CONTENTS

S.NO. TOPIC PAGE NO

1. INTRODUCTION 2

2. ELECTRONIC CONFIGURATION AND IRREGULARITIES 2

3. GENERAL CHARACTERISTICS 2

4. COLOUR 3

5. COMPLEX FORMATION 3

6. CHROMATE -DICHROMATE 4

7. MANGANATE & PERMANGANATE 5

8. SILVER AND ITS COMPOUND 6

9. ZINC COMPOUNDS 8

10 .COPPER COMPOUNDS 9

11. IRON COMPOUNDS 10

12. INNER TRANSITION ELEMENTS 11

13. LANTHANIDE CONTRACTION 12

1
d & f - block

d & f - BLOCK
1. INTRODUCTION
In these elements the last electron enters (n–1)d orbitals of atom of an element is called d-block
elements.
2. ELECTRONIC CONFIGURATION AND IRREGULARITIES
The valence shell configurations of these elements can be represented by (n – 1)d1–10ns 0,1,2 .
All the d–block elements are classified into four series viz 3d , 4d , 5d and 6d series corresponding to the
filling of 3d , 4d , 5d and 6d orbitals of (n–1)th main shell orbitals of (n–1)th main shell. Each Series has
10 element s. Cr(3d 5 , 4s 1) , Cu(3d 10 , 4s 1 ), Mo(4d 5 , 5s 1), Pd(4d 10 , 5s 0), Ag(4d 10, 5s 1 )
anAu(5d10 , 6s1) clearly show the irregularities in the configurations
These are explained on the basis of the concept that half filled and completely filled d–orbitals are
relatively more stable than other d–orbitals.
3. GENERAL CHARACTERISTICS
(i) Metallic character: They are all metal and good conductor of heat & electricity
(ii) Electronic configuration: (n–1)d1–10ns1–2
(iii) M.P. Cr — Maximum Zn  lowest m.p.
Mo  6 no. of unpaired e s – Cd  due to no unpaired e–

W are involved in metallic bonding Hg  for metallic bonding
(iv) Variation in atomic radius:
Sc ——— Mn Fe Co Ni Cu Zn

decreases remains increases
same again
(v) Variable oxidation states possible
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+ — green
Mn3+ — violet
Mn2+ — light pink
Fe2+ — light green
Fe3+ — yellow
Co2+ — pink
Ni2+ — green
Cu2+ — blue
Zn2+ — colourless

2
d & f - block
4. COLOUR
Substances appear coloured when they absorb light of a particular wavelength in the visible region of the
spectrum and transmit light of other wavelengths. The colour which we see is the colour of the transmitted
wavelengths. In other words, the colour of the compound observed by us is the complmentary colour
of the colour absorbed by the compound.
In the s- and p-block elements there cannot be any d-d transitions and the energy needed to promote s
or p electron to a higher level is much greater and may correspond to ultraviolet region, in which case the
compound will not appear coloured to the eye.
Relationship between colour and wavelength
Wavelength absorbed in nm Colour absorbed Colour observed
<400 UV region White/colourless
400—435 Violet Yellow-green
435—480 Indigo Yellow
480—490 Green-blue Orange
490—500 Blue-green Red
500—560 Green Purple
560—580 Y ellow-green Violet
580—595 Yellow Indigo
595—605 Orange Green-blue
605—750 Red Blue-green
> 750 Infra-red White/colourless
Magnetic Properties: When a substance is placed in a magnetic field of strength H, the intensity of the
magnetic field in the substance may be greater than or less than H.
diamagnetic, Substances which are weakly repelled by a magnetic field
paramagnetic the substances which are weakly attracted bythe magnetic field and lose their
magnetism when removed from the field .
Paramagnetism is expressed by magnetic moment,
  n(n  2) B.M.
n = number of unpaired electrons
B.M. = Bohr Magneton, unit of magnetic moment

5. COMPLEX FORMATION
In the case of transition metals in low oxidation states, the electrons in the d orbitals become involved in
bonding with ligands.The bonding between the ligand and the transition metal ion can either be
predominantly electrostatic or covalent or in many cases intermediate between the two extremes. Some
of the typical complexes of the transition meals are [Fe(CN) 6]3– ,[Ni(NH 3) 4]2 ,[Cu(CN) 4 ]3– ,
[Cu(NH 3) 4]2 etc.
Formation of alloys :
Transition elements have almost similar atomic sizes. Therefore , these elements can mutually
substitute their positions in their crystal lattice. The alloys are hard and have high melting points as
compared to the most metal.
Catalytic Properties: Many transition metals and their compounds have catalytic properties.
some example
TiCl 3 Used as the Ziegler-Natta catalyst in the production of polythene.
V2O 5 Converts SO 2 to SO3 in the contact process for making H 2SO 4 .
MnO 2 Used as a catalyst to decompose KClO3 to give O 2 .

3
d & f - block
Fe Promoted iron is used in the Haber-Bosch process for making NH3 .
H 2O 2 Used as Fenton’s reagent for oxidizing alcohols to aldehydes.
Pd Used for hydrogenation (e.g. phenol to cyclohexanone).
Pt/Rh Formerly used in the Ostwald process for making HNO3 to oxidize NH 3 to NO.
Ni Raney nickel, numerous reduction processes (e.g. manufacture of hexamethylenediamine,
production of H2 from NH3 , reducing anthraquinone to anthraquinol in the production of H2O2 ).

Ionisation Energies
Ionisation energies-(i) of 5d elements are higher than those of the 3d and 4d elements. This is due to
greater effective nuclear charge acting on outer valence electrons because of the weak shielding of the
nucleus by 4f electrons. The ionisation energies of the 3d and 4d elements are irregular.
Common oxidation states for each element include +2 and +3 or both. The +3 oxidation states are more
stable at the beginning of the series, whereas towards the end +2 oxidation states are more stable.
Ionisation energy increases gradually from left to right. However the third ionisation energies, when an
electron is removed from 3d orbital, increases more rapidly than the second and third ionisation
energies. Because it takes more energy to remove the third electron from the metals near the end of the
row than from those near the beginning, the metals near the end tends to form M2+ ions rather than
M3+ ions.

6. CHROMATE -DICHROMATE
Preparation :
4FeO . Cr2O3 + 8Na2CO3 + 7O2 Rosting
 8Na2CrO4 + 2Fe2O3 + 8CO2
in air
chromate ore
The roasted mass is extracted with water when Na2CrO4 goes into the solution leaving behind insoluble
Fe2O3. The solution is treated with calculated amount of H2SO4.
2Na2CrO4 + H2SO4  Na2Cr2O7 + Na2SO4 + H2O
The solution is concentrated when less soluble Na2SO4 crystallises out. The solution is further concentrated
when crystals of Na2Cr2O7 are obtained. Then a hot saturated solution of Na2Cr2O7 is treated with KCl
when reddish orange crystals of K2Cr2O7 are obtained on crystallisation.
K2Cr2O7 is preferred to Na2Cr2O7 because Na2Cr2O7 is hygroscopic but K2Cr2O7 is
not.
* Other props & test of CrO2 4
& Cr 2O 2
7
:Already discussed
* Similarities between hexavalent Cr & S-compounds:
(i) SO3 & CrO3  both acidic.

4
d & f - block

(ii) CrO42 & SO 42 are isomorphous

OH  2 2
(iii) SO2Cl2 & CrO2Cl2  SO 4 & CrO4 respectively.
OH 2  2
(iv) SO3Cl– & CrO3Cl–  SO 4 & CrO4
O O O
|| || ||
(v) CrO3 & (SO3) has same structure  Cr  O  Cr  O  Cr 
|| || ||
O O O
(vi) Potassium dichromate reacts with hydrochloric acid and evolves chlorine.
K2Cr2O7 + 14HCl  2KCl + 2CrCl3 + 7H2O + 3Cl2

(vii) It acts as a powerful oxidising agent in acidic medium (dilute H2SO4)

Cr2O 2
7 + 14H + + 6e –  2Cr3 + + 7H2O. (Eº = 1.33 V)

The oxidation state of Cr changes from + 6 to +3.

Uses
(i) As a volumetric reagent in the estimation of reducing agents such as oxalic acid,
ferrous ions, iodide ions, etc. It is used as a primary standard.
(ii) For the preparation of several chromium compounds such as chrome alum, chrome
yellow, chrome red, zinc yellow, etc.
(iii) In dyeing, chrome tanning, calico printing photography etc.
(iv) Chromic acid as a cleansing agent for glass ware.

7. MANGANATE & PERMANGANATE

Preparation
This is the most important and well known salt of permanganic acid. It is prepared from the pyrolusite
ore. It is prepared by fusing pyrolusite ore either with KOH or K2CO3 in presence of atmospheric
oxygen or any other oxidising agent such as KNO3. The mass turns green with the formation of potassium
magnate, K2MnO4.
2MnO2 + 4KOH + O2  2K2MnO4 + 2H2O
2MnO2 + 2K2CO3 + O2  2K2MnO4 + 2CO2
The fused mass is extracted with water. The solution is now treated with a current of chlorine or ozone
or carbon dioxide to convert magnate into permanganate.
2K2MnO4 + Cl2  2KMnO4 + 2KCl
2K2MnO4 + H2O + O3  2KMnO4 + 2KOH + O2
3K2MnO4 + 2CO2  2KMnO4 + MnO2 + 2K2CO3
Props : The above green solution is quite stable in alkali, but in pure water and in presence of acids,
depositing MnO2 and giving a purple solution of permanganate.
3K2MnO4 + 2H2O  2KMnO4 + MnO2  + 4KOH
purple drak brown
Prob. : Eo = 2.26 V ; Eo = – 0.56 V
MnO 42 / MnO 2 MnO 42 / MnO4

Prove that MnO42 will disproportionate in acidic medium.

Another Method of Prepn. : 3K 2MnO 4 + 2H 2SO 4  2KMnO 4 + MnO 2 + 2K 2SO 4+ 2H 2O
or 3K2MnO4 + 2H2O + 4CO2  2KMnO4 + MnO2 + 4KHCO3

5
d & f - block
1
But in the above method of Mn is lost as MnO2 but when oxidised either by Cl2 or by O3
3
2K2MnO4 + Cl2  2KMnO4 + 2KCl [Unwanted MnO2 does not form]
OR
2K2MnO4 + O3 + H2O 2KMnO4 + 2KOH + O2

Heating effect : 2KMnO4   K2MnO4 + MnO2 + O2
green 200C Black

2K2MnO4a t r ed
hot
  2K2MnO3 + O2
Oxidising Prop. of KMnO4 : (in acidic medium)
(i) MnO  + Fe+2 + H+  Fe+3 + Mn+2 + H 2O
4

(ii) MnO 4 + H2 O2 + H+  Mn+2 + O 2 + H 2O

(iii) MnO 4 + H2 S  Mn2+ + S  + H2O

In alkaline solution : KMnO4 is first reduced to magnate and then to insoluble manganese dioxide.
Colour changes first from purple to green and finally becomes colourless. However brownish precipitate
is formed.
2KMnO4 + 2KOH  2K2MnO4 + H2O + O
2K2MnO4 + 2H2O  2MnO2 + 4KOH + 2O
2KMnO4 + H2O  alkaline
  2MnO2 + 2KOH + 3[O]
or 2MnO4¯ + H2O  2MnO2 + 2OH¯ + 3[O]
Oxidising Prop. in neutral or weakly acidic solution:
in presence Zn 2 or ZnO
(i) 2KMnO4 + 3MnSO4 + 2H2O     5MnO2 + K2SO4 + 2H2SO4
Conversion of Mn+2 to MnO 4 :
(i) PbO2 (ii) Pb3O4 + HNO3 (iii) Pb2O3 + HNO3 (iv) NaBiO3 / H+
+ +
(v) (NH4)2S2O8 / H (vi) KIO4 / H

8. SILVER AND ITS COMPOUND

(I) MetallicAg

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

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

6
d & f - block
AgNO3 (Silver Nitrate)
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 devided silver (black colour)
(ii) Thermal decomposition:
(iii) Props. ofAgNO3 : [Already done in basic radical]
6AgNO3 + 3I2 + 3H2O 5AgI + AgIO3 + 6HNO3
(excess)
(iv) Ag2SO4   2Ag + SO2 + O2
B
(v) A(AgNO3)  white ppt appears quickly
added

Explain

B(Na2S2O3)   It takes time to give white ppt. 
A
added

(vi) Ag2S2O3 + H2O   Ag2S + H2SO4

AgCl .AgBr.AgI (but notAg2S) are soluble in Na2S2O3 forming
[Ag(S2O3)2]–3 complexes
(vii)AgBr : AgNO3 K
Br
 AgBr  + KNO3
Pale yellow
ppt.
Heating effect: 2AgNO3 212
C
 2AgNO2 + O2
2AgNO2 500
C
 2Ag + 2NO + O2

(viii)

Ag2O + H2O2  2Ag + H2O + O2

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

Note:
(1) AgO supposed to be paramagnetic due to d9 configuration. But actually it is diamagnetic and exists
asAgI [AgIIIO 2]
(2) Reaction involved in developer :
K2FeII(C2O4)2 + AgBr  KFe III (C2O4)2 + Ag + KBr

7
d & f - block
9. ZINC COMPOUNDS
(1) Zinc oxide, ZnO (Chinese white or philosopher's wool)
Its found in nature as zincite or red zinc ore.
Preparation :
(i) 2Zn + O2  2ZnO
(ii) ZnCO3  ZnO + CO2


(iii) 2Zn(NO3)2  2ZnO + 4NO2 + O2



(iv) Zn(OH)2  ZnO + H2O

(a) Physical Properties : It is white powder becomes yellow on heating again turns white on cooling ,
insoluble in water, sublimes at 400°C.
(b) Chemical Properties :
(i) ZnO + H2SO4  ZnSO4 + H2O
(iii) ZnO + 2NaOH  Na2ZnO2 + H2O

(iv) ZnO + H2  Zn + H2O
400º C
(v) ZnO + C  Zn + CO

ZnCl2 (Zinc Chloride)

Preparation: ZnO + 2HCl  ZnCl2 + H2O
ZnCO3 + 2HCl  ZnCl2 + H2O + CO2  It crystallis es as ZnCl 2 ·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 excess  Na2[Zn(OH)4]
" + NH4OH  Zn(OH)2 excess  [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 (Zinc Sulphate)

Preparation:
Zn + dil H2SO4  ZnSO4 + H2
ZnO + dil H2SO4 ZnSO4 + H2O
ZnCO3 + dil H2SO4  ZnSO4 + H2O + CO2

8
d & f - block

ZnS  2O2  ZnSO 4

3  parallel reaction
ZnS + O 2  ZnO + SO 2
2
ZnS + 4O3  ZnSO4 + 4O2

3970C 70C  280C

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

10. COPPER COMPOUNDS

CuO :

Preparation: (i) CuCO3.Cu(OH)2  2CuO + H2O + CO2 (Commercial process )
Malachite Green
(native Cu-carbonate)
1
(ii) 2Cu + O2  2CuO & Cu2O + O 2CuO
2 2 

Cu(OH)2 
(iii) CuO + H2O
(iv) 2Cu(NO3)2 250 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
2+
[Cu(H2O)4] 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 l [Cu(H2O)4] 2+ + [CuCl4]2– + 4H2O
(v) CuCl2 — CuCl by no. of reagents

9
d & f - block

(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 2O at 150C in presence
CuBr2 — almost black of HCl vap.
CuI2 does not exist 1 50 C
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 + O2 — CuSO4 + H2O [Commercial scale]
2
(Scrap)
Cu + dil. H2SO4  no reaction {Cu is a below H in electrochemical series}
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

(iii) Revision with all others reagent

11. IRON COMPOUNDS

FeSO4·7H2O:
Preparation: (i) Scrap Fe + H2SO4  FeSO4 + H2
(dil.)
(ii) From Kipp's waste
FeS + H2SO4(dil)  FeSO4 + H2S
7
(iii) FeS2 + 2H2O + O  FeSO4 + H2SO4
2 2
Properties: (i) It undergoes aerial oxidation forming basic ferric sulphate
4FeSO4 + H2O + O2 4Fe(OH)SO4
300C FeSO 4 h igh
 Fe2 O3 +SO2 +SO3
(ii) FeSO4·7H2O 
anh. white temp.
(iii) Aq. solution is acidic due to hydrolysis
FeSO4 + 2H2O l Fe(OH)2 + H2SO4
weak base

10
d & f - block
(iv) It is a reducing agent
(a) Fe2+ + MnO 4– + H+  Fe3+ + Mn2+ + H 2O
(b) Fe2+ + Cr 2O 72– + H+  Fe3+ + Cr3+ + H 2O
(c) Au3+ + Fe2+  Au + Fe3+
(d) Fe2+ + HgCl2  Hg 2Cl2 + 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:
Prepn: Fe + 2HCl heatedin  FeCl2 + H2
a current of HCl
OR

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 sufficiently covalent 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 by heating 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.

12. INNER TRANSITION ELEMENTS

The elements in which the additional electrons enters (n–2)f orbitals are called inner transition elements.
The valence shell elect ronic co nfiguration of these element s can be represent ed as
(n–2) f 0,2...14 (n – 1)d 0,1,2,ns 2 . These are also called f-block elements because the extra electron goes
to f-orbitals which belongs to (n–2)th main shell. 4f-block elements are also called lanthanides or rare
earths. Similarly 5f-block elements are called actinides or actinones. The name Lanthanides and actinides
have been given due to close resemblance with Lanthanum and actinium respectively. Lanthanides
constitutes the first inner transition series while actinides constitutes second inner transition series.

11
d & f - block
General Characteristics:
1. Electronic Configuration
[Xe] 4f n 1 5d 0 6s 2 or [Xe] 4f n 5d1 6s 2
2. Oxidation state: They readily form M 3 ions some of them also exhibit oxidation state of +2 and +4.
3. Colouration: Ions of Lanthanides and actinides are coloured in the solid state as well as in aqueous
solution because of absorbation of light due to f–f transition since they have partly filled f-orbitals.

13. LANTHANIDE CONTRACTION

In lanthanides, the additional electron enters 4f-sub shell but not in the valence-shell namely sixth shell.
The shielding effect of one electron in 4f-sub-shell by another in the same sub-shell is very little, being
even smaller than that of d-electrons, because the shape of f-sub shell is very much diffused, while there
is no comparable increase in the mutual shielding effect of 4f-electrons. This results in that electrons in the
outermost shell experience increasing nuclear attraction from the growing nucleus. Consequently the
atomic and ionic radii go on decreasing as we move from La57 to Lu71.
Consequence of Lanthanide contraction
1. Atomic and ionic radii of post-Lanthanide elements: The atomic radii of second row transition
elements are almost similar to those ofthe third row transition element because the increase in size on
moving down the group from second to third transition elements is cancelled by the decrease in size
due to lanthanide contraction.
2. High density of post lanthanide elements: It is because of very small size due to lanthanide
contraction.
3. Basic strength of oxides and hydroxides: Due to lanthanide contraction the decrease in size of
lanthanides ions, from La 3 to Lu 3 increases the covalent character (i.e. decreases the ionic
character) between Ln 3 and OH – ions in Ln(III) hydroxides (Fajans rules). Thus La(OH) 3 is the
most basic while Lu(OH)3 is the best basic.
Similarly, there is a decrease in the basic strength of the oxides.
4. Seperation of Lanthanides: Due to the similar size (Because of lanthanide contraction) of the
lanthanides, it is difficult to separate them. But slight variation in their properties is utilizedto separate
Consequences of Lanthanide Contraction
(i) Separation of Lanthanides.Separation oflanthanides is possible only due to lanthanide contraction.
All the lanthanides have quite similar properties and due to this reason they are difficult to separate.
However, because of lanthanide contraction their properties (such as ability to form complexes)
varyslightly. This slight variation inproperties is utilized in the separation of lanthanides byion exchange
methods.
(ii) Variation in basic strength of hydroxides. The basic strength of oxides and hydroxides decreases
from La(OH)3 to Lu(OH)3. Due to lanthanide contraction size of M3+ ions decreases and there is
increase in the covalent character in M–OH bond.
(iii) Similarity of second and third transition series. The atomic radii of second row of transition
elements are almost similar to those of the third row of transition elements. For example, among the
elements of group 3, there is normal increase in size from Sc to Yto La. But after lanthanides the
atomic radii from second to third transition series do not increase as shown below for group 4 and
group 5 i.e., for Zr – Hf and Nb – Ta pairs which have element same atomic radii.After group 5 the
effect of lanthanide contraction is not so predominant.

12
d & f - block
5. Colour. The lanthanide metals are silvery white metals and the trivalent lanthanide ions are coloured
both in the solid state and in the aqueous solution.
6. Magnetic properties. La3+ (4f0) and Lu3+ (4f14) having no unpaired electron do not show
paramagnetism while all other tripositive ions of lanthanides are paramagnetic.
7. They have low ionisation energy and are highly electropositive. Their ionisation energy values are
quite comparable with those of alkaline earth metals particularly calcium.
8. These metals do not have much tendency to form complexes.
9. The lanthanides are highly reactive. This is in agreement with the low values oftheir ionisation energies
and electronegativity.
10. The solubilityof compounds of lanthanides follow the same order as group 2 elements. Their fluorides,
oxides, hydroxides, carbonates are insoluble in water. However halides (except fluorides), nitrates,
acetates are soluble in water.

General Characteristics ofActinides – 5f Block Series – Second Inner Transition Series

1. These are silvery white metals with high melting and boiling points.
2. Besides the most common oxidation state of +3, actinides show +4, +5 and +6 oxidation states in
certain elements.
3. All the actinides are radioactive in nature.
4. All the actinides are highly electropositive and as such are strong reducing agent.
5. Actinides have a strong tendency towards complex formation and form oxocations like UO22+,
PuO22+, UO+ etc.
6. Most of the cations of actinides are coloured.
7. Actinides show actinide contraction i.e., decrease in ionic radii along the series.

13
d & f - block
SOLVED EXAMPLES
Ex.1 On what basis can you say that scandium
(Z = 21) is a transition element but since
(Z = 30) is not.
Sol. On t he basis of i incompletely filled
3d - orbitals in case of scandium atom in its
ground state 3d1), it is regarded as a transition
element. On the other hand, zinc atom has
completely filled d- orbitals (3d10) in its ground
state as well as in its oxidised state, hence it is
not regarded as transition element.
Ex.2 What is the effect of increasing pH on K2Cr2O7
solution?
Sol. In aqueous solution, we have
Cr2O72– + H2O 2CrO42– + 2H +.
When pH < 4 (acidic medium), it exists as
Cr2O72– and the colour is orange.
When pH> 7 (basic medium), it exists as
CrO42– and the colour is yellow.
Ex.5
Ex.3 What is the basic difference between the
electronic configurations of transition and inner Sol.
transition elements.
Sol. General electronic configuration of transition
element = [ Noblegas] (n –1) d1–10 ns1–2 and
for inner transition elements
= (n – 2) f1–14 (n –1)d0–1 ns0–2. Thus , in transition
elements, last electron enters d-orbitals of the Ex.6
penultimate shelll while in inner transition Sol.
elements, it enters f- orbital of the penultimate
shell.
Ex.4 Give reasons for the following
(a) Transition metals have high enthalpies of
atomizations.
(b) Among the lathanoids, Ce(III) is easily
oxidised to Ce (IV)
(c) Fe3+ | Fe2+ redox couple has less positive
electrode potential than Mn3+| Mn2+ couple.
(d) Copper (I) has d10 configuration , still Ex.7
copper (II) has d9 configuration stillcopper (II)
is more stable in aqueous solution than copper
(I). Sol.
(e) The second and third transition series
elements have almost similar atomic radii.
Sol. (a) Due to strong interatomic interaction
between valence electrons.
(b) because Ce (IV) has extra stability due to
empty f0 orbital.
Ce3+  Ce4+ + e–
[Xe] 4f1 5d06s0
(c) In Mn2+ d5 configuration leas to extra
stability of half filled configuration , so Mn2+/
Mn2+(d4) tends to get converted to stable d5,
configuration of Mn2+, by accepting an electron
so Mn3+/Mn2+ redox couple has more positive
potential than Fe3+/Fe2+(d14) couple.
(d) Due to more negative enthalpy of hydration
2+
of Cu (aq) than Cu+ (aq) which compensates
or second ionization enthalpy of copper.
(e) In the third transition series after lanthanum
their is lanthanoid contraction due to ineffective
shielding by intervening f-orbital electrons and
hence second and third transition series
elements have similar atomic radii.
Why is Cr2+ reducing and Mn3+ oxidising when
both have d4 configuration?
Cr2+ is reducing as its configuration changes
form d4 to d3, the later has half filled t 2g level.
Again the change from Mn2+ to Mn3+ results in
the half filled (d5) configuration whichhas extra
stability.
Cu+ ion is not stable inaqueous solution. Why?
Cu2+ (aq) is much more stable than Cu+(aq).
This is because although second ionization
enthalpy of copper is large but hyd H for Cu2+
(aq) is much more negative than that for Cu+
(aq) and therefore it more than compensates
for the second ionization enthalpy of copper.
Thus many copper (I) compounds ar unstable
in aque o us so lu t io n and und er go es
disproportional as follows.
2Cu+ (aq)  Cu2+(aq) + Cu(s)
Why is the Eº value for the M3+/ M2+ couple
much more positive than that of Cr3+/Cr2+ or
Fe3+/Fe2+? Explain.
Much larger third ionization energy of Mn
(Where the required change is d5 to d4) is mainly
responsible for this. This also explains why the
+3 state of Mn is of little importance.
14
d & f - block
Ex.8 Why does Mn (II) ion show the maximum Q.13
paramagnetic behvavious among bivalent ions
of the first transition series.?
Sol. The electronic configurations of Mn and Mn Sol.
(II) ion are
2 2 6 2 6 2 2
25Mn : 1s 2s 2p 3s 3p 3d 4s ,
Mn+2 : 1s2,2s22p6 3s23p63d24s0
Q.14
The Mn+2 ion has five unpaired electrons in its
3d subshell which is the maximum value for a
transition metal ion. Hence, Mn (II) shows the
maximum paramagnetic behaviour (due to Sol.
unpaired electrons) among bivalent ions of the
first transition series.
Ex.9 K2[PtCl6] is a will known compound whereas
the corresponding Nicompound is not known.
State reason for it.
Sol. The oxidation state of Pt in K2 [PtCl6] is +4,
which is a stable oxidation state for Pt. The +4 Q.15
oxidation state for Ni is verydifficult to achieve
because the sum of the first four ionization
energies is very high. Hence, the corresponding
Sol.
Ni (II) compound is not formed.
Ex.10 What is mean by ‘disproportionation‘ of an
oxidation state? Give an example.
Sol. When a particular oxidation state becomes less
stable relative to other oxidation states, one
loser one higher, it is said to undergo
disproportionation. For example manganese
(VI) becomes unstable relative to managanese
(VII) and manganese (IV) in acidic solution.
Q.16
3MnVIO42– + 4H+
 2MnVIIO– 4 + MnIVO 2 + 2H 2O
Ex.11 Whichmetalinthe first seriesoftransition metals
exhibits + 1 oxidation state most frequency and
why?
Sol. Copper metal (Cu, Z = 29) show + 1 oxidation Sol.
state, i.e. exists as Cu+ in large number of
copper compounds .e.g. cuprous oxide
(Cu2O), cuprous sulphide (Cu2S), cuprous
chlo r ide ( Cu 2 Cl2 ) et c. T he elect r o nic
configuration Cu+ is [Ar] 3d104s0.
All the five 3d orbitals are fully filled therefore
this is a very stable configuration.
Ex.12 Why is Ti+2 ionparamagnetic in nature?
Sol. Ti+2 is paramagnetic because of the presence
of two unpaired electrons in 3d-orbitals.
22Ti :
1s22s22p 63s23p 63d 24s 2,
Ti+2 : 1s2,2s22p6 3s23p63d24s0
Arranged the following in increasing order of
acdic character:
CrO3, CrO, Cr 2O3
CrO< Cr2O3< CrO3. Higher the oxidation
state , more will be acdic character.
In the series Sc (Z = 21) to Zn (Z = 30), the
enthalpy of atomization of zinc is the lowest,
i.e. 125 kJ mol–1. Why?
In the formation of metallic bond, no electrons
from 3d-orbitals are involved in case of zinc
while in all other metals of the 3d series,
electrons from the d-orbitals are always
involved inthe formation ofmetallic bonds. That
is why, the enthalpy of atomisation of zinc is
the lowest in the series.
In transition series, with an increase in atomic
number, the atomic radius does not change very
much . Why is it so?
With increase in atomic number along a
transition series the nuclear charge increases
which tends to decrease the size of the atom.
But the addition of electrons in the d subshell
increases the screening effect which
counterbalances the increased nuclear charge.
Hence alonga transition series the atomic radius
does not very much.
Account for the following :
(i) Cerium (atomic number = 58) forms tetra
positive , Ce4+ in aqueous solution.
(ii) The second and third members in each
group of transition element have similar atomic
radii.
(i) The electronic configuration of Ce (Z= 58)
is 58Ce = [Xe]4f15d16s2
Cerium can lose four electrons (4f15d16s2) in
aqueous solution to acquire stable configuration
of rate gas xenon. Moreover due to small size
and high charge , Ce4+ ion has high hydration
energy.
(ii) The second and third members in each
group of transition elements have very similar
atomic radii due to lanthanoid contration. It
arises due to poor shielding effect of f
electrons.
15
d & f - block
Ex.17 For the first row transition metals the Eº values are:
Eº V Cr Mn Fe Co Ni Cu
(M + /M) –1.18
2 – 0.91 –1.18 –0.44 –0.28 –0.25 +0.34
Explain the irregularity in the above values.
Sol. The Eº (M2+/M) values are not regular which can be explained from the irregular variation of ionisation
entthalpies (iHl+ iH2 ) and alos the sublimation enthalpies which are relatively much less for maganese
and vanadium.

Ex.18 The Eº (M2+ /M) value for coppers is positive ( + 0.34V), What is possibly the reason for this ?
Sol. Eº (M2+/M ) for any metal is related to the sum of the enthalpy change taking place in the following steps:
M(s) + aH  M(g) (a H= Enthalpy of atomisation)
M(g) +  iH  M (g)
2+
(a H= Ionization enthalpy)
M (g) + aq  M (aq) + DhydH
2+ 2+
(hydH = Hydration enthalpy)
Copper has high enthalpy of atomisation and low enthalpy of hydration . So Eº (Cu2+/Cu) is positive.
The high energy to transform Cu(s) to Cu2+(aq) is not balanced by it s hydration enthalpy.

Ex.19 (a) Complete the following chemical equation of for reactions:

(i) MnO4– (aq) + S 2O 32– (aq) + H 2O(l) 
(ii) CrO7– (aq) + H2(g) + H+ (aq) 
(b) Give an explanation for each of the following observation:
(i) The gradual decrease in size (actinoid contraction) from element to element is greater among the
actionod is than that among the lanthanoids (lanthanoids contraction).
(ii) The greatest number of oxidation states are exhibited by the members in the middle of a transi-
tion series.
(iii) With the same d- orbital configuration (d4) Cr2+ ion is a reducing agent but Mn3+ ion is an
oxidisng agent.
Sol. (a) (i) In neutral or faintly alkaline solutions
MnO4– + 2H 2O + 3e–  MnO 2 + 2H 2P + 4O–H] × 8
S2O32– + 10O–H  2SO 42– + 5H 2O + 8e–] × 3

8Mn O32– + 10O–H + H 2O  8 MnO 2 + 6SO 42– + 2O–H

(ii) In acidic solutions

Cr2O72– + 14H+ + 6e–  2Cr3+ + 7H 2O
H2S  S + 2H+ + 2e–] × 3

Cr2O72– + 3H 2S+ 8H+  2Cr3+ + 3S + 7H 2O

(b) (i) This due to poor shielding by 5f electrons from element to element in actinoid than by 4f
electrons in lanthanoids series.
(ii) This is due to involvement of both (n–1) d and ns electrons in bonding, which are unpaired in
maximum number at the middle of series.
(iii) Cr2+ has the configuration d4 and easily changes to Cr3+ which has half t 2g configuration and
hence move stable. Therefore Cr2+ is reducing. On the other hand, the change from Mn3+ to
Mn2+ results inthe halffilled, d5 configuration whichhas extra stability. Therefore Mn3+ in oxidising.

16
d & f - block
Ex.20 (a) Complete the following chemical reaction equations:
(i) MnO4–(aq) + C2O42– (aq) + H+ (aq) 
(ii) Cr2O72– (aq) + F2+ (aq) + H+ (aq) 
(b) Explain the following observation about the transition/inner transition elements:
(i) There is general an increase in density of element form titanium (Z = 22) to copper (Z = 29).
(ii) There occurs much more frequent metal-metal bonding in compounds of heavy transition
elements (3rd series).
(iii) the members in the actinoid series exhibit a large number of oxidation states than the
corresponding members in the lanthanoid sereis.
Sol. (a) (i) In acidic medium:
MnO4– + 8H+ + 5e–  Mn2+ + 4H 2O] × 2
C2O42–  2CO 2 + 3e] × 5

2MnO4– +5C 42– + 16H+  2M n2+ + 10 CO 2+ 5H 2O

(ii) In acidic medium

Cr4 O72– + 14H+ + 6e–  2Cr3+ + 7H 2O
Fe2+  Fe3+ + e– ] × 6

Cr4 O72– + 6Fe2+ +14H+  2Cr3+ + 6Fe3+ + 7H 2O

(b) (i) On moving from titanium to copper in general atomic mass increases where as atomic size
decreases, therefore density increases in general
(ii) The frequent metal-metal bonding in compounds of heavy transition elements is due to their
high enthalpyof atomization.
(iii) Thisisdueto verysmall energygap between5f, 6dand 7sorbitals inthe actinoids series.

Ex.21 Complete the following chemical reaction equations:

(i) MnO4– (aq) + C2 O42–(aq) + H+ (aq) 
(ii) Cr2O72– (aq) + Fe2+(aq) + H+ (aq) 
Sol. (i) MnO4– + 8H+ + 5e–  Mn2+ + 4H 2O] × 2
C 2O 42–  2CO2 +2e– ] × 5

2MnO4– + 5C 2O 42– + 16 H+  2Mn2+ + 10CO 2 + 8H 2O

(ii) Cr2O72– +14H+ + 6e–  2Cr3+ + 7H 2O

Fe2+  Fe3+ +e–] × 6

Cr2O72– + 6F2+ + 14H+  2Cr3+ +6Fe3+ + 7H 2O

17
d & f - block
Ex.22 (a) What may be the possible oxidation states of the transition metals with the following d-electronic
configuration in the ground state oftheir atoms.
3d3,s2,3d5,4a2 and 3d6 4s2. Indicate relative stability of oxidation states in each case.
(b) Write steps involved in the preparation of
(i) Mn2CrO4 from chromite ore and
(ii) K2MnO4 from pyrolusite ore.

Sol. (a) Electronic

Element Possible O.S. Mo re Stable O.S.
conf iguration
3d24 s2 Vanadium + 2, +3, + 4, + 5 +5
5 2 Manganese + 2, +3, + 4, + 5,
3d 4 s +2 +7
6 2 Iron + 2, +3, + 4, +6,
3d 4 s +2 +3

(b) (i) Chromite ore is fused with sodium carbonate in excess of air.
4FeCr2O4 + 8Na2CO3 + 7O 2  8Na 2CrO 4 + 2Fe 2O 3 + 8CO 2
chromite ore Sod. chromate

(ii) Pyrolusite ore (MnO2) is fused with KOH in the presence of O 2 or oxidising agent such as
KNO 3.
2MnO2 + 4KOH + O 2  2K 2MnO 4 + 2H 2O
Pyrolusite ore Postassium magnate

18
d & f - block
EXERCISE - I
Q.1 Why are Mn2+ compounds more stable than Q.11
Fe2+ towards oxidation to their +3 state?
Q.2 Write complete equation for
Oxidation of Fe2+ by Cr2O72– in acidic medium.
Q.3 Answer the following questions:
(i) Which element in the first series of transition Q.12
elements does not exhibit variable oxidation
states and why ?
(ii) Whydo actinoids, in general exhibit a greater
range of oxidation states than the lanthanoids ?
Q.4 Explain briefly how +2 state becomes more
and more stable in the first half of the first row
transition elements with increasing atomic
number? Q.13
Q.5 Write chemical equations for the reactions
involved in the manufacture of potassium
permanganate from pyrolusite ore.
Q.14
Q.6 What is misch metal ? Mention its two
important uses.
Q.7 To what extent do the electronic configurations
decide the stability of oxidation states in the
first series of the transition elements? Illustrate
your answer with examples.
Q.8 (a) Name two properties of the central metal
ion which enable it to form stable complex Q.15
entities.
(b)Account for the following : Zinc salts are
while Cu2+ salts are coloured.
Q.9 How do you account for the following :
(a)All scandium salts are white ?
(b) The first ionization energies of the 5d Q.16
transition elements are higher than those of the
3d and 4d transition elements in respective
groups ?
Q.10 What may be the stable oxidation state of the
transition element with the following d electron
configurations inthe ground state oftheir atoms
: 3d3, 3d5, 3d8 and 3d4?
Explain the following observations :
(a) The elements of the d-series exhibit a larger
number of oxidation sates than the elements of
f-series.
(b) The Cu+ salts are colurless while Cu2+ salts
are coloured.
Mention the direct consequence of the
following factors on the chemical behavior of
the transition elements :
(i) They have incompletely d-orbitals in the
ground state or in one of the oxidised states of
their atoms.
(ii) They contribute more valence electrons per
atom in the formation of metallic bonds.
What are the characteristics of the transition
elements and why are they called transition
elements? Which of the d-block elements may
not be regarded as the transition elements?
How would you account for the following
situations ?
(i) the transition metals generally formcoloured
compound .
(ii) With 3d4 configuration, Cu2+ acts as a
reducing agent but Mn3+ acts as oxidizing agent
(iii) The actinides exhibit a larger number of
oxidation states than the corresponding
lanthanides.
How would you account for the following :
(i) The transition elements have high enthalpies
of atomisation.
(ii) The transition metals and their compounds
are found to be good catalysts in many
processes.
Explain giving reasons:
(i) Transition metals and many of their
compounds show paramagnetic behaviour.
(ii) The enthalpies of atomisation of the
transition metals are high.
(iii) The transition metals generally form
coloured compounds.
(iv) Transition metals and their many
compounds act as good catalyst.
19
d & f - block
Q.17 Give reasons for each of the following :
(i) Size of trivalent lanthanoid cations decreases
with increase in the atomic number
(ii) transition metal fluorides are ionic nature,
whereas bromides and chlorides are usually Q.25
covalent in nature.
(iii) Chemistry of all the lanthanoids is quite
similar.
Q.24 Use Hund’s rule to derive the electronic
configuration of Ce3+ ion, and calculate its
magnetic moment on the basis of ‘spin-only’
formula.
Describe the preparation of potassium
dichromate from iron chromite ore. What is the
effect of increasing pH on a solution of
potassium dichromate?

Q.18 Discuss the general characteristics of the 3d Q.26 Assign reason for the following :
series of the transition elements with special (i) The enthalpies of atomisation of transition
reference to their. metals are high.
(i) atomic sizes, (ii) The transition metals and many of their
(ii) enthalpies of atomisation compounds act as catalysts.
(iii) tendency for complex formation. (iii) From element to element, the actinides
contraction is greater than lant hano id
Q.19 Predict which of the following willbe coloured
contraction.
in aqueous solution? Ti3+, V3+, Cu+, Sc3+,
(iv) The Eº value for Mn3+/Mn2+ couple is much
Mn3+, Fe3+ and Co3+. Give reasons for each.
more positive than that for Cr3+/Cr2+.
Q.20 Write down electronic configuration of the (v) Scandium (Z = 21) does not exhibit variable
following below: oxidation states and yet it is regarded as
(a) La3+ (b) Gd3+ transition element.
(c) Eu2+ (d) Zn4+
(e) Ru2+
(f) Ce4+ Q.27 Describe the oxidising action of potassium
dichromate and write the ionic equations for
Q.21 What are alloys? Name an important alloy its reaction with:
which contains some of the lanthanoid metals. (i) iodide (ii) iron(II) solution and (iii) H2S
Mention its uses.
Q.28 (a) Describe the general trends in the following
Q.22 (a) Give one example each of amphoteric and properties of the first series of the transition
acidic oxides of transition metals. elements :
(b) Describe the trends in the following cases: (i) Stability of +2 oxidation state (ii) Formation
(i) Melting points of elements in the 3d transition of oxometal ions.
series. (b)Assign reason for each of the following :
(ii) Atomic sizes of elements in the 4f transition (i) Transition elements exhibit variable oxidation
series. states.
Q.23 (ii) Transition metal ions are usually coloured
How would you account for the following ?
(i) Sc, the first member of first transition series Q.29 (a) Write the steps involved in the preparation
does not exhibit variable oxidation state. of:
(ii) K2PtCl6 is well-known compound whereas (i) K Cr O from Na CrO
2 2 7 2 4
corresponding compound of nickel is not (ii) KMnO4 from K2MnO4
known. (b) What is meant by lanthanoid contraction ?
(iii) Only transition metals for complex What effect does it have on the chemistry of
compounds with ligands such as CO. the elements which follow lanthanoids ?
Q.30 For same of first row of trnasition elements the Eº values are :
V Cr Mn Fe Co Ni Cu
– 1.18V – 0.91V – 1.18V – 0.44V – 0.28V – 0.25V  0.34V
Give suitable explanation for the irregular treand in these values.

20
d & f - block

EXERCISE - II
Q.1 Explain why the greenish solution of potassium
manganate turns purple when CO2 is bubbled
in the solution.
Q.2 Explain whymercurous compounds are formed
when mercury is oxidised in a limited amount
of an oxidising agent whereas with an excess
of oxidising agent mercuric compounds are Q.12
formed.
Q.3 Explain why [Co(NH3)6]3+ is diamagnetic and
[CoF6]3– is strongly paramagnetic.
Q.11 Acomplex has the formula Pt Cl4.2KCl. The
electrical conductance of the compound shows
that each formula unit has 3 ions. AgNO3 on
treatment with the complex does not give a
precipitate ofAgCl. What should be the correct
formula of the complex?
[Ni Cl4]2– and [Ni (CO)4] both are tetrahedral
in shape but [Ni Cl4]2– is paramagnetic whereas
[Ni(CO) 4] is diamagnetic. Explain the
difference in magnetic behaviour of both the
complexes.

Q.4 What happens when NaOH or NH4OH are Q.13 FeSO4 solution is mixed with (NH4)2SO4 in
added in excess to AlCl3 and ZnCl2? the molar ratio 1:1. It gives test of Fe2+ . When
CuSO4 is mixed with liquid ammonia (in the
Q.5 Whyis zinc oxide used in paints instead of lead ratio 1:4) the mixture does not give test of Cu2+.
salts? Explain the difference.

Q.6 Identify from [A] to [E]. Q.14 (A), (B), and (C) are three complexes of
NaOH
Cr(III). Its formula is H12O6Cl3Cr. All the three
Colourless salt [A] [B] (white precipitate) complexes have water and chloride ions as
+ Ag NO 3 dissolves in NaOH ligands. (A) does not react with conc. H 2SO 4
[E] white [C] whereas (B) and (C) lose 6.75% and 13.5%
precipitate Pass H 2 S of their original weight respectivelyon treatment
[D] (white precipitate) with conc. H2SO4. Find [A], [B], and [C].

Q.15 A metal complex having composition Cr

Q.7 Why are melting and boiling points of zinc,
cadmium, and mercury lower than those of
other transition metals?
Q.8 Why is HCl not used to acidify KMnO4 for
volumetric estimations?
Q.9 Colourless salt (A) ? (B) + (C) gas.
(B) dissolves both in acid and alkali solution. Q.16
(C) turns lime water milky and acidified
K2Cr2O7 solution green.
(A) gives white precipitate (D) with H2S when
the solution is alkaline. Identify [A] to [D].
Q.10 (a) K2MnO4 in acidic medium changes to
MnO2 and KMnO4. What would be the
equivalent weight of K2 MnO4.
(b) Draw the structures of MnO4– and CrO42–
ions.
(NH3)4Cl2.Br. has been isolated in two forms
(A) and (B). (A) reacts with AgNO3 to give a
white precipitate soluble in dilute ammonia while
(B) gives a pale yellow precipitate soluble in
concentrated ammonia. Write the formulae of
(A) and (B) and hybridisation state of Cr in the
compounds.
A monomeric compound of cobalt gives the
following data on quantitative analysis:
Co3+: 21.24% ; NH3: 24.77% ; Cl–: 12.81% ;
SO42– : 34.65% ; H2O: 6.53%.
Deduce the empirica l formula of the complex
and the possible isomers.

21
d & f - block

EXERCISE - III
Single Correct Questions Q.8 During estimation of oxalic acid Vs KMnO4,
Q.1 The number of moles of acidified KMnO4 self indicator is
required to convert one mole of sulphite ion (A) KMnO4 (B) oxalic acid
into sulphate ion is (C) K2SO4 (D) MnSO4
(A) 2/5 (B) 3/5
(C) 4/5 (D) 1 Q.9 Acompound of mercury used in cosmetics, in
Ayurvedic and Yunani medicines and known
as Vermilon is
Q.2 N2 ( g) + 3H 2 ( g) 2NH 3 ( g) ; (A) HgCl2 (B) HgS
Haber’s process, Mo is used as (C) Hg2Cl2 (D) HgI
(A) a catalyst
(B) a catalytic promoter Q.10 Acidified chromic acid + H2 O2 Org.
.solvent

(C) an oxidising agent X + Y , X and Y are
(D) as a catalytic poison (A) CrO5 and H2O (B) Cr2O3 and H2O
(C) CrO2 and H2O (D) CrO and H2O

Q.3 Cr2O 27 2CrO 2

4
, X and Y are Q.11 Transition elements are usually characterised
respectively by variable oxidation states but Zn does not
show this property because of
(A) X = OH–, Y = H+
(B) X = H+, Y = OH– (A) completion of np-orbitals
(C) X = OH–, Y = H 2O 2 (B) completion of (n–1)d orbitals
(C) completion of ns-orbitals
(D) X = H2O2, Y = OH –
(D) inert pair effect
Q.4 CrO3 dissolves in aqueous NaOH to give Q.12 (NH4)2Cr2O7 (Ammonium dichromate) is used
(A) Cr2O7 2– (B) CrO42– in fire works. The green coloured powder
(C) Cr(OH)3 (D) Cr(OH)2 blown in air is
(A) Cr2O3 (B) CrO2
Q.5 An ornamental of gold having 75% of gold, it (C) Cr2O4 (D) CrO3
is of .............. carat.
(A) 18 (B) 16 Q.13 The d-block element which is a liquid at room
(C) 24 (D) 20 temperature, having high specific heat, less
reactivity thanhydrogen and its chloride (MX2)
Q.6 Solution of MnO4– is purple-coloured due to is volatile on heating is
(A) d-d-transition (A) Cu (B) Hg
(B) charge transfer from O to Mn (C) Ce (D) Pm
(C) due to both d-d-transition and charge Q.14 Coinage metals show the properties of
transfer (A) typical elements
(D) none of these (B) normal elements
(C) inner-transition elements
Q.7 Transition elements having more tendency to
(D) transition element
form complex than representative elements
(s and p-block elements) due to Q.15 Iron becomes passive by ..................... due
(A) availability of d-orbitals for bonding to formation of .....................
(B) variable oxidation states are not shown by (A) dil. HCl, Fe2O3
transition elements (B) 80% conc. HNO3, Fe3O 4
(C) all electrons are paired in d-orbitals (C) conc. H2SO4, Fe 3O4
(D) f-orbitals are available for bonding (D) conc. HCl, Fe3O4

22
d & f - block
Q.16 Bayer’s reagent used to detect olifinic double Q.23 1 mole of Fe2+ ions are oxidised to Fe3+ ions
bond is with the help of (in acidic medium)
(A) acidified KMnO4 (A) 1/5 moles of KMnO4
(B) aqueous KMnO4 (B) 5/3 moles of KMnO4
(C) 1% alkaline KMnO4 solution (C) 2/5 moles of KMnO4
(D) KMnO4 in benzene (D) 5/2 moles of KMnO4

The transition metal used in X-rays tube is Q.24 The metals present in insulin and haemoglobin
Q.17 are respectively
(A) Mo (B) Ta
(C) Tc (D) Pm (A) Zn, Hg (B) Zn, Fe
(C) Co, Fe (D) Mg, Fe
Q.18 Cu + conc. HNO3  Cu(NO3)2 + X (oxide
Q.25 The rusting of ironis formulated as Fe2 O3 ·xH2 O
of nitrogen); then X is
which involves the formation of
(A) N2O (B) NO2
(A) Fe2O3 (B) Fe(OH)3
(C) NO (D) N2O3
(C) Fe(OH)2 (D) Fe2O3 + Fe(OH)3

Q.19 When KMnO4 solution is added to hot oxalic Q.26 Metre scales are made-up of alloy
acid solution, the decolourisation is slow in the (A) invar (B) stainless steel
beginning but becomes instantaneous after (C) elektron (D) magnalium
some time. This is because
(A) Mn2+ acts as auto catalyst Q.27 Ametal M which is not affected by strong acids
(B) CO2 is formed like conc. HNO3, conc. H2SO4 and conc.
(C) Reaction is exothermic solution of alkalies like NaOH, KOH forms
(D) MnO4– catalyses the reaction. MCl3 whichfinds use for toning in photography.
The metal M is
Q.20 CuSO4 solution reacts with excess KCN to (A)Ag (B) Hg
give (C)Au (D) Cu
(A) Cu(CN)2 (B) CuCN
(C) K2[Cu(CN)2] (D) K3[Cu(CN)4] Q.28 Solid CuSO4·5H2O having covalent, ionic as
well as co-ordinate bonds. Copper atom/ion
Q.21 The higher oxidation states of transition forms ................. co-ordinate bonds with
elements are found to be in the combination water.
withAand B, which are (A) 1 (B) 2
(C) 3 (D) 4
(A) F, O (B) O, N
(C) O, Cl (D) F, Cl
Q.29 KMnO4 + HCl  H2O + X(g), X is a
(acidified)
Q.22 Pick out the incorrect statement:
(A) red liquid
(A) MnO2 dissolves in conc. HCl, but does
(B) violet gas
not form Mn4+ ions
(C) greenish yellow gas
(B) MnO2 oxidizes hot concentrated H2SO4
(D) yellow-brown gas
liberating oxygen
(C) K2MnO4 is formed when MnO2 in fused Q.30 Purple of cassius is:
KOH is oxidised by air, KNO3 , PbO2 or (A) Pure gold
NaBiO3 (B) Colliodal solution of gold
(D) Decomposition of acidic KMnO4 is not (C) Gold (I) hydroxide
catalysed by sunlight. (D) Gold (III) chloride

23
d & f - block
Q.31 Amongst the following species, maximum Multiple Correct Question
covalent character is exhibited by Q.38 Potash alumis a double salt, its aqueous solution
(A) FeCl2 (B) ZnCl2 shows the characteristics of
(C) HgCl2 (D) CdCl2 (A) Al3+ ions (B) K+ ions
(C) SO42– ions
Q.32 Number of moles of SnCl2 required for the (D)Al3+ ions but not K+ ions
reduction of 1 mole of K2Cr2O7 into Cr2O3 is
(in acidic medium) Q.39 Addition of non-metals like B and C to the
(A) 3 (B) 2 interstitial sites of a transition metal results the
(C) 1 (D) 1/3 metal
(A) of more ductability (B) of less ductability
Q.33 The aqueous solution of CuCrO4 is green (C) less malleable (D) of more hardness
because it contains
(A) green Cu2+ ions Q.40 Mercury is a liquid at 0°C because of
(B) green CrO42– ions (A) veryhigh ionisation energy
(C) blue Cu2+ ions and green CrO42– ions (B) weak metallic bonds
(D) blue Cu2+ ions and yellow CrO42– ions (C) high heat of hydration
(D) high heat of sublimation
Q.34 Manganese steel is used for making railway
tracks because Q.41 The ionisation energies of transition elements
(A) it is hard with high percentage of Mn are
(B) it is soft with high percentage of Mn (A) less than p-block elements
(C) it is hard with small concentration of (B) more than s-block elements
manganese with impurities (C) less than s-block elements
(D) it is soft with small concentration of (D) more than p-block elements
manganese with impurities
Q.42 The metal(s) which does/do not form amalgam
Q.35 In nitroprusside ion, the iron exists as Fe2+ and is/are
NO as NO + rather than Fe 3+ and NO (A) Fe (B) Pt
respectively. These formsofions are established (C) Zn (D)Ag
with the help of
(A) magnetic moment in solid state Q.43 The highest oxidation state among transition
(B) thermal decomposition method elements is
(C) by reaction with KCN (A) + 7 by Mn (B) + 8 by Os
(D) by action with K2SO4 (C) + 8 by Ru (D) + 7 by Fe

Q.36 Transition elements in lower oxidation states Q.44 Amphoteric oxide(s) is/are
act as Lewis acid because (A) Al2O3 (B) SnO
(A) they form complexes (C) ZnO (D) Fe2O3
(B) they are oxidising agents
(C) they donate electrons Q.45 Interstitial compounds are formed by
(D) they do not show catalytic properties (A) Co (B) Ni
(C) Fe (D) Ca
Q.37 The Ziegle r-Natta cat alys t used for Q.46 The catalytic activity of transition elements is
polymerisation of ethene and styrene is TiCl4 + related to their
(C2H5)3Al, the catalysing species (active (A) variable oxidation states
species) involved in the polymerisation is (B) surface area
(A) TiCl4 (B) TiCl3 (C) complex formation ability
(C) TiCl2 (D) TiCl (D) magnetic moment

24
d & f - block
Q.47 In the equation: M + 8CN– + 2H2O + O2  Statement Type Question
4[M(CN)2]– + 4OH –, metal M is Questions given below consist of two
(A)Ag (B)Au statements each printed as Assertion (A) and
(C) Cu (D) Hg
Reason (R); while answering these questions
Q.48 An element of 3d-transition series shows two you are required to choose any one of the
oxidation states x and y, differ by two units then following four responses:
(A) compounds in oxidation state x are ionic if (A) if both (A) and (R) are true and (R) is the
x>y correct explanation of (A)
(B) compounds in oxidation state x are ionic if (B) if both (A) and (R) are true but (R) is not
x<y correct explanation of (A)
(C) compounds in oxidation state yare covalent (C) if (A) is true but (R) is false
if x < y (D) if (A) is false and (R) is true
(D) compounds in oxidation state y are covalent Q.56
Statement-1: K2CrO4 has yellow colour due
if y < x
to charge transfer.
Q.49 To an acidified dichromate solution, a pinch of Statement-2: CrO2
4
ion is tetrahedral in
Na2O2 is added and shaken. What is observed: shape.
(A) blue colour
(B) Orange colour changing to green Q.57 Statement-1: The highest oxidation state of
(C) Copious evolution of oxygen chromium in its compounds is +6.
(D) Bluish - green precipitate
Statement-2: Chromium atom has only six
Q.50 Amongst CuF2, CuCl2 and CuBr2 electrons in ns and (n–1) d orbitals.
(A) only CuF2 is ionic
(B) both CuCl2 and CuBr2 are covalent Q.58 Statement-1 : Tungsten has a very high
(C) CuF2 and CuCl2 are ionic but CuBr2 is melting point.
covalent Statement-2 : Tungsten is a covalent
(D) CuF2, CuCl2 as well as CuBr2 are ionic compound.
Q.51 CuSO4(aq) + 4NH3  X, then X is
Q.59 Statement-1: Equivalent mass of KMnO4 is
(A) [Cu(NH3)4]2+
(B) paramagnetic equal to one-third of its molecular mass whe n
(C) coloured it acts asan oxidising gent inan alkaline medium.
(D) of a magnetic moment of 1.73 BM Statement-2: Oxidation number of Mn is +7
in KMnO4.
Q.52 Amphoteric oxide(s) of Mn is/are
(A) MnO2 (B) Mn3O4 Q.60 Statement-1: Cu+ ion is colourless.
(C) Mn2O7 (D) MnO Statement-2: Four water molecules are
Acidified KMnO4 can be decolourised by coordinated to Cu+ ion.
Q.53
(A) SO2 (B) H2O2
(C) FeSO4 (D) Fe2(SO4)3
Q.54 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.55 Ion(s) having non zero magnetic moment (spin
only) is/are
(A) Sc3+ (B) Ti3+
(C) Cu2+ (D) Zn2+

25
d & f - block

ANSWER KEY
EXERCISE - II
Q.1 Formation of MnO4–
Q.2 Due to disproportionation of Hg22+
Q.3 NH3 - strong ligand causes pairing of electrons. So complex is diamagneitc. F– is a weak ligand and so
pairing is not possible.
Q.4 [Al (OH)3 and NaAlO2; Zn(OH)2 and Na2ZnO2] also [Zn(NH3)4]2+
Q.5 [Zn S is white but PbS is black].
Q.6 [A] = ZnCl2; [B] = Zn(OH)2; [C] = Na2ZnO2; [D] = ZnS; [E] = AgCl l

Q.7 All the three elements have d10

Q.8 See text for the reaction of HCl and KMnO4.
Q.9 [(A) = ZnSO3; (B) = ZnO ; (C) = SO2 ; (D) = ZnS]
Q.10 3/2 M
Q.11 K2[Pt Cl6]
Q.12 Cl– is a weak ligand—so no pairing of electrons. CO is a strong field ligand and, therefore, causes
pairing of electrons.
Q.13 In the first case, a double salt is formed. In the second case, a complex is formed. So no test.
Q.14 (A) = [Cr(H2O)6]Cl3 ; (B) = [CrCl(H2O)5]Cl2 H2O (C) = [Cr Cl2(H2O)4]Cl2.2H2O
Q.15 (A) = [Cr(NH3)4 Cl Br]+ Cl– and (B) = [Cr(NH3)4Cl2]+ Br–.
Q.16 [Co(NH3)4 Cl(H2O)] SO4 ;[Co(NH3)4(SO4)(H2O)]Cl [Co(NH3)4(SO4)(Cl)] H2O

EXERCISE - III
Q.1 A Q.2 B Q.3 A Q.4 B Q.5 A

Q.6 B Q.7 A Q.8 A Q.9 B Q.10 A

Q.11 B Q.12 A Q.13 B Q.14 D Q.15 B

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

Q.21 A Q.22 D Q.23 A Q.24 B Q.25 D

Q.26 A Q.27 C Q.28 D Q.29 C Q.30 B

Q.31 C Q.32 A Q.33 D Q.34 A Q.35 A

Q.36 A Q.37 B Q.38 A,B,C Q.39 B,C,D Q.40 A,B

Q.41 A,B Q.42 A,B Q.43 B,C Q.44 A,B,C Q.45 A,B,C
Q.46 A,B,C Q.47 A,B Q.48 B,C Q.49 A,C Q.50 A,B

Q.51 A,B,C,D Q.52 A,B Q.53 A,B,C Q.54 A,B Q.55 B,C
Q.56 B Q.57 A Q.58 C Q.59 B Q.60 C

26