < Lu3+ < Eu3+ < La3+ 54. If the spin only magnetic moment of Cu2+ is 1.73 BM,
then the number of unpaired electron's present are
46. Two stable ions of first transition series which have
(a) 2 (b) 3
the largest number of unpaired electrons and have the
(c) 0 (d) 1
highest magnetic moment are
(a) Ni2+ and Co2+ (b) Cr3+ and Fe2+ 55. Identify the correct order in which the covalent radius
(c) Fe and Mn
3+ 2+
(d) Ti4+ and Cr3+ of the following elements increases
1. Ti 2. Ca 3. Sc
47. What is the general outer configuration of the coinage
(a) 3, 2, 1 (b) 2, 1, 3
metals?
(c) 1, 3, 2 (d) 1, 2, 3
(a) ns2np6 (b) (n – 1) d9 ns2
(c) (n – 1) d ns
10 1
(d) (n – 1) d10 ns2
 Transition Metals Including Lanthanides and Actinides 19.15

56. What is the current order of spin only magnetic 63. In nitroprusside ion, the iron and NO exist as FeII and
moment (in B.M.) of Mn2+, Cr2+ and V2+? NO+ rather than FeIII and NO. These forms can be dif-
(a) Mn2+ > V2+ > Cr2+ ferentiated by
(b) V2+ > Cr2+ > Mn2+ (a) estimating the concentration of iron
(c) Mn2+ > Cr2+ > V2+ (b) measuring the concentration of CN–
(d) Cr2+ > V2+ > Mn2+ (c) measuring the solid state magnetic moment
(d) thermally decomposing the compound
57. Which statement is not correct with respect to transi-
tion metals? 64. Which of the following compounds is expected to be
(a) the colour of the hydrated ions is due to transi- coloured?
tions of electrons from different ‘d’ orbitals of the (a) Ag2SO4 (b) CuF2
same principal quantum number (c) MgF2 (d) CuCl
(b) most transition metals should, on thermodynamic
considerations, liberate hydrogen from acids 65. The aqueous solution of the following salts will be
(c) the complex formation of transition metal ions coloured in the case of
is often accompanied by a change of colour and (a) Zn(NO3)2 (b) LiNO3
sometimes by a change in the intensity of the colour (c) Co(NO3)2 (d) potash alum
(d) the compounds of the elements in low oxidation
66. The correct ground state electronic configuration for
states are generally ionic
the atom (Z = 24) is
58. Which of the following statements is not correct? (a) [Ar] 3d5 4s1 (b) [Ar] 3d4 4s2
(a) in oxyhaemoglobin, Fe2+ is paramagnetic. (c) [Ar] 3d 4s
6 0
(d) [Ar] 3d5 4s2
(b) during respiration, the size of Fe2+ increases when
67. How many unpaired electrons are present in Ni2+?
it changes from diamagnetic to paramagnetic state.
(c) four heme groups are present in haemoglobin. (a) 8 (b) 4
(d) heme is the prosthetic group and it is non protein (c) 2 (d) 0
part of haemoglobin. 68. Zinc-copper couple that can be used as a reducing
59. The pair in which both species have the same mag- agent is obtained by
netic moment (spin only value) is (a) zinc coated with copper
(a) [Cr(H2O)6]2+, [CoCl4]2– (b) zinc and copper wires welded together
(b) [Cr(H2O)6]2+, [Fe(H2O)6]2+ (c) mixing zinc dust and copper gauze
(c) [Mn(H2O)6]2+, [Cr(H2O)6]2+ (d) copper coated with zinc
(d) [CoCl4]2–, [Fe(H2O)6]2+ 69. The pair of which salts is expected to have the same
60. Transition metals despite having higher values of colour in their freshly prepared aqueous solutions.
standard reduction potentials, are poor reducing (a) VOCl2, CuCl2
agents. This is due to (b) CuCl2, FeCl2
(a) low heat of hydration (c) FeCl2, VOCl2
(b) high ionization energies (d) MnCl2, FeCl2
(c) low ionization energies 70. When sodium argentocyanide is treated with zinc
(d) high enthalpy of vapourization dust, silver precipitates because
61. The pair in which both species have iron is (a) zinc forms a complex readily with cyanide
(a) nitrogenase, cytochromes (b) zinc is more electropositive than silver
(b) carboxypeptidase, haemoglobin (c) silver is more electropositive than zinc
(c) haemocyanin, nitrogenase (d) both Zn2+ and Ag+ ions have d10 electronic
(d) haemoglobin cytochromes configuration

62. Amongst the following, identify the species with an 71. Which one of the following metals will not reduce H2O?
atom in +6 oxidation state (a) Li (b) Fe
(a) MnO4– (b) Cr(CN)63– (c) Cu (d) Ca
(c) NiF62–
(d) CrO2Cl2
19.16 Chapter 19

72. In which one of the following transition metal com- (c) TiO3, MnO2
plexes, does the metal exhibit zero oxidation state? (d) [Fe(CN)6]3–, [Co(CN)6]3–
(a) [Ni(CO)4]
80. The product formed on oxidation of I– with MnO4– in
(b) [Fe(H2O)6]X3
alkaline medium is
(c) [Co(NH3)6]Cl3
(d) [Fe(H2O)6]SO4 (a) IO4– (b) I2
(c) IO– (d) IO3–
73. Which statement is not correct?
81. An aqueous solution of [Ti(H2O)6]3+ ion has a mild
(a) La(OH)3 is less basic than Lu(OH)3 violet colour of low intensity. Which of the following
(b) in lanthanide series, ionic radius of Ln3+ ions statements is incorrect?
decreases
(a) The colour results from an electronic transition
(c) La is actually an element of transition series of one electron from the t2g to an eg orbital
(d) atomic radius of Zn and Hf are same because of (b) The ion absorbs visible light in the region of
lanthanide contraction ~5000 Å
74. Which compound is coloured due to charge transfer (c) The transition is the result of metal-ligand back
spectra and not due to d–d transitions? bonding
(a) K2Cr2O7 (b) KMnO4 (d) The low colour intensity is because of a low prob-
(c) CrO3 (d) All of these ability of transition

75. Colour in transition metal compounds is attributed to 82. When MnO2 is fused with KOH, a coloured compound
is formed. The product and its colour is
(a) small size metal ions
(b) absorption of light in uv region (a) K2MnO4, purple green
(c) complete (n, s) subshell (b) KMnO4, purple
(d) incomplete (n–1)d subshell (c) Mn2O3, brown
(d) Mn3O4, black
76. A solution, when diluted with H2O and boiled, gives
a white precipitate. On addition of excess of NH4Cl/ 83. In the process of extraction of gold,
O2
NH4OH, the volume of precipitate decreases leaving –
roasted gold ore + CN + H2O [X]+[Y] + Zn
behind a white gelatinous precipitate. Identify the + Au, [X] and [Y] are
precipitate which dissolves in NH4OH/NH4Cl. (a) [X] = [Au(CN)2]–, [Y] = [Zn(CN)4]–2
(a) Zn(OH)2 (b) Al(OH)3 (b) [X] = [Au(CN)4]–3, [Y] = [Zn(CN)4]–2
(c) Mg(OH)2 (d) Ca(OH)2 (c) [X] = [Au(CN)2]–, [Y] = [Zn(CN)6]–4
(d) [X] = [Au(CN)4]–, [Y] = [Zn(CN)4]–2
77. CuSO4 decolourizes on addition of KCN, the product is
(a) [Cu(CN)4]2– 84. Mixture of (X) = 0.02 moles of [Co(NH3)5 SO4]Br and
(b) Cu2+ gets reduced to form [Cu(CN)4]3– 0.02 mole of [Co(NH3)5Br]SO4 was prepared in 2 litre
(c) Cu(CN)2 of solution
(d) CuCN 1 litre of mixture (X) + excess AgNO3 (Y)
1 litre of mixture (X) + excess BaCl2 (Z)
78. If the bond length of CO bond in carbon monoxide is
number of moles of (Y) and (Z) are
1.128 Å, then what is the value of CO bond length in
Fe(CO)5? (a) 0.01, 0.01 (b) 0.02, 0.01
(c) 0.01, 0.02 (d) 0.02, 0.02
(a) 1.15 Å
(b) 1.128 Å 85. Anhydrous ferric chloride is prepared by
(c) 1.72 Å (a) heating hydrated ferric chloride at a high tem-
(d) 1.118 Å perature in a stream of air
79. The pair of the compounds in which both the metals (b) heating metallic iron in a stream of dry chlorine gas
are in the highest possible oxidation state is (c) reaction of ferric oxide with hydrochloric acid
(a) [Co(CN)6]3–, MnO2 (d) reaction of metallic iron with hydrochloric acid
(b) CrO2Cl2, MnO4–
 Transition Metals Including Lanthanides and Actinides 19.17

86. In the standardization of Na2S2O3 using K2Cr2O7 by 93. The equivalent weight of MnSO4 is half of its molec-
iodometry, the equivalent weight of K2Cr2O7 is ular weight, when it is converted to
(a) (molecular weight)/2 (a) Mn2O3 (b) MnO2
(b) (molecular weight)/6 (c) MnO4– (d) MnO42–
(c) (molecular weight)/3 94. Which among the following paramagnetic pairs rare?
(d) same as molecular weight. (1) [BaO2, NO2] (2) [KO2, NO]
(3) [H2O2, NO] (4) [K3Fe(CN)6, CuCl2]
87. Which of the following statement is correct with ref-
(a) 3, 4 only (b) 1, 3 only
erence to the ferrous and ferric ions?
(c) 2, 4 only (d) 1, 2, 4
1. Fe3+ gives brown colour with potassium ferricyanide
2. Fe2+ gives blue precipitate with potassium ferricyanide 95. Amongst the following, the lowest degree of para-
3. Fe3+ gives red colour with potassium thiocyanate magnetism per mole of the compound at 298 K will
4. Fe2+ gives brown colour with ammonium thiocyanate be shown by
(a) 1, 4 (b) 1, 2 (a) MnSO4.4H2O
(c) 2, 3 (d) all of these (b) CuSO4.5H2O
(c) FeSO4.6H2O
88. Which of the following statement is correct when a
(d) NiSO4.6H2O
mixture of NaCl and K2Cr2O7 is gently warmed with
concentrated H2SO4? 96. Match the following:
1. deep red coloured vapours are evolved List I List II
2. the vapours when passed into NaOH solution give 1. Cu2+ (i) colourless
a yellow solution of Na2CrO4 2. Ni2+ (ii) green
3. chlorine gas is evolved 3. Fe3+ (iii) yellow
4. chromyl chloride is formed 4. Ti3+ (iv) blue
(a) 1, 2, 4 (b) 1, 2 ,3 (v) purple
(c) 2, 3, 4 (d) all are correct The correct matching is:
1 2 3 4
89. Which of the following has the maximum number of
(a) (i) (ii) (iii) (v)
unpaired electrons?
(b) (i) (iii) (ii) (iv)
(a) Mg2+ (b) Ti3+ (c) (ii) (i) (iii) (v)
(c) V 3+
(d) Fe2+ (d) (iv) (ii) (iii) (v)
90. Which compound is formed when excess of KCN is 97. A brown ring complex compound is formulated as
added to an aqueous solution of copper sulphate? [Fe(H2O)5NO+]SO4. The oxidation state of iron here is
(a) Cu(CN)2 (b) K2[Cu(CN)6] (a) 1 (b) 2
(c) K[Cu(CN)2] (d) K3[Cu(CN)4] (c) 3 (d) 4
91. One gram of impure K2CrO4 was treated chemically, 98. In the metallurgy of iron, when limestone is added to
so as to convert all the chromium in it quantitatively the blast furnace, the calcium ions end up in
into CrO2Cl2, which was then hydrolyzed; the prod- (a) gangue (b) calcium carbonate
ucts of hydrolysis yielded 1 gram of precipitated AgCl (c) slag (d) metallic calcium
with sufficient AgNO3 and dilute HNO3. Estimate
the percentage of K2CrO4 in the original sample of 99. Iron is rendered passive by treatment with concentrated
K2CrO4. (Atomic weight of Cr = 52) (a) HCl (b) HNO3
(a) 58% (b) 68% (c) H3PO4 (d) H2SO4
(c) 62% (d) 47% 100. Sodium thiosulphate is used in photography because
92. The elements which exist in the liquid state at room of its
temperature are (a) reaction with light
1. Na 2. Br (b) oxidizing behaviour
3. Hg 4. Ga (c) reducing behaviour
(a) 1, 2, 3 (b) 2, 3 (d) complex forming behaviour
(c) 2, 4 (d) 1, 2, 3
19.18 Chapter 19

101. Match the following: (c) (iv) (i) (ii) (iii)

List I (n = un-paired e–) List II (Meg. moment) (d) (iii) (iv) (i) (ii)
1. Sc3+ = 0 (i) 5.92 B.M. 102. A blue colouration is obtained in which case?
2. V2+ = 3 (ii) 1.73 B.M.
(1) on dissolving NH4OH in copper sulphate.
3. Fe3+ = 5 (iii) zero
(2) on reacting CuSO4 solution with potassium
4. Cu2+ = 1 (iv) 3.87 B.M.
ferrocyanide.
The correct matching is:
(3) on reacting FeCl3 with sodium ferrocyanide.
1 2 3 4
(4) on dissolving anhydrous CuSO4 in water.
(a) (ii) (i) (iii) (iv)
(a) 2 , 4 only (b) 1, 3, 4
(b) (iii) (iv) (ii) (i)
(c) 1, 2, 4 (d) 3, 4 only

More than One Option Correct Type

103. Which of the following is/are characteristics of
d-block elements?
(a) They are generally diamagnetic
(b) They form coloured complexes
(c) They show variable oxidation states
(d) Their ionization energies are very high
104. Which of the following metals have both valence
shell and penultimate shell partially filled?
(a) Cu (b) Zn
(c) Cr (d) Mn
105. Which of the following d-block elements do not pos-
ses characteristics properties of transition elements?
(a) Cadmium (b) Manganese
(c) Zinc (d) Copper
106. Which of the following is/are incorrect statement(s)
(a) Equivalent wt. of KMnO4 in acidic medium is
M/5
(b) In acidic medium MnO42– disproportionates to
MnO2 and MnO4–
(c) KMnO4 spot can be bleached by H2O2
(d) Alkaline KMnO4 can be used to test
unsaturation in
107. Which of the following compounds are coloured due
to charge transfer spectra?
(a) AgNO3 (b) CuSO4
(c) K2Cr2O7 (d) KMnO4
108. Which of the following matching is/are correct here?
(a) Secondary valencies –— oxidation number
(b) Primary valencies –— hold ionisable species
(c) Primary valencies –— oxidation state
(d) Secondary valencies –— co-ordination number
109. The mixture of which of the following can produce
blue colouration?
(a) Iron (III) chloride and K4[Fe(CN)6] (aq)
(b) NH4OH (aq) and CuSO4 (aq)
(c) Adding anhydrous CuSO4 to water
(d) ZnCl2 (aq) and K[Fe(CN)6](aq)
110. Which of the following conditions is/are suitable for
the stability of the complex?
(a) Chelation
(b) Larger basic nature of the ligand
(c) Larger charge on the central metal ion.
(d) Smaller charge on the central metal ion

Passage Based Questions

Passage-1
The transition elements with some exceptions can show
a large number of oxidation states. The various oxidation
states are related to the electronic configuration of their
atoms. The variable oxidation states of a transition metal is
due to the involvement of (n – 1)d and outer ns-electrons.
For the first five elements of 3d-transition series. The mini-
mum oxidation state is equal to the number of electrons in
4s shell and the maximum oxidation state is equal to the
sum of 4s and 3d-electrons. The relative stability of various
oxidation state of a given element can be explained on the
basis of stability of d0, d5 and d10 configurations.
111. In 3d-series, the maximum oxidation state is shown
by
(a) Fe (26) (b) Mn (atomic no. : 25)
(c) Cr (24) (d) Sc (atomic no : 21)
 Transition Metals Including Lanthanides and Actinides 19.19

112. In which of the following pair, the first species is complexes. A weak ligand usually results in the formation
more stable than second one of outer orbital complex or high spin complex.
(a) Mn2+, Mn3+ (b) Sc2+, Sc3+ 114. The hybridization of Cu in [CuCl4]2− and [Cu(NH3)4]2+
(c) Ti , Ti
3+ 4+
(d) Fe2+, Fe3+ are respectively.
113. Identify the correct statement (a) sp3, dsp2 (b) dsp2, dsp2
(a) Ti4+, Mn2+ are stable oxidation states (c) dsp2, sp3 (d) sp3, sp3
(b) The most common oxidation state of 3d-series is 115. The number of unpaired electrons present in
+2. [Fe(CN)6]4− and [Fe(H2O)6]2+ are, respectively
(c) The lowest oxidation state of Cr and Cu is +1
(a) 0,0 (b) 0, 4
while for others it is +2.
(d) All of these (c) 1, 2 (d) 2, 4
116. Among the following four sets, the one having the
Passage-2
same geometry and same magnetic property for both
The d-orbitals participating in hybridization of central complexes is
metal atom may be from the outermost shell or the penul- (a) [Co(CN6)]3− and [CoF6]3−
timate shell. This depends on the nature of metal and the
(b) [Mn(CN)6]3− and [MnF6]3−
nature of ligand. The complexes involving the inner d level
(inner orbital complexes) result when the ligand is a pow- (c) [Cr(CN)6]3− and [Cr(H2O)6]3+
erful or strong ligand resulting in diamagnetic or low spin (d) [Fe(CN)6]4− and [Fe(H2O)6]2+

Match the Column Type

117. Match the following (c) Astatine (r) Highest melting point
among metals
List–I List–II (d) Iron (s) Transition metal
(a) Highest density (p) Os
(t) Shows +2 and +3 oxidation
(b) Colourless salts (q) Cr states
(c) Maximum magnetic (r) Zn 120. Match the following
moment
(d) Variable oxidation state (s) Mn List–I List–II
(a) Ti3+ (p) Paramagnetic
118. Match the following (b) Cu2+ (q) Coloured
List–I List–II (c) Co 2+
(r) One un-paired electron
(a) Coloured ion (p) Cu+ (d) Zn2+ (s) Diamagnetic
(b) μ = 1.73 B.M (q) Cu2+ 121. Match the following
(c) d configuration
10
(r) Fe 2+

Column–I Column–II
(d) More than 3 un-paired (s) Mn2+ (a) Ce4+ (p) Oxidizing agent in volu-
electrons metric analysis
119. Match the following (b) Nd3+ (q) Misch metal
(c) La3+ (r) Colourless salts
List–I List–II
(a) Mercury (p) Liquid metal (d) Pr3+ (s) Coloured glases for gog-
gles .
(b) Tungsten (q) Non-transition metal
19.20 Chapter 19

Previous Years’ Questions

122. When the sample of copper with zinc impurity is to be (a) in acidic solutions, hydration protects copper ions
purified by electrolysis, the appropriate electrodes are (b) the acidic solutions, protons coordinate with
[2002] ammonia molecules forming NH4+ ions and NH3
Cathode Anode molecules are not available
(a) pure zinc pure copper (c) in alkaline solutions, insoluble Cu(OH)2 is pre-
(b) pure copper impure sample cipitated which is soluble in excess of any alkali
(d) copper hydroxide is an amphoteric substance
(c) impure zinc impure sample
(d) impure sample pure copper 130. Which one of the following nitrates will leave behind
a metal on strong heating? [2003]
123. Number of electrons transferred in each case when (a) ferric nitrate
KMnO4 acts as an oxidizing agent to give MnO2, (b) copper nitrate
Mn2+, Mn(OH)2 and MnO42– are respectively [2002] (c) manganese nitrate
(a) 1, 3, 4 and 5 (d) silver nitrate
(b) 4, 3, 1 and 5
131. For making good quality mirrors, plates of float glass
(c) 5, 4, 3 and 1
are used. These are obtained by floating molten glass
(d) 3, 5, 4 and 1 over a liquid metal, which does not solidify before
124. The most stable ion is [2002] glass. The metal used can be [2003]
(a) [Fe(OH)5]3– (b) [FeCl6]3– (a) mercury (b) tin
(c) [Fe(CN)6]3– (d) [Fe(H2O)6]3+ (c) sodium (d) magnesium
132. Excess of KI react with CuSO4 solution and then
125. Most common oxidation states of Ce are [2002]
Na2S2O3 solution is added to it. Which of the follow-
(a) +3, +4 (b) +2, +3 ing statements is incorrect for this reaction? [2004]
(c) +2, +4 (d) +3, +5 (a) Cu2I2 is formed (b) Na2S2O3 is oxidized
126. The atomic number of V, Cr, Mn and Fe are respec- (c) CuI2 is formed (d) evolved I2 is reduced
tively 23, 24, 25 and 26. which one of these may 133. Which one of the following ores is best concentrated
be expected to have the highest second ionization by froth floatation method? [2004]
enthalpy? [2003]
(a) cassiterite (b) galena
(a) Mn (b) Fe (c) malachite (d) magnetite
(c) Cr (d) V
134. Aluminium chloride exists as dimer Al2Cl6 in solid
127. What would happen when a solution of potassium state as well as in solution of non-polar solvents such
chromate is treated with an excess of dilute nitric as benzene. When dissolved in water, it gives [2004]
acid? [2003] (a) Al2O3 + 6HCl (b) Al3+ + 3Cl–
(a) Cr2O7 and H2O are formed
2–
(c) [Al(OH)6] + 3HCl (d) [Al(H2O)6]3+ + 3Cl–
3–

(b) Cr3+ and Cr2O72– are formed

135. The soldiers of Napolean's army, while on Alps during
(c) CrO42– is oxidized to +7 state to Cr
(d) CrO42– is reduced to +3 state of Cr
128. The radius of La3+ (atomic number = 57) is 1.06 Å.
Which one of the following given values will be
closest to the radius of Lu3+ (atomic number = 71)?
[2003]
(a) 0.85 Å (b) 1.06 Å
(c) 1.40 Å (d) 1.60 Å
129. Ammonia forms the complex ion [Cu(NH3)4]2+ with
copper ions in the alkaline solutions, but not in acidic
solutions. What is the reason for it? [2003]
freezing winter, suffered a serious problem as regards
to the tin buttons of their uniforms. White metallic tin
buttons got converted to grey powder. This transfor-
mation is related to [2004]
(a) an interaction with nitrogen of the air at very low
temperatures
(b) a change in the crystalline structure of tin
(c) an interaction with water vapour contained in the
humid air
(d) a change in the partial pressure of oxygen in the
air.
 Transition Metals Including Lanthanides and Actinides 19.21
136. Among the properties (A) reducing (B) oxidizing (C)
complexing, the set of properties shown by CN– ion
towards metal species is [2004]
(a) A, B (b) B, C
(c) C, A (d) A, B, C
137. Cerium (Z=58) is an important member of the lan-
thanoids. Which of the following statements about
cerium is incorrect? [2004]
(a) the common oxidation states of cerium are +3 and
+4
(b) the +3 oxidation state of cerium is more stable
than the +4 oxidation state
(c) the +4 oxidation state of cerium is not known in
solutions
(d) cerium (IV) acts as an oxidizing agent
138. During the process of electrolytic refining of copper,
some metals present as impurity, settle as anode mud.
These are [2005]
(a) Ag and Au (b) Pb and Zn
(c) Fe and Ni (d) Sn and Ag
139. The oxidation state of chromium, in the final prod-
uct formed by the reaction between KI and acidified
potassium dichromate solution, is [2005]
(a) +2 (b) +3
(c) +4 (d) +6
140. The lanthanide contraction is responsible for the fact
that [2005]
(a) Zr and Y have about the same radius
(b) Zr and Zn have the same oxidation state
(c) Zr and Hf have about the same atomic radius
(d) Zr and Nb have similar oxidation state
141. Which of the following factors may be regarded as the
main cause of lanthanide contraction? [2005]
(a) poor shielding of one of 4f electrons by another
in the subshell
(b) effective shielding of one of 4f electrons by
another in the subshell
(c) poor shielding of 5d-electrons by 4f electrons
(d) greater shielding of 5d-electrons by 4f electrons
142. The IUPAC name of the coordination compound
K3[Fe(CN)6] is [2005]
(a) potassium hexacyanoferrate (III)
(b) potassium hexacyanoferrate (II)
(c) tripotassium hexacyaniron (II)
(d) potassium hexacyanoiron (II)
143. Which of the following cyano complexes would
exhibit the lowest value of paramagnetic behaviour?
[2005]
(a) [Fe(CN)6] 3–
(b) [Co(CN)6] 3–
(c) [Mn(CN)6] 3–
(d) [Cr(CN)6]3–
144. Lanthanoid contraction is caused due to [2006]
(a) the appreciable shielding of outer electrons by 4f-
electrons from the nuclear charge
(b) the appreciable shielding on outer electrons by
5d-electrons from the nuclear charge
(c) the same effective nuclear charge from Ce to Lu
(d) the imperfect shielding of outer electrons by 4f
electrons from the nuclear charge
145. Larger number of oxidation states are exhibited by the
actinoids than those by the lanthanoids, the main rea-
son being [2008]
(a) 4f-orbitals more diffused than the 5f-orbitals
(b) Lesser energy difference between 5f and 6d than
between 4f and 5d orbitals
(c) More energy difference between 5f and 6d than
between 4f and 5d orbitals
(d) More reactive nature of the actinoids than the
lanthanoids.
146. In context with the transition elements, which of the
following statement is incorrect? [2009]
(a) In the highest oxidation states, the transition
metal show basic character and cationic complex.
(b) In the highest oxidation states of the first five
transition element (Sc to Mn), all the 4s and 3d
electrons are used for bonding.
(c) Once the d5 configuration is exceeded, the ten-
dency to involve all the 3d electrons in bonding
decreases.
(d) In addition to the normal oxidation states, the
zero oxidation state is also shown by these ele-
ments in complex.
147. Knowing that the chemistry of lanthanoids (Ln) is
dominated by its+3 oxidation state, which of the fol-
lowing statements is incorrect? [2009]
(a) The ionic sizes of Ln (III) decrease in general
with increasing atomic number.
(b) Ln (III) compounds are generally colourless.
(c) Ln (III) hydroxides are mainly basic in character.
(d) Because of the large size of the Ln (III) ions the
bonding in its compounds is predominantly ionic
in character.
19.22 Chapter 19

148. The outer electron configuration of Gd (atomic 151. Four successive member of the first now transi-
number = 64) is: [2011] tion elements are listed below with atoms number.
(a) 4f 5d 6s
7 1 2
(b) 4f 5d 6s
3 2 2 Which one of them is expected to have the highest
(c) 4f8 5d0 6s2 (d) 4f4 5d4 6s2 E0M3+ /M2+ value? [2013]
149. In context of the lanthanoids, which of the follwoing (a) Fe(Z = 26)
statements is not correct? [2011] (b) Co(Z = 27)
(a) Availability of 4f electrons results in the forma- (c) Cr(Z = 24)
tion of compound in +4 state for all the members (d) Mn(Z = 25)
of the series.
(b) There is a gradual decrease in the radii of the 152. The color of KMnO4 is due to [2015]
members with increasing atomic number in the (a) M → L charge transfer transition
series. (b) d – d transition
(c) Because of similar properties the separation of (c) L → M charge transfer transition
lanthanoids is not easy (d) σ – σ* transition
(d) All the members exhibit +3 oxidation state. 153. Which of the following atoms has the highest first
150. Which of the following arrangements does not repre- Ionization energy? [2016]
sent the correct order of the property stated against it? (a) Na
[2013] (b) K
(a) Co < Fe < Cr < Sc stability in aqueous
3+ 3+ 3+ 3+ (c) Sc
solution. (d) Rb
(b) Sc < Ti < Cr < Mn : number of oxidation states.
(c) V2+ < Cr2+ < Mn2+ < Fe2+ : Paramagnetic behaviour.
(d) Ni2+ < Co2+ < Fe2+ < Mn2+ : ionic size

ANSWER KEYS

Single Option Correct Type

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

More than One Option Correct Type

103. (b, c) 104. (c, d) 105. (a, c) 106. (b, d) 107. (c, d) 108. (b, c, d)
109. (b, c, d) 110. (a, b, c)
 Transition Metals Including Lanthanides and Actinides 19.23

Passage Based Questions

111. (b) 112. (a) 113. (d) 114. (a) 115. (b) 116. (c)

Match the Column Type

117. a → (p); b → (r); c → (q); d → (p, q, s) 118. a → (q, r, s); b → (q); c → (p); d → (r, s)
119. a → (p, s); b → (r, s); c → (q); d → (s, t) 120. a → (p, q, r); b → (p, q, r); c → (p, q); d → (s)
121. a → (p, q, r); b → (q, s); c → (q, r); d → (s)

Previous Years’ Questions

122. (b) 123. (d) 124. (c) 125. (a) 126. (c) 127. (a) 128. (a) 129. (b) 130. (d) 131. (a)
132. (c) 133. (b) 134. (d) 135. (b) 136. (c) 137. (c) 138. (a) 139. (b) 140. (c) 141. (a)
142. (a) 143. (b) 144. (d) 145. (b) 146. (a) 147. (b) 148. (a) 149. (a) 150. (c) 151. (b)
152. (c) 153. (c)
19.24 Chapter 19

HINTS AND SOLUTIONS

Single Option Correct Type

2. Both Cu2+ and Ni2+ are coloured and paramagnatic. 48. 4Ag + 8CN– + 2H2O + O2 4[Ag(CN)2]–
–
3. Sc3+ with no electron in 3d-subshell is colourless. + 4OH
4. Corrosive sublimate, HgCl2 is highly corrosive salt. 49. Lanthanoids are 14 elements in the VIth period (atomic
6. In [Ni(CO)4], the oxidation state of Ni is zero. number = 58 to 71) that are filling the 4f-sublevel.
7. Misch metal is an alloy of lanthanoids. 51. Gold is extracted by hydrometallurgical process based on the
solubility of its cyano complex, K[Ag(CN)2].
12. (CuI4)2– does not exist as I– (strong reductant) reduces Cu2+
into Cu2+ into Cu+. 52. VO and V2O5 – basic
13. Lanthanides and actinides resemble each other in their elec- VO2 – amphoteric, CrO – basic
tronic configuration. VO2, Cr2O3 – amphoteric
+7 OH– +6 VO2 – amphoteric, CrO3 – acidic
16. KMnO4 +e– K2MnO4 53. During corrosion, Fe is oxidized to Fe2+ and dissolved oxy-
gen in water is reduced to OH .
–
20. Due to variable oxidation states, these can easily form unsta-
ble intermediates favouring the catalytic activity. 59. [Cr(H2O)6]2+ = Cr2+ = 3d4 = four unpaired electrons
21. Magnetic property of iron is lost by heating it at 1000K.
[Fe(H2O)6]2+ = Fe2+ = 3d6 = four unpaired electrons
22. CO burns with a blue flame.
61. Haemoglobin and cytochrome contain iron.
23. Ti4+, Zn2+, Sc3+ are not carrying any unpaired electrons. But x –2 –1

Ni2+ with an, electronic configuration of d8 , carries two 62. Cr O2 Cl2

unpaired electrons. So, it is coloured. x–4–2=0
x = +6
25. Zn2+, the electronic configuration is d10, therefore it appears
colourless. 63. This is clear from magnetic moment studies.
32. Au, Pt, and Pb are non-reactive towards to H2SO4. 64. CuF2 is coloured due to the presence of one unpaired d elec-
tron in Cu2+. It can undergo d–d transition.
33. Ag forms a complex ion, diammine silver(I) chloride, in
which cation is represented as [Ag(NH3)2]+. 65. Co2+ has configuration [Ar] 3d7 and has unpaired d electrons.
So it is coloured.
34. There is only one mole of Cl– ions present in one mole of the
complex compound. 66. It is Cr. It has the ground state electronic configuration of:
[Ar] 3d5 4s1.
35. Manganese shows +1, +2, +3, +4, +5, +6, +7 oxidation states.
67. 3d orbital of Ni2+ ion. Atomic number of Ni = 28
36. [Co(NO2)6] is having –3 oxidation state
68. Zinc–copper couple is obtained by combining zinc with
Thus (oxidation state of cobalt) + 6(–1) = –3
copper.
oxidation state of cobalt = –3 + 6 = +3
69. Here V is in the form of V4+ and C is in the form of Cu2+ that
37. As Cu2I2 is white in colour and not blue is, both have one unpaired electron so have same colour.
38. Zn + 2NaOH + 2H2O Na2[Zn(OH)4] + H2 70. Zinc is more electropositive than silver, therefore, it dis-
Here zinc is associated with the anionic [Zn(OH)4]2- part. places silver as metal.
1
______________
39. 2AgNO3 + Na2S2O3 Ag2S2O3 + 2NaNO3 71. Reducing strength ∝ ionization potential
Ag2S2O3 + H2O H2SO4 + Ag2S ‘Cu’ has a greater I.P. value.
Black
It cannot reduce H2O
41. 4Fe + 10HNO3 4Fe(NO3)2 + NH4NO3
72. In carboxyls, metal exhibits zero oxidation state.
+ 3H2O
Δ 73. Lanthanum hydroxide is more basic than luteium hydroxide
42. Zn + 2NaOH Na2ZnO2 + H2
since the basicity decreases in the period.
43. Gun metal contains Cu + Sn; monel metal contains Ni + Cu +
74. K2Cr2O7, KMnO4 and CrO3 are coloured due to charge
Fe and constantan contains Cu + Ni. So Cu is common to all.
transfer.
44. The correct order is
75. d–d e– transition is possible in incomplete d-subshell.
TiO > VO > CrO > FeO
76. Due to formation of tetrammine zinc(II) complex;
46. Both Fe3+ and Mn2+ have [Ar] 3d5 configuration. Zn2+ + NH4OH [Zn(NH3)4]2+
47. Cu, Ag and Au are coinage metals.
 Transition Metals Including Lanthanides and Actinides 19.25

–
77. Cu+2 + 2CN Cu(CN)2 89. Mg2+ has electronic configuration 1s2 2s2 2p6 ; no unpaired
2Cu(CN)2 2CuCN + (CN)2 electrons.
78. Due to synergic bond formation between metal and CO, the 22
Ti3+ has electronic configuration [Ar] 3d1 ; one unpaired
bond order of CO decreases. electron.
V3+ has electronic configuration [Ar] 3d2 ; two unpaired
79. Here in CrO2Cl2, the oxidation state of chromium is
electrons.
+6 and in MnO4– the oxidation state of manganese
Fe2+ has electronic configuration [Ar] 3d6 ; four unpaired
is +7, that is, maximum values.
electrons.
80. 2MnO4– + I– + H2O IO3– + 2MnO2 + 2OH–
90. Firstly Cu2+ ion is reduced to Cu+ by CN– which then forms
81. Ti(H2O)6 has one unpaired electron in its d-subshell which
3+
complex with it.
gives rise to d–d transition to impart colour.
2Cu2+ + 2CN– 2Cu+ + (CN)2
82. MnO2 + 2KOH + ½ O2 K2MnO4 + H2O Cu+ + CN– CuCN
purple green
–
K3[Cu(CN)4] 3KCN
83. 2Au + 4CN + H2O + ½ O2 2[Au(CN)4]–
– 91. K2CrO4 CrO2Cl2 2AgCl
+ 2OH (X)
(194 g) (287 g)
2[Au(CN)2]– + Zn [Zn(CN)4]–2 + 2Au 194
___
(Y) % purity is 287 × 100 = 68
84. Ag (excess) + Br (0.01 mole)
+ -
AgBr 92. Both bromine and mercury are liquids at room temperature.
(0.01 mole) Ga is low melting solid. It is not liquid at room temperature.
+2 +4
Ba2+ (excess) + SO4–2 (0.01 mole) BaSO4 93. MnSO4 MnO2
(001 mole) There is transfer of two electrons.
85. Anhydrous ferric chloride is obtained by passing dry chlo- molecular mass
____________________
Eq. mass = No. of electrons transferred
rine gas over heated metallic iron.
mol mass
_______
2Fe + 3Cl2 2FeCl3 = 2
choice (a) is not correct because it gives 95. CuSO4.5H2O has lowest number of unpaired d electrons and
Fe2O3 as: lowest degree of paramagnetism.
x +
2[FeCl3.6H2O] Δ Fe2O3 + 6HCl + 9H2O 97. [Fe(H2O)5NO]+2 SO42–
87. Fe + [Fe(CN)6]
2+ 3–
Fe3+ + [Fe(CN)6]4– x + 1 = +2
Fe3+ + [Fe(CN)6]4- + K+ K[Fe{Fe(CN)6}] x = 2 – 1 = +1
Turnbull’s blue
98. CaCO3 Heat CaO + CO2
Fe3+ + 3KCNS 3K+ + Fe(SCN)3 CaO + SiO2 CaSiO3 (slag)
Red ppt.
Δ 99. Concentrated HNO3 renders iron passive by forming a thin
88. 4NaCl + K2Cr2O7 + 6H2SO4 (conc.)
protective film of Fe3O4 on its surface.
2KHSO4 + 4NaHSO4 + 2CrO2Cl2 + 3H2O
100. Hypo solution (Na2S2O7) is used in photography to remove
(Orange red)
the unaffected AgBr in the form of soluble complex.
Chromyl chloride
AgBr + Na2S2O7 Na3[Ag(S2O3)2] + 2NaBr
Chromyl chloride vapours when passed through NaOH solu-
Sodium argentothiosulphate
tion gives a yellow solution of Na2CrO4.

Match the Column Type

121. Ce4+ and La3+ salts are colourless (no unpaired electrons). making coloured glasses for goggles. Ce4+ is an oxidizer in
Ce, Nd and La are present in Misch metal, a pyrophoric. volumetric analysis.
Nd3+ (Neodymium) and Pr3+ (Praseodymium) are used for

Previous Year’s Questions

122. During purification of copper by electrolysis, pure copper plate 133. Froth floatation is used to concentrate sulphide ores like
is made cathode and impure sample of copper is made anode. Galena (Pbs).
127. 2CrO42– + 2H+ Cr2O72– + H2O 134. AlCl3 is covalent, but in water, it become ionic due to large
132. CuSO4 + 2KI CuI2 + K2SO4 hydration energy of Al3+.
2CuI2 Cu2I2 + I2 AlCl3 + 6H2O ↔ [Al(H2O)6]3+ + 3Cl-
So, CuI2 is not formed.
19.26 Chapter 19

135. As temperature decreases, white tin (β-form) changes to 146. As in higher Oxidation states transition elements show
grey tin (α-form) acidic nature
β-Sn
13.2oC
α-Sn 147. As Ln+3 compound are mostly coloured due to presence of
unpaird f electrons (f - f e– transition)
α-Sn has a much lower density than β– Sn.
149. The common oxidation state of lanthanolds is +3. Some of
136. CN- is a better complexing agent (C) as well as a reducing
the lanthanoids may also show +2 and +4 oxidation states
agent (A)
however they easily revert to the more stable +3 state.
Thus properties (A) and (C) are shown.
150. More the unpaired electron, more is paramagnetic nature
Property (C) : Ni2+ + 4CN– → [Ni(CN)4]2– magnetic moment = n(n+2)
II I
Property (A) : CuCl2 + 5KCN → K3[Cu(CN)4] n = no of unpaired electron
+ ½ (CN)2 + 2KCl Ions unpaired electron
–
(CN reduces Cu2+ to Cu+) v+2 3
137. +3 and +4 oxidation states are shown by Ce in aqueous Cr +2
4
solution. Mn+2 5
138. During the process of electrolytic refining of copper, Ag and Fe+2 4
Au present as impurity in impure copper, settle as anode
152. Charge transfer from ligand to metal, hence KMnO4 is
mud.
+6 +3
purple colour.
139. Cr2O72– + 14H+ + 6I– 2Cr3+ + 7H2O + 3I2 157. Metal Eo
140. Due to lanthanide contraction, Zr and Hf have about the Co(Z = 27) +1.80
same atomic radius.
Cr –0.407
142. K3[Fe(CN)6] is potassium hexacyanoferrate (III)
Mn +1.54
145. It is due to lesser energy difference between 5f and 6d than
Fe +0.771
between 4f and 5d orbitals
Hence, Co has the highest value of Eo here.