D & F BLOCK

Table of Contents

 Theory .............................................................................................................................. 2

 Solved Examples .............................................................................................................. 21

 Exercise - 1 : Basic Objective Questions ........................................................................ 36

 Exercise - 2 : Previous Year JEE Mains Questions .......................................................... 40

 Exercise - 3 : Advanced Objective Questions ................................................................ 43

 Exercise - 4 : Previous Year JEE Advanced Questions ................................................... 48

 Answer Key .................................................................................................................... 51

 2 D & F BLOCK

THEORY

1.2 Electronic configuration

1. INTRODUCTION
(1) In d-block elements with increase in atomic number, the d-
1.1 Definition orbitals of penultimate shell i.e. (n-1) d are gradually filled
by electrons. The general electronic configuration of d-
“The elements in which the last differentiating electron enters
block element is,
into the d-orbitals of the penultimate shell i.e.
(n-11) d1-10, ns0-2.
(n–1) d where n is the last shell are called d-block elements”.
(2) Depending upon the d-orbitals of which penultimate shell
A transition element may also be defined as the element
i.e. n = 4, 5, 6, 7 are filled, four rows (called series) os ten
which partially filled d-orbital in their ground state or most
elements each obtained. They correspond to 3d, 4d, 5d and
stable oxidation state.
6d subshells.
Cu (Z = 29) = 1s2 2s2 2p6 3s2 3p6 3d10 4s1
(3) Energy of ‘(n–1)d’ subshell is slightly greater than ‘ns’
Cu2+ = 1s2 2s2 2p6 3s2 3p6 3d9
subshell, hence orbital is filled first then (n – 1) d orbitals.
(Cupric ion)
(4) The general electronic configuration of d-block/d-series
The properties of these elements are intermediate between elements be shown as follows :
the properties of s-block and p-block elements.
1. First (3d) Transition Series (Sc–Zn)
These elements represent a change or transition in
properties from more electropositive elements (s-block) to At. No. 21 22 23 24 25 26 27 28 29 30
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
less electropositive elements (p-block). Therefore these E.C. 1 2 2 2 3 2 5 1 5 2 6 2 7 2 8 2 10 1 10
3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s
2

elements are called transition elements.

2. Second (4d) Transition Series (Y-Cd)
Position in the periodic table
The position of d-block element has been shown in periodic At. No. 39 40 41 42 43 44 45 46 47 48
Element Y Zr Nb Mo Tc* Ru Rh Pd Ag Cd
table as follows : 1 2 2 2 4 1 5 1 6 1 7 1 8 1 10 0 10 1 10 2
E.C. 4d 5s 4d 5s 4d 5s 4d 5s 4d 5s 4d 5s 4d 5s 4d 5s 4d 5s 4d 5s

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

At. No. 57 72 73 74 75 76 77 78 79 80
Element La Hf Ta W Re Os Ir Pt Au Hg
1 2 2 2 3 2 4 2 5 2 6 2 7 2 9 1 10 1 10 2
E.C. 5d 6s 5d 6s 5d 6s 5d 6s 5d 6s 5d 6s 5d 6s 5d 6s 5d 6s 5d 6s

4. Fourth (6d) Transition Series

At. No. 89 104 105 106 107 108 109 110 111 112
Element Ac Ku Ha Sg Bh Hs Mt Uun Uuu Uub
(Unh) (Uns) (Uno) (Une)
1 2 2 2 3 2 4 2 5 2 6 2 7 2 8 2 10 1 10 2
E.C. 6d 7s 6d 7s 6d 7s 6d 7s 6d 7s 6d 7s 6d 7s 6d 7s 6d 7s 6d 7s

Exceptional configuration of Cr and Cu. The exceptions

observed in the first series are in case of electronic
(1) d-block elements lie in between ‘s’ and ‘p’ block elements, configurations of chromium (Z = 24) and copper (Z = 29). It
i.e. these elements are located in the middle of the periodic may be noted that unlike other elements, chromium and
table. copper have a single electron in the 4s-orbital. This is due
(2) d-block elements are present in, to the gain of additonal stability by the atom by either having
4th period (21Sc to 30Zn, 10 elements) 1st Transition series. half-filled configuration (i.e., containing 5 electrons in the
5th period (39Y to 48Cd, 10 elements) 2nd Transition series. d-sublevel) or completely filled configuration, (i.e.,
6th period (51La, 72Hf to 80Hg, 10 elements) 3rd Transition containing 10 electrons in the d-sublevel). The 3d-level in
series. case of chromium gets excatly half-filled with configuration
7th period (89Ac, 104Rf to 112Uub, 10 elements) 4th Transition 3d5 4s1 and that in case of copper, it gets completely filled
series. with configuration 3d10 4s1. This can be explained on the
basis of exchange energy
 D & F BLOCK 3

Thus, the electronic configuration of chromium (Z = 24)

and copper (Z = 29) are 1s2 2s2 2p6 3s2 3p6 3d5 4s1 and 1s2 2s2 1.5 Metallic character
2p6 3s6 3p6 3d10 4s1 respectively.
Except for mercury which is a liquid, all the transition
elements have typical metallic structure. They exhibit all
1.3 Properties the characteristics of metals. ductile, have high melting and
boiling points, high thermal and electrical conductivity and
1. Atomic Raddii
high tensile strength.
(i) The atomic radii of the transition metals lie in-between those Transition elements have relatively low ionization energies
of s- and p-block elements. and have one or two electrons in their outermost energy level
(ns1 or ns2). As a result, metallic bonds are formed. Hence, they
(ii) Generally the atomic radii of d-block elements in a series behave as metals. Greater the number of unpaired d electrons,
decreas with increase in atomic number but the decrease in stronger is the bonding due to the overlapping of unpaired
atomic size is small after midway. electrons between different metal atoms.
Explanation 1.6 Melting Point
The atomic radius decreases with the increase in atomic
Transition metals have high melting points which is due to
number as the nuclear charge increases whereas the their strong metallic bond. The metallic bond. The metalic
shielding effect of d-electron is small. After midway, as the bonding depends upon the number of unpaired e–. The
electrons enter the last but one (penultimate) shell, the added melting point first increases (Sc-Cr), reaches a maximum value
d-electron shields (screens) the outermost electron. Hence, (Cr) and then decreases (Fe-Zn)
with the increase in the d-electrons, screening effect * Tungsten (W) has the highest melting point.
increases. This counterbalances the increased nuclear * Mercury (Hg) has the lowest melting point.
charge due to increase in atomic number. As a result, the * Mn has the lowest melting point in 3d series typicl
atomic radii remain practically same after chromium. For transition elements.
example in Fe, the two opposing tendencies almost
1.7 Ionisation energies or Ionisation enthalpies
counterbalance and there is no change in the size from Mn
to Fe. (i) The first ionisation enthalpies of d-block elements lie between
s-block and p-block elements. They are higher than those of s-
(iii) At the end of the period, there is a slight increase in the
block elements and are lesser than those of p-block elements.
atomic radii.
The ionisation enthalpy gradually increases with increase in
Explanation atomic number along a given transition series though some
irregularities are observed
Near the end of series, the increased electron-electron
Explanation
repulsions between added electrons in the same orbitals
(i) The increasing ionization enthalpies are due to increased
are greater than the attractive forces due to the increased
nuclear charge with increase in atomic number which reduces
nuclear charge. This results in the expansion of the electron
the size of the atom making the removal of outer electron
cloud and thus the atomic radius increases. difficult.
(iv) The atomic radii increase down the group. This means that (ii) In a given series, the difference in the ionisation enthalpies
the atomic radii of second series are larger than those of between any two successive d-block elements is very much
first transition series. But the atomic radii of the second less than the difference in case of successive s-block or p-
and third transition series are almost the same. block elements.
Explanation
The atomic radii of the elements of the second and third The addition of d electrons in last but one [(n — 1) or
transition metals are nearly same due to lanthanide penultimate] shell with increase in atomic number provides
contraction (or also called lanthanoid contraction) a screening effect and thus shields the outer s electrons
discussed later. from inward nuclear pull. Thus, the effects of increased
nuclear charge and addition of d electrons tend to oppose
1.4 Ionic radii each other.

(i) The trend followed by the ionic radii is the same as that (iii) The first ionization enthalpy of Zn, Cd and Hg are, however,
very high because of the fully filled (n-1) d 10 ns 2
followed by atomic radii.
configuration.
(ii) Ionic radii of transition metals are different in different (iv) Although second and third ionization enthalpies also, in
oxidation states.
general, increase along a period, but the magnitude of
(iii) The ionic radii of the transition metals are smaller than those increase for the successive elements is much higher.
of the representative elements belonging to the same period.
 4 D & F BLOCK

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

Oxidation States

ELECTRONIC Sc Ti V Cr Mn Fe Co Ni Cu Zn

CONFIGURATION d 1s 2 d 2s 2 d 3s 2 d 4s 2 d 5s 2 d 6s 2 d 7s 2 d 8s 2 d 9s 2 d 10 s 2

d 5s 1 d 10 s 1

+1 +1
OXIDATION STATES

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

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

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

+5 +5 +5 +5 +5

+6 +6 +6

+7
 D & F BLOCK 5

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

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

absorbed. 2. COMPLEX FORMATION

Catalysts Uses Transition metal ions form a large number of complex

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

NH3  NO 2.1 Interstitital Compounds

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

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

manganese are used in the formation of alloy steels and MnO Mn 3O 4 Mn 2 O3 MnO 2 Mn 2 O 7
Basic Amphoteric Amphoteric Amphoteric Acidic
stainless steels. Some alloys of transition metals with non-
transition metals are also very common. e.g., brass Thus, Mn2O7 dissolves in water to give the acid HMnO4.
(Cu + Zn) and bronze (Cu + Sn)
3.2 KMnO4 Potassium permanganate

It is prepared from the ore called chromite or ferrochrome

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

4FeO.Cr2O3 + 8Na2CO3+ 7O2 

 8Na2CrO4 + 2Fe2O3 + 8CO2

Chromite ore Sod. chromate Ferric oxide

After the reaction, the roasted mass is extracted with water

when sodium chromate is completely dissolved while ferric
oxide is left behind. Ferric oxide is separated out by
filtration.
3. COMPOUNDS OF TRANSITION ELEMENTS
(ii) Conversion of sodium chromate into sodium dichromate.
The filtrate containing sodium chromate solution is treated
3.1 Oxides with concentrated sulphuric acid when sodium chromate
(i) The metals of the first transition series form oxides with is converted into sodium dichromate.
oxygen at high temperature. 2Na 2 CrO 4  H 2SO 4 
 Na 2 Cr2 O 7  Na 2SO 4  H 2 O
Sod.chromate  Conc. Sod. dichromate
(ii) The oxides are formed in the oxidation, states +1 to +7 (as
Sodium sulphate being less soluble crystallizes out as
given in Table 8.10, page 8/14).
decahydrate, Na2SO4. 10H2O and is removed. The clear
(iii) The highest oxidation state in the oxides of any transition solution is then evaporated in iron pans to a specific
metal is equal to its group number, e.g., 7 in Mn2O7. Beyond gravity of 1.7 when a further crop of sodium sulphate is
group 7, no higher oxides of iron abov Fe2O are known. formed. It is removed and the solution is cooled when
Some metals in higher oxidation state stabilize by forming orange crystals of sodium dichromate, Na2Cr2O7. 2H2O
oxocations, e.g., VV as VO2 , VIV as VO2+ and TiIV as TiO2+. separate on standing.
(iii) Conversion sodium dichromate into potassium
(iv) All the metals except scandium form the oxides with the
dichromate. Hot concentrated solution of sodium
formula MO which are ionic in nature. As the oxidation
dichromate is treated with calculated amount of potassium
number of the metal increases, ionic character decreases,
chloride when potassium dichromate, being much less
e.g., Mn2O7 is a covalent green oil. Even CrO3 and V2O5
soluble than sodium salt, crystallizes out on cooling as
have low melting points.
orange crystals.
2 8/ 3 3 4 7
MnO Mn 3O 4 Mn 2 O3 MnO 2 Mn 2 O7 Na Cr O  2KCl 
2 2 7  K 2 Cr2 O7  2NaCl
Sodium dichromate Potassium dichromate
(v) In general, the oxides in the lower oxidation states of the
metals are basic and in their higher oxidation states, they
are acidic whereas in the intermediate oxidation state, the
 8 D & F BLOCK

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

3.3 Properties the presence of dilute sulphuric acid, one molecule of
potassium dichromate furnishes 3 atoms of available
1. Colour and Melting point. It forms orange crystals which
oxygen as indicated by the equation :
melt at 669 K.
2. Solubility. It is moderately soluble in cold water but freely  K 2SO 4  Cr2 SO 4 3 +
K 2 Cr2 O7  4H 2SO 4 
soluble in hot water.
4H2O + 3O
3. Action of heat. When heated to a white heat, it
decomposes with the evolution of oxygen. or Cr2 O72   14H   6e 
 2Cr 3  7H 2 O

4K 2 Cr2 O7 
 4K 2 CrO4  2Cr2 O3  3O2 Mol. wt. 294
 Eq. wt. of K 2 Cr2 O 7    49
6 6
4. Action of alkalies. When an alkali is added to an orange
red solution of dichromate, a yellow solution results due (i) It liberates I2 from KI
to the formation of chromate.
 4K 2SO 4  Cr2 SO 4 3
K 2 Cr2 O7  7H 2SO 4  6KI 
K Cr O  KOH 
2 2 7  2K 2 CrO4  H 2 O
Pot. dichromate Pot.chromate 3I 2  7H 2 O

(ii) It oxidises ferrous salts to ferric salts

or Cr2 O72   2 OH  
 2 CrO42   H 2 O
 K 2SO 4  Cr2 SO 4 3
K 2 Cr2 O7  7H 2SO 4  6FeSO 4 
On acidifying, the colour again changes to orange red
due to the reformation of dichromate.
3Fe2  SO4 3  2H 2 O
2 K 2 CrO4  H 2SO4 
 K 2 Cr2 O7  K 2SO4  H 2 O (iii) It oxidises H2S to sulphur

or 2 CrO24   2 H  
 Cr2 O72   H 2 O  K 2SO 4  Cr2  SO 4 3
K 2 Cr2 O7  4H 2SO 4  3H 2S 

This interconversion is explained by the fact that in + 7H2O + 3S

dichromate solution, the Cr2 O72 ions are invariably in (iv) It oxidises sulphites to sulphates and thiosulphates to
sulphates and sulphur
equilibrium with CrO24 ions at pH = 4, i.e.,
 K 2SO 4  Cr2 SO 4 3
K 2 Cr2 O7  4H 2SO 4  3Na 2SO3 
pH  4
Cr O 2 7
2

 H 2 O  2
 2CrO 4  2H

+ 4H2O + 3Na2SO4
Orange red Yellow
 dichromate   chromate  (v) It oxidises nitrites to nitrates

On adding an alkali (i.e., increasing the pH of the solution),  K 2SO 4  Cr2  SO 4 3

K 2 Cr2 O7  4 H 2SO 4  3NaNO 2 
the H+ ions are used up and according to the law of
chemical equilibrium, the reaction proceeds in the forward + 3 NaNO3 + 4 H2O
direction producing yellow chromate solution. On the (vi) It oxidises halogen acids to halogen
other hand, when an when an acid is added (i.e., pH of the
solution is decreased), the concentration of H+ ions is K 2 Cr2 O7  14 HCl 
 2KCl  2CrCl3  7H 2 O  3Cl2
increased and the reaction proceeds in the backward (vii) It oxidises SO2 to sulphuric acid
direction producing an orange red dichromate solution.
 K 2 SO 4  Cr2  SO 4 3  3H 2 O
K 2 Cr2 O 7  H 2 SO 4  3SO 2 
5. Action of concentrated sulphuric acid
(a) In cold, red crystals of chromic anhydride (chromium (viii) It oxidises stannous salts to stannic salts
trioxide) are formed.
Cr2 O72   14 H   3Sn 2  
 2 Cr 3  3 Sn 4   3 Sn 4   7 H 2 O

K 2 Cr2 O7  2H 2SO4 
 2CrO3  2KHSO4  H 2 O (ix) It oxidises ethyl alcohol to acetaldehyde and acetic acid.

(b) On heating the mixture, oxygen is evolved.  K 2SO 4  Cr2  SO 4 3  4H 2 O  3O

K 2 Cr2 O7  4H 2SO 4 

 2K 2SO 4  2Cr2  SO 4 3
2K 2 Cr2 O7  8H 2SO 4 
CH 2 CH 2 OH  O 
 CH3CHO  H 2 O
Ethyl alcohol
+ 8H2O + 3O2
 D & F BLOCK 9

Structures of chromate and dichromate ions.

CH 3 CHO  O 
 CH 3 COOH
Acetaldehyde Acetic acid

Test for a drunken driver. The above reaction helps to

test whether a driver has consumed alcohol or not. he is or
asked to breathe into the acidified K2Cr2O7 solution taken
in a test tube. If the orange colour of the solution changes
into green colour (due to Cr2(SO4)3 formed in the reaction),
the driver is drunk, otherwise not.
7. Chromyl chloride test (Reaction with a chloride and conc.
sulphuric acid). When heated with concentrated
or
hydrochloric acid or with a chloride and strong sulphuric
acid, reddish brown vapours of chromyl chloride are
obtained.

K 2 Cr2 O7  4KCl  6H 2SO 4 

 2CrO 2 Cl2  6KHSO 4  3H 2 O 3.4 Potassium Permanganate (KMnO4)
Chromyl chloride
 Re d vapour 
Preparation
8. Reaction with hydrogen peroxide. Acidified K2Cr2O7 On a large scale, it is prepared from the mineral, pyrolusite,
solution reacts with H2O2 to give a deep blue solution MnO2. The preparation involves the following two stesp:
due to the formation of peroxo compound, CrO (O2)2.
(i) Conversion of MnO2 into potassium manganate. The finely
2  powdered pyrolusite mineral is fused with potassium
Cr2 O  2 H  4 H 2 O2 
7  2 CrO5  5 H 2 O
hydroxide or potassium carbonate in the presence of air
The blue colour fades away gradually due to the or oxidising agent such as potassium nitrate or potassium
decomposition of CrO5 into Cr3+ ions and oxygen. chlorate when green coloured potassium manganate is
formed.

The structure of CrO5 is in which Cr is in +6 2MnO2 + 4KOH + O2 

 2K2MnO4 + 2H2 O
Potassium manganate
oxidation state.
2MnO2 + 2K2CO3 + O2 
 2K2MnO4 + 2 CO2
Uses.
(i) In volumetric analysis, it is used as a primary standard for MnO2 + 2KOH + KNO3 
 K2MnO4 + KNO2 + H2O
the estimation of Fe2+ (ferrous ions) and I– (iodides) in
3MnO2 +6KOH+KClO3 
 3K2MnO4 +KCl+2H2O
redox titrations.
Potassium manganate thus formed undergoes
Note
disproportionation in the neutral or acidic solution as
Na2Cr2O7 is not used in volumetric analysis because it is follows, if allowed to stand for some time :
deliquescent. VI VII IV
3 MnO 24   4 H  
2 MnO 4  MnO 2  2 H 2 O
(ii) In industry, it is used Manganate ion Permanganate ion

(ii) Oxidation of potassium manganate to potassium

(a) In chrome tanning in leather industry.
permanganate.
(b) In the preparation of chrome alum K2SO4.Cr2(SO4)3.
(a) Chemical oxidation. The fused mass is extracted with
24H2O and other industrially important compounds
water and the solution after filtration is converted into
such as Cr2O3, CrO3, CrO2Cl2, K2CrO4, CrCl3 etc. potassium permanganate by bubbling carbon dioxide,
(c) In calico printing and dyeing. chlorine or ozonised oxygen through the green solution.
(d) In photography and in hardening gelatine film. 3K 2 MnO4  2CO2 
 2KMnO4  MnO2  2K 2 CO3
(iii) In organic chemistry, it is used as an oxidising agent. 2K 2 MnO4  Cl2 
 2KMnO4  2KCl
2K 2 MnO4  H 2 O  O3 
 2KMnO4  2KOH  O2
The carbon dioxide process is uneconomical as one third
of the original manganate is reconverted to manganese
 10 D & F BLOCK

dioxide. However, this process has the advantage that (ii) It oxidises sodium thiosulphate to sodium sulphate.
the potassium carbonate formed as a by-product can be
8KMnO4  3Na 2S2 O3  H 2 O 
 3K 2SO4  8MnO2 
used for the oxidative fusion of manganese dioxide. In
the chlorine process, potassium chloride obtained as a 3Na 2SO 4  2KOH
by-product is lost.
(iii) It oxidises hydrogen sulphide to sulphur.
PROPERTIES
2KMnO4  4H 2S 
 2MnS  S  K 2SO4  4H 2 O
1. Colour. Potassium permanganate exists as deep purple
black prisms with a greenish lustre which become dull in (b) In alkaline solution. In strongly alkaline solution, MnO24 
air due to superficial reduction. (manganate) ion is produced.
2. Solubility. It is moderately soluble in water at room
2KMnO4  2KOH 
 2K 2 MnO4  H 2 O  O or
temperature and it is more soluble in hot water.
MnO14  e 
 MnO42 
3. Action of heat. When heated to 513 K, it readily
decomposes giving oxygen. Mol. wt. 158
 Eq. wt. of KMnO 4    158
2KMnO4 
 K 2 MnO4  MnO2  O2 1 1
Pot. manganate
Potassium manganate is also further reduced to MnO2
At red heat, potassium manganate formed decomposes
into potassium manganite (K2MnO3) and oxygen. when a reducing agent is present.
2K 2 MnO4 
 2K 2 MnO3  O2
K 2 MnO4  H 2 O 
 MnO2  2KOH  O
4. Action of heat in current of hydrogen. When heated in a
current of H2, solid KMnO4 gives KOH, MnO and water or MnO24   2H 2 O  2 e 
 MnO2  4OH 
vapours.

So the complete reaction is :
2KMnO4  5H 2   2KOH  2MnO  4H 2 O
2KMnO4  H 2 O 
 2MnO2  2 KOH  3O
5. Oxidising property. Potassium permanganate is powerful
oxidising agent. The actual course of reaction depends or MnO4  2H 2 O  3 e 
 MnO2  4OH 
on the use of the permanganate in (a) neutral (b) alkaline
which is the same as that for neutral medium. Hence,
or (c) acidic solution.
equivalent weight of KMnO4 in weakly alkaline medium is
(a) In neutral solution. Potassium permanganate acts as a same as that in the neutral medium, viz., 52.67
moderate oxidising agent in neutral aqueous solution
Some oxidizing properties of KMnO4 in the alkaline medium.
because of the reaction :
These are given below :
2KMnO4  H 2 O 
 2KOH  2MnO2  3O (i) It oxidises potassium iodide to potassium iodate.
  
or MnO  2H 2 O  3 e 
4  MnO2  4OH 2KMnO 4  H 2 O  KI 
 2MnO 2  2KOH  KIO 3
Pot. iodate
Thus, MnO4 ion gains 3 electrons. Also, according to or 
I  6OH   
 IO  3H 2 O  6 e 
3
the above equation, in neutral medium, from two moles of
In this case, iodine is not liberated unlike the case of acidic
permanganate, three oxygen atoms are available. In fact,
medium.
during the course of reaction, the alkali generated renders
the medium alkaline even when we start with neutral Similar reaction takes place with KBr.
solutions. Hence, Eq. wt. of KMnO4 in neutral or weakly (ii) It oxidises olefinic compounds to glycols, i.e., when an
alkaline medium olefinic compound is shaken with alkaline KMnO4, pink
Mol. wt. 158 colour of KMnO4 is discharged.
   52.67
3 3
Some oxidizing properties of KMnO4 in the neutral medium.
These are given below :
(i) It oxidises hot manganous sulphate to manganese dioxide.
Alkaline KMnO4 used for this test is known as Baeyer’s
2KMnO4  3MnSO4  2H 2 O 
 K 2SO4  2H 2SO4  5MnO2
reagent. It is used for oxidation of a number of organic
Presence of ZnSO4 or ZnO catalyses the oxidation. compounds.
 D & F BLOCK 11

(c) In acidic medium. Potassium permanganate in the (viii) It oxidises HX (where X = Cl, Br, l) to X2
presence of dil. sulphuric acid, i.e., in acidic medium, acts
as a strong oxidising agent because of the reaction 2KMnO4  3H 2SO4  10 HX 
 K 2SO4  2MnSO4 

2KMnO4  3H 2SO4 
 K 2SO4  2MnSO4  3H 2 O  5O 8H 2 O  5X 2

(ix) It oxidises ethyl alcohol to acetaldehyde

or MnO4  8H   5 e 
 Mn 2   4H 2 O.
2KMnO4  3H 2SO4  5CH3 CH 2 OH 
 K 2SO4  2MnSO 4 
Since in the above reaction, MnO4 ion gains 5 electrons
of five atoms of oxygen are available from two molecules 5CH 3 CHO  8H 2 O.
of KMnO4. Hence. Uses.

Mol. wt. 158 (i) It is often used in volumetric analysis for the estimation
Eq. wt. of KMnO 4    31.6 of ferrous salts, oxalates, iodides and hydrogen peroxide.
5 5
However, it is not a primary standard because it is difficult
Some oxidizing properties of KMnO4 in the acidic medium. to obtain it in the pure state and free from traces of MnO2.
These are given below : It is, therefore, always first standardised with a standard
(i) It oxidises H2S to S. solution of oxalic acid.

2KMnO4  3H 2SO4  5H 2S 
 K 2SO4  2MnSO4  2H 2 O  5O
Remember that volumetric titrations inolving KMnO4 are
carried out only in presence of dilute H2SO4 but not in the
(ii) It oxidises sulphur dioxide to sulphuric acid. presene of HCl or HNO3. This is because oxygen produced
from KMnO4 + dill. H2SO4 is used only for oxidizing the
2KMnO4  5 SO2  2H 2 O 
 K 2SO4  2MnSO4  2H 2SO4
reducing agent. Moreover, H2SO4 does not give any
(iii)  
It oxidises nitrites NO 2  

to nitrates NO3 , arsenites
oxygen of its own to oxidiize the reducign agent. In case
HCl is used, the oxygen produced from KMnO4 + HCl is
 AsO 
3
3 to arsentates  AsO 
3
4 and sulphites and partly used up to oxidize Hcl to chlorine and in case HNO3
is used, it itself acts as oxidizing agent and partly oxidizes
thiosulphates to sulphates.
the reducing agent.
2KMnO4  3H 2SO4  5KNO2 
 K 2SO4  2MnSO4  (ii) It is used as a strong oxidising agent in the laboratory as
well as in industry. It is a favourite and effective oxidising
3H 2 O  5KNO3 agent used in organic synthesis Alkaline potassium
(iv) It oxidises oxalates or oxalic acid to CO2 permanganate is used for testing unsaturation in organic
chemistry and is known as Baeyer’s reagent.
2KMnO4  3H 2SO4  5C2 H 2 O4 
 K 2SO4  2MnSO4 
(iii) Potassium permanganate is also widely used as a
disinfectant and germicide. A very dilute solution of
8H 2 O  10 CO 2
permanganate is used for washing wounds and gargling
(v) It oxidises ferrous sulphate to ferric sulphate (i.e., ferrous for mouth sore. It is also used for purifying water of
salt to ferric salt). stinking wells.

2KMnO4  8H 2SO4  10FeSO4 

 K 2SO4  2MnSO4  (iv) Because of its strong oxidizing power, it is also used for
bleaching of wool, cottong, silk and other textile fibres
5Fe2  SO4 3  8H 2 O and also for decolourisation of oils.

(vi) It oxidises H2O2 to H2O and O2. This is because acidified

KMnO4 is a stronger oxidising agent than H2O2.

2KMnO4  3H 2SO4  5H 2 O2 
 K 2SO4  2MnSO4 

8H 2 O  5O 2

(vii) It oxidises potassium iodide to iodine

2KMnO 4  3H 2SO 4  10KI 

 K 2SO 4  2MnSO 4 

8H 2 O  5I 2
 12 D & F BLOCK

THE LANTHANIDE SERIES

1. INTRODUCTION

These elements are classified by the filling up of the

antipenultimate 4f energy levels.

2. PHYSICAL PROPERTIES

Electronic Configuration and oxidation states

Element Electronic Electronic Oxidation States
Configuration Configuration of M3+

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

2.1 Oxidation state Oxidation numbers (+II) and (+IV) do occur, particularly
when they lead to :
The sum of the first three ionization energies for each element
1. a noble gas configuration e.g. Ce4+ (f 0)
are low. Thus the oxidation state (+III) is ionic and Ln3+
dominates the chemistry of these elements. The Ln2+ and 2. a half filled f shell, e.g. Eu2+ and Tb4+ (f7)
Ln4+ ions that do occur are always less stable than Ln3+. 3. a completely filled f level, e.g. Yb2+ (f14).
D & F BLOCK 13

As we move along the lanthanide series, the nuclear charge

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

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

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

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

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

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

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

2.4 Colour
93 Neptunium Np 5f 4 6d1 7s2 +3, +4, +5,+ 6, +7
The Lanthanides are silvery white metals. However, most of
the trivalent metal ions are coloured, both in the solid state 94 Plutonium Pu 5f 6 7s2 +3, +4, +5, +6, +7
and in aqueous solution. This is due to the partly filled-f-
95 Americium Am 5f 7 7s2 +2, +3, +4, +5, +6
orbitals which permit f-f transition.
96 Curium Cm 5f 7 6d1 7s2 +3, +4
NOTE
97 Berkelium Bk 5f 9 7s2 +3, +4
Lanthanides ions with x f electrons have a similar colour
98 Californium Cf 5f 10 7s2 +2, +3
to those with (14–x) f electrons e.g., La3+ and Lu3+ are
colourless, Sm3+ and Dy3+ are yellow and Eu3+ and Tb3+ 99 Einsteinium Es 5f 11 7s2 +2, +3
are pink.
100 Fermium Fm 5f 12 7s2 +2, +3

101 Mendelevium Md 5f 13 7s2 +2, +3

2.5 Hydroxides
102 Nobelium No 5f 14 7s2 +2 ,+3
The hydroxides Ln(OH)3 are precipitated as gelationous
precipitates by the addition of NH4OH to aqueous solutions. 103 Lawrencium Lr 5f14 6d1 7s2 +3
These hydroxides are ionic and basic. They are less basic 104 Rutherfordium Rf 4f14 6d2 7s2
than Ca(OH) 2 but more basic than Al(OH) 3 which is
amphoteric. The metals, oxides and hydroxides all dissolve
in dilute acids, forming salts. Ln(OH)3 are sufficiently basic 1. OXIDATION STATE
to absorb CO2 from the air and form carbonates. The basicity
decreases as the ionic radius decreases from Ce to Lu. Thus Unlike Lanthanides, Actinides show a large number of
Ce(OH)3 is the most basic, and Lu(OH3), which is the least oxidation states. This is because of very small energy gap
basic, is intermediate between Scandium and Yttrium in basic between 5f, 6d and 7s subshells. Hence, all their electrons
strength. The decrease in basic properties is illustrated by can take part in bond formation. The dominant oxidation
the hydroxides of the later elements dissolving in hot state of these element is +3 (similar to Lanthanides). Besides
concentrated NaOH, forming complexes. +3 state, Actinides also exhibit an oxidation state of +4. Some
Actinides show still higher oxidation states. The maximum
Yb(OH)3 + 3NaOH  3Na+ + [Yb(OH)6]3– oxidation state first increases upto the middle of the series
and then decreases, e.g., it increases from + 4 from Th to +5,
Lu(OH)3 + 3NaOH  3Na+ + [Lu(OH)6]3– +6, and +7 for Pa, U and Np but decreases in the succeeding
elements.
ACTINIDES SERIES The Actinides resemble Lanthanides in having more
compounds in +3 state than in the +4 state. However, the
The elements and their Oxidation States compounds in the +3 and +4 state tend to undergo
hydrolysis.
Atomic Element Symbol Outer Oxidation Further, it may be noted that in case of Actinides, the distribution of
electronic states* oxidation states is so uneven that it is of no use to discuss their
chemistry in terms of their oxidation states.
structure
2. ATOMIC RADIUS
1 2
89 Actinium Ac 6d 7s +3
The Actinides show Actinide contraction (very much like
90 Thorium Th 6d2 7s2 +3, +4 Lanthanide contraction) due to poor shielding effect of the
5f-electrons. As a result, the radii of the atoms or ions of
91 Protactinium Pa 5f 2 6d1 7s2 +3, +4, +5 these metals decrease regularly across the series. The
contraction is greater from element to element in this series
92 Uranium U 5f 3 6d1 7s2 +3, +4, +5, +6 due to poorer shielding by 5f electrons. This is because 5f
orbitals extend in space beyond 6s and 6p orbitals whereas
4f orbitals are buried deep inside the atom.
 D & F BLOCK 15

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

IMPORTANT COMPOUNDS OF TRANSITION ELEMENTS

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

(a) ZnO + 2HCl ZnCl2 + H2O
I. PREPARATION :
(dil/conc.)
ZnCO3 + H2SO4  ZnSO4 + H2O + CO2
(b) ZnO + HNO3 Zn (NO3)2 + H2O
II. REACTIONS :
(dil/conc.)
(a) ZnSO4  2H 2 O 
 Zn(OH) 2  H 2SO 4
white ppt (c) ZnO + 2NaOH Na2ZnO2 + H2O
(d) ZnO + 2KOH K2ZnO2 + H2O
NaOH (e) ZnO + CoO CoZnO2
( Rinmann 's green )

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

3. ZINC CHLORIDE ZnCl2.2H2O

(c) ZnSO4 + NH4OH  Zn (OH)2 + (NH4)2 SO4
Anhydride of zinc chloride cannot be obtained by
NH4OH heating its aqueous salt.
I. PREPARATION :
(a) ZnO + 2HCl ZnCl2 + H2O
[Zn(NH3)4]SO4
(b) Zn + HgCl2 ZnCl2 + Hg
(d) Lithopone (ZnS + BaSO4) used as a white pigment.
II. PROPERTIES :
2. ZINC OXIDE, ZNO (CHINESE WHITE OR
(a) ZnCl2 + H2S  ZnS + 2HCl
PHILOSPHER’S WOOL) (b) ZnCl2 + 2NaOH  Zn(OH)2 + 2NaCl
It found in nature as zincite or red zinc ore. Zn(OH)2 + 2NaOH  Na2ZnO2 + 2H2O
I. PREPARATION : (c) ZnCl2 + 2NH4OH  Zn(OH)2 + 2NH4Cl
(a) 2Zn + O2 2ZnO
NH4OH
(b) ZnCO3 ZnO + CO2

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

[Zn(NH3)4] Cl2 + 4H2O
 D & F BLOCK 17

III. USES :
4. FERROUS SULPHATE (FeSO 4. 7H 2O - GREEN
(i) As a red pigment
VITRIOL)
(ii) As abrasive polishing powder
I. PREPARATION : (iii) As catalyst
(a) FeS + H2SO4  FeSO4 + H2S 

(b)

Fe  H 2SO 4  FeSO 4  H 2  6. FERRIC CHLORIDE, FeCl3
dil.
It is known in anhydrous and hydrated form. It is a red
2FeS2 + H2O + 7O2  2FeSO4 + 2H2SO4 deliquiscent solid.
(Commercial preparation) I. PREPARATION :
II. REACTIONS :
(a) 12FeCl2 (anhydrous) + 3O2 Fe2O3 + 8FeCl3

(a) 2FeSO 4  Fe 2O3  SO 2  SO 3 (anhydrous)
(light green) (brown) II. REACTIONS :

(b) Fe 2  [Fe (CN) 6 ]3 

 Fe3 [Fe (CN)6 ]2 (a) 2FeCl3 2FeCl2 + Cl2
Turnbull's blue
(used as pigment in ink and paint)
(b) FeCl3 + 3NH4OH Fe(OH)3 + 3NH4Cl
Or Fe4 [Fe (CN)6]3
(Reddish brown)
(Prussian blue)
(c) 4FeCl3 + 3K4Fe(CN)6 Fe4 [Fe(CN)6 ]3 + 12 KCl
(c) NO3 detection : Prussian Blue

FeSO4 + NO3 + Conc. H2SO4  [Fe(H2O)5 NO]SO . 4

(d) 2FeCl3 + 6NH4CNS Fe[Fe(CNS)6 ]  6NH4Cl
Brown ring
Deep red colour

Deep red colouration is produced due to formation

(d) FeSO4 + 2KCN  Fe(CN)2 + K2SO4 of complex.
brown
(e) Till 750ºC it exists as its dimer Fe2Cl6.

excess KCN

K4[Fe(CN)6]
III. USES :
2+ 3+ –
(e) 2Hg Cl2 + 2Fe  Hg 2Cl2 + 2Fe + 2Cl (i) Its alcoholic solution is medicine, name (Tincture
white
ferri perchloride)
(f) FeSO4 + H2O2  Fenton’s reagent for oxidation of
alcohols to aldehydes (ii) For detection of acetates and phenols

(g) FeSO4. (NH4)2 SO4. 6H2O  Mohr’s salt (iii) For making prussion blue & as an oxidising agent

7. COPPER SULPHATE
5. FERRIC OXIDE, Fe2O3 (CuSO4. 5H2O - BLUE VITRIOL)

I. PREPARATION :
I. PREPARATION :
(a) 2FeSO4 Fe2O3 + SO2 + 3SO3
(a) CuO  H 2SO 4  CuSO 4  H 2O
II. REACTIONS:
(b) Cu(OH)2.CuCO3 + 2H2SO4  2CuSO4 + 3H2O + CO2
(a) Fe2O3 + 2NaOH Fusion H2O + 2NaFeO2 Malachite Green

(sodium ferrite)
(b) Fe2O3 + 6HCl 2FeCl3 + 3H2O
 18 D & F BLOCK

Copper scrape  USES :

Cu + H2SO4 + ½O2 (air)  CuSO4 + H2O (1) Bordeaux Mix  CuSO4 + CaO
(Commerical preparation) (to kill fungi)
II. REACTIONS :
8. CUPRIC OXIDE, CuO
(a) Effect of heat
It is called black oxide of copper and is found in nature
CuSO 4 .5H 2O 100
 ºC
 CuSO 4 .H 2O 230
 ºC
 as tenorite.

pale blue. I. PREPARATION :

750º (a) By heating Cu2O in air or by heating copper for a

CuSO4   CuO  SO3
white long time in air (the temperature should not exceed
above 1100ºC)
(b) [CuSO 4  KI  CuI 2  K 2SO 4 ]  2
2Cu2O + O2 4CuO (black)
(Unstable
2Cu + O2 2CuO
dirty white)
(b) 2Cu(NO3)2 2CuO + 4NO2 + O2
2CuI 2  Cu 2 I 2  I 2
white ppt.
(c) On a commercial scale, it is obtained by heating
2CuSO4 + 4KI  Cu2I2 + 2K2SO4 + I2 malachite which is found in nature.

(c) Test of Cu
2+ CuCO3 . Cu(OH)2 2CuO + CO2 + H2O
II. REACTIONS :
CuSO 4  NH 4 OH  Cu (OH ) 2  ( NH 4 ) 2 SO 4
 (a) When heated to 1100–1200ºC, it is converted into
cuprous oxide with evolution of oxygen.
4CuO 2Cu2O + O2
NH4OH
(Black) (Red)

[Cu(NH3)4]SO4 Uses : Used to impart blue and green colour to glazes and glass.

Schwitzer’s reagent
9. CUPRIC CHLORIDE, CuCl2.2H2O
(Deep blue solution) I. PREPARATION :
(a) CuO + 2HCl CuCl2 + H2O

(d) CuSO 4  KCN  Cu (CN ) 2  K 2SO 4 Cu(OH)2 CuCO3 + 4HCl 2CuCl2 + 3H2O + CO2
150ºC
2Cu (CN ) 2  Cu 2 (CN ) 2  (CN ) 2  (b) CuCl2 . 2H2O
HCl gas
CuCl2 + 2H2O
cyanogen gas
II. REACTIONS :
Cu 2 (CN) 2  KCN  K 3 [Cu(CN) 4 ] (a) The anhydrous salt on heating forms Cu2Cl2 and Cl2
excess

2CuCl2 Cu2Cl2 + Cl2

(e) CuSO4  K 4 [Fe(CN)6 ]  Cu2[Fe(CN)6 ]  K 2SO4
Chocolate brown ppt.

3CuCl2. 2H2O CuO + Cu2Cl2 + 2HCl

(f) CuSO4 + H2S  CuS + H2SO4
( black ppt.)
+ Cl2 + 5H2O
(g) In Fehling’s test & Benedict’s test
Dilute solution of CuCl2 is blue but concentrated solution
Aldehyde  Cu 2  Cu 2O   acid is green. Its dilute solution on adding HCl becomes yellow.
( red ppt.)
[Cu(H2O)4]2+  Blue

On adding HCl  [CuCl4]2–  green

 D & F BLOCK 19

(g) 3 + 2NH4OH  Ag 2O  2 NH 4 NO3  H 2O

10. AgNO3 (LUNAR CAUSTIC)
A g N O

( brown ppt .)

I. Preparation :



(a) 3Ag  4HNO3  3AgNO3  NO  2H 2O
Colourless crystal
2[Ag(NH3)2] NO3 + 3H2O
II. REACTION :
(h) Ammonical AgNO3  Tollen’s reagent used to test

(a) 2AgNO3  2Ag  2NO 2  O 2
red hot
aldehydes
(i) It converts glucose to gluconic acid.
T  212º C
(b) 2AgNO3   2AgNO2  O 2
Ag 2 O  C6 H12 O 6 
 2Ag  C6 H12 O 7
KCN KCN
(c) AgNO3   AgCN  K [Ag(CN)2 ] (j) It oxidises formaldehyde to formic acid
white ppts. soluble
Potassium
Dicyanidoargentate(I) Ag 2 O  HCHO 
 2Ag  HCOOH

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

AgNO3  NaBr 
 AgBr  NaNO3

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

AgBr  2KCN 
 KAg(CN) 2  KBr
Potassium argento-
cyanide (Soluble)

(e) It dissolves in sodium thiosulphate.

AgBr  2Na 2S2 O3 

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

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

dilute H2SO4.

Zn  H 2SO 4 
 ZnSO 4  2H

2AgBr  2H 
 2Ag  2HBr
 20 D & F BLOCK

All above reactions are also observed in the case of

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

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

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

I. PREPARATION :
K 2 HgI4  NH 4 Cl  NH 2 HgOHgI  KCl
Brown ppt.

2HgCl2  SnCl2  Hg 2 Cl2  SnCl4

II. REACTIONS :

Hg 2 Cl 2  SnCl 2  2Hg  SnCl 4

(a) black /
grey

(b) 
Hg2Cl2  HgCl2 + Hg (grey deposit) Iodide of Millon’s Base

(c) Hg2Cl2 + 2NH3  Hg  Hg( NH 2 )Cl  NH 4Cl (d) HgCl2 + 2NH3  Hg( NH 2 )Cl + NH4Cl
   
black white

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

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

(a) Hg  2Cl  aqua regia   HgCl2

SnCl2  2HgCl2  Hg 2Cl2   SnCl 4

(b) white ppts.

Hg 2Cl2  SnCl2  2Hg  SnCl4

 D & F BLOCK 21

SOLVED EXAMPLES

Example - 1 Reason : d4  d5 occurs in case of Cr2+ to Cr3+.

10
Silver atom has a completely filled d orbitals (4d ) in
But d6 d5 occurs in case of Fe2+ to Fe3+. In a medium (like
its ground state. How can you say that it is a transition water) d3 is more stable as compared to d5.
element ?

S o l . Silver (Z = 47) can exhibit +2 oxidation state wherein it will Example - 8

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

Sol. In the formation of metallic bonds no electrons from 3d-   n  n  2

orbitals are involved in case of zinc, while in all other
metals of the 3d series, electrons from the d-orbitals are
 1 3  1.73 BM.
always involved in the formation of metallic bonds.
Example - 9
Example - 3
Which of the 3d series of the transition metals exhibits Explain why Cu+ ion is not stable in aqueous solutions ?
the largest number of oxidation states and why ? Sol. Cu+ in aqueous solution undergoes disproportionation
i.e.,
Sol. Manganese (Z = 25), as it atoms has the maximum number
of unpaired electrons.
2Cu   aq  
 Cu 2   aq   Cu  s 
Example - 4
The Eo, value for this is favourable.
The Eo (M2+/M) value for copper is positive (+0.34 V).
What is possibility the reason for this ? Example - 10
Sol. Copper has high aHo and low hyd Ho. Actinoid contraction is greater from element to element
than lanthanoid contraction. Why ?
Example - 5 Sol. The 5f electrons are more effectively shielded from nuclear
How would you account for the irregular variation of charge. In other words, the 5f electrons themselves provide
ionisation enthalpies (first and second) in the first series poor shielding from element to element in the series.
of the transition elements ?
Example - 11
Sol. Irregular variation of ionisation enthalpies in mainly
On what ground can you say that scandium (Z = 21) is a
attributed to varying degree of stability of different 3d-
transition element but zinc (Z = 30) is not ?
configurations (e.g., d0, d5, d10 are exceptionally stable).
Sol. On the basis of incompletely filled 3d orbitals in case of
Example - 6 scandium atom is its ground state (3d1), it is regarded as a
Why is the highest oxidation state of a metal exhibited transition element. On the other hand, zinc atom has
in its oxide or fluoride only ? completely filled d orbitals (3d10) in its ground state as
well as in its oxidised state, hence it is not regarded as a
Sol. Because of small size and high electronegativity oxygen transition elements.
or fluorine can oxide the metal to its highest oxidation
state. Example - 12
Why Cr and Cu show exceptional configuration ?
Example - 7
Sol. By deviating from normal configuration, Cr and Cu acquires
Which is a stronger reducing agent Cr2+ or Fe2+ and
half-filled and fully filled configurations which gives them
why ?
extra stability. Hence they show exceptional configuration.
Sol. Cr2+ is strong reducing agent than Fe2+. Cr [Ar] 3d5 4s1 and Cu [Ar] 3d10 4s1
 22 D & F BLOCK

Example - 13 fewer orbitals available in which to share electrons with

others) for higher elements at upper end of first transition
Why are Zn, Cd and Hg softer and volatile metals ? series (i.e., Cu and Zn). Thus electronic configuration, to
large extent, the existence and stability of oxidation states.
Sol. Due to their completely filled d-orbitals, they have weak
metallic bonding and least compact packing therefore they The other factors which determine stability of oxidation
all are volatile in nature. state are:

(i) Enthalpy of atomisation (ii) Ionisation energy

Example - 14
(iii) Enthalpy of solvation (iv) E.N. of other element.
Explain briefly how +2 state becomes more an more
stable in the first half of the first row transition elements Example - 16
with increasing atomic number ?
What may be the stable oxidation state of the transition
Sol. In transition elements, there are greater horizontal element with the following d electron configurations in
similarities in the properties in constrast to the main group the ground state of their atoms : 3d3, 3d5, 3d8 and 3d4 ?
elements because of similar ns2 common configuration of
Sol. The stable oxidation state of transition element with the d
the outermost shell.
electron configuration in ground state of atoms are as
An examination of common oxidation states reveals that follows :
excepts scandium, the most common oxidation state of
S. No. d-electron Symbol of Stable oxidation
first row transition elements is +2 which arises from the
configuration element states
loss of two 4s electrons. This means that after scandium, 3 2 3
1. 3d V(4s 3d ) +2, +3, +5
d-orbitals become more stable than the s-orbital.
2. 3d4 Cr(4s 3d4)
2
+2, +3, +6
5 2 5
Further, +2 state becomes more an more stable in the first 3. 3d Mn(4s 3d ) +2, +7
half of first row transition elements with increasing atomic 4. 3d8 Ni(4s23d8) +2, +4
number because 3d orbitals acquire only one electron in
each of five 3d orbitals (i.e. remains half filled) and electronic It should be noted that lower stable oxidation state
repulsion is the least and nuclear charge increases. In 2nd generally leads to ionic bond and higher oxidation state
half of first row transition elements, electrons starts pairing corresponds to covalent bond.
up in 3d orbitals.
Example - 17
(Ti2+ to Mn2+ electronic configuration changes from 3d2 to 3d5
but in 2nd half i.e. Fe2– to Zn2+ it changes from d6 to d10). Name the oxometal anions of the first series of the
transition metals in which the metal exhibits the
Example - 15 oxidation state equatl to its group number.
To what extent do the electronic configurations decide Sol.
the stability of oxidation states in the first series of the
transition elements ? Illustrate your answer with Name of oxometal Name of metal with Group no. to which
example. anion oxidation state metal belong
2–
1. CrO4 Cr in +6 state of 6th group of
Sol. One of the main characteristic of a transition element is (chromate ion) oxidation periodic table
that it can show large variety of oxidation states in its 2. MnO 4
–
Mn in +7 state 7th group
compounds. It is due to its characteristic electronic (permanganate ion)
configuration i.e., (n – 1) d and ns electrons take part in
bond formation either by loosing or by sharing of electrons
with other combining atoms. Example - 18

The stability of oxidation state depends mainly on What is lanthanoid contraction ? What are the
electronic configuration and also on the nature of other consequences of lanthanoid contraction ?
combining atom.
Sol. A group of fourteen elements following lanthanum i.e.
The elements which show largest number of oxidation from58Ce to71 Lu placed in 6th period of long form of periodic
states occur in or near the middle of series (i.e., 4s23d3 to talbe is known as lanthanoids (or lanthanide series). These
4s 23d 7 configuration). For example, Mn exhibits all fourteen elements are represented by common general
oxidation states from +2 to +7 as it has 4s 2 3d 5 symbol ‘Ln’. In these elements, the last electron enters the
configuration. The lesser number of oxidation states at 4f-subshells (pre pen ultimate shell). It may be noted that
extreme ends arise from either too few electrons to loose atoms of these elements have electronic configuration with
or share (e.g. Sc and Ti) or too many d electrons (hence 6s2 common but with variable occupancy of 4f level. However,
 D & F BLOCK 23

the electronic configuration of all the tripositive ions (the (vii) These metals form various alloys with other metals of the
most stable oxidation state of all lanthanoids) are of the form series.
4f n(n = 1 to 14) with increasing atomic number). These
elements constitute one of the two series of inner transition (viii) These metals form interstitial compounds with C, N, B and
elements or f-block. H.

Lanthanoid contraction : In the lanthanoide series with The presence of partially filled d-orbitals in the electronic
the increase in atomic number, atomic radii and ionic radii configuration of atomic and ionic species of these elements
decrease from one elements to the other, but this decrease is responsible for the characteristic properties of transition
is very small. the regular small decrease in atomic radii and elements. They are called transition elements because of
ionic radii of lanthanides with increasing atomic number their position in the periodic table. These elements lie in
along the series is called lanthanoid contraction. the middle of periodic table between s and p-block (i.e.,
between group 2 and group 13). A transitio element may
Cause of lanthanoid contraction: When one moves from be defined as a element whose atom or at least one of its
58
Ce to 71Lu along the lanthanide series nuclear charge simple ions contain partially filled d-orbitals, e.g., iron,
goes on increasing by one unit every time. Simultaneously copper, chromium, nickel etc.
an electron is also added which enters to the inner f
subshell. The shielding effect of f-orbitals in very poor The general characteristic electronic configuration may
due to their diffused shape. It results in the stronger force be written as (n – 1) d1–10ns1–2.
of nuclear attraction of the 4f electrons and the outer The elements of group 12 i.e., Zinc, Cadmium, and Mercury
electrons causing decrease in size. are generally not regarded as transition elements as their
Consequences of lanthanoid contraction: atoms and all ions formed have completely filled d-orbitals
i.e., these do not have partially filled d-orbitals in atomic
(i) Similarly in the properties of elements of second and third state or common oxidation state (Zn2+, Cd2+, Hg2+)
transition series e.g. Sr and Hf; Nb and Ta; Mo and W.
This resemblance is due to the similarity in size due to the Zn (30) = [Ar] 4s23d10 Zn2+ = [Ar] 3d10 4s0
presence of lanthanoids in between. Cd (48) = [Kr] 5s2 4d10 Cd2+ = [Kr] 4d10 5s0
(ii) Similarity among lanthanoids : Due to the very small change Hg (80) = [Xe] 6s2 5d10 Hg2+ = [Xe] 5d10 6s0
in sizes, all the lanthanoids resemble one another in
chemical properties. Example - 20
(iii) Decrease in basicity : With the decrease in ionic radii, In what way is the electronic configuration of the
covalent character of their hydroxides goes on increasing transition elements different from that of the non-
from Ce(OH)3 to Lu(OH)3 and so base strength goes on transition elements ?
decreasing.
Sol. Transition elements have incomplete penultimate d-orbitals
Example - 19 while penultimate orbitals of representative elements (s -
and p - block elements) are completely filled up. The
What are the characteristics of the transition elements general valence shell configuration of s-block (group 1
and why are they called transition elements ? Which of and 2) elements is ns1–2 and for p-block elements (group
the d-block elements may not be regarded as the 13 to 18) is ns2 np1–6. The valence shell configuration of
transition elements? transition elements can be written as (n – 1) d1–9 ns1–2 .
Sol. The important characteristics of transition metals are:
Example - 21
(i) All transition elements are metallic in nature, e.g., all are Explain giving reasons :
metals.
Sol.
(ii) These metals exhibit variable oxidation states.
(i) Transition metals and many of their compounds show
(iii) Transition metal atoms or ions generally form the paramagnetic behaviour.
complexes with neutral, negative and positive ligands.
(ii) The enthalpies of atomisation of the transition metals are
(iv) Compounds of transition metals are usually coloured. high.
(v) The compounds of these metals are usually paramagnetic (iii) The transition metals generally form coloured compounds.
in nature.
(iv) Transition metals and their many compounds act as good
(vi) Transition metals and their compounds act as good catalyst.
catalysts, i.e., they show catalytic activities.
 24 D & F BLOCK

Example - 22 Example - 24
What are interstitial compounds ? Why are such Describe the preparation of potassium dichromate from
compounds well known for transition metals ? iron chromite one. What is the effect of increasing pH
on a solution of potassium dichromate ?
Sol. Interstitial compounds are those which are formed when
small atoms like H, C, N, B etc. are trapped inside the Sol. The following steps are involved in preparation of K2Cr2O7
crystal lattices of metals. They are generally non- from iron chromite (FeCr2O4) ore :
stoichiometric and neither typically ionic nor covalent. (i) Preparation of sodium chromate : The chromite ore
(FeO.Cr2O3) is finely powdered and mixed with sodium
Most of transition metals form interstitial compounds with carbonate and quick lime and then heated to redness in a
small non-metal atoms such as hydrogen, boron, carbon reverberatory furnace with free supply of air.
and nitrogen. These small atoms enter into the void sites 4FeO.Cr2O3 + O2  2Fe2O3 + 4Cr2O3
between the packed atoms of crystalline transition metals. [4Na2CO3 + 2Cr2O3 + 3O2  4Na2CrO4 + 4CO2] × 2

For Example, steel and cast iron become hard by forming 4FeO.Cr2O3 + 8Na2CO3 + 7O2  8Na2CrO4 + 2Fe2O3 + 8CO2
interstitial compound with carbon.
The mass is then extracted with water, when sodium
The exsitence of vacant (n – 1) d orbitals in transition chromate is completely dissolved while Fe 2O3 is left
elements and their ability to make bonds with trapped small behind.
atoms in the main cause of interstitial compound formation. (ii) Conversion of sodium chromate into sodium dichromate
Other examples are : VH 0.56 , TiH 1.7 . Some main (NaCr2O7) : The sodium chromate extracted with water in
characteristics of these compounds are : previous step is acidified.

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

etc. In acidic solution, its oxidising action can be (b) It oxidised sulphur dioxide to sulphuric acid.
represented as follows :
2MnO4– + 5SO2 + 2H2O  5SO42– + 2Mn2+ 4H+
Cr2O 7
2–
+ 14H + 6e  2Cr + 7H2O; (E = 1.33 V)
+ – 3+ +
(c) It oxidises oxalic acid to CO2 and H2O
(a) It oxidises potassium iodide to iodine.
2MnO4– + 16H+ + 5C2O42–  2Mn2+ + 8H2O + 10CO2
Cr2O 7
2–
+ 14H 6I  2Cr + 7H2O + 3I2
+ – 3

Example - 27
(b) It oxidises iron(II) salt to iron (III) salt
For M2+/M and M3+/M2+ systems the Eo values for some
Cr2O72– + 14H+ + 6Fe2+  2Cr3+ + 6Fe3+ + 7H2O metals are as follows :
(c) It oxidises H2S to S Cr2+/Cr – 0.9 V Cr3+/Cr2+ – 0.4 V
Cr2O72– + 8H+ + 3H2S  2Cr3+ + 7H2O + 3S Mn2+/Mn – 1.2 V Mn3+/Mn2+ + 1.5 V

Example - 26 Fe2+/Fe – 0.4 V Fe3+/Fe2+ + 0.8 V

Describe the preparation of potassium permanganate. Use this data to comment upon
How does the acidified permanganate solution reacts
with (a) iron(II) ions (b) SO2 and (c) oxalic acid ? Write (a) The stability of Fe3+ in acid solution as compared
the ionic equations for the reactions. to that of Cr3+ or Mn3+ and

Sol. Preparation of KMnO 4 from pyrolusite ore (MnO 2) (b) In case with which iron can be oxidised as compared
involves the following steps : to the similar process for either chromium or
manganese metal.
(i) Fusion of ore with alkali in presence of air : Pyrolusite
ore is fused with alkali in the presence of air when Sol.
potassium manganate is obtained as green mass. (a) We know that higher the reduction potential of a specie,
2MnO2 + 4KOH + O2  2K2MnO4 + 2H2O there is larger tendency for tis reduction to take place. Let
(green mass) us represent the reduction potential i.e., Eo values of three
M3+/M2+ systems on number line.
The green mass is dissolved in water to obtain aqueous
Cr3+ / Cr2+ F3+/Fe2+ Mn3+/Mn2+
solution of potassium manganate. The insoluble impurities
of sand and other metal oxides are removed by filtration.
– 0.4 V 0.8 V 1.5 V
(ii) Oxidation of manganate into permanganate : The aqueous increasing reduction potential
solution of K2MnO4 is oxidised electrolytically or by using
From values of reduction potentials, it is clear that the
ozone or Cl2 to obtain potassium permanganate. The
stability of Fe3+ in acid solution is more than that Cr3+ but
process is carried out till green colour disappear and
less than that of Mn3+.
solution acquires distinct pink colour.
(b) Mn 2+/Mn Cr2+/Cr Fe2+/Fe
2  
MnO 4 
 MnO 4  e
 at anode  (oxidation at anode) – 1.2 V 0.9 V –0.4 V 0V
green coloure pink

H2O + e–  1/2H2 + (OH)– (reduction at cathodes) The lower the reduction potential of a species, its
oxidation will take place more readily.
(at cathode)
 Mn is oxidised most readily to Mn2+ and Fe is oxidised
or 2K 2 MnO4  CI 2  2KMnO4  2KCI least readily among given metals Mn, Cr and Fe.
 green colour   pink colour 
Example - 28
Potassium permanganate is crystallised out from the
Write the electronic configurations of the elements with
solution.
the atomic numbers 61, 91, 101 and 109.
Oxidising Properties : It acts as a powerful oxidising agent
Sol. Atomic number (61) = [Xa] 4f5 6s2.
in different media differentily. In acidic medium, it oxidises
iron(II) salts to iron(III) salts, SO2 to H2SO4 and oxalic acid Atomic number (91) = [rn] 5f2 6d1 7s2
to CO2 and H2O.
Atomic number (101) = [Rn] 5f14 7s1
(a) It oxidises iron(II) salt to iron(III) salts.
Atomic number (109) = [Rn] 5f14 6d7 7s2.
2MnO42- + 16+ + 10Fe2+  2Mn2+ + 8H2O + 10Fe3+ .
 26 D & F BLOCK

Here, we can say that Cr in +5 oxidation state undergo

Example - 29
disproportionation into its +6 and +3 states. Similarly, Mn
How would you account for the following : in +6 oxidation state undergo disproportionation into +7
and +7 oxidation states.
(a) Of the d4 species Cr2+ is strongly reducing while
manganese(III) is strongly oxidising. Example - 31

(b) Cobalt(II) is stable in aqueous solution but in the Give reasons for the following :
presence of complexing reagents it is easily
(a) Transition metals have high enthalpies of
oxidized.
atomisation.
(c) The d1 configuration is very unstable in ions?
(b) Among the lanthenoids Ce(III) is easily oxidised to
Ce(IV).
Sol.
(c) Fe3+/Fe2+ redox couple has less positive electrode
(a) Of d4 species, Cr2+ has 3 d4 configuration and tends to potential than Mn3+/Mn2+ couple.
loose one electron to acquire d3 configuration as it is highly
stable and best metallic specie available for complex (d) Copper (I) has d10 configuration while copper(II) hs
formation. Cr3+ can accommodate six lone pair of electrons d9 configuration, still copper(II) is more stable in
from ligands due to sp3d2 hybridisation e.g. [Cr(NH3)6]3+ aqueous solution than copper(I).
Mn3+ although have d4 configuration but tends to become
(e) The second and third transition series elements
Mn2+ stable specie by acquiring one electron to attain d5
have almost similar atomic radii.
configuration. It becomes exactly half filled on one hand
and more energy is released in gain of electron due to Sol.
higher nuclear charge.
(a) The metallic bonds in transition elements are very strong
(b) Co 2+ is stable in aqueous solution because it get due to participation of (n – 1) d electrons along with
surrounded and weakly bonded to water molecules. In valence s-electrons in the bond formation. Therefore, the
presence of strong ligands and air it gets oxidised tc Co(III) cleavage of these bonds is extremely difficult and
as strong ligands get co-ordinated more strongly with consequently, enthalpies of atomization are high.
Co(III). The electronic configuration of Co(II) and Co(III)
are : (b) Ce3 
 Ce 4  e 
 4f 5d o
6so   4f o
5d o 6so 
Co(II) = [Ar]18 4s03d7 and Co(III) = [Ar]18 4s03d6

In Co(III) specie, 6 lone pairs of electrons from ligands are Spontaneous oxidation due to more stability of Ce4+ ion
accommodated by sp 3d 2 hybridisation which is not as compared to Ce3+ ion due to more stable configu-ration
possible in Co(II). of Ce4+ ion.

(c) Some species with d1 configuration are reducing and tends (c) Mn 3  3e 
 Mn  2
to loose one electron to acquire d4 stable configuration.
Some other species with d1 configuration like Cr(V) and (more spontaneous due to higher stability of Fe3+)
Mn(VI) undergo disproportionation.
Fe3  e 
 Fe2
Example - 30
(less spontaneous due to higher stability of Fe3+)
What is meant by disproportionation ? Give two examples
of disproportionation reaction in aqueous solution. Due to stability of half filled d-orbitals, Mn2+ is more stable
than Mn3+ and thus its reduction is more spontaneous.
Sol. Some time transition metal species in same oxidation state Similarly Fe 3+ is more stable than Fe 2+ and thus its
undergo a chemical change in such a way that some species reduction is less spontaneous.
get oxidised and some other get reduced. For example, Cr(V) (d) Copper (II) has lower reduction electrode potential than
and Mn(VI) species undergo disproportionation reaction copper (I), hence. Copper(I) is oxidised to copper (II) in
in acidic medium as follows: the presence of strong ligands and air.
2
3CrO 43  8H   2CrO 4  Cr 3  4H 2 O (e) It is due to lanthanoid contraction. It arises due to poor
 Cr in  5 o.s.  Cr in  o.s. shielding effect of d and f electrons.

3MnO 43  4H   2MnO 4   MnO 2  2H 2 O

Mn in  6 o.s. Mn in Mn in
7 o.s 4 o.s.
 D & F BLOCK 27

Example - 32 Example - 34
Indicate the steps in the preparation of : The Chemistry of the actinoid elements is not so smooth
(a) K2Cr2O7 from chromite ore as that of the lanthanoids. Justify this statement by giving
some examples from the oxidation state of these elements.
(b) KMnO4 from pyrolusite ore.
Sol. Among the actinoids, there is a greater range of oxidation
Sol. states as compared to lanthanoids. This is in part due to
(a) The preparation of potassium dichromate from chromite the fact that 5f, 6d and 7s levels are of very much
involves the following main steps : comparable energies and the frequent electronic transition
among these three levels is possible. This 6d-5f transition
(i) The chromate ore is finely ground and heated strongly
with molten alkali in the presence of air. and larger number of oxidation states among actinoids
make their Chemistry more complicated particularly among
2FeCr2 O4  8NaOH  7 / 2O2  4Na 2 Cr2 O4  Fe2 O3  4H 2 O
Chromite Sodium chromate the 3rd to 7th elements. following examples of oxidation
(ii) The solution of sodium chromate is filtered and acidified states of actinoids. Justify the complex nature of their
with dilute sulphuric acid so that sodium dichromate is Chemistry.
obtained.
(i) Uranium exhibits oxidation states of +3, +4, +5, +6 in its
2Fe2Cr2O4  H3SO4  Na 2Cr2O7  Na 2SO4  H 2O compounds. However, the dominant oxidation state in
Sodium Chromate Sodium dichromate actinoides is +3.

(iii) A calculated quantity of potassium chloride is added to a (ii) Nobelium, No is stable in +2 state because of completely
hot concentrated solution of sodium dichromate. filled f14 orbitals in this state.
Potassium dichromate is less soluble therefore it
crystallizes out first. (iii) Berkelium, BK in +4 oxidation state is more stable due to f7
Na 2 Cr2 O 7  2KCl  K 2Cr2O 7  2NaCl (exactly half filled) configuration.
Sodium Potassium
dichromate dichromate
(iv) Higher oxidation states are exhibited in oxoions are UO22+,
(b) (i) Pyrolusite ore is fused with alkali in the presence of PuO22+, NpO+ etc.
air when potassium manganate is formed.
Example - 35
2MnO 2  4KOH  O 2  2K 2 MnO 4  2H 2 O
Potassium manganate Use Hund’s rule to derive the electronic configuration
of Ce3+ ion, and calculate its magnetic moment on the
(ii) Potassium manganate is oxidised by using either CO2, basis of ‘spin only’ formula.
ozone or chlorine to potassium permanganate.
2K 2 MnO 4  Cl 2  2KMnO 4  2KCl Sol. The electronic configuratio of Ce and Ce3+ ion is :
Potassium
permanganate
Ce(Z = 58) = 54[Xe] 4f15d16s2
(iii) Potassium permanganae is crystallized from the
solution. Ce3+ = 54[Xe] 4f1
Example - 33 The no. of unpaired electron = 1
What are alloys ? Mention an important alloy which
contains some of the lanthanoid metals. Mention its uses. ‘Spin only’ formula for magnetic moment of a specie,

  n  n  2  B.M.
Sol. An alloy is a mixture of a metal with other metals or non-
metals.

An important alloy which contains some of the lanthanoid  Magnetic moment of Ce3+
is mischmetall. Mischmetall consists of a lanthanoid metal
(~95%) and iron (~5%) and traces of S, C, Ca and Al.
  11  2  B.M.
Uses : (i) Mischmetall is used in Mg based alloy to produce
bullets, shell and lighter flint.
 3 B.M.  1.732 B.M.
Some individual Ln oxides are used as phosphorus in
television screens and similar fluorescing surfaces.
 28 D & F BLOCK

Example - 36 Example - 38
Name the members of the lanthanoid series which exhibit Discuss the relative stability in aqueous solutions of +2
+4 oxidation states and those which exhibit +2 oxidation oxidation state among the elements: Cr, Mn, Fe and Co.
state. Try to correlate this type of behaviour with the How would you justify this situation ?
electronic configurations of these elements.
(At. Nos. Cr = 24, Mn = 25, Fe = 26, Co = 27)
Sol. Cerium (Ce) and Terbium (Tb) show +4 oxidation state.
Their electronic configurations are given below : Sol. On the basis of electrochemical series the standard
electrode potential shows the following order
Ce = [Xn] 4f1 5d1 6s2
E o Mn 2 / Mn  E o Cr 2 / Cr  E o Fe2 / Fe  E o Co2 / Co
Tb = [Xn] 4f0 6s2
Therefore Co2+ gets easily reduced to metallic cobalt while
It is clear from the configuration of Ce that Ce+4 is favoured
it is difficult to reduce Mn2+. Hence Mn2+ will be most
by its noble gas configuration i.e., [Xn] 4f0 5d0 5s0, but can
stable and the increasing stability order will be
be easily converted into Ce3+ ([Xn]) 4f1 5d0 6s0). Due to
this reason Ce+4 is an oxidising agent. Tb4+ ion is stabilized Co2+ < Fe2+ < Cr2+ < Mn 2+
due to half filled f-subshell i.e., [Xn] 4f7. It also acts as an
oxidant. Example - 39

Europium (63) and ytterbium (70) show +2 oxidation state, Which metal in the first series of transition metals
this acts as reducing agents because they can be exhibits +1 oxidation state most frequently and why ?
converted into common oxidation state +3. The electronic Sol. Copper metal (Cu, at, no. 29) shows + 1 oxidation state i.e.,
configuration of Eu and Y are as follows : it exists as Cu+ in large number of copper compounds e.g.,
cuprous oxide (Cu2O), coprous sulphide 9Cu2S); cuprous
Eu = [Xn] 4f7 6s2
chloride (Cu2Cl2) etc. The electronic configuration of Cu+
Y = [Xn] 4f14 6s2 is [Ar] 3d10 4s0.

Formation of Eu2+ ion leaves 4f7 configuration and Y2+ ion This configuration is very stable as all five 3d orbitals are
leaves 4f14 configuration. These configurations can stable fully filled.
due to half filled and full filled f-subshell. Samarium, Sm
(62) 4f6 6s2 also shows both +2 and +3 oxidation states like Example - 40
europium. Assign a reason for each of the following :

Example - 37 (i) The third ionization energy of Mn(Z = 25) is higher

than that of either Cr (Z = 24) or Fe (Z = 26).
Explain the following facts
(ii) Simple copper (I) salts are not stable in aqueous
(a) transition metals act as catalysts.
solutions.
(b) chromium group elements have the highest melting
Sol.
points in their respective series.
(i) This is because Mn2+ is more stable as it has exactly half
(c) transition metals form coloured complexes.
filled configuration 3d5 4s0.
Sol.
(ii) Cu2+ (aq) is much more stable than Cu+ (aq). This is
(a) The catalytic activity of transition metals is attributed to because, although second ionization enthalpy of copper
the following reasons : is large but for Cu2+ (aq) is much more negative than that
of Cu + (aq) and therefore, it more compensate for the
(i) Because of their variable oxidation states transition metals second ionisation enthalpy of copper. Therefore, Cu+ ion
form unstable intermediate compounds and provide a new aqueous solution undergoes disproportionation.
path with lower activation energy for the reaction.
2Cu 2   aq  
 Cu 2   aq   Cu  s 
(ii) In some cases, the transition metal provides a suitable
large surface area with free valencies on which reactants
are adsorbed.

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

number of unpaired d electrons.

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

 D & F BLOCK 29

Example - 41 Example - 42
Describe the trends in the following properties of the Complete the following chemical reaction equations:
first series of the transition elements:

(i) Oxidation states (i) MnO4  aq   C2 O42   aq   H   aq  



(ii) Atomic sizes (ii) Cr2 O72   aq   Fe2   aq   H   aq  

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

Sol. Sol. (i) MnO 4  8H   5e  

 Mn 2   4H 2 O]  2
C 2 O 42   2CO 2  2 ]  5

(i) As there is very little energy difference between 4s and 3d
orbitals, electrons from both energy levels can be used 2MnO 4  5C 2 O 42   16H  
 2Mn 2   10CO 2  8H 2 O
for chemical bond formation. Therefore all elements except
Sc and Zn, of the first transition series show a number of
oxidation states as shown in table. (ii) Cr2 O 72   14H   6e  
 2Cr 3  7H 2 O
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Fe 2   Fe3  e  ]  6

2 2 2 2 2 2 2 1
3 3 3 3 3 3 3 3 2 2 Cr2 O72   6Fe2   14H  
 2Cr 3  6Fe3  7H 2 O
4 4 4 4 4 4 4
5 5 5
Example - 43
6 6 6
7 How would you account for the following :

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

 n  n  2  B.M. (iii) This is due to comparable energies of 5f, 6d and 7s orbital

in actinoids.
Ion Configuration Unpaired Magnetic moment ()
electrons calculated
Example - 44
In transition series, with an increase in atomic number,
Mn
2+
3d 4s
5 0
5 5 5  2   5.92 B.M. the atomic radius does not change very much. Why is it
Cu
2+
3d 4s
9 0
1 11  2   1.73B.M.
so ?

0 0  3  0 Sol. With the increase in atomic number along a transition series

2+ 10 0
Zn 3d 4s 0
the nuclear charge increases which tends to decrease the
 30 D & F BLOCK

size of the atom. But the addition of electrons in the d Example - 47

subshell increases the screening effect which
counterbalances the increased nuclear charge. Hence, Among the ionic species Sc3+, Ce4+ and Eu2+ which one
along a transition series the atomic radius does not change is a good oxidising agent? Give a suitable reason for
very much. your answer. (Atomic numbers ; Sc = 21; Ce = 58;
Eu = 63).
Example - 45
Sol. The electronic configurations of given species are:
Decide giving reasons which one of the following pairs
exhibits the property indicated: 21 18 Sc3
Sc 

(i) Sc3+ or Cr3+ exhibits paramagnetism.

 Ar  3d1 4s2  Ar  3d0 4s0
(ii) V or Mn exhibits more number of oxidation states.

(Atomic Numbers: Sc = 21; Cr = 24; V = 23; Mn = 25) 58 54 Ce 4 

Ce 

Sol. [Xe] 4f1 3d1 6s2 [Xe]

3+
(i) T h e e l e c t r o n i c c o n f i g u r a t i o n s o f S c and Cr3+ are given 61 Eu 2 
Eu 
63
below.

Sc3 :  Ar  3d 0 4s0 Cr 3 :  Ar  3d3 4s0

 Xe 4f 7 6s2  Xe 4f 7
Ce4+ is a good oxidising agent because it can readily
Because of the presence of three unpaired electrons in
change to the most stable +3 oxidation state by gaining
the 3d subshell Cr3+ is paramagnetic. Sc3+ is diamagnetic
one electron.
as it does not have any unpaired electrons.

(ii) The electronic configurations of V and Mn are given Ce4   e 

 Ce3
below:
Because of their stable configuration Sc3+ and Eu2+ cannot
V :  Ar  3d3 4s 2 Mn :  Ar  3d5 4s 2
gain electrons.
23 25

Example - 48
Mn exhibits more number of oxidation states than V
because of the greater number of electrons in its valence Write complete chemical equations for :
shell.
(i) Oxidation of Fe2+ by Cr2O72– in acid medium.
Example - 46
(ii) Oxidation of S2O32– by MnO4 in neutral aqueous
Account for the following:
solution.
(i) Cerium (atomic number = 58) forms tetra positive
ion, Ce4+ in aqueous solution. Sol. (i) 6Fe2+ + Cr2O72– + 14 H+ 
 6Fe3+ + 2Cr3+ + 7H2O
(ii) The second and third members in each group of
transition element have similar atomic radii. (ii) 2MnO4– + 3S2O32– + H2O 
 2MnO2 + 3SO42– +
3S + 2OH–.
Sol.
Example - 49
(i) The electronic configuration of Ce (Z = 58) is 58Ce = [Xe]
4f1 5d1 6s 2 What are the different oxidation states exhibited by the
lanthanoids ?
Cerium can lose four electrons (4f1 5d1 6s2) in aqueous
solution to acquire stable configuration of rare gas xenon. Sol. The most common oxidation states shown by lanthanoids
Moreover due to small size and high charge, Ce4+ ion has is +3. In some exceptional cases it may be +2 or +4 (+2 in
high hydration energy. Eu and Yb; +4 in Ce).

(ii) The second and third members in each group of transition

elements have very similar atomic radii due to lanthanoid
contraction. It arises due to poor shielding effect of f
electrons.
 D & F BLOCK 31

Example - 50 (ii) Cr2 O72   aq   6Fe2   aq   14H   aq  

 2 Cr 3
What is meant by ‘lanthanoid contraction’ ?
(aq) + 6 Fe3+ (aq) + 7H2O (l)
Sol. The regular decrease (contraction) in the atomic and ionic
radii with increasing atomic number from lanthanum to Or
lutetium along the lanthanoid series is called lanthanoid (i) Cu2+ (aq) is much more stable than Cu+ (aq. This is due to
contraction. more negative hydH more than compensates for iH2. As
a result Cu(I) is unstable in aqueous solution and
Example - 51
undergoes disproportionation as below :
How would you account for the following :
2Cu  
 Cu 2   Cu
(i) Cr2+ is reducing in nature while with the same d-
orbital configuration 9d4) Mn3+ is an oxidising (ii) The valence shell electronic configuration of Cr3+, Mn2+,
agent. Fe3+ is d3, d5 respectively. Due to symmetrical distribution
(ii) In a transition series of metals, the metal which of electrons (Either t 32g or t 32g eg2 ) they form stable
exhibits the greatest number of oxidation states cationic complexes. The atomic radii of 4d and 5d transition
occurs in the middle of the series. metal at elements are more than those of 3d series. Hence.
Sol. they generally do not form stable cationic complexes.

(i) Eo value of Cr3+/Cr2+ is negative (–0.04V) while that of Example - 53

Mn3+/Mn2+ is positive (1.5 V). This means Cr2+ can lose Explain giving reasons :
electrons to form Cr3+ and thus is reducing in nature while
Mn3+ can gain electrons to form Mn2+ and is thus oxidising (i) Transition metals and their compounds generally
in nature. exhibit a paramagnetic behaviour.

(ii) In a transition series of maximum number of oxidation states (ii) The Chemistry (XII) (XII) of actinoids is not so
are shown by that element which has maximum number of smooth as that of lanthanoids.
unpaired electrons. This is so in the element present in the
Sol.
middle of the series. That is why the metal in the middle of
the series exhibits maximum number of oxidation states. For (i) Paramagnetism is a property due to presence of unpaired
example, manganese, present in the middle of the first electrons. In case of transition metals, as they contain
transition series exhibits maximum oxidation states i.e., +2, unpaired electrons in (n – 1) d orbitals, most of the
+3, +4, +5, +6, +7. transition metal ions and their compounds are
paramagnetic.
Example - 52
(ii) The general electronic configuration of lanthanoids is
Complete the following chemical equations :
[Xe]54 4f0–4 5d0–1 6s2 and that of actinoids is [Rn]86 5f1–14
6d0–1 7s2. Unlike 4f orbitals, 5f orbitals are not deeply burried
(i) MnO4  aq   S2 O32   aq   H 2 O    
and participate in bonding to a greater extent. In actinoids
due to poor shielding effect of 5f orbitals, the effective
(ii) Cr2 O72   aq   Fe2   aq   H   aq   nuclear charge experienced by valence shell electrons is
more than those in lanthanoids. As a result the Chemistry
Or (XII) (XII) of actinoids is not so smooth as that of
lanthanoids.
State reasons for the following :

(i) Cu (I) ion is not stable in an aqueous solution. Example - 54

Assign reasons for the following :
(ii) Unlike Cr3+, Mn2+, Fe3+ and the subsequent other
M2+ ions of the 3d series of elements, the 4d and the (i) Copper (I) ion is not known in aqueous solution.
5d series metals generally do not form stable
cationic species. (ii) Actinoids exhibit greater range of oxidation states
than lanthanoids.
Sol.
Sol.
(i) 8MnO  aq   3S2 O

4
2
3  aq   H 2 O    
 6 SO 2
4 (i) Cu (I) ion is not known in aqueous solution because
Cu2+(aq) is much more stable than Cu+(aq). This is due to
(aq) + 8MnO2 + 2OH– (aq)
 32 D & F BLOCK

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

(i) Transition metals generally form coloured Example - 57

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

Sol. (b) Chromium group elements have highest meeting

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

two sets-t 2g d x 2  y2
, d z2  of lower energy and e g (a) Transition metals acts as catalyst due to the following

d
, d yz , d xz  of high energy. The electron can jump from
reasons :
xy

lower energy t2g orbitals to higher energy eg orbitals (d–d (i) Their partially empty d-orbitals provide surface area for
transition) by absorption of light of some particular reactant molecules.
wavelength from visible light. The remainder light is emitted
as coloured light and the compound appears coloured. (ii) They combine with reactant molecules to form transition
(ii) In a transition series the element with maximum oxidation states and lowers their activation energy.
state occurs in or near the middle of the transition series
and maximum oxidation state exhibited is equal to sum of (iii) They show multiple oxidation states and by giving
(n – 1) d and ns electrons. In Mn (3d5 4s2) the sum of electrons to reactants they form complexes and lower their
(n – 1) d and (ns) electron is 7 and therefore it exhibits energies.
maximum o.s. of + 7. The lesser no. of oxidation states on
extreme ends are either due to too few electrons to lose or (b) The melting point of chromium groups elements have the
share or too many d-electrons so that fewer orbitals are
available to share electrons with others. highest melting points in their respective serves due to
presence of strong intermetallic bonds (formed by valence
Example - 56 electrons and covalent bonds formed due to d–d
Explain: overlapping of impaired d-elelctrons.)
(i) CrO42– is a strong oxidizing agent while MnO42– is (c) Their colour due to the presence of incomplete d-subshell.
not.
The electrons can be excited from one energy lavel to
(ii) Zr and Hf have identical sizes. another with in the d-subshell. The energy required to
(iii) The lowest oxidation state of manganese is basic cause such d–d promotions or transition falls within the
while the highest is acidic. visible range for all transition elements. When white light
falls on an ion or compound, some of its wave lengths are
(iv) Mn (II) shows maximum paramagnetic character
amongst the divalent ions of the first transition absorbed due to d–d transition and others are reflected.
series. Therefore, coloure of the transition metal ion is that of the
reflected light.
Sol.
(i) CuF2 and CCl2 compounds will be coloured because they
incompletely filled d-orbitals and unpaired electrons, they
 D & F BLOCK 33

Example - 58
Example - 60
Give reasons :
What happens when ?
(i) Among transition metals, the highest oxidation state
(i) Ferric chloride is added to potassium ferrocyanide.
is exhibited in oxoanins of a metal.

(ii) Ce4+ is used as an oxidising agent in volumetric (ii) Iron reacts with cold dilute nitric acid.
analysis. (iii) Potassium ferricyanide is added to ferrous sulphate.
(iii) Transition metals form a number of interstitial
(iv) Excess of potassium iodide is added to mercuric
compounds.
chloride.
(iv) Zn2+ salts are white while Cu2+ salts are blue.
(v) Green vitriol is strongly heated.
Sol.
(vi) Silver chloride is treated with aqueous sodium
(i) Highest oxidation state is shown in flourides and oxides
because F2 and O2 are strong oxidising agents. cyanide and the product thus formed is allowed to
react with zinc in alkaline medium.
(ii) Ce4+ = [Xe], 4f0, 5d0, 6s0
Ce4+ has the tendency to accept one electron to get the +3 (vii) Zinc oxide is treated with excess of sodium hydroxide
oxidtion state, hence Ce4+ is a good oxidising agent. solution.
(iii) In these compounds small size atoms like hydrogen,
(viii) Ammonium thiocyanate is added to ferric chloride
carbon, nitrogen, boron, etc. occupy the empty space of
solution.
metal lattice (interstices). The small entrapped atom in the
interstices form the bonds with metals due to which Sol. (i) Prussian blue is formed.
mobility and ductility of the metals decrease, when as
tensile strength increases. Example : steel is the interstitial
compound of iron and carbon. 4FeCl3  3K 4 Fe(CN ) 6  Fe 4 [ Fe(CN ) 6 ]3  12KCl
Prussian blue
(Ferri ferrocyanide)
(iv) In Cu2+ salts (3d9) d–d transition is possible. Therefore
Cu2+ salts are coloured.
(ii) Ammonium nitrate is formed.
In Zn2+ salts (3d10) no. d–d transition is possible due to
completely filled d-orbitals. Hence Zn2+ salts are white. [Fe + 2HNO3  Fe(NO3)2 + 2H] × 4
Example - 59
HNO3 + 8H  NH3 + 3H2O
Write the main differences in lanthanides and actinides.
NH3 + HNO3  NH4NO3
Sol.
4Fe + 10HNO3  4Fe(NO3)2 + NH4NO3 + 3H2O
Lanthanides Actinides
(iii) Ferrous ion is first oxidised to ferric ion while
1. Lanthanides shows +3 1. Actinides show higher
oxidation state only oxidation states such as ferricyanide ion is reduced to ferrocyanide ion. Then,
except in few cases +4, +5, +6, +7 also in ferric ions react with ferrocyanide ions to form
where it is +2 or +4. addition to +3.
Oxidation states exhi- potassium ferric ferrocyanide (Turnbull’s blue).
bited by lanthanides is
never more than +4. Fe2+ + K3 [Fe (CN)6]3–  KFe [Fe(CN)6 ]
(Turnbull 's Blue)
2. Paramagnetic properties 2. Paramagnetic proper-
of lanthanides can be ties are difficult to
easily explained. interpret. (iv) First scarlet precipitate is formed which then dissolves
3. Lanthanides do not form 3. They have a greater in excess of potassium iodide forming a complex.
form complexes. tendency to complex
formation. Even p - HgCl2 + 2KI  HgI2 + 2KCl
complexes are formed
by actinides.
HgI2 + 2KI  K2HgI4
5.
4. 4.
Lanthanides do not form 5. These in higher oxidation
axo ions. states form axo ions. Potassiumtetraiodomercurate(II)
6.
5. Except promethium, 5.
6. Such as Uo22+, NbO+,
these are ion-radioactive PuO22+ etc. (colourless)
 34 D & F BLOCK

(v) When heated strongly, a mixture of gases consisting K2Cr2O7 + 3Na2SO3 + 4H2SO4  K2SO4 + Cr2(SO4)3
of SO2 and SO3 is evolved and a red residue, Fe2O3 is Green
formed. + 3Na2SO4 + 4H2O
[FeSO4.7H2O  FeSO4 + 7H2O] × 2 (ii) When zinc is exposed to moist air, the surface is
affected with the formation of a film of basic zinc
2FeSO4  Fe2O3 + SO2 + SO3
carbonate on it. Due to this zinc becomes dull.
SO3 + H2O  H2SO4 [2Zn + 2H2O + O2  2Zn (OH)2] × 2
2FeSO4.7H2O  Fe2O3 + SO2 + H2SO4 + 13H2O Zn(OH)2 + CO2  ZnCO3 + H2O
Green vitriol Red ZnCO3 + 3Zn(OH)2  ZnCO3.3Zn (OH)2

(vi) AgCl dissolves in KCN forming a complex, potassium 4Zn + 3H2O + CO2 + 2O2  ZnCO3.3Zn(OH)2
argentocyanide. The addition of zinc precipitates Basic zinccarbonate
silver. (iii) Ferrous sulphate is a salt of a weak base and a strong
AgCl + 2KCN  KAg(CN)2 + KCl acid. Thus, its hydrolysis occurs when it is dissolved
in water and solution becomes turbid due to formation
2KAg(CN)2 + Zn  K2Zn(CN)4 + 2Ag of ferrous hydroxide.
Potassium zincocyanide FeSO4 + 2H2O Fe(OH)2 + H2SO4
(vii) ZnO dissolves in NaOH forming sodium zincate. Addition of a small amount of acid shifts the
ZnO + 2NaOH  Na2ZnO2 + H2O equilibrium towards left and thus prevents hydrolysis.
(iv) On addition of NaOH, a white precipitate of Zn (OH)2
(viii) Deep red colouration due to the formation of a complex is formed which dissolves in excess of NaOH forming
is developed. sodium zincate.
ZnCl2 + 2NaOH  Zn(OH)2 + 2NaCl
FeCl3 + NH4CNS  Fe(CNS)Cl2 + NH4Cl
Zn (OH)2 + 2NaOH  Na2ZnO2 + 2H2O
or FeCl3 + 3NH4CNS  Fe(CNS)3 + 3NH4Cl Soluble

Example - 61 (v) NH 4OH is a weak hydroxide. It ionises slightly

furnishing OH– ions. However, the OH – ions are
Explain the following :
sufficient to cause the precipitation of Zn(OH)2 as its
(i) Acidified K 2 Cr 2 O 7 solution turns green when solubility product is exceeded.
sodium sulphite is added to it. ZnSO4 + 2NH4OH  Zn(OH)2 + (NH4)2SO4
(ii) Zinc becomes dull in moist air. white ppt.
In presence of NH4Cl, the ionisation of NH4OH is
(iii) A little acid is always added in the preparation
further suppressed and sufficient OH– ions are not
of aqueous ferrous sulphate solution.
available to cause precipitation as the solubility
(iv) The addition of NaOH solution to a solution of zinc product is not exceeded.
chloride produces a white precipitate which (vi) Zinc is cheaper as well as stronger reducing agent in
dissolves on further addition of NaOH. comparison to copper.
(v) The addition of NH 4 OH to ZnSO 4 solution Zn + 2[Ag(CN)2]–  2Ag + [Zn(CN)4]2–
produces white precipitate but no (vii) Copper sulphate dissolves in the ammonium hydroxide
precipitate is formed if it contains NH4Cl. due to formation of a copper complex. Ferrous sulphate
reacts with NH4OH to form insoluble Fe(OH)2. It does
(vi) Zinc and not copper is used for the recovery of silver not form any complex with NH4OH.
from complex [Ag(CN)2]–. CuSO4 + 4NH4OH  [Cu(NH3)4]SO4 + 4H2O
(vii) Copper sulphate dissolves in NH 4OH solution Deep blue solution
FeSO4 + 2NH4OH  Fe(OH)2 + (NH4)2SO4
but FeSO4 does not.
Insoluble
(viii) Copper hydroxide is soluble in ammonium (viii) Cu(OH)2 dissolves in NH4OH by forming a complex.
hydroxide but not in sodium hydroxide. Cu(OH)2 + 4NH4OH  [Cu(NH3)4] (OH)2 + 4H2O
Cu(OH)2 is insoluble in NaOH as no such complex is
Sol. (i) Na2SO3 is a reducing agent. It reduces acidified K2CrO7 formed.
to chromic sulphate which is green in colour.
K2Cr2O7 + 4H2SO4  K2SO4 + Cr2(SO4)3 + 4H2O + 3 [O]
[Na2SO3 + [O]  Na2SO4] × 3
 D & F BLOCK 35

Example - 62 Reactions :

A metal chloride (x) shows the following reactions : FeSO 4 .7H 2 O 
Heat
7H 2 O
 FeSO4 
Heat
 Fe 2 O3  SO 2  SO3
(A) (B) (C) (D)
Blackish
(a) When H2S is passed in an acidified solution of (x) a brown powder
black precipitate is obtained.
(b) The black precipitate is not soluble in ammonium Fe2O3  6HCl 
 2FeCl3  3H 2O
(B) (E)
sulphide. Yellow solution

(c) The solution of stannous chloride is added to an

aqueous solution of (x), a white precipitate is 2FeCl3  H 2S 
 2FeCl2  2HCl  S
(G) (F)
White
obtained which turns grey on addition of more Apple
green solution turbidity
stannous chloride.
(d) When aqueous solution of KI is added to an aqueous FeCl3  3CNS 
 Fe(CNS)3  3Cl
solution of (x), a red precipitate is obtained which (E) Blood red
coloured solution
dissolves on addition of excess of KI.
Example - 64
Identify (x) and write down the equations for the
reactions. (i) A black mineral (A) on treatment with dilute sodium
Sol. The acidified solution of (x) gives a black sulphide with cyanide solution in presence of air gives a clear
H2S indicates that the chloride is of a basic cation of second solution of (B) and (C).
group. The sulphide in insoluble in ammonium sulphide, (ii) The solution (B) on reaction with zinc gives
hence, the cation belongs to IIA group of mixture analysis. precipitate of a metal (D).
It gives white precipitate with SnCl2 which turns to grey (iii) (D) is dissolved in dilute HNO3 and the resulting
in excess of SnCl2 suggests that (x) is HgCl2. It is further solution gives a white precipitate (E) with dilute HCl.
confirmed by the reaction with KI. (iv) (E) on fusion with sodium carbonate gives (D).
Reactions : (v) (E) dissolves in ammonia solution giving a colourless
HgCl2 + H2S  HgS + 2HCl solution of (F). Identify (A) to (F) and give chemical
Black equations for reactions at steps (i) to (v).
2HgCl2 + SnCl2  Hg2Cl2 + SnCl4
Sol. On the basis of the given data, the black mineral (A) is
white
silver glance, Ag2S. It is confirmed by the following :
Hg2Cl2 + SnCl2  2Hg + SnCl4 (i) It dissolves in sodium cyanide solution in presence of
Grey air.
HgCl2 + 2KI  HgI2 + 2KCl
Ag2S + 4NaCN + 2O2  2[NaAg(CN) 2 ]  Na 2SO 4
Red ppt. Sodium Sodium
argento cyanide sulphate
HgI2 + 2KI  K2HgI4 (B) (C)

Soluble
Example - 63 (ii) 2[NaAg(CN) 2 ]  Zn  Na 2 Zn(CN) 4  2Ag
(B) (D)

A certain inorganic compound (A) on heating loses its

water of crystallisation. On further heating, a blackish (iii) 3Ag  4HNO3  3AgNO3  NO  2H 2 O
(D)
brown powder (B) and two oxides of sulphur (C and D)
are obtained. The powder (B) on boiling with hydrochloric AgNO3  HCl  AgCl  HNO3
(E)
acid gives a yellow solution (E). When H2S is passed in
(E), a white turbidity (F) and apple green solution (G) are 1
obtained. The solution (E) on treatment with thiocyanate (iv) 2AgCl Na 2 CO3  2Ag  2NaCl  CO 2  O 2
(E) (D) 2
ions gives a blood red coloured compound (H). Identify
the compounds from (A) to (H). AgCl  2NH 4 OH  Ag(NH 3 ) 2 Cl  2H 2 O
(v) (E) (F)
Colourless solution
Sol. The compound (A) on strong heating gives two oxides of
sulphur, it may be a sulphate. The solution (E) on treatment (A) = Silver glance, Ag2S
with thiocyanate ions gives blood red coloured compound (B) = Sodium argentocyanide, NaAg(CN)2
(H) indicates that the solution (E) consists Fe3+ ions. Thus, (C) = Sodium sulphate, Na2SO4
the compound (A) is ferrous sulphate, FeSO4.7H2O. (D) = Silver metal, Ag
(E) = Silver chloride, AgCl
(F) = Diamminsilver (I) chloride, Ag (NH3)2Cl
 36 D & F BLOCK

EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS

D & F Block (b) electronic configurations

1. Transition elements have (c) atomic weights (d) atomic sizes
(a) completely filled d levels 11. The electronic configuration of chromium is actually
[Ar]3d54s1 instead of normally expected [Ar]3d44s2. This
(b) completely filled s levels and d levels
is because
(c) incompletely filled s levels and completely filled d
(a) an exactly half-filled d level gives additional stability,
levels
according to the Hund rule of maximum multiplicity
(d) incompletely filled d levels
(b) the 4s orbital has higher energy than the 3d orbitals
2. The general electronic configuration of the transition
(c) the 4s orbitals has lower energy than the 3d orbitals
elements is
(d) the 3d and 4s orbitals have equal energies and hence
(a) (n – 1)d10 (n + 1)s2 electron migration occurs readily
(b) (n – 1)d1–10 (n + 1)s1–2 12. Identify the species having an atom in +6 oxidation state.
1–10 6 2
(c) (n – 1)d np ns (a) MnO4 (b) Cr(CN)36 
1–10 0–2
(d) (n – 1)d ns
(c) NiF63  (d) CrO2Cl2
3. Which of the following transition elements has completely
filled d orbitals (the d10 configuration) 13. Which of the following is not true about the transition
elements ?
(a) Co (b) Cr
(a) They show variable oxidation states
(c) Hg (d) Ni
(b) Their ions have a strong tendency to form complexes
4. In which of the following transition elements are the d
orbitals not completely filled ? (c) Their compounds usually do not absorb ultraviolet
and visible lights
(a) Zn (b) Hg
(d) Their ions and complex ions usually possess magnetic
(c) Cd (d) Ag
moments.
5. The electronic configurations of the first four members of
14. What of the following is an incorrect statement?
the actinide series cannot be written accurately in a regular
manner because of (a) The lowest oxide of a transition metal is acidic whereas
the highest one is usually basic.
(a) small difference in energy between 5f and 6d orbitals
(b) A transition metal usually exhibits higher oxidation
(b) large difference in energy between 5f and 6d orbitals
states in its fluorides than it its iodides.
(c) small difference in energy between 5f and 6s orbitals
(c) Transition metal halides become more covalent with
(d) violation of the Pauli exclusion principle the increasing oxidation state of the transition metal
6. The electronic configuration of silver is and are more susceptible to hydrolysis.
(a) [Ar]3d10 4s1 (b) [Ar]4d10 4s1 (d) The highest oxide of a transition metal is acidic whereas
the lowest one is usually basic.
(c) [Kr]4d10 5s1 (d) [Kr]4d8 5s2
15. Which of the following transition metals does not show
7. The electronic configuration of palladium is variable oxidation states ?
(a) [Ar]3d84s2 (b) [kr]4d85s2 (a) Mercury (b) Zinc
(c) [kr]5d86s2 (d) [Ar]4d105s0 (c) Gold (d) Silver
8. The electronic configuration of platinum is 16. Which of the following ions is colourless in solution ?
14
(a) [Ar] 4f 5d 6s 9 1 14
(b) [Ar] 4f 5d 6s 10 2 (a) V3+ (b) Cr3+
(c) [Ar] 4f146d107s2 (d) [Ar] 4f146d97s1 (c) Co2+ (d) Sc3+
9. Transition elements 17. Which of the following ions has the maximum number of
(a) exhibit inert-pair effect unpaired d electrons ?
(b) show nonmetallic character (a) Fe3+ (b) V3+
(c) do not form complex compounds (c) Ti3+ (d) Mg2+
(d) exhibit variable oxidation states 18. Which of the following ions possesses the maximum
10. The oxidation states shown by transition elements is number of unpaired electrons ?
related to their (a) Ni2+ (b) Fe2+
(a) electropositive characters
 D & F BLOCK 37

(c) Cu+ (d) Zn2+ 30. CrO3 dissolves in aqueous NaOH to give
19. Which of the following does not possess unpaired (a) CrO24 (b) Cr(OH)2
electrons ?
(a) Co3+ (b) Cu2+ (c) Cr2O72 (d) Cr(OH)3
(c) Ti2+ (d) Hg2+ 31. Lanthanide elements have
20. Which one of the following ionic species will impart colour (a) similar lattice energies but widely different solvation
to an aqueous solution ? and ionization energies
(a) Ti4+ (b) Cu+ (b) similar lattice and solvation energies but widely
different ionization energies
(c) Zn2+ (d) Cr3+
(c) similar lattice and ionization energies but widely
21. Which of the following elements shows the maximum different hydration energies
number of different oxidation states in its compounds ? (d) similar lattice energies, solvation energies and
(a) Eu (b) La ionization energies
(c) Gd (d) Am 32. Among the transition metals, the melting points of Zn, Cd
22. Which of the following electronic configurations and Hg are relatively low because
represents Fe3+ ? (a) their d shells are not completely filled
(a) [Ar]3d64s2 (b) [Ar]3d54s1 (b) their d electrons do not participate in metallic bonding
(c) [Ar]3d54s2 (d) [Ar]3d54s0 (c) their densities are higher
(d) of all the above
23. The last electron of a d-block element occupies the orbital
33. The noble character of platinum and gold is favoured by
(a) (n – 1)d (b) nd
(a) high enthalpies of sublimation, high ionization
(c) np (d) (n – 1)s
energies and low enthalpies of solvation
24. Which of the following ions is expected to the coloured
(b) high enthalpies of sublimation, low ionization energies
in solution ?
and low enthalpies of solvation
(a) Cu+ (b) Cu2+ (c) low enthalpies of sublimation, high ionization energies
(c) Ti4+ (d) Sc3+ and low enthalpies of solvation
25. Which of the following compounds is expected to be (d) high enthalpies of sublimation, high ionization
coloured ? energies and high enthalpies of solvation
(a) Ag2SO4 (b) CuF2 34. The transition elements are
(a) more reactive than group 1 elements
(c) MgF2 (d) CuCl
(b) more reactive than group 2 elements
26. The covalent radii of transition metals decrease from left
to right in a period because (c) less reactive than group 1 elements but more reactive
than group 2 elements
(a) the densities of the metals decrease with increasing
atomic number due to poor shielding of electrons (d) less reactive than group 1 and 2 elements
(b) the screening of nuclear charge by d electrons is poor 35. Transition metals
and hence the nuclear charge attracts all the electrons (a) form only ionic compounds
strongly, causing a decrease in size (b) form exclusively covalent compounds
(c) the ionization energies also decrease correspondingly (c) may form either ionic or covalent compounds
(d) the metallic character decreases as the atomic number depending on the condition
increases (d) exclusively form coordination compounds but no
27. The highest possible oxidation state shown by osmium simple compounds
in its compounds is 36. Which of the following statements is incorrect ?
(a) +4 (b) +8 (a) The compounds formed by the 3d transition metals in
(c) +6 (d) +10 lower valence states are ionic but those in higher
28. Which of the following oxides of chromium is amphoteric valence states are covalent.
in nature ? (b) The 4d and 5d transition metals form less ionic
(a) CrO (b) CrO3 compounds than do the 3d transition metals.
(c) The compounds formed by the 3d transition metals
(c) Cr2O3 (d) CrO5 are less ionic than the corresponding compounds
29. Permanent magnetic are generally made from the alloy of formed by the 4d and 5d transition metals.
(a) Co (b) Zn (d) The ionization energies of 3d, 4d and 5d transition
(c) Al (d) Pb metals are greater than those of group 1 and 2 metals.
 38 D & F BLOCK

37. Which of the following compounds is colourless? (b) Because of lanthanide contraction, the radii of the
(a) K2MnO4 (b) HgI2 third-row elements are almost the same as those of the
first-row elements.
(c) ZnSO4 (d) FeSO4 (c) Because of lanthanide contraction, the radii of the
38. The compound ZnSO4 is white because third-row elements are almost the same as those of the
(a) charge is transferred from the metal to the oxygen second-row elements.
atoms (d) Because of lanthanide contraction, the separation of
(b) electron transfer to d level does not occur as the level second-row elements from one another is easier.
is already filled to capacity in zinc 48. Sodium chromate is prepared by
(c) Zn2+ has d10 configuration and d–d transition occurs (a) fusing chromite (FeCr2O4) with sodium chloride in air
easily (b) fusing chromite (FeCr2O4) with sodium hydroxide in
2+
(d) Zn ions absorb light of the visible range air
39. Which of the following compounds is green in colour ? (c) fusing (NH4)2Cr2O7 with sodium hydrogen sulphate
in nitrogen
(a) KMnO4 (b) (NH4)2Cr2O7
(d) fusing sodium dichromate with carbon
(c) MnO2 (d) K2MnO4 49. When hydrogen peroxide is added to an acidic solution
40. 2
Cr2O reacts with OH as – of a dichromate, the most probable product is
7
(a) K2CrO4 (b) CrO3
Cr2O72  2(OH )  2CrO24  H2O
(c) Cr2O3 (d) CrO(O2)2
The change in oxidation number of Cr is
50. Which of the following statements is incorrect for CrO3 ?
(a) +6 (b) +3
(a) It is a bright orange solid.
(c) zero (d) +4 (b) It is commonly called chromic acid.
41. CrO 24  reacts with H+ as (c) It is prepared by adding concentrated H2SO4 to a
saturated solution of sodium dichromate.
2CrO24  2H  Cr2O72   H2O
(d) The colour arises due to d–d transition.
The change in oxidation number of Cr is 51. Chromyl chloride, CrO2Cl2, is prepared by heating a mixture
(a) +5 (b) +7 of
(c) +6 (d) zero (a) NaCl, K2Cr2O7 and NaOH
42. Which of the following ions is paramagnetic ? (b) NaCl, K2Cr2O7 and concentrated H2SO4
(a) Zn2+ (b) N3– (c) NaCl, K2Cr2O7 and MnO2
(c) Mn4+ (d) Cu+ (d) CrO3 and NaCl
43. Which of the following ions is diamagnetic ? 52. Deep red-yellow vapour of CrO2Cl2 is passed into an
(a) Ni2+ (b) Ti4+ aqueous solution of NaOH. The solution turns
(c) Cr3+ (d) Co3+ (a) yellow due to the formation of Na2Cr2O7
44. The value of magnetic moment ( spin only) for Cu2+ in (b) yellow due to the formation of Na2CrO4
CuSO4.5H2O is (c) green due to the formation of CrCl3
(a) 5.92 BM (b) 4.92 BM (d) red due to the formation of Na2CrO4
(c) 2.83 BM (d) 1.73 BM 53. Acidified K2Cr2O7 on treatment with KI produces
45. For a given ion, the magnetic moment is 2.83 BM. The (a) KIO3 (b) I2
total spin (s) of all the unpaired electrons is
(a) 2 (b) 1 (c) KIO4 (d) I3
(c) 3/2 (d) 1/2 54. Na2CrO4 on treatment with lead acetate gives a precipitate.
46. The transition metals sometimes form nonstoichiometric This precipitate is dried and the solid is used as a pigment
compounds. These compounds have for road signs and markings. The solid is known as
(a) definite structures and definite proportions (a) white lead (b) chrome green
(b) indefinite structures and definite proportions (c) chrome yellow (d) red lead
(c) definite structures and indefinite proportions 55. Which of the following oxides of manganese is
amphoteric ?
(d) indefinite structures and indefinite proportions
(a) MnO (b) Mn2O3
47. Which of the following statements is correct ?
(a) The second-row elements have smaller radii than the (c) Mn2O7 (d) MnO2
corresponding third-row ones.
 D & F BLOCK 39
56. Which of the following oxides of manganese is stable as 64. Lanthanides are characterized by the filling of the
well as strongly acidic ? (a) penultimate 4f energy level
(a) MnO2 (b) Mn2O7 (b) antepenultimate 4f energy level
(c) MnO3 (d) Mn2O3 (c) penultimate 3f energy level
57. KMnO4 is manufactured on a large scale by (d) antepenultimate 3f energy level
65. The electronic configuration of cerium is
(a) fusing MnO2 with KOH and then oxidizing the fused
mixture with KNO3 (a) [Xe]4f15d16s2 (b) [Xe]4f25d06s1

(b) fusing MnO2 with Na2CO3 in the presence of O2 (c) [Xe]4f15d26s2 (d) [Xe]4f25d06s2
66. Which of the following statements is correct for the
(c) fusing MnO2 with KOH and KNO3 to form K2MnO4
lanthanoids ?
which is then electrolytically oxidized in an alkaline
solution (a) The 4f electrons do not take part in bonding.
(d) fusing MnO2 with KNO3 and then acidifying the fused (b) The 4f electrons can neither be removed to produce
ions nor be made to take part in crystal field
mixture
stabilization of complexes.
58. MnO4 is prepared by treating a solution containing Mn2+ (c) The 4f electrons in the antepenultimate shell are very
ions with a very strong oxidizing agent such as effectively shielded by the 5s and 5p electrons.
(a) PbO2 (b) C 2O24 (d) All of these
67. The most common and stable oxidation state of a
(c) I2 (d) Fe3+ lanthanide is
59. Which of the following is an incorrect statement ? (a) +II (b) +IV
(a) In a redox reaction in acidic medium, KMnO4 produces (c) +VII (d) +III
Mn2+ ions. 68. The atomic and ionci radii (M3+ ions) of lanthanide
(b) In a redox reaction in strongly alkaline medium, KMnO4 elements decrease with increasing atomic number. This
effect is called
produces MnO24 ions.
(a) lanthanide contraction
(c) In a redox reaction in neutral medium, KMnO4 produces (b) lanthanide expansion
MnO2. (c) actinide contraction
(d) In a redox reaction in alkaline medium, KMnO 4 (d) none of these
produces Mn2O7. 69. Lanthanide contraction occurs because
60. KMnO4 in an acidic medium oxidizes (a) the 4f electrons, which are gradually added, creat a
strong shielding effect
(a) CrO24 to CO2 (b) N2H4 to N2
(b) the 4f orbitals are greater in size than the 3d and 3f
(c) S2O32  to SO24 (d) all of these orbitals
(c) the 5f orbitals strongly penetrate into the 4f orbitals
61. KMnO4 in an acidic medium will not oxidize
(d) the poor shielding effect of 4f electrons is coupled
(a) NO2 (b) SO24 with increased attraction between the nucleus and the
added electrons
(c) HN3 (d) H2O2
70. The hardness, melting point and boiling point of elements
62. Which one of the following oxides of chromium is increase from Ce to Lu because
amphoteric in nature ?
(a) the attraction between the atoms increases as the size
(a) CrO (b) Cr2O3 increases
(c) CrO3 (d) CrO5 (b) the attraction between the atoms decreases as the size
63. The electronic configuration of-block elements is increases
represented by (c) the attraction between the atoms increases as the size
decreases
(a) (n – 2)f1–14 (n – 1)d0–1ns2
(d) the attraction between the atoms remains the same as
(b) (n – 2)f1–14 (n – 1)d0–5ns0–2 the size increases
(c) (n – 2)f1–14 (n – 1)d0–10ns1–2
(d) (n – 2)f1–14 (n – 1)d0–2 (n – 1)s2
 40 D & F BLOCK

EXERCISE - 2 : PREVIOUS YEAR JEE MAINS QUESTION

1. Arrange Ce+3, La+3, Pm+3 and Yb+3 in increasing order 8. Calomel (Hg2Cl2) on reaction with ammonium hydroxide
of their ionic radii. (2002) gives (2005)
(a) Yb+3 < Pm+3 < Ce+3 < La+3
(a) HgO (b) Hg2O
(b) Ce+3 < Yb+3 < Pm+3 < La+3
(c) NH2 – Hg – Hg – Cl (d) Hg NH2 Cl
(c) Yb+3 < Pm+3 < La+3 < Ce+3
(d) Pm+3 < La+3 < Ce+3 < Yb+3 9. The lanthanide contraction is responsible for the fact that
2. When KMnO4 acts as an oxidising agent and ultimately (2005)
forms [MnO4]2–, MnO2 Mn2O3, Mn+2 then the number
(a) Zr and Zn have the same oxidation state
of electrons transferred in each case repectively is (2002)
(a) 4, 3, 1, 5 (b) 1, 5, 3, 7 (b) Zr and Hf have about the same radius
(c) 1, 3, 4, 5 (d) 3, 5, 7, 1 (c) Zr and Nb have similar oxidation state
3. The radius of La3+ (Atomic number of La = 57) is 1.06 Å.
Which one of the following given values will be closest (d) Zr and Y have about the same radius
to the radius of Lu3+ (Atomic number of Lu = 71) ? 10. Which of the following factors may be regarded as the
(2003) main cause of lanthanide contraction ? (2005)
(a) 1.40 Å (b) 1.06 Å
(a) Greater shielding of 5d electrons by 4f electrons
(c) 0.85 Å (d) 1.60 Å
4. Ammonia forms the complex ion [Cu(NH3)4]2+ with (b) Poorer shielding of 5d electrons by 4f electrons
copper ions in alkaline solutions but not in acidic (c) Effective shielding of one of 4f electrons by another in
solutions. What is the reason for it ? (2003)
the subshell
(a) In acidic solutions protons coordinate with ammonia
molecules forming NH4+ ions and NH3 molecules are (d) Poor shielding of one of 4f electron by another in the
not available subshell
(b) In alkaline solutions insoluble Cu(OH)2 is precipitated 11. How many EDTA (ethylenediaminetetraacetic acid)
which is soluble in excess of any alkali molecules are required to make an octahedral complex
(c) Copper hydroxide is an amphoteric substance with a Ca2+ ion ? (2006)
(d) In acidic solutions hydration protects copper ions
5. A red solid is insoluble in water. However it becomes (a) One (b) Two
soluble if some KI is added to water. Heating the red solid (c) Six (d) Three
in a test tube results in liberation of some violet coloured
fumes and droplets of a metal appear on the cooler parts 12. The stability of dihalides of Si, Ge, Sn and Pb increases
of the test tube. The red solid is (2003) steadily in the sequence (2007)
(a) HgI2 (b) HgO
(a) PbX2 << SnX2 << GeX2 << SiX2
(c) Pb3O4 (d) (NH4)2Cr2O7
6. What would happen when a solution of potassium (b) GeX2 << SiX2 << SnX2 << PbX2
chromate is treated with an excess of dilute nitric acid ?
(c) SiX2 << GeX2 << PbX2 << SnX2
(2003)
(a) Cr2O72– and H2O are formed (d) SiX2 << GeX2 << SnX2 << PbX2
(b) CrO42– is reduced to +3 state of Cr 13. Identify the incorrect statement among the following :
(c) CrO42– is oxidized to +7 state of Cr (a) 4f and 5f orbitals are equally shielded.

(d) Cr3+ and Cr2O72– are formed (b) d–Block elements show irregular and erratic chemical
properties among themselves.
7. Heating mixture of Cu2O and Cu2S will give (2005)
(c) La and Lu have partially filled d–orbitals and no other
(a) Cu2SO3 (b) CuO + CuS partially filled orbitals.

(c) Cu + SO3 (d) Cu + SO2 (d) The chemistry of various lanthanoids is very similar.
 D & F BLOCK 41
14. The actinoids exhibit more number of oxidation states in 20. In context of the lanthanoids, which of the following
general than the lanthanoids. This is because (2007) statements is not correct ? (2011)
(a) The 5f orbitals extend further from the nucleus than (a) There is a gradual decrease in the radii of the members
the 4f orbitals with increasing atomic number in the series.
(b) The 5f orbitals are more buried than the 4f orbitals (b) All the member exhibit +3 oxidation state.
(c) There is a similarity between 4f and 5f orbitals in their (c) Because of similar properties the separation of
angular part of the wave function lanthanoids is not easy.
(d) The actinoids are more reactive than the lanthanoids. (d) Availability of 4f electrons results in the formation of
15. Larger number of oxidation states are exhibited by the compounds in +4 state for all the members of the
actinoids than those by the lanthanoids, the main reason series.
being (2007) 21. Iron exhibits +2 and +3 oxidation states. Which of the
(a) 4f orbitals more diffused than the 5f orbitals following statements about iron is incorrect ? (2012)

(b) lesser energy difference between 5f and 6d than (a) Ferrous oxide is more basic in nature than the ferric
between 4f and 5d orbitals oxide.

(c) more energy difference between 5f and 6d than between (b) Ferrous compounds are relatively more ionic than the
4f and 5d orbitals corresponding ferric compounds.

(d) more reactive nature of the actinoids than the (c) Ferrous compounds are less volatile than the
lanthanoids corresponding ferric compounds.

16. Amount of oxalic acid present in a solution can be (d) Ferrous compounds are more easily hydrolysed than
the corresponding ferric compounds.
determined by its titration with KMnO4 solution in the
presence of H2SO4. The titration gives unsatisfactory 22. Which of the following arrangements does not represent
result when carried out in the presence of HCl, because the correct order of the property stated against it ?
HCl (2008) (2013)
(a) gets oxidised by KMnO4 to chlorine (a) V 2  Cr 2  Mn 2  Fe2 : paramagnetic behaviour
(b) furnishes H+ ions in addition to those from oxalic acd (b) Ni 2  Co 2  Fe2  Mn 2 : ionic size
(c) reduces permanganate to Mn2+
(c) Co3  Fe3  Cr 3  Sc3 : stability in aqueous solution
(d) Oxidises oxalic acid to carbon dioxide and water
(d) Sc  Ti  Cr  Mn : number of oxidation states
17. Knowing that the chemistry of lanthanoids (Ln) is
dominated by its +3 oxidation state, which of the 23. The color of KMnO4 is due to : (2015)
following statements is incorrect ? (2009)
(a) L  M charge transfer transition
(a) The ionic size of Ln (III) decrease in general with
increasing atomic number (b)    * transition
(b) Ln (III) compounds are generally colourless. (c) M  L charge transfer transition
(c) Ln (III) hydroxide are mainly basic in character. (d) d – d transition
(d) Because of the large size of the Ln (III) ions the bonding 24. Which of the following compounds is metallic and
in its compounds is predominantly ionic in character. ferromagnetic ? (2016)

18. The correct order of E o 2+ values with negative sign (a) CrO2 (b) VO2
M /M
(c) MnO2 (d) TiO2
for the four successive elements Cr, Mn, Fe and Co is
(2010) 25. In the following reactions, ZnO is respectively acting as
a/an (2017)
(a) Mn > Cr > Fe > Co (b) Cr > Fe > Mn > Co
(i) ZnO + Na2O 
 Na2ZnO2
(c) Fe > Mn > Cr > Co (d) Cr > Mn > Fe > Co
19. The outer electron configuration of Gd (At. No. 64) is (ii) ZnO + CO2 
 ZnCO2
(2011) (a) base and acid (b) base and base
(a) 4f3 5d5 6s2 (b) 4f8 d0 6s2 (c) acid and acid (d) acid and base
(c) 4f4 5d4 6s2 (d) 4f7 5d1 6s2
 42 D & F BLOCK

JEE MAINS ONLINE QUESTION 7. A pink coloured salt turns blue on heating. The presence
of which cation is most likely? Online 2015 SET (1)
(a) Co2+ (b) Cu2+
1. Which of the following is not formed when H2S reacts
(c) Zn2+ (d) Fe2+
with acidic K2Cr2O7 solution? Online 2014 SET (1)
(a) CrSO4 (b) Cr2(SO4)3 8. Which one of the following species is stable in aqueous
(c) K2SO4 (d) S solution Online 2016 SET (1)
2. Consider the following equilibrium (a) Cr2+ (b) Cu+

AgCl + 2NH3  [Ag (NH3)2]+ + Cl– (c) MnO34 (d) MnO24
White precipitate of AgCl appears on adding which of 9. Sodium extract is heated with concentrated HNO3 before
the following? Online 2014 SET (2) testing for halogens because : Online 2016 SET (2)
(a) aqueous HNO3 (b) aqueous NaCl (a) Silver halides are totally insoluble in nitric acid.
(c) aqueous NH4Cl (d) NH3 (b) Ag 2S and AgCN are soluble in acidic medium.
3. Copper becomes green when exposed to moist air for a
(c) S2 and CN , if present, are decomposed by conc.
long period. This is due to: Online 2014 SET (3)
(a) the formation of a layer of cupric oxide on the surface HNO3 and hence do not interfere in the test.
of copper. (d) Ag reacts faster with halides in acidic medium
(b) the formation of basic copper sulphate layer on the 10. Which of the following ions does not liberate hydrogen
surface of the metal gas on reaction with dilute acids ?
(c) the formation of a layer of cupric hydroxide on the Online 2017 SET (2)
surface of copper.
(a) Ti2 (b) V2
(d) the formation of a layer of basic carbonate of copper
on the surface of copper.
(c) Cr 2  (d) Mn2
4. Which one of the following exhibits the largest number
of oxidation states? Online 2014 SET (3) 11. In Wilkinson’s catalyst, the hybridization of central metal
ion and its shape are respectively :
(a) Mn (25) (b) Ti (22)
Online 2018 SET (3)
(c) Cr (24) (d) V (23)
3
(a) sp d, trigonal bipyramidal
5. Which of these statements is not true ? B is always
covalent in its compunds Online 2014 SET (4) (b) sp3, tetrahedral
(a) In aqueous solution the T1+ ion is much more stable (c) dsp2, square planar
thant Tl (III)
(d) d2sp3, octahedral
(b) LiAlH4 is a versatile reducing agent in organic
synthesis. 12. When XO2 is fused with an alkali metal hydroxide in
presence of an oxidizing agent such as KNO3; a dark
(c) NO+ is not isoelectronic with O2 green product is formed which disproportionates in acidic
(d) None of these solution to afford a dark purple solution. X is :
6. Which of the following statements is false ? Online 2018 SET (3)
Online 2015 SET (1) (a) Ti (b) V
(a) Na2Cr2O7 is less soluble than K2Cr2O7 (c) Cr (d) Mn

(b) Na2Cr2O7 is primary standard in volumetry

(c) CrO24 is tetrahedral in shape

(d) CrO27 has a CrOCr bond

 D & F BLOCK 43

EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS

1. All questions marked “S” are single choice questions

2. All questions marked “M” are multiple choice questions
3. All questions marked “C” are comprehension based questions
4. All questions marked “A” are assertion–reason type questions
(A) If both assertion and reason are correct and reason is the correct explanation of assertion.
(B) If both assertion and reason are true but reason is not the correct explanation of assertion.
(C) If assertion is true but reason is false.
(D) If reason is true but assertion is false.

8. (S) When steam is passed over red hot iron, the substances
D & F Block formed are :
1. (S) Chemically philosopher of wool is :
(a) Fe2O3 + H2 (b) Fe3O4 + H2
(a) ZnO (b) BaO
(c) FeO + H2 (d) FeO + H2 + O2
(c) HgCl (d) Hg2Cl2
9. (S) Verdigris is :
2. (S) Boiling CuCl2 with Cu in conc. HCl gives :
(a) Basic copper acetate
(a) CuCl (b) CuCl2 (b) Basic lead acetate
(c) H[CuCl2] (d) Cu2Cl (c) Basic lead
3. (S) Thermal decomposition of zinc nitrate give : (d) None
(a) Zn (b) ZnO 10. (S) Which of the following is the correct formula for a
compound of scandium and oxygen ?
(c) Zn(NO3)2 (d) NO
(a) Sc2O (b) ScO
4. (S) Malachite and azurite are used respectively are :
(a) Blue and green pigment (c) Sc3O2 (d) Sc2O3

(b) Red and green pigment 11. (S) Mercury on heating with aqua-regia gives :

(c) Green and blue pigment (a) Hg(NO3)2 (b) HgCl2

(d) Green and red pigment (c) Hg(NO2)2 (d) Hg2Cl2

5. (S) Mercury is transported in the containers made of : 12. (S) Chloroplatinic acid is :
(a) Ag (b) Pb (a) monobasic (b) dibasic
(c) Al (d) Fe (c) tribasic (d) tetrabasic
6. (S) Calomel is the name of : 13. (S) Fe is made passive by :

(a) HgCl2 (b) Hg2Cl2 (a) dil. H2SO4 (b) dil. HCl

(c) HgCl2 + Hg (d) Hg2Cl2 + Hg (c) conc. HNO3 (d) conc. H2SO4
7. (S) ZnO shows yellow colour on Heating due to : 14. (S) Na2CO3 + Fe2O3  A +CO2 what is A in the reaction ?
(a) d-d transition (b) C-T spectra (a) NaFeO2 (b) Na3FeO3
2+
(c) Higher polarisation caused by Zn ion (c) Fe3O4 (d) Na2FeO2
(d) F-centres
 44 D & F BLOCK

15. (S) Ferrous sulphate on heating gives : (W)  HNO3  Y  NO  H2O
(a) SO2 and SO3 (b) SO2 only
(Y)  Na 2S2O3 (excess) (Z)  NaNO3
(c) SO3 only (d) H2S only
Identify (W) to (Z).
16. (S) Iron is protected by coating it with a thin layer of :
(a) Cu (b) Zn (a) W = Ag X = N2O Y = AgNO3 Z = Na2[Ag(S2O3)2]

(c) Pb (d) Mg (b) W = Ag2O X=NO Y=AgNO3 Z= Na3[Ag(S2O3)2]

17. (S) The formula of azurite is : (c) W =Ag X = NO2 Y=AgNO3 Z= Na3[Ag(S2O3)2]

(a) CuCO3 . Cu(OH)2 (b) 2CuCO3 . Cu(OH)2 (d) W =Ag2O X= N2 Y=AgNO3 Z=Na[Ag(S2O3)2]

(c) CuCO3 .2Cu(OH)2 (d) CuSO4 .Cu(OH)2 25. (S) The oxidation state of copper changes when aqueous
copper (II) ions react with :
18. (S) Oxide of metal cation which is not amphoteric?
(I) NaOH (aq) (II) Fe(s)
(a) Al3+ (b) Cr3+
(III) KI (aq)
(c) Fe3+ (d) Zn2+
(a) I, II, III (b) II only
19. (S) Philosopher’s wool when heated with BaO at 1100ºC
(c) II, III (d) I only
gives the compound :
26. (S) A blood red colour is obtained when ferric chloride
(a) BaCdO2 (b) Ba + ZnO2 solution reacts with :
(c) BaO2 + Zn (d) BaZnO2 (a) KCN (b) KSCN
20. (S) Gold dissolves in a aqua-regia forming : (c) K4[Fe(CN)6] (d) K3[Fe(CN)6]
(a) Auric chloride (b) Aurous chloride 27. (S) The compound in which nickel has the lowest oxidation
(c) Chloroauric acid (d) Aurous nitrate state is :

21. (S) The solubility of silver bromide in hypo solution is due (a) Ni(CO)4 (b) (CH3COO)2Ni
to the formation of :
(c) NiO (d) NiCl2(PPh3)2
(a) Ag2SO3 (b) Ag2S2O3
28. (S) Spiegeleisen is an alloy of :
– 3–
(c) [Ag(S2O3)] (d) [Ag(S2O3)2] (a) Cu + Zn + Ni (b) Ni + Cr
22. (S) Sodium thiosulphate is used to remove the unexposed (c) Mn + Fe + C (d) Fe + Cr + Ni
AgBr from photographic films by forming a complex. In
this complex of silver, the coordination number of silver 29. (S) HgCl2 is a covalent compound, sparingly soluble in
is : water, the solubility increases by the addition of chloride
ions due to :
(a) 2 (b) 4
(a) common ion effect
(c) 6 (d) 8
23. (S) The false statement about iron (III) hydroxide is that : (b) formation of complex [HgCl4]2–
(c) weakening of Hg – Cl bonds
(a) it is a weaker base than Fe(OH)2
(d) strong ion – dipole forces
(b) with concentrated KOH, it forms a complex
K3[Fe(OH)6] 30. (S) Silver nitrate solution is kept in brown bottles in
laboratory because :
(c) it gradually loses water and transforms into Fe2O3
(a) it reacts with ordinary white bottles
(d) it exhibits amphoteri properties with acid ones
predominating (b) brown bottles cut the passage of light through


(c) brown bottles do not react with it
24. (S) AgNO3  (W)  (X)  O2
(d) ordinary bottles catalyse its decomposition
(X)  H2O  HNO2  HNO3
 D & F BLOCK 45
31. (S) Copper is very slowly oxidised on the surface in moist 37. (S) Mercury is the only metal which is liquid at 0ºC. This is
air, giving a green coating of verdigris. Verdigris is : due to its :
(a) Cu2O (b) CuCO3 (a) Very high ionisation energy and weak metallic bond

(c) Cu(CH3COO)2 . Cu(OH)2 (b) Low ionisation potential

(d) CuSO4 (c) High atomic weight

(d) High vapour pressure
32. (S) Fe(OH)2 is precipitated from Fe(II) solutions as a while
solid but turns dark green and then brown due to the 38. (S) A white precipitate of AgCl dissolves in excess of :
formation of :
(I) NH3 (aq) (II) Na2S2O3
(a) Fe(OH)2 and Fe(OH)3
(III) NaCN
(b) only Fe(OH)3
(a) III only (b) I, II, III
(c) Fe2O3 . (H2O)n (d) Fe2O3 . 2H2O
(c) I, II (d) I only
33. (S) Give the correct order of initials T or F for following
39. (S) Which of the following statements regarding copper
statements. Use T if statement is true and F if it is false.
salts is not true ?
(I) Sulphide ions reacts with Na2 [Fe(CN)5(NO)] to
(a) Copper (I) disproportionates to copper and copper
form a purple coloured compound Na4 [Fe(CN) 5 (II) ion in aqueous solution
(NOS)]. In the reaction, the oxidation state of iron
changes . (b) Copper (I) can be stablished by the formation of
(II) Pt(IV) compounds are relatively more stable than insoluble complex compounds such as CuCl2 and
NI(IV) compounds Cu(CN)2
(III) The welding of magnesium can be done in the
(c) Copper (II) oxide is red powder
atmosphere is Helium
(d) The water of crystallization of copper sulphate is
(IV) LiAlH4 on hydrolysis will give H2 five
(a) FFTT (b) FTTT 40. (S) Zinc (II) ion on reaction with NaOH first give a white
(c) TFTF (d) TFTT precipitate which dissolves in excess of NaOH due to
the formation of :
34. (S) Sodium thiosulphate, Na 2S 2O 3 . 5H 2O is used in
photography to : (a) ZnO (b) Zn(OH)2
(a) Reduce the silver bromide to metallic silver (c) [Zn(OH)4]2– (d) [Zn(H2O)4]2+
(b) Convert the metallic silver to silver salt 41. (M) Mercury is a liquid at 0ºC because of :
(c) remove undercomposed AgBr as soluble silver (a) very high ionisation energy
thiosulphate complex
(b) weak metallic bonds
(d) remove reduced silver
(c) high heat hydration
35. (S) When AgNO3 comes in contact with skin, it leaves a
black stain. This is because of : (d) high heat of sublimation

(a) HNO3 prorduced by hydrolysis of AgNO3 42. (M) An element of 3d-transition series shown two oxidation
states x and y, differ by two units then:
(b) AgOH produced by hydrolysis of AgNO3
(a) compounds in oxidation state x are ionic if x > y
(c) Its reduction of silver
(b) compounds in oxidation state x are ionic if x < y
(d) Its oxidation to silver oxide
(c) compounds in oxidation state y are covalent if x < y
36. (S) Mark the correct statements :
(d) compounds in oxidation state y are covalent if y < x
(a) Hg forms an amalgam with iron
43. (M) The metal oxide which decomposes on heating is/are :
(b) Hg vapour is non-poisonous
(a) ZnO (b) Al2O3
(c) Hg is monovalent in mercurous compound
(d) Oxysalts of mercury are thermally unstable (c) Ag2O (d) HgO
 46 D & F BLOCK

44. (M) Which of the following acids attack(s) on copper and 50. (A) Assertion : Melting point of Mn is more than that of Fe.
silver ?
Reason : Mn has higher number of unpaired e– than Fe
(a) dilute HNO3 (b) dilute HCl in atomic state.
(c) conc. H2SO4 (d) aqua regia (a) A (b) B
45. (M) Identify the correct statements : (c) C (d) D
(a) Iron belongs to first transition series of the periodic 51. (A) Assertion : Cu+ has less stable than Cu2+ but Fe3+ is
table
more stable than Fe2+.
(b) The purest form of commerical iron is wrought iron
Reason : Half filled and completely filled subshells are
(c) Anhydrous ferrous sulphate is called as yellow vitriol more stable.
(d) Iron is the most abundant transition metal (a) A (b) B
46. (M) Which statements about mercury are correct?
(c) C (d) D
(a) Hg is a liquid metal
52. (A) A s s e r t i o n : Zn gives H2 gas with dil. HCl and also with
(b) Hg forms two series of salts
dil. H2SO4.
(c) Hg forms no amalgam with iron and platinum
Reason : NO3 ion is reduced in preference to hydronium
(d) Anhydrous Hg does not show variable valency
ion.
47. (M) To an acidified dichromate solution, a pinch of Na2O2 is
added and shaken. What is observed? (a) A (b) B

(a) Blue colour (c) C (d) D

(b) Orange colour changing to green 53. (A) Assertion : KMnO4 has different equivalent weights in
(c) Copious evolution of oxygen acid, neutral or alkaline medium.

(d) Bluish-green precipitate Reason : In different medium, change in oxidation

number shown by manganese is altogether different.
48. (M) Pick out the correct statement(s) :
(a) A (b) B
(a) MnO2 dissolves in conc. HCl, but does not form
Mn4+ ions (c) C (d) D

(b) Decomposition of acidic KMnO4 is not catalysed 54. (A) Assertion : Cu2+ is more stable than Cu+.
by sunlight Reason : Electrode potential is more important in
2 determining stable oxidation state than electornic
(c) MnO is strongly oxidising and stable only in
4 configuration.
very strong alkali. In dilute alkali, water or acidic
solutions it disproportionates (a) A (b) B

(d) KMnO4 does not act as oxidising agent in alkaline (c) C (d) D
medium
55. (A) Assertion : KMnO4 is purple in colour to charge transfer.
49. (M) Choose correct statement(s) regarding the following
reaction. Reason : There is no electron present in d-orbitals of
manganese in MnO 4 .
Cr2O72 (aq)  3SO32 (aq)  8H 
(a) A (b) B
2Cr 3  (aq)  3SO24 (aq)  4H2O
(c) C (d) D
2
(a) Cr2O 7
is oxidising agent 56. (A) Assertion : CrO3 reacts with HCl to form chromyl
chloride gas.
(b) SO23 is reducing agent
Reason : Chromyl chloride (CrO2Cl2) has tetrahedral
(c) The oxidation number of per ‘S’ atom in 3SO23 is shape.
increase by two (a) A (b) B
2
(d) The oxidation number of per ‘Cr’ atom in Cr2O 7
is (c) C (d) D
decreased by three
 D & F BLOCK 47
57. (A) Assertion : Hg is the only metal which is liquid at 0ºC. (c) Zn3[Fe(CN)6]2 (d) None of these
Reason : It has very high I.P. and weak metallic bond. Comprehension
(a) A (b) B
A certain metal (X) is boiled in dilute HNO3 to give a salt
(c) C (d) D (Y) and an oxide of nitrogen (Z). An aqueous solution
58. (A) Assertion : CuSO4 . 5H2O and FeSO4 . 7H2O are blue of (Y) with brine solution gives a white precipitate (P).
and green colour compounds respectively. When (Y) was treated with Na2S2O3 solution a white
precipitate (Q) was obtained which on standing turns
Reason : Both compounds have their specific colour
to a black compound (R).
due to phenomenon of polarisation of anion.
(a) A (b) B 64. (C) Salt (Y) and the oxide of nitrogen (Z) is

(c) C (d) D (a) AgNO3 + NO2 (b) AgNO3 + NO

59. (A) Assertion : Zn(OH)2 is dissolved in both NH4OH and (c) AgNO3 + N2 (d) AgNO3 + NH3
NaOH solution.
65. (C) The precipitate (Q) formed is
Reason : Both NaOH and NH4OH being basic can
dissolve amphoteric Zn(OH)2. (a) Ag2S (b) Ag2S2O3

(a) A (b) B (c) Ag2O (d) Ag2SO3

(c) C (d) D 66. (C) The compound (R) formed is
60. (A) Assertion : AgNO3 reacts with KCN to form white ppt.
(a) Ag2O (b) Ag
of AgCN. This white ppt. disappears when excess KCN
is added.
(c) Ag2S (d) Ag2SO3
Reason : AgCN decomposes to form silver-carbide and
67. (S) Wilkinson’s catalyst consists of
evolve N2 gas.
(a) (C2H5)3 Al and TiCl4
(a) A (b) B
(c) C (d) D (b) RhCl3 and Ph3P

Comprehension (c) HCo(CO)4

A white substance ‘X’ when heated in a test tube, (d) trans-[(Rh(CO)(H)(PPh3)3]

produces a colourless, odourless gas leaving a residue,
68. (S) Which of the following mixture is known as Fenton’s
yellow when hot and while when cold. The residue was reagent ?
dissolved in dil. HCl, made alkaline with NH4Cl and
(a) FeSO4 + K4[Fe(CN)6] (b) FeSO4 + PdCl2
NH4OH and H2S gas was passed through it. A white.
ppt ‘Y’ was formed. It was dissolved in dil. HCl to give (c) FeSO4 + H2O2 (d) TiCl4 + (C6H5)3P
‘Z’ which on treatment with K4[Fe(CN)6] gave bluish
69. (S) Which of the following is known as Adams catalyst ?
white precipitate.
(a) Pt/PtO (b) V2O5/TiCl4
61. (C) ‘X’ is
(c) Cu/V (d) Pt/Rh
(a) ZnO (b) ZnSO4 . 7H2O 70. (S) Which of the following ores is known as pyrolusite ?
(c) Cu2Cl2 (d) ZnCO3 (a) Fe2O3 (b) SnO2
62. (C) ‘Y’ and ‘Z’ are respectively (c) MnO2 (d) PbS

(a) ZnO, ZnSO4 (b) ZnS, ZnCl2 71. (S) Dilute and slightly alkaline KMnO4 is called

(c) ZnCl2 Zn(OH)2 (d) ZnO, ZnS (a) Fenton’s reagent (b) Lucas reagent
(c) Baeyer’s reagent (d) Tollens reagent
63. (C) Bluish white precipitate formed is

(a) Zn2[Fe(CN)6] (b) K2[Zn(CN)4]

 48 D & F BLOCK

EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTION

Objective Questions (Only one correct option) 10. Amongst the following, the lowest degree of
paramagnetism per mole of the compound at 298 K will be
1. When same amount of zinc is treated separately with
shown by (1988)
excess of sulphuric acid and excess of sodium hydroxide,
the ratio of volume of hydrogen evolved is (1979) (a) MnSO4.4H2O (b) CuSO4.5H2O
(a) 1 : 1 (b) 1 : 2 (c) FeSO4.6H2O (d) NiSO4.6H2O
(c) 2 : 1 (d) 9 : 4 11. The reaction which proceed in the forward direction is
2. Which of the following is the weakest base (1980) (1991)
(a) NaOH (b) Ca(OH)2 (a) Fe2O3 + 6HCl  2FeCl3 + 3H2O
(c) KOH (d) Zn(OH)2 (b) NH3 + H2O + NaCl  NH4Cl + NaOH
3. One of the constituent of German silver is (1980) (c) SnCl4 + Hg2Cl2  SnCl2 + 2HgCl2
(a) Ag (b) Cu
(d) 2CuI + I2 + 4H+  2Cu2+ + 4KI
(c) Mg (d) Al
12. Which one is solder ? (1995)
4. Which of the following dissolves in hot conc. NaOH
solution (1980) (a) Cu & Pb (b) Zn & Cu

(a) Fe (b) Zn (c) Pb & Sn (d) Fe & Zn

(c) Cu (d) Ag 13. Which pair gives Cl2 at room temperature ? (1995)

5. How many unpaired electrons are present in Ni2+ ? (a) HCl (conc) + KMnO4 (b) NaCl + H2SO4(conc)

(1981) (c) NaCl + MnO2 (d) NaCl + HNO3(conc)

(a) 0 (b) 2 14. An aqueous solution of FeSO4, Al2 (SO4)3 and chrome
alum is heated with excess of Na2O2 and filtered. The
(c) 4 (d) 8 materials obtained are :
6. Sodium thiosulphate is used in photography because of
(a) a colourless filtrate and a green residue
its (1981)
(b) a yellow filtrate and a green residue
(a) reducing behaviour
(c) a yellow filtrate and a brown residue
(b) oxidising behaviour
(d) a green filtrate and a brown residue
(c) complex forming behaviour
15. Among the following, the compound that is both
(d) reaction with light
paramagnetic and coloured is (1997)
7. Iron is rendered passive by treatment with concentrated
(a) K2 Cr2O7 (b) (NH4)2(TiCl6)
(1982)
(c) CoSO4 (d) K3[Cu(CN)4]
(a) H2SO4 (b) H3PO4
16. Ammonium dichromate is used in some fireworks. The
(c) HCl (d) HNO3 green coloured powder blown in the air is (1997)
8. In the metallurgy of iron, when limestone is added to the (a) CrO3 (b) Cr2O3
blast furnace, the calcium ion ends up in (1982)
(c) Cr (d) CrO(O2)
(a) slag (b) gangue
17. The number of moles of KMnO4 that will be needed to
(c) metallic calcium (d) calcium carbonate react with one mole of sulphite ion in acidic solution is
9. Zinc–copper couple that can be used as a redcuing agent (1997)
is obtained by : (1984)
2 3
(a) mixing zinc dust and copper gauze (a) (b)
5 5
(b) zinc coated with copper
(c) copper coated with zinc 4
(c) (d) 1
(d) zinc and copper wires welded together 5
 D & F BLOCK 49

18. Which of the following is an organometallic compound ? 26. The pair of compounds having metals in their highest
(1997) oxidation state is (2004)

(a) Lithium methoxide (b) Lithium acetate (a) MnO2, FeCl3 (b) [MnO4]–, CrO2Cl2
(c) Lithium dimethylamide (d) Methyl lithium (c) [Fe(CN)6]3–, [Co(CN)3] (d) [NiCl4]2–, [CoCl4]–
19. Which of the following compounds is expected to be
coloured ? (1997) 27. When I– is oxidised by MnO4– in alkaline medium, I–

(a) Ag2SO4 (b) CuF2 converts into (2004)

(c) MgF2 (d) CuCl (a) IO3– (b) I2

20. In the dichromate anion, (1999)
(c) IO4– (d) IO–
(a) 4 Cr – O bonds are equivalent
(b) 6 Cr – O bonds are equivalent 28. Which of the following pair is expected to exhibit same
colour in solution ? (2005)
(c) all Cr – O bonds are equivalent
(a) VOCl2 ; FeCl2 (b) CuCl2 ; VOCl2
(d) all Cr – O bonds are nonequivalent
(c) MnCl2 ; FeCl2 (d) FeCl2 ; CuCl2
21. On heating ammonium dichromate, the gas evolved is
29. Which of the following will not be oxidised by O3 ?
(1999)
(2005)
(a) oxygen (b) ammonia
(a) KI (b) FeSO4
(c) nitrous oxide (d) nitrogen
22. Amongst the following, identify the species with an atom (c) KMnO4 (d) K2MnO4
in +6 oxidation state (2000) 30. Native silver metal forms a water soluble complex with a
dilute aqueous solution of NaCN in the presence of
(a) MnO4 (b) Cr(CN)3-6
(2008)
2-
(c) NiF6
(d) CrO2Cl2 (a) nitrogen (b) oxygen

23. In the process of extraction of gold. (c) carbon dioxide (d) argon
31. Among the following, the coloured compound is (2008)
Roasted gold ore + CN– + H2O 
O2
[X] + OH–
(a) CuCl (b) K3[Cu(CN)4]
[X] + Zn 
 [Y] + Au (c) CuF2 (d) [Cu(CH3CN)4]BF4
Identify the complexes [X] and [Y] (2003) 32. The colour of light abosrbed by an aqueous solution of
(a) X = [Au(CN)2]–, Y = [Zn(CN)4]2– CuSO4 is (2011)

(b) X = [Au(CN)4]3–, Y = [Zn(CN)6]4– (a) orange-red (b) blue-green

(c) X = [Au(CN)2]–, Y = [Zn(CN)6]4– (c) yellow (d) violet

(d) X = [Au(CN)4]–, Y = [Zn(CN)4]2– 33. Which of the following combination will produce H2
24. When MnO2 is fused with KOH, a coloured compound is gas ? (2018)
formed, the product and its colour is (2003) (a) Fe metal and conc. HNO3
(a) K2MnO4, purple green (b) KMnO4, purple (b) Cu metal and conc. HNO3
(c) Mn2O3, brown (d) Mn3O4, black (c) Au metal and NaCN (aq) in the presence of air
25. (NH4)2Cr2O7 on heating gives a gas which is also given (d) Zn metal and NaOH (aq)
by (2004)
(a) heating NH4NO2 (b) heating NH4NO3
(c) Mg3N2 + H2O (d) Na(comp.) + H2O2
 50 D & F BLOCK

Objective Questions (One or more than one 40. Fe3+ is reduced to Fe2+ by using (2015)
correct option) (a) H2O2 in presence of NaOH

34. Potassium manganate (K2MnO4) is formed when(1988) (b) Na2O2 in water

(a) chlorine is passed into aqueous KMnO4 solution (c) H2O2 in presence of H2SO4

(b) manganese dioxide is fused with KOH in air (d) Na2O2 in presence of H2SO4
(c) formaldehyde reacts with potassium permanganate in Assertion and Reason
presence of strong alkali (A) If both ASSERTION and REASON are true and reason
(d) potassium permanganate reacts with conc. H2SO4 is the correct explanation of the assertion.

35. The aqueous solutions of the following salts will be (B) If both ASSERTION and REASON are true but reason is
not the correct explanation of the assertion.
coloured in the case of (1990)
(C) If ASSERTION is true but REASON is false.
(a) Zn(NO3)2 (b) LiNO3
(D) If both ASSERTION and REASON are false.
(c) Co(NO3)2 (d) CrCl3
(E) If ASSERTION is false but REASON is true.
36. Which of the following alloys contains(s) Cu and Zn ?
(1993) 41. Assertion : To a solution of potassium chromate if a strong
acid is added, it changes its colour from yellow to orange.
(a) Bronze (b) Brass
Reason : The colour change is due to the change in
(c) Gun metal (d) Type metal oxidation state of potassium chromate. (1988)
37. Which of the following statement (s) is/are correct when
(a) A (b) B (c) C
a mixture of NaCl and K2Cr2O7 is gently warmed with
conc. H2SO4 ? (1998) (d) D (e) E

(a) a deep red vapours is formed 42. Assertion : Zn2+ is diamagnetic.

(b) vapours when passed into NaOH solution gives a Reason : The electrons are lost from 4s orbital to form
yellow solution of Na2CrO4 Zn2+. (1998)
(c) chlorine gas is evolved (a) A (b) B (c) C
(d) chromyl chloride is formed (d) D (e) E
38. Which of the following statement (s) is/are correct ?
Fill in the Blanks
(1998)
(a) The electronic configuration of Cr is [Ar] 3d54s1 43. Mn2+ can be oxidized to MnO4– by ........... (SnO2, PbO2,

(Atomic number of Cr = 24) BaO2) (1981)

(b) The magnetic quantum number may have a negative 44. The salts .............. and ............... are isostructural.
value (FeSO 4  7H 2 O, CuSO 4  5H 2 O, MnSO 4  4H 2 O,
(c) In silver atom, 23 electrons have a spin of one type ZnSO4  7H2O) (1990)
and 24 of the opposite type (Atomic number of 45. Fehling’s solution A consists of an aqueous solution of
Ag = 47)
copper sulphate while Fehling’s solution B consists of an
(d) The oxidation state of nitrogen in HN3 is – 3 alkaline solution of ............ (1990)
39. The correct statement(s) about Cr2+ and Mn3+ is (are) 46. The outermost electronic configuration of Cr is ............
[Atomic numbers of Cr = 24 and Mn = 25] (2015) (1994)
(a) Cr2+ is a reducing agent 47. The compound YBa 2 Cu 3 O 7 which show super
(b) Mn3+ is an oxidizing agent conductivity has copper in oxidation state ..........
assuming that the rare earth element Yttrium in its usual
(c) Both Cr2+ and Mn3+ exhibit d4 electronic configuration +3 oxidation state. (1994)
(d) When Cr2+ is used as a reducing agent, the chromium
ion attains d5 electronic configuration
 D & F BLOCK 51

55. Write the balanced chemical equations for the following

True/False reations
48. Copper metal reduces Fe2+ in an acid medium. (1982) (i) A mixture of potassium dichromate and sodium
chloride is heated with concentrated H2SO4.
49. Dipositive zinc exhibit paramagnetism due to loss of two
electrons from 3d orbitals of neutral atom. (1987) (ii) Potassium permanganate is added to a hot solution
of manganous sulphate. (1990)
Subjective Questions 56. Complete and balance the following reaction
50. Complete and balance the following reactions (1983) (NH4)2S2O8 + H2O + MnSO4  ......... + ........... + ..........
(i) Zn + NO3  Zn2+ + NH 4 (1993)
57. Complete and balance the following reactions
(ii) Cr2 O72  C2 H 4O  C2 H 4O2  Cr 3
(i) [MnO4]2– + H+  ......... + [MnO4]– + H2O
51. State the conditions under which the following
preparations are carried out. Give necessary equations (ii) SO2 (aq) + Cr2O72  2H+  ....... + .......+ (1994)
which need not be balanced.
58. Write balanced equations for the following
“Potassium permanganate from manganese dioxide”
(i) Oxidation of hydrogen peroxide with potassium
(1983) permanganate in acidic medium.
52. Show with balanced equations for the reactions when (ii) Reaction of zinc with dilute nitric acid. (1997)
(i) Potassium permanganate interacts with manganese 59. A compound of vanadium has a magnetic moment of
dioxide in presence of potassium hydroxide. 1.73 BM. Work out the electronic configuration of the
(ii) Potassium ferricyanide is heated with concentrated vanadium ion of the compound. (1997)
sulphuric acid. (1985) 60. Give reason : CrO3 is an acid anhydride. (1999)
53. Give reason in one or two sentences.
(B) 
Moist air
 MCl 4 
Zn
(A)
“Most transition metal compounds are coloured.” (1986) 61. white fumes (M=Transition (purple colour)
with pungent smell element colourless)
54. Complete and balance the following reactions
Identify the metal M and hence MCl 4 . Explain the
(i) Mn2+ + PbO2  MnO4– + H2O difference in colours of MCl4 and A. (2005)
(ii) Ag+ + AsH3  H3AsO3 + H+ (1987) 62. In neutral or faintly alkaline solution, 8 moles of
permanganate anion quantitatively oxidize thiosulphate
anions to produce X moles of a sulphur containing
product. The magnitude of X is (2016)

ANSWER KEY
Exercise - 1 (Basic Objective Questions)

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

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

61. (b) 62. (b) 63. (a) 64. (b) 65. (a) 66. (d) 67. (d) 68. (a) 69. (d) 70. (c)
 52 D & F BLOCK

Exercise - 2 (Previous Year JEE Mains Questions)

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

11. (a) 12. (d) 13. (a) 14. (a) 15. (b) 16. (c) 17. (b) 18. (a) 19. (d) 20. (d)

21. (d) 22. (a) 23. (a) 24. (a) 25. (d)

JEE Mains Online

1. (a) 2. (a) 3. (d) 4. (a) 5. (a) 6. (b) 7. (a) 8. (d) 9. (b) 10. (d)
11. (c) 12. (d)

Exercise-3 (Advanced Objective Questions)

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

11. (b) 12. (b) 13. (c) 14. (a) 15. (a) 16. (b) 17. (b) 18. (c) 19. (a) 20. (c)

21. (c) 22. (b) 23. (d) 24. (c) 25. (c) 26. (b) 27. (a) 28. (c) 29. (b) 30. (b)

31. (c) 32. (c) 33. (a) 34. (c) 35. (c) 36. (d) 37. (a) 38. (b) 39. (c) 40. (c)

41. (a,b) 42. (b,c) 43. (c,d) 44. (a,c,d) 45. (a,b,d) 46. (a,b,c,d) 47. (a,c) 48. (a,c)

49. (a,b,c,d) 50. (d) 51. (b) 52. (b) 53. (a) 54. (a) 55. (b) 56. (b) 57. (a) 58. (c)

59. (c) 60. (c) 61. (d) 62. (b) 63. (a) 64. (b) 65. (b) 66. (c) 67. (b) 68. (c)

69. (a) 70. (c) 71. (c)

Exercise - 4 (Previous Year JEE Advanced Questions)

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

11. (a) 12. (c) 13. (a) 14. (c) 15. (c) 16. (b) 17. (a) 18. (d) 19. (b) 20. (b)

21. (d) 22. (d) 23. (a) 24. (a) 25. (a) 26. (b) 27. (a) 28. (b) 29. (c) 30. (b)

31. (c) 32. (a) 33. (d) 34. (b, c) 35. (c,d) 36. (b,c) 37. (a, b, c, d) 38. (a, b, c)

39. (a,b,c) 40. (c,d) 41. (c) 42. (b) 43. PbO2 44. FeSO4.7H2O and ZnSO4.7H2O 45. Rochelle salt

7
46. 3d54s1 47. x   48. False 49. False 62. (0006)
3

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