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JEE (MAIN+ADVANCED)

d & f - BLOCK ELEMENTS


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CONTENT

S.No Pages

1. d & f - Block Elements 2 – 22


2. Exercise-1 23 – 34
3. Exercise-2 (Objective Questions) 35 – 40
4. Exercise-3 (Section-A) 41 – 43
5. Exercise-3 (Section-B) 44
6. Exercise-4 45 – 52
7. Answer Key 53 – 56
d & f-Block Elements

d -BLOCK ELEMENTS
TRANSITION ELEMENTS AND COMPLEXES

They are often called 'transition elements' because


(i) They show's variable oxidation state in their compounds.
(ii) Their outermost (nth) and as well as penultimate (n – 1) shell is incomplete.
(iii) Their position in the periodic table is between s-block and p-block elements

Typically, the transition elements have an incompletelyfilled d-level. Since Zn group has d10 configuration
and are not considered as transition elements but they are d-block elements.

(i) The first transition series : (3d series) involves the filling of 3d orbitals and has 10 elements from
scandium (Z = 21) to zinc (Z = 30)

(ii) The second transition series : (4d series) involves the filling of 4d orbitals and has 10 elements from
ytterium (Z = 39) to cadmium (Z = 48).

(iii) The third transition series : (5d series) involves the filling of 5d orbitals and has 10 elements. The first
element of this series is lanthanum (Z= 57). It is followed by14 elements (lanthanides, involving filling of
4f orbitals). The next nine elements are from hafnium (Z = 72) to mercury (Z = 80)

La Hf Ta W Re Os Ir Pt Au Hg

5d16s2 5d26s2 3
5d 6s
2
5d46s2 5d56s2 5d66s2 5d76s2 5d96s1 5d106s1 5d106s2

(iv) The fourth transition series is incomplete and contains only three elements 89Ac, 104Rf, 105Ha.
Zn (30) is [Ar] 4s23d10 , Cd (48) is [Kr] 5s24d10, Hg (80) is [Xe] 6s2 4f 14 5d10
These elements have completelyfilled (n–1)d subshell in their elementaryas well as ionic state and so are
not true transition metals. Their properties are quite different from those of transition metals.
GENERAL CHARACTERISTICS

(ii) Electronic configuration: (n–1)d1–10ns0–2


Sc Ti V Cr Mn Fe Co Ni Cu Zn
others are
as usual  4s1
3d5
4s1
3d10

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d & f-Block Elements

(a) Metallic Character


(i) All the transition elements are metals, since the number of electrons in the outermost shell is very
small being equal to 2.
(ii) They are hard, malleable and ductile, except Hg which is liquid and soft.
(iii) They exhibit all the three types of structures. Face Centred Cubic ( fcc), Hexagonal Close
packed (hcp) and Body Centred Cubic ( bcc).
(iv) Covalent and Metallic bonding both exist in the atom of transition metals.
(v) The presence of unfilled d- subshell favour covalent bonding, and metallic bonding is due to
possession of one or two electron in outermost energy shell.
(vi) These metals are good conductors of heat and electricity.
(b) Melting and Boiling Points :
(i) The transition elements have very high melting & boiling points as compared to those of s & p
block elements.
(ii) The high melting and boiling point of transition metals are attributed to the stronger force that
bind their atoms together.
(iii) As the number of d- electron increases the number of covalent bond between the atoms are
expected to increase up to Cr- Mo- W family where each of the d- orbital has only unpaired
electrons and the opportunity for covalent sharing is greatest.
(iv) Inspite of presence of five unpaired electrons in Mn, the unexpected low melting and boiling is
due to its complex structure it is unable to form metallic and covalent bonds.
(v) The absence of unpaired electron [ ( n– 1) d10 4s2] in Zn, Cd, & Hg is responsible for its low
melting & boiling point.
Cr
2000 V 1900
Ti 1710
Melting Point t/ºC

1530
1672
1500 Sc Fe 1495Ni
1397 Co 1455
Mn Cu
1244 1083
1000

500 420
Zn
IA II A IIIB IV B V B VIBVIIBVIII IA IIB

Graphic representation m.p. of 3d - series elements


(c) Atomic and Ionic Radii
Elements Sc Ti V Cr Mn Fe Co Ni Cu Zn

Metallic
radii (Aº) 1.62 1.47 1.34 1.27 1.26 1.26 1.25 1.24 1.28 1.38

Reason :
(i) This is due to the fact that an increase in the nuclear charge tends to attract the electron cloud inwards.
(ii) The radii for the elements from Cr to Cu are however very close to one another.
(iii) The simultaneous addition of electron of 3d- level exercises the reverse effect by screening the outer 4s
- electron from the inward pull of the nucleus.

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d & f-Block Elements

(iv) As a result of these two opposing effects, the atomic radii do not alter much on moving from Cr to Cu.
(v) The radii of M2+ ions, although some what smaller than that of Ca2+ ion ( = 0.99 Aº) are comparable
with it.
Oxides of first row transition metals
(i) Basic Oxides : Sc2O3, TiO2, Ti2O3, VO, V2O3, MnO, FeO, Fe2O3, Fe3O4, CoO, NiO, Cu2O.
(ii) Acidic oxides : V2O5, CrO3, Mn2O7.
(iii)Amphoteric oxides : TiO2, VO3, Cr2O3, CrO2, Mn2O3, Mn3O4, MnO2, CuO.

(d) Ionisation Potential


(i) The first ionisation potential of transitional elements lie between those of s & p block elements.
(ii) In case of transition elements the addition of the extra electron in the ( n– 1) d provides a
screening effect which shields the outer ns electron from the inward pull of positive nucleus.
(iii) Thus the effect of increasing nuclear charge & the shielding effect created due to the expansion
of ( n– 1) d orbital oppose each other.
(iv) On account of these counter affects, the ionisation potentials increases rather slowly on the
moving in a period of the first transition series.
(v) The IE1 for the first four 3d - block elements ( Sc, Ti, V & Cr) differ only slightly from one
another.
(vi) Similarly the value of Fe, Co, Ni & Cu also are fairly close to one another.

Ionisation Sc Ti V Cr Mn Fe Co Ni Cu Zn
Potential (ev.)
IE1 6.56 6.83 6.74 7.43 7.43 7.90 7.86 7.63 7.72 9.39
IE2 12.91 13.69 14.26 16.95 15.69 16.21 17.08 18.21 20.34 18.00
IE3 24.79 27.52 29.35 31.0 23.34 30.69 33.54 35.21 36.88 39.78

(e) Oxidation State


Sc Ti V Cr Mn Fe Co Ni Cu Zn
1 1
2 2 2 2 2 2 2 2 2
3 3 3 3 3 3 3 3
4 4 4 4 4 4 4
5 5 5
6 6 6
7

Colour: (aquated)
Sc3+ — colourless Ti4+ — colourless
Ti3+ — purple V4+ — blue
V3+ — green V2+ — violet
Cr2+ — blue Cr3+ — violet
Mn3+ — violet Mn2+ — light pink
Fe2+ — light green Fe3+ — yellow
Co2+ — pink Ni2+ — green
Cu2+ — blue Zn2+ — colourless

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d & f-Block Elements

(f) Relative stability of various oxidation states :


(i) The relative stabilities of various oxidation states of 3d- series element can be correlated with the extra
stability of 3dº, 3d5 & 3d10 configuration to some extent.
Example- Ti4+ ( 3dº) is more stable than Ti 3+ ( 3d1)
Mn2+ ( 3d5) is more stable than Mn3+ ( 3d4).
(ii) The higher oxidation state of 4d and 5d series element are generally more stable than those of the
element of 3d series.
Example -
(a) MoviO42–,TcviiO4–(4d- series element) & Wvi O42–, ReviiO4– ( 5d - series elements) are more stable
and in which the transition element concerned show their maximum oxidation state.
(b) Crvi O42– & Mnvii O4– ( 3d - series) are strong oxidizing agents.
(iii) Strongly reducing states probably do not form fluorides or oxides, but may well form the heavier
halides. Conversely, strong oxidizing state form oxides & fluoride, but not Bromide and Iodide.
Example -
(a) V react with halogens to form VF5, VCl4, VBr3, but doesn’t form VBr5 or VI5 because in + 5 oxidation
state V is strong oxidizing agent thus convert Br– & I– to Br2 & I2 respectively, So VBr3 & VI3 are
formed but not VBr5 & VI5.
(b) On the other hand VF5 is formed because V5+ ion unable to oxidize highly electronegative & small anion
F– .
(c) Similarly highly electronegative and small O2–ion formed oxides eg. VO43–, CrO42– & MnO4– etc.
(iv) All transition elements in their lower oxidation state like to form ionic compounds. Whereas in their
higher oxidation state they generally formed covalent compound.
Example-
+2 +3 +4 +5 +6 +7
TiCl2 TiCl3 TiCl4
VCl2 VCl3 VCl4 VOCl3
(Ionic, Less ionic basic) Amphoteric Covalent &Acidic, (Strong Lewis acid)
TiO Ti2O3 TiO2
VO V2 O 3 V2 O 5
CrO Cr2O3 CrO3
MnO Mn2O3 MnO2 MnO3 Mn2O7

Ionic Less Ionic Acidic


(Basic) (Amphoteric) (Covalent)

Formation of Complexes :
By virtue of their small size, comparatively high nuclear or ionic charge and availability of vacant
d-orbitals of suitable energy, these metals exert strong electrostatic attraction on the ligands. The species
formed on interaction of metal and the ligand (or ligands) is known as a complex.
The transition metal ions form complexes because of the following reasons :
(a) Their small cation size
(b) High effective nuclear charge
(c) Availability of vacant (n-1) d-orbitals of appropriate energy
(d) The structure commonly found in such complex are linear (i.e. co-ordination number, C.N.=2), square
planer (C.N. =4), tetrahedral (CN = 4) or octahedral (CN = 6).

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d & f-Block Elements

Metal ion Ligand C.N. Complex ion

Ag+ NH3 2 [Ag(NH3)2]+


Ni+2 CN – 4 Ni(CN)4]–2
Cu2+ NH3 4 [Cu(NH3)4]+2
Fe+2 CN – 6 [Fe(CN)6]–4

(g) Magnetic properties


* Ti+2 [Ar]3d2, Ti+3 [Ar]3d1. V+2[Ar]3d3, Cr+3[Ar]3d3
As is evident most of the transition metal ions have unpaired electrons in their ‘d’ orbitals. Hence most of
the transition metal ions are paramagnetic in nature. Transition metal ions having 3d0 and 3d10 configura-
tion exhibit diamagnetic nature.
* An unpaired electron spins and as it is a charged particle, magnetic field is created due to its spinning.
* The magnetic moment () created due to spinning of unpaired electrons can be calculated by using
 = n(n  2) : Where ‘n’ is the number of unpaired electrons in the metal ion.
 = Magnetic moment in Bohr Magnetons (B.M.)

Variation of Magnetic moment of 3d- series


Ions Outer Number of Magnetic
with configuration most configuration unpaired electron Moment  B.M.
Sc3+ 3dº 0 0
Ti3+, V4+ 3d1 1 1.75
Ti2+, V3+ 3d2 2 2.86
V2+, Cr3+ 3d3 3 3.86
Cr3+, Mn3+ 3d4 4 4.80
Mn2+, Fe3+ 3d5 5 5.95
Fe2+,Co3+ 3d6 4 5.0 – 5.5
Co2+ 3d7 3 4.0 – 5.2
Ni2+ 3d8 2 2.9 – 3.4
Cu2+ 3d9 1 1.4– 2.2
Zn2+ 3d10 0 0
(h) Formation of Coloured Compounds :
The transition metal ions have unpaired d-electrons, which on absorbing visible light can jump from one
d-orbital to another i.e. intra d-d- transition take place. Thus when light falls certain visible wavelengths
are absorbed. The reflected light appears coloured and gives the colour of compound.
(i) Formation of interstitial compounds
(i) Small non metallic atom such as H, B, C, N etc. are able to occupy interstitial space of the lattice of the
d-block elements to form combinations which are termed interstitial compounds.
(ii) These are non-stoichiometric in nature and do not follow the common rule of valency.
(iii) These interstitial compounds have similar chemical properties as the parent metal but differ appreciably
in their physical properties such as density, hardness and conductivity.

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d & f-Block Elements

(j) Catalytic properties


Many transition metals & their compounds have catalytic properties. Some common examples are-
(a) In some cases the transition metals with their variable valencymayform unstable intermediate compounds.
(b) In other cases the transition metal provide a suitable reaction surface.
Example :
(i) TiCl3 - Used as Ziegler - Natta catalyst in the production of polyethene.
(ii) V2O5 - Convert SO2 to SO3 in the contact process for making H2SO4.
(iii) MnO2 - Used as a catalyst to decompose KClO3 to give O2.
(iv) Fe - promoted iron is used in Haber- Bosch process for making NH3.
(v) FeCl3 - Used for making CCl4 from CS2 & Cl2.
(vi) FeSO4 & H2O2 - Used as Fenton's reagent for oxidizing alcohol to aldehyde.
(vii) Pt.- used as a catalyst in the manufacture of H2SO4.
(viii) Ni - used as a catalyst in the hydrogenation of oils.
(ix) Pt/ PtO- Adams catalyst, used for reduction.
(k) Alloy formation
(i) Transition metals form a large number of alloys.
(ii) d- block elements are quite similar in atomic size, the atom of one metal can substitute the atoms of other
metal in its crystal lattices.
(iii) Thus, on cooling a mixture solution of two or more transition metals, smooth solid, alloys are formed.
(iv) Alloy containing mercury as one of the constituent elements are called amalgams.
(v) The purpose of making alloyis to develop some useful properties which are absent in constituent element
COMPOUNDS OF TRANSITION ELEMENTS
(1) Potassium Dichromate (K2Cr2O7)
(a) Preparation :
(i) It is prepared from Chromite ore (FeCr2O4).
(ii) The preparation of K2Cr2O7 from chromite ore involve the following steps :
(A) Conversion of Chromite ore to Sodium Chromate :
(i) The Chromite ore is fused with Sodium hydroxide or Sodium Carbonate in the presence of air.
(a) 4FeCr2O4 + 16 NaOH + 7O2 8Na2CrO4 +2Fe2O3 + 8 H2O
Chromite ore (Air) Sod. Chromate
(b) 4 FeCr2O4 + 8 Na2CO3 + 7O2  8 Na2CrO4 + 2Fe2O3 + 8 CO2
Sod.Chromate
Sod. Chromite is extracted with water & ferric oxide is left behind.
(B) Conversion of Sodium chromate to Sodium dichromate :
(i) The Sod. chromite is acidified with dilute H2SO4 giving its dichromate
2 Na2CrO4 + H2SO4  Na2Cr2O7 + Na2SO4 + H2O
(dil.) Sod. dichromate
(ii) On concentration, the less soluble sulphate crystallises and is filtered out. The resulting solution
contains Sod. dichromate.
(C) Conversion of Sod. dichromate to Pot. dichromate :
(i) Hot concentrated solution of Na2Cr2O7 with KCl in equimolar proportion

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d & f-Block Elements

Na2Cr2O7 + 2 KCl  K2Cr2O7 + 2 NaCl


Sod.dichromate Pot.dichromate
Properties : It is orange- red crystalline compound having melting point 670 K.
Properties of K2Cr2O7 :
Heated
(i) KOH
K CrO + Cr O + O
2 4 2 3 2

K2CrO4 + H2 O
KHSO4 + CrO3 + H2 O
K2SO4 + Cr2 (SO4)3 + H2 O + O2
+
H ; KI
l2
+ ++
H ; Fe
Fe3+
HCl
–2
Cl2 + KCl + CrCl3 + H2 O
SO2/SO3
K2SO4 + Cr2 (SO4 )3 + H2 O
KCl, H2SO4 (conc.) Heated
CrO2 Cl2 + KHSO4 + H2 O
(ii) Chromyl Chloride Test :
(a) This is the test of Chloride
K2Cr2O7 + 2H2SO4  2 KHSO4 + 2 CrO3 + H2O
NaCl + H2SO4  NaHSO4 + HCl] × 4
CrO3 + 2HCl  CrO2Cl2 + H2O ] × 2

K2Cr2O7 + 6H2SO4 + 4NaCl  2 KHSO4 + 4 NaHSO4 + 2CrO2Cl2 + 3H2O


Chromyl chloride
(b) When Chromyl Chloride vapours are passed through NaOH solution, yellow coloured
solution is obtained.
4 NaOH + CrO2Cl2  Na2CrO4 + 2 NaCl + 2H2O
Chromyl Yellowsolution
Chloride (Sodium Chromate)
(iii) Action with HCl :
K2Cr2O7 + 14 HCl  2 KCl + 2CrCl3 + 7H2O + 3Cl2 
Chlorine
(iv) Oxidising character :
(A) The dichromates act. as powerful oxidizing agent in acidic medium.
K2Cr2O7 + 4 H2SO4  K2SO4 + Cr2 (SO4)3 + 4 H2O + 3 [O]
Nascent oxygen
(B) In term of electronic concept, the Cr2O72– ion take up electron inAcidic medium and
hence acts as an oxidizing agent
Cr2O72– + 14 H+ + 6e–  2Cr3+ + 7H2O
(+ 6) (+3)
Note : Both Na2Cr2O7 & K2Cr2O7 are oxidizing agents but K2Cr2O7 is preferred since it is not
hygroscopic and can be used as primary standard.
(C) Some oxidizing reactions of K2Cr2O7 are :
(a) It liberate I2 from KI
K2Cr2O7 + 4H2SO4  K2SO4 + Cr2 ( SO4)3 + 4 H2O + 3O
2 KI + H2SO4 + O  K2SO4 + H2O + I2 ] × 3
K2 Cr2O7 + 6 KI + 7H2SO4  4 K2SO4 + Cr2(SO4)3 + 7 H2O + 3I2 (Iodine)

or Cr2O72– + 14 H+ + 6I– + 6e–  2 Cr3+ + 7H2O + 3 I2 + 6e–


Cr2O72– + 14H+ + 6I–  2Cr3+ + 3I2 + 7H2O

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d & f-Block Elements

(b) It oxidises ferrous salts to ferric salts.


K2Cr2O7 + 4H2SO4  K2SO4 + Cr2 (SO4)3 + 4H2O+ 3(O)
2 FeSO4 + H2SO4 + O  Fe2(SO4)3 + H2O ] ×3

K2Cr2O7 + 7H2SO4 + 6FeSO4  3Fe2(SO4)3+ K2SO4 + Cr2(SO4)3 + 7H2O


or 6Fe2+ + Cr2O72– + 14 H+  6Fe3+ + 2Cr3+ + 7H2O
(c) It oxidises hydrogen sulphide to sulphur
K2Cr2O7 + 4H2SO4  K2SO4 + Cr2(SO4)3 + 4H2O + 3 [O]
H2S + O  H2O + S ] × 3

K2Cr2O7 + 4H2SO4 + H2S  K2SO4 + Cr2(SO4)3 + 3S + 7 H2O


Sulphur
or H2S + Cr2O7 + 8H+  2Cr3+ + 3S + 7H2O
2–

(d) It oxidises sulphites to sulphates


K2Cr2O7 + 4H2SO4  K2SO4 + Cr2 (SO4)3 + 4H2O + 3(O)
Na2SO3 + O  Na2SO4 ] x 3

3 Na2SO3 + K2Cr2O7 + 4H2SO4  K2SO4 + Cr2 (SO4)3 + 3Na2SO4 + 4H2O


Sod.Sulphite Sod.Sulphate
2– 2– + 2– 3+
or 3SO3 + Cr2O7 + 8H  3SO4 + 2 Cr + 4H2O
(e) SO2 is oxidised to H2SO4
K2Cr2O7 + 4H2SO4  K2SO4 + Cr2 (SO4)3 + 4H2O + 3[O]
SO2+ (O) + H2O  H2SO4 ] x 3

K2Cr2O7 + H2SO4 + 3SO2  K2SO4 + Cr2(SO4)3 + H2O


or Cr2O72– + 3SO2 + 2H+  2Cr3+ + 3SO42– + H2O
Note :
K2Cr2O7+ H2SO4 + 3SO4  K2SO4 + Cr2(SO4)3 + H2O
K2SO4. Cr2 (SO4)3. 24H2O
(Chrome alum)
(f) Similarly, it oxidises, chlorides to chlorine, nitrites to nitrates, arsenites to arsenates
thiosulphate to sulphate and sulphur (S2O32– + O  SO42– + S), HBr to Br2,
H to 2.
(g) It oxidises ethyl alcohol to acetaldehyde and acetic acid
K2Cr2O7 + 4H2SO4  K2SO4 + Cr2(SO4)3 + 4H2O + 3 [O]
CH3CH2OH + [O]  CH3CHO + H2O
EthylAlcohol
CH3CHO + O  CH3COOH
Acetaldehyde

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d & f-Block Elements

Specific test of CrO4 /Cr2O7 2– 2–

R R
O
O O
2– 2– + Ether layer
Acidified CrO4 /Cr2O7 + H2O 2 + H (aq) Cr + H2O
Non-redox
reaction O O O

Blue CrO5 is stable in


org. layer (ether, pyridine)
but unstable in Aq. soln.

Interconversion of yellow CrO42– (aq) into green Cr3+ (aq) :

O +6 O
Cr
) On
SO O O O st
4

2
(Blue)
an
(H
+

din
/H

g
2
H2 O

2–
CrO4 (aq) 3+
Cr (aq) (R.A.)
(yellow) (green)

Structure of Chromate and dichromate ions :

Uses : Potassium dichromate is used :


(i) As a volumetric reagent in laboratory for the estimation of ferrous ions, iodide ions etc.
(ii) For the preparation of chrome yellow (PbCrO4), Chrome red (PbCrO4.PbO), Zinc yellow
(ZnCrO4),Gugrets green (Cr2O3.2H2O), chromic acid (CrO3– orange), K3 [CrO8] (Red brown).

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d & f-Block Elements

(iii) In organic chemistryas oxidising agents.


(iv) In photographyfor hardening gelatine films.
2. Potassium Permanganate (KMnO4) :
Preparation : Potassium Permanganate is prepared from mineral pyrolusite ( MnO2).
The preparation involves the following steps.
(A) Conversion of Pyrolusite ore to Potassium Manganate
(a) The pyrolusite ( MnO2) is fused with caustic potash (KOH) or potassium carbonate in
presence of air to give a green mass due to the formation of potassium manganate.

2 MnO2 + 4 KOH + O2  2K2MnO4 + 2H2O
Pot. Manganate (Green mass)

2 MnO2 + 2K2CO3 + O2  2K2MnO4 + 2CO2
Pot. Manganate ( Green Mass)
(B) Oxidation of Potassium Manganate to Potassium permanganate :
(a) The fused mass is extracted with water and the solution is green (MnO42–). The solution
is treated with Cl2 or ozone (O3) or CO2 to oxidize K2MnO4 to KMnO4.
2K2MnO4 + Cl2  2KCl + 2KMnO4
2K2MnO4 + O3 + H2O  2KMnO4 + 2KOH + O2
2K2MnO4 + 2CO2  2K2CO3 + 2MnO2  + 2KMnO4
Purple
(b) MnO42– can be oxidized to MnO4– electrochemically at anode.
K2MnO4 2K+ + MnO42–
At anode : MnO42–  MnO4– + e–
Green Purple
At cathode : 2H + e  2H  H2
+ –

Properties :
(A) It is a dark violet crystalline solid having a metallic lustre. It has M.P. 523 K.
(B) It is fairlysoluble in water giving a purple solution.
(C) Action of heat

2KMnO4  K2MnO4 + MnO2 + O2 
Pot.Manganate
(D) Action of alkalies :
4 KMnO4 + 4KOH  4K2MnO4 + 2H2O + O2 
Pot.Manganate
(E) Oxidising character : Potassium permanganate act as an oxidizing agent in neutral, alkaline and
acidic solutions.
(a) In Neutral Medium : MnO2 is formed
2KMnO4 + H2O  2KOH + 2MnO2 + 3O
MnO4– + 2H2O + 3e–  MnO2 + 4 OH–
+7 +4

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d & f-Block Elements

Important reactions of Neutral KMnO4


(i) 2 KMnO4 + 3H2S  2KOH + 2 MnO2 + 3S + 2H2O
(ii) It oxidises manganese sulphate to manganese dioxide.
2KMnO4 + 3MnSO4 + 2H2O  5 MnO2 + K2SO4 + 2H2SO4
(iii) It oxidises sodium thiosulphate to sulphate and Sulphur
2KMnO4 + 3Na2S2O3 + H2O  2MnO2 + 3Na2SO4 + 2 KOH + 3S
(b) Alkaline medium :
(i) 2KMnO4 + 2KOH  K2MnO4 + H2O + [O]
2K2MnO4 + 2H2O  2MnO2 + 4KOH + 2[O]
2KMnO4– + H2O alkaline
  2 MnO2 + 2KOH + 3[O]

Important reactions of alkaline KMnO4 :


(i) It oxidises iodides to iodates in alkaline medium
alkaline
2KMnO4 + H2O   2MnO2 + 2KOH + 3[O]
KI + 3[O]  KIO3

or 2KMnO4 + KI + H2O  2MnO2 + 2KOH + KIO3


2MnO4– + I– + H2O  2 MnO2 + IO3— + 2OH–
(ii) Oxidises ethylene to ethylene glycol :
CH2 CH 2  OH
|| + H2O + O  |
CH2 CH 2  OH
Ethylene Glycol
In alkaline medium it is called Bayer' s Reagent

Note : (a) 2KMnO4 + H2SO4  Mn2O7 + K2SO4 + H2O
Excess Conc. (Explosive oil)
(b) Acidic solution :
2KMnO4 + 3H2SO4  K2SO4 + 2MnSO4 + 3H2O + 5O
or 2 MnO4– + 8H+ + 5e–  Mn2+ + 4H2O
Some of the important reactions of acidified KMnO4 are
(i) It oxidises acidified ferrous salt to ferric salts.
2KMnO4 + 10 FeSO4 + 8H2SO4  2MnSO4 + K2SO4 + 5Fe2(SO4)3 + 8H2O

(ii) It oxidises acidified KI to I2


2KMnO4 + 8H2SO4 + 10 KI  6 K2 SO4 + 2MnSO4 + 8H2O + 5I2

(iii) It oxidises H2S to Sulphur


2KMnO4 + 3H2SO4 + 5H2S  2MnSO4 + K2SO4 + 8H2O + 5S.

(iv) It oxidises sulphur dioxide to sulphuric acid


2KMnO4 + 5SO2 + 2H2O  K2SO4 + 2MnSO4 + 2H2SO4

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d & f-Block Elements

(v) It oxidises nitrites to nitrates


2KMnO4 + 3H2SO4 + 5KNO2  K2SO4 + 2MnSO4 + 5KNO3 + 3H2O

(vi) It oxidises oxalates or oxalic acid to carbon dioxide


2KMnO4 + 5C2H2O4 + 3H2SO4  K2SO4 + 2MnSO4 + 10 CO2 + 8H2O

COMPOUNDS OF SILVER

(I) MetallicAg

In the same way in presence of O2, Ag complexes with NaCN / KCN.


4Ag + 8KCN + 2H2O + O2  4K[Ag(CN)2] + 4KOH

AgNO3

Prepn.: already done.


Properties.: (i) It is called as lunar caustic because in contact with skin it produces burning sensation
like that of caustic soda with the formation of finely divided silver (black colour)
(ii) Thermal decomposition:
(iii) Props. of AgNO3 : [Already done in basic radical]
6AgNO3 + 3I2 + 3H2O 5AgI + AgIO3 + 6HNO3
(excess)
(iv) 
Ag2SO4  2Ag + SO2 + O2
(v) Ag2S2O3 + H2O   Ag2S + H2SO4
AgCl . AgBr.AgI (but not Ag2S) are soluble in Na2S2O3 forming
[Ag(S2O3)2]–3 complexes
(vi)  AgBr  + KNO3
AgBr : AgNO3 KBr

Pale yellow
ppt.
Heating effect: 2 AgNO3 212
ºC
 2AgNO2 + O2
2AgNO2 500C
  2Ag + 2NO + O2

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d & f-Block Elements

(viii) Ag2O + H2O2  2Ag + H2O + O2

K2S2O8 + 2AgNO3 + 2H2O  2AgO + 2KHSO4 + 2HNO3

* AgO supposed to be paramagnetic due to d9 configuration. But actually it is diamagnetic and exists as
AgI [AgIIIO2]

COMPOUNDS OF ZINC

ZnO: It is called as phillospher's wool due to its wooly flock type appearance
Preparation: 1] 2Zn + O2  2ZnO

2] ZnCO3  ZnO + CO2

3] 2Zn(NO3)2  2ZnO + 4NO2 + O2

4] Zn(OH)2  ZnO + H2O

Purest ZnO : 4ZnSO4 + 4Na2CO3 + 3H2O  ZnCO3·3Zn(OH)2  + 4Na2SO4 + 3CO2


white basic zinc
carbonate

4ZnO + 3H2O  + CO2 


pure
Properties: 1] ZnO(cold) ZnO(hot)
white yellow
2] It is insoluble in water
3] It sublimes at 400°C
4] It is amphoteric oxide
ZnO + 2HCl  ZnCl2 + H2O
ZnO + H2SO4  ZnSO4 + H2O
ZnO + 2NaOH  Na2ZnO2 + H2O
5] ZnO  Zn by H2 & C
ZnO + H2  400C
 Zn + H2O
ZnO + C  Zn + CO
6] It forms Rinmann's green with Co(NO3)2
2Co(NO3)2  2CoO + 4NO2 + O2
CoO + ZnO  CoZnO2 or CoO·ZnO
Rinmann's green

Uses: (1) As white pigment. It is superior than white lead because it does not turn into black
(2) Rinmann's green is used as green pigment
(3) It is used as zinc ointment in medicine

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d & f-Block Elements

ZnCl2

Preparation: ZnO + 2HCl  ZnCl2 + H2O 


ZnCO3 + 2HCl  ZnCl2 + H2O + CO2  It crystallises as ZnCl2 ·2 H 2O
Zn(OH)2 + 2HCl  ZnCl2 + 2H2O 

Anh. ZnCl2 cannot be made by heating ZnCl2·2H2O because



ZnCl2·2H2O  Zn(OH)Cl + HCl + H2O

Zn(OH)Cl  ZnO + HCl
To get anh. ZnCl2: Zn + Cl2  ZnCl2
Zn + 2HCl(dry)  ZnCl2 + H2
or Zn + HgCl2  ZnCl2 + Hg
Properties: (i) It is deliquescent white solid (when anhydrous)
(ii) ZnCl2 + H2S  ZnS
" + NaOH  Zn(OH)2 excess
 Na2[Zn(OH)4]
" + NH4OH  Zn(OH)2 excess  [Zn(NH3)4]
2+

Uses: 1] Used for impregnating timber to prevent destruction by insects


2] As dehydrating agent when anhydrous
3] ZnO·ZnCl2 used in dental filling

ZnSO4:
Preparation:
Zn + dil H2SO4  ZnSO4 + H2
ZnO + dil H2SO4 ZnSO4 + H2O
ZnCO3 + dil H2SO4  ZnSO4 + H2O + CO2
ZnS  2O 2  ZnSO 4 
3  parallel reaction
ZnS + O2  ZnO + SO2 
2
ZnS + 4O3  ZnSO4 + 4O2

 70C  280C
Props. 1] 
ZnSO4·7H2O 39 70C
 ZnSO4·6H2O   ZnSO4·H2O    ZnSO4
1
O + SO2 + ZnO
2 2
Uses: 1] in eye lotion
2] Lithophone making (ZnS + BaSO4) as white pigment

COMPOUNDS OF COPPER
CuO:

Preparation: (i) CuCO3.Cu(OH)2  2CuO + H2O + CO2 (Commercial process )
Malachite Green
(native Cu-carbonate)

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d & f-Block Elements

1
(ii) 2Cu + O2  2CuO & Cu2O + O  2CuO
2 2

(iii) Cu(OH)2  CuO + H2O
(iv) 2Cu(NO3)2 250C
  2CuO + 4NO2 + O2

Properties: (i) CuO is insoluble in water


(ii) Readily dissolves in dil. acids
CuO + H2SO4  CuSO4 + H2O
HCl  CuCl2
HNO3 Cu(NO3)2
(iii) It decomposes when, heated above 1100°C
4CuO  2Cu2O + O2
(iv) CuO is reduced to Cu by H2 or C under hot condition
CuO + C  Cu + CO 
CuO + H2  Cu + H2O 
CuCl2 :
Preparation: CuO + 2HCl(conc.) — CuCl2 + H2O
Cu(OH)2·CuCO3 + 4HCl — 2CuCl2 + 3H2O + CO2

Properties: (i) It is crystallised as CuCl2·2H2O of Emerald green colour


(ii) dil. solution in water is blue in colour due to formation of
[Cu(H2O)4]2+complex.
(iii) conc. HCl or KCl added to dil. solution of CuCl2 the colour changes
into yellow, owing to the formation of [CuCl4]2–
(iv) The conc. aq. solution is green in colour having the two complex ions in
equilibrium 2[Cu(H2O)4]Cl2  [Cu(H2O)4]2+ + [CuCl4]2– + 4H2O
(v) CuCl2 — CuCl by no. of reagents

(a) CuCl2 + Cu-turnings  2CuCl
(b) 2CuCl2 + H2SO3 + H2O — 2CuCl + 2HCl + 2H2SO4
(c) 2CuCl2 + Zn/HCl — 2CuCl + ZnCl2
(d) CuCl2 + SnCl2 — CuCl + SnCl4
** CuF2·2H2O — light blue Anh. CuCl 2 is dark brown mass obtained

CuCl2·2H2O — green by heating CuCl 2·2H 2 O at 150C in presence
CuBr2 — almost black of HCl vap.
150C
CuI2 does not exist CuCl2·2H2O  CuCl2 + 2H2O
HCl gas
CuSO4:
Preparation: CuO + H2SO4(dil)  CuSO4 + H2O
Cu(OH)2 + H2SO4(dil) CuSO4 + 2H2O
Cu(OH)2·CuCO3 + H2SO4 (dil)  CuSO4 + 3H2O + CO2
1
Cu + H2SO4 + O — CuSO4 + H2O [Commercial scale]
2 2
(Scrap)
Cu + dil. H2SO4  no reaction {Cu is a below H in electrochemical series}

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d & f-Block Elements

Properties: (i) It is crystallised as CuSO4·5H2O

(ii) CuSO4·5H2O CuSO4·3H2O CuSO4·H2O


Blue take places Pale blue Bluish white

CuSO4(anh.)
white

COMPOUNDS OF IRON

FeSO4·7H2O:
Preparation: (i) Scrap Fe + H2SO4  FeSO4 + H2
(dil.)
(ii) From Kipp's waste
FeS + H2SO4(dil)  FeSO4 + H2S
7
(iii) FeS2 + 2H2O + O2  FeSO4 + H2SO4
2
Properties: (i) It undergoes aerial oxidation forming basic ferric sulphate
4FeSO4 + H2O + O2 4Fe(OH)SO4
C FeSO 4
(ii) FeSO4·7H2O 300   high
 Fe2O3+SO2+SO3
anh. white temp.
(iii) Aq. solution is acidic due to hydrolysis
FeSO4 + 2H2O  Fe(OH)2 + H2SO4
weak base
(iv) It is a reducing agent
(a) Fe2+ + MnO4– + H+  Fe3+ + Mn2+ + H2O
(b) Fe2+ + Cr2O72– + H+  Fe3+ + Cr3+ + H2O
(c) Au 3+ + Fe2+  Au + Fe3+
(d) Fe2+ + HgCl2  Hg2Cl2 + Fe3+
white ppt.
(v) It forms double salt. Example (NH4)2SO4·FeSO4·6H2O
FeO(Black):
Prepn : FeC2O4   
 FeO + CO + CO2
in absence of air
Props: It is stable at high temperature and on cooling slowly disproportionates
into Fe3O4 and iron
4FeO  Fe3O4 + Fe

FeCl2:
heated in
Prepn: Fe + 2HCl   FeCl2 + H2
a current of HCl
OR
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d & f-Block Elements

2FeCl3 + H2  2FeCl2 + 2HCl
Props: (i) It is deliquescent in air like FeCl3
(ii) It is soluble in water, alcohol and ether also because it is
sufficientlycovalent in nature
(iii) It volatilises at about 1000°C and vapour density indicates the
presence of Fe2Cl4. Above 1300°C density becomes normal
(iv) It oxidises on heating in air
12FeCl2 + 3O2 — 2Fe2O3 + 8FeCl3
(v) H2 evolves on heating in steam
3FeCl2 + 4H2O — Fe3O4 + 6HCl + H2
(vi) It can exist as different hydrated form
FeCl2·2H2O — colourless
FeCl2·4H2O — pale green
FeCl2·6H2O — green
FeCl3: Prepn: Anhydrous ferric chloride is prepared byheating metallic iron in a stream
of dry chlorine gas.

(i) FeCl3 solid is almost black. It sublimes at about 300°C, giving


a dimeric gas.
(ii) FeCl3 dissolves in both ether and water, giving solvated
monomeric species.
(iii) Iron (III) chloride is usually obtained as yellow-brown lumps of
the hydrate FeCl3·6H2O.
(iv) This is very soluble in water and is used both as an oxidizing
agent, and as a mordant in dyeing.
(v) FeCl3 is also used in the manufacture of CCl4.

Illustration
Q.1 The ions of d- block elements are mostlyparamagnetic-
(A) Because their d-orbitals are complete
(B)Because theyhave mostlypaired electrons
(C) Because theyhave mostlyunpaired electrons
(D) Because theyform coloured ions.
Ans. [C]
Sol. All atomic and molecular species which contains one or more unpaired electrons are paramagnetic.
Most of the ions of transition elements have unpaired electrons. Hence they are all paramagnetic. Some
ions of d - block elements with no unpaired electrons are Sc+3,Ti+4, Zn+2 and Cu+1. These ions are not
paramagnetic and they are also without colour.

Q.2 Silver jewelrycan be made to retain its silverywhite appearance by:-


(A) Coatingthe silverwith afilm of oxide bydipping the silver inconc. HNO3
(B) Coatingwith afilm ofthe insolublechloride bydippingthesilver in conc. HNO3
(C)PlatingwithPalladium
(D)Platingwithgold
Ans. [C]

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d & f-Block Elements

Sol. Silver jewelry easily gets blackened when exposed to sulphur compounds. In order to prevent this
blackeningof silverjewelry, it is coatedwith Pd.

Q.3 The order of stabilityof complexes of ion Cu+2 , Ni+2 , Mn+2 and Fe+2 decreases in the order -
(A) Cu+2 > Ni+2 > Fe+2 > Mn+2 (B) Mn+2 > Ni+2 > Cu +2 > Fe+2
(C) Ni +2 > Cu +2 > Fe+2 > Mn+2 (D) Fe +2 > Ni +2 > Cu+2 > Mn+2
Ans. [A]
Sol. Theorderofstabilityofthecomplexes ofsomeofthe ionscarryingthesamechargebut differingin ionic
radii decrease as the ionic radii increase.
ion Cu+2 , Ni+2, Fe+2 , Mn+2
Ionic radii 0.69 0.78 0.83 0.91
The complexes of Cu are most stable while Mn+2 is least stable.
+2

Q.4 Theelementswhichexhibitbothvertical andhorizontal similaritiesare–


(A) Inert gas elements (B)Representativeelements
(C) Rare elements (D)Transitionelements
Ans. [D]
Sol. Itis acharacteristicoftransitionelements.Verticalrelationshipisduetosimilarelectronicconfiguration
in agpandhorizontal relationshipduetoshieldingeffectbeingmorepredominantinlastfiveelements in
a period.

Exercise

Q.1 Transition metals and theiroxides are used in industrial processes as –


(A)Detergents (B)Insecticides (C) Catalysts (D) None
Ans. [C]

Q.2 A blue solution of copper sulphate becomes darker when treated with excess of ammonia. This is
because–
(A) ammonia molecules replace water molecules in the solution
(B) ammonia is stronger ligand than water
(C) ammonia forms a stable complex ion [Cu(NH3)4]2+ with Cu2+ ions
(D) All are correct
Ans. [D]

Q.3 Ametal gives two chlorides 'A' and 'B'. 'A' gives black precipitate with NH4OH and 'B' gives white.
With KI 'B' gives a red precipitate, soluble in excess of Kl. 'A ' and 'B' are respectively –
(A) HgCl2 and Hg2Cl2 (B) Hg2Cl2 and HgCl2 (C) HgCl2 and HgCl (D) None of these

Ans. [B]

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d & f-Block Elements

f-Block Elements
General electronic configuration (n–2)f 0–14 (n–1)d0–1 ns2

(A) INNER TRANSITION ELEMENTS


The elements in which the additional electron enters in (n – 2) f orbitals are called inner transition
elements. or f-block elements.
(a) Position in the periodic table
The lanthanides resemble yttrium in most of their properties. So it became necessary to accomodate all
the fifteen elements together at one place. This has been done by placing the first element, lanthanum
below yttrium and placing the remaining fourteen elements separately in the lower part of the periodic
table.
Lanthanide series (Z = 58 - 71) (Ce – Lu)
Actinide series (Z = 90 - 103) (Th – Lw)
(b) Lanthanides (4f - block elements)
Lanthanides are reactive elements so do not found in free state in nature.
(c) Oxidation states

Lanthanides Ce58 Pr59 Nd60 Pm61 Sm62 Eu63 Gd64 Tb65 Dy66 Ho67 Er68 Tm69 Yb70 Lu71
Oxidation +3 +3 +3 +3 (+2) +2 +3 +3 +3 +3 (+2) (+2) +2 +3
States +4 (+4) +3 +3 +4 (+4) +3 +3 +3

(i) Oxidation states in brackets are unstable states


(ii) This corresponds to the use of two outermost electrons (6s2) alongwith one inner electron. The inner
electron used is a 5d electron (in La, Gd and Lu), or one of the 4f electron if no 5d electrons present.
(iii) All the lanthanides attains +3 oxidation state and onlycerium, Praseodymium, and terbium exhibit higher
oxidation state (+4).
Oxidation states + 2 and +4 occur particularly when they lead to
(i) A noble gas configuration e.g. Ce4+ (f0)
(ii) A half filled ‘f ‘ orbital e.g. Eu2+, Tb4+, (f7)
(iii) Acompletely filled ‘f ‘ orbital e.g. Yb2+ (f14)
Therefore, in higher oxidation state, they act as oxidising while in lower state as reducing agents.
(e) Magnetic properties
In tripositive lanthanide ions the number of unpaired electrons regularly increases from lanthanum to
Gadolinium (0 to 7) and then continuously decreases upto lutecium (7 to 0). So lanthanum and lutecium
ions which are diamagnetic, all other tripositive lanthanide ions are Paramagnetic.
Colour - The lanthanide ions have unpaired electrons in their 4f orbitals. Thus these ions absorbs visible
region of light and undergo f-f transition and hence exhibit colour. The colour exhibited depends on the
number of unpaired electrons in the 4f orbitals. The ions often with 4fn configuration have similar colour
to those ions having 4f14–n configuration.
(f) Other Properties :
(a) Highly dense metals with high m.pts. (do not show any regular trend).

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d & f-Block Elements

(b) lonisation Energies - Lanthanides have fairly low ionisation energies comparable to alkaline
earth metals.
(c) Electro positive Character - High due to low I.P.
(d) Complex formation - Do not have much tendency to form complexes due to low charge density
because of their large size.
Lu+3 is smallest in size can only form complex.
(e) Reducing Agent - They readily lose electrones so are good reducing agent.
(i) In +3 oxidation states, nitrates, perchlorates and sulphates of lanthanides and actinides
are water soluble, while their hydroxides, fluorides and carbonates are water insoluble.
(ii) Alloys of lanthanides with Fe are called misch metals.
(iii) La(OH)3 is most basic in nature while Lu(OH)3 least basic.
(iv) Lanthanides form MC2 type carbide with carbon, which on hydrolysis gives C2H2.
(B) LANTHANIDE CONTRACTION
(i) In the lanthanide series with increasing atomic number, there is a progressive decrease in the size from
lanthanum to lutecium or from La+3 to Lu+3. This contraction in size is known as lanthanide contraction.
(ii) The general electronic configuration of these elements is 4f 0–145s2p6d0-16s2. In these elements the added
electron enters the deep seated f-orbitals and therefore experiences considerable pull by the nucleus.
(iii) Such an electron cannot add to the size of the element and also because the intervening 5s2p6d1 elec-
tronic shells, it is very little screening effect on the outermost 6s2 electrons.
Hence with increasing atomic number, the enhanced nuclear charge leads to contraction in the size of
atoms and ions.
(iv) The atomic volumes of europium and ytterbium are unexceptedly large. The large atomic size of Eu and
Yb suggest weaker bonding in the solid elements. Both these elements have only two electrons extra
than the stable configurations (half filled, f7, and completelyfilled, f14), hence theyutilise two electrons in
metallic bonding as in the case with barium.
(C) EFFECTS OF LANTHANIDE CONTRACTION
(i) Close resembalace of Lanthanides :- The general decrease in the sizes of the lanthanides with an
increase in their nuclear charges result in a small increase in their ionisation energies. Hence their basic
and ionic nature gradually decreases from La to Lu.
This also explains the variations in properties such as increased tendency for hydrolysis and formation of
complex salts and decreased thermal stability. solubilityof their salts.
(ii) Similarity of yttrium with lanthanides :- The properties of yttrium are so similar to the lanthanides
that it is considered more a member of the lanthanide series than a congener of scandium.
(iii) Anomalous behaviour of post-lanthanides :- Thefollowing anomalies maybe observed in the behaviour
of post-lanthanide elements.
(a)Atomic size - The ionic radii of Zr+4 is about 9% more than Ti+4. Similar trend is not maintained on
passing from the second to third transition series. The ionic radius of Hf+4, instead of increasing (because
of inclusion of one more electronic shell). decreases (or is virtually equal to Zr+4) as a consequence of
the lanthanide contraction.
This explains the close similarities between the members of the second and third transition series than
between the elements of the first and second series.
(b) lonisation potential and electronegativity :- The effect of lanthanide contraction is also seen in
the increase in the ionisation potential values and electronegativities of the elements of the third transition
series, contrary to the general trend.
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d & f-Block Elements

Because of the lanthanide contraction, the post-lanthanide elements have stronger positive field and thus
the electrons are held more tightly.
The greater effective nuclear charge of the former make them more electronegative than the latter.
(c) High density :- Because of lanthanide contraction the atomic sizes of the post lanthanide elements
become very small. consequently, the packing of atoms in their metallic crystals become so much com-
pact that their densities are very high.
The densities of the third transition series elements are almost double to those of the second series
elements.
(D) APPLICATION OF LANTHANIDES
Cerium is most useful element in the lanthanides
(a) Ceramic application - CeO2, La2O3 ' Nd2O3 and Pr2P3 are used as decolourizing agents for
glasses.
(b) CeS (m.p. - 2000°C) is used in the manufacture of a special type of crucibles and refractories.
(c) Lanthanide compounds like cerium molybdate, cerium tungstate are used as paints and dyes.
(d) In textile and leather industries (Ce salts).
(E) ACTINIDES (5f - BLOCK ELEMENTS)
(i) The elements in which the extra electron enters 5f-orbitals of (n - 2)th main shell are known as
actinides.
(ii) The man.made eleven elements Np93 - Lr103 are placed beyond uranium in the periodic table
and are collectively called trans-uranic elements.
(iii) Th, Pa and U first three actinides are natural elements.
(a) Electronic configuration :-
The general configuration of actinides may be given as 5f1–14 6d0/1, 7s2.
Some properties of actinoids
Element Symbol Atomic number Configuration Oxidation states
1 2
Actinium Ac 89 [Rn] 6d , 7s +3
2 2
Thorium Th 90 [Rn] 6d , 7s +3,+4
2 1 2
Protactinium Pa 91 [Rn] 5f , 6d , 7s +3, +4, +5
3 1 2
Uranium U 92 [Rn] 5f , 6d , 7s +3, +4, +5, +6
4 1 2
Neptunium Np 93 [Rn] 5f , 6d , 7s +3, +4, +5, +6, +7
6 2
Plutonium Pu 94 [Rn] 5f , 7s +3, +4, +5, +6, +7
7 2
Americium Am 95 [Rn] 5f , 7s +2,+3, +4, +5, +6
7 1 2
Curium Cm 96 [Rn] 5f , 6d , 7s +3,+4
8 1 2
Berkelium Bk 97 [Rn] 5f , 6d , 7s +3,+4
10 2
Californium Cf 98 [Rn] 5f , 7s +2,+3
11 2
Einsteinium Es 99 [Rn] 5f , 7s +2,+3
12 2
Fermium Fm 100 [Rn] 5f , 7s +2,+3
13 2
Mendelevium Md 101 [Rn] 5f , 7s +2,+3
14 2
Nobelium No 102 [Rn] 5f , 7s +2,+3
14 1 2
Lawrencium Lr 103 [Rn] 5f , 6d , 7s +3

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d & f-Block Elements

EXERCISE-1
d-BLOCK COMPOUNDS
[SINGLE CORRECT CHOICE TYPE]

Salt
123 'P' few drops of  AgNO3
Q.1 Warm NaOH + 
conc. H SO  + compound 'Q' (solid) warm R  NaOH S T Excess
X
 2 4 deep red Coloured red
NH 3 Soln. 123
Z(g) vapours Solution dil. HCl
Coloured
solution
Identify (P) to (Z) Y
white
(A) P = HCl, Q = KMnO4, R = C12, Y = AgCl
(B) P = NH4Cl, Q = K2Cr2O7, R = CrO2Cl2, X = [Ag(NHa3)2]+, Y =AgCl, Z = NH3
(C) P = KCl, Q = K2CrO4, R = CrO2Cl2, X = Na2CrO4, Z = HCl
(D) P= NaCl, Q = K2MnO4, R = MnO2, Y = AgCl

Q.2 The number of moles of acidified KMnO4 required to convert one mole of sulphite ion into sulphate ion is
(A) 2/5 (B) 3/5 (C) 4/5 (D) 1

Q.3 In Haber's process of manufacture of ammonia, Mo is used as


(A) a catalyst (B) a catalytic promoter
(C) an oxidising agent (D) as a catalytic poison

Q.4 Cr2 O 72 2CrO 24 , X and Y are respectively


(A) X = NaOH, Y = H2SO4 (B) X=H+, Y= OH–
(C) X = NaOH, Y = HI (C) X = H3BO3, Y = NaOH

Q.5 CrO3 dissolves in aqueous NaOH to give


(A) Cr2O72– (B) CrO42– (C) Cr(OH)3 (D) Cr(OH)2

Q.6 Potassium sulphitesolution was mixed withpotassium hydroxide and thepotassium permanganate solution
was added into it, then final colour of the solution is
(A) Blue (B) colourless (C) light pink (D) Green

Q.7 An ornamental of gold having 75% of gold, it is of .............. carat.


(A) 18 (B) 16 (C) 24 (D) 20

Q.8 Purple-coloured of KMnO4 is due to


(A) d-d-transition
(B) charge transfer from O to Mn
(C) due to both d-d-transition and charge transfer
(D) none of these

Q.9 During estimation of oxalic acid by KMnO4, self indicator is


(A) KMnO4 (B) oxalic acid (C) K2SO4 (D) MnSO4

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d & f-Block Elements

Q.10 Mercurous ion is represented as


(A) Hg22+ (B) Hg2+ (C) Hg + Hg2+ (D) Hg2+

Q.11 Acompound of mercuryused in cosmetics, inAyurvedic andYunani medicines and known as Vermilon is
(A) HgCl2 (B) HgS (C) Hg2Cl2 (D) HgI

Q.12 Acidified chromic acid + H2O2 Org


 . solvent
 X + Y , X and Y are
(blue colour)

(A) CrO5 and H2O (B) Cr2O3 and H2O (C) CrO2 and H2O (D) CrO and H2O

KI dil H SO
Q.13  Y(g)  CuSO 4  
2
4  X(Blue colour) , X and Y are
(A) X = I2, Y = [Cu(H2O)4]2+ (B) X = [Cu(H2O)4]2+, Y = I2
(C) X = [Cu(H2O)4]+, Y = I2 (D) X = [Cu(H2O)5]2+, Y = I2

Q.14 Transition elements are usually characterised by variable oxidation states but Zn does not show this
property because of
(A) completion of np-orbitals (B) completion of (n–1)d orbitals
(C) completion of ns-orbitals (D) inert pair effect

Q.15 (NH4)2Cr2O7 (Ammonium dichromate) is used in fire works. The green coloured powder blown in air is
(A) Cr2O3 (B) CrO2 (C) Cr2O2 (D) CrO3

Q.16 The d-block metal which is liquid at room temperature and its iodide changes colour on sublimation.
(A) Cu (B) Hg (C) Zn (D)Au

Q.17 Coinage metals show the properties of


(A) typical elements (B) normal elements
(C) inner-transition elements (D) transition element

Q.18 Iron becomes passive by ..................... due to formation of .....................


(A) dil. HCl, Fe2O3 (B) 80% conc. HNO3, Fe3O4
(C) conc. H2SO4, Fe3O4 (D) conc. HCl, Fe3O4

Q.19 Bayer’s reagent used to detect olifinic double bond is


(A) acidified KMnO4 (B) aqueous KMnO4
(C) 1% alkaline KMnO4 solution (D) KMnO4 in benzene

Q.20 The transition metal used in X-rays tube is


(A) Mo (B) Ta (C) Tc (D) Pm

Q.21 Cu + conc.HNO3  Cu(NO3)2 + X (oxide of nitrogen); then X is


(hot)

(A) N2O (B) NO2 (C) NO (D) N2O3

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d & f-Block Elements

Q.22 When KMnO4 solution is added to hot oxalic acid solution, the decolourisation is slow in the beginning
but becomes instantaneous after some time. This is because
(A) Mn2+ acts as auto catalyst (B) CO2 is formed
(C) Reaction is exothermic (D) MnO4– catalyses the reaction.

Q.23 CuSO4 solution reacts with excess KCN to give


(A) Cu(CN)2 (B) CuCN (C) K2[Cu(CN)2] (D) K3[Cu(CN)4]

Q.24 The higher oxidation states of transition elements are found to be in the combination withAand B, which
are
(A) F, O (B) O, N (C) O, Cl (D) F, Cl

Q.25 Pick out the incorrect statement:


(A) MnO2 dissolves in conc. HCl, but does not form Mn4+ ions
(B) MnO2 oxidizes hot concentrated H2SO4 liberating oxygen
(C) K2MnO4 is formed when MnO2 in fused KOH is oxidised by air, KNO3 , PbO2 or NaBiO3
(D) Decomposition of acidic KMnO4 is not catalysed by sunlight.

Q.26 1 mole of Fe2+ ions are oxidised to Fe3+ ions with the help of (in acidic medium)
(A) 1/5 moles of KMnO4 (B) 5/3 moles of KMnO4
(C) 2/5 moles of KMnO4 (D) 5/2 moles of KMnO4

Q.27 The metals present in insulin and haemoglobin are respectively


(A) Zn, Hg (B) Zn, Fe (C) Co, Fe (D) Mg, Fe

Q.28 Metre scales are made-up of alloy


(A) invar (B) stainless steel (C) electron (D)magnalium

Q.29 Which of the following metal does not react with conc. HNO3
(A)Ag (B) Pb (C) Au (D) Hg

Q.30 A metal M which is not affected by strong acids like conc. HNO3, conc. H2SO4 and conc. solution of
alkalies like NaOH, KOH forms MCl3 which finds use for toning in photography. The metal M is
(A)Ag (B) Hg (C) Au (D) Cu

Q.31 Solid CuSO4·5H2O having covalent, ionic as well as co-ordinate bonds. Copper atom/ion forms
................. co-ordinate bonds with water.
(A) 1 (B) 2 (C) 3 (D) 4

Q.32 KMnO4 + HCl  H2O + X(g), X is a


(acidified)

(A) red liquid (B) violet gas


(C) greenish yellow gas (D) yellow-brown gas

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d & f-Block Elements

Q.33 Purple of cassius is:


(A) Pure gold (B) Colliodal solution of gold
(C) Gold (I) hydroxide (D) Gold (III) chloride

Q.34 Amongst the following species, maximum covalent character is exhibited by


(A) FeCl2 (B) ZnCl2 (C) HgCl2 (D) CdCl2

Q.35 Number of moles of SnCl2 required forthe reduction of 1 mole of K2Cr2O7 into Cr2O3 is (in acidic medium)
(A) 3 (B) 2 (C) 1 (D) 1/3

Q.36 Pick out the incorrect statement:


(A) MnO 24 is quite strongly oxidizing and stable only in very strong alkalies. In dilute alkali, neutral
solutions, it disproportionates.
(B) In acidic solutions, MnO 4 is reduced to Mn2+ and thus, KMnO4 is widely used as oxidising agent
(C) KMnO4 does not acts as oxidising agent in alkaline medium.
(D) KMnO4 is manufactured by the fusion of pyrolusite ore with KOH in presence of air or KNO3,
followed byelectrolytic oxidation in alkaline solution.

Q.37 The aqueous solution of CuCrO4 is green because it contains


(A) green Cu2+ ions (B) green CrO42– ions
(C) blue Cu2+ ions and green CrO42– ions (D) blue Cu2+ ions and yellow CrO42– ions

Q.38 Concentrated acid obtained from reaction between solid NaNO3 and conc. H2SO4 does not react with
(A) P4 (B) H2S (C) Au (D) Hg

Q.39 In nitroprusside ion, the iron exists as Fe2+ and NO as NO+ rather than Fe3+ and NO respectively.
These forms of ions are established with the help of
(A) magnetic moment in solid state (B) thermal decomposition method
(C) by reaction with KCN (D) by action with K2SO4

Q.40 Transition elements in lower oxidation states act as Lewis acid because
(A) they form complexes (B) theyare oxidising agents
(C) they donate electrons (D) they do not show catalytic properties

Q.41 The Ziegler-Natta catalyst used for polymerisation of ethene and styrene is TiCl4 + (C2H5)3Al, the
catalysing species (active species) involved in the polymerisation is
(A) TiCl4 (B) TiCl3 (C) TiCl2 (D)TiCl

Q.42 The electrons which take part in order to exhibit variable oxidation states by transition metals are
(A) ns only (B) (n–1)d only
(C) ns and (n–1)d only but not np (D) (n–1)d and np only but not ns

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d & f-Block Elements

Q.43 ‘Bordeaux mixture’ is used as a fungicide. It is a mixture of


(A) CaSO4 + Cu(OH)2 (B) CuSO4 + Ca(OH)2
(C) CuSO4 + CaO (D) CuO + CaO

Q.44 Which of the following reaction is possible at anode?


(A) 2Cr3+ + 7H2O  Cr2 O 72 + 14 H+ (B) F2  2 F–
1
(C) 2 O 2 + 2H+  H2O (D) None of these

Q.45 “925 fine silver” means an alloy of:


(A) 7.5 % Ag and 92.5% Cu (B) 92.5 % Ag and 7.5 % Cu
(C) 80% Ag and 20 % Cu (D) 90 % Ag and 10% Cu

Q.46 Iron salt used in blue prints is:


(A) FeC2O4 (B) Fe2(C2O4)3 (C) K4[Fe(CN)6] (D) K3[Fe(CN)6]

Q.47 Product obtained on strong heating FeCl3· 6H2O is


(A) FeCl3 (B) FeO (C) Fe2O3 (D) FeCl2

Q.48 What is the correct set of co-efficients for the reactants in following reaction:
Mn2+(aq) + PbO2(s) + H+(aq) _____ + Pb2+(aq) + _____
(A) 1 : 2 : 0 (B) 3 : 1 : 9 (C) 2 : 5 : 4 (D) 4 : 6 : 3

Q.49 In the elements of 3d-series, the element with highest melting point is
(A) Mn (B) Fe (C) Cr (D) Cu

Q.50 Heating of a blue coloured salt produces a black residue. Which of the following cations will be present
in the salt?
(A) Fe2+ (B) Fe3+ (C) Cu2+ (D) Zn2+

Q.51 Which one of the following is least covalent and least acidic?
(A) VCl2 (B) VCl3 (C) VCl4 (D)VOCl3

Q.52 Select correct order of acidic strength of their aq. solution


(A) FeCl3 > AlCl3 > MgCl2 (B) FeCl3 > MgCl2 > AlCl3
(C) AlCl3 > FeCl3 > MgCl2 (D) MgCl2 > AlCl3 > FeCl3

Q.53 When KMnO4 separatelyreacts with H2O2 in weaklyalkaline medium and acidic medium, then products
of KMnO4 are respectively.
(A) K2MnO4 and Mn2+(aq) (B) MnO2 and MnO2
2+
(C) MnO2 and Mn (aq) (D) Mn2+ (aq) and MnO2

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d & f-Block Elements

Q.54 Which oxide exhibits strongest oxidizing character among given oxides.
(A) CrO3 (B) MoO3 (C) WO3 (D) Mn2O7

Q.55 Which of the following ionic/molecular species does not disproportionate in water at room temperature.
(A) NO2 (B) Cu+ (C) MnO42– (D) Ca(OCl)Cl

Q.56 Fe (Finely powdered) + HCl(dil)  P + Q


compound 'P' does not precipitate with
(A) AgNO3 (B) K3[Fe(CN)6] (C) (NH4)2S (D) NH4Cl + NH4OH

Q.57 Colour of acidified K2Cr2O7 is not changed by


(A) H2O2 (B) Sn++(aq) (C) HF (D) HBr

Q.58 Select the salt whose aqueous solution is not green


(A) FeSO4 (C) CrCl3 (C) NiCl2 (D) MnCl2

Q.59 Which of the following compound undergoes disproportionation in presence of SO3 gas
(A) K2MnO4 (B) K2CrO4 (C) I2 (D) Hg(NO3)2

Q.60 Colour of CrO42– (aq) is not changed by


(A) dil. HCl (B) NH3 solution (C) CH3COOH (D) NO2 gas

Q.61 Which does not undergo comproportionation reaction


(A) H2S + SO2  (B) I– (aq) + IO3– (aq) + H+ (aq) 
(C) K2MnO4 + H (aq) 
+ (D) MnO4– + Mn2+ (aq) 

Q.62 I– (aq.) + MnO4– (aq) H X + Mn++ (aq)
neutral or
I– (aq.) + MnO4– (aq)   
Y + MnO2
weakly OH

MnO4– (aq) + Mn++ (aq) ZnSO 4  Z + 4H+


Products X, Y and Z are respectively
(A) I2, IO3–, MnO2 (B) IO3–, I2, MnO2
(C) I2, IO3–, MnO42– (D) IO3–, I2, MnO42–

Q.63 Which property remains same in metal and in its interstatial compound?
(A) Hardness (B) Ductility
(C) Electrical conductivity (D) Density

Q.64 The oxidation number is changed in which of following cases


(A) SO2 gas is passed into Cr2O72– / H+ soln.
(B)Aqueous solution of CrO42– is acidified
(C) CrO2Cl2 is dissolved in NaOH soln.
(D) Cr2O72– solution is made alkaline
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d & f-Block Elements

Q.65 In a transition series, as atomic number increases, paramagnetism


(A) Increases gradually
(B) Decreases gradually
(C) First increases to a maximum and then decreases
(D) First decreases to a maximum and then increases

Q.66 In the reaction. 2CuCl2 + 2H2O + SO2  A + H2SO4 + 2HCl ; A is


(A) CuSO4 (B) CuS (C) Cu2Cl2 (D) Cu

Q.67 Many transition metals form interstitial compounds. The characteristics of these interstitial compounds
are:
(I) They have high melting points as compared to pure metals.
(II) They are very hard.
(III) Theyretain metallic conductivity.
(IV) They are chemically more reactive than pure metals.
Then correct option(s) is/are
(A) I, II, III (B) I, III (C) II, IV (D) IV only

Q.68 Incorrect statement is


(A) Cr2+ (aq) has strong reducing character
(B) Mn3+ (aq) has strong oxidizing character
(C) CO2+ (aq) is stable but it is easily oxidized in presence of complexing reagent.
(D) CuCl undergoes disproportionation in excess of water

Q.69 Each of the following ion contains vanadium in + 5 oxidation state except
(A) VO2+ (B) V(OH)4+ (C) VO2+ (D) [VO3.OH]2–

Q.70 The oxoanion in which the oxidation state of central atom is same as its group number in the periodic
table is
(A) SO42– (B) VO2– (C) MnO42– (D) Cr2O72–

Q.71 Choose correct statement(s) regarding the following reaction


Cr2O72– (aq) + 3 SO32– (aq.) + 8H+  2Cr3+ (aq) + 3 SO42– (aq) + 4H2O
1. Cr2O72– is oxidising agent
2. SO32– is reducing agent
3. The oxidation number of per 'S' atom in SO32– is increase by two
4. The oxidation number of per 'Cr' atom in Cr2O72– is decrease by three
Correct code is
(A) 1, 2, 3, 4 (B) 3, 4 (C) 1, 3 (D) only 4

Q.72 Which of the following is not arranged in CORRECT sequence?


(A) MO, M2O3, MO2, M2O5 : decreasing order of basic nature.
(B) Sc, V, Cr, Mn : increasing order of oxidation states.
(C) d5, d3, d1, d4: increasing order of magnetic moment.
(D) Sc > Ti > V > Cr ; Decreasing order of atomic size.

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d & f-Block Elements

Q.73 The size of Fe2+, Fe3+ is affected by


(A) Nuclear charge (z)
(B) Valence principal quantam number
(C) Electron-electron interaction in the outer orbital
(D) None of the factor because their size is same
(x) (y)
Q.74 MnO4– Mn2+ Mn4+
(z)
MnO2
For above reaction x, y, z are respectively
(A) H2O2 / H+ , H2O2 / OH– , H2O2 / OH– (B) H2O2 / OH– , H2O2 / OH– , H2O2 / H+
(C) H2O2 / OH– , H2O2 / H+ , H2O2 / H+ (D) H2O2 / H+, H2O2 / H+ , H2O2 / OH–

Q.75 Which of them does not produce H2 gas when react with dil. HCl ?
(A) Ti2+ (B) V2+ (C) Cr2+ (D) Fe2+

Q.76 Colour of K2MnO4 does not change in the presence of


(A) O3 (B) CO2 gas (C) KOH solution (D) HCl acid

Q.77 Which of the following compound/acid does not reduceAgNO3 into MetallicAg?
(A) H3PO4 (B) H3PO2 (C) N2H4 (D) H3PO3

Q.78 Fe (s) + Cl 2 (g ) warm


 M (salt)
( excess )

Salt M does not react with solution of


(A) CH3COONa (B) AgNO3 (C) Na2S2O3 (D) SrCl2

Q.79 P(soln .) Air


 Q(soln .) KOH
 R
coloured coloured ( ppt )
(insoluble in both excess
NaOH and excess NH3 solution )

Then P contains
(A) Cu2+ (aq) (B) Fe2+ (aq) (C) Cr2+ (aq) (D) Ni2+ (aq)

Q.80 K2MnO4 is unstable in aqueous solution and the greensolution obtained is changed into purple colouration
INCORRECT statement regarding the above change is.
(A) It is a disproportionation reaction
(B) It produces KMnO4
(C) It produces brown precipitate of hydrated MnO2
(D) K2MnO4 stable in acidic medium

pH = X
Q.81 CrO42– Cr2O72–
pH = Y
The pH values of (X) and (Y) are respectively :
(A) 4 and 5 (B) 4 and 8 (C) 8 and 4 (D) 8 and 9
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d & f-Block Elements

Q.82 CORRECT stability order of oxidation state of given metal cation is :


(A) Mn+2(aq) < Mn+3(aq) (B) Fe+2(aq) < Fe+3(aq)
(C) Cr+2(aq) < Cr+3(aq) (D) Co+2 (aq) < Co+3 (aq)

Q.83 When CuSO4 reacts with KI and KCN separately which of the following statement is incorrect for
both reaction
(A) Both are redox reactions
(B) Both reactions produce diatomic gas
(C) Cu (II) cation is reduced in both reaction
(D) Both reactions produce white colour compound

Q.84 Which of the two set of reactions represent amphoteric nature of Zn(OH)2
(I) Zn(OH)2 + NaOH (II) Zn(OH)2 + H2O (III) Zn(OH)2 + HCl (IV) Zn(OH)2 + NH3
(A) I, II (B) I, III (C) II and IV (D) III and IV

Q.85 FeCr2O4 (chromite ore) is converted to Cr by following steps.


I II III
Chromite 
 Na 2 CrO 4  Cr2 O3  Cr
In above chain of reactions, steps I, II and III are:
I II III
(A) Na2CO3/air,  C C
(B) NaOH/air,  C,  Al, 
(C) NaOH/air,  C,  Mg, 
(D) Conc. H2SO4,  NH4Cl,  C, 

Q.86 Which substance does not react with dilute HCl ?


(A) ZnCO3 (B) Zn(OH)2 (C) Zn Metal (D) Zn(NO3)2

Q.87 Which metal cation absorbs violet colour in aqueous medium ?


(A) Fe2+ (aq.) (B) Fe3+ (aq.) (C) Cr3+ (aq.) (D) Cu2+ (aq.)

Q.88 Which is not oxidized by acidified K2Cr2O7 ?


(A) KF (aq.) (8) KCl (aq.) (C) KBr (aq.) (D) KI (aq.)

[REASONING TYPE]
Questions given below consist of two statements each printed as Statement-1 and Statement-2; while
answering these questions you are required to choose any one of the following four responses:
(A) if both Statement-1 and Statement-2 are true and Statement-2 is the correct explanation of
statement-1
(B) if both Statement-1 and Statement-2 are true but Statement-2 is not correct explanation of
statement-1
(C) if Statement-1 is true but Statement-2 is false
(D) if Statement-1 is false and Statement-2 is true
Q.89 Statement-1 : KMnO4 is purple in colour due to charge transfer.
Statement-2 : In MnO4¯, there is no unpaired electron present in d-orbitals of manganese.

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d & f-Block Elements

Q.90 Statement-1 : K2CrO4 has yellow colour due to charge transfer.


Statement-2 : CrO42– ion is tetrahedral in shape.

Q.91 Statement-1 : The highest oxidation state of chromium in its compounds is +6.
Statement-2 : Chromium atom has only six electrons in ns and (n-1) d orbitals.

Q.92 Statement-1 : CrO3 reacts with HCl to form chromyl chloride gas.
Statement-2 : Chromyl chloride (CrO2Cl2) has tetrahedral shape.

Q.93 Statement-1 : Zinc does not show characteristic properties of transition metals.
Statement-2 : In zinc outermost shell is completely filled.

Q.94 Statement-1 : Tungsten has a very high melting point.


Statement-2 : Tungsten is a covalent compound.

Q.95 Statement-1 : Equivalent mass of KMnO4 is equal to one-third of its molecular mass when it acts as an
oxidising agent in an alkaline medium.
Statement-2 : Oxidation number of Mn is +7 in KMnO4.

Q.96 Statement-1 : Cu+ ion is coloured in aqueous solution.


Statement-2 : Four water molecules are coordinated to Cu+ ion

f-BLOCK COMPOUNDS
Q.97 In general, actinides exhibit more number of oxidation states than lanthanoids. This is because
(A) there is a similarly between 4f and 5f orbitals in their angular part of wave function
(B) The actinoids are more reactive than lanthanoids
(C) The 5f orbitals extend farthar from nucleus than 4f-orbitals
(D) The 5f orbitals are more buried than the 4f-orbitals

Q.98 Which of the following statement is not correct?


(A) La(OH)3 is less basic than Lu(OH)3
(B) In Lanthanide series, ionic radius of Ln3+ ions decreases
(C) La metal is actually an element of transition series rather than lanthanide series
(D)Atomic radii of Zr and Hf are almost same because of lanthanide contraction

Q.99 Which of the following statements is NOT CORRECT regarding lanthanoids and actinoids?
(A) Oxidation state of +3 is predominant in both the series
(B) Both the series show contraction in ionic radii as lanthanoid contraction and actinoid contraction with
increase in atomic number .
(C) Actinoids show larger number of oxidation states than lanthanoids due to lesser energy difference
between 5f and 6d orbitals than between 4f and 5d orbitals of lanthanoids.
(D) Elements of both the series are radioactive

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d & f-Block Elements

Q.100 Incorrect statement for lanthanides is


(A) They liberate hydrogen gas with dilute acids
(B) They form carbides with carbon on heating
(C) Their hydroxides are basic
(D) Ce4+(aq) is stable towards reducing agents.

Q.101 Which of the properties has higher value for lanthanoids in comparison of actinoids
(A) Variety of oxidation state (B) Element to element size contraction
(C) Both of them (D) None of these

Q.102 The lanthanide contraction is responsible for the fact that:


(A) Zr and Nb have same oxidation state (B) Zr and Hf have about the same radius
(C) Y and La have about the same radius (D) Zr and Zn have the same oxidation state

Q.103 Incorrect statement for lanthanides is


(A) They all liberate hydrogen gas with dil HCl.
(B)All paramagnetic hydrated lanthanoid cations [Ln3+ (aq)] are coloured
(C) Separation of Hf 4+ from Zr4+ is difficult due to their comparable size
(D) Misch metal is an alloy of a lanthanide metal.

Q.104 Incorrect statement about Lanthanoids is:


(A) They liberate H2 gas with non oxidizing acids
(B) Their hydroxides are basic
(C) Ce4+ (aq) acts strong oxidant
(D)All tripositive lanthanoid ions are coloured

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d & f-Block Elements

EXERCISE-2
[PARAGRAPH TYPE]
Paragraph for question nos. 1 & 2
Excess KI
{   Y 
X Z
{ Na
2S2O3
 Y
{  Colourless products
Water Coloured White
So lub le Solution 
salt

Q.1 Salt 'X' is


(A) Fe2(SO4)3 (B) CuSO4.5H2O (C) KNO2 (D) Hg(NO3)2

Q.2 Salt 'X' does not produce precipitate with solution of


(A) K4[Fe(CN)6] (B) BaCl2 (C) NaOH (D) excess NH4OH

Paragraph for question nos. 3 & 4


The unique behaviour of Cu, having a positive Eº (Reduction potential) accounts for its inability to
liberate H2 from acids. Only oxidising acids (nitric acid and hot concentrated sulphuric acid) react with
Cu. The high energy to transform Cu(s) to Cu2+(aq) is not balanced by its hydration enthalpy.
On the other hand, all Cu (II) halides are known except iodide. In this case, Cu2+ oxidises I¯ to I2 :
2Cu2+ + 4I¯  2 CuI(s) + I2
However, copper (I) compounds are unstable in aqueous solution and undergo disproportionation.
2Cu+ (aq)  Cu2+(aq) + Cu
The stability of Cu (aq) rather than Cu+(aq) is due to the much more negative HHyd of Cu2+(aq) than
2+

Cu+(aq).
Q.3 Consider the following transformation :
CuSO4 (aq) + KI(Excess)  Product
Select the correct statement
(A) Product contains [Cu(H2O)4]2+ ion.
(B) Presence of brown colouration in product is due to I3¯ ion
(C) Oxidation state of sulphur in reactant and product is different
(D) White ppt. of CuI2 is observed in product

Q.4 Select the correct chemical change


(A) Cu + dil. H2SO2  CuSO4 + H2(g)
(B) Cu + dil. HNO3  Cu(NO3)2 + N2O(g)
(C) CuSO4 (aq) + KCN (excess)  K2[Cu(CN)4]
(D) CuSO4 (aq) + NH4OH  Cu(OH)2

Paragraph for question nos. 5 & 6


When hydrogen peroxide is added to an acidified solution of a dichromate gives a deep blue coloured
compound 'A' in presence of organic solvent, which decomposes rapidlyin aqueous solution into 'B' and
dioxygen. Compound 'A' can be extracted by dimethyl ether forming the adduct 'C'.
Q.5 The oxidation state of the metal ion in compound 'A' are
(A) 3+ (B) 10 + (C) 6+ (D) 4+

Q.6 The magnetic moment of compound 'B' is:


(A) 2.8 B.M (B) 4.9 B.M (C) 0 (D) 3.8 B.M

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d & f-Block Elements

[MULTIPLE CORRECT CHOICE TYPE]


Q.7 Correct characteristics of aqueous solution of chrome alum is/are
(A) green colour
(B) acidic character
(C) gives precipitates with BaCl2
(D) Produces precipitates with excess of NaCN

Q.8 Addition of non-metals like boron, carbon and nitrogen to the interstitial voids of a transition metal,
makes the metal
(A) more ductile (B) less ductile (C) less malleable (D) more hard

Q.9 Mercury is a liquid at 0°C because of


(A) veryhigh ionisation energy (B) weak metallic bonds
(C) high heat of hydration (D) high heat of sublimation

Q.10 The ionisation energies of transition elements are


(A) less than p-block elements (B) more than s-block elements
(C) less than s-block elements (D) more than p-block elements

Q.11 Transition metal cations have more tendency to form complex than metal cations of s- and p-block
elements. It is due to
(A) availability of d-orbitals for bonding
(B) variable oxidation states are not shown by transition elements
(C) all electrons are paired in d-orbitals
(D) Higher nuclear force of attraction at their peripheral shell in transition metal cations

Q.12 The metal(s) which does/do not form amalgam


(A) Fe (B) Pt (C) Zn (D)Ag

Q.13 Which of the following statements concern with transition metals?


(A) Hydrated paramagnetic transition metal salts are coloured
(B) common oxidation state is +3
(C) they show variable oxidation states, which differ by two units only
(D) they can form acidic oxides

Q.14 Correct statement(s) is/are


(A)Acidified solution of K2Cr2O7 liberates iodine from KI
(B)Acidified K2Cr2O7 is used as a standard solution for estimation of Fe2+ ions
(C) In acidic medium, M = N/6 for K2Cr2O7
(D) On heating (NH4)2Cr2O7 decomposes to yield Cr2O3 through an endothermic reaction

Q.15 The highest oxidation state among transition elements is


(A) + 7 by Mn (B) + 8 by Os (C) + 8 by Ru (D) + 7 by Fe

Q.16 Amphoteric oxide(s) is/are


(A) Al2O3 (B) SnO (C) ZnO (D) Fe2O3

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d & f-Block Elements

Q.17 Interstitial compounds are formed by


(A) Co (B) Ni (C) Fe (D) Ca

Q.18 The catalytic activity of transition elements is related to their


(A) variable oxidation states (B) surface area
(C) complex formation ability (D) magnetic moment

medium ‘x’ 2–
MnO4
+ n1 e¯
medium ‘y’ 2+
Q.19 MnO4¯ Mn (aq)
+ n2 e¯
medium ‘z’
+ n3 e¯ MnO2

Select correct match:


(A) n1 = 1; x = strongly alkaline medium
(B) n2 = 5, acidic medium
(C) n3 = 3, Neutral or weakly alkaline medium
(D) n1 = 1, weakly alkaline medium

Q.20 In the equation : M + 8CN¯ + 2H2O + O2  4[M(CN)2]¯ + 4OH¯, the metal M is


(A)Ag (B)Au (C) Pb (D) Hg

Q.21 An element of 3d-transition series shows two oxidation states x and y, differ by two units then
(A) If x > y then compound in oxidation state x will be ionic
(B) If x < y then compound in oxidation state x will be ionic
(C) If x < y then compound in oxidation state y will be covalent
(D) If y < x then compound in oxidation state y will be covalent

Q.22 A pinch of Na2O2 was added to an acidified dichromate solution, then observations noted are
(A) Blue colour appears in transient phase
(B) Orange colour directly changing to green
(C) Copious evolution of oxygen
(D) Bluish -green precipitate

Q.23 The rusting of iron is formulated as Fe2O3· xH2O which involves the formation of
(A) Fe2O3 (B) Fe(OH)3 (C) Fe(OH)2 (D) Fe2O3 + Fe(OH)3

Q.24 CuSO4(aq) + 4NH3  X, then X is


(A) [Cu(NH3)4]2+ (B) paramagnetic
(C) coloured (D) of a magnetic moment of 1.73 BM

Q.25 Amphoteric oxide(s) of Mn is/are


(A) MnO2 (B) Mn3O4 (C) Mn2O7 (D)MnO

Q.26 Acidified KMnO4 can be decolourised by


(A) SO2 (B) H2O2 (C) FeSO4 (D) Fe2(SO4)3

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d & f-Block Elements

Q.27 The lanthanide contraction is responsible for the fact that


(A) Zr and Hf have same atomic sizes (B) Zr and Hf have same properties
(C) Zr and Hf have different atomic sizes (D) Zr and Hf have different properties

Q.28 Ion(s) having non zero spin onlymagnetic moment:


(A) Sc3+ (B) Ti3+ (C) Cu2+ (D) Zn2+

Q.29 Colourless solutions of the following four salts are placed separately in four different test tubes and a
strip of copper is dipped in each one of these. Which solution will turn blue?
(A) KNO3 (B) AgNO3 (C) Zn(NO3)2 (D) Hg(NO3)2

Q.30 Which of the following option is correctly match ?


(A) FeSO4.White (B) FeCl2. 6H2O : Pale green
(C) NiCl2.6H2O Green (D) 2CuCO3.Cu(OH)2 : Blue

Q.31 Which of the following compound(s) produce green coloured product on thermal decomposition.
(A) K2Cr2O7 (B) KMnO4 (C) (NH4)2Cr2O7 (D) NH4NO3

Q.32 Quantitative conversion of K2MnO4 into KMnO4 can be carried out by


(A) Electrolytic oxidation of K2MnO4 in acidic medium
(B) Electrolytic oxidation of K2MnO4 in alkaline medium
(C) Oxidation of K2MnO4 by chlorine in alkaline medium
(D) Oxidation of K2MnO4 by Ozone in alkaline medium

Q.33 The element with maximum and minimum melting points in the respective transition series respectively
are-
(A) Cr and Zn (B) Mo and Ag (C) Mn and Zn (D) Mo and Cd

add of conc. H2SO4


followed by
R
Crystallization Orange Red
Q.34 P Fused with Q
(ore) Na2CO3 & Air yellow Pb (CH3COO)2
S
Solution
Yellow ppt.
Which of the following option(s) is/are correctly match.
(A) P : FeCr2O4 (B) R : K2Cr2O7 (C) PbCrO4 (D) Q : Fe(OH)3

Q.35 Select the CORRECT chemical changes


(A) Cu + dil. H2SO4 + 1/2 O2{g)  CuSO4 + H2O
(B) Cu + dil. HNO3  Cu{NO3)2 + N2O(g)
(C) CuSO4(aq) + KCN(excess)  K2[Cu(CN)4]
(D) CuSO4(aq) + NH4OH  Cu(OH)2¯

Q.36 Which of the following compound(s) undergo does /do not disproportionation in presence of SO3 gas.
(A) K2MnO4 (B) K2CrO4 (C) I2 (D) Hg(NO3)2

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d & f-Block Elements

3
Q.37 
2K2Cr2O7  2X + Y + Z
2
2KMnO4   P + Q + R
If order of molecular weight is X >Y > Z and P > Q > R, then which of the following statement is
CORRECT regarding above information
(A) Oxidation state of central metal atoms are same in X and P.
(B) Molecular weight of Z and R is same
(C) Molecular weight of Q is greater than Y.
(D) The colour of Y and P almost same

Q.38 For given reactions :


KMnO4 + KOH (conc.)  P + Q
Coloured
P + H2O  R + S
(excess) (purple) Brown
Correct statement(s) is/are :
(A) Both are redox reactions
(B) Substance 'S' on heating with solid KOH in presence of KNO3 produces 'R'
(C) 'S' is converted into mixed oxide on heating
(D) Atomic form of Q can convert I¯ (aq) into I2 in acidic medium


Q.39 KMnO 4  NaOH  Green solution excess
 water
 purple colour along with black residue (X)

purple  Hot conc.
Which of the following statement is/are correct regarding above information
(A) The oxidation state of Mn in green solution is +6
(B) Both steps take place through redox reaction
(C) MnO2 is obtained in the form of black residue (X)
(D) Black residue (X) can oxidize NaCl into Cl2 gas in acidic medium

Q.40 Correct statement is/are :


(A) Cr2+ (aq) has strong reducing character.
(B) Mn3+ (aq} has oxidizing character.
(C) Co2+ (aq) is stable but it is easily oxidized in presence of strong field ligand (SFL).
(D) CuCl undergoes disproportionation in excess of water.

Q.41 When acidified CrO42– ion reacts with H2O2 in the presence of ether solvent then correct statement(s)
is/are?
(A) Orange colour of solution turns blue
(B) Deep blue colour is due to formation of CrO5.OEt2
(C) Oxidation state of Cr-atom remains same in the reaction
(D) Orange colour of solution turns green

Q.42 Which of the following metal sulphide (s) undergo hydrolysis ?


(A) Cr2S3 (B) Al2S3 (C) MgS (D) FeS

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d & f-Block Elements

Q.43 Which of the general properties are common among group 2nd elements and 4f series elements ?
(A)Abundance in earth crust
(B) Evolution of H2 gas on reaction with dil HCl
(C) Formation of oxide and nitride when reacts with air
(D)Aqueous solution reacts with HCl

Q.44 K2CrO4 reacts with which of the following reagents


(A) dil. H2SO4 + H2O2 (B) KOH solution + I¯ (aq.)
(C) AgNO3 (D) SO2 gas

Q.45 Reduction of the metal centre in aqueous permanganate ion involves


(A) 3 electrons in neutral medium (B) 1 electron in strongly basic medium (pH  11)
(C) 3 electrons in alkaline medium (D) 5 electrons in acidic medium

Q.46 Which one of the following ionic species will impart colour to an aqueous solution?
(A) Ti4+ (aq) (B) Cu+ (aq) (C) Zn2+ (aq) (D) Cr3+ (aq)

[MATRIX TYPE]
Q.47 Column-I Column-II
(A) [Sc(H2O)6]3+ (P) Paramagnetic complex
(B) [Fe(H2O)6]3+ (Q) Diamagnetic complex
(C) [Co(H2O)6]3+ (R) Coloured complex
(D) [Cr(H2O)6]3+ (S) Colourless complex
(T) Inner orbital complex

Q.48 Column-I Column-II


(A) Highest density (P) Os
(B) Colourless salts (Q) Cr
(C) Maximum magneticmoment (R) Zn
(D) Variable oxidation state (S) Mn

Q.49 Column-I Column-II


(A) Coloured ion (P) Cu+
(B) µ = 1.73 B.M. (Q) Cu2+
(C) d10 configuration (R) Fe2+
(D) More than 3 unpaired electrons (S) Mn2+

Q.50 Column-I Column-II


(A) Zn (P) d-block metal
(B) Cu (Q) Coinage metal
(C) Ag (R) Native metal
(D) Fe (S) Transitional metal

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d & f-Block Elements

[SUBJECTIVE]
Q.51 Calculate difference between oxidation state of chromium (Cr) in blue and green coloured chromium
species formed during the following given transformation.

CrO42–(aq) H2O  Blue solution    Green solution
2 /H on s tanding

Q.52 Total number of species that can be oxidized by acidic permanganate ion (MnO4¯ / H+)
I¯, Fe2+, CO2, C2O42–, S2–, SO32–, NO2¯, PO43–, SO42–.

Q.53 Find total number of bond angles in Cr2O72– ion which are greater than 109º28'

Q.54 Find total number of process which has positive value of standard electrode potential
Cr2+/Cr3+, Mn2+/Mn3+, Fe/Fe2+, Cu/Cu2+, Fe/Fe3+
Sn/Sn2+, Cr/Cr3+, Ag/Ag+, Fe3+/Fe2+

Q.55 The oxidation state of Cr in K3CrO8.

Q.56 Find total no. of oxides which act as an acid on reacting with NaOH.
ZnO, MnO, Mn2O7, CrO3, MnO2, Cr2O3, TiO

Q.57 Find total no. of mole of I¯ required to reduce 1 mole K2Cr2O7 in acidic medium

Q.58 Find total no. of ions/molecules which are tetrahedral in shape.


MnO4–1, MnO4–2, CrO4–2, CrO2Cl2, Zn(OH)4–2 , NiCl4–2, Ni(CO)4

Q.59 Select total no. of ions which are disproportionate in aqueous medium.
Cu+, Au+, Zn+2, Hg2+2

Q.60 Find total no. of ions which are paramagnetic in nature.


Sc3+, Ti3+, V+3, Cr+3, Mn+2, Fe+2, Co+2, Ni+2, Cu+, Zn+2

Q.61 Find total no. of ions whose aqueous solution is coloured.


Sc3+, Ti3+, V+3, Cr+3, Mn+2, Fe+2, Co+2, Ni+2, Cu+2, Zn+2

Q.62 Find total number of metals which shows variably valency. Na, Zn, Fe, Cu, Hg, Cd,Au, Cr, Mn

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d & f-Block Elements

EXERCISE-3
SECTION-A
(JEE Main Previous Year's Questions)
Q.1 Arrange Ce3+, La3+, Pm3+, and Yb3+ in increasing order of their ionic radius - [AIEEE-02]
(A) Yb3+ < Pm3+ < Ce3+ < La3+ (B) Ce3+ > Yb3+ < Pm3+ < La3+
(C) Yb3+ > Pm3+ < La3+ < Ce3+ (D) Pm3+ < La3+ < Ce3+ < Yb3+

Q.2 The atomic numbers of vanadium (V). Chromium (Cr), manganese (Mn) and iron (Fe) respectively 23,
24, 25 and 26. Which one of these may be expected to have the higher second ionization enthalpy ?
[AIEEE-2003]
(A) Cr (B) Mn (C) Fe (D) V

Q.3 What would happen when a solution of potassium chromate is treated with an excess of dilute nitric
acid- [AIEEE-03]
3+ 2–
(A) Cr and Cr2O7 are formed 2–
(B) Cr2O7 and H2O are formed
2–
(C) Cr2O7 is reduced to +3 state of Cr (D) Cr2O7 2– is oxidised to +7 state of Cr

Q.4 The radius of La3+ is 1.06 Å, which of the following given values will be closest to the radius of Lu3+ (At
no. of Lu = 71, La = 57) - [AIEEE-03]
(A) 1.6 Å (B) 1.4 Å (C) 1.06 Å (D) 0.85 Å

Q.5 Cerium (Z = 58) is an important member of the lanthanoids. Which of the following statement about
cerium is incorrect - [AIEEE-04]
(A) Cerium (IV) acts as an oxidising agent
(B) The +3 oxidation state of cerium is more stable than the +4 oxidation state
(C) The +4 oxidation state of cerium is not known in solutions
(D) The common oxidation states of cerium are +3 and +4

Q.6 Excess of KI reacts with CuSO4 solution and then Na2S2O3 solution is added to it. Which of the
statements is incorrect for this reaction - [AIEEE-04]
(A) Evolved I2 is reduced (B) CuI2 is formed
(C) Na2S2O3 is oxidised (D) Cu2I2 is formed

Q.7 Calomel on reaction with NH4OH gives - [AIEEE-04]


(A) HgNH2Cl (B) NH2–Hg–Hg–Cl (C) Hg2O (D) HgO

Q.8 The lanthanoid contraction is responsible for the fact that - [AIEEE-05]
(A) Zr and Y have about the same radius (B) Zr and Nb have similar oxidation state
(C) Zr and Hf have about the same radius (D) Zr and Zn have similar oxidation state

Q.9 Lanthanoid contraction is caused due to - [AIEEE-06]


(A) the same effective nuclear charge from Ce to Lu
(B) the imperfect shielding on outer electrons by 4f electrons from the nuclear charge
(C) the appreciable shielding on outer electrons by 4f electrons from the nuclear charge
(D) the appreciable shielding on outer electrons by 5d electrons from the nuclear charge
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d & f-Block Elements

Q.10 Identify the incorrect statement among the following - [AIEEE-07]


(A) d-block elements show irregular and erratic chemical properties among themselves
(B) La and Lu have partially filled d-orbitals and no other have partially filled orbitals
(C) The chemistry of various lanthanoids is very similar
(D) 4f and 5f-orbitals are equally shielded

Q.11 The actinoids exhibits more number of oxidation states in general than the lanthanoids. This is because -
(A) The 5f-orbitals are more burried than the 4f-orbitals [AIEEE-07]
(B) There is a similarly between 4f-and-5f in the their angular part of the wave function
(C) The actinoids are more reactive than the lanthanoids
(D) The 5f-orbitals extend further from the nucleus than the 4f-orbitals

Q.12 In context with the transition elements, which of the following statements is incorrect ? [AIEEE-09]
(A) In the highest oxidation states, the transition metalshow basiccharacter and form cationic complexes.
(B) In the highest oxidation states of the first five transition elements (Sc to Mn), all the 4s and 3d
electrons are used for bonding.
(C) Once the d5 configuration is exceeded, the tendency to involve all the 3d electrons in bonding
decreases.
(D) In addition to the normal oxidation states, the zero oxidation state is also shown bythese elements in
complexes.

Q.13 Knowing that the Chemistry of lanthanoids (Ln) is dominated by its +3 oxidation state, which of the
following statements is incorrect ? [AIEEE-09]
(A) The ionic sizes of Ln (III) decrease in general with increasing atomic number.
(B) Ln (III) compounds are generally colourless.
(C) Ln (III) hydroxides are mainly basic in character.
(D) Because of the large size of the Ln (III) ions the bonding in its compounds is predominantly ionic in
character.

Q.14 In context of the lanthanoids, which of the following statements is not correct ? [AIEEE-2011]
(A) There is gradual decrease in the radii of the members with increasing atomic number in the series.
B)All the members exhibit + 3 oxidation state.
(C) Because of similar properties the separation of lanthanoids is not easy.
(D)Availability of 4f electrons results in the formation of compounds in + 4 state for all the members of
the series
Q.15 Iron exhibit + 2 and + 3 oxidation states. Which of the following statements about iron is incorrect?
[AIEEE-2012]
(A) Ferrous compounds are less volatile than the corresponding ferric compounds.
(B) Ferrous compounds are more easily hydrolysed than the corresponding ferric compounds.
(C) Ferrous oxide is more basic in nature than the ferric oxide.
(D) Ferrous compounds are relatively more ionic than the corresponding ferric compounds.

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d & f-Block Elements

Q.16 Four successive members of the first row transition elements are listed below with atomic numbers.
Which one of them is expected to have the highest E 0M3 / M 2 value? [JEE Main 2013]
(A) Mn (Z = 25) (B) Fe (Z = 26) (C) Co (Z = 27) (D) Cr (Z = 24)

Q.17 Which of the following arrangements does not represent the correct order of the property stated against
it? [JEE Main 2013]
2+ 2+ 2+ 2+
(A) Ni < Co < Fe < Mn : ionic size
(B) Co3+ < Fe3+ < Cr3+ < Sc3+ : stability in aqueous solution
(C) Sc < Ti < Cr < Mn : number of oxidation states
(D) V2+ < Cr2+ < Mn2+ < Fe2+ : paramagnetic behaviour

Q.18 The color of KMnO4 is due to : [JEE Main 2015]


(A) L  M charge transfer transition (B)   * transition
(C) M  L charge transfer transition (D) d – d transition

Q.19 Which of the following compounds is metallic and ferromagnetic ? [JEE Main 2016]
(A) MnO2 (B) TiO2 (C) CrO2 (D) VO2

Q.20 Given [JEE Main 2017]


º
E Cl 2 / Cl ¯
 1.36V, E Cr
º
3
/ Cr
 0.74V
º
E Cr O 2 / Cr 3
 1.33V, E ºMnO ¯ / Mn 2  1.51V .
2 7 4

Among the following, the strongest reducing agent is :


(A) Mn2+ (B) Cr3+ (C) Cl¯ (D) Cr

Q.21 In the following reactions, ZnO is respectively acting as a/an : [JEE Main 2017]
(a) ZnO + Na2O  Na2ZnO2
(b) ZnO + CO2  ZnCO3
(A) base and base (B) acid and acid (C) acid and base (D) base and acid

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d & f-Block Elements

SECTION-B
(JEE ADVANCED Previous Year's Questions)
Q.1 Ammonium dichromate is used in some fireworks. The green colored powder blown in the air is
(A) CrO3 (B) Cr2O3 (C) Cr (D) CrO(O2) [JEE 1997]
Q.2 Which of the following is an organometallic compound ? [JEE 1997]
(A)lithium methoxide (B) lithium acetate
(C) lithium dimethylamide (D)methyl lithium
Q.3 Which of the following compounds is expected to be colored ? [JEE 1997]
(A) Ag2SO4 (B) CuF2 (C) MgF2 (D) CuCl
Q.4 In the standardization of Na2S2O3 using K2Cr2O7 by iodometry, the equivalent weight of K2Cr2O7 is
(A) (molecular weight ) / 2 (B) (molecular weight) / 6 [JEE 1999]
(C) (molecular weight) / 3 (D) same as molecular weigh
Q.5 Amongst the following, identify the species with an atom in +6 oxidation state. [JEE 2000]
(A) MnO4¯ (B) Cr(CN)63– (C) NiF62– (D) CrO2Cl2
Q.6 The complex ion which has no "d" electrons in the central atom is (at. no Cr=24, Mn = 25, Fe = 26,
Co = 27) [JEE 2001]
(A) [MnO4]¯ (B) [Co(NH3)6] 3+ (C) [Fe(CN)6] 3– (D) [Cr(H2O)6]3+
Q.7 Anhydrous ferric chloride is prepared by: [JEE 2002]
(A) heating hydrated ferric chloride at a high temperature in a stream of air
(B) heating metallic iron in a stream of dry chlorine gas
(C) reaction of ferric oxide with HCl
(D) reaction of metallic iron with HCl
Q.8 When MnO2 is fused with KOH, a coloured compound is formed, the product and its colour is:
(A) K2MnO4, green colour (B) KMnO4, purple [JEE 2003]
(C) Mn2O3, brown (D) Mn3O4, black
Q.9 The pair of the compounds in which both the metals are in the highest possible oxidation state is
(A) [Fe(N)6]3– , [Co(CN)6]3– (B) CrO2Cl2, MnO4¯ [JEE 2004]
(C) TiO3 , MnO2 3–
(D) [Co(CN)6] , MnO2
Q.10 The product of oxidation of I¯ with MnO4¯ in alkaline medium is [JEE 2004]
(A) IO3¯ (B) I2 (C) IO¯ (D) IO4¯
Q.11 The correct statement(s) about Cr2+ and Mn3+ is (are) [JEEAdvance 2015]
[Atomic numbers of Cr = 24 and Mn = 25]
(A) Cr2+ is a reducing agent
(B) Mn3+ is an oxidizing agent
(C) Both Cr2+ and Mn3+ exhibit d4 electronic configuration
(D) When Cr2+ is used as a reducing agent, the chromium ion attains d5 electronic configuration.
Q.12 Which of the following combination will produce H2 gas? [JEE Adv. 2017]
(A) Au metal and NaCN (aq) in the presence of air
(B) Cu metal and conc. HNO3
(C) Fe metal and conc. HNO3
(D) Zn metal and NaOH (aq.)

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d & f-Block Elements

EXERCISE-4

(NCERT Exampler)
Single correct :
Q.1 Electronic configuration of a transition element X in +3 oxidation state is [Ar]3d5. What is its atomic
number?
(A) 25 (B) 26 (C) 27 (D) 24
Q.2 The electronic configuration of Cu(II) is 3d9 whereas that of Cu(I) is 3d10. Which of the following is
correct?
(A) Cu(II) is more stable
(C) Cu(II) is less stable
(B) Cu(I) and Cu(II) are equally stable
(D) Stability of Cu(I) and Cu(II) depends on nature of copper salts
Q.3 Metallic radii of some transition elements are given below. Which of these elements will have highest
density?
Element Fe Co Ni Cu
Metallic radii/pm 126 125 125 128
(A) Fe (B) Ni (C) Co (D) Cu
Q.4 Generally transition elements form coloured salts due to the presence of unpaired electrons. Which of
the following compounds will be coloured in solid state?
(A) Ag2SO4 (B) CuF2 (C) ZnF2 (D) Cu2Cl2
Q.5 On addition of small amount of KMnO4 to concentrated H2SO4, a green oily compound is obtained
which is highly explosive in nature. Identifythe compound from the following.
(A) Mn2O7 (B) MnO2 (C) MnSO4 (D) Mn2O3
Q.6 The magnetic nature of elements depends on the presence of unpaired electrons. Identifythe configuration
of transition element, which shows highest magnetic moment.
(A) 3d7 (B) 3d5 (C) 3d8 (D) 3d2
Q.7 Which of the following oxidation state is common for all lanthanoids?
(A) +2 (B) +3 (C) +4 (D) +5
Q.8 Which of the following reactions are disproportionation reactions?
(a) Cu+  Cu2+ + Cu
(b) 3MnO4– + 4H+   2MnO4– + MnO2 + 2H2O
(c) 2KMnO4   K2MnO4 + MnO2 + O2
(d) 2MnO4 + 3Mn2+ + 2H2O 
–  5MnO2 + 4H+
(A) a, b (B) a, b, c (C) b, c, d (D) a, d
Q.9 When KMnO4 solution is added to oxalic acid solution, the decolourisation is slow in the beginning but
becomes instantaneous after some time because
(A) CO2 is formed as the product. (B) Reaction is exothermic.
(C) MnO4– catalyses the reaction. (D) Mn2+ acts as autocatalyst.

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d & f-Block Elements

Q.10 There are 14 elements in actinoid series. Which of the following elements does not belong to this series?
(A) U (B) Np (C) Tm (D) Fm
Q.11 KMnO4 acts as an oxidising agent in acidic medium. The number of moles of KMnO4 that will be
needed to react with one mole of sulphide ions in acidic solution is :
2 3 4 1
(A) (B) (C) (D)
5 5 5 5

Q.12 Which of the following is amphoteric oxide?


Mn2O7, CrO3, Cr2O3, CrO, V2O5, V2O4
(A) V2O5, Cr2O3 (B) Mn2O7, CrO3
(C) CrO, V2O5 (D) V2O5, V2O4
Q.13 Gadolinium belongs to 4f series. It’s atomic number is 64.Which of the following is the correct electronic
configurationof gadolinium?
(A) [Xe] 4f75d16s2 (B) [Xe] 4f65d26s2
(C) [Xe] 4f86d2 (D) [Xe] 4f95s1
Q.14 Interstitial compounds are formed when small atoms are trapped inside the crystal lattice of metals.
Which of the following is not the characteristic property of interstitial compounds?
(A) They have high melting points in comparison to pure metals.
(B) They are very hard.
(C) They retain metallic conductivity.
(D) They are chemically very reactive
Q.15 The magnetic moment is associated with its spin angular momentum and orbital angular momentum. Spin
only magnetic moment value of Cr3+ ion is ___________.
(A) 2.87 B.M. (B) 3.87 B.M. (C) 3.47 B.M. (D) 3.57 B.M
Q.16 KMnO4 acts as an oxidising agent in alkaline medium. When alkaline KMnO4 is treated with KI, iodide
ion is oxidised to ____________.
(A) I2 (B) IO– (C) IO3– (D) IO4–
Q.17 Which of the following statements is not correct?
(A) Copper liberates hydrogen from acids.
(B) In its higher oxidation states, manganese forms stable compounds with oxygen and fluorine.
(C) Mn3+ and Co3+ are oxidising agents in aqueous solution.
(D) Ti2+ and Cr2+ are reducing agents in aqueous solution.
Q.18 When acidified K2Cr2O7 solution is added to Sn2+ salts then Sn2+ changes to
(A) Sn (B) Sn3+ (C) Sn4+ (D) Sn+
Q.19 Highest oxidation state of manganese in fluoride is +4 (MnF4) but highest oxidation state in oxides is +7
(Mn2O7) because ____________.
(A) fluorine is more electronegative than oxygen.
(B) fluorine does not possess d-orbitals.
(C) fluorine stabilises lower oxidation state.
(D) in covalent compounds fluorine can form single bond only while oxygen forms double bond.
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d & f-Block Elements

Q.20 Although Zirconium belongs to 4d transition series and Hafnium to 5d transition series even then they
show similar physical and chemical properties because___________.
(A) both belong to d-block.
(B) both have same number of electrons.
(C) both have similar atomic radius.
(D) both belong to the same group of the periodic table
Q.21 Why is HCl not used to make the medium acidic in oxidation reactions of KMnO4 in acidic medium?
(A) Both HCl and KMnO4 act as oxidising agents.
(B) KMnO4 oxidises HCl into Cl2 which is also an oxidising agent.
(C) KMnO4 is a weaker oxidising agent than HCl.
(D) KMnO4 acts as a reducing agent in the presence of HCl.
Multiple Choice Questions
Q.22 Generally transition elements and their salts are coloured due to the presence of unpaired electrons in
metal ions. Which of the following compounds are coloured?
(A) KMnO4 (B) Ce(SO4)2 (C) TiCl4 (D) Cu2Cl2
Q.23 Transition elements show magnetic moment due to spin and orbital motion of electrons. Which of the
following metallic ions have almost same spin onlymagnetic moment?
(A) Co2+ (B) Cr2+ (C) Mn2+ (D) Cr2+
Q.24 In the form of dichromate, Cr(VI) is a strong oxidising agent in acidic medium but Mo(VI) in MoO3 and
W (VI) in WO3 are not because ___________.
(A) Cr (VI) is more stable than Mo(VI) and W(VI).
(B) Mo(VI) and W(VI) are more stable than Cr(VI).
(C) Higher oxidation states of heavier members of group-6 of transition series are more stable.
(D) Lower oxidation states of heavier members of group-6 of transition series are more stable.
Q.25 Which of the following actinoids show oxidation states upto +7?
(A)Am (B) Pu (C) U (D) Np
Q.26 General electronic configuration of actionoids is (n–2)f1–14 (n-1)d0–2ns2.Which of the following actinoids
have one electron in 6d orbital?
(A) U (Atomic no. 92) (B) Np (Atomic no.93)
(C) Pu (Atomic no. 94) (D)Am (Atomic no. 95)
Q.27 Which of the following lanthanoids show +2 oxidation state besides the characteristic oxidation state +3
of lanthanoids?
(A) Ce (B) Eu (C) Yb (D) Ho

Q.28 Which of the following ions show higher spin onlymagnetic moment value?
(A) Ti3+ (B) Mn2+ (C) Fe2+ (D) Co3+

Q.29 Transition elements form binary compounds with halogens. Which of the following elements will form
MF3 type compounds?
(A) Cr (B) Co (C) Cu (D) Ni

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d & f-Block Elements

Q.30 Which of the following will not act as oxidising agents?


(A) CrO3 (B) MoO3 (C) WO3 (D) CrO42–

Q.31 Although +3 is the characteristic oxidation state for lanthanoids but cerium also shows +4 oxidation state
because ___________.
(A) it has variable ionisation enthalpy
(B) it has a tendency to attain noble gas configuration
(C) it has a tendency to attain f 0 configuration
(D) it resembles Pb4+

Short Answer Type


Q.32 Why does copper not replace hydrogen from acids?
Q.33 Why E¯ values for Mn, Ni and Zn are more negative than expected?
Q.34 Why first ionisation enthalpy of Cr is lower than that of Zn ?
Q.35 Transition elements show high melting points. Why?
Q.36 When Cu2+ ion is treated with KI, a white precipitate is formed. Explain the reaction with the help of
chemical equation
Q.37 Out of Cu2Cl2 and CuCl2, which is more stable and why?
Q.38 When a brown compound of manganese (A) is treated with HCl it gives a gas (B). The gas taken in
excess, reacts with NH3 to give an explosive compound (C). Identify compounds A, B and C.
Q.39 Although fluorineis more electronegative thanoxygen,but the abilityof oxygen to stabilisehigher oxidation
states exceeds that of fluorine. Why?
Q.40 Although Cr3+ and Co2+ ions have same number of unpaired electrons but the magnetic moment of Cr3+
is 3.87 B.M. and that of Co2+ is 4.87 B.M. Why?
Q.41 Ionisation enthalpies of Ce, Pr and Nd are higher than Th, Pa and U. Why?
Q.42 Although Zr belongs to 4d and Hf belongs to 5d transition series but it is quite difficult to separate them.
Why?
Q.43 Although +3 oxidation states is the characteristic oxidation state of lanthanoids but cerium shows +4
oxidation state also. Why?
Q.44 Explain whydoes colour of KMnO4 disappear when oxalic acid is added to its solution in acidic medium.
Q.45 When orange solution containing Cr2O72– ion is treated with an alkali, a yellow solution is formed and
when H+ ions are added to yellow solution, an orange solution is obtained. Explain whydoes this happen?
Q.46 A solution of KMnO4 on reduction yields either a colourless solution or a brown precipitate or a green
solution depending on pH of the solution. What different stages of the reduction do these represent and
how are they carried out?
Q.47 The second and third rows of transition elements resemble each other much more than they resemble the
first row. Explain why?

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d & f-Block Elements

Q.48 E– of Cu is + 0.34V while that of Zn is – 0.76V. Explain.


Q.49 The halides of transition elements become more covalent with increasing oxidation state of the metal.
Why?
Q.50 While filling up of electrons in the atomic orbitals, the 4s orbital is filled before the 3d orbital but reverse
happens during the ionisation of the atom. Explain why?
Q.51 Reactivity of transition elements decreases almost regularly from Sc to Cu. Explain.
Matching Type :
Q.52 Match the catalysts given in Column I with the processes given in Column II.
Column I (Catalyst) Column II (Process)
(i) Ni in the presence (a) Zieglar Natta catalyst
of hydrogen
(ii) Cu2Cl2 (b) Contact process
(iii) V2 O 5 (c) Vegetable oil to ghee
(iv) Finelydivided iron (d) Sandmeyer reaction
(v) TiCl4 +Al(CH3)3 (e) Haber’s Process
(f) Decomposition of KClO3
Q.53 Match the compounds/elements given in Column I with uses given in Column II.
Column I (Compound/element) Column II (Use)
(i) Lanthanoid oxide (a) Production of iron alloy
(ii) Lanthanoid (b) Television screen
(iii) Misch metal (c) Petroleum cracking
(iv) Magnesium based alloy is (d) Lanthanoid metal + iron
constituent of
(v) Mixed oxides of (e) Bullets
lanthanoids are employed (f) In X-ray screen
Q.54 Match the properties given in Column I with the metals given in Column II.
Column I (Property) Column II (Metal)
(i) An element which can show (a) Mn
+8 oxidation state
(ii) 3d block element that can show (b) Cr
upto +7 oxidation state (c) Os
(iii) 3d block element with highest (d) Fe
meltingpoint
Q.55 Match the statements given in Column I with the oxidation states given in Column II.
Column I Column II
(i) Oxidation state of Mn in MnO2 is (a) + 2
(ii) Most stable oxidation state of Mn is (b) + 3
(iii) Most stable oxidation state of (c) + 4
Mn in oxides is (d) + 5
(iv) Characteristic oxidation (e) + 7
state of lanthanoids is
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d & f-Block Elements

Q.56 Match the solutions given in Column I and the colours given in Column II.
Column I Column II
(Aqueous solution of salt) (Colour)
(i) FeSO4.7H2O (a) Green
(ii) NiCl2.4H2O (b) Light pink
(iii) MnCl2.4H2O (c) Blue
(iv) CoCl2.6H2O (d) Pale green
(v) Cu2Cl2 (e) Pink
(f) Colourless

Q.57 Match the property given in Column I with the element given in Column II.
Column I (Property) Column II (Element)
(i) Lanthanoid which shows (a) Pm
+4 oxidation state
(ii) Lanthanoid which can show +2 (b) Ce
oxidation state
(iii) Radioactive lanthanoid (c) Lu
(iv) Lanthanoid which has 4f 7 (d) Eu
electronic configuration in +3
oxidation state
(v) Lanthanoid which has 4f14 (e) Gd
electronic configuration in+3
oxidation state (f) Dy

Q.58 Match the properties given in Column I with the metals given in Column II.
Column I (Property) Column II (Metal)
(i) Element with highest second (a) Co
ionisation enthalpy
(ii) Element with highest third ionisation (b) Cr
enthalpy
(iii) M in M (CO)6 is (c) Cu
(iv) Element with highest heat of atomisation (d) Zn
(e) Ni

Assertion and Reason type :


(A) Both assertion and reason are true, and reason is the correct explanation of the assertion.
(B) Both assertion and reason are true but reason is not the correct explanation of assertion.
(C)Assertion is not true but reason is true.
(D) Both assertion and reason are false.
Q.59 Assertion : Cu2+ iodide is not known
Reason : Cu2+ oxidises I– to iodine.

Q.60 Assertion : Separation of Zr and Hf is difficult.


Reason : Because Zr and Hf lie in the same group of the periodic table.

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d & f-Block Elements

Q.61 Assertion :Actinoids form relatively less stable complexes as compared to lanthanoids.
Reason :Actinoids can utilise their 5f orbitals along with 6d orbitals in bonding but lanthanoids do not
use their 4f orbital for bonding.

Q.62 Assertion : Cu cannot liberate hydrogen from acids.


Reason : Because it has positive electrode potential.

Q.63 Assertion : The highest oxidation state of osmium is +8.


Reason : Osmium is a 5d-block element.

Long Answer Type :


Q.64 IdentifyAto E and also explain the reactions involved.

CuCO3

CuO (D)
heat with CuS
Ca(OH)2
(A) (E)
HNO3(conc.) Milky

(B) CO2

NH3(aq) Ca(HCO3) 2
clear solution
(C)
Blue solution

Q.65 When a chromite ore (A) is fused with sodium carbonate in free excess of air and the product is dissolved
in water, a yellow solution of compound (B) is obtained.After treatment of this yellow solution with
sulphuric acid, compound (C) can be crystallised from the solution. When compound (C) is treated with
KCl, orange crystals of compound (D) crystallise out. IdentifyAto D and also explain the reactions.

Q.66 When an oxide of manganese (A) is fused with KOH in the presence of an oxidising agent and dissolved
in water, it gives a dark green solution of compound (B). Compound (B) disproportionates in neutral or
acidic solution to give purple compound (C).An alkaline solution of compound (C) oxidises potassium
iodide solution to a compound (D) and compound (A) is also formed. Identify compounds Ato D and
also explain the reactions involved.

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d & f-Block Elements

Q.67 On the basis of Lanthanoid contraction, explain the following :


(i) Nature of bonding in La2O3 and Lu2O3.
(ii) Trends in the stability of oxo salts of lanthanoids from La to Lu.
(iii) Stability of the complexes of lanthanoids.
(iv) Radii of 4d and 5d block elements.
(v) Trends in acidic character of lanthanoid oxides.

Q.68
(a) Answer the following questions :
(i) Which element of the first transition series has highest second ionisation enthalpy?
(ii) Which element of the first transition series has highest third ionisation enthalpy?
(iii) Which element of the first transition series has lowest enthalpy of atomisation?
(b) Identify the metal and justify your answer.
(i) Carbonyl M (CO)5 (ii) MO3F

Q.69 Mention the type of compounds formed when small atoms like H, C and N get trapped inside the crystal
lattice of transition metals.Also give physical and chemical characteristics of these compounds.

Q.70 (a) Transition metals can act as catalysts because these can change their oxidation state. How does
Fe(III) catalyse the reaction between iodide and persulphate ions?
(b) Mention any three processes where transition metals act as catalysts.

Q.71 A violet compound of manganese (A) decomposes on heating to liberate oxygen and compounds (B)
and (C) of manganese are formed. Compound (C) reacts with KOH in the presence of potassium nitrate
to give compound (B). On heating compound (C) with conc. H2SO4 and NaCl, chlorine gas is liberated
and a compound (D) of manganese along with other products is formed. Identify compounds (A) to (D)
and also explain the reactions involved.

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d & f-Block Elements

ANSWER KEY
EXERCISE-1
Q.1 B Q.2 A Q.3 B Q.4 A Q.5 B Q.6 D Q.7 A
Q.8 B Q.9 A Q.10 A Q.11 B Q.12 A Q.13 B Q.14 B
Q.15 A Q.16 B Q.17 D Q.18 B Q.19 C Q.20 A Q.21 B
Q.22 A Q.23 D Q.24 A Q.25 D Q.26 A Q.27 B Q.28 A
Q.29 C Q.30 C Q.31 D Q.32 C Q.33 B Q.34 C Q.35 A
Q.36 C Q.37 D Q.38 C Q.39 A Q.40 A Q.41 B Q.42 C
Q.43 B Q.44 A Q.45 B Q.46 B Q.47 C Q.48 C Q.49 C
Q.50 C Q.51 A Q.52 A Q.53 C Q.54 D Q.55 D Q.56 D
Q.57 C Q.58 D Q.59 A Q.60 B Q.61 C Q.62 A Q.63 C
Q.64 A Q.65 C Q.66 C Q.67 A Q.68 D Q.69 C Q.70 D
Q.71 A Q.72 C Q.73 C Q.74 A Q.75 D Q.76 C Q.77 A
Q.78 D Q.79 B Q.80 D Q.81 B Q.82 C Q.83 B Q.84 B
Q.85 B Q.86 D Q.87 B Q.88 A Q.89 B Q.90 B Q.91 A
Q.92 B Q.93 C Q.94 C Q.95 B Q.96 C Q.97 C Q.98 A
Q.99 D Q.100 D Q.101 D Q.102 B Q.103 B Q.104 D

EXERCISE-2
Q.1 B Q.2 D Q.3 B Q.4 D Q.5 C Q.6 D Q.7 ABC
Q.8 BCD Q.9 AB Q.10 AB Q.11 AD Q.12 AB Q.13 ABD Q.14 ABC
Q.15 BC Q.16 ABC Q.17 ABC Q.18 ABC Q.19 ABC Q.20 AB Q.21 BC
Q.22 AC Q.23 BD Q.24 ABCD Q.25 AB Q.26 ABC Q.27 AB Q.28 BC
Q.29 BD Q.30 ABCD Q.31 ABC Q.32 BCD Q.33 AD Q.34 AC Q.35 AD
Q.36 BCD Q.37 ABD Q.38 ACD Q.39 ABCD Q.40 ABC Q.41 ABC Q.42 ABC
Q.43 ABCD Q.44 ACD Q.45 ABCD Q.46 BD
Q.47 (A) Q,S,T;(B)P, R;(C) Q, R, T;(D) P, R, T Q.48 (A) P (B) R (C) Q (D) P,Q,S
Q.49 (A) Q,R,S (B) Q (C) P (D) R,S Q.50 (A) P (B) P,Q,S (C) P,QR,S (D) P, S
Q.51 3 Q.52 6 Q.53 7 Q.54 6 Q.55 5 Q.56 5 Q.57 6
Q.58 7 Q.59 3 Q.60 7 Q.61 8 Q.62 6

EXERCISE-3
SECTION-A
Q.1 A Q.2 A Q.3 B Q.4 D Q.5 C Q.6 B Q.7 A
Q.8 C Q.9 B Q.10 D Q.11 D Q.12 A Q.13 B Q.14 D
Q.15 B Q.16 C Q.17 BD Q.18 A Q.19 C Q.20 D Q.21 C

SECTION-B
Q.1 B Q.2 D Q.3 B Q.4 B Q.5 D Q.6 A Q.7 B
Q.8 A Q.9 B Q.10 A Q.11 ABC Q.12 D

EXERCISE-4
Q.1 B Q.2 A Q.3 D Q.4 B Q.5 A Q.6 B Q.7 B
Q.8 A Q.9 D Q.10 C Q.11 A Q.12 A Q.13 A Q.14 D
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d & f-Block Elements

Q.15 B Q.16 C Q.17 A Q.18 C Q.19 D Q.20 C Q.21 B


Q.22 AB Q.23 AD Q.24 BC Q.25 BD Q.26 AB Q.27 BC Q.28 BC
Q.29 AB Q.30 BD Q.31 BC
Q.32 –
Cu shows positive E value.
Q.33 Hint : Negative E– values for Mn2+ and Zn2+ are related to stabilities of half filled and fully filled
configuration respectively. But for Ni2+ , E– value is related to the highest negative enthalpy of hydration
Q.34 Ionisation enthalpy of Cr is lower due to stability of d5 and the value for Zn is higher because its electron
comes out from 4s orbital
Q.35 The high melting points of transition metals are attributed to the involvement of greaternumber of electrons
in the interatomic metallic bonding from (n-1) d-orbitals in addition to ns electrons.
Q.36 Cu2+ gets reduced to Cu+
2Cu2+ + 4I– 
 Cu2I2 (white ppt.) + I2
Q.37 CuCl2 is more stable than Cu2Cl2. The stability of Cu2+ (aq.) rather than Cu+(aq.) is due to the much
more negative hydH– of Cu2+ (aq.) than Cu+(aq.).
Q.38 A = MnO2 , B = Cl2, C = NCl3
MnO2 + 4HCl 
 MnCl2 + Cl2 + 2H2O
(A) (B)
NH3 + 3Cl2(excess)   NCl3 + 3HCl
(C)
Q.39 It is due to the ability of oxygen to form multiple bonds to metals.
Q.40 Dueto symmetrical electronicconfigurationthereis no orbital contributioninCr3+ ion.However appreciable
orbital contribution takes place in Co2+ ion.
Q.41 It is because in the beginning, when 5f orbitals begin to be occupied, theywill penetrate less into the inner
core of electrons. The 5f electrons will therefore, be more effectively shielded from the nuclear charge
than 4f electrons of the corresponding lanthanoids. Therefore outer electrons are less firmly held and
they are available for bonding in the actinoids
Q.42 Due to lanthanoid contraction, they have almost same size (Zr, 160 pm) and (Hf, 159 pm).
Q.43 It is because after losing one more electron Ce acquires stable 4f 0 electronic configuration.
Q.44 KMnO4 acts as oxidising agent. It oxidises oxalic acid to CO2 and itself changes to Mn2+ ion which is
colourless.
5C2O42– + 2MnO4– + 16H+ 
 2Mn2+ + 8H2O + 10CO2
(Coloured) (Colourless)

Q.45 Cr2O72– OH

  CrO42–
H

Dichromate Chromate
(Orange) (Yellow)

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d & f-Block Elements

Q.46 Oxidising behaviour of KMnO4 depends on pH of the solution.


In acidic medium (pH < 7)
MnO4– + 8H+ + 5e–   Mn2+ + 4H2O
(Colourless)
In alkaline medium (pH>7)
MnO4– + e–   MnO42–
(Green)
In neutral medium(pH=7)
MnO4– + 2H2O + 3e– 
 MnO2 + 4OH–
(Brown precipitate)

Q.47 Due to lanthanoid contraction, the atomic radii of the second and third row transition elements is almost
same. So they resemble each other much more as compared to first row elements.
Q.48 High ionisation enthalpytotransform Cu(s) to Cu2+(aq) is not balancedbyits hydration enthalpy. However,
in case of Zn after removal of electrons from 4s-orbital, stable 3d10 configuration is acquired.
Q.49 As the oxidation state increases, size of the ion of transition element decreases. As per Fajan’s rule, as
the size of metal ion decreases, covalent character of the bond formed increases.
Q.50 n + 1 rule : For 3d = n + 1 = 5
4s = n + l = 4
So electron will enter in 4s orbital.
Ionisation enthalpyis responsible for the ionisation of atom. 4s electrons are loosely held by the nucleus.
So electrons are removed from 4s orbital prior to 3d.
Q.51 It is due to regular increase in ionisation enthalpy
Q.52 (i)  (c) (ii)  (d) (iii)  (b) (iv)  (e) (v)  (a)
Q.53 (i)  (b) (ii)  (a) (iii)  (d) (iv)  (e) (v)  (c)
Q.54 (i)  (c) (ii)  (a) (iii)  (b)
Q.55 (i)  (c) (ii)  (a) (iii)  (e) (iv)  (b)
Q.56 (i)  (d) (ii)  (a) (iii)  (b) (iv)  (e) (v)  (f)
Q.57 (i)  (b) (ii)  (d) (iii)  (a) (iv)  (e) (v)  (c)
Q.58 (i)  (c) (ii)  (d) (iii)  (b) (iv)  (a)
Q.59 A Q.60 B Q.61 C Q.62 A Q.63 B
Q.64 A = Cu, B = Cu(NO3)2, C = [Cu(NH3)4] D = CO2
E = CaCO3, F = Cu2[Fe(CN)6], G = Ca(HCO3)2
CuCO3  CuO + CO2
CuO + CuS  Cu(A) + SO2
Cu + 4HNO3(conc.)  Cu(NO3)2(B) + 2NO + 2H2O
Cu2+(B) + NH3 [Cu(NH3)4](C)
Ca(OH)2 + CO2(D)  CaCO3 + H2O
CaCO3 + H2O + CO2  Ca(HCO3)2

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d & f-Block Elements

Q.65 A = FeCr2O4, B = Na2CrO4, C = Na2Cr2O7.2H2O, D = K2Cr2O7


4FeCr2O4 (A) + 8Na2CO3 + 7O2  8Na2CrO4(B) + 2Fe2O3 + 8CO3
2NaCrO4 + 2H+  Na2Cr2O7 + 2Na+ + H2O
Na2Cr2O7(C) + 2KCl  K2Cr2O7 (D) + 2NaCl
Q.66 A = MnO2 , (B) K2MnO4 , (C) KMnO4 , (D) KIO3
2MnO2(A) + 4KOH + O2  2K2MnO4 (B) + 2H2O
3MnO42– (C) + 4H+  2MnO4– + MnO2 + 2H2O
2MnO4– + H2O + KI  2MnO2 + 2OH– + KIO
Q.67 (i)As the size decreases covalent character increases. Therefore La2O3 is more ionic and Lu2O3 is more
covalent.
(ii) As the size decreases from La to Lu, stability of oxosalts also decreases.
(iii) Stability of complexes increases as the size of lanthanoids decreases.
(iv) Radii of 4d and 5d block elements will be almost same.
(v) Acidic character of oxides increases from La to Lu.
Q.68 (a) (i) Cu, because the electronic configuration of Cu is 3d104s1. So second electron needs to be removed
from completelyfilled d-orbital.
(ii) Zn [Hint :As above]
(iii) Zn [Hint : No unpaired electron for metallic bonding]
(b) (i) Fe(CO)5 [Hint : EAN rule]
(ii) MnO3F [Hint : Mn shows +7 oxidation state; d-electrons are not involved in bonding.
Q.69 Interstitial compounds.
Characteristic properties :
(i) High melting points, higher than those of pure metals.
(ii) Very hard.
(iii) Retain metallic conductivity.
(iv) Chemicallyinert.
Q.70 (a) Reaction between iodide and persulphate ions is :
2I– + S2O82– Fe )  I2 + 2SO4
( III
2–

Role of Fe (III) ions :


2Fe3+ + 2I– 
 2Fe2+ + I2
2Fe2+ + S2O2–8  3+ 2–
 2Fe + 2SO 4
(b) (i) Vanadium (V) oxide in contact process for oxidation of SO2 to SO3.
(ii) Finely divided iron in Haber’s process in conversion of N2 and H2 to NH3.
(iii) MnO2 in preparation of oxygen from KClO3.
Q.71 A = KMnO4 , B = K2MnO4, C = MnO2, D = MnCl2

KMnO4(A)  K2MnO4(B) + MnO2(C) + O2
MnO2 + KOH + O2 
 2K2MnO4 + 2H2O
MnO2 + 4NaCl + 4H2SO4 
 MnCl2(D) + 2NaHSO4 + 2H2O + Cl2

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