d & f Block Elements

Summary
Four series of elements are formed by filling the 3d, 4d, 5d and 6d shells of electrons. Together
these comprise the d-block elements. A transition element may be defined as the element whose
atom in ground state or ion in one of common oxidation states, has partly filled d-sub shell i.e.
having electrons between 1 to 9.
The general electronic configuration of d-block elements is ( n −1) d1−10 ns 0− 2 , where n is the outer
most shell.
General trends in the chemistry of transition elements.
Metallic character:
Nearly all the transition elements display typical metallic properties such as high tensile strength,
ductility, malleability, high thermal and electrical conductivity and metallic lustre. With the
exceptions of Zn, Cd, Hg and Mn, they have one or more typical metallic structures at normal
temperatures.
The transition elements (with the exception of Zn, Cd and Hg) are very much hard and have low
volatility.

Melting and Boiling Points:

The melting and boiling points of the transition series elements are generally very high. Strong
metallic bonds between the atoms of these elements attribute to their melting and boiling points.
 The dip in melting points of Mn, Tc and Re can be attributed to their exactly half filled. d-
orbital. Due to this stable electronic configuration the electrons are held tightly by the
nucleus and hence the delocalization of electrons is less and the metallic bond is much
weaker than preceding elements.

Density:
The atomic volumes of the transition elements are low compared with the elements of group 1 and
2. This is because the increased nuclear charge is poorly screened and so attracts all the electrons
more strongly. In addition, the extra electrons added occupy inner orbitals. Consequently, the
densities of the transition metals are high. The densities of the second row are high and third row
values are even higher. Elements with the highest densities are osmium 22.57 g cm-3 and iridium
22.61 g cm-3.

Oxidation states:
With the exception of a few elements, most of transition elements show variable oxidation states.
This is due to the participation of inner (n – 1) d-electrons in addition to outer ns-electrons because,
the energies of the ns and (n – 1) d-subshells are nearly same.
The elements which show the greater number of oxidation states occur in or near the middle of the
series. Unlike p-block elements where the lower oxidation states are favored heavier members (due
to inert pair effect), the higher oxidation states are more stable in heavier transition elements.

Different oxidation states of first transition series

Element Outer electronic Oxidation states
configuration
Sc 3d14s2 +3
2 2
Ti 3d 4s +2, +3, +4
V 3d34s2 +2, +3, +4, +5
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d & f Block Elements

Cr 3d54s1 +2, +3, (+4), (+5), +6

Mn 3d54s2 +2, +3, +4, (+5), +6, +7
Fe 3d64s2 +2, +3, (+4), (+5), (+6)
Co 3d74s2 +2, +3, (+4)
Ni 3d84s2 +2, +3, +4
Cu 3d104s1 +1, +2
Zn 3d104s2 +2

Characteristics of Oxides and Some Ions of V and Cr

O.S. Oxide/Hydroxide Behavior Ion Name of Ion Color of

ion
+2 VO basic V2+ vanadium (II) violet

(vanadous)
3+
+3 V2O5 basic V vanadium (III) green

(vanadic)
+4 VO2 amphoteric VO2+ oxovanadium (IV) blue

(vanadyl)
V4O92− hypovanadate brown

(vanadate)
+5 V2O5 amphoteric VO +2 dioxovanadium yellow
(V)
colourless
VO34− orthovanadate
+2 basic Cr2+ chromium (II) light blue

(chromous)
+2 basic Cr2+ chromium (II) light blue

(chromous)
+3 amphoteric chromium (III) violet

chromic

chromite green
+5 acidic chromate yellow

dichromate orange

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d & f Block Elements

Standard electrode potentials:

The value of ionization enthalpies gives information regarding the thermodynamic stability of the
transition metal compounds in different oxidation states. Smaller the ionization enthalpy of the
metal, the stable is its compound.
Electrode potentials:
In addition to ionization enthalpy, the other factors such as enthalpy of sublimation, hydration
enthalpy, ionization enthalpy etc. determine the stability of a particular oxidation state in solution.
The overall energy change is
∆H = ∆ sub H Θ + IE + ∆ hyd H
The smaller the values of total energy change for a particular oxidation state in aqueous solution,
greater will be the stability of that oxidation state. The electrode potentials are a measure of total
energy change. Qualitative, the stability of the transition metal ions in different oxidation states
can be determined on the basis of electrode potential date. The lower the electrode potential i.e.,
more negative the standard reduction potential of the electrode, the more stable is the oxidation
state of the transition metal in the aqueous solution.
Thermochemical data (kJ mol-1) for the first row Transition Elements and the Standard
Electrode potentials for the Reduction of MII to M

Element (M) ∆ a Hq ( M ) ∆ f H1θ ∆1H θ2 (

∆ hyd H θ M 2+ ) Eθ / V
Ti 469 661 1310 -1866 -1.63

V 515 648 1370 -1895 -1.18

Cr 398 653 1590 -1925 -0.90

Mn 279 716 1510 -1862 -1.18

Fe 418 762 1560 -1998 -0.44

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 d & f Block Elements

Co 427 757 1640 -2079 -0.28

Ni 431 736 1750 -2121 -0.25

Cu 339 745 1960 -2121 0.34

Zn 130 908 1730 -2059 -0.76

Formation of coloured Ions:

Most of the compounds of transition metals are coloured in the solid form or sodium form. The
colour of the compounds of transition metals may be attributed to the presence of incomplete (n –
1) d-subshell.

The excess of other colours constituting white light are transmitted and the compound appears
coloured. The observed colour of a substance is always complementary colour of the colour which
is absorbed by the substance.

Magnetic Properties:
(i) Paramagnetic substances: The substances which are attracted by magnetic field are called
paramagnetic substance and this character arises due to the presence of unpaired electrons in the
atomic orbitals.
(ii) Diamagnetic substances: The substances which are repelled by magnetic field are called
diamagnetic substances and this character arises due to the presence of paired electrons in the
atomic orbitals.
= µ n ( n + 2 ) B.M.
where n is the number of unpaired electrons and µ is magnetic moment in Bohr magneton (BM)
units. The Para magnetism first increases in any transition series and then decreases. The maximum
Para magnetism is observed around the middle of the series (as contains maximum number of
unpaired electrons).
Formation of Interstitial Compounds:
Transition metals form interstitial compounds with elements such as hydrogen, boron, carbon and
nitrogen. The small atoms of these non-metallic elements (H, B, C, N, etc.) get trapped in vacant
spaces of the lattices of the transition metal atoms.
They are generally non-stoichiometric and are neither typically ionic nor covalent.
Catalytic properties:

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 d & f Block Elements

Many transition metals and their compounds act as good catalysts for various reactions. Of these,
the use of Fe, Co, Ni, V, Cr, Mn, Pt, etc. are very common.
(i) The catalytic property of transition metals is due to their tendency to form reaction intermediates
with suitable reactants. These intermediates give reaction paths of lower activation energy and,
therefore, increase the rate of the reaction.
(ii) In some cases, the transition meal catalysts provide a suitable large surface area for the absorption
of the reactant. This increases the concentration of the reactants at the catalyst surface and also
weakens the bonds in the reactant molecules. Consequently, the activation energy gets lowered.
(iii) In some cases, the transition metal ions can change their oxidation states and become more
effective as catalysts.
Alloy Formation:
Alloys are homogeneous solid solutions in which the atoms of one metal are distributed randomly
among the atoms of the other metal. The alloys are generally formed by those atoms which have
metallic radii within about 15% of each other. Transition metals form a large number of alloys.
The transition metals are quite similar in size and, therefore, the atoms of one metal can substitute
the atoms of other metal in its crystal lattice. Thus, on cooling a mixture solution of two or more
transition metals, solid alloys are formed. Such alloys are hard, have high melting points and are
more resistant to corrosion than parent metals.
d-Block Metal Compounds:
1. Hydrated Ferrous Sulphate ( FeSO 4 .7H 2O ) , Ferric chloride ( FeCl 3 ) and iron (III) oxide
( Fe2O 3 )

2. Hydrated copper sulphur ( CuSO 4 , 5H 2O ) :

588
 d & f Block Elements

3. Silver nitrate ( AgNO 3 ) :

4. Potassium permanganate ( KMnO 4 ) :

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 d & f Block Elements

5. Potassium dichromate ( K 2Cr2O 7 ) :

f-Block Elements
The inner transition elements (f – block)

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d & f Block Elements

Introduction:
The elements constituting the f – block are those in which the 4f and 5f orbitals are progressively
filled. These elements are the members of group 3.
The f-block elements comprise of the two series, (i) lanthanoids (the fourteen elements following
lanthanum)
and (ii) actinoids (the fourteen elements following actinium).
[A] Lanthanoids (4f - series):
Electronic configuration: The atoms of these elements have electronic configuration with 6s2
common
but with variable occupancy of 4f level. However, the electronic configurations of all the tripositive
ions which is the most stable oxidation state of all the lanthanoids, are of the form 4fn (n = 1 to 14
with increasing atomic number)
Atomic sizes: There is decrease in atomic and ionic radii from lanthanum to lutetium due to
lanthanoid
contraction. The decrease in atomic radii is not quit regular as it is regular in M3+ ion. This
contraction is of
course, similar to that observed in an ordinary transition series and is attributed to the imperfect
shielding of
one electron by another in the same subshell. However, the shielding of one 4f electron by another
is less
than a d-electron by another with the increase in nuclear charge along the series. There is fairly
regular
decrease in the sizes with increasing atomic number.
The cumulative effect of the contraction of the lanthanoids series, known as lanthanoids
contraction, causes the radii of the members of the third transition series to be very similar to those
of the corresponding members of the second series. The almost identical radii of Zr (160 pm) and
Hf (159 pm) is a result of the lanthanoid contraction. This accounts for their occurrence together
in nature and for the difficulty in their separation.
Oxidation state: In the lanthaoids, La(III) and Ln(III) compounds are predominant species.
However, occasionally +2 and +4 ions in solution or in solid compounds are also obtained. This
irregularity (as in ionisation enthalpies) arises mainly from the extra stability of empty, half filled
or filled f subshell. Thus the formation of Cetv is favoured by its noble gas configuration, but it is
a strong oxidant reverting to the common +3 state. The Eo value for Ce4+ / Ce3+ is + 1.74 V which
suggest that it can oxidise water. However, the reaction rate is very slow and hence ce(IV) is a
good analytical reagent; Pr Nd, Tb and and and Dy also exhibit +4 state but only in oxides, Mo2,
Eu2+ is formed by losing the two s electrons and its f7 configuration accounts for the formation of
this ion. However, Eu2+ a strong reducing agent changing to the +3 common oxidation state.
Similarly Yb+2 which has f14 configuration is a reductant. TbIV has half filled f – orbitals and is an
oxidant. The behaviour of samarium is very much like europium, both +2 and +3 oxidation states.

General characteristics: All the lanthanoids are silvery white soft metals and tarnish rapidly in
air. The
hardness increases with increasing atomic number, samarium is hard as steel. Their melting points
range
3etween 1000 to 1200 K but samarium melts at 1623 K. They have typical metallic structure and
are good

591
d & f Block Elements

conductors of heat and electricity. Density and other properties change smoothly except for Eu and
Yb and
occasionally for Sm and Tm. Many trivalent landthanoid ions are coloured both in the solid state
and in
aqueous solution. Colour of these ions may be attributed to the presence of f electron. Neither La3+
nor Lu3+ ion shows any colour but the rest do so. However, absorption bands are narrow probably
because of the excitation within f level. The lanthanoids ions other than the fo type (La+3 and Ce4+)
and the f14 type (Yb2+ and Lu3+) are all paramagnetic. The paramagnetism rises to maximum in
neodyamium.
The first ionisation enthalpies of the lanthanoids are around 600 kJ mol-1s, the second about 1200
kJ mol-1
comparable with those of calcium. A detailed discussion of the variation of the third ionisation
enthalpies
indicates that the exchange enthalpy considerations (as in 3d orbitals of the first transition series),
appear to impart a certain degree oi stability to empty, half-filled and completely filled orbitals f
level. This is indicated from the abnormally low value of the third ionisation enthalpy of
lanthanum, gadolinium and lutetium.
In their chemical behaviour, in general, the earlier members of the series are quit reactive similar
to calcium but, with increasing atomic number. They behave more like aluminium. Values for Es
for the half reaction
Ln3+ (aq ) + 3e −1 → Ln( S )
are in the range of -2.21o -2.4 V except for Eu for which the value is -2.0 V' This is of course, a
small
variation. The metals combine with hydrogen when gently heated in the gas. They form oxides
M2O3. and
hydroxides M(OH)3. The hydroxides are definite compounds, not just hydrate oxides' They are
basic like
alkaline earth metals oxides and hydroxides.

Uses of lanthanoids:
1. Used for the production of alloy steels for plates and pipes. e.g mischmetall which consists of
lanthanoid metal (~95%) and iron (~5%) and traces of S,C,Ca and Al. Mischmetall is used in Mg
based alloy &
produce bullets, shell and lighter flint.
2. Mixed oxides of lanthanoids are employed as catalyst in petroleum cracking'
3. Some individual Ln oxides are used as phosphors in television screens and similar fluorescing
surfaces

592
d & f Block Elements

4. Because of their paramagnetic and ferromagnetic character, their compounds are used in
making magnetic & electronic devices.
5. Ceric sulphate is a well known oxidizing agent in volumetric analysis.

[B] Actinoids (5f - series):

The actinoids include the fourteen elements from Th to Lr. The actinoids are radioactive
elements and the
earlier members have relatively long half lives, the latter ones have half life values ranging from
a day to 3
minutes for lawrencium (Z = 103).

Electronic Configuration: All the actinoids are believed to have the electronic configuration of
7s2 anc
variable occupancy of the 5f and 6d subshell. The fourteen electrons are formally added to 5f,
through not in
thorium (z = 90) but from Pa onwards the 5f orbitals are complete at element 103. The
irregularities in the
electronic configuration of the actinoid, like those in the lanthanoids are related to the stabilities
of the fo. f7 and f14 occupancies of the 5f orbitals. Thus the configurations of Am and Cm are [Rn]
5f7 7s2 and [Rn]
5f76d17s2.
lonic Sizes: The general trend in lanthanoids is observable in the actinoids as well' There is a
gradual
decrease in the size of atoms or M3+ ions across the series. This may be referred to as the
actinoids
contraction (like lanthanoids contraction). The contraction is, however, greater from elements to
element in
this series resulting from poor shielding by 5f electrons.

Oxidation states: There is a greater range of oxidation states, which is in part attributed to the
fact that the 5f. 6d and 7s levels are of comparable energies.
The actinoids show in general +3 oxidation state, The elements, in the first half to the series
frequently
exhibit higher oxidation state, e.g. The maximum oxidation state increases from +4 in Th to +5,
+6 and +7 respectively in Pa, U and Np but decreases in succeeding elements. The actinoids
resemble the lanthanoids in having more compounds in +3 state than in the +4 state, However +3
and +4 ions tends to hydrolyse.
General characteristics and comparison with Lanthanoids:

1. The actinoids metals are all silvery white in appearance but display a variety of structures. The
structural variability is obtained due to irregularities in metallic radii which are far greater than
in lanthanoids.

2. The actinoids are highly reactive metals, especially when divided, the action of boiling water
on them, for example, gives a mixture of oxide and hydride and combination with most metals

593
d & f Block Elements

takes place at moderate temperatures; hydrochloric acid attacks all metals but most are slightly
affected by nitric acid owing to the formation of protective oxide layers; alkalise have no
action.

3. It is evident from the chemistry of lanthanoids that the ionisation enthalpies of the early
actinoids, though not accurately known, but are lower than for the early lanthanoids. This is
quite reasonable since it is to be expected that when 5f orbitals are beginning to be occupied,
they will penetrate less into the inner core of electrons. The 5f electrons, will therefore, be
more effectively shielded from the nuclear charge than the 4f electrons of the corresponding
lanthanoids. Because the outer electrons are less firmly held, they are available for bonding in
the actinoids.

Note: The lanthanoids contraction is more important because the chemistry of elements
succeeding the
actinoids are much less known at the present time.
Uses of actinoids:
1. Thorium is used in atomic reactors and in the treatment of cancer. Its salts are used in making
incandescent gas mantles.
2. Uranium is used as a nuclear fuel. Its salts are used in glass industry (for imparting green
colour),
textile industry ceramic industry and in medicines.
3. Plutonium it is used as a fuel for atomic reactors as well as for making atomic bombs.

594
 d & f Block Elements

Practice Questions
1. Which one of the following alloys contains some of the lanthanoid metals?

(a) Mischmetall

(b) Brass

(c) Bronze

(d) Ziggler-Natta

2. What is the coordination number of metal in [Co(en)2Cl2]

(a) 3

(b) 4

(c) 5

(d) 6

3. Identify the incorrect statement among the following.

(a) Among V, Cr, Mn and Fe; Mn is expected to have the highest third ionization enthalpy.

(b) Eu(ll) acts as a strong reducing agent

(c) The ionic sizes of lanthanoids decrease in general with increasing atomic number.

(d) VOCI2 and FeCI2 are expected to have the same magnetic moment ('spin only')

4. Which of the following is a lanthanide?

(a) Curium

(b) Californium

(c) Uranium

(d) Europium

5. Which of the following statements is true for transition elements?

(a) They are diamagnetic

(b) They shows variable oxidation states

(c) They do not form alloy

595
 d & f Block Elements

(d) They shows inert pair effect

6. Among the following series of transition metal ions, the one where all the metal ions have 3d2
configuration is:

(a) Ti+3, V+2, Cr+3, Mn+4

(b) Ti+2, V+3, Cr+4, Mn+5

(c) Ti+, V+4, Cr+6, Mn+7

(d) Ti+2, V+3, Cr+2, Mn+3

7. The ions from among the following which are colourless are :

(i) Ti+4 (ii) Cu+1 (iii) Co+3 (iv) Fe+2

(a) (i) and (ii)

(b) (i), (ii), (iii)

(c) (iii), (iv)

(d) (ii), (iii)

8. Which of the following ions has the maximum magnetic moment in aqueous solution?

(a) Mn2+

(b) Fe2+

(c) Co2+

(d) Cr2+

9. Among the following outermost configurations of transition metals, which shows the highest
oxidation state

(a) 3d34s2

(b) 3d54s1

(c) 3d54s2

(d) 3d64s2

596
 d & f Block Elements

10. The maximum oxidation state shown by V(Z = 23), Cr(Z = 24), Co(Z = 27), Se(Z = 21) are respectively

(a) +5, +5, +3, +2

(b) +5, +6, +3, +3

(c) +5, +4, +5, +2

(d) +5, +3, +2, +1

11. Transition elements are used as catalyst because

(a) of high ionic charge

(b) of variable oxidation state

(c) large surface area of reactants

(d) of their specific nature

12. The yellow colour of chromate change to orange on acidification due to formation of

(a) Cr3+

(b) Cr2O3

(c) Cr2O72-

(d) CrO4-

13. The number of moles of KMnO4 that will be needed to react completely with one mole of ferrous
oxalate in acidic medium.

(a) 3/5

(b) 2/5

(c) 4/5

(d) 1

14. Which one of the following compounds does not decolourise an acidified aqueous solution of KMnO4

(a) Sulphur dioxide

(b) Ferric chloride

(c) H2O2

597
 d & f Block Elements

(d) FeSO4

15. When MnO2 is fused with KOH, a colored compound Is formed. The product and its colour is:

(a) K2MnO4, green

(b) Mn2O3, brown0

(c) Mn2O4, black

(d) KMnO4, purple

16. The basic character of the transition metal monoxide follows the order:

(At. no. : Ti = 22, V = 23, Cr = 24, Fe = 26)

(a) VO > CrO > TiO > FeO

(b) CrO > VO > FeO > TiO

(c) TiO > FeO > VO > CrO

(d) TiO > VO > CrO > FeO

17. Which of the following reactions represents "developing" in photography?

(a)

(b)

(c)

(d)

18. Which of the following ions are colourless in the aqueous solutions ?

598
 d & f Block Elements

(a) La3+ and Lu3+

(b) Nd3+ and Pm3+

(c) Ce3+ and Pr3+

(d) Sm3+ and Eu3+

19. Which of the following factor may be regarded as the main cause of Lanthanide contraction?

(a) Poor shielding of one of the 4f-electrons by another in the sub-shell

(b) Effective shielding of one of the 4f-electrons by another in the sub-shell

(c) Poorer shielding of 5d electron by 4f electrons

(d) Greater shielding of 5d electron by 4f electron

20. ZnO show yellow colour on Heating due to :

(a) d-d transition

(b) C-T spectra

(c) Higher polarisation caused by Zn2+ ion

(d) F- centres

21. Which of the following is arranged in order of increasing melting point ?

(a) Zn < Cu < Ni < Fe

(b) Fe < Ni < Cu < Zn

(c) Ni < Fe < Zn < Cu

(d) Cu < Zn < Fe < Ni

22. Chemically philosopher wool is :

(a) ZnO

(b) BaO

(c) HgCl

(d) Hg2Cl2

599
 d & f Block Elements

23. CrO3 dissolves in aqueous NaOH to give :

(a) Cr2 O 72−

(b) CrO 24−

(c) Cr(OH)3

(d) Cr(OH) 2

24. Mercury on heating with aqua-regia gives :

(a) Hg(NO3)2

(b) HgCl

(c) Hg(NO2)2

(d) Hg2Cl2

25. The formula of azurite is :

(a) CuCO3.Cu(OH)2

(b) 2CuCO3.Cu(OH)2

(c) CuCO3.2Cu(OH)2

(d) CuSO4.Cu(OH)2

26. Oxide of metal cation which is not amphoteric ?

(a) Al3+

(b) Cr3+

(c) Fe3+

(d) Zn2+

27. The ratio of mass of a diamagnetic substance in a magnetic field to its actual mass

(a) is greater than one

600
 d & f Block Elements

(b) is lesser than one

(c) is equal to one

(d) cannot be predicted

28. CrO 24− (yellow) changes to Cr2 O 72− (orange) in pH = x and vice-versa in pH = y. Hence, x and y are

(a) 6, 8

(b) 6, 5

(c) 8, 6

(d) 7, 7

29. An excess of Na2S2O3 react with aqueous CuSO4 to give

(a) CuS2O3

(b) Cu2S2O3

(c) Na2[Cu(S2O3)2]

(d) Na4[Cu6(S2O3)5]

30. [Cr(H2O)6]Cl3 has a magnetic moment of 3.83 BM. The correct distribution of 3d electrons in the
chromium of the complex:

(a) 3d1xy, 3d1yx, 3d1zx

(b) 3d1xy, 3d1yz, 3d1z2

(c) 3d1(x2 - y2), 3d1z2, 3d1zx

(d) 3d1xy, 3d1(x2 – y2), 3d1yz

31. Potassium manganate (K2MnO4) is formed when

(a) Cl2 is passed into an aqueous solution of KMnO4

(b) MnO2 is fused with KOH

(c) Formaldehyde reacts with KMnO4 in the presence of strong alkali

(d) KMnO4 reacts with conc. H2SO4

601
 d & f Block Elements

32. Uub is the symbol for the element with atomic number

(a) 102

(b) 108

(c) 110

(d) 112

33. Which of the following species has O–O bond ?

(a) Cr2 O 7−2

(b) MnO −4

(c) CrO5

(d) CrO −42

34. FeCr2O4 (chromite) is converted to Cr by following steps:

I II III
Chromite  → Na 2 CrO 4  → Cr2 O3  → Cr

Reagents in I, II and Ill step might be:

35. When the same amount of zinc is treated separately with excess of sulphuric acid and excess of
sodium hydroxide, the ratio of volumes of hydrogen evolved is-

(a) 1 : 1

(b) 1 : 2

(c) 2 : 1

(d) 9 : 4

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 d & f Block Elements

36. The complexes Ni(NH 3 ) 24+ & Ni(CN) 24− are paramagnetic and diamagnetic respectively Then be
correct distribution of electrons in different orbitals & expected geometry are:

(a)

(b)

(c)

(d)

37. Spin-only magnetic moment of [Co(NH 3 )3 (H 2 O)3 ]Cl3 (in Bohr Magnetons) is

(a) Zero

(b) 3

603
 d & f Block Elements

(c) 24

(d) 35

38. CO forms a volatile carbonyl complex with which of the following metals ?

(a) Na

(b) Sn

(c) Ni

(d) Hg

39. A brown ring complex compound is formulated as [Fe(H2O)5NO+]SO4. The oxidation state of iron here
is

(a) 1

(b) 2

(c) 3

(d) 4

40. A blue colouration is obtained in which ease?

(1) on dissolving NH4OH in copper sulphate.

(2) on reacting CuSO4 solution with potassium ferrocyanide.

(3) on reacting FeCl3 with sodium ferrocyanide.

(4) on dissolving anhydrous CuSO5 in water.

(a) 2, 4 only

(b) 1, 3, 4

(c) 1, 2, 4

(d) 3, 4 only

41. E0 values for couples Cr+3/Cr+2 and Mn+3/Mn+2 are -0.41 and +1.51 volts respectively. Considering the
values select the correct option from the following statements :

604
 d & f Block Elements

(a) Cr+2 (aq) is more stable than Cr+3(aq)

(b) Mn+3 (aq) is more stable than Mn+2(aq)

(c) Cr+2 acts as a reducing agent and Mn+2 acts as an oxidsing agent in their aqueous solutions.

(d) None of these

42. In the following reactions, ZnO is respectively acting as a/an (2017)

(a) base and acid

(b) base and base

(c) acid and acid

(d) acid and base

43. Sodium salt of an organic acid 'X' produces effervescence with conc. H2SO4. 'X' reacts with the
acidified aqueous CaCl2 solution to give a white precipitate which decolourises acidic solution of KMnO4.
'X' is (2017)

(a) C6H5COONa

(b) HCOONa

(c) CH3COONa

(d) Na2C2O4

44. Which of the following compounds is metallic and ferromagnetic? (2016)

(a) CrO2

(b) VO2

(c) MnO2

(d) TiO2

45. The reaction of zinc with dilute and concentrated nitric acid, respectively, produce (2016)

(a) NO2 and NO

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 d & f Block Elements

(b) NO and NO2

(c) NO2 and N2O

(d) N2O and NO2

46. The geometries of the ammonia complexes of Ni2+, Pt2+ and Zn2+, respectively are (2016)

(a) octahedral square planar and tetrahedral

(b) square planar octahedral and tetrahedral

(c) tetrahedral, square planar and octahedral

(d) octahedral, tetrahedral and square planar

47. Which of the following compounds is not yellow coloured? (2015)

(a) Zn2[Fe(CN)6]

(b) K3[Co(NO2)6]

(c) (NH4)3[As(MO3O10)4]

(d) BaCrO4

48. Which series of reactions correctly represents chemical relations related to iron and its compounds?
(2014)
Dil.H2 SO4 𝐻𝐻2 SO4 ,O2 Heat
(a) Fe �⎯⎯⎯⎯⎯⎯⎯⎯� FeSO4 �⎯⎯⎯⎯⎯⎯⎯⎯� Fe2 (SO4 )3 �⎯⎯⎯⎯� Fe2O3
O 2 ,Heat Dil.H 2SO 4 Heat
(b) Fe → FeO  → Fe 2SO 4  → Fe
Cl2 ,Heat Heat,air Zn
(c) Fe  → FeCl3  → FeCl2  → Fe
O 2 ,Heat CO,600 ° C CO,700 ° C
(d) Fe → FeCl3  → FeO  → Fe

49. Four successive members of the first row transition elements listed below with atomic numbers.
Which one of them is expected to have the highest E °M 3+ / M 2+ value? (2013)

(a) Cr (Z = 24)

(b) Mn (Z = 25)

(c) Fe (Z = 26)

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 d & f Block Elements

(d) Co (Z = 27)

50. Consider the following reaction, (2013)

The values of x, y and z in the reaction are, respectively

(a) 5, 2 and 16

(b) 2, 5 and 8

(c) 2, 5 and 16

(d) 5, 2 and 8

51. Which of the following arrangements does not represent the correct order of the property stated
against it? (2013)

(a) V2+ < Cr2+ < Mn2+ < Fe2+: paramagnetic; behaviour

(b) Ni2+ < Co2+ < Fe2+ < Mn2+: ionic size

(c) Co3+ < Fe3+ < Cr3+ < Sc3+: stability in aqueous solution

(d) Sc < Ti < Cr < Mn: number of oxidation states

52. The colour of light absorbed by an aqueous solution of CuSO4 is (2012)

(a) orange-red

(b) blue-green

(c) yellow

(d) violet

53. Which of the following wiII not will not be oxidised by O3 ? (2005)

(a) KI

(b) FeSO4

(c) KMnO4

(d) K2MnO4

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 d & f Block Elements

54. Which of the following pair is expected to exhibit same colour in solution? (2005)

(a) VOCl2 : FeCl2

(b) CuCl2 : VOCl2

(c) MnCl2 : FeCl2

(d) FeCl2 : CuCl2

55. When I- is oxidised by MnO −4 in alkaline medium, I- converts into (2004)

(a) IO3−

(b) I2

(c) IO 4−

(d) IO-

56. The pair of compounds having metals in their highest oxidation state is (2004)

(a) MnO2, FeCl3

(b) [MnO4]-, CrO2Cl2

(c) [Fe(CN)6]3-, [Co(CN)3]

(d) [NiCl4]2-, [CoCl4]-

57. (NH4)2Cr2O7 on heating gives a gas which is also given by (2004)

(a) heating NH4NO2

(b) heating NH4NO3

(c) Mg3N2 + H20

(d) Na(comp.) + H2O2

58. The oxidation state of chromium, in the final product formed by the reaction between ICI and
acidified potassium dichromate solution, is

(a) +2

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 d & f Block Elements

(b) +3

(c) +4

(d) +6

59. Amongst the following, identify the species with an atom in +6 oxidation state (2000)

(a) MnO −4

(b) Cr(CN)36−

(c) NiF62−

(d) CrO 2 Cl2

60. On heating ammonium dichromate, the gas evolved is (1999)

(a) oxygen

(b) ammonia

(c) nitrous oxide

(d) nitrogen

61. In the dichromate dianion

(a) 4 Cr—O bonds are equivalent

(b) 6 Cr-O bonds are equivalent

(c) all Cr—O bonds are equivalent

(d) all Cr—O bonds are non-equivalent

62. Which of the following compounds is expected to be coloured? (1997)

(a) Ag2SO4

(b) CuF2

(c) MgF2

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 d & f Block Elements

(d) CuCl

63. Ammonium dichromate is used in some fireworks. The green coloured powder blown in the air is
(1997)

(a) CrO3

(b) Cr2O3

(c) Cr

(d) CO

64. The reaction which proceed in the forward direction is

(a) Fe 2 O3 + 6HCl → 2FeCl3 + 3H 2 O

(b) NH 3 + H 2 O+NaCl → NH 4 Cl + NaOH

(c) SnCl4 + Hg 2 Cl2 → SnCl2 + 2HgCl2

(d) 2CuI + I 2 + 4H + → 2Cu 2+ + 4KI

65. Zinc-copper couple that can be used as a reducing agent is obtained by (1984)

(a) mixing of zinc dust and copper gauge

(b) zinc coated with copper

(c) copper coated with zinc

(d) zinc and copper wires welded together

66. How many unpaired electrons are present in Ni2+ ? (1981)

(a) 0

(b) 2

(c) 4

(d) 8

67. One of the constituent of German silver is (1980)

610
 d & f Block Elements

(a) Ag

(b) Cu

(c) Mg

(d) Al

68. Which of the following dissolves in concentrated NaOH solution? (1980)

(a) Fe

(b) Zn

(c) Cu

(d) Ag

69. Which of the following halides react(s) with AgNO3(aq) and does not produces a precipitate

(a) HCl

(b) HF

(c) HBr

(d) HI

70. Reduction of the metal centre in aqueous permanganate ion does not involves
(2011)

(a) three electrons in neutral medium

(b) five electrons in neutral medium

(c) three electrons in alkaline medium

(d) five electrons in acidic medium

71. Which of the following statement is incorrect? (1998)

(a) The electronic configuration of Cr is [Ar] 3d5 4s1 (Atomic number of Cr= 24)

(b) The magnetic quantum number does not have a negative value

(c) In silver atom, 23 electrons have a spin of one type and 24 of the opposite type (Atomic number of
Ag = 47)

611
 d & f Block Elements

(d) The oxidation state of nitrogen in HN3 is -3

72. Which of the following statement is incorrect when a mixture of NaCl and K2Cr2O7 is gently warmed
with conc. H2SO4 (1998)

(a) A deep red vapours is formed

(b) Vapours when passed into NaOH solution gives a brown solution of Na2CrO4

(c) Chlorine gas is evolved

(d) Chromyl chloride is formed

73. Which of the following alloys contains Cu, Sn and Zn?

(a) Bronze

(b) Brass

(c) Gun metal

(d) Type metal

74. The aqueous solution of the following salts will be coloured in case of (1990)

(a) Zn(NO3)2

(b) LiNO3

(c) Co(NO3)2

(d) potash alum

75. Potassium manganate (K2MnO4) is formed when (1988)

(a) chlorine is passed into aqueous KMnO4 solution

(b) manganese dioxide is fused with KOH in air

(c) formic acid reacts with potassium permanganate in the presence of strong alkali

(d) potassium permanganate reacts with cone. H2SO4

612
d & f Block Elements

Answer Keys:

1. a 2. c 3. d 4. d 5. b 6. b 7. a 8. a 9. c 10. b
11. b 12. c 13. b 14. b 15. a 16. d 17. c 18. a 19. a 20. d
21. a 22. a 23. b 24. b 25. b 26. c 27. b 28. a 29. d 30. a
31. c 32. d 33. c 34. b 35. a 36. a 37. a 38. c 39. a 40. b
41. c 42. d 43. d 44. a 45. d 46. a 47. a 48. a 49. d 50. c
51. a 52. a 53. c 54. b 55. a 56. b 57. a 58. b 59. d 60. d
61. b 62. b 63. b 64. a 65. b 66. b 67. b 68. b 69. b 70. b
71. b 72. c 73. c 74. c 75. b

“Detail solutions are mentioned in the content library”

613